Source characterization of atmospheric heavy metals in industrial/residential areas: a case study in Oman

Total suspended particulate matter (TSP) was collected from two districts: the Sohar industrial estate (SIE) and a residential area in the case study area in Oman. The TSP collected from SIE was taken from 19 different industrial activities, whereas those collected from the residential area were taken from 12 houses. The samples were analyzed for nine heavy metals: chromium (Cr), copper (Cu), manganese (Mn), nickel, lead (Pb), zinc (Zn), cadmium, vanadium, and molybdenum. The results were used to assess the source classes responsible for TSP and heavy metal levels in the atmosphere of the two districts. At each district, principal component analysis was applied to the concentrations of TSP and heavy metals to obtain the number of principal components. At SIE, three groups of elements were determined. The first component contained large factor loadings in Cu and Mn (Cu industrial processes and reinforcement steel production). The second presented most of the variance of Cr, Pb, and Zn (black and galvanized iron pipes production, mechanical industries, and vehicle construction). The third component was composed of Zn and Pb that probably reflected contributions from motor-vehicle tire wear or was associated with municipal incineration. On the other hand, results from the village showed that only one factor was able to explain the main part of the data variance, and the industrial site was polluting air quality in the village with Cu, Cr, Pb, nickel, and Mn.     

Atmospheric lead deposition to Okefenokee Swamp, Georgia, USA

Contamination of the environment from atmospheric deposition during the twentieth century is pervasive even in areas ostensibly considered pristine or remote from point sources. In this study, Pb concentrations in a 210Pb-dated peat core collected from the Okefenokee Swamp, GA were used to assess historical contaminant input via atmospheric deposition. Lead isotope ratios were determined by dynamic reaction cell ICP-MS (DRC-ICP-MS). Increases in Pb concentration occurred in the late nineteenth century and a marked rise in Pb concentrations pre-dated the widespread use of leaded gasoline within the US. The 206Pb/207Pb ratios of 1.19 during this period were consistent with coal combustion emissions. A later increase in Pb concentration, concurrent with a trend toward more radiogenic 206Pb/207Pb ratios in gasoline is consistent with an increased input of Pb from leaded gasoline emissions. However, it appears that coal combustion emissions remain a major source of Pb to the Okefenokee.     

The effect of EDTA and citric acid on phytoremediation of Cd, Cr, and Ni from soil using Helianthus annuus

The possibility to clean heavy metal contaminated soils with hyperaccumulator plants has shown great potential. One of the most recently studied species used in phytoremediation applications are sunflowers. In this study, two cultivars of Helianthus annuus were used in conjunction with ethylene diamine tetracetic acid (EDTA) and citric acid (CA) as chelators. Two different concentrations of the chelators were studied for enhancing the uptake and translocation of Cd, Cr, and Ni from a silty-clay loam soil. When 1.0 g/kg CA was used, the highest total metal uptake was only 0.65 mg. Increasing the CA concentration posed a severe phytotoxicity to both cultivars as evidenced by stunted growth and diminished uptake rates. Decreasing the CA concentration to 0.1 and 0.3 g/kg yielded results that were not statistically different from the control. EDTA at a concentration of 0.1 g/kg yielded the best results for both cultivars achieving a total metal uptake of approximately 0.73 mg compared to approximately 0.40 mg when EDTA was present at 0.3 g/kg.     

Electrochemical decolourisation of structurally different dyes

The electrochemical decolourisation of structurally different dyes (bromophenol blue, indigo, poly R-478, phenol red, methyl orange, fuchsin, methyl green and crystal violet) by means of the application of DC electric current was assessed. It was found that the electrochemical process allowed a colour removal of all dyes studied, although the decolourisation rate largely depended on the chemical structure of the different dyes. Nearly complete decolourisation was achieved for bromophenol blue followed by methyl orange and methyl green, whereas phenol red was hardly decolourised (30% in 60 min). In mixtures of two dyes, the decolourisation rate became similar for both dyes. However, the addition of a redox mediator, (Co(2+/3+)) clearly enhanced the degradation rate of all tested dyes, but the simplest dye molecules were attacked firstly, followed by dyes with more complex chemical structures. The results revealed the suitability of the process to effectively decolourise wastewaters from dyeing process.     

