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Alkyl sulfates (AS), alkyl ethoxysulfates (AES) and linear alkyl benzene sulfonates (LAS) are all High Production Volume (HPV) and 'down-the-drain' chemicals used globally in detergent and personal care products, resulting in low levels ultimately released to the environment via wastewater effluent. Due to their surfactant properties, they preferentially sorb to sediments. Hence, assessment of their levels and potential perturbations on benthos are of interest. The relative levels of AS/AES decreased with distance from the wastewater treatment plant outfall. However, this was not evident for LAS. Short chained AES and especially AS dominated the homologue distribution for AES. There were no evident patterns in LAS homologue distribution. The overall mean margin of exposure (MoE) for AS/AES and LAS is approximately 40 (range: 3 to 100) suggesting no noteworthy perturbation on biota. The findings in this study are in concordance with previous preliminary hazard screening. Comparative sediment contamination analyses principally based on Chapman and Anderson [Chapman PM, Anderson, J. A decision-making framework for sediment contamination. Integr Environ Assess Mana. 2005; 1: 163-173.] and the U.S. Environmental Protection Agency RAPID assessment methods [USEPA. Rapid bioassessment protocols for use in wadeable streams and rivers: Periphyton, benthic, macroinvertebrates, and fish. 1999. Second Edition. U.S. Environmental Protection Agency Office of Water, Washington, D.C. EPA 841-B-99-002.] did not reveal significant correlations between the surfactant concentrations and ecological status of the sampling locations. Several Lines of Evidence (LoE) of the Weight-of-Evidence (WoE) lead to the conclusion of low aquatic risk associated to the monitored compounds.

Alkyl sulfates (AS) and alkyl ethoxysulfates (AES) are High Production Volume (HPV) ‘down-the-drain’ chemicals widely used globally in detergent and personal care products, resulting in low levels (ng to μg L − 1 range) ultimately released to the environment via wastewater. These surfactants have a strong affinity for sorption to sediments. However, data regarding the fate and effects following release into the environment has not been reported. Sediment samples from both normal exposed and presumably low exposed locations (background) were analyzed to determine the levels of AS/AES. The method used in this study shows broad applicability across various sediment types and the most common congeners of AS/AES. The combined levels of AS/AES detected in the two presumed lower exposed sites ranged from 0.025 and 0.034 μg g − 1 on a dry weight (dw) basis while the presumed higher exposed site had combined levels of AS/AES of 0.117 μg g − 1 (dw) based on triplicate analyses. Results indicate that detectable levels of AS/AES can be found in sediments in the environment at these three sites that are below the concentrations expected to produce significant adverse ecological effects for individual homologues and the whole mixture, the hazard screening for these three sites had PEC porewater /PNEC total mixture ratios of 0.007–0.024. However, further investigation of potential effects and risk assessment is warranted.

Pharmaceuticals have been detected in surface waters of the US and Europe, originating largely from two sources, sewage effluent and agricultural runoff. These compounds often occur as mixtures leading to potential combined effects. In order to investigate the effects of a realistic pharmaceutical mixture on an ecosystem, a study utilizing 15 of 12,000 L aquatic microcosms treated with eight common pharmaceuticals (atorvastatin, acetaminophen, caffeine, sulfamethoxazole, carbamazepine, levofloxacin, sertraline, and trimethoprim) at total (summed) molar concentrations of 0, 0.044, 0.608, 2.664, and 24.538 μmol/L (n = 3) was conducted. Phytotoxicity was assessed on a variety of somatic and pigment endpoints in rooted (Myriophyllum sibiricum) and floating (Lemna gibba) macrophytes over a 35-day period. EC10, EC25 and EC50 values were calculated for each endpoint exhibiting a concentration-dependent response. Generally, M. sibiricum and L. gibba displayed similar sensitivity to the pharmaceutical mixture, with phytotoxic injury evident in both species, which was concentration dependent. Through single compound 7-day daily static renewal toxicity tests with L. gibba, the sulfonamide antibiotic sulfamethoxazole, the fluoroquinolone antibiotic levofloxacin and the blood lipid regulator atorvastatin were found to be the only compounds to elicit phytotoxic effects in the concentration range utilized (0–1000 μg/L). Atorvastatin concentration was highly correlated to decreased pigment content in L. gibba, likely inhibiting the known target enzyme HMGR, the rate-limiting enzyme in isoprenoid biosynthesis. Hazard quotients were calculated for both microcosm and laboratory studies; the highest HQ values were 0.235 (L. gibba) and 0.051 (L. gibba), which are below the threshold value of 1 for chronic risks. The microcosm data suggest that at an ecological effect size of >20%, biologically significant risks are low for L. gibba and M. sibiricum exposed to similar mixtures of pharmaceutical compounds. For M. sibiricum and L. gibba, respective minimum differences of 5 and 1%, were detectable, however, these effect sizes are not considered ecologically significant.

Four different classes of environmental concern are quantitatively and qualitatively assessed for environmental hazards; antibiotics (n = 226), antineoplastics (n = 81), cardiovascular (n = 272), and sex hormones (n = 92). These along with an ECOSAR scan of all pharmaceuticals (n = 2848) were then classified according to the OECD aquatic toxicity classification system. The predicted species susceptibility is: daphnid > fish > algae, and the predicted rank order of relative toxicity: sex hormones > cardiovascular = antibiotics > antineoplastics (Table 1). Generally, a relatively large proportion (1/3) of all pharmaceuticals are potentially very toxic to aquatic organisms (Table 2). The qualitative risk assessment ranking relative to probability and potential severity for human and environmental health effects is: antibiotics > sex hormones > cardiovascular > antineoplastics. (Q)SARs and pharmacodynamic information should be used to prioritize and steer experimental risk assessments of pharmaceuticals, and potentially, also be used in new drug discovery optimizing efficacy and in minimising environmental hazards of new products. Nuclear receptors are relatively well conserved in evolution. Currently, antibacterial resistance represents the most significant human health hazard, and potentially the largest non-target organism hazard is sex hormones acting as endocrine modulators in wildlife. Data for the individual compounds are accessible via http://www.uoguelph.ca/∼hsander/.

