Observations on historical, contemporary, and natural PCDD/Fs

PCDD/Fs were determined in samples of archived surface soils collected from different locations around the world in the early 1880s, in contemporary surface soils from around the world, in archived subsurface soils collected at Rothamsted Experimental Station in the 1870/1880s, and in sections of peat core deposited between 5000 BP and the present. PCDD/Fs were detected in most of the samples. The potential sources and implications of the levels and mixtures of PCDD/Fs present in the samples are discussed. The homologue and isomer patterns observed in most of the contemporary European surface soils are commonly observed for European air samples and soil samples. The homologue pattern in the Rothamsted surface soils collected in the 1800s was similar, suggesting that similar sources of atmospheric emissions of PCDD/ Fs were operating in the UK in the 1800s as currently. Very different patterns, dominated by OCDD and with contributions of HpCDD and HxCDD, were found in some other samples. It is proposed that the PCDD/Fs present in the subsurface Rothamsted soils, archived (1880s) surface soils from Illinois and the Congo, clay beneath the peat bog (deposited approximately 5000 BP), and possibly surface soil samples from Thailand and Australia are of a natural origin. The most abundant TeCDD/F congeners measured in the peat samples here were also those observed by previous workers who studied a Canadian peat bog and are consistent with the microbially mediated oxidative coupling of chlorophenols. The study provides evidence for the widespread occurrence of PCDD/Fs in the environment prior to 1900 and for a complex array of sources (including natural) and environmental transformation processes.     

PCDD/Fs in Norwegian and U.K. soils: implications for sources and environmental cycling

This paper presents data on polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in a set of well-characterized, undisturbed surface (0-5 cm) and subsurface background soils from the U.K. and Norway. The soils have been used previously to investigate the latitudinal distribution, fractionation, cold condensation, and "hopping" of other classes of persistent organic pollutants (POPs). The mono- to octa-CDD/F homologues were quantified. Woodland soils contained higher concentrations (on a dry and soil organic matter (SOM)-basis) than grassland soils, consistent with previous studies. The absolute concentrations of all the PCDDs and most of the PCDFs significantly decreased with latitude, generally supporting the idea of a "southern source region" and a "remote/ receiving northern region". There was little evidence of "fractionation" and minimal influence of PCDD/F "hopping" on PCDD/F distribution. The %SOM content had a rather minor influence on soil PCDD/F composition. These findings contrast with the trends seen in these soils for hexachlorobenzene (HCB), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs). Possible reasons for these differences are discussed and may include influences of/proximity to diffusive combustion sources and/ or sources of variable homologue emissions, formation/ conversion processes for PCDD/Fs in soils, or strong soil-PCDD/F partitioning. These soils, from regionally remote/ background locations in Europe contained between 0.2 and 78 pg sigmaTEQ/g DW. Some therefore exceed recommended levels of contamination for certain land uses by some European countries. These recommendations seem unrealistic and prohibitively restrictive in light of the dataset presented here.     

Open dumping site in Asian developing countries: a potential source of polychlorinated dibenz-p-dioxins and polychlorinated dibenzofurans

Open landfill dumping areas for municipal wastes in Asian developing countries have recently received particular attention with regard to environmental pollution problems. Because of the uncontrolled burning of solid wastes, elevated contamination by various toxic chemicals including dioxins and related compounds in these dumping sites has been anticipated. In this study, concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (PCBs) were determined in soils from dumping sites in the Philippines, Cambodia, India, and Vietnam. Residue concentrations of PCDD/Fs and coplanar PCBs in dumping site soils were apparently greater than those in soils collected in agricultural or urban areas far from dumping sites, suggesting that dumping sites are potential sources of PCDD/Fs and related compounds. Observed PCDD/F concentrations in soils from dumping sites in the Philippines and Cambodia were comparable or higher than those reported for dioxin-contaminated locations in the world (e.g., near the municipal waste incinerators and open landfill dumping sites). Homologue profiles of PCDD/Fs in dumping site soils from the Philippines and, to a lesser extent, from Cambodia and India reflected patterns of samples representing typical emissions, while profiles of agricultural or urban soils were similar to those of typical environmental sinks. This result suggests recent formation of PCDD/Fs in dumping site areas and that open dumping sites are a potential source of dioxins in Asian developing countries. Uncontrolled combustions of solid wastes by waste pickers, generation of methane gas, and low-temperature burning can be major factors for the formation of dioxins in dumping sites. Elevated fluxes of PCDD/Fs to soils in dumping sites were encountered in the Philippines, Cambodia, India, and Vietnam-Hanoi, and these levels were higher than those reported for other countries. Considerable loading rates of PCDD/Fs in the dumping sites of these countries were observed, ranging from 20 to 3900 mg/yr (0.12-35 mg TEQ/yr). PCDD/F concentrations in some soil samples from the Philippines, Cambodia, India, and Vietnam-Hanoi exceeded environmental guideline values, suggesting potential health effects on humans and wildlife living near these dumping sites. The estimated intakes of dioxins via soil ingestion and dermal exposure for children were higher than those for adults, suggesting greater risk of dioxin exposure for children in dumping sites. To our knowledge, this is the first comprehensive study on PCDD/Fs contamination in open dumping sites of Asian developing countries. On the basis of the result of this study, we have addressed a new environmental issue that open dumping sites are potential sources of PCDD/Fs and related compounds, and dioxin contamination in dumping sites may become a key environmental problem in developing countries.     

