Natural Organic Matter In Water - UMass Amherst

Natural Organic Matter in WaterFormation in Watersheds and Removal in WaterTreatment1David A. ReckhowUniversity of MassachusettsDave Reckhow

Outline Intro & Definitions NOM Generation The Hydrologic Cycle Land vsWater sources Compounds in NOM Water Treatment HistoricalIt’s one of my favoriterecipes. I call it NOM Types of Treatment Components or Processes Some current issues & popular booksNOM Natural Organic Matter22Dave Reckhow

What’s in the Water? Natural Substances Natural Organic Matter (NOM) Inorganic Substances (Iron, Manganese, sodium, chloride) Anthropogenic Substances Pesticides Organic Solvents & Other Industrial Compounds Carcinogens Pharmaceuticals Endocrine Disrupting Compounds Flame Retardants Pathogens and other microorganisms3Dave Reckhow

NOM in Natural Waters:Some definitionsGroupings Based on Origin autochthonous compounds are created within the waterbody allochthonous compounds can originate from either thesoil or from upstream water bodies aquagenic, substances originating from any water body pedogenic for substances originating from soil44Dave Reckhow

Watershed OriginsUpper Soil HorizonLower Soil HorizonLakeLitter LayerAlgaeAquiferSediment & Gravel in Lake Bed55Dave Reckhow

Watershed OriginsLakeAlgaeAquiferSediment & Gravel in Lake Bed66Dave Reckhow

Hydrologic CycleD&M, Fig 6-1 Three levels Surface runoff, overland flow, direct runoff Interflow Infiltration, percolation, groundwater flow7Dave Reckhow

During dry periods: base /a5f2e.htm8Dave Reckhow

NOM: Which is the bigger source?or Allochthonous9 land plants Autochthonous Aquatic plantsDave Reckhow

Aquatic sources: Algae From: Plummer & Edzwald, 2001 [ES&T:35:3661] 25% from EOMScenedesmus quadricaudaCyclotella sp.Algae10Dave ReckhowpH 7, 20-24ºC, chlorine excess

Terrestrial Sources: Darleen Bryan’s studyLeaching Experiments11WhitePineWhiteOakRedMapleDave Reckhow

Leaching of leaves Ultraviolet (UV254)absorbancemeasures a certainfraction The ratio of UV254to dissolved organiccarbon (DOC)concentration iscalled SUVA andreflects organicmatter reactivity129Maple UVOak UVPine UVMaple SUVAOak SUVAPine SUVA1.61.4-1UV254 Absorbance (cm )matter released asthe leaves remainsubmerged1.81.28761.050.840.630.420.210.0002 UV254 SUVA x100 DOC 468Leaching Time (days)Dave ReckhowSUVA (L/mg-C/m) More organic

Composition of an “average” leaf 250 g/m2/yr EABPHighlycoloredSomecolor13Dave Reckhow

Plant biopolymers Cellulose Lignin Phenyl-propane units Cross-linked Radical polymerization Ill defined structure Hemicellulose Terpeniods Proteins14Dave Reckhow

Tannins, Aromatic Acids and Phenols, cont. Lignin monomersCOOHCOOHOCH3OHOH15p-Hydroxybenzoic AcidVanillic Acid Dave Reckhow

HTannins, Aromatic Acidsand PhenolsOHCCCCCCH About 0.5% of TotalOHHO Plant ProductsOH Likely THM PrecursorsHOHOHOHOHO16HOHOHHOCH2OHOHCondensed TanninOHGallic Acid monomersCHCHOHH2CCHOCHOOOCHOHOCHOOOH Source of Color & DBPsHOOHChemicalSymbolsOHHydrolyzable TanninDave Reckhow

Carbohydrates empirical formula: OHHHOHHOHOHGlucose (monosaccharide)Cellulose (polysaccharide)CH2OHHOHOHGlucosamine (amino sugar)HOH17OHHHNH2Dave Reckhow

