Dibenzofurans a greater global pollutant than dioxins ? : Evidence from analyses of open ocean killer whale

Three specimens of killer whales (Orcinus orca), an open ocean carnivore, were analysed for extremely toxic polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) to understand their long-range distribution patterns. Several PCDF congeners, including the highly toxic 2,3,7,8-tetra- and 2,3,4,7,8-penta-CDFs were identified in the blubber of those specimens. The PCDF isomeric pattern in killer whale is more complex than the reported patterns in humans and birds, indicating the weaker metabolic potency of killer whales for these toxic compounds. High levels of PCBs (about 400 mg kg⁻¹) have also been detected in those specimens. The 2,3,7,8-substituted PCDF congeners identified in commercial PCBs were also found in killer whale, indicating PCBs as the possible source. Isomer-specific and trace level determinations of PCDD in killer whale, revealed no detectable quantities. The detection of comparatively high levels ( > 300 ng kg⁻¹) of PCDFs and undetection of PCDDs in open ocean killer whales suggest that PCDFs are more ubiquitous than PCDDs.     

Dioxin-like compounds in sediments from the Daliao River Estuary of Bohai Sea: distribution and their influencing factors

The concentrations, compositional profiles, and potential ecological risk of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in sediments of the Daliao River Estuary were investigated. Total concentrations of PCDD/Fs, PCBs, and PCNs were in the range of 11.3-133.2 ng/kg dry weight (dw), 1 971-37 632 ng/kg dw and 33.1-284.4 ng/kg dw, respectively. The total TEQ values varied from 0.37 to 4.08 ng/kg dw, with the dominant contributions by PCDD/Fs, then by PCBs and PCNs. The spatial distributions of PCDD/Fs, PCBs and PCNs in the river estuary were much related to hydrodynamic conditions. The risk of contamination to the deeper sea was increased in the flood seasons. Moreover, our data confirmed that both organic matter in sediments and molecular properties of dioxin-like compounds were the factors which strongly influenced the partition behavior of these dioxin-like compounds between sediments and water phase in the estuarine zone.     

Levels and patterns of polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls in surface sediments from the western Baltic Sea (Arkona Basin) and the Oder River estuarine system

Surface sediment samples were collected from the western Baltic Sea (Arkona Basin) and the Oder River estuarine system in May and August 1995 and analysed for polychlorinated dibenzo-p-dioxins, dibenzofurans and biphenyls. Contents of PCDF (sum) and PCDD (sum) varied from 2.5 to 820.0 pg g⁻¹ dw and from 12.7 to 2991.0 pg g⁻¹ dw, respectively. PCB contents (sum of 23 congeners) ranged between < 130.0 and 16267.0 pg g⁻¹ dw. Only slight variations in PCDF/D and PCB contents on dry weight basis were found between the Oder River estuarine system and the open Baltic Sea. TOC-normalization of the data showed an approximately homogen PCDF/D distribution in the study area. The distribution pattern for PCDF/D and PCB may be attributed to high sediment dynamics combined with transport processes from the temporary sedimentation basin (Oderhaff) to the deeper parts of the Baltic Sea.     

Occurence and Transport of Organic Micro-contaminants in Sediments of the Odra River Estuarine System

Over ninety surface sediment samples (0...3 cm) were collected in the Odra river estuarine system – from the Oderhaff, the Pomeranian Bight, the Peenestrom, the Greifswald Bodden – and the Arkona Basin between 1994 and 1996 and analysed for polychlorinated dibenzo-p-dioxins, dibenzofurans (PCDD/F) and biphenyls (PCB), and p,p′-dichlorodiphenyl-trichloroethane (DDT) including their metabolites. The contents of all investigated organochlorines in the sediments of the western part of the Oderhaff (Kleines Haff) were only slightly higher and more homogenously distributed compared to the values of the Pomeranian Bight and the Greifswald Bodden. PCB contents (sum of 23 congeners) in surface sediments ranged between <130 and 9 550 pg/g (given for dry weight, dw). The results of individual PCB congeners showed that high contents of hexa- and heptachlorinated compounds (PCB 138, 153, 180) were present in the entire area investigated. Generally, low levels of PCDD/F were found in surface sediments of the Odra river estuarine system due to small industrial activities in the catchment area. Contents of PCDF (sum) and PCDD (sum) varied from 2.5 to 820 pg/g (dw) and from 13 to 2 991 pg/g (dw), respectively. The congener contents of PCDF showed a nonuniform picture between the Oderhaff and the Arkona Basin. In contrast, the congener profiles of PCDD showed approximately similar patterns at nearshore and offshore stations, with highest values of OCDD (octa CDD). We assume that most of the particulate-bound micro-contaminants (PCB, PCDD/F) are deposited in the eastern part of the Oderhaff (Stettin Lagoon), which acts as a temporary trap and opurificationπ basin for the suspended particulate matter (SPM). One pathway for further transport of the particles seems to be the way on a small sedimentation strip along the island of Usedom via the “Saßnitz-trough” into the deeper parts of the western Baltic Sea.     