PCDD/F contamination over time in Japanese paddy soils

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)were analyzed in preserved paddy soils periodically collected from 7 sites around Japan since 1960 to trace the changes in concentrations, to elucidate their sources, and to estimate their mass balance in Japanese paddy fields. Concentrations of sigma PCDD/Fs in paddy soils from all sites increased during the 1960s and the 1970s, then decreased. The results of principal component analysis and chemical mass balance based on functional relationship analysis indicate that the increase in sigma PCDD/F concentrations in paddy soils was due to the increased use of pentachlorophenol (PCP) and chlornitrofen (CNP); more than 95% of PCDD/Fs in all paddy soils were derived from impurities in these herbicides. The half-lives of PCDD/F for disappearance from the paddy soils were estimated to be 10 to 20 years (mean: 17.3 years). The estimated PCDD/F mass balance using the above half-life during the past 40 years in paddy fields indicates that about 80% of PCDD/Fs have disappeared. The soil puddling (mechanically mixing of paddy soil with pooled irrigation water) is implied as one reason for the PCDD/F disappearance from paddy fields. However, as the amounts of PCDD/Fs added through the use of PCP and CNP were extremely large, PCDD/F concentrations in Japanese paddy soils will decrease gradually, and PCDD/F runoff from paddy fields to surrounding catchments will continue.     

Spatial distribution of polybrominated diphenyl ethers and polychlorinated dibenzo-p-dioxins and dibenzofurans in soil and combusted residue at Guiyu, an electronic waste recycling site in southeast China

Surface soils and combusted residue from a village located in southeast China, which has been intensely involved in the dismantling and "recycling" of computer parts (e-waste) for the past decade, were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Total PBDE concentrations were highest in combusted residue of plastic chips and cables collected from a residential area (33,000-97,400 ng/g, dry wt), in soils from an acid leaching site (2720-4250 ng/g, dry wt), and a printer roller dump site (593-2890 ng/g, dry wt). BDE-209 was the most dominant congener (35-82%) among the study sites indicating the prevalence of commercial Deca-BDE, however signature congeners from commercial Penta- and Octa-BDE were also found. PCDD/F concentrations were also highest in soil from the acid leaching site (12,500-89,800 pg/g, 203-1100 pg WHO-TEQ/g, dry wt) and in combusted residue (13,500-25,300 pg/g, 84.3-174 pg WHO-TEQ/g, dry wt) and were comparable to PCDD/F levels of some open dumping sites in Asian developing countries. Of the e-waste activities, acid leaching and open burning emitted the highest concentrations of PBDEs and PCDD/Fs. This study is among the very few studies dealing with the important issue of pollution generated from crude e-waste recycling. Our results showthatthe crude processing of e-waste has become one of the major contributors of PBDEs and PCDD/Fs to the terrestrial environment.     

Congener-specific distribution of polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in animal feed.

Polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were extracted by accelerated solvent extraction from animal feed samples and analysed by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). In all of the feed samples analysed, the concentrations of PCDD/Fs and PCBs were below the existing tolerance limit of 5 pg I-TEQ g(-1) and 200 ng g(-1) fat, respectively. The mean concentrations of the total PCDDs, total PCDFs and total PCBs were 1.73-11.50 pg g(-1), 0.23-11.91 pg g(-1) and 60.00-234.40 pg g(-1) feed, respectively. Investigation of the correlations among the concentrations of PCDDs, PCDFs and PCBs showed that samples containing increased amounts of PCDFs also contained higher concentrations of PCDDs, with an average ratio of PCDF:PCDD of about 1.23:1 (r(2)=0.72, p<0.05). The correlation between the concentrations of PCDD/Fs and PCBs was positive but not significant.     

Facilitated transport of dioxins in soil following unintentional release of pesticide-surfactant formulations

Colloids such as surfactant micelles can act as transport facilitators for highly lipophilic, generally immobile contaminants in soil. Following a fire at a pesticide facility, this study investigated vertical and lateral migration of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in heterogeneous soil beneath bunded ponds, where contaminated wastewater containing high surfactant loads was stored until remediation. Initially, surface and subsurface soil was obtained during excavation, and subsequently intact cores to 5.7 m were collected. ΣPCDD/F concentrations were elevated in the wastewater (15-81 ng/L) and correspondingly in pond surface soils (6.1-61 ng/g). Maximum ΣPCDD/F concentrations were, however, observed at 2-2.5 m depth (68-130 ng/g), far below their expected mobility range based on physicochemical properties. Congener specific analysis further indicated that PCDD/F mobility was reversed, with the least water-soluble congener migrating to the greatest extent. The presence of higher chlorinated PCDD/Fs throughout a core collected in the direction of groundwater flow indicated subsequent lateral transport. These results provide field evidence for rapid vertical migration (2.4 m in <4 months) of highly lipophilic PCDD/Fs and suggest surfactant facilitated transport as the dominant transport mechanism. Quantification and evaluation of such fundamental changes in contaminant transport and fate in the presence of surfactants is required to identify areas at risk of groundwater contamination.     

PCDD/F deposition time trend to Esthwaite Water, U.K., and its relevance to sources

PCDD/Fs were measured in 16 sections of a sediment core from a freshwater lake in rural England. Each section represented 10 yr of deposition. Concentrations greater than the limit of detection were observed for most homologues in all samples. Three eras of PCDD/F input were identified by their distinct homologue and isomer profiles. sigma(4-8)CDD/F levels in core sections deposited before 1900 were in the order of 100 pg/g dry weight (dw) as compared to 1500 pg/g dw in the most recently deposited sediment. Local industries such as mining, quarrying, charcoal burning, and iron smelting appear to have had a minor impact on the PCDD/F deposition in the lake. Since 1900, two major peaks in PCDD/F input to the lake were evident. The first, reaching a maximum in the 1930s, had an unusual homologue pattern dominated by high molecular weight PCDFs, and the source of this input is unknown. The second, with a maximum in the 1970s, is in keeping with previously reported time trends for Europe and North America. Pre-1900, the TCDD/F isomer pattern was dominated by dimerization products of 2,4-dichlorophenol. Concentrations of P(1-3)CDFs appeared to be connected with the input that peaked in the 1930s, while highest concentrations of P(1-3)CDDs were found in the deepest sediment sections. Concentrations of diCDDs were observed to have increased again over the most recent decades to levels similar to pre-1900 sections. Despite detailed knowledge of the catchment and of industry in the surrounding area, the identity of some sources and the contribution of other known sources remain unclear for each era. This indicates that there remain significant gaps in our understanding of PCDD/F sources and undermines our ability to predict future trends in PCDD/F emissions.     

Destruction of the World Trade Center and PCBs, PBDEs, PCDD/Fs, PBDD/Fs, and chlorinated biphenylenes in water, sediment, and sewage sludge

