A multi-residue method for trace analysis of pesticides in soils with special emphasis on rigorous quality control.

A multi-residue trace analytical method is presented to accurately quantify 146 currently used pesticides in (agricultural) soils with varying soil properties. Pesticides were extracted using an optimized quick, easy, cheap, effective, rugged, and safe (QuEChERS) approach and chemical analysis was carried out by liquid chromatography coupled to tandem mass spectrometry (triple quadrupole). Quantification was based on matrix-matched internal standards calibration, using 95 isotopically labeled analyte analogues. In contrast to the common approach of method validation using soils freshly spiked with analytes shortly before the extraction, our method is additionally validated via an in-house prepared partly aged soil, which contains all target pesticides and via agricultural field soils with native pesticide residues. The developed method is highly sensitive (median method limit of quantification: 0.2 ng/g), precise (e.g., median intra-day and inter-day method precision both ~ 4% based on field soils), and true ((i) quantified pesticide concentrations of the partly aged soil remained stable during 6 months, were close to the initially spiked nominal concentration of 10 ng/g, and thus can be used to review trueness in the future; (ii) median freshly spiked relative recovery: 103%; and (iii) participation in a ring trial: median z-scores close to one (good to satisfactory result)). Its application to selected Swiss (agricultural) soils revealed the presence of in total 77 different pesticides with sum concentrations up to 500 ng/g. The method is now in use for routine soil monitoring as part of the Swiss Action Plan for Risk Reduction and Sustainable Use of Plant Protection Products.

Disentangling Mechanisms in Natural Toxin Sorption to Soil Organic Carbon.

Natural toxins are multifunctional, often ionizable organic compounds increasingly detected in the environment. Surprisingly little is known about their interactions with soil organic carbon, although sorption largely controls transport, bioavailability, and dissipation. For a set of 117 natural toxins from 36 compound classes the pH-dependent organic carbon-water distribution coefficient (Doc) was quantified using a soil column chromatography approach under changing conditions with regards to pH, ionic strength, and the major inorganic cation in solution. Natural toxins could be assigned to groups with either hydrophobic partitioning or specific interactions (complexation reactions, cation exchange) as dominating sorption mechanisms. The complex interplay of interactions in the sorption of natural toxins was equally influenced by sorbate, sorbent, and solution specific characteristics. High variability in sorption was particularly observed in the presence of Ca2+ resulting in Doc being enhanced by a factor of 10 when the pH was increased from 4.5 to 6. Sorbates following this trend contain either functional groups able to form ternary complexes via Ca2+ or aromatic moieties adjacent to protonated N presumably stabilizing cation exchange reactions. Although sorption was often stronger than predicted, investigated natural toxins were highly mobile under all considered conditions.

Retrospective HRMS Screening and Dedicated Target Analysis Reveal a Wide Exposure to Pyrrolizidine Alkaloids in Small Streams.

Pyrrolizidine alkaloids (PAs) are found to be toxic pollutants emitted into the environment by numerous plant species, resulting in contamination. In this article, we investigate the occurrence of PAs in the aquatic environment of small Swiss streams combining two different approaches. Pyrrolizidine alkaloids (PAs) are toxic secondary metabolites produced by numerous plant species. Although they were classified as persistent and mobile and found to be emitted into the environment, their occurrence in surface waters is largely unknown. Therefore, we performed a retrospective data analysis of two extensive HRMS campaigns each covering five small streams in Switzerland over the growing season. All sites were contaminated with up to 12 individual PAs and temporal detection frequencies between 36 and 87%. Individual PAs were in the low ng/L range, but rain-induced maximal total PA concentrations reached almost 100 ng/L in late spring and summer. Through PA patterns in water and plants, several species were tentatively identified as the source of contamination, with Senecio spp. and Echium vulgare being the most important. Additionally, two streams were monitored, and PAs were quantified with a newly developed, faster, and more sensitive LC-MS/MS method to distinguish different plant-based and indirect human PA sources. A distinctly different PA fingerprint in aqueous plant extracts pointed to invasive Senecio inaequidens as the main source of the surface water contamination at these sites. Results indicate that PA loads may increase if invasive species are sufficiently abundant.

