Occurrence and distribution of PCB metabolites in blood and their potential health effects in humans: a review

In recent years, attention has been directed to chemicals with possible endocrine-disrupting properties. Polychlorinated biphenyls (PCBs) and their metabolites belong to one group of environmental contaminants that have been shown to interact with the endocrine system in mammals, including humans. Although recent developments have been made in terms of determination of PCB metabolites in blood samples, still limited number of studies have been able to elucidate their profiles and toxicological and health effects in humans. This review aims to evaluate and compare the levels of hydroxylated PCBs (OH-PCBs) and methyl sulfone PCBs (MeSO₂-PCBs) in blood and their relationship to parent compounds and also address the potential risks and adverse health effects in humans. Levels of OH-PCBs varied between 0.0002 and 1.6 ng g^?1 w/w in human serum/plasma from the selected literature, correlating well with ∑PCBs. In contrast, ∑OH-PCB/∑PCB ratio in animals did not show a significant correlation, which might suggest that the bioaccumulation plays an even more important role in the concentration of OH-PCBs compared to PCB metabolism. Highest levels of MeSO₂-PCBs were reported in marine mammals with high selectivity retention in the liver. Health effects of PCB metabolites included carcinogenicity, reproductive impairment, and developmental neurotoxicity, being more efficiently transferred to the brain and across the placenta from mother to fetus in comparison to the parent PCBs. Based on the lack of knowledge on the occurrence and distribution of lower chlorinated OH-PCBs in humans, further studies to identify and assess the risks associated to human exposure are essential.     

Declining coastal piscivore populations in the Baltic Sea: Where and when do sticklebacks matter?

Intraguild predation interactions make fish communities prone to exhibit alternative stable states with either piscivore or prey fish dominance. In the Baltic Sea, local declines of coastal piscivores like perch (Perca fluviatilis) have been observed to coincide with high densities of sticklebacks (Gasterosteus aculeatus). Mechanisms behind this shift between piscivore and stickleback dominance were studied both experimentally and in field. Results showed that predation by sticklebacks has a strong negative effect on perch larvae survival, but this effect rapidly decreases with increasing perch size, likely due to gape limitations and digestion constraints in sticklebacks. Large spatial and temporal variations in patterns of stickleback migration into perch spawning sites were observed. Whether or not high density of sticklebacks will cause declines in coastal piscivore populations is suggested to depend on the availability of spawning sites in which sticklebacks do not migrate into or arrive late in the reproduction season of coastal piscivores.     

Modelling atmospheric bulk deposition of Pb,Zn and Cd near a former Pb–Zn mine in West Greenland using transplanted Flavocetraria nivalis lichens

Atmospheric deposition of lead (Pb), zinc (Zn) and cadmium (Cd) was investigated near the former Black Angel Pb–Zn mine in Maarmorilik, West Greenland during 2010–2011. Thalli of the lichen Flavocetraria nivalis were transplanted from an uncontaminated site into sites near the mine and collected the following year. At 20 of the total 21 sites, concentrations of Pb, Zn and Cd were significantly elevated in lichens after 1 year of transplantation compared to initial concentrations. Elevated concentrations were observed within a distance of approx. 20 km from the mining area. Concentrations decreased with increasing distance from the mine and the relation was well described using a power function with a negative exponent (r² = 0.90; 0.83 and 0.83 for Pb; Zn and Cd). To examine the relation between metal concentrations/uptake in lichen transplants and atmospheric bulk deposition, 10 Bergerhoff dust samplers were placed near lichen transplants and samplers and lichens were collected after a 7-weeks exposure period. A significant linear correlation was observed between metal concentrations in lichen transplants and atmospheric bulk metal deposition (r² = 0.94; 0.88 and 0.89 for Pb; Zn and Cd). Combining the results and including an area distribution within a defined metal deposition area, the “annual” deposition of Pb, Zn and Cd as dust was estimated during the 2010–2011 snow-free period (～5 months). The results reveal that 20 years after mine closure, 770 kg Pb, 3700 kg Zn and 24 kg Cd were still being deposited as dust per year (snow-free period only) within a distance of 20 km from the mine.     

