Identification of urinary metabolites in rats administered the fluorine-containing pyrethroids metofluthrin,profluthrin, and transfluthrin

The major metabolites in urine of rats administered the fluorine-containing pyrethroids transfluthrin, profluthrin, and metofluthrin, which are used widely recently as mosquito repellents or mothproof repellents, were identified to establish biological indexes for evaluating the absorption amounts of these pyrethroids in the general population. A single dose of 300?mg?kg^?1 body weight of each pyrethroid was separately administered intraperitoneally to male Sprague-Dawley rats and urine samples were collected until 24 hours after the administration. The metabolites identified by gas chromatography-mass spectrometry were as follows: 2,3,5,6-tetrafluorobenzyl alcohol, 2,3,5,6-tetrafluorobenzoic acid, and 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (DCCA) for transfluthrin; 4-methyl-2,3,5,6-tetrafluorobenzyl alcohol, 4-methyl-2,3,5,6-tetrafluorobenzoic acid, 4-hydroxymethyl-2,3,5,6-tetrafluorobenzyl alcohol (HOCH₂–FB–Al), and 2,2-dimethyl-3-(1-propenyl)-cyclopropanecarboxylic acid (MCA) for profluthrin; 4-methoxymethyl-2,3,5,6-tetrafluorobenzyl alcohol, HOCH₂–FB–Al and MCA for metofluthrin. In addition, several compounds estimated to be metabolites were detected as follows: hydroxylated DCCA and its lactone for transfluthrin; 4-hydroxymethyl-2,3,5,6-tetrafluorobenzoic acid (HOCH₂–FB–Ac), hydroxylated MCA and its lactone for profluthrin; 4-methoxymethyl-2,3,5,6-tetrafluorobenzoic acid, HOCH₂–FB–Ac, hydroxylated MCA, and its lactone for metofluthrin. The pyrethroids administered underwent metabolic reactions such as ester hydrolysis and oxidation, and most of the metabolites were excreted as their conjugates into urine. These findings should be useful as basic data for evaluating the health effects of exposure to pyrethroids for the general population.     

SIMCA principal component analysis of fatty acid patterns in Day-1 and Day-8 cod (Gadus morhua) and haddock (Melanogrammus aeglefinus) eggs

Single cod [Gadus Morhua (L.)] and haddock [Melanogrammus aeglefinus (L.)] eggs from the first day and the eighth day after fertilization were acid hydrolised. Fatty acids were liberated and derivatized to methyl esters in a one-step reaction. The non-polar hexane extract was analysed by High Resolution Gas Chromatography (HRGC). Selected peaks, occuring in both types of samples and in all chromatograms, were used to create a matrix for multivariate analysis. HRGC and Mass Spectrometry have been used to identify the fatty acids. The approach is shown to be useful in distinguishing between cod and haddock eggs at both stages and information regarding changes in the fatty acid distributions are obtained. Implications on future possibilities within chemosystematics are discussed.     

Bestimmung der resorptionsverfügbaren PCDD/PCDF aus Kieselrot

For the estimation of intestinal absorption of polychlorianted dibenzodioxins/dibenzofurans (PCDD/F), ain-vitro model was developed in order to study PCDD/F mobilization by digestion of technogenic soils using ?Kieselrot” (red slag) as substrate and digestive juice model mixtures. Red slag samples were shaken successively with model mixtures of saliva, gastric juice, duodenal juice and bile. The solids were separated, the aqueous phase was extracted with hexane, the hexane extract analyzed for PCDD/F. Additionally, the PCDD/F-content of the red slag was determined. Extraction efficiency was tested with three different digestive juice model mixtures and also tap water for comparision. The percentage of PCDD/F transferred from the red slag sample into the digestive juice mixture was defined as absorption availability. In our experiments, a maximum absorption availability of 2 % was found.     