Ash-laden runoff samples collected near Ground Zero soon after the September 11, 2001 attack on the World Trade Center (WTC) and subsequent fire demonstrate the release of polychlorinated biphenyls (PCBs), polybrominated dipheyl ethers (PBDEs), polybrominated dibenzo-p-dioxins and polybrominated dibenzofurans (PBDD/Fs), polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), and tetra- and pentachlorinated biphenylenes (PCBPs) from the incident. Relative abundances of PCDD/F congeners in the runoff water and post-disaster lower Manhattan dust samples were different from those seen in pre-disaster NYC combined sewer outfall (CSO) samples. The WTC-related samples showed a greater relative abundance of 2,3,4,7,8-PeCDF than usually seen in CSOs, sludges, and treated wastewaters. This congener may be associated with certain types of incineration. Comparison of sediment and water samples collected in the lower Hudson River before and shortly after September 11, 2001 (9/11) showed no changes in PCB or PCDD/F concentrations or homologue profiles determined down to the parts per quadrillion range. Comparisons of ambient water samples collected post-9/11 with archived samples suggest that the WTC disaster did not significantly impact ambient concentrations of the target chemicals. Ambient concentrations of PBDD/Fs in New York Harbor are similar to those of PCDD/Fs, suggesting that these contaminants deserve increased scrutiny with respect to toxicity, sources, and fate in the environment.     

Polychlorinated dioxins and furans from the World Trade Center attacks in exterior window films from lower Manhattan in New York City

Samples of ambient organic films deposited on exterior window surfaces from lower Manhattan and Brooklyn in New York City were collected six weeks after the terrorist attacks at the World Trade Center (WTC) on September 11, 2001 and analyzed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Total tetra- through octa-CDD/F concentrations in window films within 1 km of the WTC site in lower Manhattan ranged up to 630,000 pg/m2 (estimated as a mass concentration of ca. 1,300,000 pg/ g) and a maximum toxic equivalent (TEQ) concentration of 4700 TEQ/m2 (ca. 10 000 pg TEQ/g). Measurements at a background site 3.5 km away in Brooklyn showed lower concentrations at 130 pg TEQ/m2 (260 pg TEQ/g). Ambient gas-phase PCDD/F concentrations estimated for each site using an equilibrium partitioning model suggested concentrations ranging from ca. 2700 fg-TEQ/m3 near the WTC site to the more typical urban concentration of 20 fg-TEQ/m3 atthe Brooklyn site. Multivariate analyses of 2,3,7,8-substitued congeners and homologue group profiles suggested unique patterns in films near the WTC site compared to that observed at background sites in the study area and in other literature-derived combustion source profiles. Homologue profiles near the WTC site were dominated by tetra-, penta-, and Hexa-CDD/Fs, and 2,3,7,8-substituted profiles contained mostly octa- and hexachlorinated congeners. In comparison, profiles in Brooklyn and near mid-Manhattan exhibited congener and homologue patterns comprised mainly of hepta- and octa-CDDs, similar to that commonly reported in background air and soil.     

Elevated levels of urinary 8-hydroxy-2'-deoxyguanosine in male electrical and electronic equipment dismantling workers exposed to high concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans, polybrominated diphenyl ethers, and polychlorinated biphenyls

To investigate the occupational exposure levels to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), indoor dust (n = 3) in workshops and hair samples from male workers (n = 64) were collected at two electrical and electronic equipmentwaste (E-waste) dismantling factories located in the LQ area in east China in July 11--13, 2006. Pre- and postworkshift urines (64 of each) were also collected from the workers to study oxidative damage to DNA using 8-hydroxy-2'-deoxyguanosine (8-OHdG) as a biomarker. The concentrations of PCDD/Fs, PCDD/F-WHO-TEQs, PBDEs, PCBs and PCB-WHO-TEQs were (50.0 +/- 8.1) x 10(3), 724.1 +/- 249.6, (27.5 +/- 5.8) x 10(6), (1.6 +/- 0.4) x 10(9), (26.2 +/- 3.0) x 10(3) pg/g dry weight (dw) in dust, and (2.6 +/- 0.6) x 10(3),42.4 +/- 9.3, (870.8 +/- 205.4) x 10(3), (1.6 +/- 0.2) x 10(6), 41.5 +/- 5.5 pg/g dw in hair, respectively. The homologue and congener profiles in the samples demonstrated that high concentrations of PCDD/Fs, PBDEs, and PCBs were originated from open burning of E-waste. The 8-OHdG levels were detected at 6.40 +/- 1.64 micromol/mol creatinine in preworkshift urines. However, the levels significantly increased to 24.55 +/- 5.96 micromol/mol creatinine in postworkshift urines (p < 0.05). Then, it is concluded that there is a high cancer risk originated from oxidative stress indicated by the elevated 8-OHdG levels in the E-waste dismantling workers exposed to high concentrations of PCDD/Fs, PBDEs, and PCBs.     