Occurrence and sorption properties of arsenicals in marine sediments

The content of total arsenic, the inorganic forms: arsenite (As(III)) and arsenate (As(V)), the methylated forms: monomethylarsonic acid and dimethylarsinic acid (DMA), trimethylarsenic oxide, tetramethylarsenonium ion and arsenobetaine was measured in 95 sediment samples and 11 pore water samples from the Baltic Sea near the island of Bornholm at depths of up to 100 m. As(III+V) and DMA were detected in the sediment and As(III+V) was detected in the sediment pore water. Average total As concentration of 10.6?±?7.4 mg/kg dry matter (DM) in the sediment corresponds to previously reported values in the Baltic Sea and other parts of the world. Existing data for on-site measurements of sorption coefficients (Kd) of arsenicals in marine and freshwater sediments show large variability from <1 to >1,000 L/kg. In this work, calculated sorption coefficients (Kd and Koc) for As(III+V) showed significant correlation with depth, dissolved oxygen (DO), salinity and sediment classification; for depths <70 m, salinity <11 %, DO >9 mg/L and sand/silt/clay sediments the Kd was 118?±?76 L/kg DM and for depths >70 m, salinity >11 %, DO?<?9 mg/L and muddy sediments the Kd was 513?±?233 L/kg DM. The authors recommend using the found Kd value for arsenic in marine sediments when conditions are similar to the Baltic Sea. At locations with significant anthropogenic point sources or where the local geology contains volcanic rock and sulphide mineral deposits, there may be significantly elevated arsenic concentrations, and it is recommended to determine on-site Kd values.     

Dispersion and bioaccumulation of elements from an open-pit olivine mine in Southwest Greenland assessed using lichens, seaweeds, mussels and fish

This study investigated dispersion and bioaccumulation of mining-related elements from an open-pit olivine mine at Seqi in Southwest Greenland (64°?N) using lichens (Flavocetraria nivalis), seaweeds (Fucus vesiculosus), mussels (Mytilus edulis) and fish (Myoxocephalus scorpius). The mine operated between 2005 and 2009, and samples were taken every year within a monitoring area 0–17 km from the mine during the period 2004–2011. A total of 46 elements were analysed in the samples. After mining began, highly elevated metal concentrations, especially nickel (Ni), chromium (Cr), iron (Fe) and cobalt (Co), were observed in lichens relative to pre-mining levels (up to a factor of 130) caused by dust dispersion from the mining activity. Elevated metal concentrations could be measured in lichens in distances up to ~5 km from the mine/ore treatment facility. Moderately elevated concentrations of Ni and Cr (up to a factor of 7) were also observed in seaweeds and mussels but only in close vicinity (<1 km) to the mine. Analyses of fish showed no significant changes in element composition. After mine closure, the elevated metal concentrations in lichens, seaweeds and mussels decreased markedly, and in 2011, significantly elevated metal concentrations could only be measured in lichens and only within a distance of 1 km from the mine.     

Entfernung von Schwermetallen aus einem Boden mit hohem Schluffanteil

A soil, containing 2.8% organic carbon and a high concentration (76.4%) of small particles (<63 μm), and which had been contaminated over a long period of time by galvanic waste waters (Ni, Cu) and lead wastes, was subjected to detailed analysis and subsequently treated with various extracting solutions in order to remove the heavy metals. For this purpose, representative samples containing 114 mg kg^?1 Cu, 1151 mg kg^?1 Ni and 366 mg kg^?1 Pb were treated with amino acids and solutions containing other complexing agents, as well as with diluted acids, in order to compare the relative effectiveness of these solutions. Satisfactory metal extractions were only achieved by the use of diluted mineral acids, notably hydrochloric acid, which released more than 90% of the nickel and approximately 80% of the copper and lead from the soil. The results obtained with weak complexing agents such as tartaric acid (0.07–2.9%, 24 h) and amino acids (0.01–36%, 24h) were worse. For reprocessing of the hydrochloric acid solutions, a direct precipitation of the heavy metals in their hydroxide forms and selective separation with N-acylthiourea modified polysiloxanes were carried out.     

A method for quick assessment of CO2 storage capacity in closed and semi-closed saline formations

Saline aquifers of high permeability bounded by overlying/underlying seals may be surrounded laterally by low-permeability zones, possibly caused by natural heterogeneity and/or faulting. Carbon dioxide (CO₂) injection into and storage in such “closed” systems with impervious seals, or “semi-closed” systems with non-ideal (low permeability) seals, is different from that in “open” systems, from which the displaced brine can easily escape laterally. In closed or semi-closed systems, the pressure buildup caused by continuous industrial-scale CO₂ injection may have a limiting effect on CO₂ storage capacity, because geomechanical damage caused by overpressure needs to be avoided. In this research, a simple analytical method was developed for the quick assessment of the CO₂ storage capacity in such closed and semi-closed systems. This quick-assessment method is based on the fact that native brine (of an equivalent volume) displaced by the cumulative injected CO₂ occupies additional pore volume within the storage formation and the seals, provided by pore and brine compressibility in response to pressure buildup. With non-ideal seals, brine may also leak through the seals into overlying/underlying formations. The quick-assessment method calculates these brine displacement contributions in response to an estimated average pressure buildup in the storage reservoir. The CO₂ storage capacity and the transient domain-averaged pressure buildup estimated through the quick-assessment method were compared with the “true” values obtained using detailed numerical simulations of CO₂ and brine transport in a two-dimensional radial system. The good agreement indicates that the proposed method can produce reasonable approximations for storage–formation–seal systems of various geometric and hydrogeological properties.     

