Analysis of snake tissue and snake eggs for 2,3,7,8-tetrachlorodibenzo-p-dioxin via fused silica GC combined with atmospheric pressure ionization MS

Several snake tissue samples and one set of snake eggs were collected and analyzed for 2,3,7,8-tetrachlorodibenzo-$\text{p}$-dioxin. The isomer-specific analysis was performed using fused silica GC combined with atmospheric pressure ionization MS. The results ranged from a low of 38 parts-per-trillion (ppt) to high levels over 500 ppt.     

Screening of compost for PAHs and pesticides using static subcritical water extraction.

Static subcritical water extraction (SubWE) along with solid phase extraction (SPE) was used for the analysis of PAHs and pesticides in municipal solid waste compost. Yields obtained for PAHs in certified reference sediment (CRM 104) were acceptable. The extraction method was simple, rapid, used small sample sizes, and no sample drying was required. Analysis of samples was performed by GC/MS and HPLC. Recovery of spiked pesticides was greatest at 110 degrees C for 20 min extraction time. The optimum extraction for PAH analysis was achieved at 150 degrees C for 20 min. Addition of C-18 resin as an "alternate sorbent" upon cooling increased recovery of PAHs but not of pesticides, however, it increased the stability of atrazine and propazine at higher temperatures. Analysis of three municipal compost samples from the Dayton, OH (USA) area showed no pesticides above the detection limit, however, PAH totals for 11 PAHs were 15.97, 14.42, and 20.79 microg g(-1). The totals of six of the seven carcinogenic PAHs, for which remediation goals in the United States is 4.6 microg g(-1), were determined to be 9.89, 6.77, and 13.06 microg g(-1) dry weight. The highest PAH totals were obtained from compost containing sewage sludge.     

Trace analysis of parabens preservatives in drinking water treatment sludge,treated, and mineral water samples

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 μg L^?1 in aqueous matrices and from 5 to 500 ng g^?1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (<?20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 μg L^?1 in mineral and treated water samples and 10 ng g^?1 in DWTS samples.     

Solid‐phase extraction and GC analyses of select agricultural pesticides and metabolites in stream water

Abstract

The occurrence of agricultural pesticides in surface waters around the USA has created a concern over the status of safe drinking water. Solid‐phase extraction (SPE) or liquid‐liquid extraction (LLE) is usually employed to concentrate trace levels of pesticides in water samples to concentrations that are measurable with advanced chromatographic instruments. We describe here a SPE and capillary gas chromatographic (GC) procedure to extract and concentrate trace levels of select agricultural pesticides and metabolites from stream water. Our SPE and GC method provides high sensitivity, with recoveries between 85% to 95%, and high reproducibility for 9 of the pesticides studied. The described method provided marginal recoveries of 19 and 60% for the atrazine metabolites.     

强化土著微生物处理硝基苯和苯胺污染地下水

以硝基苯、苯胺为主要污染物的污染地下水为研究对象,加入激活剂(乳糖、Na2HPO4、乳糖+Na2HPO4、乙醇、牛肉膏、蛋白胨)激活土著微生物,并考察其对土著微生物生长及硝基苯、苯胺降解效果的影响。加入激活剂3d后测各个水样的脱氢酶活性,对培养9d后的水样进行气相色谱/质谱(GC/MS)分析。结果表明,加入乳糖的水样中,其微生物相对增长率达157.2%,硝基苯、苯胺的相对去除率分别为14.90%和0.79%;加入Na2HPO4和乙醇的水样中,其微生物增长和硝基苯、苯胺降解情况均没有明显变化;加入乳糖+Na2HPO4的水样中,微生物相对增长率达180.3%,硝基苯、苯胺的相对去除率分别为24.20%和1.21%;加入牛肉膏的水样中,微生物的相对增长率为830.7%,硝基苯、苯胺的相对去除率分别为99.99%和99.67%;加入蛋白胨的水样中,其微生物相对增长率为686.0%,硝基苯、苯胺的相对去除率分别为99.33%和58.94%。GC/MS分析结果表明,加入激活剂后对氯苯胺、1-甲基-4-硝基苯等其他有机物的降解率均有提高。由此可见,通过激活土著微生物修复有机物污染地下水是可行的。     

