Dissipation of spiromesifen and spiromesifen-enol on tomato fruit,tomato leaf,and soil under field and controlled environmental conditions

Dissipation of spiromesifen and its metabolite, spiromesifen-enol, on tomato fruit, tomato leaf, and soil was studied in the open field and controlled environmental conditions. Sample preparation was carried out by QuEChERS method and analysis using LC-MS/MS. Method validation for analysis of the compounds was carried out as per “single laboratory method validation guidelines.” Method validation studies gave satisfactory recoveries for spiromesifen and spiromesifen-enol (71.59–105.3%) with relative standard deviation (RSD) < 20%. LOD and LOQ of the method were 0.0015 μg mL^?1 and 0.005 mg kg^?1, respectively. Spiromesifen residues on tomato fruits were 0.855 and 1.545 mg kg^?1 in open field and 0.976 and 1.670 mg kg^?1 under polyhouse condition, from treatments at the standard and double doses of 125 and 250 g a.i. ha^?1, respectively. On tomato leaves, the residues were 5.64 and 8.226 mg kg^?1 in open field and 6.874 and 10.187 mg kg^?1 in the polyhouse. In soil, the residues were 0.532 and 1.032 mg kg^?1 and 0.486 and 0.925 mg kg^?1 under open field and polyhouse conditions, respectively. The half-life of degradation of spiromesifen on tomato fruit was 6–6.5 days in the open field and 8.1–9.3 days in the polyhouse. On tomato leaves, it was 7–7.6 and 17.6–18.4 days and in soil 5.6–7.4 and 8.4–9.5 days, respectively. Metabolite, spiromesifen-enol, was not detected in any of the sample throughout the study period. Photodegradation could be the major route for dissipation of spiromesifen in the tomato leaves, whereas in the fruits, it may be the combination of photodegradation and dilution due to fruit growth. The results of the study can be utilized for application of spiromesifen in plant protection of tomato crop under protected environmental conditions.     

Residues levels of organochlorine pesticide in cow's milk from industrial farms in Hidalgo,Mexico

A survey was carried out from 2008 to 2010 to determine the concentrations of 16 organochlorine pesticide residues (OPRs) from Tizayuca, Hidalgo, Mexico. Organochlorine residue determinations were made from milk fat, using chromatographic cleanup and analysis by gas chromatography with an electron capture detector. The OPR concentrations found were from below the detection limit (DL) to 0.91 ng g^?1 in 2008, DL to 0.38 ng g^?1 in 2009 and DL to 0.59 ng g^?1 in 2010. In general concentrations of organochlorine pesticides were higher in the wet season (3.37 ng g^?1 and 4.79 ng g^?1) than the dry season (1.92 ng g^?1 and 2.71 ng g^?1) for 2009 and 2010, due to control of pests in the pasture and sheds. According to Codex Alimentarius regulations, individual pesticides did not exceed the permissible limits, which for example were 10 μg kg^?1 for alpha hexachlorocyclohexane (HCH) and endosulfan I, 20 μg kg^?1 for p,p’-DDT, and 6 μg kg^?1 for dieldrin, endrin and heptachlor. A reduction of organochlorine pesticide concentrations in cow's milk was noted, indicating that the Mexican government has achieved reduction or elimination of some organochlorine pesticides in response to global agreements on persistent organic pollutants.     

Easy and fast extraction methods to determine organochlorine pesticides in sewage sludge,soil, and water samples based at low temperature