Evasive response to ultrasound by the crepuscular butterfly<Emphasis Type="Italic"> Manataria maculata</Emphasis>

The crepuscular nymphalid butterfly Manataria maculata was studied in Monteverde cloud forest, Costa Rica, during the dry season reproductive diapause. M. maculata has ears in the form of Vogel's organs located near the base of the forewings. Its behaviour in response to bursts of ultrasonic pulses (26 kHz, 110 dB SPL at 1 m) was condition-dependent. At dusk and dawn the sound consistently elicited evasive responses, similar to those of moths, in flying individuals. In contrast day-roosting individuals always remained motionless although they were alert to other stimuli. The daily movements between day- and night-roosts coincided in time and light intensity with the activity of insectivorous bats. This is the first reported case of ultrasonic hearing connected to evasive flights in a true butterfly (Papilionoidea). It strongly supports the idea that echolocating bats were involved in the evolution of hearing in butterflies.     

Butyltin compounds in sediment and molluscs from the shipping strait between Denmark and Sweden

The distribution of tributyltin (TBT) contamination in the subtidal zone of the waters between Denmark and Sweden was investigated in relation to major international shipping lanes. Sediment and different benthic molluscs were sampled in transects along and perpendicularly to the shipping lanes in the Sound (?resund) and the Kattegat/Skagerrak region. The samples were analysed for TBT and its degradation products, dibutyltin (DBT) and monobutyltin (MBT), using GC-PFPD. In sediments, the TBT concentration ranged from <1 to 19 ng g(-1) dry weight (dw) with a strong correlation between the TBT concentration and the organic fraction in sediment (r(2)=0.90) in the samples collected in the Sound, where the highest concentrations were found. This relationship was not observed in the samples from the Kattegat because the TBT concentration in most sediment samples was below the limit of detection. In the molluscs, TBT and its degradation products were detected in all samples from the entire area with concentrations ranging from 8.1 ng g(-1) dw in Buccinum undatum to 1316 ng g(-1) dw in Nuculana pernula. The deposit-feeding bivalve N. pernula was found to have a particularly high accumulation potential for TBT. In addition, a strong correlation between TBT concentrations in sediment and N. pernula was found. Therefore this species seems to be an ideal organism for monitoring sediment contamination. The TBT concentration in N. pernula was found to decrease gradually along the shipping lanes from the Sound, through the Kattegat and into the Skagerrak.     

Correlates of boldness in three-spined sticklebacks (<Emphasis Type="Italic">Gasterosteus aculeatus</Emphasis>)

Behavioural variation is known to occur between individuals of the same population competing for resources. Individuals also vary with respect to their boldness or shyness. An individuals position along the shy-bold axis may be defined as the extent to which it is willing to trade off potentially increased predation risks for possible gains in resources. Similarly, group living may be interpreted as a trade-off between anti-predatory tactics and foraging efficiency. The responses of three-spined sticklebacks (Gasterosteus aculeatus) were tested across four social contexts to assess relative boldness or shyness and to further examine whether their behaviour would be consistent within and between contexts. Individuals displayed consistent responses within and between the first two contexts: those individuals which resumed foraging rapidly after a simulated aerial predator attack also displayed low shoaling tendencies. Such fish were deemed to be bold, whilst those which displayed the converse behaviour, slow resumption of foraging and a high shoaling tendency, were deemed to be shy. In a third context, bold individuals out-competed shy conspecifics for food. Boldness was also positively correlated with growth over a 6-week period. The position adopted by an individual within a group is usually interpreted as a trade-off between predation risk and foraging efficiency—both are greater at the front of a mobile group. Bold individuals showed significantly stronger tendencies towards front positions than shy conspecifics. The results suggest that, contrary to some previous studies on other animals, bold or shy behaviour in sticklebacks is consistent between contexts.Communicated by T. Czeschlik