Can natural levels of Al influence Cu speciation and toxicity to Daphnia magna in a Swedish soft water lake?

It is well known that chemical parameters, such as natural organic matter (NOM), cation content and pH may influence speciation and toxicity of metals in freshwaters. Advanced bioavailability models, e.g. Biotic Ligand Models (BLMs), can use these and other chemical parameters to calculate site specific recommendations for metals in the aquatic environment. However, since Al is not an input parameter in the BLM v.2.2.3, used in this study, there could be a discrepancy between calculated and measured results in Al rich waters. The aim of this study was to evaluate if the presence of Al in a circumneutral (pH ∼6) soft humic freshwater, Lake St. Envättern, will affect the Cu speciation and thereby the toxicity to the cladoceran Daphnia magna. The results show a statistically significant increase in the free Cu(2+) concentration with Al additions and that measured levels of Cu(2+) significantly differed from BLM calculated levels of Cu(2+). Furthermore, there was also a statistically significant elevated acute toxic response to D. magna at low additions of Al (10 µg/L). However, since the large difference between calculated and measured Cu(2+) resulted in a significant but minor (factor of 2.3) difference between calculated and measured toxicity, further studies should be conducted in Al rich soft waters to evaluate the importance of adding Al as an input parameter into the BLM software.

Evaluation of current copper bioavailability tools for soft freshwaters in Sweden.

The Water Framework Directive (WFD) in Europe calls for an improved aquatic ecological status. Biotic ligand models (BLM) have been suggested as a possible tool assisting in the regulatory process. The aim of this study was therefore to investigate the applicability of BLM under the WFD to set environmental quality standards (EQS), in particular regarding copper in Swedish freshwaters of which many are softer than those used for model calibration. Three different BLMs, one acute and two chronic, were applied to water chemistry data from 926 lakes and 51 rivers (1530 data entries) and evaluated with respect to their calibration range for input parameters. In addition, the predicted no-effect concentration (PNEC) for copper was calculated. From the 1530 data entries, 750 ended up outside of the BLM calibration range, when looking at the chemical parameters Ca(2+), alkalinity, pH and DOC, primarily due to low carbonate alkalinity. Furthermore, the calculated Cu PNECs were higher than the suggested Swedish limit for Cu (4µgL(-1)) in surface waters for 98% and 99% of the cases concerning lakes and rivers, respectively. To conclude, our findings show that water chemical characteristics outside of the calibration ranges are quite common in Sweden and that the investigated models differ in how they calculate toxicity concerning Cu under these conditions. As a consequence, additional work is required to validate the BLMs by use of bioassays with representative species of soft waters. Such results will show if these models can be used outside of their calibration ranges and also which of the models that gives the most reliable results.

Predictions of Cu toxicity in three aquatic species using bioavailability tools in four Swedish soft freshwaters.

BACKGROUND: The EU member countries are currently implementing the Water Framework Directive to promote better water quality and overview of their waters. The directive recommends the usage of bioavailability tools, such as biotic ligand models (BLM), for setting environmental quality standards (EQS) for metals. These models are mainly calibrated towards a water chemistry found in the south central parts of Europe. However, freshwater chemistry in Scandinavia often has higher levels of DOC (dissolved organic carbon), Fe and Al combined with low pH compared to the central parts of Europe. In this study, copper (Cu) toxicities derived by two different BLM software were compared to bioassay-derived toxicity for Pseudokirchneriella subcapitata, Daphnia magna and D. pulex in four Swedish soft water lakes. RESULTS: A significant under- and over prediction between measured and BLM calculated toxicity was found; for P. subcapitata in three of the four lakes and for the daphnids in two of the four lakes. The bioassay toxicity showed the strongest relationship with Fe concentrations and DOC. Furthermore, DOC was the best predictor of BLM results, manifested as positive relationships with calculated LC50 and NOEC for P. subcapitata and D. magna, respectively. CONCLUSION: Results from this study indicate that the two investigated BLM softwares have difficulties calculating Cu toxicity, foremost concerning the algae. The analyses made suggest that there are different chemical properties affecting the calculated toxicity as compared to the measured toxicity. We recommend that tests including Al, Fe and DOC properties as BLM input parameters should be conducted. This to observe if a better consensus between calculated and measured toxicity can be established.

