Determination of PAHs in wastewater irrigated agricultural soil using accelerated solvent extraction

A procedure was developed for determination of 16 polycyclic aromatic hydrocarbons (PAHs) in heavily contaminated paddy soil from wastewater irrigated farmland near Tianjin. The sample was distilled with accelerated solvent extraction (ASE), purified by a silica gel column, and measured with GC/MS. The optimal conditions for the distillation were at 140 degrees C (1500 psi) with a 1:1 mixture of dichloromethane and acetone for 5 min. Application of cyclohexane for extract transfer improved the recovery when the ASE extraction was followed by a silica gel cleanup procedure. Recoveries from the method for 16 PAHs ranged from 57-140% with the coefficients of variation of the results ranging from 0.35% to 5.75%. The total 16 PAHs in a composite sample collected from a wastewater irrigated paddy field near Tianjin was 3.90 mg/kg.     

Determination of 10 particle-associated multiclass polar and semi-polar pesticides from small streams using accelerated solvent extraction

A new analytical method using accelerated solvent extraction was developed for the determination of 10 particle-associated polar and semipolar pesticides. In addition, six deuterated analogues of the target compounds were evaluated as internal standards. The method yielded acceptable accuracy (73–103% recovery) and precision (<25% relative standard deviation) for eight compounds. Using size exclusion chromatography (SEC) as cleanup step resulted in higher recoveries compared to solid phase extraction (SPE) cleanup.

Deuterated standards with 10 or more deuterium atoms performed well as internal standards concerning similar recovery and correlation with the target analytes.

The method was employed to extract particle-associated pesticides from 16 streams located in an area with intense agriculture in France. Acetochlor, pirimicarb, tebuconazole, fenpropidin, -endosulfan and chlorfenvinphos were detected at concentrations up to 1 mg kg⁻¹ dry weight. A comparison with aquatic toxicity data indicated potential risk to the benthic fauna exposed to these concentrations of pirimicarb, -endosulfan and chlorfenvinphos.

We suggest that the method presented here be used for the extraction and quantitation of particle-associated polar pesticides.     

加速溶剂萃取-气相色谱法测定皮革及合成革中的五氯苯酚

建立了加速溶剂萃取(ASE)-气相色谱/电子捕获(GC/ECD)检测皮革中五氯苯酚(PCP)的方法。通过萃取剂选择实验和正交实验,确定了加速溶剂萃取的最佳参数：正己烷为萃取溶剂,萃取温度120℃,静态萃取时间3 min,循环次数3次,氮气吹扫时间80 s。提取液经浓缩、净化、乙酸酐衍生后以气相色谱法测定,以标准物质保留...     

A comparative evaluation of accelerated solvent extraction and Polytron extraction for quantification of lipids and extractable organochlorine in fish

Optimal conditions for extraction methods using an accelerated solvent extractor (ASE) and a Polytron homogenizer were established for quantification of (crude) lipids and extractable organochlorine (EOCl) in fish. The two methods, an ASE consecutive extraction at 55 and 100 degrees C for ground, freeze-dried filets, and a Polytron extraction at room temperature with four repetitions for ground, wet filets and with two repetitions for wet fish livers were evaluated in terms of reproducibility and comparability. With respect to lipid measurement, the two methods have comparable reproducibility and the experimental errors are relatively small compared to natural variations of fish to fish within a sampling site. For EOCl measurement, the relative standard deviation tends to increase with decreasing levels of EOCl in specimens. An important factor for the relative standard deviation of measurements of analytes present at trace levels in fish matrices is sampling error in taking aliquots. Statistical analysis using a paired comparison design showed that measurement values (crude lipids or EOCl) obtained from these two extraction methods are, in general, not equivalent. There is a good correlation between the two methods for lipid measurement; whereas for EOCl measurements, high degrees of correlation exist within the exposed fish group, but not in the reference group.     

