Can TK-TD modelling bridge the gap between in vitro and in vivo mammalian toxicity data?

Repeated dietary dose testing is used to assess longer term toxicity of chemicals, such as pesticides, to mammals. However, the internal pesticide concentration varies significantly as feeding rate relative to body size fluctuates over time. Toxicokinetic-toxicodynamic (TK-TD) models can estimate internal toxicant concentration over time and link this directly to observed effects on endpoints such as the growth rate of laboratory rats. Using TK-TD models it is therefore possible to predict the effects that would result from a constant internal concentration of a pesticide. This presents the possibility of comparison with data from in vitro experiments, potentially facilitating quantitative in vitro to in vivo extrapolation (QIVIVE). We used in vivo TK-TD models to identify relevant internal concentrations and then estimated the experimental conditions required to replicate these in cultured cells, using in vitro TK models. Cell population growth was measured, with a view to extrapolating through time and comparing effect sizes with in vivo predictions. However, observed cell proliferation was not significantly affected by the tested concentrations of any of the five pesticides in this study and so extrapolation was not possible. In light of this negative result, we highlight areas for future work towards QIVIVE of graded sublethal effects in mammals. The most pressing objective is improving the accuracy of in vivo TK predictions, which could be achieved with dietary dosing in TK studies.

A User-Friendly Kinetic Model Incorporating Regression Models for Estimating Pesticide Accumulation in Diverse Earthworm Species Across Varied Soils.

Existing models for estimating pesticide bioconcentration in earthworms exhibit limited applicability across different chemicals, soils and species which restricts their potential as an alternative, intermediate tier for risk assessment. We used experimental data from uptake and elimination studies using three earthworm species (Lumbricus terrestris, Aporrectodea caliginosa, Eisenia fetida), five pesticides (log Kow 1.69-6.63) and five soils (organic matter content = 0.972-39.9 wt %) to produce a first-order kinetic accumulation model. Model applicability was evaluated against a data set of 402 internal earthworm concentrations reported from the literature including chemical and soil properties outside the data range used to produce the model. Our models accurately predict body load using either porewater or bulk soil concentrations, with at least 93.5 and 84.3% of body load predictions within a factor of 10 and 5 of corresponding observed values, respectively. This suggests that there is no need to distinguish between porewater and soil exposure routes or to consider different uptake and elimination pathways when predicting earthworm bioconcentration. Our new model not only outperformed existing models in characterizing earthworm exposure to pesticides in soil, but it could also be integrated with models that account for earthworm movement and fluctuating soil pesticide concentrations due to degradation and transport.

Evaluation of models to estimate the bioaccumulation of organic chemicals in earthworms.

Modelling approaches to estimate the bioaccumulation of organic chemicals by earthworms are important for improving the realism in risk assessment of chemicals. However, the applicability of existing models is uncertain, partly due to the lack of independent datasets to test them. This study therefore conducted a comprehensive literature review on existing empirical and kinetic models that estimate the bioaccumulation of organic chemicals in earthworms and gathered two independent datasets from published literature to evaluate the predictive performance of these models. The Belfroid et al. (1995a) model is the best-performing empirical model, with 91.2% of earthworm body residue simulations within an order of magnitude of observation. However, this model is limited to the more hydrophobic pesticides and to the earthworm species Eisenia fetida or Eisenia andrei. The kinetic model proposed by Jager et al. (2003b) which out-performs that of Armitage and Gobas (2007), predicted uptake of PCB 153 in the earthworm E. andrei to within a factor of 10. However, the applicability of Jager et al.'s model to other organic compounds and other earthworm species is unknown due to the limited evaluation dataset. The model needs to be parameterised for different chemical, soil, and species types prior to use, which restricts its applicability to risk assessment on a broad scale. Both the empirical and kinetic models leave room for improvement in their ability to reliably predict bioaccumulation in earthworms. Whether they are fit for purpose in environmental risk assessment needs careful consideration on a case by case basis.

Earthworm lipid content and size help account for differences in pesticide bioconcentration between species.

