14
The impact of the hyperacid Ijen Crater Lake: risks of excess fluoride to human health Alex Heikens a , Sri Sumarti b,c , Manfred van Bergen b , Budi Widianarko d , Luuk Fokkert e , Kees van Leeuwen f , Willem Seinen a, * a Institute for Risk Assessment Sciences, Yalelaan 2, 3584 CM, The Netherlands b Faculty of Geosciences, University of Utrecht, Budapestlaan 4, 3584 CD Utrecht, The Netherlands c Volcanology and Geological Hazard Mitigation, Jalan Cendana 15, Yogyakarta, Indonesia d Soegijapranata Catholic University, Jl. Pawiyatan Luhur IV/I, Bendang Duwur, Semarang 50234, Indonesia e National Institute of Public Health and the Environment (RIVM), Antonie van Leeuwenhoeklaan 9, 3721 MA, Bilthoven, The Netherlands f European Commission, Joint Research Institute, Via E. Fermi 1, I-21020 Ispra (VA), Italy Received 15 July 2004; accepted 1 December 2004 Available online 29 January 2005 Abstract The Asembagus irrigation area (East Java, Indonesia) receives a high input of fluoride (F) via surface water that partially originates from the hyperacid crater lake of the Ijen volcano. Endemic dental fluorosis among local residents has been ascribed to F in water wells. In this study, the total F intake by children and adults was estimated, based on concentrations in well waters and foods throughout the area. These values were compared with the Lowest Observed Adverse Effect Level (LOAEL) for dental fluorosis among children and skeletal fluorosis among adults. Fluorosis hazard maps were prepared, identifying the most hazardous locations in the area. It was concluded that there is not only a high risk of dental fluorosis, but also of skeletal fluorosis. Based on the total daily intake, the lowest F concentration in drinking water that poses a risk of developing fluorosis is approximately 0.5 mg/l for dental fluorosis and 1.1 mg/l for skeletal fluorosis. This is below 1.5 mg/l, which is both the guideline value for drinking water from the World Health Organization (WHO) and the Indonesian drinking water standard. This is the first documented case of human health problems that may be directly associated with natural pollutants originating from a volcano-hosted crater lake. D 2004 Elsevier B.V. All rights reserved. Keywords: Acid crater lake; Drinking water standard; Fluorosis; F total daily intake; Groundwater; Volcanic activity 1. Introduction Dental fluorosis is endemic in residents of the Asembagus coastal area (East Java, Indonesia), where agricultural land is irrigated with F-rich river 0048-9697/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.scitotenv.2004.12.007 * Corresponding author. Tel.: +31 30 2535336; fax: +31 30 25335077. E-mail address: [email protected] (W. Seinen). Science of the Total Environment 346 (2005) 56– 69 www.elsevier.com/locate/scitotenv

The Impact of the Hyperacid Ijen Crater Lake. Part I: Concentrations of Elements in Crops and Soil

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wwwelseviercomlocatescitotenv

Science of the Total Environ

The impact of the hyperacid Ijen Crater Lake risks of excess

fluoride to human health

Alex Heikensa Sri Sumartibc Manfred van Bergenb Budi Widianarkod Luuk Fokkerte

Kees van Leeuwenf Willem Seinena

aInstitute for Risk Assessment Sciences Yalelaan 2 3584 CM The NetherlandsbFaculty of Geosciences University of Utrecht Budapestlaan 4 3584 CD Utrecht The Netherlands

cVolcanology and Geological Hazard Mitigation Jalan Cendana 15 Yogyakarta IndonesiadSoegijapranata Catholic University Jl Pawiyatan Luhur IVI Bendang Duwur Semarang 50234 Indonesia

eNational Institute of Public Health and the Environment (RIVM) Antonie van Leeuwenhoeklaan 9 3721 MA Bilthoven The NetherlandsfEuropean Commission Joint Research Institute Via E Fermi 1 I-21020 Ispra (VA) Italy

Received 15 July 2004 accepted 1 December 2004

Available online 29 January 2005

Abstract

The Asembagus irrigation area (East Java Indonesia) receives a high input of fluoride (F) via surface water that partially

originates from the hyperacid crater lake of the Ijen volcano Endemic dental fluorosis among local residents has been ascribed

to F in water wells In this study the total F intake by children and adults was estimated based on concentrations in well waters

and foods throughout the area These values were compared with the Lowest Observed Adverse Effect Level (LOAEL) for

dental fluorosis among children and skeletal fluorosis among adults Fluorosis hazard maps were prepared identifying the most

hazardous locations in the area It was concluded that there is not only a high risk of dental fluorosis but also of skeletal

fluorosis Based on the total daily intake the lowest F concentration in drinking water that poses a risk of developing fluorosis is

approximately 05 mgl for dental fluorosis and 11 mgl for skeletal fluorosis This is below 15 mgl which is both the

guideline value for drinking water from the World Health Organization (WHO) and the Indonesian drinking water standard

This is the first documented case of human health problems that may be directly associated with natural pollutants originating

from a volcano-hosted crater lake

D 2004 Elsevier BV All rights reserved

Keywords Acid crater lake Drinking water standard Fluorosis F total daily intake Groundwater Volcanic activity

0048-9697$ - see front matter D 2004 Elsevier BV All rights reserved

doi101016jscitotenv200412007

Corresponding author Tel +31 30 2535336 fax +31 30

25335077

E-mail address WSeinenirasuunl (W Seinen)

1 Introduction

Dental fluorosis is endemic in residents of the

Asembagus coastal area (East Java Indonesia)

where agricultural land is irrigated with F-rich river

ment 346 (2005) 56ndash69

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 57

water originating from the hyperacid Ijen Crater

Lake (Fig 1) The fluorosis problem has been

attributed to high fluoride concentrations in local

water wells (Rai 1980 Budipramana et al 2002)

Budipramana et al (2002) found a prevalence of

dental fluorosis of 96 among 6ndash12 year old school

children tested in ten villages of the Asembagus

subdistrict supporting earlier findings (Budipramana

et al 2002) Dental fluorosis was already observed

where well water contained as little as ~05 mgl F

which is below the World Health Organization

(WHO) guideline value of 15 mgl F for drinking

water (WHO 1996) This guideline value has been

adopted by the Indonesian government as the

national drinking water standard

Fig 1 Overview of the water system from the Ijen Crater Lake to the Ase

Lake is forming a small river with many small tributaries which is joined

and has a discharge of ~35 m3s During the dry season all river water is

Chronic exposure to F can cause various adverse

effects whereby the disturbance of bone tissue

structure due to excessive incorporation of F is

regarded as critical The first symptom is discoloration

of teeth as these become porous and brittle (dental

fluorosis) Dental fluorosis can arise until the age of 6

to 8 years when the development of teeth is more or

less completed In the second stage the skeleton is

affected (skeletal fluorosis) resulting in eg chronic

joint pain and osteosclerosis It occurs after long-term

exposure and is therefore mainly observed among

adults The most severe form is crippling skeletal

fluorosis which is associated with symptoms such as

restricted movement of the joints and skeletal deform-

ities (WHO 2002) The Lowest Observed Adverse

mbagus area on East Java Indonesia Effluent from the Ijen Crater

by two neutral rivers After this point the river is called Banyuputih

directed into irrigation canals via the sluices in Lewung

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6958

Effect Level (LOAEL) for dental fluorosis among

children is 01 mgkg body weight per day (WHO

1984) Concerning skeletal fluorosis among adults

the WHO concluded that a daily intake of 14 mgday

is clearly harmful and that the first adverse effects

may occur at 6 mgday (WHO 2002) The latter value

will be adopted as the LOAEL for skeletal fluorosis in

the present study

Cases of endemic fluorosis have been reported

from many regions worldwide especially in East

Africa India and China where millions of people are

affected In East Africa (Rift Valley area) and India it

is mainly related to high F concentrations in natural

groundwater in conjunction with a high water intake

(Choubisa 1999 Reimann et al 2003 Kloos and

Tekle Haimanot 1999 Srikanth et al 2002) Sources

other than drinking water can also contribute signifi-

cantly to the prevalence of fluorosis as well In China

for example it is also related to indoor burning of F-

rich coals and to the consumption of brick tea (Wang

and Huang 1995)

To date the total daily F intake and the potential

risks of skeletal fluorosis for residents in the

Asembagus area have not been assessed In this study

the total daily F intake by children and adults is

quantified and results are compared with the LOAEL

values for dental and skeletal fluorosis established by

the WHO As there are considerable spatial variations

in F concentrations in well waters a fluorosis hazard

map for the Asembagus area has been constructed

whereby the F intake via food drinking water and

surface water has been taken into account

2 Site description

The Asembagus coastal plain is situated in the

Situbondo district in the north-eastern part of Java

(Fig 1) The study area of approximately 1513 km

encompasses the sub-districts of Asembagus Banyu-

putih and Jangkar and is here referred to as the

dAsembagus areaT for convenience The altitude of thearea ranges between 140 m in the foothills of the Ijen

volcanic complex to the south and sea level to the north

The water table is around 10ndash30 m depth and the soil is

a volcanic ash soil Climatic conditions are typical for

tropical coastal lowland with an average daily temper-

ature of 29 8C and a relatively low average yearly

rainfall of ~700 mm Socioeconomic conditions in this

rural area are fairly homogeneous The ~100000

inhabitants of the villages largely rely on locally

produced crops and on privately owned wells for food

and water supplies Principal agricultural food products

are rice maize cassava and mixed vegetables whereas

sugarcane is produced on an industrial basis

A large part of arable land (~36 km2) is irrigated

with water taken from the Banyuputih River that is

contaminated with effluent from the hyperacid Ijen

Crater Lake some 40 km to the south of the area The

lake has a pH below 03 and contains ~1500 mgl F

whereas the river water ranges in pH between 25 and

45 and contains 5ndash14 mgl F at the irrigation inlet

point where it also used for bathing and washing

During the dry season (AprilndashOctober) all river water

is discharged into the irrigation network via a sluice

system whereas any surplus water during the rainy

season (NovemberndashMarch) is directed into the sea via

the original riverbed It has been estimated that on

average 2800 kg F is discharged into the irrigation area

per day (Delmelle and Bernard 2000)

3 Method

31 Sampling

311 Water

During the dry seasons of 1999 and 2000 54 water

wells were sampled whereby some wells were visited

twice to detect possible temporal fluctuations A

limited number of these wells were sampled again at

the end of the rainy season of 2001 to allow

comparison under different climatic conditions Sam-

ple locations were selected to obtain representative

data sets for wells both in areas irrigated with the

contaminated water and in areas irrigated with other

water sources Between May 2000 and September

2002 river water samples were collected monthly at

the irrigation inlet point near Lewung in cooperation

with staff of the Asembagus irrigation office For

comparison F concentrations were also determined in

river water samples take during earlier dry seasons

(August 1996 September 1997 July and August

1999) All samples were filtered over a 045 Amcellulose nitrate membrane filter before storage in

polyethylene bottles

Table 1

Daily consumption number of samples and F concentrations in

foods drinking water and surface water

Product Consumption

(gday)aNo of

samples

F concentration

(Agg dw)

Adult Child

Rice 227 132 20b b20

Maize 113 99 20b b20

Cassava root 40 66 5 b20

Vegetables 90 90 9 b20

Cassava leaf 10 10 3 53F13

Peanuts 18 13 3 22F11

Fruit 62 33 2 b20

Marine fish 60 22 3 172F92

Chicken 20 11 1 b20

Teac 2 05 5 217F118

(lday) (lday) mgl

Drinking waterd 4 2 54 b01ndash42

River watere 002 005 17f 55ndash142f

a Consumption of raw food items by adults was based on data

published by BPS Statistics Indonesia in 2002 (wwwbpsgoid

statbysectorconsexptable5shtml) data for children was obtained

from (Kardjati et al 1979)b 15 samples from the contaminated area and 5 from the

surrounding non-contaminated areac It is assumed that adults and children consume respectively 05 l

of tea (4 cups) and 0125 l (1 cup) per day and that 4 g of dry teal is

used and as a reasonable worst case scenario that 100 of F is

released from the tea leaves into the water (Fung 1999)d Including water used for preparation of tea and rice (Shimbo et

al 2001)e River water ingestion via bathing washing and agricultural

practices was included for adults living within the irrigation area

For children living close to the sluices at Lewung (within 1 km) or

upstream swimming was included as a source of river water

ingestion (Otte et al 2000) For calculating the F intake during

swimming the highest measured F concentration was usedf Data monthly sampling May 2000ndashSeptember 2002

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 59

312 Food

In June and August 2000 edible parts of crops (rice

maize cassava root cassava leaf and peanuts) were

collected in the area where contaminated irrigation

water is being used and in the surrounding area as a

reference Sampling focused on rice and maize as

being the most cultivated and consumed food crops in

Asembagus A stratified random sampling strategy

was applied and all sampling locations were deter-

mined with Global Positioning System (GPS) For

rice maize and peanuts one sample per field was

randomly collected A sample consisted of ~05 kg

rice ~03 kg maize or ~200 g unpeeled peanuts For

cassava one plant was regarded as one sample divided

into roots and leaves For cassava root one sample

consisted of 2ndash3 roots per plant For cassava leaf one

sample consisted of all leaves from the plant On local

markets other food items (vegetables fruit tea

chicken and fish) commonly available but not pro-

duced in the area were collected Rice and maize were

sun dried for 3 days and rice was husked with a pestle

and mortar Other food samples were rinsed with tap

water and ultrapure water (Milli-Q Millipore Billerica

USA) and dried at 40 8C in an oven with forced

ventilation for 2 days All samples were ground with

an ultra-centrifugal grinder (Retsch ZM 1000) passing

a 4 mm titanium sieve at 15000 rpm The water content

of foods was determined by drying a 2ndash5 g subsample

for 24 h at 105 8C until constant weight was achieved

A representative selection of samples (roughly 50 of

all collected samples) from the contaminated area the

non-contaminated area and the local markets was

processed for F analysis (Table 1) after initial analyses

showed that F concentrations in most food items were

below the detection limit of 2 mgkg dry weight

32 Chemical analysis

321 Water samples

F was measured with a Dionex DX120 ion

chromatograph In short 25 Al sample was injected

and was led over an Ionpac AG14 precolumn and an

AS14 column with a flow rate of 12 mlmin 35 mM

Na2CO310 mM NaHCO3 was used as eluent F was

then measured with a Pulse Electrochemical Detector

in the conductivity mode A quadratic calibration

based on five standard solutions measured in duplicate

was applied

The regression coefficient of the calibration was

0999 or higher and the calibration was repeated after

every ten samples Quality control standards were

analyzed and results were within 95 of the

expected values Blanks were also included and F

concentrations were below the detection limit of

01 mgl

322 Food samples

To extract the F from food (including tea) an

adapted alkali fusion technique was used (McQuaker

and Gurney 1977) Two millilitres of a 17 M NaOH

Table 2

Location sampling date (monthyear) pH and F concentration of water wells in the Asembagus area

