Is a dissipation half-life of 5 years for chlordecone in soils of the French West Indies relevant?

Recently, Comte et al. (2022) re-examined the natural degradation of chlordecone (CLD) in the soils of the French West Indies (FWI) by introducing an additional 'dissipation parameter' into the WISORCH model developed by Cabidoche et al. (2009). Recent data sets of CLD concentrations in FWI soils obtained by Comte et al. enabled them optimizing the model parameters, resulting in significantly shorter estimates of pollution persistence than in the original model. Their conclusions jeopardize the paradigm of a very limited degradation of CLD in FWI soils, which may lead to an entire revision of the management of CLD contamination. However, we believe that their study is questionable on several important aspects. This includes potential biases in the data sets and in the modeling approach. It results in an inconsistency between the estimated dissipation half-life time (DT50) of five years that the authors determined for CLD and the fate of CLD in soil from the application period 1972-1993 until nowadays. Most importantly, a rapid dissipation of CLD in the field as proposed by Comte et al. is not sufficiently supported by data and estimates. Hence, the paradigm of long-term persistence of CLD in FWI soils is still to be considered.

Determination of glyphosate and AMPA in freshwater and soil from agroecosystems by 9-fluorenylmethoxycarbonyl chloride derivatization and liquid chromatography - fluorescence detection and tandem mass spectrometry.

The herbicide glyphosate (GLY) and its metabolite aminophosphonic acid (AMPA) are troublesome compounds for analysis in the environment. Here we report a reliable technique for GLY and AMPA determination in freshwater and soils by means of derivatization with 9-fluorenylmethoxycarbonyl chloride (FMOC-Cl) and further liquid chromatography with fluorescence detection (FLD) and tandem mass spectrometry (MS/MS) analysis. Selected experiments were carried out to evaluate selectivity, sensitivity, repeatability, linearity and quantification performance in both matrices.

Presence of perchlorate in marine sediments from Antarctica during 2017-2020.

Perchlorate of natural origin is a persistent pollutant that affects thyroid function by inhibiting iodine uptake, and this pollutant is frequently detected in different ecosystems at concentrations that can harm human health. In this study, we measured the perchlorate concentrations in 3,000 marine sediment samples from January to March in 2017, 2018, 2019, and 2020 during the 3rd, 4th, 5th, and 6th Colombian Scientific Expeditions to Antarctica. The sampling zones were located at 15 different points on the South Shetland Islands and Antarctic Peninsula, and they were measured using a selective perchlorate electrode. The concentration data indicate that perchlorate reached a minimum concentration of 90 ppm on Horseshoe Island and a maximum concentration of 465 ppm on Deception Island, suggesting a spatial variation in perchlorate concentrations that can be attributed to the natural formation of this pollutant due to volcanic eruptions. Additionally, homogeneous distribution of perchlorate was not observed in Antarctica.

Estimating pesticide environmental concentrations in Latin America: The importance of developing local scenarios.

Data to assess pesticide exposure in soil and water are scarce and unevenly distributed in Latin America, especially due to the size of the region and the vast agricultural landscape. This makes it difficult to assess associated environmental risks. We suggest that the lack of pesticide exposure or monitoring data can be addressed by using validated models to provide estimated pesticide exposure concentrations in soil and water bodies. This exposure modeling approach has been used by regulatory agencies in other countries and regions such as the United States, Canada, and the European Union. In order to properly estimate pesticide exposure concentrations, we advocate for the development of local scenarios containing local weather, soil, and crop data to be used in the existing models. A sensitivity analysis of the models can be performed to determine parameters that are sensitive and therefore inputs to these parameters are derived locally. We believe the development of local scenarios in the region is attainable and can be a pragmatic approach for developing a more comprehensive picture of potential pesticide exposure in the region. Integr Environ Assess Manag 2021;17:901-904. © 2021 Syngenta Proteção de Cultivos Ltda.

Sequential solvent extraction as a tool for evaluating hydrocarbons speciation in soil after electrochemical treatment.