At neutral pH’s most lose H CH3-COO-Fatty Acids maybe 4% of DOC other mixed acids may account for 2%H-COOHCH3-COOHFormic Acid Acetic AcidCH3-CH2-CH2-COOHButyric Acid18CH3-CH2-COOHPropionic AcidH3-CH2-CH2-CH2-COOHValeric AcidCommon Volatile Fatty Acids in Natural WatersDave Reckhow

Amino Acids and Proteins Simple Amino AcidsNH2 Amine and acid groupsH2CCHAlanineCOOHNH2HOCH2CHCOOHTyrosine Polypeptides&Proteins19– Comprised of manyAAs Dave Reckhow

FilterNOM Quantification: TOC & DOCPrinciple: oxidize all organic matter to Carbon dioxide andwater. Then measure the amount of carbon dioxide producedb dbcCa H b N c Od (a )O2 aCO2 H 2O N 24 222Oxidation High TemperaturePyrolysis UV Irradiation Heated Persulfate 20UV/PersulfateDave Reckhow

Concentrations: Pedogenic Land Sources From Woody & non-woody plants Depends on vegetation, soil, hydrology Most biodegradable fractions are quickly lost Attenuated by adsorption to clay soils Parallel watersheds in Australia (Cotsaris et al., 1994) Clearwater Creek, high clay content: 2.5 mg/L TOC Redwater Creek, sandy soil: 31.7 mg/L TOC2121Dave Reckhow

Concentrations: Aquagenic Algal & aquatic plant Sources Depend on nutrient levels / trophic state Concentrations in Lakes (mg/L) (Thurman,1985)2222Trophic StateMean 2310301-32-43-3420-50 Groundwater average: 0.7 mg/L No algae, much soil attenuationDave Reckhow

2006John #I: Dr. John Snow1813-1858 Characterizing “theacute problem” Cholera First emergedin early 1800s 1852-1860: 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 fullyput it to rest 23Dave Reckhow

Cholera in London & Dr. John Snow During an outbreak of cholera in London in 1854, JohnSnow plotted on a map the location of all the cases helearned of. Water in that part of London was pumped fromwells located in the various neighborhoods. Snow's maprevealed a close association between the density of choleracases and a single well located on Broad Street. Removing the pump handle of the Broad Street well put anend to the epidemic. This despite the fact that theinfectious agent that causes cholera was not clearlyrecognized until 1905. John Snow's map showing cholera deaths in London in1854 (courtesy of The Geographical Journal). The BroadStreet well is marked with an X (within the red circle).24http://www.ph.ucla.edu/epi/snow.htmlDave Reckhow

Soho, Westminster25Picadilly Circus

Photo courtesy of the Lealfamily and Mike McGuireJohn #2: Dr. John L. Leal Solutions to “the acute problem” Jersey City’s Boonton Reservoir Leal experimented with chlorine,1858-1914its effectiveness and production George Johnson & George Fuller worked with Leal and designed the system(1908)“Full-scale and continuousimplementation of disinfection for thefirst time in Jersey City, NJ ignited adisinfection revolution in the United Statesthat reverberated around the world”26M.J. McGuire, JAWWA 98(3)123

Chlorination 1-2 punch of filtration &chlorinationGreenberg, 1980, WaterChlorination, Env.Impact & Health Eff.,Vol 3, pg.3, Ann ArborSci.US Death Rates forTyphoid Fever27Melosi, 2000, The Sanitary City, John Hopkins Press

Today’s Conventional Treatment Coagulation & solids separation Use of alum or another chemical coagulant rapid mix, flocculation, settling, filtration Disinfection including clearwell for contact timeRemoves some of theNOM & suspendedparticlesKills or inactivatespathogenic organisms Most common sequence for surface waterCorrosion ControlFluorideCoagulantDisinfectantClearwell28raw onDave Reckhow

Coagulation chemistryFerric SulfateFe2 ( SO4 )3 6 OH - 2Fe(OH )3 3 SO24Alum 24 Al2 ( SO4 ) 3 18 H2 O 2 Al (OH ) 3 3SO 6 H 12 H2 OMechanisms Precipitation of metal hydroxide, then: Adsorption of contaminants Enmeshment of particles29