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

Jangkar 1 Agel Pelabuan 10988 42914 0601 73 b01a

10005 44047 0601 72 b01a

2 Kombangsari Dawuhan 11048 43679 1099 76 b01a

3 Gadingan No data

4 Jangkar Pasarnangka 12644 43081 1099 72 b01a

Dami 12609 43962 1099 70 b01b

Jangkar 12714 44077 1099 66 25b

5 Pesanggrahan No data

6 Plalangan Plalangan Tengah 11450 44600 1099 75 03a

7 Curah Kalak Curah Kalak Tengah 10990 45682 1099 73 07a

8 Sopet Teteh 2 10912 47870 0601 72 b01a

10871 47656 0601 73 04a

Sopet 2 10541 46100 0601 77 05a

10541 46107 1099 73 05a

Pareyaan 10455 46510 0601 72 b01a

Batuwayang 10000 47833 0601 72 b01a

Cottok 10250 46100 0601 75 b01a

Nangger 9773 46564 0601 72 b01a

Asembagus 9 Wringianom Banongan Utara 13835 43506 0601 78 b01a

13849 43287 0601 72 25b

Asta 13277 42744 0601 74 22a

Widuri Utara 14977 42658 0601 74 27a

14670 43619 0601 76 30b

10 Asembagus Asembagus Timur 13172 44982 1099 73 b01b

Asembagus Tengah 12550 44690 1099 72 32b

11 Gudang Gudang Utara 13122 44417 0601 66 26b

13789 44213 1099 69 26b

12 Mojosari Karang Tengah 11329 45679 1099 70 b01b

13 Kertosari Lombung 12425 46121 1099 69 b01b

Krajan 12011 45278 1099 72 b01b

14 Trigonco Trigonco Tengah 12552 44914 1099 63 08b

Rarsquoasan Barat 12441 46250 1099 69 25b

15 Perante No data

16 Kedunglo Panjalinan 12611 47778 1099 66 b01a

17 Bantal Lewung 14279 48482 1099 59 14bc

14324 48313 1099 72 18bc

14329 48313 1099 64 22bc

Samir 14132 49449 1099 65 24bc

Kenanga 13961 47536 0601 65 32b

Krajan 2 13015 47313 1099 69 1b

Banyuputih 18 Banyuputih Curah Laci 14557 45169 1099 68 31b

Enoman 14863 46863 0601 66 41d

19 Sumberejo Bangeran 16617 46185 0601 73 b01a

Sodung Lao 15749 47103 1099 72 03a

Leduk Utara 14463 47468 1099 74 11d

14775 47540 1099 70 35d

Leduk Selatan 14404 48425 1099 64 25bc

Gelidik 16250 46100 0601 70 12a

Melek 15800 45867 1099 72 23d

Sukorejo 16300 44914 0601 74 32d

16187 44866 1099 70 35d

16520 44842 0601 73 42d

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6960

Table 2 (continued)

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

20 Sumberanyar Sompelan 17753 44927 0601 76 b01a

Gelidik 17050 46600 0601 75 b01a

Nyamplung 17444 45359 0601 73 03a

Bindung 16901 45396 1099 73 08a

Pandire 16475 47567 0601 73 b01a

The number before the community name refers to the number in the mapsa Located outside the contaminated irrigation areab Located within the contaminated irrigation areac Located close to the dry riverbedd Located within 1 km or upstream from the sluices at Lewung

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 61

solution was added to 025 g sample in a Ni crucible

and successively dried for 30 min at 150 8C and for

30 min at 250 8C in an oven with forced ventilation

Fig 2 F concentrations (mgl) in wate

The crucible was then covered and placed inside a

muffle furnace at 300 8C The temperature was

slowly raised to 600 8C and maintained for 1 h

r wells in the Asembagus area

Table 3

Temporal variations in F concentrations (mgl) in water wells sampled in 1999ndash2001

Village Longitude (1148 ) Latitude (078 ) Oct rsquo99a mgl June rsquo00 mgl April rsquo01 mgl May rsquo01 mgl

Lewung 14279 48482 14 09 1

Lewung 14324 48313 18 24

Lewung 14329 48313 22 13

Samir 14132 49449 24 22 18

Curah Laci 14557 45169 31 37

Sodung Selatan 15749 47103 03 02

Leduk Selatan 14404 48425 25 34

Leduk Utara 14775 4754 35 26

Dami 12609 43962 b01 b01

a Dry season AprilndashOctober rainy season NovemberndashMarch

Table 4

Daily intake of fluoride by children and adults

Source Daily intake (mgday)

Child Adult

Food 06 12

Drinking water b02ndash84 b04ndash168

River water 07 03

Total b08ndash90a b16ndash180a

a The highest value does not include intake via river water since

the water wells with the highest F concentration were neither within

1 km from the sluices at Lewung nor within the irrigation area

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6962

After cooling down to room temperature the residue

was dissolved into ultrapure water (350 ml) on a hot

plate and filtered through a 045 Am mesh width

nylon filter (Millipore) To avoid interferences from

high NaOH concentrations and carbonates the

samples were treated with a cation exchange column

containing 20 meq of H+ (Alltech Maxi-Clean IC-H

Plus) prior to analysis

F was determined with a Dionex DX500 ion

chromatography system as described by Neele and

Cleven (1999) In short 8 Al sample was injected

and led over an Ionpac AG11-HC and AG15

precolumn and an Ionpac AS15 column with a flow

rate of 03 mlmin 32 mM KOH was used as eluent

F was then measured with a Pulse Electrochemical

Detector in the conductivity mode The type of

calibration was quadratic based on 7 standards

measured in duplicate

The regression coefficient of the calibration

curve was 0999 or higher Results of additional

quality control standards (010 mgl and 100 mgl)

were within 95 of the expected value During

analyses drift standards (152 mgl F) were

measured after each 14 samples and the maximum

allowed deviation from the expected value was 5

The analytical procedure (alkali fusion technique in

combination with IC) was tested on the standard

reference material NIST-2695 (vegetation) and by

including blanks and duplicate measurements

Results showed a good recovery and reproducibil-

ity the measured F concentration in NIST-2695

was 688F06 mgkg dw (certified value 640F51

mgkg) The detection limit for F in food was

20 mgkg dw

33 Calculation of the total daily intake and hazard

quotients

The total daily intake of F (mgday) is calculated

with formula 1 in which i is the source C is the

concentration in that source (Agg or mgl) I is the

ingestion rate of the source (gday or lday) (Table 1)

Total daily intake frac14X

i

CiIi eth1THORN

For each water well the Hazard Quotient (HQ) for

dental fluorosis among children and skeletal fluorosis

among adults is calculated by dividing the total daily

intake by the applicable LOAEL If HQz1 it is likely

that the effect will occur and the risk of developing

fluorosis will increase with HQ For children calcu-

lations were made for the age of 6 years assuming a

body weight of 16 kg (Suzuki 1988) Hazard maps for

dental and skeletal fluorosis in the Asembagus area

were prepared in which the locations of all water wells

with the accompanying HQ values are given

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 63

4 Results

41 Fluoride in well water

F concentrations in the well waters were in the range

of b01 mgl to 42 mgl (Table 2) Of all the inves-

tigated wells 37 contained b01 mgl 24 contained

03ndash14 mgl and 39 contained more than 14 mgl

The average pH of the well waters was 71F04As can

be seen in Fig 2 the wells with the highest F

concentrations were found close to the riverbed and

within the area where the river water is used for

irrigation In some villages the F concentrations varied

from b01 to 25 mgl within a few hundred meters

Several wells that were repeatedly sampled show some

fluctuation in F concentrations but the available data

are insufficient to infer any pattern induced by seasonal

variations in rainfall (Table 3)

42 Fluoride in river water

Monthly river water monitoring in 2000ndash2002

yielded an average F content of 95 mgl The

concentrations fluctuated between 55 and 142 mgl

with highest values in the dry and lowest in the rainy

season In this period the pH (measured in the

laboratory) varied between 27 and 41 which was

in agreement with occasional measurements in the

field Previous sampling in the dry seasons of 1996ndash

1999 yielded F concentrations of 72ndash99 mgl

0

10

20

30

40

50

60

70

80

90

100

0 1 2F concentration in

c

ontr

ibut

ion

to d

aily

inta

ke

Fig 3 Contribution in terms of percentage to the total daily F intake by c

concentration in drinking water For those water wells closely located to t

43 Fluoride in food

The highest F concentrations were found in tea

followed by marine fish cassava leaf and peanuts

(Table 1) In other foods F concentrations were below

the detection limit of 20 mgkg dw which accounted

for rice which is the main dish as well as maize

cassava root vegetables fruit and chicken F concen-

trations in rice and maize produced in the non-

contaminated area were also below detection limit

Unpublished data obtained from method development

indicated that concentrations in most foods were equal

or below 1 mgkg dw and this value was assigned to

these items for calculations regarding the daily intake

via food

44 Total daily intake of fluoride

Based on the daily consumption pattern as listed

in Table 1 the daily intake of F via food drinking

water and river water has been calculated for each

water well location and is summarized in Table 4

The total daily intake by adults in terms of mg F

per day is a factor of 2 higher as compared to a 6-

year-old child Recalculating the daily intake per kg

body weight would show that the intake by children

(16 kg body weight) is a factor of 2 higher as

compared to adults (60 kg body weight) This is

due to the higher food and drinking water intake by

children per kg body weight

43 drinking water (mgl)

drinking waterfoodriver water

5

hildren via drinking water food and river water at each measured F

he sluices (n=5) swimming was included as a source of intake

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6964

Fig 3 illustrates the contribution of food and water

to the total daily intake by children With increasing F

concentrations in drinking water the contribution of

food to the total daily intake rapidly decreases At 03

mgl food and drinking water both contribute 50 to

the total daily intake while above 12 mgl food

contributes 20 or less For adults the picture is more

or less the same Five water wells are close to the

Fig 4 Hazard map for dental fluorosis among children in the Asembag

accompanying hazard quotient (HQ)

sluices and it can be expected that children that use

these wells will also swim in the river This contributes

07 mgday (ie 11ndash17) to their total daily intake

Adults may be exposed to river water throughout the

irrigation area However river water ingestion only

contributes substantially (03 mgday ie ~15) to the

total daily intake when they consume water from wells

with very low F concentrations (b01 mgl)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 65

The values for the intake via food should be

regarded as indicative only since most of the food

items had F concentrations below detection limit

(Table 1) Taking this into account the contribution to

the intake via food only is as follows for children tea

rice maize and vegetables each 20 and fish ~10

and for adults tea ~40 fish and rice each ~20

maize and vegetables each ~10

Fig 5 Hazard map for skeletal fluorosis among adults in the Asembag

accompanying hazard quotient (HQ)

45 Dental and skeletal fluorosis

Hazard Quotients for dental and skeletal fluorosis

calculated for all water wells have been plotted in

hazard maps (Figs 4 and 5) As drinking water is

generally the most important source of F the hazard

distribution largely coincides with the geographic

pattern in F concentrations in well water (Fig 2)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 57

water originating from the hyperacid Ijen Crater

Lake (Fig 1) The fluorosis problem has been

attributed to high fluoride concentrations in local

water wells (Rai 1980 Budipramana et al 2002)

Budipramana et al (2002) found a prevalence of

dental fluorosis of 96 among 6ndash12 year old school

children tested in ten villages of the Asembagus

subdistrict supporting earlier findings (Budipramana

et al 2002) Dental fluorosis was already observed

where well water contained as little as ~05 mgl F

which is below the World Health Organization

(WHO) guideline value of 15 mgl F for drinking

water (WHO 1996) This guideline value has been

adopted by the Indonesian government as the

national drinking water standard

Fig 1 Overview of the water system from the Ijen Crater Lake to the Ase

Lake is forming a small river with many small tributaries which is joined

and has a discharge of ~35 m3s During the dry season all river water is

Chronic exposure to F can cause various adverse

effects whereby the disturbance of bone tissue

structure due to excessive incorporation of F is

regarded as critical The first symptom is discoloration

of teeth as these become porous and brittle (dental

fluorosis) Dental fluorosis can arise until the age of 6

to 8 years when the development of teeth is more or

less completed In the second stage the skeleton is

affected (skeletal fluorosis) resulting in eg chronic

joint pain and osteosclerosis It occurs after long-term

exposure and is therefore mainly observed among

adults The most severe form is crippling skeletal

fluorosis which is associated with symptoms such as

restricted movement of the joints and skeletal deform-

ities (WHO 2002) The Lowest Observed Adverse

mbagus area on East Java Indonesia Effluent from the Ijen Crater

by two neutral rivers After this point the river is called Banyuputih

directed into irrigation canals via the sluices in Lewung

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6958

Effect Level (LOAEL) for dental fluorosis among

children is 01 mgkg body weight per day (WHO

1984) Concerning skeletal fluorosis among adults

the WHO concluded that a daily intake of 14 mgday

is clearly harmful and that the first adverse effects

may occur at 6 mgday (WHO 2002) The latter value

will be adopted as the LOAEL for skeletal fluorosis in

the present study

Cases of endemic fluorosis have been reported

from many regions worldwide especially in East

Africa India and China where millions of people are

affected In East Africa (Rift Valley area) and India it

is mainly related to high F concentrations in natural

groundwater in conjunction with a high water intake

(Choubisa 1999 Reimann et al 2003 Kloos and

Tekle Haimanot 1999 Srikanth et al 2002) Sources

other than drinking water can also contribute signifi-

cantly to the prevalence of fluorosis as well In China

for example it is also related to indoor burning of F-

rich coals and to the consumption of brick tea (Wang

and Huang 1995)

To date the total daily F intake and the potential

risks of skeletal fluorosis for residents in the

Asembagus area have not been assessed In this study

the total daily F intake by children and adults is

quantified and results are compared with the LOAEL

values for dental and skeletal fluorosis established by

the WHO As there are considerable spatial variations

in F concentrations in well waters a fluorosis hazard

map for the Asembagus area has been constructed

whereby the F intake via food drinking water and

surface water has been taken into account

2 Site description

The Asembagus coastal plain is situated in the

Situbondo district in the north-eastern part of Java

(Fig 1) The study area of approximately 1513 km

encompasses the sub-districts of Asembagus Banyu-

putih and Jangkar and is here referred to as the

dAsembagus areaT for convenience The altitude of thearea ranges between 140 m in the foothills of the Ijen

volcanic complex to the south and sea level to the north

The water table is around 10ndash30 m depth and the soil is

a volcanic ash soil Climatic conditions are typical for

tropical coastal lowland with an average daily temper-

ature of 29 8C and a relatively low average yearly

rainfall of ~700 mm Socioeconomic conditions in this

rural area are fairly homogeneous The ~100000

inhabitants of the villages largely rely on locally

produced crops and on privately owned wells for food

and water supplies Principal agricultural food products

are rice maize cassava and mixed vegetables whereas

sugarcane is produced on an industrial basis

A large part of arable land (~36 km2) is irrigated

with water taken from the Banyuputih River that is

contaminated with effluent from the hyperacid Ijen

Crater Lake some 40 km to the south of the area The

lake has a pH below 03 and contains ~1500 mgl F

whereas the river water ranges in pH between 25 and

45 and contains 5ndash14 mgl F at the irrigation inlet

point where it also used for bathing and washing

During the dry season (AprilndashOctober) all river water

is discharged into the irrigation network via a sluice

system whereas any surplus water during the rainy

season (NovemberndashMarch) is directed into the sea via

the original riverbed It has been estimated that on

average 2800 kg F is discharged into the irrigation area

per day (Delmelle and Bernard 2000)

3 Method

31 Sampling

311 Water

During the dry seasons of 1999 and 2000 54 water

wells were sampled whereby some wells were visited

twice to detect possible temporal fluctuations A

limited number of these wells were sampled again at

the end of the rainy season of 2001 to allow

comparison under different climatic conditions Sam-

ple locations were selected to obtain representative

data sets for wells both in areas irrigated with the

contaminated water and in areas irrigated with other

water sources Between May 2000 and September

2002 river water samples were collected monthly at

the irrigation inlet point near Lewung in cooperation

with staff of the Asembagus irrigation office For

comparison F concentrations were also determined in

river water samples take during earlier dry seasons

(August 1996 September 1997 July and August

1999) All samples were filtered over a 045 Amcellulose nitrate membrane filter before storage in

polyethylene bottles

Table 1

Daily consumption number of samples and F concentrations in

foods drinking water and surface water

Product Consumption

(gday)aNo of

samples

F concentration

(Agg dw)