2种活性炭协同布袋除尘对垃圾焚烧厂烟气中二恶英的去除

考察了2种活性炭（活性炭A和活性碳B）对垃圾焚烧厂烟气中二恶英去除率的影响。通过采集与分析垃圾焚烧厂“活性炭喷射+布袋除尘”协同处置工艺前口和后口的烟气样品,得到前后口2,3,7,8-PCDD/Fs的浓度,并计算去除率。结果表明：2种活性炭对2,3,7,8-PCDFs的去除率相当,均为99%左右;而对2,3,7,8-PCDDs的去除率略低,分布在83.3%~99.9%之间,并且活性炭A的去除率高于活性炭B。通过对2种活性炭性能指标测试结果的比较,具备更丰富的中孔以及更大的微孔、中孔平均孔径可能是活性炭A去除率更高的原因。此外,比较了活性炭在不同投加速率（5、10和15 kg·h-1）下对二恶英的去除率,发现低投加速率时二恶英去除率随投加速率的增加而增加,而当投加速率从10 kg·h-1增加到15 kg·h-1时二恶英去除率无明显变化。     

A multi-residue method for the analysis of organophosphorus residues in cooked and polished rice using accelerated solvent extraction and dispersive-solid phase extraction (D-SPE) technique and uncertainty measurement

Quick, simple and efficient multi-residue analytical methods were developed and validated for the determination of organophosphorous insecticides from polished and cooked rice. Polished rice was extracted using a simple, automated technique namely accelerated solvent extraction (ASE) using dichloromethane as the extraction solvent. Cooked rice was extracted with acetone and cleaned up using dispersive-solid phase extraction (D-SPE) technique. The single step extraction method adopted for polished rice using accelerated solvent extractor provided satisfactory recovery for eight organophosphorus pesticides (OPPs) which ranged from 85.5–116.7%; 90.0–110.3% and 93.5–118.8% at 1, 5 and 10 limit of quantification (LOQ) levels, respectively. The recovery of cooked rice was in the range of 74–124%; from 75–100% and from 73–87% for 1, 5 and 10 level of fortification, respectively. The total uncertainty was evaluated, taking four main independent sources viz., weighing, purity of the standard, GC calibration curve and repeatability under consideration. The expanded uncertainty was found to be in the range of 5–20%.     

High-throughput screening of dioxins in sediment and soil using selective pressurized liquid extraction with immunochemical detection

A high-throughput screening method using selective pressurized liquid extraction (SPLE) and enzyme-linked immunosorbent assay (ELISA) for monitoring dioxins in sediment and soil is described. SPLE conditions were developed by extracting sediment or soil together with alumina, 10% AgNO₃ in silica, and sulfuric acid impregnated silica (acid silica) using dichloromethane (DCM) as the solvent at 100 °C and 2000 psi. Post-extraction cleanups were not required for ELISA. Two reference sediments (National Institute of Standards and Technology SRM 1944 and Wellington Laboratories WMS01) were analyzed by the SPLE–ELISA method. The ELISA utilized a polyclonal antibody and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as the calibrant. Recoveries of ELISA-derived TCDD equivalents (EQ) relative to the expected gas chromatography/high resolution mass spectrometry (GC/HRMS) derived dioxin toxic equivalent (TEQ) values were 116 ± 11% for SRM 1944 and 102 ± 13% for WMS01. ELISA TCDD EQs were consistent with the dioxin TEQs as measured by GC/HRMS for 25 soil/sediment samples from seven different contaminated sites. The ELISA had an approximate method detection limit of 10 pg g⁻¹ with a precision of 2.6–29% based on the relative percentage difference (%RPD) for duplicate samples. Estimated sample throughput for the SPLE–ELISA was three times or more than that of the GC/HRMS method employing PLE with a multi-column cleanup.     

