Warming and drought change trace element bioaccumulation patterns in a Mediterranean shrubland

A field experiment consisting of drought and warming manipulation was conducted in a Mediterranean shrubland dominated by the shrubs Erica multiflora and Globularia alypum. The aim was to investigate the effects of the climatic changes predicted by IPCC models for the coming decades on trace element concentration and accumulation in aboveground biomass, plant litter, and soil. Warming increased concentrations and aboveground accumulation of some trace elements related to plant root uptake, such as Al, As, Cr, Cu, and partially Pb. This effect was more general in E. multiflora than in G. alypum. The stronger effects were increases in Al leaf concentrations (42%) and aboveground accumulation (500gha(-1)) in E. multiflora, in As stem biomass accumulation (0.2gha(-1)) in E. multiflora, and in Cr leaf concentrations (51%) in G. alypum and stem aboveground accumulation in E. multiflora (1.1gha(-1)). These species-specific increases were related to greater retranslocation, photosynthetic capacity and growth in E. multiflora than in G. alypum. Warming decreased the concentrations of some trace elements in leaf litter, implying the existence of an increased leaf retranslocation. Drought increased As (40%) and Cd (55%) in E. multiflora stems, whereas it decreased Cu (50%) in leaves, Ni (28%) in stems and Pb (32%) in leaf litter of G. alypum. The increasing concentrations of some trace elements in E. multiflora and not in G. alypum were related to a greater growth reduction in E. multiflora than in G. alypum. Warming increased As soil solubility (67%) and decreased total soil As (21%). Those changes were related to a greater Fe mobilization in warming plot and to a greater plant capture. Drought increased Hg (350%) concentrations in soils but had no significant effects on trace element accumulation in aboveground biomass. The different response to warming and drought in the two dominant species implies uneven changes in the quality of the plant tissues that may have implications for herbivores. This may be specially important for the performance of the studied Mediterranean ecosystems under the warmer and drier conditions predicted by the next decades by the GCM and ecophysiological models.     

Comparison of arsenic resistance in Mediterranean woody shrubs used in restoration activities

Myrtus communis, Arbutus unedo and Retama sphaerocarpa are Mediterranean shrubs widely used in revegetation of semiarid degraded soils. The aim of this work is to study the resistance of these plants to arsenic under controlled conditions, in order to evaluate their potential use in revegetation and/or phytoremediation of As-polluted soils. R. sphaerocarpa showed higher resistance to As than M. communis or A. unedo according to its higher EC50, P status and P/As molar ratio in both, roots and shoots, and the lower increases in lipid peroxidation and decrease of chlorophyll levels in response to arsenic, while the highest arsenate sensitivity was obtained for A. unedo. Arsenic was mainly retained in roots, and, although M. communis accumulated higher arsenic amounts than the other two species, R. sphaerocarpa showed the highest root to shoot transfer. Most of the studied parameters (chlorophylls, MDA and total thiols) showed significant correlation with arsenic concentration in roots and leaves of plants, so they can be useful indexes in the diagnosis of arsenic toxicity in these species. According to our results, both M. communis and R. sphaerocarpa could be used in the revegetation of moderately arsenic contaminated sites.     

Removal and degradation of aromatic compounds from a highly polluted site by coupling soil washing with photocatalysis

The possible application of two environmental remediation technologies - soil washing and photocatalysis - to remove and decompose various aromatic pollutants present in excavated soils of a contaminated industrial site has been investigated. Aqueous solutions containing the non-ionic surfactant Brij 35 were used to extract the contaminants from the soil samples. The photocatalytic treatment of the obtained washing wastes, performed in the presence of TiO(2) suspensions irradiated with simulated sunlight, showed a slow abatement of the toxic compounds due to the relevant concentrations of organics in the waste. A neat improvement of the process performances, obtained by operating in the presence of added potassium peroxydisulfate, suggests a feasible treatment route.     

Ozonation of oil sands process water removes naphthenic acids and toxicity

Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): <5% of the initial concentration in the filtered OSPW. Total organic carbon did not change with 130min of ozonation, whereas chemical oxygen demand decreased by approximately 50% and 5-d biochemical oxygen demand increased from an initial value of 2mgl(-1) to a final value of 15mgl(-1). GC-MS analysis showed that ozonation resulted in an overall decrease in the proportion of high molecular weight naphthenic acids (n> or = 22).     

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.     

Leaf accumulation of trace elements and polycyclic aromatic hydrocarbons (PAHs) in Quercus ilex L

Quercus ilex L. leaves were collected four times in one year at six urban sites and one remote area in order to determine trace element and PAH accumulation through concomitant analyses of unwashed and water-washed leaves. Both unwashed and washed leaves showed the highest amounts of trace elements and PAHs in the urban area. Unwashed leaves showed greater differences between urban and remote areas and among the urban sites than washed leaves for trace element and PAH concentrations. Water-washing resulted in a significant (P<0.001) decrease in leaf concentrations of Cr, Cu, Fe, Pb, V and Zn. By contrast, Cd and total PAH concentrations showed no differences between unwashed and washed leaves.     

