Determination of polychlorinated biphenyls in sediments, using sonication extraction and capillary column gas chromatography-electron capture detection with internal standard calibration

A sonication technique is presented for the extraction of polychlorinated biphenyls (PCBs) from sediments. In addition, a quantitation scheme is described which allows peak-specific and, in many cases, congener-specific determination of PCBs. PCBs are quantitated by capillary column gas chromatography-electron capture detection, with internal standard calibration. Results utilizing sonication extraction were compared with those obtained by Soxhlet and steam distillation extractions of 3 U.S. Environmental Protection Agency (EPA) quality control sediment samples and 3 lake sediments known to be contaminated with PCBs. Environmental lake sediments were extracted wet, with no drying prior to extraction. Recoveries by each technique varied depending on the sediment sample being extracted and degree of chlorination of PCB congeners. With proper selection of extraction solvent, the sonication technique can recover amounts of PCBs equivalent to and sometimes greater than recoveries by the Soxhlet or steam distillation techniques. A 24-h quiescent period in the extraction solvent between 2 sonications improved extraction efficiency for 2 freeze-dried sediments but did not affect results obtained for 3 environmentally contaminated sediments that were extracted without drying. Replacement of Soxhlet extraction with the sonication technique results in reduced sample preparation time, decreased volumes of solvents and sample, and substitution of common laboratory glassware in place of fragile, expensive Soxhlet glassware. Sonication extraction can also improve precision compared with Soxhlet extraction.     

High-performance liquid chromatographic determination of strychnine in grain baits.l.

A simple and rapid high-performance liquid chromatographic procedure is described for the determination of strychnine. Grain baits containing strychnine alkaloid are ground, mixed, and extracted by shaking with chloroform. Without further cleanup, extract filtrates are injected directly into a liquid chromatograph. Chromatography is complete within 7 min and peak heights are used for quantitation. Separations were made on a 30 cm times 4 mm id stainless steel column packed with mu Porasil (8-12 mum silica). The eluting solvent was methanol-chloroform (10+90) at a flow rate of 2.0 ml/min. Recovery of spiked samples ranged from 91.5 to 95.2%. Confirmation of strychnine from a commercial sample was made by high resolution mass spectrometry with mass agreement to 1.2 ppm.     

Initial sample extract stock concentration affects in vitro bioassay-based toxicological risk characterization

Purpose

Bioassays have become an alternative for sediment risk profiling, including potential compliance with sediment quality criteria (SQC). In vitro functional bioassays have evolved through standardization and validation towards a confident toxicological hazard estimate of sediments. Sample preparation is a key aspect for the improvement of bioassays. It is a standard practice to use a high single-stock concentration of extracts to further dilute test concentrations from and carry out the analysis. This study was carried out to demonstrate that high a contaminant load in a sediment extract (>20 g sediment equivalents (SEQ) ml^?1) oversaturates solubility in carrier solvents and overloads the clean-up columns, potentially resulting in an under- or overestimation of the quantified dioxin-like toxic potency.

Materials and methods

Cleaned nonpolar sediment extracts were prepared from samples collected from various locations in Luxembourg. The influence on the quantified toxic potency of the initial stock concentration, sonication assisted dissolution and exposure period in an in vitro bioassay for dioxin-like toxic potency (Bio-TEQ) was evaluated, as well as its impact on the sediment risk characterization according to SQC.

Results and discussion

Stock sonication before serial dilution strongly reduced the standard variation of the outcomes. Higher initial stock concentrations (>20 g SEQ ml^?1 for contaminated sediments) produced significantly lower Bio-TEQs g SEQ^?1 compared to those obtained with initial stock concentrations of 2 g SEQ ml^?1, probably due to solvent oversaturation. An initial stock concentration of 2 g SEQ ml^?1 is low enough to prevent mis-estimation, but 20 or even 200 g SEQ ml^?1 might be used when quantification of Bio-TEQ is required. The overload of extract on clean-up columns caused an overestimation of the dioxin-like potency probably due to PAH-induced false-positive responses.

Conclusions

Higher contaminant load in the initial extracts from sediments affects the reliability of in vitro Bio-TEQ sediment quantification. Advice is given on how to avoid underestimation because of extract oversaturation, avoid overestimation because of overload of clean-up columns and reduce variability by applying sonication in standard testing protocols for risk characterization and quantification of the sample’s toxic potency. Taking into account the new aspects revealed in this study, in addition to important issues for quality control that are already included, the in vitro bioassays based on Bio-TEQs can be applied in a comprehensive monitoring program to determine whether sediments comply with health and safety standards for humans and the environment.     

