Multi-residue determination of biocides in dairy products and slurry feed using QuEChERS extraction and liquid chromatography combined with high resolution mass spectrometry (LC-ESI-QOrbitrap™-MS).

Given that the determination of biocides in food and feed is currently not routinely done, more information on these compounds is useful for consumer's safety. This work describes a sensitive and reliable method for quantitative analysis of a wide range of biocides in dairy products and slurry feed. The method comprises acetate-buffered QuEChERS extraction without clean-up. Analyses were performed by LC-Q-Orbitrap™-MS and a full-scan acquisition event without fragmentation was followed by five fragmentation events (data-independent acquisition-DIA). The quantitative validation was performed according to SANTE/11312/2021 at 10, 50 and 200 ng g-1 spiking levels, and the results showed that the vast majority of the compounds met the criteria for trueness and precision. The LOQ was 10 ng g-1 for the majority of biocides depending on the matrix. The method was successfully applied to quantify biocides in dairy products and feed.

Hidden risk of terrestrial food chain contamination from organochlorine insecticides in a vegetable cultivation area of Northwest Bangladesh.

Organochlorine insecticide (OCI) exposures in terrestrial food chains from historical or current applications were studied in a vegetable production area in northwest Bangladesh. A total of 57 subsoil, 57 topsoil, and 57 vegetable samples, as well as 30 cow's milk samples, were collected from 57 farms. Multiple OCI residues were detected using GC-MS/MS with modified QuEChERS in 20 % of subsoils, 21 % of topsoils, 23 % of vegetables, and 7 % of cow's milk samples. Diversified OCI residues were detected in subsoils (17 residues with a concentration of 179.15 ± 148.61 µg kg-1) rather than in topsoils (3 DDT residues with a concentration of 25.76 ± 20.19 µg kg-1). Isomeric ratios indicate intensive historical applications of OCIs. According to Dutch and Chinese standards, the lower concentrations of individual OCI residues in the soil indicate negligible to slight soil pollution, assuming local farmers follow local pesticide use regulations. However, a maximum of 78.24 µg kg-1 ΣAldrines and 35.57 µg kg-1 ΣHCHs were detected (1-4 residues) in 60 % of brinjal, 28 % of cucumber, 29 % of sponge gourd, and 20 % of lady's finger samples, which could be a result of either historical or current OCI applications, or both. A strong positive correlation between aldrines in subsoils and cucurbit vegetables indicates greater bioaccumulation. Cow milk samples contained up to 6.96 µg kg-1 ΣDDTs, which resulted either from rationing contaminated vegetables or grazing on contaminated land. Individual OCI in both vegetables and cow's milk was below the respective maximum residue limits of US and FAO/WHO CODEX and poses little or no risk to human health. However, combined exposure to multiple pesticides could increase human health risks. A cumulative health risk assessment of multiple pesticide residues is suggested to assess the suitability of those soils for cultivation and grazing, as well as the safety of vegetables and cow's milk for human consumption.

Effects of pyrethroid and organophosphate insecticides on reared black soldier fly larvae (Hermetia illucens).

Black soldier fly larvae (Hermetia illucens) receive growing interest as a potential alternative animal feed source. These insects may be exposed to insecticide residues in the rearing substrate. This study aimed to investigate the effects of six different pyrethroid and organophosphate insecticides on this insect species' performance. The toxicity of two "model" substances for each of these classes (cypermethrin; pirimiphos-methyl) was quantified, with and without the synergist piperonyl butoxide (PBO). Critical effect doses corresponding to 10% yield (CED10) for cypermethrin (0.4 mg/kg) and pirimiphos-methyl (4.8 mg/kg) were determined. The addition of PBO to cypermethrin enhanced its relative potency with a factor 2.6. These data were compared against the relative toxicity of two analogue substances in each class (permethrin, deltamethrin; chlorpyrifos-methyl, malathion). Results suggest that exposure to concentrations complying with legal limits can cause significant reductions in yield. Exposure to multiple substances at lower concentrations resulted in negative additive and synergistic effects. Of the tested substances, deltamethrin was most toxic, causing 94% yield at 0.5 mg/kg. Analytical results suggested that transfer of tested substances to the larval biomass was substance- and concentration-specific, but appeared to be correlated to reduced yields and the presence of PBO. Transfer of organophosphates was overall low (<2%), but ranged from 8% to 75% for pyrethroids. Due to very low limits in insect biomass (∼0.01 mg/kg), high transfer may result in noncompliance. It is recommended that rearing companies implement lower contractual thresholds, and that policymakers consider adjusting legally allowed maximum residue levels in insect feed.

