Literature overview: Microbial metabolism of high molecular weight polycyclic aromatic hydrocarbons

High molecular weight polycyclic aromatic hydrocarbons (HMW PAHs) increase in hydrophobicity with increases in their molecular weight and ring angularity. Microbial strategies to deal with PAH hydrophobicity include biofilm formation, enzyme induction, and biosurfactants, the effect of which is variable on PAH metabolism depending on the surfactant type and concentration, substrate, and microbial strain(s). Aerobic HMW PAH metabolism proceeds via mineralization, partial degradation, and cometabolic transformations. Generally, bacteria and nonlignolytic fungi metabolize PAHs via initial PAH ring oxidation by dioxygenases to form cis‐dihydrodiols, which are transformed to catechol compounds by dehydrogenases and other mono‐ and dioxygenases to substituted catechol and noncatechol compounds, all ortho‐ or metacleaved and further oxidized to simpler compounds. However, lignolytic fungi form quinones and acids to CO₂. This review discusses the pathways for HMW PAH microbial metabolism. © 2008 Wiley Periodicals, Inc.     

Groundwater Impacts on Surface Water and Sediment—Gowanus Canal,Brooklyn, New York

The Gowanus Canal Superfund Site in Brooklyn, New York, is an approximately 1.5‐mile (1.61‐km) long estuary that was historically converted into a canal for industrial and commercial purposes. Three manufactured gas plants (MGPs) were formerly located on the Gowanus Canal and discharged waste into it. Surface sediments remain highly contaminated with polycyclic aromatic hydrocarbons (PAHs) long after the MGPs were razed. A hydrogeologic assessment indicates that groundwater passes through the deeper coal tar–contaminated sediment prior to discharging to the canal. This study was undertaken to investigate if groundwater passing through coal tar–contaminated sediment could be responsible for the ongoing contamination of both surface sediments and surface water in the canal. PAH compound distributions in surface water samples collected from the tidal canal at low tide were compared with PAH compounds found in adjacent groundwater‐monitoring wells, point sources (combined sewer overflows [CSOs]), and surface sediments. The results indicate a strong correlation between PAH contaminant distributions in groundwater, sediment, and surface water, indicating that contaminated groundwater passing through the deeper coal tar–contaminated sediments is the primary mechanism contributing to the contamination of both surface sediment and surface water in the canal. Therefore, any sediment remediation efforts in the Gowanus Canal that fail to evaluate and control the upward transport processes have a high chance of failure due to recontamination from below.  ©2016 Wiley Periodicals, Inc.     

Contaminant mass flux and forensic assessment of polycyclic aromatic hydrocarbons: Tools to inform remediation decision making at a contaminated site in Canada

Polycyclic aromatic hydrocarbons (PAHs) and metal(loid) mass flux estimates and forensic assessment using PAH diagnostic ratios were used to inform remediation decision making at the Sydney Tar Ponds (STPs) and Coke Ovens cleanup project in eastern Canada. Environmental effects monitoring of surface marine sediments in Sydney Harbor indicated significantly higher PAH concentrations during the first year of remediation monitoring compared to baseline. This was equivalent to PAH loadings of ～2,000 kg over a 15‐month period. Increases in sediment PAH concentrations raised serious concerns for regulators, who requested cessation of remediation activities early in the $400 M (CAD) project. Historically, the STPs were reported as the primary source of PAH contamination in Sydney Harbor with estimated discharges of 300 to 800 kg/year between 1989 and 2001. Mass flux estimates of PAHs and metal(loid)s and PAH diagnostic ratios were used to evaluate if increases in PAH concentrations in marine sediments were the result of the STPs remediation activities. PAH mass flux estimates approximated that 17 to 97 kg/year were discharged from the STPs during three years of remediation and were corroborated by an independent PAH flux estimate of 119 kg in year 1. PAH fluxes to the Sydney Harbor were mostly surface water derived, with groundwater contributing negligible quantities (0.002–0.005 kg/year). Fluxes of metal(loid)s to harbor sediments were stable or declining across all years and were mirrored in sediment metal(loid) concentrations, which lacked temporal variation, unlike total PAH concentrations. Flux results were also corroborated using PAH diagnostic ratios, which found a common source of PAHs. Coal combustion was likely the principal source of PAHs and not migration from the STPs during remediation. Although short‐term residual sediment PAH increases during onset of remediation raised concerns for regulators, calls for premature cessation of remediation early in the project were unwarranted based on only one year of monitoring data. Mass flux estimates and forensic assessments using PAH diagnostic ratios proved useful tools to inform remediation decision making that helped environmental protection and reduced costs associated with lost cleanup time.     