Experimental evaluation of methods to quantify dissolved organic nitrogen (DON) and dissolved organic carbon (DOC) in soil

A significant proportion of the total nutrient in soil solution can be bound to organic molecules and these often constitute a major loss from soil to freshwater. Our purpose was to determine whether chemical extractants used for measuring inorganic N could also be used to quantify dissolved organic nitrogen (DON) and carbon (DOC) in soil. In a range of soils, DOC and DON were extracted with either distilled water or 2 M KCl and the amount recovered compared with that present in soil solution recovered by centrifugal-drainage. The recovery of DON and DOC from soil was highly dependent upon the method of extraction. Factors such as soil sampling strategy (number of samples over space and time), sample preparation (sieving and drying), soil storage, extraction temperature, shaking time, and soil-to-extractant volume ratio all significantly affected the amount of DOC and DON extracted from soil. To allow direct comparison between independent studies we therefore propose the introduction of a standardized extraction procedure: Replicate samples of unsieved, field-moist soil extracted as soon as possible after collection with distilled water, 0.5 M K₂SO₄ or 2 M KCl at a 1:5 w/v ratio for 1 h at 20 °C.     

Dichloromethane as a solvent for lipid extraction and assessment of lipid classes and fatty acids from samples of different natures

The usefulness of the solvent mixture dichloromethane/methanol for lipid extraction and the determination of lipid classes and fatty acids in samples of different natures was conducted. Two different extraction methods were compared, one containing chloroform/methanol, another containing dichloromethane/methanol. Total lipid extraction showed some minor differences but no variation in the lipid classes. Regarding the fatty acid profile, in Echium virescens seeds, 17 major fatty acids could be identified and quantified, and all were equally extracted when either solvent system was employed. In Echium acanthocarpum hairy roots, 17 major fatty acids were quantified, showing some statistical differences for one cell line in favor of chloroform. The data obtained from the liquid nutrient medium were also comparable. The cod roe sample showed 31 major fatty acids, showing no statistical differences between the two solvent systems. Contrarily, the CH 2Cl 2 method was able to extract 31 main fatty acids found in European seabass dorsal muscle more efficiently than the CHCl 3 method. The results indicate that, for lipid extraction and fatty acid assessment, dichloromethane/methanol can readily replace the commonly employed chloroform/methanol, thus avoiding the major health, security, and regulatory problems associated with the use of chloroform.     

Determination of thiamphenicol in bovine plasma by liquid chromatography

A liquid chromatographic method is described for the measurement of thiamphenicol in bovine plasma. The plasma (1 mL) is extracted with ethyl acetate. After the solvent is evaporated under a stream of nitrogen, the residue is reconstituted in methanol-water and analyzed by reverse-phase liquid chromatography with UV detection at 224 nm. The intra-day recoveries for bovine plasma spiked with 5 and 50 micrograms/mL of thiamphenicol were 102 and 101%, respectively, with coefficients of variation of 2.40 and 0.28%, respectively. The interday recoveries for the 5 and 50 micrograms/mL samples were 103 and 101%, respectively, with coefficients of variation of 3.40 and 0.94%, respectively. The sensitivity of the method allows quantitation to at least the 100 ng/mL level.     

Parameters affecting extraction of selected fungicides from vineyard soils

This paper describes a sensitive method for the simultaneous quantification of eight commonly used grapevine fungicides in vineyard soils: cyprodinil, fludioxonil, metalaxyl, penconazole, pyrimethanil, procymidone, tebuconazole, and vinclozolin. The fungicides are extracted from the soil sample by sonication with water followed by shaking with ethyl acetate and are quantified by gas chromatography with mass spectrometry. Average extraction efficiencies in a sample of seven spiked, previously fungicide-free soils were > or =79% for all of the analytes, method precisions were > or =17%, and quantification limits were < or =50 microg/kg. However, because recoveries varied considerably from soil to soil, there is a need to control for soil matrix differences (mainly soil pH and exchangeable calcium content); as a consequence, soil fungicide contents must be quantified by the standard additions method. When the method was applied in this way to soil samples from vineyards belonging to the specified wine-growing region of Rias Baixas (Galicia, northwestern Spain) taken at the beginning of October (1 month after the crop's final treatment), levels of fludioxonil as high as 991 microg/kg were found, but at the start of the season (9 months after the previous crop's final treatment) only fludioxonil was detected at levels higher than its limit of quantification (45 and 52 microg/kg).     