Per- and polyfluorinated compounds in house dust and indoor air from northern Norway - a pilot study

Polyfluorinated compounds (PFCs) are an extremely versatile class of compounds and are used in a variety of consumer applications and products. Recent studies have suggested that PFCs in indoor air and dust could act as sources of human exposure and outdoor air contamination. This study presents method development and analysis of a wide range of PFCs in dust and air using active sampling techniques with commercially available sampling equipment (forensic nozzles with filter housings for dust collection and polyurethane foam (PUF)-XAD₂-PUF sandwich-tubes for air sampling) using both liquid and gas chromatography mass spectrometry. The developed method was validated and tested for applicability to analyze dust and air samples at both low and high concentrations (0.5 ng and 25 ng per analyte per air sample, respectively). Samples from private households and an office building were analyzed to explore differences in distribution patterns and concentrations. Perfluorooctane sulfonate, perfluorodecane sulfonate, perfluoroheptanoate, perfluorooctanoate and perfluorononanoate were observed in all samples of dust from private households, in the range from 1 to 80.1 ng g⁻¹. Fluorotelomer alcohols (FTOHs) were the predominant PFCs in indoor air samples with ∑FTOHs ranging between 4.7 and 17.9 ng m⁻³. The concentrations found in the present study are generally lower than those previously reported. This variation may be due to differences associated with geographical locations and lifestyles. However, use of different sampling techniques and strategies among studies can introduce large variations in PFC concentration found, making direct comparisons challenging.     

Development of a accelerated solvent extraction and gel permeation chromatography analytical method for measuring persistent organohalogen compounds in adipose and organ tissue analysis

A new analytical method has been developed for the quantification of 59 different persistent organohalogen compounds, such as polybrominated diphenyl ethers (PBDEs), polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs), PCB metabolites, organochlorine pesticides (OCPs) in biological organ tissues. The optimum extraction and cleanup procedures were examined using accelerated solvent extraction (ASE), automated gel permeation chromatography (GPC) on Biobeads S-X3 and automated solid phase extraction (SPE) on silica-gel. The target compounds were divided into two fractions, non-polar compounds and more polar compounds, which in the latter fraction was subsequently methylated using diazomethane. Detection can be achieved by GC/MS in negative chemical ionization (NCI) mode. The average recoveries of the compounds spiked in swine liver, heart, kidney, and cattle adipose tissues were considered satisfactory, and it was confirmed that the method could be used in routine analysis.     

Determination of organochlorine and organophosphorus pesticide residues in low moisture, nonfatty products using a solid phase extraction cleanup and gas chromatography

A multiresidue solid-phase extraction (SPE) method for the isolation and subsequent gas chromatographic determination of organochlorine and organophosphorus pesticide residues in low-moisture, nonfatty products is described. Residues are extracted from samples with an acetonitrile/water mixture. Cleanup of the extract is performed using graphitized carbon black and anion exchange SPE columns, and analysis is performed by gas chromatography with Hall electrolytic conductivity and flame photometric detection. Recovery data was obtained by fortifying corn, oats and wheat with pesticides. The average recoveries were 79-123% for eight organochlorine and 51-122% for 28 organophosphorus pesticide residues. The limit of quantitation for chlorpyriphos was 0.05 ppm using the Hall electrolytic conductivity detector and < 0.005 ppm using the flame photometric detector.     

Determination of organochlorine and organophosphorus pesticide residues in low moisture,nonfatty products using a solid phase extraction cleanup and gas chromatography

Abstract

A multiresidue solid‐phase extraction (SPE) method for the isolation and subsequent gas Chromatographie determination of organochlorine and organophosphorus pesticide residues in low‐moisture, nonfatty products is described. Residues are extracted from samples with an acetonitrile/water mixture. Cleanup of the extract is performed using graphitized carbon black and anion exchange SPE columns, and analysis is performed by gas chromatography with Hall electrolytic conductivity and flame photometric detection. Recovery data was obtained by fortifying corn, oats and wheat with pesticides. The average recoveries were 79–123% for eight organochlorine and 51–122% for 28 organophosphorus pesticide residues. The limit of quantitation for chlorpyriphos was 0.05 ppm using the Hall electrolytic conductivity detector and <0.005 ppm using the flame photometric detector.     