Effects of river flooding on PCDD/F and PCB levels in cows' milk, soil, and grass

This paper presents the results of a study examining whether the flooding of pasture by rivers gives rise to higher PCDD/F and PCB concentrations in cows' milk. Over 180 milk, soil, and grass samples, taken from 38 farms across 3 different river systems (River Dee, Trent, and Doe Lea/Rother/Don) in the United Kingdom, were analyzed for PCDD/Fs and PCBs. The concentrations were compared between flood-prone farms, where the animals had access to pasture that is often flooded, and control farms where the land does not flood. The results indicated that concentrations of PCDD/Fs and PCBs in cows' milk were higher in samples taken from farms prone to flooding, but only from the river systems flowing through industrial and urban areas. Raised levels of PCDD/F and PCBs were also found in soil and grass from farms prone to flooding providing strong corroborative evidence that the higher concentrations in cows' milk from such areas is likely to be due to the ingestion of contaminated grass and soil. Overall, the results provide strong evidence that flooding of pastureland can indeed result in elevated concentrations of PCDD/Fs and PCBs in milk from the farms so affected.     

Lipid reserve dynamics and magnification of persistent organic pollutants in spawning sockeye salmon (Oncorhynchus nerka) from the Fraser River, British Columbia

Pacific sockeye salmon (Oncorhynchus nerka) can travel several hundred kilometers to reach native spawning grounds and fulfill semelparous reproduction. The dramatic changes in lipid reserves during upstream migration can greatly affect internal toxicokinetics of persistent organic pollutants (POPs) such as PCBs, PCDDs, and PCDFs. We measured lipid content changes and contaminant concentrations in tissues (liver, muscle, roe/gonads) and biomarker responses (ethoxyresorufin O-deethylase or EROD activity and CYP1A levels) in two Pacific sockeye salmon stocks sampled at several locations along their spawning migration in the Fraser River, British Columbia. Muscle lipid contents declined significantly with increasing upstream migration distance and corresponded to elevated lipid normalized concentrations of PCBs and PCDD/Fs in spawning sockeye. Post-migration magnification factors (MFs) in spawning sockeye ranged between 3 and 12 and were comparable to model-predicted MFs. sigmaPCBs(150-500 ng x g(-1) lipid), sigmaPCDD/Fs (1-1000 pg x g(-1) lipid) and 2,3,7,8-TCDD toxic equivalent or TEQ levels (0.1-15 pg x g(-1) lipid) in spawning sockeye were relatively low and did not affect hepatic EROD activity/CYP1A induction. Despite a 3-fold magnification, TEQ levels in eggs of spawning Fraser River sockeye did not exceed 0.3 pg x g(-1) wet wt, a threshold level associated with 30% egg mortality in salmonids. PCBs in Fraser River sockeye are comparable to previous levels in Pacific sockeye. In contrast to Pacific sockeye from more remote coastal locations, PCDDs and PCDFs in Fraser River sockeye were generally minor components (<25%) of TEQ levels, compared to dioxin like PCB contributions (>75%). The data suggest that (i) the Fraser River is not a major contamination source of PCBs or PCDD/Fs and (ii) marine contaminant distribution, food-chain dynamics, and ocean-migration pathway are likely important factors controlling levels and patterns of POPs in returning Pacific sockeye. We estimate an annual chemical flux entering the Fraser River of up to 150 g for sigmaPCBs and 40 mg for sigmaPCDD/ Fs via returning sockeye. The results indicate that historical concentrations of PCBs and PCDD/Fs remain a potential threat to organism and ecosystem health on the west coast of Canada.     

Vertical and lateral redistribution of POPs in soils developed along a hydrological gradient

Study of the dispersion of persistent organic pollutants (POPs) throughout the environment is necessitated by their toxicological properties and propensity to accumulate in biota. In this study, we use data from the analysis of three (210)Pb dated soil profiles collected along a 30-m hydrological gradient to demonstrate postdepositional mobility of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) and polychlorinated biphenyls (PCBs). We found that (i) humus originating from litter exposed to surface fallout during the 1960-1970s contains the highest concentrations of PCDD/Fs and PCBs in the O-horizon of the soils; (ii) accumulation rates of PCDD/Fs and PCBs in the O-horizon (～5.0 and ～210 μg m(-2) yr(-1)) constituted only 9.1% and 3.5%, respectively, of the measured annual input, demonstrating that a minor fraction of the deposited material is retained within the O-horizon; (iii) POP inventories in the upper 0.5-0.9 m of the mineral soil constituted a considerable part (40-70%) of the total pool stored in the soil, implying significant vertical translocation of atmospheric derived POPs; and (iv) increasing downslope inventories of POPs suggest a lateral downward transport of POPs from uphill soils. The findings challenge the commonly accepted view that POPs fallout is effectively retained within O-horizons.     

