Pesticides in soil, groundwater and food in Latin America as part of one health.

We here report of a conference about "Pesticides in Soil, Groundwater and Food in Latin America as part of One Health" that took place at the "IV Seminario Internacional de Sanidad Agropecuaria (SISA)" in Varadero, Cuba, 8-12 May 2023. Researchers of Latin America (Argentina, Brazil, Chile, Costa Rica, Colombia, Cuba, Mexico) and Switzerland (workshop initiator) held presentations about occurrence and effects of pesticides on the environment, human health, the replacement of highly hazardous pesticides (HHP) by agroecological alternatives and the agri-food value chain. In a subsequent round table discussion, the presenters identified deficits, needs, interests and opportunities. According to them, the lack of awareness of pesticide use affects the health and safety of workers applying the chemicals. Despite Latin America representing the main agricultural area in the world with a very intense pesticide use, monitoring data of pesticides in soil, surface and groundwaters, food, as well as in humans are missing. Risks of pesticides to humans should be assessed so that authorities can withdraw or limit within "short time" the access to corresponding formulations on the market. Also, communication is not state of the art and should be improved as, e.g. the teaching of workers and farmers, how to correctly use and apply pesticides or the briefing of decision makers. Pollinators suffer from multiple stressors not the least due to pesticides, and alternatives are badly needed. On the technical side, the different analytical methods to determine residues of active ingredients and transformation products in matrices of concern should be harmonized among laboratories.Seven future actions and goals were identified to overcome the above deficits. Next steps after the publishing of this conference report are to harmonize and complete the information status of the presenters by exchanging the results/data already present. Therefore, a platform of interaction to address issues described above and to enhance collaboration shall be created. Samples of different matrices shall be exchanged to harmonize the chemical analysis and establish interlaboratory comparisons. Such activities might be facilitated by joining international associations or organizations, where researchers can offer their expertise, or by forming a new pesticide network for Central and South America that could present tailored projects to national and international organizations and funding agencies.

Knowledge and practices of commercial banana farmers related to pesticide use in Chitwan district, Nepal; a cross-sectional study and meta-analyses.

The exposure of farmers to pesticides due to inadequate safety measures is a concern in low-income countries in Africa and Asia. However, until now, there have been limited studies on the farmers' risk due to pesticide application to fruit crops. The knowledge of farmers' exposure related to pesticide use and their safety practices was studied among 100 banana farmers in three areas (Padampur, Jagatpur, and Thimura) of Chitwan district, Nepal. More than 75% of the farmers complained about problems related to insects. Most frequently used insecticides in the area were chlorpyrifos and cypermethrin. Ten percent (10%) of the applied pesticides were highly hazardous to humans, according to the World Health Organization hazard category, with skin rash being the most common acute symptom reported by 29% of the farmers. Banned organochlorine and organophosphate insecticides, such as endosulfan and triazophos, respectively, are still being used by farmers in the aforementioned areas. Spearman's correlation analysis revealed the lack of knowledge and safety practices among farmers leading to inadequate awareness related to the negative effects of pesticide use on human health and the environment. Therefore, government extension service can play a crucial role in improving banana farmers' knowledge of the toxic effects of pesticides as well as enforcing the Nepali language in the labeling of pesticide containers and packages.

High-Resolution Historical Record of Plant Protection Product Deposition Documented by Target and Nontarget Trend Analysis in a Swiss Lake under Anthropogenic Pressure.

