Centrifugal study of zone of influence during air-sparging

Air sparging (AS) is one of the groundwater remediation techniques for remediating volatile organic compounds (VOCs) in saturated soil. However, in spite of the success of air sparging as a remediation technique for the cleanup of contaminated soils, to date, the fundamental mechanisms or the physics of air flow through porous media is not well understood. In this study, centrifugal modeling tests were performed to investigate air flow rates and the evolution of the zone of influence during the air sparging under various g-levels. The test results show that with the increase in sparging pressure the mass flow rate of the air sparging volume increases. The air mass flow rate increases linearly with the effective sparging pressure ratio, which is the difference between sparging pressure and hydrostatic pressure normalized with respect to the effective overburden pressure at the sparging point. Also the slope of mass flow rate with effective sparging pressure ratio increases with higher g-levels. This variation of the slope of mass flow rate of air sparging volume versus effective sparging pressure ratio, M, is linear with g-level confirming that the air flow through soil for a given effective sparging pressure ratio only depends on the g-level. The test results also show that with increasing sparging pressure, the zone of influence (ZOI), which consists of the width at the tip of the cone or lateral intrusion and the cone angle, will lead to an increase in both lateral intrusion and the cone angle. With a further increase in air injection pressure, the cone angle reaches a constant value while the lateral intrusion becomes the main contributor to the enlargement of the ZOI. However, beyond a certain value of effective sparging pressure ratio, there is no further enlargement of the ZOI.     

A survey on the temporal and spatial distribution of perchlorate in the Potomac River

Samples of river water and treated drinking water were obtained from eight sites along the Potomac River between western Maryland and Washington DC. Samples were collected each month from October 2007 to September 2008 and analyzed for perchlorate by ion chromatography/mass spectrometry. Data on anions were also collected for seven of the twelve months. Data were analyzed to identify spatial and temporal patterns for the occurrence of perchlorate in the Potomac. Over the year of sampling, the largest monthly increase occurred from June to July, with levels then decreasing from July to September. Samples from the period between December and May had lower perchlorate concentrations, relative to the remainder of the study year. Spatially, higher levels of perchlorate were found at sites located in west-central Maryland, the eastern panhandle of West Virginia, and central northern Virginia, with levels decreasing slightly as the Potomac approaches Washington DC. Within the sampling boundaries, river (untreated) water perchlorate concentrations ranged from 0.03 μg L(-1) to 7.63 μg L(-1), averaged 0.67 ± 0.97 μg L(-1) over the year-long period and had a median value of 0.37 μg L(-1). There was no evidence that any of the existing drinking water treatment technologies at the sampling sites were effective in removing perchlorate. There were no correlations found between the presence of perchlorate and any of the anions or water quality parameters examined in the source water with the exception of a weak positive correlation with water temperature. Results from the summer (June-August) and fall (September-November) months sampled in this study were generally higher than from the winter and spring months (December-May). All but one of the locations had annual average perchlorate levels below 1 μg L(-1); however, 7 of the 8 sites sampled had river water perchlorate detections over 1 μg L(-1) and 5 of the 8 sites had treated water detections over this level.     

Water and sediment quality of dry season pools in a dryland river system: the upper Leichhardt River, Queensland, Australia

This article presents the geochemical characteristics and physicochemical properties of water and sediment from twelve semi-permanent, dryland pools in the upper Leichhardt River catchment, north-west Queensland, Australia. The pools were examined to better understand the quality of sediments and temporary waters in a dryland system with a well-established metal contamination problem. Water and sediment sampling was conducted at the beginning of the hydroperiod in May and September 2007. Water samples were analyzed for major solute compositions (Ca, Na, K, Mg, Cl, SO(4), HCO(3)) and water-soluble (operationally defined as the <0.45 μm fraction) metals (Cd, Cu, Pb, Zn). Sediment samples were analyzed for total extractable and bioaccessible metals (As, Cd, Cu, Pb, Zn), elemental composition and grain morphology. At the time of sampling a number of pools contained water and sediment with elevated concentrations, compared to Australian regulatory guidelines, of Cu (maximum: water 28 μg L(-1); sediment 770 mg kg(-1)), Pb (maximum: water 3.4 μg L(-1); sediment 630 mg kg(-1)) and Zn (maximum: water 150 μg L(-1); sediment 780 mg kg(-1)). Concentrations of Cd and As in pools were relatively low and generally within Australian regulatory guideline values. Localized factors, such as the interaction of waters with anthropogenic contaminants from modern and historic mine wastes (i.e. residual smelter and slag materials), exert influence on the quality of pool waters. Although the pools of the upper Leichhardt River catchment are contaminated, they do not appear to be the primary repository of water and sediment associated metals when compared to materials in the remainder channel and floodplain. Nevertheless, a precautionary approach should be adopted to mitigating human exposure to contaminated environments, which might include the installation of appropriate warning signs by local health and environmental authorities.     

