Uptake calibration of polymer-based passive samplers for monitoring priority and emerging organic non-polar pollutants in WWTP effluents.

The uptake calibration of more than 12 non-polar organic contaminants by 3 polymeric materials is shown: bare polydimetilsiloxane (PDMS, stir-bars), polyethersulfone tubes and membranes (PES) and polyoxymethylene membranes (POM), both in their free form and membrane-enclosed sorptive coating (MESCO). The calibration process was carried out exposing the samplers to a continuous flow of contaminated water at 100 ng mL(-1) for up to 28 days, and, consequently, the sampling rates (Rs, mL day(-1)) of several organic microcontaminants were provided for the first time. In situ Rs values were also determined disposing the samplers in the effluent of a wastewater treatment plant. Finally, these passive samplers were applied to monitor the effluents of two wastewater treatment plants. This application lead to the confirmation of the presence of galaxolide, tonalide and 4-tert-octylphenol at high ng mL(-1) levels, as well as the identification of compounds like some phthalates and alkylphenols at levels below the detection limits for active sampling methods.

Pollution-Induced Community Tolerance To Diagnose Hazardous Chemicals in Multiple Contaminated Aquatic Systems.

Aquatic ecosystems are often contaminated with large numbers of chemicals, which cannot be sufficiently addressed by chemical target analyses. Effect-directed analysis (EDA) enables the identification of toxicants in complex contaminated environmental samples. This study suggests pollution-induced community tolerance (PICT) as a confirmation tool for EDA to identify contaminants which actually impact on local communities. The effects of three phytotoxic compounds local periphyton communities, cultivated at a reference (R-site) and a polluted site (P-site), were assessed to confirm the findings of a former EDA study on sediments. The sensitivities of R- and P-communities to prometryn, tributyltin (TBT) and N-phenyl-2-naphthylamine (PNA) were quantified in short-term toxicity tests and exposure concentrations were determined. Prometryn and PNA concentrations were significantly higher at the P-site, whereas TBT concentrations were in the same range at both sites. Periphyton communities differed in biomass, but algal class composition and diatom diversity were similar. Community tolerance of P-communities was significantly enhanced for prometryn, but not for PNA and TBT, confirming site-specific effects on local periphyton for prometryn only. Thus, PICT enables in situ effect confirmation of phytotoxic compounds at the community level and seems to be suitable to support confirmation and enhance ecological realism of EDA.

Fish embryo toxicity test: identification of compounds with weak toxicity and analysis of behavioral effects to improve prediction of acute toxicity for neurotoxic compounds.

The fish embryo toxicity test has been proposed as an alternative for the acute fish toxicity test, but concerns have been raised for its predictivity given that a few compounds have been shown to exhibit a weak acute toxicity in the fish embryo. In order to better define the applicability domain and improve the predictive capacity of the fish embryo test, we performed a systematic analysis of existing fish embryo and acute fish toxicity data. A correlation analysis of a total of 153 compounds identified 28 compounds with a weaker or no toxicity in the fish embryo test. Eleven of these compounds exhibited a neurotoxic mode of action. We selected a subset of eight compounds with weaker or no embryo toxicity (cyanazine, picloram, aldicarb, azinphos-methyl, dieldrin, diquat dibromide, endosulfan, and esfenvalerate) to study toxicokinetics and a neurotoxic mode of action as potential reasons for the deviating fish embryo toxicity. Published fish embryo LC50 values were confirmed by experimental analysis of zebrafish embryo LC50 according to OECD guideline 236. Except for diquat dibromide, internal concentration analysis did not indicate a potential relation of the low sensitivity of fish embryos to a limited uptake of the compounds. Analysis of locomotor activity of diquat dibromide and the neurotoxic compounds in 98 hpf embryos (exposed for 96 h) indicated a specific effect on behavior (embryonic movement) for the neurotoxic compounds. The EC50s of behavior for neurotoxic compounds were close to the acute fish toxicity LC50. Our data provided the first evidence that the applicability domain of the fish embryo test (LC50s determination) may exclude neurotoxic compounds. However, neurotoxic compounds could be identified by changes in embryonic locomotion. Although a quantitative prediction of acute fish toxicity LC50 using behavioral assays in fish embryos may not yet be possible, the identification of neurotoxicity could trigger the conduction of a conventional fish acute toxicity test or application of assessment factors while considering the very good fish embryo-acute fish toxicity correlation for other compounds.

