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.     

A field trial for an ex-situ bioremediation of a drilling mud-polluted site

The remediation of drilling mud-polluted sites in the Southeast of Mexico is a top priority for Mexican oil industry. The objective of this work was to find a technology to remediate these sites. A field trial was performed by composting in biopiles, where four 1ton soil-biopiles were established, one treatment in triplicate and one unamended biopile. Amended biopiles were added with nutrients to get a C/N/P ratio of 100/3/0.5 plus a bulking agent (straw) at a soil/straw ratio of 97/3. Moisture content was maintained around 30-35%. Results showed that, after 180 d, total petroleum hydrocarbon (TPH) concentrations decreased from 99300+/-23000mgTPHkg(-1) soil to 5500+/-770mgTPHkg(-1) for amended biopiles and to 22900+/-7800mgTPHkg(-1) for unamended biopile. An undisturbed soil control showed no change in TPH concentrations. Gas chromatographic analysis showed residual alkyl dibenzothiophene type compounds. Highest bacterial counts were observed during the first 30 d which correlated with highest TPH removal, whereas fungal count increased at the end of the experimentation period. Results suggested an important role of the straw, nutrient addition and water content in stimulating aerobic microbial activity and thus hydrocarbon removal. This finding opens an opportunity to remediate old polluted sites with recalcitrant and high TPH concentration.     

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.     

Modeling the impact of direct phototransformation on predicted environmental concentrations (PECs) of propranolol hydrochloride in UK and US rivers

There is currently uncertainty on the persistence of active pharmaceutical ingredients (APIs) and on their depletion mechanisms in natural surface waters such as rivers, and hence predictions of their fate are often poor. In this study, a beta-adrenergic receptor, propranolol hydrochloride, was selected as a model API to explore the relative significance of direct phototransformation as a potential removal process of hydrophilic APIs in rivers. Phototransformation kinetics of propranolol was measured under simulated solar irradiation in the laboratory, which were then converted to the kinetics applicable in UK and US rivers. The effects of light intensity, light penetration, river size and flow were examined. The extrapolated phototransformation half-lives were applied in the river catchment models of GREAT-ER and PhATE. Results demonstrated that direct phototransformation significantly reduced the predicted environmental concentrations of propranolol in the water phase. Predicted reductions of mean concentrations in the River Aire (UK) were 27% in summer and 3% in winter; and for the US rivers simulated, reductions were 28-68% in summer and 11-41% in winter. The highest reductions were predicted for long rivers with low turbidity and low flow conditions.     

Sorption and desorption behavior of benzidine in different solvent-sediment systems

The sorption and desorption behavior of benzidine in eight solvent-sediment systems were studied using a batch method. The solvents tested included deionized water (DI), calcium chloride solution (CaCl2), sodium hydroxide solution (NaOH), acetonitrile (ACN), a mixture of acetonitrile and ammonium acetate solution (ACN-NH4OAc), methanol (MeOH), ammonium acetate solution (NH4OAc) and hydrochloric acid solution (HCl). Three sets of sorption isotherm experiments were conducted separately in these eight solvents with seven days, three weeks, and two months of contact times, respectively. The results demonstrated nonlinear benzidine sorption phenomena in all eight solvents with higher sorption affinities for sediment sites in the aqueous solvents than in the organic solvents. The results from the desorption experiments revealed that the benzidine desorption efficiencies in the solvents decreased in an order, which was approximately the reverse order of its sorption affinity. Results also suggested that hydrophobic partitioning and covalent binding processes dominated in the desorption experiments, while cation exchange process had little effect on desorption of benzidine. A three-stage model was subsequently applied to simulate the desorption data in the selected solvents of ACN, ACN-NH4OAc and NaOH, respectively. The rapidly desorbing initial fractions were about 0.13-0.20, 0.15-0.26, and 0.18-0.25 for ACN, ACN-NH4OAc and NaOH, respectively. Finally, the sorbed concentrations of benzidine in slowly and very slowly desorbing domains in the selected solvents were correlated with the maximum sorption capacities obtained from the Langmuir sorption isotherm model. The maximum sorption capacities of benzidine were found to be comparable to the amount of benzidine residing in the slowly and very slowly desorbing domains.     

