Benzotriazoles, Alkylphenols and Bisphenol A in Municipal Wastewaters and in the Glatt River, Switzerland

- DOI: http://dx.doi.org/10.1065/espr2006.01.295 Background Many organic micropollutants occur at trace concentrations in municipal wastewater effluents and in the aquatic environment. Some of these xenobiotic chemicals can be considered as 'emerging' contaminants and some are suspect to have endocrine disrupting effects. Among the latter are nonylphenol (NP), octylphenol (OP) and bisphenol A (BPA), which deserve special attention due to their ubiquitous occurrence in the aquatic environment. The complexing agents benzotriazole (BT) and tolyltriazole (TT) are applied as anticorrosive agents (e.g. in cooling and hydraulic fluids, in antifreezing fluids, in aircraft deicing fluids, in dish washing liquids for silver protection), as antifogging agents and as intermediates for the synthesis of various chemicals. The environmental occurrence of NP and OP is caused by the fact that they are intermediate products (metabolites) in the biodegradation of alkylphenol polyethoxylate surfactants. BPA is globally used for the production of polycarbonate and epoxy resins. Methods BT, TT, NP, OP and BPA were quantitatively determined in municipal wastewater effluents in Switzerland and in the Glatt River. The analytes were enriched by solid-phase enrichment. BT and TT were determined underivatized by electrospray LC/tandem MS. Reversed-phase LC was performed on octylsilica columns with isocratic water/methanol elution. Multiple reaction monitoring of the positive ions provided selective and sensitive detection for reliable quantifications. NP, OP and BPA were determined by GC/MS after derivatization with N-methyl-N-(trimethylsilyl)-trifluoroacetamide. Results and Discussion BT and TT concentrations in primary and secondary effluents of municipal wastewater treatment plants varied from below 10 to 100 μg/L. The ranges of the concentrations in the Glatt River in ng/L were 636–3,690 for BT, 122–628 for TT, 68–326 for NP, 6–22 for OP and 9–76 for BPA. The corresponding mass flows in g/d were 93–1,870 for BT, 18–360 for TT, 24–183 for NP, 1–16 for OP and 2–72 for BPA. The concentrations and mass flows of NP in the River Glatt were drastically lower than the analogous values found 15 years ago. Thus, a substantially decreased environmental exposure can be observed due to the reduction of the use of alkyphenol polyethoxylate surfactants in Switzerland. The current concentrations of NP, OP and BPA are within the ranges reported for weakly impacted surface waters. Conclusion The investigated contaminants occur at quantitatively measurable but varying concentrations in municipal wastewaters and in the Glatt River reflecting their ubiquitous input into wastewaters and their different behaviour during biological wastewater treatment.     

Polychlorinated biphenyls in ambient air of NW Greece and in particulate emissions

Polychlorinated biphenyls (PCBs) bound to total suspended particles (TSP) were determined in the area of Eordea basin, NW Greece, where intensive coal burning for electricity production takes place. The concentrations of PCBs exhibited high variability although within the range reported for urban industrialized areas. The presence of PCBs in fly ash generated from coal burning as well as in particulate emissions from vehicles, domestic heating, burning of refuses and biomass was also examined. The particles emitted from vehicles and central heating exhibited the higher content of PCBs, whereas fly ash the lower. The pattern of PCBs in TSP as well as in particulate emissions was discussed.     

Eutrophication and environmental policy in the Mediterranean Sea: a review

The Mediterranean Sea is a semienclosed basin connected with the open sea mainly through the Strait of Gibraltar. Due to the circulation pattern and the long residence time ranging between 80 and 100 years, the Mediterranean Sea is a sensitive environment to eutrophication pressures. The main body of water of the Mediterranean is characterized by very low nutrient concentrations, and therefore, the Mediterranean is classified among the most oligotrophic (very poor waters in nutrients) seas of the world's oceans. However, some coastal areas, mainly in the northern part of the basin, receive excessive loads of nutrients from sewage effluents, river fluxes, aquaculture farms, fertilizers, and industrial facilities, showing intense eutrophic phenomena with many adverse effects for the marine ecosystem and humans. Various national and international authorities, in addition to monitoring, have taken legal and administrative measures to mitigate eutrophication trends in the area. The Mediterranean environment is a good paradigm of integration of extensive legal framework, scientific knowledge, and administrative practices. The Barcelona Convention, the Mediterranean Action Plan, and European Union Directives on water quality and coastal management, together with scientific information derived from international research programs in the Mediterranean, provide a sound background for practical actions in eutrophication problems. In the present work, the problem of coastal eutrophication in the Mediterranean is reviewed in connection with public policies of the Mediterranean States based on national and international legislation and scientific knowledge on Mediterranean oceanography-ecology and actions coordinated by international bodies. These common actions and practices on coastal management are also discussed in relation to the need for sustainable development and protection of the coastal zone in the Mediterranean Sea.     