Assessment of the Ecological Integrity of Traunsee (Austria) Via Analysis of Sediments and Benthic Microbial Communities

Since nearly one hundred years Traunsee experiences the import of tons of liquid and solid waste originating from salt and soda production. Today, the lake exhibits chloride concentrations of up to 170 mg L^-1 and 19% of the lake floor are directly or indirectly influenced by industrial deposits (ID). Based on the comparison of several microbial parameters in unaffected, directly affected and intermediate lake bottom sediments, the ecological integrity of the lake was evaluated. The highly alkaline ID, which were exclusively colonized by microorganisms, harbored a bacterial community reduced by a factor of 10 in abundance and biomass compared to undisturbed sediment areas within the lake. The bacterial community of ID was furthermore characterized by a reduced content of actively respiring cells (INT-formazan reduction), a lower frequency of dividing cells (FDC) and a significantly reduced cell and biomass production. A 80 to 90% reduction in carbon recycling is estimated for the area exclusively covered by ID. Protists, although occasionally absent from the industrial sediments, were in general found to be less sensitive to the contaminant stress. Differences in alkalinity and dissolved organic carbon (DOC) concentrations of sediment porewaters as well as the total organic content and C/N ratios of sediments partly explain the microbial pattern observed at the various sampling sites. Possible consequences of the continuous industrial tailings for the whole lake ecosystem and the validation of the ecological integrity are discussed.     

In‐well sediment incubators to evaluate microbial community stability and dynamics following bioimmobilization of uranium

An in‐well sediment incubator (ISI) was developed to investigate the stability and dynamics of sediment‐associated microbial communities to prevailing subsurface oxidizing or reducing conditions. Herein we describe the use of these devices at the Old Rifle Uranium Mill Tailings Remedial Action (UMTRA) site. During a seven‐month period in which oxidized Rifle Aquifer background sediment (RABS) were deployed in previously biostimulated wells under iron‐reducing conditions, cell densities of known iron‐reducing bacteria, including Geobacteraceae, increased significantly, showing the microbial community response to local subsurface conditions. Phospholipid fatty acid (PLFA) profiles of RABS following in situ deployment were strikingly similar to those of adjacent sediment cores, suggesting ISI results could be extrapolated to the native material of the test plots. Results for ISI deployment with laboratory‐reduced sediments showed only slight changes in community composition and pointed toward the ability of the ISI to monitor microbial community stability and response to subsurface conditions. © 2009 Wiley Periodicals, Inc.     

Chloroethene dechlorination in acidic groundwater: Implications for combining fenton's treatment with natural attenuation

A sulfuric acid leak in 1988 at a chloroethene‐contaminated groundwater site at the Naval Air Station Pensacola has resulted in a long‐term record of the behavior of chloroethene contaminants at low pH and a unique opportunity to assess the potential impact of source area treatment technologies, which involve acidification of the groundwater environment (e.g., Fenton's‐based in situ chemical oxidation), on downgradient natural attenuation processes. The greater than 75 percent decrease in trichloroethene (TCE) concentrations and the shift in contaminant composition toward predominantly reduced daughter products (dichloroethene [DCE] and vinyl chloride [VC]) that were observed along a 30‐m groundwater flow path characterized by highly acidic conditions (pH = 3.5 ± 0.4) demonstrated that chloroethene reductive dechlorination can continue to be efficient under persistent acidic conditions. The detection of Dehalococcoides‐type bacteria within the sulfuric acid/chloroethene co‐contaminant plume was consistent with biotic chloroethene reductive dechlorination. Microcosm studies conducted with ¹⁴C‐TCE and ¹⁴C‐VC confirmed biotic reductive dechlorination in sediment collected from within the sulfuric acid/chloroethene co‐contaminant plume. Microcosms prepared with sediment from two other locations within the acid plume, however, demonstrated only a limited mineralization to ¹⁴CO₂ and ¹⁴CO, which was attributed to abiotic degradation because no significant differences were observed between experimental and autoclaved control treatments. These results indicated that biotic and abiotic mechanisms contributed to chloroethene attenuation in the acid plume at NAS Pensacola and that remediation techniques involving acidification of the groundwater environment (e.g., Fenton's‐based source area treatment) do not necessarily preclude efficient chloroethene degradation. © 2007 Wiley Periodicals, Inc.     