Influence of sample preparation on assay of phenolic acids from eggplant

Sample preparation is often overlooked and is frequently considered as "a means to an end". This systematic study with a phenolic-enriched substrate, eggplant (Solanum melongena L.), was undertaken to evaluate the substantial variations in the extraction techniques, solvents, and parameters as described in the published literature. Direct comparison of over 10 extraction procedures or conditions was performed to show the importance and influence of sample preparation on the assay of phenolic compounds. Chlorogenic acid (CA) was the most abundant phenolic acid accounting for >75% of the total phenolic acids content extracted from the eggplant sample. Optimum extraction of CA and total phenolics (TP) from Black Bell cultivar of eggplant were obtained when extractions were performed with a mixture of MeOH/H2O at a ratio of 80:20% v/v using a pressurized liquid extractor (PLE) at 100 degrees C. The amount of CA and TP extracted from eggplant by the previously reported procedures using a wrist shaker, rotary shaker, stirring, sonication, or reflux with different extraction solvents (acetone or varying composition of MeOH/H2O solvent mixtures) varied significantly between 5 and 95% as compared to PLE. The predominant phenolic acids in the free phenolic acid fraction of Black Beauty cultivar of eggplant were CA isomers. However, caffeic acid isomers were the major phenolic acids extracted from the base-hydrolyzed fraction. The total amount of caffeic acid extracted from the Italian Neon cultivar was more that twice that of four other eggplant cultivars (Orient Express, Calliope Zebra Stripe, Orient Charm Neon, and Black Beauty).     

Extraction and analysis of nitrogen,phosphorus and carbon fractions in plant material

A method is described for the extraction and analysis of various nitrogen‐, phosphorus‐ and carbon‐containing fractions from plant material. Lipids were extracted with chloroform/methanol and chloroform/methanol/water. Soluble nitrogen (nitrate, ammonia, and amino acid), phosphorus (inorganic and sugar phosphate) and carbon (sugar and tannin) fractions were extracted with cold trichloracetic acid. Hot soluble nitrogen and phosphorus (nucleic acid) and carbon (starch and tannin) fractions were extracted with hot trichloracetic acid. Protein remained in the residue. A detailed automated scheme is described for the analysis of each of the above fractions. Also included are methods for analyzing triglyceride, hydrolyzable ester phosphate and phytic acid.     

Simultaneous determination of trace levels of 10 quinolones in swine, chicken, and shrimp muscle tissues using HPLC with programmable fluorescence detection

A HPLC method using a modified sample preparation procedure was optimized and validated for the quantification of 10 quinolones (QNs), including marbofloxacin, ciprofloxacin, norfloxacin, lomefloxacin, danofloxacin, enrofloxacin, sarafloxacin, difloxacin, oxolinic acid, and flumequine, in swine, chicken, and shrimp tissues. In this method, only a small mass (相似文献   

Absence of isomerization of retinyl palmitate, retinol, and retinal in chlorinated and nonchlorinated solvents under gold light

Purified solutions of all-trans retinyl palmitate, retinol, and retinaldehyde in chloroform, methylene chloride, or hexane were exposed to white light or gold fluorescent light or were kept in the dark, and the resulting isomer distributions were determined by LC (liquid chromatography). No significant isomerization of any of the retinoids occurred either in the dark or on exposure to gold light in any of the solvents tested. However, a large amount of the 9-cis isomer and only much smaller amounts of other cis isomers were produced when retinol or retinyl palmitate in chloroform or methylene chloride solution was exposed to white light. The isomerization pattern of retinyl palmitate in chloroform was not altered by the addition of free-radical scavengers, addition of an organic base, or substitution of deuterochloroform for chloroform as solvent. Use of other polar solvents such as tetrahydrofuran, acetone, or methanol produced isomer distributions similar to those obtained in chloroform solution. Retinol and retinyl palmitate in hexane solution, on exposure to white light, were isomerized much less extensively than in chloroform or methylene chloride and produced a significant amount of the 13-cis, as well as the 9-cis, isomer. Isomerization of retinaldehyde in chloroform or in methylene chloride solution under white light yielded 13-cis, 11-cis, 9-cis, and 7-cis isomers, in order of decreasing amount, whereas in hexane solution, only the 13-cis and 9-cis isomers were produced in significant quantity.     