Myriophyllum spp. have been proposed as a new standard laboratory aquatic macrophyte test species for the registration of pesticides. The main objectives of this investigation were to determine the power of Myriophyllum sibiricum and Myriophyllum spicatum toxicity data derived from an outdoor microcosm bioassay, to evaluate the variation of 10 different aquatic plant endpoints and to calculate the minimum detectable difference for these endpoints, to determine the replication required to detect ecologically significant changes from control for these endpoints, and to make recommendations for future field studies with Myriophyllum spp. Control data from four different studies that characterized haloacetic acid toxicity with Myriophyllum spp. for durations of three to six weeks during the summer of 1999 with five treatment levels (n = 3), including control, were examined. Endpoint coefficient of variation ranged, on average, from 6 to 28%. Node number and plant length endpoints were consistently the most statistically powerful for both plant species. It was possible to detect −30% change from control in both endpoints with high statistical power (β = 0.2, α = 0.05, n = 3). The range of minimum detectable differences was 40 to 60% for the other endpoints. Replication to detect a ≥25% change from control would require an n of 2 to 21, depending on the endpoint. Myriophyllum sibiricum had slightly lower coefficients of variation and thus required fewer replicates than M. spicatum to be statistically significantly different from control values. Variation within microcosm studies was not significantly different from that of controlled laboratory studies, implying that most of the variation observed in the field is inherent in the plants. Based on statistical sensitivity, ecological relevance, and toxicological sensitivity, we recommend using plant length and root endpoints as indicators of toxicity under field conditions.

There is presently a substantial amount of information being gathered concerning the environmental risk associated with the perfluorooctane sulfonate (PFOS) compound. The U.S. Environmental Protection Agency (U.S. EPA) is requiring that more research be completed before making definitive decisions concerning the regulatory issues covered in the significant new use rule (18/10-2000) under the Toxic Substance Control Act. However, there are no risk assessment requirements under seminatural conditions in microcosms. The PFOS can enter, and has been found in, the aquatic environment through different pathways, including spills associated with use of fire-fighting foams containing PFOS, leaching from washing Scotchgard-treated clothes with the wastewater, leaching from various coatings, discharges as residual waste from fluorochemical production, or volatilization and transportation atmospherically. The biota is the sink of PFOS rather than the sediment or soil. The aim of this article is to determine a 35-d community no-observable-effect concentration (NOECcommunity) for freshwater zooplankton and the fate of PFOS during the course of study. The PFOS persisted in the water phase with only slight reductions over the study; only the decrease from 33.9 mg/L at day 1 to 29.8 mg/L at day 35 was significant. A 90 to 100% reduction (p Cladocera > Rotifera, assuming all adverse direct effects.

This paper brings together over 250 published and unpublished studies on the environmental properties, fate, and toxicity of the four major, high-volume surfactant classes and relevant feedstocks. The surfactants and feedstocks covered include alcohol sulfate or alcohol sulfate (AS), alcohol ethoxysulfate (AES), linear alkylbenzene sulfonate (LAS), alcohol ethoxylate (AE), and long-chain alcohol (LCOH). These chemicals are used in a wide range of personal care and cleaning products. To date, this is the most comprehensive report on these substance's chemical structures, use, and volume information, physical/chemical properties, environmental fate properties such as biodegradation and sorption, monitoring studies through sewers, wastewater treatment plants and eventual release to the environment, aquatic and sediment toxicity, and bioaccumulation information. These data are used to illustrate the process for conducting both prospective and retrospective risk assessments for large-volume chemicals and categories of chemicals with wide dispersive use. Prospective risk assessments of AS, AES, AE, LAS, and LCOH demonstrate that these substances, although used in very high volume and widely released to the aquatic environment, have no adverse impact on the aquatic or sediment environments at current levels of use. The retrospective risk assessments of these same substances have clearly demonstrated that the conclusions of the prospective risk assessments are valid and confirm that these substances do not pose a risk to the aquatic or sediment environments. This paper also highlights the many years of research that the surfactant and cleaning products industry has supported, as part of their environmental sustainability commitment, to improve environmental tools, approaches, and develop innovative methods appropriate to address environmental properties of personal care and cleaning product chemicals, many of which have become approved international standard methods.

This paper compiles all the measured chemical warfare agent (CWA) concentrations found in relation to the Nord Stream pipeline work in Danish waters for the past 5 years. Sediment and biota sampling were performed along the pipeline route in four campaigns, prior to (in 2008 and 2010), during (in 2011) and after (in 2012) the construction work. No parent CWAs were detected in the sediments. Patchy residues of CWA degradation products of Adamsite, Clark I, phenyldichloroarsine, trichloroarsine and Lewisite II, were detected in a total of 29 of the 391 sediment samples collected and analyzed the past 5 years. The cumulative fish community risk quotient for the different locations, calculated as a sum of background and added risk, ranged between 0 and 0.017 suggesting a negligible acute CWA risk toward the fish community. The added risk from sediment disturbance in relation to construction of the pipelines represents less than 2% of the total risk in the areas with the highest calculated risk. The analyses of benthic infauna corroborate the finding of CWA related low risk across the years. There was no significant difference in CWA risk before (2008) and after the pipeline construction (2012).