Passive sampling of herbicides above sediments at sites with losses of submerged macrophytes in a mesotrophic lake.

Declines of submerged macrophytes (SUM) were monitored in littoral zones of the deep, mesotrophic lake Suhrer See (Northern Germany) since 2017. Drastic losses coincided with intense agriculture in sandy sub-catchments and precipitation. All lines of evidence pointed to a causal connection with subsurface discharge indicating that herbicide application might have caused the effects. Passive sampling was applied in 2022 to elucidate, whether herbicides were really present at sites of losses and if so, in ecotoxicological relevant concentrations. Samplers were exposed on top of lake sediments in 2 m depth and under worst case conditions, i.e., at sites, known for losses of the whole functional group of SUM and at the beginning of the vegetation period. At this time, SUM diaspores were most vulnerable to repression of development and the subsurface discharge was high in the same instance. The potential ecotoxicological relevance of detected herbicide concentrations was assessed with a toxic units (TU) approach, with reference to acute effect concentrations (EC50 of green algae, 72 h, growth). The TU ranged from 0.001 to 0.03. Most concentrations exceeded the threshold of relevance set by an assessment factor of 1000, i.e., TU > 0.001. Locally applied herbicides acted by suppressing developmental stages, and the sum of TU exceeded 0.02 at all sites, mainly due to diflufenican. Not applied locally, terbuthylazine and its relevant metabolites, including terbutryn, acted by inhibiting photosynthesis, and the sum of TU reached 0.005. On this base, diflufenican was assessed to be likely a main stressor, all other detected herbicides to be potentially relevant. Uncertainties and knowledge gaps were specified. The result of the chemical risk assessment was counterchecked for consistence with biological monitoring data within a whole lake perspective. Concepts of empirical and advanced causal attribution methodology were applied to get a grip to the ecological causal field and to protection.

Survey of Appearance and temporal concentrations of polar organic pollutants in Saxon waters.

Integrative passive samplers such as the Chemcatcher are often proposed as alternatives for conventional grab sampling of surface waters. So far, their routine application for regulatory monitoring is hampered (among others) by the fact that TWA concentrations may depend significantly on the design and specifics of the samplers employed. The presented study addresses this issue, focusing on the uptake of polar organic pollutants in three different Chemcatcher configurations and polydimethylsiloxane (PDMS) sheets in the field. Covering waste water treatment plant effluents, creeks, and rivers, samplers were deployed for periods of 14-21 days in eight trials over the course of one year. 33 organic pesticides, 14 transformation products and 31 pharmaceuticals could be detected at least once in TWA concentrations ranging from 0.03 ng/L to 16.5 µg/L. We show that through employing generic, i.e. sampler specific, rather than compound specific sampling rates, the variation among results from three integrative passive sampler designs yields linear correlations with an offset of less than 0.1 and correlation coefficients r2 > 0.8. In this way, TWA concentrations enable the identification of low-concentration xenobiotics of concern, which may support regulatory monitoring correspondingly.

226Ra measurement via gamma-ray spectrometry of 222Rn progeny - quantification of radon losses from sample capsules.

