Trihalomethane formation potential of aquatic and terrestrial fulvic and humic acids: examining correlation between specific trihalomethane formation potential and specific ultraviolet absorbance
Mohamed Y. Z. Abouleish A and Martha J. M. Wells B C DA Department of Biology, Chemistry, and Environmental Sciences, American University of Sharjah, PO Box 26666, Sharjah, United Arab Emirates.
B Center for the Management, Utilisation, and Protection of Water Resources and Department of Chemistry, Tennessee Technological University, Cookeville, TN 38505, USA.
C Present address: EnviroChem Services, 224 Windsor Drive, Cookeville, TN 38506, USA.
D Corresponding author. Email: mjmwells@tntech.edu; info@envirochemservices.net
Environmental Chemistry 9(5) 450-461 https://doi.org/10.1071/EN12041
Submitted: 19 March 2012 Accepted: 10 August 2012 Published: 5 October 2012
Environmental context. When surface water is disinfected to produce potable drinking water, toxic by-products are generated by reaction with naturally occurring organic matter. The production of trihalomethane disinfection by-products was investigated for different types of well-characterised organic matter from various geographic locations. Increased understanding of the character of organic matter dissolved in water is needed for improving the ability to provide safe water and protect public health.
Abstract. Trihalomethanes (THMs) – a class of disinfection by-products (DBPs) including chloroform – are produced when natural water is chlorinated. Many THMs are believed to result from the reaction of chlorine with the aromatic structures in humic substances, which can be represented by ultraviolet absorbance at 254 nm (UVA). However, in the literature, plots of the specific, or carbon-normalised, UVA (SUVA) compared with the specific, or carbon-normalised, trihalomethane formation potential, THMFP (STHMFP) are poorly correlated. Therefore, well characterised samples of organic matter were obtained from the International Humic Substances Society (IHSS) to study the effect of type (fulvic acid, FA; humic acid, HA), origin (aquatic, terrestrial), geographical source (Nordic, Suwannee River, peat, soil) and pH (6, 9) on the formation of trihalomethanes. In this research, parameters expressed on a weight-average moles-of-humic substance basis were compared with those on a mass-of-carbon basis. Using factorial analysis, SUVA was statistically described by the main effect type (P = 0.0044), whereas STHMFP was statistically described by the main effects type (P = 0.0078) and origin (P = 0.0210). Separate relationships between SUVA and STHMFP normalised to moles of humic substance were defined for aquatic substances (R2 = 0.9948) and for terrestrial substances (R2 = 0.9512). The occurrence of aquatically derived fulvic-like humic acid (Suwannee River humic acid) and aquatically derived terrestrial-like humic acid (Nordic humic acid) were observed. Some aquatic substances were capable of generating levels of THMs per mole of humic substance that were greater than or equal to the most reactive terrestrial humic acid.
Additional keywords : disinfection by-products, drinking water treatment, factorial analysis, STHMFP, SUVA.
References
[1] R. J. Bull, F. C. Kopfler, Health Effects of Disinfectants and Disinfection By-Products 1991 (AWWA Research Foundation: Denver, CO).[2] H. G. Peterson, J. P. Milos, D. R. Spink, S. E. Hrudey, J. Sketchell, Trihalomethanes in finished drinking water in relation to dissolved organic carbon and treatment process for Alberta surface waters. Environ. Technol. 1993, 14, 877.
| Trihalomethanes in finished drinking water in relation to dissolved organic carbon and treatment process for Alberta surface waters.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2cXisFaqtr0%3D&md5=f50f125e8ba6cc6666da14f44f4f4f4eCAS |
[3] M. S. Fram, R. Fujii, J. L. Weishaar, B. A. Bergamaschi, G. R. Aiken, How DOC composition may explain the poor correlation between specific trihalomethane formation potential and specific UV absorbance, US Geological Survey Toxic Substances Hydrology Program, Vol. 2, 99–4018B, 1999 (Water Resource Division, US Geological Survey: Sacramento, CA).
