Extractable organohalogens in tissues of beluga whales from the Canadian Arctic and the St. Lawrence estuary

Samples of blubber, brain, kidney, liver, and muscle of individual beluga whales were extracted and analyzed for extractable organic Cl (EOCl), Br (EOBr), and I (EOI) by neutron activation analysis. The highest levels of EOCl (554 microg g(-1) lipid) were found in the kidney of Arctic beluga and the lowest (24 microg g(-1) lipid) in the blubber. Levels in brain and liver lipids were on average of equal magnitude. The unequal distribution of EOCl in tissue lipids is in marked contrast to the equal distribution, in lipid, demonstrated for organochlorines such as DDTs and PCBs by a number of investigations. The distribution of brominated (EOBr) and iodinated (EOI) compounds was similar and markedly different from that of EOCl. The tissue distribution of EOCl seems to be related to the proportion to polar lipids in the tissues. Beluga from St. Lawrence had significantly higher brain EOCl levels than the Arctic samples whereas the levels of EOCl in liver and kidney were higher in the Arctic whales.     

Sorbent-assisted liquid-liquid extraction (Chem-Elut) of polychlorinated biphenyls, dibenzo-p-dioxins and dibenzofurans in the lipid fraction of human blood plasma

This work compares two lipid extraction methods for determining 24 polychlorinated biphenyls (PCBs), seven dibenzo-p-dioxins (PCDDs) and ten dibenzofurans (PCDFs) in human blood plasma. The first method was based on conventional liquid-liquid partitioning with chloroform-methanol and the other made use of a sorbent (Chem-Elut) to facilitate the partitioning of lipids into a mixture of hexane and 2-propanol. A multi-layer-silica column including acid- and base-impregnated silica gel was used to reduce the amounts of lipid present in the samples before a basic alumina clean-up step and activated carbon fractionation of planar analytes (PCDD/Fs and non-ortho-PCBs) and non-planar analytes (including ortho-chlorinated PCBs). Gas chromatography coupled to high resolution mass spectrometry was used to identify and quantify the analytes in the two fractions. The wet weight based concentrations obtained by the two methods were in agreement but both methods suffer from large organic solvent consumption. The toxic equivalencies derived for PCBs and PCDD/Fs using the two methods were also in agreement. However, the chloroform-methanol method gave slightly higher lipid recoveries, although with greater variation, than the sorbent-assisted method. Nevertheless, despite giving lower lipid recoveries, the sorbent-assisted method has advantages in ease of use and applicability to whole blood samples. The formation of emulsions was avoided with the Chem-Elut method, which probably explains the lower variability in the lipid determinations.     

Evaluation of chloroform/methanol and dichloromethane/hexane extractable lipids as surrogate measures of sample partition capacity for organochlorines in fish tissues

Organic contaminant concentration data are often lipid normalized to provide an indication of the chemical fugacity in the sample or to compare the relative equilibrium status of samples from the same environment. This study compared lipid normalized PCB and organochlorine concentration data for tissues of individual fish when lipids were measured using chloroform/methanol (CM) or dichloromethane/hexane (DH) extractions. The CM extraction produced higher lipid yields for dorsal muscle (8-fold difference) and carcass (1.7-fold difference) compared to DH extractions, while both methods yielded comparable lipid contents for liver and adipose tissue. Lipid normalized tissue/carcass PCB and organochlorine concentration ratios were variable across tissue types when lipid contents from the CM technique were used, whereas, tissue/carcass concentration ratios approached the expected value of unity for each tissue when DH-derived lipids were used. These data suggest that the tissue lipid content as derived using the DH extraction provided a better surrogate measure of sample partition capacity than tissue lipids determined using the CM technique.     