Levels of dioxins and dibenzofurans in breast milk of women residing in two cities in the Irkutsk Region of Russian Siberia compared with American levels

The presence of dioxins, dibenzofurans, and polychlorinated biphenyls (PCBs) in human tissue, food, and environmental samples from Russia has been monitored since 1988 as part of a research collaboration between a number of countries including Finland, the United States, Germany, the former Soviet Union, and Canada. Although elevated TCDD and PnCDD levels have previously been found in blood of male and female Russian chemical manufacturing workers and in their children, dioxin levels in the general population have usually been found to be lower than in Americans and Europeans. This study continues earlier work in the Irkutsk region of Russian Siberia, where we report levels of dioxin, dibenzofurans, and PCBs in human milk samples taken from general population women living in the industrialized cities of Angarsk and Usolye-Sibirskoye, near Lake Baikal. Total polychlorinated dibenzo-p-dioxin (PCDD) toxic equivalents (TEQs) compared in this paper for the industrialized regions of Siberia, Ukraine, and the US are similar, ranging from 6.1 to 7 parts per trillion (ppt). Recent 1998 milk samples from Angarsk and Usolye-Sibirskoye have total mean polychlorinated dibenzofuran (PCDF) TEQs of 10 and 21.7 ppt, respectively, with the other industrialized countries ranging from 2.3 to 6.7 ppt. Although dioxin-like PCBs were not measured for the city of Usolye-Sibirskoye (1998), total mean PCDD/F TEQ from Angarsk and Usolye-Sibirskoye (1998) were the two highest levels in this study, with 26.9 and 28.5 ppt, respectively, followed by 1993-1994 Ukraine samples with 24 ppt, 1989 Siberian samples with 13.6 ppt, and 1996 USA with 11.4 ppt total TEQ. In this study, higher levels of dioxins are noted in milk from Angarsk and Usolye-Sibirskoye than found in earlier Russian studies, with mean levels also exceeding 1996 and 1999 US breast milk dioxin levels.     

An accelerated solvent extraction and gas chromatography-flame ionization detector method to rapidly determining and assessing total petroleum hydrocarbon contamination in soil from Fushan oilfield,China

Environmental Science and Pollution Research - A high-efficient method for determining the total petroleum hydrocarbon (TPH) was established by gas chromatography-flame ionization detection,...     

Organophosphorus flame retardants in house dust from the Philippines: occurrence and assessment of human exposure

The use of organophosphorus flame retardants (PFRs) as flame retardants and plasticizers has increased due to the ban on common polybrominated diphenyl ether mixtures. However, only limited information on PFR contamination is available so far from Southeast Asia. In the present study, residual levels of PFRs in house dust and exposure through dust ingestion were investigated in the Philippines. House dust samples (n?=?37) were collected from Malate (residential area) and Payatas (municipal dumping area) in the Philippines and analyzed using ultra-high-performance liquid chromatography coupled with tandem mass spectrometry. Among the targeted seven PFRs, triphenyl phosphate (TPP) was the predominant compound. Median levels of ΣPFRs in Malate (530 ng/g) were two times higher (p?<?0.05) than in Payatas (240 ng/g). The estimated daily intake of PFRs in the Philippines (of areas studied) via house dust ingestion was below the guideline values. House dust may be an important contributor in the overall exposure of humans to TPP even when considering dietary sources. To our knowledge, this is a first report on PFR contamination in house dust from developing country. PFRs were ubiquitously detected in the home environments in the Philippines. Although estimated exposure levels through dust ingestion were below the guideline, it was suggested that toddlers are at higher risk. Therefore, further investigations to understand the behavior of PFRs in house and other microenvironments and overall exposure pathways for the country’s populace to PFRs are necessary.     

