Dissipation pattern and residual levels of boscalid in cucumber and soil using liquid chromatography-tandem mass spectrometry

Abstract

To stipulate the rationale of spraying doses and to determine the safe interval period of boscalid suspension concentrate (SC), the degradation dynamics and residual levels were investigated in cucumber and soil using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Field trials were conducted according to Chinese Guideline on pesticide residue trials. Following application, the degradation kinetics was best ascribed to first-order kinetic models with half-life of 2.67–9.90 d in cucumber. Spraying boscalid SC at 1.5-fold the recommended dosage yield terminal residues, which are clearly lower than the maximum residue limit (MRL) established by China (MRL =5?mg.kg^?1) in cucumber. At variance, the dissipation dynamics in soil did not fit to first-order kinetics and the half-life was more than 17?days, the finding which denotes that the degradation behavior of boscalid in soil proceeds slowly. It has therefore been shown that boscalid is safe for use on cucumbers under the recommended dosage.     

环境水体中四溴双酚A的HPLC-MS/MS分析方法的建立与应用

四溴双酚A(tetrabromobisphenol A,TBBPA)是目前使用量最大的溴代阻燃剂.随着它的广泛应用,已经引起了大气、水体、沉积物和土壤等环境介质及相关生态系统的严重污染.建立了环境水体中TBBPA的高效液相色谱-串联质谱(HPLC-MS/MS)分析方法.该方法采用电喷雾电离(ESI)负离子模式进行扫描,...     

高效液相色谱-串联质谱法同时检测地表水中13种药物及个人护理品

采用高效液相色谱-串联质谱(HPLC-MS/MS)检测,建立了地表水中13种药物及个人护理品的测定方法。水样用盐酸与氢氧化钠溶液调pH值至7.0左右,过固相萃取小柱进行富集,用14 mL甲醇洗脱。以C18柱为分离柱,0.01%甲酸的甲醇-0.01%甲酸水溶液为流动相,目标物在10 min内分离,在0.50~250 μg/L范围内,13种化合物峰面积与内标物质峰面积之比与质量浓度的线性关系良好(>0.99),检出限在0.05~0.5 ng/L范围内。基质加标实验结果表明,13种化合物在水中的回收率分别在56.2%~123.2%之间(加标水平5 ng/mL)和58.0%~107.8%(加标水平50 ng/mL),相对标准偏差在1.60%~19.9%(n=6)之间。应用该方法测定了从2条纳污河流采集的10份水样,结果表明,除美托诺尔和普洛萘尔未被检出外,其余11药物的检出频率在30%~100%之间。在13种目标物质中,咖啡因的检测浓度最高达287.5 ng/L,舒必利次之,为277.5 ng/L。本方法快速、准确,适用于地表水中PPCPs类的快速测定。     

Determination of veterinary pharmaceuticals in poultry litter and soil by methanol extraction and liquid chromatography-tandem mass spectrometry

Pharmaceuticals are emerging contaminants with potential risks to the environment and human health. A liquid chromatography-tandem mass spectrometry (LC-MS-MS) method was developed for determination of the antimicrobials virginiamycin, monensin, salinomycin, narasin and nicarbazin in poultry litter and soil. This method involves methanol extraction and clean-up of extracts through glass microfibre filters, introduction of the extracts and separation of compounds on a Zorbax Eclipse XDB C8 column, and compound detection in a Quattro Micro Micromass spectrometer. For litter samples, Method Detection Limits ranged from 0.1–0.6 μg Kg^{? 1}, while Limits of Quantitation (LOQs) were 2, 1, 0.4, 1 and 2 μg Kg^{? 1} for virginiamycin, monensin, salinomycin, narasin and nicarbazin, respectively. For soil samples calculated LOQs were 2, 3, 1, 1, and 1 μg Kg^{? 1} for virginiamycin, monensin, salinomycin, narasin and nicarbazin, respectively. Application of the LC-MS-MS method for detection of veterinary pharmaceuticals in litter collected from commercial poultry farms showed that compounds were present at concentrations ranging from 10–11,000 μg Kg^{? 1}.     

Heavy metal contamination and risk assessment in water,paddy soil,and rice around an electroplating plant

Purpose  

The objective of this paper is to assess the impact of long-term electroplating industrial activities on heavy metal contamination in agricultural soils and potential health risks for local residents.     