Hg bioavailability and impact on bacterial communities in a long-term polluted soil

Different soil samples characterised by a long-term Hg-pollution were studied for Hg total content, fractionation, phytotoxicity and influence on the bacterial community. Hg pollution ranged from 1 to 50 mg kg(-1) and most of it was speciated in scarcely soluble forms. In agreement with this, the biochemical quality indexes were investigated (biomass, enzyme activities) and the bacterial community (viable heterotrophic (VH) bacteria, functional diversity) apparently was not influenced by the degree of Hg pollution. In particular, the investigated soils exhibited a low percentage of Hg-resistant (Hg(R)) bacteria ranging from less than 0.001% to 0.25% of the VH and the addition of available Hg in the form of HgCl(2) induced an enrichment of resistant Hg(R) populations. The general biodiversity of the bacterial community was evaluated by denaturing gradient gel electrophoresis of DNA of Hg spiked soil microcosms and of control soils. Hg(R) bacteria capable to grow in a minimal medium containing HgCl(2) were also isolated and identified. MerA and merB gene PCR fragments were obtained from different Hg(R) strains and the range of similarities at the DNA level and at the deduced amino acid level showed that they carried mercuric reductase and lyase. Differently from bacteria, some influence of soil Hg content on seeds' germination and root elongation was observed for Lepidium sativum L. and Solanum lycopersicum L. In conclusion, most of the Hg in these long-term polluted soils was scarcely mobile and available and did not significantly influence the soil bacterial community. The risk of potential Hg remobilization over time, that could be naturally favoured by the activity of plant roots or other inorganic processes occurring in soil, can be extenuated since bacterial community was resistant and resilient to subsequent Hg stress.     

Occurrence and distribution of organophosphorus flame retardants and plasticizers in anthropogenically affected groundwater

Occurrence and distribution of chlorinated and non-chlorinated organophosphates in 72 groundwater samples from Germany under different recharge/infiltration conditions were investigated. Tris(2-chloro-1-methylethyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP) were the most frequently detected organophosphates in groundwater samples. Highest individual organophosphate concentrations (>0.1 μg L(-1)) were determined in groundwater polluted by infiltrating leachate and groundwater recharged via riverbank filtration of organophosphate-loaded recipients. In samples from springs and deep groundwater monitoring wells that are not affected by surface waters, organophosphate concentrations were mostly below the limit of detection. The occurrence (3-9 ng L(-1)) of TCPP and TCEP in samples from aquifers with groundwater ages between 20 and 45 years indicates the persistence of both compounds within the aquifer. At urban sites organophosphate-loaded precipitation, surface runoff, and leakage of wastewater influenced groundwater quality. For rural sites, where groundwater recharge is only influenced by precipitation, organophosphates were very rarely detectable in groundwater.     