Organochlorine pesticides present in sewage sludge can contaminate soil and water when they are used as either fertilizer or agricultural soil conditioner. In this study, the technique solid–liquid extraction with low temperature purification was optimized and validated for determination of ten organochlorine pesticides in sewage sludge and soil samples. Liquid–liquid extraction with low temperature purification was also validated for the same compounds in water. Analyses were performed by gas chromatography-mass spectrometry operating in the selective ion monitoring mode. After optimization, the methods showed recoveries between 70% and 115% with relative standard deviation lower than 13% for all target analytes in the three matrices. The linearity was demonstrated in the range of 20 to 70 µg L^?1, 0.5 to 60 µg L^?1, and 3 to 13 µg L^?1, for sludge, soil, and acetonitrile, respectively. The limit of quantification ranged between 2 and 40 µg kg^?1, 1 and 6 µg kg^?1, and 0.5 µg L^?1 for sludge, soil, and water, respectively. The methods were used in the study of pesticide lixiviation carried out in a poly vinyl chlorine column filled with soil, which had its surface layer mixed with sludge. The results showed that pesticides are not leached into soil, part of them is adsorbed by the sewage sludge (4–40%), and most pesticides are lost by volatilization.     

Organochlorine pesticides and polychlorinated biphenyls in soils surrounding the Tanggu Chemical Industrial District of Tianjin, China

The spatial distribution of persistent organic pollutants (POPs) was examined in soils surrounding the Tanggu Chemical Industrial District in Tianjin, China. The concentrations of hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethanes (DDTs), hexachlorobenzenes (HCBs), and polychlorinated biphenyls (PCBs) were determined in 70 surface soils using accelerated solvent extraction and gas chromatography with electron capture detection. The results showed that the ranges of ∑HCH, ∑DDT, ΣHCB, and ∑PCB concentrations in soils were 2.1–12,549 μg?kg^?1 (average, 965 μg?kg^?1), n.d.–2,033 μg?kg^?1 (average, 88.4 μg?kg^?1), n.d.–1,924 μg?kg^?1 (average, 349 μg?kg^?1), and n.d.–373 μg?kg^?1 (average, 46.2 μg?kg^?1), respectively. Of these, HCHs were the dominant POPs, accounting for 75 % of the total organochlorine pesticide (OCP) residues. Overall, the spatial distribution of OCP concentrations showed a decreasing trend from the center of the Tanggu District to the surrounding areas. Two major pollution sources were Tianjin Dagu Chemical Co., Ltd. in the district center and the Tianjin Chemical Plant in Hangu District. In contrast, PCB concentrations were relatively high in the Haihe estuary to the east and low to the west of the study area. Component analysis of OCPs in these soils showed that they mainly came from industrial point sources. Compared with soils in other regions, soil DDT pollution was at a medium level in the Tanggu Chemical Industrial District, but associated HCH, HCB, and PCB pollution was relatively heavy. By multivariate statistical analyses, Tianjin Dagu Chemical Co., Ltd. was recognized as the main source of POPs, and soil properties were clarified to play an important role on the distribution and composition of POPs, especially the organic carbon content.     

Development,validation, and application of a method for the GC-MS analysis of fipronil and three of its degradation products in samples of water,soil, and sediment

A method for the identification and quantification of pesticide residues in water, soil, and sediment samples has been developed, validated, and applied for the analysis of real samples. The specificity was determined by the retention time and the confirmation and quantification of analyte ions. Linearity was demonstrated over the concentration range of 20 to 120 µg L^?1, and the correlation coefficients varied between 0.979 and 0.996, depending on the analytes. The recovery rates for all analytes in the studied matrix were between 86% and 112%. The intermediate precision and repeatability were determined at three concentration levels (40, 80, and 120 µg L^?1), with the relative standard deviation for the intermediate precision between 1% and 5.3% and the repeatability varying between 2% and 13.4% for individual analytes. The limits of detection and quantification for fipronil, fipronil sulfide, fipronil-sulfone, and fipronil-desulfinyl were 6.2, 3.0, 6.6, and 4.0 ng L^?1 and 20.4, 9.0, 21.6, and 13.0 ng L^?1, respectively. The method developed was used in water, soil, and sediment samples containing 2.1 mg L^?1 and 1.2% and 5.3% of carbon, respectively. The recovery of pesticides in the environmental matrices varied from 88.26 to 109.63% for the lowest fortification level (40 and 100 µg kg^?1), from 91.17 to 110.18% for the intermediate level (80 and 200 µg kg^?1), and from 89.09 to 109.82% for the highest fortification level (120 and 300 µg kg^?1). The relative standard deviation for the recovery of pesticides was under 15%.     

