Biosurfactant technology for remediation of cadmium and lead contaminated soils

This research focuses on column experiments conducted to evaluate the potential of environmentally compatible rhamnolipid biosurfactant produced by Pseudomonas aeruginosa strain BS2 to remove heavy metals (Cd and Pb) from artificially contaminated soil. Results have shown that di-rhamnolipid removes not only the leachable or available fraction of Cd and Pb but also the bound metals as compared to tap water which removed the mobile fraction only. Washing of contaminated soil with tap water revealed that approximately 2.7% of Cd and 9.8% of Pb in contaminated soil was in freely available or weakly bound forms whereas washing with rhamnolipid removed 92% of Cd and 88% of Pb after 36 h of leaching. This indicated that di-rhamnolipid selectively favours mobilization of metals in the order of Cd>Pb. Biosurfactant specificity observed towards specific metal will help in preferential elution of specific contaminant using di-rhamnolipid. It was further observed that pH of the leachates collected from heavy metal contaminated soil column treated with di-rhamnolipid solution was low (6.60-6.78) as compared to that of leachates from heavy metal contaminated soil column treated with tap water (pH 6.90-7.25), which showed high dissolution of metal species from the contaminated soil and effective leaching of metals with treatment with biosurfactant. The microbial population of the contaminated soil was increased after removal of metals by biosurfactant indicating the decrease of toxicity of metals to soil microflora. This study shows that biosurfactant technology can be an effective and nondestructive method for bioremediation of cadmium and lead contaminated soil.     

Effect of chelating agents and solubility of cadmium complexes on uptake from soil by Brassica juncea

Brassica juncea, or Indian mustard, was grown in soil artificially contaminated with either a soluble salt, CdCl(2), at 186mg Cdkg(-1), or alternately an insoluble, basic salt, CdCO(3), at 90mg Cdkg(-1). These experiments study the range of Cd uptake by Indian mustard from conditions of very high Cd concentration in a soluble form to the other extreme with an insoluble Cd salt. After plants were established, four different chelating agents were applied. Chelating agents increased plant uptake of Cd from the CdCl(2) soil but did not significantly increase plant uptake of Cd from the CdCO(3) contaminated soil. Addition of ethylenediaminetetraacetic acid (EDTA) increased the plant concentration of Cd by almost 10-fold in soils contaminated with CdCl(2), with a concentration of 1283mg Cdkg(-1) in the dried EDTA-treated plants over a concentration of 131mg Cdkg(-1) in plants without added chelate. However, EDTA increased the aqueous solubility of Cd by 36 times over the soil matrix without added chelator, and thereby, increased the possibility of leaching. Other chelators used in both experiments were ethylenebis(oxyethylenenitrilo)tetraacetic acid, trans-1,2-diaminocyclohexane-N,N,N',N'-tetraacetic acid, and diethylenetriaminepentaacetic acid (DTPA) increasing Cd in plants to 1240, 962, and 437mg Cdkg(-1), respectively. The other chelating agents increased the solubility of Cd in the leachate but not to the extent of EDTA. Comparing all chelating agents studied, DTPA increased plant uptake in terms of Cd in dried plant concentration most relative to the solubility of complexed Cd in runoff water.     

Estimates of ambient background concentrations of trace metals in soils for risk assessment

Site-specific or soil type-specific ambient background concentrations (ABCs) of trace metals in soils are needed for risk assessment. We investigated three different methods for estimating ABCs in soils using a dataset of 5691 soil samples from England and Wales. The concentrations of Co, Cr and Ni were strongly associated with Al and Fe, and multiple regressions explained 62-85% of their variation, and Al and Fe can therefore be used to predict ABCs for these metals. Soil texture had a major influence on the concentrations of Cd, Co, Cr, Cu, Ni and Zn, and the medians were 3-5 fold higher in clayey than in sandy soils. This was used to predict texture-specific ABCs. Lead concentration was higher in acidic peaty soils than in other soils. A probability graph method was used to estimate ABC for Pb in a population of relatively uncontaminated soils. Potential applications of ABCs are discussed.     

Use of (15)N-labelled nitrogen deposition to quantify the source of nitrogen in runoff at a coniferous-forested catchment at Gårdsjön, Sweden

To determine the source of dissolved inorganic nitrogen (N) in runoff, approx. 35kg N enriched with the stable isotope (15)N (2110 per thousand delta(15)N) was added to a mature coniferous forested catchment for one whole year. The total N input was approx. 50kg ha(-1) year(-1). The enrichment study was part of a long-term whole-catchment ammonium nitrate addition experiment at G?rdsj?n, Sweden. The (15)N concentrations in precipitation, throughfall, runoff and upper forest floor were measured prior to, during, and 3-9years following the (15)N addition. During the year of the (15)N addition the delta(15)N level in runoff largely reflected the level in incoming N, indicating that the leached NO(3)(-) came predominantly from precipitation. Only 1.1% of the incoming N was lost during the year of the tracer addition. The cumulative loss of tracer N over a 10-year period was only 3.9% as DIN and 1.1% as DON.     

Challenges in quantifying biosphere-atmosphere exchange of nitrogen species

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N(2) fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N(2)O, NO and bi-directional NH(3) exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols.     