Short- and medium-term effects of experimental nitrogen fertilization on arthropods associated with Calluna vulgaris heathlands in north-west Spain

We studied the short- and medium-term effects of experimental nitrogen fertilization (3 and 15 months after the treatment) on the arthropods of Calluna vulgaris heathlands in NW Spain. Three heathland sites were selected with two permanent plots per site: control and fertilized. Ammonium nitrate fertilizer (56 kg N ha(-1) yr(-1)) was applied monthly and insects were caught using pitfall traps. We found mainly species-level responses to nitrogen addition. Seven species (e.g. Lochmaea suturalis) showed a consistent trend (benefited or harmed) in both periods and were proposed as possible reliable indicators of the effects of nitrogen deposition in these ecosystems. We also found variable arthropod trophic-group responses: (a) herbivores (leaf beetles, true bugs) increased in abundance on a short-term scale; (b) predators (carabid beetles, true bugs) showed opposite and less clear responses in both periods. Further long-term studies are needed to determine the mechanisms underlying the observed arthropod responses.     

Comparison of in-house-developed ELISA with HPLC techniques for the analysis of atrazine residues

In-house developed ELISA was standardized to monitor atrazine residues in different environmental samples. The standard curve was linear, indicating an increase in log concentration with decrease in absorbance (%B/B(0)=1.075-0.042 Log C; r= -0.966). The middle of the test was at 75 ng/L and the lowest detection limit at 4 ng/L. ELISA significantly correlated with the high performance liquid chromatography (HPLC) (r=0.990). Internal validation showed good accuracy and precision. Maximum atrazine residues were present in Jehlum River water/sediments and maize/sugarcane plant roots. Most of the food samples were found to be contaminated. ELISA required less clean-up steps than HPLC, but showed matrix effect in soil/colored extracts.     

Trends in snowpack chemistry and comparison to National Atmospheric Deposition Program results for the Rocky Mountains, US, 1993–2004

Seasonal snowpack chemistry data from the Rocky Mountain region of the US was examined to identify long-term trends in concentration and chemical deposition in snow and in snow-water equivalent. For the period 1993–2004, comparisons of trends were made between 54 Rocky Mountain Snowpack sites and 16 National Atmospheric Deposition Program wetfall sites located nearby in the region. The region was divided into three subregions: Northern, Central, and Southern. A non-parametric correlation method known as the Regional Kendall Test was used. This technique collectively computed the slope, direction, and probability of trend for several sites at once in each of the Northern, Central, and Southern Rockies subregions. Seasonal Kendall tests were used to evaluate trends at individual sites.Significant trends occurred during the period in wetfall and snowpack concentrations and deposition, and in precipitation. For the comparison, trends in concentrations of ammonium, nitrate, and sulfate for the two networks were in fair agreement. In several cases, increases in ammonium and nitrate concentrations, and decreases in sulfate concentrations for both wetfall and snowpack were consistent in the three subregions. However, deposition patterns between wetfall and snowpack more often were opposite, particularly for ammonium and nitrate. Decreases in ammonium and nitrate deposition in wetfall in the central and southern rockies subregions mostly were moderately significant (p<0.11) in constrast to highly significant increases in snowpack (p<0.02). These opposite trends likely are explained by different rates of declining precipitation during the recent drought (1999–2004) and increasing concentration. Furthermore, dry deposition was an important factor in total deposition of nitrogen in the region. Sulfate deposition decreased with moderate to high significance in all three subregions in both wetfall and snowpack. Precipitation trends consistently were downward and significant for wetfall, snowpack, and snow-telemetry data for the central and southern rockies subregions (p<0.03), while no trends were noted for the Northern Rockies subregion.     

Characterizing effects of uncertainties in MSW composting process through a coupled fuzzy vertex and factorial-analysis approach

A coupled fuzzy vertex and factorial-analysis approach was developed in this study for systematically characterizing effects of uncertainties in a municipal solid waste composting process. A comprehensive composting process model was also embedded into the system framework and used to address substrate decomposition and biomass growth, as well as the interactions between moisture contents, temperatures, and oxygen concentrations. The applicability of the proposed method was verified through a custom-made pilot-scale composting system. Results from fuzzy simulation indicated that the fuzzy vertex method could effectively communicate implicit knowledge into dynamic simulations and thus provide valuable information for enhancing composting process control under uncertainty. The factorial analysis was effective in quantifying the proportion to which the uncertainty of each single or interactive effect of model parameters contributes to the overall uncertainty of the system outcomes. Thus, sensitive parameters that may lead to errors or unreasonable predictions can be determined. The proposed study system could not only be used in characterizing combined effects of uncertainties for composting processes, but was also applicable to many other environmental modelling systems.