Toxic potency of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and polychlorinated biphenyls in food samples from Catalonia (Spain)

A surveillance program on polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and polychlorinated biphenyls (PCBs) in 29 foodstuff samples produced all over the four provinces in Catalonia (Spain) is presented. The study included the analyses of milk, egg, meat (beef, chicken, and pork), mussel, and olive oil samples. A previously developed method for the simultaneous analysis of the 2,3,7,8-substituted PCDDs/PCDFs and the dioxin-like PCBs, as well as the indicator PCBs, was employed. Total toxicity equivalent (TEQ) values were calculated using the toxicity equivalent factors (TEFs) proposed by the World Health Organization (WHO) for dioxin-like PCBs, PCDDs, and PCDFs. The TEQ(PCDD/F) levels were below the limits proposed in the draft of the EC regulation for food commercialization in the European countries. These limits are the following: 2 pg WHO-TEQ/g fat for pork, 3 pg WHO-TEQ/g fat for milk and chicken, 5 pg WHO-TEQ/g fat for egg and beef, and 3 pg WHO-TEQ/g whole product for fish. The contributions of PCDDs/Fs and dioxin-like PCBs in the total toxicity of the samples were calculated for each matrix. The results showed that the TEQ(PCB) contribution varied from 27% in olive oil samples to 81% in mussel samples. These findings suggest that the regulation of TEQ contents in food should include not only the TEQ(PCDD/F), but also the TEQ(PCB).     

Survey of persistent organochlorine contaminants (PCBs, PCDD/Fs, and PAHs), heavy metals (Cu, Cd, Zn, Pb, and Hg), and arsenic in food samples from Huelva (Spain): levels and health implications

Concentrations of PCBs, PCDDs, and PCDFs, heavy metals (Cu, Cd, Zn, Pb, and Hg), and arsenic have been determined in a great variety of food samples purchased in different markets across the city of Huelva, located in southwestern Spain and under strong industrial activity. All samples analyzed presented concentrations below the maximum allowed by the European Community regarding PCDD/Fs, with the exception of samples within the meat group. An estimation of the daily intake resulted in 1.15 pg of WHO(PCDD/Fs)-TEQ/kg of body weight/day for a 70 kg person and 2.63 pg of WHO-TEQ/kg of body weight/day when PCBs were included, therefore accounting for a similar or even higher percentage than PCDD/Fs and showing the importance of their inclusion in monitoring studies. Meat and meat products, together with vegetable oils and dairy products, were the major food groups contributing to the estimated daily intake. For heavy metals and arsenic, the concentrations found were under the value proposed by European regulations, and estimated daily intakes were well below those proposed by the WHO for all metals investigated. PAHs have been analyzed in food samples from marine origin, values ranging from 8.22 to 71.4 ng/g of fresh weight. Pyrene was the most abundant compound, accounting for >80% in the samples investigated. The most carcinogenic PAHs, such as benzo[a]pyrene and dibenz[a,h]anthracene, were in all cases below the limits of detection. Therefore, the samples analyzed in this survey can be considered as safe with regard to the levels obtained and the in-force legislation.     

Application of ICP sector field MS and principal component analysis for studying interdependences among 23 trace elements in Polish beers.

Twenty-three metallic elements, including almost all essential and toxic metals such as lead, cadmium, mercury, arsenic, silver, and thallium, have been quantified in 35 types of bottled and canned Polish beer by using double-focusing sector field inductively coupled plasma mass spectrometry (ICP-MS) with ultrasonic nebulization. The samples were digested using concentrated HNO3 in closed PTFE vessels and applying microwave energy under pressure. The means and medians of the concentrations of Rb, Mn, and Fe were on the order of 200 ng/mL; Cu, Zn, V, Cr, Sn, As, Pb, and Ni were detected at 1-5 ng/mL; Ag, Ga, Cd, Co, Cs, Hg, U, and Sb were found at < 1 ng/mL; and In, Tl, Bi, and Th were present at < 0.1 ng/mL. The concentrations of Hg, Cd, As, Pb, and Zn were 1-3 orders of magnitude lower than proposed tolerance limits. The interdependences among determined trace elements were examined using the principal component analysis (PCA) method. The PCA model explained 74% of the total variance. The metals tend to cluster together (As, Tl, Cs, Sn, Th, Bi, and Hg; Cd and Co; Cs and Cr; Fe and Zn; Mn and V).     

