Developing predictive systems models to address complexity and relevance for ecological risk assessment.

Ecological risk assessments (ERAs) are not used as well as they could be in risk management. Part of the problem is that they often lack ecological relevance; that is, they fail to grasp necessary ecological complexities. Adding realism and complexity can be difficult and costly. We argue that predictive systems models (PSMs) can provide a way of capturing complexity and ecological relevance cost-effectively. However, addressing complexity and ecological relevance is only part of the problem. Ecological risk assessments often fail to meet the needs of risk managers by not providing assessments that relate to protection goals and by expressing risk in ratios that cannot be weighed against the costs of interventions. Once more, PSMs can be designed to provide outputs in terms of value-relevant effects that are modulated against exposure and that can provide a better basis for decision making than arbitrary ratios or threshold values. Recent developments in the modeling and its potential for implementation by risk assessors and risk managers are beginning to demonstrate how PSMs can be practically applied in risk assessment and the advantages that doing so could have.

Mechanistic effect modeling for ecological risk assessment: where to go from here?

Mechanistic effect models (MEMs) consider the mechanisms of how chemicals affect individuals and ecological systems such as populations and communities. There is an increasing awareness that MEMs have high potential to make risk assessment of chemicals more ecologically relevant than current standard practice. Here we discuss what kinds of MEMs are needed to improve scientific and regulatory aspects of risk assessment. To make valid predictions for a wide range of environmental conditions, MEMs need to include a sufficient amount of emergence, for example, population dynamics emerging from what individual organisms do. We present 1 example where the life cycle of individuals is described using Dynamic Energy Budget theory. The resulting individual-based population model is thus parameterized at the individual level but correctly predicts multiple patterns at the population level. This is the case for both control and treated populations. We conclude that the state-of-the-art in mechanistic effect modeling has reached a level where MEMs are robust and predictive enough to be used in regulatory risk assessment. Mechanistic effect models will thus be used to advance the scientific basis of current standard practice and will, if their development follows Good Modeling Practice, be included in a standardized way in future regulatory risk assessments.

Priorities to improve the ecological risk assessment and management for pesticides in surface water.

This article deals with prospective and retrospective ecological risk assessment (ERA) procedures for pesticides in surface waters as carried out under European legislation (Regulation 1107/2009/EC; Directive 2009/128/EC; Directive 2000/60/EC). Priorities to improve the aquatic risk assessment and management of pesticides are discussed on basis of the following 5 theses: 1) the management of the environmental risks of pesticides in surface water requires an appropriate implementation of feedback mechanisms between prospective and retrospective ERA, 2) an appropriate ERA cannot be carried out without well-defined specific protection goals, described in terms of focal vulnerable populations and related exposure assessment goals, 3) the interaction between the assessment of exposure and eco(toxico)logical effects in ERA is at a lower level of sophistication than either assessment of exposure or assessment of effects in the field, 4) there is insufficient experimental proof that, in prospective ERA, the chronic effect assessment procedures accurately predict long-term population- and community-level impacts, and 5) multiple stress by pesticides in aquatic ecosystems cannot be ignored in ERA, but in individual water bodies, toxicity usually is dominated by a limited number of substances.

A cost/effective screening method for assessing the toxicity of nutrient rich effluents to algae.

Screening whole effluent toxicity tests are cost/effective methods for detecting the presence of toxic concentrations of unknown pollutants, but the application must solve the problem associated with the effect of high and variable concentrations of nutrients in the effluent on the results of algal toxicity tests. This work proposes a cost/effective test, based on three dilution levels measured at a single point time and a discriminant model for establishing if this kind of complex samples, with difficult interpretation of dilution-response curves, should be considered toxic to algae. This procedure identified properly around 85% of the samples considered toxic by expert judgement.

In situ assessment of periphyton recovery in a river contaminated by pesticides.

