Nonylphenol in the environment: a critical review on occurrence, fate, toxicity and treatment in wastewaters

Nonylphenol is a toxic xenobiotic compound classified as an endocrine disrupter capable of interfering with the hormonal system of numerous organisms. It originates principally from the degradation of nonylphenol ethoxylates which are widely used as industrial surfactants. Nonylphenol ethoxylates reach sewage treatment works in substantial quantities where they biodegrade into several by-products including nonylphenol. Due to its physical-chemical characteristics, such as low solubility and high hydrophobicity, nonylphenol accumulates in environmental compartments that are characterised by high organic content, typically sewage sludge and river sediments, where it persists. The occurrence of nonylphenol in the environment is clearly correlated with anthropogenic activities such as wastewater treatment, landfilling and sewage sludge recycling. Nonylphenol is found often in matrices such as sewage sludge, effluents from sewage treatment works, river water and sediments, soil and groundwater. The impacts of nonylphenol in the environment include feminization of aquatic organisms, decrease in male fertility and the survival of juveniles at concentrations as low as 8.2 mug/l. Due to the harmful effects of the degradation products of nonylphenol ethoxylates in the environment, the use and production of such compounds have been banned in EU countries and strictly monitored in many other countries such as Canada and Japan. Although it has been shown that the concentration of nonylphenol in the environment is decreasing, it is still found at concentrations of 4.1 mug/l in river waters and 1 mg/kg in sediments. Nonylphenol has been referred to in the list of priority substances in the Water Frame Directive and in the 3rd draft Working Document on Sludge of the EU. Consequently there is currently a concern within some industries about the possibility of future regulations that may impose the removal of trace contaminants from contaminated effluents. The significance of upgrading sewage treatment works with advanced treatment technologies for removal of trace contaminants is discussed.     

Identification of metal toxicity in sewage sludge leachate

Sewage sludge is a source of organic matter and nutrients with the potential for being used as a fertilizer. However, metals in sewage sludge might accumulate in soil after repeated sludge applications, and metal concentrations might reach concentrations that are toxic to microorganisms, soil organisms and/or plants. This toxicity might change with time due to kinetic factors or abiotic factors such as freezing, drying or rainfall. The objective of this study was to determine toxicity of sewage sludge leachate from a lysimeter with 50 cm of sludge applied. Attempts were also made to identify the cause of toxicity of the sludge leachate by toxicity identification and evaluation (TIE) techniques. Sludge leachate was collected monthly during 1 experimental year (August 2001 to August 2002). Metal concentrations were analysed, and the toxicity was determined with Daphnia magna (48-h immobility). The effect of EDTA or sodium thiosulphate addition, filtration through a CM-resin or a Millex-resin on toxicity was also tested. The results showed that toxicity of the sludge leachate apparently varied during the year, and that filtration through the CM-resin reduced most of the toxicity followed by the addition of EDTA. None of the other treatments reduced the toxicity of the sludge leachate. This indicated that one or more metals were responsible for the observed toxicity. Further calculations of toxic units (TU) suggested that Zn contributed most to the toxicity. Results also indicated that Ca concentrations in the sludge leachate reduced the toxicity of Zn.     

Derivation of predicted no effect concentrations (PNEC) for marine environmental risk assessment: application of different approaches to the model contaminant Linear Alkylbenzene Sulphonates (LAS) in a site-specific environment

Four sediment-dwelling marine organisms were exposed to sediments spiked with increasing concentrations of Linear Alkylbenzene Sulphonate (LAS). The selected endpoint mortality was reported daily and acute LC(50) (96 h), as well as final LC(10) values were calculated for the derivation of environmentally safe predicted no effect concentrations (PNEC) for the sediment compartment. PNECs were estimated by both application of assessment factors (AF) and the equilibrium partitioning method (EPM) as proposed by the EU TGD. Finally, environmental risk assessment in a site-specific environment, the Sancti Petri Channel, South Iberian Peninsula, was carried out at three different sampling stations with known environmental LAS concentrations. PNECs obtained by the assessment factor approach with acute toxicity data were one to two orders of magnitude lower than those from the equilibrium partitioning method. On the other hand, when applying lower AFs to the estimated LC(10) values, the PNECs obtained by both approaches were more similar. Environmental risk assessment carried out with the estimated PNECs in a site specific environment with known sediment LAS concentrations revealed that PNECs obtained with acute toxicity data were over conservative whereas those obtained with AF=10 on LC(10) data and EPM produced more realistic results in accordance with field observations carried out in the study area.     