Levels and temporal trends of PCDD/PCDFs and non-ortho PCBs in ringed seals from East Greenland

The levels and temporal trend of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and non-ortho substituted PCBs (c-PCBs, i.e. CB77, CB126 and CB169) were determined in ringed seal blubber from central East Greenland collected in 1986, 1994, 1999 and 2003, respectively. Since 1986 the concentrations of PCDDs, PCDFs and c-PCBs all show a decreasing trend. The annual decreases were estimated to 5.2% and 5.3% for pg/g WHO-TEQ ww of PCDD/Fs and c-PCB, respectively. The annual median concentrations of PCDDs ranged from 5.4 to 24.4 pg/g WHO-TEQ ww and those of PCDFs from 2.5 to 5.1 pg/g WHO-TEQ ww. Compared to PCDD/Fs concentrations in ringed seals from other Arctic areas the levels of PCDD/Fs found in 1986 were the highest recorded. The annual median concentrations of c-PCBs decreased 24.2 to 9.1 pg/g WHO-TEQ ww. The levels of c-PCBs observed in 1986 are similar to levels found in ringed seals from Svalbard in 1990 and from eastern Hudson Bay in 1989–1992. The dominant and most TEQ-contributing PCDD congener was 1,2,3,7,8-PeCDD. CB126 was the dominating and most TEQ-contributing c-PCB congener. The concentrations of PCDDs, PCDFs and c-PCBs were highly significantly inter-correlated. Principal component analysis of the PCDD/PCDF congeners and c-PCBs was performed to analyse the pattern of compounds during time.     

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments from Hong Kong

Concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in 14 sediment samples collected from four sites in the Mai Po Marshes Nature Reserve (within a RAMSAR Site) and from another six sites in Victoria Harbour and along the Hong Kong coastline. Elevated levels of PCDDs, and particularly OCDD, were detectable in all samples collected from the Mai Po Marshes and five of the six sites. In contrast to PCDDs, PCDFs were mainly found in sediment samples collected from industrial areas (Kwun Tong and To Kwa Wan) in Victoria Harbour. PCDD/F levels and congener profiles in the samples from the Mai Po Marshes Nature Reserve in particular show strong similarities to those reported in studies which have attributed similar elevated PCDD concentrations to nonanthropogenic PCDD sources.     

PCDD/Fs in sediments of Central Vietnam coastal lagoons: in search of TCDD

Samples from nine Central Vietnam coastal lagoons, together with three soils and sediments collected in two freshwater reservoirs of the Thua Thien-Hué province, were analysed for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). Total concentrations are low, from 192 to 2912 pg g⁻¹ and depth profiles in Tam Giang-Cau Hai (TG-CH) sediment cores show only minor changes over time in PCDD/F input and composition. Octachloro dibenzo-p-dioxin (OCDD) is the prevailing congener (approximately 90%), indicating combustion as the main PCDD/F source to these coastal systems, whereas natural formation might be partly responsible for the presence at depth. 2,3,7,8-Tetrachloro dibenzo-p-dioxin (TCDD), largely sprayed together with Agent Orange over the study areas during the war (1961–1971), is absent or very low. This result supports the hypothesis of strong degradation soon after spraying. Multivariate statistical analyses account for the presence of local, short-range sources as observed in the northern part of the TG-CH lagoon.     

Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in sediments from Hong Kong

Concentrations of 2,3,7,8-substituted polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were determined in 14 sediment samples collected from four sites in the Mai Po Marshes Nature Reserve (within a RAMSAR Site) and from another six sites in Victoria Harbour and along the Hong Kong coastline. Elevated levels of PCDDs, and particularly OCDD, were detectable in all samples collected from the Mai Po Marshes and five of the six sites. In contrast to PCDDs, PCDFs were mainly found in sediment samples collected from industrial areas (Kwun Tong and To Kwa Wan) in Victoria Harbour. PCDD/F levels and congener profiles in the samples from the Mai Po Marshes Nature Reserve in particular show strong similarities to those reported in studies which have attributed similar elevated PCDD concentrations to nonanthropogenic PCDD sources.     

