Supported Pd/Sn bimetallic nanoparticles for reductive dechlorination of aqueous trichloroethylene

A Pd/Sn bimetallic nanoparticles resin (nano-Pd/Sn/resin) was successfully synthesized for reductive transformation of aqueous trichloroethylene (TCE). The physicochemical properties of the prepared resin were characterized using scanning electron microscopy, energy dispersive X-ray spectroscopy, N(2) isothermal sorption at and X-ray photospectroscopy. The surface-area-normalized rate constants (k(SA)) of Sn particles in the nanoscale range (50-100 nm) were 4.5 times larger than the k(SA) for powdered Sn (0.04 mm). After depositing 1 wt% Pd onto nano-Sn surface, k(SA) was further enhanced by about a factor of 2. Groundwater constituents such as sulfide nitrate and dissolved oxygen had significant negative effects on the rate of TCE degradation by the nano-Pd/Sn/resin. A wet-chemical method regeneration method was observed to effectively restore the reactivity of the poisoned nano-Pd/Sn/resin after dipping in sulfide solution for 2d. In all cases, less than 0.5% of the degraded TCE appeared as chlorinated byproducts including the three dichloroethene isomers. The nano-Pd/Sn/resin technique performs well in transforming TCE into nontoxic hydrocarbons, as compared with other published methods.     

Thermodynamic behavior of rare metals in the melting process of municipal solid waste (MSW) incineration residues

This study aims to identify the thermodynamic behavior of rare metal elements during the melting process of municipal solid waste incineration residues. The fate of several selected rare metal elements was investigated using two approaches: experimental and thermodynamic equilibrium calculation at two actual melting plants. The results revealed that Ag, Bi, Ga, Ge, In, Pd, Sb, Te, and Tl are readily volatilized as chloride and/or gaseous forms and then condensed in melting furnace fly ash. On the other hand, Cr, Ni, Ta, V, and Zr tend to mostly remain in molten slag. Sn is volatilized as SnS (g) under reducing conditions while volatilization is suppressed under oxidizing conditions. Thermodynamically, total volatilization of Mn as MnCl2 (g) occurred with highly available chlorine under oxidizing conditions. However, at the actual plants, only a small proportion was volatilized. As for Co, Mo, and W, no volatilization occurred at the actual plants although the calculations suggest that these elements can form volatile metal chloride and volatilize. Non-equilibrium and heterogeneity of the actual plant melting furnace could explain the discrepancy. This study provided a good qualitative view of the behavior of rare metals in the melting process, but further investigation is required to produce a more accurate simulation and to resolve the discrepancy.     

Wastewater treatment plants (WWTPs) as a source of sediment contamination by toxic organic pollutants and fecal sterols in a semi-enclosed bay in Korea

Toxic organic contaminants and a macrobenthic community were assayed in sediments collected near a wastewater treatment plant (WWTP) outfall to assess the impact of WWTP discharges on an aquatic environment. Average concentrations of toxic organic contaminants in sediments from 20 locations were 96.7ng TEQ/kg dry matter for PCDD/Fs, 1.84ng TEQ/kg dry matter for dioxin-like PCBs, 29.1microg/kg dry matter for PBDEs, 411microg/kg dry matter for nonylphenols, 1021microg/kg dry matter for fecal sterols, and 928microg/kg dry matter for PAHs. Concentrations of all the organic contaminants and fecal sterols varied widely and there was a clear decrease in concentration gradients with increasing distances from the WWTP outfall. This result suggests that WWTP activities contribute to contamination by organic chemicals. A survey of benthic organisms showed the dominance of a few polychaete species, indicating a deterioration of the macrobenthic community by the WWTP discharge. Non-parametric multidimensional scaling (MDS) ordination and Spearman correlation analyses showed that organic contamination is associated with the benthic community structure. For polychaete species, the sensitive species for organic contaminants was Paraprionospio pinnata, while contaminant-tolerant species were Spiochaetopterus koreana and Capitella capitata. BIOENV analyses of all locations suggested PCDDs and PCDFs as the major contaminants influencing the structure of the macrobenthic community. The present study highlights that continuous WWTP discharges contribute to severe organic contamination and risks for the benthic community in an aquatic ecosystem.     

