Abstract
The detailed characterization of the organic composition of industrial effluents discharged from various industrial branches and the distribution of the emitted pollutants in the surface waters in North Rhine-Westphalia have been done with the use of non-target screening analyses. Based on the characterization of molecular structures of wastewater constituents, their quantification as well as the available information on their origin and industrial applications, the identification of typical organic representatives for petrochemical and food effluents has been performed. Among a wide range of hydrocarbons detected in the petrochemical effluents, several novel organic wastewater constituents have been found for the first time. In the effluents from paper production plant, potential industrial indicators were distinguished, such as resin acids (abietic and dehydroabietic acids) and photoinitiators (Irgacure 184). The monitoring of the behaviour of certain environmentally relevant and newly described pollutants in the contaminated river systems allowed the identification of several industrial site-specific markers. Particularly, 2-(chloromethyl)-1,3-dioxolane, an unknown contaminant, exclusively found in the effluents from a chemical production complex, was present in the river under discharge at high concentrations downstream the contamination source. The comprehensive and detailed evaluation of the anthropogenic markers in the industrial effluents is a promising tool for the environmental assessment of industrial emissions, especially if accompanied with toxicological and ecotoxicological investigations of novel environmental contaminants.
Similar content being viewed by others
References
Antileo, C., Aspé, E., Zaror, C., Roeckel, M., Urrutia, H., & Martí, M. C. (1997). Differential bacterial growth kinetic and nitrification of fisheries wastewaters containing high ammonium and organic matter concentration by using pure oxygen. Biotechnology Letters, 19, 241–244.
Araujo, C. V. M., Nascimento, R. B., Oliveira, C. A., Strotmann, U. J., & da Silva, E. M. (2005). The use of Microtox® to assess toxicity removal of industrial effluents from the industrial district of Camacari (BA, Brazil). Chemosphere, 58, 1277–1281.
Ashitani, T., Kusumoto, N., Takahashi, K. (2009). Anti-termitic activity of sesquiterpene derivatives obtained by autoxidation or direct episulfidation. Abstracts on the 25th Annual Meeting of International Society of Chemical Ecology. Poster 2–7. (April 23–27, 2009, Neuchatel, Switzerland). p 223.
Bamber, R. N. (1990). Power station thermal effluents and marine crustaceans. Journal of Thermal Biology, 15, 91–96.
Birch, A. J., Brown, W. V., Corrie, J. E. T., & Moore, B. P. (1972). Neocembrene-A, a termite trail pheromone. Journal of the Chemical Society, Perkin Transactions 1: Organic and Bio-Organic Chemistry, 21, 2653–2658.
Botalova, O., Schwarzbauer, J., Frauenrath, T., & Dsikowitzky, L. (2009). Identification and chemical characterisation of specific organic constituents of petrochemical effluents. Water Research, 43, 3797–3812.
Brunet, S., Mey, D., Pérot, G., Bouchy, C., & Diehl, F. (2005). On the hydrodesulfurization of FCC gasoline: a review. Applied Catalysis A: General, 278, 143–172.
Castrén, M., & Oikari, A. (1987). Changes of the liver UDP-glucuronosyltransferase activity in trout (Salmo gairdneri Rich.) acutely exposed to selected aquatic toxicants. Comparative Biochemistry and Physiology. C: Comparative Pharmacology, 86, 357–360.
Catallo, W. J., Cleland, D. R., & Bender, M. E. (1990). Toxicity of nitrogen-containing aromatic compounds (NCACs). Quinoline and 4-azafluorene behavior in an Escherichia coli test system: evidence of membrane effects. In: W.G. Landis and van der Schalie W.H. (eds.) Aquatic toxicology and risk assessment. ASTM Special Technical Publications 1096. American Society for Testing and Materials, Philadelphia. pp 199–221
Christianson-Heiska, I.-L., Haavisto, T., Paranko, J., Bergelin, E., & Isomaa, B. (2008). Effects of the wood extractives dehydroabietic acid and betulinol on reproductive physiology of zebrafish (Danio rerio)—a two-generation study. Aquatic Toxicology, 86, 388–396.
