Validation of a QuEChERS-based gas chromatographic method for analysis of pesticide residues in Cassia angustifolia (senna)

A simple multi-residue method based on modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was established for the determination of 17 organochlorine (OC), 15 organophosphorous (OP) and 7 synthetic pyrethroid (SP) pesticides in an economically important medicinal plant of India, Senna (Cassia angustifolia), by gas chromatography coupled to electron capture and flame thermionic detectors (GC/ECD/FTD) and confirmation of residues was done on gas chromatograph coupled with mass spectrometry (GC-MS). The developed method was validated by testing the following parameters: linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, accuracy–precision and measurement uncertainty; the validation study clearly demonstrated the suitability of the method for its intended application. All pesticides showed good linearity in the range 0.01–1.0 μg mL^?1 for OCs and OPs and 0.05–2.5 μg mL^?1 for SPs with correlation coefficients higher than 0.98. The method gave good recoveries for most of the pesticides (70–120%) with intra-day and inter-day precision < 20% in most of the cases. The limits of detection varied from 0.003 to 0.03 mg kg^?1, and the LOQs were determined as 0.01-0.049 mg kg^?1. The expanded uncertainties were <30%, which was distinctively less than a maximum default value of ±50%. The proposed method was successfully applied to determine pesticide residues in 12 commercial market samples obtained from different locations in India.     

Validation of reliable and selective methods for direct determination of glyphosate and aminomethylphosphonic acid in milk and urine using LC-MS/MS

Simple high-throughput procedures were developed for the direct analysis of glyphosate [N-(phosphonomethyl)glycine] and aminomethylphosphonic acid (AMPA) in human and bovine milk and human urine matrices. Samples were extracted with an acidified aqueous solution on a high-speed shaker. Stable isotope labeled internal standards were added with the extraction solvent to ensure accurate tracking and quantitation. An additional cleanup procedure using partitioning with methylene chloride was required for milk matrices to minimize the presence of matrix components that can impact the longevity of the analytical column. Both analytes were analyzed directly, without derivatization, by liquid chromatography tandem mass spectrometry using two separate precursor-to-product transitions that ensure and confirm the accuracy of the measured results. Method performance was evaluated during validation through a series of assessments that included linearity, accuracy, precision, selectivity, ionization effects and carryover. Limits of quantitation (LOQ) were determined to be 0.1 and 10 µg/L (ppb) for urine and milk, respectively, for both glyphosate and AMPA. Mean recoveries for all matrices were within 89–107% at three separate fortification levels including the LOQ. Precision for replicates was ≤7.4% relative standard deviation (RSD) for milk and ≤11.4% RSD for urine across all fortification levels. All human and bovine milk samples used for selectivity and ionization effects assessments were free of any detectable levels of glyphosate and AMPA. Some of the human urine samples contained trace levels of glyphosate and AMPA, which were background subtracted for accuracy assessments. Ionization effects testing showed no significant biases from the matrix. A successful independent external validation was conducted using the more complicated milk matrices to demonstrate method transferability.     

In vivo and in vitro metabolism of tobacco-specific nitrosamine, 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), by the freshwater planarian, Dugesia japonica

Cigarette smoke is a risk factor for human health, and many studies were conducted to investigate its adverse effects on humans and other mammals. However, since large amounts of cigarette products are produced and consumed, it is possible that tobacco chemicals can end up in aquatic environments through several routes, thus influencing aquatic organisms. In this study, the presence of tobacco-specific nitrosamine (TSNA), 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK), in aquatic environment was demonstrated. Since toxic effects on and distribution patterns of tobacco chemicals in aquatic organisms were rarely studied, after results of an acute toxicity pretest were obtained, experiment was conducted to investigate the bioaccumulation pattern of NNK and distribution patterns of its metabolites, mainly 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL), in NNK-treated freshwater planarians, Dugesia japonica. Results from in vivo and in vitro studies showed that NNK was readily converted to NNAL through the carbonyl reduction in bodies of NNK-treated planarians. Tissue concentrations of both chemicals increased in time- and dose-dependent manners. Furthermore, we examined the end products of NNK/NNAL α-hydroxylation in NNK-treated planarians, but only 1-(3-pyridyl)-1,4-butanediol was detected, suggesting that NNK metabolism in planarians partially differs from that in mammalian systems. This is the first report on NNK metabolism in an aquatic organism and can be used as a foundation for developing freshwater planarians as a new in vivo model for the study of NNK toxicology in the future.     

