Occurrence and risk assessment of pesticides and their transformation products related to olive groves in surface waters of the Guadalquivir river basin.

Pesticides are considered one of the main sources of contamination of surface waters, especially in rural areas highly influenced by traditional agricultural practices. The objective of this work was to evaluate the impact caused by pesticides and their transformation products (TPs) related to olive groves in surface waters with strong agricultural pressure. 11 streams were monitored during four sampling campaigns over 2 years. A solid-phase extraction, followed by ultra-high-performance liquid chromatography coupled to tandem mass spectrometry (UHPLC-MS/MS) analysis was used in the quantitative target approach, with more than 70 validated compounds. Target method was combined with a suspect screening strategy involving more than 500 pesticides and TPs, using ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) to identify additional pesticides and TPs out of the scope of analysis. A total of 43 different compounds were detected with the target method. The herbicide MCPA was present in all samples and at the highest concentration (1260 ng L-1), followed by the fungicide carbendazim (1110 ng L-1), and the herbicide chlorotoluron (706 ng L-1). The suspect screening strategy revealed the presence of 7 compounds out of the target analysis (1 pesticide and 6 TPs). 6 analytes were confirmed with the analytical standards. Semi-quantification results revealed that TPs exhibited higher concentrations than their corresponding parent compounds, indicating higher persistency. Some small streams showed a comparable number of pesticides and concentrations to the most polluted large river. The determined pesticide and TPs concentrations represented an estimated environmental hazard in almost all sampling sites under study. This work underscores the importance of including pesticide TPs and small streams impacted by extensive agricultural activities in water quality monitoring programs.

Environmental impact assessment of the electrokinetic adsorption barriers to remove different herbicides from agricultural soils.

In this study, the sustainability of the electrokinetic remediation soil flushing (EKSFs) process integrated without and with adsorption barriers (EKABs) have been evaluated for the treatment of four soils contaminated with Atrazine, Oxyfluorfen, Chlorosulfuron and 2,4-D. To this purpose, the environmental effects of both procedures (EKSFs and EKABs) have been determined through a life cycle assessment (LCA). SimaPro 9.3.0.3 was used as software tool and Ecoinvent 3.3 as data base to carry out the inventory of the equipment of each remediation setup based on experimental measurements. The environmental burden was quantified using the AWARE, USEtox, IPPC, and ReCiPe methods into 3 Endpoint impact categories (and damage to human health, ecosystem and resources) and 7 Midpoints impact categories (water footprint, global warming potential, ozone depletion, human toxicity (cancer and human non-cancer), freshwater ecotoxicity and terrestrial ecotoxicity). In general terms, the energy applied to treatment (using the Spanish energy mix) was the parameter with the greatest influence on the carbon footprint, ozone layer depletion and water footprint accounting for around 70 % of the overall impact contribution. On the other hand, from the point of view of human toxicity and freshwater ecotoxicity of soil treatments with 32 mg kg-1 of the different pesticides, the EKSF treatment is recommended for soils with Chlorosulfuron. In this case, the carbon footprint and water footprint reached values around 0.36 kg of CO2 and 114 L of water per kg of dry soil, respectively. Finally, a sensitivity analysis was performed assuming different scenarios.

Pre-emergence herbicides widely used in urban and farmland soils: fate, and potential human and environmental health risks.

