PCDD/PCDF Isomer patterns in waste incinerator flyash and desorbed into the gas phase in relation to temperature

The influence of temperature on the PCDD and PCDF isomer profiles of a municipal waste incinerator flyash and the PCDD/PCDF desorbed from the ash under an inert atmosphere was investigated using a bench-scale reactor. Exposure to temperatures of 250 degrees C and above resulted in significant changes in the distribution of isomers within most dioxin and furan congener groups. The PCDD content tended to become more evenly distributed across the range of isomers than was the case for the raw flyash, while the PCDF content became concentrated across a relatively lower number of isomers. In most cases the desorbed PCDD/PCDF were mainly mono- to tri-chlorinated, and hence had a relatively low I-TEQ value. The isomer profiles of the desorbed species were also influenced by temperature. There were some significant differences between the PCDF isomer profiles of the desorbed species and those of the treated flyashes under the same conditions, but no clear differences between the PCDD isomer profiles.     

Risk assessment of trace elements in the stomach contents of Indo-Pacific Humpback Dolphins and Finless Porpoises in Hong Kong waters

The potential health risks due to inorganic substances, mainly metals, was evaluated for the two resident marine mammals in Hong Kong, the Indo-Pacific Humpback Dolphin (Sousa chinensis) and the Finless Porpoise (Neophocaena phocaenoides). The stomachs from the carcasses of twelve stranded dolphins and fifteen stranded porpoises were collected and the contents examined. Concentrations of thirteen trace elements (Ag, As, Cd, Co, Cr, Cs, Cu, Hg, Mn, Ni, Se, V and Zn) were determined by inductively coupled plasma mass spectrometer (ICP-MS). An assessment of risks of adverse effects was undertaken using two toxicity guideline values, namely the Reference Dose (RfD), commonly used in human health risk assessment, and the Toxicity Reference Value (TRV), based on terrestrial mammal data. The levels of trace metals in stomach contents of dolphins and porpoises were found to be similar. Risk quotients (RQ) calculated for the trace elements showed that risks to the dolphins and porpoises were generally low and within safe limits using the values based on the TRV, which are less conservative than those based on the RfD values. Using the RfD-based values the risks associated with arsenic, cadmium, chromium, copper, nickel and mercury were comparatively higher. The highest RQ was associated with arsenic, however, most of the arsenic in marine organisms should be in the non-toxic organic form, and thus the calculated risk is likely to be overestimated.     

Bioavailability and plant accumulation of heavy metals and phosphorus in agricultural soils amended by long-term application of sewage sludge

Amendment of agricultural soils with municipal sewage sludges provides a valuable source of plant nutrients and organic matter. Nevertheless, addition of heavy metals and risks of eutrophication continue to be of concern. Metal behaviour in soils and plant uptake are dependent on the nature of the metal, sludge/soil physico-chemical properties and plant species. A pot experiment was carried out to evaluate plant production and heavy metal uptake, soil heavy metal pools and bioavailability, and soil P pools and possible leaching losses, in agricultural soils amended with sewage sludge for at least 10 years (F20) compared to non-amended soils (control). Sewage sludge application increased soil pH, N, Olsen-extractable-P, DOC and exchangeable Ca, Mg and K concentrations. Total and EDTA-extractable soil concentrations of Cu and Zn were also significantly greater in F20, and soil metal (Cu, Mn and Zn) and P fractionation altered. Compared to the control, in F20 relative amounts of acid-extractable (Mn, Zn), reducible (Mn, Zn) and oxidisable (Cu, Zn) metal fractions were greater, and a dominance of inorganic P forms was observed. Analyses of F20 soil solutions highlighted risks of PO4 and Cu leaching. However, despite the observed increases in metal bioavailability sewage sludge applications did not lead to an increase in plant shoot concentrations (in wild plants or crop species). On the contrary, depending on the plant species, Mn and Zn tissue concentrations were within the deficiency level for most plants.     

Polychlorinated biphenyl contamination trends in Lake Hartwell, South Carolina (USA): sediment recovery profiles spanning two decades

To assess the ca. 20-year polychlorinated biphenyl (PCB) contamination trends in Lake Hartwell, SC, sediment cores from the Twelve Mile Creek arm were collected in July 2004 at two sites (G30 and G33) first sampled in the mid-1980s. Congener-specific PCB data as a function of depth from the sediment-water interface for the 2004 sediment samples were compared to data obtained from 1987 and 1998 samples taken from the same locations. Despite modest decreases in total PCB levels near the G30 sediment-water interface, historical increases in average degrees of chlorination may elevate the overall toxic risk at this site. Unlike G30, the more rapid recovery in the near-surface sediment of G33 suggests that the effectiveness of the U.S. EPA natural attenuation record of decision is site-specific and is unlikely to result in uniform surface sediment recovery throughout the most contaminated regions of Lake Hartwell.     

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.     

