Metal concentrations in transitional and coastal waters measured by passive (Diffusive Gradients in Thin-films) and spot sampling: MONITOOL Project Dataset.

The MONITOOL project (2017-2023) was carried out to describe the relationships between total dissolved and labile metal concentrations measured in spot water samples and in concurrently deployed Diffusive Gradients in Thin-films (DGTs) passive samplers, respectively. The ultimate aim was to adapt existing marine metal Environmental Quality Standards (EQS marine water) for DGTs, enabling their use in the context of the European Directives (the Water Framework Directive (WFD) and the Marine Strategy Framework Directive (MSFD)). Time-integrated metal concentrations provided by DGTs, representing several days, are an advantage compared to conventional spot sampling, especially in highly dynamic systems, such as transitional waters. Hence, the MONITOOL project aimed to provide a robust database of dissolved and labile metal concentrations in transitional and coastal waters, based upon co-deployments of DGTs and collection of spot water samples at several sampling sites (England, France, Ireland, Italy, Northern Ireland, Portugal, Scotland and Spain), followed subsequently by DGT and water metal analysis. Samplings were carried out in 2018 and 2022, following agreed protocols developed in the framework of the project. The MONITOOL dataset includes metal concentrations from DGTs, measured with Inductively Coupled Plasma Mass Spectrometry (ICP-MS: Cd, Co, Cu, Fe, Mn, Ni, Pb, Zn) and in concurrently collected spot water samples by ICP-MS (Al, Cd, Co, Cu, Mn, Ni, Pb, Zn) and Anodic/Cathodic Stripping Voltammetry (ASV/CSV: Cd, Pb, Ni). Moreover, data on seawater physical-chemical parameters (salinity, temperature, dissolved oxygen, pH, turbidity, total suspended solids, dissolved organic carbon, and total organic carbon) is provided. This database presents the results obtained using, concurrently, different forms of sampling and analytical techniques, enabling the comparison of the results obtained by these strategies and allowing the adaptation of EQS in marine water (EQS marine water) to DGTs (EQS DGT), in the context of the WFD. Moreover, due to the large number of sampling sites, it could also be used for other types of research, such as those dealing with metal speciation or the determination of baseline levels.

Honey contamination from plant protection products approved for cocoa (Theobroma cacao) cultivation: A systematic review of existing research and methods.

The main component of chocolate, cocoa (Theobroma cacao), is a significant commercial agricultural plant that directly sustains the livelihoods of an estimated forty to fifty million people. The economies of many cocoa producing nations, particularly those in the developing world, are supported by cocoa export revenue. To ensure satisfactory yields, however, the plant is usually intensely treated with pesticides because it is vulnerable to disease and pest attacks. Even though pesticides help protect the cocoa plant, unintended environmental contamination is also likely. Honey, produced from nectar obtained by honeybees from flowers while foraging, can serve as a good indicator for the level of pesticide residues and environmental pesticide build-up in landscapes. Here, we use a systematic literature review to quantify the extent of research on residues of pesticides used in cocoa cultivation in honey. In 81% of the 104 studies examined for this analysis, 169 distinct compounds were detected. Imidacloprid was the most frequently detected pesticide, making neonicotinoids the most frequently found class of pesticides overall. However, in cocoa producing countries, organophosphates, organochlorines, and pyrethroids were the most frequently detected pesticides. Interestingly, only 19% of studies were carried out in cocoa producing countries. We recommend prioritizing more research in the countries that produce cocoa to help to understand the potential impact of pesticide residues linked with cocoa cultivation in honey and the environment more generally to inform better pesticide usage, human health, and environmental policies.

Establishing the extent of pesticide contamination in Irish agricultural soils.