Colic, M., Morse, W., Lechter, A. (2007). Case study: contaminants removal from snack food manufacturing wastewater. Clean Water Technology, Inc. p 12.
Crowe, A. U., Plant, A. L., & Kermode, A. R. (2002). Effects of an industrial effluent on plant colonization and on the germination and post-germinative growth of seeds of terrestrial and aquatic plant species. Environmental Pollution, 117, 179–189.
Dalzell, D. J. B., Alte, S., Aspichueta, E., de la Sota, A., Etxebarria, J., Gutierrez, M., et al. (2002). A comparison of five rapid direct toxicity assessment methods to determine toxicity of pollutants to activated sludge. Chemosphere, 47, 535–545.
Danish EPA. (2001). Environmental and health assessment of alternatives to phthalates and to flexible PVC. Environmental Project No. 590.
Dayeh, V. R., Schirmer, K., & Bols, N. C. (2002). Applying whole-water samples directly to fish cell cultures in order to evaluate the toxicity of industrial effluent. Water Research, 36, 3727–3738.
Di Marzio, W. D., Saenz, M., Alberdi, J., Tortorelli, M., & Silvana, G. (2005). Risk assessment of domestic and industrial effluents unloaded into a freshwater environment. Ecotoxicology and Environmental Safety, 61, 380–391.
Ding, Z. Y., Frisch, M. A., Li, L., & Gloyna, E. F. (1996). Catalytic oxidation in supercritical water. Industrial and Engineering Chemistry Research, 35, 3257–3279.
Dsikowitzky, L., Schwarzbauer, J., Kronimus, A., & Littke, R. (2004). The anthropogenic contribution to the organic load of the Lippe River (Germany). Part I: qualitative characterisation of low-molecular weight organic compounds. Chemosphere, 57, 1275–1288.
Dunlap, R. W., & McMichael, F. C. (1976). Reducing coke plant effluent. Environmental Science & Technology, 10, 654–657.
Eganhouse, R. P. (1997). Molecular markers and environmental organic geochemistry: an overview. In R. P. Eganhuose (Ed.), Molecular markers in environmental geochemistry (pp. 1–21). Washington: American Chemical Society.
Ehrlich, K. F. (1977). Inhibited hatching success of marine fish eggs by power plant effluent. Marine Pollution Bulletin, 8, 228–229.
Fajen, J. M., Carson, G. A., & Rounbehler, D. P. (1979). N-nitrosamines in the rubber and tire industry. Science, 205, 1262–1264.
Fan, K. L. (1991). The thermal effluent problems of three nuclear power plants in Taiwan. Elsevier Oceanography Series, 54, 393–403.
Focazio, M. J., Kolpin, D. W., Barnes, K. K., Furlong, E. T., Meyer, M. T., Zaugg, S. D., et al. (2008). A national reconnaissance for pharmaceuticals and other organic wastewater contaminants in the United States—II untreated drinking water sources. The Science of the Total Environment, 402, 201–216.
Franke, S., Hildebrandt, S., Schwarzbauer, J., Link, M., & Francke, W. (1995). Organic compounds as contaminants of the Elbe River and its tributaries Part II: GC/MS screening for contaminants of the Elbe water. Fresenius’ Journal of Analytical Chemistry, 353, 39–49.
Freitas, L. S., Von Mühlen, C., Bortoluzzi, J. H., Zini, C. A., Fortuny, M., Dariva, C., et al. (2009). Analysis of organic compounds of water-in-crude oil emulsions separated by microwave heating using comprehensive two-dimensional gas chromatography and time-of-flight mass spectrometry. Journal of Chromatography A, 1216, 2860–2865.
