Effect of some heavy metals and soil humic substances on the phytochelatin production in wild plants from silver mine areas of Guanajuato, Mexico

Phytochelatins (PCs) were determined in the wild plants, focusing on their relationship with the levels of heavy metals and humic substances (HS) in soil. Ricinus communis and Tithonia diversifolia were collected from several sites in Guanajuato city (Mexico), which had long been the silver and gold mining center. The analysis of PCs in root extracts was carried out by liquid chromatography (derivatization with monobromobimane). Total Ag, Cd, Cu and Pb in plant roots and in soil samples, as well as soil HS were determined. The association of metals with HS in soils was evaluated by size exclusion chromatography (SEC) with UV and ICP-MS detection. The results obtained revealed the induction of PCs in R. communis but not in T. diversifolia. The levels of Cd and Pb in plant roots presented strong positive correlation with PC-2 (r = 0.9395, p = 0.005; r = 0.9573, p = 0.003, respectively), indicating that these two metals promote PCs induction in R. communis. On the other hand, the inverse correlation was found between soil HS and metal levels in roots of R. communis (Cu > Pb > Cd > Ag), in agreement with the decreasing affinity of these metals to HS. Importantly, the inverse correlation between soil HS and plant PC-2 was observed (r = −0.7825, p = 0.066). These results suggest that metals strongly bound to HS could be less bioavailable to plants, which in turn would limit their role in the induction of PCs. Indeed, the SEC elution profiles showed Pb but not Cd association with HS and the correlation between metal in soil and PC-2 in plant was statistically significant only for Cd (r = 0.7857, p = 0.064). Based on these results it is proposed that the role of heavy metals in PCs induction would depend on their uptake by R. communis, which apparently is controlled by the association of metals with soil HS. This work provides further evidence on the role of environmental conditions in the accumulation of heavy metals and phytochelatin production in plants.     

Emissions tradeoffs among alternative marine fuels: total fuel cycle analysis of residual oil, marine gas oil, and marine diesel oil

Worldwide concerns about sulfur oxide (SOx) emissions from ships are motivating the replacement of marine residual oil (RO) with cleaner, lower-sulfur fuels, such as marine gas oil (MGO) and marine diesel oil (MDO). Vessel operators can use MGO and MDO directly or blended with RO to achieve environmental and economic objectives. Although expected to be much cleaner in terms of criteria pollutants, these fuels require additional energy in the upstream stages of the fuel cycle (i.e., fuel processing and refining), and thus raise questions about the net impacts on greenhouse gas emissions (primarily carbon dioxide [CO2]) because of production and use. This paper applies the Total Energy and Environmental Analysis for Marine Systems (TEAMS) model to conduct a total fuel cycle analysis of RO, MGO, MDO, and associated blends for a typical container ship. MGO and MDO blends achieve significant (70-85%) SOx emissions reductions compared with RO across a range of fuel quality and refining efficiency assumptions. We estimate CO2 increases of less than 1% using best estimates of fuel quality and refinery efficiency parameters and demonstrate how these results vary based on parameter assumptions. Our analysis suggests that product refining efficiency influences the CO2 tradeoff more than differences in the physical and energy parameters of the alternative fuels, suggesting that modest increases in CO2 could be offset by efficiency improvements at some refineries. Our results help resolve conflicting estimates of greenhouse gas tradeoffs associated with fuel switching and other emissions control policies.     

In situ assay with the midge Kiefferulus calligaster for contamination evaluation in aquatic agro-systems in central Thailand

The aims of this study were to verify the suitability of in situ tests using the tropical midge Kiefferulus calligaster and to evaluate the most sensitive endpoint for the assessment of aquatic pesticide contamination. In situ tests were carried out in freshwater drainage channels (farm channels) that supply vegetable crops and receive considerable pesticide spray drift, and at channels outside farms (main channels). Moreover a pesticide-free farm was used as reference site. The endpoints analysed were: survival of the larvae, body length increment, capsule width increment, cholinesterase activity and glutathione S-transferase activity. Seasonal change was investigated as rainy season and dry season. Deleterious effects were observed at some farms especially during the rainy season when farmers apply heavier doses of pesticides. However, high mortality rates observed in main channels suggest that these water bodies are also affected by other impacts besides pesticide use. This work shows the potential of the in situ assay with K. calligaster as a tool for the environmental quality assessment of tropical aquatic ecosystems.     

An enzyme-linked immunosorbent assay for the determination of dioxins in contaminated sediment and soil samples

A 96-microwell enzyme-linked immunosorbent assay (ELISA) method was evaluated to determine PCDDs/PCDFs in sediment and soil samples from an EPA Superfund site. Samples were prepared and analyzed by both the ELISA and a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. Comparable method precision, accuracy, and detection level (8 ng kg(-1)) were achieved by the ELISA method with respect to GC/HRMS. However, the extraction and cleanup method developed for the ELISA requires refinement for the soil type that yielded a waxy residue after sample processing. Four types of statistical analyses (Pearson correlation coefficient, paired t-test, nonparametric tests, and McNemar's test of association) were performed to determine whether the two methods produced statistically different results. The log-transformed ELISA-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin values and log-transformed GC/HRMS-derived TEQ values were significantly correlated (r=0.79) at the 0.05 level. The median difference in values between ELISA and GC/HRMS was not significant at the 0.05 level. Low false negative and false positive rates (<10%) were observed for the ELISA when compared to the GC/HRMS at 1,000 ng TEQ kg(-1). The findings suggest that immunochemical technology could be a complementary monitoring tool for determining concentrations at the 1,000 ng TEQ kg(-1) action level for contaminated sediment and soil. The ELISA could also be used in an analytical triage approach to screen and rank samples prior to instrumental analysis.     