Alcohol ethoxylates (AE) are high production volume (HPV) chemicals globally used in detergent and personal care products and are truly a work-horse for the household and personal care industries. Commercial AE generally consist of a mixture of several homologues of varying carbon chain length and degree of ethoxylation. Homologues that are not ethoxylated are also known as aliphatic alcohols or simply fatty alcohols (FA). This group of homologues represents a special interest in the context of environmental risk, as these are also abundant and ubiquitous naturally occurring compounds (e.g. animal fats and in human feces). Hence, in a risk assessment one needs to distinguish between the natural (background) concentrations and the added contribution from anthropogenic activities. We conducted a weight-of-evidence risk assessment in three streams, documenting the exposure and predicted risk, and compared these to the habitat and in situ biota. We found that the parameters (e.g., habitat quality and total perturbations hereunder total suspended solids (TSS) and other abiotic and biotic stressors) contributed to the abundance of biota rather than the predicted risk from AE and FA. Moreover, the documented natural de novo synthesis and rapid degradation of FA highlight the need to carefully consider the procedures for environmental risk assessment of naturally occurring compounds such as FA, e.g. in line with the added risk concept known from metal risk assessment.

A combination platform–debate session was held at the Society of Environmental Toxicology and Chemistry (SETAC) North America annual meeting in Boston (November 2011). The session was organized by members of the Advisory Group on Sustainability, newly formed and approved as a global entity by the SETAC World Council just prior to the meeting. The platform portion of the session provided a historical backdrop for the debate that was designed to explore SETAC's role in the sustainability dialogue. The debate portion presented arguments for and against the proposition that “Science is the primary contribution of SETAC to the global dialogue on sustainability.” Although the debate was not designed to achieve a definitive sustainability policy for SETAC, the audience clearly rejected the proposition, indicating a desire from the SETAC membership for an expanded role in global sustainability forums. This commentary details the key elements of the session, identifies the contribution the Advisory Group will have at the World Congress in Berlin (May 2012), and invites interested persons to become active in the Advisory Group. Integr Environ Assess Manag 2013; 9: 7–11. © 2012 SETAC

The fish early life-stage (FELS) test guideline (OECD 210 or OCSPP 850.1400) is the most frequently used bioassay for predicting chronic fish toxicity and supporting aquatic ecological risk assessments around the world. For each chemical, the FELS test requires a minimum of 360 fish and 1 to 3 months from test initiation to termination. Although valuable for predicting fish full life-cycle toxicity, FELS tests are labor and resource intensive and, due to an emphasis on apical endpoints, provide little to no information about chemical mode of action. Therefore, the development and implementation of alternative testing strategies for screening and prioritizing chemicals has the potential to reduce the cost and number of animals required for estimating FELS toxicity and, at the same time, provides insights into mechanisms of toxicity. Using three reference chemicals with well-established yet distinct adverse outcome pathways (AOPs) in early life stages of fish, we proposed FELS-specific AOPs as conceptual frameworks for identifying useful chemical screening and prioritization strategies. The reference chemicals selected as case studies were a cardiotoxic aryl hydrocarbon receptor agonist (2,3,7,8-tetrachlorodibenzo-p-dioxin), neurotoxic acetylcholinesterase inhibitor (chlorpyrifos), and narcotic surfactant (linear alkylbenzene sulfonate). Using qualitative descriptions for each chemical during early fish development, we developed generalized AOPs and, based on these examples, proposed a three-tiered testing strategy for screening and prioritizing chemicals for FELS testing. Linked with biologically based concentration-response models, a tiered testing strategy may help reduce the reliance on long-term and costly FELS tests required for assessing the hazard of thousands of chemicals currently in commerce.

Trace amounts of pharmaceuticals have been detected in surface waters in the nano- to microgram per liter range, and in drinking water in the nanogram/L range. The environmental risks of pharmaceuticals in surface waters have been evaluated and generally found to be low if the wastewater is treated before release to the environment. The human health risks of trace amounts of pharmaceuticals in drinking water have however not been evaluated in any great depth. Preliminary screening level assessments suggest risk to be low – but the public and decision-makers are concerned and would like the matter investigated more thoroughly, especially with regards to mixture effects, chronic long-term effects and sensitive sub-populations. The World Health Organization is currently evaluating the need for credible health based guidance associated with low concentrations of pharmaceuticals in drinking water. The aim of this paper is to summarize the state-of-the-science and the ongoing international debate on the topic.

Naphthenic acids (NAs) are a complex mixture of carboxylic acids that are natural constituents of oil sand found in north-eastern Alberta, Canada. NAs are released and concentrated in the alkaline water used in the extraction of bitumen from oil sand sediment. NAs have been identified as the principal toxic components of oil sands process-affected water (OSPW), and microbial degradation of lower molecular weight (MW) NAs decreases the toxicity of NA mixtures in OSPW. Analysis by proton nuclear magnetic resonance spectroscopy indicated that larger, more cyclic NAs contain greater carboxylic acid content, thereby decreasing their hydrophobicity and acute toxicity in comparison to lower MW NAs. The relationship between the acute toxicity of NAs and hydrophobicity suggests that narcosis is the probable mode of acute toxic action. The applicability of a (Quantitative) Structure-Activity Relationship ((Q)SAR) model to accurately predict the toxicity of NA-like surrogates was investigated. The USEPA’s ECOSAR model predicted the toxicity of NA-like surrogates with acceptable accuracy in comparison to observed toxicity values from Vibrio fischeri and Daphnia magna assays, indicating that the model has potential to serve as a prioritization tool for identifying NA structures likely to have an increased toxicity. Investigating NAs of equal MW, the ECOSAR model predicted increased toxic potency for NAs containing fewer carbon rings. Furthermore, NA structures with a linear grouping of carbon rings had a greater predicted toxic potency than structures containing carbon rings in a clustered grouping.

This paper presents screening-level assessment as a conservative model-based scope assessment of potential risks to help guide environmental risk assessment of chemical warfare agents (CWAs) in fish communities. The paper also presents the DPSIR approach to complex environmental issues. The two approaches are applied to a case study involving CWA munitions dumped in the Baltic Sea after the Second World War.