Determination of tris(4-chlorophenyl)methanol and tris(4-chlorophenyl)methane in fish, marine mammals and sediment

Tris(4-chlorophenyl)methanol (TCP) and tris(4-chlorophenyl)methane (TCPMe) were determined in aquatic organisms and sediment by a method based on Soxhlet extraction, gel permeation chromatography, fractionation over silica and gas chromatography/mass spectrometry (GC/MS) analysis. TCPMe was identified as the 4-substituted isomer after synthesis of this compound. TCP could be determined by GC/MS with negative chemical ionistation (GC/NCI-MS) with a detection limit of 0.02 g kg(-1) and a recovery of 90%. TCP concentrations in marine mammals from the North Sea and Dutch Wadden Sea ranged from 0.2 to 2 mg kg(-1), and those in marine and freshwater fish samples from 0.005 to 0.4 mg kg(-1) on a lipid wt basis. TCP concentrations in two Rhine delta sediment samples were 1.2 and 3.0 microg kg(-1) dry wt, respectively. TCPMe concentrations, determined by GC/MS with electron impact (GC/EI-MS), were 10-50% of the TCP concentration in all samples analysed.     

Rapid resolution liquid chromatography-tandem mass spectrometry method for the determination of endocrine disrupting chemicals (EDCs), pharmaceuticals and personal care products (PPCPs) in wastewater irrigated soils

A multiresidue analytical method was developed for the determination of 9 endocrine disrupting chemicals (EDCs) and 19 pharmaceuticals and personal care products (PPCPs) including acidic and neutral pharmaceuticals in water and soil samples using rapid resolution liquid chromatography-tandem mass spectrometry (RRLC-MS/MS). Solid phase extraction (SPE), and ultrasonic extraction combined with silica gel purification were applied as pretreatment methods for water and soil samples, respectively. The extracts of the EDCs and PPCPs in water and soil samples were then analyzed by RRLC-MS/MS in electrospray ionization (ESI) mode in three independent runs. The chromatographic mobile phases consisted of Milli-Q water and acetonitrile for EDCs and neutral pharmaceuticals, and Milli-Q water containing 0.01 % acetic acid (v/v) and acetonitrile: methanol (1:1, v/v) for acidic pharmaceuticals at a flow rate of 0.3 mL/min. Most of the target compounds exhibited signal suppression due to matrix effects. Measures taken to reduce matrix effects included use of isotope-labeled internal standards, and application of matrix-match calibration curves in the RRLC-MS/MS analyses. The limits of quantitation ranged between 0.15 and 14.08 ng/L for water samples and between 0.06 and 10.64 ng/g for solid samples. The recoveries for the target analytes ranged from 62 to 208 % in water samples and 43 to 177 % in solid samples, with majority of the target compounds having recoveries ranging between 70–120 %. Precision, expressed as the relative standard deviation (RSD), was obtained less than 7.6 and 20.5 % for repeatability and reproducibility, respectively. The established method was successfully applied to the water and soil samples from four irrigated plots in Guangzhou. Six compounds namely bisphenol-A, 4-nonylphenol, triclosan, triclocarban, salicylic acid and clofibric acid were detected in the soils.     

Air and groundwater pollution in an agricultural region of the Turkish Mediterranean coast