Gabriele, B., Salerno, G., Fazio, A., & Pittelli, R. (2003). Versatile synthesis of (Z)-1-alkylidene-1, 3-dihydroisobenzofurans and 1H-isochromenes by palladium-catalyzed cycloisomerization of 2-alkynylbenzyl alcohols. Tetrahedron, 59, 6251–6259.
Gana, J. M., Ordóñez, R., Zampini, C., Hidalgo, M., Meoni, S., & Isla, M. I. (2008). Industrial effluents and surface waters genotoxicity and mutagenicity evaluation of a river of Tucuman, Argentina. Journal of Hazardous Materials, 155, 403–406.
Gartiser, S., Hafner, C., Hercher, C., & Kronenberger-Schäfer, K. (2009). Bewertung von Direkt- und Indirekteinleitern mit Biotests. Tl.1: Abwasser der Papierindustrie. KA Korrespondenz Abwasser, Abfall., 9, 915–920.
Ginn, T. C., & O’Connor, J. M. (1978). Response of the estuarine amphipod Gammarus daiberi to chlorinated power plant effluent. Estuarine and Coastal Marine Science, 6, 459–469.
Gravato, C., & Santos, M. A. (2002). Juvenile sea bass liver biotransformation and erythrocytic genotoxic responses to pulp mill contaminants. Ecotoxicology and Environmental Safety, 53, 104–112.
Grigoriadou, A., Schwarzbauer, J., & Georgakopoulos, A. (2008). Molecular indicators for pollution source identification in marine and terrestrial water of the industrial area of Kavala city, North Greece. Environmental Pollution, 151, 231–242.
Gu, J. D., Fan, Y., & Shi, H. C. (2002). Relationship between structure of substituted indolic compounds and their degradation by marine anaerobic microorganisms. Marine Pollution Bulletin, 45, 379–384.
Gustafson, J. B., Tell, J. G., Orem, D. (1997). Selection of representative TPH fractions based on fate and transport considerations, vol 3. Total petroleum hydrocarbon criteria working group series. p 102.
Hartnik, T., Norli, H. R., Eggen, T., & Breedveld, G. D. (2007). Bioassay-directed identification of toxic organic compounds in creosote-contaminated groundwater. Chemosphere, 66, 435–443.
Hayman, A. R., & Weavers, R. T. (1990). Terpenes of foliage oils from Halocarpus bidwillii. Phitochemistry, 29, 3157–3162.
Helmick, J. S. (1994). Thermal decomposition of the rubber vulcanization agent, zinc dibenzyldithiocarbamate and its potential role in nitrosamine formation in hams processed in elastic nettings. Journal of Agricultural and Food Chemistry, 42, 2541–2544.
Hendricks, A. J., Maas-Diepeveen, J. L., Noordsij, A., & van der Gaag, M. A. (1994). Monitoring response of XAD-concentrated water in the Rhine delta: a major part of the toxic compounds remains unidentified. Water Research, 28, 581–598.
Hesselberg, R. J., & Seelye, J. G. (1982). Identification of organic compounds in Great Lakes fishes by gas chromatography/mass spectrometry: 1977. Great Lakes Fishery Laboratory, Ann Arbor, Michigan, Administrative Report No. 82–1. p 49.
Jenkin, M. E., Passant, N. R., Rudd, H. J. (2000). Development of species profiles for UK emissions of VOCs. A report produced for the Department of the Environment, Transport & the Regions. AEAT\EPSC-0044 Issue 1.
Kennedy, K. J., McCarthy, P. J., & Droste, R. L. (1992). Batch and continuous anaerobic toxicity of resin acids from chemithermomechanical pulp wastewater. Journal of Fermentation and Bioengineering, 73, 206–212.
Kirk-Othmer (1991-Present). Encyclopedia of Chemical Technology, 4th edn. Volume 1. New York: Wiley. p V4 223.
Knepper, T. P., Müller, J., Wulff, T., & Maes, A. (2000). Unknown bisethylisooctanollactone isomers in industrial waste water. Isolation, identification and occurrence in surface water. Journal of Chromatography A, 889, 245–252.