We determined the distribution, fate, and health hazards of dimethenamid-P, metazachlor, and pyroxasulfone, the effective pre-emergence herbicides widely used both in urban and agricultural settings globally. The rate-determining phase of sorption kinetics of these herbicides in five soils followed a pseudo-second-order model. Freundlich isotherm model indicated that the herbicides primarily partition into heterogeneous surface sites on clay minerals and organic matter (OM) and diffuse into soil micropores. Principal component analysis revealed that soil OM (R2, 0.47), sand (R2, 0.56), and Al oxides (R2, 0.33) positively correlated with the herbicide distribution coefficient (Kd), whereas clay (R2, ‒ 0.43), silt (R2, ‒ 0.51), Fe oxides (R2, ‒ 0.02), alkaline pH (R2, ‒ 0.57), and EC (R2, ‒ 0.03) showed a negative correlation with the Kd values. Decomposed OM rich in C=O and C-H functional groups enhanced herbicide sorption, while undecomposed/partially-decomposed OM facilitated desorption process. Also, the absence of hysteresis (H, 0.27‒0.88) indicated the enhanced propensity of herbicide desorption in soils. Leachability index (LIX, < 0.02-0.64) and groundwater ubiquity score (GUS, 0.02‒3.59) for the soils suggested low to moderate leaching potential of the herbicides to waterbodies, indicating their impact on water quality, nontarget organisms, and food safety. Hazard quotient and hazard index data for human adults and adolescents suggested that exposure to soils contaminated with herbicides via dermal contact, ingestion, and inhalation poses minimal to no non-carcinogenic risks. These insights can assist farmers in judicious use of herbicides and help the concerned regulatory authorities in monitoring the safety of human and environmental health.

Sensitive detection of herbicide residues using field-amplified sample injection coupled with electrokinetic supercharging in flow-gated capillary electrophoresis.

Residues of glyphosate (GlyP) and its major degradation product, aminomethylphosphonic acid (AMPA), widely exist in the water system and plant products and thus are also present in the bodies of animals and humans. Although no solid evidence has been obtained, the concern about the cancer risk of GlyP is persistent. The measurement of GlyP and AMPA in trace levels is often needed but lacks readily available analytical approaches with detection sensitivity, accuracy and speed. This study aims to develop a simple and robust technique for the sensitive detection of GlyP and AMPA residues in a surface water system with flow-gated capillary electrophoresis (CE). Experimentally, water samples were first fluorogenically derivatized with 4-fluoro-7-nitrobenzofurazan (NBD-F) in a low-conductivity buffer at room temperature, and the mixture was injected and concentrated in the capillary based on field-amplified sample injection (FASI) coupled with electrokinetic supercharging (EKS). This scheme included a step of sample buffer injection upon electroosmotic pumping, where negatively charged analytes were electrophoretically rejected, followed by automatic voltage reversal for FASI-EKS. The detection sensitivity was improved by 296, 444, and 861 times for glufosinate (GluF), AMPA, and GlyP, respectively. The proposed method was validated in terms of accuracy, precision, limits of detection (LODs), and linearity. The LODs were estimated to be 50.0 pM, 5.0 pM, and 10.0 pM for GluF, AMPA, and GlyP, respectively. Its application was demonstrated by measuring GluF and AMPA in water samples collected from a local water system. This study provides an effective approach for the online preconcentration of negatively charged analytes, thus enabling the sensitive detection of herbicide residues in water samples. The method can also be applied to analyze other samples, including biological fluids and plant products, upon appropriate sample preparation such as solid phase extraction of analytes.

Determining pyroxasulfone herbicide in honey samples using liquid-liquid extraction with low temperature purification (LLE-LTP).

Pyroxasulfone is a selective, systemic, pre-emergence herbicide which acts to inhibit weeds in potato, coffee, sugar cane, eucalyptus, and soybean plantations, among others. This active ingredient was classified by Brazilian legislation as a very dangerous product for the environment, and to date there are no studies involving the development of extraction methods for monitoring this compound in environmental matrices. Therefore, the objective of this study was to optimize and validate liquid-liquid extraction with low temperature purification followed by a gas chromatography coupled to mass spectrometry analysis to determine this herbicide in honey samples. The results showed that the best extractor phase was acetonitrile and ethyl acetate (6.5 mL:1.5 mL), with recovery rates close to 100% and relative standard deviations below 11%. The validation proved that the extraction method was selective, precise, accurate and linear in the range of 3-225 µg kg-1, reaching a limit of quantification of 3 µg kg-1, with a -25.95% matrix effect. Monitoring on real samples did not reveal episodes of environmental contamination with pyroxasulfone residue.