Validation of a pressurized solvent extraction and GC-NCI-MS method for the low level determination of 40 polybrominated diphenyl ethers in mothers' milk

This study reports an efficient method for the determination of 40 PBDEs from mono- to hepta-brominated in human milk. Pressurized liquid extraction (PLE) was optimized to recover PBDEs in a quantitative way using 1g of freeze dried milk. Due to the great amount of coextracted compounds, the clean-up step was optimized using alumina SPE disposable cartridges of 2 and 5g. Whereas 2g alumina SPE failed in providing good extraction yields, all PBDEs were satisfactorily recovered using 5g alumina SPE cartridges. Detection was performed with gas chromatography coupled to mass spectrometry with negative chemical ionization and method detection limits ranged from 0.01 to 0.05mugkg(-1) wet weight (ww) with a good intra and inter-day variation (coefficient of variation lower than 13.4%). This method was validated by participating in an interlaboratory exercise from Quasimeme (United Kingdom), where a standard solution containing seven congeners and a certified unspiked mothers' milk were analyzed. In the standard mixture, levels between 96.915 and 570.172mugl(-1) were quantified, whereas in certified mothers' milk, BDEs 47, 99, 100 and 154 were detected at levels from 0.010 and 0.061mugkg(-1) ww, with an error <30%. The applicability of the method was tested experimentally in five mothers' milk samples, where only BDE 47 was detected at a maximum concentration of 10.45mugkg(-1) lipid weight (lw). PLE succeeded in extracting all PBDEs from the sample with good reproducibility although the clean-up step had to be severely performed to eliminate sample interferences such as milk lipids and proteins.     

ASE提取GPC净化双塔双柱气相色谱法测定土壤中有机氯农药

对土壤中8种有机氯农药(α-HCH、β-HCH、γ-HCH、δ-HCH、p,p’-DDE、p,p’-DDD、o,p’-DDT、p,p’-DDT)进行了分析,使用加速溶剂萃取(ASE)仪对土壤样品中的目标组分进行萃取、凝胶渗透色谱(GPC)仪对萃取液净化、双塔双柱同时进样分析,采用双电子捕获检测器(ECD)同时定性定量测定。结果表明,该方法检测效果较好,8种有机氯农药的回收率在81.3%～88.6%,相对标准偏差为3.9%～5.7%,检出限为0.18～0.37μg/kg。与传统的方法相比,该方法操作简便、重复性好,定性定量更准确。     

Extraction and cleanup methods of dioxins in house dust from two cities in Japan using accelerated solvent extraction and a disposable multi-layer silica-gel cartridge

A simple and rapid method for the extraction and cleanup of dioxins from house dust was developed using an accelerated solvent extraction (ASE) method and a multi-layer silica-gel cartridge. It was found that the WHO-TEQ levels of dioxins extracted from the house dust obtained by both a conventional soxhlet extraction and the ASE were almost equal, when the data obtained by both methods were compared. As for the cleanup method, a multi-layer silica-gel cartridge yielded higher dioxin recoveries than the alkaline digestion method. The average values of the dioxins in house dust from Kumagaya city and Sendai city in Japan (Sendai city is bigger than Kumagaya city with respect to the population and industry), were 15.6 pg TEQ/g (8.6-26.0 pg TEQ/g, n=5, Kumagaya city) and 16.0 pg TEQ/g (5.9-30.5 pg TEQ/g, n=5, Sendai city), respectively.     

Effect of condensed organic matter on solvent extraction and aqueous leaching of polycyclic aromatic hydrocarbons in soils and sediments

The contents of nonhydrolyzable organic matter (NHC) and black carbon (BC) were measured in soils and sediments from the Pearl River Delta, South China. Polycyclic aromatic hydrocarbons (PAHs) were extracted respectively by Soxhlet and an accelerated solvent extraction device (ASE) using different solvents. In addition, sequential aqueous leaching at different temperatures was carried out. The PAH content extracted with the sequential three solvent ASE is two times higher than that using the Soxhlet extraction method. The relationship of the PAH content with the NHC content is very significant. The PAH concentrations measured at various temperature steps fit well to the Van't Hoff equation and the enthalpy was estimated. The investigation indicates that condensed organic matter such as kerogen carbon, aged organic matter, and BC is relevant for the extraction and distribution of native PAHs in the investigated field soils and sediments.     