Intensive vegetable production under plastic mulch: A field study on soil plastic and pesticide residues and their effects on the soil microbiome.

Intensive agriculture relies on external inputs to reach high productivity and profitability. Plastic mulch, mainly in the form of Low-Density Polyethylene (LDPE), is widely used in agriculture to decrease evaporation, increase soil temperature and prevent weeds. The incomplete removal of LDPE mulch after use causes plastic contamination in agricultural soils. In conventional agriculture, the use of pesticides also leaves residues accumulating in soils. Thus, the objective of this study was to measure plastic and pesticide residues in agricultural soils and their effects on the soil microbiome. For this, we sampled soil (0-10 cm and 10-30 cm) from 18 parcels from 6 vegetable farms in SE Spain. The farms were under either organic or conventional management, where plastic mulch had been used for >25 years. We measured the macro- and micro-light density plastic debris contents, the pesticide residue levels, and a range of physiochemical properties. We also carried out DNA sequencing on the soil fungal and bacterial communities. Plastic debris (>100 µm) was found in all samples with an average number of 2 × 103 particles kg-1 and area of 60 cm2 kg-1. We found 4-10 different pesticide residues in all conventional soils, for an average of 140 µg kg-1. Overall, pesticide content was ∼100 times lower in organic farms. The soil microbiomes were farm-specific and related to different soil physicochemical parameters and contaminants. Regarding contaminants, bacterial communities responded to the total pesticide residues, the fungicide Azoxystrobin and the insecticide Chlorantraniliprole as well as the plastic area. The fungicide Boscalid was the only contaminant to influence the fungal community. The wide spread of plastic and pesticide residues in agricultural soil and their effects on soil microbial communities may impact crop production and other environmental services. More studies are required to evaluate the total costs of intensive agriculture.

Multilaboratory Collaborative Study of a Nontarget Data Acquisition for Target Analysis (nDATA) Workflow Using Liquid Chromatography-High-Resolution Accurate Mass Spectrometry for Pesticide Screening in Fruits and Vegetables.

Nontarget data acquisition for target analysis (nDATA) workflows using liquid chromatography-high-resolution accurate mass (LC-HRAM) spectrometry, spectral screening software, and a compound database have generated interest because of their potential for screening of pesticides in foods. However, these procedures and particularly the instrument processing software need to be thoroughly evaluated before implementation in routine analysis. In this work, 25 laboratories participated in a collaborative study to evaluate an nDATA workflow on high moisture produce (apple, banana, broccoli, carrot, grape, lettuce, orange, potato, strawberry, and tomato). Samples were extracted in each laboratory by quick, easy, cheap, effective, rugged, and safe (QuEChERS), and data were acquired by ultrahigh-performance liquid chromatography (UHPLC) coupled to a high-resolution quadrupole Orbitrap (QOrbitrap) or quadrupole time-of-flight (QTOF) mass spectrometer operating in full-scan mass spectrometry (MS) data-independent tandem mass spectrometry (LC-FS MS/DIA MS/MS) acquisition mode. The nDATA workflow was evaluated using a restricted compound database with 51 pesticides and vendor processing software. Pesticide identifications were determined by retention time (tR, ±0.5 min relative to the reference retention times used in the compound database) and mass errors (δM) of the precursor (RTP, δM ≤ ±5 ppm) and product ions (RTPI, δM ≤ ±10 ppm). The elution profiles of all 51 pesticides were within ±0.5 min among 24 of the participating laboratories. Successful screening was determined by false positive and false negative rates of <5% in unfortified (pesticide-free) and fortified (10 and 100 µg/kg) produce matrices. Pesticide responses were dependent on the pesticide, matrix, and instrument. The false negative rates were 0.7 and 0.1% at 10 and 100 µg/kg, respectively, and the false positive rate was 1.1% from results of the participating LC-HRAM platforms. Further evaluation was achieved by providing produce samples spiked with pesticides at concentrations blinded to the laboratories. Twenty-two of the 25 laboratories were successful in identifying all fortified pesticides (0-7 pesticides ranging from 5 to 50 µg/kg) for each produce sample (99.7% detection rate). These studies provide convincing evidence that the nDATA comprehensive approach broadens the screening capabilities of pesticide analyses and provide a platform with the potential to be easily extended to a larger number of other chemical residues and contaminants in foods.

