Editor's perspective‐‐‐Shale gas development: Environmental issues and opportunities

Many professionals in the environmental industry have questioned whether the rapid expansion in shale gas development, particularly in the Marcellus Shale Play, is providing business opportunities. While gas production is a routine practice, the development of shale gas requires a process (fracturing, or, more commonly, “fracing'') that uses chemicals and is far more intrusive to the subsurface environment than traditional gas production. In this Editor's Perspective, we evaluate the environmental issues surrounding shale gas development, with a specific focus on the Marcellus Shale Play because it is currently the most active play in the United States, from both the drilling and political perspectives. In addition, we examine where the business opportunities are likely to be for environmental professionals relative to shale gas development. © 2011 Wiley Periodicals, Inc.     

1,4‐Dioxane Treatment Technologies

The chlorinated solvent stabilizer 1,4‐dioxane (DX) has become an unexpected and recalcitrant groundwater contaminant at many sites across the United States. Chemical characteristics of DX, such as miscibility and low sorption potential, enable it to migrate at least as far as the chlorinated solvent from which it often originates. This mobility and recalcitrance has challenged remediation professionals to redesign existing treatment systems and monitoring networks to accommodate widespread contamination. Furthermore, remediation technologies commonly applied to chlorinated solvent co‐contaminants, such as extraction and air stripping or in situ enhanced reductive dechlorination, are relatively ineffective on DX removal. These difficulties in treatment have required the industry to identify, develop, and demonstrate new and innovative technologies and approaches for both ex situ and in situ treatment of this emerging contaminant. Great strides have been made over the past decade in the development and testing of remediation technologies for removal or destruction of DX in groundwater. This article briefly summarizes the fate and transport characteristics of DX that make it difficult to treat, and presents technologies that have been demonstrated to be applicable to groundwater treatment at the field scale.  ©2016 Wiley Periodicals, Inc.     

Smart Characterization—An Integrated Approach for Evaluating a Complex 1,4‐Dioxane Site

Smart characterization approaches apply the latest high‐resolution site characterization methods to find the contaminant mass flux, by integrating relative permeability mapping, classical hydrostratigraphy interpretation, and high‐density groundwater and saturated soil sampling. The key factor that makes Smart characterization different is the application of quantitative saturated soil sampling in less permeable slow advection and storage zones to diagnose plume maturity and understand its implications for remedy selection and performance. Because direct sensing tools like the membrane interface probe are capable of providing screening‐level assessments for hydrocarbons and chlorinated solvents in storage zones, but not 1,4‐dioxane, the recommended Smart approach involves application of specialized high‐capacity mobile laboratories or rapid turn‐around using fixed commercial labs. In addition to the benefit of rapidly characterizing sites, Smart characterization facilitates a flux‐based conceptual site model, which allows stakeholders to focus remedies on the mobile portion of the contaminant mass or, in effect, the mass that matters. Through systematic planning and implementation, predesign characterization can be completed to optimize source and plume remedy strategies, balancing investment in Smart characterization with reductions in total life‐cycle costs to ensure that an appropriate return on investigation is obtained.  © 2016 Wiley Periodicals, Inc.     

Optimization and validation of enhanced biological reduction of 1,2,3‐trichloropropane in groundwater