Polychlorinated dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxins,dibenzofurans, and biphenyls in soils of Moscow

The contents of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), and biphenyls (PCBs) in the soils of Moscow were estimated. The concentrations of PCDDs and PCDFs mainly vary in the range of 0.27–16.1 ng WHO-TEQ/kg with single points of very high contamination up to 57.3 ng WHO-TEQ/kg; the concentrations of PCBs are in the range of 2.1–50.8 ng/g with sites of high contamination up to 4020 ng/g. The contribution of dioxin-like PCBs to the total dioxin toxic equivalent is very high: from 16 to 85%. The high levels of PCDDs and PCDFs in the soils indicate the strong contamination of the atmospheric air. The main source of these compounds is apparently motor transport.     

Determination of polychlorinated dibenzo-p-dioxins and dibenzofurans in commercial pentachlorophenols by combined gas chromatography-mass spectrometry.

Samples of commercial pentachlorophenol (PCP) and its sodium salt (PCP-Na) were examined for the presence of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), using a rapid, highly specific method of analysis. Phenolic compounds are removed by alkaline extraction, and the neutral components are fractionated on an alumina minicolumn. After gas chromatographic separation, individual PCDDs and PCDFs are detected by mass fragmentography and their presence is confirmed by complete mass spectral analysis. While some samples had only low amounts of PCDDs and PCDFs, others contained much higher amounts of these components. PCP-Na samples showed the unexpected presence of a tetrachlorodibenzo-p-dioxin. Re-analysis of PCP and PCP-Na samples with high PCDD contents on a high-resolution glass capillary column showed the presence of 3 hexa- and the 2 heptachlorodibenzo-p-dioxins with nearly constant isomeric ratios.     

Trace metal concentrations in borehole waters from the Upper Regions and the Accra Plains of Ghana

The concentrations of Hg, Cu, Pb, Zn, Cd, Fe, Mn, Cr and As were measured in groundwaters from the Upper West and Upper East Regions and the Accra Plains of Ghana. Apart from Fe, the trace metal levels for the two Upper Regions were similar. Samples from the Accra Plains had the highest trace metal concentration. However, Hg and As were undetected in all the samples. While the mean Cd, Mn and Cu concentrations for all the 3 study areas fell below the WHO limit, values for Pb and Cr exceeded the WHO limits for drinking water. Iron exceeded the limits in the Upper West Region and the Accra Plains. Overall, the most abundant elements in groundwaters were Zn, Fe and Cr.     

Essential and toxic elements in seafood available in poland from different geographical regions

The concentrations of 15 elements (Cu, Fe, Mn, Zn, Co, Ni, Cr, Se, Cd, Pb, Hg, Ca, Na, K, and Mg) were determined in the edible parts of shellfish on sale in the local market in Gdańsk. The samples consisted of three groups--crustaceans, molluscs, and surimi--that are processed to different degrees. For the purposes of this analysis, they were dried, homogenized, and digested in an automatic microwave system. The samples were analyzed quantitatively for Cu, Zn, Fe, Mn, Co, Ni, Cr, Mg, Na, K, and Ca (F-AAS), Cd and Pb (GF-AAS), Se (HG-AAS), and Hg (CV-AAS). The elemental levels detected in shellfish were compared to those in cod, herring, pork, beef, chicken, and eggs. The recommended dietary allowance (RDA) of essential elements and the provisional tolerable weekly intake (PTWI) of toxic elements were estimated. With factor analysis of the data, taxonomically different groups of raw and processed shellfish could be distinguished.     

企业密集区土壤主要污染物的空间分布及其预测性初步探讨

用克里格空间插值方法研究了城乡民营企业密集区土壤中Cu、Pb、Zn、Cd、Ni、Cr、Hg、As和多氯联苯(PCBs)等9种污染物的空间分布特征,对比该区的企业布局,初步探讨了企业布局对土壤污染物浓度预测的可行性.结果表明,该区污染物的高浓度区主要分布在废旧拆解园区周边地区和小冶炼集中地带,且存在多污染物的复合污染.当在约1 km2 的范围内有金属类生产企业、电机生产企业或(和)电线电缆生产企业存在时,土壤中可能有Cu和Pb积累.电机、电线电缆和(或)自动喷雾器生产企业的密集分布可能出现土壤中Pb的累积.而金属类生产企业的空间布局与土壤中Cd、Ni和Cr的浓度间存在显著的相关关系.汽摩配生产企业和金属配件生产企业可能分别会带来土壤As和PCBs积累.     