Soluble and total extractable concentrations used for predicting contaminants' environmental fate may lead to uncertainties due to the lack of understanding of soil-contaminants interactions. The present study focuses on the influence of a controlled electric field on the distribution of polycyclic aromatic hydrocarbons in soil samples evaluated through a speciation scheme. Soil samples were spiked with 25,000 mg (hexadecane, phenanthrene, and pyrene 100:1:1 w/w) per kg of soil, and speciation of hydrocarbons was determined by employing a novel Sequential Solvent Extraction procedure, resulting in five fractions: soluble, pseudosoluble, desorbable, extractable, and sequestered. The distribution of hydrocarbons was then changed through the application of an electric field (72 h, 0.708 mA cm-2, 2.95 ±â€¯0.13 V cm-1), which modified the interactions in the soil-water interface. The electrochemical treatment significantly increased the pyrene soluble, desorbable and sequestered fractions by 340, 1.3 and 19-fold (p < 0.05); the hexadecane soluble fraction increased in 6-fold (p < 0.05) and the phenanthrene desorbable fraction increased in 1.3-fold (p < 0.05). The use of the speciation scheme proposed in this study provides a wider view of hydrocarbons distribution in soils, rather than using water-soluble or total extractable concentrations. Finally, this speciation scheme is proposed as a tool to evaluate the environmental fate of organic contaminants in soils.

Influence of anthropogenic activities and risk assessment on protected mangrove forest using traditional and emerging molecular markers (Ceará coast, northeastern Brazil).

Anthropogenic molecular markers were used to assess chemicals inputs and ecological risks associated from multiple sources to sediments in one of the largest tropical mangrove forests of South America, with a particular focus on lesser studied compounds resulting from rural activities. Total concentrations ranged from 23.4 to 228.2 ng g-1 for polycyclic aromatic hydrocarbons (∑PAHs), 750.4 to 5912.5 ng g-1 for aliphatic hydrocarbons (∑AHs), 32.4 to 696.6 ng g-1 for pesticides (∑pesticides), 23.1 to 2109.7 ng g-1 for coprostanol and sterols (∑sterols), 139.3 to 580.2 ng g-1 for naturals hormones (∑natural hormones) and 334.1 to 823.4 ng g-1 for synthetics hormones (∑synthetic hormones). The PAHs and AHs used as traditional anthropogenic markers showed a mixture between natural and anthropogenic sources, related mainly to inputs from higher plants, phytoplankton and both, biomass and petroleum combustion. Rural activities linked to agricultural pest control are the predominant source of pesticides, although minor inputs from pesticides used in urban public health campaigns and household activities were also detected. Synthetic hormones levels are two to three orders of magnitude greater than natural hormones levels and no correlations were observed between the main sewage markers and synthetic hormone concentrations, rural activities such as animal husbandry, which use drugs in management, may be the predominant anthropogenic sources of these compounds in the region. Traditional markers failed to detect ecological risks in rural areas, where synthetic substances (e.g. pesticides and hormones) are widely used and introduced in the environment.

Adsorption-desorption and hysteresis phenomenon of tebuconazole in Colombian agricultural soils: Experimental assays and mathematical approaches.

The adsorption-desorption, hysteresis phenomenon, and leachability of tebuconazole were studied for Inceptisol and Histosol soils at the surface (0-10 cm) and in the subsurface (40-50 cm) of an agricultural region from Colombia by the batch-equilibrium method and mathematical approaches. The experimental Kfa and Kd (L kg-1) values (7.9-289.2) decreased with depth for the two Inceptisols and increased with depth for the Histosol due to the organic carbon content, aryl and carbonyl carbon types. Single-point and desorption isotherms depended on adsorption reversibility and suggested that tebuconazole showed hysteresis; which can be adequately evaluated with the single-point desorption isotherm and the linear model using the hysteresis index HI. The most suitable mathematical approach to estimate the adsorption isotherms of tebuconazole at the surface and in the subsurface was that considering the combination of the n-octanol-water partition coefficient, pesticide solubility, and the mass-balance concept. Tebuconazole had similar moderate mobility potential as compared with the values of other studies conducted in temperate amended and unamended soils, but the risk of the fungicide to pollute groundwater sources increased when the pesticide reached subsurface soil layers, particularly in the Inceptisols.

The Fate of Glyphosate and AMPA in a Freshwater Endorheic Basin: An Ecotoxicological Risk Assessment.

