Polychlorinated dibenzo-p-dioxins and dibenzofurans in River Po sediments

The River Po is the main Italian river draining one of the most populated and industrialised regions in Italy. As part of a monitoring project to assess environmental quality in the River Po, we measured the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) in bottom sediments collected along the whole course of the river, from the spring to the delta, downstream from the confluence of its main tributaries. The aim was to investigate the level of contamination in the main Italian river and the contribution of contaminant loads from the subbasins. Composite sediment samples were collected in summer and winter surveys in low-flow water conditions and analysed by HRGC-HRMS for PCDD and PCDF homologue groups and for the 2,3,7,8-substituted congeners. The spatial trend observed in the Po River for PCDD and PCDF concentrations varied depending on the load of contaminants received from the tributaries and the processes of sedimentation. The sum of PCDD and PCDF concentrations, and the toxic equivalent content, ranged from 121 to 814 and from 1.3 to 13 ng/kg dry weight sediment, respectively. These levels of contamination seem lower than in the sediments of rivers draining highly industrialised areas. The PCDD and PCDF homologue profiles in all the samples were very similar, suggesting a common source of this contamination in the River Po. Principal component analysis suggested that widespread sources, such as urban runoff and domestic wastewaters, are probably the main cause of these levels of PCDDs and PCDFs.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in paddy soils and river sediments in Akita, Japan

Paddy soils and sediments from the Yoneshirogawa, Omonogawa, and Koyoshigawa River Basins in Akita were analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The levels and compositions in those samples including soils from non-agricultural areas (non-agricultural soils) were investigated using isomer-specific analysis to determine characteristic sources. The PCDD/PCDF compositions in the samples were compared with respect to possible sources. The PCDD/PCDF concentrations in paddy soils were much higher than those in the non-agricultural soils and much higher than those found in other parts of Japan. Although PCDD/PCDFs were ubiquitous in sediments from river sources to mouths of the respective river basins, those concentrations were much lower than those from paddy soils and non-agricultural soils, and from other parts of Japan. Comparison of PCDD/PCDF homologues and isomer compositions for samples indicated that compositions of paddy soils and sediments, except for those from river sources, had similar characteristics to PCDD/PCDFs originating from impurities in herbicides, 2,4,6-trichlorophenyl 4-nitrophenyl ether (CNP) and pentachlorophenol (PCP), and that compositions of river-source sediments and non-agricultural soils resembled those of atmospheric depositions. Results of statistical analyses suggest that PCDD/PCDF contamination of paddy soils and sediments is attributable mainly to three sources: CNP, PCP, and atmospheric deposition. Results of this study also demonstrate that CNP and PCP are not only important contaminants of local areas of Japan, but that they exist throughout Akita, in northern Japan. We therefore conclude that PCDD/PCDF pollution caused by those compounds has a widespread influence on paddy soils and river sediments in Japan.     

Persistent organic pollutants in Detroit River suspended sediments: polychlorinated dibenzo-p-dioxins and dibenzofurans,dioxin-like polychlorinated biphenyls and polychlorinated naphthalenes

Suspended sediments from the Detroit River were collected in 1999 and 2000 using sediment traps at sites ranging from western Lake Erie to southern Lake St. Clair and analyzed to determine the spatial distributions of contaminants including polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/PCDFs), dioxin-like PCBs (DLPCBs) and polychlorinated naphthalenes (PCNs). Concentrations of all three contaminant classes were clearly elevated at sites in the lower reaches of the river in the Trenton Channel. The potential influence of the Trenton Channel as a source of contamination to western Lake Erie was further evidenced by PCDD/PCDF homologue profiles, which indicated a contribution from chemical manufacturing in addition to the normal background combustion profile. Toxic equivalents (TEQs) for PCDDs/PCDFs generally exceeded those for DLPCBs; combined total TEQs in July 2000 for these two compound classes ranged from 2.30 pg/g in southern Lake St. Clair to 306 pg/g at a station just downstream of the outflow of Monguagon Creek in the Trenton Channel. The spatial distribution of PCN contamination was similar to that of PCDDs/PCDFs and DLPCBs, with the highest level of total PCNs (8200 ng/g) detected at a site in the Trenton Channel near Elizabeth Park; TEQs for PCNs in the Trenton Channel ranged from 73 to 3300 pg/g. The data indicate that PCNs represent a significant contribution to dioxin-like biological activity in Detroit River suspended sediments.     

