Assessment of intensive periurban agriculture soil quality applying biomarkers in earthworms.

Periurban agriculture in Argentina is carried out by farmers without adequate control. The indiscriminate agrochemical application for productivity improvement negatively impacts the environment. The objective of this work was to test the quality of periurban agricultural soils by performing bioassays with Eisenia andrei as an indicator. Soils belonging to two orchards with intensive production (S: strawberry/broccoli crop plot and G: tomato/pepper crop greenhouse - Moreno District, Buenos Aires, Argentina) were sampled during 2015 and 2016. As subcellular biomarkers, cholinesterases (ChE), carboxylesterases (CaE), and glutathione-S-transferases (GST) activities were analysed in E. andrei (7-day exposure). While no effect on ChE activities was observed, CaE activities were significantly reduced 18% (S-2016 soil). GST activities were increased 35% and 30% by S-2016 and G-2016, respectively. CaE decrease together with GST increase could be indicative of a negative disturbance. Concerning whole organism biomarkers, reproduction (56-day exposure), avoidance (3-day exposure), and feeding activity (bait-lamina test, 3-day exposure) were analysed. A reduced cocoons' viability (50%), hatchability (55%), accompanied by a low number of juveniles (50%) were observed in all cases. Additionally, the earthworms exhibited significant avoidance responses to S-2015, S-2016 and G-2016 whereas G-2015 soil induced migration. No significant effect on the feeding activity was registered in any case. Most of the E. andrei biomarkers tested could constitute an early warning of harmful effects produced by polluted periurban soils, even if the agrochemical treatment applied remains unknown. The results reveal the need to develop an action plan to avoid further deterioration of the productive soil.

Exposure assessment of 170 pesticide ingredients and derivative metabolites in people from the Central Andes of Peru.

The Central Andes of Peru are a region of great concern regarding pesticide risk to the health of local communities. Therefore, we conducted an observational study to assess the level of pesticide contamination among Andean people. Analytical chemistry methods were used to measure the concentrations of 170 pesticide-related compounds in hair samples from 50 adult Andean subjects living in rural and urban areas. As part of the study, a questionnaire was administered to the subjects to collect information regarding factors that increase the risk of pesticide exposure. Our results indicate that Andean people are strongly exposed to agrochemicals, being contaminated with a wide array of pesticide-related compounds at high concentration levels. Multivariate analyses and geostatistical modeling identified sociodemographic factors associated with rurality and food origin that increase pesticide exposure risk. The present study represents the first comprehensive investigation of pesticide-related compounds detected in body samples collected from people living in the Central Andes of Peru. Our findings pinpoint an alarming environmental situation that threatens human health in the region and provide a rationale for improving public policies to protect local communities.

Correlation between dietary and dislodgeable foliar (DFR) crop residues decline data; A proposed approach to refine non-dietary risk assessment.

Pesticide residues in crop plants are routinely measured in an edible commodity or in feed items to determine safe use. Pesticides present as dislodgeable foliar residues (DFR) are measured for use in non-dietary risk assessments where worker, resident and bystander re-entry may lead to contact with the treated foliage. Possible correlations between dietary and DFR residue decline have been investigated considering data from 177 dietary residue trials along with 56 DFR trials from outdoor studies on the same crops besides residue decline data available in the Plant Properties Database (PPDB).The residue studies proved to follow the non-normal distribution and the comparison between DT50 of both types of residues for all the active substances revealed higher numerical DT50 mean values of the dietary residue compared to the DFRs. The dissipation from dietary residue studies is slower with a higher population mean compared to the mean for DFR studies for most active substances studied. A DT50 value from dietary residue studies could potentially act as a conservative surrogate DT50 for DFR which could be useful in determining the length of DFR studies and benefit both the agrochemical industry and the regulatory bodies in supporting non-dietary pesticide risk assessment.

Assessment of Gene Expression Biomarkers in the Chilean Pencil Catfish, Trichomycterus areolatus, from the Choapa River Basin, Coquimbo Chile.

