Pesticide mixture toxicity to algae in agricultural streams - Field observations and laboratory studies with in situ samples and reconstituted water.

Long-term pesticide water concentrations were investigated in four agricultural streams and their mixture toxicity on algae was assessed, based on realistic (i.e. observed) concentrations in laboratory tests using (i) natural weekly water samples and (ii) reconstituted pesticide-spiked water samples representing mixtures with predicted high mixture. This approach both covered the full complexity of natural water samples and the controlled approach of reconstituted water samples. Long-term monitoring data (time-integrated, weekly samples) revealed more than 11 pesticides (range 11.0 ± 0.25-24.0 ± 0.44) in 75% or more of the almost 1600 samples collected between 2002 and 2018. ∑TUalgae exceeded 0.1 for 29 observations (or 1.8%). Despite the multitude of pesticides in a sample, ∑TUalgae was frequently set by one or a few dominating pesticides that contribute to more than 90% of the mixture's toxicity. Algal growth inhibition tests with in situ stream water showed a high frequency of inhibition, despite the low ∑TU for most of these samples (range 0.000014-0.3858). These "false positive" results were attributed to confounding effects of turbidity, the complexation of nutrients, and toxic effects of metals and/or other unknown contaminants. Algal inhibition tests with spiked reconstituted water showed significant inhibitory effects in the range of 1-10x the ∑TUalgae observed in worst-case field samples. Although these tests disregard the chemical complexity of natural water, they show that inhibitory effects of pesticides on algae may occur at the ∑TUalgae observed in monitoring. Furthermore, considering that the ∑TUalgae of stream water are based on weekly average concentrations and likely underestimate short-term peak concentrations of pesticides, these results strongly suggest that inhibitory effects on algae may occur in the agricultural streams of southern Sweden. We conjecture, however, that the rapid recovery of algae contributes to ameliorate these short-term effects and that pesticide contamination should be seen as one of many stressors in the streams that drain agricultural landscapes.

Inverting nutrient fluxes across the land-water interface - Exploring the potential of zebra mussel (Dreissena polymorpha) farming.

We studied the potential of zebra mussel farming for nutrient retention in a eutrophic lake. Duplicate experimental long-line cultivation units were deployed and mussel growth and nutrient retention were quantified after 28 months. Mussels grew well at shallow water depth (<3 m) and our 625 m2 (lake area) experimental units produced 507 and 730 kg dry biomass, respectively, of which 94% were shells. These yields corresponded to an average retention of 92.7 ± 23.1 kg C, 6.1 ± 0.68 kg N, and 0.43 ± 0.04 kg P retention, or 742 kg C, 49 kg N, and 3.5 kg P for a full-size (0.5 ha) mussel farm. We estimate that concentrating the long-lines to a depth of 2.5 m would probably have doubled these yields, based on the differences in mussel growth among depths. We further estimate that a full-size cultivation unit (0.5 ha) thus could compensate for the annual total-P run-off from 23 ha, or the biologically available P from approximately 49 ha of agricultural soils. As traditional measures have proven insufficient, decision-makers need to facilitate novel approaches to mitigate the negative effects of cultural eutrophication. We envision that zebra mussel farming, within their invaded range, provides a promising approach to invert nutrient losses in lakes and coastal lagoons.

History matters: Heterotrophic microbial community structure and function adapt to multiple stressors.

Ecosystem functions in streams (e.g., microbially mediated leaf litter breakdown) are threatened globally by the predicted agricultural intensification and its expansion into pristine areas, which is associated with increasing use of fertilizers and pesticides. However, the ecological consequences may depend on the disturbance history of microbial communities. To test this, we assessed the effects of fungicides and nutrients (four levels each) on the structural and functional resilience of leaf-associated microbial communities with differing disturbance histories (pristine vs. previously disturbed) in a 2 × 4 × 4-factorial design (n = 6) over 21 days. Microbial leaf breakdown was assessed as a functional variable, whereas structural changes were characterized by the fungal community composition, species richness, biomass, and other factors. Leaf breakdown by the pristine microbial community was reduced by up to 30% upon fungicide exposure compared with controls, whereas the previously disturbed microbial community increased leaf breakdown by up to 85%. This significant difference in the functional response increased in magnitude with increasing nutrient concentrations. A pollution-induced community tolerance in the previously disturbed microbial community, which was dominated by a few species with high breakdown efficacies, may explain the maintained function under stress. Hence, the global pressure on pristine ecosystems by agricultural expansion is expected to cause a modification in the structure and function of heterotrophic microbial communities, with microbially mediated leaf litter breakdown likely becoming more stable over time as a consequence of fungal community adaptions.