The uptake and elimination kinetics of pesticides from soil to earthworms are important in characterising the risk of pesticides to soil organisms and the risk from secondary poisoning. However, the understanding of the relative importance of chemical, soil, and species differences in determining pesticide bioconcentration into earthworms is limited. Furthermore, there is insufficient independent data in the literature to fully evaluate existing predictive bioconcentration models. We conducted kinetic uptake and elimination experiments for three contrasting earthworm species (Lumbricus terrestris, Aporrectodea caliginosa, Eisenia fetida) in five soils using a mixture of five pesticides (log Kow 1.69 - 6.63). Bioconcentration increased with pesticide hydrophobicity and decreased with soil organic matter. Bioconcentration factors were comparable between earthworm species for hydrophilic pesticides due to the similar water content of earthworm species. Inter-species variations in bioconcentration of hydrophobic pesticides were primarily accounted for by earthworm lipid content and specific surface area (SSA). Existing bioconcentration models either failed to perform well across earthworm species and for more hydrophilic compounds (log Kow < 2) or were not parameterised for a wide range of compounds and earthworm species. Refined models should incorporate earthworm properties (lipid content and SSA) to account for inter-species differences in pesticide uptake from soil.

Intermediate-tier options in the environmental risk assessment of plant protection products for soil invertebrates-Synthesis of a workshop.

The European environmental risk assessment (ERA) of plant protection products follows a tiered approach. The approach for soil invertebrates currently consists of two steps, starting with a Tier 1 assessment based on reproduction toxicity tests with earthworms, springtails, and predatory mites. In case an unacceptable risk is identified at Tier 1, field studies can be conducted as a higher-tier option. For soil invertebrates, intermediate tiers are not implemented. Hence, there is limited possibility to include additional information for the ERA to address specific concerns when the Tier 1 fails, as an alternative to, for example, a field study. Calibrated intermediate-tier approaches could help to address risks for soil invertebrates with less time and resources but also with sufficient certainty. A multistakeholder workshop was held on 2-4 March 2022 to discuss potential intermediate-tier options, focusing on four possible areas: (1) natural soil testing, (2) single-species tests (other than standard species), (3) assessing recovery in laboratory tests, and (4) the use of assembled soil multispecies test systems. The participants acknowledged a large potential in the intermediate-tier options but concluded that some issues need to be clarified before routine application of these approaches in the ERA is possible, that is, sensitivity, reproducibility, reliability, and standardization of potential new test systems. The definition of suitable assessment factors needed to calibrate the approaches to the protection goals was acknowledged. The aims of the workshop were to foster scientific exchange and a data-driven dialog, to discuss how the different approaches could be used in the risk assessment, and to identify research priorities for future work to address uncertainties and strengthen the tiered approach in the ERA for soil invertebrates. This article outlines the background, proposed methods, technical challenges, difficulties and opportunities in the ERA, and conclusions of the workshop. Integr Environ Assess Manag 2024;20:780-793. © 2023 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Modelling the effects of variability in feeding rate on growth - a vital step for DEB-TKTD modelling.

A major limitation of dietary toxicity studies on rodents is that food consumption often differs between treatments. The control treatment serves as a reference of how animals would have grown if not for the toxicant in their diet, but this comparison unavoidably conflates the effects of toxicity and feeding rate on body weight over time. A key advantage of toxicity models based on dynamic energy budget theory (DEB) is that chemical stress and food consumption are separate model inputs, so their effects on growth rate can be separated. To reduce data requirements, DEB convention is to derive a simplified feeding input, f, from food availability; its value ranges from zero (starvation) to one (food available ad libitum). Observed food consumption in dietary toxicity studies shows that, even in the control treatment, rats limit their food consumption, contradicting DEB assumptions regarding feeding rate. Relatively little work has focused on addressing this mismatch, but accurately modelling the effects of food intake on growth rate is essential for the effects of toxicity to be isolated. This can provide greater insight into the results of chronic toxicity studies and allows accurate extrapolation of toxic effects from laboratory data. Here we trial a new method for calculating f, based on the observed relationships between food consumption and body size in laboratory rats. We compare model results with those of the conventional DEB method and a previous effort to calculate f using observed food consumption data. Our results showed that the new method improved model accuracy while modelled reserve dynamics closely followed observed body fat percentage over time. The new method assumes that digestive efficiency increases with body size. Verifying this relationship through data collection would strengthen the basis of DEB theory and support the case for its use in ecological risk assessment.