Development of supercritical carbon dioxide extraction with a solid phase trap for dioxins in soils and sediments

A method involving supercritical fluid extraction (SFE) with a solid phase trap containing activated alumina was investigated for the rapid analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin like polychlorinated biphenyls (DL-PCBs) in soils and sediments. The samples were extracted by using supercritical carbon dioxide with water (2% versus CO(2) flow velocity) being used as an entrainer at a pressure of 30 MPa and a temperature of 130 degrees C for 50 min. The extracts were adsorbed on an activated alumina trap that was maintained at a temperature of 150 degrees C, and then, PCDD/DFs and DL-PCBs were eluted with 20 ml of hexane at 60 degrees C. After concentration, they were measured with a high-resolution gas chromatograph interfaced to a high-resolution mass spectrometric detector. The average concentrations of PCDD/DFs and DL-PCBs corresponded to the results obtained by the conventional method, and the reproducibility of this SFE method was below 21% of the relative standard deviations for all samples. The total time required for the analysis of the pretreatment of this method was only 2 h.     

Environmental hazard screening of a metal-polluted site using pressurized liquid extraction and two in vitro bioassays

Rapid screening methods can improve the cost effectiveness, throughput, and quality of risk assessments of contaminated sites. In the present case study, the objective was to evaluate a combination of pressurized liquid extraction and 2 in vitro bioassays for the hazard assessment of surface soil sampled from 46 points across a pyrotechnical industrial site. Pressurized liquid extraction was used to rapidly produce soil-water extracts compatible with 2 high-capacity bioassays. Hazard assessment using combined toxicological and chemical screening revealed zones with relatively high potential risks of metal pollution. Multivariate data analysis provided indications that significant inhibition in the bioassays was correlated with levels of metals in the extracts, suggesting an elevated toxic potential from certain metals. Low pH and high concentrations of dissolved organic carbon were associated with increased cytotoxicity of extracts, indicating that these factors influence metal bioavailability. The cytotoxicity observed was more strongly correlated to metal concentrations in the extracts than in the soil, suggesting that measurements of total metal concentrations in soils do not provide good indications of the soil's potential toxicity.     

基于2种采样方法的北京市夏季道路扬尘的监测及积尘负荷分布特征

为探究不同采样方法对积尘负荷结果的影响,使用样方采样法和以克论净车采样法采集2018年夏季样品的数据,对北京市3个行政区的11条道路扬尘样品进行现场监测,计算不同道路类型及不同车道的积尘负荷,并对积尘负荷的变化规律进行分析。结果表明：基于样方采样法和以克论净车采样法的北京市夏季不同道路类型积尘负荷从大到小顺序依次为次干道(0.46 g·m⁻²、0.99 g·m⁻²) >支路(0.31 g·m⁻²、0.88 g·m⁻²)>主干道(0.24 g·m⁻²、0.78 g·m⁻²);2种采样方法所得积尘负荷差异的检验结果具有显著性(P=0.00<0.05)且存在线性关系;北京市夏季道路积尘负荷(0.34 g·m⁻²)稍高于天津市(0.24 g·m⁻²),低于石家庄市(1.06 g·m⁻²)、乌鲁木齐市(0.96 g·m⁻²)和西安市(0.70 g·m⁻²);基于样方采样法和以克论净车采样法采集的不同城区道路积尘负荷水平排序为大兴区(0.39 g·m⁻²、1.83 g·m⁻²)>朝阳区(0.38 g·m⁻²、1.00 g·m⁻²)>东城区(0.26 g·m⁻²、0.92 g·m⁻²),朝阳区、东城区和大兴区积尘负荷差异的检验结果均不具有显著性(P>0.05);基于样方采样法的机动车慢车道与机动车快车道积尘负荷分别为0.04~1.30 g·m⁻²和0.02~1.08 g·m⁻²;慢车道积尘负荷略高于快车道,但二者差异的检验结果不具有显著性(P=0.51>0. 05)。本研究成果可为遴选道路扬尘采样方法、构建北京市道路扬尘排放清单和制定管控措施提供参考。     