Widespread Occurrence of Pesticides in Organically Managed Agricultural Soils-the Ghost of a Conventional Agricultural Past?

Pesticides are applied in large quantities to agroecosystems worldwide. To date, few studies assessed the occurrence of pesticides in organically managed agricultural soils, and it is unresolved whether these pesticide residues affect soil life. We screened 100 fields under organic and conventional management with an analytical method containing 46 pesticides (16 herbicides, 8 herbicide transformation products, 17 fungicides, seven insecticides). Pesticides were found in all sites, including 40 organic fields. The number of pesticide residues was two times and the concentration nine times higher in conventional compared to organic fields. Pesticide number and concentrations significantly decreased with the duration of organic management. Even after 20 years of organic agriculture, up to 16 different pesticide residues were present. Microbial biomass and specifically the abundance of arbuscular mycorrhizal fungi, a widespread group of beneficial plant symbionts, were significantly negatively linked to the amount of pesticide residues in soil. This indicates that pesticide residues, in addition to abiotic factors such as pH, are a key factor determining microbial soil life in agroecosystems. This comprehensive study demonstrates that pesticides are a hidden reality in agricultural soils, and our results suggest that they have harmful effects on beneficial soil life.

Pest trade-offs in technology: reduced damage by caterpillars in Bt cotton benefits aphids.

The rapid adoption of genetically engineered (GE) plants that express insecticidal Cry proteins derived from Bacillus thuringiensis (Bt) has raised concerns about their potential impact on non-target organisms. This includes the possibility that non-target herbivores develop into pests. Although studies have now reported increased populations of non-target herbivores in Bt cotton, the underlying mechanisms are not fully understood. We propose that lack of herbivore-induced secondary metabolites in Bt cotton represents a mechanism that benefits non-target herbivores. We show that, because of effective suppression of Bt-sensitive lepidopteran herbivores, Bt cotton contains reduced levels of induced terpenoids. We also show that changes in the overall level of these defensive secondary metabolites are associated with improved performance of a Bt-insensitive herbivore, the cotton aphid, under glasshouse conditions. These effects, however, were not as clearly evident under field conditions as aphid populations were not correlated with the amount of terpenoids measured in the plants. Nevertheless, increased aphid numbers were visible in Bt cotton compared with non-Bt cotton on some sampling dates. Identification of this mechanism increases our understanding of how insect-resistant crops impact herbivore communities and helps underpin the sustainable use of GE varieties.

Life-cycle exposure to the estrogenic mycotoxin zearalenone affects zebrafish (Danio rerio) development and reproduction.

Zearalenone (ZON) is one of the worldwide most common mycotoxin and exhibits estrogenic activity in the range of natural steroid estrogens. The occurrence of ZON has been reported in soil, drainage water, wastewater effluents, and rivers, but its ecotoxicological effects on fish have hardly been investigated. The consequences of continuous long-term ZON exposure, including a subsequent depuration period, as well as transgenerational effects of F0 short-term exposure on F1 generation were investigated. Effects on growth, reproduction activity, physiology, and morphology of zebrafish (Danio rerio) were examined in a 182 day live-cycle experiment. Life-long exposure to ZON for 140 days increased wet weight, body length, and condition factor of female fish at 1000 ng/L, and sex ratio was shifted toward female from 320 ng/L ZON. Only females at 1000 ng/L ZON revealed a 1.5-fold induction of plasma vitellogenin (VTG). Relative fecundity at 1000 ng/L recovered significantly during the depuration period. An increased condition factor in adult female F1 fish implies that exposure of F0 generation to 1000 ng/L ZON affected growth of F1 generation. A negative correlation between relative fecundity in the F1 generation (all groups exposed to 320 ng/L ZON) and the nominal ZON concentrations of the F0 exposure might indicate an influence of F0 exposure on reproductive performance of F1 generation. No exposure scenario affected fertility, hatch, embryo survival, and gonad morphology of zebrafish. Evaluating the environmental relevance of this data, the risk for fish to be harmed by exposure to ZON solely seems rather marginal, but ZON might contribute to the overall estrogenicity in the environment. © 2011 Wiley Periodicals, Inc. Environ Toxicol 2013.

