Ongoing Laboratory Performance Study on Chemical Analysis of Hydrophobic and Hydrophilic Compounds in Three Aquatic Passive Samplers.

The quality of chemical analysis is an important aspect of passive sampling-based environmental assessments. The present study reports on a proficiency testing program for the chemical analysis of hydrophobic organic compounds in silicone and low-density polyethylene (LDPE) passive samplers and hydrophilic compounds in polar organic chemical integrative samplers. The median between-laboratory coefficients of variation (CVs) of hydrophobic compound concentrations in the polymer phase were 33% (silicone) and 38% (LDPE), similar to the CVs obtained in four earlier rounds of this program. The median CV over all rounds was 32%. Much higher variabilities were observed for hydrophilic compound concentrations in the sorbent: 50% for the untransformed data and a factor of 1.6 after log transformation. Limiting the data to the best performing laboratories did not result in less variability. Data quality for hydrophilic compounds was only weakly related to the use of structurally identical internal standards and was unrelated to the choice of extraction solvent and extraction time. Standard deviations of the aqueous concentration estimates for hydrophobic compound sampling by the best performing laboratories were 0.21 log units for silicone and 0.27 log units for LDPE (factors of 1.6 to 1.9). The implications are that proficiency testing programs may give more realistic estimates of uncertainties in chemical analysis than within-laboratory quality control programs and that these high uncertainties should be taken into account in environmental assessments.

Inter-laboratory study for the certification of trace elements in seawater certified reference materials NASS-7 and CASS-6.

Certification of trace metals in seawater certified reference materials (CRMs) NASS-7 and CASS-6 is described. At the National Research Council Canada (NRC), column separation was performed to remove the seawater matrix prior to the determination of Cd, Cr, Cu, Fe, Pb, Mn, Mo, Ni, U, V, and Zn, whereas As was directly measured in 10-fold diluted seawater samples, and B was directly measured in 200-fold diluted seawater samples. High-resolution inductively coupled plasma mass spectrometry (HR-ICPMS) was used for elemental analyses, with double isotope dilution for the accurate determination of B, Cd, Cr, Cu, Fe, Pb, Mo, Ni, U, and Zn in seawater NASS-7 and CASS-6, and standard addition calibration for As, Co, Mn, and V. In addition, all analytes were measured using standard addition calibration with triple quadrupole (QQQ)-ICPMS to provide a second set of data at NRC. Expert laboratories worldwide were invited to contribute data to the certification of trace metals in NASS-7 and CASS-6. Various analytical methods were employed by participants including column separation, co-precipitation, and simple dilution coupled to ICPMS detection or flow injection analysis coupled to chemiluminescence detection, with use of double isotope dilution calibration, matrix matching external calibration, and standard addition calibration. Results presented in this study show that majority of laboratories have demonstrated their measurement capabilities for the accurate determination of trace metals in seawater. As a result of this comparison, certified/reference values and associated uncertainties were assigned for 14 elements in seawater CRMs NASS-7 and CASS-6, suitable for the validation of methods used for seawater analysis.

The influence of vegetation, mesoclimate and meteorology on urban atmospheric microclimates across a coastal to desert climate gradient.

Many cities are increasing vegetation in part due to the potential for microclimate cooling. However, the magnitude of vegetation cooling and sensitivity to mesoclimate and meteorology are uncertain. To improve understanding of the variation in vegetation's influence on urban microclimates we asked: how do meso- and regional-scale drivers influence the magnitude and timing of vegetation-based moderation on summertime air temperature (Ta), relative humidity (RH) and heat index (HI) across dryland cities? To answer this question we deployed a network of 180 temperature sensors in summer 2015 over 30 high- and 30 low-vegetated plots in three cities across a coastal to inland to desert climate gradient in southern California, USA. In a followup study, we deployed a network of temperature and humidity sensors in the inland city. We found negative Ta and HI and positive RH correlations with vegetation intensity. Furthermore, vegetation effects were highest in evening hours, increasing across the climate gradient, with reductions in Ta and increases in RH in low-vegetated plots. Vegetation increased temporal variability of Ta, which corresponds with increased nighttime cooling. Increasing mean Ta was associated with higher spatial variation in Ta in coastal cities and lower variation in inland and desert cities, suggesting a climate dependent switch in vegetation sensitivity. These results show that urban vegetation increases spatiotemporal patterns of microclimate with greater cooling in warmer environments and during nighttime hours. Understanding urban microclimate variation will help city planners identify potential risk reductions associated with vegetation and develop effective strategies ameliorating urban microclimate.