The mode of bioturbation triggers pesticide remobilization from aquatic sediments.

After their release into the aquatic environment, contaminants may - depending on the physicochemical properties - adsorb to sediments. From there these contaminants can either be buried or remobilised by abiotic factors (e.g., resuspension) as well as by the bioturbating activity of sediment dwelling invertebrates. Little is, however, know about the effects of bioturbation on the fate of pesticides. Therefore, the present study quantified the impact of the bioturbation mode of benthic invertebrate species (bio-diffusor vs. bio-irrigation), the invertebrate density (i.e. 0-8 individuals per replicate), and the substance-inherent properties (i.e. hydrophobicity, water solubility) on the remobilization of sediment-associated pesticides in a laboratory-based set-up over 13 days. We found that both the bioturbation mode (i.e., species identity) and species density, as well as pesticide properties (i.e., hydrophobicity) affected the direction and magnitude of remobilisation of sediment-bound pesticides. The oligochaeta Lumbriculus variegatus showed a density-dependent effect on the remobilization of lindane to the water phase, whereas those with the amphipod Monoporeia affinis and larvae of the midge Chironomus riparius did not. Although these findings show that sediments not per definition are a sink for pesticides, the rates of pesticide remobilization are limited. This observation, thus, suggests that the risk for aquatic communities posed by the remobilization of pesticides from the sediment due to bioturbation is low.

Phenanthrene bioaccumulation in the nematode Caenorhabditis elegans.

The contribution of food to the bioaccumulation of xenobiotics and hence toxicity is still an ambiguous issue. It is becoming more and more evident that universal statements cannot be made, but that the relative contribution of food-associated xenobiotics in bioaccumulation depends on species, substance, and environmental conditions. Yet, small-sized benthic or soil animals such as nematodes have largely been disregarded so far. Bioaccumulation of the polycyclic aromatic hydrocarbon phenanthrene in the absence and presence of bacterial food was measured in the nematode Caenorhabditis elegans. Elimination of phenanthrene in the nematodes was biphasic, suggesting that there was a slowly exchanging pool within the nematodes or that biotransformation of phenanthrene took place. Even with food present, dissolved phenanthrene was still the major contributor to bioaccumulated compound in nematode tissues, whereas the diet only contributed about 9%. Toxicokinetic parameters in the treatment without food were different from the ones of the treatment with bacteria, possibly because nematodes depleted their lipid reserves during starvation.

Autochthonous resources are the main driver of consumer production in dystrophic boreal lakes.

Dystrophic lakes are widespread in temperate regions and intimately interact with surrounding terrestrial ecosystems in energy and nutrient dynamics, yet the relative importance of autochthonous and allochthonous resources to consumer production in dystrophic lakes remains controversial. We argue that allochthonous organic matter quantitatively dominates over photosynthetic autotrophs in dystrophic lakes, but that autotrophs are higher in diet quality and more important for consumers as they contain essential polyunsaturated fatty acids (PUFA). In a field study, we tested the hypotheses that (1) autochthonous primary production is the main driver for consumer production, despite being limited by light availability and low nutrient supplies, and greater supply of allochthonous carbon, (2) the relative contribution of autotrophs to consumers is directly related to their tissue PUFA concentrations, and (3) methane-oxidizing bacteria (MOB) provide an energy alternative for consumers. Pelagic and benthic consumer taxa representing different trophic levels were sampled from five dystrophic lakes: isopod Asellus aquaticus, megalopteran Sialis lutaria, dipteran Chaoborus flavicans, and perch Perca fluviatilis. Based on carbon and nitrogen stable isotopes, the relative contributions of autochthonous (biofilms and seston) and allochthonous (coarse particulate and dissolved organic matter) resources and MOB to these taxa were 47-79%, 9-44% and 7-12% respectively. Results from fatty acid (FA) analyses show that the relative omega3-FA and PUFA concentrations increased with trophic level (Asellus < Sialis and Chaoborus < Perca). Also, eicosapentaenoic-acid (EPA), omega3-FA and PUFA concentrations increased with the autochthonous contribution in consumers, i.e., a 47-79% biofilm and/or seston diet resulted in tissue EPA of 4.2-18.4, omega3 FAs of 11.6-37.0 and PUFA of 21.6-61.0 mg/g dry mass. The results indicate that consumers in dystrophic lakes predominantly rely on energy from autotrophs and that their PUFA concentrations are dependent on the relative contribution of these autochthonous resources. The limited energy support from MOB suggests they are not negligible and are potentially an integral part of the food webs. Our findings show that autochthonous resources are the main driver of secondary production even in dystrophic lakes and offer new insights into the functioning of these ecosystems.