Recovery of bacterial and eukaryotic communities in biofilms naturally grown on stones was studied for 9 weeks after transferring them from a pesticide polluted downstream site of the river Morcille (Beaujolais, France) to a non-contaminated upstream site. Site-specific periphyton present on stones at both the down- and the upstream sampling site were collected to analyze the site-specific colonization. Throughout the experiment, structural and functional parameters were analyzed for the periphyton transferred and for the site-specific up- and downstream periphyton. Comparison between these three communities allowed quantifying recovery of the transferred one. Denaturing Gradient Gel Electrophoresis of PCR-amplified 16S and 18S rRNA gene fragments were used to assess prokaryotic and eukaryotic microbial community composition, respectively. Microscopy counts allowed characterizing the diatom taxa abundances. The sensitivity of the microalgal communities towards diuron and copper was investigated at the laboratory by short-term photosynthesis inhibition assays. The functional reaction of the bacterial communities towards copper was assessed by short-term respiration inhibition assays. The structure of transferred eukaryotic, bacterial and diatom communities was more similar to the structure of the downstream communities than to upstream ones even after 9 weeks acclimatization in particular for the bacterial community. In the same way, the community tolerance towards diuron and copper, as estimated by the EC50 values, was intermediate for the transferred biofilms compared to the local up- or downstream biofilm, even after 9 weeks of acclimatization. These results strongly suggest slow recovery, likely to be linked to long lasting exposure of pesticides and in particular copper adsorbed to the biofilm matrices and to the toughness for pioneer microorganisms to invade mature biofilms.

Whole effluent assessment of industrial wastewater for determination of bat compliance: Part 1: Paper manufacturing industry.

BACKGROUND, AIM AND SCOPE: The applicability of the Whole Effluent Assessment concept for the proof of compliance with the "best available techniques" has been analysed with paper mill wastewater from Germany by considering its persistency (P), potentially bio-accumulative substances (B) and toxicity (T). MATERIALS AND METHODS: Twenty wastewater samples from 13 paper mills using different types of cellulose fibres as raw materials have been tested in DIN or ISO standardised bioassays: the algae, daphnia, luminescent bacteria, duckweed (Lemna), fish-egg and umu tests with lowest ineffective dilution (LID) as test result. The potentially bio-accumulative substances (PBS) were determined by solid-phase microextraction and referred to the reference compound 2,3-dimethylnaphthalene. Usually, a primary chemical-physical treatment of the wastewater was followed by a single or multi-stage biological treatment. One indirectly discharged wastewater sample was pre-treated biologically in the Zahn-Wellens test before determining its ecotoxicity. RESULTS: No toxicity or genotoxicity at all was detected in the acute daphnia and fish egg as well as the umu assay. In the luminescent bacteria test, moderate toxicity (up to LIDlb=6) was observed. Wastewater of four paper mills demonstrated elevated or high algae toxicity (up to LIDA=128), which was in line with the results of the Lemna test, which mostly was less sensitive than the algae test (up to LIDDW=8). One indirectly discharged wastewater sample was biodegraded in the Zahn-Wellens test by 96% and was not toxic after this treatment. Low levels of PBS have been detected (median 3.27 mmol L(-1)). The colouration of the wastewater samples in the visible band did not correlate with algae toxicity and thus is not considered as its primary origin. Further analysis with a partial wastewater stream from thermomechanically produced groundwood pulp (TMP) revealed no algae or luminescent bacteria toxicity after pre-treatment of the sample in the Zahn-Wellens test (chemical oxygen demand elimination 85% in 7 days). Thus, the algae toxicity of the respective paper mill cannot be explained with the TMP partial stream; presumably other raw materials such as biocides might be the source of algae toxicity. DISCUSSION: Comparative data from wastewater surveillance of authorities confirmed the range of ecotoxicity observed in the study. Wastewater from paper mills generally has no or a moderate ecotoxicity (median LID 1 and 2) while the maximum LID values, especially for the algae and daphnia tests, are considerably elevated (LIDA up to 128, LIDD up to 48). CONCLUSIONS: Wastewater from paper mills generally is low to moderately ecotoxic to aquatic organisms in acute toxicity tests. Some samples show effects in the chronic algae growth inhibition test which cannot be explained exclusively with colouration of the samples. The origin of elevated algae ecotoxicity could not be determined. In the algae test, often flat dose-response relationships and growth promotion at higher dilution factors have been observed, indicating that several effects are overlapping. RECOMMENDATIONS AND PERSPECTIVES: At least one bioassay should be included in routine wastewater control of paper mills because the paper manufacturing industry is among the most water consuming. Although the algae test was the most sensitive test, it might not be the most appropriate test because of the complex relationship of colouration and inhibition and the smooth dose-effect relationship or even promotion of algae growth often observed. The Lemna test would be a suitable method which also detects inhibitors of photosynthesis and is not disturbed by wastewater colouration.

