Determination and health risk assessment of enrofloxacin,flumequine and sulfamethoxazole in imported Pangasius catfish products in Thailand

The goals of this study were to determine the levels of three antibiotics – enrofloxacin, flumequine and sulfamethoxazole – in Pangasius catfish products imported into Thailand and to assess the health risks from consumption. To extract these antibiotic residues, acetonitrile, methanol and a small amount of formic acid were used as solvents. Determination of the antibiotics after extraction steps was carried out by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) technique. The results showed that 14 and 3 samples of Pangasius catfish products were contaminated with enrofloxacin and sulfamethoxazole, respectively. No flumequine residue was found. While the concentration levels of these antibiotics in most contaminated samples were lower than the European Union (EU) standard, one sample was found to contain sulfamethoxazole at 245.91 µg kg^?1, which was higher than the EU standard (100 µg kg^?1), indicating the likelihood that some contaminated freshwater fish products are widely distributed in Thai markets. Notably, the concentration levels of enrofloxacin in samples of Pangasius catfish with skin were higher than in non-skin products, suggesting that products with skin might retain more antibiotic residues than non-skin products. Although the hazard quotient showed that consuming imported Pangasius catfish products, based on the current consumption rate, will not adversely affect consumer health, antibiotic residues in Pangasius catfish products imported into Thailand should be continually monitored.     

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.     

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%.     

Antibiotic uptake by plants from manure-amended soils

Antibiotics are extensively given to livestock to promote growth and reduce diseases. Therefore, animal manure often contains antibiotics. Once manure is applied to agricultural land to improve soil productivity, crops would be exposed to antibiotics which may persist in soils from a few to several hundred days. The objective of this study was to evaluate the uptake of gentamicin and streptomycin by carrot (Daucus carota), lettuce (Lactuca sativa) and radish (Rhaphanus sativus) from manure-amended soil. The treatments were 0, 0.5 and 1 mg of antibiotic kg^?1 of soil. Two pot experiments were carried out in the greenhouse. The first was conducted on the three crops and the second exclusively on radish. In radish, the increase in the concentrations of gentamicin was significant between the 0 and both of 0.5 and 1.0 mg kg^?1 treatments, but not significant between the 0.5 and 1.0 mg kg^?1. The average values were 35.5, 60.0 and 57.4 μg kg^?1 for the 0, 0.5 and 1 mg kg^?1 rates, respectively. However, the increase in streptomycin concentration in radish was not significant between the three treatments, and the average values were, 12.1, 15.2 and 17.4 μg kg^?1 for the 0, 0.5 and 1 mg kg^?1 rates, respectively. In carrot roots and lettuce leaves no significant increase in the concentrations of gentamicin or streptomycin was observed between the treatments. The three crops absorbed relatively higher amounts of gentamicin (small molecule) than streptomycin (large molecule). Generally the levels of antibiotics in plant tissue increased with increasing the antibiotic concentration in the manure (1 mg kg^?1 > 0.5 mg kg^?1).     

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.     

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.     

Fast extraction of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran in sewage sludge and soil samples

The current environmental legislations recommend monitoring chemical contaminants such as polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans before the use of sewage sludge on the agricultural land. In this study, a solid–liquid extraction with low-temperature purification (SLE-LTP) was optimized and validated to determine 2,3,7,8-tetrachlorodibenzo-p-dioxin and 2,3,7,8-tetrachlorodibenzofuran in sewage sludge and soil samples. The analyses were performed by gas chromatography-mass spectrometry operating in the selective ion mode (GC-MS-SIM). Acetonitrile:ethyl acetate 6.5:1.5 (v/v) was the best extraction phase, and the recoveries percentages were close to 100%. The linearity was demonstrated in the range of 1.25–25 µg L^?1 of 1.25–20 µg L^?1 for sewage sludge and soil, respectively. Matrix effect was proved for the two compounds and in the two matrices studied. Extraction percentages were between 78 and 109% and relative standard deviations ≤ 19%. The proposed method is faster than methods described in the literature because showed a few steps. The quantification limits (LOQ) in sewage sludge were 6.4 and 32 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. In soil, LOQs were 0.8 and 8.0 ng TEQ kg^?1 for 2,3,7,8-TCDF and 2,3,7,8-TCDD, respectively. These values are lower than the maximum residue limits established by European Legislation. The method was applied to 22 agricultural soil samples from different Brazilian cities and 2,3,7,8-TCDF was detected in one of these samples.     

