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.     

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.     

The search for an alternative to piped water and sewer systems in the Alaskan Arctic

Forty-two communities in rural Alaska are considered unserved or underserved with water and sewer infrastructure. Many challenges exist to provide centralized piped water and sewer infrastructure to the homes, and they are exacerbated by decreasing capital funding. Unserved communities in rural Alaska experience higher rates of disease, supporting the recommendation that sanitation infrastructure should be provided. Organizations are pursuing alternative solutions to conventional piped water and sewer in order to maximize water use and reuse for public health. This paper reviews initiatives led by the State of Alaska, the Alaska Native Tribal Health Consortium, and the Yukon Kuskokwim Health Corporation to identify and develop potential long-term solutions appropriate and acceptable to rural communities. Future developments will likely evolve based on the lessons learned from the initiatives. Recommendations include Alaska-specific research needs, increased end-user participation in the design process, and integrated monitoring, evaluation, and information dissemination in future efforts.     

Disinfection and removal of human pathogenic bacteria in arctic waste stabilization ponds

Wastewater stabilization ponds (WSPs) are commonly used to treat municipal wastewater in Arctic Canada. The biological treatment in the WSPs is strongly influenced by climatic conditions. Currently, there is limited information about the removal of fecal and pathogenic bacteria during the short cool summer treatment season. With relevance to public health, the objectives of this paper were to determine if treatment in arctic WSPs resulted in the disinfection (i.e., removal of fecal indicator bacteria, Escherichia coli) and removal of selected human bacterial pathogens from the treated effluent. The treatment performance, with focus on microbial removal, was assessed for the one-cell WSP in Pond Inlet (Nunavut [NU]) and two-cell WSP in Clyde River (NU) over three consecutive (2012–2014) summer treatment seasons (late June-early September). The WSPs provided a primary disinfection treatment of the wastewater with a 2–3 Log removal of generic indicator E. coli. The bacterial pathogens Salmonella spp., pathogenic E. coli, and Listeria monocytogenes, but not Campylobacter spp. and Helicobacter pylori, were detected in the untreated and treated wastewater, indicating that human pathogens were not reliably removed. Seasonal and annual variations in temperature significantly (p < 0.05) affected the disinfection efficiency. Improved disinfection and pathogen removal was observed for the two-cell system in Clyde River as compared to the one-cell system in Pond Inlet. A quantitative microbial risk assessment should be performed to determine if the release of low levels of human pathogens into the arctic environment poses a human health risk.     

Contamination of marine fauna by chlordecone in Guadeloupe: evidence of a seaward decreasing gradient

Chlordecone is an organochlorine pesticide, used in the Lesser Antilles from 1972 to 1993 to fight against a banana weevil. That molecule is very persistent in the natural environment and ends up in the sea with runoff waters. The objective of the present study is to evaluate the level of contamination in several trophic groups of marine animals according to their distance from the source of pollution. Samples of suspended matter, macroalgae, herbivorous fishes, detrivorous crustaceans, zooplanktivorous fishes, first- and second-order of carnivorous fishes, and piscivorous fishes have been collected in two sites, located downstream the contaminated sites (Goyave and Petit-Bourg), in three marine habitats (coastal mangroves, seagrass beds located 1.5 km from the shoreline, and coral reefs at 3 km offshore). Animals collected in mangroves were the most contaminated (mean concentrations 193 μg kg^?1 in Goyave and 213 μg kg^?1 in Petit-Bourg). Samples from seagrass beds presented intermediate concentrations of chlordecone (85 μg kg^?1 in Goyave and 107 μg kg^?1 in Petit-Bourg). Finally, samples from coral reefs were the less contaminated (71 μg kg^?1 in Goyave and 74 μg kg^?1 in Petit-Bourg). Reef samples, collected 3 km offshore, were two to three times less contaminated than those collected in mangroves.     

Comparison on surface properties and desulfurization of MnO2 and pyrolusite blended activated carbon by steam activation

In this study, MnO₂ and pyrolusite were used as the catalysts to prepare modified activated carbon, that is, AC-Mn and AC-P, respectively, from coals by blending method and steam activation. The Brunauer–Emmett–Teller (BET) results indicated that the AC-P had higher surface areas and micropore volumes than the AC-Mn with the same blending ratio. The relative contents of basic functional groups (i.e., C = O, π-π*) on AC-P were slightly lower than those on AC-Mn, while both contained the same main metal species, namely, MnO. The desulfurization results showed that with 3 wt% of blending ratio, AC-Mn3 and AC-P3 had higher sulfur capacities at 220 and 205 mg/g, respectively, which were much higher than for the blank one (149.6 mg/g). Moreover, the AC-P had relatively higher sulfur capacity than the AC-Mn with the same contents of Mn, which might be attributed to the existence of other metals in pyrolusite. After the desulfurization process, MnO were gradually transferred into MnSO₄, and the relative contents of basic functional groups decreased evidently for both AC-Mn3 and AC-P3. The results demonstrated that pyrolusite could be one good alternative to MnO₂ to prepare modified activated carbon for desulfurization.

Implications: MnO₂ and pyrolusite were used as the additives to prepare modified activated carbon from coals by a blending method and by steam activation, that is, AC-Mn and AC-P, respectively. The AC-P had higher surface areas and micropore volumes than the AC-Mn with the same blending ratio. The AC-Mn and AC-P had higher sulfur capacities than a blank one. Moreover, the AC-P had relatively higher sulfur capacity than the AC-Mn with the same contents of Mn. The results demonstrated that pyrolusite could be one good alternative to MnO₂ to prepare modified activated carbon for desulfurizatio.     

Trace metal (Cd,Cu, Pb,Zn) fractionation in urban-industrial soils of Ust-Kamenogorsk (Oskemen), Kazakhstan—implications for the assessment of environmental quality

Ust-Kamenogorsk is one of the largest cities and industrial centers in Kazakhstan. Non-ferrous metallurgy (Zn–Pb smelter) has acted as a predominating industrial branch in the city since late 1940s. The industrial plants are situated directly adjacent to the residential area of the city which creates grievous ecotoxicological hazard. In the present paper, we aimed at assessing the trace metal pollution of top soils in Ust-Kamenogorsk and its potential threats to the local population. The top soils were sampled at 10 sites throughout the city center. We determined the physical and chemical properties of soils as well as the contents of Cd, Cu, Pb, and Zn. In addition, the soil samples were subjected to a five-step sequential extraction to ascertain the fractionation of trace metals. On this basis, we calculated the geoaccumulation index (I_geo) and pollution load index (PLI) and assessed bioavailability of the elements. From our data, it emerged that the soils displayed a strong polymetallic pollution. PLI was as high as 33.4. Throughout the city, the trace metal contents exceeded the geochemical background and allowable values for residential, recreational, and institutional areas. The I_geo obtained were 3.7–6.5 for Cd, 1.5–4.7 for Cu, 2.8–5.7 for Pb, and 2.6–4.6 for Zn. The soils in Ust-Kamenogorsk displayed extremely high contamination with Cd, moderate to strong contamination with Pb and Zn, and low to moderate contamination with Cu. Cd and Pb were found to be the most bioavailable elements. The mobility of trace metals in the soils changed in the order Cd > Pb > Zn > Cu.