土壤硝态氮含量检测和分布图生成中的最优样本量

土壤参数的时空变异是实施精细农业时要考虑的重要因素，在土壤检测的栅格采样中有必要确定最优样本量。本研究的试验田是一块生长中的玉米地块，试验区的面积为4.2 m×4.2 m，该试验区被假定为土壤采样中的一个栅格，该栅格又被细分为49个0.6 m×0.6 m的子栅格。采样时，所分析的土壤参数为土壤硝态氮含量，从播种到收获共进行了7次采样。通过对土壤样本土壤硝态氮时空变异的分析，揭示了样本量和土壤硝态氮含量预测误差之间的相关关系。土壤硝态氮含量呈非正态分布，通过对玉米各个生长期获得的数据分析表明：含量水平的预测误差随深度的增加而增大；当从一个栅格只采集1个土壤样本时(样本量为1)，预测误差基本在50％左右(显著水平：α≈0.10)，而当从一个栅格采集5个土壤样本时(样本量为5)，预测误差将降至25％左右。另一方面，当要求预测误差低于30％时，对于普通生长条件下的土壤需要从1个栅格至少采集3个样本，而对于追肥后的土壤则至少需采集15个样本。     

Anaerobic Incubation without Shaking over a Prolonged Period as a Method to Determine Mineralizable Nitrogen in Rice Soils

Fertilization rates of nitrogen (N) in rice crop are based on crop needs and the capacity of the soil to supply N, which is determined by several methods. This study evaluated a method of anaerobic incubation without shaking for extended periods of time. Three rice soils of the Inceptisol, Alfisol, and Vertisol orders were fertilized with N rates of 0, 80, and 160 kg ha^?1 and incubated for 0, 7, 14, 21, and 28 d at 20 and 40 °C. The methodology also used short-term anaerobic incubation and constant shaking for 7 d at 40 °C. Field experiments were conducted with rice in the same soils with equal N rates, and extracted plant N was compared with mineralized N. Results indicated that the methodology without shaking is comparable to the constant shaking procedure for short-term incubations. However, incubations without shaking for longer periods of time had the greatest relation to crop extracted N.     

Effect of the storage conditions of soil samples on carbon and nitrogen extractability

Concentrations of carbon and nitrogen extractable by 0.05 M K₂SO₄ (C_ext and N_ext, respectively) in 14 soils of different ecosystems vary from 16 to 205 and from 4 to 53 mg/kg, respectively. The portion of C_ext in soil organic matter is 0.06 to 0.38% of total carbon, and the portion of N_ext is 0.12–1.05% of total nitrogen. The storage of samples and their preparation to analysis differently affect the extractability of elements. The concentration of C_ext is less variable than the concentration of N_ext. An increase in C extractability (by 1.4–6.7 times) is a common feature of all soils under drying; at the following incubation of dried soils, the extractability of C decreases by 28–56%. The extractability of N increases not only under drying (by 1.5–7.1 times) and the following incubation of samples (by 25–60% to 2–3 times), but also under freezing of most soils and at the incubation of fresh and defrozen samples. A close direct correlation is observed between the initial water content of soil and the relative increase in C extractability under drying and N extractability under freezing and drying.     

Tissue‐to‐solvent ratio and other factors affecting determination of soluble polyphenols in tropical leaves

Abstract

Soluble polyphenol concentrations of tropical leaves are believed to affect nitrogen (N) mineralization potential during decomposition. However, polyphenol concentrations reported for the same species have varied several‐fold among studies. Testing potential explanations for these discrepancies, we found high tissue‐to‐solvent ratios, as specified in one of two popular extraction procedures, led to reduced estimates. Use of aqueous methanol rather than water increased recovered polyphenols somewhat, but was not adequate to explain differences among studies. Elevated drying temperatures decreased recovery of soluble polyphenols. Folin‐Ciocalteu reagent produced less precipitate and was more reproducible than Folin‐Denis reagent.     

Comparison of methods for the exhaustive extraction of hypericins, flavonoids, and hyperforin from Hypericum perforatum L

Renewed interest in plant-derived drugs has led to an increased need for efficient extraction methods. Hypericum perforatum L. contains several groups of bioactive compounds with noteworthy pharmacological activities. Direct sonication of H. perforatum was investigated and compared with conventional maceration, indirect sonication, Soxhlet extraction, and accelerated solvent extraction (ASE). Highly selective liquid chromatography/tandem mass spectrometry analysis showed that the content of six investigated active compounds (hypericin, pseudohypericin, hyperoside, rutin, quercitrin, and hyperforin) in extracts obtained by direct sonication was significantly higher than in extracts obtained by the other methods. The active compound contents increased on increasing the ultrasonic power from 40 to 60 W when using direct sonication. Conventional maceration gave the lowest amount of analyzed active compounds. Soxhlet extraction gave better results than ASE or indirect sonication.     

