Long-term column experiments were conducted to evaluate the effects of secondary carbonate minerals on permeability and reactivity of commercial granular iron treating trichloroethene (TCE). The ...results showed that carbonate precipitates caused a decrease in reactivity of the iron, and spatially and temporally varying reactivity loss resulted in migration of mineral precipitation fronts, as well as profiles of TCE, pH, alkalinity, calcium, and dissolved iron. In the columns receiving solutions of dissolved calcium carbonate, porosity gradually decreased in proportion to the source concentrations, as carbonate minerals accumulated. However, the rate of porosity loss slowed over time because of the declining reactivity of the iron. Thus, secondary minerals are not likely to accumulate to the extent that there is a substantial reduction in hydraulic conductivity. The reactivity of the iron was found to decrease as an exponential function of the carbonate mineral volume fraction. This changing reactivity of iron should be incorporated into predictive models for improved designs of iron permeable reactive barriers (PRBs).
•Industrial sludge with high As content was treated by composting and vermicomposting.•The volume of compost decreased, which led to an increase in total As content.•The labile arsenic fraction was ...significantly decreased.•AsV was the predominant arsenic species formed.•The mobile fraction was not directly related to bioavailability to earthworms.
Composting and vermicomposting are traditional processes for the treatment of sludge. During these processes, the humification of organic matter has a significant effect on the physicochemical form and distribution of heavy metals. In this study, industrial sludge (groundwater treatment waste) contaminated by arsenic (396±1mgkg−1) was used. Such sludge poses a significant challenge with respect to effective treatment. Composting, vermicomposting (with Eisenia fetida), and the combined approach of composting and vermicomposting were performed to determine the evolution of arsenic speciation, mobility and bioavailability. The composting/vermicomposting was done with sludge, horse manure, and grass in the ratios of 3:6:1. A solution of 0.1M NH4COOCH3 was used as a single extraction solvent for determination of the mobile arsenic pool and targeted arsenic species (AsIII, AsV, monomethylarsenic acid – MMAV, dimethylarsenic acid – DMAV). The analysis of arsenic in the extracts was carried out by means of HPLC–ICP-MS spectrometry. In addition, the earthworm species E. fetida was used for bioaccumulation tests that followed the compost and vermicompost processes. The obtained results indicate a reduction in arsenic mobility and bioavailability in all matured composts and vermicomposts. The combined process exhibited a greater effect than compost or vermicompost alone.
The iron oxide-catalyzed production of hydroxyl radical (•OH) from hydrogen peroxide (H2O2) has been used to oxidize organic contaminants in soils and groundwater. The goals of this study are to ...determine which factors control the generation rate of •OH (V OH) and to show that if V OH and the rate constants of the reactions of •OH with the system's constituents are known, the oxidation rate of a dissolved organic compound can be predicted. Using 14C-labeled formic acid as a probe, we measured V OH in pH 4 slurries of H2O2 and either synthesized ferrihydrite, goethite, or hematite or a natural iron oxide-coated quartzitic aquifer sand. In all of our experiments, V OH was proportional to the product of the concentrations of surface area of the iron oxide and H2O2, although different solids produced •OH at different rates. We used these results to develop a model of the decomposition rate of formic acid as a function of the initial formic acid and hydrogen peroxide concentrations and of the type and quantity of iron oxide. Our model successfully predicted the V OH and organic compound oxidation rates observed in our aquifer sand experiment and in a number of other studies but overpredicted V OH and oxidation rates in other cases, possibly indicating that unknown reactants are either interfering with •OH production or consuming •OH in these systems.
By using life cycle assessment (LCA) modeling, this paper compares the environmental performance of six landfilling technologies (open dump, conventional landfill with flares, conventional landfill ...with energy recovery, standard bioreactor landfill, flushing bioreactor landfill and semi-aerobic landfill) and assesses the influence of the active operations practiced on these performances. The environmental assessments have been performed by means of the LCA-based tool EASEWASTE, whereby the functional unit utilized for the LCA is “landfilling of 1
ton of wet household waste in a 10
m deep landfill for 100 years”. The assessment criteria include standard categories (global warming, nutrient enrichment, ozone depletion, photo-chemical ozone formation and acidification), toxicity-related categories (human toxicity and ecotoxicity) and impact on spoiled groundwater resources.