Earthworm distributions are not driven by measurable soil properties. Do they really indicate soil quality?

Abundance and distribution of earthworms in agricultural fields is frequently proposed as a measure of soil quality assuming that observed patterns of abundance are in response to improved or degraded environmental conditions. However, it is not clear that earthworm abundances can be directly related to their edaphic environment, as noted in Darwin's final publication, perhaps limiting or restricting their value as indicators of ecological quality in any given field. We present results from a spatially explicit intensive survey of pastures within United Kingdom farms, looking for the main drivers of earthworm density at a range of scales. When describing spatial variability of both total and ecotype-specific earthworm abundance within any given field, the best predictor was earthworm abundance itself within 20-30 m of the sampling point; there were no consistent environmental correlates with earthworm numbers, suggesting that biological factors (e.g. colonisation rate, competition, predation, parasitism) drive or at least significantly modify earthworm distributions at this spatial level. However, at the national scale, earthworm abundance is well predicted by soil nitrate levels, density, temperature and moisture content, albeit not in a simple linear fashion. This suggests that although land can be managed at the farm scale to promote earthworm abundance and the resulting soil processes that deliver ecosystem services, within a field, earthworm distributions will remain patchy. The use of earthworms as soil quality indicators must therefore be carried out with care, ensuring that sufficient samples are taken within field to take account of variability in earthworm populations that is unrelated to soil chemical and physical properties.

Arable fields as potential reservoirs of biodiversity: Earthworm populations increase in new leys.

Managing soil to support biodiversity is important to sustain the ecosystem services provided by soils upon which society depends. There is increasing evidence that functional diversity of soil biota is important for ecosystem services, and has been degraded by intensive agriculture. Importantly, the spatial distribution of reservoirs of soil biota in and surrounding arable fields is poorly understood. In a field experiment, grass-clover ley strips were introduced into four arable fields which had been under continuous intensive/conventional arable rotation for more than 10 years. Earthworm communities in arable fields and newly established grass-clover leys, as well as field boundary land uses (hedgerows and grassy field margins), were monitored over 2 years after arable-to-ley conversions. Within 2 years, earthworm abundance in new leys was 732 ± 244 earthworms m-2, similar to that in field margin soils (619 ± 355 earthworms m-2 yr-1) and four times higher than in adjacent arable soil (185 ± 132 earthworms m-2). Relative to the arable soils, earthworm abundance under the new leys showed changes in community composition, structure and functional group, which were particularly associated with an increase in anecic earthworms; thus new leys became more similar to grassy field margins. Earthworm abundance was similar in new leys that were either connected to biodiversity reservoirs i.e. field margins and hedgerows, or not (installed earthworm barriers). This suggests that, for earthworm communities in typical arable fields, biodiversity reservoirs in adjacent field margins and hedgerows may not be critical for earthworm populations to increase. We conclude that the increase in earthworm abundance in the new leys observed over 2 years was driven by recruitment from the existing residual population in arable soils. Therefore, arable soils are also potential reservoirs of biodiversity.

Dual stresses of flooding and agricultural land use reduce earthworm populations more than the individual stressors.