Dioxin contamination in soils of Southern Vietnam

Dioxin is the common name for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), and is abbreviated as PCDD/Fs. In the case of Southern Vietnam, is of high concern dioxin contamination in the areas affected by past-use chemical defoliants. Our study related to the zone considered as a "hot spot"--Bien Hoa Airbase and surrounding areas (Bien Hung Lake). Although the war ended over 30 years ago, the adverse effects on this territory still continue. Soil and sediment were selected for our research as they act as a sink for PCDD/Fs. The samples were taken and analyzed in CECOTOX laboratory following certified procedures. The total amounts of PCDD/Fs (2,3,7,8 related congeners) in the samples were converted into WHO-TEQ and compared with standard values proposed by Canadian environmental quality guidelines. The obtained data shows a relatively high risk (up to 20.4 times higher than (probable effect level) PEL value for sediment and 46 times higher than standard value for soil). The research is continuing on the assessment of dioxin transport in food chain. Moreover, considering the obtained data a complete solution should be found urgently to solve the problem of dioxin contamination in the studied areas.     

Temporal trends in polychlorinated dibenzo-p-dioxins and dibenzofurans, dioxin-like PCBs, and polybrominated diphenyl ethers in Niagara river suspended sediments

Archived suspended sediment samples collected over the period 1980-2002 at Niagara-on-the-Lake in the Niagara river were analyzed to assess temporal trends in contaminants associated with historical industrial activities in the watershed (PCDDs/PCDFs, DLPCBs), compared to more modern industrial chemicals (PBDEs). The temporal trends for PCDDs/PCDFs and DLPCBs were generally similar, and showed a general trend toward decreasing concentrations, which was presumably due to implementation of control measures in the Niagara river watershed, including the remediation of hazardous waste facilities. The temporal trend in PBDEs contrasted with those of PCDDs/PCDFs and DLPCBs. Prior to 1988, PBDEs (sum of 16 congeners including deca-BDE) were generally detected at low-ppb concentrations, but showed a trend toward increasing concentrations over the period 1980-1988. After 1988, PBDE concentrations in the Niagara river showed a more rapidly increasing trend to a maximum of approximately 35 ng/g in 1995, with deca-BDE as the predominant congener detected. Samples collected over the period February 2003 to March 2004 at the head and mouth of the Niagara river were also analyzed for PBDEs; in all cases PBDE concentrations were higher at the mouth of the river at the outflow to Lake Ontario, indicating the Niagara river watershed is a source of PBDE contamination to Lake Ontario. However, PBDE concentrations in suspended sediments of the Niagara river were comparable to, or lower than, concentrations in bottom sediments in other industrialized/urbanized areas of the world. Based on these comparisons of global PBDE bottom sediment concentrations, the Niagara river watershed does not appear to be a significant local source of PBDEs to Lake Ontario, and concentrations in suspended sediments appear to be indicative of general PBDE contamination from a contamination of local, regional, and continental sources.     

Vertical profile of PCDD/Fs, dioxin-like PCBs, other PCBs, PAHs, chlorobenzenes, DDX, HCHs, organotin compounds and chlorinated ethers in dated sediment/soil cores from flood-plains of the river Elbe, Germany

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125 km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350-400 km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region. Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.     

Evidence for the presence of a widespread PCDD source in coastal sediments and soils from Queensland, Australia

Recent studies have demonstrated the occurrence of elevated levels of higher chlorinated PCDDs in the coastal environment of Queensland, Australia. This study presents new data for OCDD contamination and full PCDD/F profile analysis in the environment of Queensland. Marine sediments, irrigation drain sediments and topsoil were collected from sites that were expected to be influenced by specific land-use types. High OCDD concentrations were associated mainly with sediments collected near the mouth of rivers which drain into large catchments in the tropical and subtropical regions. Further, analysis of sediments from irrigation drains could be clearly differentiated on the basis of OCDD contamination, with high concentrations in samples from sugarcane drains collected from coastal regions, and low concentrations in drain sediments from drier inland cotton growing areas. PCDD/F congener-specific analysis demonstrated almost identical congener profiles in all samples collected along the coastline. This indicates the source to be widespread. Profiles were dominated by higher chlorinated PCDDs, in particular OCDD whereas 2,3,7,8-substituted PCDFs were below the limit of quantification in the majority of samples. The full PCDD/F profile analysis of samples strongly resemble those reported for lake sediments from Mississippi and kaolinite samples from Germany. Strong similarities to these samples with respect to congener profiles and isomer patterns may indicate the presence of a similar source and/or formation process that is yet unidentified.     

