A side-by-side comparison of bioaugmentation, biostimulation, and a recirculation-only control was implemented in a chloroethene-contaminated aquifer. The objective was to develop a contaminant mass balance based on the analysis of groundwater and aquifer solids and to quantify key dechlorinating populations during treatment to determine their relation to the rate of chloroethenes removed. The bioaugmentation strategy, using a Dehalococcoides-containing PCE-to-ethene dechlorinating inoculum enriched from the same aquifer, resulted in a nearstoichiometric dechlorination of both sorbed and dissolved chloroethenes to ethene within 6 weeks. In the biostimulation plot, continuous lactate and nutrient injection resulted in dechlorination but only following a 3-month lag period. Molecular tools targeting the 16S rRNA genes of Dehalococcoides and Desulfuromonas spp. were used to qualitatively monitor the distribution and quantitatively (Real-Time PCR) measure the abundance of the dechlorinating populations during the test. In the bioaugmentation plot, Dehalococcoides populations increased 3-4 orders of magnitude throughout the test area. Dehalococcoides populations also increased in the biostimulation plot but at a slower rate and immediately before the onset of rapid dechlorination. Terminal Restriction Fragment Length Polymorphism analysis indicated that the inoculum only impacted the bioaugmentation plot. This work extends the knowledge gained from previous field studies which reported qualitative relationships between the occurrence of Dehalococcoides populations and ethene production. Furthermore, the results demonstrate that bioreactive barriers capitalizing on reductively dechlorinating populations to control the migration of chloroethene plumes can be effectively designed once hydrologic information is incorporated.

Green (vegetated) roofs have gained global acceptance as a technologythat has the potential to help mitigate the multifaceted, complex environmental problems of urban centers. While policies that encourage green roofs exist atthe local and regional level, installation costs remain at a premium and deter investment in this technology. The objective of this paper is to quantitatively integrate the range of stormwater, energy, and air pollution benefits of green roofs into an economic model that captures the building-specific scale. Currently, green roofs are primarily valued on increased roof longevity, reduced stormwater runoff, and decreased building energy consumption. Proper valuation of these benefits can reduce the present value of a green roof if investors look beyond the upfront capital costs. Net present value (NPV) analysis comparing a conventional roof system to an extensive green roof system demonstrates that at the end of the green roof lifetime the NPV for the green roof is between 20.3 and 25.2% less than the NPV for the conventional roof over 40 years. The additional upfront investment is recovered at the time when a conventional roof would be replaced. Increasing evidence suggests that green roofs may play a significant role in urban air quality improvement For example, uptake of N0x is estimated to range from $1683 to $6383 per metric ton of NOx reduction. These benefits were included in this study, and results translate to an annual benefit of $895-3392 for a 2000 square meter vegetated roof. Improved air quality leads to a mean NPV for the green roof that is 24.5-40.2% less than the mean conventional roof NPV. Through innovative policies, the inclusion of air pollution mitigation and the reduction of municipal stormwater infrastructure costs in economic valuation of environmental benefits of green roofs can reduce the cost gap that currently hinders U.S. investment in green roof technology.

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.

Contributions of biotic (cell-mediated) and abiotic (mineral-mediated) reactions to carbon tetrachloride (CT) transformation were studied in a model iron-reducing system that used hydrous ferric oxide (HFO) as the electron acceptor, acetate as the substrate, and Geobacter metallireducens as a representative dissimilative iron-reducing bacteria (DIRB). Over a period of 2-3 weeks, nanoscale magnetite particles, Fe3O4, were consistently formed as a product of iron respiration in this system. CT transformation rates were measured independently in resting cell suspensions of G. metallireducens or in suspensions of washed magnetite particles recovered from spent cultures. Protein and surface area-normalized expressions were derived for the biotic and abiotic reaction rates, respectively. Using the yield of total protein and magnetite surface area formed during growth in the model system as a basis for comparison, the mineral-mediated (abiotic) reaction was estimated to be 60-260-fold faster than the biotic reaction throughout the incubation period. We conclude that G. metallireducens induces CT transformation in this system primarily through the formation of reactive mineral surfaces rather than via co-metabolic mechanisms. The findings indicate that reactive biogenic minerals could play a significant role in the natural attenuation of chlorinated solvents in iron-reducing environments. A novel approach for stimulating reductive transformation of contaminants may be to enhance the formation of reactive biogenic minerals in situ.

