Long-term dispersion and availability of metals from submarine mine tailing disposal in a fjord in Arctic Norway

Mining of Cu took place in Kvalsund in the Arctic part of Norway in the 1970s, and mine tailings were discharged to the inner part of the fjord, Repparfjorden. Metal speciation analysis was used to assess the historical dispersion of metals as well as their potential bioavailability from the area of the mine tailing disposal. It was revealed that the dispersion of Ba, Cr, Ni, Pb and Zn from the mine tailings has been limited. Dispersion of Cu to the outer fjord has, however, occurred; the amounts released and dispersed from the mine tailing disposal area quantified to be 2.5–10 t, less than 5% of Cu in the original mine tailings. An estimated 80–390 t of Cu still remains in the disposal area from the surface to a depth of 16 cm. Metal partitioning showed that 56–95% of the Cu is bound in the potential bioavailable fractions (exchangeable, reducible and oxidisable) of the sediments, totalling approximately 70–340 t, with potential for continuous release to the pore water and re-precipitation in over- and underlying sediments. Surface sediments in the deposit area were affected by elevated Cu concentrations just above the probable effect level according to the Norwegian sediment quality criteria, with 50–80% Cu bound in the exchangeable, reducible and oxidisable fractions, potentially available for release to the water column and/or for uptake in benthic organisms.     

Trace analysis of parabens preservatives in drinking water treatment sludge,treated, and mineral water samples

Parabens have been widely used as antimicrobial agents, mainly in food products, pharmaceuticals, and cosmetics. Although they are known as safe preservatives, they also cause some harm to human health, which has been discussed lately. Therefore, the aim of this study was to evaluate the occurrence of nine parabens (including isomers) in mineral and drinking waters, besides in drinking water treatment sludge (DWTS) samples with determination by liquid chromatography tandem mass spectrometry (LC-MS/MS). Both methods solid phase extraction (SPE) and QuEChERS were validated. Calibration curves showed a correlation coefficient of 0.99 for all compounds. LOQ values ranged from 0.04 to 4 μg L^?1 in aqueous matrices and from 5 to 500 ng g^?1 in DWTS. Recoveries between 70 and 115% were reached with RSD below 20% for all compounds in SPE whereas recoveries between 62 and 119% were found with RSD below 20% for almost all compounds in QuEChERS. Matrix effect had low values (<?20%); it was only above 20% for methylparaben in the SPE and for pentylparaben in the QuEChERS. Using a quick and simple extraction procedures with SPE, QuEChERS, and LC-MS/MS analyses, these methods proved to be selective and sensitive. They were successfully applied to real samples (treated water, mineral water, and sludge), and methylparaben was detected at concentration levels below 0.242 μg L^?1 in mineral and treated water samples and 10 ng g^?1 in DWTS samples.     

Life cycle of PCBs and contamination of the environment and of food products from animal origin

This report gives a summary of the historic use, former management and current release of polychlorinated biphenyls (PCBs) in Germany and assesses the impact of the life cycle of PCBs on the contamination of the environment and of food products of animal origin. In Germany 60,000 t of PCBs were used in transformers, capacitors or as hydraulic oils. The use of PCB oils in these “closed applications”, has been banned in Germany in 2000. Thirty to 50% of these PCBs were not appropriately managed. In West Germany, 24,000 t of PCBs were used in open applications, mainly as additive (plasticiser, flame retardant) in sealants and paints in buildings and other construction. The continued use in open applications has not been banned, and in 2013, an estimated more than 12,000 t of PCBs were still present in buildings and other constructions. These open PCB applications continuously emit PCBs into the environment with an estimated release of 7–12 t per year. This amount is in agreement with deposition measurements (estimated to 18 t) and emission estimates for Switzerland. The atmospheric PCB releases still have an relevant impact on vegetation and livestock feed. In addition, PCBs in open applications on farms are still a sources of contamination for farmed animals. Furthermore, the historic production, use, recycling and disposal of PCBs have contaminated soils along the lifecycle. This legacy of contaminated soils and contaminated feed, individually or collectively, can lead to exceedance of maximum levels in food products from animals. In beef and chicken, soil levels of 5 ng PCB-TEQ/kg and for chicken with high soil exposure even 2 ng PCB-TEQ/kg can lead to exceedance of EU limits in meat and eggs. Areas at and around industries having produced or used or managed PCBs, or facilities and areas where PCBs were disposed need to be assessed in respect to potential contamination of food-producing animals. For a large share of impacted land, management measures applicable on farm level might be sufficient to continue with food production. Open PCB applications need to be inventoried and better managed. Other persistent and toxic chemicals used as alternatives to PCBs, e.g. short chain chlorinated paraffins (SCCPs), should be assessed in the life cycle for exposure of food-producing animals and humans.     