The objective of this study was to describe changes in the gene expression in the Chilean catfish, Trichomycterus areolatus, based on their geographic location within the Choapa River. Genes of choice included those that are biomarkers of exposure to metals, oxidative stress, and endocrine disruption. Male and female T. areolatus were sampled from four sites in January 2015 differently impacted by human activities. In males, but not females, hepatic gene expression of heat shock protein (HSP70) and cytochrome P450 1A (CYP1A) were significantly elevated at the site adjacent to the small city of Salamanca, relative to the other sites. In females, hepatic HSP70, the aryl hydrocarbon receptor (AHR), and the estrogen responsive genes, vitellogenin (VTG) and estrogen receptor alpha (ERα), were significantly lower at the site located furthest downstream. A similar downstream pattern of lower expression levels also was found in ovarian tissue for the genes, HSP70 and ERα. Gill gene expression showed a unique pattern in females as levels of metallothionein were elevated at the site furthest downstream. While analytical chemistry of water samples provided limited evidence of agrichemical contamination, the gene expression data are consistent with an exposure to agrichemicals and metals. T. areolatus may be a valuable sentinel organism and its use as a bioindicator species in some rivers within Chile can provide considerable insight, particularly in situations analytical chemistry is limited by environmental constraints.

Synthetic agrochemicals: a necessary clarification about their use exposure and impact in crop protection.

Synthetic pesticides are largely decried. A common attitude against the synthetic agrochemicals is to avoid, criticise or ban these substances. Along with chemical pesticides to defend crops from bioagressors are microorganisms, semiochemical and natural substances used as plant protection products including biocontrol agents (BCAs) and crop protection products in organic production. Nevertheless, a natural substance status does not confer or imply safety, security or absence of residues (in the context of plant protection). Although in this paper we do not consider the toxicological perspective of highly toxic chemicals with adverse effects on humans and non-target organisms sprayed on crops, we have applied ourselves to working on the safe use of synthetic agrochemicals. Thus, along with biopesticides (either BCA or others) allowed in organic farming, we show that some synthetic chemical pesticides may be used in safe manner. HIGHLIGHTS: • Synthetic agrochemicals are widely criticised. • Some pesticide usages are not sprayed on crops. • Some biocontrol agents are of synthetic origin.

Trace metals accumulation in soil irrigated with polluted water and assessment of human health risk from vegetable consumption in Bangladesh.

Trace metals accumulation in soil irrigated with polluted water and human health risk from vegetable consumption was assessed based on the data available in the literature on metals pollution of water, soil, sediment and vegetables from the cites of Bangladesh. The quantitative data on metal concentrations, their contamination levels and their pollution sources have not been systematically gathered and studied so far. The data on metal concentrations, sources, contamination levels, sample collection and analytical tools used were collected, compared and discussed. The USEPA-recommended method for health risk assessment was used to estimate human risk from vegetable consumption. Concentrations of metals in water were highly variable, and the mean concentrations of Cd, Cr, Cu and As in water were found to be higher than the FAO irrigation water quality standard. In most cases, mean concentrations of metals in soil were higher than the Bangladesh background value. Based on geoaccumulation index (I geo) values, soils of Dhaka city are considered as highly contaminated. The I geo shows Cd, As, Cu, Ni, Pb and Cr contamination of agricultural soils and sediments of the cities all over the Bangladesh. Polluted water irrigation and agrochemicals are identified as dominant sources of metals in agricultural soils. Vegetable contamination by metals poses both non-carcinogenic and carcinogenic risks to the public. Based on the results of the pollution and health risk assessments, Cd, As, Cr, Cu, Pb and Ni are identified as the priority control metals and the Dhaka city is recommended as the priority control city. This study provides quantitative evidence demonstrating the critical need for strengthened wastewater discharge regulations in order to protect residents from heavy metal discharges into the environment.

