Occurrence of organochlorine pesticides and polychlorinated biphenyls in soils and sediments from Eastern Romania

Polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), such as DDT and analogues, hexachlorocyclohexane (HCH) isomers and hexachlorobenzene (HCB), were measured in surface soils and sediments from Eastern Romania. Thirty-nine soil samples from the forested zone, eight soil samples from a municipal waste-disposal site, and 10 sediment samples from the Bahlui River along the Iassy city were analysed using accelerated solvent extraction (ASE) and gas chromatography coupled to electron capture detection or mass spectrometry. The low mean concentrations of OCPs (11–31 and 22–84?ng?g^?1 for HCHs and DDTs, respectively) and PCBs (8–43?ng?g^?1) in soil samples from the forested zone suggest that contamination at most of these sites occurred predominantly through atmospheric transport from zones where these compounds were used and subsequently through atmospheric deposition. Contrarily, soil samples collected in the vicinity of a waste-disposal site near Iassy contained higher mean levels of PCBs (278?ng?g^?1, range 34–1132?ng?g^?1) than OCPs (6 and 101?ng?g^?1 of soil for HCHs and DDTs, respectively). The sediment samples collected along the Bahlui river throughout the Iassy city revealed higher mean levels of PCBs (59?ng?g^?1, range 24–158?ng?g^?1) compared with OCP levels (2 and 37?ng?g^?1 of soil for HCHs and DDTs, respectively). Furthermore, PCB profiles and concentrations in the sediment samples varied considerably along the river due to a wide variety of sources, such as different industries and waste sites. Although their sources are difficult to evaluate, the presence of POPs at most sites (especially at the waste-disposal site) may constitute a potential health hazard.     

Organochlorine Pesticides and PCBs In Tissues from Dutch Citizens (1968–1986)

Abstract

Adipose tissue, milk and blood from Dutch citizens have been investigated for the occurrence of organochlorine compounds since 1968. In this paper, median values for HCB, α-HCH, β-HCH, γ-HCH, β-Hepo (heptachlorepoxide), dieldrin, p.p′-DDE, o.p′-DDT, TDE and PCBs (first determined by the perchlorination method, later by a selection of individual congeners) are given. Time trends, influence of age and sex of the donors, changes in concentrations of milk during lactation, the possible effect of life-style, and statistical evaluation of the data collected over the past twenty years will be discussed.

PCBs and p.p′-DDE occur in the highest concentrations in all tissues investigated, followed by HCB and β-HCH. Especially the p.p′-DDT levels decreased dramatically over the years of the investigation. Blood/fat accumulation factors were derived; they decrease in the order PCBs?p.p′-DDE >β-HCH?HCB > β-Hepo?dieldrin > α-HCH?γ-HCH.     

Persistent organochlorines in human breast milk from Al-Sharkia Governorate,Egypt

In the present study, 23 human breast milk samples were collected in January 2009 from Fakous city, Al-Sharkia Governorate, Egypt. The samples were analysed for organochlorine pesticides such as dichlorodiphenyltrichloroethane (DDT) and its metabolites, α, β, and γ-hexachlorocyclohexane (HCH) isomers. The average concentrations of ΣHCHs and ΣDDTs were 225 and 1315?ng?g^?1 lipid respectively. There was no significant difference between the levels of OCP and mother age, while there was a significant difference and correlation between the levels of OCP and the number of times the mother had breast fed (primiparae and multiparae) (p?<?0.05). The results suggested that DDT is still entering the environment depending on the observed ratio of DDE/DDT. The levels of OCP in human milk elucidated that we need to do more regular pollutant monitoring programs.     

Determination of persistent organochlorine compounds in blood by solid phase micro extraction and GC-ECD

Biomonitoring of persistent organochlorine compounds in blood using the solid phase microextraction technique (SPME) and gas chromatography with electron capture detection (GC-ECD) is described. Polar substances as tri-, tetra- and penta-chlorophenols are analyzed simultaneously with less polar compounds such as hexachlorobenzene (HCB), α-, β-, and γ-hexachlorocyclohexane (HCH), dichlorodiphenyltrichloroethane (DDT) and its derivatives and with some important congeners of the polychlorinated biphenyls (PCB). No derivatization is needed for the determination of the phenolic compounds. The results show a good reproducibility down to the lower μg/L-region. The method is very fast and of low cost compared to the classic extraction and determination procedures.     