Global climate change is leading to a significant increase in flooding events in many countries. Current practices to prevent damage to downstream urban areas include allowing the flooding of upstream agricultural land. Earthworms are ecosystem engineers, but their abundances in arable land are already reduced due to pressure from farming practices. If flooding increases on agricultural land, it is important to understand how earthworms will respond to the dual stresses of flooding and agricultural land use. The earthworm populations under three land uses (pasture, field margin, and crops), across two UK fields, were sampled seasonally over an 18-month period in areas of the fields which flood frequently and areas which flood only rarely. Earthworm abundance in the crop and pasture soils and total earthworm biomass in the crop soils was significantly lower in the frequently flooded areas than in the rarely flooded areas. The relative percentage difference in the populations between the rarely and frequently flooded areas was greater in the crop soils (-59.18% abundance, -63.49% biomass) than the pasture soils (-13.39% abundance, -9.66% biomass). In the margin soils, earthworm abundance was significantly greater in the frequently flooded areas (+140.56%), likely due to higher soil organic matter content and lower bulk density resulting in soil conditions more amenable to earthworms. The findings of this study show that earthworm populations already stressed by the activities associated with arable land use are more susceptible to flooding than populations in pasture fields, suggesting that arable earthworm populations are likely to be increasingly at risk with increased flooding.

Mechanistic Effect Modeling of Earthworms in the Context of Pesticide Risk Assessment: Synthesis of the FORESEE Workshop.

Earthworms are important ecosystem engineers, and assessment of the risk of plant protection products toward them is part of the European environmental risk assessment (ERA). In the current ERA scheme, exposure and effects are represented simplistically and are not well integrated, resulting in uncertainty when the results are applied to ecosystems. Modeling offers a powerful tool to integrate the effects observed in lower tier laboratory studies with the environmental conditions under which exposure is expected in the field. This paper provides a summary of the (In)Field Organism Risk modEling by coupling Soil Exposure and Effect (FORESEE) Workshop held 28-30 January 2020 in Düsseldorf, Germany. This workshop focused on toxicokinetic-toxicodynamic (TKTD) and population modeling of earthworms in the context of ERA. The goal was to bring together scientists from different stakeholder groups to discuss the current state of soil invertebrate modeling and to explore how earthworm modeling could be applied to risk assessments, in particular how the different model outputs can be used in the tiered ERA approach. In support of these goals, the workshop aimed at addressing the requirements and concerns of the different stakeholder groups to support further model development. The modeling approach included 4 submodules to cover the most relevant processes for earthworm risk assessment: environment, behavior (feeding, vertical movement), TKTD, and population. Four workgroups examined different aspects of the model with relevance for risk assessment, earthworm ecology, uptake routes, and cross-species extrapolation and model testing. Here, we present the perspectives of each workgroup and highlight how the collaborative effort of participants from multidisciplinary backgrounds helped to establish common ground. In addition, we provide a list of recommendations for how earthworm TKTD modeling could address some of the uncertainties in current risk assessments for plant protection products. Integr Environ Assess Manag 2021;17:352-363. © 2020 SETAC.

Increased yield and CO2 sequestration potential with the C4 cereal Sorghum bicolor cultivated in basaltic rock dust-amended agricultural soil.

Land-based enhanced rock weathering (ERW) is a biogeochemical carbon dioxide removal (CDR) strategy aiming to accelerate natural geological processes of carbon sequestration through application of crushed silicate rocks, such as basalt, to croplands and forested landscapes. However, the efficacy of the approach when undertaken with basalt, and its potential co-benefits for agriculture, require experimental and field evaluation. Here we report that amending a UK clay-loam agricultural soil with a high loading (10 kg/m2 ) of relatively coarse-grained crushed basalt significantly increased the yield (21 ± 9.4%, SE) of the important C4 cereal Sorghum bicolor under controlled environmental conditions, without accumulation of potentially toxic trace elements in the seeds. Yield increases resulted from the basalt treatment after 120 days without P- and K-fertilizer addition. Shoot silicon concentrations also increased significantly (26 ± 5.4%, SE), with potential benefits for crop resistance to biotic and abiotic stress. Elemental budgets indicate substantial release of base cations important for inorganic carbon removal and their accumulation mainly in the soil exchangeable pools. Geochemical reactive transport modelling, constrained by elemental budgets, indicated CO2 sequestration rates of 2-4 t CO2 /ha, 1-5 years after a single application of basaltic rock dust, including via newly formed soil carbonate minerals whose long-term fate requires assessment through field trials. This represents an approximately fourfold increase in carbon capture compared to control plant-soil systems without basalt. Our results build support for ERW deployment as a CDR technique compatible with spreading basalt powder on acidic loamy soils common across millions of hectares of western European and North American agriculture.