Soil column experiments used as a means to assess transport,sorption, and biodegradation of pesticides in groundwater

Soil column experiments are used to investigate the fate of three pesticides of high, intermediate, and low solubility in groundwater: N- phosphonomethyl glycine (glyphosate); O,O-diethyl-S-[(ethylthio)methyl]phosphorodithioate (phorate); (2,4-dichlorophenoxy)acetic acid (2,4-D). Feed solutions are prepared by adding each pesticide (100 mg/L glyphosate, 50 μ g/L phorate, 50 mg/L 2,4-D) along with conservative tracer, KBr, in synthetic groundwater. The concentration of the pesticides in effluents is detected by ion chromatography (glyphosate, 2,4-D) and GC-FID (phorate). The Br^? breakthrough curves are employed to estimate the dispersion coefficient and mean pore velocity in each column. Solute transport and reactive models accounting for equilibrium/non-equilibrium sorption and biodegradation are coupled with inverse modeling numerical codes to estimate the kinetic parameters for all pesticides.     

Assessment of Human and Ecosystem Risk Due to Agricultural Waste Compost Application on Soils: A Review

Agricultural wastes (AW) are often characterized by varying pH and substantial contamination potential, which are mainly related to their high organic load, thus affecting—when improperly disposed of—soils, living organisms, and water bodies. Composting of AW is the most commonly used management option and results in the production of soil improver that enhances crop growth and contributes to agricultural sustainability. This study aims to present the framework for assessing human and ecosystem risk when compost produced from AW is applied on soil. In order to develop this framework, issues such as origin, composition and pre-treatment of AW, application rates on soils, bioavailability and mobility of contaminants present in compost, exposure routes and rates as well as determination of the fate of contaminants in soil, air, and water, should be taken into consideration.     

Soil column experiments used as a means to assess transport, sorption, and biodegradation of pesticides in groundwater

Soil column experiments are used to investigate the fate of three pesticides of high, intermediate, and low solubility in groundwater: N- phosphonomethyl glycine (glyphosate); O,O-diethyl-S-[(ethylthio)methyl]phosphorodithioate (phorate); (2,4-dichlorophenoxy)acetic acid (2,4-D). Feed solutions are prepared by adding each pesticide (100 mg/L glyphosate, 50 micro g/L phorate, 50 mg/L 2,4-D) along with conservative tracer, KBr, in synthetic groundwater. The concentration of the pesticides in effluents is detected by ion chromatography (glyphosate, 2,4-D) and GC-FID (phorate). The Br(-) breakthrough curves are employed to estimate the dispersion coefficient and mean pore velocity in each column. Solute transport and reactive models accounting for equilibrium/non-equilibrium sorption and biodegradation are coupled with inverse modeling numerical codes to estimate the kinetic parameters for all pesticides.     

Partitioning of endocrine disrupting compounds in inland waters and wastewaters discharged into the coastal area of Thessaloniki,Northern Greece

Background, aim, and scope  

In the Water Framework Directive 2000/60/EC, environmental objectives for the proper quality of inland, surface, transitional, coastal, and ground waters have been set. Member states are required to identify chemical pollutants of significance in the water bodies, to establish emission control measures, and to achieve quality standards. A specific category of pollutants are the compounds that may possess endocrine-related functions known as endocrine disrupting compounds (EDCs). This means that member states have the obligation to take action in order to prevent human exposure to these compounds via aquatic environment. The objective of this research was to study the occurrence and distribution of phenolic and steroid EDCs in inland waters and wastewaters discharged in the area of Thermaikos Gulf, Thessaloniki, Northern Greece.     