Glyphosate is the most widely used herbicide worldwide. However, there are some uncertain aspects with respect to its environmental fate. To evaluate the existence and distribution of this pesticide and its metabolite, aminomethylphosphonic acid (AMPA), their presence in fresh water, sediment, and suspended particulate matter (SPM) was measured in samples collected in a river running across a large city and through areas with intensive and extensive agriculture. The aquatic risk associated to the occurrence of these compounds was estimated using the hazard quotient (HQ) calculation for water and sediment. From the analyzed samples, overall 35% contained glyphosate, AMPA, or both compounds. Concentrations of the analytes were spread in different percentages depending on the environmental matrices considered, with levels ranging from 12 to 20 times higher for glyphosate and AMPA in sediment and SPM, as compared with the levels found in water. The most polluted area was situated within a green belt zone of the city; while in second place were sites located in areas of extensive agriculture. Aquatic organisms inhabiting areas both inside and outside agricultural areas are threatened by water glyphosate concentrations. Benthic organisms inside the greenbelt zone and inside the lower basin are threatened by the concentrations of glyphosate in sediment. Even when the concentrations measured in water were below the levels of concern for wildlife, results showed the risk of agricultural practices to aquatic biota. An update of the limits established for freshwater biota protection is needed.

Leaching of Diuron, Hexazinone, and Sulfometuron-methyl Applied Alone and in Mixture in Soils with Contrasting Textures.

When herbicides are applied in mixture, interactions among them could potentially promote changes in herbicide behavior in the soil. Thus, application mode (isolated or in mixture) and soil texture (sandy or clayey) were investigated in the total leaching of the commercial mixture diuron + hexazinone + sulfometuron-methyl, and of each isolated compound. Experiments in soil columns also evaluated the movement of each herbicide and mixtures across soil layers. In the sandy soil, the greatest total leaching was observed with hexazinone compared to diuron and sulfometuron. Most of the applied diuron remained at the top layer of the soil, indicating that this herbicide has low soil mobility. Overall, our results show that hexazinone has greater leaching potential and mobility along the soil profile compared to diuron and sulfometuron. Our data can be used in assessing the fate of diuron, hexazinone, and sulfometuron alone or in mixture on natural ecosystems, under different soil types and application modes.

Persistence of pentolite (PETN and TNT) in soil microcosms and microbial enrichment cultures.

Pentolite is a mixture (1:1) of 2,4,6-trinitrotoluene (TNT) and pentaerythritol tetranitrate (PETN), and little is known about its fate in the environment. This study was aimed to determine the dissipation of pentolite in soils under laboratory conditions. Microcosm experiments conducted with two soils demonstrated that dissipation rate of PETN was significantly slower than that of TNT. Interestingly, the dissipation of PETN was enhanced by the presence of TNT, while PETN did not enhanced the dissipation of TNT. Pentolite dissipation rate was significantly faster under biostimulation treatment (addition of carbon source) in soil from the artificial wetland, while no such stimulation was observed in soil from detonation field. In addition, the dissipation rate of TNT and PETN in soil from artificial wetland under biostimulation was significantly faster than the equivalent abiotic control, although it seems that non-biological processes might also be important for the dissipation of TNT and PETN. Transformation of PETN was also slower during establishment of enrichment culture using pentolite as the sole nitrogen source. In addition, transformation of these explosives was gradually reduced and practically stopped after the forth cultures transfer (80 days). DGGE analysis of bacterial communities from these cultures indicates that all consortia were dominated by bacteria from the order Burkholderiales and Rhodanobacter. In conclusion, our results suggest that PETN might be more persistent than TNT.

Modeling the dynamics of DDT in a remote tropical floodplain: indications of post-ban use?