Optimization of Carbon Dioxide and Valeric Acid Utilization for Polyhydroxyalkanoates Synthesis by Cupriavidus necator

The utilization of captured CO₂ as a part of the CO₂ capture and storage system to produce biopolymers could address current environmental issues such as global warming and depletion of resources. In this study, the effect of feeding strategies of CO₂ and valeric acid on cell growth and synthesis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] in Cupriavidus necator was investigated to determine the optimal conditions for microbial growth and biopolymer accumulation. Among the studied CO₂ concentrations (1–20 %), microbial growth and poly(3-hydroxybutyrate) accumulation were optimal at 1 % CO₂ using a gas mixture at H₂:O₂:N₂ = 7:1:91 % (v/v). When valeric acid was fed together with 1 % CO₂, (R)-3-hydroxyvalerate synthesis increased with increasing valeric acid concentration up to 0.1 %, but (R)-3-hydroxybutyrate synthesis was inhibited at >0.05 % valeric acid. Sequential addition of valeric acid (0.05 % at Day 0 followed by 0.025 % at Day 2) showed an increase in 3HV fraction without inhibitory effects on 3HB synthesis during 4 d accumulation period. The resulting P(3HB-co-3HV) with 17–32 mol  % of 3HV is likely to be biocompatible. The optimal concentrations and feeding strategies of CO₂ and valeric acid determined in this study for microbial P(3HB-co-3HV) synthesis can be used to produce biocompatible P(3HB-co-3HV).     

A Geochemical Multi-Methodological Approach in Hazard Assessment of CO2-Rich Gas Emissions at Mt. Amiata Volcano (Tuscany, Central Italy)

The present work aims to assess the hazard for human health related to CO₂ anomalous concentrations in air emitted from dry gas vents located in the NE area of Mt. Amiata volcano (Tuscany, central Italy). A geochemical multi-methodological approach is adopted to determine the composition and the flux rate of the gas discharges in order to establish (1) the origin of the gas vents and (2) the behaviour of the discharged gases in the areas surrounding the emission sites. The gas vents are hosted within sub-circular morphological depressions (??～?10–30 m), which likely originated by the collapse of cavities formed at shallow depth in the ground by dissolution of Triassic anhydrite formations and recent travertine deposits. CaCO₃ and CaSO₄ dissolution is mainly related to the underground circulation of CO₂-rich fluids whose hydrological pattern is regulated by local and regional tectonics. The CO₂-rich (up to 996,070 μmol/mol) gases tend to accumulate within the topographic lows, thus creating a sort of CO₂ ponds, and the knowledge of their evolution in time and space is important to evaluate the related hazard. Consequently, a conceptual model of CO₂ diffusion in air is developed to understand the dynamic of the CO₂ accumulation/dispersion process based on (1) a 24-h continuous measurement of the CO₂ flux from one of the main emission sites and (2) the recording of the main meteoric parameters, i.e. air temperature, wind direction and speed to check their influence. The results indicate that the threshold of CO₂ concentrations considered dangerous for the human health is frequently overcome. Moreover, when meteoric conditions, i.e. low wind and cloudy weather, did not allow a rapid dispersion of the gas phase emitted from the dry vents, CO₂-rich clouds periodically overflowed the morphological depressions for several tens of meters without any significant mixing with air. On the basis of these considerations, the monitoring of the output rate from the main gas emissions, combined with the continuous control of the local meteorological parameters, may be considered an efficient procedure to mitigate the CO₂ hazard deriving from dry gas vents. An improvement of the protocol can be achieved in case of installations of CO₂ sensors located in the most sensitive areas and connected to a telemetry system able to transmit the data in real time to the closest Civil Defence centre. The CO₂ degassing sites can also represent a tourist attraction after the installation of suitable metallic fences and a proper campaign of information about these natural phenomena.     

