Uncrewed Aerial Spray Systems (UASS), commonly called drones, have become an important application technique for plant protection products in Asia and worldwide. As such, environmental variables and spray system parameters influencing spray drift deserve detailed investigations. This study presents the data analysis of 114 UASS drift trials conducted between December 2021 and December 2022 in China. Study design was based on the ISO 22866:2005 protocol for spray drift trials and considered different UASS platforms, nozzles, and release heights, and specifically continuously measured weather conditions. The relative importance of the environmental variables and spray system parameters was evaluated by a random forest (RF) feature importance analysis, a Sobol sensitivity analysis and partial dependence plots. This approach was preferred to linear ranking techniques such as ANOVA (analysis of variance) due to the non-linearity of the system. In addition, partial dependence plots are proposed to visualize the relationship between specific input parameters within the system.Drift deposition curves calculated from the 114 trials show good agreement with previous UASS trials reported in the literature. As reported in previous studies, spray drift following UASS applications is lower than for manned aerial vehicles, greater than for ground spray applications, and similar to drift observed from orchard air blast applications. In addition, 9 trials were conducted on corn fields in order to evaluate the potential effect of crop cover on spray drift. Spray drift was observed to be reduced over the cropped soil, suggesting that plant cover might possibly reduce spray drift. These findings could help supporting drift mitigation policies, stewardship advice and product labelling around the world.

There is growing concern globally about the occurrence of anthropogenic organic contaminants in the environment, including pharmaceuticals and personal care products. This concern extends to groundwater, which is a critical water resource in Europe, and its protection is a priority to the European Commission, the European Union (EU) Member States and national agencies across Europe. Maintaining good groundwater status supports improved public health, economic growth and sustains groundwater dependant ecosystems. A range of measures have been introduced for regulating several substances that have impacted groundwater (e.g. nitrate and pesticides). However, these measures only cover a small fraction of anthropogenic substances that could pollute groundwater. Monitoring for these unregulated substances is currently very limited or not carried out at all. Therefore, a coordinated European-wide approach is needed to identify, monitor and characterise priority substances or groups of substances that have the potential to pollute groundwater. This evidence base is critical for policy development and controls on these currently unregulated substances. The European Commission highlighted this as a need during the review of the EU Groundwater Directive Annexes in 2014, when the requirement to develop a Groundwater Watch List (GWWL) was established. This paper describes the approach that has been developed through a voluntary initiative as part of the EU CIS Working Group Groundwater to establish the voluntary EU GWWL. The process for developing the GWWL is one that has brought together researchers, regulators and industry, and is described here for the first time. A summary of the key principles behind the methodology is presented as well as results from pilot studies using per- and polyfluoroalkyl substances and pharmaceuticals. These explore and support the viability of the GWWL process, an important step towards its adoption and its future use for groundwater protection across Europe.

Biopurification systems, such as biofilters, are biotechnological tools to prevent point sources of pesticide pollution stemming from on-farm operations. For the purification processes pesticide sorption and mineralization and/or dissipation are essential and both largely depend on the type of filling materials and the pesticide in use. In this paper the mineralization and dissipation of three contrasting (14)C-labeled pesticides (bentazone, boscalid, and pyrimethanil) were investigated in laboratory incubation experiments using sandy soil, biochar produced from Pine woodchips, and/or digestate obtained from anaerobic digestion process using maize silage, chicken manure, beef and pig urine as feedstock. The results indicate that the addition of digestate increased pesticide mineralization, whereby the mineralization was not proportional to the digestate loads in the mixture, indicating a saturation effect in the turnover rate of pesticides. This effect was in correlation with the amount of water extractable DOC, obtained from the digestate based mixtures. Mixing biochar into the soil generally reduced total mineralization and led to larger sorption/sequestration of the pesticides, resulting in faster decrease of the extractable fraction. Also the addition of biochar to the soil/digestate mixtures reduced mineralization compared to the digestate alone mixture but mineralization rates were still higher as for the biochar/soil alone. In consequence, the addition of biochar to the soil generally decreased pesticide dissipation times and larger amounts of biochar led to high amounts of non-extractable residues of pesticide in the substrates. Among the mixtures tested, a mixture of digestate (5%) and biochar (5%) gave optimal results with respect to mineralization and simultaneous sorption for all three pesticides.