[4] J. Fawell, Risk assessment case study-chloroform and related substances. Food Chem. Toxicol. 2000, 38, S91.
| Risk assessment case study-chloroform and related substances.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXhslams7g%3D&md5=bed78a16e936fb4461e440d1a3069312CAS |
[5] M. J. Nieuwenhuijsen, M. B. Toledano, N. E. Eaton, J. Fawell, P. Elliott, Chlorination disinfection byproducts in water and their association with adverse reproductive outcomes: a review. Occup. Environ. Med. 2000, 57, 73.
| Chlorination disinfection byproducts in water and their association with adverse reproductive outcomes: a review.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXps12jtA%3D%3D&md5=a1a55cde0662fe1015fc2f9dbf8969dfCAS |
[6] T. A. Bellar, J. J. Lichtenberg, R. C. Kroner, The occurrence of organohalides in chlorinated drinking water. J. Am. Water Works Ass. 1974, 66, 703.
| 1:CAS:528:DyaE2MXhtFGqt7s%3D&md5=cfc5594f9b9ceb97d1d92fc67870ad0dCAS |
[7] J. J. Rook, Formation of haloforms during chlorination of natural waters. Water Treat. Exam. 1974, 23, 234.
[8] J. M. Symons, T. A. Bellar, J. K. Carswell, J. DeMarco, K. L. Kropp, G. G. Robeck, D. R. Seeger, C. J. Slocum, B. L. Smith, A. A. Stevens, National organics reconnaissance survey for halogenated organics. J. Am. Water Works Ass. 1975, 67, 634.
| 1:CAS:528:DyaE28Xks1yjtL8%3D&md5=3ef99eea3ba71b286a6a497221b52861CAS |
[9] R. J. Karlin, Disinfection by-products – a view from North America, in Disinfection By-products in Drinking Water, Current Issues (Eds M. Fielding, M. Farrimond) 1999, pp. 9–18 (The Royal Society of Chemistry: Cambridge, UK).
[10] S. D. Richardson, Environmental mass spectrometry: emerging contaminants and current issues. Anal. Chem. 2012, 84, 747.
| Environmental mass spectrometry: emerging contaminants and current issues.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhsF2itrbI&md5=4aef98e7462fe1e6b3f53ff3ad1450f3CAS |
[11] D. A. Reckhow, P. C. Singer, R. L. Malcolm, Chlorination of humic materials: byproduct formation and chemical interpretations. Environ. Sci. Technol. 1990, 24, 1655.
| Chlorination of humic materials: byproduct formation and chemical interpretations.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3cXlsFygtr4%3D&md5=35bed8bb9a0425bc1b9e3964b8397a27CAS |
[12] G. W. Harrington, A. Bruchet, D. Rybacki, P. C. Singer, Characterization of natural organic matter and its reactivity with chlorine, in Water Disinfection and Natural Organic Matter: Characterization and Control, ACS Symposium Series 649 (Eds R. A. Minear, G. L. Amy) 1996, pp. 138–158 (American Chemical Society: Washington, DC).
[13] P. C. Singer, Humic substances as precursors for potentially harmful disinfection by-products. Water Sci. Technol. 1999, 40, 25.
| Humic substances as precursors for potentially harmful disinfection by-products.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXlslWltQ%3D%3D&md5=440a2c39315b5341c29b0b5605d687aaCAS |
[14] J. L. Weishaar, G. R. Aiken, B. A. Bergamaschi, M. S. Fram, R. Fujii, K. Mopper, Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon. Environ. Sci. Technol. 2003, 37, 4702.
| Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3sXotFCgtLY%3D&md5=58bd455466851062a59f45487baf88c4CAS |
[15] M. Filella, Quantifying ‘humics’ in freshwaters: purpose and methods. Chem. Ecol. 2010, 26, 177.
| Quantifying ‘humics’ in freshwaters: purpose and methods.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhsVGgsL7J&md5=39f8412c4f4359923aa14480fc11d42eCAS |
[16] F. C. Kopfler, R. G. Melton, R. D. Lingg, W. E. Coleman, GC/MS Determination of volatiles for the national organics reconnaissance survey (NORS) of drinking water, in Identification and Analysis of Organic Pollutants in Water (Ed. L. H. Keith) 1976, pp. 87–104 (Ann Arbor Science Publishers: MI).