The dependence of organohalogen compound concentrations on herring age and size in the Bothnian Sea, northern Baltic

The concentrations and composition profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans, polychlorinated biphenyls, polybrominated diphenyl ethers and polychlorinated naphthalenes were determined in herring individuals collected from the commercial catches of the Bothnian Sea, northern Baltic. The median age of herring was 5.0 years and in the muscle the median toxic equivalent concentration of PCDD/Fs was 5.6 WHO(PCDD/F)-TEQ pg/g fresh weight (fw) and that of PCBs 2.7 WHO(PCB)-TEQ pg/g fw. The median sum concentration of PBDEs was 1.4 ng/g fw and that of PCNs 0.1 ng/g fw. Differences in age-dependent accumulation between the organohalogen groups and individual congeners were major. In the Bothnian Sea the content of organohalogen compounds in herring is obviously elevated due to the availability and large proportion of Mysis crustaceans in their diet. More intensive fishing could reduce the concentrations of organohalogens, including the abundant, accumulative and toxic 2,3,4,7,8-PeCDF congener in the Baltic herring catch.     

电子顺磁共振技术在沉积盆地有机质及热史研究中的应用：现状和进展

由于沉积有机质都存在有自由基，使其具有顺磁性。因此，它可以用于电子顺磁共振的分析和研究。近年来，电子顺磁共振应用于沉积有机质的研究无论在理论方面还是应用方面都有很大的进展。本文主要概述沉积有机质中自由基形成与演化机理及电子顺磁共振在研究有机质成熟度、油气源岩评价和古地温方面的研究现状和主要进展。     

贝加尔湖的污染与富营养化

The long term systematic investigations of ion composition components (bicarbonates, chlorides, sulphates, magnesium, calcium, sodium, potassium) and trophic status components (suspension, chlorophyll-a, mineral and organic forms phosphorus and nitrogen, carbon, silica) of water from the lake proper, its tributaries and atmospheric precipitation, which make up the main share of substance supply in to the lake, as well as the Angara river, being the source of substance discharge allowed the lake recent state to be evaluated in terms of both chemical pollution and possible eutrophication of its water. The similar (in terms of river runojf) periods of 50-ies and 80-ies have been compared. It was revealed that as a result of industrial activity 409 thousand tons of mineral substances (27.2 thousand tons of chlorides, 162 thousand tons of sulphates and over 200 thousand tons of organic substances) are supplied in the lake annually. The supply of substances of the anthropogenic origin is higher for the South Baikal than that for the North and Middle Baikal (the sum of mineral substances in 3.6 times; sulphates in 5 times, organic substances, including hydrocarbons in 7 times).The absence of abundant phytoplankton in the period studied when the ratio of silica to phosphorus is optimum (over 100), as well as a revers correlation between winter nitrogen content and spring of chlorophyll-a concentration in the Baikal water and revers dependence between the suspension and chlorophyll-a along the Selenga river valley lead to the conclusion that Baikal water contains toxicants. It is verified by the presence of polychlorbiphenyls (PCB), poly-chlordibenzo-p-dioxins (PCDD) and dibenzofurans (PCDF) for the whole food web with the maximum PCDD/PCDF (TEQ to 175 P g · g^-1) concentration in the seal blubber. The levels are comparable with those reported for ringed seal (phoca hispida), living in the Baltic sea and Bar-row Strait Inlet in the Canadian Arctic.     

Early contamination of European flounder (Platichthys flesus) by PCDD/Fs and dioxin-like PCBs in European waters

Contamination levels and profiles of 7 polychlorinated-p-dioxins, 10 polychlorinated furans (PCDD/Fs) and 12 dioxin-like polychlorinated biphenyls (dl-PCBs) were investigated in juvenile European flounder (Platichthys flesus) captured in different nursery areas in the northeastern Atlantic coast across its geographical distribution range. The toxic equivalent concentrations (WHO-TEQ_fish) were also determined in order to evaluate which P. flesus population was more exposed to dioxin-like toxicity. Juveniles caught in the Sørfjord (Norway) showed the lowest WHO-TEQ_fish concentration (0.052 pg WHO-TEQ_fish g⁻¹ wet weight) whereas the highest value was observed in fish from the Wadden Sea (The Netherlands; 0.291 pg WHO-TEQ_fish g⁻¹ ww), mainly due to the greater contribution of 2,3,7,8-tetrachlorodibenzo-p-dioxin, the most toxic congener. Nonetheless, when comparing the results with existent tissue residue-based toxicity benchmarks, no adverse effects resulting from PCDD/Fs and dl-PCBs are expected to occur in flounder from the studied systems.     