Development of in-house ELISA for detection of chloramphenicol in bovine milk with subsequent confirmatory analysis by LC-MS/MS

This study was undertaken to develop and validate direct competitive ELISA for the determination of chloramphenicol residues in bovine milk. Antisera and an enzyme-tracer for chloramphenicol were prepared and used to develop an ELISA with inhibition concentrations, IC₂₀ and IC₅₀, of 0.09 and 0.44 ng mL^?1, respectively. Milk samples were spiked with standards equivalent to 0, 0.2, 0.3, 0.5, 1.0 &; 1.5 ng mL^?1 and extracted in methanol. The mean recoveries were found to be 73–100% with coefficient of variance 7–11%. The decision limit (CCα) and detection capability (CCβ) were calculated as 0.10 and 0.12 ng mL^?1, respectively. The results were found comparable with the commercial ELISA, having recoveries of 87 to 100%, CCα 0.09 ng mL^?1 and CCβ 0.12 ng mL^?1. As per Commission Decision 2002/657/EC, in-house ELISA was further validated by using LC-MS/MS. Mass spectral acquisition was done by using electrospray ionization in the negative ion mode applying single reaction monitoring of the diagnostic transition reaction for CAP (m/z 152, 194 and 257). The calibration curve showed good linearity in concentrations from 0.025 to 1.6 ng mL^?1 with correction coefficient 0.9902. The mean recoveries were found to be 88 to 100%. The CCα was calculated as 0.057 ng mL^?1 and CCβ 0.10 ng mL^?1. Since CCα and CCβ are less than half of the MRPL (0.15 ng mL^?1), the test was found suitable for screening and quantification of CAP residues in bovine milk samples. Results of surveillance studies indicated that out of 31 analyzed milk samples, 12.9% samples were found with CAP residues but only 3.2% samples were declared positive with maximum concentration 0.31 ng mL^?1, slightly above the MRPL.     

Novel pipette-tip graphene/poly (vinyl alcohol) cryogel composite extractor for the analysis of carbofuran and carbaryl in water

A novel pipette-tip extractor of a graphene/poly (vinyl alcohol) cryogel (graphene/PVA) composite sorbent was prepared to preconcentrate carbamate pesticides in environmental water samples before analysis with a gas chromatograph-flame ionization detector (GC-FID). This novel pipette-tip extractor with the graphene/PVA sorbent exhibited a high porosity when observed through a scanning electron micrograph (SEM). Under optimal conditions, using only 1.0 mL of sample and 0.75 mL of eluting solvent, the developed method provided a wide linear range of 10–700 ng mL^?1 and 10–500 ng mL^?1 with limit of detection (LOD) of 6.40 ± 0.18 and 9.17 ± 0.34 ng mL^?1 for carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl methylcarbamate) and carbaryl (1-naphthyl methylcarbamate), respectively. The pipette-tip extractor provided high extraction efficiency with high accuracy indicated, by good recoveries in the range of 74.5 ± 4.8% to 119.7 ± 1.6% and 76 ± 15% to 114 ± 19% for carbofuran and carbaryl, respectively. In addition, the fabrication procedure showed a good pipette-tip extractor-to-pipette-tip extractor reproducibility with a relative standard deviation of 1.3–9.8% (n = 5). When the developed pipette-tip extractor was applied for the extraction of carbofuran and carbaryl in surface water samples near vegetable plantation areas, 25.9 ± 8.2 ng mL^?1 of carbofuran was found, and carbaryl was also detected in concentrations that ranged from 45.0 ± 4.0 to 191 ± 13 ng mL^?1.     

