Assessment of chemical, biochemical and ecotoxicological aspects in a mine soil amended with sludge of either urban or industrial origin

A greenhouse pot experiment was conducted to evaluate the effect of sewage sludge (SS), of sugar beet sludge (SBS), or of a combination of both, in the remediation of a highly acidic (pH 3.6) metal-contaminated soil, affected by mining activities. The SS was applied at 100 and 200 Mg ha(-1) (dry weight basis), and the SBS at 7 Mg ha(-1). All pots were sown with Italian ryegrass (Lolium multiflorum Lam.). After 60 d of growth, shoot biomass was quantified and analysed for Cu, Pb and Zn. The pseudo-total and bioavailable contents of Cu, Pb and Zn and the enzymatic activities of beta-glucosidase, acid phosphatase, cellulase, protease and urease were determined in the soil mixtures. Two indirect acute bioassays with leachates from the soil (luminescent inhibition of Vibrio fischeri and Daphnia magna immobilization) were also used. The SS, in particular when in combination with SBS, corrected soil acidity, while increasing the total organic matter content and the cation exchange capacity. The application of SS led to a decrease in the level of effective bioavailable metals (extracted by 0.01 M CaCl(2), pH 5.7, without buffer), but caused an increase in their potential bioavailability (extracted by a solution of 0.5M NH(4)CH(3)COO, 0.5 M CH(3)COOH and 0.01 M EDTA, pH 4.7). Plant biomass increased more than 10 times in the presence of 100 Mg SS ha(-1), and more than five times with the combined use of 100 Mg SS ha(-1) and SBS, but a considerable phytotoxic effect was observed for the application rate of 200 Mg SS ha(-1). Copper, Pb and Zn concentrations in the shoots of L. multiflorum decreased significantly when using 100 Mg SS ha(-1) or SBS. The activities of beta-glucosidase, urease and protease increased with increasing SS applications rates, but cellulase had a reduced activity when using 200 Mg ha(-1)SS. Both amendments were able to suppress soil toxicity to levels that did not affect D. magna, but increased the soil leachate toxicity towards V. fischeri, especially with the application of 200 Mg SS ha(-1). This study showed that for this type of mine soils, and when using SS of similar composition, the maximum SS application rate should be 100 Mg ha(-1), and that liming the SS amended soil with SBS did not contribute to a further improvement in soil quality.     

Levels and trends of HBCD and BDEs in the European and Asian environments, with some information for other BFRs

In this paper, we review recent data for brominated flame retardants (particularly BDEs, HBCD and TBBP-A) in samples from the European and Asian environments, including recent temporal trend studies. Research is active and we cite over 100 studies published during 2005-2007. Environmental compartments studied comprise the atmosphere, indoor and outdoor air, sewage sludges, soils and sediments and a variety of biological samples and food chains. Findings include that the lack of reference materials for use in analytical quality control and method validation identified earlier has been addressed, and certified concentrations are now available for a number of BDE congeners in six pre-existing and one new reference materials. BDE209 was certified in three samples of indoor dust. The analysis of BDE209 remains problematic, but suitable methods for its determination are available and need to be applied. The contamination of indoor environments with BFRs has been recognised as representing a significant uptake pathway, particularly via dust. Additional data for TBBP-A are needed from areas, where it is produced and used, primarily Asia, as the worst-case scenario. As a reactive flame retardant it is less likely to leach from finished products. Also, issues regarding the importance of e-waste recycling as a source of BFRs to the local populations and the local environment require urgent study, certainly in China and possibly elsewhere. Generally, trends show a levelling in concentrations of BDEs and increases in concentrations of HBCD wherever determined and BDE209 in Asia.     

Influence of gas flow-induced shear stress on the operation of the Anammox process in a SBR

The start up and performance of the Anammox process were tested in sequencing batch reactors with two different configurations: a bubble column (SBR-B) and a gas-lift reactor (SBR-G). Different off-gas upflow velocities were tested (3.53-12.3 cm min(-1)) in order to expose the biomass to different shear conditions and to study their effects on both efficiency and physical properties of the Anammox granular biomass. For the SBR-B the minimum gas upflow velocity needed to achieve biomass suspension inside the reactor was 12.3 cm min(-1). Such velocity made impossible the stable operation of the process. The fluidization of biomass for the SBR-G was reached at a gas upflow velocity of 3.52 cm min(-1). This system maintained an efficiency of nitrite removal around 98% at values up to 5.29 cm min(-1) but when the gas upflow velocity was increased from 5.29 to 9.70 cm min(-1) a significant decrease of the specific Anammox activity of the biomass from 0.35 to 0.05 g Ng(-1) VSS d(-1) was measured. The system lost 85% of its nitrogen removal efficiency which was not restored in spite of returning the gas upflow velocity to its initial value.     