Inductively coupled plasma optical emission spectrometric determination of minerals in thyme honeys and their contribution to geographical discrimination

Twenty-four Spanish thyme honey samples were analyzed using inductively coupled plasma optical emission spectrometry (ICP-OES). Twenty-four minerals were quantified for each honey. The elements Al, As, Ba, Ca, Cr, Cu, Fe, K, Li, Mg, Mn, Na, P, Pb, S, Se, Si, Sr, and Zn were detected in all samples; seven elements are very abundant (Ca, K, Mg, Na, P, S, and Si), and six are not abundant (Al, Cu, Fe, Li, Mn, and Zn). Eleven of them are trace elements (As, Ba, Cd, Co, Cr, Ni, Mo, Pb, Se, Sr, and V) at <1 mg kg(-)(1). Classification of thyme honeys according to their origin (coast, mountains) was achieved by pattern recognition techniques on the mineral data. By means of principal component analysis, a good separation by geographical origin is obtained when scores for the two first principal components are plotted. Classification functions of 11 metals (Al, As, Cr, Cu, K, Li, Mg, Na, P, S, and V) were obtained using stepwise discriminant analysis and applied to classify correctly approximately 100% of the honey samples.     

Historical trends of airborne trace metals in Detroit from 1971 to 1992

Ambient concentrations of particulate Fe, Zn, Ph, Ni, Cr, Cd and Hg were measured at nine sites located in the metropolitan area of Detroit from 1971 to 1992. The ambient concentrations of all the trace metals were found to be generally higher at industrial and commercial sites. The concentrations show significant variations between residential and commercial areas and between residential and industrial areas; however, no significant variation was found between the industrial and commercial settings. The spatial variation of trace metal levels within the urban area was influenced by the frequency distribution of the wind direction as well as type and location of emission sources. The ambient concentrations of the trace metals during the decade of 1971–1981 declined by 37–88%. In the 1980s many of the trace metals reversed this trend with the exception of Fe and Pb which continued to decline at annual rates of 2% and 9.8%, respectively. The sharp decrease in Pb concentrations during the 1980s, reflected the significant reduction of Pb content in gasoline from 0.28 g/liter in the 1982 to 0.026 g/liter in the 1989. The ambient concentrations of Zn, Ni, Cr, Cd and Hg showed an upward trend during the 1980s with an annual rate in the range of 0.6% to 10.6%. The long-term trends of selected U.S. market parameters, analyzed as potential long-term indicators of emission sources activityies, were consistent with the changes of ambient concentrations, the correlation coefficient being in the range of 0.58 to 0.84 for most of the trace metals.     

北京市农业土壤重金属状态评价

以北京市土壤重金属背景值为标准,对比分析了农业土壤中Cr、Ni、Cu、Zn、As、Cd、Ph、Hg 8种重金属的含量及累积情况,并采用单因子污染指数法和综合污染指数法进行了土壤重金属污染评价。结果表明,北京市农业土壤存在着一定的Cr、Cu、Zn、As、Cd累积趋势,其含量的平均值分别为53．61、21．95、65．42、9．14、0．125mg·kg^-1,比相应的背景值高79．9％、17．4％、13．8％、28．9％、5．0％;Ni和Pb的累积则不明显,平均值比相应的背景值低7．9％、29．2％,分别为24．84和19．04mg·kg^-1;而Hg含量的平均值与背景值一致,为0．08mg·kg^-1。从单因子评价结果来说,Cr污染指数在1．06-2．93之间,所有的样点都处于轻度或中度污染状态;As、Cu、Zn、Cd的污染指数相对较小,平均值分别为1．29、1．17、1．13、1．05,有50％以上的样点处于轻度污染状态;而Ni、Ph、Hg的污染指数均小于1,有60％以上的样点处于清洁或尚清洁状态,污染较轻。若从综合评价结果来说,综合污染指数处于0．96～2．16之间,平均值为1．45,几乎所有的土壤样点都属于轻度污染状态。     

Cabbage (Brassica oleracea var. capitata) as possible indicator of wartime metal and metalloid contamination in eastern Croatia (ICP-MS method)

Biomonitoring of the local population and environmental monitoring in eastern Croatia have revealed abnormalities in metal and metalloid distribution that could be related to war activities during the 1990s. The goal of this study was to determine whether there are differences in the concentrations of metals and metalloids by comparing locations of high and low-intensity combat activity; we also evaluated a possible connection between metal contamination in soil and in humans. We sampled 14 locations and measured the concentrations of 20 war related metals and metalloids (Al, As, B, Ba, Cd, Co, Cr, Cu, Fe, Hg, Li, Mg, Ni, Pb, Sb, Si, Sr, U, V and Zn). The results of principal components analysis showed two main clusters: locations Dopsin and Dalj (both characterized by high-intensity combat activity), where the concentrations of most elements (except Hg) were increased. Although the concentrations of metals and metalloids in cabbage samples collected in eastern Croatia did not exceed the maximum allowed values, the results of our study confirmed existance of environmental ‘hotspot’ with higher concentrations of war metals and metalloids. Our findings indicate that there is a possible common source and mechanism of transferring metals from the environment to the population.     