Laboratory and field demonstration studies were conducted to assess the efficacy of enhanced biological reduction of 1,2,3‐trichloropropane (TCP) in groundwater. Laboratory studies evaluated the effects of pH and initial TCP concentrations on TCP reduction and the activity of a microbial inoculum containing Dehalogenimonas (Dhg). Laboratory results showed successful reduction at a pH of 5 to 9 with optimal reduction at 7 to 9 and at initial TCP concentrations ranging from 10 to over 10,000 micrograms per liter (μg/L). Based on findings from the laboratory study, the effects of TCP concentration, geochemical conditions, and amendment concentration on bioremediation efficacy were investigated during a field demonstration at a site with relatively low initial concentrations of TCP (< 2 μg/L). The field demonstration included injection of emulsified vegetable oil (EVO) and lactate as a carbon substrate for biostimulation, followed by bioaugmentation using the microbial inoculum containing Dhg. Post‐injection performance monitoring demonstrated reduction of TCP to below laboratory detection limits (< 0.005 μg/L) after an initial lag period of approximately six months following injections. TCP reduction was accompanied by generation of the degradation byproduct propene. A marginal increase in TCP concentrations, potentially due to an influx of upgradient aerobic groundwater containing TCP, was observed eight months after injections thereby demonstrating the sensitivity of this bioaugmentation application to changes in geochemical parameters. Despite this marginal increase, performance monitoring results indicate continued TCP biodegradation 15 months after implementation of the injection program. This demonstration suggests that enhanced biodegradation of TCP by combining biostimulation and bioaugmentation may be a promising solution to the challenges associated with remediation of TCP, even when present at low part per billion concentrations in groundwater.     

Pseudomonas sp. (Strain 10–1B): A potential inoculum candidate for green and sustainable remediation

Soil pollution caused by polycyclic aromatic hydrocarbons (PAHs) is a consequence of various industrial processes which destabilizes the ecosystem. Bioremediation by bacteria is a cost‐effective and environmentally safe solution for reducing or eliminating pollutants in soils. In the present study, we artificially polluted agricultural soil with used automobile engine oil with a high PAH content and then isolated bacteria from the soil after 10 weeks. Pseudomonas sp. strain 10–1B was isolated from the bacterial community that endured this artificial pollution. We sequenced its genomic DNA on Illumina MiSeq sequencer and evaluated its ability to solubilize phosphate, fix atmospheric nitrogen, and produce indoleacetic acid, in vitro, to ascertain its potential for contribution to soil fertility. Its genome annotation predicted several dioxygenases, reductases, ferredoxin, and Rieske proteins important in the ring hydroxylation initiating PAH degradation. The strain was positive for the soil fertility attributes evaluated. Such combination of attributes is important for any potential bacterium partaking in sustainable bioremediation of PAH‐polluted soil.     

Distribution of Cd,Ck, Pb and Zn in Soil and Vegetation Compartments in Stands of Five Boreal Tree Species in N.E. Sweden

Concentrations and total quantity of cadmium (Cd), cupper (Cu),lead (Pb) and zink (Zn) were determined in biomass and soil compartments in a replicated tree species experiment with 27-yr-old stands growing on former farmland in N.E. Sweden. Sequentialextractions of soil samples were performed in order to estimate the exchangeable and an organically bound fraction of each element. The tree species included were Picea abies (L.)H. Karst., Pinus sylvestris L., Pinus contorta Dougl., Larix sibirica Ledeb., and Betula pendula Roth.Tree species influenced the rate of removal of Cu, Pb and Zn incase of stemwood harvesting, and of Cd, Cu and Zn in the case ofwhole-tree harvesting. B. pendula and P. abies had higher quantities and average concentrations of Zn in the biomass. For all species, >50% of the Zn in the stems was found in the bark. P. abies and L. sibirica had higher quantities of Cu in the biomass than the other species.P. abies and P. contorta had high quantities of Cd inthe biomass in relation to the other species. Branches and stembark contained high concentrations of Cd and Pb in relation to foliage and stemwood. Dead branches had especially high concentrations of Pb. The high accumulation rate of Zn in thebiomass of B. pendula was related to a low exchangeable amount of Zn in the A horizon. In the superficial centimeters ofthe A horizon, a depletion similar to that found for Zn was detected for Cu, whereas for Cd and Pb, no correlations were found between quantities of elements in the trees and element pools in the soil.     

