Pesticide Residues in Organic and Conventional Agricultural Soils across Europe: Measured and Predicted Concentrations.

During the growing season of 2021, 201 soil samples from conventionally and organically managed fields from 10 European countries and 8 cropping systems were taken, and 192 residues of synthetic pesticides were analyzed. Pesticide residues were found in 97% of the samples, and 88% of the samples contained mixtures of at least 2 substances. A maximum of 21 substances were found in conventionally managed fields, and a maximum of 12 were found in organically managed fields. The number and concentration of pesticide residues varied significantly between conventional and organic fields in 70 and 50% of the case study sites, respectively. Application records were available for a selected number of fields (n = 82), and these records were compared to the detected substances. Residues from 52% of the applied pesticides were detected in the soils. Only 21% of the pesticide residues detected in the soil samples were applied during the 2021 growing season. From the application data, predicted environmental concentrations of residues in soil were calculated and compared to the measured concentrations. These estimates turned out not to be accurate. The results of this study show that most European agricultural soils contain mixtures of pesticide residues and that current calculation methods may not reliably estimate their presence.

Particle Leaching Rates from a Loamy Soil Are Controlled by the Mineral Fines Content and the Degree of Preferential Flow.

The mobilization and transport of colloid particles in soils can have negative agronomic and environmental effects. This work investigates the controls of particle release and transport from undisturbed soil columns sampled from an agricultural, loamy field with clay and silt contents of 0.05 to 0.14 and 0.07 to 0.16 kg kg, respectively. Forty-five soil columns (20 × 20 cm) were collected from the field and exposed to a constant irrigation of 10 mm h for 8 h. The accumulated mass of particles in the outflow from each column was highly correlated ( = 0.88) with the volumetric mass of fines (MF). The MF is defined as the sum of clay and fine silt (<20 µm) multiplied by the soil bulk density and divided by the particle density of the mineral fines. Thereby, MF represents both the particle source available for mobilization and leaching and an indicator of soil structure. The particle release process showed two linear particle release rates. Although the two particle release rates were distinctly different, both were strongly correlated with MF. The difference between the two rates was related to the degree of preferential flow characterized by the 5% arrival time of an applied tracer pulse. Soil columns with a longer 5% arrival time (less preferential flow) showed a distinct difference between the two rates, whereas soil columns with a short 5% arrival time and fast water transport showed resemblance between the two particle release rates. Thus, the combined effects of particle source, type, and pathways (via soil structure and compaction) need consideration to understand and predict particle transport dynamics through intact topsoil.

Field-scale Variation in Colloid Dispersibility and Transport: Multiple Linear Regressions to Soil Physico-Chemical and Structural Properties.

Water-dispersible soil colloids (WDC) act as carriers for sorbing chemicals in macroporous soils and hence constitute a significant risk for the aquatic environment. The prediction of WDC readily available for facilitated chemical transport is an unsolved challenge. This study identifies key parameters and predictive indicators for assessing field-scale variation of WDC. Samples representing three measurement scales (1- to 2-mm aggregates, intact 100-cm rings, and intact 6283 cm columns) were retrieved from the topsoil of a 1.69-ha agricultural field in a 15-m by 15-m grid to determine colloid dispersibility, mobilization, and transport. The amount of WDC was determined using (i) a laser diffraction method on 1- to 2-mm aggregates and (ii) an end-over-end shaking method on 100-cm intact rings. The accumulated amount of colloids leached from 20-cm by 20-cm intact columns was determined as a measure of the integrated colloid mobilization and transport. The WDC and the accumulated colloid transport were higher in samples from the northern part of the field. Using multiple linear regression (MLR) analyses, WDC or amount of colloids transported were predicted at the three measurement scales from 24 measured, geo-referenced parameters to identify parameters that could serve as indicator parameters for screening for colloid dispersibility, mobilization, and transport. The MLR analyses were performed at each sample scale using all, only northern, and only southern field locations. Generally, the predictive power of the regression models was best on the smallest 1- to 2-mm aggregate scale. Overall, our results suggest that different drivers controlled colloid dispersibility and transport at the three measurement scales and in the two subareas of the field.