Adult Child

Rice 227 132 20b b20

Maize 113 99 20b b20

Cassava root 40 66 5 b20

Vegetables 90 90 9 b20

Cassava leaf 10 10 3 53F13

Peanuts 18 13 3 22F11

Fruit 62 33 2 b20

Marine fish 60 22 3 172F92

Chicken 20 11 1 b20

Teac 2 05 5 217F118

(lday) (lday) mgl

Drinking waterd 4 2 54 b01ndash42

River watere 002 005 17f 55ndash142f

a Consumption of raw food items by adults was based on data

published by BPS Statistics Indonesia in 2002 (wwwbpsgoid

statbysectorconsexptable5shtml) data for children was obtained

from (Kardjati et al 1979)b 15 samples from the contaminated area and 5 from the

surrounding non-contaminated areac It is assumed that adults and children consume respectively 05 l

of tea (4 cups) and 0125 l (1 cup) per day and that 4 g of dry teal is

used and as a reasonable worst case scenario that 100 of F is

released from the tea leaves into the water (Fung 1999)d Including water used for preparation of tea and rice (Shimbo et

al 2001)e River water ingestion via bathing washing and agricultural

practices was included for adults living within the irrigation area

For children living close to the sluices at Lewung (within 1 km) or

upstream swimming was included as a source of river water

ingestion (Otte et al 2000) For calculating the F intake during

swimming the highest measured F concentration was usedf Data monthly sampling May 2000ndashSeptember 2002

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 59

312 Food

In June and August 2000 edible parts of crops (rice

maize cassava root cassava leaf and peanuts) were

collected in the area where contaminated irrigation

water is being used and in the surrounding area as a

reference Sampling focused on rice and maize as

being the most cultivated and consumed food crops in

Asembagus A stratified random sampling strategy

was applied and all sampling locations were deter-

mined with Global Positioning System (GPS) For

rice maize and peanuts one sample per field was

randomly collected A sample consisted of ~05 kg

rice ~03 kg maize or ~200 g unpeeled peanuts For

cassava one plant was regarded as one sample divided

into roots and leaves For cassava root one sample

consisted of 2ndash3 roots per plant For cassava leaf one

sample consisted of all leaves from the plant On local

markets other food items (vegetables fruit tea

chicken and fish) commonly available but not pro-

duced in the area were collected Rice and maize were

sun dried for 3 days and rice was husked with a pestle

and mortar Other food samples were rinsed with tap

water and ultrapure water (Milli-Q Millipore Billerica

USA) and dried at 40 8C in an oven with forced

ventilation for 2 days All samples were ground with

an ultra-centrifugal grinder (Retsch ZM 1000) passing

a 4 mm titanium sieve at 15000 rpm The water content

of foods was determined by drying a 2ndash5 g subsample

for 24 h at 105 8C until constant weight was achieved

A representative selection of samples (roughly 50 of

all collected samples) from the contaminated area the

non-contaminated area and the local markets was

processed for F analysis (Table 1) after initial analyses

showed that F concentrations in most food items were

below the detection limit of 2 mgkg dry weight

32 Chemical analysis

321 Water samples

F was measured with a Dionex DX120 ion

chromatograph In short 25 Al sample was injected

and was led over an Ionpac AG14 precolumn and an

AS14 column with a flow rate of 12 mlmin 35 mM

Na2CO310 mM NaHCO3 was used as eluent F was

then measured with a Pulse Electrochemical Detector

in the conductivity mode A quadratic calibration

based on five standard solutions measured in duplicate

was applied

The regression coefficient of the calibration was

0999 or higher and the calibration was repeated after

every ten samples Quality control standards were

analyzed and results were within 95 of the

expected values Blanks were also included and F

concentrations were below the detection limit of

01 mgl

322 Food samples

To extract the F from food (including tea) an

adapted alkali fusion technique was used (McQuaker

and Gurney 1977) Two millilitres of a 17 M NaOH

Table 2

Location sampling date (monthyear) pH and F concentration of water wells in the Asembagus area

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

Jangkar 1 Agel Pelabuan 10988 42914 0601 73 b01a

10005 44047 0601 72 b01a

2 Kombangsari Dawuhan 11048 43679 1099 76 b01a

3 Gadingan No data

4 Jangkar Pasarnangka 12644 43081 1099 72 b01a

Dami 12609 43962 1099 70 b01b

Jangkar 12714 44077 1099 66 25b

5 Pesanggrahan No data

6 Plalangan Plalangan Tengah 11450 44600 1099 75 03a

7 Curah Kalak Curah Kalak Tengah 10990 45682 1099 73 07a

8 Sopet Teteh 2 10912 47870 0601 72 b01a

10871 47656 0601 73 04a

Sopet 2 10541 46100 0601 77 05a

10541 46107 1099 73 05a

Pareyaan 10455 46510 0601 72 b01a

Batuwayang 10000 47833 0601 72 b01a

Cottok 10250 46100 0601 75 b01a

Nangger 9773 46564 0601 72 b01a

Asembagus 9 Wringianom Banongan Utara 13835 43506 0601 78 b01a

13849 43287 0601 72 25b

Asta 13277 42744 0601 74 22a

Widuri Utara 14977 42658 0601 74 27a

14670 43619 0601 76 30b

10 Asembagus Asembagus Timur 13172 44982 1099 73 b01b

Asembagus Tengah 12550 44690 1099 72 32b

11 Gudang Gudang Utara 13122 44417 0601 66 26b

13789 44213 1099 69 26b

12 Mojosari Karang Tengah 11329 45679 1099 70 b01b

13 Kertosari Lombung 12425 46121 1099 69 b01b

Krajan 12011 45278 1099 72 b01b

14 Trigonco Trigonco Tengah 12552 44914 1099 63 08b

Rarsquoasan Barat 12441 46250 1099 69 25b

15 Perante No data

16 Kedunglo Panjalinan 12611 47778 1099 66 b01a

17 Bantal Lewung 14279 48482 1099 59 14bc

14324 48313 1099 72 18bc

14329 48313 1099 64 22bc

Samir 14132 49449 1099 65 24bc

Kenanga 13961 47536 0601 65 32b

Krajan 2 13015 47313 1099 69 1b

Banyuputih 18 Banyuputih Curah Laci 14557 45169 1099 68 31b

Enoman 14863 46863 0601 66 41d

19 Sumberejo Bangeran 16617 46185 0601 73 b01a

Sodung Lao 15749 47103 1099 72 03a

Leduk Utara 14463 47468 1099 74 11d

14775 47540 1099 70 35d

Leduk Selatan 14404 48425 1099 64 25bc

Gelidik 16250 46100 0601 70 12a

Melek 15800 45867 1099 72 23d

Sukorejo 16300 44914 0601 74 32d

16187 44866 1099 70 35d

16520 44842 0601 73 42d

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6960

Table 2 (continued)

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

20 Sumberanyar Sompelan 17753 44927 0601 76 b01a

Gelidik 17050 46600 0601 75 b01a

Nyamplung 17444 45359 0601 73 03a

Bindung 16901 45396 1099 73 08a

Pandire 16475 47567 0601 73 b01a

The number before the community name refers to the number in the mapsa Located outside the contaminated irrigation areab Located within the contaminated irrigation areac Located close to the dry riverbedd Located within 1 km or upstream from the sluices at Lewung

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 61

solution was added to 025 g sample in a Ni crucible

and successively dried for 30 min at 150 8C and for

30 min at 250 8C in an oven with forced ventilation

Fig 2 F concentrations (mgl) in wate

The crucible was then covered and placed inside a

muffle furnace at 300 8C The temperature was

slowly raised to 600 8C and maintained for 1 h

r wells in the Asembagus area

Table 3

Temporal variations in F concentrations (mgl) in water wells sampled in 1999ndash2001

Village Longitude (1148 ) Latitude (078 ) Oct rsquo99a mgl June rsquo00 mgl April rsquo01 mgl May rsquo01 mgl

Lewung 14279 48482 14 09 1

Lewung 14324 48313 18 24

Lewung 14329 48313 22 13

Samir 14132 49449 24 22 18

Curah Laci 14557 45169 31 37

Sodung Selatan 15749 47103 03 02

Leduk Selatan 14404 48425 25 34

Leduk Utara 14775 4754 35 26

Dami 12609 43962 b01 b01

a Dry season AprilndashOctober rainy season NovemberndashMarch

Table 4

Daily intake of fluoride by children and adults

Source Daily intake (mgday)

Child Adult

Food 06 12

Drinking water b02ndash84 b04ndash168

River water 07 03

Total b08ndash90a b16ndash180a

a The highest value does not include intake via river water since

the water wells with the highest F concentration were neither within

1 km from the sluices at Lewung nor within the irrigation area

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6962

After cooling down to room temperature the residue

was dissolved into ultrapure water (350 ml) on a hot

plate and filtered through a 045 Am mesh width

nylon filter (Millipore) To avoid interferences from

high NaOH concentrations and carbonates the

samples were treated with a cation exchange column

containing 20 meq of H+ (Alltech Maxi-Clean IC-H

Plus) prior to analysis

F was determined with a Dionex DX500 ion

chromatography system as described by Neele and

Cleven (1999) In short 8 Al sample was injected

and led over an Ionpac AG11-HC and AG15

precolumn and an Ionpac AS15 column with a flow

rate of 03 mlmin 32 mM KOH was used as eluent

F was then measured with a Pulse Electrochemical

Detector in the conductivity mode The type of

calibration was quadratic based on 7 standards

measured in duplicate

The regression coefficient of the calibration

curve was 0999 or higher Results of additional

quality control standards (010 mgl and 100 mgl)

were within 95 of the expected value During

analyses drift standards (152 mgl F) were

measured after each 14 samples and the maximum

allowed deviation from the expected value was 5

The analytical procedure (alkali fusion technique in

combination with IC) was tested on the standard

reference material NIST-2695 (vegetation) and by

including blanks and duplicate measurements

Results showed a good recovery and reproducibil-

ity the measured F concentration in NIST-2695

was 688F06 mgkg dw (certified value 640F51

mgkg) The detection limit for F in food was

20 mgkg dw

33 Calculation of the total daily intake and hazard

quotients

The total daily intake of F (mgday) is calculated

with formula 1 in which i is the source C is the

concentration in that source (Agg or mgl) I is the

ingestion rate of the source (gday or lday) (Table 1)

Total daily intake frac14X

i

CiIi eth1THORN

For each water well the Hazard Quotient (HQ) for

dental fluorosis among children and skeletal fluorosis

among adults is calculated by dividing the total daily

intake by the applicable LOAEL If HQz1 it is likely

that the effect will occur and the risk of developing

fluorosis will increase with HQ For children calcu-

lations were made for the age of 6 years assuming a

body weight of 16 kg (Suzuki 1988) Hazard maps for

dental and skeletal fluorosis in the Asembagus area

were prepared in which the locations of all water wells

with the accompanying HQ values are given

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 63

4 Results

41 Fluoride in well water

F concentrations in the well waters were in the range

of b01 mgl to 42 mgl (Table 2) Of all the inves-

tigated wells 37 contained b01 mgl 24 contained

03ndash14 mgl and 39 contained more than 14 mgl

The average pH of the well waters was 71F04As can

be seen in Fig 2 the wells with the highest F

concentrations were found close to the riverbed and

within the area where the river water is used for

irrigation In some villages the F concentrations varied

from b01 to 25 mgl within a few hundred meters

Several wells that were repeatedly sampled show some

fluctuation in F concentrations but the available data

are insufficient to infer any pattern induced by seasonal

variations in rainfall (Table 3)

42 Fluoride in river water

Monthly river water monitoring in 2000ndash2002

yielded an average F content of 95 mgl The

concentrations fluctuated between 55 and 142 mgl

with highest values in the dry and lowest in the rainy

season In this period the pH (measured in the

laboratory) varied between 27 and 41 which was

in agreement with occasional measurements in the

field Previous sampling in the dry seasons of 1996ndash

1999 yielded F concentrations of 72ndash99 mgl

0

10

20

30

40

50

60

70

80

90

100

0 1 2F concentration in

c

ontr

ibut

ion

to d

aily

inta

ke

Fig 3 Contribution in terms of percentage to the total daily F intake by c

concentration in drinking water For those water wells closely located to t

43 Fluoride in food

The highest F concentrations were found in tea

followed by marine fish cassava leaf and peanuts

(Table 1) In other foods F concentrations were below

the detection limit of 20 mgkg dw which accounted

for rice which is the main dish as well as maize

cassava root vegetables fruit and chicken F concen-

trations in rice and maize produced in the non-

contaminated area were also below detection limit

Unpublished data obtained from method development

indicated that concentrations in most foods were equal

or below 1 mgkg dw and this value was assigned to

these items for calculations regarding the daily intake

via food

44 Total daily intake of fluoride

Based on the daily consumption pattern as listed

in Table 1 the daily intake of F via food drinking

water and river water has been calculated for each

water well location and is summarized in Table 4

The total daily intake by adults in terms of mg F

per day is a factor of 2 higher as compared to a 6-

year-old child Recalculating the daily intake per kg

body weight would show that the intake by children

(16 kg body weight) is a factor of 2 higher as

compared to adults (60 kg body weight) This is

due to the higher food and drinking water intake by

children per kg body weight

43 drinking water (mgl)

drinking waterfoodriver water

5

hildren via drinking water food and river water at each measured F

he sluices (n=5) swimming was included as a source of intake

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6964

Fig 3 illustrates the contribution of food and water

to the total daily intake by children With increasing F

concentrations in drinking water the contribution of

food to the total daily intake rapidly decreases At 03

mgl food and drinking water both contribute 50 to

the total daily intake while above 12 mgl food

contributes 20 or less For adults the picture is more

or less the same Five water wells are close to the

Fig 4 Hazard map for dental fluorosis among children in the Asembag

accompanying hazard quotient (HQ)

sluices and it can be expected that children that use

these wells will also swim in the river This contributes

07 mgday (ie 11ndash17) to their total daily intake

Adults may be exposed to river water throughout the

irrigation area However river water ingestion only

contributes substantially (03 mgday ie ~15) to the

total daily intake when they consume water from wells

with very low F concentrations (b01 mgl)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 65

The values for the intake via food should be

regarded as indicative only since most of the food

items had F concentrations below detection limit

(Table 1) Taking this into account the contribution to

the intake via food only is as follows for children tea

rice maize and vegetables each 20 and fish ~10

and for adults tea ~40 fish and rice each ~20

maize and vegetables each ~10

Fig 5 Hazard map for skeletal fluorosis among adults in the Asembag

accompanying hazard quotient (HQ)

45 Dental and skeletal fluorosis

Hazard Quotients for dental and skeletal fluorosis

calculated for all water wells have been plotted in

hazard maps (Figs 4 and 5) As drinking water is

generally the most important source of F the hazard

distribution largely coincides with the geographic

pattern in F concentrations in well water (Fig 2)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6958

Effect Level (LOAEL) for dental fluorosis among

children is 01 mgkg body weight per day (WHO

1984) Concerning skeletal fluorosis among adults

the WHO concluded that a daily intake of 14 mgday

is clearly harmful and that the first adverse effects

may occur at 6 mgday (WHO 2002) The latter value

will be adopted as the LOAEL for skeletal fluorosis in

the present study

Cases of endemic fluorosis have been reported

from many regions worldwide especially in East

Africa India and China where millions of people are

affected In East Africa (Rift Valley area) and India it

is mainly related to high F concentrations in natural

groundwater in conjunction with a high water intake

(Choubisa 1999 Reimann et al 2003 Kloos and

Tekle Haimanot 1999 Srikanth et al 2002) Sources

other than drinking water can also contribute signifi-

cantly to the prevalence of fluorosis as well In China

for example it is also related to indoor burning of F-

rich coals and to the consumption of brick tea (Wang

and Huang 1995)

