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Organic Compounds in Water and Wastewater Origins of NOM II - - PowerPoint PPT Presentation

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Print version CEE 697z Organic Compounds in Water and Wastewater Origins of NOM II Lecture #5 Dave Reckhow - Organics In W & WW Carbohydrates empirical formula: C x (H 2 O) y CH 2 OH CH 2 OH CH 2 OH H OH H H O O O H H O OH

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CEE 697z

Organic Compounds in Water and Wastewater

Origins of NOM II

Print version

Dave Reckhow - Organics In W & WW

Lecture #5

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Carbohydrates

2

  • empirical formula: Cx(H2O)y

O H OH H OH OH H OH CH2OH H H

O H H OH OH OH CH2OH H H O H OH OH OH CH2OH H H O OH

Glucose (monosaccharide) Cellulose (polysaccharide)

O H OH H OH NH2 OH H CH2OH H H

Glucosamine (amino sugar)

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Carbohydrates, cont.

 Nomenclature

 Monosaccharide: 1 simple sugar

 1% of DOC

 Oligosaccharide: ≤10 simple sugars  Polysaccharide: > 10 simple sugars

 5% of DOC

 Special interest in distribution systems

 Food for microbial regrowth  Major constituents of:

 soluble metabolic byproducts  biofilms

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Carbohydrates, cont.

 Function in plants

 Structural – cell walls

 Cellulose (~10,000 ᴅ-glucose units)

 Most abundant natural organic compound  Mostly in higher plants; some algae have none

 Hemicelluloses (50-2000 monosaccharides of many types)

 Forms a matrix around cellulose fibers in cell walls

 Chitin (N-acetyl-ᴅ-glucosamine units)

 Second most abundant natural organic (~tied with lignin)  Role of cellulose in most fungi, some algae & arthropods

 Murein or “peptidoglycan”, a major group of Acylheteropolysaccharides

 N-acetyl-ᴅ-glucosamine & N-acetylmuiramic acid cross linked by AA chains  Dominant in Eubacteria: up to 75% of bacterial dry mass

 Energy – polysaccharides

 Starch in plants (80% amylopectin, 20% amylose)

 Anti-dessicants

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Carbohydrates, cont.

Algae etc., Heteropolysaccharides Nitrogen-containing

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Carbohydrates, cont.

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Acylheteropolysaccharides (APS)

 10-35% of river and lake water DOC  Produced by algae in fresh and salt waters  Similar to structural polysaccharides?  Comprised of a nearly fixed ratio of simple sugars, acetate

and lipids

 Refractory like humic substances

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8 From: Perdue & Ritchie, 2004

Sugars in Natural Waters

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Fatty Acids

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  • maybe 4% of DOC
  • other mixed acids may account for 2%

H-COOH CH3-COOH CH3-CH2-COOH Formic 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+

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Amino Acids and Proteins

 Simple Amino Acids

 some may form THMs and

HANs

 Proteins

 much larger, comprised of

many AAs

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H2C C H COOH NH2

HO C H2 C H NH2 COOH

Tyrosine Alanine Special interests in DWT

– nutrients for bacterial regrowth – role in chlorine decay and DBP formation

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Amino Acids

From: Perdue & Ritchie, 2004

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Terpenes and Terpenoids

 The terpenoids, sometimes called isoprenoids, are a large and diverse class of

naturally occurring organics similar to terpenes, derived from five- carbon isoprene units assembled and modified in thousands of ways.

T erpenoids can be thought of as modified terpenes, wherein methyl groups have been moved or removed, or oxygen atoms added.

 Plant terpenoids are used extensively for their aromatic qualities. They play a role in

traditional herbal remedies and are under investigation for antibacterial, antineoplastic, and other pharmaceutical functions. T erpenoids contribute to the scent of eucalyptus, the flavors of cinnamon, cloves, and ginger, the yellow color in sunflowers, and the red color in tomatoes.

 T

erpenoids can be classified according to the number of isoprene units used:

Hemiterpenoids, 1 isoprene unit (5 carbons)

Monoterpenoids, 2 isoprene units (10C)

Sesquiterpenoids, 3 isoprene units (15C)

Diterpenoids, 4 isoprene units (20C) (e.g. ginkgolides)

Sesterterpenoids, 5 isoprene units (25C)

Triterpenoids, 6 isoprene units (30C) (e.g. sterols)

T etraterpenoids, 8 isoprene units (40C) (e.g. carotenoids)

Polyterpenoid with a larger number of isoprene units

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From Wikipedia

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Terpenoids

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Terpenoids, cont.

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Iron Complexation

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Van Krevlin Plot

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Putting it all together?

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COOH O COOH COOH COOH HOOC HOOC HO OH COOH H3CO OH Hydroxy Acid Aromatic Dicarboxylic Acid Aromatic Acid Aliphatic Acid Aliphatic Dicarboxylic Acid Phenolic-OH HO

From Thurman, 1985

 Many identifiable precursor

structures

 Not practical or even possible

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Concentrations: Pedogenic

 Land Sources

 From Woody & non-woody plants, lignin, etc.  Depends on vegetation, soil, hydrology

 Attenuated by adsorption to clay soils

 Parallel watersheds in Australia (Cotsaris et al., 1994 [Chamonix

proceedings])

 Clearwater Creek, high clay content: 2.5 mg/L TOC  Redwater Creek, sandy soil: 31.7 mg/L TOC

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Concentrations: Aquagenic

 Algal & aquatic plant Sources

 Depend on nutrient levels / trophic state

 Concentrations in Lakes (mg/L) (Thurman, 1985)  Groundwater average: 0.7 mg/L

 No algae, much soil attenuation

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Trophic State Mean DOC Range

Oligotrophic 2 1-3 Mesotrophic 3 2-4 Eutrophic 10 3-34 Dystrophic 30 20-50

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MW vs type

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Henderson et al., 2008

 Algogenic organic matter

(AOM)

 Proteins & carbohydrates  Large polymers with

monomers

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Algae as THM Precursors

 From: Plummer & Edzwald, 2001

 [ES&T:35:3661]

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Scenedesmus quadricauda Cyclotella sp.