Fatty-acid based assessment of benthic food-web responses to multiple stressors in a large river system.

Rivers are often exposed to multiple stressors, such as nutrients and contaminants, whose impacts on the river food webs may not be distinguished by sole assessment of biological community structures. We examined the benthic algal assemblages and the fatty acids (FA) of benthic macroinvertebrates in the lower Athabasca River in Canada, aiming to assess the changes in algal support and nutritional quality of the benthic food web in response to cumulative exposure to natural bitumen, municipal sewage discharge (hereafter, "sewage"), and oil sands mining ("mining"). Data show that the decline in water quality (increases in nutrient concentrations and total suspended solids) was associated with decreases in benthic diatom abundance, and was driven mainly by sewage-induced nutrient enrichment. Responses in nutritional quality of benthic macroinvertebrates, indicated by their polyunsaturated FA (PUFA) concentrations, were taxon- and stressor-specific. Nutritional quality of the larval dragonfly predator, Ophiogomphus, decreased nonlinearly with decreasing benthic diatom abundance and was lowest at the sewage-affected sites, although exposure to natural bitumen also resulted in reduced Ophiogomphus PUFA concentrations. In contrast, the PUFA concentrations of mayfly grazers/collector-gatherers were not affected by natural bitumen exposure, and were higher at the sewage and sewage+mining sites. The PUFA concentrations of the shredder Pteronarcys larvae did not change with cumulative exposure to the stressors. Sediment metal and polycyclic aromatic compound concentrations were not associated with the macroinvertebrate FA changes. Overall, we provide evidence that sewage induced reduction in trophic support by PUFA-rich diatoms, and was the predominant driver of the observed changes in FA composition and nutritional quality of the benthic macroinvertebrates. Fatty-acid metrics are useful to untangle effects of concurrent stressors, but the assessment outcomes depend on the functional feeding guilds used. A food-web perspective using multiple trophic levels and feeding guilds supports a more holistic assessment of the stressor impacts.

Interactions with DOM and biofilms affect the fate and bioavailability of insecticides to invertebrate grazers.

We studied the fate and bioavailability of insecticides in short-term experiments (48 h) with different hydrophobicity (3.8 pM carbofuran, 3.0 pM lindane, and 5.3 pM chlorpyrifos) across gradients in dissolved organic matter (low-, medium-, and high-DOM) in freshwater microcosms, mimicking runoff events of pesticides. The effects of biofilms were studied by including treatments with biofilms cultivated under different DOM-concentrations. The presence of biofilms negatively affected chlorpyrifos water concentrations, indicating rapid sorption of this hydrophobic pesticide, while lindane concentrations instead increased and carbofuran concentrations were unaffected. Associations of lindane and chlorpyrifos with biofilms were 1.6-2.0 times higher in low- and high-DOM than in medium-DOM treatments, indicating that sorption was affected not only by the quantity, but also by the quality of DOM. Although the proportion of pesticides recovered in biofilms was consistently less than 1 % of added pesticide, pesticide concentrations in biofilms were on average more than 75- (carbofuran) and 382-times (lindane) higher than those in water. Snail accumulation of all three pesticides was significantly affected by DOM-concentrations and correlated to pesticide hydrophobicity, but the relationships were not straightforward. For example, carbofuran uptake in treatments without biofilms was higher in low-DOM than in medium- and high-DOM treatments, while chlorpyrifos uptake instead increased across the DOM-gradient. Biofilms played a role only for the uptake of chlorpyrifos, which decreased markedly in the presence of biofilms. Bioconcentration factors (BCF) calculated for snails and biofilms differed for the three pesticides and were related to their sorption behaviour (i.e., hydrophobicity). The relative proportion of pesticide uptake through biofilm consumption was consistently less than 2 %, showing that passive uptake was by far the predominant uptake pathway for all three pesticides.