To date the total daily F intake and the potential

risks of skeletal fluorosis for residents in the

Asembagus area have not been assessed In this study

the total daily F intake by children and adults is

quantified and results are compared with the LOAEL

values for dental and skeletal fluorosis established by

the WHO As there are considerable spatial variations

in F concentrations in well waters a fluorosis hazard

map for the Asembagus area has been constructed

whereby the F intake via food drinking water and

surface water has been taken into account

2 Site description

The Asembagus coastal plain is situated in the

Situbondo district in the north-eastern part of Java

(Fig 1) The study area of approximately 1513 km

encompasses the sub-districts of Asembagus Banyu-

putih and Jangkar and is here referred to as the

dAsembagus areaT for convenience The altitude of thearea ranges between 140 m in the foothills of the Ijen

volcanic complex to the south and sea level to the north

The water table is around 10ndash30 m depth and the soil is

a volcanic ash soil Climatic conditions are typical for

tropical coastal lowland with an average daily temper-

ature of 29 8C and a relatively low average yearly

rainfall of ~700 mm Socioeconomic conditions in this

rural area are fairly homogeneous The ~100000

inhabitants of the villages largely rely on locally

produced crops and on privately owned wells for food

and water supplies Principal agricultural food products

are rice maize cassava and mixed vegetables whereas

sugarcane is produced on an industrial basis

A large part of arable land (~36 km2) is irrigated

with water taken from the Banyuputih River that is

contaminated with effluent from the hyperacid Ijen

Crater Lake some 40 km to the south of the area The

lake has a pH below 03 and contains ~1500 mgl F

whereas the river water ranges in pH between 25 and

45 and contains 5ndash14 mgl F at the irrigation inlet

point where it also used for bathing and washing

During the dry season (AprilndashOctober) all river water

is discharged into the irrigation network via a sluice

system whereas any surplus water during the rainy

season (NovemberndashMarch) is directed into the sea via

the original riverbed It has been estimated that on

average 2800 kg F is discharged into the irrigation area

per day (Delmelle and Bernard 2000)

3 Method

31 Sampling

311 Water

During the dry seasons of 1999 and 2000 54 water

wells were sampled whereby some wells were visited

twice to detect possible temporal fluctuations A

limited number of these wells were sampled again at

the end of the rainy season of 2001 to allow

comparison under different climatic conditions Sam-

ple locations were selected to obtain representative

data sets for wells both in areas irrigated with the

contaminated water and in areas irrigated with other

water sources Between May 2000 and September

2002 river water samples were collected monthly at

the irrigation inlet point near Lewung in cooperation

with staff of the Asembagus irrigation office For

comparison F concentrations were also determined in

river water samples take during earlier dry seasons

(August 1996 September 1997 July and August

1999) All samples were filtered over a 045 Amcellulose nitrate membrane filter before storage in

polyethylene bottles

Table 1

Daily consumption number of samples and F concentrations in

foods drinking water and surface water

Product Consumption

(gday)aNo of

samples

F concentration

(Agg dw)

Adult Child

Rice 227 132 20b b20

Maize 113 99 20b b20

Cassava root 40 66 5 b20

Vegetables 90 90 9 b20

Cassava leaf 10 10 3 53F13

Peanuts 18 13 3 22F11

Fruit 62 33 2 b20

Marine fish 60 22 3 172F92

Chicken 20 11 1 b20

Teac 2 05 5 217F118

(lday) (lday) mgl

Drinking waterd 4 2 54 b01ndash42

River watere 002 005 17f 55ndash142f

a Consumption of raw food items by adults was based on data

published by BPS Statistics Indonesia in 2002 (wwwbpsgoid

statbysectorconsexptable5shtml) data for children was obtained

from (Kardjati et al 1979)b 15 samples from the contaminated area and 5 from the

surrounding non-contaminated areac It is assumed that adults and children consume respectively 05 l

of tea (4 cups) and 0125 l (1 cup) per day and that 4 g of dry teal is

used and as a reasonable worst case scenario that 100 of F is

released from the tea leaves into the water (Fung 1999)d Including water used for preparation of tea and rice (Shimbo et

al 2001)e River water ingestion via bathing washing and agricultural

practices was included for adults living within the irrigation area

For children living close to the sluices at Lewung (within 1 km) or

upstream swimming was included as a source of river water

ingestion (Otte et al 2000) For calculating the F intake during

swimming the highest measured F concentration was usedf Data monthly sampling May 2000ndashSeptember 2002

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 59

312 Food

In June and August 2000 edible parts of crops (rice

maize cassava root cassava leaf and peanuts) were

collected in the area where contaminated irrigation

water is being used and in the surrounding area as a

reference Sampling focused on rice and maize as

being the most cultivated and consumed food crops in

Asembagus A stratified random sampling strategy

was applied and all sampling locations were deter-

mined with Global Positioning System (GPS) For

rice maize and peanuts one sample per field was

randomly collected A sample consisted of ~05 kg

rice ~03 kg maize or ~200 g unpeeled peanuts For

cassava one plant was regarded as one sample divided

into roots and leaves For cassava root one sample

consisted of 2ndash3 roots per plant For cassava leaf one

sample consisted of all leaves from the plant On local

markets other food items (vegetables fruit tea

chicken and fish) commonly available but not pro-

duced in the area were collected Rice and maize were

sun dried for 3 days and rice was husked with a pestle

and mortar Other food samples were rinsed with tap

water and ultrapure water (Milli-Q Millipore Billerica

USA) and dried at 40 8C in an oven with forced

ventilation for 2 days All samples were ground with

an ultra-centrifugal grinder (Retsch ZM 1000) passing

a 4 mm titanium sieve at 15000 rpm The water content

of foods was determined by drying a 2ndash5 g subsample

for 24 h at 105 8C until constant weight was achieved

A representative selection of samples (roughly 50 of

all collected samples) from the contaminated area the

non-contaminated area and the local markets was

processed for F analysis (Table 1) after initial analyses

showed that F concentrations in most food items were

below the detection limit of 2 mgkg dry weight

32 Chemical analysis

321 Water samples

F was measured with a Dionex DX120 ion

chromatograph In short 25 Al sample was injected

and was led over an Ionpac AG14 precolumn and an

AS14 column with a flow rate of 12 mlmin 35 mM

Na2CO310 mM NaHCO3 was used as eluent F was

then measured with a Pulse Electrochemical Detector

in the conductivity mode A quadratic calibration

based on five standard solutions measured in duplicate

was applied

The regression coefficient of the calibration was

0999 or higher and the calibration was repeated after

every ten samples Quality control standards were

analyzed and results were within 95 of the

expected values Blanks were also included and F

concentrations were below the detection limit of

01 mgl

322 Food samples

To extract the F from food (including tea) an

adapted alkali fusion technique was used (McQuaker

and Gurney 1977) Two millilitres of a 17 M NaOH

Table 2

Location sampling date (monthyear) pH and F concentration of water wells in the Asembagus area

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

Jangkar 1 Agel Pelabuan 10988 42914 0601 73 b01a

10005 44047 0601 72 b01a

2 Kombangsari Dawuhan 11048 43679 1099 76 b01a

3 Gadingan No data

4 Jangkar Pasarnangka 12644 43081 1099 72 b01a

Dami 12609 43962 1099 70 b01b

Jangkar 12714 44077 1099 66 25b

5 Pesanggrahan No data

6 Plalangan Plalangan Tengah 11450 44600 1099 75 03a

7 Curah Kalak Curah Kalak Tengah 10990 45682 1099 73 07a

8 Sopet Teteh 2 10912 47870 0601 72 b01a

10871 47656 0601 73 04a

Sopet 2 10541 46100 0601 77 05a

10541 46107 1099 73 05a

Pareyaan 10455 46510 0601 72 b01a

Batuwayang 10000 47833 0601 72 b01a

Cottok 10250 46100 0601 75 b01a

Nangger 9773 46564 0601 72 b01a

Asembagus 9 Wringianom Banongan Utara 13835 43506 0601 78 b01a

13849 43287 0601 72 25b

Asta 13277 42744 0601 74 22a

Widuri Utara 14977 42658 0601 74 27a

14670 43619 0601 76 30b

10 Asembagus Asembagus Timur 13172 44982 1099 73 b01b

Asembagus Tengah 12550 44690 1099 72 32b

11 Gudang Gudang Utara 13122 44417 0601 66 26b

13789 44213 1099 69 26b

12 Mojosari Karang Tengah 11329 45679 1099 70 b01b

13 Kertosari Lombung 12425 46121 1099 69 b01b

Krajan 12011 45278 1099 72 b01b

14 Trigonco Trigonco Tengah 12552 44914 1099 63 08b

Rarsquoasan Barat 12441 46250 1099 69 25b

15 Perante No data

16 Kedunglo Panjalinan 12611 47778 1099 66 b01a

17 Bantal Lewung 14279 48482 1099 59 14bc

14324 48313 1099 72 18bc

14329 48313 1099 64 22bc

Samir 14132 49449 1099 65 24bc

Kenanga 13961 47536 0601 65 32b

Krajan 2 13015 47313 1099 69 1b

Banyuputih 18 Banyuputih Curah Laci 14557 45169 1099 68 31b

Enoman 14863 46863 0601 66 41d

19 Sumberejo Bangeran 16617 46185 0601 73 b01a

Sodung Lao 15749 47103 1099 72 03a

Leduk Utara 14463 47468 1099 74 11d

14775 47540 1099 70 35d

Leduk Selatan 14404 48425 1099 64 25bc

Gelidik 16250 46100 0601 70 12a

Melek 15800 45867 1099 72 23d

Sukorejo 16300 44914 0601 74 32d

16187 44866 1099 70 35d

16520 44842 0601 73 42d

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6960

Table 2 (continued)

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

20 Sumberanyar Sompelan 17753 44927 0601 76 b01a

Gelidik 17050 46600 0601 75 b01a

Nyamplung 17444 45359 0601 73 03a

Bindung 16901 45396 1099 73 08a

Pandire 16475 47567 0601 73 b01a

The number before the community name refers to the number in the mapsa Located outside the contaminated irrigation areab Located within the contaminated irrigation areac Located close to the dry riverbedd Located within 1 km or upstream from the sluices at Lewung

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 61

solution was added to 025 g sample in a Ni crucible

and successively dried for 30 min at 150 8C and for

30 min at 250 8C in an oven with forced ventilation

Fig 2 F concentrations (mgl) in wate

The crucible was then covered and placed inside a

muffle furnace at 300 8C The temperature was

slowly raised to 600 8C and maintained for 1 h

r wells in the Asembagus area

Table 3

Temporal variations in F concentrations (mgl) in water wells sampled in 1999ndash2001

Village Longitude (1148 ) Latitude (078 ) Oct rsquo99a mgl June rsquo00 mgl April rsquo01 mgl May rsquo01 mgl

Lewung 14279 48482 14 09 1

Lewung 14324 48313 18 24

Lewung 14329 48313 22 13

Samir 14132 49449 24 22 18

Curah Laci 14557 45169 31 37

Sodung Selatan 15749 47103 03 02

Leduk Selatan 14404 48425 25 34

Leduk Utara 14775 4754 35 26

Dami 12609 43962 b01 b01

a Dry season AprilndashOctober rainy season NovemberndashMarch

Table 4

Daily intake of fluoride by children and adults

Source Daily intake (mgday)

Child Adult

Food 06 12

Drinking water b02ndash84 b04ndash168

River water 07 03

Total b08ndash90a b16ndash180a

a The highest value does not include intake via river water since

the water wells with the highest F concentration were neither within

1 km from the sluices at Lewung nor within the irrigation area

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6962

After cooling down to room temperature the residue

was dissolved into ultrapure water (350 ml) on a hot

plate and filtered through a 045 Am mesh width

nylon filter (Millipore) To avoid interferences from

high NaOH concentrations and carbonates the

samples were treated with a cation exchange column

containing 20 meq of H+ (Alltech Maxi-Clean IC-H

Plus) prior to analysis

F was determined with a Dionex DX500 ion

chromatography system as described by Neele and

Cleven (1999) In short 8 Al sample was injected

and led over an Ionpac AG11-HC and AG15

precolumn and an Ionpac AS15 column with a flow

rate of 03 mlmin 32 mM KOH was used as eluent

F was then measured with a Pulse Electrochemical

Detector in the conductivity mode The type of

calibration was quadratic based on 7 standards

measured in duplicate

The regression coefficient of the calibration

curve was 0999 or higher Results of additional

quality control standards (010 mgl and 100 mgl)

were within 95 of the expected value During

analyses drift standards (152 mgl F) were

measured after each 14 samples and the maximum

allowed deviation from the expected value was 5

The analytical procedure (alkali fusion technique in

combination with IC) was tested on the standard

reference material NIST-2695 (vegetation) and by

including blanks and duplicate measurements

Results showed a good recovery and reproducibil-

ity the measured F concentration in NIST-2695

was 688F06 mgkg dw (certified value 640F51

mgkg) The detection limit for F in food was

20 mgkg dw

33 Calculation of the total daily intake and hazard

quotients

The total daily intake of F (mgday) is calculated

with formula 1 in which i is the source C is the

concentration in that source (Agg or mgl) I is the

ingestion rate of the source (gday or lday) (Table 1)

Total daily intake frac14X

i

CiIi eth1THORN

For each water well the Hazard Quotient (HQ) for

dental fluorosis among children and skeletal fluorosis

among adults is calculated by dividing the total daily

intake by the applicable LOAEL If HQz1 it is likely

that the effect will occur and the risk of developing

fluorosis will increase with HQ For children calcu-

lations were made for the age of 6 years assuming a

body weight of 16 kg (Suzuki 1988) Hazard maps for

dental and skeletal fluorosis in the Asembagus area

were prepared in which the locations of all water wells

with the accompanying HQ values are given

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 63

4 Results

41 Fluoride in well water

F concentrations in the well waters were in the range

of b01 mgl to 42 mgl (Table 2) Of all the inves-

tigated wells 37 contained b01 mgl 24 contained

03ndash14 mgl and 39 contained more than 14 mgl

The average pH of the well waters was 71F04As can

be seen in Fig 2 the wells with the highest F

concentrations were found close to the riverbed and

within the area where the river water is used for

irrigation In some villages the F concentrations varied

from b01 to 25 mgl within a few hundred meters

Several wells that were repeatedly sampled show some

fluctuation in F concentrations but the available data

are insufficient to infer any pattern induced by seasonal

variations in rainfall (Table 3)

42 Fluoride in river water

Monthly river water monitoring in 2000ndash2002

yielded an average F content of 95 mgl The

concentrations fluctuated between 55 and 142 mgl

with highest values in the dry and lowest in the rainy

season In this period the pH (measured in the

laboratory) varied between 27 and 41 which was

in agreement with occasional measurements in the

field Previous sampling in the dry seasons of 1996ndash

1999 yielded F concentrations of 72ndash99 mgl

0

10

20

30

40

50

60

70

80

90

100

0 1 2F concentration in

c

ontr

ibut

ion

to d

aily

inta

ke

Fig 3 Contribution in terms of percentage to the total daily F intake by c

concentration in drinking water For those water wells closely located to t

43 Fluoride in food

The highest F concentrations were found in tea

followed by marine fish cassava leaf and peanuts

(Table 1) In other foods F concentrations were below

the detection limit of 20 mgkg dw which accounted

for rice which is the main dish as well as maize

cassava root vegetables fruit and chicken F concen-

trations in rice and maize produced in the non-

contaminated area were also below detection limit

Unpublished data obtained from method development

indicated that concentrations in most foods were equal

or below 1 mgkg dw and this value was assigned to

these items for calculations regarding the daily intake

via food

44 Total daily intake of fluoride

Based on the daily consumption pattern as listed

in Table 1 the daily intake of F via food drinking

water and river water has been calculated for each

water well location and is summarized in Table 4

The total daily intake by adults in terms of mg F

per day is a factor of 2 higher as compared to a 6-

year-old child Recalculating the daily intake per kg

body weight would show that the intake by children

(16 kg body weight) is a factor of 2 higher as

compared to adults (60 kg body weight) This is

due to the higher food and drinking water intake by

children per kg body weight

43 drinking water (mgl)

drinking waterfoodriver water

5

hildren via drinking water food and river water at each measured F

he sluices (n=5) swimming was included as a source of intake

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6964

Fig 3 illustrates the contribution of food and water

to the total daily intake by children With increasing F

concentrations in drinking water the contribution of

food to the total daily intake rapidly decreases At 03

mgl food and drinking water both contribute 50 to

the total daily intake while above 12 mgl food

contributes 20 or less For adults the picture is more

or less the same Five water wells are close to the

Fig 4 Hazard map for dental fluorosis among children in the Asembag

accompanying hazard quotient (HQ)

sluices and it can be expected that children that use

these wells will also swim in the river This contributes

07 mgday (ie 11ndash17) to their total daily intake

Adults may be exposed to river water throughout the

irrigation area However river water ingestion only

contributes substantially (03 mgday ie ~15) to the

total daily intake when they consume water from wells

with very low F concentrations (b01 mgl)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 65

