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Formation in Watersheds and Removal in Water Treatment
1
Natural Organic Matter in Water
David A. ReckhowUniversity of Massachusetts Dave Reckhow
Outline
2
Intro & DefinitionsNOM Generation
The Hydrologic CycleLand vs Water sourcesCompounds in NOM
Water TreatmentHistorical Types of TreatmentComponents or Processes
Some current issues & popular books
It’s one of my favorite recipes. I call it NOM
2
NOM = Natural Organic MatterDave Reckhow
What’s in the Water?Natural Substances
Natural Organic Matter (NOM)Inorganic Substances (Iron, Manganese, sodium,
chloride)Anthropogenic Substances
PesticidesOrganic Solvents & Other Industrial CompoundsCarcinogensPharmaceuticalsEndocrine Disrupting CompoundsFlame Retardants
Pathogens and other microorganisms
Dave Reckhow3
NOM in Natural Waters: Some definitions
4
Groupings Based on Origin
autochthonous compounds are created within the water body
allochthonous compounds can originate from either the soil or from upstream water bodies
aquagenic, substances originating from any water body pedogenic for substances originating from soil
4 Dave Reckhow
Watershed Origins
5
Aquifer
Lake
Upper Soil Horizon
Lower Soil Horizon
Sediment & Gravel in Lake BedSediment & Gravel in Lake Bed
Litter Layer
Algae
5 Dave Reckhow
Watershed Origins
6
Aquifer
Lake
Sediment & Gravel in Lake Bed
Algae
6 Dave Reckhow
Dave Reckhow7
Hydrologic Cycle
Three levelsSurface runoff, overland flow, direct
runoffInterflowInfiltration, percolation, groundwater
flow
D&M, Fig 6-1
Dave Reckhow8http://www.ec.gc.ca/water/images/nature/grdwtr/a5f2e.htm
During dry periods: base flow
9
NOM: Which is the bigger source?
AutochthonousAquatic plants
or
Allochthonous land plants
Dave Reckhow
10
Aquatic sources: Algae
Scenedesmus quadricaudaScenedesmus quadricauda
Cyclotella sp.Cyclotella sp.~25% from EOM
pH 7, 20-24ºC, chlorine excess
Algae
From: Plummer & Edzwald, 2001 [ES&T:35:3661]
Dave Reckhow
11
Terrestrial Sources: Leaching Experiments
WhitePine
RedMaple
WhiteOak
Darleen Bryan’s study
Dave Reckhow
Leaching of leaves More organic
matter released as the leaves remain submerged
Ultraviolet (UV) absorbance reflects certain types of NOM
100254 xDOC
UVSUVA
Dave Reckhow12
Plant biopolymers
CelluloseLignin
Phenyl-propane units
Cross-linkedRadical
polymerizationIll defined
structureHemicelluloseTerpeniodsProteins
Dave Reckhow13
Tannins, Aromatic Acids and Phenols, cont.
COOH
OH
COOH
OH
OCH3
•Lignin monomers
p-Hydroxybenzoic Acid Vanillic AcidDave Reckhow14
Tannins, Aromatic Acidsand Phenols
About 0.5% of Total Plant Products Likely THM Precursors Source of Color & DBPs
O
HO
HO
HO H
H OH
H
H
OH
OH
OH
CH
CH
CH
H2C
CH2O
OH
O
OH
OC
C
C
O
O
O
HO
HOHO
HO
HOHO
HO
HO
HO
Hydrolyzable Tannin
Condensed Tannin
Gallic Acid monomersGallic Acid monomers
ChemicalSymbols
C C
CC
CC
OHH
H OH
OH
Dave Reckhow15
Carbohydrates empirical formula: Cempirical formula: Cxx(H(H22O)O)yy
OH
OH
H
OH
OH
H
OH
CH2OH
HH
OH
H
OH
OH
OH
CH2OH
HH
O
H
OH
OH
OH
CH2OH
HHO
OH
Glucose (monosaccharide) Cellulose (polysaccharide)
OH
OH
H
OH
NH2
OH
H
CH2OH
HHGlucosamine (amino sugar)
Dave Reckhow16
Fatty Acids
maybe 4% of DOCother mixed acids may account for 2%