Air pollution and groundwater pollution in conjunction with agricultural activity were investigated in Antayla province on the Turkish Mediterranean coast. The air pollution was investigated in terms of gas-phase nitric acid (HNO3), sulfur dioxide (SO2), ammonia (NH3), and particulate matter for a 6-month period in the atmosphere using a "filter pack" system, which was developed and optimized in our laboratory. Ozone was measured by using an automated analyzer. Among all of the gas-phase pollutants, HNO3 had the lowest concentration (0.42 microg x m(-3)) followed by NH3. Agricultural activities seem to be the major source of observed NH3 in the air. The current state of water pollution was investigated in terms of organochlorine and organophosphorus pesticides around the greenhouses, in which mainly tomato, pepper, and eggplant are cultivated. Water samples were collected from 40 points, 28 of which were wells and 12 of which were surface water. The pesticide concentrations in water samples were determined by means of solid-phase extraction (SPE) followed by a gas chromatography (GC)-electron capture detector (ECD)/nitrogen phosphorus detector (NPD) system. In general, surface water samples were more polluted by the pesticides than groundwater samples. The most frequently observed pesticides were chlorpyriphos (57%) and aldrin (79%) in groundwater, and chlorpyriphos (75%), aldrin, and endosulfan sulfate (83%) in surface water samples. The highest concentrations were observed for fenamiphos (394.8 ng/L) and aldrin (68.51 ng/L) in groundwater, and dichlorvos (322.2 ng/L) and endosulfan sulfate (89.5 ng/L) in surface water samples. At least one pesticide had a concentration above the health limit in 38% of all the water samples analyzed.     

Application of a permethrin immunosorbent assay method to residential soil and dust samples

A low-cost, high throughput bioanalytical screening method was developed for monitoring cis/trans-permethrin in dust and soil samples. The method consisted of a simple sample preparation procedure [sonication with dichloromethane followed by a solvent exchange into methanol:water (1:1)] with bioanalytical detection using a magnetic particle enzyme-linked immunosorbent assay (ELISA). Quantitative recoveries (83–126 %) of cis/trans-permethrin were obtained for spiked soil and dust samples. The percent difference of duplicate ELISA analyses was within ± 20 % for standards and ± 35 % for samples. Similar sample preparation procedures were used for the conventional gas chromatography/mass spectrometry (GC/MS) analysis except that additional cleanup steps were required. Recoveries of cis/trans-permethrin ranged from 81 to 108 % for spiked soil and dust samples by GC/MS. The ELISA-derived permethrin concentrations were highly correlated with the GC/MS-derived sum of cis/trans-permethrin concentrations with a correlation coefficient (r) of 0.986. The ELISA method provided a rapid qualitative screen for cis/trans-permethrin in soil and dust while providing a higher sample throughput with a lower cost as compared to the GC/MS method. The ELISA can be applied as a complementary, low-cost screening tool to prioritize and rank samples prior to instrumental analysis for exposure studies.     

Comparison of dioxin and furan TEQ determination in contaminated soil using chemical,micro-EROD,and immunoassay analysis

High resolution mass spectrometry gas chromatography (GC/MS) is the standard method for dioxin and furan analysis in environmental matrices. Considered as very accurate, this method is however time consuming and expensive. Methods based on biological interactions have the necessary sensitivity but began only recently to be investigated in the context of environmental applications. We have compared dioxin and furan toxicity levels (expressed as toxic equivalent quantities (TEQs)) in soil samples by three analytical approaches: the micro-ethoxyresorufin-o-deethylase (EROD) bioassay (a receptor-based method), an immunoassay (antibody-based method) and GC/MS analysis (used as a reference) using a shortened extraction-purification method. Both biological methods were sensitive to interferences from compounds co-extracted from samples. Most samples were underestimated by the immunoassay and, at a greater extent, overestimated by the EROD bioassay. The average accuracy of TEQ estimation (86 +/- 45% of values established by GC/MS) and the absence of false-negatives showed by the immunoassay suggest the usefulness of this method for semi-quantitative, preliminary characterization of potentially contaminated sites.     