Implications of urine-to-feces ratio in the thermophilic anaerobic digestion of swine waste.

Thermophilic anaerobic digestion of swine manure represents a potential waste treatment technology to address environmental concerns, such as odor emissions and removal of pathogenic microorganisms. However, there are concerns relative to the stability of this process when swine manure is the sole substrate. In this study, the potential of biogas production from swine manure as the sole substrate under thermophilic (50 degrees C) conditions was investigated in the laboratory, to determine whether separation of urine and feces as part of the waste collection process would benefit anaerobic digestion. Effluent from a continuously stirred tank reactor was used as the inoculum for batch tests, in which the substrate contained three different concentrations of urine (urine-free, as-excreted urine-to-feces ratio and double the as-excreted urine-to-feces ratio). Inocula were acclimated to these same urine-to-feces ratios to determine methane production. Results show that both urine-free and as-excreted substrates were not inhibitory to anaerobic inocula. Anaerobic microorganisms can be readily acclimated to substrate with double the as-excreted urine concentration, which contained nitrogen concentrations up to 7.20 g/L. Cumulative methane production reached similar levels in the batch tests, regardless of the substrate urine concentration.     

Electrolytic debromination of PBDEs in DE-83 technical decabromodiphenyl ether

Electrochemical debromination of the commercial decabromodiphenyl ether flame retardant DE-83 in partly aqueous tetrahydrofuran (THF) solution gave lower brominated congeners by sequential loss of bromine atoms. Hydrodebromination was most facile for the most heavily brominated congeners. It involves initial electron transfer and proton transfer from water, rather than hydrogen atom abstraction from THF, as shown by experiments with deuterated water. The product distribution from electrolysis involves preferential loss of bromine meta- and para- to the ether linkage, comparable with the products of metabolism of BDE-209 in various organisms. Significantly, the environmentally relevant congeners BDE-47, BDE-99, and BDE-154 were not major products of debromination of BDE-209 by the electron transfer mechanism.     

Changes in sewage sludge carbon forms along a treatment stream

The behaviour and fate of macronutrients and pollutants in sewage sludge applied to the land are affected by the chemical composition of the sludge organic matter, which in turn is influenced by both sewage source and by sewage treatment processes. In this study, (13)C nuclear magnetic resonance (NMR) spectroscopy was used to characterise the organic matter of sludges collected at three different points along the treatment stream of a municipal sewage works with a domestic catchment. Sludge at the first point, an undigested liquid (UL) sludge, had a substantially different composition to the anaerobically digested (AD) and dewatered sludge cake (DC) materials, which were similar to each other. In particular, the UL sludge contained more alkyl C than the AD or DC sludges. All three sludges were found to contain mobile alkyl C that is poorly observed using the cross polarisation (CP) technique, necessitating the use of the less sensitive, but more quantitatively reliable direct polarisation (DP) technique to obtain accurate distributions of C types.     

Conditioning of aluminium-based water treatment sludge with Fenton's reagent: effectiveness and optimising study to improve dewaterability

Alternative conditioning of aluminium-based drinking water treatment sludge using Fenton reagent (Fe2+/H2O2) was examined in this study. Focuses were placed on effectiveness and factors to affect such novel application of Fenton process. Experiments have demonstrated that considerable improvement of alum sludge dewaterability evaluated by capillary suction time (CST) can be obtained at the relative low concentrations of Fenton reagent. A Box-Behnken experimental design based on the response surface methodology was applied to evaluate the optimum of the influencing variables, i.e. iron concentration, hydrogen peroxide concentration and pH. The optimal values for Fe2+, H2O2, and pH are 21 mg g(-1)DS(-1)(dry solids), 105 mg g(-1)DS(-1) and 6, respectively, at which the CST reduction efficiency of 48+/-3% can be achieved, this agreed with that predicted by an established polynomial model in this study.     

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.     

Separating the effects of organic matter-mineral interactions and organic matter chemistry on the sorption of diuron and phenanthrene

Even though it is well established that soil C content is the primary determinant of the sorption affinity of soils for non-ionic compounds, it is also clear that organic carbon-normalized sorption coefficients (K(OC)) vary considerably between soils. Two factors that may contribute to K(OC) variability are variations in organic matter chemistry between soils and interactions between organic matter and soil minerals. Here, we quantify these effects for two non-ionic sorbates-diuron and phenanthrene. The effect of organic matter-mineral interactions were evaluated by comparing K(OC) for demineralized (HF-treated) soils, with K(OC) for the corresponding whole soils. For diuron and phenanthrene, average ratios of K(OC) of the HF-treated soils to K(OC) of the whole soils were 2.5 and 2.3, respectively, indicating a substantial depression of K(OC) due to the presence of minerals in the whole soils. The effect of organic matter chemistry was determined by correlating K(OC) against distributions of C types determined using solid-state (13)C NMR spectroscopy. For diuron, K(OC) was positively correlated with aryl C and negatively correlated with O-alkyl C, for both whole and HF-treated soils, whereas for phenanthrene, these correlations were only present for the HF-treated soils. We suggest that the lack of a clear effect of organic matter chemistry on whole soil K(OC) for phenanthrene is due to an over-riding influence of organic matter-mineral interactions in this case. This hypothesis is supported by a correlation between the increase in K(OC) on HF-treatment and the soil clay content for phenanthrene, but not for diuron.