Porphyrin-based covalent organic framework as oxidase mimic for highly sensitive colorimetric detection of pesticides.

A covalent organic framework-based strategy was designed for label-free colorimetric detection of pesticides. Covalent organic framework-based nanoenzyme with excellent oxidase-like catalytic activity was synthesized. Unlike other artificial enzymes, porphyrin-based covalent organic framework (p-COF) as the oxidase mimic showed highly catalytic chromogenic activity and good affinity toward TMB without the presence of H2O2, which can be used as substitute for peroxidase mimics and H2O2 system in the colorimetric reaction. Based on the fact that the pesticide-aptamer complex can inhibit the oxidase activity of p-COF and reduced the absorbance at 650 nm in UV-Vis spectrum, a label-free and facile colorimetric detection of pesticides was designed and fabricated. Under the optimized conditions, the COF-based colorimetric probe for pesticide detection displayed high sensitivity and selectivity. Taking fipronil for example the limit of detection was 2.7 ng/mL and the linear range was 5 -500,000 ng/mL. The strategy was successfully applied to the detection of pesticides with good recovery , which was in accordance with that of HPLC-MS/MS. The COF-based colorimetric detection was free of complicated modification H2O2, which guaranteed the accuracy and reliability of measurements. The COF-based sensing strategy is a potential candidate for the sensitive detection of pesticides of interests.

Physical function as a marker to assess the effects of occupational long-term pesticide exposure.

In this cross-sectional study, we determined the relative impact of long-term occupational exposure to pesticides on physical performance and perception of tiredness. Experimental data was collected in locus from agricultural communities and included surveys to assess the duration of exposure to pesticides, social status, habitual physical activity levels, presence of common mental disorders (CMD), and self-reported tiredness. Plasmatic cholinesterase (PChE), body composition and traditional functional performance tests (Handgrip strength-HGS; Time up and go-TUG; and Sit-to-stand-STS) were obtained. From the 127 individuals tested, cluster analysis yielded 80 individuals divided in Direct Exposed (n = 37) and Indirect Exposed (n = 43); Tired (n = 16), and Not Tired (n = 64). PChE values were within the reference values (5209.64-13943.53 U/L). Pesticide exposure had no influence on PChE levels, CMD or fatigue (p > 0.05), while Self-reported tiredness had (p < 0.05). Principal Component Analyses showed that HGS; STS and TUG (i.e., physical performance variables) are negatively influenced by two independent factors: pesticide exposure and self-reported tiredness. We conclude that chronic pesticide exposure and tiredness can negatively impact physical performance, independently, without clinically significant changes in PChE levels that is a biomarker used to track pesticide intoxication. Functional physical tests can be a useful tool to identify chronic pesticide exposure, and help with the limitations of commonly used parameters (i.e. PChE and CMD). Self-reported tiredness is a confounding variable.

The effect of education on safe use of pesticides based on the health belief model.

OBJECTIVE: In agricultural activities, pesticide use is critical, but poisoning issues are one of the most important occupational hazards for farmers. Training can help protect farmers' health from pesticide hazards. This study aimed to investigate the effect of education on farmers' behavior in the safe use of pesticides using the health belief model. METHODS: A quasi-experimental (pretest-post-test) study conducted on 84 farmers who were selected using the convenience sampling method. The data collection tool was a two-part questionnaire including demographic information and a questionnaire designed based on the constructs of the health belief model in using personal protective equipment while working with the pesticides. The instrument was completed before and two weeks after an educational intervention. Data analysis was performed using SPSS software version 26. RESULTS: The mean age of the participants was 48.94 ± 9.14 years and 69% were male. The study showed that with increasing age, the mean score of health belief model constructs in the safe use of pesticides decreased. Female and higher-educated farmers had higher scores. After the intervention, the mean scores of health belief model constructs in the safe use of pesticides increased significantly, except perceived barriers construct which decreased significantly. Also, the frequency of protective equipment uses while working with pesticides increased significantly after the intervention and safe behaviors increased, while unsafe behaviors decreased. CONCLUSION: The education as an effective intervention, improves farmers' safety attitudes and behaviors in pesticide use and it is recommended that educational programs be designed according to the characteristics of the audience.