Influence of leaching conditions for ecotoxicological classification of ash.

The Waste Framework Directive (WFD; 2008/98/EC) states that classification of hazardous ecotoxicological properties of wastes (i.e. criteria H-14), should be based on the Community legislation on chemicals (i.e. CLP Regulation 1272/2008). However, harmonizing the waste and chemical classification may involve drastic changes related to choice of leaching tests as compared to e.g. the current European standard for ecotoxic characterization of waste (CEN 14735). The primary aim of the present study was therefore to evaluate the influence of leaching conditions, i.e. pH (inherent pH (∼10), and 7), liquid to solid (L/S) ratio (10 and 1000 L/kg) and particle size (<4 mm, <1 mm, and <0.125 mm), for subsequent chemical analysis and ecotoxicity testing in relation to classification of municipal waste incineration bottom ash. The hazard potential, based on either comparisons between element levels in leachate and literature toxicity data or ecotoxicity testing of the leachates, was overall significantly higher at low particle size (<0.125 mm) as compared to particle fractions <1mm and <4mm, at pH 10 as compared to pH 7, and at L/S 10 as compared to L/S 1000. These results show that the choice of leaching conditions is crucial for H-14 classification of ash and must be carefully considered in deciding on future guidance procedures in Europe.

An ecotoxicological evaluation of aged bottom ash for use in constructions.

Municipal and Industrial Solid Waste Incineration (MISWI) bottom ash is mainly deposited in landfills, but natural resources and energy could be saved if these ash materials would be used in geotechnical constructions. To enable such usage, knowledge is needed on their potential environmental impact. The aim of this study was to evaluate the ecotoxicity of leachates from MISWI bottom ash, aged for five years, in an environmental relevant way using a sequential batch leaching method at the Liquid/Solid-ratio interval 1-3, and to test the leachates in a (sub)chronic ecotoxicity test. Also, the leachates were characterized chemically and with the technique of diffusive gradients in thin films (DGTs). By comparing established ecotoxicity data for each element with chemically analysed and labile concentrations in the leachates, potentially problematic elements were identified by calculating Hazard Quotients (HQ). Overall, our results show that the ecotoxicity was in general low and decreased with increased leaching. A strong correspondence between calculated HQs and observed toxicity over the full L/S range was observed for K. However, K will likely not be problematic from a long-term environmental perspective when using the ash, since it is a naturally occurring essential macro element which is not classified as ecotoxic in the chemical legislation. Although Cu was measured in total concentrations close to where a toxic response is expected, even at L/S 3, the DGT-analysis showed that less than 50% was present in a labile fraction, indicating that Cu is complexed by organic ligands which reduce its bioavailability.

In the shadow of the Cosmetic Directive--inconsistencies in EU environmental hazard classification requirements for UV-filters.

UV-filters are chemicals with potentially environmental hazardous properties. In the European Union (EU), UV-filters contained in sunscreen products are currently regulated by the Cosmetic Directive (from July 2013 by the Cosmetic Products Regulation). Environmental hazard classifications according to the regulation on classification, labelling and packaging of substances and mixtures (CLP) must be determined for UV-filters contained in industrial chemical products, whereas UV-filters contained in sunscreens are exempted from CLP. In this study we determined the potential environmental hazard classifications of UV-filters and sunscreen products if the CLP regulation was to be required for cosmetic products. Two sunscreen products were evaluated in accordance with the aquatic environmental hazard criteria for mixtures. The results highlight that the inconsistencies in the current EU regulation of UV filters hamper the risk management of environmental hazards of UV filters used in cosmetic products. Almost 50% of the investigated UV-filters approved for use in cosmetic products on the European market according to the current Cosmetic Directive were identified to meet the CLP classification as being hazardous to the aquatic environment. Assuming a worst-case scenario, the two examined sunscreens could both be classified as hazardous to the aquatic environment with long-lasting effects according to CLP classification criteria. Hence, if the CLP regulation was applicable to sunscreen products, both brands could potentially be labelled with the environmental hazard pictogram and associated hazard and precautionary statements. Including cosmetic products, and thereby sunscreens, in the CLP regulation would contribute to a more harmonized and transparent regulation of potentially hazardous substances on the EU market.