Distribution of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and non-ortho coplanar polychlorinated biphenyls in river and offshore sediments

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and non-ortho chlorine substituted coplanar polychlorinated biphenyl (Co-PCBs, non-ortho Cl CBs) in river and offshore sediment samples were analyzed isomer-specifically using (13)C-labeled their respective internal standards and a selected ion monitoring method of high resolution gas chromatograph-mass spectrometry (GC-MS). These compounds were found in all samples analyzed. The average concentrations of the total PCDDs, PCDFs and Co-PCBs in the 23 sediment samples taken from rivers were 11 000, 1300 and 160 pgg(-1) of dry wt, respectively, those in six offshore sediments were 7600, 980 and 52 pgg(-1), respectively. The concentrations of Co-PCBs were much lower than those of PCDDs and PCDFs in all sediment samples. The magnitude of these concentrations was in the order of lower reach of river > offshore area > upper reach of river. The concentrations of PCDDs and PCDFs in the rural river were higher than those in the urban river, whereas the Co-PCB concentration in an urban river was six times higher than that in a rural river. The Co-PCB concentrations in the urban area and industrial area were higher than that in any other area. These findings suggest that the pollution by PCDDs and PCDFs was derived from some kinds of incinerations and herbicides applied in the past and that Co-PCB pollution was caused by PCB preparation used in the past in urban and industrial areas and by municipal waste incineration in urban areas.     

Levels and homologue profiles of PCDD/Fs in sediments along the Swedish coast of the Baltic Sea

Background, aim, and scope  The primary aim of this study was to explore the variations in PCDD/F levels and homologue profiles of Baltic surface sediments by comprehensively analyzing polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in samples from a large number of sites, encompassing not only previously known hotspot areas, but also sites near other potential PCDD/F sources, in pristine reference areas (in which there was no industrial activity) and offshore sites. Materials and methods  Surface sediment samples (146 in total) were collected at various points along the Swedish coast and offshore areas. In addition, bulk deposition was sampled, monthly, at a single site in northern Sweden during 1 year. The concentrations of tetra- through octa-substituted CDD/Fs were determined in both matrices. Results  Highly elevated concentrations of PCDD/Fs were found at many sites in coastal areas and concentrations were also slightly elevated in some offshore areas. Homologue profiles varied substantially amongst samples from coastal sites, while those from offshore and other pristine sediments were relatively similar. The offshore sediments showed different profiles from those observed in the deposition samples. Sediment levels of PCDD/Fs were not generally significantly correlated to organic carbon levels, except in some pristine areas. Comparison of data obtained in this and previous studies suggest that both their levels and profiles are similar today to those observed 20 years ago in coastal and offshore areas. The only detected trend is that their levels appear to have decreased slightly in the offshore area of the Bothnian Sea. Discussion  The localization of hotspot areas along the coast, the lack of consensus between PCDD/F profiles of sediments and general background, and their weak correlations with organic carbon suggest that PCDD/Fs in the study area largely originate from local/regional emissions. However, due to complicating factors such as sediment dynamics and land upheaval, it is not possible to conclude whether these pollutants derive from recent emissions or from a combination of recent emissions and re-distribution of previous inputs. Conclusions  The results show that: elevated levels of PCDD/Fs are present in both coastal and offshore areas of the Baltic Sea, the major hotspots are close to the shore, and there are large variations in profiles, indicating that local emissions are (or have been) the major causes of pollution. Recommendations and perspectives  In order to identify other hotspot areas and trace sources, comprehensive analysis of PCDD/Fs in surface sediments is needed in all areas of the Baltic Sea that have not been previously investigated. The high levels of PCDD/Fs observed in surface sediments also indicate a need to elucidate whether they are due mainly to current emissions or a combination of recent pollution and re-distribution of historically deposited pollutants. To do so, better understanding of sediment dynamics and present-day inputs, such as riverine inputs, industrial effluents, and leakage from contaminated soil is required. There are indications that contaminated sediments have a regional impact on fish contamination levels. However, as yet there is no statistically robust evidence linking contaminated sediments with elevated levels in Baltic biota. It should also be noted that the Baltic Sea is being massively invaded by the deep-burrowing polychaete Marenzielleria ssp., whose presence in sediments has been shown to increase water concentrations of hydrophobic pollutants. In awareness of this, it is clear that high levels in sediments cannot be ignored in risk assessments. In order to investigate the emission trends more thoroughly, analysis of PCDD/Fs in offshore sediment cores throughout the Baltic Sea is also recommended. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Occurrence of PCDD/Fs and dioxin-like PCBs in superficial sediment of Portuguese estuaries