Dioxins, dioxin-like PCBs and non-dioxin-like PCBs in dairy products on the German market and the temporal tendency in Schleswig-Holstein

Levels of polychlorinated dibenzodioxins and dibenzofurans, dioxin-like polychlorinated biphenyls (PCBs) and non-dioxin-like PCBs were measured in 140 dairy products collected in 2006 from different regions of Germany. The samples (a total of 66 cheese, 23 butter and 51 curd products) were taken from super markets and retail stores on the basis of production volumes in different states of the Federal Republic of Germany. The dioxin and total WHO-TEQ concentrations of all 140 samples were clearly below the EU limits of 3?pg WHO-polychlorinated dibenzo-p-dioxin (PCDD)/F-TEQ/g fat and 6?pg WHO-PCDD/F-PCB-TEQ/g fat, as laid down in the EU regulation No 199/2006. Dioxin concentrations ranged from low 0.07 to 0.53?pg WHO-PCDD/F-TEQ/g fat with a mean value of 0.19?pg WHO-PCDD/F-TEQ/g fat. The WHO-TEQ concentrations (PCDD/F?+?dl-PCBs TEQ) ranged from 0.21 and 2.1?pg WHO-TEQ/g fat with an average value of 0.76?pg WHO-TEQ/g fat. Significant differences of the WHO-TEQ contamination levels at regional level and between the different product groups could not be identified. The temporal tendency of dioxin concentrations in butter and cheese from Schleswig-Holstein was studied over the past 13?years that showed a decrease by more than 50?% from 0.43 to 0.19?pg WHO-PCDD/F-TEQ/g fat.     

婴儿配方乳粉中二噁英及其类似物污染分析

目的 了解婴儿配方乳粉中二噁英及其类似物污染水平,为相关研究提供基础数据.方法 采集601份市售婴儿配方乳粉,按照GB 5009.205-2013《食品安全国家标准食品中二噁英及其类似物毒性当量的测定》对17种多氯代苯并二噁英和多氯代苯并呋喃(PCDD/Fs)和12种二噁英样多氯联苯(dl-PCBs)进行测定.结果 P...     

Effects of cooking on concentrations of polychlorinated dibenzo-p-dioxins and related compounds in green leafy vegetable 'Komatsuna'.

The effects of ordinary household cooking processes on concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (PCBs) (dioxins) were investigated in 'komatsuna', a green leafy vegetable popular in Japan. The concentrations of dioxins were compared using isomer-specific analyses of both uncooked and cooked edible parts of the plant. The mean total 2,3,7,8-chlorine substituted PCDD and PCDF concentrations were reduced from 46.53 pg/g and 0.714 pg/g to 8.301 pg/g and 0.210 pg/g by washing with tap water, and further reduced to 6.054 pg/g and 0.148 pg/g by subsequent boiling, respectively. The cooking processes markedly decreased the concentrations of PCDD/Fs, while having little effect on those of dioxin-like PCBs. The mean total concentration as 2,3,7,8-tetraCDD equivalents (TEQ) was reduced from 0.058 pgTEQ/g to 0.026 pgTEQ/g by washing with tap water and further reduced to 0.019 pgTEQ/g by subsequent boiling. These results suggest that ordinary cooking processes provide a means of reducing the level of dioxins in green leafy vegetables.     

Dietary intakes of polychlorinated dibenzo- p -dioxins, dibenzofurans and polychlorinated biphenyls in Finland

Samples of cow milk, pork, beef, eggs, rainbow trout, flours and vegetables were analysed for 17 polychlorinated dibenzo- p -dioxins and dibenzofurans (PCDD/F) and 36 polychlorinated biphenyls (PCB). Daily dietary intake of PCDD/Fs as toxic equivalent (I-TEq) and PCBs (PCB-TEq) was assessed using food consumption data from a 24-h dietary recall study for 2862 Finnish adults. The calculated intake of PCDD/F was 46pg I-TEq day -1 . The current level was about half of the earlier estimation of intake in Finland made in 1992. The assessed PCB intake was 53pg PCBTEqday -1 . Thus, the total intake of PCDD/Fs and PCBs was 100pg TEqday -1 (1.3pg TEqkg -1 b.w.day -1 ), which is within the range of tolerable daily intake (TDI) proposed by the WHO (1-4pg TEqkg -1 b.w.day -1 ).     