Field test of the TOXSWA pesticide fate model: Comparison of simulated and observed chlorpyrifos in water, sediment and macrophytes in four stagnant ditches.

TOXSWA is a numerical model describing pesticide behavior in an edge-of-field waterbody. It is widely used to predict exposure in regulatory risk assessment for aquatic ecosystems. Exposure concentrations are predicted based upon pesticide process parameters obtained in standardized laboratory experiments. However, few tests of the model performance based on field data have been carried out. We compare simulated concentrations to observations from a field experiment with four shallow stagnant ditches over sprayed with chlorpyrifos, a moderately volatile pesticide with a significant sorption capacity. Input parameters describing the four ditches, such as dimensions, water depth, sediment and macrophyte characteristics were measured in detail. Additionally, laboratory experiments were carried out to determine site-specific values for parameters describing chlorpyrifos degradation in water and sediment, as well as sorption to the two dominant macrophyte species. Based upon these estimated parameters, the correspondence between simulated and measured concentrations in water, sediment and macrophytes is poor. We attribute this discrepancy to a lack of site-specific input for the processes of volatilization and sorption to sediment, which both are important processes for chlorpyrifos. Therefore, we calibrated TOXSWA using the optimization tool PEST. The transfer coefficient for volatilization and the coefficient for sorption to sediment were optimized based on the observed concentrations in water and sediment. This resulted in a substantial improvement of correspondence. Optimized values of the transfer coefficient for volatilization and the coefficient for sorption to sediment are substantially higher than their initial estimates (4-8-fold and 2-4-fold increase, respectively), but can be well explained. The optimized coefficients vary less than a factor 2 between the four ditches. We conclude that TOXSWA can adequately predict chlorpyrifos behavior in the four ditches, provided that reliable site-specific parameter estimates are available. Field tests for other pesticides, waterbodies and agro-environmental conditions are warranted.

Variability in the dynamics of mortality and immobility responses of freshwater arthropods exposed to chlorpyrifos.

The species sensitivity distribution (SSD) concept is an important probabilistic tool for environmental risk assessment (ERA) and accounts for differences in species sensitivity to different chemicals. The SSD model assumes that the sensitivity of the species included is randomly distributed. If this assumption is violated, indicator values, such as the 50% hazardous concentration, can potentially change dramatically. Fundamental research, however, has discovered and described specific mechanisms and factors influencing toxicity and sensitivity for several model species and chemical combinations. Further knowledge on how these mechanisms and factors relate to toxicologic standard end points would be beneficial for ERA. For instance, little is known about how the processes of toxicity relate to the dynamics of standard toxicity end points and how these may vary across species. In this article, we discuss the relevance of immobilization and mortality as end points for effects of the organophosphate insecticide chlorpyrifos on 14 freshwater arthropods in the context of ERA. For this, we compared the differences in response dynamics during 96 h of exposure with the two end points across species using dose response models and SSDs. The investigated freshwater arthropods vary less in their immobility than in their mortality response. However, differences in observed immobility and mortality were surprisingly large for some species even after 96 h of exposure. As expected immobility was consistently the more sensitive end point and less variable across the tested species and may therefore be considered as the relevant end point for population of SSDs and ERA, although an immobile animal may still potentially recover. This is even more relevant because an immobile animal is unlikely to survive for long periods under field conditions. This and other such considerations relevant to the decision-making process for a particular end point are discussed.

Fate and effects of the insecticide chlorpyrifos in outdoor plankton-dominated microcosms in Thailand.