Cocktails of pesticide residues in conventional and organic farming systems in Europe - Legacy of the past and turning point for the future.

Considering that pesticides have been used in Europe for over 70 years, a system for monitoring pesticide residues in EU soils and their effects on soil health is long overdue. In an attempt to address this problem, we tested 340 EU agricultural topsoil samples for multiple pesticide residues. These samples originated from 4 representative EU case study sites (CSS), which covered 3 countries and four of the main EU crops: vegetable and orange production in Spain (S-V and S-O, respectively), grape production in Portugal (P-G), and potato production in the Netherlands (N-P). Soil samples were collected between 2015 and 2018 after harvest or before the start of the growing season, depending on the CSS. Conventional and organic farming results were compared in S-V, S-O and N-P. Soils from conventional farms presented mostly mixtures of pesticide residues, with a maximum of 16 residues/sample. Soils from organic farms had significantly fewer residues, with a maximum of 5 residues/sample. The residues with the highest frequency of detection and the highest content in soil were herbicides: glyphosate and its main metabolite AMPA (P-G, N-P, S-O), and pendimethalin (S-V). Total residue content in soil reached values of 0.8 mg kg-1 for S-V, 2 mg kg-1 for S-O and N-P, and 12 mg kg-1 for P-G. Organic soils presented 70-90% lower residue concentrations than the corresponding conventional soils. There is a severe knowledge gap concerning the effects of the accumulated and complex mixtures of pesticide residues found in soil on soil biota and soil health. Safety benchmarks should be defined and introduced into (soil) legislation as soon as possible. Furthermore, the process of transitioning to organic farming should take into consideration the residue mixtures at the conversion time and their residence time in soil.

Organophosphate and carbamate pesticide residues and accompanying risks in commonly consumed vegetables in Kenya.

The current study was conducted to assess the levels of organophosphates and carbamates in vegetables in Kenya and to examine potential consumer health risks. A total of 90 samples were analysed by liquid chromatography/high-resolution tandem mass spectrometry. Residues of acephate, chlorpyrifos, methamidophos, omethoate and profenofos were found in 22% of the samples, ranging from 10 to 1343 µg/kg. The EU MRL was exceeded in 21%, 10%, 8% and 22% of the samples of French beans, kales, spinach and tomatoes, respectively. Chlorpyrifos in spinach had an acute HQ of 3.3 and 2.2 for children and adults, respectively, implying that potential health risks with respect to acute dietary exposure cannot be excluded. For chronic dietary exposure, all chronic HQs were below 1. The HI for the pesticides was 0.54 and 0.34 for children and adults. Routine monitoring of OPs and carbamates in vegetables is recommended to minimise consumer's health risks.

A laboratory comparison of the interactions between three plastic mulch types and 38 active substances found in pesticides.