The values for the intake via food should be

regarded as indicative only since most of the food

items had F concentrations below detection limit

(Table 1) Taking this into account the contribution to

the intake via food only is as follows for children tea

rice maize and vegetables each 20 and fish ~10

and for adults tea ~40 fish and rice each ~20

maize and vegetables each ~10

Fig 5 Hazard map for skeletal fluorosis among adults in the Asembag

accompanying hazard quotient (HQ)

45 Dental and skeletal fluorosis

Hazard Quotients for dental and skeletal fluorosis

calculated for all water wells have been plotted in

hazard maps (Figs 4 and 5) As drinking water is

generally the most important source of F the hazard

distribution largely coincides with the geographic

pattern in F concentrations in well water (Fig 2)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

Table 1

Daily consumption number of samples and F concentrations in

foods drinking water and surface water

Product Consumption

(gday)aNo of

samples

F concentration

(Agg dw)

Adult Child

Rice 227 132 20b b20

Maize 113 99 20b b20

Cassava root 40 66 5 b20

Vegetables 90 90 9 b20

Cassava leaf 10 10 3 53F13

Peanuts 18 13 3 22F11

Fruit 62 33 2 b20

Marine fish 60 22 3 172F92

Chicken 20 11 1 b20

Teac 2 05 5 217F118

(lday) (lday) mgl

Drinking waterd 4 2 54 b01ndash42

River watere 002 005 17f 55ndash142f

a Consumption of raw food items by adults was based on data

published by BPS Statistics Indonesia in 2002 (wwwbpsgoid

statbysectorconsexptable5shtml) data for children was obtained

from (Kardjati et al 1979)b 15 samples from the contaminated area and 5 from the

surrounding non-contaminated areac It is assumed that adults and children consume respectively 05 l

of tea (4 cups) and 0125 l (1 cup) per day and that 4 g of dry teal is

used and as a reasonable worst case scenario that 100 of F is

released from the tea leaves into the water (Fung 1999)d Including water used for preparation of tea and rice (Shimbo et

al 2001)e River water ingestion via bathing washing and agricultural

practices was included for adults living within the irrigation area

For children living close to the sluices at Lewung (within 1 km) or

upstream swimming was included as a source of river water

ingestion (Otte et al 2000) For calculating the F intake during

swimming the highest measured F concentration was usedf Data monthly sampling May 2000ndashSeptember 2002

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 59

312 Food

In June and August 2000 edible parts of crops (rice

maize cassava root cassava leaf and peanuts) were

collected in the area where contaminated irrigation

water is being used and in the surrounding area as a

reference Sampling focused on rice and maize as

being the most cultivated and consumed food crops in

Asembagus A stratified random sampling strategy

was applied and all sampling locations were deter-

mined with Global Positioning System (GPS) For

rice maize and peanuts one sample per field was

randomly collected A sample consisted of ~05 kg

rice ~03 kg maize or ~200 g unpeeled peanuts For

cassava one plant was regarded as one sample divided

into roots and leaves For cassava root one sample

consisted of 2ndash3 roots per plant For cassava leaf one

sample consisted of all leaves from the plant On local

markets other food items (vegetables fruit tea

chicken and fish) commonly available but not pro-

duced in the area were collected Rice and maize were

sun dried for 3 days and rice was husked with a pestle

and mortar Other food samples were rinsed with tap

water and ultrapure water (Milli-Q Millipore Billerica

USA) and dried at 40 8C in an oven with forced

ventilation for 2 days All samples were ground with

an ultra-centrifugal grinder (Retsch ZM 1000) passing

a 4 mm titanium sieve at 15000 rpm The water content

of foods was determined by drying a 2ndash5 g subsample

for 24 h at 105 8C until constant weight was achieved

A representative selection of samples (roughly 50 of

all collected samples) from the contaminated area the

non-contaminated area and the local markets was

processed for F analysis (Table 1) after initial analyses

showed that F concentrations in most food items were

below the detection limit of 2 mgkg dry weight

32 Chemical analysis

321 Water samples

F was measured with a Dionex DX120 ion

chromatograph In short 25 Al sample was injected

and was led over an Ionpac AG14 precolumn and an

AS14 column with a flow rate of 12 mlmin 35 mM

Na2CO310 mM NaHCO3 was used as eluent F was

then measured with a Pulse Electrochemical Detector

in the conductivity mode A quadratic calibration

based on five standard solutions measured in duplicate

was applied

The regression coefficient of the calibration was

0999 or higher and the calibration was repeated after

every ten samples Quality control standards were

analyzed and results were within 95 of the

expected values Blanks were also included and F

concentrations were below the detection limit of

01 mgl

322 Food samples

To extract the F from food (including tea) an

adapted alkali fusion technique was used (McQuaker

and Gurney 1977) Two millilitres of a 17 M NaOH

Table 2

Location sampling date (monthyear) pH and F concentration of water wells in the Asembagus area

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

Jangkar 1 Agel Pelabuan 10988 42914 0601 73 b01a

10005 44047 0601 72 b01a

2 Kombangsari Dawuhan 11048 43679 1099 76 b01a

3 Gadingan No data

4 Jangkar Pasarnangka 12644 43081 1099 72 b01a

Dami 12609 43962 1099 70 b01b

Jangkar 12714 44077 1099 66 25b

5 Pesanggrahan No data

6 Plalangan Plalangan Tengah 11450 44600 1099 75 03a

7 Curah Kalak Curah Kalak Tengah 10990 45682 1099 73 07a

8 Sopet Teteh 2 10912 47870 0601 72 b01a

10871 47656 0601 73 04a

Sopet 2 10541 46100 0601 77 05a

10541 46107 1099 73 05a

Pareyaan 10455 46510 0601 72 b01a

Batuwayang 10000 47833 0601 72 b01a

Cottok 10250 46100 0601 75 b01a

Nangger 9773 46564 0601 72 b01a

Asembagus 9 Wringianom Banongan Utara 13835 43506 0601 78 b01a

13849 43287 0601 72 25b

Asta 13277 42744 0601 74 22a

Widuri Utara 14977 42658 0601 74 27a

14670 43619 0601 76 30b

10 Asembagus Asembagus Timur 13172 44982 1099 73 b01b

Asembagus Tengah 12550 44690 1099 72 32b

11 Gudang Gudang Utara 13122 44417 0601 66 26b

13789 44213 1099 69 26b

12 Mojosari Karang Tengah 11329 45679 1099 70 b01b

13 Kertosari Lombung 12425 46121 1099 69 b01b

Krajan 12011 45278 1099 72 b01b

14 Trigonco Trigonco Tengah 12552 44914 1099 63 08b

Rarsquoasan Barat 12441 46250 1099 69 25b

15 Perante No data

16 Kedunglo Panjalinan 12611 47778 1099 66 b01a

17 Bantal Lewung 14279 48482 1099 59 14bc

14324 48313 1099 72 18bc

14329 48313 1099 64 22bc

Samir 14132 49449 1099 65 24bc

Kenanga 13961 47536 0601 65 32b

Krajan 2 13015 47313 1099 69 1b

Banyuputih 18 Banyuputih Curah Laci 14557 45169 1099 68 31b

Enoman 14863 46863 0601 66 41d

19 Sumberejo Bangeran 16617 46185 0601 73 b01a

Sodung Lao 15749 47103 1099 72 03a

Leduk Utara 14463 47468 1099 74 11d

14775 47540 1099 70 35d

Leduk Selatan 14404 48425 1099 64 25bc

Gelidik 16250 46100 0601 70 12a

Melek 15800 45867 1099 72 23d

Sukorejo 16300 44914 0601 74 32d

16187 44866 1099 70 35d

16520 44842 0601 73 42d

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6960

Table 2 (continued)

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

20 Sumberanyar Sompelan 17753 44927 0601 76 b01a

Gelidik 17050 46600 0601 75 b01a

Nyamplung 17444 45359 0601 73 03a

Bindung 16901 45396 1099 73 08a

Pandire 16475 47567 0601 73 b01a

The number before the community name refers to the number in the mapsa Located outside the contaminated irrigation areab Located within the contaminated irrigation areac Located close to the dry riverbedd Located within 1 km or upstream from the sluices at Lewung

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 61

solution was added to 025 g sample in a Ni crucible

and successively dried for 30 min at 150 8C and for

30 min at 250 8C in an oven with forced ventilation

Fig 2 F concentrations (mgl) in wate

The crucible was then covered and placed inside a

muffle furnace at 300 8C The temperature was

slowly raised to 600 8C and maintained for 1 h

r wells in the Asembagus area

Table 3

Temporal variations in F concentrations (mgl) in water wells sampled in 1999ndash2001

Village Longitude (1148 ) Latitude (078 ) Oct rsquo99a mgl June rsquo00 mgl April rsquo01 mgl May rsquo01 mgl

Lewung 14279 48482 14 09 1

Lewung 14324 48313 18 24

Lewung 14329 48313 22 13

Samir 14132 49449 24 22 18

Curah Laci 14557 45169 31 37

Sodung Selatan 15749 47103 03 02

Leduk Selatan 14404 48425 25 34

Leduk Utara 14775 4754 35 26

Dami 12609 43962 b01 b01

a Dry season AprilndashOctober rainy season NovemberndashMarch

Table 4

Daily intake of fluoride by children and adults

Source Daily intake (mgday)

Child Adult

Food 06 12

Drinking water b02ndash84 b04ndash168

River water 07 03

Total b08ndash90a b16ndash180a

a The highest value does not include intake via river water since

the water wells with the highest F concentration were neither within

1 km from the sluices at Lewung nor within the irrigation area

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6962

After cooling down to room temperature the residue

was dissolved into ultrapure water (350 ml) on a hot

plate and filtered through a 045 Am mesh width

nylon filter (Millipore) To avoid interferences from

high NaOH concentrations and carbonates the

samples were treated with a cation exchange column

containing 20 meq of H+ (Alltech Maxi-Clean IC-H

Plus) prior to analysis

F was determined with a Dionex DX500 ion

chromatography system as described by Neele and

Cleven (1999) In short 8 Al sample was injected

and led over an Ionpac AG11-HC and AG15

precolumn and an Ionpac AS15 column with a flow

rate of 03 mlmin 32 mM KOH was used as eluent

F was then measured with a Pulse Electrochemical

Detector in the conductivity mode The type of

calibration was quadratic based on 7 standards

measured in duplicate

The regression coefficient of the calibration

curve was 0999 or higher Results of additional

quality control standards (010 mgl and 100 mgl)

were within 95 of the expected value During

analyses drift standards (152 mgl F) were

measured after each 14 samples and the maximum

allowed deviation from the expected value was 5

The analytical procedure (alkali fusion technique in

combination with IC) was tested on the standard

reference material NIST-2695 (vegetation) and by

including blanks and duplicate measurements

Results showed a good recovery and reproducibil-

ity the measured F concentration in NIST-2695

was 688F06 mgkg dw (certified value 640F51

mgkg) The detection limit for F in food was

20 mgkg dw

33 Calculation of the total daily intake and hazard

quotients

The total daily intake of F (mgday) is calculated

with formula 1 in which i is the source C is the

concentration in that source (Agg or mgl) I is the

ingestion rate of the source (gday or lday) (Table 1)

Total daily intake frac14X

i

CiIi eth1THORN

For each water well the Hazard Quotient (HQ) for

dental fluorosis among children and skeletal fluorosis

among adults is calculated by dividing the total daily

intake by the applicable LOAEL If HQz1 it is likely

that the effect will occur and the risk of developing

fluorosis will increase with HQ For children calcu-

lations were made for the age of 6 years assuming a

body weight of 16 kg (Suzuki 1988) Hazard maps for

dental and skeletal fluorosis in the Asembagus area

were prepared in which the locations of all water wells

with the accompanying HQ values are given

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 63

4 Results

41 Fluoride in well water

F concentrations in the well waters were in the range

of b01 mgl to 42 mgl (Table 2) Of all the inves-

tigated wells 37 contained b01 mgl 24 contained

03ndash14 mgl and 39 contained more than 14 mgl

The average pH of the well waters was 71F04As can

be seen in Fig 2 the wells with the highest F

concentrations were found close to the riverbed and

within the area where the river water is used for

irrigation In some villages the F concentrations varied

from b01 to 25 mgl within a few hundred meters

Several wells that were repeatedly sampled show some

fluctuation in F concentrations but the available data

are insufficient to infer any pattern induced by seasonal

variations in rainfall (Table 3)

42 Fluoride in river water

Monthly river water monitoring in 2000ndash2002

yielded an average F content of 95 mgl The

concentrations fluctuated between 55 and 142 mgl

with highest values in the dry and lowest in the rainy

season In this period the pH (measured in the

laboratory) varied between 27 and 41 which was

in agreement with occasional measurements in the

field Previous sampling in the dry seasons of 1996ndash

1999 yielded F concentrations of 72ndash99 mgl

0

10

20

30

40

50

60

70

80

90

100

0 1 2F concentration in

c

ontr

ibut

ion

to d

aily

inta

ke

Fig 3 Contribution in terms of percentage to the total daily F intake by c

concentration in drinking water For those water wells closely located to t

43 Fluoride in food

The highest F concentrations were found in tea

followed by marine fish cassava leaf and peanuts

(Table 1) In other foods F concentrations were below

the detection limit of 20 mgkg dw which accounted

for rice which is the main dish as well as maize

cassava root vegetables fruit and chicken F concen-

trations in rice and maize produced in the non-

contaminated area were also below detection limit

Unpublished data obtained from method development

indicated that concentrations in most foods were equal

or below 1 mgkg dw and this value was assigned to

these items for calculations regarding the daily intake

via food

44 Total daily intake of fluoride

Based on the daily consumption pattern as listed

in Table 1 the daily intake of F via food drinking

water and river water has been calculated for each

water well location and is summarized in Table 4

The total daily intake by adults in terms of mg F

per day is a factor of 2 higher as compared to a 6-

year-old child Recalculating the daily intake per kg

body weight would show that the intake by children

(16 kg body weight) is a factor of 2 higher as

compared to adults (60 kg body weight) This is

due to the higher food and drinking water intake by

children per kg body weight

43 drinking water (mgl)

drinking waterfoodriver water

5

hildren via drinking water food and river water at each measured F

he sluices (n=5) swimming was included as a source of intake

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6964

Fig 3 illustrates the contribution of food and water

to the total daily intake by children With increasing F

concentrations in drinking water the contribution of

food to the total daily intake rapidly decreases At 03

mgl food and drinking water both contribute 50 to

the total daily intake while above 12 mgl food

contributes 20 or less For adults the picture is more

or less the same Five water wells are close to the

Fig 4 Hazard map for dental fluorosis among children in the Asembag

accompanying hazard quotient (HQ)

sluices and it can be expected that children that use

these wells will also swim in the river This contributes

07 mgday (ie 11ndash17) to their total daily intake

Adults may be exposed to river water throughout the

irrigation area However river water ingestion only

contributes substantially (03 mgday ie ~15) to the

total daily intake when they consume water from wells

with very low F concentrations (b01 mgl)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 65

The values for the intake via food should be

regarded as indicative only since most of the food

items had F concentrations below detection limit

(Table 1) Taking this into account the contribution to

the intake via food only is as follows for children tea

rice maize and vegetables each 20 and fish ~10

and for adults tea ~40 fish and rice each ~20

maize and vegetables each ~10

Fig 5 Hazard map for skeletal fluorosis among adults in the Asembag

accompanying hazard quotient (HQ)

45 Dental and skeletal fluorosis

Hazard Quotients for dental and skeletal fluorosis

calculated for all water wells have been plotted in

hazard maps (Figs 4 and 5) As drinking water is

generally the most important source of F the hazard

distribution largely coincides with the geographic

pattern in F concentrations in well water (Fig 2)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

Table 2

Location sampling date (monthyear) pH and F concentration of water wells in the Asembagus area