Pesticide residues in agricultural soils in light of their on-farm application history.

The application of synthetic pesticides to agricultural fields for the protection of crops leads to the formation of residues in soils. While the short-term behavior of pesticide residues in soils after an application is generally known from laboratory and field studies required for authorization (prospective risk assessments), there is still a lack of in-situ observations that address their long-term fate. Long-term soil monitoring programs, with comprehensive site-specific records of pesticide application data, constitute an invaluable, complementary, retrospective exposure assessment tool to address this gap. Considering the pesticide applications over the past 10-15 years, this study assessed the occurrence of pesticides in agricultural soils of Switzerland and put their presence or absence, as well as their concentrations, in the context of their previous application. The results showed that pesticides could also be detected at sites without a connection to previous applications and that small residual mass fractions of pesticides, even of some non-persistent compounds, were found in soils, years or decades after their last application. This finding points to an environmental issue that may not be adequately captured in prospective risk assessment and calls attention to the need for comprehensive long-term recording and monitoring as a complementary retrospective exposure assessment.

Frequent biphasic cellular responses of permanent fish cell cultures to deoxynivalenol (DON).

Contamination of animal feed with mycotoxins is a major problem for fish feed mainly due to usage of contaminated ingredients for production and inappropriate storage of feed. The use of cereals for fish food production further increases the risk of a potential contamination. Potential contaminants include the mycotoxin deoxynivalenol (DON) which is synthesized by globally distributed fungi of the genus Fusarium. The toxicity of DON is well recognized in mammals. In this study, we confirm cytotoxic effects of DON in established permanent fish cell lines. We demonstrate that DON is capable of influencing the metabolic activity and cell viability in fish cells as determined by different assays to indicate possible cellular targets of this toxin. Evaluation of cell viability by measurement of membrane integrity, mitochondrial activity and lysosomal function after 24 h of exposure of fish cell lines to DON at a concentration range of 0-3000 ng ml(-1) shows a biphasic effect on cells although differences in sensitivity occur. The cell lines derived from rainbow trout are particularly sensitive to DON. The focus of this study lies, furthermore, on the effects of DON at different concentrations on production of reactive oxygen species (ROS) in the different fish cell lines. The results show that DON mainly reduces ROS production in all cell lines that were used. Thus, our comparative investigations reveal that the fish cell lines show distinct species-related endpoint sensitivities that also depend on the type of tissue from which the cells were derived and the severity of exposure.

Occurrence and mass balance of isoflavones on an experimental grassland field.

Isoflavones and coumestrol (COU) are estrogenic compounds that are naturally produced by plants (e.g., red clover, soybeans). Although these compounds have been extensively studied in food and feed, only little is known about their environmental fate. Therefore, we investigated the occurrence of isoflavones (formononetin, daidzein, equol, biochanin A, and genistein) and COU over 3.5 years in red clover, manure, and soil of a grassland field with and without manure application, as well as their emission via drainage water. Isoflavones were regularly quantified in plant (≤ 15 × 10(6) ng/g(dry weight (dw))), manure (≤ 230 × 10(3) ng/g(dw)), soil (≤ 3.4 × 10(3) ng/g(dw)), and drainage water samples (≤ 3.6 × 10(3) ng/L). In contrast, COU was observed only in manure and soil. Cumulative isoflavone loads emitted via drainage water were around 0.2 × 10(-3) kg/ha/y, which is very little compared to the amounts present in red clover (105-220 kg/ha/y), manure (0.5-1.0 kg/ha/y), and soil (0.1-5.1 kg/ha/y). Under good agricultural practice, no additional emission of isoflavones into drainage water was observed after manure application. With calculated 17ß-estradiol equivalents up to 0.46 ng/L in drainage water, isoflavones can constitute a dominant and ecotoxicological relevant portion of the total estrogenicity in small rural river catchments.