An environmental assessment of amine oxides has been conducted under the OECD SIDS High Production Volume (HPV) Program via the Global International Council of Chemical Associations (ICCA) Amine Oxides Consortium. Amine oxides are primarily used in conjunction with surfactants in cleaning and personal care products. Given the lack of persistence or bioaccumulation, and the low likelihood of these chemicals partitioning to soil, the focus of the environmental assessment is on the aquatic environment. In the United States, the E-FAST model is used to estimate effluent concentrations in the United States from manufacturing facilities and from municipal facilities resulting from consumer product uses. Reasonable worst-case ratios of predicted environmental concentration (PEC) to predicted no effect concentration (PNEC) range from 0.04 to 0.003, demonstrating that these chemicals are a low risk to the environment.

Zooplankton abundance and species richness in 15 untreated 12,000 L outdoor microcosms (n = 15) were monitored over the course of 1 year to document the inherent variability and statistical detectability between replicates. Statistical power analysis were applied to derive the statistically minimal detectable difference (MDD) between replicates with default values set at; alpha = 0.1 and beta = 0.2. Copepod abundance and species richness generally demonstrated the best detectability at 0.31 and 0.16, respectively, (n = 15); 0.59 and 0.33 (n = 3). Total zooplankton abundance and species richness had the lowest detectabilities at 0.19 and 0.14, respectively, (n = 15); 0.35 and 0.3 (n = 3). Rotifers, due to their opportunistic and rapid life traits, had the lowest single-species abundance detectabilities at 0.54 (n = 15); 0.8 (n = 3), whereas macroinvertebrate species richness had the lowest detectability at 0.43 (n = 15); 0.7 (n = 3) over 1 year. We recommend a priori calibration of the study design relative to relevant MDDs. Moreover, it is suggested to consider alternatives to statistical null hypothesis testing.

Chemical warfare agents (CWAs) have been disposed of in various fashions over the past decades. Significant amounts of CWA, roughly 11,000ton, have been dumped in the Baltic Sea east of the island Bornholm following the disarmament of Germany after World War II. This has caused concerns over potential human and environmental health risks, and resulted in restrictions on fishing in the dumpsite area. The purpose of this paper is to assess the potential indirect human health risks due to consumption of CWA-contaminated fish from the dumpsite area east of Bornholm. Earlier studies suggest that the fish community may be at risk from CWA exposure in the Bornholm basin. Moreover, elevated frequencies of lesions on fish caught in a CWA dumpsite in the Mediterranean Sea have been observed. The fish at the Mediterranean dumpsite had elevated total arsenic (As) concentrations in their tissue, and elevated total As levels were also observed in the sediment. Elevated total sediment As concentrations have also been recorded in CWA dumpsites in the Skagerrak and the Baltic Sea. Triphenylarsine and sulfur mustard gas (Yperite) are the CWAs with the greatest indirect human health risk potential. There are recognized uncertainties concerning Yperite's and CWA-derived arsenical's fate and speciation in the environment, as well as their inherent toxicity, warranting caution and further site-specific environmental and human health risk assessments of CWAs dumped in the Bornholm basin.

Udgivelsesdato: 1/6-09 Pharmaceuticals have been reported to be ubiquitously present in surface waters prompting concerns of effects of these bioactive substances. Meanwhile, there is a general scarcity of publicly available ecotoxicological data concerning pharmaceuticals. The aim of this paper was to compile a comprehensive database based on OECD's standardized measured ecotoxicological data and to evaluate if there is generally cause of greater concern with regards to pharmaceutical aquatic toxicological profiles relative to industrial chemicals. Comparisons were based upon aquatic ecotoxicity classification under the United Nations Global Harmonized System for classification and labeling of chemicals (GHS). Moreover, we statistically explored whether the predominant mode-of-action (MOA) for pharmaceuticals is narcosis. We found 275 pharmaceuticals with 569 acute aquatic effect data; 23 pharmaceuticals had chronic data. Pharmaceuticals were found to be more frequent than industrial chemicals in GHS category III. Acute toxicity was predictable (>92%) using a generic (Q)SAR ((Quantitative) Structure Activity Relationship) suggesting a narcotic MOA. Analysis of model prediction error suggests that 68% of the pharmaceuticals have a non-specific MOA. Additionally, the acute-to-chronic ratio (ACR) for 70% of the analyzed pharmaceuticals was below 25 further suggesting a non-specific MOA. Sub-lethal receptor-mediated effects may however have a more specific MOA. © 2009 Elsevier Ireland Ltd. All rights reserved.

An environmental assessment of long-chain alcohols (LCOH) has recently been conducted under the OECD SIDS High Production Volume (HPV) Program via the Global International Council of Chemical Associations (ICCA) Aliphatic Alcohols Consortium. LCOH are used primarily as intermediates, as a precursor to alcohol-based surfactants and as alcohol per se in a wide variety of consumer product applications. Global production volume is approximately 1.58 million metric tonnes. The OECD HPV assessment covers linear to slightly branched LCOH ranging from 6 to 22 alkyl carbons (C). LCOH biodegrade exceptionally rapidly in the environment (half-lives on the order of minutes); however, due to continuous use and distribution to wastewater treatment systems, partitioning properties, biodegradation of alcohol-based surfactants, and natural alcohol sources, LCOH are universally detected in wastewater effluents. An environmental risk assessment of LCOH is presented here by focusing on the most prevalent and toxic members of the linear alcohols, specifically, from C 12−15 . The assessment includes environmental monitoring data for these chain lengths in final effluents of representative wastewater treatment plants and covers all uses of alcohol (i.e., the use of alcohol as a substance and as an intermediate for the manufacturing of alcohol-based surfactants). The 90th percentile effluent discharge concentration of 1.979 μg/L (C 12 −C 15 ) was determined for wastewater treatment plants in 7 countries. Chronic aquatic toxicity studies with Daphnia magna demonstrated that between C 13 and C 15 LCOH solubility became a factor and that the structure–activity relationship was characterized by a toxicity maximum between C 13 and C 14 . Above C 14 the LCOH was less toxic and become un-testable due to insolubility. Risk quotients based on a toxic units (TU) approach were determined for various scenarios of exposure and effects extrapolation. The global average TU ranged from 0.048 to 0.467 depending on the scenario employed suggesting a low risk to the environment. The fact that environmental exposure calculations include large fractions of naturally derived alcohol from animal, plant, and microbially mediated biotransformations further supports a conclusion of low risk.

