CEE 697z Organic Compounds in Water and Wastewater

Size: px

Start display at page:

Download "CEE 697z Organic Compounds in Water and Wastewater"

Candace Farmer
5 years ago
Views:

1 Print version CEE 697z Organic Compounds in Water and Wastewater Isolation of NOM Lecture #3

2 A USGS Preparative-based method Leenheer, J.A. and Noyes, T.I. (1984) A Filtration and Column- Adsorption System for Onsite Concentration and Fractionation of Organic Substances from Large Volumes of Water, U.S. Geological Survey Water Supply Paper 2230, U.S. Government Printing Office, Washington, D.C. Filter Hydrophobic Resin Amberlite XAD-8 Cation Exchange Resin MSC-1 Anion Exchange Resin Duolite A-7 Water Sample Hydrophobic Bases Weak Hydrophobic Acids Hydrophobic Neutrals Hydrophilic Bases Humic Acid Hydrophilic Neutrals Amberlite XAD-8 Fulvic Acid Hydrophilic Acids

3 Elemental Composition: Humics Elemental Composition of Aquatic Humic Substances (average of 15 riverine samples, after Thurman, 1985) Fraction C H O N P S Ash Fulvic Humic High oxygen content FA and HA Similar, except: humics tend to have more N 3

4 Molecular Size: Ultrafiltration % of Isolate DOC Humic Acid Polydisperse Moderate to large % of Raw Water DOC Fulvic Acid Polydisperse Small to Moderate > 3000 AMU AMU AMU < 500 AMU 0 > 5000 AMU AMU AMU < 500 AMU

5 Aromaticity: 13 C-NMR Aromatic More reactive with disinfectants Absorbs UV light Aliphatic Aromatic and Aliphatic Content of Aquatic Humic Substances (from Reckhow et al., 1990) Fraction Percent Aromatic Percent Aliphatic Average Range Average Range Fulvic Humic

6 Functional Groups: Titration C O OH OH C O Phenolic Group Carboxyl Groups OH Functional Group Content of Aquatic Humic Substances (meq/g-c, After Thurman, 1985) Fraction Carboxyl Phenolic Fulvic 11 3 Humic Source of electrical charge; responsible for coagulant demand

7 An Aquatic Humic Structure HOOC HOOC Aromatic Dicarboxylic Acid Hydroxy Acid HO COOH Phenolic-OH OH HO H 3 CO COOH OH O COOH COOH Aliphatic Acid COOH Aliphatic Dicarboxylic Acid Features Aromatic rings Reactive with oxidants Aliphatic carbon chains Many oxygenated groups that can bind with coagulants Phenolic -OH Aliphatic -OH Carboxylic (COOH) 7 Aromatic Acid From Thurman, 1985

The Humics and Non-humics: Comprehensive NOM Fractionation Filter Water Sample Hydrophobic Resin Amberlite XAD-8 Cation Exchange Resin MSC-1 Anion Exchange Resin Duolite A-7 Hydrophobic Bases Weak

8 The Humics and Non-humics: Comprehensive NOM Fractionation Filter Water Sample Hydrophobic Resin Amberlite XAD-8 Cation Exchange Resin MSC-1 Anion Exchange Resin Duolite A-7 Hydrophobic Bases Weak Hydrophobic Acids Hydrophobic Neutrals Hydrophilic Bases Humic Acid USGS method adapted by water industry Idea: separate NOM into groups of compound of similar properties Hydrophilic Neutrals Amberlite XAD-8 Fulvic Acid 8 Hydrophilic Acids

9 UMass Lab setup Pre-filters Hydrophobic resin XAD-8 Cation Exchanger MSC-1 Anion Exchanger A-7 9

42% HPL-N 11% HPL-B 5% HPL-A 15% HA 0% FA 29% 10 Forge Pond Granby, MA Northeast MA

10 NOM Fractions: Mass Balance HPL-N 25% HA 8% HPL=Hydrophilic HPO=Hydrophobic A=Acids B=Bases N=Neutrals W=Weak u=ultra HPL-B 3% HPL-A 9% HPO-N 7% HPO-B 2% W-HPO-A 4% FA 42% HPL-N 11% HPL-B 5% HPL-A 15% HA 0% FA 29% 10 Forge Pond Granby, MA Northeast MA Tap Water uhpl-a Dave Reckhow - Organics In W 22% & WW W-HPO- 16% HPO-B HPO-N0% 2%