Synergistic mechanism and environmental behavior of tank-mix adjuvants to topramezone and atrazine.

An effective way to reduce herbicide quantity is to use adjuvants in order to optimize the amount of herbicide and improve its control efficiency. In order to screen for efficient herbicide tank-mix adjuvants, improve the control of weeds in maize fields, reduce the amount of effective ingredients, and improve the adsorption and digestion behavior of herbicides in soil, this study evaluated the synergistic effects and soil behavior of four types of tank-mix adjuvants combined with herbicides. Different types of adjuvants can enhance herbicide production. Surface tension was significantly reduced by 13% after the pesticide solution was applied with AgroSpred™ Prime. The contact angle with the foliar surface was significantly reduced and solution wettability improved using Atp Lus 245-LQ-(TH). The permeability of topramezone and atrazine in leaves of Amaranthus retroflexus L. and Digitaria sanguinalis (L.) Scop. was increased by 22-96% after adding either tank-mix adjuvant. The solution drying time and maximum retention on leaves were not affected by the tank-mix adjuvants. Ethyl and methylated vegetable oils can reduce the adsorption of topramezone in the soil, thus reducing its half-life in soil. The tank-mix adjuvants had no significant effect on soil dissipation or adsorption of atrazine. AgroSpred™ Prime and Atp Lus 245-LQ-(TH) have the best synergistic effect on topramezone and atrazine in the control of A. retroflexus L. and D. sanguinalis (L.) Scop. in maize fields.

Assessing the ecological impact of pesticides/herbicides on algal communities: A comprehensive review.

The escalating use of pesticides in agriculture for enhanced crop productivity threatens aquatic ecosystems, jeopardizing environmental integrity and human well-being. Pesticides infiltrate water bodies through runoff, chemical spills, and leachate, adversely affecting algae, vital primary producers in marine ecosystems. The repercussions cascade through higher trophic levels, underscoring the need for a comprehensive understanding of the interplay between pesticides, algae, and the broader ecosystem. Algae, susceptible to pesticides via spillage, runoff, and drift, experience disruptions in community structure and function, with certain species metabolizing and bioaccumulating these contaminants. The toxicological mechanisms vary based on the specific pesticide and algal species involved, particularly evident in herbicides' interference with photosynthetic activity in algae. Despite advancements, gaps persist in comprehending the precise toxic effects and mechanisms affecting algae and non-target species. This review consolidates information on the exposure and toxicity of diverse pesticides and herbicides to aquatic algae, elucidating underlying mechanisms. An emphasis is placed on the complex interactions between pesticides/herbicides, nutrient content, and their toxic effects on algae and microbial species. The variability in the harmful impact of a single pesticide across different algae species underscores the necessity for further research. A holistic approach considering these interactions is imperative to enhance predictions of pesticide effects in marine ecosystems. Continued research in this realm is crucial for a nuanced understanding of the repercussions of pesticides and herbicides on aquatic ecosystems, mainly algae.

Development of an immunoassay based on a specific antibody for the detection of diphenyl ether herbicide fomesafen.

Fomesafen belongs to the diphenyl ether herbicide, and is widely used in the control of broadleaf weeds in crop fields due to its high efficiency and good selectivity. The residual of fomesafen in soil has a toxic effect on subsequent sensitive crops and the microbial community structure because of its long residual period. Therefore, an efficient method for detecting fomesafen is critical to guide the correct and reasonable use of this herbicide. Rapid and sensitive immunoassay methods for fomesafen is unavailable due to the lack of specific antibody. In this study, a specific antibody for fomesafen was generated based on rational design of haptens and a sensitive immunoassay method was established. The half maximal inhibitory concentration (IC50) of the immunoassay was 39 ng/mL with a linear range (IC10-90) of 1.92-779.8 ng/mL. In addition, the developed assay had a good correlation with the standard UPLC-MS/MS both in the spike-recovery studies and in the detection of real soil samples. Overall, the developed indirect competitive enzyme immunoassay reported here is important for detecting and quantifying fomesafen contamination in soil and other environmental samples with good sensitivity and high reproducibility.