Radium-226 detection in sediment samples is generally executed by means of gamma-ray spectrometry. Data evaluation relies (besides the 186.2 keV 226Ra gamma peak) on the combined analysis of major gamma peaks that are produced by the short-lived radon (222Rn) daughters 214Pb and 214Bi. Precondition for this detection approach is equilibrium decay of all members of the decay chain between 226Ra and 214Bi. In closed systems, this equilibrium is reached after about five half-lives of 222Rn (19 days). However, a closed system can only be guaranteed if the capsule which contains the sample prevents diffusive escape of radon. Such radon-tightness cannot be guaranteed for a wide range of plastic materials. Due to its polymer structure, plastic material generally tends to allow radon diffusion and hence radon loss from the sample resulting in a disturbance of the required decay equilibrium. The paper introduces an approach that allows quantifying radon loss from sample capsules by direct radon measurements using mobile radon detection equipment. The experimental findings are supported by theoretical considerations. An examined alternative approach based on the offset of the 186.2 keV data point from an efficiency function that is calculated exclusively from short-lived radon progeny peaks in the gamma-ray spectrum did not prove to be applicable due to a lack of supporting peaks in the low-energy section of the spectrum.

Calibration of the Chemcatcher® passive sampler and derivation of generic sampling rates for a broad application in monitoring of surface waters.

We determined sampling rates for 34 pesticides, five pesticide transformation products, and 34 pharmaceutical compounds with the Chemcatcher (CC) passive sampler in a laboratory-based continuous-flow system at 40 cm/s and ambient temperature. Three different sampling phases were used: styrene divinylbenzene disks (SDB-XC), styrene divinylbenzene reversed phase sulfonate disks (SDB-RPS), and hydrophilic lipophilic balance disks (HLB), in all cases covered with a diffusion-limiting polyethersulfone membrane. The measured sampling rates range from 0.007 L/d to 0.193 L/d for CC with SDB-XC (CC-XC), from 0.055 L/d to 0.796 L/d for CC with SDB-RPS (CC-RPS), and from 0.018 L/d to 0.073 L/d for CC equipped with HLB (CC-HLB). Comparison with sampling rates from literature enabled to derive generic sampling rates that can be used for compounds with unknown uptake kinetics such as transformations products and new compounds of interest. Field trial results demonstrate that the presently derived generic sampling rates are suitable for estimating time-weighted average concentrations within reasonable uncertainty limits. In this way, Chemcatcher passive sampling can be applied approximately to a broad range of solutes without the need for deriving compound-specific sampling rates, which enable compliance checks against environmental quality standards and further risk assessment.

Structural alerts for the excess toxicity of acrylates, methacrylates, and propiolates derived from their short-term and long-term bacterial toxicity.

For eight acrylates, three methacrylates, and three propiolates as three subclasses of α,ß-unsaturated esters, short-term and long-term bacterial toxicity with Vibrio fischeri was determined in terms of EC(50) (effective concentration 50%) values for the 30-min bioluminescence and 24-h growth inhibition. To this end, experimental exposure concentrations were corrected for volatilization through a thermodynamic model based on Henry's law constant of the compounds. Moreover, toxicity enhancements T(e) as the ratio of narcosis-predicted over actual EC(50) were determined and discussed in terms of underlying mechanisms of reaction of the electrophiles with endogenous nucleophiles such as glutathione (GSH) and proteins. Overall, log EC(50) [M] ranges from -2.28 to -3.70 (30 min) and from -2.80 to -5.28 (24 h), respectively, indicating a significantly larger sensitivity of the growth inhibition bioassay for the reactive toxicity of these Michael acceptors. The latter is also reflected in the observed toxicity enhancements, where log T(e) > 1 was obtained for only 5 of 14 30-min EC(50) values but for 11 of 13 24-h EC(50) values. Moreover, the average long-term to short-term difference in log T(e) is 1 unit for the acrylates and 0.7 units for both methacrylates and propiolates. Methacrylates exert narcosis-level toxicity except for the methyl derivative in the long-term assay. The log EC(50) (24 h) of a subset of 10 mostly excess-toxic acrylates and a propiolate correlates with their logarithmic rate constants of reaction with GSH, log k(GSH), significantly more than with log K(ow) (r(2) 0.76 vs 0.47), yielding a respective regression rms of 0.34 log units. For allyl and propargyl acrylate as well as propargyl methacrylate, the observed excess toxicity is likely caused by initial enzymatic hydrolysis and subsequent oxidation of the α,ß-unsaturated alcohols to the respective carbonyls. The latter shows that in the context of nonanimal testing schemes such as for REACH, the metabolic capacity of in vitro screens requires attention.