Significant knowledge gaps exist regarding the fate and transport of persistent organic pollutants like dichlorodiphenyltrichloroethane (DDT) in tropical environments. In Brazil, indoor residual spraying with DDT to combat malaria and leishmaniasis began in the 1950s and was banned in 1998. Nonetheless, high concentrations of DDT and its metabolites were recently detected in human breast milk in the community of Lake Puruzinho in the Brazilian Amazon. In this work, we couple analysis of soils and sediments from 2005 to 2014 at Puruzinho with a novel dynamic floodplain model to investigate the movement and distribution of DDT and its transformation products (dichlorodiphenyldichloroethylene (DDE) and dichlorodiphenyldichloroethane (DDD)) and implications for human exposure. The model results are in good agreement with the accumulation pattern observed in the measurements, in which DDT, DDE, and DDD (collectively, DDX) accumulate primarily in upland soils and sediments. However, a significant increase was observed in DDX concentrations in soil samples from 2005 to 2014, coupled with a decrease of DDT/DDE ratios, which do not agree with model results assuming a post-ban regime. These observations strongly suggest recent use. We used the model to investigate possible re-emissions after the ban through two scenarios: one assuming DDT use for IRS and the other assuming use against termites and leishmaniasis. Median DDX concentrations and p,p'-DDT/p,p'-DDE ratios from both of these scenarios agreed with measurements in soils, suggesting that the soil parameterization in our model was appropriate. Measured DDX concentrations in sediments were between the two re-emission scenarios. Therefore, both soil and sediment comparisons suggest re-emissions indeed occurred between 2005 and 2014, but additional measurements would be needed to better understand the actual re-emission patterns. Monte Carlo analysis revealed model predictions for sediments were very sensitive to highly uncertain parameters associated with DDT degradation and partitioning. With this model as a tool for understanding inter-media cycling, additional research to refine these parameters would improve our understanding of DDX fate and transport in tropical sediments.

Effects of soil attributes and straw accumulation on the sorption of hexazinone and tebuthiuron in tropical soils cultivated with sugarcane.

Brazil is the largest sugarcane producer in the world in which hexazinone (3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione) and tebuthiuron (1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea) are heavily used. Sugarcane harvesting is changing from the manual system with previous straw burning to the mechanized system without straw burning. The lack of burning results in soil organic carbon accumulation mainly in clayey soils, which should affect herbicides availability and fate. Therefore, we evaluated sorption of these herbicides in soil samples with and without straw burning. Both herbicides presented low apparent sorption coefficients (mean K(d,app)= 0.6 and 2.4 L kg(-1) for hexazinone and tebuthiuron, respectively), suggesting that they may leach to groundwater. Moreover, their sorption correlated primarily with soil organic carbon (SOC), but iron oxide contents extracted with ammonium oxalate (Fe2O3(AOX)) also affected it (K(d,app) = -0.228 + 0.0397 SOC + 0.117 Fe2O3(AOX) for hexazinone and K(d,app) = -1.407 + 0.201 SOC + 0.348 Fe2O3(AOX) for tebuthiuron). Soil organic carbon accumulation due to straw maintenance in the field positively affected sorption of both herbicides, but its effects were not enough to classify them as "non-leachers."

Sorption, desorption and displacement of ibuprofen, estrone, and 17ß estradiol in wastewater irrigated and rainfed agricultural soils.

Sorption and leaching potential of ibuprofen, estrone and 17ß estradiol were tested in two agricultural soils: one irrigated using municipal wastewater and the other used in rainfed agriculture. Batch sorption-desorption experiments and undisturbed soil column assays were carried out using both soils to which were added a mixture of the target compounds. The three compounds were sorbed to a different extent by both soils: estrone>17ß estradiol>ibuprofen. Higher sorption was observed in the irrigated soil, which was attributed to the accumulation of organic matter caused by wastewater irrigation. Desorption of hormones was hysteretic in the irrigated soil, while ibuprofen showed low hysteresis in both soils. Retardation of the compounds' displacement was consistent with the sorption pattern observed in the batch tests. Retardation factor (RF) was similar for the three compounds in the two tested soils, indicating that the target compounds are much more mobile in the soil columns than would be predicted based on their equilibrium sorption parameters. The results obtained in the experiments clarify the role of wastewater irrigated soils as a filter and degradation media for the target micropollutants.