Triclosan in wastewaters and biosolids from Australian wastewater treatment plants

Triclosan (TCS) is an antimicrobial agent widely used in many personal care products. This study investigated the occurrence of TCS in effluents, biosolids and surface waters, and its fate in wastewater treatment plants (WWTPs). The aqueous concentrations of TCS in nineteen effluents from Australian WWTPs ranged from 23 ng/L to 434 ng/L with a median concentration of 108 ng/L, while its concentrations in nineteen biosolids ranged from 0.09 mg/kg to 16.79 mg/kg on dry weight basis with a median concentration of 2.32 mg/kg. The removal rates for TCS in five selected WWTPs were found to range between 72% and 93%. Biological degradation was believed to be the predominant removal mechanism for TCS in the WWTPs. However, adsorption onto sludge also played a significant role in the removal of TCS in the WWTPs. TCS at concentrations up to 75 ng/L was detected in surface waters (outfall, upstream, and downstream) from five rivers receiving effluent discharge from WWTPs. Preliminary risk assessment based on the worst-case scenario showed that the TCS concentrations in surface waters might lead to risks to aquatic organisms such as algae. Based on the TCS levels in the biosolids, application of biosolids on agricultural land may also cause adverse effects in the soil environment.     

Environmental fate of alkylphenols and alkylphenol ethoxylates--a review

Alkylphenol ethoxylates (APEs) are widely used surfactants in domestic and industrial products, which are commonly found in wastewater discharges and in sewage treatment plant (STP) effluents. Degradation of APEs in wastewater treatment plants or in the environment generates more persistent shorter-chain APEs and alkylphenols (APs) such as nonylphenol (NP), octylphenol (OP) and AP mono- to triethoxylates (NPE1, NPE2 and NPE3). There is concern that APE metabolites (NP, OP, NPE1-3) can mimic natural hormones and that the levels present in the environment may be sufficient to disrupt endocrine function in wildlife and humans. The physicochemical properties of the APE metabolites (NP, NPE1-4, OP, OPE1-4), in particular the high K(ow) values, indicate that they will partition effectively into sediments following discharge from STPs. The aqueous solubility data for the APE metabolites indicate that the concentration in water combined with the high partition coefficients will provide a significant reservoir (load) in various environmental compartments. Data from studies conducted in many regions across the world have shown significant levels in samples of every environmental compartment examined. In the US, levels of NP in air ranged from 0.01 to 81 ng/m3, with seasonal trends observed. Concentrations of APE metabolites in treated wastewater effluents in the US ranged from < 0.1 to 369 microg/l, in Spain they were between 6 and 343 microg/l and concentrations up to 330 microg/l were found in the UK. Levels in sediments reflected the high partition coefficients with concentrations reported ranging from < 0.1 to 13,700 microg/kg for sediments in the US. Fish in the UK were found to contain up to 0.8 microg/kg NP in muscle tissue. APEs degraded faster in the water column than in sediment. Aerobic conditions facilitate easier further biotransformation of APE metabolites than anaerobic conditions.     

Emission of artificial sweeteners,select pharmaceuticals,and personal care products through sewage sludge from wastewater treatment plants in Korea

Concern over the occurrence of artificial sweeteners (ASWs) as well as pharmaceuticals and personal care products (PPCPs) in the environment is growing, due to their high use and potential adverse effects on non-target organisms. The data for this study are drawn from a nationwide survey of ASWs in sewage sludge from 40 representative wastewater treatment plants (WWTPs) that receive domestic (WWTP_D), industrial (WWTP_I), or mixed (domestic plus industrial; WWTP_M) wastewaters in Korea. Five ASWs (concentrations ranged from 7.08 to 5220 ng/g dry weight [dw]) and ten PPCPs (4.95–6930 ng/g dw) were determined in sludge. Aspartame (concentrations ranged from 28.4 to 5220 ng/g dw) was determined for the first time in sewage sludge. The median concentrations of ASWs and PPCPs in sludge from domestic WWTPs were 0.8–2.5 and 1.0–3.4 times, respectively, the concentrations found in WWTPs that receive combined domestic and industrial wastewaters. Among the five ASWs analyzed, the median environmental emission rates of aspartame through domestic WWTPs (both sludge and effluent discharges combined) were calculated to be 417 μg/capita/day, followed by sucralose (117 μg/capita/day), acesulfame (90 μg/capita/day), and saccharin (66 μg/capita/day). The per-capita emission rates of select PPCPs, such as antimicrobials (triclocarban: 158 μg/capita/day) and analgesics (acetaminophen: 59 μg/capita/day), were an order of magnitude higher than those calculated for antimycotic (miconazole) and anthelmintic (thiabendazole) drugs analyzed in this study. Multiple linear regression analysis of measured concentrations of ASWs and PPCPs in sludge revealed that several WWTP parameters, such as treatment capacity, population-served, sludge production rate, and hydraulic retention time could influence the concentrations found in sludge.     