土壤中不同老化时间的DDT对小麦根系的生物有效性

研究了水、正己烷、正己烷/丙酮ASE对土壤中不同老化时间的DDT的逐级提取量的差别及其与小麦根吸收的关系。结果表明,有机氯的水提量随老化时间增加而下降,正己烷提取量随老化时间增加而下降,正己烷/丙酮提取量随老化时间增加而上升。植物根吸收随老化时间增加而下降。根吸收与水提量没有确定关系,与正己烷提取量具正相关关系,与正己烷/丙酮提取量有负相关关系。正己烷提取量可被作为土壤有机氯DDT的有效态部分。     

Assessment of solid waste and dumpsite leachate and topsoil

Dumpsite leachate contains different hazardous substances, some of which threaten the environment. In this study, municipal solid waste, dumpsite leachate and topsoil from seven different dumpsites in Lagos and Ibadan, Nigeria were analysed using standard methods. The parameters analysed in the composite leachate samples collected are pH, solids, alkalinity, chloride, nitrate, sulfate, phosphate, biochemical oxygen demand, chemical oxygen demand turbidity, heavy metals (e.g. Zn, Pb, Co, Ni, Cd) and some persistent organic pollutants (e.g. polyaromatic hydrocarbons [PAHs] and polychlorinated biphenyls [PCBs]). Total organic carbon, heavy metals (e.g. Zn, Pb, Co, Ni, Cd) and organic pollutants (e.g. PAHs, PCBs) were analysed in the dumpsite topsoil and the control samples. The samples for heavy metal determination were digested using concentrated nitric acid and the digestate was analysed using atomic absorption spectrometry, whereas organic pollutants were extracted using cold extraction and quantified by gas chromatography-mass spectrometry (GC-MS). The study revealed that dumpsites in Ibadan have ～90% domestic and 10% industrial waste, whereas the figures for Lagos are 80% and 20%, respectively. In the leachate samples, concentrations of PAHs and PCBs ranged from 0.85 to 1.47 mg/L and 0.01 to 0.08 mg/L, respectively; the values were 0.94–2.79 mg/kg and 10.0–412 μg/kg in the topsoil. If not properly managed, dumpsite leachate can seep into groundwater and surface water via run-off, and can have adverse effects on human health and the entire ecosystem.     

Substitution of toxicologically critical solvents in the residue analysis of acetamiprid: Towards green chemistry

The article presents the reduced use of toxicologically critical solvents for the extraction and clean-up of a neo-nicotinoid pesticide, acetamiprid from vegetables. Acetamiprid was extracted from spiked vegetable samples of cabbage by the use of different techniques like microwave-assisted extraction (MWAE), sonication and by the conventional method of homogenization. The study revealed that though higher percent recoveries of 78–92 were obtained in the blending method, solvent use was high as compared to MWAE. In MWAE, the percent recoveries recorded were in the range of 46–89 depending upon the solvent used and power employed. A mixture of methanol–water and methanol–acetone at 400 W power levels gave percent recoveries of 72 and 82, respectively, as compared to solvent mixtures, namely, acetone–hexane and acetone–hexane–water, which recorded recoveries of 49 and 67%. The study indicates that the choice of solvent and power employed plays a significant role in MWAE for enhanced recoveries.     

Particle size distribution and pollutants in road-deposited sediments in different areas of Zhenjiang,China

An understanding of road-deposited sediment (RDS) characteristics on an impervious surface is essential to estimate pollutant washoff characteristics and to minimise the impacts of pollutants on the water environment. A total of 62 RDS samples were collected from four different land-use types (commercial, residential, intense traffic and riverside park) in Zhenjiang City, China. The samples were fractionated into seven grain-size classes and analysed for particle size distribution and concentrations of pollutants. The samples are found to consist predominantly of fine particles (60–80%, <250 μm). The maximum mean concentrations of zinc, lead and copper were 686.93, 589.19 and 158.16 mg/kg, respectively, with the highest metal concentrations found in samples from the intense traffic area. The maximum mean contents of organic matter (12.55%), nitrogen (6.31 mg/g) and phosphorus (5.15 mg/g) were found in samples from the commercial area. The concentrations of heavy metals were highest in the smallest particle size fraction analysed (63 μm). The organic matter and nitrogen content generally increased with decreasing particle sizes in the <500-μm particle size range. The results also revealed that most of the total nitrogen (TN) is attached to the finer sediments and that to effectively reduce TN loads in particulates, treatment facilities must be able to remove the finer particles (down to 125 μm for TN).     