A multiproxy workflow was used to assess >60 plant protection products (PPPs) in sediment samples from a Swiss lake under heavy agricultural pressure. The results show the appearance of PPPs for the first time in the early 1960s with an overall detection of 34 PPPs and with herbicides and fungicides found in equal proportions. Paleolimnological data [e.g., chronology, hyperspectral imaging of sedimentary green pigments, and semiquantitative elemental composition (µXRF scans)] suggest that PPP concentrations and fluxes to the sediment over time are not related to land surface processes such as soil erosion or lake biogeochemistry but are attributed mainly to PPP application (inferred from sales) or regulatory measures (bans). Additional compounds with similar sources of contamination as the target PPPs captured by nontarget trend analysis (≥2000 unknown profiles) reveal significant inputs of contaminants to the lake starting in the 1970s, followed by a decrease of contamination at the beginning of the 1990s and a constant increase by ∼28% of the unknown compounds since the year 2000. An ecological risk assessment conducted on detected PPPs indicates that since the 1980s, the sediment quality is insufficient with risk quotient values displaying maximum levels in the most recent sediments (∼2010) despite bans of specific PPPs and environmental regulations.

Target and suspect screening analysis reveals persistent emerging organic contaminants in soils and sediments.

An approach to identifying persistent organic contaminants in the environment was developed and executed for Switzerland as an example of an industrialized country. First, samples were screened with an in-house list using liquid chromatography high-resolution mass spectrometry (LC-HRMS/MS) and gas chromatography tandem mass spectrometry (GC-MS/MS) in 13 samples from the Swiss National Soil Monitoring Network and three sediment cores of an urban and agricultural contaminated lake. To capture a broader range of organic contaminants, the analysis was extended with a suspect screening analysis by LC-HRMS/MS of >500 halogenated compounds obtained from a Swiss database that includes industrial and household chemicals identified, by means of fugacity modeling, as persistent substances in the selected matrices. In total, the confirmation of 96 compounds with an overlap of 34 in soil and sediment was achieved. The identified compounds consist generally of esters, tertiary amines, trifluoromethyls, organophosphates, azoles and aromatic azines, with azoles and triazines being the most common groups. Newly identified compounds include transformation products, pharmaceuticals such as the flukicide niclofolan, the antimicrobial cloflucarban, and the fungicide mandipropamid. The results indicate that agricultural and urban soils as well as sediments impacted by agriculture and wastewater treatment plants (WWTPs) are the most contaminated sites. The plausibility of this outcome confirms the combination of chemical inventory, modeling of partitioning and persistence, and HRMS-based screening as a successful approach to shed light on less frequently or not yet investigated environmental contaminants and emphasizes the need for more soil and sediment monitoring in the future.

Retrospective screening of high-resolution mass spectrometry archived digital samples can improve environmental risk assessment of emerging contaminants: A case study on antifungal azoles.

Environmental risk assessment associated with aquatic and terrestrial contamination is mostly based on predicted or measured environmental concentrations of a limited list of chemicals in a restricted number of environmental compartments. High resolution mass spectrometry (HRMS) can provide a more comprehensive picture of exposure to harmful chemicals, particularly through the retrospective analysis of digitally stored HRMS data. Using this methodology, our study characterized the contamination of various environmental compartments including 154 surface water, 46 urban effluent, 67 sediment, 15 soil, 34 groundwater, 24 biofilm, 41 gammarid and 49 fish samples at 95 sites widely distributed over the Swiss Plateau. As a proof-of-concept, we focused our investigation on antifungal azoles, a class of chemicals of emerging concern due to their endocrine disrupting effects on aquatic organisms and humans. Our results demonstrated the occurrence of antifungal azoles and some of their (bio)transformation products in all the analyzed compartments (0.1-100 ng/L or ng/g d.w.). Comparison of actual and predicted concentrations showed the partial suitability of level 1 fugacity modelling in predicting the exposure to azoles. Risk quotient calculations additionally revealed risk of exposure especially if some of the investigated rivers and streams are used for drinking water production. The case study clearly shows that the retrospective analysis of HRMS/MS data can improve the current knowledge on exposure and the related risks to chemicals of emerging concern and can be effectively employed in the future for such purposes.

Tracing Urban Wastewater Contaminants into the Atlantic Ocean by Nontarget Screening.