Concentrations, transport, fate, and releases of polybrominated diphenyl ethers in sewage treatment plants in the Pearl River Delta, South China

Wastewater has proved to be a significant source of polybrominated diphenyl ethers (PBDEs) in the environment. Seventeen congeners from tri- to deca-BDEs were determined to characterize the occurrence, fate, and transport of PBDEs in two sewage treatment plants in the Pearl River Delta, South China. The PBDE concentrations varied substantially from 13.3 to 2496.4 ng L(-1) in the raw wastewater, depending on the wastewater types and contents of the suspended particulate matter (SPM). The concentrations declined to 0.9 to 4.4 ng L(-1) in the treated effluent and were closely associated with SPM contents. BDE-209 was the predominant congener in the wastewater and sewage sludge. Most of PBDEs might have ended up in the sewage sludge, with <4.7% being discharged with the treated effluent. The results revealed that PBDEs were not significantly degraded by biological treatment and chlorination in the STPs. An annual release of PBDEs was estimated at 2280 kg/year through wastewater from the Pearl River Delta.     

Comprehensive study of endocrine disrupting compounds using grab and passive sampling at selected wastewater treatment plants in South East Queensland, Australia

Chemical (gas chromatography-mass spectrometry, GC-MS) and biological (E-Screen assay) analyses were used to determine the concentrations of 15 endocrine disrupting compounds (EDCs) and estrogen equivalent (EEq) in grab and passive samples from five municipal wastewater treatment plants (WWTPs) in South East Queensland, Australia. EEq concentrations derived by E-Screen assays for the grab samples were between 108-356 ng/L for the influents and < 1-14.8 ng/L for the effluents with the exception of one effluent sample which was at 67.8 ng/L EEq. The EDC concentrations and EEq values for the passive samples were several times lower than those of the grab samples: a decrease probably caused by, but not limited to biofouling, low flow rate, biodegradation and temperature which can progressively reduce the uptake of compounds into the sampler. At this stage, grab sampling is the most reliable method for field monitoring; nevertheless, passive sampler is a useful sampling tool but the method requires more research to ensure that the information obtained can be interpreted appropriately. Although alkylphenols and phthalates were detected at higher concentrations in the wastewater samples as compared to natural hormones, the environmental risk may be negligible as their estrogenic potencies are several orders of magnitude lower than that of the natural estrogens. In most wastewater samples, the natural estrogens contributed to 60% or more of the EEq value. Removal efficacy of most estrogenic and xenoestrogenic compounds from the conventional activated sludge or biological nutrient removal (BNR) WWTPs monitored in this study was in the range of 80-> 99%. The efficiency of the WWTPs in removing estrogenic activity was > 95%. The EEqs of the E-Screen and those calculated from the results of extensive chemical analyses using the estradiol equivalency factors were comparable for most of the WWTPs samples.     

Fate of glutaraldehyde in hospital wastewater and combined effects of glutaraldehyde and surfactants on aquatic organisms

