Study on PCDDs/PCDFs and co-PCBs content in food samples from Catalonia (Spain)

The results of a surveillance programme on polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and co-planar polychlorinated biphenyls (co-PCBs) determination in 70 foodstuffs samples produced all over the four provinces of Catalonia is presented. The study included the analyses of raw milk, pure virgin olive oil, butter, chicken, pork and mussel samples collected between November 1999 and January 2000. Milk, virgin oil, pork or butter presented a variable dioxin and co-PCBs content, even though the limits proposed in the draft of the EC Regulation for its commercialization in the European countries were not reached. The levels of PCDDs/PCDFs and co-PCBs determined in chicken samples varied between 0.36–3.59 pg I-TEQ/g fat chicken (0.4–3.8 WHO-TEQ/g fat). Just one case presented remarkable content of dioxins (about 30 pg I-TEQ/g fat) with a complex congener-specific profile which indicates the presence of an external contamination. On the other hand, a congener-specific profile dominated by 2,3,7,8-TCDF and OCDD was observed in mussel samples from Catalonia. This fact was also observed in mussel samples from other sites in Spain.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in invertebrate animals from a rural beach in Japan

PCDDs and PCDFs were analyzed by high resolution GC MS in several invertebrate animals collected from a rural beach in Japan. PCDDs and PCDFs were detected in all samples. Total concentration of PCDDs and PCDFs ranged 8.8–120 pg g⁻¹ wet and 3.5–38 pg g⁻¹ wet, respectively. TEQs of invertebrate animals examined ranged from 0.048 pg g⁻¹ wet in sea slug to 0.91 pg g⁻¹ wet in mussel. Isomer profiles in all samples were similar to each other despite of variety of species. Their major sources are estimated to be herbicides such as CNP and PCP, and combustion by using a statistical analysis of isomer profiles.     

Organic chlorine compounds in lake sediments. IV. Dioxins, furans and related chloroaromatic compounds

Polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs), polychloronaphthalenes (PCNs) and coplanar PCBs were measured in surface sediments from 18 lake areas in Central Finland. Toxic 2, 3, 7, 8-substituted PCDD and PCDF congeners occurred at low levels (<20 − 230 pg/g dw). PCNs appeared at few ng/g (total PCNs) levels. Pulp mills or any other local sources could not be associated with the sedimented PCDDs, PCDFs and PCNs. Coplanar PCB congeners 77 and 105 (IUPAC Nr) were generally found at 20–550 pg/g levels. The most toxic congener 126 was measured (110 pg/g) only at one area near a local PCB leakage. Pulp mill originated aromatic chlorocompounds which coelute with PCDDs and PCDFs in clean up, probably alkyl polychlorobibenzyls (R-PCBBs) appeared at ng/g levels and showed a clear gradient dowstreams from pulp mill effluent points.     

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant

Chlorohydrocarbons, PCB congeners, polychlorodioxins, furans and dibenzothiophenes in pine needles in the vicinity of a metal reclamation plant were analyzed by GC/ECD and GC/MS. Wax and the rest of the needles were analyzed separately. As a rule the concentrations of -HCH (0.5–13.6 ng/g), γ-HCH (0.4–7.3 ng/g), HCB (0.2–3.4 ng/g), PCB congeners (0.2–67 ng/g), PCDDs and PCDFs were higher in the older needles. The ratio of the concentration in the wax to the concentration in the rest of the needles was higher in the younger needles. The concentrations of PCB congeners, TeCDDs and TeCDFs were higher in the needles collected in the area nearest to the plant. The samples, obviously, contained tri- and tetrachlorodibenzothiophenes but these were not determined quantitatively due to interfering peaks in GC/MS.     

PCDDs and PCDFs in sewage sludge, river and lake sediments from south west Germany

Sewage sludges and sediments of rivers and lakes are sinks for “persistent” organic compounds entering the environment. These matrices are therefore useful in the assessment of local and global pollution with certain compounds or classes of compounds. In recent years we have analyzed sediments of the rivers Neckar, Rhine, and Danube, from Lake Constance, and samples of sewage sludge from municipal waste water treatment plants of south-west Germany for PAH, phthalates, organochlorine pesticides, and PCBs. ¹ We have now analyzed a number of these samples for PCDDs and PCDFs. Isomer-specific analyses for 2,3,7,8-subsituted PCDDs/PCDFs were carried out in all cases.