Assessing pesticide residues occurrence and risks in water systems: A Pan-European and Argentina perspective.

Freshwater ecosystems face a particularly high risk of biodiversity loss compared to marine and terrestrial systems. The use of pesticides in agricultural fields is recognized as a relevant stressor for freshwater environments, exerting a negative impact worldwide on the overall status and health of the freshwater communities. In the present work, part of the Horizon 2020 funded SPRINT project, the occurrence of 193 pesticide residues was investigated in 64 small water bodies of distinct typology (creeks, streams, channels, ditches, rivers, lakes, ponds and reservoirs), located in regions with high agricultural activity in 10 European countries and in Argentina. Mixtures of pesticide residues were detected in all water bodies (20, median; 8-40 min-max). Total pesticide levels found ranged between 6.89 and 5860 ng/L, highlighting herbicides as the dominant type of pesticides. Glyphosate was the compound with the highest median concentration followed by 2,4-D and MCPA, and in a lower degree by dimethomorph, fluopicolide, prothioconazole and metolachlor(-S). Argentina was the site with the highest total pesticide concentration in water bodies followed by The Netherlands, Portugal and France. One or more pesticides exceeded the threshold values established in the European Water Framework Directive for surface water in 9 out of 11 case study sites (CSS), and the total pesticide concentration surpassed the reference value of 500 ng/L in 8 CSS. Although only 5 % (bifenthrin, dieldrin, fipronil sulfone, permethrin, and terbutryn) of the individual pesticides denoted high risk (RQ > 1), the ratios estimated for pesticide mixtures suggested potential environmental risk in the aquatic compartment studied.

Comparative mapping of soil physical-chemical and structural parameters at field scale to identify zones of enhanced leaching risk.

Preferential flow and particle-facilitated transport through macropores contributes significantly to the transport of strongly sorbing substances such as pesticides and phosphorus. The aim of this study was to perform a field-scale characterization of basic soil physical properties like clay and organic carbon content and investigate whether it was possible to relate these to derived structural parameters such as bulk density and conservative tracer parameters and to actual particle and phosphorus leaching patterns obtained from laboratory leaching experiments. Sixty-five cylindrical soil columns of 20-cm height and 20-cm diameter and bulk soil were sampled from the topsoil in a 15-m × 15-m grid in an agricultural loamy field. Highest clay contents and highest bulk densities were found in the northern part of the field. Leaching experiments with a conservative tracer showed fast 5% tracer arrival times and high tracer recovery percentages from columns sampled from the northern part of the field, and the leached mass of particles and particulate phosphorus was also largest from this area. Strong correlations were obtained between 5% tracer arrival time, tracer recovery, and bulk density, indicating that a few well-aligned and better connected macropores might change the hydraulic conductivity between the macropores and the soil matrix, triggering an onset of preferential flow at lower rain intensities compared with less compacted soil. Overall, a comparison mapping of basic and structural characteristics including soil texture, bulk density, dissolved tracer, particle and phosphorus transport parameters identified the northern one-third of the field as a zone with higher leaching risk. This risk assessment based on parameter mapping from measurements on intact samples was in good agreement with 9 yr of pesticide detections in two horizontal wells and with particle and phosphorus leaching patterns from a distributed, shallow drainage pipe system across the field.

Occurrence of pesticide residues in indoor dust of farmworker households across Europe and Argentina.

Pesticides are widely used as plant protection products (PPPs) in farming systems to preserve crops against pests, weeds, and fungal diseases. Indoor dust can act as a chemical repository revealing occurrence of pesticides in the indoor environment at the time of sampling and the (recent) past. This in turn provides information on the exposure of humans to pesticides in their homes. In the present study, part of the Horizon 2020 funded SPRINT project, the presence of 198 pesticide residues was assessed in 128 indoor dust samples from both conventional and organic farmworker households across Europe, and in Argentina. Mixtures of pesticide residues were found in all dust samples (25-121, min-max; 75, median). Concentrations varied in a wide range (<0.01 ng/g-206 µg/g), with glyphosate and its degradation product AMPA, permethrin, cypermethrin and piperonyl butoxide found in highest levels. Regarding the type of pesticides, insecticides showed significantly higher levels than herbicides and fungicides. Indoor dust samples related to organic farms showed a significantly lower number of residues, total and individual concentrations than those related to conventional farms. Some pesticides found in indoor dust were no longer approved ones (29 %), with acute/chronic hazards to human health (32 %) and with environmental toxicity (21 %).