Chemoassay screening of DNA-reactive mutagenicity with 4-(4-nitrobenzyl)pyridine - application to epoxides, oxetanes, and sulfur heterocycles.

Organic electrophiles have the potential to covalently attack DNA bases, and thus initiate mutagenic and carcinogenic processes. In this context, aromatic nitrogen sites of the DNA bases are often particularly nucleophilic, with guanine N7 being one of the most favored sites of adduct formation with electrophilic xenobiotics. Employing 4-(4-nitrobenzyl)pyridine (NBP) as model nucleophile with a respective aromatic ═N- unit, a new kinetic variant of a photometric chemoassay for sensing the DNA reactivity of organic compounds is introduced and applied to 21 three- and four-membered oxygen and sulfur heterocycles (15 epoxides, two thiiranes, three oxetanes, and one thietane). Besides six unreactive compounds (oxetanes, thietane, and aliphatic epoxides with six or more side-chain carbons), second-order rate constants of the electrophile-NBP reaction, k(NBP), were obtained for 15 compounds, ranging from (1.16 ± 0.05)·10⁻³ to (36.5 ± 0.6)·10⁻³ L mol⁻¹ min⁻¹ in a methanol/tris-HCl buffer (16/84 v/v) reaction medium. Solvolysis as confounding factor was addressed by determining respective first-order rate constants k(solv). Analysis of the k(NBP) values resulted in structure-reactivity relationships, and comparison with literature data from the Ames test bacterial strains TA100, TA1535, and TA97 (Salmonella typhimurium) as well as from WP2 uvrA (Escherichia coli) revealed significant log-log relationships between the mutagenic potency of the heterocycles and their reactivity toward NBP. The latter demonstrates the potential of the NBP chemoassay as a nonanimal component of integrated testing strategies for REACH, enabling an efficient screening of organic electrophiles with respect to their DNA reactivity and associated mutagenicity and carcinogenicity.

Air-water partitioning of 222Rn and its dependence on water temperature and salinity.

Radon is useful as a tracer of certain geophysical processes in marine and aquatic environments. Recent applications include detection of groundwater discharges into surface waters and assessment of air/sea gas piston velocities. Much of the research performed in the past decade has relied on continuous measurements made in the field using a radon stripping unit connected to a radon-in-air detection system. This approach assumes that chemical equilibrium is attained between the water and gas phases and that the resulting air activity can be multiplied by a partition coefficient to obtain the corresponding radon-in-water activity. We report here the results of a series of laboratory experiments that describes the dependence of the partition coefficient upon both water temperature and salinity. Our results show that the temperature dependence for freshwater closely matches results that were previously available. The salinity effect, however, has largely been ignored and our results show that this can result in an overestimation of radon concentrations, especially in cooler, more saline waters. Related overestimates in typical situations range between 10 (warmer less saline waters) and 20% (cooler, more saline waters).

Kinetics of the water/air phase transition of radon and its implication on detection of radon-in-water concentrations: practical assessment of different on-site radon extraction methods.