Improving suitability of urban canals and canalized rivers for transportation,thermal energy extraction and recreation in two European delta cities

Canals and canalized rivers form a major part of surface water systems in European delta cities and societal ambitions to use these waters increase. This is the first assessment of how suitability of these waters can improve for three important uses: transportation, thermal energy extraction (TEE) and recreation. We assess suitability with Suitability Indices (SIs) and identify which alterations in the water system are needed to improve SI scores in Amsterdam, The Netherlands, and Ghent, Belgium. The results show spatial variability in suitability scores. Current suitability for transportation is low (SI score = 1) to excellent (SI score = 4), for TEE fair (SI score = 2) to excellent (SI score = 4), and suitability for recreation is low (SI score = 1). Suitability could improve by enlarging specific waterway dimensions, increasing discharge and clarity, and by enhancing microbiological water quality. The same methodology can be applied to optimize designs for new water bodies and for more water uses.Supplementary InformationThe online version contains supplementary material available at 10.1007/s13280-022-01759-3.     

Occurrence of Fipronil in residential house dust in the presence and absence of pets: a hint for a comprehensive toxicological assessment

The presence of the insecticide Fipronil and its main products of toxicological relevance, namely Sulfone and Desulfinyl, was assessed in 161 residential house dust samples in the absence (N?=?101) and presence (N?=?60) of cats and dogs in Italy. High-resolution mass spectrometry analysis revealed a significant difference (p?<?0.001) in the dust contamination in the presence of pets (median: 467 vs. 24?ng/g dry weight), even if the highest value was found in the absence of pets (82,069 vs. 67,799?ng/g dry weight). Fipronil intake estimates from dust in toddlers, computed according to US-EPA and EU-ECHA guidelines, ranged from 333 to 556 and from 20 to 34?ng/kg per day for acute and chronic scenario, respectively. Dust seemed not able itself to lead to Fipronil overexposure with respect to acute and chronic toxicity health-based guidance values. Kittens were potentially overexposed to Fipronil under both acute (26,076?ng/kg per day) and chronic (1,633?ng/kg per day) scenarios. The mild symptomatology associated with acute intoxication could possibly determine case underreporting within pharmacosurveillance schemes. Its administration was estimated in 7.3–9.7 tons per year. Such a range suggests its prudent use under strict veterinary control to prevent pest resistance and ecotoxicological outcomes.     

A comparison of contaminant plume statistics from a Gaussian puff and urban CFD model for two large cities

This paper quantitatively assesses the spatial extent of modeled contaminated regions resulting from hypothetical airborne agent releases in major urban areas. We compare statistics from a release at several different sites in Washington DC and Chicago using a Gaussian puff model (SCIPUFF, version 1.3, with urban parameter settings) and a building-resolving computational fluid dynamics (CFD) model (FAST3D-CT). For a neutrally buoyant gas source term with urban meteorology, we compare near-surface dosage values within several kilometers of the release during the first half hour, before the gas is dispersed beyond the critical lethal level. In particular, using “fine-grain” point-wise statistics such as fractional bias, spatial correlations and the percentage of points lying within a factor of two, we find that dosage distributions from the Gaussian puff and CFD model share few features in common. Yet the “coarse-grain” statistic that compares areas contained within a given contour level reveals that the differences between the models are less pronounced. Most significant among these distinctions is the rapid lofting, leading to enhanced vertical mixing, and projection downwind of the contaminant by the interaction of the winds with the urban landscape in the CFD model. This model-to-model discrepancy is partially ameliorated by supplying the puff model with more detailed information about the urban boundary layer that evolves on the CFD grid. While improving the correspondence of the models when using the “coarse-grain” statistic, the additional information does not lead to quite as substantial an overall agreement between the models when the “fine-grain” statistics are compared. The taller, denser and more variable building landscape of Chicago created increased sensitivity to release site and led to greater divergence in FAST3D-CT and SCIPUFF results relative to the flatter, sparser and more uniform urban morphology of Washington DC.