Photodegradation of multiclass fungicides in the aquatic environment and determination by liquid chromatography-tandem mass spectrometry

Environmental Science and Pollution Research - The photodegradation behaviour for nine widespread fungicides (benalaxyl, cyprodinil, dimethomorph, fenhexamide, iprovalicarb, kresoxim-methyl,...     

Detection of free and covalently bound microcystins in animal tissues by liquid chromatography-tandem mass spectrometry

Microcystins are cyanobacterial hepatotoxins capable of accumulation into animal tissues. The toxins act by inhibiting specific protein phosphatases and both non-covalent and covalent interactions occur. The 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) method determines the total, i.e. the sum of free and protein-bound microcystin in tissues. The aim of the method development in this paper was to tackle the problems with the MMPB methodology: the rather laborious workflow and the loss of material during different steps of the method. In the optimised workflow the oxidation recovery was of acceptable level (29-40%), the extraction efficiency good (62-97%), but the signal suppression effect from the matrix remained severe in our system (16-37% signal left). The extraction efficiency for the determination of the free, extractable microcystins, was found to be good, 52-100%, depending on the sample and the toxin variant and concentration.     

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.     

Continental bottled water assessment by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry (SBSE-GC-MS/MS)

This study was aimed to determine the presence of 69 organic contaminants in 77 representative bottled waters collected from 27 countries all over the world. All water samples were contained in polyethylene terephthalate bottles. Target compounds were (1) environmental contaminants (including 13 polycyclic aromatic hydrocarbons (PAHs), 31 pesticides including organochlorine (OCPs), organophosphorus, and pyrethroids; 7 polychlorinated biphenyls (PCBs); and 7 triazines) and (2) plasticizers (including 6 phthalates and 5 other compounds). Samples were analyzed by stir bar sorptive extraction followed by gas chromatography-tandem mass spectrometry. PAHs, OCPs, PCBs, and triazines, which are indicators of groundwater pollution, were not detected in most of the samples, except for naphthalene (0.005–0.202 μg/L, n?=?16). On the other hand, plastic components were detected in 77 % of the samples. Most frequently detected compounds were dimethyl phthalate and benzophenone at concentrations of 0.005–0.125 (n?=?41) and 0.014–0.921 (n?=?32), respectively. Levels detected are discussed in terms of contamination origin and geographical distribution. Target compounds were detected at low concentrations. Results obtained showed the high quality of bottled water in the different countries around the world.     

Determination of chloramphenicol, enrofloxacin and 29 pesticides residues in bovine milk by liquid chromatography-tandem mass spectrometry

A sensitive method for determination of chloramphenicol, enrofloxacin and 29 pesticides residues in bovine milk by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed. Residues of the targets were extracted from milk with acetonitrile, cleaned up by C₁₈-SPE cartridge, and then determined by HPLC-MS/MS. The MS detection was operated in positive or negative ionization mode, depending on the compounds. For confirmation of each target compound, two precursor ion > product ion transitions were selected by multi-reaction monitoring mode (MRM). The method showed good linearity for all the tested compounds over the studied concentration range with correlation coefficient higher than 0.9910. Recoveries for the studied compounds at three spiked levels (0.05, 0.10, 0.19 mg kg⁻¹) in bovine milk were in the range of 71-107% with RSDs not larger than 13.7%, except that recoveries of trifluralin ranged between 62% and 70% at the spiked levels. Limits of quantitation for the analytes were estimated to range between 0.03 × 10⁻³ and 14.5 × 10⁻³ mg kg⁻¹. The proposed method was applied for the determination of the analytes residues in real samples. The found levels of the analytes in milk samples were lower than maximum residues levels (MRL).     

Multiresidue determination of pesticides in tea by gas chromatography-tandem mass spectrometry

An efficient and reliable GC-MS/MS method for the multiresidue determination of pesticides in tea was developed by modifying the Japanese official multiresidue method. Sample preparation was carefully optimized for the efficient removal of coextracted matrix components. The optimal sample preparation procedure involved swelling of the sample in water; extraction with acetonitrile; removal of water by salting-out; and sequential cleanup by ODS, graphitized carbon black/primary secondary amine (GCB/PSA) and silica gel cartridges prior to GC-MS/MS analysis. The recoveries of 162 pesticides from fortified (at 0.01 mg kg^?1) green tea, oolong tea, black tea and matcha (powdered green tea) were mostly (95–98% of the tested pesticides) within the range of 70–120%, with relative standard deviations of <20%. Poor recovery of triazole pesticides was considered to be due to low recovery from the silica gel cartridges. The test solutions obtained by the modified method contained relatively small amounts of pigments, caffeine and other matrix components and were cleaner than those obtained by the original Japanese official multiresidue method. No interfering peaks were observed in the blank chromatograms, indicating the high selectivity of the modified method. The overall results suggest that the developed method is suitable for the quantitative analysis of GC-amenable pesticide residues in tea.     