Chloramphenicol influence on antioxidant enzymes with preliminary approach on microsomal CYP1A immunopositive-protein in Chamelea gallina

Chloramphenicol (CA) is a largely used antibiotic and it is an inhibitor of protein synthesis that also induces ROS production. In this work there were investigated activities and expressions in the Adriatic bivalve Chamelea gallina of some antioxidant and detoxification proteins like superoxide dismutase (Mn-SOD, Cu/Zn-SOD), catalase (CAT) and Cytochrome P450 (CYP1A). Clams exposed to 5mgl(-1) of chloramphenicol were sampled 2, 4 and 8 days after treatment (CA2, CA4 and CA8). SODs, CAT, and CYP1A activity and/or expression were detected in pooled digestive glands by Western blotting and by spectrophotometrical analysis. Enzymes activities increase during the entire antibiotic exposure. With respect to the control Cu/Zn-SOD expression increases, while Mn-SOD expression decreases significantly after 4 days. Two CYP1A immunopositive-proteins (57.7 and 59.8kDa) were detected. The lower band significantly decreases in CA8, the upper one also in CA4 condition. High levels of Mn-SOD, CAT activity and Cu/Zn-SOD expression, indicate intense ROS production while Mn-SOD expression inhibition might be ascribable to mitochondrial alterations due to CA and indirectly to ROS. CYP1A1 action determines H(2)O(2) production that would contribute to a CYP1A1 gene promoter down regulation, a response to oxidative stress with the antioxidant enzymes activation as a final result. This study highlights the close association, in C. gallina, in presence of chloramphenicol, between SOD/CAT and CYP system, and it appear particularly interesting to the lack of similar researches on mollusc species.     

Synthesis and analytical follow-up of the mineralization of a new fluorosurfactant prototype

Fluorinated surfactants have become essential in numerous technical applications due to their unparalleled effectiveness and efficiency. The environmental persistence of the non-biodegradable perfluorinated alkyl moiety has become a matter of concern. Therefore, it was searched for new molecules with chemically stable fluorinated end groups which can be microbially transformed into labile fluorinated substances. One prototype substance, 10-(trifluoromethoxy)decane-1-sulfonate, has shown biomineralization. Monitoring the formation of metabolites over time elucidated the mechanism of biotransformation. Analysis was performed utilizing liquid chromatography-single quadrupole mass spectrometry (LC-MS) and quadrupole-time of flight tandem mass spectrometry (QqTOF-MS). It was possible to distinguish between two major degradation pathways of the fluorinated alkylsulfonate derivative: (i) a desulfonation and subsequent oxidation and degradation of the alkyl chain being predominant and (ii) an insertion of oxygen with a subsequent cleavage and degradation of the molecule. The utilized trifluoromethoxy-endgroup resulted in instable trifluoromethanol after degradation of the alkyl chain, which led to a high degree of mineralization of the molecule.     

Treatment of PAHs in contaminated soil by extraction with aqueous DNA followed by biodegradation with a pure culture of Sphingomonas sp

The biodegradation of polycyclic aromatic hydrocarbons (PAHs) in aqueous deoxyribonucleic acid (DNA) solution from contaminated soil washing was investigated. Initial data with a model effluent consisting of anthracene, phenanthrene, pyrene and benzo[a]pyrene that were individually dissolved in 1% aqueous DNA solution confirmed their positive degradation by Sphingomonas sp. at around 10(8)CFU mL(-1) initial cell loading. For anthracene and phenanthrene, complete removal was achieved within 1h treatment. Degradation of pyrene and benzo[a]pyrene took a relatively longer time of a few days and weeks, respectively. DNA-dissolved PAHs were also degraded relatively faster than PAH crystals in aqueous medium to suggest that the binding of the PAHs in the polymer does not pose serious constraint to bacterial uptake. The DNA was stable against the PAH-degrading bacteria. Parallel experiments with actual DNA solutions obtained during pyrene extraction from an artificially spiked soil also showed similar results. Close to 100% pyrene degradation was achieved after 1d treatment. With its chemical stability, the cell-treated DNA was re-used up to four cycles without a considerable decline in extraction performance.     