Comparison of drinking water mutagenicity with leaching of polycyclic aromatic hydrocarbons from water distribution pipes

The primary objectives of this study were to examine the changes in concentration of six polycyclic aromatic hydrocarbons (PAH) and the possibility of changes in mutagenic potential of treated waters as a result of their passage through commonly used distribution pipes. With the exception of the finished water taken at one treatment plant in which the total concentration of the six PAH was 138.5 parts per trillion (ppt), the total initial concentration in all other treated water ranged from 0 to 13.4 ppt. The corresponding total PAH concentration in water after passage through the distribution pipes varied from 0 to 61.6 ppt. This demonstrated that PAH concentration in water can increase as a result of their passage through coated distribution pipes. Mutagenic activity was also detected in many of the treated water samples, however, the levels of this activity did not correlate with either the transit of water through the distribution system or the levels of PAH in the water. There was some evidence to indicate that the water treatment process itself may have contributed to the mutagenicity observed in the finished water.     

北方某城市饮用水中多环芳烃的来源及其在水处理过程中的行为研究

采用固相萃取(SPE)样品富集前处理技术和气相色谱/质联联用(GC/MS)分析方法,对北方某工业城市给水系统中的多环芳烃类化合物的含量水平进行了研究.结果表明,该城市多环芳烃污染水平较高,但总浓度均未超过城市供水水质标准(CJ/T206-2005)中限值(2μg/L).近郊水库由于受到燃料燃烧产生的多环芳烃的污染,成为该市饮用水中多环芳烃污染的主要来源.传统的混凝-砂滤工艺对多环芳烃有较好的去除效果,总去除率可达55.9%.     

Relevance study of bare and coated zero valent iron nanoparticles for lindane degradation from its by-product monitorization

Zero-valent iron nanoparticles (NZVI) as well as polymer–stabilized nanoparticles were synthesized and used for lindane (γ-hexachlorocyclohexane) degradation in aqueous solution. To study the effectiveness of the different coated nanoparticles, simple and rapid analytical methods have been developed to measure and to detect lindane and its by-products. For the monitorization of lindane degradation solid-phase extraction (SPE) was used, while volatile by-products formation measurement was carried out by headspace-solid phase microextraction (HS–SPME) followed by GC/MS. The SPE–GC/MS method provides low detection limits (0.2 μg L⁻¹), high recovery (above 95%) and it is a valuable tool for kinetic studies of the degradation process for each polymer used, while HS–SPME–GC/MS has proved to be an effective tool for the extraction and evaluation of volatile degradation by-products.     

A new rapid method for quantification of PCBs in transformer oil

In order to improve the efficiency and cost-effectiveness of the PCB analysis, the DMSO partition and SPE extraction were applied to clean up the PCB-contaminated transformer oils and PCB level was determined by means of the quadrupole GC/MS. The analysis data obtained from this method were compared statistically to that from the standard method.     

Contamination of fish by 2,3,7,8-tetrachlorodibenzo-P-dioxin: A survey of fish from major watersheds in the United States

A survey of contamination of fish from major watersheds in the United States by 2,3,7,8-TCDD has been conducted by the U.S. EPA. Bottom feeding and predator fish were collected at 90 statistically selected and 305 regionally selected sites and analyzed by GC/MS. It was found that 19% of the statistically sampled sites and 31% of the regionally selected sites were contaminated at or above a minimum level of detection varying from 0.5 to 2.0 pg/g. Ten percent of all samples were contaminated at levels greater than 5.0 pg/g. It was also observed that a subset of samples collected at sites near discharge from pulp/paper manufacture (N=28) had a higher frequency of TCDD contamination above 5.0 pg/g (38%). This subset of samples also contained the sample of the greatest level of TCDD contamination (85 pg/g).     

Concentrations of dioxins and related compounds in the blood of Fukuoka residents