Interactions with freshwater biofilms cause rapid removal of common herbicides through degradation - evidence from microcosm studies.

We investigated the role of periphyton biofilms for the fate of three common herbicides, i.e. bentazone, metazachlor and metribuzin, at low, environmental levels and 100 times higher, during a 16 days laboratory experiment. We found that herbicide water concentrations were stable during the first 8 days, whereas substantial declines (>78%) occurred between days 8-16 for all three herbicides. These rapid declines were explained only to a small extent (<8% of the total herbicide loss) by biofilm sorption. As herbicide concentrations in light and dark treatments without biofilms were similar, and the applied light regimen did not cover the UV-spectrum, herbicide photolysis was ruled out as a possible explanation for the observed declines. Furthermore, based on the compounds' characteristics, also volatilization was judged negligible. Therefore, we conjecture that the observed declines in herbicides were due to biodegradation and subsequent evasion of 14CO2 that was driven by enzymatic action from heterotrophic microbes. We reason that heterotrophic microbes used herbicide molecules as labile organic C-sources during C-limitation. Future studies should identify the microbial communities and genes involved in biodegradation in order to understand better the role of biofilms for the self-purification of surface waters.

Identifying resilience mechanisms to recurrent ecosystem perturbations.

The complex nature of ecological systems limits the unambiguous determination of mechanisms that drive resilience to natural disturbance or anthropogenic stress. Using eight-year time series data from boreal lakes with and without bloom formation of an invasive alga (Gonyostomum semen, Raphidophyceae), we studied resilience of phytoplankton communities in relation to recurring bloom impacts. We first characterized phytoplankton community dynamics in both lake types using univariate metrics of community structure (evenness, species richness, biovolume and Simpson diversity). All metrics, except species richness, were substantially altered and showed an inherent stronger variability in bloom lakes relative to reference lakes. We assessed resilience mechanisms using a multivariate time series modelling technique. The models captured clear successional dynamics of the phytoplankton communities in all lakes, whereby different groups of species were substituted sequentially over the ice-free period. The models also identified that G. semen impacts in bloom lakes were only manifested within a single species group, not across species groups, highlighting the rapid renewal of the phytoplankton communities upon bloom collapse. These results provide empirical support of the cross-scale resilience model. Cross-scale resilience could provide an explanation for the paradox that similar species richnesses are seen in bloom-forming lakes and reference lakes despite the clear difference between the community features of the two different sets of lakes investigated.

Effects of extracellular polymeric and humic substances on chlorpyrifos bioavailability to Chironomus riparius.

The role of sediment organic matter quality and quantity for chlorpyrifos bioavailability was studied in experiments with Chironomus riparius larvae and with four types of organic matter; (1) commercially available extracellular polymeric substances (EPS), (2) EPS produced by sediment microbes, (3) commercially available humic substances and, (4) humic substances extracted from a boreal lake. The effects of each type of organic matter were assessed at three concentrations. We used a (14)C-tracer approach to quantify uptake of chlorpyrifos in the larvae, and the partitioning of the insecticide within the microcosm. Carbon-normalised larval uptake was reduced both by EPS and humic substances. However, the reduction in uptake was much greater for EPS than for humic substances: uptake was reduced by 94 and 88% for commercial and complex EPS, and by 59 and 57% for commercial and complex humic substances, respectively. We also found differences in chlorpyrifos uptake, and sediment concentrations between treatments with commercially available and complex polymers, suggesting that minor differences in the quality of relatively simple organic molecules can affect contaminant behaviour in ecotoxicological studies. Passive uptake in dead controls was 40% of that in living larvae. Therefore, both passive and digestive uptake were important processes for chlorpyrifos uptake by larvae. Our results show that both EPS and humic substances affect chlorpyrifos bioavailability to sediment biota negatively and contribute to the understanding of the processes that regulate organic contaminant bioavailability in aquatic environments.