BACKGROUND: In semi-arid regions, the use of plastic mulch and pesticides in conventional agriculture is nearly ubiquitous. Although the sorption of pesticides on Low Density Polyethylene (LDPE) has been previously studied, no data are available for other plastics such as Pro-oxidant Additive Containing (PAC) plastics or "biodegradable" (Bio) plastics. The aim of this research was to measure the sorption pattern of active substances from pesticides on LDPE, PAC and Bio plastic mulches and to compare the decay of the active substances in the presence and absence of plastic debris. METHODS: For this purpose, 38 active substances from 17 insecticides, 15 fungicides and six herbicides commonly applied with plastic mulching in South-east Spain were incubated with a 3 × 3 cm2 piece of plastic mulch (LDPE, PAC and Bio). The incubation was done in a solution of 10% acetonitrile and 90% distilled water at 35 °C for 15 days in the dark. The Quick Easy Cheap Effective Rugged Safe approach was adapted to extract the pesticides. RESULTS: The sorption behavior depended on both the pesticide and the plastic mulch type. On average, the sorption percentage was ~23% on LDPE and PAC and ~50% on Bio. The decay of active substances in the presence of plastic was ~30% lesser than the decay of active substances in solution alone. This study is the first attempt at assessing the behavior of a diversity of plastic mulches and pesticides to further define research needs.

Pesticide residues in Nepalese vegetables and potential health risks.

We conducted this study in order to assess the pesticide residues in vegetables and examine the related human health risk. Therefore, residues of 23 pesticides (organophosphates, organochlorines, acaricides, fungicides, and insecticides of biological origin) were analysed in the three main vegetable crops grown in Southern Nepal: 27 eggplant, 27 chilli and 32 tomato samples representing (i) conventional (N = 67) and ii) integrated pest management (IPM) fields (N = 19). Pesticide residues were found in 93% of the eggplant samples and in all of the chilli and tomato samples. Multiple residues were observed in 56% of the eggplant samples, 96% of chilli samples and all of the tomato samples. The range (µg/kg) of total detected pesticide residues in eggplants, chillies and tomatoes was 1.71-231, 4.97-507, 13.1-3465, respectively. The most frequently detected pesticides in these vegetables were carbendazim and chloropyrifos. Pesticide residues in 4% of the eggplant, 44% of the tomato and 19% of the chilli samples exceeded the EU maximum residue limits (MRLs). The residues of triazophos, omethoate, chloropyrifos and carbendazim exceeded the EU MRLs. Compared to chilli and eggplant crops, more carbendazim was sprayed onto tomato crops (p < 0.05). We assessed adolescent and adult dietary exposure using hazard quotient (HQ) and hazard index (HI) equations for the identified pesticides. HQ> 1 was observed for chloropyrifos, triazophos and carbendazim in eggplants; profenofos, triazophos, dimethoate, omethoate, chloropyrifos and carbendazim in tomatoes; and dichlorvos and chloropyrifos in chillies. Of all of the HQs, the highest acute HQ (aHQ) was for triazophos (tomato) in adolescents (aHQ=657) and adults (aHQ=677), showing the highest risks of dietary exposure. The cumulative dietary exposure showed a higher HI for organophosphates (HI>83) and a lower HI for organochlorines, acaricides and biological insecticides (HI<1). The concentration of pesticide residues in the vegetable crops from the IPM field was considerably lower, suggesting a greater ability of IPM systems to reduce the dietary risks from exposure to pesticides.

Pesticide residues in European agricultural soils - A hidden reality unfolded.

Pesticide use is a major foundation of the agricultural intensification observed over the last few decades. As a result, soil contamination by pesticide residues has become an issue of increasing concern due to some pesticides' high soil persistence and toxicity to non-target species. In this study, the distribution of 76 pesticide residues was evaluated in 317 agricultural topsoil samples from across the European Union. The soils were collected in 2015 and originated from 11 EU Member States and 6 main cropping systems. Over 80% of the tested soils contained pesticide residues (25% of samples had 1 residue, 58% of samples had mixtures of two or more residues), in a total of 166 different pesticide combinations. Glyphosate and its metabolite AMPA, DDTs (DDT and its metabolites) and the broad-spectrum fungicides boscalid, epoxiconazole and tebuconazole were the compounds most frequently found in soil samples and the compounds found at the highest concentrations. These compounds occasionally exceeded their predicted environmental concentrations in soil but were below the respective toxic endpoints for standard in-soil organisms. Maximum individual pesticide content assessed in a soil sample was 2.05 mg kg-1 while maximum total pesticide content was 2.87 mg kg-1. This study reveals that the presence of mixtures of pesticide residues in soils are the rule rather than the exception, indicating that environmental risk assessment procedures should be adapted accordingly to minimize related risks to soil life and beyond. This information can be used to implement monitoring programs for pesticide residues in soil and to trigger toxicity assessments of mixtures of pesticide residues on a wider range of soil species in order to perform more comprehensive and accurate risk assessments.