The fate and effects of the insecticide chlorpyrifos were studied in plankton-dominated, freshwater microcosms in Thailand. Disappearance rates of chlorpyrifos from the water column in the present study were similar to those in temperate regions. Insecticide accumulation in the sediment was relatively small, with the major part in the top layer (depth, 1.5 cm). Application of chlorpyrifos led to significant changes in freshwater biological communities. Clam shrimps (Conchostraca) and the cladoceran Moina micrura were the most susceptible species (no-observed-effect concentration [NOEC], 0.1 microg/L) and macroinvertebrates the most sensitive community (NOEC, 0.1 microg/L). These results are in agreement with those from semifield experiments with chlorpyrifos in temperate regions. The results of an in situ bioassay were used to calculate a NOEC of 0.1 microg/L and a 48-h median lethal concentration of 0.6 microg/L for M. micrura, which are similar to toxicity values reported for Daphnia magna in studies in temperate regions. Overall, these findings support the use of toxicity data from temperate regions for the risk assessment of low-persistent insecticides like chlorpyrifos for aquatic communities in tropical regions.

Responses of zooplankton in lufenuron-stressed experimental ditches in the presence or absence of uncontaminated refuges.

Outdoor experimental ditches were used to evaluate the influence of untreated refuges on the recovery of zooplankton communities following treatment with the fast-dissipating insecticide lufenuron. Each experimental ditch was divided into three sections of the same surface area. The treatments differed in the proportion of ditch (0, 33, 67, and 100% of the surface area) to which the insecticide was applied at the same nominal treatment (3 mug/L). During the first week postapplication, a barrier was placed between treated and untreated ditch sections. The untreated sections were included to provide a source of organisms for recovery of affected zooplankton populations in the treated sections of the ditch after the removal of the barrier. Cyclopoida were the most affected by lufenuron treatment, followed by Daphnia gr. galeata. These and other direct effects of treatment on larvae of the phantom midge Chaoborus spp. resulted in clear indirect effects on populations of Calanoida, Ceriodaphnia, and Rotifera. Overall, faster recovery of the zooplankton community was observed in the treated sections of ditches that were sprayed for a smaller proportion of their surface area. Nevertheless, individual zooplankton populations showed considerable differences in rate of recovery. Cyclopoida showed a relatively slow rate of recovery even in the partially treated ditches. Daphnia gr. galeata recovered more rapidly in treated ditch sections in the presence of unsprayed ditch sections, illustrating the potential influence of unexposed refuges. Furthermore, the presence of refuges most likely dampened the magnitude and duration of indirect effects in the ditches treated with lufenuron.

Determination of total dissolved nitrogen in seawater by isotope dilution gas chromatography mass spectrometry following digestion with persulfate and derivatization with aqueous triethyloxonium.

In this study, we propose a novel approach for the determination of total dissolved nitrogen (TDN) in seawater combining high-precision isotope dilution GC-MS with persulfate digestion. A 2 mL sample aliquot was digested with an alkaline solution of persulfate to convert nitrogen containing compounds to nitrate. Digested samples were spiked with 15NO3- internal standard and treated with aqueous triethyloxonium to convert the analyte into volatile EtONO2. This derivative was readily separated from the matrix under gaseous form and could be sampled from the headspace before GC-MS analysis. The resulting chromatograms showed a stable flat baseline with EtONO2 as the only eluting peak (retention time 2.75 min on a DB 5.625 column). Such an approach provides specificity and obviates the shortcomings of current detection methods employed to analyze seawater samples after digestion with persulfate. In negative chemical ionization mode, the method reached a detection limit of 0.5 µmol/kg TDN (7 ng/g N) and could be applied to quantify seawater samples with 1-25 µmol/kg TDN. On the upper end of the range, quantitation could be repeated within 1%, whereas on a 6 µmol/kg TDN sample repeatability was 2.3% on eight measurements. The method was employed in two proficiency testing exercises providing results in agreement with consensus values. We investigated the impact of reagent blank and we implemented a blank-matching optimal design to account for such contribution. Finally, we performed a study on the yield of persulfate oxidation for organic and inorganic nitrogen compounds typically present in seawater. Whilst nitrite and ammonium are fully converted to nitrate, more complex organic molecules showed recoveries varying from 70% to 100%.

Laboratory performance study for passive sampling of nonpolar chemicals in water.