A PCE groundwater plume discharging to a river: influence of the streambed and near-river zone on contaminant distributions

An investigation of a tetrachloroethene (PCE) groundwater plume originating at a dry cleaning facility on a sand aquifer and discharging to a river showed that the near-river zone strongly modified the distribution, concentration, and composition of the plume prior to discharging into the surface water. The plume, streambed concentration, and hydrogeology were extensively characterized using the Waterloo profiler, mini-profiler, conventional and driveable multilevel samplers (MLS), Ground Penetrating Radar (GPR) surveys, streambed temperature mapping (to identify discharge zones), drivepoint piezometers, and soil coring and testing. The plume observed in the shallow streambed deposits was significantly different from what would have been predicted based on the characteristics of the upgradient plume. Spatial and temporal variations in the plume entering the near-river zone contributed to the complex contaminant distribution observed in the streambed where concentrations varied by factors of 100 to 5000 over lateral distances of less than 1 to 3.5 m. Low hydraulic conductivity semi-confining deposits and geological heterogeneities at depth below the streambed controlled the pattern of groundwater discharge through the streambed and influenced where the plume discharged into the river (even causing the plume to spread out over the full width of the streambed at some locations). The most important effect of the near-river zone on the plume was the extensive anaerobic biodegradation that occurred in the top 2.5 m of the streambed, even though essentially no biodegradation of the PCE plume was observed in the upgradient aquifer. Approximately 54% of the area of the plume in the streambed consisted solely of PCE transformation products, primarily cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC). High concentrations in the interstitial water of the streambed did not correspond to high groundwater-discharge zones, but instead occurred in low discharge zones and are likely sorbed or retarded remnants of past high-concentration plume discharges. The high-concentration areas (up to 5529 microg/l of total volatile organics) in the streambed are of ecological concern and represent potential adverse exposure locations for benthic and hyporheic zone aquatic life, but the effect of these exposures on the overall health of the river has yet to be determined. Even if the upgradient source of PCE is remediated and additional PCE is prevented from reaching the streambed, the high-concentration deposits in the streambed will likely take decades to hundreds of years to flush completely clean under natural conditions because these areas have low vertical groundwater flow velocities and high retardation factors. Despite high concentrations of contaminants in the streambed, PCE was detected in the surface water only rarely due to rapid dilution in the river and no cDCE or VC was detected. Neither the sampling of surface water nor the sampling of the groundwater from the aquifer immediately adjacent to the river gave an accurate indication of the high concentrations of PCE biodegradation products present in the streambed. Sampling of the interstitial water of the shallow streambed deposits is necessary to accurately characterize the nature of plumes discharging to rivers.     

The uptake of uranium by Eleocharis dulcis (Chinese water chestnut) in the Ranger Uranium Mine constructed wetland filter

Eleocharis dulcis has proliferated in a constructed wetland used to treat uranium mine runoff water, where it rapidly accumulates significant quantities of uranium (U) in its roots and relatively little in its stems. We investigated the mechanism of U uptake and accumulation by E. dulcis using field-sampling techniques and microcosm test work. Results from the microcosm trials and outcomes from statistical tests of field sampled macrophyte, water and sediment indicate that the primary source of U for E. dulcis is the water column. Basipetal translocation of U to the plant's roots was indicated by significant correlations between the U content of stems, taproots and rhizomes and XPS detection of U inside root segments. U sequestering from sediment interstitial water by Fe hydroxides on root surfaces was also evident. No basipetal translocation was evident following the 28-day duration of the microcosm experiments, indicating that it is a longer-term process.     

Sorption and oxic degradation of the explosive CL-20 during transport in subsurface sediments