Glutaraldehyde (GA), an aliphatic dialdehyde disinfectant, and surfactants, one of the major components of detergents, are widely used in hospitals in order to eliminate pathogenic organisms causing nosocomial infectious diseases. After their use, disinfectants and surfactants reach the wastewater network together. The discharge of chemical compounds from hospital activities into wastewater is also a well-known problem, causing pollution of water resources and constituting an ecological risk for aquatic organisms. In this study, the chemistry and toxicology of GA and surfactant mixtures were reviewed in order to estimate their fate in aquatic ecosystems. Furthermore, their joint effects on aquatic organisms were experimentally assessed in the laboratory. A simple model of the additive joint action of toxicants was used to determine combined acute toxicity effects on the bacteria luminescence and Daphnia mobility of three mixtures containing GA at 1.5 x EC50 24 h [in mg/L] on Daphnia and anionic, cationic and nonionic surfactants at twice their critical micellar concentration (CMC). The mixture of GA and a cationic surfactant gave an EC50 30 min on Vibrio fischeri of 0.158%, with a concentration of 0.04 mg GA/L and 1.04 mg CTAB/L, which provided an additive action. The interaction between GA and an anionic surfactant on V. fischeri produced an antagonistic joint action with an EC50 30 min of 3.95%, containing 1.06 mg GA/L and 33.2 mg SDS/L. A synergistic action with an EC50 30 min of 8.4% on V. fischeri was observed for the mixture containing GA and a nonionic surfactant. Antagonistic interactions were observed for the joint action between GA and the surfactants studied on Daphnia. The mixture of GA and CTAB was more toxic (EC50 24 h=0.02%) than the two other mixtures (EC50 24 h GA+SDS=6%; EC50 24 h GA+TX 100=10%). This study provides new data on the toxicity of certain hospital pollutants entering the aquatic environment and detected in surface and groundwaters. It is necessary to study the joint effects of GA and surfactant mixtures following chronic and sublethal standard bioassays in order to estimate the contribution of the additive joint action models in assessing the environmental risk of hospital wastewater (HW).     

Diclofenac and its transformation products: Environmental occurrence and toxicity - A review

Diclofenac (DCF) is a prevalent anti-inflammatory drug used throughout the world. Intensive researches carried out in the past few decades have confirmed the global ubiquity of DCF in various environmental compartments. Its frequent occurrence in freshwater environments and its potential toxicity towards several organisms such as fish and mussels makes DCF an emerging environmental contaminant. At typical detected environmental concentrations, the drug does not exhibit toxic effects towards living organisms, albeit chronic exposure may lead to severe effects. For DCF, about 30–70% removal has been obtained through the conventional treatment system in wastewater treatment plant being the major primary sink. Thus, the untreated DCF will pass to surface water. DCF can interact with other inorganic contaminants in the environment particularly in wastewater treatment plant, such as metals, organic contaminants and even with DCF metabolites. This process may lead to the creation of another possible emerging contaminant. In the present context, environmental fate of DCF in different compartments such as soil and water has been addressed with an overview of current treatment methods. In addition, the toxicity concerns regarding DCF in aquatic as well as terrestrial environment along with an introduction to the metabolites of DCF through consumption as well as abiotic degradation routes are also discussed. Further studies are required to better assess the fate and toxicological effects of DCF and its metabolites and must consider the possible interaction of DCF with other contaminants to develop an effective treatment method for DCF and its traces.     

Biological activity and environmental impact of anionic surfactants

The newest results concerning the biological activity and environmental fate of anionic surfactants are collected and critically evaluated. The chemical and physicochemical parameters related to the biological activity and the field of application are briefly discussed. Examples on the effect of anionic surfactants on the cell membranes, on the activity of enzymes, on the binding to various proteins and to other cell components and on their human toxicity are presented and the possible mode of action is elucidated. The sources of environmental pollution caused by anionic surfactants are listed and the methods developed for their removal from liquid, semiliquid and solid matrices are collected. Both the beneficial and adversary effects of anionic surfactants on the environment are reported and critically discussed. It was concluded that the role of anionic surfactants in the environment is ambiguous: they can cause serous environmental pollution with toxic effect on living organisms; otherwise, they can promote the decomposition and/or removal of other inorganic and organic pollutants from the environment. The relationship between their chemical structure, physicochemical parameters, biological activity and environmental impact is notwell understood. A considerable number of data are needed for the development of new anionic surfactants and for the successful application of the existing ones to reduce the adversary and to promote beneficial effects.     

