Organic Compounds in Water and Wastewater Isolation of NOM Lecture - PDF document

9/18/2014 Print version CEE 697z Organic Compounds in Water and Wastewater Isolation of NOM Lecture #3 Dave Reckhow - Organics In W & WW A USGS Preparative-based method Water Sample Leenheer, J.A. and Filter Noyes, T.I. (1984) A Filtration and Column- Adsorption System for Hydrophobic Bases Hydrophobic Resin Onsite Concentration and Weak Hydrophobic Acids Amberlite Fractionation of Organic XAD-8 Hydrophobic Neutrals Substances from Large Volumes of Water , U.S. Geological Survey Cation Exchange Resin Hydrophilic Bases MSC-1 Water Supply Paper 2230, U.S. Government Printing Office, Washington, D.C. Anion Exchange Resin Duolite Humic Acid A-7 Amberlite Fulvic Acid XAD-8 Dave Reckhow - Organics In W & WW Hydrophilic Neutrals Hydrophilic Acids 1

9/18/2014 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 51.9 5.0 40.3 1.1 0.2 0.6 1.5 Humic 50.0 4.7 39.6 2.0 5.0 High oxygen content FA and HA Similar, except: • humics tend to have more N 3 Dave Reckhow - Organics In W & WW Molecular Size: Ultrafiltration 70 25 Humic Fulvic 60 Acid 20 Acid 50 % of Raw Water DOC % of Isolate DOC Polydisperse  40 15  Polydisperse Small to  Moderate 30  Moderate to large 10 20 5 10 0 0 1000-3000 AMU 500-1000 AMU > 3000 AMU < 500 AMU 1000-5000 AMU 500-1000 AMU > 5000 AMU < 500 AMU Dave Reckhow - Organics In W & WW 2

9/18/2014 Aromaticity: 13 C-NMR More reactive with Aromatic 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 17 14-19 59 54-64 Humic 32 30-35 45 38-49 5 Dave Reckhow - Organics In W & WW Functional Groups: Titration O C O OH OH C OH Phenolic Group Carboxyl Groups Functional Group Content of Aquatic Humic Substances (meq/g-C, After Thurman, 1985) Fraction Carboxyl Phenolic Fulvic 11 3 Humic 8 4 6 Dave Reckhow - Organics In W & WW Source of electrical charge; responsible for coagulant demand 3

9/18/2014 An Aquatic Humic “Structure”  Features  Aromatic rings  Reactive with Hydroxy Acid OH COOH oxidants  Aliphatic carbon HO COOH chains COOH  Many oxygenated Aliphatic HOOC groups that can bind Dicarboxylic Phenolic-OH with coagulants Acid O  Phenolic -OH OH HOOC  Aliphatic -OH HO  Carboxylic (COOH) Aromatic Aliphatic Acid Dicarboxylic Acid H 3 CO COOH COOH 7 Dave Reckhow - Organics In W & WW Aromatic From Thurman, 1985 Acid The Humics and Non-humics: Comprehensive NOM Fractionation Water Sample Filter Hydrophobic Bases  USGS method Hydrophobic Resin Weak Hydrophobic Acids Amberlite adapted by water XAD-8 Hydrophobic Neutrals industry Cation Exchange Resin  Idea: separate NOM Hydrophilic Bases MSC-1 into groups of compound of similar properties Anion Exchange Resin Duolite Humic Acid A-7 Amberlite Fulvic Acid XAD-8 8 Dave Reckhow - Organics In W & WW Hydrophilic Neutrals Hydrophilic Acids 4

9/18/2014 UMass Lab setup  Pre-filters  Hydrophobic resin  XAD-8  Cation Exchanger  MSC-1  Anion Exchanger  A-7 9 Dave Reckhow - Organics In W & WW HPL=Hydrophi l ic HPO=Hydroph o bic NOM Fractions: A=Acids Mass Balance W=Weak B=Bases u=ultra N=Neutrals HA 8% HPL-N 25% HA HPL-A 0% HPL-B 15% 3% FA FA 29% HPL-A 42% 9% HPL-N 11% HPO-N 7% HPO-B HPL-B W-HPO-A 2% 5% 4% Northeast MA W-HPO- Tap Water 16% Forge Pond uHPL-A HPO-B Granby, MA Dave Reckhow - Organics In W & 22% HPO-N 0% 10 WW 2% 5