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

Jangkar 1 Agel Pelabuan 10988 42914 0601 73 b01a

10005 44047 0601 72 b01a

2 Kombangsari Dawuhan 11048 43679 1099 76 b01a

3 Gadingan No data

4 Jangkar Pasarnangka 12644 43081 1099 72 b01a

Dami 12609 43962 1099 70 b01b

Jangkar 12714 44077 1099 66 25b

5 Pesanggrahan No data

6 Plalangan Plalangan Tengah 11450 44600 1099 75 03a

7 Curah Kalak Curah Kalak Tengah 10990 45682 1099 73 07a

8 Sopet Teteh 2 10912 47870 0601 72 b01a

10871 47656 0601 73 04a

Sopet 2 10541 46100 0601 77 05a

10541 46107 1099 73 05a

Pareyaan 10455 46510 0601 72 b01a

Batuwayang 10000 47833 0601 72 b01a

Cottok 10250 46100 0601 75 b01a

Nangger 9773 46564 0601 72 b01a

Asembagus 9 Wringianom Banongan Utara 13835 43506 0601 78 b01a

13849 43287 0601 72 25b

Asta 13277 42744 0601 74 22a

Widuri Utara 14977 42658 0601 74 27a

14670 43619 0601 76 30b

10 Asembagus Asembagus Timur 13172 44982 1099 73 b01b

Asembagus Tengah 12550 44690 1099 72 32b

11 Gudang Gudang Utara 13122 44417 0601 66 26b

13789 44213 1099 69 26b

12 Mojosari Karang Tengah 11329 45679 1099 70 b01b

13 Kertosari Lombung 12425 46121 1099 69 b01b

Krajan 12011 45278 1099 72 b01b

14 Trigonco Trigonco Tengah 12552 44914 1099 63 08b

Rarsquoasan Barat 12441 46250 1099 69 25b

15 Perante No data

16 Kedunglo Panjalinan 12611 47778 1099 66 b01a

17 Bantal Lewung 14279 48482 1099 59 14bc

14324 48313 1099 72 18bc

14329 48313 1099 64 22bc

Samir 14132 49449 1099 65 24bc

Kenanga 13961 47536 0601 65 32b

Krajan 2 13015 47313 1099 69 1b

Banyuputih 18 Banyuputih Curah Laci 14557 45169 1099 68 31b

Enoman 14863 46863 0601 66 41d

19 Sumberejo Bangeran 16617 46185 0601 73 b01a

Sodung Lao 15749 47103 1099 72 03a

Leduk Utara 14463 47468 1099 74 11d

14775 47540 1099 70 35d

Leduk Selatan 14404 48425 1099 64 25bc

Gelidik 16250 46100 0601 70 12a

Melek 15800 45867 1099 72 23d

Sukorejo 16300 44914 0601 74 32d

16187 44866 1099 70 35d

16520 44842 0601 73 42d

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6960

Table 2 (continued)

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

20 Sumberanyar Sompelan 17753 44927 0601 76 b01a

Gelidik 17050 46600 0601 75 b01a

Nyamplung 17444 45359 0601 73 03a

Bindung 16901 45396 1099 73 08a

Pandire 16475 47567 0601 73 b01a

The number before the community name refers to the number in the mapsa Located outside the contaminated irrigation areab Located within the contaminated irrigation areac Located close to the dry riverbedd Located within 1 km or upstream from the sluices at Lewung

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 61

solution was added to 025 g sample in a Ni crucible

and successively dried for 30 min at 150 8C and for

30 min at 250 8C in an oven with forced ventilation

Fig 2 F concentrations (mgl) in wate

The crucible was then covered and placed inside a

muffle furnace at 300 8C The temperature was

slowly raised to 600 8C and maintained for 1 h

r wells in the Asembagus area

Table 3

Temporal variations in F concentrations (mgl) in water wells sampled in 1999ndash2001

Village Longitude (1148 ) Latitude (078 ) Oct rsquo99a mgl June rsquo00 mgl April rsquo01 mgl May rsquo01 mgl

Lewung 14279 48482 14 09 1

Lewung 14324 48313 18 24

Lewung 14329 48313 22 13

Samir 14132 49449 24 22 18

Curah Laci 14557 45169 31 37

Sodung Selatan 15749 47103 03 02

Leduk Selatan 14404 48425 25 34

Leduk Utara 14775 4754 35 26

Dami 12609 43962 b01 b01

a Dry season AprilndashOctober rainy season NovemberndashMarch

Table 4

Daily intake of fluoride by children and adults

Source Daily intake (mgday)

Child Adult

Food 06 12

Drinking water b02ndash84 b04ndash168

River water 07 03

Total b08ndash90a b16ndash180a

a The highest value does not include intake via river water since

the water wells with the highest F concentration were neither within

1 km from the sluices at Lewung nor within the irrigation area

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6962

After cooling down to room temperature the residue

was dissolved into ultrapure water (350 ml) on a hot

plate and filtered through a 045 Am mesh width

nylon filter (Millipore) To avoid interferences from

high NaOH concentrations and carbonates the

samples were treated with a cation exchange column

containing 20 meq of H+ (Alltech Maxi-Clean IC-H

Plus) prior to analysis

F was determined with a Dionex DX500 ion

chromatography system as described by Neele and

Cleven (1999) In short 8 Al sample was injected

and led over an Ionpac AG11-HC and AG15

precolumn and an Ionpac AS15 column with a flow

rate of 03 mlmin 32 mM KOH was used as eluent

F was then measured with a Pulse Electrochemical

Detector in the conductivity mode The type of

calibration was quadratic based on 7 standards

measured in duplicate

The regression coefficient of the calibration

curve was 0999 or higher Results of additional

quality control standards (010 mgl and 100 mgl)

were within 95 of the expected value During

analyses drift standards (152 mgl F) were

measured after each 14 samples and the maximum

allowed deviation from the expected value was 5

The analytical procedure (alkali fusion technique in

combination with IC) was tested on the standard

reference material NIST-2695 (vegetation) and by

including blanks and duplicate measurements

Results showed a good recovery and reproducibil-

ity the measured F concentration in NIST-2695

was 688F06 mgkg dw (certified value 640F51

mgkg) The detection limit for F in food was

20 mgkg dw

33 Calculation of the total daily intake and hazard

quotients

The total daily intake of F (mgday) is calculated

with formula 1 in which i is the source C is the

concentration in that source (Agg or mgl) I is the

ingestion rate of the source (gday or lday) (Table 1)

Total daily intake frac14X

i

CiIi eth1THORN

For each water well the Hazard Quotient (HQ) for

dental fluorosis among children and skeletal fluorosis

among adults is calculated by dividing the total daily

intake by the applicable LOAEL If HQz1 it is likely

that the effect will occur and the risk of developing

fluorosis will increase with HQ For children calcu-

lations were made for the age of 6 years assuming a

body weight of 16 kg (Suzuki 1988) Hazard maps for

dental and skeletal fluorosis in the Asembagus area

were prepared in which the locations of all water wells

with the accompanying HQ values are given

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 63

4 Results

41 Fluoride in well water

F concentrations in the well waters were in the range

of b01 mgl to 42 mgl (Table 2) Of all the inves-

tigated wells 37 contained b01 mgl 24 contained

03ndash14 mgl and 39 contained more than 14 mgl

The average pH of the well waters was 71F04As can

be seen in Fig 2 the wells with the highest F

concentrations were found close to the riverbed and

within the area where the river water is used for

irrigation In some villages the F concentrations varied

from b01 to 25 mgl within a few hundred meters

Several wells that were repeatedly sampled show some

fluctuation in F concentrations but the available data

are insufficient to infer any pattern induced by seasonal

variations in rainfall (Table 3)

42 Fluoride in river water

Monthly river water monitoring in 2000ndash2002

yielded an average F content of 95 mgl The

concentrations fluctuated between 55 and 142 mgl

with highest values in the dry and lowest in the rainy

season In this period the pH (measured in the

laboratory) varied between 27 and 41 which was

in agreement with occasional measurements in the

field Previous sampling in the dry seasons of 1996ndash

1999 yielded F concentrations of 72ndash99 mgl

0

10

20

30

40

50

60

70

80

90

100

0 1 2F concentration in

c

ontr

ibut

ion

to d

aily

inta

ke

Fig 3 Contribution in terms of percentage to the total daily F intake by c

concentration in drinking water For those water wells closely located to t

43 Fluoride in food

The highest F concentrations were found in tea

followed by marine fish cassava leaf and peanuts

(Table 1) In other foods F concentrations were below

the detection limit of 20 mgkg dw which accounted

for rice which is the main dish as well as maize

cassava root vegetables fruit and chicken F concen-

trations in rice and maize produced in the non-

contaminated area were also below detection limit

Unpublished data obtained from method development

indicated that concentrations in most foods were equal

or below 1 mgkg dw and this value was assigned to

these items for calculations regarding the daily intake

via food

44 Total daily intake of fluoride

Based on the daily consumption pattern as listed

in Table 1 the daily intake of F via food drinking

water and river water has been calculated for each

water well location and is summarized in Table 4

The total daily intake by adults in terms of mg F

per day is a factor of 2 higher as compared to a 6-

year-old child Recalculating the daily intake per kg

body weight would show that the intake by children

(16 kg body weight) is a factor of 2 higher as

compared to adults (60 kg body weight) This is

due to the higher food and drinking water intake by

children per kg body weight

43 drinking water (mgl)

drinking waterfoodriver water

5

hildren via drinking water food and river water at each measured F

he sluices (n=5) swimming was included as a source of intake

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6964

Fig 3 illustrates the contribution of food and water

to the total daily intake by children With increasing F

concentrations in drinking water the contribution of

food to the total daily intake rapidly decreases At 03

mgl food and drinking water both contribute 50 to

the total daily intake while above 12 mgl food

contributes 20 or less For adults the picture is more

or less the same Five water wells are close to the

Fig 4 Hazard map for dental fluorosis among children in the Asembag

accompanying hazard quotient (HQ)

sluices and it can be expected that children that use

these wells will also swim in the river This contributes

07 mgday (ie 11ndash17) to their total daily intake

Adults may be exposed to river water throughout the

irrigation area However river water ingestion only

contributes substantially (03 mgday ie ~15) to the

total daily intake when they consume water from wells

with very low F concentrations (b01 mgl)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 65

The values for the intake via food should be

regarded as indicative only since most of the food

items had F concentrations below detection limit

(Table 1) Taking this into account the contribution to

the intake via food only is as follows for children tea

rice maize and vegetables each 20 and fish ~10

and for adults tea ~40 fish and rice each ~20

maize and vegetables each ~10

Fig 5 Hazard map for skeletal fluorosis among adults in the Asembag

accompanying hazard quotient (HQ)

45 Dental and skeletal fluorosis

Hazard Quotients for dental and skeletal fluorosis

calculated for all water wells have been plotted in

hazard maps (Figs 4 and 5) As drinking water is

generally the most important source of F the hazard

distribution largely coincides with the geographic

pattern in F concentrations in well water (Fig 2)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

Table 2 (continued)

Subdistrict Community Village Longitude (1148 ) Latitude (078 ) Date pH F (mgl)

20 Sumberanyar Sompelan 17753 44927 0601 76 b01a

Gelidik 17050 46600 0601 75 b01a

Nyamplung 17444 45359 0601 73 03a

Bindung 16901 45396 1099 73 08a

Pandire 16475 47567 0601 73 b01a

The number before the community name refers to the number in the mapsa Located outside the contaminated irrigation areab Located within the contaminated irrigation areac Located close to the dry riverbedd Located within 1 km or upstream from the sluices at Lewung

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 61

solution was added to 025 g sample in a Ni crucible

and successively dried for 30 min at 150 8C and for

30 min at 250 8C in an oven with forced ventilation

Fig 2 F concentrations (mgl) in wate

The crucible was then covered and placed inside a

muffle furnace at 300 8C The temperature was

slowly raised to 600 8C and maintained for 1 h

r wells in the Asembagus area

Table 3

Temporal variations in F concentrations (mgl) in water wells sampled in 1999ndash2001

Village Longitude (1148 ) Latitude (078 ) Oct rsquo99a mgl June rsquo00 mgl April rsquo01 mgl May rsquo01 mgl

Lewung 14279 48482 14 09 1

Lewung 14324 48313 18 24

Lewung 14329 48313 22 13

Samir 14132 49449 24 22 18

Curah Laci 14557 45169 31 37

Sodung Selatan 15749 47103 03 02

Leduk Selatan 14404 48425 25 34

Leduk Utara 14775 4754 35 26

Dami 12609 43962 b01 b01

a Dry season AprilndashOctober rainy season NovemberndashMarch

Table 4

Daily intake of fluoride by children and adults

Source Daily intake (mgday)

Child Adult

Food 06 12

Drinking water b02ndash84 b04ndash168

River water 07 03

Total b08ndash90a b16ndash180a

a The highest value does not include intake via river water since

the water wells with the highest F concentration were neither within

1 km from the sluices at Lewung nor within the irrigation area

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6962

After cooling down to room temperature the residue

was dissolved into ultrapure water (350 ml) on a hot

plate and filtered through a 045 Am mesh width

nylon filter (Millipore) To avoid interferences from

high NaOH concentrations and carbonates the

samples were treated with a cation exchange column

containing 20 meq of H+ (Alltech Maxi-Clean IC-H

Plus) prior to analysis

F was determined with a Dionex DX500 ion

chromatography system as described by Neele and

Cleven (1999) In short 8 Al sample was injected

and led over an Ionpac AG11-HC and AG15

precolumn and an Ionpac AS15 column with a flow

rate of 03 mlmin 32 mM KOH was used as eluent

F was then measured with a Pulse Electrochemical

Detector in the conductivity mode The type of

calibration was quadratic based on 7 standards

measured in duplicate

The regression coefficient of the calibration

curve was 0999 or higher Results of additional

quality control standards (010 mgl and 100 mgl)

were within 95 of the expected value During

analyses drift standards (152 mgl F) were

measured after each 14 samples and the maximum

allowed deviation from the expected value was 5

The analytical procedure (alkali fusion technique in

combination with IC) was tested on the standard

reference material NIST-2695 (vegetation) and by

including blanks and duplicate measurements

Results showed a good recovery and reproducibil-

ity the measured F concentration in NIST-2695

was 688F06 mgkg dw (certified value 640F51

mgkg) The detection limit for F in food was

20 mgkg dw

33 Calculation of the total daily intake and hazard

quotients

The total daily intake of F (mgday) is calculated

with formula 1 in which i is the source C is the

concentration in that source (Agg or mgl) I is the

ingestion rate of the source (gday or lday) (Table 1)

Total daily intake frac14X

i

CiIi eth1THORN

For each water well the Hazard Quotient (HQ) for

dental fluorosis among children and skeletal fluorosis

among adults is calculated by dividing the total daily

intake by the applicable LOAEL If HQz1 it is likely

that the effect will occur and the risk of developing

fluorosis will increase with HQ For children calcu-

lations were made for the age of 6 years assuming a

body weight of 16 kg (Suzuki 1988) Hazard maps for

dental and skeletal fluorosis in the Asembagus area

were prepared in which the locations of all water wells

with the accompanying HQ values are given

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 63

4 Results

41 Fluoride in well water

F concentrations in the well waters were in the range

of b01 mgl to 42 mgl (Table 2) Of all the inves-

tigated wells 37 contained b01 mgl 24 contained

03ndash14 mgl and 39 contained more than 14 mgl

The average pH of the well waters was 71F04As can

be seen in Fig 2 the wells with the highest F

concentrations were found close to the riverbed and

within the area where the river water is used for

irrigation In some villages the F concentrations varied

from b01 to 25 mgl within a few hundred meters

Several wells that were repeatedly sampled show some

fluctuation in F concentrations but the available data

are insufficient to infer any pattern induced by seasonal

variations in rainfall (Table 3)