Effects of cement production on the elemental composition of soils in the neighborhood of two cement factories

The effects of cement production on the elemental composition of soils in the neighborhood of two cement factories in Nigeria have been investigated using the XRF and PIXE/RBS techniques. The concentration of 21 elements viz:-Mg, Al, Si, P, S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Sr, Pb, As, Zr, Rb and Br, were determined in about 30 samples. Calcium, P, S, Cr, Ni, Cu and Zn, were found to be relatively enriched in the soils of the cement factory premises. Calcium, a cement marker element, was found to be well correlated with Mg, S, Fe, Ni and Cu in the soils, and inversely proportional to the Si and Ti concentrations. From Ca/Si ratios and enrichment factors of the marker elements, it was found that soil contamination due to cement drops sharply with distance from the factories, and with increasing depth from the surface.     

用HRGC／HRMS测定开放式生活垃圾焚烧残余物及周边土壤中的PCDDs／PCDFs

以广东省东南沿海某开放式生活垃圾焚烧场为研究对象,用高分辨气相色谱／高分辨质谱同位素稀释法测定了垃圾焚烧场底灰、焚烧残余物及周边土壤中的多氯代二苯并对二嗯英和多氯代二苯并呋喃（PCDDs／PCDFs）。结果表明,PCDDs／PCDFs的总浓度为161～4670ng·kg^-1,毒性当量为1．10～45．8ngWHO1998-TEQ·kg^-1,其中采自垃圾焚烧场的3个样品浓度为30～45ngWHO1998-TEQ·kg^-1,剩余的土壤样品中有3个样品其浓度为4～35ngWHO1998-TEQ·kg^-1,其余的2个样品浓度〈4ngWHO1998-TEQ·kg^-1。对比加拿大的土壤指导性标准,75％的测定样品浓度高于该标准,即土壤背景浓度,有25％的样品低于此背景浓度。将垃圾焚烧场焚烧残余物作为土壤改良剂造成受施土壤的PCDDs／PCDFs污染严重,需引起有关部门的高度重视。     

Multielement analysis and mercury speciation in atmospheric samples from the Toronto area

Inductively coupled plasma atomic emission spectrometry. (ICP-AES), graphite furnace atomic absorption (GFAAS) and gas chromatography with an atomic absorption detector (GC-AAS) were used for the analysis of atmospheric samples collected in the Toronto area of Southern Ontario. Airborne particulate matter and particulate and soluble fractions of snow were analyzed for S, Al, Fe, Ca, Mg, P, Pb, Zn, Cu, Cr, Cd, Ni, As, and Hg. Also, determinations of organic Hg compounds in filtered snow were performed. The element concentrations in airborne particulate matter from Toronto were similar in amount to those found in other major cities and were the highest in winter. Regional differences in the chemical composition of snow were shown to be related to industrial density. The majority of elements existed in the highest concentrations in the soluble fraction of snow, except for Al, Fe, and Pb, which were largely present in particulate matter. Differences in the distribution of elements in particulate matter in fresh and old snow were observed and depended on particle size and element. The results demonstrated the usefulness of snow as an indicator of atmospheric pollution.     

Heavy Metal Monitoring Around the Nesting Environment of Green Sea Turtles in Turkey

The concentrations of Cd, Pb, Fe, Cr, Ni, Se, Sb, As and Cu were investigated in the nesting environment of green turtles in Mediterranean Sea near Kazanl?, Mersin-Turkey. Tissues of plants growing on the beach and the adjacent environment, beach sand, sea ground sediment, sea grass as well as the egg shells from the nests were analyzed and the results showed no significant high levels of heavy metals detected. The higher levels of metals (Cr, Cu, Pb, Cd and As) were found in the samples from ground sea sediments. Ni and Sb were found at higher levels in river waters and Fe was at the highest in field soil. The high levels of Pb, Fe and Cd were also detected in sea grass, and the Cr, Cu and Ni in sea lily when comparison made with other plants. The levels of essential elements such as Fe and Cu were detected as the highest in most of the specimens. The herbivorous green turtles might be affected from the heavy metal concentrations in the future, since they feed on mainly sea grass. The accumulation of heavy metals via rivers into the sea might cause some pollution problems.     