Superficial sediments collected from seven estuarine systems located along the Portuguese coast were analyzed for 7 polychlorinated dibenzo-p-dioxins (PCDDs), 10 polychlorinated dibenzofurans (PCDFs), and 12 dioxin-like polychlorinated biphenyls (dl-PCBs). Total PCDD/F concentration ranged from 4.6 to 464 pg g^?1 dry weight (dw), while that of dl-PCBs varied from 26.6 to 8,693 pg g^?1 dw. In general, the highest PCDD/F and dl-PCB concentrations were associated with densely populated and industrially impacted areas. Additionally, PCDD/F revealed a predominance of octachlorodibenzodioxin (OCDD) to total PCDD/Fs, while PCB 118 was the major contributor to total dl-PCBs. This study provided a global perspective of the contamination status of Portuguese estuaries by dioxin-like compounds and allowed a comparison between the investigated systems and other systems worldwide. PCDD/F and dl-PCB levels found in the collected sediments were lower than those of highly impacted areas from different parts of the globe. Nevertheless, comparison with guidelines and quality standards from other countries indicated that some Portuguese estuarine areas with a high industrialization level present PCDD/F and dl-PCB concentrations in superficial sediment that may constitute a risk to aquatic organisms.     

Polychlorinated biphenyl, polychlorinated dibenzo-p-dioxin and polychlorinated dibenzofuran residues in sediments and fish of the River Nile in the Cairo region

The levels of organohalogenated contaminants, i.e. PCBs, PCDDs and PCDFs were determined in sediment and fish samples collected from different locations in the River Nile, Egypt. Thirty-six sediment and eighteen fish samples were carried out during a period of 12 months from February 2003 to February 2004. Determination of PCBs and dioxins was carried out using a high resolution GC mass spectrometer. The results indicated that the PCB and PCDD/F mean concentrations in sediment samples ranged from 1461 to 2244 and from 240 to 775pgg(-1) dry wt basis, respectively. The mean concentration of PCBs and PCDD/Fs in fish samples were found to be in the range from 695 to 853pgg(-1) fresh wt for PCB congeners and from 27.7 to 121pgg(-1) lipid for total PCDD/Fs. Moreover, the concentrations of both PCBs and PCDD/Fs were found to be different at different locations along the River Nile. It could be concluded that the contamination of the River Nile is within the permissible limits set by the FDA and the Egyptian Standards for fish and shellfish.     

Sources of PCDD/Fs, non-ortho PCBs and PAHs in sediments of high and low impacted transboundary rivers (Belgium-France)

PAHs, PCDD/Fs and non-ortho PCBs have been assessed in Yser and Upper-Scheldt river sediments. Higher contamination levels were observed in the Upper-Scheldt sediments: maximum concentrations for the 16 US-EPA PAHs, PCDD/Fs and non-ortho PCBs respectively amount to 8.9 mg kg⁻¹, 12 ng TEQ kg⁻¹ and 5.1 ng TEQ kg⁻¹. Diagnostic PAH ratios in sediments and atmospheric samples suggest that the PAH compounds are from pyrolytic origin, more specifically combustion processes. The huge consumption of coal in cokes-ovens and smelters and its use for house-heating in Northern France, although decreasing during the last decades, are in support of that suggestion. PCDD/F fingerprints in sediments and deposition material indicate that OCDD is the dominant congener. In addition use of pentachlorophenol (PCP) in the past led to a minor contribution of PCDD/Fs in our sediment samples. Non-ortho PCBs form a substantial fraction of the total TEQ concentrations observed in the sediments. Since the 1980s and 1990s a substantial reduction of the PCDD/F sediment concentrations is observed, but this is not the case for the PAHs.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in marine mussels from French coasts: levels, patterns and temporal trends from 1981 to 2005