Impact of landscape composition on honey bee pollen contamination by pesticides: A multi-residue analysis.

The honey bee is the most common and important managed pollinator of crops. In recent years, honey bee colonies faced high mortality for multiple causes, including land-use change and the use of plant protection products (hereafter pesticides). This work aimed to explore how contamination by pesticides of pollen collected by honey bees was modulated by landscape composition and seasonality. We placed two honey bee colonies in 13 locations in Northern Italy in contrasting landscapes, from which we collected pollen samples monthly during the whole flowering season in 2019 and 2020. We searched for almost 400 compounds, including fungicides, herbicides, insecticides, and acaricides. We then calculated for each pollen sample the Pollen Hazard Quotient (PHQ), an index that provides a measure of multi-residue toxicity of contaminated pollen. Almost all pollen samples were contaminated by at least one compound. We detected 97 compounds, mainly fungicides, but insecticides and acaricides showed the highest toxicity. Fifteen % of the pollen samples had medium-high or high levels of PHQ, which could pose serious threats to honey bees. Fungicides showed a nearly constant PHQ throughout the season, while herbicides and insecticides and acaricides showed higher PHQ values in spring and early summer. Also, PHQ increased with increasing cover of agricultural and urban areas from April to July, while it was low and independent of landscape composition at the end of the season. The cover of perennial crops, i.e., fruit trees and vineyards, but not of annual crops, increased PHQ of pollen samples. Our work highlighted that the potential toxicity of pollen collected by honey bees was modulated by complex interactions among pesticide category, seasonality, and landscape composition. Due to the large number of compounds detected, our study should be complemented with additional experimental research on the potential interactive effects of multiple compounds on honey bee health.

Pesticides and PPCPs in aquatic ecosystems of the andean central region: Occurrence and ecological risk assessment in the Uco valley.

Uco valley (Mendoza, Argentina) suffers the concomitant effect of climate change, anthropic pressure and water scarcity. Moreover chemical pollution to aquatic ecosystems could be another pressuring factor, but it was not studied enough to the present. In this sense, the aim of this study was to assess the occurrence of pesticides, pharmaceuticals and personal care products (PPCPs) in aquatic ecosystems of the Uco Valley and to perform an ecological risk assessment (ERA). The presence of several insecticides (mainly neonicotinoids), herbicides (atrazine, diuron, metolachlor, terbutryn) and fungicides (strobilurins, triazolic and benzimidazolic compounds) in water samples in two seasons, related to crops like vineyards, garlic or fruit trees was associated to medium and high-risk probabilities for aquatic biota. Moreover, PPCPs of the group of non-steroidal anti-inflammatory drugs, parabens and bisphenol A were detected in all the samples and their calculated risk quotients also indicated a high risk. This is the first record of pesticides and PPCPs with an ERA in this growing agricultural oasis. Despite the importance of these findings in Uco Valley for decision makers in the region, this multilevel approach could bring a wide variety of tools for similar regions in with similar productive and environmental conditions, in order to afford actions to reach Sustainable Development Goals. SYNOPSIS: Aquatic ecosystems in arid mountain regions are threatened worldwide. This study reports relevant data about chemical pollution in Central Andes, which could be a useful tool to enhance SDGs' accomplishment.

Recent technologies for glyphosate removal from aqueous environment: A critical review.

The growing demand for food has led to an increase in the use of herbicides and pesticides over the years. One of the most widely used herbicides is glyphosate (GLY). It has been used extensively since 1974 for weed control and is currently classified by the World Health Organization (WHO) as a Group 2A substance, probably carcinogenic to humans. The industry and academia have some disagreements regarding GLY toxicity in humans and its effects on the environment. Even though this herbicide is not mentioned in the WHO water guidelines, some countries have decided to set maximum acceptable concentrations in tap water, while others have decided to ban its use in crop production completely. Researchers around the world have employed different technologies to remove or degrade GLY, mostly at the laboratory scale. Water treatment plants combine different technologies to remove it alongside other water pollutants, in some cases achieving acceptable removal efficiencies. Certainly, there are many challenges in upscaling purification technologies due to the costs and lack of factual information about their adverse effects. This review presents different technologies that have been used to remove GLY from water since 2012 to date, its detection and removal methods, challenges, and future perspectives.

