Dehalogenation of polychlorinated biphenyls and polybrominated diphenyl ethers using a hybrid bioinorganic catalyst

The environmentally prevalent polybrominated diphenyl ether (PBDE) #47 and polychlorinated biphenyls (PCBs) #28 and #118 were challenged for 24 hours with a novel biomass-supported Pd catalyst (Bio-Pd(0)). Analysis of the products via GC-MS revealed the Bio-Pd(0) to cause the challenged compounds to undergo stepwise dehalogenation with preferential loss of the least sterically hindered halogen atom. A mass balance for PCB #28 showed that it is degraded to three dichlorobiphenyls (33.9%), two monochlorobiphenyls (12%), and biphenyl (30.7%). The remaining mass was starting material. In contrast, while PCB #118 underwent degradation to yield five tetra- and five trichlorinated biphenyls, no less chlorinated products or biphenyl were detected, and the total mass of degraded products was 0.3%. Although the Bio-Pd(0) material was developed for treatment of PCBs, a mass balance for PBDE #47 showed that the biocatalyst could prove a potentially useful method for treatment of PBDEs. Specifically, 10% of PBDE #47 was converted to identifiable lower brominated congeners, predominantly the tribrominated PBDE #17 and the dibrominated PBDE #4, 75% remained intact, while 15% of the starting mass was unaccounted for.     

The impact of artisanal gold mining,ore processing and mineralization on water quality in Marmato,Colombia

Marmato, Colombia, has been an important centre of gold mining since before the first Spanish colonizers arrived in 1536. The Marmato deposit is hosted in a dacite and andesite porphyry stock as sheeted sulphide-rich veinlet systems. The district is currently experiencing a surge in both major mining projects and artisanal mining, driven by sustained high gold prices. Ore from small-scale and artisanal gold mining is processed in numerous small mills (entables) around Marmato, which impact surface water quality through the discharge of milled waste rock slurry, highly alkaline cyanide-treated effluent, and high dissolved metal loads. To investigate the impact of artisanal mining and ore processing, water samples were collected in January 2012 from streams around Marmato. The average dissolved metal concentrations in impacted streams were Zn, 78 mg L^?1; Pb, 0.43 mg L^?1; Cu, 403 µg L^?1 Cd, 255 µg L^?1; As, 235 µg L^?1; Ni, 67 µg L^?1; Co, 55 µg L^?1; Sb, 7 µg L^?1; and Hg, 42 ng L^?1, exceeding World Health Organization drinking water guidelines. In addition, arsenic speciation was conducted in-situ and indicated that 91–95% of inorganic arsenic species is in the form of As(V). Spatial analysis of the data suggests that entables processing ore for artisanal miners are the main contributor to water pollution, with high sediment loads, alkalinity and elevated concentrations of dissolved arsenic, cadmium, mercury and lead, caused by the processing of gold-bearing sulphides in the entables. Geochemical data from surface water were compared to a comprehensive data set of whole rock analyses from drill core and channel samples from the deposit, indicating that the deposit is significantly enriched in gold, silver, lead, zinc, arsenic, antimony, and cadmium compared to crustal averages, which is reflected in the surface water geochemistry. However, elevated mercury levels in surface water cannot be explained by enrichment of mercury in the deposit and strongly suggest that mercury is being added to concentrates during ore processing to amalgamate fine gold.