Extrapolation is commonly used in human health and ecotoxicological risk assessment, either in a formal process or, more commonly, through the use of uncertainty factors derived from empirical experience or observation. Extrapolation is used in predictive risk assessment procedures, such as the setting of criteria or guidelines, as well as retrospective risk assessments, where organisms have already been exposed to a stressor. Matrix extrapolations are critical in understanding the bioavailability and fate of toxic substances and are driven by interactions between the matrix and the toxicant. Levels of biological organization are important for extrapolation, because more extrapolation data are available for lower levels of organization. Extrapolation between levels of biological organization is predicated on the correct choice of parameters to measure. Because most of the routine toxicity testing of environmentally important substances is carried out using species from temperate regions, spatial extrapolation is an important process in extending risk assessments to tropical or polar regions.

This paper examined active pharmaceutical ingredients (APIs) acute ecotoxicological modes of action (MOA). It was concluded that the vast majority of APIs acute MOA was non-specific narcosis as; 85% out of 59 APIs had an excess toxicity ratio

The toxicity of SSRIs to algae/phytoplankton was investigated using the US EPA ECOSAR, acute single-species growth inhibition assays, species sensitivity distributions (SSDs), and an outdoor microcosm mixture experiment. Worst-case ECOSAR estimates of SSRI toxicity to algae ranged from 0.73 to 13.08 mg/L. Sertraline was the most toxic SSRI tested in single-species growth inhibition assays followed by fluoxetine and fluvoxamine with worst-case 96-h IC10s of 4.6, 31.3, and 1662 microg/L, respectively. HC5s of 2.4, 3.6, and 1100 microg/L were estimated, respectively, for sertraline, fluoxetine, and fluvoxamine toxicity to algae-using SSDs. Microcosm phytoplankton structural endpoints were more sensitive than functional endpoints in the short term. However, in the long term, structural endpoints were resilient and functional endpoints remained impacted even after a period of recovery. The worst-case EC10 determined from the outdoor microcosm mixture toxicity to phytoplankton communities was 15.2 nM. Although SSRIs are toxic to algae, hazard quotients using worst-case PECs represent a margin of safety of 20 to phytoplankton. Although SSRIs do not appear to pose a hazard to primary production, this assessment is not protective of higher aquatic organisms and further research into the chronic toxicity to low levels of SSRIs to higher-level aquatic species is recommended.

Chemical warfare agents (CWAs) have been used and disposed of in various fashions over the past decades. Significant amounts have been dumped in the Baltic Sea following the disarmament of Germany after World War II causing environmental concerns. There is a data gap pertaining to chemical warfare agents, environmental properties not the least their aquatic toxicities. Given this gap and the security limitations relating to working with these agents we applied Quantitative Structure-Activity Relationship ((Q)SAR) models in accordance with the European Technical Guidance Document (2003) to 22 parent CWA compounds and 27 known hydrolysis products. It was concluded that conservative use of EPI Suite (Q)SAR models can generate reliable and conservative estimations of chemical warfare agents acute aquatic toxicity. From an environmental screening point of view the organoarsenic chemical warfare agents Clark I and Adamsite comprise the most problematic of the screened CWA compounds warranting further investigation in relation to a site specific environmental risk assessment. The mustard gas agents (sulphur and nitrogen) and the organophosphorous CWAs (in particular Sarin and Soman) are a secondary category of concern based upon their toxicity alone. The undertaken approach generates reliable and conservative estimations for most of the studied chemicals but with some exceptions (e.g. the organophosphates).

The toxicity and hazard of a mixture of selective serotonin reuptake inhibitors (SSRIs), including fluoxetine, fluvoxamine, and sertraline, to zooplankton communities were evaluated using 120,00l outdoor microcosms. Acute (day 4) and chronic (day 35) zooplankton abundance and species richness were assessed for Rotifera, Cladocera, and Copepoda. For acute SSRI exposures, rotifers were the most sensitive zooplankton taxa to changes in abundance (predicted no effect concentration (PNEC)=19 nM); however, no effects in zooplankton species richness were observed for this treatment period. A decrease in Copepoda abundance and species richness was observed following chronic exposures of SSRIs (PNEC=9.1 nM). A 99th-centile predicted environmental concentration (PEC=0.51 nM) yielded HQs at least two orders of magnitude below 1. Therefore, mixtures of SSRIs do not appear to present a hazard to zooplankton communities at environmentally relevant concentrations.