[17] I. Ivancev-Tumbas, B. Dalmacija, Z. Tamas, E. Karlovic, The effect of different drinking water treatment processes on the rate of chloroform formation in the reactions of natural organic matter with hypochlorite. Water Res. 1999, 33, 3715.
| The effect of different drinking water treatment processes on the rate of chloroform formation in the reactions of natural organic matter with hypochlorite.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXmvFSjsQ%3D%3D&md5=3136873f3982cd7502bb5374a5220982CAS |
[18] W. Schmidt, U. Bohme, F. Sacher, H. Brauch, Minimization of disinfection by-products formation in water purification process using chlorine dioxide – case studies. Ozone Sci. Eng. 2000, 22, 215.
| Minimization of disinfection by-products formation in water purification process using chlorine dioxide – case studies.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXjtFWlt7c%3D&md5=b257d9183d064ea68b9d7b33787b974dCAS |
[19] K. M. Qaisi, M. Al-Zoubi, The role of powdered activated carbon and potassium permanganate in trihalomethanes control in drinking water. Dirasat: Eng. Sci. 2000, 27, 239.
[20] American Public Health Association (APHA), American Water Works Association (AWWA), and Water Environment Federation (WEF), Standard Methods for the Examination of Water and Wastewater (21st edn) 1998 (American Public Health Association: Washington, DC).
[21] M. Y. Z. Aboul Eish, M. J. M. Wells, Assessing the trihalomethane formation potential of aquatic fulvic and humic acids fractionated using thin-layer chromatography. J. Chromatogr. A 2006, 1116, 272.
| Assessing the trihalomethane formation potential of aquatic fulvic and humic acids fractionated using thin-layer chromatography.Crossref | GoogleScholarGoogle Scholar |
[22] J. V. Camp, D. B. George, M. J. M. Wells, P. E. Acre, Monitoring advanced oxidation of Suwannee River fulvic acid. Environ. Chem. 2010, 7, 225.
| Monitoring advanced oxidation of Suwannee River fulvic acid.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtFOgu70%3D&md5=f499bd4996260799369cd8c6c06753faCAS |
[23] Enhanced Coagulation and Enhanced Precipitative Softening Guidance Manual, EPA 815-R-99-012 1999 (US Environmental Protection Agency: Washington, DC).
[24] J. K. Edzwald, W. C. Becker, K. L. Wattier, Surrogate parameters for monitoring organic matter and THM precursors. J. Am. Water Works Ass. 1985, 77, 122.
| 1:CAS:528:DyaL2MXkt1Kqtr8%3D&md5=e0777d0782d9b48cb42e5f2f31a6a1f7CAS |
[25] G. V. Korshin, C. W. Li, M. M. Benjamin, Use of UV spectroscopy to study chlorination of natural organic matter, in Water Disinfection and Natural Organic Matter: Characterization and Control. ACS Symposium Series 649 (Eds R. A. Minear, G. L. Amy) 1996, pp. 182–195 (American Chemical Society: Washington, DC).
[26] R. A. Minear, G. L. Amy, Water disinfection and natural organic matter: history and overview, in Water Disinfection and Natural Organic Matter: Characterization and Control. ACS Symposium Series 649 (Eds R. A. Minear, G. L. Amy) 1996, pp. 1–9 (American Chemical Society: Washington, DC).
[27] M. C. White, J. D. Thompson, G. W. Harrington, P. C. Singer, Evaluating criteria for enhanced coagulation compliance. J. Am. Water Works Ass. 1997, 89, 64.
| 1:CAS:528:DyaK2sXjtFGqsbs%3D&md5=ca144e5e5e1447f5f1fc182af072270eCAS |
[28] Alternative Disinfectants and Oxidants Guidance Manual, EPA 815-R-99-014 1999 (US Environmental Protection Agency: Washington, DC).
[29] M. Kitis, T. Karanfil, J. E. Kilduff, A. Wigton, The reactivity of natural organic matter to disinfection by-products formation and its relation to specific ultraviolet absorbance. Water Sci. Technol. 2001, 43, 9.
| 1:CAS:528:DC%2BD3MXjtFWgtr4%3D&md5=07ae1a8029ca038ba8a3c1117c214e18CAS |
[30] S. Platikanov, R. Tauler, P. M. S. M. Rodrigues, M. C. G. Antunes, D. Pereira, J. C. G. Esteves da Silva, Factorial analysis of the trihalomethane formation in the reaction of colloidal, hydrophobic, and transphilic fractions of DOM with free chlorine. Environ. Sci. Pollut. Res 2010, 17, 1389.