Sublethal and sex-specific cypermethrin effects in toxicity tests with the midge Chironomus riparius Meigen.

We quantified sublethal and sex-specific cypermethrin effects in experiments (29 days) with the midge Chironomus riparius at different levels of sediment organic matter content (0, 5, and 20%). We found highly significant effects of cypermethrin concentrations and sediment type on emergence, mean development rate, and adult size. For example, emergence/survival rates were 70-100% below 0.8 µg/l and unaffected by organic matter content. At 3.2 µg/l, however, no larvae survived in sediment without organic matter, but survival successively increased to 26 ± 11% in sediment with 20% organic matter. Mean development rates were always higher for males than for females, and significant differences between sexes occurred consistently in controls and in treatments with our lowest concentration of 0.05 µg/l. Sex-specific differences in mean development rate decreased across the cypermethrin gradient, suggesting that male development was affected more than that of females at similar concentrations. We also found an increase in adult size across the concentration gradient in sediments lacking organic matter and suggest an increased feeding activity due to sublethal toxic stress as a probable causal mechanism. We speculate that the observed sex-specific effects on development rates and adult size can have strong repercussions on emergence timing and fecundity, respectively.

Pesticide Mixtures Cause Short-Term, Reversible Effects on the Function of Autotrophic Periphyton Assemblages.

In a laboratory experiment we investigated the effects of pesticide mixtures on the structure and function of freshwater biofilms, with focus on their photoautotrophic component. We identified 6 herbicides and 1 fungicide commonly found in Swedish streams at relatively high concentrations and created 3 ternary mixtures that were tested in concentration series ranging from observed environmental concentrations to up to 100 times higher. Biofilms were exposed to these pesticide mixtures for 8 d and then allowed to recover for another 12 d. Our results show a rapid and consistent inhibition of photosynthesis after just 24-h exposure to the highest test concentration of pesticides, as well as in some treatments with lower concentrations (i.e., 10 times the environmental level), on exposure. Interestingly, the observed effects were reversible because biofilm photosynthesis recovered rapidly and completely in clean media in all but one treatment. In contrast to the functional response, no effects were observed on the algal assemblage structure, as assessed by diagnostic pigments. We conclude that the pesticide mixtures induce a rapid but reversible inhibition of photosynthesis, without short-term effects on biofilm structure. Environ Toxicol Chem 2020;39:1367-1374. © 2020 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Limited effects of pesticides on stream macroinvertebrates, biofilm nematodes, and algae in intensive agricultural landscapes in Sweden.

Pesticides are frequently detected in surface waters, sometimes at levels exceeding ecotoxicological guidelines. We screened for almost 100 pesticides in 32 streams from intense agricultural areas in Southern Sweden, in concert with water chemistry parameters. In addition, we investigated the communities of benthic macroinvertebrates, biofilm nematodes and algae and calculated multiple bioassessment metrics. The number of pesticides found in each stream ranged between 2 and 52, but the sum of Toxic Units (ΣTU) for the mixtures was generally low, and exceeded the European Uniform Principles only in a single sample for algae and in 2% of the samples for Daphnia. Only nematode communities were significantly correlated with the ΣTU, potentially due to their higher pesticide exposure in biofilms. Diatom metrics showed that most streams were impacted by eutrophication and macroinvertebrate metrics showed good status in most streams, whereas the SPEARpesticides (SPEcies At Risk) index, specifically designed to indicate pesticide effects, showed that about half of the samples were at risk. Interestingly, SPEARpesticides was not correlated to ΣTUDaphnia, and this discrepancy suggests that redefining the boundaries for quality classes might be necessary for this index. Moreover, SPEARpesticides was positively correlated with the commonly used macroinvertebrate index ASPT, although disparate results were found for several streams. We argue that this questions the scaling of both metrics and the specificity of their responses. We discuss that the overall good/moderate status of the streams, despite the intense agriculture in the catchments, can be due to the fact that i) a sampling strategy with repeated grab samples did not capture peak pesticide concentrations, thus underestimating acute exposure, ii) pesticide run-off indeed was low, due to measures such as buffer strips, and iii) the nutrient-rich conditions and high sediment loads counteracted pesticide toxicity. We conclude that agricultural land use was the overriding stressor in the investigated streams, including strong effects of nutrients, less apparent effects of pesticides and likely impact of hydromorphological alterations (not specifically addressed in this study).