Comparisons of PBDE composition and concentration in fish collected from the Detroit River,MI and Des Plaines River,IL

Polybrominated diphenyl ethers (PBDEs) were identified in fish collected from the Detroit River, MI and Des Plaines Rivers, IL. In the Detroit River fish, carp and large mouth bass, the congener patterns were dominated by the 2,2',4,4'-tetrabromo (BDE-47) congener, however, in Des Plaines River carp the dominant isomers were the heptabromo congeners BDE-181 and BDE-183 and lesser amounts of another heptabromo congener, BDE-190, and two hexabromo congeners, BDE-154 and BDE-153. Three possible sources exist for these less-commonly identified PBDE congeners: (a) waste discharge from manufacturing or discarded products near the river, (b) public owned treatment work (POTW) effluents which constitute more than 75% of the flow in the Des Plaines River, (c) or formation of these congeners by debromination of in-place deposits of decabromodiphenyl ether. Average concentration totals (sum of concentrations for seven of the dominant PBDE congeners) were similar on a wet weight bases for the carp (5.39 ng/g wet weight) and large mouth bass (5.25 ng/g) in the Detroit River samples; however, the bass were significantly higher, p = 0.01, when compared on a lipid basis (bass--163 ng/g vs. carp--40.5 ng/g lipid weight). Some of the PBDE congeners were positively correlated with increasing lipid levels in both fish species. Average total PBDE concentrations in the carp from the Des Plaines River (12.48 ng/g wet weight) were significantly higher, p = 0.01, than in carp from the Detroit River. The residues were isolated using standard organochlorine methods for fish and analyzed using gas chromatography/mass spectrometry-negative chemical ionization methods.     

Variability and reliability of POP concentrations in multiple breast milk samples collected from the same mothers

Risk assessment of infant using a realistic persistent organic pollutant (POP) exposure through breast milk is essential to devise future regulation of POPs. However, recent investigations have demonstrated that POP levels in breast milk collected from the same mother showed a wide range of variation daily and monthly. To estimate the appropriate sample size of breast milk from the same mother to obtain reliable POP concentrations, breast milk samples were collected from five mothers living in Japan from 2006 to 2012. Milk samples from each mother were collected 3 to 6 times a day through 3 to 7 days consecutively. Food samples as the duplicated method were collected from two mothers during the period of breast milk sample collection. Those were employed for POP (PCBs, DDTs, chlordanes, and HCB) analysis. PCB concentrations detected in breast milk samples showed a wide range of variation which was maximum 63 and 60% of relative standard deviation (RSD) in lipid and wet weight basis, respectively. The time course trend of those variations among the mothers did not show any typical pattern. A larger amount of PCB intake through food seemed to affect 10 h after those concentrations in breast milk in lipid weight basis. Intraclass correlation coefficient (ICC) analyses indicated that the appropriate sample size for good reproducibility of POP concentrations in breast milk required at least two samples for lipid and wet weight basis.     

Equilibrium sampling: partitioning of organochlorine compounds from lipids into polydimethylsiloxane

Polydimethylsiloxane (PDMS) can be used for equilibrium sampling of environmental pollutants in a large variety of matrices including biota. For comparison with lipid-normalized concentrations e.g. from biota monitoring programmes, reliable lipid to PDMS partition ratios (K(Lipid,PDMS)) are required. Additionally, K(Lipid,PDMS) facilitate comparison of equilibrium sampling data obtained in various environmental media and can be helpful to convert equilibrium sampling data into a more informative form. This work investigated the equilibrium partitioning of polychlorinated biphenyls (PCBs) and selected organochlorine pesticides (OCPs) between lipids from biota of different trophic levels and PDMS. One vegetable oil, a fish oil and seal oil were investigated. The lipid to PDMS partition ratios were compound-specific and ranged from 14.5 to 62.9 g/g with correction for lipid uptake into the PDMS and from 13.0 to 54.8 g/g without correction. Additionally, PDMS served as a reference partitioning phase for the accurate determination of lipid to lipid partition ratios, which for all analytes were close to unity. Evaluating the results in a bioaccumulation context, they indicate that the equilibrium partitioning of neutral lipophilic environmental contaminants into the lipids of the three investigated species will be very similar, although they represent three distinct trophic levels.     

