Priority assessment of toxic substances in life cycle assessment. Part I: calculation of toxicity potentials for 181 substances with the nested multi-media fate, exposure and effects model USES-LCA

Toxicity potentials are standard values used in life cycle assessment (LCA) to enable a comparison of toxic impacts between substances. In most cases, toxicity potentials are calculated with multi-media fate models. Until now, unrealistic system settings were used for these calculations. The present paper outlines an improved model to calculate toxicity potentials: the global nested multi-media fate, exposure and effects model USES-LCA. It is based on the Uniform System for the Evaluation of Substances 2.0 (USES 2.0). USES-LCA was used to calculate for 181 substances toxicity potentials for the six impact categories freshwater aquatic ecotoxicity, marine aquatic ecotoxicity, freshwater sediment ecotoxicity, marine sediment ecotoxicity, terrestrial ecotoxicity and human toxicity, after initial emission to the compartments air, freshwater, seawater, industrial soil and agricultural soil, respectively. Differences of several orders of magnitude were found between the new toxicity potentials and those calculated previously.     

Priority assessment of toxic substances in life cycle assessment. Part II: assessing parameter uncertainty and human variability in the calculation of toxicity potentials

Toxicity potentials are standard values used in life cycle assessment (LCA) to enable a comparison of toxic impacts between substances. This paper presents the results of an uncertainty assessment of toxicity potentials that were calculated with the global nested multi-media fate, exposure and effects model USES-LCA. The variance in toxicity potentials resulting from input parameter uncertainties and human variability was quantified by means of Monte Carlo analysis with Latin Hypercube sampling (LHS). For Atrazine, 2,3,7,8-TCDD and Lead, variation, expressed by the ratio of the 97.5%-ile and the 2.5%-ile, ranges from about 1.5 to 6 orders of magnitude. The major part of this variation originates from a limited set of substance-specific input parameters, i.e. parameters that describe transport mechanisms, substance degradation, indirect exposure routes and no-effect concentrations. Considerable correlations were found between the toxicity potentials of one substance, in particular within one impact category. The uncertainties and correlations reported in the present study may have a significant impact on the outcome of LCA case studies.     

Implications of geographic variability on Comparative Toxicity Potentials of Cu, Ni and Zn in freshwaters of Canadian ecoregions

Current methods of estimating potential environmental impacts of metals in hazard and Life Cycle Impact Assessment (LCIA) do not consider differences in chemistry and landscape properties between geographic sites. Here, we developed and applied a model for regional aquatic impact characterization of metals using an updated method for estimating environmental fate factor (FF), bioavailability factor (BF) and aquatic ecotoxicity factor (EF). We applied the model to analyze differences in Comparative Toxicity Potentials (CTPs) of Cu, Ni and Zn for 24 Canadian ecoregions. The combined impacts of regional variability in ambient chemistry (in particular DOC, pH and hardness) and landscape properties (water residence time) can change the CTPs of these metals for freshwater by up to three orders of magnitude and change the relative ranking of metal hazard between ecoregions. Variation among Canadian freshwater chemistries and landscape characteristics influence the FFs within two orders of magnitude, BFs within two orders of magnitude for Ni and Zn and four orders of magnitude for Cu, and EFs within one order of magnitude. Sensitivity of metal FFs to environmental parameters alone spans three orders of magnitude when a constant water chemistry was used for all ecoregions. These results indicate that application of regionalised metal CTPs can have a significant influence in the analysis of ecotoxicological impacts in the life cycle assessment of products and processes.     

