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.     

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.     

Development of an efficient and sensitive analytical method for the determination of copper at trace levels by slotted quartz tube atomic absorption spectrometry after vortex-assisted dispersive liquid-liquid microextraction in biota and water samples using a novel ligand

This study describes the determination of trace levels of copper by slotted quartz tube atomic absorption spectrometry after dispersive liquid-liquid microextraction. A ligand synthesized from the reaction of salicylaldehyde and 1-naphthylamine was used to form coordinate copper complex prior to extraction. All parameters that influence the output of complex formation, extraction, and instrumental measurement were optimized to enhance the absorbance signal of copper. Under the optimum conditions, about 104-fold enhancement in sensitivity was recorded over the conventional flame atomic absorption spectrometer, corresponding to a 0.51 ng/mL detection limit. The percent relative standard deviation calculated for the lowest concentration (4.8%) indicated high precision for the experimental procedure. Accuracy and applicability of the optimum method were determined by performing spiked recovery tests on urine, lake water, and mineral water samples. Satisfactory recovery results were obtained between 82.2 and 106.3% at four different concentrations. Matrix matching method was also performed to increase the accuracy of quantification, and the percent recovery calculated for 175 ng/mL was 105.14%.     

Quantification of forest fragmentation in pre- and post-establishment periods,inside and around Apuseni Natural Park,Romania

Protected areas (PAs) represent real cornerstones in the conservation of biodiversity and natural habitats. Their protection must be a priority today for each society. The enhanced socio-economic requirements increase the pressure upon protected areas, and the effect can result in a reduction of biodiversity. The aim of this study is to quantify forest fragmentation in the pre- (1986–2002) and post-establishment (2002–2016) periods, inside and around (buffer 1, buffer 2 and buffer 3) Apuseni Natural Park (ANP), Romania, using a series of classified Landsat satellite images and six landscape metrics. The results show that forest fragmentation occurred both in the pre- and post-establishment periods, inside and around ANP. Inside the park, the deforestation rate increased four times, from 0.03% year^?1 in the pre-establishment period to 0.14% year^?1 in the post-establishment period. Around the park, the deforestation rate decreased from 0.31% year^?1 in the pre-establishment period (buffer 1) to 0.10% year^?1 in the post-establishment period (buffer 1). Forest fragmentation resulted in an increase in the patch density and edge density, and a decrease in the total core area and mean patch size leading to isolation of patches and fragmentation of landscape, especially in ANP in the post-establishment period. Several measures can be taken in order to stop forest fragmentation inside and around ANP, including the education of buffer-zone communities, reforestation, enforcement of park regulations, and forest legislation.