气相色谱/质谱测定苯酚丙酮生产废水中半挥发性有机物

建立了用二氯甲烷液液萃取对苯酚丙酮生产废水进行预处理,气相色谱/质谱法同时测定废水中半挥发性有毒有机物异丁酸、异丙苯、α-甲基苯乙烯、2-苯基丙醛、苯乙酮、2-苯基-2-丙醇、α-甲基苯甲醇、苯酚和苯甲酸等的定性定量分析方法。色谱条件为:DB-17MS型色谱柱,程序升温,进样量为1μL,质量选择检测器(MSD)。实验结果表明,该色谱条件对苯酚丙酮生产废水中各半挥发性组分具有较好的分离效果。而对9种组分的最低检出限均低于0.04mg/L,精密度实验相对标准偏差2.14%～5.15%,实际水样的加标回收率稳定。苯酚丙酮生产废水中的主要污染物为2-苯基-2-丙醇,其次为苯酚、异丁酸和异丙苯。     

4种重金属离子对间接火焰原子吸收光谱法测定铝的干扰

空气-乙炔间接火焰原子吸收法是我国目前运用较多且易于推广的铝检测方法,研究了Mg2+、Ca2+、Zn2+和Ni2+4种离子对此法测定0.40 mg/L Al3+的干扰情况。得出如下结论:(1)在±5%误差范围内,15.10 mg/L Mg2+、105.00mg/L Ca2+、0.23 mg/L Zn2+、0.88 mg/L Ni2+对0.40 mg/L Al3+无干扰。(2)本方法虽然操作复杂,但成本较低、灵敏度高,检测的浓度范围宽、稳定性好,加标回收率为96%~99%,检出限为0.04 mg/L,适宜测定范围为0.05~100.00 mg/L,适用于饮用水、河水及地下水中Al3+的测定。     

Application of indoxacarb for managing shoot and fruit borer of eggplant (Solanum melongena L.) and its decontamination

Indoxacarb was applied at 75 and 150 g a.i. ha^{? 1} for two years to an eggplant (Solanum melongena L.) crop grown in the field plots in order to evaluate its efficacy for management of the lepidopteron pest, shoot and fruit borer. The residues of the insecticide were quantified by high-pressure liquid chromatography (HPLC). The mean initial deposits of indoxacarb on eggplant fruits were found to be 2.60–2.634 mg kg^{? 1} and 3.64–3.68 mg kg^{? 1} from the two rates of applications, respectively. They declined with time and reached to non-detectable (< 0.02 mg kg^{? 1}) after 15–20 d. Residues dissipated with a half-life of 3.0–3.8 d from both first and second-year application. A 3 d waiting period for harvest of fruits after insecticide application and processing resulted in the residue levels that were below the Codex maximum residue limit (MRL) of 0.5 mg kg^{? 1} thereby achieving a maximum safety and minimum risk to consumers. The best combination of chemicals for decontamination of indoxacarb was found to be by washing with a mixture of alkali and potassium permanganate (KMnO₄) thereby resulting in the removal of 67.5% and 59.2 % residues for 5 and 10 μ g g^{? 1} spiking doses, respectively. Major products formed on reaction of indoxacarb with alkali were identified by electron spray ionization chromatography/mass spectrometry (ESI/MS). The per cent reduction on the weight and number basis of treated eggplant plots were compared to those observed in control plots to demonstrate the effectiveness of indoxacarb treatment on shoot and fruit borer population.     

Trace level determination of selected sulfonylurea herbicides in wetland sediment by liquid chromatography electrospray tandem mass spectrometry

Sulfonylurea herbicides are widely used in crop production on the Canadian prairies and a portion of these herbicides applied to cropland are inevitably lost to surrounding aquatic ecosystems. Little is known regarding the presence of sulfonylurea herbicides in wetlands located amongst cropland. This paper describes a new analytical method for the extraction and the determination of seven sulfonylurea herbicides (thifensulfuron-methyl, tribenuron-methyl, ethametsulfuron-methyl, metsulfuron-methyl, rimsulfuron, nicosulfuron and sulfosulfuron) in wetland sediment. The method provided > 85% analyte recovery from fortified sediment for six of the seven sulfonylurea herbicides with a limit of quantification (LOQ) of 1.0 μ g kg^{? 1}. Tribenuron-methyl had significantly lower recovery compared to the other six sulfonylurea herbicides (LOQ = 2 μ g kg^{? 1}). Mean recovery standard deviations were < 10%. This methodology was used to quantify sulfonylurea herbicide residues in sediment samples collected from prairie wetlands situated within the agricultural landscape of Saskatchewan and Manitoba, Canada. This is the first-known detection of sulfonylurea herbicide residues in prairie wetland sediments. Ethametsulfuron-methyl, sulfosulfuron and metsulfuron-methyl, the three most environmentally persistent of the seven sulfonylurea herbicides monitored in the surveillance component of this study, were most frequently detected in wetland sediment with mean concentrations ranging from 1.2 to 10 μ g kg^{? 1}.     