Perfluoroalkyl compounds in Danish wastewater treatment plants and aquatic environments

This study reports the results of a screening survey of perfluoroalkyl compounds (PFCs) in the Danish environment. The study included point sources (municipal and industrial wastewater treatment plants and landfill sites) and the marine and freshwater environments. Effluent and influent water and sewage sludge were analysed for point sources. Sediment, blue mussels (Mytilus edulis) and liver from plaice (Pleuronectes platessa), flounder (Platichthys flesus) and eel (Anguilla anguilla) were analysed for the freshwater and marine environments. The results obtained show a diffuse PFCs contamination of the Danish environment with concentrations similar to those measured in other countries with the absence of primary contamination sources such as fluorochemical production. PFOS and PFOA were generally the most dominating PFCs measured in both point sources and the aquatic environments. PFCs were found in both inflow and outflow water and sewage sludge from municipal and industrial wastewater treatment plants (WWTPs), indicating that WWTPs can be significant sources to PFCs in the environment. This is also reflected in the locally elevated PFCs concentrations found in fish like eels from shallow freshwater and marine areas. However, the highest PFCs concentrations found in fish in this study was in plaice from the Skagerrak (156 ng/g wet weight PFOS), but it is unknown if this can be related to significant sources in the North Sea region or to differences between species. The concentrations of PFCs were below the detection limit in all analysed freshwater and marine samples of sediment and mussels. Despite the relatively low PFCs concentrations measured in marine fish, the high bioaccumulation potential of PFCs, particularly PFOS, may lead to high concentrations of PFCs in marine mammals as shown by previous investigations.     

The ecological effects of trichloroacetic acid in the environment

Trichloroacetic acid (TCAA) is a member of the family of compounds known as chloroacetic acids, which includes mono-, di- and trichloroacetic acid. The significant property these compounds share is that they are all phytotoxic. TCAA once was widely used as a potent herbicide. However, long after TCAA's use as a herbicide was discontinued, its presence is still detected in the environment in various compartments. Methods for quantifying TCAA in aqueous and solid samples are summarized. Concentrations in various environmental compartments are presented, with a discussion of the possible formation of TCAA through natural processes. Concentrations of TCAA found to be toxic to aquatic and terrestrial organisms in laboratory and field studies were compiled and used to estimate risk quotients for soil and surface waters. TCAA levels in most water bodies not directly affected by point sources appear to be well below toxicity levels for the most sensitive aquatic organisms. Given the phytotoxicity of TCAA, aquatic plants and phytoplankton would be the aquatic species to monitor for potential effects. Given the concentrations of TCAA measured in various soils, there appears to be a risk to terrestrial organisms. Soil uptake of TCAA by plants has been shown to be rapid. Also, combined uptake of TCAA from soil and directly from the atmosphere has been shown. Therefore, risk quotients derived from soil exposure may underestimate the risk TCAA poses to plants. Moreover, TCE and TCA have been shown to be taken up by plants and converted to TCAA, thus leading to an additional exposure route. Mono- and di-chloroacetic acids can co-occur with TCAA in the atmosphere and soil and are more phytotoxic than TCAA. The cumulative effects of TCAA and compounds with similar toxic effects found in air and soil must be considered in subsequent terrestrial ecosystem risk assessments.     

Prediction of environmental concentrations of glucocorticoids: The River Thames,UK, as an example

Synthetic glucocorticoids (GCs) are consumed in large amounts as anti-inflammatory and immunosuppressive drugs worldwide. Based on what has been learnt from studies of other human pharmaceuticals, they are likely to be present in the aquatic environment. However, to date, information on the environmental concentrations of GCs is very limited. The situation is complicated by the fact that a considerable number of GCs are in everyday use in most developed countries. Hence, obtaining a full picture of GC concentrations in the aquatic environment using the traditional analytical chemistry approach would be time-consuming and expensive. Thus, we took a modelling approach to predict the total environmental concentration of all synthetic GCs (consisting of 28 individual GCs) in the River Thames, as a first step in risk assessment of these drugs. Using reliable data on consumption, the LF2000-WQX model predicts mean concentrations up to 30 ng/L of total GCs in surface water as a best case scenario when the lowest excretion and highest removal rates in sewage treatment works were used, whereas mean concentrations up to 850 ng/L were predicted when the highest excretion and lowest removal rates are considered. We also present the 10th and 90th percentile concentrations (which indicate the likely range of concentrations seen from high flow to low flow conditions in the river) of the highest and lowest consumed GCs, to show the spatial and temporal variations of the concentrations of individual GCs. These data probably provide reliable estimates of the likely range of concentrations of GCs in a typical river impacted by effluent from many sewage treatment plants. Results also identify the hot spots where field studies on fish could be focused. To determine if aquatic organisms face any threat from GCs, laboratory toxicity studies should be conducted using concentrations similar to those reported here.     