Improved understanding of key elements governing the toxicity of energy ash eluates.

Ash from incinerated waste consists mainly of a complex mixture of metals and other inorganic elements and should be classified based on its inherent hazardous effects according to EUs Waste Framework Directive. In a previous study, we classified eight eluates from ash materials from Swedish incineration plants, both chemically and ecotoxicologically (using bacteria, algae, crustacean and fish). Based on measured concentrations in the eluates together with literature acute toxicity data on the crustacean Nitocra spinipes we identified six elements (i.e. Zn, Cu, Pb, Al, K and Ca) potentially responsible for the observed ecotoxicity. However, comparing the used test methods with N. spinipes, the acute test was relatively insensitive to the eluates, whereas the (sub)chronic test (i.e. a partial life cycle test, investigating larval development ratio) was very sensitive. The overall aim of this follow-up study was to verify if the pinpointed elements could be responsible for the observed (sub)chronic toxicity of the eluates. Individual effect levels (i.e. NOEC values) for these six elements were therefore generated using the (sub)chronic test. Our results show that for six of the eight eluates, the observed ecotoxicity can be explained by individual elements not classified as ecotoxic (Al, K and Ca) according to chemical legislation. These elements will not be considered using summation models on elements classified as ecotoxic in solid material for the classification of H-14, but will have significant implications using ecotoxicological test methods for this purpose.

Reporting and evaluation criteria as means towards a transparent use of ecotoxicity data for environmental risk assessment of pharmaceuticals.

Ecotoxicity data with high reliability and relevance are needed to guarantee the scientific quality of environmental risk assessments of pharmaceuticals. The main advantages of a more structured approach to data evaluation include increased transparency and predictability of the risk assessment process, and the possibility to use non-standard data. In this collaboration, between the research project MistraPharma and the German Federal Environment Agency, a new set of reporting and evaluation criteria is presented and discussed. The new criteria are based on the approaches in the literature and the OECD reporting requirements, and have been further developed to include both reliability and relevance of test data. Intended users are risk assessors and researchers performing ecotoxicological experiments, but the criteria can also be used for education purposes and in the peer-review process for scientific papers. This approach intends to bridge the gap between the regulator and the scientist's needs and way of work.

An ecotoxicological approach for hazard identification of energy ash.

Within the EU, ash should be classified by its inherent hazardous effects under criterion H-14 (ecotoxic) in the Directive on waste (2008/98/EC). Today, however, there are no harmonized quantitative criterions for such a classification, but it is stated that biological test systems can be used. In this study seven ash materials were leached and characterized, both biologically and chemically. The objectives were to evaluate if (a) clear concentration-response relationships could be achieved for the selected toxicity tests (bacteria, algae, crustacean and fish), (b) some test(s) are generally more sensitive and (c) the toxic responses were consistent with the chemical analyzes. Interestingly, our results indicate that high concentrations of non-hazardous components (Ca, K) influenced the toxicity of almost all ash eluates, whereas hazardous components (e.g. Zn, Pb) only influenced the toxicity of the eluates ranked as most hazardous. If considering both hazardous and non-hazardous substances, the observed toxic responses were relatively consistent with the chemical analyzes. Our results further showed that the (sub)chronic tests were much more sensitive than the acute tests. However, the use of extrapolation factors to compensate for using the less sensitive acute tests will likely lead to either over- or underestimations of toxicity. Our recommendation is therefore that classification of waste according to H-14 should be based on (sub)chronic test data. Finally, given that treatment of the eluates prior to toxicity testing has a major significance on the concentration and speciation of released substances, further studies are needed in order to propose a relevant testing scheme.

Chemical risks and consumer products: the toxicity of shoe soles.