The on-site measurement of radon-in-water concentrations relies on extraction of radon from the water followed by its detection by means of a mobile radon-in-air monitor. Many applications of radon as a naturally occurring aquatic tracer require the collection of continuous radon concentration time series, thus necessitating the continuous extraction of radon either from a permanent water stream supplied by a water pump or directly from a water body or a groundwater monitoring well. Essentially, three different types of extraction units are available for this purpose: (i) a flow-through spray chamber, (ii) a flow-through membrane extraction module, and (iii) a submersible (usually coiled) membrane tube. In this paper we discuss the advantages and disadvantages of these three methodical approaches with particular focus on their individual response to instantaneously changing radon-in-water concentrations. After a concise introduction into theoretical aspects of water/air phase transition kinetics of radon, experimental results for the three types of extraction units are presented. Quantitative suggestions for optimizing the detection setup by increasing the water/air interface and by reducing the air volume circulating through the degassing unit and radon detector are made. It was shown that the flow-through spray chamber and flow-through membrane perform nearly similarly, whereas the submersible membrane tubing has a significantly larger delay in response to concentration changes. The flow-through spray chamber is most suitable in turbid waters and to applications where high flow rates of the water pump stream can be achieved (e.g., where the power supply is not constrained by field conditions). The flow-through membrane is most suited to radon extraction from clear water and in field conditions where the power supply to a water pump is limited, e.g., from batteries. Finally, the submersible membrane tube is most suitable if radon is to be extracted in situ without any water pumping, e.g., in groundwater wells with a low yield, or in long-term time series, in which short-term variations in the radon concentration are of no relevance.

Exploring the partitioning of hydrophobic organic compounds between water, suspended particulate matter and diverse fish species in a German river ecosystem.

Background: Bioaccumulation of hydrophobic organic compounds (HOCs) along freshwater food chains is a major environmental concern as top predators in food webs are relevant for human consumption. To characterize and manage the associated risks, considerable numbers of organisms are sampled regularly for monitoring purposes. However, ethical and financial issues call for an alternative, more generic and more robust approach for assessing the internal exposure of fish that circumvents large variability in biota sampling due to interindividual differences. Passive sampling devices (PSDs) offer a fugacity-based approach for pollutant enrichment from different abiotic environmental compartments with a subsequent estimation of bioaccumulation in fish which we explored and compared to HOC concentrations in fish as determined using traditional approaches. Results: In this study, concentrations in silicone-based PSDs applied to the water phase and suspended particulate matter (SPM) of a river polluted with HOCs were used to estimate the concentration in model lipids at thermodynamic equilibrium with either environmental compartment. For comparison, muscle tissue of seven fish species (trophic level 1.8 to 2.8) was extracted using traditional exhaustive solvent extraction, and the lipid-normalized concentrations of HOCs were determined. The PSD-based data from SPM proved to be a more conservative estimator for HOCs accumulated in fish than those from water. Body length of the fish was found to be more suitable to describe increasing accumulation of HOCs than their trophic level as derived from stable isotope analysis and might offer a suitable alternative for future studies. Conclusions: By combining fugacity-based sampling in the abiotic environment, translation into corresponding concentrations in model lipids and body length as an indicator for increasing bioaccumulation in fish, we present a suggestion for a robust approach that may be a meaningful addition to conventional monitoring methods. This approach potentially increases the efficiency of existing monitoring programs without the need to regularly sacrifice vertebrate species. Supplementary Information: The online version contains supplementary material available at 10.1186/s12302-022-00644-w.

Complex chemical cocktail, containing insecticides diazinon and permethrin, drives acute toxicity to crustaceans in mountain lakes.

Mountain lakes have long been perceived as pristine environments. However, atmospheric deposition of persistent organic pollutants (POPs) have been shown to expose these sensitive ecosystems to chemical pollution. Little is known on how this pollution impacts aquatic ecosystems at high altitudes. We combined passive sampling with liquid and gas chromatography high resolution mass spectrometry (LC- and GC-HRMS) to screen the water of eight lakes in three different regions of the French Pyrenees. In total, we screened for 479 organic chemicals including POPs, polycyclic aromatic hydrocarbons (PAHs), legacy and current-use pesticides, biocides, and musk fragrances. We detected a complex cocktail of 151 individual chemicals and used their toxic unit summation (ΣTU) to assess toxicity for crustaceans and algae. While risks for algae never reached chronic risks, this was always the case for crustaceans. Acute toxic risk thresholds for crustaceans were even exceeded in several of our sites. At sites with acute toxic risk levels (> 0.1 ΣTU) crustaceans were completely absent or showed a low abundance. We conclude that crustaceans were at least partly impacted by the high toxic risks driven by the insecticides diazinon and permethrin. These drugs are widely used to protect livestock from blue tongue disease transmitted by sucking insects, suggesting free roaming livestock as local source. Our results provide important evidence on toxic chemical pollution in relatively remote mountain areas, with important consequences for aquatic mountain ecosystems.