To establish meaningful and sustainable policy directives for sustainable pesticide use in agriculture, baseline knowledge of pesticide levels in soils is required. To address this, five pesticides and one metabolite widely used in Irish agriculture and five neonicotinoid compounds pesticides were screened from soils from 25 fields. These sites represented a diversity of soil and land use types. Prothioconazole was detected in 16 of the 18 sites where it had been recently applied, with the highest maximum concentration quantified of 46 µg/kg. However, a week after application only four fields had prothioconazole concentrations above the limit of quantification (LOQ). Fluroxypyr was applied in 11 sites but was not detected above LOQ. Glyphosate and AMPA were not detected. Interestingly, neonicotinoids were detected in 96% of all sampling sites, even though they were not reported as recently applied. Excluding neonicotinoids, 60% of sites were found to contain pesticide residues of compounds that were not previously applied, with boscalid and azoxystrobin detected in 15 of the 25 sites sampled. The total number of pesticides detected in Irish soils were significantly negatively correlated with clay fraction, while average pesticide concentrations were significantly positively correlated with log Kow values. 17 fields were found to have total pesticide concentrations in excess of 0.5 µg/kg, even when recently applied pesticides were removed from calculations. Theoretical consideration of quantified pesticides determined that azoxystrobin has high leaching risk, while boscalid, which was detected but not applied, has an accumulation risk. This information provides insight into the current level of pesticide contamination in Irish agricultural soil and contributes to the European-level effort to understand potential impacts of pesticide contamination in soil.

Honey bees and bumble bees may be exposed to pesticides differently when foraging on agricultural areas.

In an agricultural environment, where crops are treated with pesticides, bees are likely to be exposed to a range of chemical compounds in a variety of ways. The extent to which different bee species are affected by these chemicals, largely depends on the concentrations and type of exposure. We quantified the presence of selected pesticide compounds in the pollen of two different entomophilous crops; oilseed rape (Brassica napus) and broad bean (Vicia faba). Sampling was performed in 12 sites in Ireland and our results were compared with the pollen loads of honey bees and bumble bees actively foraging on those crops in those same sites. Detections were compound specific, and the timing of pesticide application in relation to sampling likely influenced the final residue contamination levels. Most detections originated from compounds that were not recently applied on the fields, and samples from B. napus fields were more contaminated compared to those from V. faba fields. Crop pollen was contaminated only with fungicides, honey bee pollen loads contained mainly fungicides, while more insecticides were detected in bumble bee pollen loads. The highest number of compounds and most detections were observed in bumble bee pollen loads, where notably, all five neonicotinoids assessed (acetamiprid, clothianidin, imidacloprid, thiacloprid, and thiamethoxam) were detected despite the no recent application of these compounds on the fields where samples were collected. The concentrations of neonicotinoid insecticides were positively correlated with the number of wild plant species present in the bumble bee-collected pollen samples, but this relationship could not be verified for honey bees. The compounds azoxystrobin, boscalid and thiamethoxam formed the most common pesticide combination in pollen. Our results raise concerns about potential long-term bee exposure to multiple residues and question whether honey bees are suitable surrogates for pesticide risk assessments for all bee species.

International Comparison, Risk Assessment, and Prioritisation of 26 Endocrine Disrupting Compounds in Three European River Catchments in the UK, Ireland, and Spain.

Endocrine-disrupting compounds (EDCs) constitute a wide variety of chemistries with diverse properties that may/can pose risks to both humans and the environment. Herein, a total of 26 compounds, including steroids, flame retardants, and plasticizers, were monitored in three major and heavily urbanized river catchments: the R. Liffey (Ireland), the R. Thames (UK), and the R. Ter (Spain), by using a single solid-phase extraction liquid chromatography-mass spectrometry (SPE-LC-MS/MS) method. Occurrence and frequency rates were investigated across all locations over a 10-week period, with the highest concentration obtained for the flame retardant tris(2-chloroethyl) phosphate (TCEP) at 4767 ng∙L-1 in the R. Thames in Central London. Geographical variations were observed between sites and were partially explained using principal component analysis (PCA) and hierarchical cluster analysis (HCA). In particular, discrimination between the R. Ter and the R. Thames was observed based on the presence and concentration of flame retardants, benzotriazole, and steroids. Environmental risk assessment (ERA) across sites showed that caffeine, a chemical marker, and bisphenol A (BPA), a plasticizer, were classified as high-risk for the R. Liffey and R. Thames, based on relative risk quotients (rRQs), and that caffeine was classified as high-risk for the R. Ter, based on RQs. The total risks at each location, namely ΣRQriver, and ΣrRQriver, were: 361, 455, and 723 for the rivers Liffey, Thames, and Ter, respectively. Caffeine, as expected, was ubiquitous in all 3 urban areas, though with the highest RQ observed in the R. Ter. High contributions of BPA were also observed across the three matrices. Therefore, these two compounds should be prioritized independently of location. This study represents a comprehensive EDC monitoring comparison between different European cities based on a single analytical method, which allowed for a geographically independent ERA prioritization to be performed.