Programa de análise de resíduos de agrotóxicos (PARA) no Rio Grande do Sul / Pesticide residue analysis program (PRAP) in Rio Grande do Sul

Análise de resíduos de agrotóxicos utilizados nos alimentos. (AU)

Seasonal and occupational trends of five organophosphate pesticides in house dust.

Since 1998, the University of Washington's Center for Child Environmental Health Risks Research has followed a community-based participatory research strategy in the Lower Yakima Valley of Washington State to assess pesticide exposure among families of Hispanic farmworkers. As a part of this longitudinal study, house dust samples were collected from both farmworker and non-farmworker households, across three agricultural seasons (thinning, harvest and non-spray). The household dust samples were analyzed for five organophosphate pesticides: azinphos-methyl, phosmet, malathion, diazinon, and chlorpyrifos. Organophosphate pesticide levels in house dust were generally reflective of annual use rates and varied by occupational status and agricultural season. Overall, organophosphate pesticide concentrations were higher in the thinning and harvest seasons than in the non-spray season. Azinphos-methyl was found in the highest concentrations across all seasons and occupations. Farmworker house dust had between 5- and 9-fold higher concentrations of azinphos-methyl than non-farmworker house dust. Phosmet was found in 5-7-fold higher concentrations in farmworker house dust relative to non-farmworker house dust. Malathion and chlorpyriphos concentrations in farmworker house dust ranged between 1.8- and 9.8-fold higher than non-farmworker house dust. Diazinon showed a defined seasonal pattern that peaked in the harvest season and did not significantly differ between farmworker and non-farmworker house dust. The observed occupational differences in four out of five of the pesticide residues measured provides evidence supporting an occupational take home pathway, in which workers may bring pesticides home on their skin or clothing. Further, these results demonstrate the ability of dust samples to inform the episodic nature of organophosphate pesticide exposures and the need to collect multiple samples for complete characterization of exposure potential.

Development of REACH Generic Exposure Scenarios for Substances Used as Coformulants in Plant Protection Products.

This article reviews the interactions between the REACH (Registration, Evaluation, Authorization and restriction of Chemicals) regulation and the plant protection product regulation for substances used as coformulants in the European Union, and describes generic exposure scenarios developed for their exposure and risk assessment. The REACH exposure scenarios describe the operational conditions and risk management measures used in the risk assessment of a coformulant, and as such these translate as the boundaries of safe use. The generic exposure scenarios are designed to be simple, and closely integrate with REACH use descriptors and customized exposure models. Clustering of application methods and exposure determinants resulted in four generic exposure scenarios, each covering professional workers or consumers, and application of products in liquid, granular form, or applied on seeds. When used in conjunction with appropriate exposure models, the generic exposure scenarios support efficient first-tier risk assessment of coformulants by utilizing a higher level of abstraction and conservatism than typically used in plant protection product assessments.

Utilization of long duration high-volume sampling coupled to SPME-GC-MS/MS for the assessment of airborne pesticides variability in an urban area (Strasbourg, France) during agricultural application.

Atmospheric samples have been collected between 14 March and 12 September 2012 on a 2-week basis (15 days of sampling and exchange of traps each 7 days) in Strasbourg (east of France) for the analysis of 43 pesticides. Samples (particle and gas phases) were separately extracted using Accelerated Solvent Extraction (ASE) and pre-concentrated by Solid Phase Micro-Extraction (SPME) before analysis by gas chromatography coupled to tandem mass spectrometry (GC-MS/MS). Four SPME consecutive injections at distinct temperatures were made in order to increase the sensitivity of detection for the all monitored pesticides. Currently used detected pesticides can be grouped in four classes; those used in maize crops (acetochlor, benoxacor, dicamba, s-metolachlor, pendimethalin, and bromoxynil), in cereal crops (benoxacor, chlorothalonil, fenpropimorph, and propiconazole), in vineyards (tebuconazole), and as herbicides for orchards, meadows of green spaces (2,4-MCPA, trichlopyr). This is in accordance with the diversity of crops found in the Alsace region and trends observed are in accordance with the period of application of these pesticides. Variations observed permit also to demonstrate that the long time sampling duration used in this study is efficient to visualize temporal variations of airborne pesticides concentrations. Then, long time high-volume sampling could be a simple method permitting atmospheric survey of atmospheric contamination without any long analysis time and consequently low cost.