Natural estrogen emissions to subsurface tile drains from experimental grassland fields in Switzerland after application of livestock slurries and free compounds.

Natural estrogens are present in high concentrations in livestock slurries, which are often applied to agricultural fields in large quantities. As such, the export of slurry-derived natural estrogens from tile-drained fields is a potential source for estrogenic pollution in surface waters. Yet despite the abundance of tile-drained fields in Central Europe, export of natural estrogens from agricultural fields receiving livestock slurries is rarely studied in this region. In an effort to fill this knowledge gap, here we applied natural estrogens to Swiss experimental fields in the form of cattle slurry, pig slurry or dissolved in water, and quantified them in flow-proportionally collected drainage water over 18 months. After pig and cattle slurry applications, concentration maxima in drainage water of 73, 8, 37, and 60 ng L-1 for 17α-estradiol (E2α), 17ß-estradiol (E2ß), estrone (E1), and estriol (E3), respectively, were observed shortly after rain events. The exported fractions of individual natural estrogens to tile drains were on average 0.26% (ranging from 0.08 to 0.41%) after cattle, and 0.18% (0.03-0.40%) after pig slurry applications. Such numbers were higher than expected from the leaching potential based on substance properties, and comparable to those of more mobile micropollutants previously studied on the same fields. Natural estrogens were mainly exported to tile drains through preferential flow. Exported fractions were lower when applied in aqueous solution than when applied in slurry, pointing to particle-facilitated transport to tile drains when applied in slurry. In Switzerland, the estimated 6.3, 0.6, 7.4, and 7.7 g of E2α, E2ß, E1, and E3, respectively, exported through the tile-drained agricultural area per year contribute little to the total natural estrogen load received by surface waters. However, after slurry applications in highly drained catchments, natural estrogen emissions to tile drains can cause short term (i.e. less than 1 week) estrogenic exposure in nearby streams.

Phytoestrogens and mycotoxins in Iowa streams: an examination of underinvestigated compounds in agricultural basins.

This study provides the first broad-scale investigation on the spatial and temporal occurrence of phytoestrogens and mycotoxins in streams in the United States. Fifteen stream sites across Iowa were sampled five times throughout the 2008 growing season to capture a range of climatic and crop-growth conditions. Basin size upstream from sampling sites ranged from 7 km2 to > 836,000 km2. Atrazine (herbicide) also was measured in all samples as a frame-of-reference agriculturally derived contaminant. Target compounds were frequently detected in stream samples: atrazine (100%), formononetin (80%), equol (45%), deoxynivalenol (43%), daidzein (32%), biochanin A (23%), zearalenone (13%), and genistein (11%). The nearly ubiquitous detection of formononetin (isoflavone) suggests a widespread agricultural source, as one would expect with the intense row crop and livestock production present across Iowa. Conversely, the less spatially widespread detections of deoxynivalenol (mycotoxin) suggest a more variable source due to the required combination of proper host and proper temperature and moisture conditions necessary to promote Fusarium spp. infections. Although atrazine concentrations commonly exceeded 100 ng L(-1) (42/75 measurements), only deoxynivalenol (6/56 measurements) had concentrations that occasionally exceeded this level. Temporal patterns in concentrations varied substantially between atrazine, formononetin, and deoxynivalenol, as one would expect for contaminants with different source inputs and processes of formation and degradation. The greatest phytoestrogen and mycotoxin concentrations were observed during spring snowmelt conditions. Phytoestrogens and mycotoxins were detected at all sampling sites regardless of basin size. The ecotoxicological effects from long-term, low-level exposures to phytoestrogens and mycotoxins or complex chemicals mixtures including these compounds that commonly rake place in surface water are poorly understood and have yet to be systematically investigated in environmental studies.

Natural estrogens in surface waters of a catchment with intensive livestock farming in Switzerland.