Biochar-amended soil has been proven to possess superior sorption capacities for several environmental pollutants compared with pure soil. However, the role of biochar in the immobilization of polar pesticides and their metabolites has hardly been tested. The aim of this study was therefore to investigate the effect of a soil amendment with biochar on the sorption of selected polar herbicides and herbicide metabolites (log Kow 0.3-<2). To simulate worst-case sorption, a sandy soil (1.7% organic matter) was amended with 1.5% biochar (fresh or composted) to determine sorption/desorption isotherms of the test compounds. One herbicide (imazamox) and three herbicide metabolites (methyl-desphenyl-chloridazon, metazachlor oxalic acid, metazachlor sulfonic acid) were tested, i.e. three anionic and one neutral polar compound. The results showed that the presence of biochar increased the sorption capacity of the soil only in the case of the uncharged compound methyl-desphenyl-chloridazon, for which the average distribution coefficients in biochar-amended soils were higher than in pure soil by a factor of 2.1-2.5. However, this effect rather seemed to reflect the increased soil organic carbon content after the addition of biochar than a preferred sorption of methyl-desphenyl-chloridazon to biochar. In the case of the three anionic compounds imazamox, metazachlor oxalic acid and metazachlor sulfonic acid, biochar amendment did not increase the sorption capacity of the soil for these compounds, presumably as a result of its negative net charge. Similarly, desorption experiments did not show any significant effect of the biochar amendment on desorption. This suggests that the potential of using biochar to mitigate the leaching of the tested polar pesticides or metabolites is limited.

The spatial distribution of organic compounds in the microscopic soil/pore-water system due to sorption has fundamental implications on determining first-order or non-first order behaviour and assessing bioavailability/biodegradability. If only the fraction of the organic compounds in the microbe-accessible region (e.g., soil pore water) is directly subject to intracellular transformation, sorption into microbe-absent regions (e.g., intra-particle/intra-aggregate micro-pores/interstitial spaces) may become rate-limiting to biodegradation, thus a non-first order decline may be expected in the soil-water system. In this paper, several data sets with direct measurements of soil pore water concentrations are used to elucidate the effect of sorption/desorption on biodegradation. Macro rate constants equivalent to the Double First-Order in Parallel (DFOP) model are derived for gauging the non-first order behavior and for calculating the micro kinetic rate constants of sorption and biodegradability from standard laboratory soil metabolism and batch sorption studies. Two new bioavailability factors (short-term and long-term) are developed to delineate the confounding effect of sorption and a compound's specific biodegradability on the overall degradation rate in the bulk soil system. The bioavailability factors are shown to be useful in the development of predictive regressions for degradation using soil and environmental factors. Discussions on data interpretation and implications for coordinated study designs of different fate studies are provided.

The slow alteration of the surface of charred biomass (biochar) over time may contribute to an improved nutrient retention and thus fertility of tropical soils. Here, we investigated soils from temperate climates and investigated whether a technical steam activation of biochar could accelerate its positive effects on nutrient retention and uptake by plants relative to nonactivated biochar. To this aim, we performed microcosm experiments with sandy or silty soil, mixed with 2.0, 7.5 and 15.0 g/kg soil of fine (<2 mm) or coarse-sized (210 mm) biochar from beech wood (Fagus sp.). After initial fertilizer (NPK), ashes and excess nutrients were leached with water, and the microcosms were planted for 142 days with Italian Ryegrass (Lolium multiflorum ssp. italicum). Thereafter, leachate, soil and plant samples were analysed for their nutrient contents. The results showed that biochar additions of =15 g/kg soil left elevated contents of available P and N in the surface soil but reduced their uptake into the plants. As a result, total biomass production was unchanged. Different particle size and application amounts influenced these findings only marginally. Nitrate leaching was enhanced in the sandy soil (+41% for nitrate, but reduced in the silty soil -17%) and P was immobilized. Hence, the fertility of the temperate soils under study was only marginally affected by pure biochar amendments. Steam activation, however, almost doubled the positive effects of biochars in all instances, thus being an interesting option for future biochar applications.