~25% from EOM

pH 7, 20-24ºC, chlorine excess Algae

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Algae as TCAA Precursors

 Not much impact?

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pH 7, 20-24ºC, chlorine excess Algae

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Algae as DCAA Precursors

 Are Algae important sources of dihalo-AA precursors?

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pH 7, 20-24ºC, chlorine excess Algae

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Annual TOC Cycles

 Edisto River

 Former source

for Charleston’s (SC) Hanahan WTP

 Flushing of TOC

during high rainfall months (cold period)

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ICR Month

2 4 6 8 10 12 14 16 18 20

TOC (mg/L) or SUVA (m-1)

2 4 6 8 10 12 14 16 18

Approximate Date

6/1/1997 7/1/1997 8/1/1997 9/1/1997 10/1/1997 11/1/1997 12/1/1997 1/1/1998 2/1/1998 3/1/1998 4/1/1998 5/1/1998 6/1/1998 7/1/1998 8/1/1998 9/1/1998 10/1/1998 11/1/1998 12/1/1998 1/1/1999 2/1/1999 TOC: Kornegay SUVA: ICR TOC: ICR

Hanahan WTP Charleston, SC

Influent Water

Period

  • f High

Runoff

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Annual TOC Cycles

 Lake Lanier

 Source for

Gwinnett Co.’s (GA) Lanier WTP

 High clay content

in watershed

25 ICR Month

2 4 6 8 10 12 14 16 18 20

TOC (mg/L) or SUVA (m-1)

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Approximate Date

6/1/1997 7/1/1997 8/1/1997 9/1/1997 10/1/1997 11/1/1997 12/1/1997 1/1/1998 2/1/1998 3/1/1998 4/1/1998 5/1/1998 6/1/1998 7/1/1998 8/1/1998 9/1/1998 10/1/1998 11/1/1998 12/1/1998 1/1/1999 2/1/1999 TOC: Kornegay data SUVA: ICR TOC: ICR

Lake Lanier WTP Gwinnet Co., GA

Influent Water

High photosynthetic activity

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Day of Year

50 100 150 200 250 300 350

UV285 (cm

  • 1)

0.00 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.10 DOC (mg/L) 1 2 3 4 5 6

DOC (mg/L)

1 2 3 4 5

Depth (m)

2 4 6 8 10 12 14 16 18 20 UV285 (cm-1) 0.00 0.02 0.04 0.06 0.08 UV DOC

DOC (mg/L)

1 2 3 4 5

Depth (m)

2 4 6 8 10 12 14 16 18 20 UV285 (cm-1) 0.00 0.02 0.04 0.06 0.08 UV DOC DOC UV

Spatial and Temporal Distribution of DOC and UV absorbing Substances in Lake Bret (from Zumstein & Buffle, 1989; and Krasner et al., 1996)

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THM Precursor Study

 Cannonsville

Reservoir

 Catskill-

Delaware water supply for NYC

 Stepczuk et al.,

1998

 J. Lake Res. Mgmt.

14(2-3)356

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Both Epilimnion Epilimnion Hypolimnion

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Plant biochemicals

 Sugars, starches  Proteins  Cellulose  Hemicellulose  Fats & waxes  Lignins & phenolics  Low  Moderate  Low  Low  Low  high Decreasing biodegradability Simplification: Doesn’t explicitly consider bacterial metabolites

Terpenoids - ??

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Dihalo and Trihalo DBPs

 NOM Fractions

 Evidence for

greater importance of dihalo species in non-lignin based NOM

30 Specific UV absorbance @ 254 nm (L/m/mg-C)

1 2 3 4 5 6 7 8 9 10

CX2/CX3 Formation Potential (µM/µΜ)

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 Humic Acid Fulvic Acid Weak Hydrophobic Acids Hydrophobic Bases Hydrophobic Neutrals Hydrophilic Acids Ultra Hydrophilic Acids Hydrophilic Bases Hydrophilic Neutrals regression

Raw Waters

b[0]=0.4813029679 b[1]=-0.0290898677 r ²=0.1466315169

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DHAN/THM Ratio vs SUVA

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Specific UV absorbance @ 254 nm (L/m/mg-C)

1 2 3 4 5 6 7 8 9 10 11

DHAN/THM Formation Potential (µg/µg)

0.0 0.1 0.2 0.3 0.4 1.5 1.6 1.7 1.8 1.9 2.0 2.1 Humic Acid Fulvic Acid Weak Hydrophobic Acids Hydrophobic Bases Hydrophobic Neutrals Hydrophilic Acids Ultra Hydrophilic Acids Hydrophilic Bases Hydrophilic Neutrals regression

All Samples

b[0]=0.20 b[1]=-0.0177 r ²=9.2e-3

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DOC and runoff

 Ogeechee River (GA)

 From Aiken & Cotsaris, 1995

 [JAWWA 87(1)36]

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Drinking water source Water treatment plant Municipal use NOM, DBPs NOM, DBPs plant Wastewater treatment EfOM: NOM, DBPs SMPs Ambient water (river) NOM

Wastewater reclamation and reuse

What is EfOM?

EfOM ≈ NOM + SMPs

from : Krasner & Am y

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Dave Reckhow - Organics In W & WW

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