Screening of antibiotic residues in fresh milk of Kathmandu Valley,Nepal

The prevalence of two groups of antibiotics; namely penicillin and sulfonamides was studied in fresh milk available in Kathmandu Valley of Nepal. The milk samples (n = 140) were collected from three different sources; individual farmers, cottage dairies and organized dairies of Kathmandu valley. Qualitative and semi-quantitative analysis with rapid screening kits revealed that 23% samples were positive for antibiotic residues in the fresh milk for penicillin and sulfonamide groups (1–256 µg/kg). High performance liquid chromatography (HPLC) analyses detected 81% samples positive for amoxicillin (68–802 µg/kg), 41% for sulfadimethoxine (31–69 µg/kg), 27% for penicillin G (13–353 µg/kg), and 12% for ampicillin (0.5–92 µg/kg). Due to the precision and accuracy of liquid chromatography method, it detected more positive samples and consequently presented higher prevalence than the rapid screening kits. The antibiotic residues were found above the maximum residue limits that presented serious threat to consumer health and raised a serious concern regarding the implementation and monitoring of international regulations in developing countries.     

Dietary risk evaluation for 28 polycyclic aromatic hydrocarbons (PAHs) in tea preparations made of teas available on the Polish retail market

The aim of this work was to assess dietary risk resulting from consumption of polycyclic aromatic hydrocarbons (PAHs) with tea infusions. To this end, levels of 28 PAHs in black, green, red and white teas available on the Polish retail market have been assessed. Profiles and correlation between concentrations of individual PAHs have been identified. A model study on transfer of PAHs from tea leaves into tea preparations has been conducted. Relatively high concentrations of 28 evaluated PAHs have been found in 58 tested samples of black, green, red and white teas sampled on the Polish retail market. Total concentration ∑28PAH ranged from 57 to 696 µg kg^?1 with mean 258 µg kg^?1 (dry tea leaves). The most mature tea leaves fermented to a small degree contained relatively the highest PAH levels among all four tested tea types. Relatively low PAH transfer rates into tea infusions and limited volumes of the consumed tea keep the risks associated with PAH dietary intake at a safely low level.

The worst-case scenario dietary intake values were 7.62/0.82/0.097 ng kg^?1 b.w. day^?1 (estimated on the basis of the maximum found concentrations 696/113/23 µg kg^?1 and maximum observed transfer rates 24/16/9%) for ∑28PAH/∑PAH4/B[a]P, respectively. MOE values calculated using the above worst case estimates exceeded 700,000 and 400,000 (BMDL₁₀ 0.07 and 0.34 mg kg^?1 b.w. day^?1) for B[a]P and PAH4, respectively. Both B[a]P and PAH4 concentrations may be used as indicators of total PAH concentration in tea leaves; PAH4 slightly better fits low molecular weight PAHs. Several correlations between various PAHs/groups of PAHs have been identified, the strongest one (R² = 0.92) between PAH4 and EU PAH 15+1.     

The transfer of active ingredients of insecticides and fungicides from an orchard to beehives

This investigation was undertaken to determine whether active ingredients (AIs) of currently recommended plant protection products (PPPs) could be transferred to beehives from apple and pear trees. A field trial was carried out with apple trees of Ligol and Idared variety, and pear trees of Conference variety. For pest and diseases control of fungal origin, recommended PPPs were applied. Samples of flowers from the above-mentioned varieties of fruit trees, of bees, brood and honey from beehives located in their direct neighborhood were collected regularly and analyzed for the presence of lambda-cyhalothrin (an insecticide) and cyprodinil, captan, fluopyram, kresoxim-methyl, penthiopyrad and trifloxystrobin (fungicides). In samples of flowers of Ligol variety, fluopyram residues (on average 0.621 µg single flower^?1) were at the highest levels, whereas in samples of pear flowers of Conference variety, and in flowers of Idared variety, captan residues (on average, respectively, 0.705 and 165.7 µg single flower^?1). In samples of bees and honey, residues of five AIs were detected, and in brood six AIs, whereby in each case captan residues prevailed, respectively, up to 585.2, 51.52 and 126.5 µg kg^?1 bees and honey. In the honey, significantly larger residues of captan were found out than maximum residue level (MRL) for this AI – 103.04% MRL. In the case of any AI, the daily intake did not exceed 0.002% acceptable daily intake (ADI).     