11 10 Absorbance of Acid Fractions Sp. Abs. (L/m/mg-C) 1 Humic Acid Weak Hydrophobic Acids Fulvic Acid Same DOC Hydrophilic Acids nm Wavelength (nm)

12 Different Water Types Percent Carbon Total S. Platte R. 7.5 mg/l Percent Carbon South Platte River (Leenheer) Thoreau s Bog (Leenheer) Forge Pond (Bose & Reckhow) Percent Carbon Percent Carbon Thoreau's Bog 31 mg/l Weak Acids Strong Acids Weak Acids Humic Acid Fulvic Acid Forge Pond 6.6 mg/l Percent Carbon Percent Carbon Acids Bases Neutrals Acids Bases Neutrals Hydrophobic Hydrophilic Strong Acids Total Recovery

Reservoir Spring FA 37% HPL-N 23% HPL-B 4% New England

13 NOM Fractions: Seasonal Effects HPL-N 17% HPL-B 7% HPL-A 7% HA 4% uhpl-a 9% HPO-N W-HPO-A 3% HPO-B 15% 1% New England Reservoir Spring FA 37% HPL-N 23% HPL-B 4% New England Reservoir Fall HPL-A 9% HA 4% uhpl-a 9% HPO-N 1% HPO-B 1% W-HPO-A 17% FA 32%

14 Abundance From: Perdue & Ritchie, 2004

15 Chemical Interpretation s k ow Hydrophilic Neutrals Hydrophobic Neutrals Nitriles May be related to known Octanol:water partition coefficients Hydrophilic Bases Hydrophobic Bases 8 9 Methyl Ketones Alcohols Alkanes Alkyl Pyridines Amines Strong Hydrophobic Acids Weak Hydrophobic Acids ph ph2 Hydrophilic Acids Fulvic Acid k ow

16 Other Qualitative Interpretations Hydrophobic Fraction Acids Weak Bases Strong Neutrals Composition Tannins; phenols; intermediate MW alkyl :monocarboxylic acids (C5-C8), dicarboxylic acids (C8- C11) Fulvic acids; humic acids; high MW alkyl monocarboxylic acids (C9), and dicarboxylic acids (C12); aromatic acids Amphoteric proteinaceous materials; high MW (C12) alkyl amines; alkyl pyridines; aromatic amines Hydrocarbons; high MW (C6) methyl ketones; furans; most ethers; high MW (C5) alkyl alcohols, and aldehydes; lactones; pyrrole Hydrophilic Acids hydroxy acids; sugar acids; sulfonic acids; low MW alkyl monocarboxylic acids (C1-C4), and,dicarboxylic acids (C2-C7) Bases Neutrals low MW (C1-C11) alkyl amines; amino acids; purines; pyrimidines; pyridine; hydroxy pyridines polysaccharides; Low MW (C1-C4) alkyl alcohols, aldehydes, and ketones; poly-ketones; amides Based on: Leenheer and Noyes, Dave Reckhow 1984; Leenheer - Organics In et W al., & WW 1982; and others

17 Proposed Assignments for Organic Fractions Fraction Composition Colloidal Bacterial peptidoglycan cell wall components (hydrophilic neutral) 1 Hydrophobic Acids Weak Bases Strong Neutrals Hydrophilic Acids Bases Neutrals tannins; phenols; intermediate MW alkyl monocarboxylic acids (C5-C8), dicarboxylic acids (C8-C11) fulvic acids; humic acids; high MW alkyl monocarboxylic acids ( C9), and dicarboxylic acids ( C12); aromatic acids amphoteric proteinaceous materials; high MW (JC12) alkyl amines; alkyl pyridines; aromatic amines hydrocarbons; high MW ( C6) methyl ketones; furans; most ethers; high MW ( C5) alkyl alcohols, and aldehydes; lactones; pyrrole, alkyl aromatic sulfonates 1 hydroxy acids; sugar acids; sulfonic acids; low MW alkyl monocarboxylic acids (C1- C4), and dicarboxylic acids (C2-C7) low MW (C1-C11) alkyl amines; amino acids; purines; pyrimidines; pyridine; hydroxy pyridines polysaccharides; Low MW (C1-C4) alkyl alcohols, aldehydes, and ketones; polyketones; amides, N-acetyl amino sugars 1, non-carbohydrate alcohols 1 +Based on: Leenheer and Noyes, 1984; Leenheer et al., 1982; and Reckhow et al., 1992

18 To next lecture

CEE 697z Organic Compounds in Water and Wastewater

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 H H O H OH H OH OH