Elemental Analysis of Water and Sediments by External Beam Pixe Part 3: Axios (Vardar) River, Greece

The Axios (Vardar) River originates from the south west part of Yugoslavia, transverses Greece, and discharges into the Thermaikos bay in the north Aegean Sea.

The proton induced X-ray emission (PIXE) method with external beam was used for the elemental analysis of water and sediment samples, while measurements of water temperature, dissolved oxygen content, conductivity, pH, and the water flow were made in situ. Water samples were also analysed for total phosphates, nitrates, chlorophyll, and BOD. The data collected for a 16-month period indicate that the Axios River is polluted as far as the metal content is concerned; its primary productivity is low and it is slightly enriched during its course into the Greek territory.     

Geological sources of fluoride and acceptable intake of fluoride in an endemic fluorosis area, southern Iran

The present study is the first attempt to put forward possible source(s) of fluoride in the Dashtestan area, Bushehr Province, southern Iran. In response to reports on the high incidence of dental fluorosis, 35 surface and groundwater samples were collected and analysed for fluoride. The results indicate that dissolved fluoride in the study area is above the maximum permissible limit recommended by the World Health Organization (WHO). An additional 35 soil and rock samples were also collected and analysed for fluoride, and rock samples were subjected to petrographic investigations and X-ray diffraction. The results of these analyses show that the most likely source for fluoride in the groundwater is from clay minerals (chlorite) and micas (muscovite, sericite, and biotite) in the soils and rocks in the area. We also note that due to the high average temperatures all year round and excessive water consumption in the area, the optimum fluoride dose level should be lower than that recommended by the WHO.     

Persistent organochlorine contaminants in human tissues of the Czech and Slovak populations

The persistence of lipophilic organochlorine substances leads to their incorporation into the food chain and subsequent uptake by humans. Due to their use in the past, Czech and Slovak countries belong to the countries with a relatively high body burden of organochlorines. Levels of PCBs in human tissues based on the congener‐specific analysis are reported in this paper. Samples were analysed for the most abundant PCB congeners. Prevalent persistent organochlorine pesticides and their isomers/metabolites have also been included. The present study is focused on following areas: i) distribution of analysed substances in the various human tissue samples from selected regions of the Czech and Slovak Republic and ii) comparison with the results from other foreign and local studies.     

Determination of trace elements in total suspended particles at the Southwest of Mexico City from 2003 to 2004

The purpose of the present study is to describe the relationships of eight elements analysed in total suspended particles collected in Mexico City, during 2003 and 2004. Al, Cd, Cr, Fe, Mn, Ni, Pb and V were analysed in to the atmospheric samples and the results were treated by Principal Components Analysis and Cluster Analysis trying to identify the possible sources of aerosols in the sampling site. Factor analysis calculations allowed the elements classification, related to their source on oil combustion, crustal and urban dust, smelting industries and motor vehicle emissions. A further statistical analysis of chemical results from the atmospheric samples was also performed, in order to see what environmental concentrations of those elements have been affected by industrial and mining activities. The eight elements analysed were arranged into two groups that presents high and positive Pearson r values suggesting common emission sources.     

植物类脂的提取及对菲吸附的影响

讨论了有机溶剂极性对植物类脂提取的影响,分别采用(Ⅰ)非极性正己烷和(Ⅱ)极性三氯甲烷∶甲醇(2∶1)溶液从青椒和油麦菜干样中索氏提取植物类脂,进一步研究了上述植物干样、提取类脂和去类脂组分对菲的吸附.实验结果表明,两种方法提取得到的类脂含量不同,方法(Ⅰ)从青椒和油麦菜中提取得到类脂含量为(1.9±0.1)%和(5.0±0.4)%;而方法 (Ⅱ)提取得到的相应值分别为(2.6±0.2)%和(9.5±0.5)%.两种方法得到提取类脂对菲的吸附贡献无显著性差异(P>0.05),均约占整个青椒干样对菲吸附的20%,而油麦菜的这一比例约为60%.但采用正己烷提取可避免极性物质的析出而更好地分离类脂和去类脂组分.去类脂组分在青椒和油麦菜中对菲的吸附贡献分别约为80%和40%,即去类脂组分对菲仍有较强的吸附能力,因此不能简单视为碳水化合物.     