NOM removal by alumcoagulation Impacts of pH and dose8450Control (no alum)400735024 mg/L doseDOC (mg/L)630048 mg/L dose5250420096 mg/L dose3150Manganese2100Mn precipitationRennes IV Raw Water(France) 11/19/84150Reckhow & Bourbigot (unpublished data)030045678pH9101112Soluble Manganese ( g/L)9

Flocculation An Empty full-scale rectangular flocculation tank in SouthernCACan be done inthe lab by slowlymixing yoursample with astirrer or on ashaking tableMWDSCWeymouth Plant31 12 Dec 05Dave Reckhow

Settling Circular andrectangular designsMWDSCWeymouth Plant32 12 Dec 05Can be done in thelab by letting yoursample sit in a jarquiescently

Filtration Sand media Empty filter, not in service (Cincinnati)33Dave Reckhow

Chlorination Chlorine tanks Left side is34currently feeding Right side is onDave Reckhowreserve

Other Types: Ozone Plants Many types Simplest type: ozone, non-filtration shown below examples: MWRA (Boston), Portland ME More complex: including coagulation & Filtration examples: Andover MA, Amherst MA Always includes final disinfection with chlorine or chloraminesCl235O3Cl2NH3Dist.Sys.Dave Reckhow

Ozone Generator DiffusersCan be done in the labwith a 70 fish tanksized ozone generator36

Ultraviolet Light Waterloo, Ont37

Membrane Treatment National City,CA38

1921-2010John #III: John Rook Chlorine: “the chronic problem” Brought headspace analysis from thebeer industry to drinking water Found trihalomethanes (THMs) in finishedwater Carcinogens !?! Published in Dutch journal H2O, Aug 19,1972 issue Deduced that they were formed asbyproducts of chlorination Proposed chemical pathways39Rook, 1974, Water Treat. & Exam., 23:234

Reactions with Disinfectants: ChlorineOxidized NOMand inorganic chloride AldehydesThe Precursors!HOCl natural organics(NOM)Chlorinated Organics TOX THMs HAAsThe THMsBrClCl CHClChloroform40Cl CBrBrHClBromodichloromethaneBr CHClChlorodibromomethaneBr CHBrBromoform

aHours of transit timefrom the water filtration plantto your house41

Multiple Routes of Exposure Inhalation in the showerproduces highest blood leveland response is fastGordon et al., 2006 [Env.Health Persp.114:514-521]43

Epidemiology Bladder Cancer DBPs linked to 9,300 US cases everyyear Other Cancers Rectal, colon Reproductive & developmentaleffects Neural tube defects Miscarriages & Low birth weight Cleft palate137,000 atrisk in US? Other Kidney & spleen disorders Immune system problems, neurotoxiceffects“I think you should be more explicit here44in step two”

Observational:The DBP IcebergTHMs, THAAsDHAAsICR Compounds50 MWDSC DBPs 700 Known DBPsSusan undsStuart Krasner

Another Sandra Hempel Journalist 2007 publication date Similar in many ways toJohnson’s book46Dave Reckhow

Biography A serious biography 2003 publication Primarily written by MDs47Dave Reckhow

Cholera & beyond Robert Morris Environmentalepidemiologist 2007 publication date More comprehensive Cholera to DBPs toCrypto48Dave Reckhow

Lead Hazards 2006 publication date Werner Troesken Professor of History Presents many historicallessons on society’sfailure to balance publichealth with profit49Dave Reckhow

The EndClNOMHC ClCl5050Dave Reckhow

What's in the Water? Natural Substances Natural Organic Matter (NOM) Inorganic Substances (Iron, Manganese, sodium, chloride) Anthropogenic Substances Pesticides Organic Solvents & Other Industrial Compounds Carcinogens Pharmaceuticals Endocrine Disrupting Compounds Flame Retardants Pathogens and other microorganisms Dave Reckhow