Temporal trends in dioxins (polychlorinated dibenzo-p-dioxin and dibenzofurans) and dioxin-like polychlorinated biphenyls in Baltic herring (Clupea harengus)

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyl (dl-PCBs) concentrations in Baltic herring (Clupea harengus) have been relatively stable since the mid to late 1990s. It is unclear why concentrations in Baltic herring are not following the observed decreases in other environmental matrices. Here, changes in long-term temporal trends in Baltic herring were examined. A number of biological variables were examined alongside the temporal trends to investigate whether fish biology e.g., growth (length, weight, age), lipid content, reproductive phase or fishing date may provide an explanation for the temporal trends observed.     

PCDD/Fs and PCBs in seafood species from Moreton Bay, Queensland, Australia

Previous studies have identified elevated levels of polychlorinated dibenzo-p-dioxins (PCDDs) in sediments and megafauna (dugongs and green turtles) in the marine environment of southeast Queensland, Australia. Little information exists, however, regarding the levels of PCDDs, polychlorinated dibenzofurans (PCDFs) and related polychlorinated biphenyls (PCBs) in seafood from this area. This study aims to establish baseline information on PCDD/F and PCB contamination in a range of seafood species from Moreton Bay and to investigate contaminant variability due to harvesting season, size, habitat location and trophic level. In addition, different seafood extraction methods were tested to evaluate their impact on lipid yields and contaminant concentration. Overall, the median TEQ(DF&PCB) levels in seafood from Moreton Bay were elevated compared to background levels in Australian marine/estuarine and retail fish. However, TEQ(DF&PCB) levels of most seafood analysed were below the respective EU maximum limits. High inter- and intraspecies variability was observed, which could be partially attributed to differences in trophic level, season harvested and habitat location.     

Polychlorierte Dibenzo-p-dioxine, -furane (PCDD/F) und Analoga in Oberflächensedimenten und datierten aquatischen Sedimentkernen

Polychlorinated Dibenzo-p-dioxins, -furans (PCDD/F) and Analogues in Surface Sediments and Dated Aquatic Sediment Cores Aquatic sediments are the final sinks of unintentionally formed PCDD/Fs. Still not known are the conditions of formation of PCDD/Fs in the 8120 years old sediments in Japan and in 350 to 400 years old sediments in the Baltic. Sediments are means of source identification if transformation processes are taken into consideration in view of hydrological conditions. PCDD/Fs have been analysed 30 km from the source in sediments and over a distance of 50 km in benthos indicating a remarkable bioaccumulation potential. Elaborated data of the PCDD/F sediment contamination are missing as well as information on internal diagenetic processes, interactions at the sediment/water interface, and on the aerobic and anaerobic biodegradation and bioavailability of PCDD/Fs in sediments. Quality criteria for sediments and aquatic ecosystems remain to be elaborated.     

Spatial patterns of chemical contamination (metals, PAHs, PCBs, PCDDs/PCDFS) in sediments of a non-industrialized but densely populated coral atoll/small island state (Bermuda)

There is a recognized dearth of standard environmental quality data in the wider Caribbean area, especially on coral atolls/small island states. Extensive surveys of sediment contamination (n = 109 samples) in Bermuda revealed a wide spectrum of environmental quality. Zinc and especially copper levels were elevated at some locations, associated with boating (antifouling paints and boatyard discharges). Mercury contamination was surprisingly prevalent, with total levels as high as 12 mg kg⁻¹ DW, although methyl mercury levels were quite low. PAH, PCB and PCDD/PCDF contamination was detected a several hotspots associated with road run-off, a marine landfill, and a former US Naval annexe. NOAA sediment quality guidelines were exceeded at several locations, indicating biological effects are possible, or at some locations probable. Overall, and despite lack of industrialization, anthropogenic chemicals in sediments of the atoll presented a risk to benthic biodiversity at a number of hotspots suggesting a need for sediment management strategies.     

Point source identification using a simple permutation test: a case study of elevated PCDD/F levels in ambient air and soil and their relation to the distance to a local municipal solid waste incinerator

A point source for environmental pollution may be identified by the spatial association of samples collected in the vicinity of the emission source. In this study, we used a simple permutation test to explore the spatial correlations between the ambient air and soil polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) congener profile concentrations and their distances to a municipal solid waste incinerator (MSWI) in northern Taiwan. Kendall’s τ was applied for the correlation between the PCDD/F concentrations of a total of 9 airborne and 12 soil sampling sites and their distances to the incinerator. The results showed that the correlation was highly negatively associated for soil PCDD/Fs (τ = −0.515, p-value = 0.011) and was marginal for airborne PCDD/Fs (τ = −0.667, p-value = 0.055), conditional on the seasonal wind attributions. For the 17 individual congener profiles, most of the air and soil samples had a negative association, with 7 and 10 reaching statistical significance (p-value < 0.05) or borderline significance (p-value < 0.10), respectively. The permutation test provides a simple and robust statistical method for the identification of a potential pollution source from a limited sample size. Our analytical results show that dioxin emissions from the investigated MSWI had a definite environmental impact on the surrounding area.     