Geochemical fractions of copper in soil chronosequences of selected European floodplains

The influence of soil formation on copper sorption is documented based on chronosequences of soils from three river floodplains in Europe (Danube, Ebro and Elbe). Sequential extraction was used to fractionate copper in original and spiked soils in order to study the long-term and short-term behaviour of copper retention. Copper partitioning among defined geochemical fractions was mainly determined by soil pH and the contents of carbonates, organic matter and Fe-/Mn-oxides and hydroxides. Copper extracted with NH(2)OH.HCl correlated well with the contents of crystalline Fe-oxides and hydroxides, demonstrating increasing retention capacity with progressing soil development. Copper retained in original soils was found in more strongly bound fractions, whereas sorption of freshly added copper was primarily influenced by the presence of carbonates. Beyond the effect of progressing soil formation, variations in organic carbon contents due to different land use history affected the copper retention capacity of the investigated soils.     

Effects of flow regime and flooding on heavy metal availability in sediment and soil of a dynamic river system

The acid volatile sulphide (AVS) and simultaneously extracted metals (SigmaSEM) method is increasingly used for risk assessment of toxic metals. In this study, we assessed spatial and temporal variations of AVS and SigmaSEM in river sediments and floodplain soils, addressing influence of flow regime and flooding. Slow-flowing sites contained high organic matter and clay content, leading to anoxic conditions, and subsequent AVS formation and binding of metals. Seasonality affected these processes through temperature and oxygen concentration, leading to increased levels of AVS in summer at slow-flowing sites (max. 37micromolg(-1)). In contrast, fast-flowing sites hardly contained AVS, so that seasonality had no influence on these sites. Floodplain soils showed an opposite AVS seasonality because of preferential inundation and concomitant AVS formation in winter (max. 3-30micromolg(-1)). We conclude that in dynamic river systems, flow velocity is the key to understanding variability of AVS and SigmaSEM.     

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.     

Seasonal Variation of Toxic Benzene Emissions in Petroleum Refinery

Petroleum refineries are largest chemical industries that are responsible for the emission of several pollutants into the atmosphere. Benzene is among the most important air pollutants that are emitted by petroleum refineries, since they are involved in almost every refinery process. Volatile organic compounds (VOCs) are a major group of air pollutants, which play a critical role in atmospheric chemistry. These contribute to toxic oxidants, which are harmful to ecosystem, human health and atmosphere. The variability of pollutants is an important factor in determining human exposure to these chemicals. The ambient air concentrations of benzene were measured in several sites around the Digboi petroleum refinery, near the city of Gowahati in northeast India, during winter and summer 2004. The seasonal and spatial variations of the ambient air concentrations of this benzene were investigated and analyzed. An estimation of the contribution of the refinery to the measured atmospheric levels of benzene was also performed. The ambient air mixing ratios of benzene in a large area outside the refinery was generally low, in ppbv range, much lower than the ambient air quality standards. This article presents the temporal and spatial variation of air pollution in and around petroleum refinery and showed that no health risk due to benzene is present in the areas adjacent to the refinery.     

Suspended Particulate Matter Distribution in Rural-Industrial Satna and in Urban-Industrial South Delhi

An air quality sampling program was designed and implemented to collect the baseline concentrations of respirable suspended particulates (RSP = PM₁₀), non-respirable suspended particulates (NRSP) and fine suspended particulates (FSP = PM_2.5). Over a three-week period, a 24-h average concentrations were calculated from the samples collected at an industrial site in Southern Delhi and compared to datasets collected in Satna by Envirotech Limited, Okhla, Delhi in order to establish the characteristic difference in emission patterns. PM_2.5, PM₁₀, and total suspended particulates (TSP) concentrations at Satna were 20.5 ± 6.0, 102.1 ± 41.1, and 387.6 ± 222.4 μg m⁻³ and at Delhi were 126.7 ± 28.6, 268.6 ± 39.1, and 687.7 ± 117.4 μg m⁻³. Values at Delhi were well above the standard limit for 24-h PM_2.5 United States National Ambient Air Quality Standards (USNAAQS; 65 μg m⁻³), while values at Satna were under the standard limit. Results were compared with various worldwide studies. These comparisons suggest an immediate need for the promulgation of new PM_2.5 standards. The position of PM₁₀ in Delhi is drastic and needs an immediate attention. PM₁₀ levels at Delhi were also well above the standard limit for 24-h PM₁₀ National Ambient Air Quality Standards (NAAQS; 150 μg m⁻³), while levels at Satna remained under the standard limit. PM_2.5/PM₁₀ values were also calculated to determine PM_2.5 contribution. At Satna, PM_2.5 contribution to PM₁₀ was only 20% compared to 47% in Delhi. TSP values at Delhi were well above, while TSP values at Satna were under, the standard limit for 24-h TSP NAAQS (500 μg m⁻³). At Satna, the PM₁₀ contribution to TSP was only 26% compared to 39% in Delhi. The correlation between PM₁₀, PM_2.5, and TSP were also calculated in order to gain an insight to their sources. Both in Satna and in Delhi, none of the sources was dominant a varied pattern of emissions was obtained, showing the presence of heterogeneous emission density and that nonrespirable suspended particulate (NRSP) formed the greatest part of the particulate load.