Pesticide mixtures detected in crop and non-target wild plant pollen and nectar.

Cultivation of mass flowering entomophilous crops benefits from the presence of managed and wild pollinators, who visit flowers to forage on pollen and nectar. However, management of these crops typically includes application of pesticides, the presence of which may pose a hazard for pollinators foraging in an agricultural environment. To determine the levels of potential exposure to pesticides, their presence and concentration in pollen and nectar need assessing, both within and beyond the target crop plants. We selected ten pesticide compounds and one metabolite and analysed their occurrence in a crop (Brassica napus) and a wild plant (Rubus fruticosus agg.), which was flowering in field edges. Nectar and pollen from both plants were collected from five spring and five winter sown B. napus fields in Ireland, and were tested for pesticide residues, using QuEChERS and Liquid Chromatography tandem mass spectrometry (LC-MS/MS). Pesticide residues were detected in plant pollen and nectar of both plants. Most detections were from fields with no recorded application of the respective compounds in that year, but higher concentrations were observed in recently treated fields. Overall, more residues were detected in B. napus pollen and nectar than in the wild plant, and B. napus pollen had the highest mean concentration of residues. All matrices were contaminated with at least three compounds, and the most frequently detected compounds were fungicides. The most common compound mixture was comprised of the fungicides azoxystrobin, boscalid, and the neonicotinoid insecticide clothianidin, which was not recently applied on the fields. Our results indicate that persistent compounds like the neonicotinoids, should be continuously monitored for their presence and fate in the field environment. The toxicological evaluation of the compound mixtures identified in the present study should be performed, to determine their impacts on foraging insects that may be exposed to them.

A year-long study of the occurrence and risk of over 140 contaminants of emerging concern in wastewater influent, effluent and receiving waters in the Republic of Ireland.

Despite being a developed country in the European Union (EU), knowledge of the nature and extent of contamination of water bodies with contaminants of emerging concern (CECs) in Ireland is limited. In this study, >140 CECs including pharmaceuticals, pesticides and personal care products were monitored in monthly samples of wastewater treatment plant (WWTP) influent, effluent and receiving surface waters at both an urban and a rural location (72 samples in total) in Ireland over a 12-month period in 2018-2019. In total, 58 CECs were detected, including several EU Water Framework Directive Watch List compounds. Of all classes, the highest concentrations were measured for pharmaceuticals across all media, i.e., propranolol in surface waters (134 ng·L-1), hydrochlorothiazide in effluent (1067 ng·L-1) and venlafaxine in influent wastewater (8273 ng·L-1). Overall, high wastewater treatment removal was observed and a further reduction in CEC occurrence and concentration was measured via dilution in the receiving river environment. Lastly, an environmental risk assessment (ERA) was performed using risk quotients (RQ), which revealed that in surface waters, total RQ for all CECs was an order of magnitude lower than in effluents. The majority of CECs in surface waters posed a lower risk except E2 and EE2 which presented a medium risk (RQs of 3.5 and 1.1, respectively) in the rural area. This work represents the most comprehensive CEC monitoring dataset to date for Ireland which allowed for an ERA prioritisation to be performed for the first time.

Glyphosate used as desiccant contaminates plant pollen and nectar of non-target plant species.