Assessing microbial contamination and antibiotic resistant bacteria using zebra mussels (Dreissena polymorpha).

Aquatic pollution with faecal bacteria and subsequent consumption of contaminated water or food is a worldwide issue that causes severe health effects (e.g. meningitis, salmonellosis, dysentery). In addition, the excessive use of antibiotics in animal husbandry and human medicine has enhanced the selective pressure on pathogenic bacteria, further increasing human health risks and detrimental effects on natural microbial communities. This urges the need to monitor faecal contamination using a time-integrated approach, as grab water samples can miss pathogen peaks. We tested the ability of zebra mussels (Dreissena polymorpha) to take up and depurate faecal indicator bacteria such as Escherichia coli and intestinal enterococci. Furthermore, we quantified the frequency of antibiotic resistant bacteria in water and mussels both in controlled laboratory tests and under in situ conditions downstream of a sewage treatment plant (STP). Laboratory results show that bacterial indicators in mussels were 132 times higher than their concentration in water, and that mussels retained bacteria up to 2 days after pulse exposure. Field results show decreasing bacterial concentrations in both water and mussels downstream the STP, with maximum E. coli concentrations ranging 173-9 cfu mL-1 in water and 2970-330 cfu g-1 in mussels. Similarly, enterococci ranged 59-4 cfu mL-1 and 1450-240 cfu g-1 in water and mussels, respectively. High proportions of antibiotic resistant E. coli were found in mussels (72%) and water (65%), and slightly lower proportion of resistant enterococci was found in mussels (47%) and in water (34%). Moreover, 33% of the bacteria isolated from mussels were resistant to multiple antibiotics, which emphasizes that resistance is a common feature in surface waters and highlights the need for safe water management. Our results show that zebra mussels provide an efficient, time-integrating tool for quantifying faecal indicators, including resistant and multidrug resistant bacteria.

Climate-induced changes in carbon flows across the plant-consumer interface in a small subarctic lake.

Reconstructions of past food web dynamics are necessary for better understanding long-term impacts of climate change on subarctic lakes. We studied elemental and stable isotopic composition of sedimentary organic matter, photosynthetic pigments and carbon stable isotopic composition of Daphnia (Cladocera; Crustacea) resting eggs (δ13CClado) in a sediment record from a small subarctic lake. We examined how regional climate and landscape changes over the last 5800 years affected the relative importance of allochthonous and autochthonous carbon transfer to zooplankton. Overall, δ13CClado values were well in line with the range of theoretical values of aquatic primary producers, confirming that zooplankton consumers in subarctic lakes, even in the long-term perspective, are mainly fuelled by autochthonous primary production. Results also revealed greater incorporations of benthic algae into zooplankton biomass in periods that had a warmer and drier climate and clearer water, whereas a colder and wetter climate and lower water transparency induced higher contributions of planktonic algae to Daphnia biomass. This study thus emphasizes long-term influence of terrestrial-aquatic linkages and in-lake processes on the functioning of subarctic lake food webs.

Effects of pesticides on community composition and activity of sediment microbes--responses at various levels of microbial community organization.

A freshwater sediment was exposed to the pesticides captan, glyphosate, isoproturon, and pirimicarb at environmentally relevant and high concentrations. Effects on sediment microorganisms were studied by measuring bacterial activity, fungal and total microbial biomass as community-level endpoints. At the sub-community level, microbial community structure was analysed (PLFA composition and bacterial 16S rRNA genotyping, T-RFLP). Community-level endpoints were not affected by pesticide exposure. At lower levels of microbial community organization, however, molecular methods revealed treatment-induced changes in community composition. Captan and glyphosate exposure caused significant shifts in bacterial community composition (as T-RFLP) at environmentally relevant concentrations. Furthermore, differences in microbial community composition among pesticide treatments were found, indicating that test compounds and exposure concentrations induced multidirectional shifts. Our study showed that community-level end points failed to detect these changes, underpinning the need for application of molecular techniques in aquatic ecotoxicology.