42 Fluoride in river water

Monthly river water monitoring in 2000ndash2002

yielded an average F content of 95 mgl The

concentrations fluctuated between 55 and 142 mgl

with highest values in the dry and lowest in the rainy

season In this period the pH (measured in the

laboratory) varied between 27 and 41 which was

in agreement with occasional measurements in the

field Previous sampling in the dry seasons of 1996ndash

1999 yielded F concentrations of 72ndash99 mgl

0

10

20

30

40

50

60

70

80

90

100

0 1 2F concentration in

c

ontr

ibut

ion

to d

aily

inta

ke

Fig 3 Contribution in terms of percentage to the total daily F intake by c

concentration in drinking water For those water wells closely located to t

43 Fluoride in food

The highest F concentrations were found in tea

followed by marine fish cassava leaf and peanuts

(Table 1) In other foods F concentrations were below

the detection limit of 20 mgkg dw which accounted

for rice which is the main dish as well as maize

cassava root vegetables fruit and chicken F concen-

trations in rice and maize produced in the non-

contaminated area were also below detection limit

Unpublished data obtained from method development

indicated that concentrations in most foods were equal

or below 1 mgkg dw and this value was assigned to

these items for calculations regarding the daily intake

via food

44 Total daily intake of fluoride

Based on the daily consumption pattern as listed

in Table 1 the daily intake of F via food drinking

water and river water has been calculated for each

water well location and is summarized in Table 4

The total daily intake by adults in terms of mg F

per day is a factor of 2 higher as compared to a 6-

year-old child Recalculating the daily intake per kg

body weight would show that the intake by children

(16 kg body weight) is a factor of 2 higher as

compared to adults (60 kg body weight) This is

due to the higher food and drinking water intake by

children per kg body weight

43 drinking water (mgl)

drinking waterfoodriver water

5

hildren via drinking water food and river water at each measured F

he sluices (n=5) swimming was included as a source of intake

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6964

Fig 3 illustrates the contribution of food and water

to the total daily intake by children With increasing F

concentrations in drinking water the contribution of

food to the total daily intake rapidly decreases At 03

mgl food and drinking water both contribute 50 to

the total daily intake while above 12 mgl food

contributes 20 or less For adults the picture is more

or less the same Five water wells are close to the

Fig 4 Hazard map for dental fluorosis among children in the Asembag

accompanying hazard quotient (HQ)

sluices and it can be expected that children that use

these wells will also swim in the river This contributes

07 mgday (ie 11ndash17) to their total daily intake

Adults may be exposed to river water throughout the

irrigation area However river water ingestion only

contributes substantially (03 mgday ie ~15) to the

total daily intake when they consume water from wells

with very low F concentrations (b01 mgl)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 65

The values for the intake via food should be

regarded as indicative only since most of the food

items had F concentrations below detection limit

(Table 1) Taking this into account the contribution to

the intake via food only is as follows for children tea

rice maize and vegetables each 20 and fish ~10

and for adults tea ~40 fish and rice each ~20

maize and vegetables each ~10

Fig 5 Hazard map for skeletal fluorosis among adults in the Asembag

accompanying hazard quotient (HQ)

45 Dental and skeletal fluorosis

Hazard Quotients for dental and skeletal fluorosis

calculated for all water wells have been plotted in

hazard maps (Figs 4 and 5) As drinking water is

generally the most important source of F the hazard

distribution largely coincides with the geographic

pattern in F concentrations in well water (Fig 2)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

Table 3

Temporal variations in F concentrations (mgl) in water wells sampled in 1999ndash2001

Village Longitude (1148 ) Latitude (078 ) Oct rsquo99a mgl June rsquo00 mgl April rsquo01 mgl May rsquo01 mgl

Lewung 14279 48482 14 09 1

Lewung 14324 48313 18 24

Lewung 14329 48313 22 13

Samir 14132 49449 24 22 18

Curah Laci 14557 45169 31 37

Sodung Selatan 15749 47103 03 02

Leduk Selatan 14404 48425 25 34

Leduk Utara 14775 4754 35 26

Dami 12609 43962 b01 b01

a Dry season AprilndashOctober rainy season NovemberndashMarch

Table 4

Daily intake of fluoride by children and adults

Source Daily intake (mgday)

Child Adult

Food 06 12

Drinking water b02ndash84 b04ndash168

River water 07 03

Total b08ndash90a b16ndash180a

a The highest value does not include intake via river water since

the water wells with the highest F concentration were neither within

1 km from the sluices at Lewung nor within the irrigation area

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6962

After cooling down to room temperature the residue

was dissolved into ultrapure water (350 ml) on a hot

plate and filtered through a 045 Am mesh width

nylon filter (Millipore) To avoid interferences from

high NaOH concentrations and carbonates the

samples were treated with a cation exchange column

containing 20 meq of H+ (Alltech Maxi-Clean IC-H

Plus) prior to analysis

F was determined with a Dionex DX500 ion

chromatography system as described by Neele and

Cleven (1999) In short 8 Al sample was injected

and led over an Ionpac AG11-HC and AG15

precolumn and an Ionpac AS15 column with a flow

rate of 03 mlmin 32 mM KOH was used as eluent

F was then measured with a Pulse Electrochemical

Detector in the conductivity mode The type of

calibration was quadratic based on 7 standards

measured in duplicate

The regression coefficient of the calibration

curve was 0999 or higher Results of additional

quality control standards (010 mgl and 100 mgl)

were within 95 of the expected value During

analyses drift standards (152 mgl F) were

measured after each 14 samples and the maximum

allowed deviation from the expected value was 5

The analytical procedure (alkali fusion technique in

combination with IC) was tested on the standard

reference material NIST-2695 (vegetation) and by

including blanks and duplicate measurements

Results showed a good recovery and reproducibil-

ity the measured F concentration in NIST-2695

was 688F06 mgkg dw (certified value 640F51

mgkg) The detection limit for F in food was

20 mgkg dw

33 Calculation of the total daily intake and hazard

quotients

The total daily intake of F (mgday) is calculated

with formula 1 in which i is the source C is the

concentration in that source (Agg or mgl) I is the

ingestion rate of the source (gday or lday) (Table 1)

Total daily intake frac14X

i

CiIi eth1THORN

For each water well the Hazard Quotient (HQ) for

dental fluorosis among children and skeletal fluorosis

among adults is calculated by dividing the total daily

intake by the applicable LOAEL If HQz1 it is likely

that the effect will occur and the risk of developing

fluorosis will increase with HQ For children calcu-

lations were made for the age of 6 years assuming a

body weight of 16 kg (Suzuki 1988) Hazard maps for

dental and skeletal fluorosis in the Asembagus area

were prepared in which the locations of all water wells

with the accompanying HQ values are given

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 63

4 Results

41 Fluoride in well water

F concentrations in the well waters were in the range

of b01 mgl to 42 mgl (Table 2) Of all the inves-

tigated wells 37 contained b01 mgl 24 contained

03ndash14 mgl and 39 contained more than 14 mgl

The average pH of the well waters was 71F04As can

be seen in Fig 2 the wells with the highest F

concentrations were found close to the riverbed and

within the area where the river water is used for

irrigation In some villages the F concentrations varied

from b01 to 25 mgl within a few hundred meters

Several wells that were repeatedly sampled show some

fluctuation in F concentrations but the available data

are insufficient to infer any pattern induced by seasonal

variations in rainfall (Table 3)

42 Fluoride in river water

Monthly river water monitoring in 2000ndash2002

yielded an average F content of 95 mgl The

concentrations fluctuated between 55 and 142 mgl

with highest values in the dry and lowest in the rainy

season In this period the pH (measured in the

laboratory) varied between 27 and 41 which was

in agreement with occasional measurements in the

field Previous sampling in the dry seasons of 1996ndash

1999 yielded F concentrations of 72ndash99 mgl

0

10

20

30

40

50

60

70

80

90

100

0 1 2F concentration in

c

ontr

ibut

ion

to d

aily

inta

ke

Fig 3 Contribution in terms of percentage to the total daily F intake by c

concentration in drinking water For those water wells closely located to t

43 Fluoride in food

The highest F concentrations were found in tea

followed by marine fish cassava leaf and peanuts

(Table 1) In other foods F concentrations were below

the detection limit of 20 mgkg dw which accounted

for rice which is the main dish as well as maize

cassava root vegetables fruit and chicken F concen-

trations in rice and maize produced in the non-

contaminated area were also below detection limit

Unpublished data obtained from method development

indicated that concentrations in most foods were equal

or below 1 mgkg dw and this value was assigned to

these items for calculations regarding the daily intake

via food

44 Total daily intake of fluoride

Based on the daily consumption pattern as listed

in Table 1 the daily intake of F via food drinking

water and river water has been calculated for each

water well location and is summarized in Table 4

The total daily intake by adults in terms of mg F

per day is a factor of 2 higher as compared to a 6-

year-old child Recalculating the daily intake per kg

body weight would show that the intake by children

(16 kg body weight) is a factor of 2 higher as

compared to adults (60 kg body weight) This is

due to the higher food and drinking water intake by

children per kg body weight

43 drinking water (mgl)

drinking waterfoodriver water

5

hildren via drinking water food and river water at each measured F

he sluices (n=5) swimming was included as a source of intake

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6964

Fig 3 illustrates the contribution of food and water

to the total daily intake by children With increasing F

concentrations in drinking water the contribution of

food to the total daily intake rapidly decreases At 03

mgl food and drinking water both contribute 50 to

the total daily intake while above 12 mgl food

contributes 20 or less For adults the picture is more

or less the same Five water wells are close to the

Fig 4 Hazard map for dental fluorosis among children in the Asembag

accompanying hazard quotient (HQ)

sluices and it can be expected that children that use

these wells will also swim in the river This contributes

07 mgday (ie 11ndash17) to their total daily intake

Adults may be exposed to river water throughout the

irrigation area However river water ingestion only

contributes substantially (03 mgday ie ~15) to the

total daily intake when they consume water from wells

with very low F concentrations (b01 mgl)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 65

The values for the intake via food should be

regarded as indicative only since most of the food

items had F concentrations below detection limit

(Table 1) Taking this into account the contribution to

the intake via food only is as follows for children tea

rice maize and vegetables each 20 and fish ~10

and for adults tea ~40 fish and rice each ~20

maize and vegetables each ~10

Fig 5 Hazard map for skeletal fluorosis among adults in the Asembag

accompanying hazard quotient (HQ)

45 Dental and skeletal fluorosis

Hazard Quotients for dental and skeletal fluorosis

calculated for all water wells have been plotted in

hazard maps (Figs 4 and 5) As drinking water is

generally the most important source of F the hazard

distribution largely coincides with the geographic

pattern in F concentrations in well water (Fig 2)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 63

4 Results

41 Fluoride in well water

F concentrations in the well waters were in the range

of b01 mgl to 42 mgl (Table 2) Of all the inves-

tigated wells 37 contained b01 mgl 24 contained

03ndash14 mgl and 39 contained more than 14 mgl

The average pH of the well waters was 71F04As can

be seen in Fig 2 the wells with the highest F

concentrations were found close to the riverbed and

within the area where the river water is used for

irrigation In some villages the F concentrations varied

from b01 to 25 mgl within a few hundred meters

Several wells that were repeatedly sampled show some

fluctuation in F concentrations but the available data

are insufficient to infer any pattern induced by seasonal

variations in rainfall (Table 3)

42 Fluoride in river water

Monthly river water monitoring in 2000ndash2002

yielded an average F content of 95 mgl The

concentrations fluctuated between 55 and 142 mgl

with highest values in the dry and lowest in the rainy

season In this period the pH (measured in the

laboratory) varied between 27 and 41 which was

in agreement with occasional measurements in the

field Previous sampling in the dry seasons of 1996ndash

1999 yielded F concentrations of 72ndash99 mgl

0

10

20

30

40

50

60

70

80

90

100

0 1 2F concentration in

c

ontr

ibut

ion

to d

aily

inta

ke

Fig 3 Contribution in terms of percentage to the total daily F intake by c

concentration in drinking water For those water wells closely located to t

43 Fluoride in food

The highest F concentrations were found in tea

followed by marine fish cassava leaf and peanuts

(Table 1) In other foods F concentrations were below

the detection limit of 20 mgkg dw which accounted

for rice which is the main dish as well as maize

cassava root vegetables fruit and chicken F concen-

trations in rice and maize produced in the non-

contaminated area were also below detection limit

Unpublished data obtained from method development

indicated that concentrations in most foods were equal

or below 1 mgkg dw and this value was assigned to

these items for calculations regarding the daily intake

via food

44 Total daily intake of fluoride

Based on the daily consumption pattern as listed

in Table 1 the daily intake of F via food drinking

water and river water has been calculated for each

water well location and is summarized in Table 4

The total daily intake by adults in terms of mg F

per day is a factor of 2 higher as compared to a 6-

year-old child Recalculating the daily intake per kg

body weight would show that the intake by children

(16 kg body weight) is a factor of 2 higher as

compared to adults (60 kg body weight) This is

due to the higher food and drinking water intake by

children per kg body weight

43 drinking water (mgl)

drinking waterfoodriver water

5

hildren via drinking water food and river water at each measured F

he sluices (n=5) swimming was included as a source of intake

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6964

Fig 3 illustrates the contribution of food and water

to the total daily intake by children With increasing F

concentrations in drinking water the contribution of

food to the total daily intake rapidly decreases At 03

mgl food and drinking water both contribute 50 to

the total daily intake while above 12 mgl food

contributes 20 or less For adults the picture is more

or less the same Five water wells are close to the

Fig 4 Hazard map for dental fluorosis among children in the Asembag

accompanying hazard quotient (HQ)

sluices and it can be expected that children that use

these wells will also swim in the river This contributes

07 mgday (ie 11ndash17) to their total daily intake

Adults may be exposed to river water throughout the

irrigation area However river water ingestion only

contributes substantially (03 mgday ie ~15) to the

total daily intake when they consume water from wells

with very low F concentrations (b01 mgl)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 65

The values for the intake via food should be

regarded as indicative only since most of the food

items had F concentrations below detection limit

(Table 1) Taking this into account the contribution to

the intake via food only is as follows for children tea

rice maize and vegetables each 20 and fish ~10

and for adults tea ~40 fish and rice each ~20

maize and vegetables each ~10

Fig 5 Hazard map for skeletal fluorosis among adults in the Asembag

accompanying hazard quotient (HQ)

45 Dental and skeletal fluorosis

Hazard Quotients for dental and skeletal fluorosis

calculated for all water wells have been plotted in

hazard maps (Figs 4 and 5) As drinking water is

generally the most important source of F the hazard

distribution largely coincides with the geographic

pattern in F concentrations in well water (Fig 2)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6964

Fig 3 illustrates the contribution of food and water

to the total daily intake by children With increasing F

concentrations in drinking water the contribution of

food to the total daily intake rapidly decreases At 03

mgl food and drinking water both contribute 50 to

the total daily intake while above 12 mgl food

contributes 20 or less For adults the picture is more

or less the same Five water wells are close to the

Fig 4 Hazard map for dental fluorosis among children in the Asembag

accompanying hazard quotient (HQ)

sluices and it can be expected that children that use

these wells will also swim in the river This contributes

07 mgday (ie 11ndash17) to their total daily intake

Adults may be exposed to river water throughout the

irrigation area However river water ingestion only

contributes substantially (03 mgday ie ~15) to the

total daily intake when they consume water from wells

with very low F concentrations (b01 mgl)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 65

The values for the intake via food should be

regarded as indicative only since most of the food

items had F concentrations below detection limit

(Table 1) Taking this into account the contribution to

the intake via food only is as follows for children tea

rice maize and vegetables each 20 and fish ~10

and for adults tea ~40 fish and rice each ~20

maize and vegetables each ~10

Fig 5 Hazard map for skeletal fluorosis among adults in the Asembag

accompanying hazard quotient (HQ)

45 Dental and skeletal fluorosis

Hazard Quotients for dental and skeletal fluorosis

calculated for all water wells have been plotted in

hazard maps (Figs 4 and 5) As drinking water is

generally the most important source of F the hazard

distribution largely coincides with the geographic

pattern in F concentrations in well water (Fig 2)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 65

The values for the intake via food should be

regarded as indicative only since most of the food

items had F concentrations below detection limit

(Table 1) Taking this into account the contribution to

the intake via food only is as follows for children tea

rice maize and vegetables each 20 and fish ~10

and for adults tea ~40 fish and rice each ~20

maize and vegetables each ~10

Fig 5 Hazard map for skeletal fluorosis among adults in the Asembag

accompanying hazard quotient (HQ)