Environmental risk assessment of pharmaceuticals in rivers: relationships between hazard indexes and aquatic macroinvertebrate diversity indexes in the Llobregat River (NE Spain).

Continuous input of pharmaceuticals into rivers, through wastewater treatment systems, may cause adverse effects on the aquatic ecosystems of the receiving waterbodies, due to the intrinsic biological activity of these compounds. To investigate this issue, we have carried out an Environmental Risk Assessment in the lower part of the Llobregat River basin (NE Spain). The survey was carried out along three campaigns in 7 sampling points, located in the main river and in one of its tributaries (Anoia River). In each sample, 29 commonly used pharmaceuticals, belonging to different therapeutical classes (analgesics and non-steroidal anti-inflammatories (NSAIDs), lipid regulators, psychiatric drugs, anti-histamines, anti-ulcer agents, antibiotics and beta-blockers) have been determined. Simultaneously, the macroinvertebrate community status of the same points has been also studied. Hazard quotient indexes have been estimated for the most representative compounds as the ratio between concentrations and EC(50) reported values, for three bioassays commonly used in environmental toxicology, namely, fish, Daphnia and algae. Hazard indexes are obtained for each sample by summing up the hazard quotients of all the compounds present, and taking its average along the three sampling campaigns. In general, hazard quotients tend to increase when going downstream. Only those points located most upstream of the two rivers can be qualified under low risk for the three bioassays. The most sensitive bioassay seems to be algae, followed by Daphnia and fish. Log-transformed hazard indexes show fairly good inverse correlations (r=-0.58 to -0.93, p<0.05) with Shannon diversity indexes of macroinvertebrates, determined from both densities and biomasses. Best correlations are obtained for Daphnia based hazard indexes, as expected from its taxonomical proximity to macroinvertebrates. The abnormal correlation behaviour found in one point located in the Anoia River is explained by the presence of other previously reported pollutants of industrial origin, generated by the nearby existing industry.

Removal of pharmaceuticals during wastewater treatment and environmental risk assessment using hazard indexes.

In a long term study, which covered 4 sampling periods over three years, a total number of 84 samples, specifically 28 influent, effluent, from seven WWTP located in the main cities along the Ebro river Basin (North East of Spain), as well as receiving river waters, were analyzed to assess the occurrence of 73 pharmaceuticals covering several medicinal classes. Results indicated that pharmaceuticals are widespread pollutants in the aquatic environmental. Linking the calculation of removal rates with half-lives, assuming that compound degradation followed pseudo-first order kinetics, suggested that conventional wastewater treatments applied at the seven WWTP were unable to completely remove most of the pharmaceuticals under study. The evaluation of compound degradability, in terms of half-lives, is an important task to discuss integrated solutions for mitigation of pollutants entry into the water cycle. High half-lives observed for the majority of pharmaceuticals in WWTP suggest that, in order to enhance compound degradation, higher hydraulic retention times should be required. The wide spectrum of substances detected in receiving river waters indicates that WWTP outlets are major contributors of pharmaceuticals in the aquatic environment. However, municipal wastewater treatment represents an obligatory and final treatment step prior to their release into the aquatic media, since load of pharmaceuticals in outlets were considerably reduced after treatment. Finally, hazard posed by pharmaceuticals in both surface and effluent wastewaters was assessed toward different aquatic organisms, (algae, daphnids and fish). The overall relative order of susceptibility was estimated to be algae>daphnia>fish. Results indicate that no significant risks could be associated to the presence of pharmaceuticals in those matrices, indicating that reduction of compound concentration after wastewater treatment as well as dilution factor once pharmaceuticals are discharged in receiving river water efficiently mitigate possible environmental hazards.