Combining steam injection with hydraulic fracturing for the in situ remediation of the unsaturated zone of a fractured soil polluted by jet fuel

A steam injection pilot-scale experiment was performed on the unsaturated zone of a strongly heterogeneous fractured soil contaminated by jet fuel. Before the treatment, the soil was stimulated by creating sub-horizontal sand-filled hydraulic fractures at three depths. The steam was injected through one hydraulic fracture and gas/water/non-aqueous phase liquid (NAPL) was extracted from the remaining fractures by applying a vacuum to extraction wells. The injection strategy was designed to maximize the heat delivery over the entire cell (10 m × 10 m × 5 m). The soil temperature profile, the recovered NAPL, the extracted water, and the concentrations of volatile organic compounds (VOCs) in the gas phase were monitored during the field test. GC-MS chemical analyses of pre- and post-treatment soil samples allowed for the quantitative assessment of the remediation efficiency. The growth of the heat front followed the configuration of hydraulic fractures. The average concentration of total hydrocarbons (g/kg of soil) was reduced by ～ 43% in the upper target zone (depth = 1.5-3.9 m) and by ～ 72% over the entire zone (depth = 1.5-5.5 m). The total NAPL mass removal based on gas and liquid stream measurements and the free-NAPL product were almost 30% and 2%, respectively, of those estimated from chemical analyses of pre- and post-treatment soil samples. The dominant mechanisms of soil remediation was the vaporization of jet fuel compounds at temperatures lower than their normal boiling points (steam distillation) enhanced by the ventilation of porous matrix due to the forced convective flow of air. In addition, the significant reduction of the NAPL mass in the less-heated deeper zone may be attributed to the counter-current imbibition of condensed water from natural fractures into the porous matrix and the gravity drainage associated with seasonal fluctuations of the water table.     

Growth rate effects, responses of antioxidant enzymes and metabolic fate of the herbicide Propanil in the aquatic plant Lemna minor

Propanil (3,4-dichloropropionanilide) is a selective contact pesticide, recommended for post-emergence use in rice. This herbicide may end up in surface waters and present potential risk for aquatic vascular plants. Therefore, its toxicity was evaluated on Lemna minor L., an aquatic plant regularly used for toxicological studies, during time- and concentration-dependent exposure. Toxicity assessments were based on inhibition of growth of L. minor cultures after 24 days. The obtained results showed that the growth of Lemna was affected by the herbicide. The responses of the guaiacol peroxidase (G-POD) and glutathione S-transferase (GST) involved in the xenobiotic metabolism and antioxidative system were also investigated following Propanil exposure. Our results showed that Propanil has not induced enzymatic antioxidative defenses of L. minor. Both 3,4-dichloroaniline (3,4-DCA) and 3,4-dichloroacetanilide are the major metabolites in this plant. On the contrary, only 3,4-DCA was found in culture media after 4 days. Probably, the enzymatic hydrolysis by acyl acylamidase and the acetylation by acetyl-CoA are the major pathways for these transformation products, respectively. The results of this study showed that the selected aquatic plant has the potential to accumulate and metabolize rice herbicide, like Propanil. Based on these toxicity data this herbicide should impair the establishment of non-target aquatic plants.     

The status of pesticide pollution in surface waters (rivers and lakes) of Greece. Part I. Review on occurrence and levels

This review evaluates and summarizes the results of long-term research projects, monitoring programs and published papers concerning the pollution of surface waters (rivers and lakes) of Greece by pesticides. Pesticide classes mostly detected involve herbicides used extensively in corn, cotton and rice production, organophosphorus insecticides as well as the banned organochlorines insecticides due to their persistence in the aquatic environment. The compounds most frequently detected were atrazine, simazine, alachlor, metolachlor and trifluralin of the herbicides, diazinon, parathion methyl of the insecticides and lindane, endosulfan and aldrin of the organochlorine pesticides. Rivers were found to be more polluted than lakes. The detected concentrations of most pesticides follow a seasonal variation, with maximum values occurring during the late spring and summer period followed by a decrease during winter. Nationwide, in many cases the reported concentrations ranged in low ppb levels. However, elevated concentrations were recorded in areas of high pesticide use and intense agricultural practices. Generally, similar trends and levels of pesticides were found in Greek rivers compared to pesticide contamination in other European rivers. Monitoring of the Greek water resources for pesticide residues must continue, especially in agricultural regions, because the nationwide patterns of pesticide use are constantly changing. Moreover, emphasis should be placed on degradation products not sufficiently studied so far.