Simultaneous determination of organochlorine and pyrethriod pesticide residues in the Chinese patent medicines by gas chromatography-tandem mass spectrometry

A simple, sensitive, reliable method was developed for the simultaneous determination of organochlorine and pyrethriod pesticide residues in Chinese patent medicines Six ingredient rehmannia pills and Xiaoyao pills. These pesticides were extracted by ethyl acetate. The extraction time and volume of ethyl acetate were optimized. Cleanup of extracts was performed with dispersive-solid phase extraction using graphitized carbon black as the sorbent. The determination of pesticides in the final extracts was carried out by gas chromatography–tandem mass spectrometry in multiple reaction monitoring mode (GC-MS/MS, MRM). The linearity of the calibration curves is good in matrix-matched standard and yields the coefficients of determination (R²) ≥0.99 for all of the target analytes. Under optimized conditions, the average recoveries (five replicates) for most pesticides range from 75.5% to 114.6%, and RSDs are less than 10.0%. The LODs of 18 pesticides in Six ingredient rehmannia pill and Xiaoyao pills are in the range of 0.01–8.82 μg kg^?1. The developed method meets the requirements of pesticide residue analysis and could be effectively used for routine analysis of the organochlorine and pyrethriod pesticide residues in Six ingredient rehmannia pills and Xiaoyao pills.     

Biopesticide and formulation processes based on starch industrial wastewater fortified with soybean medium

Abstract

The aim of this study was to produce Bacillus thuringiensis-based biopesticide using starch-producing industry wastewater (SIW) fortified with soybean medium and optimize the formulated product using different adjuvants. This study was necessary as low endotoxin concentration is obtained in formulated biopesticide when SIW alone is used as fermentation medium. The fermentation runs were conducted using SIW alone and SIW fortified with 25% soybean (w/v) medium in 2000?L and 150?L bioreactor, respectively. SIW supplemented with soybean medium showed an increase in cell count (from 1.95?×?10⁸ to 1.65?×?10⁹ CFU mL^–1), spore synthesis (from 1.5?×?10⁸ to 1.35?×?10⁹ CFU mL^–1) and endotoxin concentration (from 436 to 1170?μg mL^–1) when compared to SIW medium alone. The fermented broth was concentrated using continuous centrifugation and adjuvants were added for biopesticide formulation in order to enhance its resistance against UV rays and rainfastness. Entomotoxicity of the formulation produced using fermented broth of SIW fortified with soybean (38,000?IU μL^–1) was higher than that obtained by SIW medium alone (21,000?IU μL^–1), commercial biopesticide Foray 76B (20,000?IU μL^–1) and Btk sander’s (12,500?IU μL^–1).     

Effect of triazole pesticide formulation on bovine culture cells

To date, most data about the possible genotoxic effect of triazole pesticides are focused on laboratory animals resulting in limited information on further non-target organisms such as cattle. The objective of the present study was to investigate the effect of triazole (tebuconazole/prothioconazole) fungicide formulation on the induction of chromosomal aberrations (CAs), sister chromatid exchanges (SCEs) and DNA fragmentation in bovine cultured lymphocytes. Our results showed that the fungicide formulation did not induce significant number of CAs in bovine cells after 24 h treatment. Nevertheless, the dose-dependent reduction of mitotic division was observed, with the strongest effect at 30.0 μg mL^?1 in both donors (P < 0.01 and P < 0.001, respectively). Prolonged 48 h exposure caused the increased level of breaks in treated cultures (3.0?15.0 μg mL^?1; P < 0.05) and significant decrease in mitotic index (MI). The tested fungicide failed to produce any statistical changes in the SCE frequency neither after 24 h nor 48 h treatment. However, the significant decline of the proliferation index (PI) was observed after 24 h indicating the fungicide influence on cell cycle kinetics. Prolonged 48 h exposure caused cytotoxicity reflecting in lower PI value relative to control mainly at the highest fungicide concentrations (30.0 μg mL^?1, P < 0.001). Using painting probes for bovine chromosomes 1, 5 and 7 (BTA1, BTA5 and BTA7) only low levels of aneuploidies were detected. Significant increase of polyploidy cells (P < 0.05) was induced by a 3.0 μg mL^?1 dose of the fungicide after 48 h. DNA fragmentation assay didn't reveal the presence of DNA nucleosome ladder in cell cultures at any time (24 h and 48 h) and fungicide concentration.     