The environmental risks caused by the use of fluoroquinolone antibiotics in human therapeutics and animal husbandry are associated with their persistence and (bio)accessibility in soil. To assess these aspects, we administered difloxacin to pigs and applied the contaminated manure to soil. We then evaluated the dissipation and sequestration of difloxacin in soil in the absence and presence of plants within a laboratory trial, a mesocosm trial, and a field trial. A sequential extraction yielded antibiotic fractions of differing binding strength. We also assessed the antibiotic's effects on nitrogen turnover in soil (potential nitrification and denitrification). Difloxacin was hardly (bio)accessible and was very persistent under all conditions studied (dissipation half-life in bulk soil, >217 d), rapidly forming nonextractable residues. Although varying environmental conditions did not affect persistence, dissipation was accelerated in soil surrounding plant roots. Effects on nitrogen turnover were limited due to the compound's strong binding and small (bio)accessibility despite its persistence.

Veterinary antibiotics introduced into the environment may change the composition and functioning of soil microbial communities and promote the spreading of antibiotic resistance. Actual risks depend on the antibiotic's persistence and (bio)accessibility, which may differ between laboratory and field conditions. We examined the dissipation and sequestration of sulfadiazine (SDZ) and its main metabolites in soil under field conditions and how it was influenced by temperature, soil moisture, plant roots, and soil aggregation compared to controlled laboratory experiments. A sequential extraction accounted for easily extractable (CaCl(2)-extractable) and sequestered (microwave-extractable, residual) SDZ fractions. Dissipation from both fractions was largely temperature-dependent and could be well predicted from laboratory data recorded at different temperatures. Soil moisture additionally seemed to control sequestration, being accelerated in dry soil. Sequestration, as indicated by increasing apparent distribution coefficients and decreasing rates of kinetic release into CaCl(2), governed the antibiotic's long-term fate in soil. Besides, we observed spatial gradients of antibiotic concentrations across soil aggregates and in the vicinity of roots. The former were short-lived and equilibrated due to aggregate reorganization, while dissipation of the easily extractable fraction was accelerated near roots throughout the growth period. There was little if any impact of the plants on residual SDZ concentrations.

It is not the total but the (bio)accessible concentration of veterinary medicines that determines their toxicity in the environment. We elucidate the changes in (bio)accessibility of manure-applied sulfadiazine (SDZ) with increasing contact time in soil. Fattening pigs were medicated with 14C-labeled SDZ, and the contaminated manure (fresh and aged) was amended to 2 soil types (Cambisol, Luvisol) and incubated for 218 days at 10 degrees C in the dark. Antibiotic residues of different bioaccessibility were approached by sequential extractions with 0.01 M CaCl2 (CaCl2 fraction), methanol (MeOH fraction), and finally acetonitrile/water (residual fraction, microwave extraction at 150 degrees C). In each fraction, total radioactivity, SDZ, and its major metabolites were quantified. The results showed that both SDZ and,to a lesser extent 4-hydroxysulfadiazine (4-OH-SDZ) were rapidly reformed from N-acetylsulfadiazine (N-ac-SDZ) during the first 2-4 weeks after fresh manure application, i.e., the N-acetylated metabolite does not sequester in soil to a significant extent Yet, the water and methanol extractable SDZ and 4-OH-SDZ also dissipated rapidly (DT50 = 6.0-32 days) for the fresh manure treatment with similar rate constants for both soil types. In the residual fractions, however, the concentrations of both compounds increased with time. We conclude that the residual fraction comprises the sequestered pool of SDZ and its hydroxylated metabolite. There they are entrapped and may persist in soil for several years. Including the residual fraction into fate studies thus yields dissipation half-lives of SDZ which exceed those previously reported for sulfonamides by a factor of about 100.

There have been several reports published which suggest that it is possible that the polycyclic aromatic hydrocarbons (PAHs) naphthalene (NAPH), phenanthrene (PHEN) and perylene (PERY) in tropical environments have a biological source. This source might be related to the activity of termites or their associated microorganisms. We aimed to provide direct evidence for the biological production of NAPH, PHEN and PERY by conducting microcosm experiments in the State of Tocantins, Brazil, in which termite nests (with or without termites) were placed in an enclosed environment in which we controlled all PAH fluxes and monitored changes of PAH stocks. The experiments were carried out with termites from a tropical floodplain forest environment at the Estação Canguçu (Ilha do Bananal) in the State of Tocantins, Brazil. We set up the following treatments: live nest of Nasutitermes cf. minor using PAH-poor wood as food (LNW), live nest of Nasutitermes cf. minor using PAH-poor corn as food (LNC), termite nest without live termites called dead nest (DNC) and dead nest with additional treatment by a combined fungicide/bactericide (FDN) in several replicates. In LNW, LNC, and DNC, there were mean increases of 43%, 21%, and 46% in NAPH stock after 20d while the stocks of the 20 other PAHs studied did not change or even decreased. In contrast, FDN lost 20% of the NAPH stock after 20d of the microcosm experiment because of dissipation and lack of microbial synthesis of new NAPH. In LNW and LNC, low-molecular weight PAHs (acenaphthylene to chrysene) were significantly lost at a mean percentage which was strongly correlated with the octanol–water partitioning coefficient (KOW, r=0.78). This was not the case in DNC and FDN. There were no indications that in the studied termite nests PHEN and PERY were produced. Our microcosm experiments suggest that NAPH can be produced by fungi and bacteria in termite mounds while all other low-molecular weight PAHs are degraded in microcosms with live termite nests. PAH degradation seems to be enhanced by the combined activity of termites and microorganisms.