H-COOH CH3-COOH CH3-CH2-COOHFormic Acid Acetic Acid Propionic Acid
CH3-CH2-CH2-COOH H3-CH2-CH2-CH2-COOH Butyric Acid Valeric Acid
Common Volatile Fatty Acids in Natural Waters
CH3-COO-
At neutral pH’s most lose H+
Dave Reckhow17
Amino Acids and Proteins
H2C CH
COOH
NH2
HO CH2
CH
NH2
COOH
Tyrosine
Simple Amino AcidsAmine and acid groups
Alanine
Polypeptides & Proteins– Comprised of many
AAs
H2N
NH
HN
O
O
O
NH
HN
O
O
OH
CH3
CH2
CH2
CH2
NH
C
NH2
HN
CH2
N
NH
CH2
CH2
C
OH
O
Dave Reckhow18
2222 22)
24( N
cOH
baCOO
dbaONHC dcba
NOM Quantification: TOC & DOC
19
Oxidation High Temperature
Pyrolysis UV Irradiation Heated Persulfate UV/Persulfate
PrinciplePrinciple: oxidize all organic matter to Carbon dioxide and water. Then measure the amount of carbon dioxide produced
Filter
Dave Reckhow
Concentrations: Pedogenic
20
Land SourcesFrom Woody & non-woody plantsDepends on vegetation, soil, hydrologyMost biodegradable fractions are quickly
lostAttenuated by adsorption to clay soils
Parallel watersheds in Australia (Cotsaris et al., 1994)Clearwater Creek, high clay content: 2.5 mg/L
TOCRedwater Creek, sandy soil: 31.7 mg/L TOC
20 Dave Reckhow
Concentrations: Aquagenic
21
Algal & aquatic plant SourcesDepend on nutrient levels / trophic state
Concentrations in Lakes (mg/L) (Thurman, 1985)
Groundwater average: 0.7 mg/LNo algae, much soil attenuation
21 Dave Reckhow
22
John #I: Dr. John Snow
Characterizing “the acute problem”
CholeraFirst emerged
in early 1800s1852-1860: The third cholera pandemic
Snow showed the role of water in disease transmissionLondon’s Broad Street pump (Broadwick St)
Miasma theory was discredited, but it took decades to fully put it to rest
1813-1858
2006
Dave Reckhow
Dave Reckhow23
Cholera in London & Dr. John Snow
During an outbreak of cholera in London in 1854, John Snow plotted on a map the location of all the cases he learned of. Water in that part of London was pumped from wells located in the various neighborhoods. Snow's map revealed a close association between the density of cholera cases and a single well located on Broad Street.
Removing the pump handle of the Broad Street well put an end to the epidemic. This despite the fact that the infectious agent that causes cholera was not clearly recognized until 1905.
John Snow's map showing cholera deaths in London in 1854 (courtesy of The Geographical Journal). The Broad Street well is marked with an X (within the red circle).http://www.ph.ucla.edu/epi/snow.html
24Picadilly Circus
Soho, Westminster
John #II: Dr. John L. Leal
25
Solutions to “the acute problem”Jersey City’s Boonton ReservoirLeal experimented with chlorine,
its effectiveness and productionGeorge Johnson & George Fuller worked with Leal and
designed the system (1908)
“Full-scale and continuous implementation of disinfection for the first time in Jersey City, NJ ignited a disinfection revolution in the United States that reverberated around the world”
M.J. McGuire, JAWWA 98(3)123
1858-1914
Dave Reckhow
26
Chlorination
1-2 punch of filtration & chlorination
Melosi, 2000, The Sanitary City, John Hopkins Press
Greenberg, 1980, Water Chlorination, Env. Impact & Health Eff., Vol 3, pg.3, Ann Arbor Sci.