Occurrence and human dietary assessment of sulfonamide antibiotics in cultured fish around Tai Lake,China

As the most important fishery medicines, sulfonamides are widely used to prevent diseases caused by pathogens in aquaculture. However, relatively little is known about the residues and dietary risks associated with cultured fish around Tai Lake. In the present study, a sampling strategy for a complete aquaculture period was conducted. Specifically, 12 selected sulfonamide antibiotics were measured among 116 fish samples recruited from four sampling periods, four species, four areas, and 18 fish ponds. All 12 antibiotics were detected at detection frequencies of 4.31–28.45%. Total sulfonamides were detected in 77.59% of the fish samples, with 57.76% of fish samples containing from 0.1 to 10 μg kg^?1. Sulfadiazine (SDZ), sulfamethoxazole (SMZ), sulfamethazine (SDD), and sulfamonomethoxine (SMM) were the main types of antibiotics used, and these were present at high concentrations (>100 μg kg^?1) with high occurrences, especially in the middle of the aquaculture season. Dietary assessment showed that residual antibiotics in all fish that were being sent to market were far below the maximum residue limit (MRL) of total sulfonamides and that there was almost no risk associated with fish consumption. The results of the present study will facilitate development of effective measures to produce safe aquatic products and meaningful suggestions for consuming aquatic products.     

Simultaneous determination of pesticides,mycotoxins, tropane alkaloids,growth regulators,and pyrrolizidine alkaloids in oats and whole wheat grains after online clean-up via two-dimensional liquid chromatography tandem mass spectrometry

In this study, a two-dimensional liquid chromatography tandem mass spectrometry method was developed and validated for the determination of pesticide residues and contaminants in whole wheat grains and oats. The samples were extracted with a mixture of acetonitrile and water and were injected into the two-dimensional LC-MS/MS system without any further clean-up or sample preparation. Samples were analyzed with four different matrix matched calibrations. Matrix effects were evaluated by comparing analyte signals in the respective matrix matched standard with the neat solvent standards. The final method was validated according to the current Eurachem validation guide and SANTE document. The number of successfully validated analytes throughout all three validation levels in oats and wheat, respectively, were as follows: 330 and 316 out of 370 pesticides, 6 and 13 out of 18 pyrrolizidine alkaloids and 7 out of 9 regulated mycotoxins. Moreover, both plant growth regulators mepiquat and chlormequat as well as the tropane alkaloids atropine and scopolamine met the validation criteria. The majority of pesticides showed limits of detection below 1?µg kg^?1, pyrrolizidine alkaloids below 0.7?µg kg^?1, tropane alkaloids below 0.2?µg kg^?1, growth regulators below 0.7?µg kg^?1 and mycotoxins below 8?µg kg^?1 in both matrices.     

Risk estimation to human health caused by the mercury content of Sushi and Sashimi sold in Japanese restaurants in Brazil

Although fish is a healthy alternative for meat, it can be a vehicle for mercury (Hg), including in its most toxic organic form, methylmercury (MeHg). The objective of the present study was to estimate the risk to human health caused by the consumption of sushi and sashimi as commercialized by Japanese food restaurants in the city of Campinas (SP, Brazil). The total Hg content was determined by atomic absorption spectrometry with thermal decomposition and amalgamation, and the MeHg content calculated considering that 90% of the total Hg is in the organic form. The health risk was estimated from the values for the provisional tolerable weekly ingestion (PTWI) by both adults and children. The mean concentrations for total Hg were: 147.99, 6.13, and 3.42 µg kg^?1 in the tuna, kani, and salmon sushi samples, respectively, and 589.09, 85.09, and 11.38 µg kg^?1 in the tuna, octopus and salmon sashimi samples, respectively. The tuna samples showed the highest Hg concentrations. One portion of tuna sashimi exceeded the PTWI value for MeHg established for children and adults. The estimate of risk for human health indicated that the level of toxicity depended on the type of fish and size of the portion consumed.     