Effects of cooking on concentrations of polychlorinated dibenzo-p-dioxins and related compounds in fish and meat

We investigated the cooking-induced changes in concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) (dioxins) using mackerel and beef. The concentrations of dioxins (29 congeners) were determined by isomer specific analyses and were compared between uncooked and cooked samples. The cooking procedures examined in this study included grilling as a fillet, boiling as a fillet, and boiling as tsumire (small, hand-rolled balls) for mackerel and boiling as a slice, broiling as a slice, and broiling as a hamburger for beef. Three trials were carried out for each cooking method. Generally, concentrations of dioxins were reduced in every cooking trial. When nondetected congener concentrations were assumed to be half the limit of detection for mackerel, the maximum percentage reductions of total concentrations given as 2,3,7,8-tetraCDD equivalents (TEQ) were 31% in grilling as a slice, 14% in boiling as a slice, and 21% in boiling as tsumire under the conditions of this study. In contrast, for beef, the reductions were 42% in boiling as a slice, 42% in broiling as a slice, and 44% in broiling as a hamburger. These results suggest that ordinary cooking processes with heating undoubtedly reduce the dioxin content in animal products, and the reductions estimated should be considered when dioxin intake is evaluated using contamination data for individual food items.     

Elemental Analysis of Composted Source Separated Municipal Solid Waste

? Samples from composted source separated municipal solid waste were analyzed for 25 elements, including heavy metals and trace nutrients. The results were compared to a rural soil. The precision and recoveries for the various analytes using microwave digestion and atomic spectroscopic methods were determined. The recoveries ranged from 30 percent to 130 percent, depending on the analyte. The concentrations of the regulated elements were all well below proposed EPA 503 limits. The average values (mg/kg, dry weight) were 2.1(As), 1.2(Cd), 20(Cr), 173(Cu), <2(Hg), <22(Mo), 17(Ni), 92(Pb), <1(Se), and 395(Zn). The sampling strategy followed a two-stage nested design, allowing for assignment of the errors to the various sampling components. The average errors were 7.2% (samples), 3.5% (sub-samples), and 3.6% (replicates) for the compost, and 10.8% (samples) and 4.7% (replicates) for the rural soil. Reducing the grind size dramatically reduced the error between replicates. The implication of these errors, in terms of estimating the number of samples needed for analysis, is demonstrated.     

Biomonitoring of Metal Availability in the Southern Basin of the Lagoon of Venice (Italy) by Means of Macroalgae

Macroalgae of the following species: Ulva laetevirens, Enteromorpha intestinalis, Gracilaria verrucosa and Sargassum mutycum, were used to monitor metal concentrations (Al, Mn, Fe, Cu, Zn, Cr, Co, Ni, Cd) in the waters of the southern basin of the Lagoon of Venice. Sampling was performed at 5 sites, gradually moving north from the town of Chioggia. Species-specific seasonal variability was observed, with significant increases of Cd in U. laetevirens in January,Al and Pb in E. intestinalis in May, and Al and Ni in S. mutycum in January. Seasonal relative frequencies of metalpeak concentrations emphasize the occurrence of Pb peaks in May for all the studied species. Analysis of inter-site variability shows significant increases of Al, Fe, Cr and Pb in U. laetevirens at the Hydro-Biological Station, located within the town of Chioggia. Metal concentrations in algae are comparable with those in other areas of the lagoon, although Fe, Cr and Ni concentrations are lower than in the northern and central basins.This result fits dissolved metal concentrations determined byother authors, but does not correspond to the reported presence ofCr in the sediments of the southern basin. The hypothesis isdiscussed according to which low Cr levels in algae reflect Crspeciation in sediments.     

北京地区基本农田土壤环境质量分析与评价

对北京地区基本农田的土壤环境质量和污染状况进行了系统的调研，并对采样区农田土壤的环境质量按照国家标准进行了单因子评价和综合评价。结果表明，重金属的污染程度依次为Cd > Cu > As > Pb > Cr > Hg，Cd，Cu，As高于北京市土壤重金属背景值，Pb、Cr接近或略低于背景值，相比较而言，Cd污染为北京市基本农田中的主要污染元素。土壤中的农药残留的主要成分为滴滴涕。只有1处农田的Cd含量超过了国家二级标准限量，其余指标均低于二级标准。整体而言，北京地区的基本农田土壤环境质量属于清洁和安全范围，符合发展都市型现代农业的要求。