Catalytic hydrogenation of polyaromatic hydrocarbon (PAH) compounds in supercritical carbon dioxide over supported palladium

A series of supported palladium catalysts were evaluated for their ability to mediate the complete hydrogenation of polycyclic aromatic hydrocarbon (PAH) compounds. Benzo[a]pyrene (B[a]P) or phenanthrene (Phe) in hexane was merged with a hydrogen-carbon dioxide [5% (w/w) H(2)/CO(2)] stream and transferred to a flow through mini-reactor (capacity ca. 1 g) that was maintained at 90 degrees C under a back-pressure of 20.68 MPa. Effluent from the reactor trapped in hexane was monitored/quantified by gas chromatography-mass spectrometry. Catalyst formulations supported on iron powder, high density polyethylene (HDPE) or gamma-alumina were prepared and compared in terms of hydrogenation activity as measured by the quantity of substrate per unit time that could be perhydrogenated to toxicologically innocuous products. Both of the Pd preparations supported on gamma-alumina were more efficient than a commercial Pd(0) (5% w/w) on gamma-Al(2)O(3) formulation or preparations supported on HDPE or the iron powder. Bimetallic mixtures with Pd increased the hydrogenation activity when co-deposited with Cu or Ni but not with Ag or Co. However, increases in hydrogenation activity by increasing the loading of Pd (or bimetallic mixture) on this surface were limited. Despite using supercritical carbon dioxide (scCO(2)) to swell the surfaces of the polymer, the deposition of nanoparticles within the polyethylene formulation was appreciably less active than either the oxidic or the Fe(0) formulations.     

Real-time PCR for detection of the Aspergillus genus

Aspergillus is a genus of mold that has strong indoor sources, including several species capable of acting as opportunistic pathogens. Previous studies suggest that Aspergillus could serve as an indicator for abnormal mold growth or moisture, making it an important genus for environmental monitoring. Here, a quantitative polymerase chain reaction (qPCR, or real-time PCR) assay is presented for Aspergillus. The assay shows good specificity for the genus, detecting all Aspergillus species tested, although a few non-Aspergillus species are also amplified. Sensitivity testing demonstrates that DNA representing one conidium can be detected. A validation study compared qPCR results against direct microscopy counts using A. fumigatus conidia aerosolized into a laboratory chamber. The assay was then used to quantify Aspergillus in indoor air samples, demonstrating its utility for environmental monitoring. Analysis of a small number of clinical sputum samples showed complete agreement with culturing results.     

Estimating aquatic phosphorus concentrations 30 metres down-current from a rainbow trout cage array

Aquatic total phosphorus (Tot-P) is measured 30 m distant from rainbow trout (Oncorhynchus mykiss) cages, for regulatory compliance on the Canadian side of Lake Huron. The ability to predict changes in near-field Tot-P concentrations from changes in production, or to explain near-field concentrations in the event of compromised reference sites, would be very useful for managers and farmers. A logical first step in the development of a near-field model is the estimation of down-current Tot-P concentrations. A nutritional mass balance approach was used to calculate the amount of non-settleable Tot-P which was divided by the corresponding flushing volume over four separate production periods. Despite a number of uncertainties, such as cage effects on flushing volume, the contribution of particulate phosphorus, fish distribution, feed conversion ratio, and ingestion-excretion time; accuracy (slope = 1.06) and precision (r(2) = 0.75) of modelled estimates fit well with empirical results. It was concluded that 30 m down-current Tot-P concentrations could be modelled under a diverse set of culture and environmental conditions, suggesting typical 'near-field' concentrations of Tot-P can be explained on the basis of farm activities.     

Growth performance and biochemical responses of three rice (Oryza sativa L.) cultivars grown in fly-ash amended soil

The disposal of fly-ash (FA) from coal-fired power stations causes significant economic and environmental problems. Use of such contaminated sites for crop production and use of contaminated water for irrigation not only decreases crop productivity but also poses health hazards to humans due to accumulation of toxic metals in edible grains. In the present investigation, three rice cultivars viz., Saryu-52, Sabha-5204, and Pant-4 were grown in garden soil (GS, control) and various amendments (10%, 25%, 50%, 75% and 100%) of FA for a period of 90 days and effect on growth and productivity of plant was evaluated vis-a-vis metal accumulation in the plants. The toxicity of FA at higher concentration (50%) was reflected by the reduction in photosynthetic pigments, protein and growth parameters viz., plant height, root biomass, number of tillers, grain and straw weight. However, at lower concentrations (10-25%), FA enhanced growth of the plants as evident by the increase of studied growth parameters. The cysteine and non-protein thiol (NP-SH) content showed increase in their levels up to 100% FA as compared to control, however, maximum content was found at 25% FA in Saryu-52 and Pant-4 and at 50% FA in Sabha-5204. Accumulation of Fe, Si, Cu, Zn, Mn, Ni, Cd and As was investigated in roots, leaves and seeds of the plants. Fe accumulation was maximum in all the parts of plant followed by Si and both showed more translocation to leaves while Mn, Zn, Cu, Ni and Cd showed lower accumulation and most of the metal was confined to roots in all the three cultivars. As was accumulated only in leaves and was not found to be in detectable levels in roots and seeds. The metal accumulation order in three rice cultivars was Fe > Si > Mn > Zn > Ni > Cu > Cd > As in all the plant parts. The results showed that rice varieties Saryu-52 and Sabha-5204 were more tolerant and could show improved growth and yield in lower FA application doses as compared to Pant-4. Thus, Sabha-5204 and Saryu-52 are found suitable for cultivation in FA amended agricultural soils for better crop yields.     