Fast determination of phenoxy acid herbicides in carrots and apples using liquid chromatography coupled triple quadrupole mass spectrometry

A fast, simple and inexpensive method has been developed for the analysis of phenoxy acid herbicides: 2,4-dichlorophenoxyacetic acid (2,4-D), 4-chloro-2-methylphenoxyacetic acid (MCPA), 2-(4-chloro-o-tolyloxy)propionic acid (MCPP), 2-(4-aryloxyphenoxy)propionic acid (Fluazifop) and 2-(4-aryloxyphenoxy)propionic acid (Haloxyfop) in carrots and apples by liquid chromatography coupled to triple quadrupole mass spectrometry (LC/MS/MS). The compounds were analyzed by QuEChERS (quick, easy, cheap, effective, rugged, safe) methodology without cleanup.

The recoveries were performed at two spiked levels (0.05 and 0.5 mg/kg) for both matrices with six replicates for each level. The mean recoveries ranged from 70–92% for both apples and carrots. The precision of the method expressed as relative standard deviation (RSD%) was found to be in the range 3–15%. For all compounds, good linearity (r² > 0.99) was obtained over the range of concentration from 0.05 μ g/mL to 0.5 μ g/mL, corresponding to the pesticide concentrations of 0.05 mg/kg and 0.5 mg/kg, respectively. The determination limits (LOQs) ranged from 0.01 ng/mL to 1.3 ng/mL in solvent, whereas, the LOQs calculated in matrix ranged from 0.05 ng/g to 21.0 ng/g for apples and from 0.06 ng/g to 10.2 ng/g for carrots. The developed methodology combines the advantages of both QuEChERS and LC/MS/MS producing a very rapid, sensitive and cheap method useful for the routine analytical laboratories.     

Validation of a hydride generation atomic absorption spectrometry methodology for determination of mercury in fish designed for application in the Brazilian national residue control plan

In the present study, a method for the determination of mercury (Hg) in fish was validated according to ISO/IEC 17025, INMETRO (Brazil), and more recent European recommendations (Commission Decision 2007/333/EC and 2002/657/EC) for implementation in the Brazilian Residue Control Plan (NRCP) in routine applications. The parameters evaluated in the validation were investigated in detail. The results obtained for limit of detection and quantification were respectively, 2.36 and 7.88 μg kg^?1 of Hg. While the recovery varies between 90–96%. The coefficient of variation was of 4.06–8.94% for the repeatability. Furthermore, a comparison using an external proficiency testing scheme was realized. The results of method validated for the determination of the mercury in fish by Hydride generation atomic absorption spectrometry were considered suitable for implementation in routine analysis.     

Characterization of an urban landfill soil by using physicochemical analysis and solid phase microextraction (SPME)—GC/MS

We have aimed at characterizing top soil samples taken in-situ from five different locations of the unregulated dumping site in Eskişehir/Turkey for a period of six months. The study is the first attempt in the city and in Turkey, regarding particularly the SPME (Solid Phase Microextraction Technique) analysis method utilized. A comprehensive research has been conducted to produce critical soil data to be used for indicating current risks as well as the urgency of rehabilitating the site and establishing a sanitary landfill in the site. Conventional physicochemical analytical methods and SPME technique were used to analyze the samples. Physicochemical analyses were performed for determining the pH, total dried matter, volatile matter, total nitrogen, phosphorus, macro elements and heavy metals. Meteorological data were also recorded for the same period. SPSS.10.0 statistical program was used to determine the correlation between meteorological data and physicochemical analysis results. Mean values were used in the correlation analyses. These data indicated that the air temperature and precipitation have significant effects on soil characteristics. SPME, coupled with GC/MS, was used to identify eighty six volatile and semi-volatile organic compounds contained in soil samples. The samples were extracted by headspace SPME with heating (δHS-SPME). SPME analyses were conducted using a commercially available polydimethylsiloxane/divinylbenzene (PDMS/DVB) fiber having a film thickness of 65 μm (Supelco) as a capture medium. The experimentally optimized headspace sampling conditions were arranged (15 min. at 50^˚C) before a 30 min. sampling period.