Evaluating and Enhancing an Educational Intervention to Reduce Smallholder Farmers' Exposure to Pesticides in Uganda Through a Digital, Systematic Approach to Behavior Change: Protocol for a Cluster-Randomized Controlled Trial.

BACKGROUND: Smallholder farmers receive educational interventions on safe pesticide handling by governmental agencies, industries, or nongovernmental organizations to reduce exposure risks. However, existing educational interventions have limited effects on changing behaviors. Targeting psychosocial determinants of behavior change in educational interventions through theory- and evidence-based approaches may enhance their effectiveness. OBJECTIVE: We aim at describing the intervention development and study design of a 3-arm cluster-randomized controlled trial to assess the effects in improving safe pesticide handling and reducing pesticide exposure of (1) an existing educational intervention and (2) a newly developed SMS text messaging intervention based on the Risks, Attitudes, Norms, Abilities, and Self-regulation (RANAS) behavior change approach. METHODS: We enrolled 539 Ugandan smallholder farmers in 12 clusters (subcounties). The clusters, each with 45 farmers, were randomly allocated to one of the three arms: (1) educational intervention, (2) educational intervention+RANAS-based SMS text messages, or (3) control group. The educational intervention comprised a 2-day workshop that targeted multiple aspects of safe pesticide handling, whereas the SMS text messages targeted the use of personal protective equipment (PPE) and were based on the RANAS approach. For intervention development in this study, this approach includes identifying psychosocial determinants of PPE use at baseline and selecting behavior change techniques to target them in SMS text messages. The primary outcomes of the study are (1) pesticide knowledge, attitude, and practice scores indicating performance throughout the educational intervention; and (2) frequency of PPE use. Secondary outcomes are the RANAS-based behavioral determinants of PPE use, the frequency of glove use, algorithm-based pesticide exposure intensity scores, and signs and symptoms of pesticide poisoning. The outcomes were assessed in structured interviews before the intervention (baseline) and at the 12-month follow-up. The effect of the interventions among the arms will be analyzed using the intervention arms and baseline measures as predictors and the follow-up measures as outcomes in linear multivariable mixed models including the clusters as random effects. The mediating psychosocial determinants of the interventions will be assessed in multiple mediation models. RESULTS: The study was conducted from 2020 to 2021-baseline interviews were conducted in October 2020, and the educational intervention was delivered in November 2020. The RANAS-based SMS text messages were developed based on the baseline data for relevant behavioral determinants of PPE use and sent between February 2021 and September 2021. Follow-up interviews were conducted in October 2021. Overall, 539 farmers were enrolled in the study at baseline; 8.3% (45/539) were lost to follow-up by the end of the study. CONCLUSIONS: This study will contribute to a better understanding of the effectiveness and behavior change mechanisms of educational interventions by using an experimental, cluster-randomized study design to improve pesticide handling among smallholder farmers. TRIAL REGISTRATION: International Standard Randomised Controlled Trial Number (ISRCTN) 18237656; https://doi.org/10.1186/ISRCTN18237656. INTERNATIONAL REGISTERED REPORT IDENTIFIER (IRRID): DERR1-10.2196/55238.

A new sustainable filtration membrane extraction method based on nanoconfined liquid phase extraction: Determination of organochlorinated pesticides and pyrethroids in tea samples.

BACKGROUND: Pesticides are used in agricultural production for prevent and control crop diseases and pests, but it is easy to cause excessive pesticides residues in agricultural products, polluting the environment and endangering human health. Due to their unmatched and sustainable capabilities, nanoextraction procedures are becoming every day more important in Analytical Chemistry. In particular, nanoconfined liquid phase extraction has shown extraction capabilities toward polar, medium polar, and/or nonpolar substances, which can be easily modulated depending on the nanoconfined solvent used. Furthermore, this "green" technique showed excellent characteristics in terms of recoveries, extraction time (≤1 min), reliability, and versatility. (97) RESULTS: In this work, the advantages of this technique have been coupled with those of filtration membrane extraction, making use of carbon nanofibers (CnFs) growth on carbon microspheres (CµS). This substrate has been deposited on a filter, which combined with gas chromatographic mass spectrometry (GC-MS) analysis successfully employed for the nanoextraction of 30 pesticides (18 organochlorine and 12 pyrethroids) in tea samples. Under the optimized extraction conditions, the linear range with standard solutions was from 1 to 1000 ng mL-1 (R2 ≥ 0.99), the limit of detections in tea samples were in the range 0.56-17.98 µg kg-1. The accuracy of the developed method was evaluated by measuring the extraction recovery of the spiked tea samples, and recoveries between 74.41 % and 115.46 %. (119) SIGNIFICANCE: Considering the versatility of nanoconfined liquid phase extraction and the functionality of the filtration membrane extraction procedure, this new extraction method can be considered a powerful candidate for automatized high-throughput analyses of real samples. (34).