Microbial biomass in soil: Effects of some experimental variables on biochemical estimations

The effects of experimental variables on estimates of biomass C and mineral-N (Min-N) flush by the chloroform fumigation technique were determined in near neutral to slightly alkaline topsoil samples of a Typic Haplaquoll taken at three different times under grazed grass-clover pastures. The variables were soil mesh size ( < 3.3 and < 2 mm), water content [50 and 60% of water-holding capacity (WHC)], the use of samples that were “fresh” or that had been previously incubated (7 days at 50% of WHC at 25°C), and, for the biomass C estimates, various incubation periods for measuring CO₂C production.Estimates of biomass C were most strongly influenced by the incubation period selected for CO₂C production by unfumigated soil. The effects of soil mesh size and water content were significant for some samples, but were not consistent. Prior incubation lowered all biomass C estimates significantly, except for some samples where a 0–10 day period was used for measuring CO₂C production by unfumigated soil; (the presence or absence of soda-lime during incubation had no influence on subsequent rates of CO₂ production by the unfumigated samples).Min-N flush was not consistently influenced by these variables, although some significant treatment effects occurred. Biomass C-to-Min-N flush ratios were predictably dependent upon the biomass C estimates used. They averaged 9.0 in “fresh” samples and 6.0 in incubated samples, when the incubation periods for CO₂C production by unfumigated samples were 10–20 and 0–10 days respectively.Results indicate that care should be taken in interpreting and comparing biochemical indices of microbial biomass, and their ratios, obtained by different or modified experimental procedures.     

Rapid sample preparation method for LC-MS/MS or GC-MS analysis of acrylamide in various food matrices

A fast and easy sample preparation procedure for analysis of acrylamide in various food matrices was developed and optimized. In its first step, deuterated acrylamide internal standard is added to 1 g of homogenized sample together with 5 mL of hexane, 10 mL of water, 10 mL of acetonitrile, 4 g of MgSO4, and 0.5 g of NaCl. Water facilitates the extraction of acrylamide; hexane serves for sample defatting; and the salt combination induces separation of water and acetonitrile layers and forces the majority of acrylamide into the acetonitrile layer. After vigorous shaking of the extraction mixture for 1 min and centrifugation, the upper hexane layer is discarded and a 1 mL aliquot of the acetonitrile extract is cleaned up by dispersive solid-phase extraction using 50 mg of primary secondary amine sorbent and 150 mg of anhydrous MgSO4. The final extract is analyzed either by liquid chromatography-tandem mass spectrometry or by gas chromatography-mass spectrometry (in positive chemical ionization mode) using the direct sample introduction technique for rugged large-volume injection.     

A validated multianalyte LC-MS/MS method for quantification of 25 mycotoxins in cassava flour, peanut cake and maize samples

This study was designed to develop a sensitive liquid chromatography tandem mass spectrometry (LC-MS/MS) method for the simultaneous detection and quantification of 25 mycotoxins in cassava flour, peanut cake and maize samples with particular focus on the optimization of the sample preparation protocol and method validation. All 25 mycotoxins were extracted in a single step with a mixture of methanol/ethyl acetate/water (70:20:10, v/v/v). The method limits of quantification (LOQ) varied from 0.3 μg/kg to 106 μg/kg. Good precision and linearity were observed for most of the mycotoxins. The method was applied for the analysis of naturally contaminated peanut cake, cassava flour and maize samples from the Republic of Benin. All samples analyzed (fifteen peanut cakes, four maize flour and four cassava flour samples) tested positive for one or more mycotoxins. Aflatoxins (total aflatoxins; 10-346 μg/kg) and ochratoxin A (相似文献   

Determination of dapsone in muscle tissue and milk using high-performance liquid chromatography-tandem mass spectrometry

A precise and selective liquid chromatography-tandem mass spectrometry (LC-MS/MS) method for the determination of dapsone in muscle tissue and milk has been developed. The sample preparation was based on extraction with organic solvent and automated solid-phase extraction (SPE) cleanup. At least three product ions were monitored for the analyte. The method was validated according to the European Decision 2002/657/EC. Estimated analytical limits were 0.0018 ng/g for CCα and 0.0031 ng/g for CCβ in meat and milk. An excellent linear concentration range was observed for both matrices with a correlation coefficient better than 0.997. Recoveries were 105-117% in meat and 101-108% in milk, with satisfactory precision and coefficients of variance (CV) less than 8%. Additionally, a simplified quantification approach was successfully evaluated depending only on the response factor (F) without the use of calibration curve. The developed method provides reliable and sensitive identification and quantification of dapsone in meat and milk.