The abiotic sorption and oxic degradation processes that control the fate of the explosive CL-20, Hexanitrohexaazaisowurtzitane, in the subsurface environment were investigated to determine the potential for vadose and groundwater contamination. Sorption of aqueous CL-20 is relatively small (K(d) = 0.02-3.83 cm3 g(-1) for 7 sediments and 12 minerals), which results in only slight retardation relative to water movement. Thus, CL-20 could move quickly through unsaturated and saturated sediments of comparable composition to groundwater, similar to the subsurface behavior of RDX. CL-20 sorption was mainly to mineral surfaces of the sediments, and the resulting isotherm was nonlinear. CL-20 abiotically degrades in oxic environments at slow rates (i.e., 10s to 100s of hours) with a wide variety of minerals, but at fast rates (i.e., minutes) in the presence of 2:1 phyllosilicate clays (hectorite, montmorillonite, nontronite), micas (biotite, illite), and specific oxides (MnO2 and the ferrous-ferric iron oxide magnetite). High concentrations of surface ferrous iron in a dithionite reduced sediment degraded CL-20 the fastest (half-life < 0.05 h), but 2:1 clays containing no structural or adsorbed ferrous iron (hectorite) could also quickly degrade CL-20 (half-life < 0.2 h). CL-20 degradation rates were slower in natural sediments (half-life 3-800 h) compared to minerals. Sediments with slow degradation rates and small sorption would exhibit the highest potential for deep subsurface migration. Products of CL-20 oxic degradation included three high molecular weight compounds and anions (nitrite and formate). The 2-3.5 moles of nitrite produced suggest CL-20 nitro-groups are degraded, and the amount of formate produced (0.2-1.2 moles) suggests the CL-20 cage structure is broken in some sediments. Identification of further degradation products and CL-20 mineralization rates is needed to fully assess the impact of these CL-20 transformation rates on the risk of CL-20 (and degradation product) subsurface movement.     

Monitoring of toxicity during degradation of selected pesticides using ionizing radiation

The optimization of experimental conditions for radiolytic removal of organic pollutants from water and waste with the use of ionizing radiation via controlling the concentration of target compound(s) requires also monitoring the toxicity changes during the process. Commonly used herbicides 2,4-D and dicamba were shown to increase toxicity measured with the Microtox test at low irradiation doses resulting from formation of more toxic transient products, which can be decomposed at larger doses. The changes of toxicity were examined with respect to dose magnitude and the presence of commonly occurring scavengers of radiation.     

Occurrence and abatement of volatile sulfur compounds during biogas production

Volatile sulfur compounds (VSCs) in biogas originating from a biogas production plant and from a municipal sewage water treatment plant were identified. Samples were taken at various stages of the biogas-producing process, including upgrading the gas to vehicle-fuel quality. Solid-phase microextraction was used for preconcentration of the VSCs, which were subsequently analyzed using gas chromatography in combination with mass spectrometry. Other volatile organic compounds present also were identified. The most commonly occurring VSCs in the biogas were hydrogen sulfide, carbonyl sulfide, methanethiol, dimethyl sulfide, and dimethyl disulfide, and hydrogen sulfide was not always the most abundant sulfur (S) compound. Besides VSCs, oxygenated organic compounds were commonly present (e.g., ketones, alcohols, and esters). The effect of adding iron chloride to the biogas reactor on the occurrence of VSCs also was investigated. It was found that additions of 500-g/m3 substrate gave an optimal removal of VSCs. Also, the use of a prefermentation step could reduce the amount of VSCs formed in the biogas process. Moreover, in the carbon dioxide scrubber used for upgrading the gas, VSCs were removed efficiently, leaving traces (ppbv levels). The scrubber also removed other organic compounds.     

Growth response to ozone of annual species from Mediterranean pastures

Ozone (O3) phytotoxicity has been reported on a wide range of plant species. However, scarce information has been provided regarding the sensitivity of semi-natural grassland species, especially those from dehesa Mediterranean grasslands, in spite of their great biological diversity and the high O3 levels recorded in the region. A screening study was carried out in open-top chambers (OTCs) to assess the O3-sensitivity of representative therophytes of these ecosystems based on the response of selected growth-related parameters. Three O3 treatments and 3 OTCs per treatment were used. Legume species were very sensitive to O3, because 78% of the tested species showed detrimental effects on their total biomass relative growth rate (RGR) following their exposure to O3. The Trifolium genus was particularly sensitive showing O3-induced adverse effects on most of the assessed parameters. Gramineae plants were less sensitive than Leguminosae species because detrimental effects on total biomass RGR were only observed in 14% of the assessed species. No relationship was found between relative growth rates when growing in clean air and O3 susceptibility. The implications of these effects on the performance of dehesa acidic grasslands and on the definition of ozone critical levels for the protection of semi-natural vegetation are discussed.