Epoxide and thiirane toxicity in vitro with the ciliates Tetrahymena pyriformis: structural alerts indicating excess toxicity.

The 48 h toxicity of 18 organic narcotics, 13 epoxides, and 2 thiiranes toward the ciliates Tetrahymena pyriformis was determined in terms of 50% growth inhibition EC(50). Nominal EC(50) was corrected for volatilization and sorption to quantify the freely dissolved compound fraction in solution. The derived baseline narcosis model served to evaluate toxicity enhancements T(e) as ratios of narcosis-predicted over experimental EC(50) values. Among the nine heterocycles with aliphatic side chains that include two thiiranes, three compounds yielded T(e) > 10, suggesting their covalent binding at nucleophilic protein sites such as -OH, -NHR, and -SH through S(N)2-type ring-opening. As a general trend of this group, T(e) decreases with increasing alkyl group size. Moreover, four of the six nonaliphatic epoxides exerted substantial excess toxicities with T(e) > 10, which could be rationalized by ring-opening activation through negative inductive effect, benzylic stabilization, and phenyl ring H-bonding. By contrast, 1,2 substituted epoxides showed narcosis-level toxicity, despite the opportunity of side-chain Schiff-base formation with protein amino groups. The resulting structural alerts enable an in silico screening of epoxides and thiiranes for their potential to exert excess toxicity. Note that observed differences in T(e) sensitivity between ciliates, bacteria and fish should be taken into account when designing in vitro alternatives to fish toxicity studies.

Calibration and field application of the Atlantic HLB Disk containing Chemcatcher® passive sampler - Quantitative monitoring of herbicides, other pesticides, and transformation products in German streams.

The Chemcatcher® (CC) passive sampler containing an Atlantic HLB-L Disk (AD) was calibrated in a laboratory-based flow-through tank over 21 days under stirring for 38 polar organic pesticides with log Kow ranging from -1.7 to 3.8. The resultant sampling rates Rs range from 0.025 to 0.068 L/d. In 2018, field trials were conducted in the German rivers Mulde and Havel, as well as in 7 agricultural streams in Lower Saxony and Saxony-Anhalt. For 36 detected pesticides, the overall low concentrations were 0.2 to 49.4 ng/L. The determined pesticide profiles reflect agricultural use and were dominated by triazine herbicides including transformation products, by neonicotinoid insecticides, and by the herbicide mecoprop. Additional single hot spots were provided by the herbicides metamitron, isoproturon, and MCPA (showing the overall largest value of 49.4 ng/L). Notably, the detected waterborne pesticides include banned herbicides and associated transformation products in concentration ratios suggesting also recent input. This concerns in particular atrazine and its transformation products 2-OH-atrazine, deethylatrazine and deisopropylatrazine. An extended target screening of AD-CC extracts from the river Havel revealed the additional presence of other organic micropollutants including biocides, surfactants and industrial chemicals, and demonstrated the AD-CC applicability up to log Kow of 4.5.

Pesticides are the dominant stressors for vulnerable insects in lowland streams.

