9/26/2014 Print version CEE 697z Organic Compounds in Water and Wastewater NOM Characterization II Lecture #8 Dave Reckhow - Organics In W & WW UV-Vis Absorbance Spectra Do we see “signatures of” Proteins (Bovine Serum Albumin – a typical one) Lignin 0.25 Kensico January 0.20 Ashokan January Cannonsville January Pepacton January Absorbance (cm -1 ) Neversink January 0.15 Lignin Bovine Serum Albumin 0.10 A 280 nm shoulder? 5 mg/L lignin 0.05 0.00 200 250 300 350 400 450 500 Wavelength (nm) 10 mg/L BSA 1
9/26/2014 10 Absorbance of Acid Fractions Humic Acid Sp. Abs. (L/m/mg-C) Weak Hydrophobic Acids Fulvic Acid 1 Hydrophilic Acids 0.1 Same DOC 200 250 300 350 400 450 500 550 600 650 Wavelength (nm) Absorbance of Bases & Neutrals 10 Hydrophilic Neutrals Sp. Abs. (L/m/mg-C) Hydrophobic Neutrals 1 Hydrophilic Bases Hydrophobic Bases 0.1 200 250 300 350 400 450 500 550 600 650 Wavelength (nm) 2
9/26/2014 UV absorbance vs TOC: raw waters 0.7 0.6 UV absorbance (cm- 1 ) 0.5 Correlation Between TOC 0.4 and UV 0.3 absorbance for 53 samples of 0.2 Grasse River SUVA = (0.7/15) * 100 0.1 = 4.7 L/mg-m Water (from Edzwald et al., 0.0 1985) 0 3 6 9 12 15 TOC (mg/L) 5 UV absorbance vs DOC: treated waters surrogate for many Black Lake Fulvic Acid organic parameters SUVA: specific UV 0.20 absorbance, (UV/DOC) 0.18 0.16 UV Absorbance (/cm) Correlation Between DOC and 0.14 UV absorbance for an Aquatic 0.12 Fulvic Acid Subject to Coagulation 0.10 at Various Alum Doses and 0.08 various pHs (5-9) (from Reckhow, 0.06 1984) 0.04 0.02 0.00 0 1 2 3 4 DOC (mg/L) 3
9/26/2014 Specific UV Absorbance (SUVA) UV absorbance at 254nm (cm -1 ) divided by the DOC in mg/L (usually multiplied by 100) Relates to character of NOM SUVA>4, water has a high humic character high in hydrophobic organics, high MW, aromatic SUVA=2-4, intermediate humic content mix of hydrophobic and hydrophilic, medium MW SUVA<2, mostly non-humic hydrophilic organics, low MW, aliphatic 7 Source SUVA (L/mg-m) Typical HA 6 Typical FA 4 Lake Manatee, FL 5.7 Grasse River, NY 4.6 Mississippi, R., LA 3.1 Some SUVA Wachusett Res., MA 2.5 Values Quabbin Res., MA 1.8 Colorado R., CA 1.5 Aysgarth Falls, Yorkshire Dales 8 4
9/26/2014 SUVA of NOM Fractions 7 Since treatment often results in preferential 6 removal of humics, Sp. UV Abs (L/m/mg-C) 5 the SUVA in finished water is usually lower 4 than in the raw water 3 Bleaching of NOM by 2 chlorine makes this 1 even more 0 pronounced Weak Acids Fulvic Acid Humic Acid Neutrals Neutrals Bases Bases Acids Hydrophobic Hydrophilic 9 9 Surrogate Parameters/Correlations: (Normalized) THM Formation Potential (FP) versus SUVA (Croué) 10 from : Krasner & Am y 5
9/26/2014 Bulk NOM Absorbance Spectra What information can we extract from this? Problem of particles 0.5 Kensico January Shoharie January Ashokan January Cannonsville January 0.4 Pepacton January Absorbance (cm -1 ) Neversink January 0.3 0.2 Problem with light 0.1 scattering 0.0 200 250 300 350 400 450 500 Wavelength (nm) Lignins Responsible for much of the tri-HAA? Absorbance spectra of Coniferous Lignin Pew and Connors Tappi, 54 (1971), 245-251 Local Absorbance max at 280 nm 6
9/26/2014 Proteins Proteins generally exhibit a UVabs peak near 280 nm. This absorption is due to the constituent amino acids tyrosine, tryptophan, and phenylalanine (aromatic amino acids). Spectra from Shimadzu Compare with NOM Spectra Do we see “signatures of” Proteins (Bovine Serum Albumin – a typical one) Lignin 0.25 Kensico January 0.20 Ashokan January Cannonsville January Pepacton January Absorbance (cm -1 ) Neversink January 0.15 Lignin Bovine Serum Albumin 0.10 A 280 nm shoulder? 5 mg/L lignin 0.05 0.00 200 250 300 350 400 450 500 Wavelength (nm) 10 mg/L BSA 7
9/26/2014 UV absorbance as a surrogate A good surrogate for DOC especially when the character of the DOC is reasonably constant A very good surrogate for THMFP, HAAFP takes into account reactivity of DOC as well as amount of DOC Oxidation processes (ozonation) disrupt relationships between UV and DOC or THMFP Commercial field probe 15 15 UV absorbance and THMFP Correlation Between 600 TTHMFP and UV absorbance for 31 500 samples of raw and treated water from TTHMFP ( g/L) 400 the Oneida WTP (from Edzwald et al., 1985) 300 200 100 0 0.0 0.1 0.2 0.3 0.4 UV Absorbance (cm -1 ) 8