The politics of glyphosate regulation: lessons from Sri Lanka's short-lived ban.

BACKGROUND: Glyphosate is the world's most used herbicide and a central component of modern industrial agriculture. It has also been linked to a variety of negative health and environmental effects. For instance, the International Agency for Research on Cancer classified glyphosate as "probably carcinogenic to humans" in 2015. This has motivated widespread political demands for stricter glyphosate regulation but so far few governments have followed through. METHODS: We conduct a case study of Sri Lanka, which in 2015 became the first and so far only country in the world to adopt and implement a complete glyphosate ban. But this ban proved to be short-lived, as it was partially reversed in 2018 (and later fully revoked in 2022). To explain the political causes of Sri Lanka's pioneering glyphosate ban and its subsequent reversal, we employ process tracing methods drawing on publicly available documents. Our analysis is theoretically guided by the multiple streams framework and the concept of self-undermining policy feedback. RESULTS: Glyphosate regulation rose to the top of the Sri Lankan political agenda in 2014 when a local scientist linked glyphosate exposure to an epidemic of Chronic Kidney Disease of Unknown Origin (CKDu). A glyphosate ban was eventually adopted in June 2015 by the newly elected government of Maithripala Sirisena. The ban was a political commitment made to the Buddhist monk Rathana Thero and his party, which had supported Sirisena during his presidential campaign. The ban's partial reversal in 2018, implemented through sectoral exceptions, was the result of continued lobbying by export-oriented plantation industries and increased political concerns about potential negative effects on the large and structurally powerful tea sector. The reversal was further aided by the scientific community's failure to corroborate the hypothesized link between glyphosate and CKDu. CONCLUSIONS: The case of Sri Lanka suggests that strict glyphosate regulation becomes more likely when coupled with locally salient health risks and when decision-making authority is de-delegated from regulatory agencies back to the political executive. Meanwhile, the short-lived nature of the Sri Lankan ban suggests that strict glyphosate regulation faces political sustainability threats, as the apparent lack of cost-effective alternative herbicides motivates persistent business lobbying for regulatory reversal.

Occurrence, distribution, and risk assessment of pesticides in surface water and sediment in Jiangsu Province, China.

The occurrence and distribution of 157 pesticides were investigated in surface water and sediment in Jiangsu Province, China. Gas chromatography-mass spectrometry was used to analyze and quantify these pesticides, and the risk quotient method was used to evaluate their respective environmental risk. The results showed that 91 pesticides were detected in surface water. The organophosphates (OPPs), fungicides, and amide herbicides were predominant. The total concentration in surface water ranged from 63.7 to 22,463 ng/L, 3.90 to 7262 ng/L, and ND to 34,120 ng/L, respectively. The mean concentration was 3479 ng/L, 1644 ng/L, and 1878 ng/L, respectively. The concentration range of detected pesticides in the Yangtze River Basin was generally lower than that in the Huai River Basin. In sediment samples, a total of 63 pesticides were detected. OPPs and amide herbicides were also ranked highest; the total concentration in sediment samples ranged from 2951 to 47,739 ng/g and 106 to 12,996 ng/g, respectively. And the mean concentrations was 6971 ng/g and 5130 ng/g, respectively. Suqian City had the highest concentration for OPPs and amide herbicides in the Huai River Basin, followed by Huai'an City, while Nanjing City and Yangzhou City ranked highest in the Yangtze River Basin. The spatial distribution of pesticides in Jiangsu Province indicated a concentration significantly higher in the western and northern regions than in the eastern and southern regions, and a concentration generally higher in lakes than in rivers. The risk assessment results showed that OPPs, fungicides, amide herbicides, organochlorines, and triazine herbicides in most surface water samples posed a high risk and had regional pollution characteristics. In sediment samples, organochlorines, carbamates, other herbicides, and other insecticides posed a high risk in northern Jiangsu Province, whereas OPPs, amide herbicides, and triazine herbicides posed high risks everywhere in Jiangsu Province.