Ko, F.-C., & Baker, J. E. (2004). Seasonal and annual loads of hydrophobic organic contaminants from the Susquehanna River basin to the Chesapeake Bay. Marine Pollution Bulletin, 48, 840–851.
Koistinen, J., Lehtonen, M., Tukia, K., Soimasuo, M., Lahtiperä, M., & Oikari, A. (1998). Identification of lipophilic pollutants discharged from a finnish pulp and paper mill. Chemosphere, 98, 219–235.
Labunska, I., Santillo, D., Johnston, P., Stringer, R., Stephenson, A. (2000). Heavy metals and organic contaminants in the vicinity of the Teshima Island illegal dumpsite, Kagawa Prefecture, Japan. Greenpeace Research Laboratories. Technical Note 02/00. p 58.
Lee, H.-B., Peart, T. E., & Kaiser, K. L. E. (1996). Determination of nitrilotriacetic, ethylenediaminetetraacetic and diethylenetriaminepentaacetic acids in sewage treatment plant and paper mill effluents. Journal of Chromatography A, 738, 91–99.
Lefebvre, O., & Moletta, B. (2006). Treatment of organic pollution in industrial saline wastewater: a literature review. Water Research, 40, 3671–3682.
Li, M., & Larter, S. R. (2001). Potential bias in the isolation of pyridinic nitrogen fractions from crude oils and rock extracts using acid extraction and liquid chromatography. Organic Geochemistry, 32, 1025–1030.
Ma, M., Rao, K., & Wang, Z. (2007). Occurrence of estrogenic effects in sewage and industrial wastewaters in Beijing, China. Environmental Pollution, 147, 331–336.
Martino, C. J., & Savage, P. E. (1999). Supercritical water oxidation kinetics and pathways for ethylphenols, hydroxyacetophenones, and other monosubstituted phenols. Industrial and Engineering Chemistry Research, 38, 1775–1783.
Osho, A., Mabekoje, O. O., & Bello, O. O. (2010). Preliminary evaluation of wastewater effluents from two food companies in Nigeria. African Journal of Microbiology Research, 4, 1395–1399.
Passino, D. R. M., & Smith, S. B. (1987). Acute bioassays and hazard evaluation of representative contaminants detected in Great Lakes fish. Environmental Toxicology and Chemistry, 6, 901–907.
Poornima, E. H., Rajadurai, M., Rao, T. S., Anupkumar, B., Rajamohan, R., Narasimhan, S. V., et al. (2005). Impact of thermal discharge from a tropical coastal power plant on phytoplankton. Journal of Thermal Biology, 30, 307–316.
Riboulleau, A., Derenne, S., Largeau, C., & Baudin, F. (2001). Origin of contrasting features and presentation pathways in kerogens from Kashpir oil shales (Upper Jurassic, Russian Platform). Organic Geochemistry, 32, 647–665.
Rojas, F. S., & Ojeda, C. B. (2005). Effluent analysis in analytical chemistry: an overview. Analytical and Bioanalytical Chemistry, 382, 978–991.
Sanches-Silva, A., Pastorelli, S., Cruz, J. M., Simoneau, C., Castanheira, I., & Paseiro-Losada, P. (2008). Development of an analytical method for the determination of photoinitiators used for food packaging materials with potential to migrate into milk. Journal of Dairy Science, 91, 900–909.
Schmezer, P., Pool, B. L., Lefevre, P. A., Callander, R. D., Ratpan, F., Tinwell, H., et al. (1990). Assay-specific genotoxicity of N-nitrosodibenzylamine to the rat liver in vivo. Environmental and Molecular Mutagenesis, 15, 190–197.
Schwarzbauer, J., & Heim, S. (2005). Lipophilic organic contaminants in the Rhine river (Germany). Water Research, 39, 4735–4748.