[Gas chromatography-mass spectrometric studies of volatile emissions from plants for the assessment of the effectiveness and chemical safety of the implementation of environment improving phytotechnologies].

The chromato-mass-spectrometric studies of volatile emissions of fresh-cut roses have revealed the persistence of wide range of organic compounds. The most large content was consist of terpene hydrocarbons. The contribution of oxygen-containing components (alcohols, ethers, aldehydes and ketones) varied in wide ranges in dependence on the content of the feeding solution. The significant part of plants ' volatiles has no hygienic norm. Among the substances released into the air space ofpremises with volatile emissions ofplants, a significant part has not hygienic standards. Purposeful change in composition of the mixture of volatile organic compounds released by the plants, in the combination with chemical-analytical control of the content of these substances by gas chromatography-mass spectrometry in terms of ecological and hygienic aspects may be useful in the development, use and determination of the optimal conditions of the implementation of environment improving phytotechnologies and evaluation of the efficacy and safety of their impact on public health.

Assessment of the Polychlorinated Biphenyl (PCB) Occurrence in Copper Sulfates and the Influential Role of PCB Levels on Grapes.

Copper sulfates (CuSO4) are widely used as the primary component of fungicides in the grape industry. The agricultural-grade CuSO4 that we collected from Chinese nationwide markets were found to be contaminated by polychlorinated dibenzo-p-dioxins and dibenzofurans and high levels of polychlorinated biphenyls (Σ19PCBs: 0.32~9.51 ng/g). In the following research, we studied the impact of CuSO4 application on PCB levels in grape products through a field experiment, and conducted a national survey to speculate the role that CuSO4 played on the occurrence of PCB in grapes. In the field experiment, an obvious increase of PCBs in grape leaves (from 174 to 250 pg/g fw) was observed after Bordeaux mixture (the main component of which is CuSO4) application. As to the main PCB congener in CuSO4, the most toxic CB 126 (toxic equivalency factor = 0.1) also increased in grape peels (from 1.66 to 2.93 pg/g fw) after pesticide spray. Both the correlation study and the principal component analysis indicated that environmental factors were dominant PCB contributors to grapes, and grapes from e-waste dismantling area containing the highest PCBs also proved the notion. It is worth noting that this report describes the first research examining PCBs in CuSO4 and its influence on agricultural products to date.

Distribution and risk assessment of hydrocarbons (aliphatic and PAHs), polychlorinated biphenyls (PCBs), and pesticides in surface sediments from an agricultural river (Durance) and an industrialized urban lagoon (Berre lagoon), France.

The distributions of organic pollutants (like hydrocarbons, polychlorinated biphenyls (PCBs), and pesticides) and the risks on the ecosystem were studied in the Durance River and the Berre lagoon (France). High levels of aliphatic hydrocarbons were observed in all stations (1399 to 11,202 µg kg(-1) dw). The n-alkanes were mainly from terrigenous origin confirmed by the values of different ratios calculated (carbon preference index (CPI), natural n-alkanes ratio (NAR), terrigenous/aquatic ratio (TAR), and ratio of low molecular weight to high molecular weight (LMW/HMW)). Total polycyclic aromatic hydrocarbon (PAH) concentrations in the surface sediments of the Durance River and Berre lagoon are 57-1528 and 512-863 µg kg(-1) dw, respectively. Several ratios between parent polycyclic aromatic hydrocarbons showed that the sources of hydrocarbons in the sediments were generally more pyrolytic than petrogenic. The sum of seven PCB contents ranged from 0.03 to 13.13 µg kg(-1) dw. Higher levels of PCBs were detected in sediments from the northern parts of the Berre lagoon (stations B1 and B3). Total pesticides contents ranged from 0.02 to 7.15 µg kg(-1) dw. Among these compounds, ∑DDE and ∑DDT contents ranged, respectively, from 0.35 to 1.65 and from 0.37 to 1.52 µg kg(-1) dw. However, PAH and PCB levels are not high enough to be a threat to aquatic organisms and human beings. Total PAH levels were below the effects range low (ERL) of 3500 µg kg(-1) dw. For PCBs, only two stations (B1 and B3) are higher than the effect range median (ERM) of 180 µg kg(-1) dw. For endrin (pesticide), the concentrations are between the ERL (0.02 µg kg(-1) dw) and the ERM (45 µg kg(-1) dw).