Diversity and Functionality of Bacteria Associated with Different Tissues of Spider Heteropoda venatoria Revealed through Integration of High-Throughput Sequencing and Culturomics Approaches.

Spiders host a diverse range of bacteria in their guts and other tissues, which have been found to play a significant role in their fitness. This study aimed to investigate the community diversity and functional characteristics of spider-associated bacteria in four tissues of Heteropoda venatoria using HTS of the 16S rRNA gene and culturomics technologies, as well as the functional verification of the isolated strains. The results of HTS showed that the spider-associated bacteria in different tissues belonged to 34 phyla, 72 classes, 170 orders, 277 families, and 458 genera. Bacillus was found to be the most abundant bacteria in the venom gland, silk gland, and ovary, while Stenotrophomonas, Acinetobacter, and Sphingomonas were dominant in the gut microbiota. Based on the amplicon sequencing results, 21 distinct cultivation conditions were developed using culturomics to isolate bacteria from the ovary, gut, venom gland, and silk gland. A total of 119 bacterial strains, representing 4 phyla and 25 genera, with Bacillus and Serratia as the dominant genera, were isolated. Five strains exhibited high efficiency in degrading pesticides in the in vitro experiments. Out of the 119 isolates, 28 exhibited antibacterial activity against at least one of the tested bacterial strains, including the pathogenic bacteria Staphylococcus aureus, Acinetobacter baumanii, and Enterococcus faecalis. The study also identified three strains, GL312, PL211, and PL316, which exhibited significant cytotoxicity against MGC-803. The crude extract from the fermentation broth of strain PL316 was found to effectively induce apoptosis in MGC-803 cells. Overall, this study offers a comprehensive understanding of the bacterial community structure associated with H. venatoria. It also provides valuable insights into discovering novel antitumor natural products for gastric cancer and xenobiotic-degrading bacteria of spiders.

Analyzing the impact of pesticides on the indus river: contamination levels in water, sediment, fish, and associated human health risks.

Pesticides are frequently used to protect crop yields and manage malaria vectors; however, their inadvertent transport into aquatic habitats poses a significant concern. Various anthropogenic activities influence the Indus River in Pakistan. This study aimed to assess the presence of eight pesticide residues at three different sites (Kalabagh, Kundian, and Chashma) in water, sediment, and the fish species (Labeo rohita) during both dry and wet seasons to measure the intensity of this pressure. Pesticide analysis was carried out using gas chromatography equipped with an electron capture detector. The results revealed the highest concentrations of pesticides during both dry and wet seasons at all sites, measuring 0.83 and 0.62 µg/l (water), 12.37 and 9.20 µg/g/dw (sediment), and 14.27 and 11.29 µg/g/ww (L. rohita), respectively. Overall, pesticide concentrations were higher in the dry season than in the wet season across all study sites. Based on detection frequency and concentration in both seasons at all sites, dominant pesticides included cypermethrin and carbofuran (in water), as well as endosulfan and cypermethrin (in sediment and fish tissue). Levels of endosulfan and cypermethrin exceeded standard limits. Moreover, principal component analysis (PCA) indicated no correlation among pesticides in fish tissue, sediment, and water. However, pesticides exhibited different behavior in different seasons. Furthermore, endosulfan and triazophos impose great human health risk, as indicated by the THQ value (> 1). The overall HI value was greater for site 1 in the dry season (8.378). The study concluded that the presence of agricultural pesticides in the Indus River poses a risk to aquatic life and has the potential to disrupt the entire food chain. This highlights the importance of sustainable practices for the study area and Pakistan overall agricultural and environmental sustainability. It is further recommended to strengthen regulations for reduced pesticide use and promote eco-friendly pest management.