In all samples PCDDs could be detected, and in most cases PCDFs as well. 2,3,7,8-TCDD was never detected at a detection limit of 0.01 ppb. In sediments (14 samples) the total PCDDs ranged from 0.1 to 2.9 ppb and PCDFs from “not detectable” to 1.2 ppb. The highest concentration for a 2,3,7,8-substituted PCDD^* was found for 1,2,3,6,7,8-hexaCDD with 0.06 ppb. In sewage sludges (15 samples) the total PCDDs ranged from 4 to 65 ppb and PCDFs from 1 to 7 ppb. The highest concentration for a 2,3,7,8-substituted PCDD^* was found for 1,2,3,6,7,8-hexaCDD with 0.57 ppb.

Comparison of PCDD/PCDF patterns of congeners and isomers for the sewage sludge and river sediment samples with those of stack gas emissions of waste incinerators and of pentachlorophenol allows the conclusion that the main source of PCDDs and PCDFs found in these samples is pentachlorophenol. Results of the Lake Constance sediment core indicate that here the atmospheric immission from waste incineration might be predominant.     

Formation of PCDDs and PCDFs by the chlorination of water

Two samples of tab water and double distilled water were chlorinated using chlorine gas. A series of PCDFs could be identified from these experiments, however no PCDDs could be found. The two water samples gave very similar isomeric patterns ( . . tetra-CDFs), however the congener profile (Cl₄ --- Cl₈) was different. These experiments indicate that all products formed by chlorination reactions are potentially contaminated by PCDFs by a specific “chlorine pattern”.     

Levels of dioxins, dibenzofurans and selected other chlorinated organic compounds in food from Russia

Food is considered to be the main source of dioxins (PCDDs) and dibenzofurans (PCDFs) for human intake, but there are relatively few publications reporting the levels of dioxins and furans in food samples.^(1–4) Food samples from western to eastern Russia were collected during three recent trips by one of us (AS), and tested for dioxins and dibenzofurans to provide some indication of environmental contamination. The results show that in specific food samples there are more dioxins present than dibenzofurans, but in fish samples the opposite is true. We compare the levels found in Russian food with levels found in samples from other countries, on both wet weight and lipid basis. These Russian samples show ranges similar to but slightly lower than those seen in other industrial countries.     

PCBs fires: Correlation of chlorobenzene isomer and PCB homolog contents of PCB fluids with PCDD and PCDF contents of soot

PCBs, PCDDs, and PCDFs are subject to new regulations promulgated under the Toxic Substances Control Act and the Resource Conservation and Recovery Act. The finding of PCDDs and PCDFs in PCBs could restrict disposal options for PCBs. A review of major fire incidents in the U.S., indicates that PCDDs have been found only in the Binghamton, N.Y., transformer fire incident. Laboratory combustion studies further support PCDFs formation from PCBs and PCDDs from chlorobenzenes. No PCDDs were found in analyses of fluids from transformers involved in transformer fire incidents. PCDFs do not appear to increase in PCBs askarel fluids from normal usage in electrical equipment.     

Effects of dioxins and polychlorinated biphenyls (PCBs) on thyroid function in infants born in Japan – the second report from research on environmental health

Dioxins (PCDD + PCDF) and polychlorinated biphenyl (PCB) are potentially hazardous compounds and have structural similarity to thyroid hormones. Our research group on “Dioxins and PCB in Human Milk” was organized in 1997 and has been active for the past three years. We collected breast milk from 80 mothers living in Tokyo, Saitama, Ishikawa and Osaka Prefecture in Japan at 5, 30, 150, 300 postpartum days and measured PCDDs, PCDFs and PCBs during 1998–1999. We added another 20 prefectures and cities during 1999–2000. Breast milk was obtained from 415 mothers at 30 postpartum days (breast-feeding group). Blood was taken from infants who were breast-fed at the age of 1 year for evaluation of thyroid and immune functions. Blood was also taken from 53 infants who were bottle-fed (bottle-feeding group) as a control. Serum T4, T3, FT4 and TSH levels in the breast-feeding (n=337) and bottle-feeding (n=53) groups were within normal ranges and were not significantly different between the two groups. Although there were a large geographic differences of dioxins and co-PCB content in breast milk, there were no differences in serum T4, T3, FT4, TSH levels and no significant correlation between the mean serum levels of TSH and TEQ in breast milk. There was a significant correlation between serum TSH at 1 year of age and that from blood on dried filter paper TSH at 5 days of age. We concluded that dioxin intake from breast milk in Japanese infants did not impair thyroid function. However, long-term effects remain to be evaluated.     