Schwarzbauer, J., & Ricking, M. (2010). Non-target screening analysis of river water as compound related base for monitoring measures. Environmental Science and Pollution Research, 17, 934–947.
Schwarzbauer, J., Sindern, S., Dsikowitzky, L., & Liebezeit, G. (2010). Geochemical analysis of Lake Bant sediments to ascertain inorganic and organic indicators for warfare residues. Journal of Soils and Sediments, 10, 104–118.
Soupilas, A., Papadimitriou, C. A., Samaras, P., Gudulas, K., & Petridis, D. (2008). Monitoring of industrial effluent ecotoxicity in the greater Thessaloniki area. Desalination, 224, 261–270.
Spanggord, R. J., Glbson, B. W., Keck, R. G., & Thomas, D. W. (1982). Effluent analysis of wastewater generated in the manufacture of 2, 4, 6-trinitrotoluene. 1. Characterization study. Environmental Science & Technology, 16, 229–232.
Stover, E. L., & Eckhoff, T. H. (2003). Effluents from food processing. Disposal of waste water. Encyclopaedia of food science, food technology and nutrition, 2nd edn. Academic, New York. pp 1985–1991.
Sweet, L. I., & Meier, P. G. (1997). Lethal and sublethal effects of azulene and longifolene to Microtox, Ceriodaphnia dubia, Daphnia magna, and Pimephales promelas. Bulletin of Environmental Contamination and Toxicology, 58, 268–254.
Takada, H., & Eganhouse, R. P. (1998) Molecular markers of anthropogenic waste. Encyclopedia of environmental analysis and remediation. New York: Wiley. pp 2883–2940.
Tarbox, M. (1993). Effluents from food processing. Composition and analysis. Encyclopaedia of food science, food technology and nutrition, 2nd edn. New York: Academic. pp 1991–1996.
Thorhaug, A., Blake, N., & Schroeder, P. B. (1978). The effect of heated effluents from power plants on seagrass (Thalassia) communities quantitatively comparing estuaries in the subtropics to the tropics. Marine Pollution Bulletin, 9, 181–187.
Tusseau-Vuillemin, M. H., Gourlay, C., Lorgeoux, C., Mouchel, J.-M., Buzier, R., Gilbin, R., et al. (2007). Dissolved and bioavailable contaminants in the Seine river basin. The Science of the Total Environment, 375, 244–256.
Vanderah, D. J., Rutledge, N., Schmitz, F. J., & Ciereszko, L. S. (1978). Marine natural products: cembrene-A and cembrene-C from a soft coral, Nephthea sp. The Journal of Organic Chemistry, 43, 1614–1616.
Vitolo, S., Petarca, L., & Bresci, B. (1999). Treatment of olive oil industry wastes. Bioresource Technology, 67, 129–137.
Willey, C., Iwao, M., Castle, R. N., & Lee, M. L. (1981). Determination of sulfur heterocycles in coal liquids and shale oils. Analytical Chemistry, 53, 400–407.
Wilson, D., & Hrutfiord, B. (1975). The fate of turpentine in aerated lagoons. Pulp and Paper Canada, 76, 91–93.
Zaror, C., Carrasco, V., Perez, L., Soto, G., Mondaca, M. A., & Mansilla, H. (2001). Kinetics and toxicity of direct reaction between ozone and 1, 2-dihydrobenzene in dilute aqueous solution. Water Science and Technology, 43, 321–326.
Acknowledgements
We especially thank the local Environmental Protection Agency in Herten (Germany) for their help and cooperation. This work was financially supported by a grant from the Deutsche Forschungsgemeinschaft (DFG, Schw750/10).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Botalova, O., Schwarzbauer, J. Geochemical Characterization of Organic Pollutants in Effluents Discharged from Various Industrial Sources to Riverine Systems. Water Air Soil Pollut 221, 77–98 (2011). https://doi.org/10.1007/s11270-011-0771-3
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11270-011-0771-3