Concentration and dissipation of chlorantraniliprole and thiamethoxam residues in maize straw,maize, and soil

To study the dissipation rates and final residual levels of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil, two independent field trials were conducted during the 2014 cropping season in Beijing and Anhui Provinces of China. A 40% wettable powder (20% chlorantraniliprole?+?20% thiamethoxam) was sprayed onto maize straw and soil at an application rate of 118 g of active ingredient per hectare (g a.i.ha^?1). The residual concentrations were determined by ultra-high-performance liquid chromatography–tandem mass spectrometry. The chlorantraniliprole half-lives in maize straw and soil were 9.0–10.8 and 9.5–21.7 days, respectively. The thiamethoxam half-lives in maize straw and soil were 8.4–9.8 and 4.3–11.7 days, respectively. The final residues of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil were measured after the pesticides had been sprayed two and three times with an interval of 7 days using 1 and 1.5 times the recommended rate (72 g a.i. ha^?1 and 108 g a.i. ha^?1, respectively). Representative maize straw, maize, and soil samples were collected after the last treatment at pre-harvest intervals of 7, 14, and 28 days. The chlorantraniliprole residue was below 0.01 mg kg^?1 in maize, between 0.01 and 0.31 mg kg^?1 in maize straw, and between 0.03 and 1.91 mg kg^?1 in soil. The thiamethoxam residue concentrations in maize, maize straw, and soil were <0.01, <0.01, and 0.01–0.03 mg kg^?1, respectively. The final pesticide residues on maize were lower than the maximum residue limit (MRL) of 0.02 mg kg^?1 after a 14-day pre-harvest interval. Therefore, a dosage of 72 g a.i. ha^?1 was recommended, as it can be considered safe to human beings and animals.     

Bisphenol A and Bisphenol S release in milk under household conditions from baby bottles marketed in Italy

A simple and sensitive validated analytical method based on liquid chromatography coupled to tandem fluorescence (FD) and ultraviolet (UV) spectrophotometry was applied to monitor the presence of bisphenol A and bisphenol S in plastic baby bottles marketed in Italy. The limits of detection (LOD) were 3.75 ng mL^?1 and 80.00 ng mL^?1, and those of quantification (LOQ) were 12.51 ng mL^?1 and 260.00 ng mL^?1 for BPA (FD detection) and for BPS (UV detection), respectively. BPA was found in only four samples, two samples undergone to microwave heating and two samples undergone to bottle warmer heating either at 40°C or at 80°C. Although the quantities of leached BPA were well below the reference dose for daily intake established by the European Food Safety Authority (EFSA) (4.0 µg kg^?1 bw/day), the release of BPA and BPS from these plastic materials should be carefully considered by the government authorities to increase people's awareness on this issue and to protect the most vulnerable population group.     

Emission factors of atmospheric and climatic pollutants from crop residues burning

Biomass burning is a common agricultural practice, because it allows elimination of postharvesting residues; nevertheless, it involves an inefficient combustion process that generates atmospheric pollutants emission, which has implications on health and climate change. This work focuses on the estimation of emission factors (EFs) of PM_2.5, PM₁₀, organic carbon (OC), elemental carbon (EC), carbon monoxide (CO), carbon dioxide (CO₂), and methane (CH₄) of residues from burning alfalfa, barley, beans, cotton, maize, rice, sorghum, and wheat in Mexico. Chemical characteristics of the residues were determined to establish their relationship with EFs, as well as with the modified combustion efficiency (MCE). Essays were carried out in an open combustion chamber with isokinetic sampling, following modified EPA 201-A method. EFs did not present statistical differences among different varieties of the same crop, but were statistically different among different crops, showing that generic values of EFs for all the agricultural residues can introduce significant uncertainties when used for climatic and atmospheric pollutant inventories. EFs of PM_2.5 ranged from 1.19 to 11.30 g kg^?1, and of PM₁₀ from 1.77 to 21.56 g kg^?1. EFs of EC correlated with lignin content, whereas EFs of OC correlated inversely with carbon content. EFs of EC and OC in PM_2.5 ranged from 0.15 to 0.41 g kg^?1 and from 0.33 to 5.29 g kg^?1, respectively, and in PM₁₀, from 0.17 to 0.43 g kg^?1 and from 0.54 to 11.06 g kg^?1. CO₂ represented the largest gaseous emissions volume with 1053.35–1850.82 g kg^?1, whereas the lowest was CH₄ with 1.61–5.59 g kg^?1. CO ranged from 28.85 to 155.71 g kg^?1, correlating inversely with carbon content and MCE. EFs were used to calculate emissions from eight agricultural residues burning in the country during 2016, to know the potential mitigation of climatic and atmospheric pollutants, provided this practice was banned.