Determination of 4-tert-octylphenol, 4-nonylphenol and bisphenol A in surface waters from the Haihe River in Tianjin by gas chromatography-mass spectrometry with selected ion monitoring

The estrogenic pollutants 4-tert-octylphenol (OP), 4-nonylphenol (NP) and bisphenol A (BPA) were determined in surface water samples from the Haihe River, Tianjin, China. The analytes were extracted and concentrated from 300 ml acidified water samples by liquid–liquid extractions using dichloromethane, derivatized with trifluoroacetic anhydride, and quantified by gas chromatography–mass spectrometry (GC–MS) with selected ion monitoring (SIM). Among the samples collected from 14 sampling sites, only one sample was found to have a relatively high concentration of BPA (8.30 μg l⁻¹) and NP (0.55 μg l⁻¹). The concentrations of OP, NP and BPA in the other samples were in the range of 18.0–20.2, 106–296 and 19.1–106 ng l⁻¹, respectively. Recoveries for OP, NP and BPA in the spiked water samples were all over 80%.     

Baseline levels of PCDD/Fs in soil and herbage samples collected in the vicinity of a new hazardous waste incinerator in Catalonia,Spain

The construction in Constantí (Catalonia, Spain) of a new hazardous waste incinerator (HWI), which is the first one in Spain, finished in 1999. In order to determine the temporal variation (1996–1998) in the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in the vicinity of the new HWI, 40 soil and 40 herbage samples were collected (1998) at the same sampling points in which samples had been taken two years before (1996). Each sample was analyzed for PCDDs and PCDFs by high resolution gas chromatography/high resolution mass spectrometry. In the 1996 survey, PCDD/F concentrations in soils ranged from 0.13 to 24.20 ng I-TEQ/kg (d.m.), with median and mean values of 0.67 and 1.68 ng I-TEQ/kg (d.m.), respectively. In the present study, PCDD/F concentrations ranged from 0.12 to 17.20 ng I-TEQ/kg (d.m.), with a median value of 0.75 ng I-TEQ/kg (d.m.) and a mean value of 1.59 ng I-TEQ/kg (d.m.). In turn, in the present study PCDD/F concentrations in vegetation ranged from 0.14 to 2.01 ng I-TEQ/kg (d.m.) (median and mean values: 0.23 and 0.31 ng I-TEQ/kg, respectively), while in the 1996 survey PCDD/F concentrations ranged from 0.24 to 1.22 ng I-TEQ/kg (d.m.) (median and mean values: 0.53 and 0.61 ng I-TEQ/kg, respectively). According to the present (1998) and the previous (1996) levels of PCDD/Fs found in soils and vegetation, the area under potential influence of the new facility shows a rather low contamination by these compounds. The current results should be useful to establish the environmental impact of the HWI.     

Serum levels of PCDDs, PCDFs and PCBs in non-occupationally exposed population groups living near two incineration plants in Tuscany, Italy

A pilot study was carried out in Tuscany, Italy, to provide preliminary information on the concentrations of polychlorinated dibenzodioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorobiphenyls (DL-PCBs), and selected non-dioxin-like PCBs (NDL-PCBs) in groups of subjects living in the vicinity of two incineration plants. Seventy-four volunteers were enrolled from areas identified as under a potential impact from incinerator emissions and from not exposed areas. No significant differences were observed between subjects living in the two types of areas. Total concentrations of PCDDs, PCDFs, and DL-PCBs resulted to be in the range 23-30 pg WHO-TEQ g(-1), lipid base, for subjects in the 27-54 year age groups, while concentrations increased to 40-44 pgTEQ g(-1) for the two 55-67 year age groups. The levels of PCDDs and PCDFs were in good agreement with those observed for unexposed population groups in Italy, while the contribution to total TEQ from DL-PCBs was appreciably higher than those currently observed in the general population in Italy and other countries. As to NDL-PCBs, serum levels of the six "indicator" congeners were in the range 240-300 ng g(-1), lipid base, for subjects in the 27-54 year age groups. A raise in NDL-PCB body burden (430-470 ng g(-1), lipid base) was observed for the two 55+ year age groups, in agreement with the expected age-dependent increase. The findings from this study do not show an incremental exposure to PCDDs and PCDFs in the samples from subjects living around the two incineration plants, whereas PCB congener profiles in all samples suggest a possible impact on the area of interest of industrial activities from near industrial settlements.     