Oceans are the ultimate sink for many of the over 100 million man-made substances. Until now, monitoring was limited to a reduced number of targeted persistent organic pollutants, reaching open waters mainly via atmospheric deposition. However, the composition and fate of the thousands of pollutants reaching the marine environment though wastewater discharges from coastal sources remain largely unexplored. By combining a newly developed nontarget screening (NTS) workflow and high-resolution mass spectrometry (HRMS), we have identified over 500 sewage-derived contaminants occurring in the ocean. Samples from the NE Atlantic contained this anthropogenic imprint at distances over 50 km from the coastline and >500 m depth, beyond the continental margin. The range of identified compounds spans from pharmaceuticals and personal care products to food additives and industrial chemicals, including several that have never been reported in the environment, as they escaped conventional targeted analytical methods. Predicting the effects of the continuous input of this chemical "cocktail" on marine ecosystems is a formidable challenge, since 40% of the detected compounds lack information regarding their use and ecotoxicity.

Suspect Screening of Hydrocarbon Surfactants in AFFFs and AFFF-Contaminated Groundwater by High-Resolution Mass Spectrometry.

Aqueous film-forming foams (AFFFs) are proprietary mixtures containing hydrocarbon surfactants and per- and polyfluoroalkyl substances (PFASs) that are used to extinguish hydrocarbon-based fuel fires. There is limited information on hydrocarbon surfactants in AFFFs and AFFF-contaminated groundwater even though hydrocarbon surfactants are more abundant (5-10% w/w) than PFASs (0.9-1.5% w/w) in AFFFs. Eight commercial AFFFs manufactured between 1988 and 2012 and 10 AFFF-contaminated groundwaters collected from near source zones of fire-fighter training areas were analyzed for suspect hydrocarbon surfactants by liquid chromatography quadrupole time-of-flight mass spectrometry. A suspect list and a homologous series detection computational tool, enviMass, were combined to screen for hydrocarbon surfactants. Nine classes of hydrocarbon surfactants were detected in AFFFs including octylphenol polyethoxylates, linear alcohol ethoxylates, ethoxylated cocoamines, alkyl ether sulfates, alkyl amido dipropionates, linear alkyl benzenesulfonates, alkyl sulfates, and polyethylene glycols. Of those, six were also found in groundwater along with diethanolamines and alkyl amido betaines, which were not found in the eight archived AFFFs. This indicates that although aerobically biodegradable, hydrocarbon surfactants likely persist in groundwater due to anaerobic aquifer conditions. To the best of our knowledge, this is the first screening for hydrocarbon surfactants in AFFFs and in AFFF-contaminated groundwater.

Unravelling Contaminants in the Anthropocene Using Statistical Analysis of Liquid Chromatography-High-Resolution Mass Spectrometry Nontarget Screening Data Recorded in Lake Sediments.

The significant increase in traces of human activity in the environment worldwide provides evidence of the beginning of a new geological era, informally named the Anthropocene. The rate and variability of these human modifications at the local and global scale remain largely unknown, but new analytical methods such as high-resolution mass spectrometry (HRMS) can help to characterize chemical contamination. We therefore applied HRMS to investigate the contamination history of two lakes in Central Europe over the preceding 100 years. A hierarchical clustering analysis (HCA) of the collected time series data revealed more than 13 000 profiles of anthropogenic origin in both lakes, defining the beginning of large-scale human impacts during the 1950s. Our results show that the analysis of temporal patterns of nontarget contaminants is an effective method for characterizing the contamination pattern in the Anthropocene and an important step in prioritizing the identification of organic contaminants not yet successfully targeted by environmental regulation and pollution reduction initiatives. As proof of the concept, the success of the method was demonstrated with the identification of the pesticide imazalil, which probably originated from imported fruits. This new approach applicable to palaeoarchives can effectively be used to document the time and rate of change in contamination over time and provide additional information on the onset of the Anthropocene.

Long-Term Persistence of Pesticides and TPs in Archived Agricultural Soil Samples and Comparison with Pesticide Application.