Exposure of the general French population to herbicides, pyrethroids, organophosphates, organochlorines, and carbamate pesticides in 2014-2016: Results from the Esteban study.

Esteban is a nationwide cross-sectional study conducted in France in 2014-2016, including 2503 adults aged 18-74 years old and 1104 children aged 6-17 years old, as part of the French Human Biomonitoring programme. The present paper describes the biological levels of five families of pesticides analysed on random sub-samples of 900 adults and 500 children for urine concentrations, and 759 adults and 255 children for serum concentrations, and the determinants of exposure. Organophosphates, carbamates and herbicides were measured in urine by UPLC-MS/MS; chlorophenols and pyrethroids were measured in urine by GC-MS/MS; specific organochlorines were measured in serum by GC-HRMS. Multivariate analyses were performed to identify the determinants of exposure using a generalized linear model. Pyrethroid metabolites were quantified in 99% of adults and children, with the exeption of F-PBA, which was quantified in 31% of adults and 27% of children, respectively. Carbamates and some specific organophosphates were barely or not quantified. DMTP was quantified in 82% of adults and 93% of children, and γ-HCH (lindane) was quantified in almost 50% of adults and children. Concentration levels of pesticide biomarkers were consistent with comparable international studies, except for ß-HCH, DMTP, and the deltamethrin metabolite Br2CA, whose levels were sometimes higher in France. Household insecticide use and smoking were also associated with higher levels of pyrethroids. All pyrethroids concentration levels were below existing health-based HBM guidance values, HBM-GVsGenPop, except for 3-PBA, for which approximately 1% and 10% of children were above the lower and upper urine threshold values of 22 µg/L and 6.4 µg/L, respectively. Esteban provides a French nationwide description of 70 pesticide biomarkers for the first time in children. It also describes some pesticide biomarkers for the first time in adults, including glyphosate and AMPA. For the latter, urine concentration levels were overall higher in children than in adults. Our results highlight a possible beneficial impact of existing regulations on adult exposure to organochlorine and organophosphate pesticides between 2006 and 2016, as concentration levels decreased over this period.

Removal of an agricultural herbicide (2,4-Dichlorophenoxyacetic acid) using magnetic nanocomposite: A combined experimental and modeling studies.

This study focused on modeling the removal of one of the widely used agricultural herbicides known as 2,4-Dichlorophenoxyacetic acid (2,4-D) using polypyrrole-coated Fe2O3 nanoparticles (Fe2O3@PPy). The Fe2O3@PPy nanocomposite was synthesized by surface-coating the Tabebuia aurea leaf extract synthesized Fe2O3 nanoparticles with polypyrrole. After characterization, the adsorptive potential of the nanocomposite for removing 2,4-D from aqueous solution was examined. Central composite design (CCD) was employed for optimizing the adsorption, revealing an adsorption efficiency of 90.65% at a 2,4-D concentration of 12 ppm, a dosage of 3.8 g/L, an agitation speed of 150 rpm, and 196 min. Adsorption dataset fitted satisfactorily to Langmuir isotherm (R2: 0.984 & χ2: 0.054) and pseudo-second-order kinetics (R2: 0.929 & χ2: 0.013) whereas the exothermic and spontaneous nature were confirmed via the thermodynamic study. The predictive models, including adaptive neuro-fuzzy inference system (ANFIS), artificial neural network (ANN), and response surface methodology (RSM), demonstrated good precision for the prediction of 2,4-D adsorption, with respective R2 of 0.9719, 0.9604, and 0.9528. Nevertheless, statistical analysis supported ANFIS as the better forecasting tool, while RSM was the least effective. The maximum adsorption capacity of 2,4-D onto the Fe2O3@PPy nanocomposite was 7.29 mg/g, significantly higher than a few reported values. Therefore, the Fe2O3@PPy nanocomposite could serve as a competent adsorbent to remove 2,4-D herbicide from aqueous streams.