Tidal salt marsh sediment in California, USA. Part 2: occurrence and anthropogenic input of trace metals

Surface sediment samples (0–5 cm) from 5 tidal salt marshes along the coast in California, USA were analyzed to investigate the occurrence and anthropogenic input of trace metals. Among study areas, Stege Marsh located in the central San Francisco Bay was the most contaminated marsh. Concentrations of metals in Stege Marsh sediments were higher than San Francisco Bay ambient levels. Zinc (55.3–744 μg g⁻¹) was the most abundant trace metal and was followed by lead (26.6–273 μg g⁻¹). Aluminum normalized enrichment factors revealed that lead was the most anthropogenically impacted metal in all marshes. Enrichment factors of lead in Stege Marsh ranged from 8 to 49 (median = 16). Sediments from reference marshes also had high enrichment factors (2–8) for lead, indicating that lead contamination is ubiquitous, possibly due to continuous input from atmospherically transported lead that was previously used as a gasoline additive. Copper, silver, and zinc in Stege Marsh were also enriched by anthropogenic input. Though nickel concentrations in Stege Marsh and reference marshes exceeded sediment quality guidelines, enrichment factors indicated nickel from anthropogenic input was negligible. Presence of nickel-rich source rock such as serpentinite in the San Francisco Bay watershed can explain high levels of nickel in this area. Coefficients of variation were significantly different between anthropogenically impacted and non-impacted metals and might be used as a less conservative indicator for anthropogenic input of metals when enrichment factors are not available.     

A comparison of PCDD/PCDFs exposure in infants via formula milk or breast milk feeding

Food is the major source for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) accumulation in human body. In infant period, breast milk and formula milk are the major food sources. Congener-specific analyses of 17 PCDD/PCDFs were performed on 10 brands of formula milk samples which were milk-based and 37 breast milk samples collected from women living in southern Taiwan. The levels of 17 PCDD/PCDFs in 10 formula milk samples ranged from 0.468 to 0.962 pg WHO-TEQ/g lipid, with a mean value of 0.713+/-0.163 pg WHO-TEQ/g lipid. For the 37 breast milk samples, their PCDD/PCDF levels were 14.7+/-9.36 pg WHO-TEQ/g lipid, with a range between 4.21 and 52.8 pg WHO-TEQ/g lipid. At 12th month of age for infants, average daily intakes (ADI) of PCDD/PCDFs were 2.1 pg WHO-TEQ/kg/day for the formula-feeding infants, and 13 pg WHO-TEQ/kg/day for the breast-feeding infants. The present data may provide useful information for risk-benefit evaluation of formula- and breast-feeding.     

Temporal variation of fluoride concentration in antlers of roe deer (Capreolus capreolus) living in an area exposed to emissions from iron and steel industry, 1948-2000

Temporal changes of environmental fluoride concentration in the industrialized area of Siegen, western Germany were assessed by studying the fluoride content of antlers (n=116) collected between 1948 and 2000 from the resident roe deer (Capreolus capreolus) population. During the analyzed period, major fluoride emission sources in the study area have been iron- and steelworks. Fluoride concentrations in the antlers ranged between 118 and 5428 mg/kg of bone ash. There was an overall increase in antler fluoride content from the late 1940s/early 1950s to the late 1950s/mid-1960s. Thereafter, antler fluoride levels overall steadily declined. For statistical analysis, the data were grouped into five periods (1948–1959, 1960–1969, 1970–1979, 1980–1989, and 1990–2000). Geometric mean fluoride concentrations of the samples ranged from 323 (period 1990–2000) to 2096 mg/kg of bone ash (period 1960–1969). Sample means for the periods 1980–1989 and 1990–2000, respectively, were always significantly lower than those of older samples. The decrease in antler fluoride concentrations during recent decades suggests a drop of ambient fluoride levels, that is hypothetically attributed to a reduction in the number of emission sources in the area and a decline of fluoride discharges from both local and more distant sources due to improved emission control measures. Comparison with antler fluoride data for other roe deer populations from western Germany further suggests that the roe deer from the Siegen area were recently exposed to an only moderate additional fluoride load from industrial sources. Studying antler fluoride concentrations is a convenient and cost-effective method of monitoring temporal changes in ambient fluoride levels.     

Variation of dioxins and furans in human tissues

A number of chlorinated dibenzo-p-dioxins (PCDDs) and chlorinated dibenzofurans (PCDFs) occur in human adipose tissue at levels from 5 pg/g for 2, 3, 7, 8-TCDD to approximately 1000 pg/g for octachlorodibenzo-p-dioxin (OCDD). The variation of these compounds in tissues has been studied with respect to age, sex, tissue type, and country. A sampling of 46 adipose tissues from Canada in 1976 has shown a positive correlation of 2,3,7,8-TCDD level of detectable samples with age but not sex. This relationship is supported by the analysis for the first time of tissue from a 6 month old infant and the demonstration of little or no measurable levels of PCDDs/PCDFs. Three additional tissue types, pancreas, brain, and testis, from two autopsies were assayed for PCDDs/PCDFs for the first time but little or none were found even though the first two tissues had up to 10% lipid. A small sampling of adipose tissue from the general population in Japan in 1984 contained generally the same types and concentrations of PCDDs/PCDFs as are found in tissues from other industrialized countries.     

