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.

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.

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 () 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 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.

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).

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.

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

Natural estrogens such as 17α-estradiol (E2α), 17β-estradiol (E2β), 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.

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 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.

Cotton Defense Induction Patterns Under Spatially, Temporally and Quantitatively Varying Herbivory Levels.

In its defense against herbivores, cotton ( sp.) relies in part on the production of a set of inducible, non-volatile terpenoids. Under uniform damage levels, allocation of induced cotton terpenoids has been found to be highest in youngest leaves, supporting assumptions of the optimal defense theory (ODT) which predicts that plants allocate defense compounds to tissues depending on their value and the likelihood of herbivore attack.

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.

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.

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.

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.

Fusarium head blight control and prevention of mycotoxin contamination in wheat with botanicals and tannic acid.

Suspensions or solutions with 1% of Chinese galls (Galla chinensis, GC) or 1% of tannic acid (TA), inhibited germination of conidia or mycelium growth of Fusarium graminearum (FG) by 98%-100% or by 75%-80%, respectively, whereas dried bark from buckthorn (Frangula alnus, FA) showed no effect at this concentration. In climate chamber experiments where the wheat variety "Apogee" was artificially inoculated with FG and F. crookwellense (FCr) and treated with 5% suspensions of TA, GC and FA, the deoxynivalenol (DON) content in grains was reduced by 81%, 67% and 33%, respectively.

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.

Incidence of Fusarium species and mycotoxins in silage maize.

Maize is frequently infected by the Fusarium species producing mycotoxins. Numerous investigations have focused on grain maize, but little is known about the Fusarium species in the entire plant used for silage. Furthermore, mycotoxins persist during the ensiling process and thus endanger feed safety.

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.

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).

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.

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.

Quantification of five isoflavones and coumestrol in various solid agroenvironmental matrices using ¹³c₃-labeled internal standards.

We developed and validated three different sample preparation and extraction methods followed by HPLC-MS/MS (negative electrospray ionization) analysis for the quantification of estrogenic isoflavones (formononetin, daidzein, equol, biochanin A, and genistein) and coumestrol in red clover, soil, and manure. Plant and manure samples were solid-liquid extracted, whereas soil was extracted with accelerated solvent extraction. Absolute recoveries were between 80 and 93%, 20 and 30%, and 14 and 91% for plant, soil, and manure samples, respectively.

Short-term exposure to the environmentally relevant estrogenic mycotoxin zearalenone impairs reproduction in fish.

Zearalenone (ZON) is one of the worldwide most common mycotoxins and exhibits estrogenic activity in the range of natural steroid estrogens such as 17β-estradiol (E2). The occurrence of ZON has been reported in drainage water, soil, wastewater effluents and rivers, but its ecotoxicological effects on fish have hardly been investigated. In this study the estrogenic potency of the ZON was compared to E2 in a recombinant yeast estrogen screen (rYES) and the effects of waterborne ZON exposure on reproduction, physiology and morphology of zebrafish (Danio rerio) were investigated in a 42-day reproduction experiment.

Poor elimination rates in waste water treatment plants lead to continuous emission of deoxynivalenol into the aquatic environment.

Deoxynivalenol (DON) is one of the most prominent mycotoxins generated by fungi of the generus Fusarium on crops. Its presence in surface waters was recently demonstrated. Here, we elucidate the occurrence and behaviour of DON in three Swiss waste water treatment plants (WWTP) as a result of human consumption and excretion.

Occurrence and origin of estrogenic isoflavones in Swiss river waters.

We report results from a systematic one-and-a-half year survey of the estrogenic isoflavones formononetin (FOR), biochanin A (BIO), daidzein (DAI), genistein (GEN), and equol in Swiss midland rivers. FOR was detected in about 90%, the other compounds in 13-56% of the weekly and fortnightly integrated flow proportional samples. Concentrations were mostly in the lower ng/L-range, with a maximum of 524 ng/L and 217 ng/L for equol and FOR, respectively.