In Sub-Saharan Africa, horticulture provides livelihood opportunities for millions of people, especially in urban and peri-urban areas. Although the vegetable agroecosystems are often characterized by intensive pesticide use, risks resulting therefrom are largely unknown under tropical horticultural conditions. The objective of this study therefore was to study the fate of pesticides in two representative horticultural soils (Acrisol and Arenosol) and plants (Solanum macrocarpon L.) after field application and thus to gain first insight on environmental persistence and dispersion of typical insecticides used in vegetable horticulture in Benin, West Africa. On plant surfaces, dissipation was rapid with half lives ranging from 2 to 87 h (alpha-endosulfan < beta-endosulfan < deltamethrin). Soil dissipation was considerably slower than dissipation from plant surfaces with half-lives ranging from 3 (diazinon) to 74 d (total endosulfan), but persistence of pesticides in soil was still reduced compared to temperate climates. Nevertheless, for deltamethrin and endosulfan, a tendency for mid-term accumulation in soil upon repeated applications was observed. The soil and plant surface concentrations of the metabolite endosulfan sulfate increased during the entire trial period, indicating that this compound is a potential long-term pollutant even in tropical environments.

An efficient extraction of sulfadiazine residues from soils is difficult, as sulfadiazine is known to form quickly sequestering residues. The objective of this study was to optimize an exhaustive extraction for aged residues of sulfadiazine and its two major metabolites, N-acetylsulfadiazine and 4-hydroxysulfadiazine, from soil. For this purpose two representative used agricultural soils (Luvisol, Cambisol) were blended with manure derived from [14C]sulfadiazine-treated pigs and incubated at 10 °C in the laboratory. After different extraction tests with various solvent mixtures (two- to four-component mixtures with water, methanol, acetonitrile, acetone, and/or ethyl acetate), different pH values (pH 4 and 9), and extraction temperatures (up to 200 °C), soil extracts were measured by liquid scintillation counting and liquid chromatography coupled to tandem mass spectrometry. With respect to sulfadiazine yields, stability of soil extracts, and the amount of coextracted matrix, a microwave extraction of soil (15 min, 150 °C) using acetonitrile/water 1:4 (v/v) is the method of choice for the exhaustive extraction of aged sulfadiazine residues from soils.

Tropical and temperate soils differ with respect to their chemical conditions and mineral composition. Consequently, assessment of the contamination of tropical soils with pesticides requires methods that provide exhaustive extraction from the specific soil matrix and reliable quantification. Our objective was to optimize the simultaneous extraction and determination of 32 representative pesticides (organophosphates, organochlorines, synthetic pyrethroids, triazines, acetamides, carbamates, diphenyl ethers, acylalanines, oxadiazoles, thiadiazoles, and phenoxy compounds) frequently used in Thailand. The compounds were added to a clayey Ultisol-topsoil (45% clay) from the Yom Region in Northern Thailand. Ten different solvent mixtures were tested; the use of a shake extraction with acetone-ethyl acetate-water (3 + 1 + 1, v/v/v) was most effective in providing exhaustive and reproducible extraction of pesticides both from freshly fortified soil and from fortified soil after incubation for 14-28 days. The pesticides were separated and quantified by using gas chromatography with mass selective detection. Except for methamidophos, which was almost completely lost during sample workup, the recoveries of all pesticides from soil ranged from 68.6 to 104% (mean standard error, 2.8%) for freshly spiked samples and from 45.9 to 107% (mean standard error, 2.3%) for spiked samples incubated for 14 days. The use of internal standards compensated for the losses of most pesticides during workup and increased the mean recovery of the pesticides from freshly fortified soil to 96%. The method was successfully applied to the determination of environmental concentrations of pesticides in a range of Thai agricultural soils.