Pyrene toxicity is affected by the nutrient status of a marine sediment community: implications for risk assessment.

Risk assessment of toxicants often disregards that environmental conditions, like changing nutrient status, may affect ecosystem response to a toxicant even within an ecosystem. We investigated if effects of pyrene on shallow-water sediments depended on nutrient status of the sediment during 58 days of incubation. Natural undisturbed sediment cores were pre-exposed to two concentrations of inorganic nutrients (nitrogen and phosphorous) for 14 days. After terminating nutrient additions, pyrene was applied once to half the Nu(high) and half the Nu(low) cores in a concentration of 2 mg/kg DW, normalized to 1% TOC. Pyrene affected the sediment systems in both Nu(high) and Nu(low), but effects of pyrene differed between nutrient regimes. In the Nu(low) system, effects of pyrene were mainly seen on the sediment community structure, such as meiofauna community structure. On the contrary, effects of pyrene in Nu(high) were mainly seen on community functions, such as changes in inorganic nutrient fluxes. Direct and indirect effects of pyrene were observed in both nutrient regimes, but they operated on different timescales depending on the variable in focus. This study shows the need to include environmental factors such as nutrient status in risk assessment of toxicants.

An environmental risk assessment for oseltamivir (Tamiflu) for sewage works and surface waters under seasonal-influenza- and pandemic-use conditions.

In the event of an influenza pandemic, anti-viral medications such as oseltamivir (Tamiflu) are expected to be used in high amounts over a duration of several weeks. Oseltamivir has been predicted to reach high concentrations in surface waters and sewage works. New oseltamivir environmental fate and toxicity studies permit an environmental risk assessment (ERA) under seasonal- and pandemic-use scenarios. The environmental fate data for sewage works (no removal), surface waters (no significant degradation), and water/sediment systems (>50% primary degradation in 100 days) were used for the derivation of new predicted environmental concentrations (PECs) for western Europe and the River Lee catchment in the UK. Existing worst-case PECs for western Europe, the River Lee catchment in the UK and the Lower Colorado basin in the USA under pandemic conditions (< or =98.1 microg/L for surface waters, < or =348 microg/L for sewage works) were also considered for the ERA. PECs were compared with predicted no-effect concentrations (PNECs) based on new chronic ecotoxicity data (no observed effect concentration for algae, daphnia, and fish > or =1 mg/L). Based on all PEC/PNEC risk ratios, no significant risk is evident to surface waters or sewage works during both regular seasonal-use and high pandemic-use of oseltamivir.

Proteomic assessment of caffeine effects on coral symbionts.

Caffeine isthe mostwidely consumed and excreted psychoactive drug in the world. It is a ubiquitous tracer of urban wastewater, but its ecological effects are notwell understood. We hypothesized that caffeine exposure is associated with coral bleaching. Here we report the effects of caffeine on four species of coral algae endosymbionts belonging to three widely distributed clades: Clade A Symbiodinium microadriaticum (A), Clade B Symbiodinium sp. from Aiptasia pallida (B6), Clade B Symbiodinium sp. from Pseudoterogorgia bipinnata (B7), and Clade C Symbiodinium goreaui (C). To assess the effect of caffeine on algal physiology we used two-dimensional polyacrylamide gel electrophoresis and peptide mass spectrometry to identify protein sensitive to caffeine exposure. The results show several upregulated and several downregulated polypeptides in all algae species tested. The heat-shock proteins are among the commonly affected proteins, suggesting that caffeine exposure associated with sewage discharge into natural waters may exacerbate the effects of stress from other environmental factors such as changes in ocean temperature and pH.