Life cycle toxicity assessment of pesticides used in integrated and organic production of oranges in the Comunidad Valenciana, Spain

The relative impacts of 25 pesticides including acaricides, fungicides, herbicides, insecticides, and post-harvest fungicides, used in the production of oranges in Spain were assessed with current life cycle impact assessment (LCIA) tools. Chemical specific concentrations were combined with pesticide emission data and information on chemical toxicity to assess human toxicity and freshwater ecotoxicity impacts. As a case study, the relative impacts of two orange production systems in the region of Valencia, integrated pest management (IP) and organic production (OP), were assessed. The evaluation of active ingredients showed that on average acaricides have the highest human toxicity impact scores, while for freshwater ecotoxicity insecticides show the highest impact. In both impact categories the lowest impact scores were calculated for herbicides. In the production of 1 kg of orange fruits, where several kinds of pesticides are combined, results show that post-harvest fungicides can contribute more than 95% to the aggregate human toxicity impacts. More than 85% of aquatic ecotoxicity is generated by fungicides applied before harvest. The potential to reduce impacts on freshwater ecosystems is seven orders of magnitude, while impacts on human health can be reduced by two orders of magnitude. Hence, this stresses the importance of a careful pre-selection of active ingredients. In both impact categories, organic production represents the least toxic pest-control method.     

Temperature and salinity effects on the toxicity of common pesticides to the grass shrimp,Palaemonetes pugio

This study investigated the effects of increased temperature and salinity, two potential impacts of global climate change, on the toxicity of two common pesticides to the estuarine grass shrimp, Palaemonetes pugio. Larval and adult grass shrimp were exposed to the fungicide chlorothalonil and the insecticide Scourge® under standard toxicity test conditions, a 10°C increase in temperature, a 10 ppt increase in salinity, and a combined increased temperature and salinity exposure. Toxicity of the fungicide chlorothalonil increased with temperature and salinity. Toxicity of the insecticide Scourge® also increased with temperature; while increased salinity reduced Scourge® toxicity, but only in adult shrimp. These findings suggest that changes in temperature and salinity may alter the toxicity of certain pesticides, and that the nature of the effect will depend on both the organism's life stage and the chemical contaminant. Standard toxicity bioassays may not be predictive of actual pesticide toxicity under variable environmental conditions, and testing under a wider range of exposure conditions could improve the accuracy of chemical risk assessments.     

Toxicity profile of labile preservative bronopol in water: the role of more persistent and toxic transformation products

Transformation products usually differ in environmental behaviors and toxicological properties from the parent contaminants, and probably cause potential risks to the environment. Toxicity evolution of a labile preservative, bronopol, upon primary aquatic degradation processes was investigated. Bronopol rapidly hydrolyzed in natural waters, and primarily produced more stable 2-bromo-2-nitroethanol (BNE) and bromonitromethane (BNM). Light enhanced degradation of the targeted compounds with water site specific photoactivity. The bond order analysis theoretically revealed that the reversible retroaldol reactions were primary degradation routes for bronopol and BNE. Judging from toxicity assays and the relative pesticide toxicity index, these degradation products (i.e., BNE and BNM), more persistent and higher toxic than the parent, probably accumulated in natural waters and resulted in higher or prolonging adverse impacts. Therefore, these transformation products should be included into the assessment of ecological risks of non-persistent and low toxic chemicals such as the preservative bronopol.     

Concentration of Organochlorine Pollutants in Surface Waters of the Central European Biosphere Reserve Krivoklatsko (8 pp)

