Pesticide Transformation Products Research Articles

Investigation of occurrence of aromatic amines in municipal wastewaters using passive sampling

Aromatic amines (AAs) are human-made compounds known for their mutagenic properties, entering surface waters from various sources, often originating as transformation products of dyes or pesticides. Despite their low concentrations in surface waters, AAs can exhibit mutagenicity. Our study focused on evaluating three passive samplers (PSs) for enriching these compounds from influent and effluent of a wastewater treatment plant (WWTP) in Brno, Czech Republic. The PSs tested included variants containing AttractSPE™ SDB-RPS sorbent disk, one with and one without a diffusive agarose hydrogel layer, and a modified Speedisk (Bakerbond Speedisk® H2O-Philic). PSs were deployed in wastewater (WW) for one to four weeks in various overlapping combinations, and the uptake of AAs to PSs was compared to their concentrations in 24-hour composite water samples. A targeted LC/MS analysis covered 42 amines, detecting 11 and 13 AAs in daily composite influent and effluent samples, respectively. In the influent, AAs ranged from 1.5 ng L−1 for 1-anilinonaphthalene to 1.0 μg L−1 for aniline, and the highest concentration among all measured amines was observed for cyclohexylamine at 2.9 μg L−1. In the effluent, concentrations ranged from 0.5 ng L−1 for 1-anilinonaphthalene to 88 ng L−1 for o-anisidine. PSs demonstrated comparable accumulation of amines, with integrative uptake up to 28 days in both influent and effluent and detection of up to 23 and 27 amines in influent and effluent, respectively; altogether 34 compounds were detected in the study. Sampling rates (Rs) were estimated for compounds present in at least 50 % of the samples and showing <40 % aqueous concentration variability, with robustness evaluated by comparing values for compounds in WWTP influent and effluent. Although all devices performed similarly, hydrogel-based PS exhibited superior performance in several criteria, including time integration and robustness of sampling rates, making it a suitable monitoring tool for AAs in WW.

Determination of the efficiency of electrolyzed water devices for the removal of pesticides in aqueous solutions and the characteristics of the pesticide residues and their transformation products

The effect of electrolyzed water treatment on the degradation of pesticide residues (malathion, fenitrothion, p,p′-DDT, and 2-hydroxybiphenyl) in tap water was investigated. Electrolyzed water was generated by electrolysis in commercially available kitchen devices. Three devices with different parameters were tested. The transformation products of pesticides, which are formed after the electrolysis process, were also investigated. Results show that the reduction percentage for electrolyzed water was from 6.2 to 99.7 % for 2-hydroxyphenyl, from 75.5 to approx. 100 % for fenitrothion, from 79.7 to approx. 100 % for malathion, and from 52.1 to 78 % for p,p′-DDT. It was also shown that the obtained transformation products of selected pesticides are more toxic than the parent compounds. Extending the electrolysis time in water electrolysis devices results in more effective degradation of pesticides and transformation products. Our research has shown that electrolyzed water devices can effectively remove pesticide residues, but they can also be a source of other toxic transformation products that may have a synergistic effect.

Identification and Coexposure of Neonicotinoid Insecticides and Their Transformation Products in Retail Cowpea (Vigna unguiculata).

There is growing evidence that the transformation products of emerging contaminants in foodstuffs may pose a health risk to humans. However, the exact identities, levels, and estimated dietary intake (EDI) of neonicotinoid transformation products in crops remain poorly understood. We established an extended suspect screening strategy to investigate neonicotinoid insecticides and their transformation products in retail cowpea from 11 cities in Hainan Province, China. Forty-nine transformation products were identified in retail cowpea, of which 22-36 were found in 98.6% of the samples. Notably, 31 new transformation products were derived from new processes or a combination of different transformation processes. The mean concentrations of neonicotinoids and nine of the transformation products (with authentic standards) were in the ranges of 0.0824-5.34 and 0.0636-1.50 ng/g, respectively. The cumulative EDIs of the quantified transformation products were lower than those of parent neonicotinoids with the exception of clothianidin desmethyl, which had a ratio of 1157%. However, the coexistence of the other 40 transformation products (without authentic standards) in cowpea suggested that the exposure risk from all of the transformation products might be higher. This study demonstrated that pesticide transformation products should be considered in food chain risk assessments and included in future regulatory management.