For polar and more degradable pesticides, not many data on long-term persistence in soil under field conditions and real application practices exist. To assess the persistence of pesticides in soil, a multiple-compound screening method (log Kow 1.7-5.5) was developed based on pressurized liquid extraction, QuEChERS and LC-HRMS. The method was applied to study 80 polar pesticides and >90 transformation products (TPs) in archived topsoil samples from the Swiss Soil Monitoring Network (NABO) from 1995 to 2008 with known pesticide application patterns. The results reveal large variations between crop type and field sites. For the majority of the sites 10-15 pesticides were identified with a detection rate of 45% at concentrations between 1 and 330 µg/kgdw in soil. Furthermore, TPs were detected in 47% of the cases where the "parent-compound" was applied. Overall, residues of about 80% of all applied pesticides could be detected with half of these found as TPs with a persistence of more than a decade.

Local Recurrence and Breast Oncological Surgery in Young Women With Breast Cancer: The POSH Observational Cohort Study.

OBJECTIVE: To assess clinical and surgical factors affecting local recurrence and survival in young breast cancer patients in the Prospective study of Outcomes in Sporadic versus Hereditary breast cancer (POSH). BACKGROUND: Emerging data suggest young age is a predictor of increased local recurrence. METHODS: POSH is a prospective cohort of 3024 women of 18 to 40 years with breast cancer. Cohort characteristics were grouped by mastectomy or BCS. Endpoints were local-recurrence interval (LRI), distant disease-free interval (DDFI), and overall survival (OS); described using cumulative-hazard and Kaplan-Meier plots and multivariable analyses by Flexible Parametric and Cox regression models. RESULTS: Mastectomy was performed in 1464 patients and breast-conserving surgery (BCS) in 1395. Patients undergoing mastectomy had larger tumors and higher proportions of positive family history, estrogen receptor+, progesterone receptor+, and/or human epidermal growth factor receptor 2+ tumors. Local events accounted for 15% of recurrences. LRI by surgical type varied over time with LRI similar at 18 months (1.0% vs 1.0%, P = 0.348) but higher for BCS at 5 and 10 years (5.3% vs 2.6%, P < 0.001; and 11.7% vs 4.9%, P < 0.001, respectively). Similar results were found in the adjusted model. Conversely, distant-metastases and deaths were lower for BCS but not after adjusting for prognostic factors. After mastectomy chest-wall radiotherapy was associated with improved LRI (hazard ratio, HR = 0.46, P = 0.015). Positive surgical margins, and development of local recurrence predicted for reduced DDFI (HR = 0.50, P < 0.001; and HR = 0.29, P = 0.001, respectively). CONCLUSIONS: Surgical extent appears less important for DDFI than completeness of excision or, where appropriate, chest-wall radiotherapy. Despite higher local-recurrence rates for BCS, surgical type does not influence DDFI or OS after adjusting for known prognostic factors in young breast cancer patients.

International Conference on Contaminated Sediments - ContaSed 2015 8-13 March 2015, Monte Verità, Ascona, Switzerland.

About 80 participants from 22 countries from industry and academia gathered at the International Conference on Contaminated Sediments (ContaSed 2015) held at the Congressi Stefano Franscini (CSF), the conference center of ETH Zurich, located at Monte Verità, Ascona, Switzerland. ContaSed 2015 provided a platform for top experts as well as for junior researchers from different scientific disciplines to present recent results and novel approaches on the analysis, assessment and remediation of contaminated sediments. ContaSed 2015 served as a unique communication and discussion opportunity for environmental scientists with an emphasis on chemistry, sedimentology, ecotoxicology or remediation engineering.

International Conference on Contaminated Sediments - ContaSed 2015 8-13 March 2015, Monte Verità, Ascona, Switzerland.

About 80 participants from 22 countries from industry and academia gathered at the International Conference on Contaminated Sediments (ContaSed 2015) held at the Congressi Stefano Franscini (CSF), the conference center of ETH Zurich, located at Monte Verità, Ascona, Switzerland. ContaSed 2015 provided a platform for top experts as well as for junior researchers from different scientific disciplines to present recent results and novel approaches on the analysis, assessment and remediation of contaminated sediments. ContaSed 2015 served as a unique communication and discussion opportunity for environmental scientists with an emphasis on chemistry, sedimentology, ecotoxicology or remediation engineering.