Ozonation catalyzed by homogeneous and heterogeneous catalysts for degradation of DEHP in aqueous phase

Di-(2-ethyl hexyl) phthalate (DEHP), a recalcitrant and an endocrine disrupting chemical, was studied for its removal from wastewater by advanced oxidation process. The effects of pH, transition metal ions, and granular activated carbon (GAC) were investigated. Removal of DEHP increased with increase in pH and among metal ions Cr(III) was found to be the most active catalyst to remove DEHP. In the case of GAC, original carbon (G0) and GAC pre-ozonated in gas phase for 10 min (G10) were tested as catalysts in catalytic ozonation and found G0 to be more active than G10. This is because, during pre-ozonation, basic groups like chromene, pyrones and also graphene layers were oxidized to acidic surface oxygen groups. These basic surface groups are reported to be active catalytic centres for ozone decomposition into .OH which is a strong oxidant. According to kinetic manipulations, DEHP degradation rate constant due to .OH was affected by the catalyst while that due to direct ozonation is same in all cases with or without catalyst. G0 was doped with chromia gels (G0/CrA) to combine the benefits of homogeneous and heterogeneous catalysis. G0/CrA showed lower catalytic efficiency than that of only G0. This might be because of changes in surface structure of GAC caused by doping of chromia gel and changes in chemical nature of Cr(III) during formation of gel. A good correlation was found between the rate constants of ozone decay and DEHP degradation (R2=0.96). This correlation confirms that ozone decomposition into .OH is a critical factor for the activity of a catalyst during ozonation.     

Spectroscopic Distribution of Dissolved Organic Matter in a Dam Reservoir Impacted by Turbid Storm Runoff

Spectroscopic characteristics of dissolved organic matter (DOM) in a large dam reservoir were determined using ultraviolet absorbance and fluorescence spectroscopy to investigate spatial distribution of DOM composition after turbid storm runoff. Water samples were collected along a longitudinal axis of the reservoir at three to four depths after a severe storm runoff. Vertical profiles of turbidity data showed that a turbid water layer was located at a middle depth of the entire reservoir. The spectroscopic characteristics of DOM samples in the turbid water layer were similar to those of terrestrial DOM, as demonstrated by the higher specific UV absorbance (SUVA) and the lower fluorescence emission intensity ratio (F ₄₅₀/F ₅₀₀) compared to other surrounding DOM samples in the reservoir. Synchronous fluorescence spectroscopy revealed that higher content of humic-like DOM composition was contained in the turbid water. Fluorescence excitation–emission matrix (EEM) showed that lower content of protein-like aromatic amino acids was present in the turbid water DOM. The highest protein-like fluorescence was typically observed at a bottom layer of each sampling location. The bottom water DOM exhibited extremely high protein-like florescence near the dam site. The particular observation was attributed to the low water temperature and the isolation of the local bottom water due to the upper location of the withdrawal outlet near the dam. Our results suggest that the distribution of DOM composition in a dam reservoir is strongly influenced by the outflow operation, such as selective withdrawal, as well as terrestrial-origin DOM inputs from storm runoff.     