Systematic Handling of Environmental Fate Data for Model Development-Illustrated for the Case of Biodegradation Half-Life Data.

The assessment of environmental hazard indicators such as persistence, mobility, toxicity, or bioaccumulation of chemicals often results in highly variable experimental outcomes. Persistence is particularly affected due to a multitude of influencing environmental factors, with biodegradation experiments resulting in half-lives spanning several orders of magnitude. Also, half-lives may lie beyond the limits of reliable half-life quantification, and the number of available data points per substance may vary considerably, requiring a statistically robust approach for the characterization of data. Here, we apply Bayesian inference to address these challenges and characterize the distributions of reported soil half-lives. Our model estimates the mean, standard deviation, and corresponding uncertainties from a set of reported half-lives experimentally obtained for a single substance. We apply our inference model to 893 pesticides and pesticide transformation products with experimental soil half-lives of varying data quantity and quality, and we infer the half-life distribution for each compound. By estimating average half-lives, their experimental variability, and the uncertainty of the estimations, we provide a reliable data source for building predictive models, which are urgently needed by regulatory authorities to manage existing chemicals and by industry to design benign, nonpersistent chemicals. Our approach can be readily adapted for other environmental hazard indicators.

Closing the gap: Ion chromatography coupled to high-resolution mass spectrometry to trace highly polar anionic substances in groundwater

Persistent, mobile and toxic (PMT), and very persistent and very mobile (vPvM) substances pose a threat to the water cycle but are often not covered in conventional environmental monitoring programs. Within this realm of substances, one compound class of concern are pesticides and their transformation products as they are deliberately introduced into the environment. To detect very polar anionic substances, including many pesticide transformation products with log DOW values ranging between −7.4 and 2.2, an ion chromatography high-resolution mass spectrometry method was developed in this study. Since inorganic anions, such as chloride and sulfate, interfere with the analysis of organic species, their removal via precipitation with Ba/Ag/H cartridges was assessed. To improve LOQs, vacuum-assisted evaporative concentration (VEC) was evaluated. By using VEC and removing inorganic salt ions, the median LOQ improved from 100 ng/L in evian® water without sample treatment to 10 ng/L after enrichment and 30 ng/L in karst groundwater. Using this method, twelve out of 64 substances covered by the final method were found in karst groundwater in concentrations of up to 5600 ng/L, and seven exceeded 100 ng/L. To the authors' knowledge, the dimethenamid TP M31 and chlorothalonil TP SYN548008 were detected for the first time in groundwater samples. The coupling to a high-resolution mass spectrometer also allows for non-target screening and hence, this method presents a powerful tool to tackle PMT/vPvM substances.

Multiresidue extraction of current-use pesticides from complex solid matrices using energized dispersive guided extraction with analysis by gas and liquid chromatography tandem mass spectroscopy

The development of sample processing techniques that recover a broad suite of pesticides from solid matrices, while mitigating coextracted matrix interferences, and reducing processing time is beneficial for high throughput analyses. The objective of this study was to evaluate the effectiveness of an automated extraction system for pesticide analyses in solid environmental samples. An Energized Dispersive Guided Extraction (EDGE) system was used to evaluate two different extraction solvents in optimizing the extraction of 210 pesticides and pesticide transformation products. A graphitized carbon cleanup step was implemented, and three elution solvents were evaluated separately for analyte recoveries. Recoveries between 70 and 130% were achieved for 167 compounds in a test soil using acetonitrile as an extraction solvent and carbon cleanup with acetonitrile and dichloromethane elutions. Nine field samples (soil, sediment, and biosolids) were extracted using the newly developed method and were compared with a previously validated pressurized liquid extraction (PLE) method using an Accelerated Solvent Extraction (ASE) system. Concentrations obtained from the two methods were comparable (linear R2 > 0.999), suggesting similar performance between the EDGE and PLE extractions in complex matrices. The new method provided slightly better sensitivities in comparison to the PLE method, ranging from 0.09 to 2.56 ng g−1. The method presented here significantly reduces extraction setup and runtimes while also minimizing the volume of carcinogenic solvents (e.g., dichloromethane) used in the laboratory and presents a sensitive multiresidue method for a wide range of pesticides in solid matrices.