Chloride leaching from air pollution control residues solidified using ground granulated blast furnace slag

Ground granulated blast furnace slag (ggbs) has been used to solidify air pollution control (APC) residues obtained from a major UK energy-from-waste plant. Samples were prepared with ggbs additions between 10 and 50 wt% of total dry mass and water/solids ratios between 0.35 and 0.80. Consistence, setting time, compressive strength and leaching characteristics have been investigated. Results indicated that the highly alkaline nature of APC residues due to the presence of free lime can be used to activate ggbs hydration reactions. Increasing ggbs additions and reducing the water content resulted in increased compressive strengths, with 50 wt% ggbs samples having average 28 d strengths of 20.6 MPa. Leaching tests indicate low physical encapsulation and minimal chemical fixation of chloride in ggbs solidified APC residues. The results suggest that more than 50 wt% ggbs additions would be required to treat APC residues to meet the current waste acceptance criteria limits for chloride.     

Increased thyroid volume, prevalence of thyroid antibodies and impaired fasting glucose in young adults from organochlorine cocktail polluted area: outcome of transgenerational transmission?

In 137 females (F) and 94 males (M) aged 21-35 years from organochlorines (OCs) polluted area (POLL) increased thyroid volume (ThV), prevalence of antibodies to thyroperoxidase (TPOab), thyrotropin receptor (TRab) and of impaired fasting glucose (IFG) was found compared to 116 F and 107 M from background pollution area (BCGR). In F and M from POLL also strikingly increased level of PCBs, DDE and HCB was found. Such findings were compared to the generation of their parents aged 41-55 years consisting of 320F/213M from POLL and 406F/231M from BCGR. However, in spite of strikingly lower level of those OCs in young adults from POLL, they showed about the same prevalence of adverse health signs as the old generation. From such reason 44 young F and 40 young M with lowest PCBs level from POLL were selected to obtain nearly the same PCB level as found in all young F and M from BCGR. In such PCB adjusted groups the prevalence of TPOab, TRab, IFG and increased ThV was still significantly higher than that in all young subjects from BCGR. At the same time, also the level of DDE and HCB in such PCBs adjusted groups was considerably lower. It was concluded that such adverse effects in young adults from POLL possibly did not result from their actual OCs levels, but very likely from their exposure to high OCs levels of their mothers during their prenatal and perinatal life. Thus, the data may be compatible with present views on transgenerational transmission of endocrine disruptors action.     

Combustion characteristics of Malaysian municipal solid waste and predictions of air flow in a rotary kiln incinerator

Malaysia is in dire need of alternatives to landfilling for solid waste management. Recently, landfills have faced the problems of overfilling, overflowing of leachates leading to pollution of water resources, and uncontrolled dust emissions adversely affecting the local environment. With the rising cost of urbanization coupled with the high rate of waste generation, one possible method of waste treatment that is receiving particular attention by the government is incineration. Incineration of solid waste is rather new in Malaysia, with limited usage in handling small sources of waste generation such as the municipal solid waste (MSW) of resort islands; however, its potential in ameliorating the problems associated with solid waste treatment may make it an attractive alternative to landfill. This article presents the results of test runs conducted to investigate the performance of a locally designed and manufactured rotary kiln incinerator (RKI). The test runs were conducted using MSW collected from the Shah Alam municipality. The combustion efficiency was analyzed by looking at the temperature profiles and chemical species concentrations. To complement the combustion characteristics measurements, predictions of the air flow in the incinerator during the process were also investigated. The overall performance of the RKI suggests that it is suitable for treating MSW.     

The greenhouse gas balance of the Province of Siena

There is a profound debate over how to assign greenhouse gas (GHG) responsibilities; therefore, we have decided to follow IPCC guidelines, as they offer the only standardized method. We have identified each type of greenhouse emission and its level of absorption. We have studied the province and its districts and municipalities. We have determined that the energy sector is that with the highest level of emissions, even if the per capita emissions of the Province of Siena are very low. This is caused by a very low level of industrialization and the presence of a local geothermal production of energy. In order to highlight this aspect, we have considered scenarios both with and without geothermal production. Our research was then focused on single districts (groups of homogenous municipalities) and municipalities, where we found great differences among the greenhouse emissions of the areas. We have constructed a map of the greenhouse emissions of the whole province. It has been interesting to note that there are 14 municipalities with net negative emissions, seven with low positive emissions, 12 with medium positive emissions and three with elevated positive emissions. These latter correspond to the main city and to two of the most industrialized municipalities.