Predicting pesticide environmental risk in intensive agricultural areas. II: Screening level risk assessment of complex mixtures in surface waters.

In a previous article, a procedure for assessing pesticide ecotoxicological risk for surface water was applied to all active ingredients in a pilot basin. This data set has been used to assess the composition of pesticide mixtures that are likely to be present in surface waters as a consequence of pesticide emissions from the crops grown within the basin (maize, soybean, sugar beet, and vineyard). Temporal evolution of the mixture composition has been evaluated as a function of the different contamination patterns (drift and runoff). Ecotoxicological risk has been assessed for the mixtures released by individual crops and from all the relevant crops cultivated in the basin. The different role of drift and runoff, as well as the temporal trends of exposure and risk are compared. Daphnia is the most affected among the three indicator organisms considered, particularly from drift mixtures after insecticide application on vineyard. The highest risk for algae occurs during runoff events in spring. In most risk events, one or a few chemicals are usually responsible for more than 80% of the toxic potency of the mixture. The CA model for predicting mixture response is assumed to be a reliable approach for assessing risk for ecologically relevant pesticide mixtures.

Natural impacted freshwaters: in situ use of alginate immobilized algae to the assessment of algal response.

The objective of this study was to investigate the feasibility of an in situ phytotoxicity test using alginate-immobilized algae for 60 days, in the assessment of water quality in an impacted small peri-urban stream. After laboratory optimization of algae immobilization/de-immobilization processes, the performance of immobilized/de-immobilized algae was compared to the performance of free algae in terms of specific algal growth and sensitivity. This was done by comparing 72 h EC50 values obtained with zinc and the pesticides clomazone and carbofuran. The results showed a similar performance, which allow us to conclude that immobilization for 60 days do not cause any significant alteration in algae physiology. In the field, immobilized algae were exposed at different times (2, 4 and 7 days) to water samples in both disturbed and undisturbed sites. Both laboratory and field experiments indicated that alginate-immobilized algae for 60 days were sufficiently sensitive for use in the in situ assessment of water quality.

Direct toxicity assessment of volatile chlorinated hydrocarbon-contaminated groundwater and derivation of a site-specific guideline.

Groundwater contaminated with a mixture of 14 volatile chlorinated hydrocarbons (VCHs) discharges to an estuarine embayment in Sydney, Australia. A screening-level hazard assessment identified a potential risk to aquatic organisms from surface water contaminated by the groundwater. Direct toxicity assessment of the groundwater was undertaken on 5 indigenous marine species to assess toxicity and derive a site-specific guideline. The testing included acute tests, subchronic tests on early life stages, and a chronic test. Test organisms included a microalga (Nitzschia closterium), an amphipod (Allorchestes compressa), a polychaete worm (Diopatra dentata), and sea urchin (Heliocidaris tuberculata) and oyster larvae (Saccostrea commercialis). Toxicity testing was undertaken in sealed containers to prevent loss of VCHs, and concentrations of VCHs were measured to accurately assess exposure concentrations. No observed effect concentration (NOEC) values varied from 1.56% dilution (1.11 mg total VCHs) to 50% dilution (45.5 mg total VCHs). EC50 values varied from 4.8% dilution (3.77 mg total VCHs) to more than 50% dilution (45.5 mg total VCHs). NOEC data were used to derive species sensitivity distributions (SSDs) and a site-specific guideline. SSDs were derived from Burr type III (including the Pareto) and log-normal distributions. The log-normal distribution represented the best fit, and because the Pareto distribution is a finite threshold model more suited to toxicants with a threshold mode of action, the log-normal SSD and the associated 95% trigger value (TV) of 830 microg/L of total VCHs, was adopted as the site-specific TV for the groundwater.

