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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)
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Asembagus Indonesia Int J Paediatr Dent 200212415ndash22
Cao J Zhao Y Liu J Brick tea consumption as the cause of dental
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Cao J Zhao Y Liu J Xirao R Danzeng S Daji D et al Brick tea
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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
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Fluoride 199730223ndash8
Dabeka RW McKenzie AD Survey of lead cadmium fluoride
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Deely JM Sheppard DS Whangaehu River New Zealand geo-
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Delmelle P Bernard A Downstream composition changes of acidic
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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
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Kardjati S Kusin JA With Cd East Java nutrition studies food
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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
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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
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Moturi WKM Tole MP Davies TC The contribution of drinking
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Otte P Van Elswijk M Blijenberg M Swartjes F Van de Guchte K
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Pedrozo F Kelly L Diaz M Temporetti P Baffico G Kringel
R et al First results on the water chemistry algae and
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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
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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
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Rowe Jr GL Brantley SL Fernandez JF Borgia A The chemical
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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
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Srikanth R Viswanatham KS Kahsai F Fisahatsion A Asmellash
M Fluoride in groundwater in selected villages in Eritrea (North
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Sriwana T Bergen van MJ Sumarti S Hoog de JCM Os van BJH
Wahyuningsih R et al Volcanogenic pollution by acid water
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Taran Y Fischer TP Pokrovsky B Sano Y Aurora Armienta M
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Varekamp JC Kreulen R The stable isotope geochemistry of
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Wang LF Huang JZ Outline of control practice of endemic
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WHO Fluorides (Environmental Health Criteria document no227)
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Zevenbergen C Van Reeuwijk LP Frapporti G Louws RJ
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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