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

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

Prioritizing Pesticides of Potential Concern and Identifying Potential Mixture Effects in Great Lakes Tributaries Using Passive Samplers.

To help meet the objectives of the Great Lakes Restoration Initiative with regard to increasing knowledge about toxic substances, 223 pesticides and pesticide transformation products were monitored in 15 Great Lakes tributaries using polar organic chemical integrative samplers. A screening-level assessment of their potential for biological effects was conducted by computing toxicity quotients (TQs) for chemicals with available US Environmental Protection Agency (USEPA) Aquatic Life Benchmark values. In addition, exposure activity ratios (EAR) were calculated using information from the USEPA ToxCast database. Between 16 and 81 chemicals were detected per site, with 97 unique compounds detected overall, for which 64 could be assessed using TQs or EARs. Ten chemicals exceeded TQ or EAR levels of concern at two or more sites. Chemicals exceeding thresholds included seven herbicides (2,4-dichlorophenoxyacetic acid, diuron, metolachlor, acetochlor, atrazine, simazine, and sulfentrazone), a transformation product (deisopropylatrazine), and two insecticides (fipronil and imidacloprid). Watersheds draining agricultural and urban areas had more detections and higher concentrations of pesticides compared with other land uses. Chemical mixtures analysis for ToxCast assays associated with common modes of action defined by gene targets and adverse outcome pathways (AOP) indicated potential activity on biological pathways related to a range of cellular processes, including xenobiotic metabolism, extracellular signaling, endocrine function, and protection against oxidative stress. Use of gene ontology databases and the AOP knowledgebase within the R-package ToxMixtures highlighted the utility of ToxCast data for identifying and evaluating potential biological effects and adverse outcomes of chemicals and mixtures. Results have provided a list of high-priority chemicals for future monitoring and potential biological effects warranting further evaluation in laboratory and field environments. Environ Toxicol Chem 2023;42:340-366. Published 2022. This article is a U.S. Government work and is in the public domain in the USA. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Use of wood and cork in biofilters for the simultaneous removal of nitrates and pesticides from groundwater

About 13% and 7% of monitored groundwater stations in Europe exceed the permitted levels of nitrates (50 mg NO3− L−1) or pesticides (0.1 μg L−1), respectively. Although slow sand filtration can remove nitrates via denitrification when oxygen is limited, it requires an organic carbon source. The present study evaluates the performance of the use of wood pellets and granulated cork as carbon sources in bench-scale biofilters operated under water-saturated and water-unsaturated conditions for more than 400 days. The biofilters were monitored for nitrate (200 mg L−1) and pesticide (mecoprop, diuron, atrazine, and bromacil, each at a concentration of 5 μg L−1) attenuation, as well as for the formation of nitrite and pesticide transformation products. Microbiological characterization of each biofilter was also performed. The water-saturated wood biofilter achieved the best nitrate removal (>99%), while the cork biofilters lost all denitrification power over time (from 38% to no removal). The unsaturated biofilter columns were not effective for removing nitrates (20–30% removal). As for pesticides, all the biofilters achieved high removal rates of mecoprop and diuron (>99% and >75%, respectively). Atrazine removal was better in the wood-pellet biofilters than the cork ones (68–96% vs. 31–38%). Bromacil was only removed in the water-unsaturated cork biofilter (67%). However, a bromacil transformation product was formed there. The water-saturated wood biofilter contained the highest number of denitrifying microorganisms, with Methyloversatilis as the characteristic genus. Microbial composition could explain the high removal of pesticides and nitrates achieved in the wood-pellet biofilter. Overall, the results indicate that wood-pellet biofilters operated under water-saturated conditions are a good solution for treating groundwater contaminated with nitrates and pesticides.