9/18/2014 10 Absorbance Humic Acid of Acid Sp. Abs. (L/m/mg-C) Weak Hydrophobic Acids Fractions Fulvic Acid 1 Hydrophilic Acids 0.1 Same DOC 200 250 300 350 400 450 500 550 600 650 254 nm Wavelength (nm) Dave Reckhow - Organics In W & WW 60 120 Different Water S. Platte R. 50 100 7.5 mg/L Percent Carbon Percent Carbon 40 80 Types 30 60 Total 20 40 10 20  South Platte River 0 0 Thoreau's Bog 50 31 mg/L 100 (Leenheer) Weak Acids Percent Carbon Percent Carbon 40 80 30 60 Strong Acids 20 40  Thoreau’s Bog 10 20 (Leenheer) 0 0 Forge Pond 50 100 6.6 mg/L Weak Acids Percent Carbon Percent Carbon Humic Acid 40 80 30 60  Forge Pond (Bose & Fulvic Acid 20 40 Reckhow) 10 20 0 0 Neutrals Recovery Neutrals Strong Acids Acids Bases Acids Bases Total Dave Reckhow - Organics In W & WW Hydrophobic Hydrophilic 6

9/18/2014 NOM Fractions: Seasonal Effects HA HPL-A New England Reservoir 4% 7% Fall HPL-N 17% HA HPL-A FA 4% 9% 37% HPL-B 7% FA HPL-N 32% uHPL-A 23% 9% HPO-N W-HPO-A 3% HPO-B 15% HPL-B 1% 4% New England Reservoir uHPL-A Spring 9% HPO-N W-HPO-A 1% HPO-B 17% Dave Reckhow - Organics In W & WW 1% Abundance From: Perdue & Ritchie, 2004 Dave Reckhow - Organics In W & WW 7

9/18/2014 Chemical k ow Interpretation 0.1 1 10 100 1000 10000 100000 Hydrophilic Neutrals Hydrophobic Neutrals s 2 3 4 5 6 8 Nitriles 3 4 5 6 7 8 9 Methyl Ketones  May be related to known Alcohols 1 2 3 4 5 6 7 8 9 Octanol:water Alkanes 5 6 7 partition Hydrophilic Bases Hydrophobic Bases coefficients Alkyl Pyridines 5 6 7 8 9 Amines 6 7 8 9 Strong Hydrophobic Acids Weak Hydrophobic Acids 3 4 5 6 8 Acids @ pH7 1 2 3 4 5 6 8 Acids @ pH2 Hydrophilic Acids Fulvic Acid 0.1 1 10 100 1000 10000 100000 Dave Reckhow - Organics In W & WW k ow Other Qualitative Interpretations Fraction Composition Hydrophobic Acids Weak Tannins; phenols; intermediate MW alkyl :monocarboxylic acids (C5-C8), dicarboxylic acids (C8- C11) Strong Fulvic acids; humic acids; high MW alkyl monocarboxylic acids (C9), and dicarboxylic acids (C12); aromatic acids Bases Amphoteric proteinaceous materials; high MW (C12) alkyl amines; alkyl pyridines; aromatic amines Neutrals 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 low MW (C1-C11) alkyl amines; amino acids; purines; pyrimidines; pyridine; hydroxy pyridines Neutrals polysaccharides; Low MW (C1-C4) alkyl alcohols, aldehydes, and ketones; poly-ketones; amides Based on: Leenheer and Noyes, 1984; Leenheer et al., 1982; and others Dave Reckhow - Organics In W & WW 8

9/18/2014 Proposed Assignments for Organic Fractions Fraction Composition Bacterial peptidoglycan cell wall components (hydrophilic neutral) 1 Colloidal Hydrophobic Acids Weak tannins; phenols; intermediate MW alkyl monocarboxylic acids (C5-C8), dicarboxylic acids (C8-C11) fulvic acids; humic acids; high MW alkyl monocarboxylic acids (  C9), and Strong dicarboxylic acids (  C12); aromatic acids Bases amphoteric proteinaceous materials; high MW (JC12) alkyl amines; alkyl pyridines; aromatic amines hydrocarbons; high MW (  C6) methyl ketones; furans; most ethers; high MW (  C5) Neutrals alkyl alcohols, and aldehydes; lactones; pyrrole, alkyl aromatic sulfonates 1 Hydrophilic Acids hydroxy acids; sugar acids; sulfonic acids; low MW alkyl monocarboxylic acids (C1- C4), and dicarboxylic acids (C2-C7) Bases low MW (C1-C11) alkyl amines; amino acids; purines; pyrimidines; pyridine; hydroxy pyridines Neutrals polysaccharides; Low MW (C1-C4) alkyl alcohols, aldehydes, and ketones; poly- ketones; 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 Dave Reckhow - Organics In W & WW  To next lecture Dave Reckhow - Organics In W & WW 9