Effect of earthworms on soil physico-hydraulic and chemical properties, herbage production, and wheat growth on arable land converted to ley.

Effects of earthworms on soil physico-hydraulic and chemical properties, herbage production and wheat growth in long-term arable soils following conversion to ley were investigated. Seven intact soil monoliths were collected from each of four arable fields. One monolith per field served as a control. The other six were defaunated by deep-freezing; three were left defaunated (DeF) and three (DeF+E) were repopulated with earthworms to mimic pasture field density and diversity. The monoliths were planted with a grass-clover ley and inserted into pre-established ley strips in their original fields for 12 months. Hydraulic conductivity measurements at -0.5 cm tension (K0.5) were taken five times over the year. K0.5 significantly increased in summer 2017 and spring 2018 and decreased in winter 2017-18. K0.5 was significantly greater (47%) for DeF+E than DeF monoliths. By the end of the experiment, pores >1 mm diameter made a significantly greater contribution to water flow in DeF+E (98%) than DeF (95%) monoliths. After only a year of arable to ley conversion, soil bulk density significantly decreased (by 6%), and organic matter (OM) content increased (by 29%) in the DeF treatments relative to the arable soil. Earthworms improved soil quality further. Compared to DeF monoliths, DeF+E monoliths had significantly increased water-holding capacity (by 9%), plant-available water (by 21%), OM content (by 9%), grass-clover shoot dry biomass (by 58%), water-stable aggregates >250 µm (by 15%) and total N (by 3.5%). In a wheat bioassay following the field experiment, significantly more biomass (20%) was produced on DeF+E than DeF monolith soil, likely due to the changed soil physico-hydraulic properties. Our results show that earthworms play a significant role in improvements to soil quality and functions brought about by arable to ley conversion, and that augmenting depleted earthworm populations can help the restoration of soil qualities adversely impacted by intensive agriculture.

Polyester-derived microfibre impacts on the soil-dwelling earthworm Lumbricus terrestris.

Microplastic (MP) pollution is everywhere. In terrestrial environments, microfibres (MFs) generated from textile laundering are believed to form a significant component of MPs entering soils, mainly through sewage sludge and compost applications. The aim of this study was to assess the effect of MFs on a keystone soil organism. We exposed the earthworm Lumbricus terrestris to soil with polyester MFs incorporated at rates of 0, 0.1 and 1.0 %w/w MF for a period of 35 days (in the dark at 15 °C; n = 4 for each treatment). Dried plant litter was applied at the soil surface as a food source for the earthworms. We assessed earthworm vitality through mortality, weight change, depurate production and MF avoidance testing. In addition, we measured stress biomarker responses via the expression of metallothionein-2 (mt-2), heat shock protein (hsp70) and superoxide dismutase (sod-1). Our results showed that exposure and ingestion of MFs (as evidenced by subsequent retrieval of MFs within earthworm depurates) were not lethal to earthworms, nor did earthworms actively avoid MFs. However, earthworms in the MF1.0% treatment showed a 1.5-fold lower cast production, a 24.3-fold increase in expression of mt-2 (p < 0.001) and a 9.9-fold decline in hsp70 expression (p < 0.001). Further analysis of soil and MF samples indicated that metal content was not a contributor to the biomarker results. Given that burrowing and feeding behaviour, as well as molecular genetic biomarkers, were modulated in earthworms exposed to MFs, our study highlights potential implications for soil ecosystem processes due to MF contamination.

Specificity of the Metallothionein-1 Response by Cadmium-Exposed Normal Human Urothelial Cells.