Occurrence of Pharmaceutical and Pesticide Transformation Products in Freshwater: Update on Environmental Levels, Toxicological Information and Future Challenges

Pharmaceuticals and pesticides are recognized micropollutants in freshwater systems. Their ever-increasing frequency of detection, levels found and little information available about their effects on non-target organisms, make them emerging contaminants. However, parental compounds are not the only substances of concern. Their metabolites and degradation products, hereby referred to as transformation products, are increasingly detected in freshwater samples and wastewater effluents. In the past years, a wealth of publications provided concentration levels detected in freshwater and some toxicological data, which required critical systematization. This review identified concentrations for 190 transformation products (92 from pesticides and 98 from pharmaceuticals) in water bodies and wastewater effluents. A concentration heatmap was produced to easily spot the substances found at higher levels and plan future research. The very limited available toxicological data link exposure to transformation products to adverse outcomes in humans (genotoxicity and alteration in detoxification processes) and aquatic species (mostly related to apical endpoints). Overall, environmental levels of these transformation products may pose a severe threat to aquatic organisms and need to be further investigated in sound experimental designs, testing for the effects of the single substances as well as of their mixtures. Such toxicological information is highly needed to improve both water treatment technologies and monitoring programmes.

Assessment of a novel microalgae-cork based technology for removing antibiotics, pesticides and nitrates from groundwater

Groundwater pollution has increased in recent years due to the intensification of agricultural and livestock activities. This results in a significant reduction in available freshwater resources. Here, we have studied the long term assessment of a green technology (1-4L/day) based on a photobioreactor (PBR) containing immobilised microalgae-bacteria in polyurethane foam (PF) followed by a cork filter (CF) for removing nitrates, pesticides (atrazine and bromacil), and antibiotics (sulfamethoxazole and sulfacetamide) from groundwater. The prototype was moderately effective for removing nitrates (58%) at an HRT of 8 days, while its efficiency decreased at a HRT of 4 and 2 days (<20% removal). The combined use of PBR-CF enabled antibiotics and pesticides to be attenuated by up to 95% at an HRT of 8 days, but their attenuation decreased with shorter HRT, with pesticides being the compounds most affected (reducing from 97 to 98% at an HRT of 8 days to 23-45% at an HRT of 2 days). Pesticide transformation products were identified after the CF, supporting biodegradation as the main attenuation process. A gene-based metataxonomic assessment linked the attenuation of micropollutants to the presence of specific pesticide biodegradation species (e.g. genus Phenylobacterium, Sphingomonadaceae, and Caulobacteraceae). Therefore, the results highlighted the potential use of microalgae and cork to treat polluted groundwater.

Enhanced database creation with in silico workflows for suspect screening of unknown tebuconazole transformation products in environmental samples by UHPLC-HRMS

The search and identification of organic contaminants in agricultural watersheds has become a crucial effort to better characterize watershed contamination by pesticides. The past decade has brought a more holistic view of watershed contamination via the deployment of powerful analytical strategies such as non-target and suspect screening analysis that can search more contaminants and their transformation products. However, suspect screening analysis remains broadly confined to known molecules, primarily due to the lack of analytical standards and suspect databases for unknowns such as pesticide transformation products. Here we developed a novel workflow by cross-comparing the results of various in silico prediction tools against literature data to create an enhanced database for suspect screening of pesticide transformation products. This workflow was applied on tebuconazole, used here as a model pesticide, and resulted in a suspect screening database counting 291 transformation products. The chromatographic retention times and tandem mass spectra were predicted for each of these compounds using 6 models based on multilinear regression and more complex machine-learning algorithms. This comprehensive approach to the investigation and identification of tebuconazole transformation products was retrospectively applied on environmental samples and found 6 transformation products identified for the first time in river water samples.