Multifunctional 2D hemin-bridged MOF for the efficient removal and dual-mode detection of organophosphorus pesticides.

The high-residual and bioaccumulation property of organophosphorus pesticides (OPs) creates enormous risks towards the ecological environment and human health, promoting the research for smart adsorbents and detection methods. Herein, 2D hemin-bridged MOF nanozyme (2D-ZHM) was fabricated and applied to the efficient removal and ultrasensitive dual-mode aptasensing of OPs. On the one hand, the prepared 2D-ZHM contained Zr-OH groups with high affinity for phosphate groups, endowing it with selective recognition and high adsorption capacity for OPs (285.7 mg g-1 for glyphosate). On the other hand, the enhanced peroxidase-mimicking biocatalytic property of 2D-ZHM allowed rapid H2O2-directed transformation of 3,3',5,5'-tetramethylbenzidine to oxidic product, producing detectable colorimetric or photothermal signals. Using aptamers of specific recognition capacity, the rapid quantification of two typical OPs, glyphosate and omethoate, was realized with remarkable sensitivity and selectivity. The limit of detections (LODs) of glyphosate were 0.004 nM and 0.02 nM for colorimetric and photothermal methods, respectively, and the LODs of omethoate were 0.005 nM and 0.04 nM for colorimetric and photothermal methods, respectively. The constructed dual-mode aptasensing platform exhibited outstanding performance for monitoring OPs in water and fruit samples. This work provides a novel pathway to develop MOF-based artificial peroxidase and integrated platform for pollutant removal and multi-mode aptasensing.

Simultaneous Analysis of 272 Pesticides in Agricultural Products by the QuEChERS Method and Gas Chromatography with Tandem Mass Spectrometry.

The aim of this study is to develop a rapid and accurate method for simultaneous analysis of multi-residue pesticides and conduct pesticide monitoring in agricultural products produced by the production and distribution stage in Korea. The representative agricultural products were selected as brown rice, soybean, potato, mandarin, and green pepper and developed using gas chromatography with tandem mass (GC-MS/MS) for the analysis of 272 pesticide residues. The experimental samples were extracted by the QuEChERS-EN method and then cleaned up by using d-SPE, including MgSO4 and primary secondary amine (PSA) sorbents. The established method was validated in accordance with Codex CAC-GL/40, and the limit of quantitation (LOQ) was determined to be 0.01 mg/kg. A total of 243 pesticides satisfied the guidelines in five samples at three levels with values of 60 to 120% (recovery) and ≤45% (coefficient of variation, CV). The remaining 29 pesticides did not satisfy the guidelines, and these pesticides are expected to be used as a screening method for the routine inspection of agricultural products. As a result of analyzing 223 agricultural products in South Korea by applying the simultaneous analysis method, none of the detected levels in the samples exceeded the standard values based on maximum residue limits (MRLs). The developed method in this study will be used to inspect residual pesticides in agricultural products, and it is anticipated to contribute to the distribution of safe agricultural products to consumers.

The research landscape concerning environmental factors in neurodevelopmental disorders: Endocrine disrupters and pesticides-A review.

In recent years, environmental epidemiology and toxicology have seen a growing interest in the environmental factors that contribute to the increased prevalence of neurodevelopmental disorders, with the purpose of establishing appropriate prevention strategies. A literature review was performed, and 192 articles covering the topic of endocrine disruptors and neurodevelopmental disorders were found, focusing on polychlorinated biphenyls, polybrominated diphenyl ethers, bisphenol A, and pesticides. This study contributes to analyzing their effect on the molecular mechanism in maternal and infant thyroid function, essential for infant neurodevelopment, and whose alteration has been associated with various neurodevelopmental disorders. The results provide scientific evidence of the association that exists between the environmental neurotoxins and various neurodevelopmental disorders. In addition, other possible molecular mechanisms by which pesticides and endocrine disruptors may be associated with neurodevelopmental disorders are being discussed.

Transfer and bioaccumulation of pesticides in terrestrial arthropods and food webs: State of knowledge and perspectives for research.