Assessing contamination of smoked sprats (Sprattus sprattus) with polycyclic aromatic hydrocarbons (PAHs) and changes in its level during storage in various types of packaging

The analysis of material used in this study demonstrated that the amount of polycyclic aromatic hydrocarbons (PAHs) in smoked sprats varies from the level below the lowest detection limit in muscles up to 9.99 µg kg^?1 of benzo[a]pyrene (BaP) in fish skin. Such a high level of PAHs in skin was reported only in one of six batches of sprats, while mean BaP level was at 1.69 µg kg^?1. Regardless such a high BaP level in skin, its concentration in muscles did not exceed the maximum acceptable level. The study objective was to assess to what extent packaging materials adsorb PAH compounds from food. Changes in the PAH levels were monitored in fish during their storage in packages made of various materials. The storage time was from 0 to 168 hours. The obtained results varied considerably, therefore their scatter did not allow to confirm unequivocally the preliminary hypothesis about the reduction of PAHs due to their migration to packaging material. However, analysis of the packaging used in this study demonstrated a significant increase in the level of total 16 PAHs. When high-density polyethylene (HDPE) packaging was analysed, a six-fold increase in the total 16 PAHs was observed comparing to the blank sample.     

Tetracycline and 4-epitetracycline modified the in vitro catabolic activity and structure of a sediment microbial community from a tropical tilapia farm idiosyncratically

Aquaculture farmers commonly add tetracycline to fish feed or to their ponds to prevent or treat bacterial infections in their crops. To assess the short-term effect of tetracycline (TET) and of one of its reversible epimers, 4-epitetracycline (ETC), on the function and structure of a sediment microbial community from a tropical tilapia farm, we contrasted community-level physiological profiles (CLPP) and phospholipid fatty acid profiles (PLFA) obtained from microcosms exposed for 12 days to 5, 10, 50, or 75 mg kg^?1of these antibiotics. Notwithstanding that the concentration of the antibiotics during the experiment decreased between 13–100% (TET) or 16–61% (ETC), both compounds provoked opposing metabolic responses that did not revert. TET displayed a tendency to inhibit respiration at concentrations < 50 mg kg^?1, whereas ETC showed the opposite effect. As revealed by the finding of the fatty acids 11:0 iso 3OH, 16:1w6c, and 18:1w6c, the sediment analyzed was predominantly colonized by Gram-negative bacteria. A marked decrease in fatty acid diversity accompanied the aforementioned metabolic responses, with TET concentrations > 50 mg kg^?1leading to an enrichment of yeast and fungal biomarkers and both antibiotics at concentrations < 10 mg kg^?1selecting for microorganisms with 11:0 iso 3OH. In agreement with CLPP data, differences between the PLFA profiles of control and treated microcosms were more pronounced for TET than for ETC. We conclude that high, yet field-relevant, concentrations of TET and ETC have the potential to modify the composition, and to a lesser extent, the functioning of a sediment microbial community. This study highlights the importance of considering antibiotic degradation products in ecotoxicological research.     

Detection of free microcystins in the liver and muscle of freshwater fish by liquid chromatography-tandem mass spectrometry

MC analysis of biological tissue is considered to be very difficult due to the lack of validated methods. This is the primary limiting factor for monitoring potential risks in both the flesh of aquatic organisms and the aquatic ecosystem. In this study, an effective method to determine free MCs (MC-LR and MC-RR) in the muscle and liver tissues of freshwater cultured fish was developed using solid-phase extraction (SPE) and liquid chromatography-tandem mass spectrometry (LC/MS-MS). The extraction solvent, time of extraction, eluent and purification of the extract were optimized. Various SPE cartridges were also investigated. In this optimized analytical procedure, an 85% methanol/water solution (v/v) was selected as the extraction solvent, after which the extracts were purified by removing fats and proteins; a HLB cartridge was chosen for MCs enrichment; and 90% methanol containing 0.02% formic acid/water solution (v/v) was used as the eluent. Under the optimized pretreatment conditions and instrument parameters, good recoveries of MC-LR and MC-RR were obtained at three concentrations (0.5, 1.0 and 2.0 µg g^?1 dry weight (DW)), with values ranging from 92.5 to 98.3% and 92.1 to 98.6%, respectively. The method detection limit (MDL) for muscle samples was 0.5 µg kg^?1 and 0.4 µg kg^?1 (DW) for MC-LR and MC-RR, respectively. The MDL for the liver samples was 0.8 µg kg^?1 (DW) for both MC-LR and MC-RR. The developed procedure was successfully applied to analyze MCs in the muscle and liver of fish samples collected from a Chinese freshwater aquaculture pond during bloom seasons. The MC-LR concentrations ranged from below the MDL to 4.17 µg kg^?1 and the MC-RR concentrations ranged from below the MDL to 2.64 µg kg^?1.     