| Factorial analysis of the trihalomethane formation in the reaction of colloidal, hydrophobic, and transphilic fractions of DOM with free chlorine.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhtVSisLvJ&md5=e1db5a54db4d0fe4539bdf3496014538CAS |
[31] P. M. S. M. Rodrigues, J. C. G. Esteves da Silva, M. C. G. Antunes, Factorial analysis of the trihalomethanes formation in water disinfection using chlorine. Anal. Chim. Acta 2007, 595, 266.
| Factorial analysis of the trihalomethanes formation in water disinfection using chlorine.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXntF2rs70%3D&md5=1b5e035f79d7ff4367a498c7aeca99a1CAS |
[32] P. J. M. Dycus, K. D. Healy, G. K. Stearman, M. J. M. Wells, Diffusion coefficients and molecular weight distributions of humic and fulvic acids determined by flow field-flow fractionation. Sep. Sci. Technol. 1995, 30, 1435.
| Diffusion coefficients and molecular weight distributions of humic and fulvic acids determined by flow field-flow fractionation.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXlsF2jtLw%3D&md5=93edd01706861015a5fa0230bc3d6620CAS |
[33] J. A. Leenheer, P. A. Brown, T. I. Noyes, Implications of mixture characteristics on humic-substance chemistry, in Aquatic Humic Substances: Influence on the Fate and Transport of Pollutants. Advances in Chemistry Series 219 (Eds I. H. Suffet, P. MacCarthy) 1989, pp. 25–39 (American Chemical Society: Washington, DC).
[34] N. Senesi, T. M. Miano, M. R. Provenzano, G. Brunetti, Spectroscopic and compositional characterization of I.H.S.S. reference and standard fulvic and humic acids of various origin. Sci. Total Environ. 1989, 81–82, 143.
| Spectroscopic and compositional characterization of I.H.S.S. reference and standard fulvic and humic acids of various origin.Crossref | GoogleScholarGoogle Scholar |
[35] K. Kalbitz, S. Geyer, W. Geyer, A comparative characterization of dissolved organic matter by means of original aqueous samples and isolated humic substances. Chemosphere 2000, 40, 1305.
| A comparative characterization of dissolved organic matter by means of original aqueous samples and isolated humic substances.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXit1yru70%3D&md5=f0479c0c913aa8f0ef27439f68efd109CAS |
[36] S. J. Traina, J. Novak, N. E. Smeck, An ultraviolet absorbance method of estimating the percent aromatic carbon content of humic acids. J. Environ. Qual. 1990, 19, 151.
| An ultraviolet absorbance method of estimating the percent aromatic carbon content of humic acids.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3cXhtFOktLs%3D&md5=b4cf6c186ce939fbdd7255f4c4675a5bCAS |
[37] Y. Chin, G. Aiken, E. O’Loughlin, Molecular weight, polydispersity, and spectroscopic properties of aquatic humic substances. Environ. Sci. Technol. 1994, 28, 1853.
| Molecular weight, polydispersity, and spectroscopic properties of aquatic humic substances.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2cXls1ems7g%3D&md5=be4e6b78ca24fed7025a1fa6e0f0a1e9CAS |
[38] T. K. Nissinen, I. T. Miettinen, P. J. Martikainen, T. Vartiainen, Disinfection by-products in Finnish drinking waters. Chemosphere 2002, 48, 9.
| Disinfection by-products in Finnish drinking waters.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XjvVGjtLk%3D&md5=dfaffdd6042a11fd77bd99ff03d30077CAS |
[39] B. Deflandre, J. Gagne, Estimation of dissolved organic carbon (DOC) concentrations in nanoliter samples using UV spectroscopy. Water Res. 2001, 35, 3057.
| Estimation of dissolved organic carbon (DOC) concentrations in nanoliter samples using UV spectroscopy.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXltFOisrw%3D&md5=58939c46b807cad06b5fbf69f13f3f16CAS |
[40] A. Brandstetter, R. S. Sletten, A. Mentler, W. W. Wenzel, Estimating dissolved organic carbon in natural waters by UV absorbance (254 nm). Z. Pflanzenernahr. Bodenk. 1996, 159, 605.
| Estimating dissolved organic carbon in natural waters by UV absorbance (254 nm).Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2sXltV2isA%3D%3D&md5=dfc6e5c622515daf51f9a1e2ead07e7fCAS |
[41] A. T. Chow, R. A. Dahlgren, Q. Zhang, P. K. Wong, Relationships between specific ultraviolet absorbance and trihalomethane precursors of different carbon sources. J. Water Supply Res. T. 2008, 57, 471.