Occupational and environmental exposure to cadmium is associated with the development of urothelial cancer. The metallothionein (MT) family of genes encodes proteins that sequester metal ions and modulate physiological processes, including zinc homeostasis. Little is known about the selectivity of expression of the different MT isoforms. Here, we examined the effect of cadmium exposure on MT gene and isoform expression by normal human urothelial (NHU) cell cultures. Baseline and cadmium-induced MT gene expression was characterized by next-generation sequencing and RT-PCR; protein expression was assessed by Western blotting using isoform-specific antibodies. Expression of the zinc transporter-1 (SLC30A1) gene was also assessed. NHU cells displayed transcription of MT-2A, but neither MT-3 nor MT-4 genes. Most striking was a highly inducer-specific expression of MT-1 genes, with cadmium inducing transcription of MT-1A, MT-1G, MT-1H, and MT-1M. Whereas MT-1G was also induced by zinc and nickel ions and MT-1H by iron, both MT-1A and MT-1M were highly cadmium-specific, which was confirmed for protein using isoform-specific antibodies. Protein but not transcript endured post-exposure, probably reflecting sequestration. SLC30A1 transcription was also affected by cadmium ion exposure, potentially reflecting perturbation of intracellular zinc homeostasis. We conclude that human urothelium displays a highly inductive profile of MT-1 gene expression, with two isoforms identified as highly specific to cadmium, providing candidate transcript and long-lived protein biomarkers of cadmium exposure.

Investigating the use of synthetic humic-like acid as a soil washing treatment for metal contaminated soil.

Humic acid can effectively bind several metals and is regarded as a promising soil washing agent. Previous studies indicate that carboxylic groups dominate metal binding to humic acid. In this study, a synthetic humic-like acid (SHLA) with high COOH content (5.03 mmol/g) was used as a washing agent to remove metals (Cu, Zn, Ni, Pb, As) from two contaminated agricultural soils (Soil 1 (pH: 6.17 ±â€¯0.11; organic carbon: 5.91 ±â€¯0.40%; Cu: 302.86 ±â€¯3.97 mg/kg; Zn: 700.45 ±â€¯14.30 mg/kg; Pb 323.56 ±â€¯4.84 mg/kg; Ni: 140.16 ±â€¯1.59 mg/kg) and Soil 2 (pH: 9.83 ±â€¯0.01; organic carbon: 2.52% ±â€¯0.25%; Cu: 242.81 ±â€¯10.66 mg/kg; Zn: 841.00 ±â€¯22.31 mg/kg, Pb 451.21 ±â€¯1,92 mg/kg, As: 242.23 ±â€¯5.24 mg/kg)). The effects of solution pH (4 to 11), liquid/solid ratio (L/S ratio, 5:1 (mL:g) to 80:1 (mL:g)), SHLA concentration (100 mg/L to 2000 mg/L), and contact time (0 to 1440 min) on % metal removal were investigated and optimum conditions identified: pH of 9, L/S ratio of 1:80, SHLA concentration of 1500 mg/L at 25 °C for 4 h. Under optimum conditions, a single washing removed 45.2% of Cu, 34.6% of Zn. 42.2% of Ni and 15.6% of Pb from Soil 1, and 30.6% of Cu, 28.1% of Zn. 14.6% of As and 18.1% of Pb from Soil 2. A modified BCR extraction of the two soils before and after washing indicated that the SHLA mainly removed metals in the exchangeable and acid soluble fraction and reducible fraction, which could effectively reduce bioavailability and environmental risk of metals. On a molar basis, SHLA was a more effective washing agent than commercial humic acid, Na2EDTA, citric acid and tartaric acid. Overall, SHLA shows great potential for use as a soil washing agent.

The impact of varying abiotic humification conditions and the resultant structural characteristics on the copper complexation ability of synthetic humic-like acids in aquatic environments.