Determination of pentachlorophenol (PCP) in waste wood--method comparison by a collaborative trial

Two independently developed and validated procedures for the determination of pentachlorophenol (PCP) in waste wood were compared by means of a collaborative trial. Both methods foresee quantification of PCP by gas chromatography (GC-ECD) after acetylation and differ with regard to the use of methanol or toluene/sulphuric acid, respectively, as solvent in the sonication extraction step. Test samples with established analyte homogeneity were prepared from a ground "real life" starting material. A total of 23 participating laboratories with experience in wood preservative analysis were instructed to apply both methods to three levels of content in the range of 0.5-20 mg PCP/kg. In case of the toluene/sulphuric acid extraction, lower recoveries and higher interlaboratory dispersion of results at the higher PCP contents were observed. Seen against the background of the Horwitz equation a reproducibility standard deviation of approximately 19% for the methanol extraction at the 4.5 mg/kg level meets the requirement for a sound analytical method. Thus, the sonication extraction procedure with methanol has been annexed as a reference method to the German waste wood regulation.     

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%.     

Testing the efficiency of extraction of incurred residues from soil with optimized multi-residue method

The reproducibility of extraction of residues from spiked soil samples and from soils containing incurred residues was tested with ¹⁴C-labeled test compounds of different physical-chemical properties. Nearly 100% of the compounds added to the sample before extraction could be recovered with an average reproducibility relative standard deviation (CV) of 5.4%. The additional steps of the determination process (cleanup, evaporation, etc.) contributed to the major part of the variability of the results (CV = 10–20%). The incurred residues were most efficiently extracted with acetone for 30 min followed by the mixture of acetone/ethyl acetate 1:1 for additional 30 min. However, they could only be recovered at various extent (64–90% of total residues), underlying the importance of testing the efficiency of extraction. The residues were identified and quantified by gas chromatography applying thermionic detector. The performance parameters of the method complied with the international method validation guidelines, and they proved to be robust and suitable for determination of pesticide residues in soils of widely different physical–chemical properties.     

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.     

Method validation for control determination of mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry

A method for the determination of total mercury in fresh fish and shrimp samples by solid sampling thermal decomposition/amalgamation atomic absorption spectrometry (TDA AAS) has been validated following international foodstuff protocols in order to fulfill the Brazilian National Residue Control Plan. The experimental parameters have been previously studied and optimized according to specific legislation on validation and inorganic contaminants in foodstuff. Linearity, sensitivity, specificity, detection and quantification limits, precision (repeatability and within-laboratory reproducibility), robustness as well as accuracy of the method have been evaluated. Linearity of response was satisfactory for the two range concentrations available on the TDA AAS equipment, between approximately 25.0 and 200.0 μg kg^?1 (square regression) and 250.0 and 2000.0 μg kg^?1 (linear regression) of mercury. The residues for both ranges were homoscedastic and independent, with normal distribution. Correlation coefficients obtained for these ranges were higher than 0.995. Limits of quantification (LOQ) and of detection of the method (LDM), based on signal standard deviation (SD) for a low-in-mercury sample, were 3.0 and 1.0 μg kg^?1, respectively. Repeatability of the method was better than 4%. Within-laboratory reproducibility achieved a relative SD better than 6%. Robustness of the current method was evaluated and pointed sample mass as a significant factor. Accuracy (assessed as the analyte recovery) was calculated on basis of the repeatability, and ranged from 89% to 99%. The obtained results showed the suitability of the present method for direct mercury measurement in fresh fish and shrimp samples and the importance of monitoring the analysis conditions for food control purposes. Additionally, the competence of this method was recognized by accreditation under the standard ISO/IEC 17025.     