Characterization of Losses of Chlorinated Pollutants during Lyophilization of Mussels

The influence of the lyophilization process on the recovery of ten organochlorine compounds, (9 polychlorinated biphenyls (PCBs) and pp′-DDE [1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene)] during the pretreatment step of mussels was studied at three concentration levels. Losses of more polar and water-soluble compounds were approximately 50% in samples pulverized prior to lyophilization. Two variables, moisture and lipid concentrations, had statistical influences in the losses of the lower chlorinated compounds (CB 31 and CB 28). In some PCB congeners (CB 52, CB 101, and CB 118), the variation of losses with the PCB concentrations was also statistically significant.     

Marine mammal blubber reference and control materials for use in the determination of halogenated organic compounds and fatty acids

The National Institute of Standards and Technology (NIST) has a diverse collection of control materials derived from marine mammal blubber, fat, and serum. Standard Reference Material (SRM) 1945 Organics in Whale Blubber was recertified for polychlorinated biphenyl (PCB) congeners, organochlorine pesticides, and polybrominated diphenyl ether (PBDE) congeners. SRM 1945 has also been assigned mass fraction values for compounds not frequently determined in marine samples including toxaphene congeners, coplanar PCBs, and methoxylated PBDE congeners which are natural products. NIST also has assigned mass fraction values, as a result of interlaboratory comparison exercises, for PCB congeners, organochlorine pesticides, PBDE congeners, and fatty acids in six homogenate materials produced from marine mammal blubber or serum. The materials are available from NIST upon request; however, the supply is very limited for some of the materials. The materials include those obtained from pilot whale blubber (Homogenates III and IV), Blainville’s beaked whale blubber (Homogenate VII), polar bear fat (Homogenate VI), and California sea lion serum (Marine Mammal Control Material-1 Serum) and blubber (Homogenate V).     

Could gingko foliage serve as a bio-monitor for organochlorine pesticides in air?

The feasibility of gingko (Gingo Biloba) foliage as a passive bio-monitor for organochlorine pesticides in air was explored. The accumulation patterns of hexachlorocyclohexanes (HCHs), dichlorodiphenyl- trichloroethanes (DDTs) and hexachlorobenzene (HCB) in gingko foliage were similar; the amounts of HCHs, DDTs and HCB increased with foliage growth in spring and decreased thereafter. This accumu-lation pattern is likely related to the growing process of the gingko foliage, which was observed for the first time in our work, giving a piece of evidence for the "bud burst effect" in plants. Compared with those in pine needles in 1980's, the residual levels of HCHs and DDTs have declined obviously in Bei-jing, indicating that the ban on the production and use of organochlorine pesticides (OCPs) in our country is effective; however, the amount of HCB has increased, indicating great progress of chemical industry in Beijing. The analysis for the source of OCPs in the gingko foliage showed that the technical HCHs and DDTs were used largely in history, but were not used in recent years. A little lidane has been used and there was a new input of o,p′-DDT in recent years; dicofol usage may be the main source of o,p′-DDT. Concentrations of HCHs, DDTs and HCB in gingko foliages were similar to those in pine nee-dles in the corresponding period and there is a strong positive correlation between the OCPs concen-tration data obtained from these two kinds of trees. It presents no difference in the accumulation style between these two kinds of trees. The level of OCPs in the gingko foliage reflects the pollution status of OCP in air. The result of this work shows that the gingko foliage can be used as a bio-monitor of OCPs in air.     

Rapid multiresidue determination of organochlorine and organophosphorus compounds in human serum by solid-phase extraction and gas chromatography coupled to tandem mass spectrometry

A rapid analytical method for the multiresidue determination of several organochlorine and organophosphorus pesticides and polychlorinated biphenyls in human serum samples has been developed. Analytes were isolated by solid-phase extraction using C18 cartridges with subsequent analysis by GC-MS/MS using a glass liner packed with CarboFrit in the GC injection port. Labelled surrogate internal standards (fenitrothion D6, HCB (13)C6, p, p'-DDE D8 and PCB 138 (13)C12) were added to the samples before the extraction and were used for quantitation and for quality control in the analysis of real-world samples. Accuracy and precision were evaluated by using serum samples fortified at two concentration levels for the three families of compounds, with satisfactory results in the majority of cases. The high selectivity and sensitivity of GC-MS/MS allowed low detection limits of 0.05-0.5 ng mL(-1) for most of the analytes investigated. The developed procedure improves other current methodologies for the analysis of pesticides and PCBs in biological fluids, especially as regards to analysis time and simplicity of sample treatment. The method was applied to several serum samples obtained from farmers devoted to citrus crop production. Chlorpyrifos, HCB, p, p'-DDE and the higher chlorinated PCBs (153, 138 and 180) were the most frequently detected compounds.     