Natural estrogens such as 17α-estradiol (E2α), 17ß-estradiol (E2ß), estrone (E1), and estriol (E3), released to surface waters from both urban and agricultural sources, are endocrine disrupting for fish. Here, we assess the prevalence of livestock farming derived natural estrogens in tributaries and ponds in the agriculturally dominated catchment of Lake Baldegg, Switzerland. Passive samplers were deployed in the main tributary and daily time-proportional water samples were collected in five tributaries for 30 days at the beginning of the vegetation period. Furthermore, we took grab samples of 12 ponds in the catchment. Aqueous samples were liquid-liquid extracted, derivatized, and analysed with LC-MS/MS and stream water samples additionally with ERα-CALUX, a bioassay for assessing total estrogenic activity. Natural estrogens were regularly detected, with mean concentrations ranging from below the limit of detection to 0.55 ng L-1 for E2ß and E1, respectively, and passive sampling and bioassay results largely confirmed these findings. Monte Carlo simulated mean natural estrogen concentrations underestimated measured ones by a factor of three to 11. An agricultural area's hydrological contribution and connectivity to surface waters seemed to be more important for the development of estrogen concentrations in streams than livestock densities in a catchment or the actual loads of slurry applied. Pond water occasionally contained natural estrogens in concentrations up to 8.6 ng L-1 for E2α. The environmental quality standards of the European Union (0.4 ng L-1 for E2ß and 3.6 ng L-1 for E1) were never exceeded for longer than a day in tributaries, but E1 reached critical concentrations for aquatic organisms in ponds.

Fusarium mycotoxins: overlooked aquatic micropollutants?

Deoxynivalenol and zearalenone are among the most prevalent toxins produced by Fusarium spp. They have been investigated in food and feed products for decades but rarely in the environment. We therefore established solid-phase extraction and liquid chromatography-mass spectrometry (LC-MS) methods to quantify these mycotoxins at trace concentrations in aqueous natural samples. In a model emission study, we inoculated a winter wheat field with Fusarium graminearum and subsequently monitored deoxynivalenol and zearalenone in its drainage water. Before during and after harvest in June and July 2007, these toxins were emitted in concentrations from 23 ng/L to 4.9 microg/L for deoxynivalenol and from not detected to 35 ng/L for zearalenone. Simultaneously, in July and August 2007, deoxynivalenol was also detected in a number of Swiss rivers in concentrations up to 22 ng/L and zearalenone was present in several river samples below the method quantification limit. Other mycotoxins might be emitted from Fusarium-infected fields as well, because some of them are produced in similar amounts as deoxynivalenol and zearalenone and exhibit similar or even higher water solubility than deoxynivalenol. The ecotoxicological consequences of the presence of mycotoxins in surface waters remain to be elucidated.

Quantification of zearalenone in various solid agroenvironmental samples using D6-zearalenone as the internal standard.

Because of its pronounced estrogenicity, zearalenone may be of concern not only in the aqueous but also in the terrestrial environment. Therefore, we developed several analytical methods to quantify zearalenone in different solid matrices of agroenvironmental relevance (i.e., plant organs, soil, manure, and sewage sludge). The use of D(6)-zearalenone as the internal standard (IS) was essential to render the analytical method largely matrix-independent because it compensated for target analyte losses during extract treatment and ion suppression during ionization. Soil and sewage sludge samples were extracted with Soxhlet, whereas plant material and manure samples were extracted by liquid solvent extraction at room temperature. Absolute recoveries for zearalenone were 70-104% for plant materials, 105% for soil, 76% for manure, and 30% for sewage sludge. Relative recoveries ranged from 86 to 113% for all matrices, indicating that the IS was capable to largely compensate for losses during analysis. Ion suppression, between 8 and 74%, was in all cases compensated by the IS but influenced the method quantification levels. These were 3.2-26.2 ng/g(dryweightdw) for plant materials, 0.7 ng/g(dw) for soil, 12.3 ng/g(dw) for manure, and 6.8 ng/g(dw) for sewage sludge. Plant material concentrations varied from 86 ng/g(dw) to more than 16.7 microg/g(dw), depending on the organ and crop. Soil concentrations were between not detectable and 7.5 ng/g(dw), depending on the sampling depth. Zearalenone could be quantified in all manure samples in concentrations between 8 and 333 ng/g(dw). Except for two of the 85 investigated sewage sludge samples, zearalenone concentrations were below quantification limit.