The practicality of a probabilistic ecological hazard assessment (PEHA) methodology using intraspecies endpoint sensitivity distributions (IESDs) and chemical toxicity distributions (CTDs) was evaluated on data sets of pharmaceutical toxicity to aquatic macrophytes. A PEHA does not use an exposure distribution but rather uses a point estimate, which is useful for applications with sufficient effects data but lacking in comprehensive exposure data or when a criterion concentration is desired. The probability of finding an effect measure or potency value below a threshold can be calculated from the effects distribution. PEHA analyses using CTDs for both EC(10) and EC(25)Lemna gibba toxicity values indicated a

A feasible and relatively readily available analytical method was adapted for the assessment of alcohol ethoxylates (AE) and fatty alcohols (FA) in sediments. This study illustrates the simultaneous measurement of 38 of 114 possible alcohol ethoxylate ethoxymers (AE) and fatty alcohols (FA) found in commercially important AE products. We predicted toxicity for all identified fractions, as well as the total mixture toxicity, relative to three exposure scenarios via sewage treatment plants (STP) for these widely used chemicals in consumer products and hence generate a preliminary environmental risk screening for AE and FA in sediments. The method is based on derivatization of solvent or solid-phase extracts with 2-fluoro-N-methylpyridinium p-toluenesulfonate (Pyr+). The derivatized extracts were analyzed with liquid chromatography/mass spectrometry (LC/MS) operating in the positive ion electrospray mode. The extraction efficiency of AE and FA in three different sediments of varying composition was evaluated with spike-recovery studies, ranging from 64% to 80%. The detection limits for individual ethoxymers typically ranged from 1 to 5 ngg(-1)on a dry weight basis. The mean limit of detection (LOD) was 6 ngg(-1)and the median LOD was 3 ngg(-1). AE and FA in sediments were found to be stable for two weeks if preserved with 3% (v/v) formalin and stored at 4-6( composite function)C. Based on equilibrium partitioning, background concentrations of AE and FA were predicted to be below concentrations known to elicit chronically toxic effects. Total worst case mixture toxicities for all AE ethoxymers combined with FA were predicted to result in a risk quotient less than 0.6. Activated sludge treatment (STP) significantly reduced the release of total AE and FA by four-fold, suggesting that the total mixture risk quotient would be0.15 for sediment dependent organisms.

The exposure and fate of selective serotonin reuptake inhibitors (SSRIs) was evaluated using modeled predicted environmental concentrations (PECs) according to the U.S. and the European Union (EU) guidelines and microcosm model ecosystems. According to the U.S. guidance, crude environmental introduction concentrations, the only SSRI that would require environmental assessment would be sertraline. However, the more conservative EU draft guidance PEC would require further assessment of all five SSRIs. Refined PECs developed using the U.S. and the EU guidelines along with estimates of removal by sewage treatment and receiving water dilution factors indicate that the U.S. methodology corresponds better to MEC data determined in the U.S. and Canada. Worst-case (99th centile) PECs for citalopram, fluoxetine, fluvoxamine, paroxetine, and sertraline were 30, 19, 30, 65, and 122 ng/L, respectively, using the U.S. methodology and 142, 182, 841, 144, and 575 ng/L, respectively, using the EU draft methodology. The dissipation of fluoxetine and fluvoxamine from the water column in aquatic microcosms was best described using a two-compartment model while sertraline followed a one-compartment model. Fluoxetine and fluvoxamine water concentrations initially dissipated with first phase half-lives of 3.8 and 1.8 days, respectively, but levelled off at concentrations around 10 microg/L with second phase half-lives of 76.7 and 59.3 days, respectively, not including those estimated as infinity. Sertraline dissipation tended toward the detection limit with a half-life of 3.4 days. Fluoxetine was found to be the most persistent followed by fluvoxamine and sertraline. Estimated log(K(OC)) values for all SSRIs were >4.3 indicating that SSRIs are expected to adsorb to sediment or sludge. Partitioning into other environmental compartments such as this may act as a reservoir from which SSRIs may be re-released into surface waters and indicates the potential susceptibility of benthos.

Quantitative uncertainty assessments and the distribution of risk are under scrutiny and significant criticism has been made of null hypothesis testing when careful consideration of Type I (false positive) and II (false negative) error rates have not been taken into account. An alternative method, equivalence testing, is discussed yielding more transparency and potentially more precaution in the quantifiable uncertainty assessments. With thousands of chemicals needing regulation in the near future and low public trust in the regulatory process, decision models are required with transparency and learning processes to manage this task. Adaptive, iterative, and learning decision making tools and processes can help decision makers evaluate the significance of Type I or Type II errors on decision alternatives and can reduce the risk of committing Type III errors (accurate answers to the wrong questions). Simplistic cost-benefit based decision-making tools do not incorporate the complex interconnectedness characterizing environmental risks, nor do they enhance learning, participation, or include social values and ambiguity. Hence, better decision-making tools are required, and MIRA is an attempt to include some of the critical aspects.

The impact of a mixture of oxytetracycline, chlortetracycline, tetracycline and doxycycline on Myriophyllum sibiricum and Lemna gibba was investigated using fifteen 12,000-L microcosms (k=5, n=3). Significant concentration-response relationships were only found for M. sibiricum, where dry mass was 69, 47, 30, and 7% of controls at respective treatment concentrations of 0.080, 0.218, 0.668, and 2.289 micromol/L. Somatic endpoints were strongly and negatively correlated with percent light transmission, except plant length, which was positively correlated. Treated microcosms experienced a reduction in the percent of surface irradiance penetrating the water column as high as 99.8% at a depth of 70 cm, relative to controls. Position relative to the water column was likely responsible for the differential effects observed between floating (L. gibba) and submerged (M. sibiricum) species of macrophytes. A hazard quotient assessment of the lowest EC10 value indicated significant risk, exceeding the critical HQ value, but not the lowest EC25 value.

Pharmaceuticals are routinely detected at low concentrations in surface waters, but effects on non-target organisms are not well understood. Microcosms were used to assess ecological responses in freshwater ecosystems to a mixture offourtetracyclines commonly used in veterinary and human medicine. Triplicate microcosms were treated with tetracycline, oxytetracycline, doxycycline, and chlortetracycline, resulting in measured time-weighted average total mixture concentrations of 0, 0.080, 0.218, 0.662, and 2.29 microM, respectively. Responses were assessed in terms of structure and function based on measurements of zooplankton and phytoplankton communities, ecosystem productivity, and water quality. Effects were observed for some endpointsor = the 0.218 microM treatment. The largest responses were concentration-dependent reductions in total phytoplankton abundance and species richness. Phytoplankton abundance recovered to control levels in all microcosms after treatment was terminated, and resilience (time to return to normal operating range during stress) was observed with respectto phytoplankton species richness. Zooplankton were generally unaffected by the tetracyclines. Responses also included decreased water clarity, lower oxygen concentration, and water temperature. Functional endpoints showed varying sensitivity. On the basis of dissolved oxygen concentrations, community respiration (R) increased while primary productivity (P) was unchanged with increased treatment concentration. The effects observed occurred at considerably greater concentrations than are currently measured in the environment, indicating minimal risk to aquatic organisms.

