Transport and degradation of toluene and o-xylene in an unsaturated soil with dipping sedimentary layers

A lysimeter trench was established at the Gardermoen delta (50 km north of Oslo, Norway) to study the flow of water and transport and degradation of aromatic jet fuel components (toluene and o-xylene) in the undisturbed unsaturated zone. Site investigations with ground-penetrating radar revealed the presence of dipping sedimentary layers within the foreset unit. This study has shown that the foreset bed of the Gardermoen delta structure provided a preferential flow path for the transport of the solute plumes, but did not have dramatic effects on the degradation potential under the current conditions. The degradation potential for toluene and o-xylene in the unsaturated zone at Gardermoen was very high and almost all of the injected hydrocarbons were biodegraded before reaching the saturated zone. However, the horizontal displacement of the plume showed that knowledge about sedimentary structures in the unsaturated zone is important for a sufficient monitoring of contaminant transport and for remediation purposes. Carbon dioxide and O2 were measured in situ simultaneously with extraction of water samples, and indicated aerobic biodegradation of toluene and o-xylene. Overall, first-order degradation coefficients were calculated to be in the range of 0.19 to 0.21 d(-1) and 0.10 to 0.11 d(-1) for toluene and o-xylene, respectively.     

Column studies on transport of deicing additive benzotriazole in a sandy aquifer and a zerovalent iron barrier

Benzotriazole (BTA), a chemical with wide industrial applications, is a typical additive in deicer/anti-icer used at airport. To achieve a better understanding of the transport behaviour and environmental fate of BTA, laboratory column studies have been performed on subsoil samples from Oslo Airport, Gardermoen. To explore possibilities for aquifer remediation, BTA behaviour was also studied in a column of granular zerovalent iron (Fe(0)). The subsoil column study demonstrates a very limited retardation of BTA. Consecutive loadings of BTA of the subsoil column showed no change of the break-through curve (BTC) and complete desorption was observed. The sorption behaviour of BTA to metallic iron (Fe(0)) was rather complex. Considerable retardation was observed in the Fe(0) column and repeated BTA loading resulted in an earlier break-through. Between 20% and 50% of the input concentration was retained permanently in the iron (Fe(0)) column. The BTA sorption to metallic iron was found to be enhanced by chloride which lowered the break-through concentration (i.e the C/C(0) plateau). The fraction of BTA remaining in the iron column was found to vary with the flow rate, indicating a time dependant multilayer sorption mechanism. The steady increase in the amount of adsorbed BTA to the iron column during loading corresponds to a rather strong bonding of 4-15 BTA layers to the iron surface. A very slow desorption of BTA was observed; even after flushing with 753 pore volumes of BTA free water, 7.5% of the BTA remained in the column. A geochemical model was developed based on PHREEQC-2 to simulate the sorption and transport of BTA in the tested materials. The BTA sorption was modelled with Freundlich sorption isotherms, as earlier determined in batch experiments. A slight adjustment of the Freundlich parameters was required to fit the observed column break-through. However, our model was not able to simulate the long-term retainment of BTA in the granular iron columns. The simulations confirm the high mobility of BTA in groundwater aquifers and suggest that zerovalent iron could be used to retain a BTA plume, although oxidation of the sorbent might reduce the long-term performance of such a remediation scheme and slow desorption has been observed.     

Diffusion of PAH and PCB from contaminated sediments with and without mineral capping; measurement and modelling

A novel laboratory microcosm test was developed to measure the diffusion of native PAHs and PCBs from sediments in the presence and absence of a capping layer. Diffusive flux of 15 PAHs and 7 PCBs from uncapped sediment from Oslo harbour was 3.8+/-0.9 microg m(-2)d(-1) and 0.010+/-0.003 microg m(-2)d(-1), respectively. The flux from sediments capped with 1cm mineral cap (crushed limestone or crushed gneiss (0-2mm)), observed during the first 410 d, was 3.5-7.3% of the flux from uncapped sediments. By measuring freely dissolved pore water concentrations of 10 PAHs the flux in the microcosm was modelled with steady state and transient diffusion models. The measured flux from uncapped sediment was 27-290% of modelled steady state flux. Good agreement was also found between the measured flux of pyrene from capped sediment and the flux modelled with the transient model when fitting only with the distribution coefficients for pyrene between the cap material and water (Kd_pyr). Fitted Kd_pyr, (210 and 23 l kg(-1) for limestone and gneiss, respectively) was in the same order of magnitude as K(d) calculated from organic carbon content in the cap materials (68 and 14 l kg(-1) respectively). Calculation of the efficiency of a hypothetical cap with 10 cm diffusion path shows that the increased diffusion path length alone can yield a flux reduction >99% through a strong increase in the stagnant diffusive boundary layer from <1 to 100mm.     

Metal accumulation in intertidal litter through decomposing leaf blades, sheaths and stems of Phragmites australis

Metal contents of decomposing leaf blades, leaf sheaths and stems of common reed (Phragmites australis) were monitored by a litter bag method on the sediment of an intertidal brackish marsh in the Scheldt estuary (The Netherlands). On monthly intervals, two litter bags were retrieved from the marsh during 9 months for both leaf blades and sheaths and during 16 months for stems. All samples were dried, weighed and analysed for ash and Cd, Cu, Cr, Ni, Pb and Zn contents. Most concentrations increased considerably during the decomposition. Generally, also a very important net metal inflow into the litter bags could be observed. The inflow was highest for leaf blades. High correlations between ash contents and metal concentrations for leaf blades suggest that the increase of leaf blade metal contents can be due to physicochemical sorption of dissolved metals and an important infiltration of mud particles, which were not removed by rinsing the leaf blades with distilled water preceding the analyses. For stems, smaller amounts of inflowing ash and even outflowing ash amounts were found, which suggests that inflow of inorganic particles is not the major factor determining metal accumulation by stems on medium term. Ergosterol concentrations in stem tissue however proved to be correlated with metal contents, which suggests a significant role of fungal litter colonizers in metal accumulation. For leaf sheaths, the effects of physicochemical sorption, infiltration of mud particles and incorporation by microbial litter colonizers do not seem to be as pronounced as for stems and leaf blades.     