Implications: The emission factors of particles, short-lived climatic pollutants, and atmospheric pollutants from the crop residues burning of eight agricultural wastes crops, determined in this study using a standardized method, provides better knowledge of the emissions of those species in Latin America and other developing countries, and can be used as inputs in air quality models and climatic studies. The EFs will allow the development of more accurate inventories of aerosols and gaseous pollutants, which will lead to the design of effective mitigation strategies and planning processes for sustainable agriculture.     

Occurrence and distribution of veterinary antibiotics and tetracycline resistance genes in farmland soils around swine feedlots in Fujian Province, China

Six antibiotics, tetracyclines (TCs), and quinolones (QNs) in farmland soils from four coastal cities in Fujian Province of China were investigated. Oxytetracycline was most frequently detected, followed by enrofloxacin, ciprofloxacin, chlorotetracycline, ofloxacin, and tetracycline, with maximum concentrations of 613.2, 637.3, 237.3, 2668.9, 205.7, and 189.8 μg kg^?1, respectively. Samples from Putian City contained the highest maximum concentration of ∑TCs (3,064.2 μg kg^?1), whereas those from Fuzhou City contained the highest maximum concentration of ∑QNs (897.8 μg kg^?1). It is noteworthy that the ∑TCs and ∑QNs in 46.4 and 28.6 % of samples exceeded the ecotoxic effect trigger value (100 μg kg^?1), respectively. The concentrations of these antibiotics and five tetracycline resistance genes in four soil plots at depth profiles were quantified thereafter. In most cases, both antibiotics and resistance genes decreased with the increase of depth. Some antibiotics can be detected at a depth of 60–80 cm where the abundance of tetO, tetM, and tetX reached up to 10⁷ copies g^?1. Additionally, the sum of all tet genes (normalized to 16S rRNA genes) correlated with ∑TCs significantly (r?=?0.676). Our results suggest that resistance determinants can migrate to deeper soil layers and would probably contaminate groundwater by vertical transport.     

Sources of polycyclic hydrocarbons and pesticides in soluble fraction of deposition samples in Kocaeli,Turkey

A wet–dry deposition sampler was located at The Scientific and Technological Research Council of Turkey-National Metrology Institute (TUBITAK-UME) station, and a bulk deposition sampler was placed at the Kad?ll? village to determine the atmospheric deposition flux of polycyclic aromatic hydrocarbons (PAHs) and pesticides (organochlorine and organophosphorus) in soluble fraction of samples in Kocaeli, Turkey. The 28 samples for each wet, dry, and total deposition were collected weekly from March 2006 to March 2007. Gas chromatography-tandem mass spectrometry was used to analyze the samples which were prepared by using solid-phase extraction (SPE) method. The sum of volume weighted mean of deposition fluxes was obtained as 7.43 μg m^?2 day^?1 for wet deposition, 0.28 μg m^?2 day^?1 for dry deposition and 0.54 μg m^?2 day^?1 for bulk deposition samples for PAHs and 9.88 μg m^?2 day^?1 for wet deposition, 4.49 μg m^?2 day^?1 for dry deposition, and 3.29 μg m^?2 day^?1 for bulk deposition samples for pesticides. While benzo(a)anthracene had the highest fluxes among PAH compounds for all types of depositions, guthion and phosphamidon had the highest deposition flux compared with the other pesticides. Benzo(ghi)perylene, dibenz(a,h)anthracene, indeno(1,2,3-c,d)pyrene, benzo(a)pyrene, and acenaphthene were not detected in any of the samples. Beta-HCH, gamma-HCH, and endrin aldehyde were the only compounds among 18 organochlorine pesticides to be detected in all deposition samples. The main sources of pesticides were the high number of greenhouses around the sampling stations. However, all of the organophosphorus pesticides were detected in all deposition samples. The pollution sources were identified as coal and natural gas combustion, petrogenic sources, and traffic for TUBITAK-UME station whereas coal and natural gas combustion and traffic were the main sources for Kad?ll? station by considering the results of factor analysis, ratios, and wind sector analysis.     

