Natural dissolved organic carbon (DOC) consists of different bio-molecular classes of compounds that are currently very difficult and time-consuming to isolate as individual compounds. However, it is possible to separate natural DOC into hydrophobic and hydrophilic fractions. Such characterisation approaches are becoming increasingly important because, over the past 20 years natural DOC concentrations have been rising rapidly in many parts of the world, most likely influenced by climate change. Higher DOC concentrations in drinking water catchments present a serious problem for the water industry because DOC can form disinfection by-products DBPs during water treatment (e.g. chlorination). Hence, there is an urgent need to better characterise natural DOC before, during and after water treatment. However, current DOC fractionation procedures are extremely laborious requiring days and continual manual monitoring to separate sufficient quantities of DOC for subsequent analysis. This seriously limits sample throughput and the parameter space which can be studied. In this paper, we propose a much more rapid semi-automated method (12.5 hours/litre/sample) which utilises readily available equipment, i.e., HPLC pump or similar and sequential columns of Amberlite DAX 8 and XAD 4 resins. The method reduces the manual input from continual attention to minutes. This paper describes the development of the method and its application in the fractionation of natural DOC from reservoir and lake samples fed from upland peat-land catchments. Recoveries are found to be comparable to those using the manual technique, with the dominant component being hydrophobic acid accounting for 35% - 40% of the natural DOC with the second largest, being hydrophilic acid at 20% - 27%.
Gorham, E. (1991) Northern Peatlands: Role in the Carbon Cycle and Probable Responses to Climatic Warming. Ecological Applications, 1, 182-195. http://dx.doi.org/10.2307/1941811
Freeman, C., Ostle, N.J., Fenner, N., Kang, H., Dowrick, D.J., Reynolds, B., Lock, M.A., Sleep, D., Hughes, S. and Hudson, J. (2004) Export of Dissolved Organic Carbon from Peatlands under Elevated Carbon Dioxide Levels. Nature, 430, 195-198. http://dx.doi.org/10.1038/nature02707
Evans, C.D., Chapman, P.J., Clark, J.M., Monteith, D.T. and Cressers, C. (2006) Alternative Explanations for Rising Dissolved Organic Carbon Export from Organic Soils. Global Change Biology, 12, 2044-2053. http://dx.doi.org/10.1111/j.1365-2486.2006.01241.x
Rook, J.J. (1977) Chlorination Reactions of Fulvic Acids in Natural Waters. Environmental Science & Technology, 11, 478-482. http://dx.doi.org/10.1021/es60128a014
Hirose, Y. and Okitsu, T. (1982) Formation of Trihalomethanes by Reaction of Halogenated Phenols or Halogenated Anilines with Sodium Hypochlorite. Chemosphere, 11, 81-87. http://dx.doi.org/10.1016/0045-6535(82)90096-0
Sánchez, M.C., Pedraza Domínguez, A. and CachazaSilverio, J.M. (1993) Reaction Kinetics of Humic Acid with Sodium Hypochlorite. Water Research, 27, 815-820. http://dx.doi.org/10.1016/0043-1354(93)90145-8
Shah, A.D., Dotson, A.D., Linden, K.G. and Mitch, W.A. (2011) Impact of UV Disinfection Combined with Chlorination/Chloramination on the Formation of Halonitromethanes and Haloacetonitriles in Drinking Water. Environmental Science & Technology, 45, 3657-3664. http://dx.doi.org/10.1021/es104240v
Chen, C.-Y., Chang, S.-N. and Wang, G-S. (2009) Determination of Ten Haloacetic Acids in Drinking Water Using High-Performance and Ultra-Performance Liquid Chromatography-Tandem Mass Spectrometry. Journal of Chromatographic Science, 47, 67-74. http://dx.doi.org/10.1093/chromsci/47.1.67
Al-Shatri, M.A., Nuhu, A.A. and Basheer, C. (2014) Determination of Haloacetic Acids in Bottled and Tap Water Sources by Dispersive Liquid-Liquid Microextraction and GC-MS Analysis. The Scientific World Journal, Article ID: 695049.
Bull, R.J., Meier, J.R., Robinson, M., Ringhand, H.P., Laurie, R.D. and Stober, J.A. (1985) Evaluation of Mutagenic and Carcinogenic Properties of Brominated and Chlorinated Acetonitriles: By-Products of Chlorination. Fundamental and Applied Toxicology, 5, 1065- 1074. http://dx.doi.org/10.1016/0272-0590(85)90142-3
Daniel, F.B., Schenck, K.M., Mattox, J.K., Lin, E.L.C., Haas, D.L. and Pereira, M.A. (1986) Genotoxic Properties of Haloacetonitriles: Drinking Water By-Products of Chlorine Disinfection. Fundamental and Applied Toxicology, 6, 447-453. http://dx.doi.org/10.1016/0272-0590(86)90218-6
Porter, C.K., Putnam, S.D., Hunting, K.L. and Riddle, M.R. (2005) The Effect of Trihalomethane and Haloacetic Acid Exposure on Fetal Growth in a Maryland County. American Journal of Epidemiology, 162, 334-344. http://dx.doi.org/10.1093/aje/kwi211
McDonald, S., Bishop, A.G., Prenzler, P.D. and Robards, K. (2004) Analytical Chemistry of Freshwater Humic Substances. Analytica Chimica Acta, 527, 105-124. http://dx.doi.org/10.1016/j.aca.2004.10.011
Piccolo, A. (2001) The Supramolecular Structure of Humic Substances. Soil Science, 166, 810-832.