Blood samples of 152 residents (male 75 and female 77) aged 20-60 years in Fukuoka, Japan, were analyzed for dioxin toxic compounds of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho polychlorinated biphenyls (non-ortho PCBs) and mono-ortho polychlorinated biphenyls (mono-ortho PCBs) as well as 35 PCB congeners and 12 chlorinated pesticides by high-resolution gas chromatography/high-resolution mass spectrometry. Average concentrations of dioxin toxic equivalents (TEQ) from PCDDs, PCDFs, non-ortho PCBs, mono-ortho PCBs and their total in the blood of 152 residents were 10.28, 5.56, 7.75, 4.57 and 28.15 ppt in lipid, respectively. These total TEQ levels were comparable to the blood TEQ levels of normal Japanese (n=735). Lipid basis total TEQ levels progressively increased in the males from 17.1 ppt at age 20s to 47.5 ppt at age 50s and in the females from 19.5 ppt at age 20s to 54.5 ppt at age 50s. Dioxin toxic contribution of PCBs to total TEQ was increased from 31% at age 20s to 55% at age 50s. Average concentrations of total 35 PCBs and total 12 pesticides in the blood of 151 residents were 386 and 1079 ppb in lipid, respectively. Average concentrations (ppb in lipid) of total PCBs and total pesticides also progressively increased in the males from 213 and 444 at age 20s to 868 and 2140 at age 50s, respectively, and in the females from 199 and 588 at age 20s to 550 and 1977 at age 50s, respectively. The levels of TEQ, PCBs, hexachlorobenzene, beta-hexachlorocyclohexane, dieldrin, p,p'-dichlorodiphenyldichloroethylene, p,p'-dichlorodiphenyltrichloroethane, trans-nonachlor and cis-nonachlor were positively correlated with each other in most of the combinations, and the highest correlations (r>0.8) were observed between total TEQ and PCBs in both sexes.     

2,4-D levels in the South Saskatchewan River in 1973 as determined by GLC method.

2,4-D levels in the South Saskatchewan River near Saskatoon in 1973 at the height of the spraying season, and at harvestime, were determined by a method involving direct glc analysis, ankaline hydrolysis, followed by n-butylation of the liberated free acid after acidification of the alkaline solution, and confirmed by subsequent n-octylation. GC/MS also confirmed the presence of 2,4-D. 2,4-D was detected during the spraying season but not at harvest time or in river mud samples. The average level was ca. 2mug of acid equivalent to 2,4-D per liter of river water at the height of the spraying season.     

Solid phase extraction with pyrenebutyric acid-bonded silica for analysis of polychlorinated biphenyls in sewage water by gas chromatography-mass spectrometry

A solid phase extraction (SPE) method using pyrenebutyric acid-bonded silica (PYB) as sorbent was developed to determine 23 polychlorinated biphenyls (PCBs) in sewage water by gas chromatography-mass spectrometry (GC-MS). Factors were optimized in SPE procedures including elution solvent, pH, and cartridge burden. The recoveries of 23 PCB congeners were 69.44-111.91% under optimized conditions. Comparisons were also conducted among PYB-SPE, C(18)-SPE and United States Environmental Protection Agency 608 (USEPA608) methods in the analysis of PCBs in sewage water samples. The results showed that the performance of PYB-SPE method was similar with USEPA608 method and better than C(18)-SPE method. Both PYB-SPE and USEPA608 methods were then employed to analyze PCBs in real spiked sewage water samples. The recoveries of PCB congeners determined by PYB-SPE method ranged from 70.6% to 92.4% in real spiked sewage water samples which were identified to be in accordance with USEPA608 method. Limits of detection (LOD) were in the range of 0.06-0.22ngL(-1) for PCB congeners. The optimized PYB-SPE method was successfully applied to the determination of PCBs in sewage water samples.     

A method for determining pyrene in mucus using synchronous fluorimetry with multiple standard additions

A new method was proposed to determine pyrene in mucus, which combined the synchronous fluorimetry with the multiple standard addition method (SFMSA). The method was used to determine pyrene in mucus directly without pretreatment. The method detection limit (MDL) for pyrene in mucus was measured as 0.47 ng/ml with a relative standard deviation of 12.7% (n = 7). The standard addition graph was linear in the range 0.05-50.00 ng/ml (r(2) = 0.9989). SFMSA was validated using a GC/MS method as a reference method, and nice agreement was found. The pyrene in mucus can be directly monitored by SFMSA without solvent extraction of samples. This indicates that SFMSA is more timesaving, less laborious and cheaper than the GC/MS method with solvent extraction. SFMSA has lower MDL and higher average recovery than the GC/MS method.