Geochemical matrix differently affects the response of internal standards and target analytes for pesticide transformation products measured in groundwater samples

Electrospray ionization (ESI) is the most common technique in liquid chromatography coupled to tandem mass spectrometry (LC-MS-MS) allowing for sensitive detection of polar compounds with online water concentration. The technique is popular in groundwater monitoring programs and has permitted great progress in the detection and quantification of polar pesticide transformation products (TP) in recent years. However, ESI is also known to be prone to matrix effects. The common solution to this potential bias is the use of labelled internal standards. Unfortunately, these are not available for all target compounds, which leads to the linkage of target compounds to non-homologue internal standards with unknown consequences for quantification in variable geochemical settings. We investigated these matrix effects for polar TP with a molecular mass range of 225–350 Da and logDpH7 between −0.27 and −1.7 as well as for parent compounds with logDpH3 between 0.84 and 3.22. The acquired internal standards were tested on a gradient of DOC, anions, conductivity and inorganic carbon with a set of ten carefully chosen groundwater samples. Internal standards that were measured in positive ionization mode proved to be insensitive to geochemical variations while those that were measured in negative ionization mode showed reduced response with increasing anion concentration. All pairs of internal standards and target analytes were investigated for deviating matrix effects using standard addition experiments. Positive ionization compounds and target compounds with deuterated homologues showed little deviation while non-homologue pairs in negative mode proved to be strongly biased. Although bias was up to factor five for some compounds it was remarkably stable over the entire gradient studied, suggesting an identical suppression mode at varying matrix levels for different compounds. We advocate the conduct of standard addition experiments if homologue internal standards are not available.

A study using QSAR/QSPR models focused on the possible occurrence and risk of alloxydim residues from chlorinated drinking water, according to the EU Regulation

Any active substance with phytosanitary capacity intended to be marketed in Europe must pass exhaustive controls to assess its risk before being marketed and used in European agriculture. Since the implementation of Regulation (EC) No 1107/2009, agrochemical companies have been obliged to study the formation of pesticide transformation products (TPs) during the treatment of drinking water containing pesticide residues. However, there is no consensus on how to address this requirement.In this research work, the open literature collection on alloxydim was used to propose potential chlorination paths from alloxydim isomers. Furthermore, several QSAR/QSPR models have been used to fill the of knowledge gap relative to some key parameters in the physico-chemical, environmental and ecotoxicological areas of potential alloxydim TPs from chlorinated water for which little information exists. In this way, it has been possible to estimate the state of aggregation of these TPs (they exist mainly as liquids) as well as their ease of transit between the different phases, to predict their possible behaviour in the three environmental compartments (e.g., thermophysical properties point to a change in their evolution with respect to the parent alloxydim isomers) and to anticipate their potential risk to human and animal health (e.g., all of them cause developmental toxicity).These and other results highlight that the hazards of several TPs, i.e., both chlorinated and nonchlorinated from parent alloxydim or from those obtained after cleavage of the N − O bond and the subsequent reaction with chlorine, should be seriously considered. The obtained results reopen the debate on the implications of the use of QSAR/QSPR models for pesticide risk assessment in the legislative framework.

Profiling of pesticides and pesticide transformation products in Chinese herbal teas

Herbal teas have potential health benefits, but they also contain a variety of pesticides and pesticide transformation products (PTPs) that might brings health risks. Our study maps the pesticides and PTPs in two herbal teas (chrysanthemum and Lusterleaf Holly) from two main producing areas in China. Almost all 122 samples contain pesticides, with concentration ranging from 0.0005 to 10.305 mg/kg. Nearly 40% carbendazim and imidacloprid in chrysanthemum teas and λ-cyhalothrin in Lusterleaf Holly have higher concentration levels than the values permitted in EC Regulation No. 396/2005. Distinct distributions of pesticides were found in different teas and production areas. Eight PTPs were identified along with their parents, and were confirmed using a biosynthetic strategy. Acute, chronic and cumulative health risk assessments of pesticides revealed acceptable results. Our study uncovers the profile of pesticides in herbal teas, and provides new insight into discovering the potential environmental pollution and food contaminants.