MacCarthy, R.L., Malcolm, C.E., Clapp, P.R. and Bloom, P.R., Eds. (1990) Composition of Humin in Stream Sediments and Peat. In: Humic Substances in Soil and Crop Sciences, Soil Science Society of America, Madison, USA.
Shapiro, J. (1961) Freezing-Out, a Safe Technique for Concentration of Dilute Solutions. Science, 133, 2063-2064. http://dx.doi.org/10.1126/science.133.3470.2063
National Academy of Sciences (1977) Organic Solutes. In: Drinking Water and Health, National Academy of Sciences, Washington DC, 489-856.
Wu, C. and Suffet, I.H. (1977) Table of Contents. Analytical Chemistry, 49, 463-466. http://dx.doi.org/10.1021/ac50014a703
Deinzer, M., Meltin, R. and Mitchell, D. (1975) Trace Organic Contaminants in Drinking Watert-Their Concentration by Reverse Osmosis. Water Resources Research, 9, 799-805.
Mantoura, R.F.C. and Riley, J.P. (1975) The Analytical Concentration of Humic Substances from Natural Waters. Analytica Chimica Acta, 76, 97-106. http://dx.doi.org/10.1016/S0003-2670(01)81990-5
Thurman, E.M. and Malcolm, R.L. (1981) Preparative Isolation of Aquatic Humic Substances. Environmental Science & Technology, 15, 463-466. http://dx.doi.org/10.1021/es00086a012
Leenheer, J.A. (1981) Comprehensive Approach to Preparative Isolation and Fractionation of Dissolved Organic Carbon from Natural Waters and Wastewaters. Environmental Science & Technology, 15, 578-587. http://dx.doi.org/10.1021/es00087a010
Aiken, G.R., Thurman, E.M., Malcolm, R.L. and Walton, H.F. (1979) Comparison of XAD Macroporous Resins for the Concentration of Fulvic Acid from Aqueous Solution. Analytical Chemistry, 51, 1799-1803. http://dx.doi.org/10.1021/ac50047a044
Junk, G.A., Richard, J.J., Grieser, M.D., Witiak, D., Witiak, J.L., Arguello, M.C., Vick, R., Svec, H.J., Fritz, J.S. and Calder, G.V. (1974) Use of Macroreticular Resins in the Analysis of Water for Trace Organic Contaminants. Journal of Chromatography A, 99, 745-762. http://dx.doi.org/10.1016/S0021-9673(00)90900-2
Ratpukdi, T., Rice, J.A., Chilom, G., Bezbaruah, A. and Khan, E. (2009) Rapid Fractionation of Natural Organic Matter in Water Using a Novel Solid-Phase Extraction Technique. Water Environment Research, 81, 2299-2308. http://dx.doi.org/10.2175/106143009X407302
Malcolm, R.L. and MacCarthy, P. (1992) Quantitative Evaluation of XAD-8 and XAD-4 Resins Used in Tandem for Removing Organic Solutes from Water. Environment International, 18, 597-607. http://dx.doi.org/10.1016/0160-4120(92)90027-2
Wei, Q., Wang, D., Wei, Q., Qiao, C., Shi, B. and Tang, H. (2007) Size and Resin Fractionations of Dissolved Organic Matter and Trihalomethane Precursors from Four Typical Source Waters in China. Environmental Monitoring and Assessment, 141, 347-357. http://dx.doi.org/10.1007/s10661-007-9901-1
Gough, R., Holliman, P.J., Willis, N., Jones, T.G. and Freeman, C. (2012) Influence of Habitat on the Quantity and Composition of Leachable Carbon in the O2 Horizon: Potential Implications for Potable Water Treatment. Lake and Reservoir Management, 28, 282-292. http://dx.doi.org/10.1080/07438141.2012.741187
Hughes, D.D., Holliman, P.J., Jones, T. and Freeman, C. (2013) Temporal Variations in Dissolved Organic Carbon Concentrations in Upland and Lowland Lakes in North Wales. Water and Environment Journal, 27, 275-283. http://dx.doi.org/10.1111/wej.12025
Gough, R., Holliman, P.J., Cooke, G.M. and Freeman, C. (2015) Characterisation of Algogenic Organic Matter during an Algal Bloom and Its Implications for Trihalomethane Formation. Sustainability of Water Quality and Ecology, 6, 11-19. http://dx.doi.org/10.1016/j.swaqe.2014.12.008
Gough, R. Holliman, P.J., Heard, T.R. and Freeman, C. (2014) Dissolved Organic Carbon and Trihalomethane Formation Potential Removal during Coagulation of a Typical UK Upland Water with Alum, PAX-18 and PIX-322. Journal of Water Supply: Research and Technology-AQUA, 63, 650-660. http://dx.doi.org/10.2166/aqua.2014.007
Gough, R., Holliman, P.J., Willis, N. and Freeman, C. (2014) Dissolved Organic Carbon and Trihalomethane Precursor Removal at a UK Upland Water Treatment Works. Science of The Total Environment, 468-469, 228-239. http://dx.doi.org/10.1016/j.scitotenv.2013.08.048
UK Govt. (2000) The Water Supply (Quality) Regulations 2000.