Despite elaborate regulation of agricultural pesticides, their occurrence in non-target areas has been linked to adverse ecological effects on insects in several field investigations. Their quantitative role in contributing to the biodiversity crisis is, however, still not known. In a large-scale study across 101 sites of small lowland streams in Central Europe, Germany we revealed that 83% of agricultural streams did not meet the pesticide-related ecological targets. For the first time we identified that agricultural nonpoint-source pesticide pollution was the major driver in reducing vulnerable insect populations in aquatic invertebrate communities, exceeding the relevance of other anthropogenic stressors such as poor hydro-morphological structure and nutrients. We identified that the current authorisation of pesticides, which aims to prevent unacceptable adverse effects, underestimates the actual ecological risk as (i) measured pesticide concentrations exceeded current regulatory acceptable concentrations in 81% of the agricultural streams investigated, (ii) for several pesticides the inertia of the authorisation process impedes the incorporation of new scientific knowledge and (iii) existing thresholds of invertebrate toxicity drivers are not protective by a factor of 5.3 to 40. To provide adequate environmental quality objectives, the authorisation process needs to include monitoring-derived information on pesticide effects at the ecosystem level. Here, we derive such thresholds that ensure a protection of the invertebrate stream community.

Acute and chronic toxicity toward the bacteria Vibrio fischeri of organic narcotics and epoxides: structural alerts for epoxide excess toxicity.

The acute and chronic bacterial toxicity of 34 organic compounds comprising 19 baseline narcotics and 15 epoxides has been determined with regard to 30-min bioluminescence and 24-h growth inhibition in terms of EC50 (effective concentration 50%) values employing Vibrio fischeri. For the narcotics, linear regression of log EC50 on log Kow (octanol/water partition coefficient) yields r2 (squared correlation coefficient) and rms (root-mean-square error) values of 0.95 and 0.44 (30-min), and 0.94 and 0.34 (24-h), respectively. Employing the resultant baseline narcosis models, toxicity enhancement (Te) values were derived as a ratio of narcosis-predicted over experimental EC50 for the epoxides. For seven aliphatic epoxides, log Te was below 1 in both assays, indicating narcosis-range toxicity with regard to 30-min bioluminescence and 24-h growth inhibition. Concerning eight nonaliphatic epoxides, log Te values up to 2.4 were observed, reflecting excess toxicity through an enhanced electrophilic reactivity of the compounds. Here, however, the intercorrelation between both assays was very low (r2 = 0.09). The results are discussed in terms of electronic substituent effects activating an SN2-type epoxide reaction with nucleophilic protein sites and side-chain activation offering alternative electrophile-nucleophile reaction routes at side-chain sites, leading to respective structural alerts as indicators of excess toxicity. Surprisingly, 30-min bioluminescence appears to be slightly more sensitive to chemical stress than 24-h growth, which holds both for baseline narcotics and for most of the epoxides. This is also reflected by effective narcosis doses 50%, ED50, of 7.1 mmol/kg (30-min) and 7.7 mmol/kg (24-h) estimated from narcosis theory. Keeping in mind the different end points (bioluminescence vs growth) involved, this finding demonstrates that chronic toxicity is not always more sensitive than acute toxicity, calling for analyses with regard to further respective cases and associated mechanistic causes.

Thiol reactivity and its impact on the ciliate toxicity of α,ß-unsaturated aldehydes, ketones, and esters.

A recently introduced chemoassay has been used to determine second-order rate constants of the electrophile-nucleophile reaction of 15 α,ß-unsaturated aldehydes with glutathione. The respective kGSH values vary for more than 3 orders of magnitude, and are within the range determined previously for 31 α,ß-unsaturated ketones and esters. Structure-reactivity analyses yield distinct relationships between kGSH and structural features of the compounds. Moreover, increasing kGSH increases the aldehyde toxicity toward ciliates in terms of 48 h-EC50 values (effective concentration yielding 50% growth inhibition of Tetrahymena pyriformis within 48 h). A respective log-log regression equation including both kGSH and the octanol/water partition coefficient, Kow, yields a squared correlation coefficient of 0.96. Comparative analysis with corresponding data for 15 ketones and 16 esters reveals systematic differences between the three compound classes with regard to the individual contributions of hydrophobicity and electrophilic reactivity to aquatic toxicity. The former is particularly pronounced for aldehydes, while the ester toxicity is largely governed by reactivity, with ketones showing an intermediate pattern that is more similar to the one of esters than of aldehydes. It follows that within the Michael acceptor domain of α,ß-unsaturated carbonyls, a distinction between aldehydes and nonaldehydic derivatives appears necessary when employing electrophilic reactivity as a component for the quantitative prediction of their reactive toxicity toward aquatic organisms.