Full‐scale bioremediation of a dilute 50‐acre plume

Enhanced anaerobic dechlorination is being conducted to remediate a 50‐acre groundwater area impacted with chlorinated volatile organic compounds (CVOCs). The plume, which is over 3,000 feet (ft) long, initially contained tetrachloroethene and breakdown products at concentrations of 2 to 3 milligrams per liter. The site's high groundwater flow velocity (greater than 1,000 ft per year) was incorporated into the design to help with amendment distribution. Bioaugmentation was conducted using a mixed culture containing Dehalococcoides ethenogenes. There is evidence that it has migrated to distances exceeding 600 ft. The major benefit of the high groundwater flow velocity is greater areal coverage by the remediation system, but the downside is the difficulty in delivering sufficient donor to create the required anaerobic conditions. Overall performance has been excellent with total CVOC reductions and conversion to ethene of 98 percent within a 25‐acre area downgradient of the treatment transect that has operated the longest. © 2011 Wiley Periodicals, Inc.     

Integrated approach to PCE‐impacted site characterization,site management,and enhanced bioremediation

Tetrachloroethene (PCE)‐ and trichloroethene (TCE)‐impacted sites pose significant challenges even when site characterization activities indicate that biodegradation has occurred naturally. Although site‐specific, regulatory, and economic factors play roles in the remedy‐selection process, the application of molecular biological tools to the bioremediation field has streamlined the assessment of remedial alternatives and allowed for detailed evaluation of the chosen remedial technology. The case study described here was performed at a PCE‐impacted site at which reductive dechlorination of PCE and TCE had led to accumulation of cis‐dichlorethene (cis‐DCE) with concentrations ranging from approximately 10 to 100 mg/L. Bio‐Trap® samplers and quantitative polymerase chain reaction (qPCR) enumeration of Dehalococcoides spp. were used to evaluate three remedial options: monitored natural attenuation, biostimulation with HRC®, and biostimulation with HRC‐S®. Dehalococcoides populations in HRC‐S‐amended Bio‐Traps deployed in impacted wells were on the order of 10³ to 10⁴ cells/bead but were below detection limits in most unamended and HRC‐amended Bio‐Traps. Thus the in situ Bio‐Trap study identified biostimulation with HRC‐S as the recommended approach, which was further evaluated with a pilot study. After the pilot HRC‐S injection, Dehalococcoides populations increased to 10⁶ to 10⁷ cells/bead, and concentrations of cis‐DCE and vinyl chloride decreased with concurrent ethene production. Based on these results, a full‐scale HRC‐S injection was designed and implemented at the site. As with the pilot study, full‐scale HRC‐S injection promoted growth of Dehalococcoides spp. and stimulated reductive dechlorination of the daughter products cis‐DCE and vinyl chloride. © 2008 Wiley Periodicals, Inc.     

Stable Isotope Probing to Confirm Field‐Scale Co‐Metabolic Biodegradation of 1,4‐Dioxane

1,4‐Dioxane, a common co‐contaminant with chlorinated solvents, is present in groundwater at Site 24 at Vandenberg Air Force Base in California. Historical use of chlorinated solvents resulted in concentrations of 1,4‐dioxane in groundwater up to approximately 2,000 μg/L. Starting in 2013, an in situ propane biosparge system operation demonstrated reductions in 1,4‐dioxane concentrations in groundwater. The work detailed herein extends the efforts of the first field demonstration to a second phase and confirms the biodegradation mechanism via use of stable isotope probing (SIP). After two months of operation, 1,4‐dioxane concentrations decreased approximately 45 to 83 percent at monitoring locations in the test area. The results of the SIP confirmed ¹³C‐enriched 1,4‐dioxane was transformed into dissolved inorganic carbon (suggesting mineralization to carbon dioxide) and incorporated into microbial biomass (likely attributed to metabolic uptake of biotransformation intermediates or of carbon dioxide).  ©2016 Wiley Periodicals, Inc.     