Determination of selected persistent organochlorine pollutants in human milk using solid phase disk extraction and narrow bore capillary GC-MS

Summary A simple and rapid procedure based on solid phase disk extraction (SPDE), adsorption chromatography on acidified silica gel and GC-MS analysis was developed for the determination of 8 organochlorine pesticides and 19 PCB congeners in human milk. By using the SPDE procedure, a high throughput and parallel sample processing could be achieved. Method variables were optimized on whole cow's milk (3.5% fat) fortified at levels close to concentrations found in human milk. Recoveries of target analytes were acceptable and ranged from 69 to 102% and 86 to 120% for whole and skimmed milk, respectively. By the use of two stage clean-up and narrow bore capillary columns, detection limits as low as 20 pg mL⁻¹ could be obtained. The method was used for the determination of organochlorine pollutants in human milk from 19 individuals from Romania. The concentrations of PCBs were low, whereas those of organochlorine pesticides were higher than the values reported from other European countries.     

Determination of persistent organochlorine compounds in blood by solid phase micro extraction and GC-ECD

Biomonitoring of persistent organochlorine compounds in blood using the solid phase microextraction technique (SPME) and gas chromatography with electron capture detection (GC-ECD) is described. Polar substances as tri-, tetra- and penta-chlorophenols are analyzed simultaneously with less polar compounds such as hexachlorobenzene (HCB), α-, β-, and γ-hexachlorocyclohexane (HCH), dichlorodiphenyltrichloroethane (DDT) and its derivatives and with some important congeners of the polychlorinated biphenyls (PCB). No derivatization is needed for the determination of the phenolic compounds. The results show a good reproducibility down to the lower μg/L-region. The method is very fast and of low cost compared to the classic extraction and determination procedures. Received: 7 July 1997 / Revised: 6 October 1997 / Accepted: 21 October 1997     

气相色谱-串联质谱法测定土壤中的有机氯农药

建立了气相色谱-串联质谱测定土壤中有机氯农药的方法,同时测定了上海郊区的20个农业土壤。样品前处理包括加速溶剂萃取(弗罗里硅土池内净化)和凝胶渗透色谱净化在线浓缩。采用多反应监测模式的气相色谱-串联质谱分析有机氯农药,降低了背景干扰,提高了分析的灵敏度。在0.001～2 mg/L的质量浓度范围内,各种农药标准溶液的线性相关系数均大于0.995。分别向3种实际土壤样品中添加农药的混合标准溶液,所测定的有机氯农药的平均回收率为65.9%～140.0%,相对标准偏差为1.5%～20.3%(n=5)。有机氯农药的检出限（S/N=3）为0.1～3.0 μg/kg,定量限（S/N=10）为0.3～8.0 μg/kg。实际土壤样品的测定结果表明：六六六(1.82～3.70 μg/kg)和六氯苯(0.94～9.8 μg/kg)有少量检出,滴滴涕的检出率高达100%,其含量范围较宽(1.08～308.76 μg/kg),平均值为53.28 μg/kg,其中85%的样品中滴滴涕含量/(滴滴伊+滴滴滴)含量的比值小于1,表明滴滴涕主要来自于早期的使用     

沉积物内多氯联苯测定中有机氯农药的排除及质量控制/质量保证研究

报道了沉积物样品中多氯联苯(PCBs)的分析方法及质量控制/质量保证(QA/QC)研究,结果表明多级复合硅胶柱对有机氯农药去除效果良好.采用25种PCBs同族体标样PCB25对分析方法进行了QA/QC研究,PCBs的平均回收率在97%～118%之间.用本方法测定25种多氯联苯同族体的检测限范围在0.5～1.4ng/g之间.     

Levels of polychlorinated biphenyls in the lower troposphere of the North- and South-Atlantic Ocean