A contamination of off-site aquatic environments with pesticides has been observed in the tropics, yet only sparse information exists about pesticide fate in such ecosystems. The objective of our semi-field study was to elucidate the fate of alachlor, atrazine, chlorpyrifos, endosulfan, metolachlor, profenofos, simazine, and trifluralin in the aqueous environment of the Pantanal wetland (MT, Brazil). To this aim, water and water/sediment microcosms of two sizes (0.78 and 202 l) were installed in the outskirts of this freshwater lagoon environment and pesticide dissipation was monitored for up to 50 d after application. The physical-chemical water conditions that developed in the microcosms were reproducible among field replicates for both system sizes. Pesticide dissipation was substantially enhanced for most pesticides in small microcosms relative to the large ones (reduced DT50 by a factor of up to 5.3). The presence of sediment in microcosms led to increased persistence of chlorpyrifos, endosulfan, and trifluralin in the test systems, while for polar pesticides (alachlor, atrazine, metolachlor, profenofos, and simazine) a lesser persistence was observed. Atrazine, simazine, metolachlor, and alachlor were identified as the most persistent pesticides in large water microcosms (DT50 ⩾ 47 d); in large water/sediment systems endosulfan β, atrazine, metolachlor, and simazine showed the slowest dissipation (DT50 ⩾ 44 d). A medium-term accumulation in the sediment of tropical ecosystems can be expected for chlorpyrifos and endosulfan isomers (11–35% of applied amount still extractable at 50 d after application). We conclude that the persistence of the studied pesticides in aquatic ecosystems of the tropics is not substantially lower than during summer in temperate regions.

The efficacy and fate of pesticides in soil strongly depend on sorption reversibility that is known to decrease with increasing contact time (aging). We elucidated the aging dynamics of eight different pesticides in two contrasting agricultural soils of tropical Brazil (Ustox and Psamments), using batch equilibrium experiments and sequential extractions of field samples. Adsorption was best described by Langmuir isotherms for the entire and by Freundlich equations for the lower concentration range. In field samples, water extractable pesticide fractions mostly dissipated at least twice as fast as did the solvent extractable fractions. Hence, in comparison to 0 days K-OC values, measured field K-OC values were higher by a factor of 2.6-38 for the clayey Ustox and 2.1-72 for the sandy Psamments toward the end of the experimental period at 80 days after application. The extent of such aging basically increased with increasing polarity of the pesticide. An absolute enrichment of polar pesticides within the final exhaustive acetone-ethyl acetate-water extracts was observed during the experimental period, so that we may deduce that pesticides had redistributed into stronger sorption sites. The time course of the K-OC development was well-described using a semiempirical equation, which had been employed for temperate soils before.

Sorption hysteresis of pesticides is commonly observed in batch adsorption/desorption experiments. For a range of temperate soils it has been shown that in most cases observed hysteresis can be explained by slow sorption kinetics. However, for tropical soils this has not been investigated yet. Therefore, a kinetic evaluation of pesticide batch sorption experiments with two tropical soils was performed. The Streck two-stage, one-rate model subdivides the sorption sites into a fraction with instantaneous sorption equilibrium and a kinetic fraction with ratelimited sorption. Four parameters were estimated simultaneously: sorption rate coefficient  (d -1 ), equilibrium fraction f (kg kg -1 ), equilibrium Freundlich coefficient keq and exponent m. Experimental data were taken from standard batch adsorption/desorption studies with nine common corn and soybean pesticides, using a Typic Haplustox and an Ustic Quartzipsamment from the Brazilian Cerrado. Also for these tropical soils, observed sorption hysteresis could be largely explained by kinetic sorption phenomena. The generally stronger hysteresis in the Psamment was reflected by smaller equilibrium fractions than in the Ustox. Kinetic sorption phenomena were strongly pronounced for polar compounds (metribuzine, cyanazine) and less pronounced for triallate, endosulfan-, atrazine, and metolachlor. Thus, for polar pesticides the leaching risk in tropical soils is diminished in comparison to the one assessed on basis of simple equilibrium sorption models.