Local deposition of mercury in topsoils around coal-fired power plants: is it always true?

Mercury (Hg) is a toxic element that is emitted to the atmosphere through human activities, mainly fossil fuel combustion. Hg accumulations in soil are associated with atmospheric deposition, while coal-burning power plants remain the most important source of anthropogenic mercury emissions. In this study, we analyzed the Hg concentration in the topsoil of the Kozani–Ptolemais basin where four coal-fired power plants (4,065 MW) run to provide 50 % of electricity in Greece. The study aimed to investigate the extent of soil contamination by Hg using geostatistical techniques to evaluate the presumed Hg enrichment around the four power plants. Hg variability in agricultural soils was evaluated using 276 soil samples from 92 locations covering an area of 1,000 km². We were surprised to find a low Hg content in soil (range 1–59 μg kg^?1) and 50 % of samples with a concentration lower than 6 μg kg^?1. The influence of mercury emissions from the four coal-fired power plants on soil was poor or virtually nil. We associate this effect with low Hg contents in the coal (1.5–24.5 μg kg^?1) used in the combustion of these power plants (one of the most Hg-poor in the world). Despite anthropic activity in the area, we conclude that Hg content in the agricultural soils of the Kozani–Ptolemais basin is present in low concentrations.     

Determination of glyphosate residue in maize and rice using a fast and easy method involving liquid chromatography–mass spectrometry (LC/MS/MS)

A fast and easy method was developed for the determination of glyphosate in maize and rice by using liquid chromatography triple quadrupole mass spectrometry with a Dionex Ion Pack column and phosphate buffer mobile phase. Samples were extracted with an acidified methanol solution. An isotope-labeled internal standard was added to the sample before extraction to ensure accurate tracking and quantification. The method’s performance was evaluated through a series of assessments to determine the accuracy, precision, linearity, matrix effect, limit of detection (LOD), and limit of quantification (LOQ). The mean recoveries for both matrices were within 70–105% at three fortification levels, including the LOQ. The precision for replicates was <20% (RSD%) for both matrices. Good linearity (R²=0.9982) was obtained over the concentration range of 0.01–1.5?mg kg^?1. The LOD was determined to be 0.002?mg kg^?1 for rice and 0.004?mg kg^?1 for maize. The LOQ was 0.01?mg kg^?1 for both maize and rice. Due to its versatility, the proposed method could be considered useful for the determination of glyphosate in cereals in routine analysis.     

Validation of QuEChERS method for the determination of 36 pesticide residues in fruits and vegetables from Ghana,using gas chromatography with electron capture and pulsed flame photometric detectors

In this study, “Quick, Easy, Cheap, Effective, Rugged and Safe” ‘QuEChERS’ method was modified for the determination of 36 pesticides fortified at (0.01–1.0) mg kg^?1 in three vegetables and a fruit (lettuce, carrot, tomatoes and pineapples respectively) from Ghana. The method involved extraction with acetonitrile, phase separation with primary secondary amine and magnesium sulfate; the final injection solution was reconstituted in ethyl acetate. Organochlorine and synthetic pyrethroids residues were detected with electron capture detector whereas organophosphorus, pulsed flame photometric detector was used. The recoveries at different concentration levels (0.01, 0.1 and 1.0 mg kg^?1) were in the range of 83% and 93% with relative standard deviation ranging from 2% to 10% (n = 5) and the coefficient of determination (R²) was greater than 0.99 for all the 36 pesticides. The method was successfully tested on 120 real samples from Accra markets and this proved to be useful for monitoring purposes particularly in laboratories that have no gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry.     