Effects of different vermicompost extracts of palm oil mill effluent and palm-pressed fiber mixture on seed germination of mung bean and its relative toxicity

Several treatment technologies are available for the treatment of palm oil mill wastes. Vermicomposting is widely recognized as efficient, eco-friendly methods for converting organic waste materials to valuable products. This study evaluates the effect of different vermicompost extracts obtained from palm oil mill effluent (POME) and palm-pressed fiber (PPF) mixtures on the germination, growth, relative toxicity, and photosynthetic pigments of mung beans (Vigna radiata) plant. POME contains valuable nutrients and can be used as a liquid fertilizer for fertigation. Mung bean seeds were sown in petri dishes irrigated with different dilutions of vermicomposted POME-PPF extracts, namely 50, 60, and 70% at varying dilutions. Results showed that at lower dilutions, the vermicompost extracts showed favorable effects on seed germination, seedling growth, and total chlorophyll content in mung bean seedlings, but at higher dilutions, they showed inhibitory effects. The carotenoid contents also decreased with increased dilutions of POME-PPF. This study recommends that the extracts could serve as a good source of fertilizer for the germination and growth enhancement of mung bean seedlings at the recommended dilutions.     

PCDD/PCDF formation in the chlor-alkali process—laboratory study and comparison with patterns from contaminated sites

Studies on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) during the electrolysis of sodium chloride solution (brine) using graphite or titanium electrodes were carried out at a laboratory scale. High concentrations of PCDFs but no PCDDs were formed in tests using graphite electrodes. With titanium electrodes, PCDFs were only formed when tar pitch was added and mainly originated from the dibenzofuran present in the tar. For the first time, a detailed assessment of the formation of mono- to octachlorinated PCDD/PCDF from tar pitch was investigated. The assessment included of the chlorination steps proved that PCDFs were formed by successive lateral chlorinated from dibenzofuran to MonoCDFs, DiCDFs, and TriCDFs to form the typical known “chlorine pattern” of TetraCDF to OctaCDF with a dominance of 1,2,7,8- and 2,3,7,8-TetraCDFs, 1,2,3,7,8-PentaCDF, and 1,2,3,4,7,8-HexaCDF as marker congeners. The final homologue distributions depended on reaction time and reaction temperature. In addition, electrolysis with non-chlorinated dibenzo-p-dioxins, dibenzofuran, and biphenyl was carried out. As a result, PCDDs, PCDFs, and PCB were formed at comparable yields. Congener patterns in soil samples from a PCDD/F-contaminated site where chlor-alkali electrolysis had been operated for decades in Japan had identical isomer distribution demonstrating the source and contamination potential and risk of these processes. Therefore, sites where in the past 120 years chlor-alkali electrolysis has been operated or where residues from chlor-alkali production or other chlorine using industries have been disposed should be assessed for their pollution level and exposure relevance. The assessment of total organohalogen content revealed that PCDF is only a small fraction of organohalogens in the contaminated soils. For an appropriate risk assessment, also other chlorinated aromatic compounds such as PCBs or PCNs need to be considered.     