Pesticide products containing glyphosate as a systemic active ingredient are some of the most extensively used herbicides worldwide. After spraying, residues have been found in nectar and pollen collected by bees foraging on treated plants. This dietary exposure to glyphosate could pose a hazard for flower-visiting animals including bees, and for the delivery of pollination services. Here, we evaluated whether glyphosate contaminates nectar and pollen of targeted crops and non-target wild plants. Oilseed rape was selected as focal crop species, and Rubus fruticosus growing in the hedgerows surrounding the crop was chosen as non-target plant species. Seven fields of oilseed rape, where a glyphosate-based product was applied, were chosen in east and southeast Ireland, and pollen and nectar were extracted from flowers sampled from the field at various intervals following glyphosate application. Pollen loads were taken from honeybees and bumblebees foraging on the crop at the same time. Glyphosate and aminomethylphosphonic acid (AMPA) residues were extracted using acidified methanol and their concentrations in the samples were determined by a validated liquid chromatography tandem mass spectrometry (LC-MS/MS) method. Glyphosate was detected in R. fruticosus nectar and pollen samples that were taken within a timeframe of two to seven days after the application on the crop as a desiccant. No glyphosate was detected when the application took place before or more than two months prior to our sampling in any of the evaluated matrices. The metabolite AMPA was not detected in any samples. To gain further insight into the potential extent of translocation within both plants and soil when a crop is desiccated using glyphosate before harvesting, and the potential impacts on bees, we recommend a longitudinal study of the presence and fate of glyphosate in non-target flowering plants growing nearby crop fields, over a period of several days after glyphosate application.

Assessing availability of European plant protection product data: an example evaluating basic area treated.

Besides the benefits of plant protection products (PPPs) for agricultural production, there is an increasing acknowledgement of the associated potential environmental risks. Here, we examine the feasibility of summarizing the extent of PPP usage at the country level, using Ireland as a case study, as well as at the European level. We used the area over which PPPs are applied (basic area) as an example variable that is relevant to initially assess the geographic extent of environmental risk. In Irish agricultural systems, which are primarily grass-based, herbicides fluroxypyr and glyphosate are the most widely applied active substances (ASs) in terms of basic area, followed by the fungicides chlorothalonil and prothioconazole that are closely associated with arable crops. Although all EU countries are subject to Regulation (EC) No 1185/2009, which sets the obligation of PPP usage data reporting at the national level, we only found usable data that met our criteria for Estonia, Germany, Finland, and Spain (4 of 30 countries reviewed). Overall, the most widely applied fungicide and herbicide in terms of basic area were prothioconazole (20%, 7% and 5% of national cultivated areas of Germany, Estonia and Ireland) and glyphosate (11%, 8% and 5% of national cultivated areas of Spain, Estonia and Ireland) respectively, although evaluations using application frequency may result in the observation of different trends. Several recommendations are proposed to tackle current data gaps and deficiencies in accessibility and usability of pesticide usage data across the EU in order to better inform environmental risk assessment and promote evidence-based policymaking.

Bumblebees can be Exposed to the Herbicide Glyphosate when Foraging.

Herbicides are the most widely used pesticides globally. Although used to control weeds, they may also pose a risk to bee health. A key knowledge gap is how bees could be exposed to herbicides in the environment, including whether they may forage on treated plants before they die. We used a choice test to determine if bumblebees would forage on plants treated with glyphosate at two time periods after treatment. We also determined whether glyphosate and its degradation product aminomethylphosphonic acid were present as residues in the pollen collected by the bees while foraging. Finally, we explored if floral resources (nectar and pollen) remained present in plants after herbicide treatment. In general bees indiscriminately foraged on both plants treated with glyphosate and controls, showing no avoidance of treated plants. Although the time spent on individual flowers was slightly lower on glyphosate treated plants, this did not affect the bees' choice overall. We found that floral resources remained present in plants for at least 5 days after lethal treatment with glyphosate and that glyphosate residues were present in pollen for at least 70 h posttreatment. Our results suggest that bees could be exposed to herbicide in the environment, both topically and orally, by foraging on plants in the period between herbicide treatment and death. Identifying this route of exposure is a first step in understanding the risks of herbicides to bees. The effects of herbicides on bees themselves are uncertain and warrant further investigation to allow full risk assessment of these compounds to pollinating insects. Environ Toxicol Chem 2022;41:2603-2612. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

An international intercomparison exercise on passive samplers (DGT) for monitoring metals in marine waters under a regulatory context.