Humic acid (HA) has a high complexation ability with metal ions due to its functional groups. In this study, 11 synthetic humic-like acids (SHLAs) were prepared under varying abiotic humification conditions: precursor species (glycine-catechol and glycine-catechol-glucose), precursor concentrations (from 0.25 M:0.25 M to 1 M:1 M), pH (6-8), temperature (25-45 °C) and mass of MnO2 catalyst (1.3-2.5% w/v). The effect of the varying humification conditions on the complexation ability of the SHLA for Cu2+ were investigated together with the relationships between Cu complexation ability and the structure of the SHLAs (elemental composition, type and content of functional groups, AL/AR, E4/E6). Conditional stability constants (log K) of the SHLAs ranged from 6.00 to 6.42 and complexation capacities ranged from 1.76 mmol/g to 2.61 mmol/g. SHLAs synthesized at lower temperature (25 ℃), pH 8, low precursor concentrations (glycine:catechol= 0.25 M:0.25 M) and a larger proportion of catalyst (2.5% w/v) had a larger copper complexation ability. Log K values of SHLAs had significant positive correlations with carboxylic carbon (r = 0.671, p < 0.05), carboxylic group content (r = 0.890, p < 0.01) and O/C ratio (r = 0.618, p < 0.05), and significant negative correlations with aliphatic carbon (r = -0.616, p < 0.05), total C (r = -0.685, p < 0.05) and total H contents (r = -0.654, p < 0.05). Complexation capacities had a significant positive correlation with total N (r = 0.826, p < 0.01) and a significant negative correlation with C/N ratio (r = -0.823, p < 0.01).

Quantifying pesticide deposits and spray patterns at micro-scales on apple (Malus domesticus) leaves with a view to arthropod exposure.

BACKGROUND: Pesticides used in commercial crop systems can adversely affect non-target arthropod populations. The spatial distribution of pesticide residues is rarely studied at scales relevant to these populations. Here, we combine two methods for assessing pesticide spray deposits at spatial scales relevant to non-target arthropods found in apple orchards. Pesticide residues were determined on individual apple leaves through conventional residue analysis; water-sensitive paper was used to investigate spatial distributions in deposits at the micro-scale. We also evaluated how accurately a digital image analysis program estimated pesticide residues. RESULTS: We found that mean pesticide spray coverage on water-sensitive paper varied by up to 6.1% (95% CI 9.4%, 2.7%) within an apple orchard, and leaf residues varied by up to 0.95 (95% CI 0.54, 1.36) mg kg-1 within a tree. Leaf residues based on analytical chemistry were six times lower than pesticide deposition estimated through image analysis of water-sensitive paper, although these correlated strongly. This correlation allowed estimation of actual residues by application of a correction factor. CONCLUSION: Our method demonstrates accurate estimation of pesticide deposits at the individual leaf scale through digital analysis of water-sensitive paper and is a low-cost, rapid alternative to conventional residue analysis techniques. © 2018 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Investigating the potential of synthetic humic-like acid to remove metal ions from contaminated water.

Humic acid can effectively bind metals and is a promising adsorbent for remediation technologies. Our studies initially focussed on Cu2+ as a common aqueous contaminant. Previous studies indicate that carboxylic groups dominate Cu2+ binding to humic acid. We prepared a synthetic humic-like acid (SHLA) with a high COOH content using catechol (0.25 M) and glycine (0.25 M) with a MnO2 catalyst (2.5% w/v) at pH = 8 and 25 °C and investigated the adsorption behaviour of Cu2+ onto it. The SHLA exhibited a range of adsorption efficiencies (27%-99%) for Cu2+ depending on reaction conditions. A pseudo-second-order kinetic model provided the best fit to the experimental data (R2 = 0.9995-0.9999, p ≤ 0.0001), indicating that chemisorption was most likely the rate-limiting step for adsorption. The equilibrium adsorption data showed good fits to both the Langmuir (R2 = 0.9928-0.9982, p ≤ 0.0001) and Freundlich (R2 = 0.9497-0.9667, p ≤ 0.0001) models. The maximum adsorption capacity (qm) of SHLA increased from 46.44 mg/g to 58.78 mg/g with increasing temperature from 25 °C to 45 °C. Thermodynamic parameters (ΔG0 = 2.50-3.69 kJ/mol; ΔS0 = 0.06 kJ/(mol·K); ΔH0 = 15.23 kJ/mol) and values of RL (0.0142-0.3711) and n (3.264-3.527) show that the adsorption of Cu2+ onto SHLA was favourable, spontaneous and endothermic in nature. Over six adsorption/desorption cycles using 0.5 M HCl for the desorption phase, there was a 10% decrease of the adsorption capacity. A final experiment using a multi-metal solution indicated adsorption efficiencies of up to 84.3-98.3% for Cu, 86.6-98.8% for Pb, 30.4-82.9% for Cr, 13.8-77.4% for Ni, 9.2-62.3% for Cd, 8.6-51.9% for Zn and 4.6-42.1% for Co. Overall, SHLA shows great potential as an adsorbent to remove metals from water and wastewater.