Summary Fourteen polychlorinated biphenyl (PCB) congeners were quantified in air samples of the tropospheric boundary layer of the Atlantic Ocean. The samples were taken on the German research vessel Polarstern during north-south cruises across the Atlantic Ocean (1990, 1991), and on the Capo Verde islands in the North Atlantic Ocean (1992). Values for the sum of PCB were between 48 pg/m³ (values for the seven indicator congeners were [in pg/m³]: PCB 28: 1.3; PCB 52: 5.0; PCB 101: 3.0; PCB 118: 0.5; PCB 138: 1; PCB 153: 1; PCB 180: <0.2) in the Westwind Belt of the eastern North Atlantic and 22 pg/m³ (values for the seven indicator congeners were [in pg/m³]: PCB 28: 2.3; PCB 52: 3.4; PCB 101: 0.5; PCB 118: <0.2; PCB 138: <0.2; PCB 153: <0.2; PCB 180: <0.2) in the Westwind Belt of the central South Atlantic. Up to 385 pg/m³ (values for the seven indicator congeners were [in pg/m³]: PCB 28: 2.6; PCB 52: 11.7; PCB 101: 28.4; PCB 118: 9; PCB 138: 21; PCB 153: 18; PCB 180: 5.5) were measured of the coast of South Patagonia. A difference depending on latitude and on terrestrial influenced air masses between the lower and the higher chlorinated congeners was observed. The levels of three- and tetrachlorinated congeners were highest in the Trade Wind regions. The contents of the higher chlorinated congeners had maxima in samples influenced by continental air masses. A correlation of the levels of the lower chlorinated congeners in air over the South Atlantic with the surface water temperature and thus with the temperature dependent gas/water partition coefficient K_gw was observed. Part XVI: Fischer RC, Krämer W, Ballschmiter K (1991) Chemosphere 23:889–900     

Improved analytical procedure for determination of chlorinated pesticide residues in human serum using solid phase disc extraction (SPDE), single-step clean-up and gas chromatography

Summary An improved analytical methodology based on solid-phase disc extraction (SPDE) and a single-step clean-up on Florisil is proposed for a large number of organochlorine pesticide residues in serum. Extraction was performed following denaturation of proteins with formic acid after it was shown that it has no degradation effect on targeted analytes (α, β, γ-HCH isomers, HCB, DDT with its 5 analogues, endrin, aldrin, dieldrin, alachlor; heptachlor, heptachlorepaxide, α, β-endosulphan, endosulphansulphate, methoxychlor and mirex). Determination and quantification were by GC-ECD and GC-MS on two different, analytical capillary-columns using PCNB (pentachlonitrobenzene) and PCB 190 internal standards. Recoveries and limits of detection determined on pooled serum ranged 54–102% (for medium spiking level) and 10–50 pg ml⁻¹ serum respectively. Twenty-one individuals serum samples from the University Hospital of Antwerp were analysed and results were related to the ages of the donors. For compounds not detected by GC-MS, eventual coelution with PCBs in GC-ECD analysis was studied.     

气相色谱法测定禽蛋中微量有机氯农药及多氯联苯的残留

建立了以正己烷振荡提取，以及PCB2和PCB209为内标的快速检测禽蛋中微量有机氯污染物的气相色谱法。与传统的索氏提取法相比，在保证足够的准确度，精确度和灵敏度的前提下，具有前处理简单，测试成本低，标本用量少的特点。而且可同时测定有机氯农药和典型的多氯联苯类化合物的残留，特别适于检测食品中的微量有机污染物。用该方法测试的结果表明，标准全蛋粉添加ng/g级待测物时，各种待测物的回收率为84．31％－116．77％（3次测定平均值）；相对标准偏差为6％－18％（7次测定平均值）；最低检出量为0.07ng/g-0.35ng/g。中国部分城市市售鸡蛋中的有机氯农药以p,p'-DDE的检出量最高，p,p'-DDT次之；多氯联苯的检出量很低，大多数样品中多氯联苯的总检出量低于10ng/g。在所检出的多氯联苯中，绝大部分为含氯低的（氯原子数为3－5）的氯化物。     

Biomonitoring and risk assessment of organochlorine pesticides among Saudi adults

The present study aimed to determine the serum organochlorine pesticides (OCPs) levels and risk of exposure among Saudi adults. Most OCPs are considered as endocrine-disrupting chemicals, and exposure can induce adverse health effects in both humans and wildlife. Serum OCP levels have not been documented in the Saudi population. Serum OCP concentrations were quantified using gas chromatography mass spectrometry (GC-MS/MS) in 302 serum samples collected from adult Saudis. All studied OCPs were detected in all participants. High concentrations of DDT and its metabolites (DDE and DDD) were detected in both males and females, with concentrations being significantly higher in males. High concentrations of 2,4-DDE, 4,4-DDE, and gamma-HCH were detected (18.31, 16.12, and 15.15 ng g⁻¹ lipid and 5.9, 7.1, and 8.6 ng g⁻¹ lipid for males and females, respectively). Alpha-HCH, Beta-HCH, 2,4-DDT, and 4,4-DDT were detected at concentrations lower than 2 ng g⁻¹. Levels of OCPs varied according to age and body mass index (BMI). Serum concentrations of OCPs significantly differed between Saudi males and females and were influenced by age and BMI. This study is the first to document serum OCP concentrations in Saudi adults from Riyadh, KSA. Monitoring programs are suggested for evaluating serum OCP concentrations in the general population to track toxicity levels and serve as an indicator of possible adverse health effects.     