Two laboratory performance studies with 21 and 11 participants were carried out for passive sampling of nonpolar chemicals in water, using silicone samplers that were deployed for 7 wk and 13 wk at 2 river sites in the Netherlands. Target analytes were polychlorinated biphenyls, polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs), hexachlorobutadiene, hexachlorobenzene, and a number of performance reference compounds (PRCs). Calculation of aqueous concentrations based on prescribed input values and a prescribed uptake model was also included. Between-laboratory coefficients of variation (CVs) in the analysis of target compounds were approximately 20% at concentrations of 100 ng g-1 and approximately 100% at concentrations of 0.01 ng g-1 , which was similar to previous results for the analysis of biota samples. The analysis of PRCs yielded water sampling rates with a between-laboratory CV of 18% to 30%. The sampling rate model showed a nearly perfect match with the consensus values of retained PRCs. The implications of the present study for future interlaboratory exercises are discussed. Environ Toxicol Chem 2017;36:1156-1161. © 2016 SETAC.

Variation in the urban vegetation, surface temperature, air temperature nexus.

Our study examines the urban vegetation - air temperature (Ta) - land surface temperature (LST) nexus at micro- and regional-scales to better understand urban climate dynamics and the uncertainty in using satellite-based LST for characterizing Ta. While vegetated cooling has been repeatedly linked to reductions in urban LST, the effects of vegetation on Ta, the quantity often used to characterize urban heat islands and global warming, and on the interactions between LST and Ta are less well characterized. To address this need we quantified summer temporal and spatial variation in Ta through a network of 300 air temperature sensors in three sub-regions of greater Los Angeles, CA, which spans a coastal to desert climate gradient. Additional sensors were placed within the inland sub-region at two heights (0.1m and 2m) within three groundcover types: bare soil, irrigated grass, and underneath citrus canopy. For the entire study region, we acquired new imagery data, which allowed calculation of the normalized difference vegetation index (NDVI) and LST. At the microscale, daytime Ta measured along a vertical gradient, ranged from 6 to 3°C cooler at 0.1 and 2m, underneath tall canopy compared to bare ground respectively. At the regional scale NDVI and LST were negatively correlated (p<0.001). Relationships between diel variation in Ta and daytime LST at the regional scale were progressively weaker moving away from the coast and were generally limited to evening and nighttime hours. Relationships between NDVI and Ta were stronger during nighttime hours, yet effectiveness of mid-day vegetated cooling increased substantially at the most arid region. The effectiveness of vegetated Ta cooling increased during heat waves throughout the region. Our findings suggest an important but complex role of vegetation on LST and Ta and that vegetation may provide a negative feedback to urban climate warming.

Comparing aquatic risk assessment methods for the photosynthesis-inhibiting herbicides metribuzin and metamitron.

Three different risk assessment procedures are described that aim to protect freshwater habitats from risks of the photosynthesis-inhibiting herbicides metribuzin and metamitron. These procedures are (1) the first-tier approach, based on standard toxicity tests and the application of an assessment factor, (2) the Species Sensitivity Distribution (SSD) approach, based on laboratory tests with a wider array of species and the application of a statistical model to calculate the HCx (the Hazardous Concentration for x% of the species), and (3) the model ecosystem approach, based on the evaluation of treatment-related effects in field enclosures. A comparison of the risk assessment procedures reveals that the first-tier approach is the most conservative for metamitron and metribuzin, and that HC5 values (and even HC10 values) based on acute EC50 values of algae and aquatic vascular plants may be used to derive maximum permissible concentrations for single applications. For both compounds these HC5 values were very similar to the ecological threshold concentrations in the enclosure studies. In contrast to model ecosystem experiments, however, HCx values based on lab toxicity tests do not provide information on the recovery potential of sensitive endpoints and on indirect effects, which may be important for regulatory decision-making. In the enclosure study, indirect effects of metribuzin on invertebrate populations were observed at an exposure concentration that was approximately 20 times lower than the corresponding HC5 value based on lab toxicity data for aquatic invertebrates.

Aquatic risk assessment of a realistic exposure to pesticides used in bulb crops: a microcosm study.