Results demonstrate that it is crucially important to ensure the highest collection efficiency of landfill gas and leachate since a poor capture compromises the overall environmental performance. Once gas and leachate are collected and treated, the potential impacts in the standard environmental categories and on spoiled groundwater resources significantly decrease, although at the same time specific emissions from gas treatment lead to increased impact potentials in the toxicity-related categories. Gas utilization for energy recovery leads to saved emissions and avoided impact potentials in several environmental categories. Measures should be taken to prevent leachate infiltration to groundwater and it is essential to collect and treat the generated leachate.
The bioreactor technologies recirculate the collected leachate to enhance the waste degradation process. This allows the gas collection period to be reduced from 40 to 15 years, although it does not lead to noticeable environmental benefits when considering a 100 years LCA-perspective. In order to more comprehensively understand the influence of the active operations (i.e., leachate recirculation, waste flushing and air injection) on the environmental performance, the time horizon of the assessment has been split into two time periods: years 0–15 and 16–100. Results show that if these operations are combined with gas utilization and leachate treatment, they are able to shorten the time frame that emissions lead to environmental impacts of concern.
Statistical techniques can be used in groundwater pollution problems to determine the relationships among observed contamination (impacted wells representing an occurrence of what has to be ...predicted), environmental factors that may influence it and the potential contamination sources. Determination of a threshold concentration to discriminate between impacted or non impacted wells represents a key issue in the application of these techniques. In this work the effects on groundwater vulnerability assessment by statistical methods due to the use of different threshold values have been evaluated. The study area (Province of Milan, northern Italy) is about 2000 km
2 and groundwater nitrate concentration is constantly monitored by a net of about 300 wells. Along with different predictor factors three different threshold values of nitrate concentration have been considered to perform the vulnerability assessment of the shallow unconfined aquifer. The likelihood ratio model has been chosen to analyze the spatial distribution of the vulnerable areas. The reliability of the three final vulnerability maps has been tested showing that all maps identify a general positive trend relating mean nitrate concentration in the wells and vulnerability classes the same wells belong to. Then using the kappa coefficient the influence of the different threshold values has been evaluated comparing the spatial distribution of the resulting vulnerability classes in each map. The use of different threshold does not determine different vulnerability assessment if results are analyzed on a broad scale, even if the smaller threshold value gives the poorest performance in terms of reliability. On the contrary, the spatial distribution of a detailed vulnerability assessment is strongly influenced by the selected threshold used to identify the occurrences, suggesting that there is a strong relationship among the number of identified occurrences, the scale of the maps representing the predictor factors and the model efficiency in discriminating different vulnerable areas.
Factors controlling arsenic (As) mobilization in the aquifers of the Río Dulce alluvial cone were investigated. Groundwater analyses show severe As contamination (average concentration of 743 μg/L) ...from geogenic sources, but spatial variability of As concentration is considerable. Sequential leaching of sediment samples from unsaturated zone using de-ionised water, bicarbonate, acetate, and oxalate extracted As to different extents. Sediment oxalate extraction showed that Al and Mn oxide and hydroxides are more abundant than Fe oxides and hydroxides, in spite of similar total Fe, Mn, and Al concentrations in the sediment. Speciation calculations performed for saturated zone samples indicated that Fe and Al oxides and hydroxides are stable in groundwater, suggesting that As adsorption processes may be to some extent controlled by the presence of Fe and Al mineral phases. Principal Component Analysis (PCA) showed that As is related to F, V, Mo, B, Si, most likely due to their common origin in volcanic ash. This suggests the volcanic ash as the probable source of groundwater As. Locally, elevated pH values linked to carbonate dissolution, cation exchange, and dissolution of silicates promote release of adsorbed As. Another factor contributing to the release of As locally may be the input of organic matter from excessive irrigation. The conceptual model of As release includes: i) As influx from dissolution of volcanic glass in volcanic ash, ii) adsorption of As on the surface of Fe and Al mineral phases in relatively low pH zones, and iii) high mobility of As in high pH zones. Future work should be focused on the determination of mineralogical forms of As in volcanic ash and on detailed investigation on factors controlling As mobility.