A mixture of four tetracyclines; oxytetracycline (OTC), chlortetracycline (CTC), tetracycline (TC), and doxycycline (DC) was applied in fifteen 12000l outdoor microcosms at four treatment levels plus controls each with three replicates (n = 3). The dissipation times of parent compounds were monitored and half-lives (DT50) of 1-4 days, depending on treatment level were recorded. This is in accordance with half-lives from previous findings in bench-top experiments. Parent compound DT50, were determined using HPLC-UV. Furthermore, the samples were analyzed for ten different tetracycline products using LC/MS/MS. Two products were found for chlortetracycline; 4-epi-anh-chlortetracyline and the iso-chlortetracycline. Iso-forms were only found for CTC and only at the highest treatment (300 microg l(-1)). The half-lives, trajectories, and relative amounts of the products were analogous for all four tetracyclines. DT50 for products were less than 1.2 days. Formation of 4-epi-anh-tetracyclines, occurred at neutral to weak alkaline conditions.

Tylosin is a macrolide antibiotic commonly used for therapeutic treatment and prophylaxis in livestock. As part of a larger ecotoxicological study, the potential phytotoxic effects of tylosin on the rooted macrophyte Myriophyllum spicatum and the floating macrophyte Lemna gibba were assessed under semi-field conditions using 15 12 000-L microcosms. Concentrations of 0, 10, 30, 300 μg/L ( n = 3), and 600, 1000, and 3000 μg/L ( n = 1) were evaluated as part of separate ANOVA and regression analyses over an exposure period of 35 days. Fate of tylosin was monitored over time in the highest three treatments, where dissipation followed pseudo-first order kinetics with associated half-lives ranging from 9 to 10 days. For both M. spicatum and L. gibba , tylosin was found to cause no biologically significant changes to any endpoint assessed compared to controls at a Type I error rate of 0.1. However, subsequent power analyses revealed that there was generally insufficient power to declare that there were no significant differences at a Type II error rate of 0.2. Conclusions concerning biologically significant impacts were therefore further assessed based on other statistical criteria including comparisons of percent differences between replicated treatments and controls, minimum significant and minimum detectable differences, and coefficients of variation. Based on these criteria, at an ecological effect size of >20% change, tylosin was concluded to elicit no biologically or ecologically significant toxicity to M. spicatum or L. gibba . A hazard quotient assessment indicated that tylosin poses little risk to either species of macrophyte, with an HQ value calculated to be nearly three orders of magnitude below 1 (0.002).

The risks associated with occurrence of pharmaceuticals in water resources are mostly unknown. In the absence of extensive toxicological data, we scanned all the compounds observed in the environment for toxicological properties by (Quantitative) Structure Activity Relationship ((Q)SAR). The results of the probabilistic distribution of environmental and effect concentrations and hazard quotients (HQs) do not indicate significant acute risks prior to application of assessment factors. Compared with measured effect concentrations SAR predictions were more "sensitive" 80% of the time. The long-term effects of subtle and chronic changes, additive or synergistic effects and effects on other endpoints e.g. reproduction, behavior, metabolism, bacterial resistance etc. are still uncertain. (Q)SAR's can be important prioritization tools for subsequent experimental risk assessment of pharmaceuticals in surface waters, due to the prevalent lack of ecotoxicological data.

Myriophyllum spp. have been proposed as a new standard laboratory aquatic macrophyte test species for the registration of pesticides. The main objectives of this investigation were to determine the power of Myriophyllum sibiricum and Myriophyllum spicatum toxicity data derived from an outdoor microcosm bioassay, to evaluate the variation of 10 different aquatic plant endpoints and to calculate the minimum detectable difference for these endpoints, to determine the replication required to detect ecologically significant changes from control for these endpoints, and to make recommendations for future field studies with Myriophyllum spp. Control data from four different studies that characterized haloacetic acid toxicity with Myriophyllum spp. for durations of three to six weeks during the summer of 1999 with five treatment levels (n = 3), including control, were examined. Endpoint coefficient of variation ranged, on average, from 6 to 28%. Node number and plant length endpoints were consistently the most statistically powerful for both plant species. It was possible to detect approximately 30% change from control in both endpoints with high statistical power (beta = 0.2, alpha = 0.05, n = 3). The range of minimum detectable differences was 40 to 60% for the other endpoints. Replication to detect aor = 25% change from control would require an n of 2 to 21, depending on the endpoint. Myriophyllum sibiricum had slightly lower coefficients of variation and thus required fewer replicates than M. spicatum to be statistically significantly different from control values. Variation within microcosm studies was not significantly different from that of controlled laboratory studies, implying that most of the variation observed in the field is inherent in the plants. Based on statistical sensitivity, ecological relevance, and toxicological sensitivity, we recommend using plant length and root endpoints as indicators of toxicity under field conditions.