Analysis of persistent organic pollutants in marine sediments using a novel microwave assisted solvent extraction and liquid-phase microextraction technique

A simple and novel analytical method for quantifying persistent organic pollutants (POPs) in marine sediments has been developed using microwave assisted solvent extraction (MASE) and liquid-phase microextraction (LPME) using hollow fibre membrane (HFM). POPs studied included twelve organochlorine pesticides (OCP) and eight polychlorinated biphenyl (PCB) congeners. MASE was used for the extraction of POPs from 1 g of sediment using 10 ml of ultrapure water at 600 W for 20 min at 80 degrees C. The extract was subsequently subjected to a single step LPME-HFM cleanup and enrichment procedure. Recovery varied between 73 and 111% for OCPs; and 86-110% for PCBs, and exceeded levels achieved for conventional multi-step Soxhlet extraction coupled with solid-phase extraction. The method detection limit for each POP analyte ranged from 0.07 to 0.70 ng g(-1), and peak areas were proportional to analyte concentrations in the range of 5-500 ng g(-1). Relative standard deviations of less than 20% was obtained, based on triplicate sample analysis. The optimized technique was successfully applied to POP analysis of marine sediments collected from the northeastern and southwestern areas of Singapore's coastal environment.     

Organic contamination in clams,Venerupis aurea laeta and Cerastoderma edule glaucum,from Sicily (Italy)

Two species of edible clams Venerupis aurea laeta and Cerastoderma edule glaucum from Ganzirri Lake (Sicily, Italy) were investigated to determine OCP and PCB residues by GC-MS. Thirty-five samples were examined for two years in order to perform: a) their actual contamination; b) the daily dietary exposure of seafood consumers to the pollutants in question. In all the clams analysed in this study, PCB and OCP (4,4′-DDE) residues are always below the limits fixed by law. It seems that there is some seasonality of concentrations observed. In fact the more high concentrations of residues are detected in the hot months, for both species and years. Given the consumption of clams and the values obtained in this study for the two species analysed, it is possible estimate that the average daily dietary intake of NDL-PCB and of 4,4′-DDE for adults is really low.     

Simple solid-phase extraction method for determination of polychlorinated biphenyls and selected organochlorine pesticides in human serum

A simple off-line solid-phase extraction (SPE) method for isolation of polychlorinated biphenyls (PCBs) and selected organochlorine pesticides (OCPs) from human serum has been developed. The procedure includes denaturation of serum proteins by a mixture of water-1-propanol, application of the sample by aspiration twice repeatedly through the SPE column and elution with a mixture of n-hexane-dichlormethane. After final clean-up the compounds of interest were analysed by gas chromatography with micro-electron capture detection (GC-microECD). The recoveries achieved for PCB congeners using spiked porcine serum samples were 99-120% and for OCPs 88-115%. Relative standard deviations (RSD) ranged from 3 to 7%. The method was applied to real human serum samples and the recoveries of analytes in the serum were proportionally recalculated considering the recovery of the internal standard PCB-174. PCB-103 served as a syringe standard to correct volume of samples analysed. The aim of this study was to develop an effective off-line SPE procedure by optimization of existing SPE methods to supply laborious, solvent- and time-consuming liquid-liquid extraction (LLE) in routine analytical process.     

Application of solid phase micro extraction for the rapid analysis of chlorinated organics in breast milk

The method presented here allows the monitoring of persistent organochlorine compounds in breast milk using the solid phase microextraction technique (SPME) and gas chromatography with electron capture detection (GC-ECD). It describes the determination of hexachlorobenzene (HCB), α-, β-, and γ-hexachlorocyclohexane (HCH), dichlorodiphenyltrichloroethane (DDT) and its derivatives, and some important congeners of the polychlorinated biphenyls (PCB). Also included are more polar substances such as tri-, tetra- and penta-chlorophenols, which can be analyzed simultaneously with the afore-mentioned less polar compounds without the need of a derivatization for the determination of the phenolic compounds. The reproducibility of the results is very good down to the lower μg/L-region. The method is very fast and of low cost compared to the classic extraction and determination procedures.