Multi-residue method for the analysis of pesticides in Arabica coffee using liquid chromatography/tandem mass spectrometry

Coffee is a major tropical agricultural commodity and represents a significant fraction of the economy of many countries. However, certain plant and animal species can damage coffee crops, affecting trade. A solution to this issue is the use of pesticides, some of which are harmful to human health and the environment. This work consisted of the development of a multi-residue method for the analysis of pesticides in coffee by using LC-MS/MS. The QuEChERS extraction procedure was used. The following analytical parameters were optimised: selectivity, analytical range, linearity, LOD, LOQ, precision (RSD%) and recovery of the method. The results showed that the method is selective, as they were linear in the range of 10.0–100.0 µg kg^?1. The sensitivity, recovery and precision were adequate for the multi-residue analysis of pesticides in coffee. The method was applied to the analyses of 15 Brazilian coffee samples.     

Depletion of metronidazole in brook trout (Salvelinus fontinalis)

Metronidazole (MNZ), which is effective in the treatment of intestinal infections in fish, is also a suspected carcinogen and has been banned in numerous jurisdictions for use in any food-producing animal, including fish. Few reports have been published on the depletion of MNZ in fish. A depletion study was therefore undertaken using MNZ in feed provided to trout under controlled conditions. The water was maintained at 17.5 ± 0.9°C throughout the medication and depletion periods in the study. Following a 20-day acclimatisation period in the holding tanks, the trout (approximately 150–200 g bodyweight at the start of the study) were subjected to two separate medication and withdrawal periods: (A) 5 day medication/5 day withdrawal and (B) 5 day medication/16 day withdrawal. This simulated a potential multiple dosing in an aquaculture setting. In both medication periods, the trout were dosed with medicated feed containing 3 g MNZ kg^–1 fish. Fish were sacrificed in accordance with accepted animal care protocols and tissue samples were analysed by UPLC-MS/MS. Analyte concentrations in trout muscle ranged from a high of 27 000 ± 10 000 ng g^–1 for MNZ and 830 ± 570 ng g^–1 for MNZ-OH on day 1 of withdrawal period A to a low of 1.8 ± 2.3 ng g^–1 for MNZ and < 0.4 ng g^–1 for MNZ-OH on day 16 of withdrawal period B. The results demonstrate that when using the UPLC-MS/MS method, residues of MNZ may be detected in fish treated with MNZ after 16 days of withdrawal.     

6-Iso-chlortetracycline or keto form of chlortetracycline? Need for clarification for relevant monitoring of chlortetracycline residues in food

Chlortetracycline (CTC) is a broad-spectrum antibiotic used in veterinary medicine for pulmonary or digestive infections and having a regulatory maximum residue limit (MRL) necessitating an official analytical control method. The purpose of this study was to clarify the identification of different forms of CTC observed in standard solution, in spiked muscle samples and in naturally incurred muscle samples of pigs analysed by LC-MS/MS and to demonstrate the in vivo formation of 6-iso-chlortetracycline and 4-epi-6-iso-CTC as a metabolite of CTC and 4-epi-CTC in muscle. The six following forms were identified, all being isobaric with a protonated molecule at m/z 479 (precursor ion): the keto-enol forms of CTC and the keto-enol forms of 4-epi-chlortetracycline (4-epi-CTC), 6-iso-chlortetracycline (6-iso-CTC) and 4-epi-6-iso-chlortetracycline (4-epi-6-iso-CTC). The 6-iso-CTC and 4-epi-6-iso-CTC were observed only in incurred pig samples so were identified for the first time as metabolites of CTC and 4-epi-CTC. Identification of the different forms was obtained by comparing incurred muscle samples with standard solutions and with spiked samples. Then the differences between the features of the chromatograms obtained by LC-TQ-MS and the fragmentation study of the different forms of CTC obtained by LC-Q-TOF-MS helped us to support this identification. The extraction steps and the LC-MS/MS conditions developed to analyse muscle tissue samples are described. This clarification concerning the rigorous identification of chromatographic peaks allowed us to evaluate the relevance of our monitoring method with regard to the regulations in place in the European Union and could be of help to laboratories involved in official control of antibiotic residues in food of animal origin. Additional results are also presented highlighting the transformation of the CTC when prepared in a mixture with other antibiotics.     

Novel approach to fast determination of multiple pesticide residues using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)

A rapid, high-throughput method employing ultra-performance liquid chromatography with tandem quadrupole mass spectrometry (UPLC-MS/MS) was developed and optimized for simultaneous quantification and confirmation of 64 pesticide residues and their toxic metabolites in fruit extracts prepared by a buffered QuEChERS procedure. The total time required for UPLC-MS/MS analysis was 8 min plus 2 min for re-equilibration to the initial UPLC conditions. Performance characteristics were determined for apple extracts spiked at 10 µg kg^?1. The repeatability of measurements expressed as relative standard deviations was in the range 1.5–13% at this level for most analytes. Thanks to very low limits of quantification (<10 µg kg^?1for the majority of pesticides), an optimized method allows for the reliable control of not only common maximum residue limits (MRLs) set by European Union regulation for various pesticides/fruit combinations, but also of a uniform MRL of 10 µg kg^?1endorsed for baby food.     