Arthropods represent an entry point for pesticide transfers in terrestrial food webs, and pesticide accumulation in upper chain organisms, such as predators can have cascading consequences on ecosystems. However, the mechanisms driving pesticide transfer and bioaccumulation in food webs remain poorly understood. Here we review the literature on pesticide transfers mediated by terrestrial arthropods in food webs. The transfer of pesticides and their potential for bioaccumulation and biomagnification are related to the chemical properties and toxicokinetic of the substances, the resistance and detoxification abilities of the contaminated organisms, as well as by their effects on organisms' life history traits. We further identify four critical areas in which knowledge gain would improve future predictions of pesticides impacts on terrestrial food webs. First, efforts should be made regarding the effects of co-formulants and pesticides mixtures that are currently understudied. Second, progress in the sensitivity of analytical methods would allow the detection of low concentrations of pesticides in small individual arthropods. Quantifying pesticides in arthropods preys, their predators, and arthropods or vertebrates at higher trophic level would bring crucial insights into the bioaccumulation and biomagnification potential of pesticides in real-world terrestrial food webs. Finally, quantifying the influence of the trophic structure and complexity of communities on the transfer of pesticides could address several important sources of variability in bioaccumulation and biomagnification across species and food webs. This narrative review will inspire future studies aiming to quantify pesticide transfers in terrestrial food webs to better capture their ecological consequences in natural and cultivated landscapes.

Assessing glyphosate and AMPA pesticides in the Ofanto River waters and sediments.

In the present study, we determined glyphosate (GPS) and aminomethylphosphonic acid (AMPA) in the water and sediments of the Ofanto River (Italy), evaluating their transport from the mouth to the sea. Sediments were collected twice in 2021 during low and high tide; waters were sampled on a seasonal basis. The results showed the prevalence of GPS and AMPA in the water with concentrations equal to 190 and 3053 ng/l, respectively. We also found GPS and AMPA in the sediments with values of 0.95 and 11.34 ng/g. In water, pesticides were detected in all seasons with peaks in concentrations during summer and spring. A significant positive correlation between the pesticides in the sediments and the water pH and a negative correlation with salinity was observed. An estimation of the average loads revealed a discharge of 64.11 kg/yr. of GPS and 958.37 kg/yr. of AMPA from the river to the marine environment.

Swellable microneedle-coupled light-addressable photoelectrochemical sensor for in-situ tracking of multiple pesticides pollution in vivo.

In vivo monitoring of multiple pesticide contamination is of great significance for evaluating the health risks of different pesticides, agricultural production safety, and ecological and environmental assessment. Here, we report a hydrogel microneedle array coupled light-addressable photoelectrochemical sensor for tracking multiple pesticide uptake and elimination in living animals and plants, holding three prominent merits: i) enables in-situ detection of in vivo pesticides, avoiding cumbersome and complex sample transportation and handling processes; ii) allows repeated in vivo sampling of the same organism, improving tracking test controllability and accuracy; iii) avoids lethal sampling, providing a better understanding of the pesticides fate in living organisms. The coupled sensor is mechanically robust for withstanding more than 0.35 N per needle and highly swellable (800 %) for timely extraction of sufficient in vivo solution for analysis. For proof-of-concept, it achieves in-situ detection of atrazine, acetamiprid, and carbendazim efficiently and quantitatively in artificial agarose skin models, mouse skin interstitial fluids, and plant leaves with little inflammatory reaction. This simple, highly integrated, minimally invasive, and high-throughput in vivo monitoring method is ideal for future field environmental monitoring and plant and animal disease diagnosis.

Optimization and validation of high throughput methods for the determination of 132 organic contaminants in green and roasted coffee using GC-QqQ-MS/MS and LC-QqQ-MS/MS.

Recently some major safety concerns have been raised on organic contaminants in widely consumed plants such as coffee. Hence, this study aimed to develop specifically optimized methods for determining organic contaminants, such as pesticides and polychlorinated biphenyls (PCBs), in coffee using GC-MS/MS and LC-MS/MS. QuEChERS method was used as a base extraction method, and 27 experiments were studied using design of experiments with categorical variables (extraction buffers, cleanup sorbents, and coffee roasting degree) to find the optimum method for each matrix type. The optimum method for green coffee was acetate buffer and chitosan for clean-up, while no-buffer extraction and the PSA + C18 method were ideal for light and dark-roasted coffee. The optimized methods were validated in accordance with SANTE/11312/2021. Furthermore, ten real samples (4 green, and 6 roasted) from the markets were analysed; ortho-phenylphenol was found in all the roasted coffee samples, and carbendazim was found in one green coffee sample.