Organohalogenated compounds in pine needles from Beijing city, China

Pine needles collected from 22 sites of six areas in Beijing city, China, were analyzed by instrumental neutron activation analysis (INAA) combined with organic extraction for extractable organohalogens (EOX) and extractable persistent organohalogens (EPOX). The concentrations of EOX (EOX = ECl + EOBr + EOI) were in the order of EOCl > EOBr > EOI. About 1.6-34% of EOCl remained as extractable persistent organochlorine (EPOCl) after treatment with concentrated sulfuric acid, which suggested that major fractions of EOCl in pine needles were an acid-liable or acid-soluble fraction. The fact that pine needle contained higher EOCl contents in chemical industrial and traffic hub areas indicated that chemical industries and exhaust emission from vehicle were the main sources of organochlorines in the Beijing's air. The relative proportions of the known organochlorines (such as HCHs, DDTs, chlordanes, HCB and PCBs) to total EOCl and EPOCl were 0.32-0.76% and 2.5-11.4%, respectively, which implied that a major portion of the EOCl and EPOCl measured in pine needles was unknown. The organochlorinated pesticides (OCPs) and PCBs concentrations in six areas were as follows: sigma HCH (sigma HCH = alpha- + beta- + gamma- + delta-HCH), 11.7-20.8 ng/g; sigma DDT (p,p'-DDT + p,p'-DDE + p,p'-DDD), 12.5-113.3 ng/g; hexachlorobenzene (HCB), 1.1-5.3 ng/g; sigma chlordane (cis-chlordane + trans-chlordane + heptachlor), 1.7-9.5 ng/g, sigma PCB, 41.8-270.5 ng/g, on dry weight basis. The samples from chemical industrial area and residential area nearby chemical industries contained the highest concentrations of sigma DDT, HCB, sigma chlordane and sigma PCB, while the contamination levels of most OCPs and PCBs in iron-steel industrial area were the lowest. The ratios of alpha/gamma-HCH (ranged from 0.9-1.5) and p,p'-DDT/DDTs (ranged from 72.1% to 91.0%) revealed the presence of the recent use of lindane and DDTs or impure dicofol in Beijing.     

Routine analysis of hydrocarbons, PCB and PAH in marine sediments using supercritical CO2 extraction

Automated Supercritical Fluid Extraction (SFE), using CO2, was tested and optimised for routine analysis of hydrocarbons (THC), polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH) in marine sediments. The aim of the exercise was to reduce the amount of solvents used and to reduce the manual handling time for each sample. The sediments contained elemental sulphur, which was removed during the extraction step using activated Cu. Similar recoveries and reproducibility where found for THC when conventional solvent extractions and SFE where compared. Modifying the CO2 with methanol was necessary to obtain extraction recoveries similar to conventional extraction methods for PCB and PAH.     

Aqueous accelerated solvent extraction of native polycyclic aromatic hydrocarbons (PAHs) from carbonaceous river floodplain soils

In this study, three river floodplain soils with different compositions of carbonaceous materials and a reference coal sample were extracted with water using the accelerated solvent extraction (ASE) method. The desorption enthalpy values for 2-ring PAHs were highest in the coal sample, with values in the soil samples decreasing with decrease in coal content. The values for the higher condensed PAHs showed that the highest desorption enthalpies were from the samples with the largest amount of coal-derived particles. Elevated desorption enthalpies indicated a strong bonding between PAHs and geosorbents. Moreover, with the application of ASE this study was able to conclude that the PAHs in the samples were preferentially adsorbed to carbonaceous materials with high surface areas.     

Validation of pyrithiobac sodium (Staple herbicide) ELISA for Australian cotton soils

An enzyme-linked immunosorbent assay (ELISA) for pyrithiobac-sodium (Staple) produced by DuPont was validated in Australian soils. This pyrithiobac-sodium ELISA was shown to be highly sensitive with the limit of detection of 4-5 ppt. Soil samples were extracted either in PBS buffer by shaking or by accelerated solvent extraction (ASE). While pyrithiobac sodium can be analyzed directly by ELISA after ASE extraction with 1/10 or more dilutions, the analysis of PBS extract required filtration and dilution 1/20 or more depending on the concentration. Immunoassay results compared favorably with GC-MS results for both ASE and PBS extract of incurred residue of pyrithiobac sodium in soil samples, indicating that this ELISA can be an inexpensive and reliable alternative to conventional residue analysis methods for quantification of pyrithiobac-sodium. This validation provided the basis for applying the ELISA to a field study of pyrithiobac-sodium.