Measurements of oxidation−reduction potential (E h) and concentrations of dissolved hydrogen (H2) were made in a shallow groundwater system contaminated with solvents and jet fuel to delineate the zonation of redox processes. E h measurements ranged from +69 to −158 mV in a cross section of the contaminated plume and accurately delineated oxic from anoxic groundwater. Plotting measured E h and pH values on an equilibrium stability diagram indicated that Fe(III) reduction was the predominant redox process in the anoxic zone and did not indicate the presence of methanogenesis and sulfate reduction. In contrast, measurements of H2 concentrations indicated that methanogenesis predominated in heavily contaminated sediments near the water table surface (H2 ∼ 7.0 nM) and that the methanogenic zone was surrounded by distinct sulfate-reducing (H2 ∼ 1−4 nM) and Fe(III)-reducing (H2 ∼ 0.1−0.8 nM) zones. The presence of methanogenesis, sulfate reduction, and Fe(III) reduction was confirmed by the distribution of dissolved oxygen, sulfate, Fe(II), and methane in groundwater. These results show that H2 concentrations were more useful for identifying anoxic redox processes than E h measurements in this groundwater system. However, H2-based redox zone delineations are more reliable when H2 concentrations are interpreted in the context of electron-acceptor (oxygen, nitrate, sulfate) availability and the presence of final products [Fe(II), sulfide, methane] of microbial metabolism.

The ability of a microbial consortium eluted from dioxin-contaminated Passaic River sediments to dechlorinate polychlorinated dibenzo-p-dioxins (PCDDs) was investigated under methanogenic conditions. Aged 2,3,7,8-tetraCDD, which had partitioned into the microbial consortium from sediments, was stoichiometrically converted to tri-and monoCDD congeners. During dechlorination, dominant microbial activity within the consortium shifted from methanogenic to nonmethanogenic activity. Freshly spiked octaCDD was converted to hepta-, hexa-, penta-, tetra-, tri-, di-, and monochlorinated isomers, but the reaction stoichiometry was not determined. No methanogenic activity was observed, and the maximum yield of protein coincided with the production of less-chlorinated DD congeners. Two distinct pathways of dechlorination were observed: the peri-dechlorination pathway of 2,3,7,8-substituted hepta-to pentaCDDs, resulting in the production of 2,3,7,8-tetraCDD, and the peri-lateral dechlorination pathway of non-2,3,7,8-substituted congeners. Direct evidence of further lateral dechlorination of 2,3,7,8-tetraCDD was obtained from the historically contaminated incubations; no isomer-specific identification of triCDDs in spiked incubations was determined. Pasteurized cells exhibited no peri-dechlorination pathway, and triCDDs were the least-chlorinated congeners produced in these treatments. These results demonstrate that (i) both freshly spiked and aged PCDDs are available to microbial reductive dechlorination, (ii) the peri and triCDD dechlorinations are attributed to activities of nonmethanogenic, non-spore-forming microbial subpopulations, and (iii) the 2,3,7,8-residue patterns in historically contaminated sediments are likely affected by microbial activity.

Polychlorinated dibenzo-p-dioxins (PCDD) are ubiquitous and considered to be unreactive to biotic and abiotic transformation processes. Here we demonstrate that sediment-associated 2,3,7,8-substituted dioxin residues in general, and 2,3,7,8-TCDD in particular, are in a state of flux, as they are produced from peri-dechlorination of octaCDD, and further laterally dechlorinated to 2-MCDD. This reaction can be stimulated in the presence of organic acids, 2-monobromodibenzo-p-dioxin (2-MBDD) and hydrogen, which result in the production of HpCDD, 2,3,7,8-TCDD, and 2-MCDD, respectively. The results indicate that dechlorination of 2,3,7,8-TCDD is not likely a rate-limiting step in the hydrogen-stimulated reaction, which presents a potential strategy to decontaminate dioxin-contaminated environments.

The reverse KM estimator is recommended for estimation of the distribution function and population percentiles in preference to commonly used methods such as substituting LOD/2 or LOD/ radical2 for values below the LOD, assuming a known parametric distribution, or using imputation to replace the left-censored values.