Spatial and temporal trends of 64 pesticides and their removal from Australian wastewater.

Pesticides are necessary for the control of pest plant, fungi and insect species. After application, they may find their way into waste streams, such as municipal sewage, where their spatio-temporal distribution has not been well characterised. To further understand the spatio-temporal distribution and to evaluate potential sources and fate after treatment, 64 pesticides were analysed in matched influents and effluents of 22 wastewater treatment plants (WWTPs) from across Australia. The pesticides consisted of 30 herbicides and 8 herbicide metabolites or transformation products, 16 insecticides and 10 fungicides. The samples were 1084 24-hr composite samples pooled into 113 samples. Pools represented two influent and one effluent pools at each of 22 sites in 2019, as well as two pools per year from 2009 to 2021 for an 11-year long-term temporal trend at a subset of two locations. The total population served by the 22 sites was equivalent to ~41 % of the Australian population. Of the 64 pesticides, 25 were detected in influent, with highest influent concentrations up to 100 µg/L and effluent concentrations up to 16 µg/L for the herbicide 2,4-D. The total mass of pesticides was extrapolated to Australia, suggesting ~33 t of the targeted pesticides entered WWTP influent annually nation-wide, with 14 t emitted into effluents annually. Long-term trends varied by analyte and for carbendazim decreases over time, may be related to restrictions in use. Risk quotients (RQs) were calculated for 14 analytes in the effluent. 35 % had an RQ above one, indicating a potential environmental risk. Fipronil had the highest RQ (49) at Site 6. The population-normalized mass loads of pesticides were site-specific, and in some cases correlated with land use attributes suggestive of point sources. This reflects a need to better characterise sources to enable prevention, or possible pre-treatment of pesticide-containing wastewater entering municipal sewage streams.

Human health risk assessment based on direct and indirect exposure to endocrine disrupting herbicides in drinking, ground, and surface water in Croatia.

The recognition of certain herbicides as endocrine disrupting compounds has raised concerns due to their ability to interfere with the normal functioning of the endocrine system, which regulates various physiological processes in organisms. The objective of this study was to assess the possible human health risks associated with terbuthylazine and endocrine-disrupting herbicides atrazine, acetochlor, and metolachlor in the drinking, surface, and groundwater of the Zagreb city region, Croatia. We relied on advanced statistical methods and principal component analysis (PCA), which revealed higher levels of atrazine and acetochlor in drinking and groundwater samples and higher presence of metolachlor and terbuthylazine in surface waters. To evaluate the danger to human health, various exposure scenarios have been assessed. The risk of direct human exposure to analyzed herbicides through drinking or bathing with drinking (tap) or groundwater, as well as from recreational activities like swimming in rivers, streams, and lakes, has been quantified. In addition to these direct exposure scenarios, indirect ones based on consumer goods, fruits, and vegetables, treated with surface and groundwater for irrigation, were assessed to investigate the danger to human health. Judging by the reported herbicide levels there was no significant risk of carcinogenic (CR ≤ 1 × 10-6) or non-carcinogenic (HI < 1) diseases, not even when we assessed the so-called "cocktail effect" of combined the herbicide exposure in different waters.

Herbicide and Cytogenotoxic Activity of Inclusion Complexes of Psidium gaudichaudianum Leaf Essential Oil and ß-Caryophyllene on 2-Hydroxypropyl-ß-cyclodextrin.