Photodegradation of autochthonous and allochthonous dissolved organic matter in a natural tropical lake

Dissolved organic carbon (DOC) is one of the most abundant fractions of organic matter in aquatic systems and plays an important role in the dynamics of aquatic environments, controlling both the penetration and the underwater light radiation climate. DOC can be photodegraded by light, thus facilitating biodegradation, especially in regions where the incidence of solar radiation is high, such as higher altitudes and lower latitudes. This study quantified the photodegradation of dissolved organic material in a natural tropical lake surrounded by native forests (Brazilian Atlantic Forest) through two experiments: i) the first experiment exposed concentrated autochthonous, allochthonous, and lake water to in situ solar radiation; ii) this experiment also exposed the same organic material to artificial UV radiation in an incubator under controlled conditions. The quality and quantity of dissolved organic carbon were measured using indices based on carbon absorbance and fluorescence spectrum. In the in situ experiment, it was observed that the DOC degradation profile of the concentrated allochthonous and autochthonous organic material were distinct from each other in the absorbance indices, and the lake water mostly resembled the latter one. On the other hand, we did not see evidence of any significant difference among treatments in the laboratory experiment. An increase in the SR index and a concomitant decrease in the fluorescence of humic compounds and SUVA₂₅₄ over time were observed. In both experiments, the amount of degraded organic material over time was low and some possible explanations are discussed.     

Long term ionospheric electron content variations over Delhi

Ionospheric electron content (IEC) observed at Delhi (geographic co-ordinates: 28.63°N, 77.22°E; geomagnetic co-ordinates: 19.08°N, 148.91E; dip Latitude 24.8°N), India, for the period 1975/80 and 1986/89 belonging to an ascending phase of solar activity during first halves of solar cycles 21 and 22 respectively have been used to study the diurnal, seasonal, solar and magnetic activity variations. The diurnal variation of seasonal mean of IEC on quiet days shows a secondary peak comparable to the daytime peak in equinox and winter in high solar activity. IEC_max (daytime maximum value of IEC, one per day) shows winter anomaly only during high solar activity at Delhi. Further, IEC_max shows positive correlation with F_10.7 up to about 200 flux units at equinox and 240 units both in winter and summer; for greater F_10.7 values, IEC_max is substantially constant in all the seasons. IECmax and magnetic activity (A_p) are found to be positively correlated in summer in high solar activity. Winter IEC_max shows positive correlation with A_p in low solar activity and negative correlation in high solar activity in both the solar cycles. In equinox IEC_max is independent of A_p in both solar cycles in low solar activity. A study of day-to-day variations in IEC_max shows single day and alternate day abnormalities, semi-annual and annual variations controlled by the equatorial electrojet strength, and 27-day periodicity attributable to the solar rotation.     

Point source identification using a simple permutation test: a case study of elevated PCDD/F levels in ambient air and soil and their relation to the distance to a local municipal solid waste incinerator

A point source for environmental pollution may be identified by the spatial association of samples collected in the vicinity of the emission source. In this study, we used a simple permutation test to explore the spatial correlations between the ambient air and soil polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F) congener profile concentrations and their distances to a municipal solid waste incinerator (MSWI) in northern Taiwan. Kendall’s τ was applied for the correlation between the PCDD/F concentrations of a total of 9 airborne and 12 soil sampling sites and their distances to the incinerator. The results showed that the correlation was highly negatively associated for soil PCDD/Fs (τ = −0.515, p-value = 0.011) and was marginal for airborne PCDD/Fs (τ = −0.667, p-value = 0.055), conditional on the seasonal wind attributions. For the 17 individual congener profiles, most of the air and soil samples had a negative association, with 7 and 10 reaching statistical significance (p-value < 0.05) or borderline significance (0.05 < p-value < 0.10), respectively. The permutation test provides a simple and robust statistical method for the identification of a potential pollution source from a limited sample size. Our analytical results show that dioxin emissions from the investigated MSWI had a definite environmental impact on the surrounding area.