Background, Aim and Scope The article is focused on dioxin, furan, PCB and organochlorine pesticide monitoring in the surface waters of the Central European, protected natural reserve Krivoklatsko, under the UNESCO programme Man and Biosphere. Persistent compounds are presently transported via different means throughout the entire world. This contamination varies significantly between sites. This raises the question of what constitutes the naturally occurring background levels of POPs in natural, unpolluted areas, but which are close to industrialised regions. Information of real background POP contamination can be of high value for risk assessment management of those sites evidently polluted and for the defining of de-contamination limits. Preserved areas should not be seen as isolated regions in which the impacts of human activities and natural factors are either unexpected or overlooked. Every ambient region, even those protected by a law or other means, are still closely connected to neighbouring human developed and impacted areas, and are therefore subject to this anthropogenic contamination. These areas adjacent to natural reserves are sources of diverse substances, via entry of air, water, soil and/or biota. After an extended period of industrial activities, organochlorine pollutants, even those emitted in trace concentrations have reached detectable levels. For future research and for the assessment of environmental changes, present levels of contamination would be of high importance. This work publishes data of the contamination with organochlorine pollutants of this natural region, where biodiversity and ecological functions are of the highest order. Materials and Methods: Semipermeable membrane devices (SPMDs) were utilised as the sampling system. SPMDs were deployed in two small creeks and one water reservoir selected in the central part of the Krivoklatsko Natural Reserve, where it could be expected that any possible contamination by POPs would be lowest. The exposed SPMDs were analysed both for chemical contents of POPs and for toxicity properties. The chemical analyses of dibenzo-dioxins, dibenzo-furans, PCBs and OCPs were analysed by GC/MS/MS on GCQ or PolarisQ (Thermoquest). Toxicity bioassays were performed on the alga Desmodesmus subspicatus, bacteria Vibrio fischeri and crustacean Daphnia magna. All toxicity data were expressed as the effective volume Vtox. Vtox is a toxicity parameter, the determination of which is independent of SPMD deployment time and pre-treatment dilution (unlike, for example, the EC50 of the SPMD extract). Results: The following chemical parameters were monitored: 1) tetra, penta, hexa and hepta dibenzo-p-dioxins and furans; 2) all those detectable from tri- through deca-polychloriated biphenyls (PCBs) and 3) a group of organochlorine pesticides: hexachlorobenzene and isomers of hexachlorocyclohexane, DDE, DDD and DDT. The concentrations of dioxins and furans on the assessed sites varied from under detection levels up to 7 pg.l-1; PCBs were detected in a sum concentration up to 2.8 ng.l-1; and organochlorine pesticides up to 346 pg.l-1. The responses of bioassays used were very low, with the values obtained for Vtox being under 0.03 l/d. Discussion: Toxicity testing showed no toxicity responses, demonstrating that the system used is in coherence with the ecological status of the assessed sites. Values of Vtox were under the critical value – showing no toxicity. The PCA of chemical analysis data and toxicity responses resulted in no correlations between these two groups of parameters. This demonstrated that the present level of contamination has had no direct adverse effects on the biota. Conclusions: The concentration values of six EPA-listed, toxic dioxins and sums of tetra-hepta dioxins; nine EPA toxic dibenzofurans and the sums of tetra-hepta bibenzofurans are presented together with all tri-deka PCBs and organochlorine pesticides (alfa-, beta-, gama-, delta-HCH, HCB, opDDE, ppDDE, opDDD, ppDDD, opDDT, ppDDT). These values represent possible current regional natural background values of these substances monitored within the Central European region, with no recorded adverse effects on the freshwater ecosystem (up until the present time). Recommendations and Perspectives: Assessment of dioxins, furans and other organochlorine compounds within natural reserves can be important for the monitoring of human-induced impacts on preserved areas. No systematic monitoring of these substances in areas not directly affected by industry has generally been realised. There is a paucity of data of the presence of any of these substances within natural regions. Further monitoring of contamination of both soil and biota by dioxins and furans in preserve regions is needed and can be used for future monitoring of man-made activities and/or accidents. Semipermeable membrane devices proved to be a very good sampling system for the monitoring of trace concentrations of ambient organochlorine compounds. Toxicity evaluation using the Vtox concept demonstrated that those localities assessed expressed no toxicity.     

Framework for the environmental impact assessment of operational shipping

Shipping is an important source of pollution affecting both atmospheric and aquatic environments. To allow for efficient mitigation of environmental degradation, it is essential to know the extent of the impacts of shipping in relation to other sources of pollution. Here, we give a perspective on a holistic approach to studies of the environmental impacts of operational shipping through presentation of an assessment framework developed and applied on a case of shipping in the Baltic Sea. Through transfer of knowledge and concepts, previously used in assessments of air pollution, now applied to assessments of marine pollution and underwater noise, the horizon of understanding of shipping-related impacts is significantly improved. It identifies the main areas of environmental degradation caused by shipping and potential improvements through legislation and technological development. However, as the vast majority of contaminants discharged into the sea are not routinely monitored and assessed, the links between pressure of contaminants from shipping and environmental state and impacts will not be caught in the current environmental regulatory frameworks.     