Multiple kinetic Langmuir modeling to predict the environmental behaviour of As(v) in soils

A soil with a relatively high Fe content (2.82% [w/w]) was loaded for up to one year with As(v) by equilibrating it with a solution containing 1000 mg l(-1) As(v) at a soil mass-to-solution ratio of 0.1 kg l(-1). The incorporation of As(v) into the soil and its distribution over the soil phases were monitored by sampling at strategic time intervals using an operationally defined five-step sequential extraction procedure (Wenzel et al., Anal. Chim. Acta, 2001, 436, 309) and subsequent As measurement. A multiple kinetic Langmuir model was developed to retrieve the dynamic parameters (adsorption and desorption rate constants, capacities and Langmuir equilibrium constants) for each of the soil phases by numerical fitting of the experimental adsorption data to the model. Under the equilibration conditions used the adsorption rate constants for all five operationally defined soil phases were very similar but the desorption rate constants decreased by a factor of ca. 150 from soil phase 1 (non-specifically sorbed As) to 5 (residual phases). This implies that As(v) incorporation "deeper" into the soil leads to stronger binding which is associated with the Langmuir equilibrium constants (adsorption rate constants/desorption rate constants). Equilibration of the soil with As(v) was complete in ca. 10 days with As(v) predominantly bound to soil phase 2 (specifically sorbed As) and soil phase 3 (amorphous and poorly crystalline hydrous oxides). X-Ray absorption spectroscopy techniques revealed that these binding characteristics may be related to adsorption of As(v) on Si- and/or Al-containing structures and natural hydrous iron oxide (HFO) surface sites, respectively. Since the model is independent of the initial As(v) concentration in the solution and the soil mass-to-solution ratio, the behaviour of the thus characterized soil-As(v) system can be predicted for a range of conditions. Simulations showed that in an accidental As(v) spill the soil studied would actively scavenge As(v) by instantaneous adsorption onto all soil phases followed by redistribution of As(v) from weaker binding sites to stronger ones over time.     

Using condition factor and blood variable biomarkers in fish to assess water quality

The condition factor and blood variables, including erythrocyte lipid peroxidation (LPO) and the activity of antioxidant enzymes such as superoxide dismutase (SOD), catalase (CAT), and glutathione peroxidase (GPx), in two ecologically distinct fish species (Astyanax fasciatus and Pimelodus maculatus) were evaluated at five sites in the Furnas Hydroelectric Power Station reservoir (Brazil) to assess water quality. Aldrin/dieldrin, endosulfan, heptachlor epoxide, and metolachlor were detected at different concentrations in four of the sites. Condition factor was not directly affected by such contaminants. A negative correlation between hematocrit and heptachlor was detected in P. maculatus. Positive correlations between red blood cells and heptachlor as well as an interactive effect of metolachlor and aldrin/dieldrin were detected in A. fasciatus. The erythrocytes of both species collected from the contaminated sites showed high levels of LPO, an increase in SOD and GPx activities and a decrease in CAT activity. Although the leukocyte number and the differential percentage of leukocytes varied among the sites, the hematological variables, the LPO levels, and the antioxidant enzyme activities could be used to assess water quality, regardless of the differences in the responses of the fish species.     

Okadaic acid induces morphological changes, apoptosis and cell cycle alterations in different human cell types

Okadaic acid (OA) is a marine toxin produced by dinoflagellate species which is frequently accumulated in molluscs usual in the human diet. The exact action mechanism of OA has not been described yet and the results of most reported studies are often conflicting. The aim of this work was to evaluate the OA effects on morphology, cell cycle and apoptosis induction by means of light microscopy and flow cytometry, in three different types of human cells (leukocytes, HepG2 cells and SHSY5Y cells). Cells were treated with a range of OA concentrations in the presence and absence of S9 fraction. OA induced morphological changes in all the cell types studied, and cell cycle disruption only in leukocytes and neuronal cells. SHSY5Y cells were the most sensitive to OA assault. Results obtained in the presence and absence of metabolic activation were similar, suggesting that OA acts both directly and indirectly. Furthermore, OA was found to increase the subG(1) region in the flow cytometry cell cycle analysis, suggesting induction of apoptosis. These results were confirmed by the employment of specific methodologies for studying apoptosis such as caspase 3 activation and annexin V staining. Increases in the apoptosis rate were obtained in all the cells treated in the absence of S9 fraction, accompanied by increases in caspase 3 activation, suggesting that apoptosis induced by OA is a caspase 3-dependent process. Nevertheless, in the presence of S9 fraction no apoptosis was detected, indicating a metabolic detoxifying activity, although necrosis was observed in neuroblastoma cells.