The present investigation aimed to develop inclusion complexes (ICs) from Psidium gaudichaudianum (GAU) essential oil (EO) and its major compound ß-caryophyllene (ß-CAR), and to evaluate their herbicidal (against Lolium multiflorum and Bidens pilosa) and cytogenotoxic (on Lactuca sativa) activities. The ICs were obtained using 2-hydroxypropyl-ß-cyclodextrin (HPßCD) and they were prepared to avoid or reduce the volatility and degradation of GAU EO and ß-CAR. The ICs obtained showed a complexation efficiency of 91.5 and 83.9% for GAU EO and ß-CAR, respectively. The IC of GAU EO at a concentration of 3000 µg mL-1 displayed a significant effect against weed species B. pilosa and L. multiflorum. However, the ß-CAR IC at a concentration of 3000 µg mL-1 was effective only on L. multiflorum. In addition, the cytogenotoxic activity evaluation revealed that there was a reduction in the mitotic index and an increase in chromosomal abnormalities. The produced ICs were able to protect the EO and ß-CAR from volatility and degradation, with a high thermal stability, and they also enabled the solubilization of the EO and ß-CAR in water without the addition of an organic solvent. Therefore, it is possible to indicate the obtained products as potential candidates for commercial exploration since the ICs allow the complexed EO to exhibit a more stable chemical constitution than pure EO under storage conditions.

Adsorption kinetics and mechanism of atrazine on iron-modified algal residue biochar in the presence of soil.

Atrazine has been widely used as an herbicide, and its harm has attracted more and more attention. In this study, magnetic algal residue biochar (MARB) was prepared from algae residue, a by-product of aquaculture, by ball milling it with ferric oxide to study the adsorption and removal of the triazine herbicide atrazine in a soil medium. The adsorption kinetics and isotherm results showed that atrazine removal by MARB reached 95.5% within 8 h at a concentration of 10 mg·L-1, but the removal rate dropped to 78.4% in the soil medium. The pseudo-first- and pseudo-second-order kinetics and Langmuir isotherms best described atrazine adsorption on MARB. It is estimated that the maximum adsorption capacity of MARB can reach 10.63 mg·g-1. The effects of pH, humic acids, and cations on the adsorption performance of MARB for atrazine were also studied. When pH was 3, the adsorption capacity of MARB was twice that of other pHs. Only in the presence of 50 mg·L-1 HA and 0.1 mol·L-1 NH4+, Na, and K, the adsorption capacity of MARB to AT decreased by 8% and 13%, respectively. The results showed that MARB had a stable removal profile over a wide range of conditions. The adsorption mechanisms involved multiple interaction forms, among which the introduction of iron oxide promoted hydrogen bonding formation and π-π interactions by enriching -OH and -COO on the surface of MARB. Overall, the magnetic biochar prepared in this study can be used as an effective adsorbent to remove atrazine in complex environments and is ideal for algal biomass waste treatment and environmental governance.+.

Highly-Selective Analytical Strategy for 90 Pesticides and Metabolites Residues in Fish and Shrimp Samples.

The analysis of pesticide residues in aquatic products is challenging due to low residue levels and the complex matrix interference. In this study, we developed a simple, fast method for the trace analysis of 90 pesticides and metabolites in aquatic products. The analytes covered a wide polarity range with log Kow (log octanol-water partition coefficient) ranging from -1.2 to 6.37. Grass carp (Ctenopharyngodon idellus) and prawn (Penaeus chinensis) samples were chosen to validate the quantification method. The samples were extracted by 0.2% formic-acetonitrile, cleaned by solid-phase extraction (PRiME HLB), and analyzed by high performance liquid chromatography-tandem mass spectrometry. The results showed good linearities for the analytes and were observed in the range of 0.05-50 µg/L. The recoveries of the method were within 50.4-118.6%, with the relative standard deviations being lower than 20%. The limits of quantifications (LOQs) of the method were in the range of 0.05-5.0 µg/kg, which were superior to values compared with other research. The developed method was applied to detect pesticide residues in prawn samples from eastern coastal areas of China. Three herbicide residues of diuron, prometryn, and atrazine were detected in prawn samples. The method was sensitive and efficient, which is of significance in expanding the screening scope and improving the quantitative analysis efficiency in aquatic products.