45 Dental and skeletal fluorosis

Hazard Quotients for dental and skeletal fluorosis

calculated for all water wells have been plotted in

hazard maps (Figs 4 and 5) As drinking water is

generally the most important source of F the hazard

distribution largely coincides with the geographic

pattern in F concentrations in well water (Fig 2)

us area Each dot represents the location of a water well with its

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6966

Hence risks to human health are highest close to the

(dry) riverbed and within the area where the river

water is used for irrigation

For dental fluorosis more than half of the water

wells (30 out of 54) are associated with an HQz1

ranging from an HQ of 10 at a F concentration of 05

mgl in drinking water to a HQ of 56 at 42 mgl (total

daily intake of 90 mgday) For skeletal fluorosis

water wells with F concentrations z11 mgl are

associated with a HQz1 (24 out of 54 water wells) At

the highest concentration of 42 mgl (total daily

intake of 181 mgday) the HQ is 30

5 Discussion

Various cases of fluorosis due to high F

concentrations in groundwater have been reported

in volcanic areas (Kloos and Tekle Haimanot 1999

Moturi et al 2002) Of all active volcanoes 12

contains an acid crater lake which are often rich in

F and effluent from these lakes may pose a hazard

to the environment (Taran et al 1998 Varekamp

and Kreulen 2000 Rowe et al 1995 Pedrozo et

al 2001 Sriwana et al 1998 Deely and

Sheppard 1996) In this study we have estimated

the total daily intake of F via drinking waterwells

food and surface water in the vicinity of the

hyperacid Ijen Crater Lake where river water

contaminated with effluent from the lake is used

for irrigation We also prepared fluorosis hazard

maps identifying the most hazardous locations in

terms of dental and skeletal fluorosis within the

Asembagus area

The extent to which the present results can be

extrapolated to assess the long-term exposure to F-rich

drinking water depends on possible temporal changes

in F concentrations The F concentrations in the well

waters presented here are consistent with 1999 data of

Budipramana et al (2002) who reported mean

concentrations ranging between 05 and 32 mgl for

ten villages in the Asembagus subdistrict (Budipra-

mana et al 2002) On average these results were

somewhat higher than the 1978ndash1979 data from Rai

(1980) who found a range of 02ndash27 mgl for wells in

the same villages (Rai 1980) Since exact sample

locations in these earlier studies are unknown and

different analytical techniques were applied a direct

comparison with our data is difficult to make Never-

theless the present data show the same spatial

distribution although the concentrations seem to be

somewhat higher (b01ndash42 mgl) The results listed in

Table 2 in combination with the previous work

identify water wells in the following communities as

the most seriously affected by high F concentrations

(N05 mgl) Asembagus Bantal Kedunglo Perante

Trigonco Wringinanom Banyuputih Sumberejo

Curah Kalak and Jangkar Highest concentrations

are thus found within the irrigation area and near the

riverbed whereas wells in the same communities with

low F concentrations are generally situated outside the

irrigated area The evidence that this geographic

pattern in F levels in well waters has existed over

decades together with the monitoring results for wells

repeatedly sampled in 1999 2000 and 2001 (Table 3)

indicates that residents who obtain their drinking

water from a single water source may be subject to

long-term exposure to excess F

Contamination of the groundwater may occur via

vertical infiltration of river water as a result of the

long-term irrigation practices or via lateral transport

through aquifers that are connected to the riverbed

Given the unknown transfer times in either case a

direct correspondence between fluctuations in the

quality of river and well water is unlikely It is

conceivable that the groundwater may undergo some

dilution during or after the rainy season as has been

observed in other fluorosis areas (Moturi et al 2002

Karthikeyan et al 1996) but more extensive mon-

itoring would be required to test potential effects of

seasonal variations in rainfall

Despite the high F concentration in the river

water locally produced rice and maize contained less

than 2 mgkg dw which is in agreement with

literature (WHO 2002 Dabeka and McKenzie

1995 Kabata-Pendias and Pendias 1984) The lack

of accumulation could be the result of a low

bioavailability of F in the soil or a limited uptake

and translocation within the grown crops This issue

is beyond the scope of this study and will not be

discussed here further

51 Dental and skeletal fluorosis

Taking into account the total daily F intake the

hazard map for dental fluorosis shows that most

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 67

water wells within the irrigation area and close to the

riverbed contain hazardous concentrations of F

Based on the total daily intake the lowest F

concentration in drinking water that pose a risk of

developing dental fluorosis is 05 mgl which is in

agreement with observations of Rai (1980) and

Budipramana et al (2002) the latter reporting a

prevalence of dental fluorosis of 92 at 05 mgl

(Budipramana et al 2002)

Budipramana et al (2002) suggested that the

prevalence of dental fluorosis among children at this

low concentration was caused by fish consumption

(Budipramana et al 2002) Our calculations show

that at 05 mgl F in drinking water ~60 (10 mg

day) of the intake comes from drinking water and

~40 (06 mgday) from food However fish

contributes only ~10 (007 mgday) to the daily

intake via food which is ~ 5 of the total daily

intake Hence there seems to be no specific food item

that dominates the intake via food but it is the sum of

intake via various food items For most food items the

F intake could only be estimated since the concen-

trations were mostly below detection limit However

the assumed concentration of 1 mgkg in those foods

is in agreement with literature and the estimated intake

via food consumption is in good agreement with

values reported by others (WHO 2002 Dabeka and

McKenzie 1995 Kabata-Pendias and Pendias 1984

Cao et al 1997 Zohouri and Rugg-Gunn 2000)

The fluorosis hazard map also shows a high risk of

skeletal fluorosis among adults In a study from

China a prevalence of more than 80 has been

reported at a total daily intake of 9ndash12 mgday (Cao et

al 2003) In Asembagus 20 water wells are

associated with a total daily intake equal or above

10 mgday The most severe form of fluorosis

(crippling skeletal fluorosis) associated with a total

daily intake of 14 mgday cannot be excluded in

Asembagus since the total daily intake can reach up

to 181 mgday in the area (WHO 2002) Based on

the total daily intake the F concentration in water

wells posing a risk of developing skeletal fluorosis is

11 mgl Although at the lower end this value is in

agreement with findings elsewhere For example in a

study from Choubisa et al (1997) skeletal fluorosis

was first observed at 25 mgl and crippling skeletal

fluorosis was consistently observed at F concentra-

tions of 3 mgl (Choubisa et al 1997) In another

study he found a prevalence of skeletal fluorosis

among adults of 75 at 15 mgl (Choubisa 1999)

Misra et al (1988) cited a study that reported skeletal

fluorosis at 12ndash14 mgl (Misra et al 1988)

Summarizing the WHO guideline value of 15 mgl

for F in drinking water is too high to avoid dental and

skeletal fluorosis in Asembagus and tropical areas in

general The guideline value is based on the assump-

tion of a drinking water consumption of 2 lday which

is an underestimation for tropical conditions Various

authors have suggested that F in drinking water should

not exceed 06ndash07 mgl to avoid dental fluorosis in

tropical areas (Reimann et al 2003 Kloos and Tekle

Haimanot 1999 Lesan 1987)

52 Remediation

Water distribution from the low-F drinking water

wells in neighboring areas bordered by the Curah

Kalak River to the west and the Curah Bangeran

River to the east of the Asembagus area may be

considered to avoid health problems Referring to a

similar approach Budipramana et al (2002) reported

that in 1990 the local municipality supplied water

from the subdistrict of Jangkar which contained a

relatively low amount of F (045 mgl) (Budipramana

et al 2002) This attempt failed since residents

preferred their own wells because of the taste and for

economic reasons A general problem with water

distribution in the area is that most wells are

privately owned and that wells may produce less at

the end of the dry season which may endanger the

continuity of water supply A second option is water

defluoridation for which various techniques are

available (Moturi et al 2002 Zevenbergen et al

1996) Some of them are applicable on a small

village or household level others are designed for

water distribution centres at larger scales So far it

seems difficult to implement available methods in

affected areas due to eg a lack of social awareness

and acceptance (Kloos and Tekle Haimanot 1999)

A third possibility is to treat surface water (eg the

Curah Kalak River or the Curah Bangeran River) and

make it suitable for consumption However setting

up water treatment plants and a distribution network

will require a significant economic investment

Finally it is recommended to discourage children

to swim in the contaminated river since river water

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

A Heikens et al Science of the Total Environment 346 (2005) 56ndash6968

ingestion during swimming contributes 07 mgday

which is already ~50 of the LOAEL

6 Conclusion

At numerous locations in the Asembagus area

the total daily F intake exceeds the LOAEL not

only for dental fluorosis but also for skeletal

fluorosis Drinking water from local wells is the

principal source of F and clearly prevails over the

intake via locally produced foods It is estimated

that the lowest F concentration in drinking water

that poses a risk is approximately 05 mgl for

dental fluorosis and 11 mgl for skeletal fluorosis

These values are below the guideline value for safe

drinking water as recommended by WHO The

spatial pattern of elevated F levels in the water

wells suggests that F-rich river water originating

from the hyperacid Ijen Crater Lake is the main

cause of the health problems observed in local

residents The Asembagus irrigation area represents

the first case where an acid crater lake has been

identified as a source of natural pollutants that pose

a risk to human health

Acknowledgements

We are grateful to the government authorities and

inhabitants of Asembagus Banyuputih and Jangkar

for generous support and warm hospitality the

Situbondo Irrigation Office in particular Mr Basuki

Mr Djaelani and Mr Sugiarto and the staff of the

Asembagus branch for providing assistance and

information the Health Department of the Province

of East Java for exchange of information Ansje LfhrThom Bogaard Martin Hendriks Inge Dewi Mr

Kelik staff members of UNIKA and The Nether-

lands Embassy in Jakarta for cooperation Part of the

field campaign was financed by VTRC (Yogyakarta)

We thank Syamsul Rizal MSc and Dr A Ratdomo-

purbo for support and the VTRC staff Siti Mariana

Heri Arief Djilal Dalijo and Ngadiyono for

assistance in the field This project was financed

under numbers WAE 98139 and WB 75359 by

The Netherlands Foundation for the Advancement of

Tropical Research (WOTRO) residing under The

Netherlands Organization for Scientific Research

(NWO)

References

Budipramana ES Hapsoro A Irmawati ES Kuntari S Dental

fluorosis and caries prevalence in the fluorosis endemic area of

Asembagus Indonesia Int J Paediatr Dent 200212415ndash22

Cao J Zhao Y Liu J Brick tea consumption as the cause of dental

fluorosis among children from Mongol Kazak and Yugu

populations in China Food Chem Toxicol 199735827ndash33

Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea

fluoride as a main source of adult fluorosis Food Chem Toxicol

200341535ndash42

Choubisa SL Chronic fluoride intoxication (fluorosis) in tribes and

their domestic animals Int J Environ Stud 199936703ndash16

Choubisa SL Choubisa DK Joshi SC Choubisa L Fluorosis in

some tribal villages of Dungarpur district of Rajasthan India

Fluoride 199730223ndash8

Dabeka RW McKenzie AD Survey of lead cadmium fluoride

nickel and cobalt in food composites and estimation of dietary

intakes of these elements by Canadians J-Assoc Off Anal Chem

199578(4)897ndash909

Deely JM Sheppard DS Whangaehu River New Zealand geo-

chemistry of a river discharging from an active crater lake Appl

Geochem 199611447ndash60

Delmelle P Bernard A Downstream composition changes of acidic

volcanic waters discharged into the Banyupahit stream Ijen

caldera Indonesia J Volcanol Geotherm Res 20009755ndash75

Fung KF Fluoride contents in tea and soil from tea plantations and

the release of fluoride into tea liquor during infusion Environ

Pollut 1999104197ndash205

Kabata-Pendias A Pendias H Trace elements in soils and plants

Boca Raton FL USA7 CRC Press 1984

Kardjati S Kusin JA With Cd East Java nutrition studies food

consumption and nutritional status of mothers and preschool

children in Sidoarjo and Sampang Amsterdam The Nether-

lands7 Royal Tropical Institute (KIT) 1979

Karthikeyan G Pius A Apparao BV Contribution of fluoride in

water and food to the prevalence of fluorosis in areas of Tamil

Nadu in South India Fluoride 199629151ndash5

Kloos H Tekle Haimanot R Distribution of fluoride and fluorosis

in Ethiopia and prospects for control Trop Med Int Health

19994355ndash64

Lesan WR Dental fluorosis a review of literature with comments

on tropical characteristics East Afr Med J 198764493ndash8

McQuaker NR Gurney M Determination of total fluoride in soil

vegetation using an alkali fusion-selective ion electrode

technique Anal Chem 19774953ndash6

Misra UK Nag D Ray PK Husain M Newton G Endemic

fluorosis presenting as cervical cord compression Arch Environ

Health 19884318ndash21

Moturi WKM Tole MP Davies TC The contribution of drinking

water towards dental fluorosis a case study of Njoro Division

Nakuru District Kenya Environ Geochem Health 2002

24123ndash30

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25

A Heikens et al Science of the Total Environment 346 (2005) 56ndash69 69

Neele J Cleven RFMJ Anion chromatographic analysis with an

on-line eluent generator Bilthoven The Netherlands7 RIVM

1999

Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K

Calculating permissible levels for human health of contaminants

in sediments (report in Dutch Berekening van humane

risicogrenzen voor waterbodems) Bilthoven the Netherlands7

RIVMRIZA 2000

Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel

R et al First results on the water chemistry algae and

trophic status of an Andean acidic lake system of volcanic

origin in Pantagonia (Lake Caviahue) Hydrobiologia 2001

452129ndash37

Rai IGN The incidence of endemic dental hypoplasia among

children in relation to fluoride concentrations drinking water and

urine (in Indonesian Hubungan antara prevalensi hipoplasia

gigi yang endemis pada anakndashanak dengan konsentrasi fluorida

dalam air minum dan urine dan dengan karies gigi) PhD thesis

Dental department Airlangga University Surabaya Indonesia

1980

Reimann C Bjorvatn K Frengstad B Melaku Z Tekle-Haimanot

R Siewers U Drinking water quality in the Ethiopian section of

the East African Rift Valley Imdashdata and health aspects Sci Total

Environ 200331165ndash80

Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical

and hydrologic structure of Poas Volcano Costa Rica J Volcanol

Geotherm Res 199564233ndash67

Shimbo S Zhang ZW Watanabe T Nakatsuka H Matsuda-

Inoguchi N Higashikawa K et al Cadmium and lead contents

in rice and other cereal products in Japan in 1998ndash2000 Sci

Total Environ 2001281165ndash75

Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash

M Fluoride in groundwater in selected villages in Eritrea (North

East Africa) Environ Monit Assess 200275169ndash77

Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH

Wahyuningsih R et al Volcanogenic pollution by acid water

discharges along Ciwidey River West Java (Indonesia)

J Volcanol Geotherm Res 199862161ndash82

Suzuki S editor Health ecology in Indonesia Tokyo Japan7

Gyosei 1988

Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M

Macias JL Geochemistry of the volcano-hydrothermal system

of El Chichon Volcano Chiapas Mexico Bull Volcanol 1998

59436ndash49

Varekamp JC Kreulen R The stable isotope geochemistry of

volcanic lakes with examples from Indonesia J Volcanol

Geotherm Res 200097309ndash27

Wang LF Huang JZ Outline of control practice of endemic

fluorosis in China Soc Sci Med 1995411191ndash5

WHO Fluorine and fluorides (Environmental Health Criteria

document no36) vol 36 Geneva Switzerland 1984

WHO Guidelines for drinking-water quality 2nd ed Geneva

Switzerland 1996

WHO Fluorides (Environmental Health Criteria document no227)

Geneva Switzerland 2002

Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ

Schuiling RD A simple method for defluoridation of drinking

water at village level by adsorption on Ando soil in Kenya Sci

Total Environ 1996188225ndash32

Zohouri FV Rugg-Gunn AJ Total fluoride intake and urinary

excretion in 4-year-old Iranian children residing in low-fluoride

areas Br J Nutr 20008315ndash25