The fungicide fluazinam, the insecticide lambda-cyhalothrin, and the herbicides asulam and metamitron were applied to indoor freshwater microcosms (water volume approximately 0.6 m3). The treatment regime was based on a realistic application scenario in tulip cultivation. Concentrations of each pesticide were equal to 0%, 0.2%, 0.5%, 2%, and 5% spray drift emission of label-recommended rates. Contribution of compounds to the toxicity of the pesticide package was established by expressing their concentrations as fractions of toxic units. The fate of the compounds in the water, and responses of phytoplankton, zooplankton, periphyton, macroinvertebrates, macrophytes, decomposition, and water quality were followed for 13 weeks. The half-lives of lambda-cyhalothrin, metamitron, and fluazinam were 1 to 2 d; that of asulam was >30 d. No consistent effects could be demonstrated for the 0.2% treatment regime that was therefore considered the no-observed-effect concentration community (NOEC). The macroinvertebrate populations of Gammarus pulex, Asellus aquaticus, and Proasellus meridianus were the most sensitive end points, followed by species of copepods and cladocerans. Responses mainly were due to lambda-cyhalothrin. The 0.5% treatment regime resulted in short-term effects. Pronounced effects were observed at the 2% and 5% treatment levels. At the end of the experiment, the macrophyte biomass that consisted of Elodea nuttallii, showed a decline at the two highest treatment levels, asulam being the causal factor (NOEC: 0.5% treatment level). Primary production was reduced at the 5% treatment level only. In our experiment, the first-tier risk assessment procedure for individual compounds was adequate for protecting sensitive populations exposed to realistic combinations of pesticides. Spray drift reduction measures seem to be efficient in protecting aquatic ecosystems in agricultural areas.

Fate of the insecticide lambda-cyhalothrin in ditch enclosures differing in vegetation density.

Use of the insecticide lambda-cyhalothrin in agriculture may result in the contamination of water bodies, for example by spray drift. Therefore, the possible exposure of aquatic organisms to this insecticide needs to be evaluated. The exposure of the organisms may be reduced by the strong sorption of the insecticide to organic materials and its susceptibility to hydrolysis at the high pH values in the natural range. In experiments done in May and August, formulated lambda-cyhalothrin was mixed with the water body of enclosures in experimental ditches containing a bottom layer and macrophytes (at different densities) or phytoplankton. Concentrations of lambda-cyhalothrin in the water body and in the sediment layer, and contents in the plant compartment, were measured by gas-liquid chromatography at various times up to 1 week after application. Various water quality parameters were also measured. Concentrations of lambda-cyhalothrin decreased rapidly in the water column: 1 day after application, 24-40% of the dose remained in the water, and by 3 days it had declined to 1.8-6.5%. At the highest plant density, lambda-cyhalothrin residue in the plant compartment reached a maximum of 50% of the dose after 1 day; at intermediate and low plant densities, this maximum was only 3-11% of the dose (after 1-2 days). The percentage of the insecticide in the ditch sediment was 12% or less of the dose and tended to be lower at higher plant densities. Alkaline hydrolysis in the water near the surface of macrophytes and phytoplankton is considered to be the main dissipation process for lambda-cyhalothrin.

Effects of an extract of oystercatcher (Haematopus ostralegus) eggs from the Zeehavenkanaal in The Netherlands, and of its major contaminant, hexachlorobenzene, on the chicken embryo.

Oystercatchers (Haematopus ostralegus) foraging on the canal 'Zeehavenkanaal' in the Netherlands have been shown to accumulate appreciable amounts of contaminants, especially hexachlorobenzene. The present study was performed to assess the embryotoxic effects of the present contaminants. To this end, a two step approach was followed. In step one, the toxic effects of hexachlorobenzene were studied in the chicken embryo bioassay, using concentrations realistic for the field situation. In step two, yolks of oystercatcher eggs were extracted and the embryotoxic potency of this extract was studied in the same bioassay, using doses of 1, 10 and 100% of the contaminant load in one average egg. The extract contained hexachlorobenzene and PCBs. However, presence of other compounds could not be excluded, since these were not analysed. Hexachlorobenzene induced a nonsignificant decrease in lymphocyte density in the bursa of Fabricius. The egg extract caused a 3.5 fold induction of EROD activity at the highest dose applied, and decreased lymphocyte density in the bursa of Fabricius.

Estimating degradation rates in outdoor stagnant water by inverse modelling with TOXSWA: a case study with prosulfocarb.