Silver nanoparticles: behaviour and effects in the aquatic environment

This review summarises and evaluates the present knowledge on the behaviour, the biological effects and the routes of uptake of silver nanoparticles (Ag NPs) to organisms, with considerations on the nanoparticle physicochemistry in the ecotoxicity testing systems used. Different types of Ag NP syntheses, characterisation techniques and predicted current and future concentrations in the environment are also outlined. Rapid progress in this area has been made over the last few years, but there is still a critical lack of understanding of the need for characterisation and synthesis in environmental and ecotoxicological studies. Concentration and form of nanomaterials in the environment are difficult to quantify and methodological progress is needed, although sophisticated exposure models show that predicted environmental concentrations (PECs) for Ag NPs in different environmental compartments are at the range of ng L(-1) to mg kg(-1). The ecotoxicological literature shows that concentrations of Ag NPs below the current and future PECs, as low as just a few ng L(-1), can affect prokaryotes, invertebrates and fish indicating a significant potential, though poorly characterised, risk to the environment. Mechanisms of toxicity are still poorly understood although it seems clear that in some cases nanoscale specific properties may cause biouptake and toxicity over and above that caused by the dissolved Ag ion. This review concludes with a set of recommendations for the advancement of understanding of the role of nanoscale silver in environmental and ecotoxicological research.     

Polybrominated diphenyl ether flame retardants in the U.S. marine environment: A review

Polybrominated diphenyl ethers (PBDEs) are used as flame retardants in polymeric materials such as furnishing foam, rigid plastics and textiles. The U.S. has historically led the world production of these man-made chemicals and was responsible for about 50% of the total global demand in 2001. Paradoxically, scientific studies addressing sources, behavior and fate of PBDEs in the U.S. environment are limited when compared to those in Europe. This paper reviews the distribution of PBDEs in marine and estuarine matrices of the three U.S. coasts (Atlantic, Pacific and Gulf of Mexico) and Alaska. PBDEs are ubiquitous in all compartments including water, sediment and biota. Contamination is higher in urbanized regions such as the coast of California. In numerous cases, concentrations of PBDEs in U.S. marine matrices are among the highest in the world. Higher PBDE levels in the U.S. marine environment reflect that over 90% of the Penta-BDE global production has been utilized in the United States. BDEs 47, 99 and 100 typically dominate the composition of PBDEs in most samples and exhibit high concentrations in several matrices. BDEs 17, 28, 33, 49, 153, 154 and 155 are also of concern since they are known to be present in a minor proportion in the Penta-BDE products. BDEs 206, 207, 208 and 209 which occur in Deca-BDE products do not appear to accumulate in most marine organisms although they may be debrominated into more toxic congeners. There is still no regulation addressing PBDEs contamination in the U.S. aquatic environments. Thus, efforts to understand the cycling of PBDEs in the environment as well as toxic effects in organisms are needed to support the development of quality criteria. Some PBDE congeners fulfill the criteria to be recognized as persistent organic pollutants (POPs). The addition of PBDEs to the list of POPs established by the United Nations Stockholm Convention will be important in elevating environmental concerns regarding these chemicals to an appropriate level of awareness.     

Enchytraeus albidus (Enchytraeidae): a test organism in a standardised avoidance test? Effects of different chemical substances

Enchytraeids (Enchytraeus albidus) directly improve the pore structure of the soil and are indirectly involved in regulating the degradation of organic matter. Due to their behavior they are able to avoid unfavorable environmental conditions. Avoidance tests allow a first assessment of toxicity of a contaminated or spiked soil within 48 h, by using the reaction of the enchytraeids as measurement endpoint. In this period, the organisms can choose between the control soil and the test soil. In the tests reported here, enchytraeids were exposed to LUFA 2.2 soil spiked with the following set of toxic substances: copper chloride, zinc chloride, cadmium chloride, phenmedipham, benomyl, carbendazim, dimethoate, atrazine, pentachlorophenol, chlorpyriphos, lindane, TBTO, Linear Alkylbenzene Sulfonates (LAS) and boric acid. Different chemical concentrations were tested. EC50s ranged from 8 mg/kg (Carbendazim) to >1000 mg/kg (e.g. LAS). While the tested heavy metals showed clear dose-response relationships, the effect pattern differed considerably in the tests with organic chemicals, e.g. no avoidance behaviour was observed in LAS, even at very high doses. Here we proposed to standardize the Enchytraeid avoidance test in a way similar to what is currently done for the earthworm and collembolan avoidance tests by the International Standardisation Organisation (ISO).     