Quantification of estrogenic mycotoxins at the ng/L level in aqueous environmental samples using deuterated internal standards.

Because of their pronounced estrogenicity, resorcyclic acid lactones (RALs) are of concern in aqueous environments even at the low ng/L level. Therefore, we developed an accurate, precise and sensitive HPLC-MS/MS method to detect these mycotoxins in different aqueous environmental samples. The compounds investigated included zearalenone (ZON), alpha- and beta-zearalenol, zearalanone as well as alpha- and beta-zearalanol. The use of isotope labelled internal standards (in this case deuterated RAL-analogues) ensured an accurate quantification of the target analytes, independent of matrix compounds interfering with the analytes during ionisation and analyte losses occurring during sample preparation. Sample enrichment was carried out by solid-phase extraction (SPE) using Supelclean Envi-18 cartridges. Absolute method recoveries for all analytes ranged from 95 to 108%, 70 to 102%, and 76 to 109%, method detection limits from 0.5 to 2.1 ng/L, 0.4 to 1.1 ng/L, and 0.8 to 12.4 ng/L and precision from 3 to 14%, 2 to 13% and 4 to 16% in drainage water, river water and wastewater treatment plant (WWTP) effluent, respectively. The method was applied to verify the emission of RALs from a Fusarium graminearum infested crop field into the drainage system. Zearalenone was present in drainage water in concentrations up to 30 ng/L. So far, none of the other five investigated compounds have been detected.

Fusarium Mycotoxins in Swiss Wheat: A Survey of Growers' Samples between 2007 and 2014 Shows Strong Year and Minor Geographic Effects.

To assess the occurrence of Fusarium toxins in wheat in Switzerland, an eight-year survey was conducted by analysing a total of 686 harvest samples from growers using LC-MS/MS. Between 2007 and 2010, 527 samples were obtained from 17 cantons. Between 2011 and 2014, 159 samples were collected from the canton Berne. The most frequent toxins detected were deoxynivalenol (DON), zearalenone (ZEA) and nivalenol (NIV). The overall mean DON content in all samples was 607 µg/kg, and 11% exceeded the European limit for unprocessed cereals for foodstuffs (1250 µg/kg). For ZEA (mean 39 µg/kg), 7% exceeded the respective limit (100 µg/kg), and the mean content of NIV (no limit established) was 15 µg/kg. Between the years, the ratio of mycotoxin-contaminated samples ranged between 52% and 98% for DON, 9% and 43% for ZEA and 0% and 49% for NIV. The yearly mean contents varied substantially between 68 and 1310 µg/kg for DON, 5 and 56 µg/kg for ZEA and 6 and 29 µg/kg for NIV. The geographic origin showed a significant effect on DON and ZEA contamination, but was inconsistent between the years. This study has shown that the majority of Swiss-produced wheat is, in terms of Fusarium toxins, fit for human consumption and feed purposes. Nevertheless, depending on the year, high toxin contents can be expected, an issue that growers, cereal collection centres and the food industry have to deal with to ensure food and feed safety.

Stereoselective Metabolism of the Sterol Biosynthesis Inhibitor Fungicides Fenpropidin, Fenpropimorph, and Spiroxamine in Grapes, Sugar Beets, and Wheat.

Metabolism of chiral pesticides in crops is typically studied using achiral analytical methods and, consequently, the stereoisomer composition of residues is unknown. In this study, we developed an enantioselective GC-MS/MS method to quantify residues of the fungicides fenpropidin, fenpropimorph, and spiroxamine in plant matrices. In field trials, the fungicides were applied to grapevines, sugar beets, or wheat. Fenpropidin was metabolized with no or only weak enantioselectivity. For fenpropimorph, slightly enantioselective metabolism was observed in wheat but more pronounced in sugar beets. This enantioselectivity was due to different rates of metabolism and not due to interconversion of enantiomers. The four stereoisomers of spiroxamine were also metabolized at different rates, but selectivity was only found between diastereomers and not between enantiomers. trans-Spiroxamine was preferentially degraded in grapes and cis-spiroxamine in wheat. These findings may affect the consumer dietary risk assessment because toxicological end points were determined using racemic test substances.