Factors affecting polycyclic aromatic hydrocarbon biodegradation by Aspergillus flavus

This study investigated the ability of fungi isolated from highly contaminated soil to biodegrade polycyclic aromatic hydrocarbon (PAH) compounds, as well as the effect of several parameters on the biodegradation ability of these fungi. The isolated fungi were identified using ITS rDNA sequencing and tested using 2,6‐dichlorophinolendophenol to determine their preliminary ability to degrade crude oil. The top‐performing fungi, Aspergillus flavus and Aspergillus fumigatus, were selected to test their ability to biodegrade PAH compounds as single isolates. After 15 days of incubation, A. flavus degraded 82.7% of the total PAH compounds, with the complete degradation of six compounds, whereas A. fumigatus degraded 68.9% of the total PAHs, with four aromatic compounds completely degraded. We also tested whether different temperatures, pH, and nitrogen sources influenced the growth of A. flavus and the degradation rate. The degradation process was optimal at a temperature of 30°C, pH of 5.5, and with nitrogen in the form of yeast extract. Finally, the ability of the fungal candidate, A. flavus, to degrade PAH compounds under these optimum conditions was studied. The results showed that 95.87% of the total PAHs, including 11 aromatic compounds, were completely degraded after 15 days of incubation. This suggests that A. flavus is a potential microorganism for the degradation of PAH compounds in aqueous cultures.     

Reduction–melting combined with a Na2CO3 flux recycling process for lead recovery from cathode ray tube funnel glass

With large quantity of flux (Na₂CO₃), lead can be recovered from the funnel glass of waste cathode-ray tubes via reduction–melting at 1000 °C. To reduce flux cost, a technique to recover added flux from the generated oxide phase is also important in order to recycle the flux recovered from the reduction–melting process. In this study, the phase separation of sodium and the crystallization of water-soluble sodium silicates were induced after the reduction–melting process to enhance the leachability of sodium in the oxide phase and to extract the sodium from the phase for the recovery of Na₂CO₃ as flux. A reductive atmosphere promoted the phase separation and crystallization, and the leachability of sodium from the oxide phase was enhanced. The optimum temperature and treatment time for increasing the leachability were 700 °C and 2 h, respectively. After treatment, more than 90% of the sodium in the oxide phase was extracted in water. NaHCO₃ can be recovered by carbonization of the solution containing sodium ions using carbon dioxide gas, decomposed to Na₂CO₃ at 50 °C and recycled for use in the reduction–melting process.     

Microbial communities and greenhouse gas emissions associated with the biodegradation of specified risk material in compost

Provided that infectious prions (PrP^Sc) are inactivated, composting of specified risk material (SRM) may be a viable alternative to rendering and landfilling. In this study, bacterial and fungal communities as well as greenhouse gas emissions associated with the degradation of SRM were examined in laboratory composters over two 14 day composting cycles. Chicken feathers were mixed into compost to enrich for microbial communities involved in the degradation of keratin and other recalcitrant proteins such as prions. Feathers altered the composition of bacterial and fungal communities primarily during the first cycle. The bacterial genera Saccharomonospora, Thermobifida, Thermoactinomycetaceae, Thiohalospira, Pseudomonas, Actinomadura, and Enterobacter, and the fungal genera Dothideomycetes, Cladosporium, Chaetomium, and Trichaptum were identified as candidates involved in SRM degradation. Feathers increased (P < 0.05) headspace concentrations of CH₄ primarily during the early stages of the first cycle and N₂O during the second. Although inclusion of feathers in compost increases greenhouse gas emissions, it may promote the establishment of microbial communities that are more adept at degrading SRM and recalcitrant proteins such as keratin and PrP^Sc.     