Presence, biotransformation and effects of sulfophenylcarboxylic acids in the benthic fish Solea senegalensis

The presence of linear alkylbenzene sulfonates (LAS) and their degradation intermediates, sulfophenylcarboxylic acids (SPCs), with concentrations up to 100 ppb has been found in surface waters taken from the estuary of the river Guadalete (Cádiz, SW of Spain). Higher concentrations were found at the sampling site located adjacent to the discharge outlet of a wastewater treatment plant (WWTP). The concentrations decreased downstream to a few ppb as a result of dilution, sorption, and degradation processes, which were taking place along the estuary. Once the presence of both xenobiotics was confirmed in the environment, an in vivo assay was conducted to study their biotransformation and effects in the benthic fish Solea senegalensis. A flow-through system was employed, consisting of an exposure phase (120 h) with environmental levels of the surfactant (200, 500 and 800 microg/L of 2?C(10)LAS), followed by a depuration stage (72 h). The generation of SPCs has been quantified during these phases in both water and fish, with LAS biotransformation shown in all cases. The antioxidant enzymes catalase (CAT), glutathione peroxidase (GPX), glutathione reductase (GR), the phase II enzyme glutathione S-transferase (GST), and the phase III acid and alkaline phosphatases (AcP, ALP) were also estimated and utilized as biomarkers.     

Evaluation of chemical and ecotoxicological characteristics of biodegradable organic residues for application to agricultural land

The use of organic waste and compost as a source of organic matter and nutrients is a common practice to improve soil physico-chemical properties, meanwhile reducing the need for inorganic fertilisers. Official guidelines to assess sewage sludge and compost quality are mostly based on total metal content of these residues. Measurement of the total concentration of metals may be useful as a general index of contamination, but provides inadequate or little information about their bioavailability, mobility or toxicity when the organic residue is applied to the soil. However, ecotoxicity tests provide an integrated measure of bioavailability and detrimental effects of contaminants in the ecosystem. In the present study, three different types of biodegradable organic residues (BORs) have been considered: sewage sludge from municipal wastewater treatment (SS), compost from the organic fraction of unsorted municipal solid waste (MSWC), and garden waste compost (GWC). The BORs were subjected to chemical characterisation and total metal quantification (Cd, Cr, Cu, Ni, Pb and Zn), in order to verify their suitability for land application. Water leachability was determined through the DIN 38414-S4 method, while the modified BCR sequential extraction procedure was used for metal speciation. Ecotoxicity of the BORs was studied by direct and indirect bioassays. Direct toxicity bioassays were: plant growth tests with cress (Lepidium sativum L.) and barley (Hordeum vulgare L.), and earthworm (Eisenia fetida) mortality. On the other hand, indirect exposure bioassays, with leachate from the residues, took into account: luminescent bacteria (Vibrio fischeri), seed germination (L. sativum and H. vulgare) and Daphnia magna immobilization. As far as total metal concentration is concerned, with particular reference to Zn, SS resulted neither suitable for the use in agriculture nor compatible to be disposed of as an inert material into landfill, according to the Directive 1999/31/EC. Zinc in SS was mainly present in exchangeable form (28.5%), appearing as highly bioavailable. As a consequence, SS exhibited either high ecotoxicity effects with the indirect exposure bioassays or significant mortality with the earthworm bioassay. Total content of metals in MSWC allowed its classification as "stabilised biowaste", according to 2nd draft [DG Env.A.2. Working document of Biological treatment of biowaste - 2nd draft. Directorate-General Environment, Brussels, 12th February; 2001. accessed in:http://europa.eu.int/comm/environment/waste/facts_en.htm, at 10/09/2002] while leachate, on the basis of the concentration of these contaminants, could be classified as "inert waste". This residue showed significant ecotoxicity effects with direct exposure bioassays as well as with the luminescent bacteria bioassay. However, it resulted less toxic than SS. Finally, GWC could be classified as a Class 2 compost, with no detectable toxic effects on the organisms used in the bioassays, except for the luminescent bacteria. In this case, an EC(50) of 73.0% was observed. Considering the results, the use of a battery of toxicity test in conjunction with chemical analysis should be suggested, in order to correctly assess possible environmental risks deriving from disposal or land application of biodegradable organic residues.