A whole sample toxicity assessment to evaluate the sub-lethal toxicity of water and sediment elutriates from a lake exposed to diffuse pollution.

The impact of diffuse pollution in aquatic systems is of great concern due to the difficult to measure and regulate it. As part of an ecological risk assessment (ERA), this study aims to use a whole sample toxicity assessment to evaluate the toxicity of water and sediment from Lake Vela, a lake that has been exposed to diffuse pollution. In this way, standard (algae: Pseudokirchneriella subcapitata; cladoceran: Daphnia magna) and local species (algae: Aphanizomenon flos-aquae; cladoceran: Daphnia longispina) were exposed to surface water, and sediment elutriates were collected seasonally from two sites at Lake Vela: one near the east bank (ES), surrounded by agricultural lands; and the other near the west bank (WS), surrounded by a forest. The results confirmed the seasonal contamination of both environmental compartments by pesticides, including organochlorine pesticides, and the presence of high concentrations of nutrients. Although both sites were contaminated, higher levels of pesticides and nutrients were detected in ES, particularly in the sediments. Bioassays showed that water samples (100% concentration) collected in summer and autumn significantly affected the growth rate of P. subcapitata, which could be attributed to the presence of pesticides. Likewise, they revealed an apparent toxicity of elutriates for P. subcapitata and for both daphnids, in summer and autumn. In fact, although pesticides were not detected in elutriates, high levels of un-ionized ammonia were recorded, which is considered highly toxic to aquatic life. By comparing the several species, P. subcapitata was revealed to be the most sensitive one, followed by the daphnids, and then by A. flos-aquae. Results obtained in this study underlined the importance of whole samples toxicity assessment for characterizing the ecological effects of complex mixtures from diffuse inputs, in the ERA processes.

Community-level assessment of the effects of the broad-spectrum antimicrobial chlorhexidine on the outcome of river microbial biofilm development.

Chlorhexidine is a common-use antibacterial agent found in a range of personal-care products. We used rotating annular reactors to cultivate river biofilms under the influence of chlorhexidine or its molar equivalent in nutrients. Studies of the degradation of [(14)C]chlorhexidine demonstrated that no mineralization of the compound occurred. During studies with 100 microg liter(-1) chlorhexidine, significant changes were observed in the protozoan and micrometazoan populations, the algal and cyanobacterial biomass, the bacterial biomass, and carbon utilization. Denaturing gradient gel electrophoresis (DGGE) in combination with statistical analyses showed that the communities developing under control and 100 microg liter(-1) chlorhexidine were significantly different. At 10 microg liter(-1) chlorhexidine, there was significantly increased algal and cyanobacterial biomass while the bacterial biomass was not significantly affected (P < 0.05). No significant effects on protozoan or metazoan grazing were detected at the 10-microg liter(-1) chlorhexidine level. Fluorescent in situ hybridization indicated a significant reduction in the abundance of betaproteobacteria and gammaproteobacteria (P < 0.05). Archaeal cell counts were significantly reduced by both chlorhexidine and nutrient treatments. DGGE and statistical analyses indicated that 10 microg liter(-1) chlorhexidine and molar equivalent nutrient treatments were significantly different from control communities. In contrast to community level observations, toxicological testing with a panel of cyanobacteria, algae, and protozoa indicated no detectable effects at 10, 50, and 100 microg liter(-1) chlorhexidine. Thus, community level assessment indicated a risk of low levels of chlorhexidine in aquatic habitats while conventional approaches did not.

Cost-effective experimental design to support modeling of concentration-response functions.