There is presently, a substantial amount of information being gathered concerning the environmental risk associated with the perfluorooctanoic acid (PFOA) compound. The aim of this paper was to determine a 35 day community no observable effect concentration (NOEC(community)) or lowest observable effect concentration (LOEC) for freshwater zooplankton exposed to PFOA during a study in 30 l indoor aquatic microcosms. Some significant (P0.01) temporal fluctuations in zooplankton abundance were observed, however, a NOEC(community) could not be calculated. LOEC for various species varied between 10 and 70 mg l(-1). According to LOEC values, the tentative order of descriptors sensitivity was as follows: Daphnia magnarichnessor = Cyclops canthocamptus staphylinusCyclops diaptomustotal zooplanktonor = Rotifera sp. The long term ecological significance of these temporal fluctuations could not be determined in this study, however, the overall study cessation analysis showed that the structure of the ecosystem was changed from a more diverse community dominated by larger species towards a less diverse community dominated by smaller more and robust species (P0.05). Additional chronic toxicity testing should also be addressed since these compounds are so persistent and recalcitrant.

The objective of this state-of-the-art review was to quantify the replicability of pesticide studies using micro/ mesocosms. Low interpretability of micro/mesocosm studies, and inconclusive and highly variable data, resulted in a discontinuation of the use of these studies for the registration of pesticides. Coefficients of variation, CV%, were calculated on the basis of data tables as a measure of statistical 'effectiveness' taken from the literature. The average CV in the investigated studies was 45%; larger out-door mesocosms averaged 51%, and smaller indoor micro/mesocosms averaged 32%. CVs on variables involving animals were higher than CVs on plant end-points, which in turn were higher than abiotic variables for all experiments. However, to enhance the interpretability and implementation of micro/mesocosm studies for pesticide registration, a number of context-dependent steps could be incorporated; 1) determine the appropriate experimental design and number of replicates by using power analysis, 2) Utilise advanced statistical analysis, such as probabilistic effect distribution and principal response curves, 4) report, preferably in quantitative terms using power analysis, the risk of Type II error. The author's primary conclusion is that the level of CVs is context dependent and, therefore, it is not possible to suggest a generally acceptable level of CVs for all experiments. This has been suggested both directly and indirectly in the literature. Moreover, the number of insignificant (p > 0.05) results is high, 88% of all test biotic variables had no statistical significance. The average number of replicates were 3-4, which theoretically should yield significant effects at least at the highest test-concentration, then resulting in 75-66% insignificant results.

This comparative survey summarizes six individual studies on the ecological effects of two common perfluorinated surfactants, PFOS and PFOA, on zooplankton. We compare the test designs and quantify the relative sensitivity and statistical power (1-betaor = 0.8). The survey compares 30-L indoor microcosm to 12,000-L outdoor microcosm experiments, with 225-mL single species laboratory tests as reference. By this we elucidate the extrapolation of ecological effects in space and complexity. Generally, zooplankton had lower tolerance toward PFOS than toward PFOA. With increasing concentrations the zooplankton community became simplified toward more robust rotifer species, which, as an indirect effect, increased their abundance due to a shift in competition and predation. The statistical power of the designs exhibits inverse proportionality between complexity and realism, indoor microcosmoutdoor microcosm. Surprisingly, the 30-L study had a lower LOEC value for Daphnia magna than the laboratory chronic test, indicating that D. magna and D. pulicaria were not the most sensitive species and that laboratory tests are not always conservative relative to microcosm experiments. Food scarcity due to phytotoxicity was not the reason for the difference.

There is presently a substantial amount of information being gathered concerning the environmental risk associated with the perfluorooctane sulfonate (PFOS) compound. The U.S. Environmental Protection Agency (U.S. EPA) is requiring that more research be completed before making definitive decisions concerning the regulatory issues covered in the significant new use rule (18/10-2000) under the Toxic Substance Control Act. However, there are no risk assessment requirements under seminatural conditions in microcosms. The PFOS can enter, and has been found in, the aquatic environment through different pathways, including spills associated with use of fire-fighting foams containing PFOS, leaching from washing Scotchgard-treated clothes with the wastewater, leaching from various coatings, discharges as residual waste from fluorochemical production, or volatilization and transportation atmospherically. The biota is the sink of PFOS rather than the sediment or soil. The aim of this article is to determine a 35-d community no-observable-effect concentration (NOECcommunity) for freshwater zooplankton and the fate of PFOS during the course of study. The PFOS persisted in the water phase with only slight reductions over the study; only the decrease from 33.9 mg/L at day 1 to 29.8 mg/L at day 35 was significant. A 90 to 100% reduction (p0.01) of the total zooplankton population was found after one week of exposure to 30 mg PFOS/L and a similar reduction after two weeks at 10 mg PFOS/L. The Daphnia magna 21-d NOECsurvival of 12 mg/L has previously been found in a standard laboratory bioassay by 3M. The rank order of susceptibility for the test community was CopepodaCladoceraRotifera, assuming all adverse direct effects.

Antibiotics are known to have antichloroplastic properties, but their effects on aquatic higher plants are virtually unknown. In order to address this issue, 25 pharmaceuticals, including 22 antibiotics, were assessed for phytotoxicity to the aquatic higher plant Lemna gibba. A 7-d static-renewal test was used, and plants were treated with 0, 10, 30, 100, 300, and 1,000 microg/L of pharmaceutical-containing growth media. Phytotoxicity was assessed using multiple growth and biochemical endpoints. Effective concentration (EC)50, EC25, and EC10 values as well as tests for significant differences between treatments and controls lowest-observed-effect concentration (LOECs) were calculated for each endpoint. Twelve different classes of antibiotics were assessed; however, only members of the fluoroquinolone, sulfonamide, and tetracycline classes of antibiotics displayed significant phytotoxicity. The most toxic members of each of these classes tested were lomefloxacin, sulfamethoxazole, and chlortetracycline, with wet weight EC25 values of 38, 37, and 114 microg/L, respectively. Injury symptoms were comparatively uniform and consistent among chemical classes while degree of phytotoxicity varied considerably. Both of these criteria varied markedly between classes. Wet mass was consistently the most sensitive endpoint above 100 microg/L; conversely, frond number was the most sensitive below 100 microg/L. Pigment endpoints were significantly less sensitive than growth endpoints.