Influence of microplastic addition on glyphosate decay and soil microbial activities in Chinese loess soil.

The intensive use of pesticide and plastic mulches has considerably enhanced crop growth and yield. Pesticide residues and plastic debris, however, have caused serious environmental problems. This study investigated the effects of the commonly used herbicide glyphosate and micrometre-sized plastic debris, referred as microplastics, on glyphosate decay and soil microbial activities in Chinese loess soil by a microcosm experiment over 30 days incubation. Results showed that glyphosate decay was gradual and followed a single first-order decay kinetics model. In different treatments (with/without microplastic addition), glyphosate showed similar half-lives (32.8 days). The soil content of aminomethylphosphonic acid (AMPA), the main metabolite of glyphosate, steadily increased without reaching plateau and declining phases throughout the experiment. Soil microbial respiration significantly changed throughout the entirety of the experiment, particularly in the treatments with higher microplastic addition. The dynamics of soil ß-glucosidase, urease and phosphatase varied, especially in the treatments with high microplastic addition. Particles that were considerably smaller than the initially added microplastic particles were observed after 30 days incubation. This result thus implied that microplastic would hardly affect glyphosate decay but smaller plastic particles accumulated in soils which potentially threaten soil quality would be further concerned especially in the regions with intensive plastic mulching application.

Persistence of glyphosate and aminomethylphosphonic acid in loess soil under different combinations of temperature, soil moisture and light/darkness.

The dissipation kinetics of glyphosate and its metabolite aminomethylphosphonic acid (AMPA) were studied in loess soil, under biotic and abiotic conditions, as affected by temperature, soil moisture (SM) and light/darkness. Nonsterile and sterile soil samples were spiked with 16mgkg-1 of glyphosate, subjected to three SM contents (20% WHC, 60% WHC, saturation), and incubated for 30days at 5°C and 30°C, under dark and light regimes. Glyphosate and AMPA dissipation kinetics were fit to single-first-order (SFO) or first-order-multicompartment (FOMC) models, per treatment combination. AMPA kinetic model included both the formation and decline phases. Glyphosate dissipation kinetics followed SFO at 5°C, but FOMC at 30°C. AMPA followed SFO dissipation kinetics for all treatments. Glyphosate and AMPA dissipation occurred mostly by microbial activity. Abiotic processes played a negligible role for both compounds. Under biotic conditions, glyphosate dissipation and AMPA formation/dissipation were primarily affected by temperature, but also by SM. Light regimes didn't play a significant role. Glyphosate DT50 varied between 1.5 and 53.5days, while its DT90 varied between 8.0 and 280days, depending on the treatment. AMPA persisted longer in soil than glyphosate, with its DT50 at 30°C ranging between 26.4 and 44.5days, and its DT90 between 87.8 and 148days. The shortest DT50/DT90 values for both compounds occurred at 30°C and under optimal/saturated moisture conditions, while the largest occurred at 5°C and reaching drought stress conditions. Based on these results, we conclude that glyphosate and AMPA dissipate rapidly under warm and rainy climate conditions. However, repeated glyphosate applications in fallows or winter crops in countries where cold and dry winters normally occur could lead to on-site soil pollution, with consequent potential risks to the environment and human health. To our knowledge, this study is the first evaluating the combined effect of temperature, soil moisture and light/dark conditions on AMPA formation/dissipation kinetics and behaviour.