Modeling concentration-response function became extremely popular in ecotoxicology during the last decade. Indeed, modeling allows determining the total response pattern of a given substance. However, reliable modeling is consuming in term of data, which is in contradiction with the current trend in ecotoxicology, which aims to reduce, for cost and ethical reasons, the number of data produced during an experiment. It is therefore crucial to determine experimental design in a cost-effective manner. In this paper, we propose to use the theory of locally D-optimal designs to determine the set of concentrations to be tested so that the parameters of the concentration-response function can be estimated with high precision. We illustrated this approach by determining the locally D-optimal designs to estimate the toxicity of the herbicide dinoseb on daphnids and algae. The results show that the number of concentrations to be tested is often equal to the number of parameters and often related to the their meaning, i.e. they are located close to the parameters. Furthermore, the results show that the locally D-optimal design often has the minimal number of support points and is not much sensitive to small changes in nominal values of the parameters. In order to reduce the experimental cost and the use of test organisms, especially in case of long-term studies, reliable nominal values may therefore be fixed based on prior knowledge and literature research instead of on preliminary experiments.

Preliminary risk assessment database and risk ranking of pharmaceuticals in the environment.

There is increasing concern about pharmaceuticals entering surface waters and the impacts these compounds may have on aquatic organisms. Many contaminants, including pharmaceuticals, are not completely removed by wastewater treatment. Discharge of effluent into surface waters results in chronic low-concentration exposure of aquatic organisms to these compounds, with unknown impacts. Exposure of virulent bacteria in wastewater to antibiotic residues may also induce resistance, which could threaten human health. The purpose of this study was to provide information on pharmaceutical threats to the environment. A preliminary risk assessment database for common pharmaceuticals was created and put into a web-accessible database named "Pharmaceuticals in the Environment, Information for Assessing Risk" (PEIAR) to help others evaluate potential risks of pharmaceutical contaminants in the environment. Information from PEIAR was used to prioritize compounds that may threaten the environment, with a focus on marine and estuarine environments. The pharmaceuticals were ranked using five different combinations of physical-chemical and toxicological data, which emphasized different risks. The results of the ranking methods differed in the compounds identified as high risk; however, drugs from the central nervous system, cardiovascular, and anti-infective classes were heavily represented within the top 100 drugs in all rankings. Anti-infectives may pose the greatest overall risk based upon our results using a combination of factors that measure environmental transport, fate, and aquatic toxicity. The dataset is also useful for highlighting information that is still needed to assuredly assess risk.

Environmental assessment of ester-based lubricants after application.