Remediation of Soil and Ground Water Contaminated with PAH using Heat and Fe(II)-EDTA Catalyzed Persulfate Oxidation

The feasibility of degrading 16 USEPA priority polycyclic aromatic (PAH) hydrocarbons (PAHs) with heat and Fe(II)-EDTA catalyzed persulfate oxidation was investigated in the laboratory. The experiments were conducted to determine the effects of temperature (i.e. 20 ^∘C, 30 ^∘C and 40 ^∘ C) and iron-chelate levels (i.e., 250 mg/L-, 375 mg/L- and 500 mg/L-Fe(II)) on the degradation of dissolved PAHs in aqueous systems, using a series of amber glass jars as the reactors that were placed on a shaker inside an incubator for temperature control. Each experiment was run in duplicate and had two controls (i.e., no persulfate in systems). Samples were collected after a reaction period of 144 hrs and measured for PAHs, pH and sodium persulfate levels. The extent of degradation of PAHs was determined by comparing the data for samples with the controls. The experimental results showed that persulfate oxidation under each of the tested conditions effectively degraded the 16 target PAHs. All of the targeted PAHs were degraded to below the instrument detection limits (∼4 μ/L) from a range of initial concentration (i.e., 5 μ/L for benzo(a)pyrene to 57 μ/L for Phenanthrene) within 144 hrs with 5 g/L of sodium persulfate at 20 ^∘ C, 30 ^∘C and 40 ^∘C. The data indicated that the persulfate oxidation was effective in degrading the PAHs and that external heat and iron catalysts might not be needed for the degradation of PAHs. The Fe(II)-EDTA catalyzed persulfate also effectively degraded PAHs in the study. In addition, the data on the variation of persulfate concentrations during the experiments indicated that Fe(II)-EDTA accelerated the consumption of persulfate ions. The obtained degradation data cannot be used to evaluate the influence of temperature and Fe(II) levels on the PAH degradation because the PAHs under each of the tested conditions were degraded to below the instrument detection limit within the first sampling point. However, these experiments have demonstrated the feasibility of degrading PAHs in aqueous systems with persulfate oxidation. Additional tests are being conducted to evaluate the effectiveness of treating PAHs in soils and obtaining the rate of degradation of PAHs with persulfate oxidation. Two sets of laboratory experiments were conducted to evaluate the ability of sodium persulfate in oxidizing real world PAH-contaminated soils collected from a Superfund site in Connecticut. The first set of soil sample were treated only with persulfate and to the second batch, mixture of persulfate and Fe(II)-EDTA solutions were added. The results of the second test showed that within 24 hours, 75% to 100% of the initial concentrations of seven PAH compounds detected in the soil samples were degraded by sodium persulfate mixed with FE(II)-EDTA.     

Polycyclic aromatic hydrocarbon (PAH) emission from co-firing municipal solid waste (MSW) and coal in a fluidized bed incinerator

Polycyclic aromatic hydrocarbons (PAH) emissions from a commercial municipal solid waste incinerator (MSWI) were studied. A MSW–coal mixture and coal only were used as fuel for the fluidized bed incinerator. Seven sampling points were chosen according to the classified four PAH emission pathways: flue gas, residue, ash and water. The mixture of MSW and coal resulted in PAH emission more than that of coal only, and PAH emission increased with increasing MSW mass percentage. Calcium oxide (CaO) or calcium carbonate (CaCO₃) was added as a desulfurizer. PAH emission also changed with different desulfurizers because of their different influences on heat balance. The PAH toxic equivalent (TEQ) of all operating conditions was also examined, showing that total daily PAH emission from MSWI can be determined.     

Spatial Distribution of Geobacteraceae and Sulfate‐Reducing Bacteria During In Situ Bioremediation of Uranium‐Contaminated Groundwater