Transformation products of pesticides and veterinary drugs in food and raw materials (analytical review)

Transformation products of pesticides and veterinary drugs in food and raw materials (analytical review)

Enhanced Database Creation with in Silico Workflows for Suspect Screening of Unknown Pesticide Transformation Products in Environmental Samples by Uhplc-Hrms

Enhanced Database Creation with in Silico Workflows for Suspect Screening of Unknown Pesticide Transformation Products in Environmental Samples by Uhplc-Hrms

The regenerative role of biofilm in the removal of pesticides from stormwater in biochar-amended biofilters

We studied the impact of a microbial biofilm on biochar-amended biofilter performance and lifetime, and the potential for leaching of pesticide transformation products.

Assessment of Environmental Pollution and Human Exposure to Pesticides by Wastewater Analysis in a Seven-Year Study in Athens, Greece.

Pesticides have been used in large amounts around the world for decades and are responsible for environmental pollution and various adverse effects on human health. Analysis of untreated wastewater can deliver useful information on pesticides’ use in a particular area and allow the assessment of human exposure to certain substances. A wide-scope screening method, based on liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry, was applied, using both target and suspect screening methodologies. Daily composite influent wastewater samples were collected for seven or eight consecutive days in Athens between 2014 and 2020 and analyzed for 756 pesticides, their environmental transformation products and their human metabolites. Forty pesticides were quantified at mean concentrations up to 4.9 µg/L (tralkoxydim). The most abundant class was fungicides followed by herbicides, insect repellents, insecticides and plant growth regulators. In addition, pesticide transformation products and/or metabolites were detected with high frequency, indicating that research should be focused on them. Human exposure was evaluated using the wastewater-based epidemiology (WBE) approach and 3-ethyl-carbamoyl benzoic acid and cis-1,2,3,6-tetrahydrophthalimide were proposed as potential WBE biomarkers. Wastewater analysis revealed the presence of unapproved pesticides and indicated that there is an urgent need to include more transformation products in target databases.

Modelling the Fate of Pesticide Transformation Products From Plot to Catchment Scale—State of Knowledge and Future Challenges

Transformation products (TP) of pesticides are found everywhere in the aquatic environment. Their dynamic formation and subsequent transport from agricultural fields to adjacent water bodies can be estimated by using environmental fate models, which is done in the registration process for plant protection products in the European Union. In this study, peer-reviewed applications of such models, the model complexity and their structure are documented and analysed. In total, 20 publications of 10 models – eight leaching models (GLEAMS, MACRO, RZWQM2, PEARL, PRZM, Pelmo, LEACHM, HYDRUS 1-D) and two catchment scale models (Zin-AgriTra, FRM) – were identified. The reviewed models greatly differ in their process complexity regarding the formation rate and the formation pathways of TPs.The major reason given for models failing to reproduce sampled TP concentrations in case studies was an erroneous substance transport, especially missing preferential flow simulation in soil. However, the contribution of TP formation processes to simulation uncertainty was not analysed at all in most of the studies. By comparing the structure of existing models, the state of knowledge on TP fate and requirements of TP fate assessment, the following recommendations were drawn: i) It is suggested that the models should be updated to reflect the current state of knowledge in process research, especially more complex transformation schemes and the formation of different TPs in different compartments, which was not included in most of the models. ii) Even though there are pesticide parent compound fate models at the catchment scale with a temporal resolution of one day, none of these models is able to simulate TP fate. Such models would enable scientists and authorities to estimate the environmental fate of TPs at the larger catchment scale or the regional scale. iii) To get over the assessment of the huge number of TPs formed in the environment, an integration of Quantitative Structure Properties Relationship models predicting TP fate characteristics, TP pathway prediction models and environmental fate models is suggested. This would allow for a largely automated and comprehensive assessment of the fate of a pesticide parent compound and all its TPs for regulatory purposes.