Residue depletion of sulfachlorpyrazine in edible tissues of broiler chickens

The residue depletion profile of sulfachlorpyrazine was studied in healthy broilers after oral administration of Sulfatyf®, given at a dose of 50?mg sulfachlorpyrazine (SCP) per kg body weight once daily for 3 consecutive days. Twenty-five medicated broilers were slaughtered on the 5th, 10th, 14th and 16th day of post-medication, and muscle, fat with skin, liver and kidney tissues were sampled and analysed using an high-performance liquid chromatography (HPLC) method with satisfactory recovery (74.5%?±?2.9%) and specificity. The estimated values of LOD and LOQ were 18.40 and 55.70?ng?ml^?1, respectively. On the 5th and 10th day of post-medication, the concentrations of SCP residue in all samples examined were higher than the corresponding MRLs established by the European Union and the highest SCP concentrations were measured in muscle. A maximum withdrawal time of 14 days was calculated to ensure consumer safety.     

Job demands and pesticide exposure among immigrant Latino farmworkers.

The goal of this study was to understand the potential threat of job stressors to farmworker health. To accomplish this goal we studied pesticide exposure, an issue with immediate and long-term health consequences, and predictions from the Demands-Control model of occupational stress. Longitudinal, self-report data and urine samples were collected at monthly intervals from a cohort of Latino farmworkers (N = 287) during the 2007 agricultural season. The primary hypothesis was that greater exposure to psychological demands, physical exertion, and hazardous work conditions are associated with greater odds of detecting dialkylphosphate (DAP) urinary pesticide metabolites, biomarkers indicating exposure to pesticides. Contrary to this hypothesis, results indicated that none of the elements of the Demands-Control model were independently associated with detection of DAP urinary pesticide metabolites. However, analyses produced several interaction effects, including evidence that high levels of control may buffer the effects of physical job demands on detection of DAP urinary pesticide metabolites. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

An efficient extraction and clean‐up procedure for pesticide determination in olive oil

This work reports a simple, rapid, and effective extraction method based on liquid–liquid extraction (LLE) followed by matrix solid‐phase dispersion‐sonication for detection, identification and quantification of multiclass pesticides in virgin olive oil using liquid chromatography mass spectrometry (LC‐QTOF‐MS). LLE to extract pesticide residues in virgin olive oil was performed in order to study the centrifugation efficiency to obtain high recovery yield and low co‐extract fat residue in the final extract. Different suitable parameters of MSPD procedure were evaluated, such as nature of dispersing phase, clean‐up adsorbent, and volume of eluting solvent (acetonitrile) in different extraction conditions, with or without sonication. The best results were obtained using 5 g of virgin olive oil, 2 g of PSA as dispersant sorbent, 2 g of Florisil/GCB (70:30 w/w) as clean‐up sorbent, and 15 mL of acetonitrile as eluting solvent under conditions of 15 min ultrasonic bath at RT. Method validation was performed in order to study sensitivity, linearity, precision, and accuracy. Average recoveries ranged between 73.7 and 104.2% with relative SDs 5.3–13.4% at three concentration levels (25, 50, and 100 µg/kg). Detection and quantification limits ranged from 1.5 to 5 µg/kg and 3 to 9 µg/kg, respectively.     

Predictive models of forest logging residues in Romanian spruce and beech forests

Forest logging residues are systematically left after exploitation. In Romania, logging residues were traditionally used by population for fuel but have not been considered at large scale for industrialization. The estimation of the resource needed a more accurate assessment and the development of devoted biomass models for large-scale applications. Our study aims at estimating the amount of logging residues based on direct biomass measurements for the two main species of Romanian Carpathian forests: Norway spruce and beech. A country-scale field measurement campaign resulted in the sampling of 100 Norway spruce and 74 beech trees. Models of logging residues biomass were developed for both species. The amount of potential logging residues per tree was greater in beech than in Norway spruce. The models developed, nonlinear by essence, showed that diameter-based equations enable the evaluation of individual logging residues potential. Using tree height as an additional independent variable did not improve the models. The models fitted were applied to yield tables in order to estimate the resource potential in spruce and beech stands for each productivity class, and its dynamic during the production cycle. The calculations proved that the potential amount of logging residue is larger in spruce stands. The amount in beech is very sensitive to the productivity class, unlike in spruce stands. The potential biomass produced during early thinnings is however greater in beech stands than in spruce ones. A more systematic and organized collecting of residues could offer a fast answer to the need of increasing renewable energy share.     

Analysing the effect of five operational factors on forest residue supply chain costs: A case study in Western Australia

In Australia the use of forest biomass has been developing in recent years and initial efforts are built on adopting and trialling imported European technology. Using a linear programming-based tool, BIOPLAN, this study investigated the impact of five operational factors: energy demand, moisture mass fraction, interest rate, transport distance, and truck payload on total forest residues supply chain cost in Western Australia. The supply chain consisted four phases: extraction of residues from the clear felled area to roadside by forwarders, storage at roadside, chipping of materials by mobile chippers, and transport of chips to an energy plant. For an average monthly energy demand of 5 GWh, the minimum wood supply chain cost was about 29.4 $ t⁻¹, which is lower than the maximum target supply cost of 30–40 $ t⁻¹, reported by many industry stakeholders as the breakeven point for economically viable bioenergy production in Australia. The suggested volume available for chipping in the second year was larger than in the first year indicating that the optimisation model proposed storing more materials in the first year to be chipped in the second year. The sensitivity analysis showed no strong correlation between energy demand and supply chain cost per m³. For higher interest rates, the total storage cost increased which resulted in larger operational cost per m³. Longer transport distances and lower truck payloads resulted in higher transport cost per unit of delivered chips. In addition, the highest supply chain costs occurred when moisture mass fraction ranged between 20% and 30%.     

废弃农林生物质在废水处理中环境友好利用的研究进展

综述近年来国内外利用废弃农林生物质环境友好处理各种废水的现状,重点阐述了废弃农林生物质作为吸附剂对印染、重金属等工业废水的处理以及通过改性手段来提高农林生物质处理效果的研究进展。