Bioaccumulation and human health risk assessment of chromium and nickel in paddy rice grown in serpentine soils

The natural abundance of Cr and Ni in serpentine soils is well-known, but the food safety of rice grown in these hazardous paddy soils is poorly understood. The study evaluated the bioaccumulation of chromium (Cr) and nickel (Ni) in rice (Oryza sativa) grown in serpentine-derived paddy soils in the Philippines. Surface soil (0–20 cm) samples were collected and characterized across three (i.e., Masinloc, Candelaria, and Sta. Cruz) paddy areas in Luzon Island, Philippines. At least 3 to 4 whole rice plants at mature stage were uprooted manually in each sampling point where the soil samples were collected. The total Cr and Ni concentrations in rice (i.e., roots, shoots, and grains) and soil, soil physicochemical properties, bioaccumulation factor (BAF), translocation factor (TF), and the hazard quotients (HQ) were determined. Results revealed that Cr and Ni in rice were accumulated mostly in the roots. Although paddy soils had elevated total Cr and Ni concentrations, the BAF and soil-to-root TF values for Cr and Ni were < 1. In terms of human health risks, results further revealed low risk for both male and female Filipino adults as HQ values for Cr and Ni were < 1. While it is safe to consume rice grown in the area in terms of Cr and Ni dietary intake, more studies are necessary to understand the dynamics and bioavailability of these heavy metals in other crops and drinking water from tube wells in these areas in order to provide a more holistic human health-based assessments and to ensure consumer safety in serpentine areas. In addition, a more reliable data on Cr and Ni speciation in serpentine soils and crops is critically important. Further studies are also needed to understand the contribution of bioavailable heavy metals in improving the soil health to achieve food safety.

     

Stability considerations of aspartame in the direct analysis of artificial sweeteners in water samples using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS)

A HPLC-MS/MS method is presented for the simultaneous determination of frequently used artificial sweeteners (ASs) and the main metabolite of aspartame (ASP), diketopiperazine (DKP), in environmental water samples using the direct-injection (DI) technique, thereby achieving limits of quantification (LOQ) of 10 ng L⁻¹. For a reliable quantification of ASP pH should be adjusted to 4.3 to prevent formation of the metabolite. Acesulfame (ACE), saccharin (SAC), cyclamate (CYC) and sucralose (SUC) were ubiquitously found in water samples. Highest concentrations up to 61 μg L⁻¹ of ACE were found in wastewater effluents, followed by surface water with concentrations up to 7 μg L⁻¹, lakes up to 600 ng L⁻¹ and groundwater and tap water up to 70 ng L⁻¹. The metabolite DKP was only detected in wastewater up to 200 ng L⁻¹ and at low detection frequencies.     

Spatial distribution of heavy metals in rice grains and human health risk assessment in Hunan Province,China

Environmental Science and Pollution Research - Rice is the main food in China, and its pollution by heavy metals has attracted widespread attention. In this study, rice grain samples were collected...     

Long-term effects of fertilization on the forms and availability of soil phosphorus in rice paddy

The changes in total P accumulation and P compounds with time in the plough layer in a paddy soil in southern Korea were investigated in relation to the continuous application of chemical fertilizers (NPK), straw based compost (Compost), combination these two (NPK+Compost) for 31 years. Continuous fertilization increased the total and inorganic P contents in plough layers. In NPK, inorganic P fraction did not change with time, but organic P content increased significantly. Long-term application of chemical fertilizer together with compost accelerated the decrease in the organic P fraction, presumably due to promoting microbial activity in the plow layer, and then increased significantly inorganic P fraction. Compost application decreased the residual P and Fe-P fractions and then increased inorganic P fraction, in spite of continuous compost application. Increase in total, inorganic and extractable P with time may be closely related to the increase in the availability of accumulated P for rice growth.     

Determination of carbamazepine and 12 degradation products in various compartments of an outdoor aquatic mesocosm by reliable analytical methods based on liquid chromatography-tandem mass spectrometry

Environmental Science and Pollution Research - The aims of this work are to develop suitable analytical methods to determine the widely used anticonvulsant carbamazepine and 12 of its...     