| Relationships between specific ultraviolet absorbance and trihalomethane precursors of different carbon sources.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhtlyjtbjJ&md5=63fe558a888c7e9a38e91008f61bf632CAS |
[42] R. Fujii, A. J. Ranalli, G. R. Aiken, B. A. Bergamaschi, Dissolved Organic Carbon Concentrations and Compositions, and Trihalomethane Formation Potentials in Waters from Agricultural Peat Soils, Sacramento–San Joaquin Delta, California; Implications for Drinking-Water Quality, WRI 98-4147 1998 (Water-Resources Investigations, US Geological Survey: Sacramento, CA).
[43] A. T. Chow, S. Gao, R. A. Dahlgren, Physical and chemical fractionation of dissolved organic matter and trihalomethane precursors: a review. J. Water Supply Res. T. 2005, 54, 475.
| 1:CAS:528:DC%2BD28XitVWjt7o%3D&md5=f01ac692c610e2a9b3a42fa3cf1efaabCAS |
[44] A. T. Chow, F. Guo, S. Gao, R. S. Breuer, Trihalomethane reactivity of water- and sodium hydroxide-extractable organic carbon fractions from peat soils. J. Environ. Qual. 2006, 35, 114.
| Trihalomethane reactivity of water- and sodium hydroxide-extractable organic carbon fractions from peat soils.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28XhtFGisb4%3D&md5=1d6a05e240fdfd40108854d0b5b13271CAS |
[45] C. Chang, Y. Ma, G. Fang, F. Zing, Characterization and isolation of natural organic matter from a eutrophic reservoir. J. Water Supply Res. T. 2000, 49, 269.
| 1:CAS:528:DC%2BD3cXnsFCiurs%3D&md5=062f70ce584bdb6bd9ab6bd8185a1a17CAS |
[46] A. Ågren, I. Buffam, M. Berggren, K. Bishop, M. Jansson, H. Laudon, Dissolved organic carbon characteristics in boreal streams in a forest–wetland gradient during the transition between winter and summer. J. Geophysical Res. 2008, 113, G03031.
| Dissolved organic carbon characteristics in boreal streams in a forest–wetland gradient during the transition between winter and summer.Crossref | GoogleScholarGoogle Scholar |
[47] P. Vidon, L. E. Wagner, E. Soyeux, Changes in the character of DOC in streams during storms in two midwestern watersheds with contrasting land uses. Biogeochemistry 2008, 88, 257.
| Changes in the character of DOC in streams during storms in two midwestern watersheds with contrasting land uses.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXmslOkur8%3D&md5=2514f0cf40635301524baac9ce1954c9CAS |
[48] H. V. Nguyen, J. Hur, H. Shin, Changes in spectroscopic and molecular weight characteristics of dissolved organic matter in a river during a storm event. Water Air Soil Pollut. 2010, 212, 395.
| Changes in spectroscopic and molecular weight characteristics of dissolved organic matter in a river during a storm event.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhtFOntr7J&md5=8ab8950b8e1a9a0de8e86e24a4f0d7dcCAS |
[49] M. Rautio, H. Mariash, L. Forsstrom, Seasonal shifts between autochthonous and allochthonous carbon contributions to zooplankton diets in a subarctic lake. Limnol. Oceanogr. 2011, 56, 1513.
| Seasonal shifts between autochthonous and allochthonous carbon contributions to zooplankton diets in a subarctic lake.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhtVCrurvE&md5=29c08373e254e02b9e6ab471b2389d8aCAS |
[50] A. T. Chow, Disinfection byproduct reactivity of aquatic humic substances derived from soils. Water Res. 2006, 40, 1426.
| Disinfection byproduct reactivity of aquatic humic substances derived from soils.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD28Xisl2kt70%3D&md5=7d23b2801cb0a2b94f55113537dddf63CAS |
[51] T. E. C. Kraus, B. A. Bergamaschi, P. J. Hernes, D. Doctor, C. Kendall, B. D. Downing, R. F. Losee, How reservoirs alter drinking water quality: organic matter sources, sinks, and transformations. Lake Reservior Manage. 2011, 27, 205.
| How reservoirs alter drinking water quality: organic matter sources, sinks, and transformations.Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXhsVamtrfE&md5=c1edaac3ba563c73c68587f950a6edc1CAS |