Community drinking water quality monitoring data: utility for public health research and practice.

CONTEXT: Environmental Public Health Tracking (EPHT) tracks the occurrence and magnitude of environmental hazards and associated adverse health effects over time. The EPHT program has formally expanded its scope to include finished drinking water quality. OBJECTIVES: Our objective was to describe the features, strengths, and limitations of using finished drinking water quality data from community water systems (CWSs) for EPHT applications, focusing on atrazine and nitrogen compounds in 8 Midwestern states. METHODS: Water quality data were acquired after meeting with state partners and reviewed and merged for analysis. RESULTS: Data and the coding of variables, particularly with respect to censored results (nondetects), were not standardized between states. Monitoring frequency varied between CWSs and between atrazine and nitrates, but this was in line with regulatory requirements. Cumulative distributions of all contaminants were not the same in all states (Peto-Prentice test P < .001). Atrazine results were highly censored in all states (76.0%-99.3%); higher concentrations were associated with increased measurement frequency and surface water as the CWS source water type. Nitrate results showed substantial state-to-state variability in censoring (20.5%-100%) and in associations between concentrations and the CWS source water type. CONCLUSIONS: Statistical analyses of these data are challenging due to high rates of censoring and uncertainty about the appropriateness of parametric assumptions for time-series data. Although monitoring frequency was consistent with regulations, the magnitude of time gaps coupled with uncertainty about CWS service areas may limit linkage with health outcome data.

Spatio-temporal changes in agrochemical inputs and the risk assessment before and after the Grain-For-Green Policy in China.

China's Grain-For-Green Policy (GFGP) of returning marginal cropland to forest or grassland is one of the most important large-scale initiatives to combat land degradation in its ecologically vulnerable regions. In order to maintain and increase crop production from decreasing areas of cropland, substantial spatio-temporal changes in agrochemical inputs have occurred, which have strongly influenced the ecological and environmental status of land in China. Based on the agrochemical inputs (chemical fertilizer, pesticide, plastic sheeting, and agricultural diesel oil) at the provincial level between 1993 and 2009, cluster analysis and gravity center modeling were used to trace these spatio-temporal changes. A regional comparative study was also undertaken to investigate the changes in the relative size of agrochemical inputs in the eastern, central, and western regions of China. It was found that the agrochemical inputs increased considerably at the nation level after the GFGP, which in order of increasing rate were: plastic sheeting > agricultural diesel oil > pesticide > chemical fertilizer. The gravity centers of agrochemical inputs moved substantially towards the northwest or west during the latter period of GFGP and regional comparative analysis showed that the agrochemical inputs increased substantially in the western region between 2004 and 2009. The ecological degradation caused by the expansion of the area devoted to crop production in the western region and the potential risk of agricultural non-point pollution caused by the increasing agrochemical inputs are the main factors restricting this area's sustainable development.

Xplicit, a novel approach in probabilistic spatiotemporally explicit exposure and risk assessment for plant protection products.