The copper complexation ability of a synthetic humic-like acid formed by an abiotic humification process and the effect of experimental factors on its copper complexation ability.

Humic acids have an important impact on the distribution, toxicity, and bioavailability of hazardous metals in the environment. In this study, a synthetic humic-like acid (SHLA) was prepared by an abiotic humification process using catechol and glycine as humic precursors and a MnO2 catalyst. The effect of physico-chemical conditions (ionic strength from 0.01 to 0.5 M NaNO3, pH from 4 to 8, temperature from 25 to 45 °C, and humic acid concentration from 5 to 100 mg/L) on the complexation ability of SHLA for Cu2+ were investigated. A commercial humic acid (CHA, CAS: 1415-93-6) from Sigma-Aldrich was also studied for comparison. The results showed that for pH 4 to 8, the conditional stability constants (log K) of SHLA and CHA were in the range 5.63-8.62 and 4.87-6.23, respectively, and complexation capacities (CC) were 1.34-2.61 and 1.42-2.31 mmol/g, respectively. The Cu complexation ability of SHLA was higher than that of the CHA due to its higher number of acidic functional groups (SHLA 19.19 mmol/g; CHA 3.87 mmol/g), extent of humification and aromaticity (AL/AR: 0.333 (SHLA); 1.554 (CHA)), and O-alkyl functional groups (SHLA 15.56%; CHA 3.45%). The log K and complexation efficiency (fraction of metal bound to SHLA) of SHLA were higher at higher pH, lower ionic strength, higher temperature, and higher SHLA concentration. Overall, SHLA was a good and promising complexation agent for copper in both soil washing of copper contaminated soil and the treatment of copper-containing wastewater.

Fate, uptake, and distribution of nanoencapsulated pesticides in soil-earthworm systems and implications for environmental risk assessment.

Nanopesticides are novel plant protection products offering numerous benefits. Because nanoparticles behave differently from dissolved chemicals, the environmental risks of these materials could differ from conventional pesticides. We used soil-earthworm systems to compare the fate and uptake of analytical-grade bifenthrin to that of bifenthrin in traditional and nanoencapsulated formulations. Apparent sorption coefficients for bifenthrin were up to 3.8 times lower in the nano treatments than in the non-nano treatments, whereas dissipation half-lives of the nano treatments were up to 2 times longer. Earthworms in the nano treatments accumulated approximately 50% more bifenthrin than those in the non-nano treatments. In the non-nano treatments, most of the accumulated material was found in the earthworm tissue, whereas in the nano treatments, the majority resided in the gut. Evaluation of toxicokinetic modeling approaches showed that models incorporating the release rate of bifenthrin from the nanocapsule and distribution within the earthworm provided the best estimations of uptake from the nano-formulations. Overall, our findings indicate that the risks of nanopesticides may be different from those of conventional formulations. The modeling presented provides a starting point for assessing risks of these materials but needs to be further developed to better consider the behavior of the nanoencapsulated pesticide within the gut system. Environ Toxicol Chem 2018;37:1420-1429. © 2018 SETAC.