Sediment microbes and biofilms increase the bioavailability of chlorpyrifos in Chironomus riparius (Chironomidae, Diptera).

In a microcosm study, the importance of different sources of organic matter (humic acids, sterile sediment, sediment, and a microbial extract) for the bioavailability of the hydrophobic pesticide chlorpyrifos to Chironomus riparius larvae was quantified. In the last two treatments biofilms were allowed to grow before (14)C-chlorpyrifos addition. Chlorpyrifos accumulation was quantified after 25 h of exposure and after 21 h of depuration. Larval accumulation was twice as high in the microbial extract treatment (447+/-79 microg/kg ww larvae) and 1.7 times higher in the sediment treatment (371+/-33 microg/kg). After depuration, chlorpyrifos accumulation in larval tissue showed even higher differences; 3.1 times higher tissue concentrations in the microbial extract treatment (218+/-21 microg/kg) and 2.2 times higher in the sediment treatment (156+/-35 microg/kg). In contrast, chlorpyrifos accumulation in the humic acid and sterile sediment did not differ from that in controls. These results show that living microbes and biofilms, by creating a microenvironment and providing food for larvae, markedly increase the bioavailability of chlorpyrifos to Chironomus riparius.

Deltamethrin toxicity to the midge Chironomus riparius Meigen-effects of exposure scenario and sediment quality.

We investigated how exposure scenario and sediment characteristics affected deltamethrin bioavailability and toxicity to Chironomus riparius. We designed whole-sediment experiments, including separate spiked-water and spiked-sediment experiments and using both a peat-based artificial and a natural sediment. Deltamethrin was highly toxic to larvae in artificial sediments, with LC(50)-values (28 d) of 11 microg/kg for sediment-exposures and 16 pg/L for water-exposures. In contrast, deltamethrin-induced mortality was absent in experiments with natural sediment, both in spiked water and in spiked sediment. This was attributed to the higher organic matter content of the natural sediment, 12.5+/-0.05%, compared with that in the artificial sediments, 4.1-4.8%, resulting in an efficient and fast sorption and lower bioavailability. Deltamethrin degradation was absent in artificial sediment, while in natural sediment, 50% degraded during 10 days of test-vessel acclimation. Despite a faster degradation, the highest measured concentration in spiked-natural sediment was more than seven times higher than the LC(50)-value obtained in tests with spiked-artificial sediment, indicating that low bioavailability, and not compound degradation, was the main reason for the observed lack of deltamethrin toxicity.

Assessing the effects of field-relevant pesticide mixtures for their compliance with the concentration addition model - An experimental approach with Daphnia magna.

The environmental risk assessment of pesticides is mainly performed on individual active ingredients. In surface waters within the agricultural landscape, however, contamination is usually characterized by complex pesticide mixtures. To estimate the joint effects caused by these complex mixtures, mathematical models have been proposed. Among these, the model of concentration addition (CA) is suggested as default model for the risk assessment of chemical mixtures as it is considered protective for mixtures composed of similar and dissimilar acting substances. Here we assessed the suitability of CA predictions for seven field relevant pesticide mixtures using acute (immobility) and chronic (reproduction) responses of the standard test species Daphnia magna. Pesticide mixtures indicated largely additive or less than additive effects when using CA model predictions as a reference. Moreover, we revealed that deviations from CA predictions are lower for chronic (up to 3.2-fold) relative to acute (up to 7.2-fold) response variables. Additionally, CA predictions were in general more accurate for complex mixtures relative to those composed of only a few pesticides. Thus, this study suggests CA models as largely protective for the risk assessment of pesticide mixtures justifying its use as default model. At the same time, extrapolating conclusions about the joint effects of pesticides from acute to chronic responses is uncertain, due to partly large discrepancies with regards to the deviation of model prediction and observed effects between exposure scenarios.