The quantification of risk (the likelihood and extent of adverse effects) is a prerequisite in regulatory decision making for plant protection products and is the goal of the Xplicit project. In its present development stage, realism is increased in the exposure assessment (EA), first by using real-world data on, e.g., landscape factors affecting exposure, and second, by taking the variability of key factors into account. Spatial and temporal variability is explicitly addressed. Scale dependencies are taken into account, which allows for risk quantification at different scales, for example, at landscape scale, an overall picture of the potential exposure of nontarget organisms can be derived (e.g., for all off-crop habitats in a given landscape); at local scale, exposure might be relevant to assess recovery and recolonization potential; intermediate scales might best refer to population level and hence might be relevant for risk management decisions (e.g., individual off-crop habitats). The Xplicit approach is designed to comply with a central paradigm of probabilistic approaches, namely, that each individual case that is derived from the variability functions employed should represent a potential real-world case. This is mainly achieved by operating in a spatiotemporally explicit fashion. Landscape factors affecting the local exposure of habitats of nontarget species (i.e., receptors) are derived from geodatabases. Variability in time is resolved by operating at discrete time steps, with the probability of events (e.g., application) or conditions (e.g., wind conditions) defined in probability density functions (PDFs). The propagation of variability of parameters into variability of exposure and risk is done using a Monte Carlo approach. Among the outcomes are expectancy values on the realistic worst-case exposure (predicted environmental concentration [PEC]), the probability p that the PEC exceeds the ecologically acceptable concentration (EAC) for a given fraction of habitats, and risk curves. The outcome can be calculated at any ecologically meaningful organization level of receptors. An example application of Xplicit is shown for a hypothetical risk assessment for nontarget arthropods (NTAs), demonstrating how the risk quantification can be improved compared with the standard deterministic approach.

Health risk assessment procedures for endocrine disrupting compounds within different regulatory frameworks in the European Union.

In this study we have investigated how different regulatory frameworks in Europe cope with identification and risk assessment of endocrine disrupting compounds (EDCs). Four regulatory groups were selected for the investigation: existing industrial chemicals, environmental pollutants in food, pharmaceuticals and plant protection products. The legislation and guidelines for each of these groups were scrutinized and compared in detail. In addition, one recent European risk assessment document each for three identified EDCs, i.e. bisphenol A, dioxins and vinclozolin, were reviewed and compared. We found that the requirements for toxicity testing and availability and scope of risk assessment guidelines varied between the four regulatory frameworks. Also, the general principles regarding the human relevance of the mode of action identified in animal tests differed in the different risk assessments. In conclusion, there is little conformity in the risk assessment processes between these groups of chemicals. Because of the complicated nature of endocrine disruption, test methods, principles and criteria for data interpretation traditionally used might not be directly applicable to EDCs and further development of a transparent and reliable risk assessment process for this type of substances is needed.

Assessment of in-stream phosphorus dynamics in agricultural drainage ditches.

The intensive agricultural systems in the Midwestern United States can enrich surface waters with nutrients. Agricultural drainage ditches serve as the first and second order streams throughout much of this region, as well as other highly productive agricultural areas in humid regions throughout the world. This project was conducted to evaluate in-stream processing of soluble P (SP) in agricultural drainage ditches. Soluble P injection studies were conducted at seven sites along three drainage ditches (298 to 4300 ha drainage area), and one site on a third-order stream that receives the discharge from the agricultural ditches (19,000 ha drainage area) by increasing the SP concentration in the ditch water by approximately 0.25 mg L(-1). Sediments collected from smaller watersheds contained greater amounts of Mehlich 3 and exchangeable P (ExP), silt and clay size particles, and organic matter. Phosphorus uptake lengths (S(net)) ranged from 40 to 1900 m, and SP uptake rates (U) ranged from 0.4 to 52 mg m(-2) h(-1). Phosphorus S(net) was correlated with ditch geomorphological (i.e. width) and sediment properties (i.e. organic matter, ExP, and equilibrium P concentration; r(2)=1.00, P<0.001), indirect drainage in the watershed (r(2)=0.92, P<0.001), and the amount of small grains, forest, urban area, alfalfa and corn (r(2)=1.00, P<0.0001). Agricultural drainage ditches actively process nutrients and could potentially be managed to optimize this processing to minimize SP export from these landscapes.