In order to move forward in the acceptance of a novel contaminant monitoring technique (Diffusive Gradients in Thin-films: DGT) for assessment of marine water bodies, sensu the WFD, an Inter-Laboratories Comparison (ILC) exercise (nine Europeans laboratories) was organized in the framework of the Interreg Atlantic Area MONITOOL project, which focused on the use of the DGT technique for the measurement of WFD priority metals (Cd, Ni and Pb). Reproducible results were obtained for each metal by several laboratories, supporting the assertion that DGT analysis can be performed satisfactorily by laboratories experienced in measuring metals at trace levels in marine environments, even if they have limited practice in DGT analysis. According to the Z-score analysis, among the 9 participating laboratories, 3 had 100 % of satisfactory results for Cd, Ni, and Pb, 3 had >80 % satisfactory results and 2 had about 60 % satisfactory results. This work highlights the need to clearly describe the DGT method in order to control sources of contamination during analytical steps, in particular the resin gel retrieval and the elution steps. Such international intercomparison exercise is an important step to develop the laboratory network involved in DGT analysis and contributes to the improvement of data quality.

Metals concentrations in transitional and coastal waters by ICPMS and voltammetry analysis of spot samples and passive samplers (DGT).

This study investigates the relationships among Ni, Cd and Pb's different chemical forms determined by different methodologies in coastal and transitional waters across a broad geographical scale. Concentrations were measured in spot samples and through passive sampling (DGT). High variability of metal concentrations was found among sampling sites and methodologies due to natural water fluctuations rather than to a given metal or method. Total dissolved metal concentrations in spot samples were lower than the EQS-WFD values. The labile fractions of Cd and Pb, measured in spot samples by Anodic Stripping Voltammetry and by DGT-ICPMS, were highly correlated. Similar labilities were found for Cd, while for Pb, the ASV labile fraction was ≈50% lower. These results reflect the pool of mobile and labile species available towards each technique kinetic window, and they seem not to be affected by discrete sampling flaws.

Simultaneous determination of pesticides from soils: a comparison between QuEChERS extraction and Dutch mini-Luke extraction methods.

The expanding nature of the agricultural sector has fuelled the intensification of plant protection products usage, including pesticides. These pesticides may persist in soils, necessitating their accurate determination in a variety of soil types. However, due to their complex nature, the effective extraction of pesticide residues from soil matrices can present challenges to pesticide detection and quantification. This research compared two well-known extraction methods, QuEChERS and Dutch mini-Luke, by assessing their specificity, sensitivity, accuracy, precision and reproducibility in extracting seven distinct pesticides with a range of chemico-physical characteristics from Irish soils. The HPLC-UV conditions were optimised to separate the seven pesticides, and it was shown that both extraction methods successfully extracted neonicotinoids with recovery values ranging between 85 and 115%. Fluroxypyr and prothioconazole could not be efficiently extracted using QuEChERS, however, the recovery values of both the analytes ranged between 59 and 117% using Dutch mini-Luke. Furthermore, with the exception of prothioconazole using Dutch mini-Luke, both extraction methods resulted in reproducibility and precision values below or equal to 20%. Lastly, Dutch mini-Luke is noted to have a lower matrix effect than QuEChERS, except for prothioconazole. The comparison results showed that Dutch mini-Luke resulted in superior method sensitivity, better recovery, and lower matrix effect towards most investigated analytes and was the only extraction technique that successfully extracted all pesticides analysed in soil matrices.

Monitoring of emerging contaminants of concern in the aquatic environment: a review of studies showing the application of effect-based measures.