Magnetic molecularly imprinted polymer prepared by microwave heating for confirmatory determination of chloramphenicol in chicken feed using high-performance liquid chromatography-tandem mass spectrometry

Abstract

A magnetic molecularly imprinted polymer (MMIP) for chloramphenicol was prepared using a surface-imprinted and microwave-heating-induced polymerization method. The surfaces of the magnetic particles were first double-bond functionalized with 3-(trimethoxysilyl)propyl methacrylate (γ-MPS), followed by the copolymerization of 4-vinyl pyridine (4-VP) and trimethylolpropane trimethacrylate (TRIM) in the presence of chloramphenicol as a template and 1,1-azobis(cyclohexane-carbonitrile) (ABCN) as an initiator in a mixture of dimethyl sulfoxide and water with microwave heating at 80°C. The magnetic polymer possesses supraparamagnetic properties and was used to concentrate and cleanup chicken feed extract, followed by chromatographic separation using a Lichrospher®100 RP C8 column and detection with two multi-reaction monitoring transitions at m/z 321→ 152 and m/z 321→ 257. The mean recoveries obtained at two spiking levels were in the range of 94.6–100% The relative intra- and inter-day standard deviations were in the range of 1.4–2.6% and 5.1–5.7%, respectively. The detection limit of the method was 0.12 µg kg^?1. This confirmatory method was successfully applied to determine chloramphenicol in chicken feed samples.     

复配钝化剂对稻田重金属有效性及其水稻吸收的影响

针对红壤稻米中重金属Cd超标的问题,通过筛选钝化剂并将其复配用于大田实验,以研究复配钝化剂对土壤有效态重金属(Cd、Pb和Cu)及水稻吸收重金属的影响及其作用机理。室内筛选实验表明,在11种无机和有机钝化剂中,海泡石、生石灰和聚丙烯酰胺对土壤重金属钝化效果较好,使有效态Cd、Pb和Cu分别降低了32.4% ~ 89.2%、19.5% ~ 99.1%和49.4% ~ 92.4%,并将它们确定为复配钝化剂的成分。大田实验结果表明,生石灰、聚丙烯酰胺和海泡石复配对土壤中重金属钝化效果最佳,使有效态Cd、Pb和Cu分别降低了28.6%、20.2%和23.5%(p<0.05),其钝化机制为离子交换和络合作用。而且,该复配钝化剂对土壤化学性质影响最小。复配钝化剂使稻米中Cd的质量分数降低了21.7% ~ 93.1%(p<0.05)。另外,复配钝化剂对土壤微生物丰度和多样性没有显著影响。考虑到土壤的安全性和稳定性,推荐将生石灰、聚丙烯酰胺和海泡石复配钝化剂用于降低红壤稻米对Cd的吸收以确保粮食安全生产。本研究结果可为重金属污染红壤稻田的安全利用提供参考。     

The effect of water flooding at grain-filling stage on the uptake of heavy metal(loid)s by rice in slightly alkaline paddy soil

Environmental Science and Pollution Research - Continuous flooding has been widely used in paddy field to decrease the accumulation of heavy metal(loid)s by rice due to their decreased solubility...     

Determination of estrogenic compounds in wastewater using liquid chromatography-tandem mass spectrometry with electrospray and atmospheric pressure photoionization following desalting extraction

Two complementary LC-MS ionization methods, electrospray (ESI) and atmospheric pressure photoionization (APPI), have been optimized to determine three natural estrogenic compounds (estrone, 17beta-estradiol and estriol) and two synthetic estrogenic compounds (17alpha-ethynylestradiol and diethylstilbestrol) in the influent and effluent of wastewater treatment plants (WWTPs). The wastewater samples were first subjected to solid-phase extraction coupled with desalting extraction to remove matrix interference. The analytes were then detected using liquid chromatography-tandem mass spectrometry (LC-MS-MS) with ESI and dopant-assisted (DA) APPI to evaluate the ion suppression effect and to complement the detection and quantification of estrogenic compounds in complex wastewater samples. The average ion suppression factors for the extracts of the WWTP influent analyzed using ESI and APPI were 52+/-5% and 27+/-7%, respectively. The sensitivity and ionization efficiency of the LC-ESI-MS-MS system decreased dramatically when a complex matrix was present in the WWTP influent sample. Estrogenic compounds could be detected in the WWTP influent and effluent samples at concentrations below the parts-per-billion level. The lower detection limits obtained when using ESI and the higher matrix tolerance of the APPI method allowed the complete quantification of estrogenic compounds in very complex samples in a complementary manner.