Pesticide residues with hazard classifications relevant to non-target species including humans are omnipresent in the environment and farmer residences.

Intensive and widespread use of pesticides raises serious environmental and human health concerns. The presence and levels of 209 pesticide residues (active substances and transformation products) in 625 environmental samples (201 soil, 193 crop, 20 outdoor air, 115 indoor dust, 58 surface water, and 38 sediment samples) have been studied. The samples were collected during the 2021 growing season, across 10 study sites, covering the main European crops, and conventional and organic farming systems. We profiled the pesticide residues found in the different matrices using existing hazard classifications towards non-target organisms and humans. Combining monitoring data and hazard information, we developed an indicator for the prioritization of pesticides, which can support policy decisions and sustainable pesticide use transitions. Eighty-six percent of the samples had at least one residue above the respective limit of detection. One hundred residues were found in soil, 112 in water, 99 in sediments, 78 in crops, 76 in outdoor air, and 197 in indoor dust. The number, levels, and profile of residues varied between farming systems. Our results show that non-approved compounds still represent a significant part of environmental cocktails and should be accounted for in monitoring programs and risk assessments. The hazard profiles analysis confirms the dominance of compounds of low-moderate hazard and underscores the high hazard of some approved compounds and recurring "no data available" situations. Overall, our results support the idea that risk should be assessed in a mixture context, taking environmentally relevant mixtures into consideration. We have uncovered uncertainties and data gaps that should be addressed, as well as the policy implications at the EU approval status level. Our newly introduced indicator can help identify research priority areas, and act as a reference for targeted scenarios set forth in the Farm to Fork pesticide reduction goals.

Collection of human and environmental data on pesticide use in Europe and Argentina: Field study protocol for the SPRINT project.

Current farm systems rely on the use of Plant Protection Products (PPP) to secure high productivity and control threats to the quality of the crops. However, PPP use may have considerable impacts on human health and the environment. A study protocol is presented aiming to determine the occurrence and levels of PPP residues in plants (crops), animals (livestock), humans and other non-target species (ecosystem representatives) for exposure modelling and impact assessment. To achieve this, we designed a cross-sectional study to compare conventional and organic farm systems across Europe. Environmental and biological samples were/are being/will be collected during the 2021 growing season, at 10 case study sites in Europe covering a range of climate zones and crops. An additional study site in Argentina will inform the impact of PPP use on growing soybean which is an important European protein-source in animal feed. We will study the impact of PPP mixtures using an integrated risk assessment methodology. The fate of PPP in environmental media (soil, water and air) and in the homes of farmers will be monitored. This will be complemented by biomonitoring to estimate PPP uptake by humans and farm animals (cow, goat, sheep and chicken), and by collection of samples from non-target species (earthworms, fish, aquatic and terrestrial macroinvertebrates, bats, and farm cats). We will use data on PPP residues in environmental and biological matrices to estimate exposures by modelling. These exposure estimates together with health and toxicity data will be used to predict the impact of PPP use on environment, plant, animal and human health. The outcome of this study will then be integrated with socio-economic information leading to an overall assessment used to identify transition pathways towards more sustainable plant protection and inform decision makers, practitioners and other stakeholders regarding farming practices and land use policy.

Visible-Near-Infrared Spectroscopy can predict Mass Transport of Dissolved Chemicals through Intact Soil.