Impacts of climate change on indirect human exposure to pathogens and chemicals from agriculture: [review] / Impactos das mudanças climáticas sobre a exposição humana indireta a elementos patogênicos e químicos da agricultura: [revisão]

Climate change is likely to affect the nature of pathogens/ chemicals in the environment and their fate and transport. We assess the implications of climate change for changes in human exposures to pathogens/chemicals in agricultural systems in the UK and discuss the effects on health impacts, using expert input and literature on climate change; health effects from exposure to pathogens/chemicals arising from agriculture; inputs of chemicals/pathogens to agricultural systems; and human exposure pathways for pathogens/chemicals in agricultural systems. We established the evidence base for health effects of chemicals/pathogens in the agricultural environment; determined the potential implications of climate change on chemical/pathogen inputs in agricultural systems; and explored the effects of climate change on environmental transport and fate of various contaminants. We merged data to assess the implications of climate change in terms of indirect human exposure to pathogens/chemicals in agricultural systems, and defined recommendations on future research and policy changes to manage adverse increases in risks.

É provável que a mudança climática afete a natureza, destino e transporte de elementos patogênicos/químicos no ambiente . Avaliamos as implicações das mudanças climáticas em mudanças na exposição humana a elementos patogênicos/químicos nos sistemas agrícolas no Reino Unido e discutimos os efeitos sobre os impactos à saúde, usando a contribuição de especialistas e literatura; efeitos à saúde da exposição a elementos patogênicos/químicos provenientes da agricultura; introdução de elementos químicos/patogênicos e caminhos de exposição humana a elementos patogênicos/químicos nos sistemas agrícolas. Definimos a base de evidência para efeitos de saúde de elementos químicos/patogênicos no ambiente agrícola; determinamos as possíveis implicações da mudança climática na introdução de elementos químicos/patogênicos nos sistemas agrícolas; e exploramos os efeitos da mudança climática no transporte ambiental e destino de diversos contaminantes. Consolidamos dados para avaliar as implicações das mudanças climáticas em relação à exposição humana indireta a elementos patogênicos/químicos nos sistemas agrícolas e recomendamos futuras pesquisas e mudanças políticas para administrar aumentos adversos nos riscos.

Monitoramento de agrotóxicos em águas superficiais de regiões orizícolas no sul do Brasil / Pesticides monitoring in surface water of rice production areas in southern Brazil

Os agrotóxicos aplicados em lavouras de arroz irrigado podem ser transportados aos mananciais hídricos. A determinação da extensão dessa contaminação é importante para alertar a sociedade e seus governantes para esse problema. Dessa forma, o objetivo deste trabalho foi monitorar a ocorrência de agrotóxicos em águas superficiais de sete regiões do sul do Brasil associadas ao cultivo de arroz irrigado em três épocas, na safra 2007/2008. As amostras de águas superficiais foram coletadas em três locais por região, totalizando 21 locais. Os agrotóxicos avaliados foram: clomazone, quinclorac, penoxsulam, imazethapyr, imazapic, carbofuran, 3-hydroxy-carbofuran, fipronil e tebuconazole. As amostras foram analisadas por LC-MS/MS. Imazethapyr, carbofuran e fipronil foram detectados em todas as regiões estudadas. Foi detectado maior número de agrotóxicos nas regiões da Depressão Central e Planície Costeira Externa à Lagoa dos Patos, com detecção de oito agrotóxicos, dos nove estudados. A Região Sul apresentou a menor contaminação, com a detecção de apenas quatro agrotóxicos. Todas as amostras em todas as épocas continham ao menos um agrotóxico.

Pesticides applied in paddy rice can be transported to water bodies. The determination of the contamination extent is very important to alert the society and the politicians about the contamination issue. The objective of this study was to monitor pesticides in surface water in seven regions of south Brazil associated with the rice cropping in three different moments of the 2007/2008 growing season. Surface water samples were collected at three locations per region, with a total of 21 locations. The pesticides evaluated were: clomazone, quinclorac, penoxsulam, imazethapyr, imazapic, carbofuran, 3-hydroxy-carbofuran, fipronil and tebuconazole. The samples were analyzed by LC-MS/MS. Imazethapyr, carbofuran and fipronil were detected in all regions studied. A higher number of pesticides were detected in the 'Depressão Central' and in the 'Planície Costeira Externa à Lagoa dos Patos' regions, with eight pesticides. The 'Região Sul' had the lowest contamination, with detection of only four pesticides in surface water. All samples in all season contained at least one pesticide.