Development and validation of LC-MS/MS method for the determination of Ochratoxin A and its metabolite Ochratoxin α in poultry tissues and eggs

The objective of this study was to develop a liquid chromatography tandem mass spectrometry (LC-MS/MS) method for the determination of Ochratoxin A (OTA) and Ochratoxin α (OTα) in poultry tissues and eggs. The two toxins were extracted by a mixture of acetonitrile/water, purified with a reversed phase C18 solid phase extraction column (SPE) and determined by LC-MS/MS. The LC-MS/MS method performances were evaluated in terms of linearity in solvent and in matrix (ranged from 0.5 to 15.10 µg L^?1 for OTA and from 0.60 to 17.85 µg L^?1 for OTα), limit of detection (LOD), limit of quantitation (LOQ), specificity, accuracy and precision in repeatability conditions. Recovery experiments were performed by spiking poultry liver, kidney, muscle and eggs around 1 µg kg^?1 and 10 µg kg^?1. LODs were 0.27 and 0.26 µg kg^?1 while LOQs were fixed at 1.0 and 1.2 µg kg^?1 for OTA and OTα, respectively. Main recoveries for OTA ranged from 82 to 109% and for OTα ranged from 55 to 89%. The values of within-laboratory relative standard deviation (RSD_r) were equal to or below 20%. Considering the results obtained and that all analytical performance criteria were fulfilled, the new extraction and purification method developed for OTA and OTα determination in animal tissues and eggs was found appropriate for control laboratories and research activities designed to ensure food safety.     

Cobalt-induced hormonal and intracellular alterations in rat ovarian fragments in vitro

The objective of this in vitro study was to examine dose-dependent changes in the secretion activity (progesterone, 17β-estradiol and insulin-like growth factor-I) of rat ovarian fragments after experimental cobalt (Co) administration including the apoptotic potential of Co on rat ovarian fragments by evaluating the expression of apoptotic markers Bax and caspase-3. Ovarian fragments were incubated with cobalt sulphate (CoSO₄.7H₂O) at the doses 90, 170, 330 and 500 μg.mL^?1 for 24 h and compared with control group without Co addition. Release of progesterone (P₄) 17β-estradiol and insulin-like growth factor-I (IGF-I) by ovarian fragments was assessed by RIA, expression of Bax and caspase-3 by SDS-PAGE and Western blotting. Observations show that P₄ release by ovarian fragments was significantly (P < 0.05) inhibited after cobalt sulphate addition at higher doses 170–500 μg.mL^?1 used in the study in comparison to control. However, cobalt sulphate addition did not cause any significant change in the release of 17β-estradiol by ovarian fragments at all the doses used in the study (90–500 μg.mL^?1) in comparison to control. On the contrary, IGF-I release by ovarian fragments was significantly (P < 0.05) stimulated after cobalt sulphate addition at the lowest dose 90 μg.mL^?1 in comparison to control, while other doses did not cause any significant change. Also, addition of cobalt sulphate decreased the expression of both the apoptotic peptides Bax and caspase-3 at the higher doses 170, 330 and 500 μg.mL^?1, but not at the lowest dose 90 μg.mL^?1 used in the study. Obtained results suggest Co induced (1) inhibition in secretion of steroid hormone progesterone, (2) dose-dependent increase in the release of growth factor IGF-I, and (3) decrease in the expression of markers of apoptosis (Bax and caspase-3) of rat ovarian fragments.