Removal of multiple pesticides from water by different types of membranes.

Pesticides are used in agriculture to protect crops from pathogens, insects, fungi and weeds, but the release of pesticides into surface/groundwater by agriculture runoff and rain has raised serious concerns not only for the environment but also for human health. This study aimed to investigate the impact of surface properties on the performance of seven distinct membrane types utilized in nanofiltration (NF), reverse osmosis (RO) and forward osmosis (FO) processes in eliminating multiple pesticides from spiked water. Out of the membranes tested, two are self-fabricated RO membranes while the rest are commercially available membranes. Our results revealed that the self-fabricated RO membranes performed better than other commercial membranes (e.g., SW30XLE, NF270, Duracid and FO) in rejecting the targeted pesticides by achieving at least 99% rejections regardless of the size of pesticides and their log Kow value. Despite the marginally lower water flux exhibited by the self-fabricated membrane compared to the commercial BW30 membrane, its exceptional ability to reject both mono- and divalent salts renders it more apt for treating water sources containing not only pesticides but also various dissolved ions. The enhanced performance of the self-fabricated RO membrane is mainly attributed to the presence of a hydrophilic interlayer (between the polyamide layer and substrate) and the incorporation of hydrophilic nanosheets in tuning its surface characteristics. The findings of the work provide insight into the importance of membrane surface modification for the application of not only the desalination process but also for the removal of contaminants of emerging concern.

Optimization and uncertainty assessment of a gas chromatography coupled to Orbitrap mass spectrometry method to determine organic contaminants in blood: A case study of an endangered seabird.

Birds are excellent bioindicators of environmental pollution, and blood provides information on contaminant exposure, although its analysis is challenging because of the low volumes that can be sampled. The objective of the present study was to optimize and validate a miniaturized and functional extraction and analytical method based on gas chromatography coupled to Orbitrap mass spectrometry (GCOrbitrap-MS) for the trace analysis of contaminants in avian blood. Studied compounds included 25 organochlorine pesticides (OCPs), 6 polychlorinated biphenyls (PCBs), 8 polybrominated diphenyl ethers (PBDEs) and 15 polycyclic aromatic hydrocarbons (PAHs). Four extraction and clean-up conditions were optimized and compared in terms of efficiency, accuracy, and uncertainty assessment. Extraction with hexane:dichloromethane and miniaturized Florisil pipette clean-up was the most adequate considering precision and accuracy, time, and costs, and was thereafter used to analyse 20 blood samples of a pelagic seabird, namely the Bermuda petrel (Pterodroma cahow). This species, endemic to the Northwest Atlantic, is among the most endangered seabirds of the region that in the '60 faced a decrease in the breeding success likely linked to a consistent exposure to dichloro-diphenyl-trichloroethane (DDT). Indeed, p,p'-DDE, the main DDT metabolite, was detected in all samples and ranged bewteen 1.13 and 6.87 ng/g wet weight. Other ubiquitous compounds were PCBs (ranging from 0.13 to 6.76 ng/g ww), hexachlorobenzene, and mirex, while PAHs were sporadically detected at low concentrations, and PBDEs were not present. Overall, the extraction method herein proposed allowed analysing very small blood volumes (∼ 100 µL), thus respecting ethical principles prioritising the application of less-invasive sampling protocols, fundamental when studying threatened avian species.

A novel honeycomb-like 3D-printed device for rotating-disk sorptive extraction of organochlorine and organophosphorus pesticides from environmental water samples.