The levels and temporal trends of toxic polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in archived marine mussels collected between 1981 and 2005 from selected sites along French coasts. The geographical distribution and levels of PCDD/Fs generally reflect regional inputs of these contaminants: the highest concentrations were determined in samples from the Seine river estuary (English Channel) and Toulon area (Mediterranean coast); the lowest levels were determined in Corsica (Mediterranean Sea). PCDD/F isomeric composition showed a fairly homogeneous distribution pattern throughout the various sampling sites. This pattern, dominated by 2,3,7,8-TCDF and OCDD, can be considered as typical for the study species. However, on a more local scale, some differences in isomeric composition in mussels were identified in relation to local source characteristics. The time trend study showed a pronounced decrease in PCDD/F concentrations over the 24-year period at most sites, except Toulon on the Mediterranean Sea, where the decrease was not significant. This overall decrease probably reflects the general drop in PCDD/F emissions in Europe since 1980. However, high concentrations were determined in mussels collected in recent years (1999, 2001 and 2005) from the mouth of the Seine river. These concentrations are related to particular hydrological conditions, and intensive sediment dredging due to a new port construction at the mouth of the estuary. The results presented in this paper provide reference data on the contamination of shellfish by persistent organic pollutants in the marine environment.     

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.     

Contamination of River Kymijoki sediments with polychlorinated dibenzo-p-dioxins, dibenzofurans and mercury and their transport to the Gulf of Finland in the Baltic Sea

Kymijoki, the fourth largest river in Finland, has been heavily polluted by pulp mill effluents as well as the chemical industry. Up to 24,000 ton of wood preservative, chlorophenol known as Ky-5, was manufactured in the upper reaches of the river, an unknown amount of which was discharged into the river between 1940 and 1984. Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) occurred as impurities in the final Ky-5 product. The PCDD/F concentrations and burden in the river sediments were studied and the transport of PCDD/Fs from contaminated sites downstream and into the Gulf of Finland in the Baltic Sea was estimated. More than 190 sediment cores were sampled to estimate the volume of contaminated sediments and the total PCDD/F burden. The transport of PCDD/Fs was estimated using sediment traps placed at several sites. The survey revealed that sediments in the river were heavily polluted by PCDD/Fs, the main toxic congener being 1,2,3,4,6,7,8-heptachlorodibenzofuran, a major contaminant in the Ky-5 product. The mean total concentration at the most polluted river site downstream from the main source was 42000 microg kg(-1) d.w. (106 microg I-TEQ kg(-1)). The elevated concentrations in the coastal region and the present estimated transport from the River Kymijoki confirm earlier assessments that the river is a major source of PCDD/F for the Gulf of Finland.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in soils and sediments from Daliao River Basin, China

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F) were analyzed in surface sediments and top soils collected from 30 sites in Daliao River Basin. The concentrations of PCDD/F ranged from 0.28 to 29.01 ng TEQ kg(-1) dw (mean value, 7.45 ng TEQ kg(-1)dw) in sediments, and from 0.31 to 53.05 ng TEQ kg(-1)dw (mean value, 7.00 ng TEQ kg(-1)dw) in soils. PCDD/F pollution in sediments from the mid- and downstream sections of Hun River was found to be relatively heavy, and the levels of PCDD/F contamination in paddy soils were generally higher than those of upland soils. Using multivariate statistical analysis, the PCDD/F homologue and congener profiles of all soil and sediment samples were compared with those of suspected PCDD/F sources. The results showed that, PCDD/F contamination in most sediments of Hun River should mainly originated from the production of organochlorine chemicals, while metal smelting was the important potential source of PCDD/F in the drainage area of Taizi River. PCDD/F contamination in paddy soils should be simultaneously attributed to the polluted water irrigation and the organochlorine pesticide application.     