DNAPL Source Depletion: 2. Attainable Goals and Cost–Benefit Analyses

It is difficult to quantify the range in source strength reduction (MdR) that may be attainable from in situ remediation of a dense nonaqueous‐phase liquid (DNAPL) site given that available studies typically report only the median MdR without providing insights into site complexity, which is often a governing factor. An empirical study of the performance of in situ remediation at a wide range of DNAPL‐contaminated sites determined MdRs for in situ bioremediation (EISB), in situ chemical oxidation (ISCO), and thermal treatment remedies. Median MdR, geometric mean MdR, and lower/upper 95 percent confidence interval for the mean were: 49x, 105x, 20x/556x, respectively, for EISB; 9x, 21x, and 4x/110x for ISCO; and 19x, 31x, and 6x/150x for thermal treatment. Lower MdR values were determined for large, complex sites and for sites with DNAPL pool‐dominated source zones. A feasibility analysis of partial DNAPL depletion is described for a pool‐dominated source zone. Back‐diffusion from low‐hydraulic conductivity units within a pool‐dominated source zone is shown to potentially sustain a secondary source for more than 1,000 years, indicating that aggressive source treatment may not reduce the remediation timeframe. Estimated plume response demonstrates there may be no reduction in cost associated with aggressive treatment, and little difference in risk reduction associated with the various alternatives. Monitored natural attenuation (MNA) for the source zone is shown to be a reasonable alternative for the pool‐dominated source zone considered in this example. It is demonstrated that pool‐dominated source zones with a large range in initial DNAPL mass (250 to 1,500 kg) may correspond to a narrow range in source strength (20 to 30 kg/year). This demonstrates that measured source strength is nonunique with respect to DNAPL mass in the subsurface and, thus, source strength should not be used as the sole basis for predicting how much DNAPL mass remains or must be removed to achieve a target goal. If aggressive source zone treatment is to be implemented due to regulatory requirements, strategic pump‐and‐treat is shown to be most cost effective. These remedial decisions are shown to be insensitive to a range of possible DNAPL pool conditions. At sites with an existing pump‐and‐treat system, a significant increase in mass removal and source strength reduction may be achieved for a low incremental cost by strategic placement of extraction wells and pumping rate selection. © 2014 Wiley Periodicals, Inc.     

Removal of substituted phenols onto iron‐treated Nostoc sp. biomass

This study explored the possibility of removing 4‐nitrophenol (4‐NP) and 2,4‐dichlorophenol (2,4‐DCP) from water by using a dead blue‐green algae, Nostoc sp., dried and untreated and dried and treated with iron (Fe‐treated with 0.1 M ferric chloride solution for 1 day). The Nostoc sp. untreated and Fe‐treated biomass were used to study the sorption and desorption of 4‐NP and 2,4‐DCP. The effects of solute concentration, ionic strength, and temperature on sorption and desorption in the presence of untreated and treated Nostoc sp. biomass were investigated. The Fe‐treated Nostoc sp. biomass sorbed higher amounts of both 4‐NP and 2,4‐DCP than the untreated biomass. The percent cumulative desorption decreased from 6.41% to 0.28% and 1.84% to 0.19%, respectively, for 4‐NP and 2,4‐DCP for the Fe‐treated biomass. Biosorption of 4‐NP and 2,4‐DCP onto untreated and Fe‐treated Nostoc sp. biomass conformed to Freundlich isotherms. Iron treatment of Nostoc sp. biomass increased the value of ln K from 8.07 to 8.59 for 4‐NP and from 8.04 to 8.51 for 2,4‐DCP but decreased their desorption. An increase in ionic strength (0.003–0.03) increased the biosorption of both substituted phenols and decreased their percent desorption. An increase in temperature in the range of 15–35°C decreased the sorption of 4‐NP and 2,4‐DCP onto both untreated and Fe‐treated Nostoc sp. biomass and increased their desorption, indicating that the biosorption of both substituted phenols onto untreated and Fe‐treated Nostoc sp. biomass was principally a physical process. The results of this study suggest that Fe‐treated dried Nostoc sp. biomass could be explored as an inexpensive and eco‐friendly material for the effective removal of these phenols and, potentially, other chemicals from industrial wastewater and contaminated groundwater.     