Enhanced photocatalytic activity using GO/TiO<Subscript>2</Subscript> catalyst for the removal of DCA solutions

This work aimed to optimize high-performance photocatalysts based on graphene oxide/titanium dioxide (GO/TiO₂) nanocomposites for the effective degradation of aqueous pollutants. The catalytic activity was tested against the degradation of dichloroacetic acid (DCA), a by-product of disinfection processes that is present in many industrial wastewaters and effluents. GO/TiO₂ photocatalysts were prepared using three different methods, hydrothermal, solvothermal, and mechanical, and varying the GO/TiO₂ ratio in the range of 1 to 10%. Several techniques were applied to characterize the catalysts, and better coupling of GO and TiO₂ was observed in the thermally synthesized composites. Although the results obtained for DCA degradation showed a coupled influence of the composite preparation method and its composition, promising results were obtained with the photocatalysts compared to the limited activity of conventional TiO₂. In the best case, corresponding to the composite synthesized via hydrothermal method with 5% of GO/TiO₂ weight ratio, an enhancement of 2.5 times of the photocatalytic degradation yield of DCA was obtained compared to bare TiO₂, thus opening more efficient ways to promote the application of photocatalytic remediation technologies.     

Photocatalytic reduction of carbon dioxide over Cu/TiO<Subscript>2</Subscript> photocatalysts

The photocatalytic reduction of CO₂ with H₂O was investigated using Cu/TiO₂ photocatalysts in aqueous solution. For this purpose, Cu/TiO₂ photocatalysts (with 0.2, 0.9, 2, 4, and 6 wt.% of Cu) have been synthesized via sol-gel method. The photocatalysts were extensively characterized by means of inductively coupled plasma optical emission spectrometry (ICP-OES), N₂ physisorption (BET), XRD, UV-vis DRS, FT-IR, Raman spectroscopy, TEM-EDX, and photoelectrochemical measurements. The as-prepared photocatalysts contain anatase as a major crystalline phase with a crystallite size around 13 nm. By increasing the amount of Cu, specific surface area and band gap energy decreased in addition to the formation of large agglomeration of CuO. Results revealed that the photocatalytic reduction of CO₂ decreased in the presence of Cu/TiO₂ in comparison to pure TiO₂, which might be associated to the formation of CuO phase acting as a recombination center of generated electron-hole pair. Decreasing of photoactivity can also be connected with a very low position of conduction band of photocatalysts with high Cu content, which makes H₂ production necessary for CO₂ reduction more difficult.     

A mini review of fluoride-induced apoptotic pathways

Fluorine or fluoride can have toxic effects on bone tissue and soft tissue at high concentrations. These negative effects include but not limited to cytotoxicity, immunotoxicity, blood toxicity, and oxidative damage. Apoptosis plays an important role in fluoride-induced toxicity of kidney, liver, spleen, thymus, bursa of Fabricius, cecal tonsil, and cultured cells. Here, apoptosis activated by high level of fluoride has been systematically reviewed, focusing on three pathways: mitochondrion-mediated, endoplasmic reticulum (ER) stress-mediated, and death receptor-mediated pathways. However, very limited reports are focused on the death receptor-mediated apoptosis pathways in the fluoride-induced apoptosis. Therefore, understanding and discovery of more pathways and molecular mechanisms of fluoride-induced apoptosis may contribute to designing measures for preventing fluoride toxicity.     

Spatial distribution of metals within the liver acinus and their perturbation by PCB126

Animal studies show that exposure to the environmental pollutant 3,3′,4,4′,5-pentachlorobiphenyl (PCB126) causes alterations in hepatic metals as measured in acid-digested volume-adjusted tissue. These studies lack the detail of the spatial distribution within the liver. Here we use X-ray fluorescence microscopy (XFM) to assess the spatial distribution of trace elements within liver tissue. Liver samples from male Sprague Dawley rats, treated either with vehicle or PCB126, were formalin fixed and paraffin embedded. Serial sections were prepared for traditional H&E staining or placed on silicon nitride windows for XFM. With XFM, metal gradients between the portal triad and the central vein were seen, especially with copper and iron. These gradients change with exposure to PCB126, even reverse. This is the first report of how micronutrients vary spatially within the liver and how they change in response to toxicant exposure. In addition, high concentrations of zinc clusters were discovered in the extracellular space. PCB126 treatment did not affect their presence, but did alter their elemental makeup suggesting a more general biological function. Further work is needed to properly evaluate the gradients and their alterations as well as classify the zinc clusters to determine their role in liver function and zinc homeostasis.