Environmental degradation of atrazine,linuron and fenitrothion in soil samples

The persistence of atrazine, linuron and fenitrothion in soil samples from an estuarine area (Ebro delta, Tarragona, Spain) has been studied. Soil samples from the top surface (10 cm) were collected during 1989–91, freeze‐dried, sieved through 200 μm, Soxhlet extracted with methanol, cleaned‐up with Florisil and analysed either by gas chromatography‐nitrogen phosphorus detection (GC‐NPD), in the case of atrazine and fenitrothion, or by liquid chromatography with diode array detection (LC‐DAD), for linuron. Confirmation of the samples analysed by GC‐NPD was carried out using GC‐mass spectrometric detection (MS) in the electron impact mode. The soil half lives obtained under the real environmental conditions have been calculated and the values obtained have been correlated with the physicochemical properties of each pesticide and the soil type. Degradation was affected by volatilization since temperatures in the area of study are relatively high, ca. 30°C, in the summer period. In the case of atrazine it has been shown that deethylatrazine is formed in all the samples studied..     

Presumed decomposition pathway of pentachlorophenol through atomic charge calculation and photodecomposition experiments

Batch photodegradation of pentachlorophenol (PCP) was conducted with ultraviolet irradiation. The main intermediates were identified as 2,3,5,6-tetrachlorophenol, 2,3,4,6-tetrachlorophenol and 2,5-dichlorophenol. Based on the density functional theory, atomic charge values were applied to reveal the photodegradation pathway. A comparison of the results of the experiment confirms that PCP molecules are dechlorinated in the descending order of their atomic charge values. From these results, it appears that determining the atomic charge values of organohalogen compounds is a promising method for predicting the dechlorination position in photodegradation.     

Site-Specific Characterization of Castromil Brownfield Area Related to Gold Mining Activities

Castromil is one of the gold mining areas in Portugal that has been abandoned since 1940. This area, which was first mined in Roman times, is located within a Hercynian granite body near the contact with Silurian metasediments. Gold is essentially disseminated along veins in the silicified granite, running NW-SE, related with a shear zone and frequently associated with sulphides (arsenopyrite and basically pyrite). In paragenetic terms, three stages of mineralization are considered: ferro-arseniferous (quartz + arsenopyrite I + pyrite I + pyrrhotite + bismuth), zinciferous (sphalerite + chalcopyrite), and remobilization (arsenopyrite II + galena + gold). Due to the lack of laws and environmental education, Castromil is today a gold mining heritage site where we can detect the consequences of an incautious exploration (tailings, wells and adits located in the old explored zone) and where a residential area is located. In order to characterize the actual state of the old mining area the trace metal contamination of soils and waters by mining activities was investigated. In the studied area 106 soil samples, 15 waters and 20 plants were sampled and analysed. The soil samples were analysed for 32 elements by ICP-AES. Waters were analysed by ionic chromatography and ICP-MS for major and trace elements. Plants were analysed for As, Fe and Pb by AAS. The results are discussed taking into account the risk-based standards for soils and groundwater's (target and intervention values) proposed by Swartjes (1999). The results show elevated concentration of As and Pb which were found in soils collected from agricultural areas. Foodstuff plants species collected in the Castromil agricultural area show high concentrations of As in the leaves (cabbage and lettuce) and in the tubers (potatoes). Groundwaters in the mining area contain high concentrations of As that exceeds the intervention values. The area must to be subject to a remediation process, considering the actual risks to humans and ecosystems and the risks due to contaminant migration.     

Investigation of bioremediation potential of zymogenous bacteria and fungi for crude oil degradation

Bioremediation potential of bacteria and fungi isolated from sludge samples has been investigated (Danube alluvium, Pančevo, Serbia). Total isolated microorganisms were divided into three parts. One part was added with actidione antifungicide. The second part was added with streptomycin antibiotic. The third part was without additives. Paraffinic type of crude oil was a substrate for assessment of bioremediation potential. The simulated oil biodegradation lasted 30, 60 and 90 days. Parallel with that, the experiments with blind trial were conducted. Extracts were isolated from the samples with chloroform in a separate funnel. They were assayed for the group composition (alkanes, aromatics, alcohols and fatty acids) by column chromatography. Alkane fraction was analysed by gas chromatography—mass spectrometry (GC–MS). The most intense oil degradation was achieved in the experiments with bacteria, somewhat weaker with consortium of fungi and bacteria, and the weakest bioremediation potential in these experiments was shown by fungi.     