A daunting challenge facing the water industry and regulators is how to simultaneously control microbial pathogens, residual disinfectant, and disinfection byproducts in drinking water, and to do so ...at an acceptable cost. Of the different pathogens, viruses are especially problematic due to their small size, high mobility, and resistance to chlorination and filtration. In the past decade, zerovalent iron has been used to treat a wide variety of organic and inorganic contaminants from groundwater. However, iron has not been tested against biological agents. This study examined the effectiveness of commercial zerovalent iron to remove two viruses, φX174 and MS-2, from water. Removal of these viruses by iron granules in batch reactors was first-order, and the rate was likely controlled by external mass transfer. Most of the viruses removed from solution were either inactivated or irreversibly adsorbed to iron. In a flow-through column containing zerovalent iron (with 20 min of iron contact time), the removal efficiency for both viruses was 4-log in an initial pulse test, and over 5-log in the second pulse test after passage of 320 pore volumes of artificial groundwater. We assume that the improved efficiency was due to continuous formation of new iron (oxyhydr)oxides which served as virus adsorption sites. To our knowledge, this is the first demonstration of biological agent removal from water by zerovalent iron. Results of this study suggest zerovalent iron may be potentially useful for disinfecting drinking water and wastewater, thereby reducing our dependence on chlorine and reducing the formation of disinfection byproducts.
Iron-reducing conditions in subsurface environments promote dechlorination reactions via both biotic and abiotic pathways, the latter often mediated via biologically activated minerals formed by ...dissimilatory iron-reducing bacteria (DIRB). Here we report the major products and pathways associated with the abiotic transformation of carbon tetrachloride (CT) by nanoscale biogenic magnetite/maghemite particles produced by the DIRB Geobacter metallireducens. Product formation and free radical/carbene trapping studies indicate that CT transformation occurs via three parallel pathways. The first pathway (hydrogenolysis) results in the formation of chloroform (45−50%) via a trichloromethyl free radical (·CCl3) and possibly a trichloromethyl carbanion (:CCl3 -). The second and third pathways involve a dichlorocarbene intermediate (:CCl2), which either hydrolyzes to form CO (∼38%) (carbene hydrolysis), or undergoes further reduction to yield methane (8−10%) (carbene reduction). The mechanism of methane formation from :CCl2 is not known, but is speculated to involve a sequence of surface coordinated carbenoid and free radical complexes. The large fraction of relatively benign products formed by the carbene-mediated pathways suggests that magnetite/maghemite particles may have a beneficial application in the remediation of CT contaminated environments.
To perform a general assessment of treatment efficiency, a mass balance study was undertaken for two types of constructed wetlands (CWs), planted gravel filters and plant root mat systems, for ...treating VOC (benzene; MTBE) polluted groundwater under field conditions. Contaminant fate was investigated in the respective water, plant, and atmosphere compartments by determining water and atmospheric contaminant loads and calculating contaminant plant uptake, thereby allowing for an extended efficiency assessment of CWs. Highest total VOC removal was achieved during summer, being pronounced for benzene compared to MTBE. According to the experimental results and the calculations generated by the balancing model, degradation in the rhizosphere and plant uptake accounted for the main benzene removal processes, of 76% and 13% for the gravel bed CW and 83% and 11% for the root mat system. Volatilization flux of benzene and MTBE was low (<5%) for the gravel bed CW, while in the root mat system direct contact of aqueous and gaseous phases favored total MTBE volatilization (24%). With this applied approach, we present detailed contaminant mass balances that allow for conclusive quantitative estimation of contaminant elimination and distribution processes (e.g., total, surface, and phytovolatilization, plant uptake, rhizodegradation) in CWs under field conditions.