Discrimination of aerial deposition sources of polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran downwind from a pulp mill near Ketchikan, Alaska

Drinking water is supplied by individual roof-catchment systems for homes and businesses near a dissolving sulfite pulp mill (now closed) located just north of Ketchikan in southeast Alaska. This study was conducted to determine if polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) found in the sediments of the roof-catchment cisterns resulted from historical deposition of stack emissions from the pulp mill's multi-fuel power boilers. Fly ash from the power boilers had maximum total PCDD/F concentrations of 3.08 x 10(5)-3.10 x 10(6) ng/kg, which resulted from combustion of bleach plant wastewater sludge and saltwater-soaked wood waste. Cistern sediments had maximum total PCDD/F concentrations of 7.71 x 10(4) ng/kg. Potential sources of PCDDs/Fs in the cistern sediments were considered to be automobile exhaust, heating oil combustion, and private trash burning as well as pulp mill boiler emissions. Discriminant analysis was used to analyze differences between profiles of tetra through octa homologue classes of PCDDs/ Fs (defined as proportional contributions to total concentration) from different source terms. Homologue profiles of potential sources from Ketchikan included in this analysis were fly ash collected from the mill's power boilers and soils collected from background areas (areas with similar PCDD/F sources as the residences [e.g., auto exhaust and burn barrels] near the mill but beyond the zone of aerial deposition of emissions from the mill). Profiles for emissions from automobile exhaust, fertilizers, oil heating, residential trash burning, and residential wood heating were also included in the source "training" data set (for the discriminant analysis) using data from published literature. The classification rules developed from the discriminant analysis were applied to the following test media sampled at Ketchikan: roof-catchment cistern sediments and soils collected from areas in the vicinity of the mill's power boilers (i.e., nearby residential or commercial [developed] areas, on the mill property, and nearby forestlands). The homologue profiles of cistern sediment and nearby developed area soil samples were similar to background soils, whereas the profiles for the forestland soil samples (influenced by emissions from the mill but not other anthropogenic sources) closely matched the fly ash pattern. The homologue profiles of the emission sources from published data were more similar to one another than either background soils or fly ash. Soil samples from the mill property were classified as members of all source groups. On the basis of these analyses, the composition of PCDDs/Fs detected in the cistern sediments is typical of Ketchikan background conditions and not reflective of mill emissions.     

Dioxin congener patterns in commercial catfish from the United States and the indication of mineral clays as the potential source

Since 1991 the US Department of Agriculture (USDA) has conducted annual surveys of pesticide residues in foods under the Agricultural Marketing Service's Pesticide Data Program (PDP). To assess chemical residues in domestically marketed catfish products, 1479 catfish samples were collected during the 2008–2010 PDPs. A subset of 202 samples was analysed for 17 toxic polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). The average pattern of the individual PCDD/F congener concentrations in the catfish was rather unique in that it had almost no measurable amounts of polychlorinated dibenzofurans (PCDFs), but all PCDDs were present. This pattern was more dominant in the domestically produced catfish products than in the imported products (China/Taiwan). Comparison of the pattern to known sources of PCDD/Fs showed strong similarities to the pattern of PCDD/Fs found in kaolin clays which have often been used as anti-caking agents in animal feeds. To investigate whether catfish feeds may be the source of the PCDD/Fs found in the catfish, archived catfish feed data from a US Food and Drug Administration (USFDA) database were examined. In 61 out of 112 feed samples, the PCDD concentrations were 50 times higher than the PCDF concentrations and resembled the pattern found in the catfish products and in clays mined in the south-eastern United States. Although the source of PCDD/Fs in domestically marketed catfish products cannot be definitively established, mined clay products used in feeds should be considered a likely source and, given the wide concentration range of PCDD/Fs that has been found in clays, a critical control point for PCDD/Fs entrance to the food supply.