Pilot scale testing composite swellable organosilica nanoscale zero‐valent iron—Iron‐Osorb®—for in situ remediation of trichloroethylene

Iron‐Osorb^® is a solid composite material of swellable organosilica with embedded nanoscale zero‐valent iron that was formulated to extract and dechlorinate solvents in groundwater. The unique feature of the highly porous organosilica is its strong affinity for chlorinated solvents, such as trichloroethylene (TCE), while being impervious to dissolved solids. The swellable matrix is able to release ethane after dechlorination and return to the initial state. Iron‐Osorb^® was determined to be highly effective in reducing TCE concentrations in bench‐scale experiments. The material was tested in a series of three pilot scale tests for in situ remediation of TCE in conjunction with the Ohio Environmental Protection Agency at a site in central Ohio. Results of these tests indicate that TCE levels were reduced for a period of time after injection, then leveled out or bounced back, presumably due to depletion of zero‐valent iron. Use of tracer materials and soil corings indicate that Iron‐Osorb^® traveled distances of at least 20 feet from the injection point during soil augmentation. The material appears to remain in place once the injection fluid is diluted into the surrounding groundwater. Overall, the technology is promising as a remediation method to treat dilute plumes or create diffuse permeable reactive barriers. Keys to future implementation include developing injection mechanisms that optimize soil distribution of the material and making the system long‐lasting to allow for continual treatment of contaminants emanating from the soil matrix. © 2011 Wiley Periodicals, Inc.     

Purification and biochemical characterization of recombinant alcohol dehydrogenase from the psychrophilic bacterium <Emphasis Type="Italic">Pseudomonas</Emphasis><Emphasis Type="Italic">frederiksbergensis</Emphasis>

A gram-negative psychrophilic bacterium, with potential for biodegradation of long-chain n-alkanes was isolated from ice samples collected in Spitzbergen, Denmark. On the basis of results of biochemical and morphological tests and sequence analysis of 16S rRNA, the strain was identified as Pseudomonas frederiksbergensis. In this work, a short-chain NAD⁺-dependent alcohol dehydrogenase (alcDH) (Accession number: AAR13804) from the P. frederiksbergensis was cloned and transformed in E. coli BL21 (3DE) competent cells. The alcDH activity was highest in the crude extract of cells induced with 1.0 mM IPTG. The recombinant alcDH enzyme was purified to 93.4% homogeneity using three consecutive purification steps including ammonium sulphate, Q-Sepharose Fast Flow column and gel filtration chromatography employing Superdex 200 10/30 HR column. Enzyme enrichment and yield levels of 31.4 folds and 25.5%, respectively, were achieved. While the subunit molecular mass of the enzyme was determined on SDS-PAGE to be ~38 kDa, the aggregated native form of the enzyme had a molecular mass of ~238 kDa by gel filtration analysis. Reaction conditions optima for the recombinant alcDH were determined with propan-1-ol as the substrate. While the optimum pH was 9, the optimum temperature was 35 °C. The alcDH enzyme exhibited moderate thermal stability with half-lives of 150 min at 55 °C, 27 min at 65 °C and 8 min at 75 °C. Results for kinetic parameters indicated that the apparent K _m value for alcDH with propan-1-ol as the substrate was found to be 1.42 mM and the V _max value was 0.63 mmol mg⁻¹ min⁻¹. Experimental evidence revealed that the recombinant alcDH exhibited a wide range of substrate specificity, with higher levels of specific activity for aliphatic alcohols as compared to secondary alcohols. Taken together, the present study highlights the potential of alcDH as a member of cold-adapted enzymes in several key biotechnological applications including environmental bioremediation and biotransformations. It is envisaged that, with the ongoing screening of microorganisms and metagenomes, directed evolution approaches and the subsequent overexpression of recombinant proteins, more enzymes will be found that are suitable for bioremediation purposes.     

Gene Cloning and Characterization of a Poly(<Emphasis Type="SmallCaps">l</Emphasis>-Lactic Acid) Depolymerase from <Emphasis Type="Italic">Pseudomonas</Emphasis> sp. Strain DS04-T

A gene encoding a poly(l-lactic acid) (PLA) depolymerase from Pseudomonas sp. strain DS04-T was cloned and overexpressed in Escherichia coli. The recombinant PLA depolymerase with a molecular weight of 19.2 kDa was purified to homogeneity. The optimum pH and temperature of the PLA depolymerase are 8.5 and 60 °C, respectively. K⁺, Ca²⁺ and Ni²⁺ enhance the enzyme activity, while Na⁺, Zn²⁺, Mg²⁺, Cu²⁺, Fe²⁺, Mn²⁺ and Co²⁺ inhibit it. The inhibition of different chemicals on the PLA depolymerase activity were examined, in which EDTA was found to have a significantly inhibitory effect. The main degradation product of the depolymerase is identified as lactic acid monomer by mass spectrometric analysis. Physicochemical properties, substrate specificity and sequence analysis indicated that PME is a new type of PLA depolymerase.     