BACKGROUND: The regulatory risk assessment of pesticides requires the assessment of exposure of aquatic ecosystems in small surface waters adjacent to agricultural fields. This exposure is predicted using simulation models, for which an important input parameter is the degradation rate in water. In regulatory dossiers, the decline rate in water from outdoor mesocosms is often available, but this rate encompasses more processes than degradation. Therefore, a procedure was designed for estimating the degradation rate in water that was suitable for mesocosm studies with limited datasets, e.g. datasets lacking site-specific sorption coefficients and relevant sediment properties. The procedure, based upon inverse modelling with TOXSWA, has been tested on a dataset for prosulfocarb in stagnant ditches. RESULTS: A degradation half-life in the ditch water of 2.9 days (20 °C) was found. This short half-life was to a significant extent accounted for by biodegradation rather than hydrolysis or photolysis. This half-life was considerably shorter than the half-life in the water layer of two laboratory water-sediment system experiments. CONCLUSION: The estimation procedure resulted in a unique half-life for the degradation rate in water. Such outdoor mesocosm studies seem to be better suited to assessing the degradation rate in water in ditches than the conventional water-sediment studies.

Effects of linuron on a rooted aquatic macrophyte in sediment-dosed test systems.

Effects of linuron on the sediment-rooted aquatic macrophyte Myriophyllum spicatum L. were studied in sediment-dosed test systems following a proposed guideline with extended test duration. Sediment, pore water, overlying water and macrophyte shoots were sampled weekly for chemical analyses. Linuron was stable in the sediments. Sediment and pore water concentrations were in equilibrium after 48 h. Overlying water concentrations increased over time, but did not reach equilibrium with pore water concentrations and were 100 times lower. Mass balances showed a rapid uptake of linuron by macrophyte roots. Known pathways and the compound's properties support the conclusion that Myriophyllum takes up linuron from pore water directly through the roots. Hence, effects on macrophytes in this type of sediment toxicity test should be expressed in terms of pore water concentrations. Pore water concentration is the most relevant parameter for describing effects on macrophytes.

Effects of a herbicide-insecticide mixture in freshwater microcosms: risk assessment and ecological effect chain.

Effects of chronic application of a mixture of the herbicide atrazine and the insecticide lindane were studied in indoor freshwater plankton-dominated microcosms. The macroinvertebrate community was seriously affected at all but the lowest treatment levels, the zooplankton community at the three highest treatment levels, with crustaceans, caddisflies and dipterans being the most sensitive groups. Increased abundance of the phytoplankton taxa Cyclotella sp. was found at the highest treatment level. Threshold levels for lindane, both at population and community level, corresponded well with those reported in the literature. Atrazine produced fewer effects than expected, probably due to decreased grazer stress on the algae as a result of the lindane application. The safety factors set by the Uniform Principles for individual compounds were also found to ensure protection against chronic exposure to a mixture of a herbicide and insecticide at community level, though not always at the population level.

Effects of a mixture of two insecticides in freshwater microcosms: I. Fate of chlorpyrifos and lindane and responses of macroinvertebrates.

Effects of chronic application of a mixture of the insecticides chlorpyrifos and lindane were studied in indoor freshwater microcosms. The exposure concentrations (based on 0, 0.005, 0.01, 0.05, 0.1 and 0.5 times the LC50 of the most sensitive standard test organism for each compound) were kept at a constant level for four weeks. The calculated mean concentrations for chlorpyrifos were found to be almost at their corresponding nominal level during the treatment period. The mean calculated lindane concentrations, however, were found to be 15-40% higher than intended. In the post treatment period both insecticides dissipated fast (t 1/2: chlorpyrifos 9 days, lindane 22 days) from the water phase. The concentrations of the mixture at the highest treatment level corresponded to 0.53 toxic units (TU) for Daphnia magna and 0.61 TU for the most sensitive fish. The decomposition of Populus leaves in litter bags was significantly lower at the three highest insecticide concentrations. The macroinvertebrate community was seriously affected at the three highest treatment levels, with Crustacea and the Chironomidae Corynoneura proving to be the most sensitive groups. Gastropoda and Oligochaeta were relatively insensitive and some taxa (e.g. Valvata piscinalis, juvenile Physa fontinalis, Nemertea and Stylaria lacustris) increased in numbers. The observed effects could be explained from the individual toxicity of the insecticides to the invertebrates, and did not indicate synergistic effects. A second paper (Van den Brink et al., 2002) addresses the effects on other endpoints, as well as the overall risk assessment of the insecticide mixture.