Water scarcity is increasingly a global cause of concern mainly due to widespread changes in climate conditions and increased consumptive water use driven by the exponential increase in population growth. In addition, increased pollution of fresh water sources due to rising production and consumption of pharmaceuticals and organic chemicals will further exacerbate this concern. Although surface water contamination by individual chemicals is often at very low concentration, pharmaceuticals for instance are designed to be efficacious at low concentrations, creating genuine concern for their presence in freshwater sources. Furthermore, the additive impact of multiple compounds may result in toxic or other biological effects that otherwise will not be induced by individual chemicals. Globally, different legislative frameworks have led to pre-emptive efforts which aim to ensure good water ecological status. Reports detailing the use and types of effect-based measures covering specific bioassay batteries that can identify specific mode of actions of chemical pollutants in the aquatic ecosystem to evaluate the real threat of pollutants to aquatic lives and ultimately human lives have recently emerged from monitoring networks such as the NORMAN network. In this review, we critically evaluate some studies within the last decade that have implemented effect-based monitoring of pharmaceuticals and organic chemicals in aquatic fauna, evaluating the occurrence of different chemical pollutants and the impact of these pollutants on aquatic fauna with special focus on pollutants that are contaminants of emerging concern (CEC) in urban wastewater. A critical discussion on studies that have used effect-based measures to assess biological impact of pharmaceutical/organic compound in the aquatic ecosystem and the endpoints measurements employed is presented. The application of effect-based monitoring of chemicals other than assessment of water quality status is also discussed.

Concurrent sampling of transitional and coastal waters by Diffusive Gradient in Thin-films (DGT) and spot sampling for trace metals analysis.

This protocol was developed based on the knowledge acquired in the framework of the Interreg MONITOOL project (EAPA_565/2016) where extensive sampling campaigns were performed in transitional and coastal waters covering eight European countries. It provides detailed procedures and guidelines for the sampling of these waterbodies by concurrent collection of discrete water samples and the deployment of Diffusive Gradient in Thin-films (DGT) passive samplers for the measurement of trace metal concentrations. In order to facilitate the application of this protocol by end-users, it presents steps to follow in the laboratory prior to sampling campaigns, explains the procedures for field campaigns (including in situ measurement of supporting parameters) and subsequent sample processing in the laboratory in preparation for trace metal analyze by inductively coupled plasma-mass spectrometry (ICP-MS) and voltammetry. The protocol provides a systematic, coherent field sampling and sample preparation strategy that was developed in order to ensure comparability and reproducibility of the data obtained from each project Partner in different regions. • Standardization of the concurrent sampling of transitional and coastal waters by DGT passive samplers and spot sampling. • Robust procedures and tips based on existing international standards and comprehensive practical experience. • Links to demonstration videos produced within the MONITOOL project.

Deoxynivalenol and Zearalenone-Synergistic or Antagonistic Agri-Food Chain Co-Contaminants?

Deoxynivalenol (DON) and Zearalenone (ZEN) are two commonly co-occurring mycotoxins produced by members of the genus Fusarium. As important food chain contaminants, these can adversely affect both human and animal health. Critically, as they are formed prior to harvesting, their occurrence cannot be eliminated during food production, leading to ongoing contamination challenges. DON is one of the most commonly occurring mycotoxins and is found as a contaminant of cereal grains that are consumed by humans and animals. Consumption of DON-contaminated feed can result in vomiting, diarrhoea, refusal of feed, and reduced weight gain in animals. ZEN is an oestrogenic mycotoxin that has been shown to have a negative effect on the reproductive function of animals. Individually, their mode of action and impacts have been well-studied; however, their co-occurrence is less well understood. This common co-occurrence of DON and ZEN makes it a critical issue for the Agri-Food industry, with a fundamental understanding required to develop mitigation strategies. To address this issue, in this targeted review, we appraise what is known of the mechanisms of action of DON and ZEN with particular attention to studies that have assessed their toxic effects when present together. We demonstrate that parameters that impact toxicity include species and cell type, relative concentration, exposure time and administration methods, and we highlight additional research required to further elucidate mechanisms of action and mitigation strategies.

Assessing variability in the ratio of metal concentrations measured by DGT-type passive samplers and spot sampling in European seawaters.