Evaluation of gas chromatography - electron ionization - full scan high resolution Orbitrap mass spectrometry for pesticide residue analysis.

Gas chromatography with electron ionization and full scan high resolution mass spectrometry with an Orbitrap mass analyzer (GC-EI-full scan Orbitrap HRMS) was evaluated for residue analysis. Pesticides in fruit and vegetables were taken as an example application. The relevant aspects for GC-MS based residue analysis, including the resolving power (15,000 to 120,000 FWHM at m/z 200), scan rate, dynamic range, selectivity, sensitivity, analyte identification, and utility of existing EI-libraries, are assessed and discussed in detail. The optimum acquisition conditions in full scan mode (m/z 50-500) were a resolving power of 60,000 and an automatic-gain-control target value of 3E6. These conditions provided (i) an optimum mass accuracy: within 2 ppm over a wide concentration range, with/without matrix, enabling the use of ±5 ppm mass extraction windows (ii) adequate scan speed: minimum 12 scans/peak, (iii) an intra-scan dynamic range sufficient to achieve LOD/LOQs ≤0.5 pg in fruit/vegetable matrices (corresponding to ≤0.5 µg kg(-1)) for most pesticides. EI-Orbitrap spectra were consistent over a very wide concentration range (5 orders) with good match values against NIST (EI-quadrupole) spectra. The applicability for quantitative residue analysis was verified by validation of 54 pesticides in three matrices (tomato, leek, orange) at 10 and 50 µg/kg. The method involved a QuEChERS-based extraction with a solvent switch into iso-octane, and 1 µL hot splitless injection into the GC-HRMS system. A recovery between 70 and 120% and a repeatability RSD <10% was obtained in most cases. Linearity was demonstrated for the range ≤5-250 µg kg(-1). The pesticides could be identified according to the applicable EU criteria for GC-HRMS (SANTE/11945/2015). GC-EI-full scan Orbitrap HRMS was found to be highly suited for quantitative pesticide residue analysis. The potential of qualitative screening to extend the scope makes it an attractive alternative to GC-triple quadrupole MS.

Application of Fragment Ion Information as Further Evidence in Probabilistic Compound Screening Using Bayesian Statistics and Machine Learning: A Leap Toward Automation.

In this work, we introduce an automated, efficient, and elegant model to combine all pieces of evidence (e.g., expected retention times, peak shapes, isotope distributions, fragment-to-parent ratio) obtained from liquid chromatography-tandem mass spectrometry (LC-MS/MS/MS) data for screening purposes. Combining all these pieces of evidence requires a careful assessment of the uncertainties in the analytical system as well as all possible outcomes. To-date, the majority of the existing algorithms are highly dependent on user input parameters. Additionally, the screening process is tackled as a deterministic problem. In this work we present a Bayesian framework to deal with the combination of all these pieces of evidence. Contrary to conventional algorithms, the information is treated in a probabilistic way, and a final probability assessment of the presence/absence of a compound feature is computed. Additionally, all the necessary parameters except the chromatographic band broadening for the method are learned from the data in training and learning phase of the algorithm, avoiding the introduction of a large number of user-defined parameters. The proposed method was validated with a large data set and has shown improved sensitivity and specificity in comparison to a threshold-based commercial software package.

Determination of Glyphosate Levels in Breast Milk Samples from Germany by LC-MS/MS and GC-MS/MS.

This study describes the validation and application of two independent analytical methods for the determination of glyphosate in breast milk. They are based on liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatography-tandem mass spectrometry (GC-MS/MS), respectively. For LC-MS/MS, sample preparation involved an ultrafiltration followed by chromatography on an anion exchange column. The analysis by GC-MS/MS involved an extraction step, cleanup on a cation exchange column, and derivatization with heptafluorobutanol and trifluoroacetic acid anhydride. Both methods were newly developed for breast milk and are able to quantify glyphosate residues at concentrations as low as 1 ng/mL. The methods were applied to quantify glyphosate levels in 114 breast milk samples, which had been collected from August to September of 2015 in Germany. The mothers participated at their own request and thus do not form a representative sample. In none of the investigated samples were glyphosate residues above the limit of detection found.