US Death Rates for Typhoid Fever
Dave Reckhow
Dave Reckhow27
Today’s Conventional Treatment
Coagulation & solids separationUse of alum or another chemical coagulantrapid mix, flocculation, settling, filtration
Disinfectionincluding clearwell for contact time
Most common sequence for surface water
Dist.Sys.Clear
well
Coagulant Disinfectant
Settling
Corrosion Control Fluoride
raw water flocculationrapidmix
Filtration
Removes some of the NOM & suspended particles
Kills or inactivates pathogenic organisms
Coagulation chemistry
2 4 3-
3 42-Fe ( SO ) + 6 OH 2Fe(OH ) + 3 SO
Ferric Sulfate
Alum
Al SO H O Al OH SO H H O2 4 3 2 3 42
218 2 3 6 12( ) ( )
Mechanisms• Precipitation of metal hydroxide, then:
• Adsorption of contaminants• Enmeshment of particles
28
29
NOM removal by alum coagulation
Impacts of pH and dose
Mn precipitationRennes IV Raw Water(France) 11/19/84
Reckhow & Bourbigot (unpublished data)
Dave Reckhow30
FlocculationAn Empty full-scale rectangular flocculation
tank in Southern CA
MWDSCWeymouth Plant
12 Dec 05
Can be done in the lab by slowly mixing your sample with a stirrer or on a shaking table
31
SettlingCircular and
rectangular designs
Can be done in the lab by letting your sample sit in a jar quiescently
MWDSCWeymouth Plant
12 Dec 05
FiltrationSand media
Empty filter, not in service (Cincinnati)
32 Dave Reckhow
Chlorination
Chlorine tanksLeft side is
currently feedingRight side is on
reserveDave Reckhow33
Dave Reckhow34
Other Types: Ozone PlantsMany types
Simplest type: ozone, non-filtration shown belowexamples: MWRA (Boston), Portland ME
More complex: including coagulation & Filtrationexamples: Andover MA, Amherst MA
Always includes final disinfection with chlorine or chloramines
Dist.Sys.
Cl2 Cl2 NH3
O3
OzoneGeneratorDiffusers
35
Can be done in the lab with a $70 fish tank sized ozone generator
Waterloo, Ont
36
Ultraviolet Light
Membrane Treatment
National City, CA
37
38
John #III: John Rook
Chlorine: “the chronic problem”Brought headspace
analysis from the beer industry to drinking water
Found trihalomethanes (THMs) in finished water Carcinogens !?!
Published in Dutch journal H2O, Aug 19, 1972 issue
Deduced that they were formed as byproducts of chlorination
Proposed chemical pathwaysRook, 1974, Water Treat. & Exam., 23:234
1921-2010
Reactions with Disinfectants: Chlorine
39
HOCl + natural organics (NOM)
Oxidized NOMand inorganic chloride
•Aldehydes
Chlorinated Organics•TOX•THMs•HAAs
Cl
Cl
Cl C H
Br
Cl
Cl C HBr
Cl
Br C H
Br
Br
Br C H
Chloroform Bromodichloromethane ChlorodibromomethaneBromoform
The THMsThe THMs
The Precursors!
a
40
Hours of transit timefrom the water filtration plant
to your house
Inhalation in the shower produces highest blood level and response is fast
42
Gordon et al., 2006 [Env. Health Persp.114:514-521]
Multiple Routes of Exposure
43
Epidemiology
137,000 at risk in US?
“I think you should be more explicit here in step two”
Bladder CancerDBPs linked to 9,300 US cases
every yearOther Cancers
Rectal, colonReproductive &
developmental effectsNeural tube defectsMiscarriages & Low birth
weightCleft palate
OtherKidney & spleen disordersImmune system problems,
neurotoxic effects
Observational:The DBP Iceberg
HalogenatedCompounds Non-halogenatedNon-halogenated
CompoundsCompounds
ICR CompoundsICR Compounds
50 MWDSC DBPs50 MWDSC DBPs
~700 Known DBPs~700 Known DBPs
THMs, THAAs
DHAAs
Stuart Krasner
Susan Richardson
AnotherSandra Hempel
Journalist2007 publication
dateSimilar in many
ways to Johnson’s book
45 Dave Reckhow
BiographyA serious biography
2003 publicationPrimarily written by MDs
46 Dave Reckhow
Cholera & beyondRobert Morris
Environmental epidemiologist
2007 publication date
More comprehensiveCholera to DBPs to
Crypto
47 Dave Reckhow
Lead Hazards2006 publication
dateWerner Troesken
Professor of History
Presents many historical lessons on society’s failure to balance public health with profit
48 Dave Reckhow
The End
49
NOM HC Cl
Cl
Cl
49 Dave Reckhow