Fusarium and mycotoxin spectra in Swiss barley are affected by various cropping techniques.

Fusarium head blight is one of the most important cereal diseases worldwide. Cereals differ in terms of the main occurring Fusarium species and the infection is influenced by various factors, such as weather and cropping measures. Little is known about Fusarium species in barley in Switzerland, hence harvest samples from growers were collected in 2013 and 2014, along with information on respective cropping factors. The incidence of different Fusarium species was obtained by using a seed health test and mycotoxins were quantified by LC-MS/MS. With these techniques, the most dominant species, F. graminearum, and the most prominent mycotoxin, deoxynivalenol (DON), were identified. Between the three main Swiss cropping systems, Organic, Extenso and Proof of ecological performance, we observed differences with the lowest incidence and toxin accumulation in organically cultivated barley. Hence, we hypothesise that this finding was based on an array of growing techniques within a given cropping system. We observed that barley samples from fields with maize as previous crop had a substantially higher F. graminearum incidence and elevated DON accumulation compared with other previous crops. Furthermore, the use of reduced tillage led to a higher disease incidence and toxin content compared with samples from ploughed fields. Further factors increasing Fusarium infection were high nitrogen fertilisation as well as the application of fungicides and growth regulators. Results from the current study can be used to develop optimised cropping systems that reduce the risks of mycotoxin contamination.

Leaching of the Neonicotinoids Thiamethoxam and Imidacloprid from Sugar Beet Seed Dressings to Subsurface Tile Drains.

Pesticide transport from seed dressings toward subsurface tile drains is still poorly understood. We monitored the neonicotinoid insecticides imidacloprid and thiamethoxam from sugar beet seed dressings in flow-proportional drainage water samples, together with spray applications of bromide and the herbicide S-metolachlor in spring and the fungicides epoxiconazole and kresoxim-methyl in summer. Event-driven, high first concentration maxima up to 2830 and 1290 ng/L for thiamethoxam and imidacloprid, respectively, were followed by an extended period of tailing and suggested preferential flow. Nevertheless, mass recoveries declined in agreement with the degradation and sorption properties collated in the groundwater ubiquity score, following the order bromide (4.9%), thiamethoxam (1.2%), imidacloprid (0.48%), kresoxim-methyl acid (0.17%), S-metolachlor (0.032%), epoxiconazole (0.013%), and kresoxim-methyl (0.003%), and indicated increased leaching from seed dressings compared to spray applications. Measured concentrations and mass recoveries indicate that subsurface tile drains contribute to surface water contamination with neonicotinoids from seed dressings.

Unraveling the mechanisms involved in zearalenone-mediated toxicity in permanent fish cell cultures.

The world-wide occurrence of zearalenone (ZEN) as a contaminant in feed for farm animals and fish requires the evaluation of toxicity mechanisms of action of ZEN. The present study investigates possible metabolization of ZEN in fish cell lines suggesting that mainly glucuronidation takes place. It demonstrates that concentrations up to 20,000 ng ml(-1) ZEN are capable of influencing cell viability in permanent fish cell cultures in a dose-response manner with different response patterns between the five tested cell lines, whereby lysosomes appeared to be the main target of ZEN. ZEN toxicity is often discussed in the context of oxidative stress. Our study shows a biphasic response of the cell lines when reactive oxygen species (ROS) production is monitored. Damage in cells was observed by measuring lipid peroxidation, DNA strand breaks, and alterations of intracellular glutathione levels. Metabolization of ZEN, especially at concentrations above 7500 ng ml(-1) ZEN, does not prevent cytotoxicity. ZEN as an estrogenic compound may involve processes mediated by binding to estrogen receptors (ER). Since one cell line showed no detectable expression of ER, an ER-mediated pathway seems to be unlikely in these cells. This confirms a lysosomal pathway as a main target of ZEN in fish cells.