Simultaneous quantitative determination, identification and qualitative screening of pesticides in fruits and vegetables using LC-Q-Orbitrap™-MS.

A method based on QuEChERS extraction and LC-quadrupole-Orbitrap™ MS detection was established utilising an improved fully non-targeted way of data acquisition with and without fragmentation. A full-scan acquisition event without fragmentation (resolving power 70,000) was followed by five consecutive fragmentation events (variable data independent acquisition - vDIA; resolving power 35,000) where all ions from the full-scan range are fragmented. Compared with fragmentation in a single event (all-ion fragmentation - AIF), this improves both selectivity and sensitivity for the fragment ions, which is beneficial for screening performance and identification capability. The method was validated, using the data from the same measurements, for two types of analysis: quantitation/identification and qualitative screening. The quantitative validation, performed according to the guidelines in SANCO/12571/2013, tested the performance of the method for 184 compounds in lettuce and orange at two spiking levels: 10 and 50 ng g(-1). The validation showed that the vast majority of the compounds met the criteria for trueness and precision set in the SANCO guidance document. In the qualitative validation the same 184 compounds were used to test the untargeted screening capabilities of the method. In this validation the compounds were spiked at three levels into 11 different fruit and vegetable matrices, which were measured twice on separate days. Taking all data from the qualitative validation together, an overall detection rate of 92% was achieved at the 10 ng g(-1) level, increasing to 98% at 200 ng g(-1). A screening detection limit (as defined in the SANCO guidelines) of 10 ng g(-1) could be achieved for 134 compounds. For 39 and two pesticides the SDL was 50 and 200 ng g(-1), respectively. For the other nine compounds no SDL could be established. The identification (ion ratio) criteria as recommended in the SANCO document could be met for 93% of the detected pesticide/matrix/concentration combinations. The outcome of both validations shows that the described method can be used to combine quantitative analysis and the identification of frequently detected pesticides (so far typically done using triple quadrupole MS/MS) with a qualitative screening to be used for a wide range of less frequent detected compounds in one measurement.

High gain hybrid graphene-organic semiconductor phototransistors.

Hybrid phototransistors of graphene and the organic semiconductor poly(3-hexylthiophene-2,5-diyl) (P3HT) are presented. Two types of phototransistors are demonstrated with a charge carrier transit time that differs by more than 6 orders of magnitude. High transit time devices are fabricated using a photoresist-free recipe to create large-area graphene transistors made out of graphene grown by chemical vapor deposition. Low transit time devices are fabricated out of mechanically exfoliated graphene on top of mechanically exfoliated hexagonal boron nitride using standard e-beam lithography. Responsivities exceeding 10(5) A/W are obtained for the low transit time devices.

Identification in residue analysis based on liquid chromatography with tandem mass spectrometry: Experimental evidence to update performance criteria.

Liquid chromatography-tandem mass spectrometry (LC-MS/MS) is one of the most widely used techniques for identification (and quantification) of residues and contaminants across a number of different chemical domains. Although the same analytical technique is used, the parameters and criteria for identification vary depending on where in the world the analysis is performed and for what purpose (e.g. determination of pesticides, veterinary drugs, forensic toxicology, sports doping). The rationale for these differences is not clear and in most cases the criteria are essentially based on expert opinions rather than underpinned by experimental data. In the current study, the variability of the two key identification parameters, retention time and ion ratio, was assessed and compared against requirements set out in different legal and guidance documents. The study involved the analysis of 120 pesticides, representing various chemical classes, polarities, molecular weights, and detector response factors, in 21 different fruit and vegetable matrices of varying degrees of complexity. The samples were analysed non-fortified, and fortified at 10, 50 and 200 µg kg(-1), in five laboratories using different LC-MS/MS instruments and conditions. In total, over 135,000 extracted-ion chromatograms were manually verified to provide an extensive data set for the assessment. The experimental data do not support relative tolerances for retention time, or different tolerances for ion ratios depending on relative abundance of the two product ions measured. Retention times in today's chromatographic systems are sufficiently stable to justify an absolute tolerance of ±0.1 min. Ion ratios are stable as long as sufficient response is obtained for both product ions. Ion ratio deviations are typically within ±20% (relative), and within ±45% (relative) in case the response of product ions are close to the limit of detection. Ion ratio tolerances up to 50% did not result in false positives and reduced the false negative rate for pesticides with product ions in the low S/N range to <5%. Without ion ratio criterion, two false positives were obtained in 105 non-fortified samples. Although the study has been conducted for pesticides residues in fruits and vegetables, the impact of these findings is believed to extend towards other application areas and possibly support adjustment or consolidation of criteria across other analytical domains.