The intensification of agricultural production to meet the growing demand for agricultural commodities is increasing the use of chemicals. The ability of soils to transport dissolved chemicals depends on both the soil's texture and structure. Assessment of the transport of dissolved chemicals (solutes) through soils is performed using breakthrough curves (BTCs) where the application of a solute at one site and its appearance over time at another are recorded. Obtaining BTCs from laboratory studies is extremely expensive and time- and labour-consuming. Visible-near-infrared (vis-NIR) spectroscopy is well recognized for its measurement speed and for its low data acquisition cost and can be used for quantitative estimation of basic soil properties such as clay and organic matter. In this study, for the first time ever, vis-NIR spectroscopy was used to predict dissolved chemical breakthrough curves obtained from tritium transport experiments on a large variety of intact soil columns. Averaged across the field, BTCs were estimated with a high degree of accuracy. So, with vis-NIR spectroscopy, the mass transport of dissolved chemicals can be measured, paving the way for next-generation measurements and monitoring of dissolved chemical transport by spectroscopy.

When does the fluazifop-P-butyl degradate, TFMP, leach through an agricultural loamy soil to groundwater?

In intensely cultivated regions, it is crucial to have knowledge of the leaching potential related to pesticides in agricultural production. This is especially true in countries, like Denmark, that base its drinking water supply on untreated groundwater. Since fluazifop-P-butyl (FPB) is applied to control perennial and annual weed grasses in agricultural fields, the objective of this study was to evaluate leaching of its two degradation products - fluazifop-P (FP; free acid; (R)-2-(4-(5-trifluoromethyl-2-pyridyloxy)phenoxy)propionic acid) and TFMP (5-(trifluoromethyl)-2(1H)-pyridinone) - through an agricultural field consisting of loamy soil. Drainage and groundwater samples were collected over a five-year period following four spring/summer applications of FPB, and analysed for both FP and TFMP. FP was only detected once in groundwater, whereas TFMP within the first year after the first and fourth application was detected in concentrations exceeding the value of 0.1µgL(-1) in 100% and 24% of the drainage samples and 9% and 14% of the groundwater samples, respectively. Detections of TFMP up to 18months after application were obtained both in the drainage and groundwater. What differentiated the first and fourth FPB applications from the two others were heavy precipitation events within one week of FPB application, which resulted in rapid transport of TFMP through the discontinuities in the soil and contributed to relatively high TFMP detections in drainage and groundwater. This study indicated that pesticide degradates like TFMP, often being more soluble than the pesticide, have a relatively high leaching potential especially associated with heavy precipitation events shortly after the application. Hence, such pesticide degradates should like in Denmark be considered "relevant" meaning that the EU value for drinking water applies to them, having its leaching potential regulatory assessed based on high quality estimations of their persistence, and be exposed to an assessment of the risk to consumers of drinking contaminated groundwater.

Water and solute transport in agricultural soils predicted by volumetric clay and silt contents.

Solute transport through the soil matrix is non-uniform and greatly affected by soil texture, soil structure, and macropore networks. Attempts have been made in previous studies to use infiltration experiments to identify the degree of preferential flow, but these attempts have often been based on small datasets or data collected from literature with differing initial and boundary conditions. This study examined the relationship between tracer breakthrough characteristics, soil hydraulic properties, and basic soil properties. From six agricultural fields in Denmark, 193 intact surface soil columns 20cm in height and 20cm in diameter were collected. The soils exhibited a wide range in texture, with clay and organic carbon (OC) contents ranging from 0.03 to 0.41 and 0.01 to 0.08kgkg(-1), respectively. All experiments were carried out under the same initial and boundary conditions using tritium as a conservative tracer. The breakthrough characteristics ranged from being near normally distributed to gradually skewed to the right along with an increase in the content of the mineral fines (particles ≤50µm). The results showed that the mineral fines content was strongly correlated to functional soil structure and the derived tracer breakthrough curves (BTCs), whereas the OC content appeared less important for the shape of the BTC. Organic carbon was believed to support the stability of the soil structure rather than the actual formation of macropores causing preferential flow. The arrival times of 5% and up to 50% of the tracer mass were found to be strongly correlated with volumetric fines content. Predicted tracer concentration breakthrough points as a function of time up to 50% of applied tracer mass could be well fitted to an analytical solution to the classical advection-dispersion equation. Both cumulative tracer mass and concentration as a function of time were well predicted from the simple inputs of bulk density, clay and silt contents, and applied tracer mass. The new concept seems promising as a platform towards more accurate proxy functions for dissolved contaminant transport in intact soil.