GOAL, SCOPE AND BACKGROUND: Lubricants based on renewable resources are an environmentally friendly alternative to petrochemical products due to their better ecotoxicological performance and their excellent biodegradability. To improve the technical performance of lubricants, and to reduce friction and wear, the use of additives is nowadays obligatory. The collaborative research center SFB 442 aims at developing environmentally acceptable lubricants that facilitate the avoidance of these additives by transferring their function to suitable coatings. For a complete assessment of the ecological performance of these newly developed lubricants, the whole life cycle including production, application as well as disposal and fate in the environment is studied. In the following study the focus was on the application and its influence on the environmental behavior of the lubricant. The application of lubricants leads, among other things, to the intake of metals due to abrasion from tools, work pieces or mechanical components. Previous examinations indicated a possible influence of metals on the toxicity of eluates prepared from used lubricants (Erlenkaemper et al. 2005). To clarify if the apparent toxicity of used lubricants solely results from the intake of metals, the extractability of these metals from the oil matrix is determined. By combining chemical analyses with bioassays, the bioavailability of metals that are present in the extract is estimated. To further investigate the relevance of metals on toxicity, toxic units (TU) were calculated and related to the results of the bioassays. Interactions between the metals were investigated with aqueous mixtures of metal chlorides and calculations based on the concept of concentration addition and independent action. METHODS: A lubricant mixture was applied to a tribological test bench that simulates real conditions of use and extremely short time load, respectively. Samples were taken at particular times, water soluble fractions (WSF) of these fluids were prepared and dilution series were investigated in several bioassays. Concentration of metals and total organic carbon (TOC) were determined in the eluates. TUs were calculated according to Sprague (1970) and mixture toxicity was calculated according to the concept of concentration addition (Loewe and Muischnek 1926) and independent action (Bliss 1939). RESULTS: Analyses of the metal content of the lubricant and the eluates clearly revealed the availability of the metals in the aqueous extracts. Especially copper, zinc, nickel and chromium were found and their concentrations increased during the time of use. The water extractable fraction, e.g., of copper, rose from 8.8% to 45.3% of the total content in the lubricant after 33.5 hours of use. Tests performed with the algal growth inhibition assay and the luminescence inhibition assay revealed the uptake or absorption by the organisms and, thus, the bioavailability of the metals. The calculation of TUs partly indicated a possible influence of the metals on ecotoxicity of the eluates. Copper reached concentrations equal to or higher than the EC50 value of copper chloride in the growth inhibition assays with algae and Ps. putida as well in the immobilization assay with daphnids. TUs for copper are also larger than 1 for the algal growth inhibition assay. The EL50 values indicated that the luminescence inhibition assay was the most sensitive test system, with values between 4.7% and 9.6%. While the toxicity towards algae and V. fischeri in the growth inhibition assay decreased until both organisms were no longer influenced by the exposure, the EL50 values for the D. magna immobilization assay and the Ps. putida growth inhibition assay decreased with the progressing use of the lubricant. The tested metal salt mixtures showed that Ps. putida, algae and daphnids are the most sensitive organisms with EC50 values below 1 mg/l. DISCUSSION: Although the intake of metals mainly occurred via abrasion of particles, the results revealed the availability of these metals in water. The availability varied for each of the four metals. For both the algal growth inhibition assay and the luminescence inhibition assay, an uptake or absorption of the metals could be demonstrated. The calculated TUs indicated an effect in some bioassays that was not verified in the test itself. The influence of copper on V. fischeri, for example, was not confirmed while the EL50 values for the daphnid bioassay decreased, meaning that the eluates became more toxic with progressing use of the lubricant. The calculations of mixture toxicity based on the concept of concentration addition demonstrated good correlations with the tested metal mixtures, but also a different sensitivity of the organisms. CONCLUSIONS: The results presented here reveal the availability of those metals in water that were taken in during the use of the lubricant in a tribological test bench and, thus, have the possibility of interacting with the organisms. The availability of the metals in the bioassays was proven by chemical analyses. The calculation of TUs and the corresponding EL50 values, however, indicate different availabilities of the metals. The results of the metal salt mixtures show good correlations with calculations of mixture toxicity based on concentration addition. Moreover, the varying sensitivity of the organisms when exposed to eluates or metal mixtures indicates a different bioavailability of the metals and/or the presence of other compounds that exert toxic action. RECOMMENDATIONS AND PERSPECTIVES: For further investigations, the organic oil matrix and its influence on the toxicity have to be taken into account. The toxicity of the eluates may not only be due to metals; additional effects could arise from changes in the lubricant itself.

Biomonitoring: an appealing tool for assessment of metal pollution in the aquatic ecosystem.

Wide occurrence of aquatic metal pollution has caused much attention. Biomonitoring offers an appealing tool for the assessment of metal pollution in aquatic ecosystem. The bioindicators including algae, macrophyte, zooplankton, insect, bivalve mollusks, gastropod, fish, amphibian and others are enumerated and compared for their advantages and disadvantages in practical biomonitoring of aquatic metal pollution. The common biomonitoring techniques classified as bioaccumulation, biochemical alterations, morphological and behavior observation, population- and community-level approaches and modeling are discussed. The potential applications of biomonitoring are proposed to mainly include evaluation of actual aquatic metal pollution, bioremediation, toxicology prediction and researches on toxicological mechanism. Further perspectives are made for the biomonitoring of metal pollution in aquatic ecosystem.