Risk assessment approaches for ecosystem responses to transient pollution events in urban receiving waters

Alternative risk assessment approaches are reviewed for the evaluation of the ecological status and health of urban receiving waters subject to intermittent pollution events. Performance-based criteria founded on exceedance probabilities and related to the end-of-pipe discharge of chemical-specific substances comprise the conventional basis for setting regulatory standards in both North America and Europe. The difficulties and limitations of this approach, particularly in identifying realistic chronic, sub-lethal toxic risks arising from complex effluents are discussed. The potential role of Toxicity Based Criteria (TBC) for setting ecological consent limits for stormwater effluents is considered and the capabilities and limitations of Direct Toxicity Assessment (DTA) are identified. The inability of DTA procedures to satisfactorily evaluate chronic, sub-lethal risks has led to increasing interest in the potential use of in-situ biomarker techniques for the fingerprinting of stress-response properties as a means of diagnosing risk assessment for integrated urban runoff management.     

Toxic substances in rivers and streams

Many of the toxic substances entering freshwaters today are those which were present several decades ago, but others have become significant recently. The effects of toxicants in flowing waters are modified by unidirectional transport and dispersion which afford the potential for a degree of 'self-purification'. The chemical quality of the receiving water also affects toxicity. Biological factors also contribute to the ultimate effect of pollutants. The potential for accumulation of toxic substances within tissues increases the significance of certain pollutants which may be present in water even though ambient concentrations are very low. The biota of flowing waters may be restored, following catastrophic entry of pollutants, by drift from unaffected regions upstream. The range of potential toxic substances is very extensive and includes inorganic poisons, organic poisons, heavy metals, pesticides and PCBs. Metals, pesticides and PCBs have the greatest potential for bioaccumulation. Few generalisations can be made regarding the effects of toxic substances on the biota. Each species tends to respond to different toxicants in different ways and even at different stages in its life-history. Toxicity tests conducted under controlled laboratory conditions sometimes produce conflicting results: it is not then to be unexpected that field observations should sometimes vary widely. Determinations of toxicity in laboratory tests must be applied with caution to field conditions and it is not wise to extrapolate findings to other species or environments.     

Efficacy and toxicity of self-polishing biocide-free antifouling paints

The ban on harmful substances in antifouling paints requires the development of new antifouling strategies. Alternatives should be as effective as conventional paints but of lower toxicity. In the present study two commercially available, self-polishing antifouling paints were examined in order to get information on their antifouling properties and toxicological potential. Efficacy was shown in settlement assays with the marine barnacle species Balanus amphitrite, however, efficacy was related to toxic effects observed on target and non-target organisms. Toxicity of the paint extracts was concentration-dependent and differed according to the paint and the species investigated. Toxicity could at least partially be attributed to zinc leached from the paints. Effects of a water-soluble paint were more pronounced in larvae of B. amphitrite, Artemia salina and in the green algae Dunaliella tertiolecta. Embryos of the freshwater species Danio rerio and Vibrio fisheri were more affected by a paint based on organic solvents.     

Aquatic fate assessment of the polycyclic musk fragrance HHCB. Scenario and variability analysis in accordance with the EU risk assessment guidelines

By means of the environmental fate and distribution models laid down in the Technical Guidance Documents (TGD) and implemented in the European Union System for the Evaluation of Substances (EUSES) environmental concentrations of the polycyclic musk fragrance HHCB (1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-[g]-2- benzopyrane; trade name: e.g. Galaxolide) were calculated for the aquatic environment under consideration of various scenarios. The results were then compared to monitoring data from the region of North Rhine-Westphalia (River Ruhr). An uncertainty analysis was carried out to determine sensitive parameters, to integrate environmental variability and to confirm the model's calculations. The standard scenario of EUSES overestimates the measured concentrations, which confirms the conservative nature of the calculations. The regional-specific scenarios lead to lower deviations from the measured values than the standard scenario. Deviations range from one to two orders of magnitude in the effluent of sewage treatment plants; they amount to one order of magnitude for surface water concentrations on a local scale and conform to monitoring data on a regional scale. The use of measured bioconcentration factors for fish instead of estimated ones reduces deviations remarkably. The investigation reveals that unrealistic worst-case calculations of HHCB can at best be ameliorated by the application of more realistic emission rates and measured bioconcentration factors. The use of regional-specific parameters also diminishes the deviations of the calculations from the measured concentrations.     