A decision framework for possible remediation of contaminated sediments in the River Kymijoki, Finland

Background, aim, and scope  The paper describes the spatial contamination of the River Kymijoki, South-Eastern Finland, and the coastal region of the Gulf of Finland with PCDD/Fs and mercury. The findings of ecotoxicologial and human health studies are also reported, including environmental and human risk assessments. Sediments from the River Kymijoki, draining into the Gulf of Finland, have been heavily polluted by the pulp and paper industry and by chemical industries. A wood preservative, known as Ky-5, was manufactured in the upper reaches of the river between 1940 and 1984 causing severe pollution of river sediments with polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF). Moreover, the sediments have been polluted with mercury (Hg) from chlor-alkali production and the use of Hg as a slimicide in pulp and paper manufacturing. Materials and methods  An extensive sediment survey was conducted as well as sediment transport modeling, toxicity screening of sediment invertebrates, and a survey of contaminant bioaccumulation in invertebrates and fish. Studies on human exposure to PCDD/Fs and the possible effects on hypermineralization of teeth as well as an epidemiological study to reveal increased cancer risk were also conducted. An assessment of the ecological and human health risks with a null hypothesis (no remediation) was undertaken. Results  The sediment survey revealed severe contamination of river and coastal sediments with PCDD/Fs and Hg. The total volume of contaminated sediments was estimated to reach 5 × 10⁶ m³ and hot spots with extremely high concentrations (max 292,000 ng g⁻¹ or 1,060 ng I-TEQ g⁻¹ d.w.) were located immediately downstream from the pollution source (approximately 90,000 m³). Sediment contamination was accompanied by changes in benthic assemblages, but direct effects were masked by many factors. The fish showed only slightly elevated PCDD/F levels in muscle, but orders of magnitude higher in the liver compared with reference freshwater sites and the Baltic Sea. The concentrations in human fat did not reveal high human exposure in the Kymijoki area in general and was lower than in sea fishermen. The relative risk for total cancer among farmers was marginally higher (RR = 1.13) among those living close to the river, compared with farmers living further away, and the possibility of increased cancer risk cannot be ruled out. A conservative risk assessment revealed that the present probability of exceeding the WHO upper exposure limit of 4 pg WHO-TEQ kg⁻¹ d⁻¹ for PCDD/Fs and DL-PCBs was 6%. The probability of exceeding the WHO limit value of 0.23 μg kg⁻¹ d⁻¹ for methyl mercury was estimated to be notably higher at 62%. Based on these studies and the estimated risks connected with different remediation techniques a general remediation plan with cost benefit analysis was generated for several sub-regions in the river. Dredging, on-site treatment, and a close disposal of the most contaminated sediments (90,000 m³) was suggested as the first phase of the remediation. The decision regarding the start of remediation will be made during autumn 2008. Conclusions  The sediments in the River Kymijoki are heavily polluted with PCDD/Fs and mercury from earlier chlorophenol, chlor-alkali, and pulp and paper manufacturing. A continuous transport of contaminants is taking place to the Gulf of Finland in the Baltic Sea. The highly increased PCDD/F and Hg levels in river sediments pose an ecotoxicological risk to benthic fauna, to fish-eating predators and probably to human health. The risks posed by mercury exceed those from PCDD/Fs and need to be evaluated for (former) chlor-alkali sites and other mercury releasing industries as one basis for remediation decision making. Recommendations and perspectives  The studies form the basis of a risk management strategy and a plan for possible remediation of contaminated sediments currently under consideration in the Southeast Finland Regional Environment Centre. It is recommended that a detailed restoration plan for the most seriously contaminated areas should be undertaken. Based on current knowledge, the restoration of the whole river is not feasible, considering the current risk caused by the contaminated sediment in the river and the costs of an extensive restoration project. The experiences gained in the present case should be utilized in the evaluation of PCDD/F- and mercury-contaminated sites in other countries. The case demonstrates that the historic reservoirs are of contemporary relevance and should be addressed, e.g., in the national implementation plans of the Stockholm Convention. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Landfill mining from a deposit of the chlorine/organochlorine industry as source of dioxin contamination of animal feed and assessment of the responsible processes