Comparison of lead residues among avian bones

To determine if significant differences exist in lead (Pb) accumulation in different bones, especially those most often used for bone-Pb studies in wildlife, we compared Pb concentrations in radius, ulna, humerus, femur, and tibia of Common Eider (Somateria mollissima); and radius/ulna (combined), femur, and tibia of American Woodcock (Scolopax minor). There were no significant differences in bone-Pb concentrations among woodcock bones over a wide range of Pb concentrations (3-311 microg/g). In eider, where bone-Pb concentrations were low (<10 microg/g), leg bones had significantly higher Pb concentrations (approximately 30-40%) than wing bones from the same individuals. The variation among individual birds was greater than the variation among different bones within a bird. Based on our findings, we conclude that one type of bone may be substituted for another in bone-Pb studies although the same bone type should be analyzed for all birds within a study, whenever possible.     

An innovative technique for lake management with reference to aeration unit installed at lower lake, Bhopal, India

Water is key element in human life. All forms of life upon the earth depend upon water for their mere existence. Life & water may be aptly said to be two facets of the same coin. Most of the water bodies are getting polluted due to domestic waste, sewage, industrial waste and agricultural effluent. The present study is designed to ascertain the effectiveness of artificial aeration cum Ozonizer unit installed at Lower Lake, Bhopal for assessment of water quality. Various physico- chemical parameters like pH, Dissolved oxygen, Biochemical Oxygen demand, Chemical oxygen demand, nitrate, phosphate and bacteriological status were studied to assess the extent of deterioration in water quality of Lower lake and at the same time to assess the performance of the dual aeration system in improvement of water quality.     

Factors affecting river health and its assessment over broad geographic ranges: the Western Australian experience

AusRivAS is an Australia-wide program that measures river condition using predictive models to compare the macroinvertebrate families occurring at a river site with those expected if the site were in natural condition. Results of assessment of 685 sites across all major rivers in Western Australia are presented. Most rivers were in relatively natural condition in the northern half of the state where the human population is low and pastoralism is the major land use. In the south, where the human population is higher and agriculture is more intensive, rivers were mostly more disturbed. AusRivAS assessment produced some erroneous results in rivers of the south-west cropping zone because of the lack of appropriate reference site groups and biased distribution of sampling sites. Collecting low numbers of animals from many forested streams, because of low stream productivity and samples that were difficult to sort, also affected assessments. Overall, however, AusRivAs assessment identified catchment processes that were inimical to river health. These processes included salinisation, high nutrient and organic loads, erosion and loss of riparian vegetation. River regulation, channel modification and fire were also associated with river degradation. As is the case with other assessment methods, one-off sampling at individual sites using AusRivAS may be misleading. Seasonal drought, in particular, may make it difficult to relate conditions at the time of sampling to longer-term river health. AusRivAS has shown river condition in Western Australia is not markedly different from other parts of Australia which, as a whole, lacks the substantial segments of severely degraded river systems reported in England.     

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.     

Comparative evaluation of a bioluminescent bacterial assay in terrestrial ecotoxicity testing

Despite the widespread and successful use of luminescence-based bioassays in water testing, their applications to soils and sediments is less proven. In part this is because such bioassays have mainly been carried out in an aqueous-based medium and, as such, favour contaminants that are readily water-soluble. In this study, aqueous solutions and soils contaminated with heavy metals (HM), polar organic contaminants and hydrophobic organic contaminants (HOCs) were tested using a range of luminescence-based bioassays (Vibrio fischeri, Escherichia coli HB101 pUCD607 and Pseudomonas fluorescens 10586r pUCD607). For the first two chemical groups, the assays were highly reproducible when optimised extraction procedures were employed but for HOCs the bioassay response was poor. Quantitative structure-activity relationships (QSARs) obtained from aqueous solutions had a linear response although correlation for the chemicals tested using bacterial bioassays was significantly less sensitive than that of sublethal tests for Tetrahymena pyriformis. Bacterial and Dendrobaena veneta bioassay responses to extracts from HM amended soils showed that a clear relationship between trophic levels could be obtained. There is no doubt that the wide range of bioluminescent-based bioassays offers complementary applications to traditional testing techniques but there is a significant need to justify and optimise the extraction protocol prior to application.     

Comparison of leaching tests to determine and quantify the release of inorganic contaminants in demolition waste

The changes in waste management policy caused by the massive generation of waste materials (e.g. construction and demolition waste material, municipal waste incineration products) has led to an increase in the reuse and recycling of waste materials. For environmental risk assessment, test procedures are necessary to examine waste materials before they can be reused. In this article, results of column and lysimeter leaching tests having been applied to inorganic compounds in a reference demolition waste material are presented. The results show a good agreement between the leaching behaviour determined with the lysimeter unit and the column units used in the laboratory. In view of less time and system requirements compared to lysimeter systems, laboratory column units can be considered as a practicable instrument to assess the time-dependent release of inorganic compounds under conditions similar to those encountered in a natural environment. The high concentrations of elements in the seepage water at the initial stage of elution are reflected by the laboratory column leaching tests. In particular, authorities or laboratories might benefit and have an easy-to-use, but nevertheless reliable, method to serve as a basis for decision-making.