State of the art of the environmental behaviour and removal techniques of the endocrine disruptor 3,4-dichloroaniline

In recent years, the presence of Endocrine Disrupting Chemicals (EDCs) in wastewater discharges from agricultural and industrial sources,[1] Angioi, S.; Polati, S.; Roz, M.; Rinaudo, C.; Gianotti, V.; Gennaro, M.C. Sorption studies of chloroanilines on kaolinite and montmorillonite. Environ. Poll. 2005, 134(1), 35–43.[Crossref], [PubMed], [Web of Science ®] , [Google Scholar] fresh- and estuarine-waters, as well as soils, has been reported in the literature.[2] Bevan, R.; Harrison, P.; Youngs, L.; Whelan, M.; Goslan, E.; Macadam, J.; Holmes, P.; Persich, T. A Review of Latest Endocrine Disrupting Chemicals Research Implications for Drinking Water. Final Report DWI:70/2/266. Institute of Environment and Health Cranfield Health: Bedfordshire, MK43 OAL, UK, 2012; 1–205. [Google Scholar] Studies of adverse changes in wildlife, linked to environmental exposure to these substances, and the suggestion that humans could also be at similar risk of adverse health effects,[3–5] Cook, J. C.; Mullin, L. S.; Frame, S. R.; Biegel, L. B. Investigation of a mechanism for leydig-cell tumorigenesis by linuron in rats. Toxicol. Appl. Pharmacol. 1993, 119(2), 195–204. Crossland, N. O.; Hillaby, J. M. Fate and effects of 3,4-dichloroaniline in the laboratory and in outdoor ponds. 2. Chronic toxicity to daphnia spp and other invertebrates. Environ. Toxicol. Chem. 1985, 4(4), 489–499. Groshart, Ch.; Okkerman, P.C. Towards the establishment of a priority list of substances for further evaluation of their role in endocrine disruption, European Commission DG ENV. Final report. Consulting Engineers: Delft, The Netherlands, 2000; 1–29. have raised concern for urgent action to understand and reduce such risks. 3,4-Dichloroaniline (3,4-DCA) has been recognized as an EDC, with regards to endocrine disruption data for both wildlife populations and human health.[5] Groshart, Ch.; Okkerman, P.C. Towards the establishment of a priority list of substances for further evaluation of their role in endocrine disruption, European Commission DG ENV. Final report. Consulting Engineers: Delft, The Netherlands, 2000; 1–29. [Google Scholar]3,4-DCA is present in the environment as a product of the biodegradation of phenylurea and phenylcarbamate pesticides[6,7] Ucan, M.; Ayar, A. Sorption equilibria of chlorinated anilines in aqueous solution on resin-bound cobalt ion. Colloids Surf.-Physicochem. Eng. Aspects. 2002, 207(1–3), 41–47. Muller, L.; Fattore, E.; Benfenati, E. Determination of aromatic amines by solid-phase microextraction and gas chromatography mass spectrometry in water samples. J. Chromatogr. A. 1997, 791(1–2), 221–230. ; furthermore, it can be introduced from industrial and municipal wastewater that is insufficiently purified, or via accidental spills.[8–10] Flores-Cespedes, F.; Fernandez-Perez, M.; Villafranca-Sanchez, M.; Gonzalez-Pradas, E. Cosorption study of organic pollutants and dissolved organic matter in a soil. Environ. Pollut.. 2006, 142(3), 449–456. Parris, G. E. Covalent binding of aromatic-amines to humates. 1. Reactions with carbonyls and quinones. Environ. Sci. Technol. 1980, 14(9), 1099–1106. Park, J. W.; Dec, J.; Kim, J. E.; Bollag, J. M. Effect of humic constituents on the transformation of chlorinated phenols and anilines in the presence of oxidoreductive enzymes or Birnessite. Environ. Sci. Technol. 1999, 33(12), 2028–2034. Increasing concentrations of 3,4-DCA in soil and water are the result of its high persistence and accumulation, as well as its low biodegradability.[11,12] Padmini, E.; Miranda, L. R. Nanocatalyst from sol-sol doping of TiO2 with vanadium and cerium and its application for 3,4 dichloroaniline degradation using visible light. Chem. Eng. J. 2013, 232, 249–258. Szczepanik, B.; Slomkiewicz, P.; Garnuszek, M.; Czech, K. Adsorption of chloroanilines from aqueous solutions on the modified halloysite. Appl. Clay Sci. 2014, 101, 260–264. Hence, remediation techniques require in-depth study, especially when considering the low removal achieved by traditional activated sludge treatments, and the generation of carcinogenic trihalomethanes as a consequence of the chlorine oxidation methods frequently used in drinking water plants.[13] Ormad, M. P.; Miguel, N.; Claver, A.; Matesanz, J. M.; Ovelleiro, J. L. Pesticides removal in the process of drinking water production. Chemosphere. 2008, 71(1), 97–106.[Crossref], [PubMed], [Web of Science ®] , [Google Scholar] Fe0/H2O2 systems, photodegradation using doped TiO2, and the use of dielectric barrier discharge reactors, seem to be the most promising techniques for the removal of 3,4-DCA from water.