Pesticide contaminants in selected species of edible wild mushrooms from the north-eastern part of Poland

ABSTRACT

The aim of this study was to determine the level of chlorinated hydrocarbon residues in selected edible mushrooms from north-eastern Poland. The experiment was carried out on 45 samples consisting of 15 fruiting bodies each of the following species: Boletus edulis, Imleria badia and Cantharellus cibarius. Dried samples were subjected to extraction of lipids with a Soxhlet and a standard procedure—based on the decomposition of lipids by concentrated sulfuric acid and the release of organic insecticides to the hexane layer—was used to determine chlorinated hydrocarbons. The quantitative determination of DDT, DDE, DDD and γ-HCH were conducted using gas chromatography with electron capture detection (GC-ECD). Chlorinated hydrocarbons were found in all tested samples. The contents of these compounds varied between all three species. Mean content of γ-HCH in B. edulis, I. badia and C. cibarius was: 2.60; 4.83; 7.52 µg kg^?1 of lipids, while the content of ΣDDT was: 57.02; 25.20; 127.10 µg kg^?1 of lipids, respectively. These results show that mushrooms from the north-eastern part of Poland can be used as potential bio-indicators of environmental contamination with chlorinated hydrocarbons. Moreover, the studied fungi could still be used as food due to the low levels of analyzed organochlorine compounds.     

Quantification of ionophores in aged poultry litter using liquid chromatography tandem mass spectrometry

Veterinary anticoccidials, biochemically known as ionophores, are widely used in poultry feed at therapeutic levels to treat Coccidiosis and at sub-therapeutic levels for growth- promotion. Commonly used ionophores in the US poultry industry are monensin, salinomycin, lasalocid and narasin. There is an increasing concern regarding the persistence of these anticoccidials in the environment. However, little attention has been directed to methods development for quantitatively measuring ionophores in complex environmental matrices such as poultry litters that are land applied. Here, we describe a rapid and sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS)-based method developed for simultaneous quantification of monensin, lasalocid, salinomycin, and narasin in aged poultry litter samples. Results show significant level of monensin (97.8 ± 3.2 μg kg^?1), lasalocid (19.2 ± 6.6 μg kg^?1), salinomycin (70 ± 2.7 μg kg^?1) and narasin (57.3 ± 2.6 μg kg^?1) in poultry litter stored for over three years at < 5°C. Our findings indicate that even after several years of unmanaged storage of poultry litter, ionophores may continue to persist in this matrix, raising the possibility of prolonged release into the environment.     

Leaching of S-metolachlor,terbuthylazine, desethyl-terbuthylazine,mesotrione, flufenacet,isoxaflutole, and diketonitrile in field lysimeters as affected by the time elapsed between spraying and first leaching event

The effect of elapsed time between spraying and first leaching event on the leaching behavior of five herbicides (terbuthylazine, S-metolachlor, mesotrione, flufenacet, and isoxaflutole) and two metabolites (desethyl-terbuthylazine and diketonitrile) was evaluated in a 2011–2012 study in northwest Italy. A battery of 12 lysimeters (8.4 m² long with a depth of 1.8 m) were used in the study, each filled with silty-loam soil and treated during pre-emergence with the selected herbicides by applying a mixture of commercial products Lumax (4 L ha^?1) and Merlin Gold (1 L ha^?1). During treatment periods, no gravity water was present in lysimeters. Irrigation events capable of producing leaching (40 mm) were conducted on independent groups of three lysimeters on 1 day after treatment (1 DAT), 7 DAT, 14 DAT, and 28 DAT. The series was then repeated 14 days later. Leachate samples were collected a few days after irrigation; compounds were extracted by solid phase extraction and analyzed by high-performance liquid chromatography and gas chromatography–mass spectrometry. Under study conditions, terbuthylazine and S-metolachlor showed the highest leaching potentials. Specifically, S-metolachlor concentrations were always found above 0.25 µg L^?1. Desethyl-terbuthylazine was often detected in leached waters, in most cases at concentrations above 0.1 µg L^?1. Flufenacet leached only when irrigation occurred close to the time of herbicide spraying. Isoxaflutole and mesotrione were not measured (<0.1 µg L^?1), while diketonitrile was detected in concentrations above 0.1 µg L^?1 on 1 DAT in 2011 only.     

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.