9/26/2014 UV absorbance and THMFP Black Lake Fulvic Acid Correlation Between TTHMFP and UV absorbance for an Aquatic Fulvic Acid 300 Subject to Coagulation at THM Formation Potential ( g/L) Various Alum Doses and 250 various pHs (5-9) (from Reckhow, 1984) 200 150 100 50 0 0.00 0.04 0.08 0.12 0.16 0.20 UV Absorbance (cm -1 ) Whole cells extracellular Algal Organics Microsystis aeruginosa I: protein-like NOM intracellular II: protein-like III: humic-like IV: protein-like V: humic-like Fang et al., 2010 18 9
9/26/2014 Fluorescence - EEMs Terrestrial/ Excitation-Emission Terrestrial Anthro- Matrices: Fluorescence Humic pogenic intensity across the Humic range of emission wavelengths while also Marine & Amino scanning across Terrestrial Acid excitation wavelengths Humic Terrestrial Contour plots of 7 Marine & Humic components identified Terrestrial from the complete F- Humic EEMs dataset. Correlates well with some Baghoth et al., Amino 2011 acid NOM properties, but fundamental understanding is 19 still not good Assignment of EEM Regions Location of EEM peaks (symbols) based on literature reports and operationally defined excitation and emission wavelength boundaries (dashed lines) for five EEM regions 20 Chen et al., 2003 10
9/26/2014 NOM Characterization Analytical Tests elemental analysis spectral properties functional group chemistry Separation/Fractionation resin adsorption size exclusion chromatography Combinations Practical Characterization of NOM Two necessary components A set of useful, and accessible characterization tools (i.e., analytical methods) A means by which NOM characteristics can be translated into information of practical importance (i.e., what does it all mean?) Progress is being made in both areas NOM characterization is still more “scientific” that “practical” exception: SUVA However, NOM characterization will become far more important in the near future 11
9/26/2014 Most Useful Characterization Methods Current, accessible methods SUVA Hydrophilic/hydrophobic Absorbance at 272 nm??? Future methods HPLC & spectral based methods Deconvolution of UV/Vis Spectrum Research methods (require expensive equipment) Pyrolysis - GC/MS 13 C-NMR LC/MS Pyrolysis GC/MS high temperature, rapid thermal decomposition followed by mass spectrometry for identification of pyrolysis byproducts difficult, and not quantitative, or at best, semi-quantatitive can attribute pyrolysis byproducts to starting structures .proteins (form pyrroles, indoles, phenol, p-cresol, nitriles) .amino sugars (form acetamide) .polyhydroxy aromatics (various phenolic derivatives) .carbohydrates (form furans, acetic acid, and many carbonyl compounds) .carboxylic acids THMFP may be related to polyhydroxy aromatic content 24 12
9/26/2014 11 Miscellaneous Proteins 25 Amino Sugars Hydroxy Aromatics 61 Carbohydrates 1 2 Fulvic Acid from Bruchet et al., 1990 (Sept. J.AWWA) HILIC - NMR Figure 1. A) Chromatogram of HILIC separation. Blue line: DAD, 280 nm, units on left axis. Red line: fluorescence, 320/430 nm ex/em, units on right axis. Dashed lines: HPLC fraction intervals. Arrow: signal predominated by tryptophan. B) PCA plot of the scores for the NMR data. C) Major structural groups with increasing polarity; assignments explained in the main text. Correlations have a significance of p < 0.0005 except aromatics ( p = 26 Woods et al., 2011 0.578). ( avg% ) indicates average percentage of NMR signal for all fractions 13
9/26/2014 The Future??: Higher MW ID NOM research ESI with Ultra High- Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Benefits Unambiguous molecular formulae Raw Water - Winnipeg 4.00E+02 -ve ion + ve ion 3.50E+02 3.00E+02 Intensity 2.50E+02 ESI -TOF MS 2.00E+02 1.50E+02 1.00E+02 5.00E+01 0.00E+00 150 250 350 450 550 650 m/z 12 11 ESI -FTI CR MS 10 9 Abundance 8 7 6 5 4 3 2 1 300 400 500 600 700 800 900 28 m/z Same: comparison side-by-side 14
9/26/2014 Chlorinated Water + Br Winnipeg 7 6 Abundance 5 4 3 2 1 390 395 400 405 410 415 420 425 m/z 7 6 Abundance 5 4 3 2 1 408.863 408.945 409.027 409.108 409.19 409.272 409.354 409.436 29 m/z Ultra-high resolution MS Reemtsma et al., 2006 [ES&T: 40:19:5839] Zone of low solubility Area of predicted fulvic acid molecules in a C- vs molecular mass diagram for the mass range m / z 310-370 (marked by the lines) and fulvic acid molecules detected by SEC-FTICR- 30 MS in the river isolate (dots (island no. 24) and triangles (island no. 25)). 15
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