Dissolved organic matter fractions formed during composting of winery and distillery residues: evaluation of the process by fluorescence excitation-emission matrix

The aim of the present paper is to assess the maturity degree reached by different samples of several mixtures from winery and distillery residues composted using the Rutgers composting system, by means of excitation-emission matrix (EEM) fluorescence spectroscopy. The composts were sampled once a week for about 200d. EEM spectra indicate the presence of different fluorophores. The fluorescence intensities of these peaks show trends related to the maturity of the composting samples selected. The "contour density" of EEM maps is strongly modified through time. We have used the quantitative method of fluorescence regional integration (FRI). The EEMs were delineated into five excitation-emission regions. The degree of compost maturity could be correlated with the percentage of the volumetric integration under the EEM within each region. Further refinement of these techniques should provide a relatively rapid method for assessing the suitability of the compost to soil application.     

Comparative toxicity of chlorpyrifos, diazinon, malathion and their oxon derivatives to larval Rana boylii

Organophosphorus pesticides (OPs) are ubiquitous in the environment and are highly toxic to amphibians. They deactivate cholinesterase, resulting in neurological dysfunction. Most chemicals in this group require oxidative desulfuration to achieve their greatest cholinesterase-inhibiting potencies. Oxon derivatives are formed within liver cells but also by bacterial decay of parental pesticides. This study examines the toxicity of chlorpyrifos, malathion and diazinon and their oxons on the foothill yellow-legged frog (Rana boylii). R. boylii is exposed to agricultural pesticides in the California Central Valley. Median lethal concentrations of the parental forms during a 96 h exposure were 3.00 mg/L (24h) for chlorpyrifos, 2.14 mg/L for malathion and 7.49 mg/L for diazinon. Corresponding oxons were 10 to 100 times more toxic than their parental forms. We conclude that environmental concentrations of these pesticides can be harmful to R. boylii populations.     

Isolation and characterization of 1,2,4-trichlorobenzene mineralizing Bordetella sp. and its bioremediation potential in soil

A soil which has been polluted with chlorinated benzenes for more than 25 years was used for isolation of adapted microorganisms able to mineralize 1,2,4-trichlorobenzene (1,2,4-TCB). A microbial community was enriched from this soil and acclimated in liquid culture under aerobic conditions using 1,2,4-TCB as a sole available carbon source. From this community, two strains were isolated and identified by comparative sequence analysis of their 16S-rRNA coding genes as members of the genus Bordetella with Bordetella sp. QJ2-5 as the highest homological strain and with Bordetella petrii as the closest related described species. The 16S-rDNA of the two isolated strains showed a similarity of 100%. These strains were able to mineralize 1,2,4-TCB within two weeks to approximately 50% in liquid culture experiments. One of these strains was reinoculated to an agricultural soil with low native 1,2,4-TCB degradation capacity to investigate its bioremediation potential. The reinoculated strain kept its biodegradation capability: (14)C-labeled 1,2,4-TCB applied to this inoculated soil was mineralized to about 40% within one month of incubation. This indicates a possible application of the isolated Bordetella sp. for bioremediation of 1,2,4-TCB contaminated sites.     

Enhanced stability of hydrogen peroxide in the presence of subsurface solids

The stabilization of hydrogen peroxide was investigated as a basis for enhancing its downgradient transport and contact with contaminants during catalyzed H(2)O(2) propagations (CHP) in situ chemical oxidation (ISCO). Stabilization of hydrogen peroxide was investigated in slurries containing four characterized subsurface solids using phytate, citrate, and malonate as stabilizing agents after screening ten potential stabilizers. The extent of hydrogen peroxide stabilization and the most effective stabilizer were solid-specific; however, phytate was usually the most effective stabilizer, increasing the hydrogen peroxide half-life to as much as 50 times. The degree of stabilization was nearly as effective at 10 mM concentrations as at 250 mM or 1 M concentrations. The effect of stabilization on relative rates of hydroxyl radical activity varied between the subsurface solids, but citrate and malonate generally had a greater positive effect than phytate. The effect of phytate, citrate, and malonate on the relative rates of superoxide generation was minimal to somewhat negative, depending on the solid. The results of this research demonstrate that the stabilizers phytate, citrate, and malonate can significantly increase the half-life of hydrogen peroxide in the presence of subsurface solids during CHP reactions while maintaining a significant portion of the reactive oxygen species activity. Use of these stabilizers in the field will likely improve the delivery of hydrogen peroxide and downgradient treatment during CHP ISCO.     

Occurrence of alkylphenolic substances in a Great Lakes coastal marsh, Cootes Paradise, ON, Canada

Occurrence and fate of alkylphenols (APs), known endocrine disruptors, were investigated in a Great Lakes coastal wetland, Cootes Paradise, ON. The wetland, which receives discharges from a Wastewater Treatment Plant (WTP) and several Combined Sewer Overflows (CSOs), is an important spawning ground for fish and crucial habitat for other fauna. Elevated concentrations of nonylphenol ethoxylates (NPEs) and their degradation product nonylphenol (NP) were found in water and sediment samples near the sources. Since transfer of APs through the food chain is of concern, we compared their concentrations in invertebrates from clean and contaminated sites. The results reveal transfer of alkylphenolics from sediments to biota and their accumulation in the invertebrate tissue, particularly the highly hydrophobic 4-NP, whose concentrations ranged from 1.9 to 6.3 microg g(-1). To our knowledge, this is the first study to evaluate AP concentrations in tissue of benthic invertebrates under real environmental conditions.