In this study, 3D-printing based on fused-deposition modeling (FDM) was employed as simple and cost-effective strategy to fabricate a novel format of rotating-disk sorptive devices. As proof-of-concept, twenty organochlorine and organophosphorus pesticides were determined in water samples through rotating-disk sorptive extraction (RDSE) using honeycomb-like 3D-printed disks followed by gas chromatography coupled to mass spectrometry (GC-MS). The devices that exhibited the best performance were comprised of polyamide + 15 % carbon fiber (PA + 15 % C) with the morphology being evaluated through X-ray microtomography. The optimized extraction conditions consisted of 120 min of extraction using 20 mL of sample at stirring speed of 1100 rpm. Additionally, liquid desorption using 800 µL of acetonitrile for 25 min at stirring speed of 1100 rpm provided the best response. Importantly, the methodology also exhibited high throughput since an extraction/desorption platform that permitted up to fifteen simultaneous extractions was employed. The method was validated, providing coefficients of determination higher than 0.9706 for all analytes; limits of detection (LODs) and limits of quantification (LOQs) ranged from 0.15 to 3.03 µg L-1 and from 0.5 to 10.0 µg L-1, respectively. Intraday precision ranged from 4.01 to 18.73 %, and interday precision varied from 4.83 to 20.00 %. Accuracy was examined through relative recoveries and ranged from 73.29 to 121.51 %. This method was successfully applied to analyze nine groundwater samples from monitoring wells of gas stations in São Paulo. Moreover, the greenness was assessed through AGREEprep metrics, and an overall score of 0.69 was obtained indicating that the method proposed can be considered sustainable.

Exposure Assessment of Pesticides in Surface Waters of Ontario, Canada Reveals Low Probability of Exceeding Acute Regulatory Thresholds.

The objectives of this study were to: (1) characterize the exposure of aquatic ecosystems in Southern Ontario, Canada to pesticides between 2002 and 2016 by constructing environmental exposure distributions (EEDs), including censored data; and (2) predict the probability of exceeding acute regulatory guidelines. Surface water samples were collected over a 15-year period by Environment and Climate Change Canada. The dataset contained 167 compounds, sampled across 114 sites, with a total of 2,213 samples. There were 67,920 total observations of which 55,058 were non-detects (81%), and 12,862 detects (19%). The most commonly detected compound was atrazine, with a maximum concentration of 18,600 ngL- 1 and ~ 4% chance of exceeding an acute guideline (1,000 ngL- 1) in rivers and streams. Using Southern Ontario as a case study, this study provides insight into the risk that pesticides pose to aquatic ecosystems and the utility of EEDs that include censored data for the purpose of risk assessment.

Occupational risks associated with chronic kidney disease of non-traditional origin (CKDnt) in Brazil: it is time to dig deeper into a neglected problem.

In the past decades, an epidemic of chronic kidney disease (CKD) has been associated with environmental and occupational factors (heat stress from high workloads in hot temperatures and exposure to chemicals, such as pesticides and metals), which has been termed CKD of non-traditional origin (CKDnt). This descriptive review aims to present recent evidence about heat stress, pesticides, and metals as possible causes of CKDnt and provide an overview of the related Brazilian regulation, enforcement, and health surveillance strategies. Brazilian workers are commonly exposed to extreme heat conditions and other CKDnt risk factors, including increasing exposure to pesticides and metals. Furthermore, there is a lack of adequate regulation (and enforcement), public policies, and strategies to protect the kidney health of workers, considering the main risk factors. CKDnt is likely to be a significant cause of CKD in Brazil, since CKD's etiology is unknown in many patients and several conditions for its development are present in the country. Further epidemiological studies may be conducted to explore causal associations and estimate the impact of heat, pesticides, and metals on CKDnt in Brazil. Moreover, public policies should prioritize reducing workers´ exposure and promoting their health and safety.

Photochemical Degradation of the New Nicotine Pesticide Acetamiprid in Water.

Acetamiprid is a novel nicotinic pesticide widely used in modern agriculture because of its low toxicity and specific biological target properties. The objective of this study was to understand the photolysis pattern of acetamiprid in the water column and elucidate its degradation products and mechanism. It was observed that acetamiprid exhibited different photolysis rates under different light source conditions in pure water, with ultraviolet > fluorescence > sunlight; furthermore, its photolysis half-life ranged from 17.3 to 28.6 h. In addition, alkaline conditions (pH 9.0) accelerated its photolysis rate, which increased with pH. Using gas chromatography-mass spectrometry, five direct photolysis products generated during the exposure of acetamiprid to pure water were successfully separated and identified. The molecular structure of acetamiprid was further analyzed using density functional theory, and the active photodegradation sites of acetamiprid were predicted. The mechanism of the photolytic transformation of acetamiprid in water was mainly related to hydroxyl substitution and oxidation. Based on these findings, a comprehensive transformation pathway for acetamiprid was proposed.