Antimony distribution and mobility in topsoils and plants (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa) from polluted Sb-mining areas in Extremadura (Spain)

A study about topsoil antimony distribution and mobility from the soils to the biomass has been afforded in three abandoned Sb mining areas located at Extremadura. Physico-chemical characteristics of the soils and total antimony levels were measured in soils and autochthonous plant species (Cytisus striatus, Cistus ladanifer and Dittrichia viscosa). Comparison with corresponding values in reference areas isolated from the mining activities is discussed. Antimony mobility in the soils was estimated by measuring the water extractable fraction; low results were obtained for the three soil areas, with no statistical differences. Plant ability to accumulate antimony was estimated by use of plant accumulation coefficients (PAC). Seasonal (spring vs. autumn) effects on the antimony content in the plant species. Cytisus striatus from Mari Rosa mine presented antimony excluder characteristics, whereas Dittrichia viscosa specimens growing in San Antonio mine showed a significant antimony bioaccumulation.     

Evaluation of hydrophobicity in PAH-contaminated soils during phytoremediation

The impact of recalcitrant organic compounds on soil hydrophobicity was evaluated in contaminated soil from a manufactured gas plant site following 12 months of phytoremediation. Significant reduction in soil wetting and water retention was observed in contaminated soil compared to an uncontaminated control. Phytoremediation was effective at reducing total PAHs by 69% with corresponding changes in soil classification from extremely hydrophobic (initial sample) to moderately-strongly hydrophobic (planted) and hydrophilic-very hydrophilic (unplanted) after 12 months. The greatest reduction in soil hydrophobicity was observed in the unplanted, unfertilized treatments that had the lowest removal rate of PAHs. The presence of plants may contribute to hydrophobicity in contaminated soil.     

Lichen biomonitoring of ammonia emission and nitrogen deposition around a pig stockfarm

Effects of high ammonia emissions and nitrogen deposition were investigated on lichens around a pig stockfarm (ca. 7,000 animals) in central Italy. Four sites were selected along a transect at 200, 400, 1000 and 2500 m from the stockfarm, the diversity of epiphytic lichens was measured and transplanted thalli of Xanthoria parietina and Flavoparmelia caperata exposed, together with passive NH3 (diffusion tubes) samplers. Ammonia dramatically decreased from the centre of the stockfarm to the sampled sites, where it was correlated with bark pH. Total lichen diversity was not associated with either NH3 concentrations or bark pH, but the diversity of strictly nitrophytic species was highly correlated with both parameters. Physconia grisea was the best indicator species for NH3 pollution. Total N accumulated in X. parietina and F. caperata was correlated with NH3 concentrations.     

Assessment of atmospheric metallic pollution in the metropolitan region of São Paulo, Brazil, employing Tillandsia usneoides L. as biomonitor

Tillandsia usneoides L. is an epiphytic bromeliad plant able to absorb water and nutrients directly from the air. For this reason this species was selected to carry out a monitoring study of air pollution in the metropolitan region of S?o Paulo, Brazil. Five consecutive transplantation experiments (8 weeks each) were performed in 10 sites of the city, submitted to different sources of air pollution (industrial, vehicular), using plants collected from an unpolluted area. After exposure, trace metals were analyzed in the plant by instrumental neutron activation analysis. Traffic-related elements such as Zn and Ba presented high concentrations in exposure sites near to heavy traffic avenues (cars, buses and trucks) and may be associated to vehicular sources. For Zn and Co the highest contents were related to industrial zones and can be associated to the presence of anthropogenic emission sources. The rare earth elements, Fe and Rb, probably have soil particles as main source.