Selective catalytic reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> using RDF char and municipal solid waste char based catalyst

Experiments were performed in order to investigate the possibility for the development of catalysts for low-temperature selective catalytic reduction (SCR) using municipal waste char and RDF byproduct. Physical and chemical activations, using water, and HCl and KOH, were employed to increase the catalytic activities. The characteristics of the activated catalysts were investigated using N₂ adsorption–desorption and FT-IR. The catalysts activated chemically using basic treatment showed higher NO _x removal efficiencies than those activated physically or chemically using acidic treatment. The de-NO _x performance of the activated catalysts was dependent on the chemical properties, such as oxygen functional groups as well as physical properties, such as specific surface area and pore volume. In order to investigate the effect of MnO _x , which has been reported to be efficient for the removal of NO _x in low-temperature SCR processes, the chemically activated catalyst was impregnated with manganese. The Mn-impregnated catalyst had the highest NO _x conversion at all of the temperatures tested in this study.     

Kinetic Study of Biopolymer (PHB) Synthesis in <Emphasis Type="Italic">Alcaligenes</Emphasis> sp. in Submerged Fermentation Process Using TEM

Poly-β-hydroxybuyrate (PHB) is a carbon—energy storage material which is accumulated as intracellular granule in variety of microorganism under nutrient starved conditions. Solid PHB is a biodegradable thermoplastic polymer and is utilizable in various ways similar to many conventional plastics. Ralstonia eutropha (Alcaligenes sp.), a gram negative bacteria accumulates PHB as insoluble granules inside the cells when nutrients other than carbon are limited. In this report effort has been made to analyze PHB granule synthesis inside Alcaligenes sp. NCIM 5085 by transmission electron microscopy and qualitative estimation of PHB was carried out by fourier transform infrared spectroscopy which provide better precision compared to other conventional techniques previously applied for PHB determination. Maximum PHB concentration of 2.20 ± 0.40 g/L and cell biomass of 3.42 ± 0.20 g/L was obtained after 48.0 h of fermentation. Leudking-Piret equation deduced mixed growth associated product formation which varies from earlier reports.     

Perils of categorical thinking: “Oxic/anoxic” conceptual model in environmental remediation

Given ambient atmospheric oxygen concentrations of about 21 percent (by volume), the lower limit for reliable quantitation of dissolved oxygen concentrations in groundwater samples is in the range of 0.1–0.5 mg/L. Frameworks for assessing in situ redox condition are often applied using a simple two‐category (oxic/anoxic) model of oxygen condition. The “oxic” category defines the environmental range in which dissolved oxygen concentrations are clearly expected to impact contaminant biodegradation, either by supporting aerobic biodegradation of electron‐donor contaminants like petroleum hydrocarbons or by inhibiting anaerobic biodegradation of electron‐acceptor contaminants like chloroethenes. The tendency to label the second category “anoxic” leads to an invalid assumption that oxygen is insignificant when, in fact, the dissolved oxygen concentration is less than detection but otherwise unknown. Expressing dissolved oxygen concentrations as numbers of molecules per volume, dissolved oxygen concentrations that fall below the 0.1 mg/L field detection limit range from 1 to 10¹⁷ molecules/L. In light of recent demonstrations of substantial oxygen‐linked biodegradation of chloroethene contaminants at dissolved oxygen concentrations well below the 0.1–0.5 mg/L field detection limit, characterizing “less than detection” oxygen concentrations as “insignificant” is invalid. © 2012 Wiley Periodicals, Inc.