Short-term exposure testing of six different passive samplers for the monitoring of hydrophobic contaminants in water.

Passive sampling devices are increasingly relied upon for monitoring non-polar organic contaminants in water. While many types of devices are available they have seldom been evaluated alongside each other. We tested six passive sampling devices namely: Chemcatcher, two modified versions of the membrane enclosed sorptive coating (MESCO I (m) and MESCO II), silicone rod and strip and semipermeable membrane device (SPMD). Samplers spiked with a range of performance reference compounds (PRCs) were exposed (5 days) in a continuous flow-through tank using Meuse river water fortified with fluctuating concentrations (20-700 ng L(-1)) of polycyclic aromatic hydrocarbons, polychlorinated biphenyls, hexachlorobenzene and p,p'-DDE. Dissipation rates of PRCs appeared to provide reliable information on exchange kinetics even under these short-term exposure conditions. They accounted for differences between masses of contaminants accumulated by replicate samplers, indicating that the variability between replicates was in part due to differences in water turbulences and hence boundary layer thickness. In this system, resistances in the membrane and boundary layers are likely to be in the same order of magnitude for PRCs. Sampler performance was evaluated by comparing masses accumulated in the devices only for analytes for which uptake was linear (integrative) and limited by transport across the boundary layer. Consistent data were obtained across the range of samplers despite their different configurations, and the analysis being conducted in three separate laboratories. The pattern in analyte masses accumulated by Chemcatcher and MESCO II data could be explained by the extraction and analysis being conducted only on the receiving phase of the samplers and a significant impact of the lag-phase prior to obtaining a steady flux of contaminants across the polyethylene membranes.

Diffusion coefficients of polar organic compounds in agarose hydrogel and water and their use for estimating uptake in passive samplers.

Diffusion coefficient (D) is an important parameter for prediction of micropollutant uptake kinetics in passive samplers. Passive samplers are nowadays commonly used for monitoring trace organic pollutants in different environmental matrices. Samplers utilising a hydrogel layer to control compound diffusion are gaining popularity. In this work we investigated diffusion of several perfluoroalkyl substances, currently used pesticides, pharmaceuticals and personal care products in 1.5% agarose hydrogel by measuring diffusion coefficients using two methods: a diffusion cell and a sheet stacking technique. Further, diffusion coefficients in water were measured using Taylor dispersion method. The sheet stacking method was used to measure D at 5, 12, 24, and 33 °C in order to investigate temperature effect on diffusion. Median D values ranged from 2.0 to 8.6 × 10-6 cm2 s-1 and from 2.1 to 8.5 × 10-6 cm2 s-1 for the diffusion cell and sheet stack methods respectively. For most compounds, the variability between replicates was higher than the difference between values obtained by the two methods. Rising temperature from 10 to 20 °C increases the diffusion rate by the factor of 1.41 ± 0.10 in average. In water, average D values ranged from 3.03 to 10.0 × 10-6 cm2 s-1 and were comparable to values in hydrogel, but some compounds including perfluoroalkyl substances with a long aliphatic chain could not be evaluated properly due to sorptive interactions with capillary walls in the Taylor dispersion method. Sampling rates estimated using the measured D values were systematically higher than values estimated from laboratory sampler calibration in our previously published study, by the factor of 2.2 ± 1.0 in average.