A mixture of environmental organic contaminants in lake sediments affects hatching from Daphnia resting eggs.

Despite the relevance of resting eggs for ecology and evolution of many aquatic organisms and their exposure to contaminants accumulating in sediments, ecotoxicological studies using resting eggs are vastly underrepresented. The authors established a method to perform exposure assays with resting eggs produced by the Daphnia longispina species complex, key species in large lake ecosystems. A mixture of organic contaminants previously detected in sediments of Lake Greifensee was selected to test the potential effect of organic contaminants present in sediments on the hatching process. Resting eggs were exposed to a mix of 10 chemicals, which included corrosion inhibitors, biocides, pesticides, and personal care products, for a period of 15 d. Using an automated counting software, the authors found a significant increase in hatching success in the exposed resting eggs compared with controls. Such an effect has not yet been reported from ecotoxicological assays with resting eggs. Possible mechanistic explanations as well as the potential implications on the ecology and evolution of aquatic species that rely on a resting egg banks are discussed. Observed increased mortality and developmental abnormalities for hatchlings in the exposure treatments can be explained by toxic contaminant concentrations. The results of the present study highlight the need for additional studies assessing the effects of organic contaminants on resting egg banks and aquatic ecosystems.

Suspect and nontarget screening approaches to identify organic contaminant records in lake sediments.

Sediment cores provide a valuable record of historical contamination, but so far, new analytical techniques such as high-resolution mass spectrometry (HRMS) have not yet been applied to extend target screening to the detection of unknown contaminants for this complex matrix. Here, a combination of target, suspect, and nontarget screening using liquid chromatography (LC)-HRMS/MS was performed on extracts from sediment cores obtained from Lake Greifensee and Lake Lugano located in the north and south of Switzerland, respectively. A suspect list was compiled from consumption data and refined using the expected method coverage and a combination of automated and manual filters on the resulting measured data. Nontarget identification efforts were focused on masses with Cl and Br isotope information available that exhibited mass defects outside the sample matrix, to reduce the effect of analytical interferences. In silico methods combining the software MOLGEN-MS/MS and MetFrag were used for direct elucidation, with additional consideration of retention time/partitioning information and the number of references for a given substance. The combination of all available information resulted in the successful identification of three suspect (chlorophene, flufenamic acid, lufenuron) and two nontarget compounds (hexachlorophene, flucofuron), confirmed with reference standards, as well as the tentative identification of two chlorophene congeners (dichlorophene, bromochlorophene) that exhibited similar time trends through the sediment cores. This study demonstrates that complementary application of target, suspect, and nontarget screening can deliver valuable information despite the matrix complexity and provide records of historical contamination in two Swiss lakes with previously unreported compounds.

Bioconcentration of organic contaminants in Daphnia resting eggs.

Organic contaminants detected in sediments from Lake Greifensee and other compounds falling in the log Dow range from 1 to 7 were selected to study the bioconcentration of organic contaminants in sediments in Daphnia resting eggs (ephippia). Our results show that octocrylene, tonalide, triclocarban, and other personal care products, along with pesticides and biocides can accumulate in ephippia with log BCF values up to 3. Data on the uptake and depuration kinetics show a better fit toward a two compartment organism model over a single compartment model due to the differences in ephippial egg content in the environment. The obtained BCFs correlate with hydrophobicity for neutral compounds. Independence between BCF and hydrophobicity was observed for partially ionized compounds with log Dow values around 1. Internal concentrations in ephippia in the environment were predicted based on sediment concentrations using the equilibrium partitioning model and calculated BCFs. Estimated internal concentration values ranged between 1 and 68,000 µg/kglip with triclocarban having the highest internal concentrations followed by tonalide and triclosan. The outcomes indicate that contaminants can be taken up by ephippia from the water column or the pore water in the sediment and might influence fitness and sexual reproduction in the aquatic key species of the genus Daphnia.