An introduction to the sources, fate, occurrence and effects of endocrine disrupting chemicals released into the environment.

Many classes of compounds are known or suspected to disrupt the endocrine system of vertebrate and invertebrate organisms. This review of the sources and fate of selected endocrine disrupting chemicals (EDCs) in the environment includes classes of compounds that are "legacy" contaminants, as well as contaminants of emerging concern. EDCs included for discussion are organochlorine compounds, halogenated aromatic hydrocarbons, brominated flame retardants, per- and polyfluoroalkyl substances, alkylphenols, phthalates, bisphenol A and analogues, pharmaceuticals, drugs of abuse and steroid hormones, personal care products, and organotins. An exhaustive survey of the fate of these contaminants in all environmental media (e.g., air, water, soil, biota, foods and beverages) is beyond the scope of this review, so the priority is to highlight the fate of EDCs in environmental media for which there is a clear link between exposure and endocrine effects in humans or in biota from other taxa. Where appropriate, linkages are also made between the fate of EDCs and regulatory limits such as environmental quality guidelines for water and sediments and total daily intake values for humans.

Methods for the analysis of endocrine disrupting chemicals in selected environmental matrixes.

Endocrine disrupting chemicals (EDCs) are heterogenous in structure, chemical and physical properties, and their capacity to partition into various environmental matrixes. In many cases, these chemicals can disrupt the endocrine systems of vertebrate and invertebrate organisms when present at very low concentrations. Therefore, sensitive and varied analytical methods are required to detect these compounds in the environment. This review summarizes the analytical methods and instruments that are most used to monitor for EDCs in selected environmental matrixes. Only those matrixes for which there is a clear link between exposures and endocrine effects are included in this review. Also discussed are emerging methods for sample preparation and advanced analytical instruments that provide greater selectivity and sensitivity.

An ultrasound-assisted photocatalytic treatment to remove an herbicidal pollutant from wastewaters.

Pollutants of emerging concern contaminate surface and ground water. Advanced oxidation processes treat these molecules and degrade them into smaller compounds or mineralization products. However, little information on coupled advanced oxidation techniques and on the degradation pathways of these pollutants is available to identify possible ecotoxic subproducts. In the present work, we investigate the ultrasound assisted photocatalytic degradation pathway of the herbicide Isoproturon. We worked in batch mode in a thermostatic glass reactor. We compared the activity of nanometric TiO2 P25 with that of Kronos 1077, a micrometric TiO2. We discuss the individual, additive and synergistic degradation action of photolysis, sonolysis, sonophotolysis, and sonophotocatalysis by varying catalyst loading and/or ultrasound power for the last three techniques. With 0.1 g L-1 catalyst, photocatalysis and sonophotopcatalysis completely degrade Isoproturon within 240 min and 60 min, respectively (>99% conversion). Sonophotocatalysis breaks Isoproturon down into smaller molecules than photocatalysis alone.

Chemical oxidation of ibuprofen in the presence of iron species at near neutral pH.

The objective of this work was to evaluate the removal of ibuprofen (IBP) using the oxidants hydrogen peroxide (H(2)O(2)) and sodium persulfate (Na(2)S(2)O(8)). The ability of magnetite (Fe(3)O(4)) to activate persulfate (PS) and H(2)O(2) for the oxidation of IBP at near neutral pH was evaluated as well. The use of soluble Fe(2+) to activate H(2)O(2) and Na(2)S(2)O(8) was also investigated. H(2)O(2) and Na(2)S(2)O(8) were inactive during the sixty-minute experiments when used alone. However, activation using Fe(2+) increased the removal to 95% in the presence of H(2)O(2) (Fenton reaction) and 63% in the presence of Na(2)S(2)O(8) at pH 6.6. Chemical oxygen demand (COD) removal was also greater for Fenton oxidation (65%) than for iron-activated PS oxidation (25%). Activation of H(2)O(2) and PS by Fe(3)O(4) was only observed at a high oxidant concentration and over 48 h of reaction time. A second order rate kinetic constant was determined for H(2)O(2) (3.0∗10(-3) M(-1) s(-1)) and Na(2)S(2)O(8) (1.59∗10(-3) M(-1) s(-1)) in the presence of Fe(3)O(4). Finally, several of the degradation products formed during oxidation of IBP in the presence of H(2)O(2) and Na(2)S(2)O(8) (activated by Fe(2+)) were identified. These include oxalic acid, pyruvic acid, formic acid, acetic acid, 4-acetylbenzoic acid, 4-isobutylacetophenone (4-IBAP) and oxo-ibuprofen.

The effect of structure and a secondary carbon source on the microbial degradation of chlorophenoxy acids.

Pseudomonas putida, Aspergillus niger, Bacillus subtilis, Pseudomonas fluorescens, Sphingomonas herbicidovorans and Rhodococcus rhodochrous growing on glucose in a medium containing one of three chlorophenoxy acids at a concentration of 0.1 g L(-1) (clofibric acid, (R)-2-(4-chloro-2-methylphenoxy)propionic acid (mecoprop or MCPP) and 4-chloro-2-methylphenoxyacetic acid (MCPA)) degraded these compounds to varying degrees; from nonmeasurable to almost complete removal. These results with the addition of glucose (2.5 g L(-1)) as an easy to use carbon source indicated the formation of metabolites different from results reported in the literature for growth studies in which the chlorophenoxy acid was the sole carbon source. The metabolite, 4-chloro-2-methylphenol, which had been reported previously, was only observed in trace amounts for MCPP and MCPA in the presence of S. herbicidovorans and glucose. In addition, three other compounds (M1, M3 and M4) were observed. It is suggested that these unidentified metabolites resulted from ring opening of the metabolite 4-chloro-2-methylphenol (M2). The rate of biodegradation of the chlorophenoxy acids was influenced by the degree of steric hindrance adjacent to the internal oxygen bond common to all three compounds. The most hindered compound, clofibric acid, was converted to ethyl clofibrate by R. rhodochrous but was not degraded by any microorganisms studied. The more accessible internal oxygen bonds of the other two chlorophenoxy acids, MCPP and MCPA, were readily broken by S. herbicidovorans.

Potential of ozonation for the degradation of antibiotics in wastewater.

Increasing concern in recent years over the occurrence and fate of low-level concentrations of pharmaceuticals in the aquatic environment stimulates research on alternative treatment methods. This paper presents a study of the degradation of sulphamethoxazole, an antibiotic used on humans and animals in order to treat various bacterial infections, by ozonation. After 4.5 min of treatment, the concentration of sulphamethoxazole was below the HPLC detection limit of 0.6 mgL(-1), indicating degradation efficiency higher than 99.24%. This value is comparable and in some cases higher than published data on the degradation in drinking water. Kinetic analysis of the data indicated an overall first-order reaction with a rate constant of 1.0594 min(-1) at 20 degrees C. The reaction order differs with the second-order reaction observed by other researchers. This change of reaction order could be explained by the different treatment conditions used. Preliminary analysis using the FT-IR technique was also performed in order to obtain information on the structure of the degradation products. Further analysis using a GC-MS is needed in order to elucidate the structure of the degradation products. Finally, based on the experiments performed, ozonation seems to be a promising technique for the degradation of antibiotics, even in wastewater.