Dioxin contents in fly ash from large-scale MSW incinerators in Taiwan

In this study, fly ash samples were collected from three municipal waste incinerators (MWI) in Taiwan. These MWIs investigated are equipped with different air pollution control devices (APCDs). Preliminary results indicated that 2,3,7,8-PCDD/Fs homologue patterns of various types of fly ash were quite similar for all three MWIs. Concentrations of higher-chlorinated congeners of PCDDs and PCDFs were remarkably higher than those of lower-chlorinated congeners. In the case of MSW-A, the PCDD/PCDF ratios of ashes were found in the decreasing order for cyclone, boiler and baghouse. The PCDD/PCDF ratios in various types of fly ash of MWI-B was boiler-A < boiler-B < ESP < boiler-C. As for MSW-C, no obvious trend has been observed for PCDD/PCDF ratio. However, the ratio in boiler ash was higher than that in baghouse ash of MWI-A. The dioxin contents in fly ash would increase as the fly ash passed through APCD zones. In other words, the environmental conditions of APCD may actually cause the increase of the dioxin contents in fly ash. The trend for dioxin contents in fly ash collected from three MSW incinerators investigated was MSW-C < MSW-A < MSW-B.     

Analysis of polychlorodibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs) in baked-salt food additives in Korea

Thirty-one samples of baked-salt products used in commercial food additives were analyzed for the presence of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). Dioxins were highly detected in 12 samples of baked salts. The amount of dioxins found in the samples ranged from 12.47 pg/g to 406.56 pg/g (0.71 pg TEQ/g to 23.51 pg TEQ/g, respectively). The most abundant congeners, as TEQ values, were 2,3,4,7,8-PeCDF; 1,2,3,7,8-PeCDF; and 1,2,3,4,7,8-HxCDF in PCDF congeners and 1,2,3,7,8-PeCDD; 1,2,3,6,7,8-HxCDD; and 1,2,3,7,8,9-HxCDD in PCDD congeners. Meanwhile, PCDDs/PCDFs were analyzed in high-temperature-treated samples of natural sea salt alone and natural sea salt to which di-(2-ethylhexyl)phthalate (DEHP) had been added. In the former case, PCDD/PCDF formation was most evident at temperatures near 450 degrees C, the total amount of dioxins was 90.07 pg/g (6.07 pg TEQ/g), and PCDD congeners comprised less than 50% of the total PCDDs/PCDFs. However, when the latter samples were heated, the total PCDD/PCDF concentration was 512.30 pg/g (21.53 pg TEQ/g), with PCDD congeners comprising over 87% of the total PCDDs/PCDFs.     

Pesticides in rain

40 rainwater samples were collected in Hannover and near Peine (Lower Saxony, Germany) in 1992 using a wet-only collector. The samples were extracted by solid phase extraction and analyzed by GC/MS for 59 pesticides. 11 pesticides were found in more than 10 samples. The highest concentrations were observed for terbuthylazine (0.003 – 0.52 μg/L ), metolachlor (0.003 – 0.51 pg/L, mean: 0.10 μg/L), metalaxyl (0.006 – 0.48 μg/L, mean: 0.10 pg/L) and chlorothalonil (0.003 – 1.1 μg/L, mean: 0.16 μg/L). The concentrations show a seasonal dependence reflecting the application periods.     

Monitoring of air pollution by polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans of pine needles in Korea

The atmospheric contamination levels of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were evaluated from the analysis of pine needles in South Korea. Pine needles were collected from 30 sampling points at five main cities in South Korea (Busan, Daegu, Gwangju, Changwon and Jeju island). The highest concentrations of PCDDs/DFs (2.19–26.88 pg I-TEQ/g of dry weight) were measured at Busan, where is the city of the highest population density and traffic volume among five cities. The lowest concentration was detected at Jeju with 0.62 pg I-TEQ/g dry weight, suggesting Jeju could be an environmental background area in Korea. The dominant homologues of PCDDs/DFs in pine needles were the lower chlorine-substituted compounds such as tetra CDDs and CDFs, and the distribution ratios of PCDDs/DFs decreased with increase of the number of chlorine substituents. Homologue profiles of pine needle samples were similar to PCDDs/DFs profiles of the vapor phase in the ambient air, and thus the pine needles absorbed the vapor phase of PCDDs/DFs from air. Results suggested that pine needles could be used as an indicator of the atmospheric contamination for PCDDs/DFs in Korea.