The European chemicals legislation, REACH, aims to ensure a high level of protection of human health and the environment. However, chemicals included in consumer products are covered only to a very limited extent even though they constitute the main source of chemical emissions. Shoes are large volume products and the overall aim of the present study was to study the ecotoxicological effects of three types of shoe soles and relate these effects to chemical emissions to the aquatic environment. The shoe soles were abraded and leached in water for 29 days and the alga Ceramium tenuicorne and the crustacean Nitocra spinipes were exposed to different concentrations of the leachate. Chemical analyses were performed to determine the chemical contents of the leachate. The main conclusions are that the shoe soles contain substances that are toxic to both test organisms, and that the toxicity is mainly explained by the presence of zinc. The estimated concentration of zinc from shoe soles in storm water runoff is low, but it still contributes to the overall load of chemicals and metals in the environment. The outlined test procedures may, in our view, provide a useful screening tool for assessing the risk that chemicals in consumer articles pose to the environment.

Toxic substances and reproductive disorders in Baltic fish and crustaceans.

In the Baltic Sea ecosystem reproductive disorders have occurred in top consumers such as seals and some fish-eating birds, due to biomagnification of toxic substances, e.g. DDT and PCBs. Reproductive disturbances have also affected fish during the last 25 years. However, there is no strong evidence that toxic substances have caused these problems. Rather, the disorders seem to result from a combination of two or more biotic or abiotic factors. The M74 syndrome, which kills fry of salmon and sea trout, is characterized by a deficiency of thiamine (vitamin B1). Several factors may contribute to the thiamine deficiency, including the diet of salmon in the sea and halogenated organic compounds. Cod do not develop M74, and poor cod recruitment is mainly due to poor oxygen conditions in the spawning areas in combination with overfishing. Toxic compounds in pulp-mill effluents retard gonadal development in perch, but the mechanisms and the active substances have not been identified. Recruitment problems in perch in the coastal waters outside some pulp mills may also be explained by a lack of food items for juvenile fish, rather than reproductive failure. There are very limited data on reproductive disorders in crustaceans from the Baltic Sea. Most data come from studies of the benthic amphipod Monoporeia affinis, which has been used in monitoring programs. Several signs of reproductive disorder have been reported in this amphipod, e.g. malformation and death of embryos, and asynchronous maturation of males and females.

Oestrogens have no hormonal effect on the development and reproduction of the harpacticoid copepod Nitocra spinipes.

In recent years, reports have described endocrine-disruptive effects of environmental oestrogens in fish, but little is known about similar effects in crustaceans. The objective of the present study was therefore to examine whether the oestrogens 17-beta-oestradiol, 17-alpha-ethynylestradiol and diethylstilbestrol (DES), could affect mortality, larval development rate, fecundity and sex ratio in the sexually reproducing harpacticoid copepod Nitocra spinipes. Newly released nauplii (<24-h old) were exposed to 1/1,000, 1/100 and 1/10 (nominal concentrations) of each oestrogen's 96 h-LC50 value for < or = 18 days at 22 +/- 1 degrees C. The percentage of gravid females and the number of developed copepodites were both reduced at 0.03 mg l(-1) DES, although the latter response was not significant. None of the other two oestrogens induced any measurable effects. Since the only observed significant response appeared at a DES concentration no more than 10 times below the 96 h-LC50 value, there is no evidence of endocrine-disruptive activity in N. spinipes exposed to oestrogens.

Prosthetic rehabilitation in bilateral high above elbow amputation.

Rehabilitation in patients with bilateral high above elbow amputation presents a considerable prosthetic problem. A patient with high upper arm amputations after a high-voltage injury is presented. He was successfully fitted with multifunctional myoelectric hand prostheses. The problems in rehabilitation of adult bilateral arm amputees are discussed and the value of fitting these patients with electrically powered prostheses is assessed. The balance between technical and clinical aspects is discussed in relation to patient acceptance. In our case good acceptance and functional benefit was noted. The fact is stressed that the bilateral upper extremity amputee can regain considerable physical function with the fitting of suitable prostheses, even if the limb remnants are short and provide little or no function. An extensive team approach at specialized centres will favour the results.