Development and validation of a confirmative LC-MS/MS method for the determination of ß-exotoxin thuringiensin in plant protection products and selected greenhouse crops.

Bacterial products based on Bacillus thuringiensis are registered in many countries as plant protection products (PPPs) and are widely used as insecticides and nematocides. However, certain B. thuringiensis strains produce harmful toxins and are therefore not allowed to be used as PPPs. The serotype B. thuringiensis thuringiensis produces the beta-exotoxin thuringiensin (ßeT) which is considered to be toxic for almost all forms of life including humans (WHO 1999). The use of a non-registered PPP based on B. thuringiensis thuringiensis called bitoxybacillin was established through the determination of ßeT. First, an analytical reference standard of ßeT was characterized by nuclear magnetic resonance, liquid chromatography-high-resolution mass spectrometry and liquid chromatography-tandem mass spectrometry (LC-MS/MS). Then, a confirmatory quantitative method for the determination of ßeT in PPPs and selected greenhouse crops based on LC-MS/MS was developed and validated. A limit of quantitation of 0.028 mg/kg was established, and average recoveries ranged from 85.6 % to 104.8 % with repeatability (RSDr) of 1.5-7.7 % and within-lab reproducibility (RSD(WLR)) of 17 %. The method was used for analysis of >100 samples. ßeT was found in leaves of ornamentals, but no evidence was found for use in edible crops.

Qualitative aspects and validation of a screening method for pesticides in vegetables and fruits based on liquid chromatography coupled to full scan high resolution (Orbitrap) mass spectrometry.

The analytical capabilities of liquid chromatography with single-stage high-resolution mass spectrometry have been investigated with emphasis on qualitative aspects related to selective detection during screening and to identification. The study involved 21 different vegetable and fruit commodities, a screening database of 556 pesticides for evaluation of false positives, and a test set of 130 pesticides spiked to the commodities at 0.01, 0.05, and 0.20 mg/kg for evaluation of false negatives. The final method involved a QuEChERS-based sample preparation (without dSPE clean up) and full scan acquisition using alternating scan events without/with fragmentation, at a resolving power of 50,000. Analyte detection was based on extraction of the exact mass (±5 ppm) of the major adduct ion at the database retention time ±30 s and the presence of a second diagnostic ion. Various options for the additional ion were investigated and compared (other adduct ions, M + 1 or M + 2 isotopes, fragments). The two-ion approach for selective detection of the pesticides in the full scan data was compared with two alternative approaches based on response thresholds. Using the two-ion approach, the number of false positives out of 11,676 pesticide/commodity combinations targeted was 36 (0.3 %). The percentage of false negatives, assessed for 2,730 pesticide/commodity combinations, was 13 %, 3 %, and 1 % at the 0.01-, 0.05-, and 0.20-mg/kg level, respectively (slightly higher with fully automated detection). Following the SANCO/12495/2011 protocol for validation of screening methods, the screening detection limit was determined for 130 pesticides and found to be 0.01, 0.05, and ≥0.20 mg/kg for 86, 30, and 14 pesticides, respectively. For the detected pesticides in the spiked samples, the ability for unambiguous identification according to EU criteria was evaluated. A proposal for adaption of the criteria was made.