Assessment of metal contamination in soil banks of the Rhumel wadi (Northeast Algeria)

Levels of six trace metals were assessed in bank soils of the Rhumel wadi (Northeast Algeria) and their association with soil properties was investigated. Samples were collected at 10 sites. The soils are neutral to moderately alkaline, have high contents of carbonate, and are low in organic carbon and clay. Mean metal concentrations are 1.1 (Cd), 63 (Cr), 20 (Cu), 26 (Ni), 31 (Pb), and 98 (Zn) mg kg^?1. The Cd, Cu, Pb, and Zn contents in soil from sites closest to Constantine City were higher than in uncontaminated soils worldwide, indicating accumulation due to human activities (residential, industrial, and agricultural). Statistical analyses (correlation and principal component analysis) demonstrated that Cd, Pb, and Zn are of anthropogenic origin in the urban areas, whereas Cr and Cu enrichment in some situations is caused by industrial activities, while Ni was geogenic.     

The importance of biological factors affecting trace metal concentration as revealed from accumulation patterns in co-occurring terrestrial invertebrates

As physicochemical properties of the soil highly influence the bioavailable fraction of a particular trace metal, measured metal body burdens in a particular species are often assumed to be more reliable estimators of the contamination of the biota. To test this we compared the Cd, Cu and Zn content of three spiders (generalist predators) and two amphipods (detritivores), co-occurring in seven tidal marshes along the river Schelde, between each other and with the total metal concentrations and the concentrations of four sequential extractions of the soils. Correlations were significant in only one case and significant site x species interactions for all metals demonstrate that factors affecting metal concentration were species and site specific and not solely determined by site specific characteristics. These results emphasize that site and species specific biological factors might be of the utmost importance in determining the contamination of the biota, at least for higher trophic levels. A hypothetical example clarifies these findings.     

Quantification of activated carbon contents in soils and sediments using chemothermal and wet oxidation methods

Activated carbon (AC) strongly sorbs organic pollutants and can be used for remediation of soils and sediments. A method for AC quantification is essential to monitor AC (re)distribution. Since AC is black carbon (BC), two methods for BC quantification were tested for AC mixed in different soils and sediments: i) chemothermal oxidation (CTO) at a range of temperatures and ii) wet-chemical oxidation with a potassium dichromate/sulfuric acid solution. For three soils, the amount of AC was accurately determined by CTO at 375 °C. For two sediments, however, much of the AC disappeared during combustion at 375 °C, which could probably be explained by catalytic effects by sediment constituents. CTO at lower temperatures (325-350 °C) was a feasible alternative for one of the sediments. Wet oxidation effectively functioned for AC quantification in sediments, with almost complete AC recovery (81-92%) and low remaining amounts of native organic carbon (5-16%).     

Passive samplers versus surfactant extraction for the evaluation of PAH availability in sediments with variable levels of contamination

The purpose of this study was to test the efficiency of passive solid samplers, polyoxymethylene (POM) strips and polydimethylsiloxane (PDMS) silicon tubing, to predict the bioavailability of native PAHs in contaminated sediments. Results were compared with worm bioaccumulation data and solid/liquid extraction using the surfactant Brij((R)) 700 (B700). The two passive samplers were found to act differently. The PDMS sampler overestimated the availability of PAHs in all studied sediments. The POM method provided results in accordance with those obtained with the B700 extraction. However, POM and B700 methods underestimated PAH availability in low contaminated sediments where biological factors (digestible organic matter) become important. Bioavailability of total PAHs was correctly predicted by POM and B700 in highly contaminated aluminum smelter sediments. A closer examination of individual PAH results indicated that both techniques overestimated the availability of large molecules with logK(ow)>6 suggesting a biological mechanism limiting uptake of larger PAHs which seems to be related to the molecular size of compounds.     

Effect of submergence-emergence sequence and organic matter or aluminosilicate amendment on metal uptake by woody wetland plant species from contaminated sediments

Site-specific hydrological conditions affect the availability of trace metals for vegetation. In a greenhouse experiment, the effect of submersion on the metal uptake by the wetland plant species Salix cinerea and Populus nigra grown on a contaminated dredged sediment-derived soil and on an uncontaminated soil was evaluated. An upland hydrological regime for the polluted sediment caused elevated Cd concentrations in leaves and cuttings for both species. Emergence and soil oxidation after initial submersion of a polluted sediment resulted in comparable foliar Cd and Zn concentrations for S. cinerea as for the constant upland treatment. The foliar Cd and Zn concentrations were clearly higher than for submerged soils after initial upland conditions. These results point at the importance of submergence-emergence sequence for plant metal availability. The addition of foliar-based organic matter or aluminosilicates to the polluted sediment-derived soil in upland conditions did not decrease Cd and Zn uptake by S. cinerea.     

Adsorption of As(III) versus As(V) from aqueous solutions by cerium-loaded volcanic rocks

Environmental Science and Pollution Research - Contamination of drinking water with arsenic causes severe health problems in various world regions. Arsenic exists predominantly as As(III) and As(V)...