In 1997, the Polychlorinated dibenzo-para-dioxin (PCDD)/Polychlorinated dibenzofuran (PCDF) concentrations in dairy products in Germany and other European countries increased. The PCDD/PCDF source was contaminated lime used in Brazilian citrus pulp pellets. The contaminated lime was mined from an industrial dump site. However, the detailed origin of the PCDD/PCDFs in the lime was not revealed. This paper investigates the contamination origin and describes the link between lime milk from the dumpsite of a chlorine/organochlorine industry and the contaminated lime. The contaminated lime stem from mining at the corporate landfill of Solvay Indupa in Sao Paulo. The landfill was used for 40 years for deposition of production residues and closed in 1996. The factory operated/operates at least two processes with potentially high PCDD/PCDFs releases namely the oxychlorination process for production of ethylene dichloride (EDC) and the chlor-alkali process. The main landfilled waste was lime milk (1.4 million tons) from the vinyl chloride monomer production (via the acetylene process) along with residues from other processes. The PCDD/PCDF fingerprint revealed that most samples from the chemical landfill showed an EDC PCDD/PCDF pattern with a characteristic octachlorodibenzofuran dominance. The PCDD/PCDF pattern of a Rio Grande sediment samples downstream the facility showed a chlor-alkali pattern with a minor impact of the EDC pattern. The case highlights that PCDD/PCDF- and persistent organic pollutants-contaminated sites need to be identified in a comprehensive manner as required by the Stockholm Convention (article 6) and controlled for their impact on the environment and human health. Landfill mining and reuse of materials from contaminated deposits should be prohibited.     

Occurrence, possible sources, and temporal trends of polychlorinated dibenzo-p-dioxins and dibenzofurans in water and sediment from the lower Yangtze River basin, Jiangsu and Shanghai areas of Eastern China

The concentrations, compositional profiles, and possible sources of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) in water column and surface sediment samples from the lower reaches of the Yangtze River were investigated, and the potential risks posed by these chemicals were evaluated. Concentrations of the 17 2,3,7,8-substituted PCDD/PCDF in the water and sediment samples ranged from 0.45 to 10.0 pg TEQ/L (mean 2.34 pg TEQ/L) and from 0.31 to 51 pg TEQ/g dw (mean 5.25 pg TEQ/g dw), respectively. Water and sediments from the Nanjing–Nantong sections of the Yangtze River were found to have elevated PCDD/PCDF levels, and the PCDD/PCDF TEQ concentrations in 13 sediment samples exceeded the probable effect levels (PEL), above which adverse biological effects are likely. Multivariate statistical analysis indicated that the principal PCDD/PCDF contamination source for the water and sediment was the production and use of pentachlorophenol (PCP) or sodium pentachlorophenate (PCP-Na). PCDD/PCDF concentrations were stable over time near the Yangtze River Estuary but had increased sharply in recent decades in the Nanjing–Nantong section, which will have been related to the growth in industrial activities and other anthropogenic PCDD/PCDF sources. Total organic carbon (TOC) and PCDD/PCDF concentrations correlated significantly (R?=?0.474, P?<?0.01), suggesting that TOC plays an important role in the transport and re-distribution of PCDD/PCDF in the Yangtze River basin.     

Levels and congener profiles of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans and dioxin-like polychlorinated biphenyls in cow’s milk collected in Campania, Italy

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and certain dioxin-like polychlorinated biphenyls (dl-PCBs) are a family of chemically-related lipophilic compounds characterized by similar toxicity. Due to their properties they are universally distributed in the environment and classified as persistent organic pollutants (POPs). From most of studies carried out to evaluate human dietary intake, milk and dairy products result as a major contributors of PCDD/Fs uptake. Of course the main source of milk contamination is animal feeds. Lactating ruminants, cows included, transfer these compounds to the food chain by ingestion of contaminated vegetables or soil. Their resistance to degradation and a high lipophilicity means that PCDD/Fs and dl-PCBs may be accumulated into fat tissues from which they are transferred to milk during lactation period.Seventy-nine cows milk samples, collected in the monitoring plan 2008, were analyzed for PCDD/Fs and dl-PCBs. Eleven milk samples were non-compliant corresponding to five breeding livestock located in Caserta province. The distribution of PCDD/Fs and dl-PCBs congeners in these samples was examined in order to determine the likely sources of dioxins. The results show that the congener profile is characterized by a prevalence of PCDFs in respect of PCDDs, that represents the typical pattern of thermal origin contamination.