The current study evaluates the effect of seawater physico-chemical characteristics on the relationship between the concentration of metals measured by Diffusive Gradients in Thin films (DGT) passive samplers (i.e., DGT-labile concentration) and the concentrations measured in discrete water samples. Accordingly, Inductively Coupled Plasma Mass Spectrometry (ICP-MS) was used to measure the total dissolved metal concentrations in the discrete water samples and the labile metal concentrations obtained by DGT samplers; additionally, lead and cadmium conditional labile fractions were determined by Anodic Stripping Voltammetry (ASV) and total dissolved nickel was measured by Cathodic Stripping Voltammetry (CSV). It can be concluded that, in general, the median ratios of DGT/ICP and DGT/ASV(CSV) were lower than 1, except for Ni (median ratio close to 1) and Zn (higher than 1). This indicates the importance of speciation and time-integrated concentrations measured using passive sampling techniques, which is in line with the WFD suggestions for improving the chemical assessment of waterbodies. It is the variability in metal content in waters rather than environmental conditions to which the variability of the ratios can be attributed. The ratios were not significantly affected by the temperature, salinity, pH, oxygen, DOC or SPM, giving a great confidence for all the techniques used. Within a regulatory context such as the EU Water Framework Directive this is a great advantage, since the simplicity of not needing to use corrections to minimize the effects of environmental variables could help in implementing DGTs within monitoring networks.

Neonicotinoid residues in honey from urban and rural environments.

Pesticide residues in honey can negatively affect bee health. Although recent studies have detected neonicotinoid residues in honeys from around the world, little is known about how residues relate to land use and vegetation composition. To investigate potential relationships, we sampled multi-floral honey from 30 Apis mellifera hives from urban, agricultural and semi-natural habitats (SNH), identified and quantified three neonicotinoids present (clothianidin, imidacloprid and thiacloprid) using UHPLC-MS, and classified surrounding land use up to 5 km around hive sites. Neonicotinoids were most frequently detected in honeys from hives in agricultural habitats, and 70% of all samples contained at least one of the three neonicotinoid compounds. Imidacloprid was the most frequently detected neonicotinoid (found in 43% of honey samples) followed by clothianidin (40%) and thiacloprid (37%). Almost half (48%) of samples contained at least two neonicotinoids, and two of the 30 samples contained all three. Clothianidin and thiacloprid were more frequently detected in honeys from urban habitats, highlighting that exposure to pesticides does not just occur in agricultural settings. This suggests that pesticide use in urban domestic, sport and amenity contexts, given potential exposure of bees and other pollinators, needs urgent consideration.

A review of pharmaceutical occurrence and pathways in the aquatic environment in the context of a changing climate and the COVID-19 pandemic.

Active pharmaceutical ingredients (APIs) are increasingly being identified as contaminants of emerging concern (CECs). They have potentially detrimental ecological and human health impacts but most are not currently subject to environmental regulation. Addressing the life cycle of these pharmaceuticals plays a significant role in identifying the potential sources and understanding the environmental impact that pharmaceuticals may have in surface waters. The stability and biological activity of these "micro-pollutants" can lead to a pseudo persistence, with ensuing unknown chronic behavioural and health-related effects. Research that investigates pharmaceuticals predominantly focuses on their occurrence and effect within surface water environments. However, this review will help to collate this information with factors that affect their environmental concentration. This review focuses on six pharmaceuticals (clarithromycin, ciprofloxacin, sulfamethoxazole, venlafaxine, gemfibrozil and diclofenac), chosen because they are heavily consumed globally, have poor removal rates in conventional activated sludge wastewater treatment plants (CAS WWTPs), and are persistent in the aquatic environment. Furthermore, these pharmaceuticals are included in numerous published prioritisation studies and/or are on the Water Framework Directive (WFD) "Watch List" or are candidates for the updated Watch List (WL). This review investigates the concentrations seen in European Union (EU) surface waters and examines factors that influence final concentrations prior to release, thus giving a holistic overview on the source of pharmaceutical surface water pollution. A period of 10 years is covered by this review, which includes research from 2009-2020 examining over 100 published studies, and highlighting that pharmaceuticals can pose a severe risk to surface water environments, with each stage of the lifecycle of the pharmaceutical determining its concentration. This review additionally highlights the necessity to improve education surrounding appropriate use, disposal and waste management of pharmaceuticals, while implementing a source directed and end of pipe approach to reduce pharmaceutical occurrence in surface waters.