自动化前处理-气相色谱串联质谱法测定淡水鱼体中的有机磷阻燃剂

应用自动化前处理设备和气相色谱串联四级杆质谱仪建立了淡水鱼体中10种有机磷阻燃剂的检测方法。该方法先采用自动索氏提取仪进行样品的提取,再应用凝胶渗透色谱净化仪和florisil柱对提取液进行两级净化,最后用气相色谱串联四级杆质谱法(多反应监测模式)对样品中的有机磷阻燃剂(OPFRs)定性定量。实验表明,凝胶渗透色谱净化系统在以乙酸乙酯∶环己烷(1∶1,V/V)为流动相,流速为5.0 m L·min-1的条件下,收集OPFRs的最佳时间为900~1 680 s;方法的检出限为0.002~0.192 ng·g~(-1)湿重,加标水平为5.000 ng·g~(-1)湿重时,平均加标回收率为48.7%~122%,相对偏差除磷酸三乙酯(TEP)(17.7%)和磷酸三(1,3-二氯异丙基)酯(TDCP)(11.9%)外均小于10%。应用该方法测定采集于东江某污水处理厂入河排污口的鱼类样品时,回收率指示物(d27-TBP)的回收率为82.4%~114%,鱼类样品中∑OPFRs的浓度范围为nd~6.41 ng·g~(-1)湿重。     

Soxhlet extraction parameters’ influence on the recovery of polychlorinated dibenzo‐p‐dioxins and dibenzofurans (PCDD/F) from a sediment,and artifact formation of PCDD

Soxhlet extraction of polychlorinated dibenzo‐p‐dioxins/dibenzofurans (PCDD/F) from sediment was studied using a designed experimental set‐up. Three variables were studied: three solvent combinations n‐hexane/methanol, dichloromethane/acetone and toluene/methanol; two extraction times, 8 and 16 h, and addition of bulk substances (sodium carbonate). The extraction efficiency was almost identical in all extractions, with the exception of extraction where toluene/ methanol was combined with sodium carbonate. In these samples a major effect was observed, due to formation of Hx‐, Hp‐ and OCDD isomers. Composition of formed PCDD was similar to PCDD isomers found in pentachlorophenol products.     

Estimating zooplankton biomass through image analysis

Zooplankton biomass can be reliably estimated by a non-destructive method based on the statistical relationship between biovolume and the contents of carbon and nitrogen. Integrated zooplankton biovolume and the corresponding organic C and N contents were analysed in paired fresh and fixed (hexamine-buffered formalin) samples. Sample biovolume was estimated through the integration of individual volumes obtained by semi-automatic image analysis on fixed zooplankton samples. The corresponding C and N contents of paired fresh and preserved zooplankton were analysed with a Carlo-Erba C-H-N Analyser. The method allows simultaneous measurement of integrated and individual numbers and biomass (biovolume, C and N) spectrum. It is non-destructive and allows the minimization of errors and variability attributable to differences in the handling processes of samples and to the presence of particles other than zooplankton, like phytoplankton or detritus particulate matter.     

不同有机质含量的土壤中DDT对小麦根系的生物有效性

对不同有机质含量的土壤中，分别选用水、正己烷、正己烷／丙酮混合溶剂作为DDT的提取剂，用这3种提取剂逐级连续提取，研究了这3级提取剂所提取的DDT量的差别及其与小麦根吸收的关系。结果表明，有机氯的水提取量随土壤D0c的增加而上升，正己烷提取量随土壤TOC的增加而下降，正己烷／丙酮提取量随土壤TOC的增加而上升。根吸收与水提取量没有确定的关系，但与正己烷提取量具正相关关系，与正己烷／丙酮提取量有负相关关系。