Compositional data analysis of smoke emissions from debris piles with low-density polyethylene

ABSTRACT

Data describing the composition of smoke are inherently multivariate and always non-negative parts of a whole. The data are relative and the information is contained in the ratios between parts of the composition. A prior analysis of smoke emissions produced from the burning of manzanita wood mixed with low-density polyethylene plastic applied traditional statistical methods to the compositional data and found no effect. The current paper applies compositional data techniques to these smoke emissions to determine if the prior analysis was accurate. Analysis of variance of the isometric log-ratios showed that LDPE significantly affected the CO₂ emission ratio for 8 of the 191 trace gases; this analysis showed none of the gases identified in the previous analysis were affected by LDPE. LDPE did not affect the CO₂ emission ratios for the alkanes, alkenes, alkynes, aldehydes, cycloalkanes, cycloalkenes, diolefins, ketones, MAHs, and PAHs. Compositional data analysis should be used to analyze smoke emissions data. Burning contaminant-free LDPE should produce emissions like wood.     

First-trimester screening for Down syndrome; the role of nasal bone assessment in the Korean population

Objectives The aim of this study was to evaluate the role of nasal bone assessment in first-trimester screening for Down syndrome (DS) in the Korean population. Methods From July 2004 to March 2006, we prospectively evaluated the fetal nasal bones at 11–14 weeks' gestation in the Korean population. Results A successful evaluation was possible in 6490 of 6787 fetuses (95.6%). Absent, hypoechoic, and short nasal bones were seen in 4 (26.7%), 4 (26.7%), and 1 (6.7%) of 15 fetuses with DS, respectively, whereas in 5 (0.1%), 11 (0.2%), and 246 (3.8%) of 6456 normal fetuses. The incidence of absent and hypoechoic nasal bone showed significant differences between normal fetuses and fetuses with DS (P < 0.0005, both). Screening for DS using an absent or hypoechoic nasal bone resulted in a sensitivity of 53.3%, a specificity of 99.8%, a positive likelihood ratio of 215.2, and a negative likelihood ratio of 0.5. Conclusion Our study showed that nasal bone abnormality at 11–14 weeks of gestation had a high association with DS in the Korean population. This suggests that nasal bone assessment can be used to supplement the current first-trimester screening for DS in the Korean population. Copyright © 2007 John Wiley & Sons, Ltd.     

Welfare gains from aluminium recycling in the USA

In this paper we estimate a flexible form cost function of the aluminium industry in the USA and use our estimates to obtain derived demand curves for aluminium inputs such as electricity and bauxite. We then calculate the welfare gains arising from decreased energy use when the level of secondary recycling is increased. The process is repeated for several model specifications. All of our tests, however, yield similar results and indicate that substitution of scrap for only 5% of the bauxite presently used in US aluminium manufacturing would result in annual savings of close to a quarter of a billion dollars.     

Anthropogenic impacts on natural nitrogen isotope variations in Pinus sylvestris stands in an industrially polluted area

Natural variations of the nitrogen isotopes 15N/14N (delta15N values) and the N concentrations of one-year-old needles from 7-12-year-old pine trees (Pinus sylvestris L.) were determined on 27 sites in the heavily polluted Leipzig-Halle region (former GDR). At three selected sites measurements were repeated over a period of 2 years. N concentrations and delta15N values in different needle age classes were compared at the three sites. The delta15N values of the N in the humus layer and the potential plant available N in the A(h) horizon of the local soil were determined. The 15N/14N isotope ratios (delta15N values) of one-year-old pine needles in the region of Leipzig-Halle were found to vary depending on their specific location by a factor of up to one order of magnitude (-9.6 per thousand to + 0.4 per thousand ). N concentrations in one-year-old pine needles varied between 0.71 and 1.38 mmol eq N g dw(-1). Pine stands with positive or slightly negative delta15N values and high N concentrations in one-year-old needles were concentrated around the cities of Leipzig and Halle and in the industrial areas. More negative delta15N values and lower N concentrations in one-year-old pine needles were found on sites at greater distances from the industrial agglomerations, mainly in the NE forested part. Site specific differences in the delta15N values of the N in the humus layer from three selected sites were similar to those found for the needles. No site specific differences, however, were found for the delta15N values of the water soluble nitrogen fraction from the mineral soil horizons of the same sites.