Monitoramento de agrotóxicos em águas superficiais de regiões orizícolas no sul do Brasil

Pesticides applied in paddy rice can be transported to water bodies. The determination of the contamination extent is very important to alert the society and the politicians about the contamination issue. The objective of this study was to monitor pesticides in surface water in seven regions of south Brazil associated with the rice cropping in three different moments of the 2007/2008 growing season. Surface water samples were collected at three locations per region, with a total of 21 locations. The pesticides evaluated were: clomazone, quinclorac, penoxsulam, imazethapyr, imazapic, carbofuran, 3-hydroxy-carbofuran, fipronil and tebuconazole. The samples were analyzed by LC-MS/MS. Imazethapyr, carbofuran and fipronil were detected in all regions studied. A higher number of pesticides were detected in the 'Depressão Central' and in the 'Planície Costeira Externa à Lagoa dos Patos' regions, with eight pesticides. The 'Região Sul' had the lowest contamination, with detection of only four pesticides in surface water. All samples in all season contained at least one pesticide.

Os agrotóxicos aplicados em lavouras de arroz irrigado podem ser transportados aos mananciais hídricos. A determinação da extensão dessa contaminação é importante para alertar a sociedade e seus governantes para esse problema. Dessa forma, o objetivo deste trabalho foi monitorar a ocorrência de agrotóxicos em águas superficiais de sete regiões do sul do Brasil associadas ao cultivo de arroz irrigado em três épocas, na safra 2007/2008. As amostras de águas superficiais foram coletadas em três locais por região, totalizando 21 locais. Os agrotóxicos avaliados foram: clomazone, quinclorac, penoxsulam, imazethapyr, imazapic, carbofuran, 3-hydroxy-carbofuran, fipronil e tebuconazole. As amostras foram analisadas por LC-MS/MS. Imazethapyr, carbofuran e fipronil foram detectados em todas as regiões estudadas. Foi detectado maior número de agrotóxicos nas regiões da Depressão Central e Planície Costeira Externa à Lagoa dos Patos, com detecção de oito agrotóxicos, dos nove estudados. A Região Sul apresentou a menor contaminação, com a detecção de apenas quatro agrotóxicos. Todas as amostras em todas as épocas continham ao menos um agrotóxico.

Monitoramento de agrotóxicos em águas superficiais de regiões orizícolas no sul do Brasil

Pesticides applied in paddy rice can be transported to water bodies. The determination of the contamination extent is very important to alert the society and the politicians about the contamination issue. The objective of this study was to monitor pesticides in surface water in seven regions of south Brazil associated with the rice cropping in three different moments of the 2007/2008 growing season. Surface water samples were collected at three locations per region, with a total of 21 locations. The pesticides evaluated were: clomazone, quinclorac, penoxsulam, imazethapyr, imazapic, carbofuran, 3-hydroxy-carbofuran, fipronil and tebuconazole. The samples were analyzed by LC-MS/MS. Imazethapyr, carbofuran and fipronil were detected in all regions studied. A higher number of pesticides were detected in the 'Depressão Central' and in the 'Planície Costeira Externa à Lagoa dos Patos' regions, with eight pesticides. The 'Região Sul' had the lowest contamination, with detection of only four pesticides in surface water. All samples in all season contained at least one pesticide.

Os agrotóxicos aplicados em lavouras de arroz irrigado podem ser transportados aos mananciais hídricos. A determinação da extensão dessa contaminação é importante para alertar a sociedade e seus governantes para esse problema. Dessa forma, o objetivo deste trabalho foi monitorar a ocorrência de agrotóxicos em águas superficiais de sete regiões do sul do Brasil associadas ao cultivo de arroz irrigado em três épocas, na safra 2007/2008. As amostras de águas superficiais foram coletadas em três locais por região, totalizando 21 locais. Os agrotóxicos avaliados foram: clomazone, quinclorac, penoxsulam, imazethapyr, imazapic, carbofuran, 3-hydroxy-carbofuran, fipronil e tebuconazole. As amostras foram analisadas por LC-MS/MS. Imazethapyr, carbofuran e fipronil foram detectados em todas as regiões estudadas. Foi detectado maior número de agrotóxicos nas regiões da Depressão Central e Planície Costeira Externa à Lagoa dos Patos, com detecção de oito agrotóxicos, dos nove estudados. A Região Sul apresentou a menor contaminação, com a detecção de apenas quatro agrotóxicos. Todas as amostras em todas as épocas continham ao menos um agrotóxico.