Aquatic toxicity of two Corexit dispersants

The oil spill dispersants, Corexit 9500 and Corexit 9527 have low to moderate toxicity to most aquatic species in laboratory tests. Toxicity estimates are significantly affected by test variables such as species, lifestage, exposure duration, and temperature. Aquatic toxicity data generated from spiked, declining exposures (107 min half-life) are more reflective of actual dispersant use conditions. Decisions to use oil spill response chemicals should not be based solely on aquatic toxicity. Factors to consider include product effectiveness, toxicity of dispersed oil, species/habitats requiring priority protection, and recovery potential of sensitive habitats and populations. An environmental risk assessment approach is recommended where dispersant toxicity data generated under environmentally relevant exposures are compared to estimated environmental concentrations of dispersants.     

Eco-certification of Farmed Seafood: Will it Make a Difference?

Eco-certification is widely considered a tool for reducing environmental impacts of aquaculture, but what are the likely environmental outcomes for the world’s fastest growing animal-food production sector? This article analyzes a number of eco-certification schemes based on species choice, anticipated share of the global seafood market, size of eligible producers, and targeted environmental impacts. The potential of eco-certification to reduce the negative environmental impacts of aquaculture at scale presently appears uncertain as: (a) certification schemes currently focus on species predominantly consumed in the EU and US, with limited coverage of Asian markets; (b) the share of certified products in the market as currently projected is too low; (c) there is an inequitable and non-uniform applicability of certification across the sector; (d) mechanisms or incentives for improvement among the worst performers are lacking; and (e) there is incomplete coverage of environmental impacts, with biophysical sustainability and ecosystem perspectives generally lacking.     

Toxicity testing with luminescent bacteria – Characterization of an automated method for the combined assessment of acute and chronic effects

The luminescent bacteria test according to EN ISO 11348 is frequently applied in (eco) toxicity testing and is applicable for a huge variety of environmental and industrial samples. A big disadvantage of this method is the very short exposure time, which is expressed in a low sensitivity in regard to substances with a delayed effect. Chronic effects, i.e. interference with cell growth, cannot be assessed with this conventional standard method. The goal of this research was to develop an automated testing system for long term toxicity towards the luminescent bacteria Vibrio fischeri by implementing microtitration-based instrumentation. The optimized method, hereinafter referred to as “kinetic luminescent bacteria test”, can be described as a miniaturized combination of the conventional short-term luminescence inhibition test according to EN ISO 11348 and the Photobacterium phosphoreum growth inhibition test (DIN 38412-37). The validation procedure included the evaluation of six reference compounds (3,4-Dichloroaniline, 3,5-Dichlorophenol, Chloramphenicol, Streptomycin sulfate, Potassium dichromate, Zinc sulfate heptahydrate) and three different endpoints that are acute luminescence inhibition (acute LI) after 30 min, chronic luminescence inhibition (chronic LI) after 24 h and growth inhibition (GI) after 14 h. The optimized method allows the assessment of acute and chronic effects within one test, by what a misinterpretation of the toxicity of substances with delayed bacterial toxicity can be prevented, without abandoning most of the advantages of the conventional short-term test. Therefore, the kinetic luminescent bacteria test is exceptional as an initial screening test for environmental samples or substances with unknown (eco) toxicological characteristics.     

Evidence for the "grasshopper" effect and fractionation during long-range atmospheric transport of organic contaminants

Although there is indisputable evidence that long-range atmospheric transport (LRAT) of organic contaminants occurs on a global scale, uncertainties remain about the detailed mechanism and extent of this phenomenon as well as the physical-chemical properties which facilitate LRAT. In this study, we discuss how mass balance models and monitoring data can contribute to a fuller understanding of the mechanism and extent of LRAT. Specifically we address the issues of "grasshopping" or "hopping" (the extent to which molecules are subject to multiple hops as distinct from a single emission-deposition event) and "global fractionation" (the differing behavior of chemicals as they are transported). It is shown that simple mass balance models can be used to assist the interpretation of monitoring data while also providing an instrument that can be used to assess the LRAT potential and the extent of hopping that organic substances may experience. The available evidence supports the notion that many persistent organic pollutants experience varying degrees of "hopping" during their environmental journey and as a consequence become fractionated with distance from source.     

Comparative environmental impacts of glyphosate and conventional herbicides when used with glyphosate-tolerant and non-tolerant crops

The introduction of glyphosate-tolerant (GT) crops is expected to mitigate the environmental contamination by herbicides because glyphosate is less persistent and toxic than the herbicides used on non-GT crops. Here, we compared the environmental balances of herbicide applications for both crop types in three French field trials. The dynamic of herbicides and their metabolites in soil, groundwater and air was simulated with PRZM model and compared to field measurements. The associated impacts were aggregated with toxicity potentials calculated with the fate and exposure model USES for several environmental endpoints. The impacts of GT systems were lower than those of non-GT systems, but the accumulation in soils of one glyphosate metabolite (aminomethylphosphonic acid) questions the sustainability of GT systems. The magnitude of the impacts depends on the rates and frequency of glyphosate application being highest for GT maize monoculture and lowest for combination of GT oilseed rape and non-GT sugarbeet crops.     

Comparative toxicity of acrylic acid to marine and freshwater microalgae and the significance for environmental effects assessments.

In this study, we compared the sensitivity of freshwater and marine organisms to two structurally similar substances, acrylic acid and methacrylic acid. Reported acute toxicity data (L(E)C50-values) for freshwater organisms range from 0.1 to 222 mg/l and 85 to >130 mg/l for acrylic acid and methacrylic acid, respectively. The large variation in toxicity data for acrylic acid is due to a specific toxicity to certain species of freshwater microalgae, with algae EC50-values being two to three orders of magnitude lower than L(E)C50-values reported for fish and invertebrates. To evaluate the sensitivity of marine organisms, ecotoxicity data was generated for ten species of microalgae, one invertebrate species and one fish species. For methacrylic acid, we found a marine acute toxicity that ranged from 110 to >1260 mg/l, which is comparable to reported data on freshwater organisms. In strong contrast, the resulting L(E)C50-values for acrylic acid ranged from 50 to >1000 mg/l, and there was no specific sensitivity of marine algae when compared to marine invertebrates and fish. For acrylic acid, therefore, use of the available freshwater toxicity data for an effects assessment for the marine environment is likely to overestimate the hazard and risk from this substance. Overall, the results of the study suggest that ecotoxicity data generated on freshwater species may not always be appropriate for the effects assessments of organic chemicals in the marine environment, thus emphasising the importance of using ecologically relevant data to assess environmental risk.     

循环流化床锅炉燃煤技术热电厂生命周期评价

运用生命周期评价方法,应用Gabi5.0软件对采用循环流化床锅炉燃煤技术的热电企业进行资源耗竭和环境影响分析,计算各生产单元生命周期清单的全球变暖潜值、酸化效应潜值、富营养化潜值、非生物资源耗竭潜值、人体毒性潜值以及光化学烟雾和臭氧生成潜值等主要环境影响类型,对燃煤发电过程进行生命周期评价。结果表明,全球变暖和非生物资源耗竭为发电运行过程中主要的环境影响因素,分别占53%和15.05%;锅炉燃烧阶段的环境影响最重,占整个生命周期影响值的77.12%,并且除生物耗竭潜值外的其他5项指标均为发电运行阶段各个单元中最高。采用SNCR脱硝技术减少燃烧过程中NOx的排放量,并对该技术方案进行生命周期评价,比较方案实施前后的环境影响。