Analysis of the physiological status of subsurface microbial communities generally relies on the study of unattached microorganisms in the groundwater. These approaches have been employed in studies on bioremediation of uranium‐contaminated groundwater at a study site in Rifle, Colorado, in which Geobacter species typically account for over 90 percent of the microbial community in the groundwater during active uranium reduction. However, to develop efficient in situ bioremediation strategies it is necessary to know the status of sediment‐associated microorganisms as well. In order to evaluate the distribution of the natural community of Geobacter during bioremediation of uranium, subsurface sediments were packed into either passive flux meters (PFMs) or sediment columns deployed in groundwater monitoring wells prior to acetate injection during in situ biostimulation field trials. The trials were performed at the Department of Energy's (DOE's) Rifle Integrated Field Research Challenge site. Sediment samples were removed either during the peak of Fe(III) reduction or the peak of sulfate reduction over the course of two separate field experiments and preserved for microscopy. Direct cell counts using fluorescence in situ hybridization (FISH) probes targeting Geobacter species indicated that the majority of Geobacter cells were unattached during Fe(III) reduction, which typically tracks with elevated rates of uranium reduction. Similar measurements conducted during the sulfate‐reducing phase revealed the majority of Geobacter to be attached following exhaustion of more readily bioavailable forms of iron minerals. Laboratory sediment column studies confirmed observations made with sediment samples collected during field trials and indicated that during Fe(III) reduction, Geobacter species are primarily unattached (90 percent), whereas the majority of sulfate‐reducing bacteria and Geobacter species are attached to sediment surfaces when sulfate reduction is the predominant form of metabolism (75 percent and 77 percent, respectively). In addition, artificial sediment experiments showed that pure cultures of Geobacter uraniireducens, isolated from the Rifle site, were primarily unattached once Fe(III) became scarce. These results demonstrate that, although Geobacter species must directly contact Fe(III) oxides in order to reduce them, cells do not firmly attach to the sediments, which is likely an adaptive response to sparsely and heterogeneously dispersed Fe(III) minerals in the subsurface. © 2013 Wiley Periodicals, Inc.     

Estimating PAH sources in harbor sediments using diagnostic ratios

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the global environment and are subsequently transported into aquatic sediments. As PAHs are formed by various processes, source identification using diagnostic ratios can provide insight to PAH emission sources to distinguish between pyrogenic and petrogenic PAH sources. PAH diagnostic ratios were applied as a forensic source apportionment technique to assess aggregate historical sediment data from 31 small craft harbors (SCHs) across Nova Scotia, Canada. Multiple diagnostic ratios suggest that PAHs present in Nova Scotia SCH sediments are pyrogenic (combustion) in origin, while consistently suggesting that coal‐related PAH sources are potential dominant specific sources. National Institute of Standards and Technology Standard Reference Materials (SRMs) were used as reference for coal tar, urban dust, and diesel exhaust particulates in ratio applications. The SRM for coal tar was most similar to Nova Scotia SCH sediments in multiple ratio applications. Diagnostic ratio results were corroborated by comparing the PAH profile of sediments to source profiles from the literature. Results indicate that Nova Scotia SCH sediments follow global trends by exhibiting a dominant pyrogenic PAH signature, and the specific coal‐related PAH signature of Nova Scotia SCH sediments may be influenced by contamination inputs related to historical industrial coal mining and combustion activities in the province.     

Degradation and mineralization of cellulose acetate in simulated thermophilic compost environments

Residual cellulose acetate (CA) films with initial degree of substitution (DS) values of 1.7 and 2.5 (CA DS-1.7 and DS-2.5) were recovered from a simulated thermophilic compost exposure and characterized by gel permeation chromatography (GPC), proton nuclear magnetic resonance (¹H NMR), and scanning electron microscopy (SEM) to determine changes in polymer molecular weight and DS and to study microbial colonization and surface morphology, respectively. During the aerobic degradation of CA DS-1.7 and CA DS-2.5 films exposed for 7 and 18 days, respectively, the number-average molecular weight (M _n) of residual polymer decreased by 30.4% on day 5 and 20.3% on day 16, respectively. Furthermore, a decrease in the degree of substitution from 1.69 to 1.27 (4-day exposure) and from 2.51 to 2.18 (12-day exposure) was observed for the respective CA samples. In contrast, CA films (DS-1.7 and DS-2.5) which were exposed to abiotic control vessels for identical time periods showed no significant changes inM _n and DS. SEM photographs of CA (DS-1.7 and DS-2.5) film surfaces after compost exposures revealed severe erosion and corresponding microbial colonization. Similar exposure times for CA films in abiotic control vessels resulted in only minor changes in surface characteristics by SEM observations. The conversion of CA DS-1.7 and DS-2.5 to CO₂ was monitored by respirometry. In these studies, powdered CA was placed in a predigested compost matrix which was maintained at 53°C and 60% moisture content throughout the incubation period. A lag phase of 10- and 25-day duration for CA DS-1.7 and DS-2.5, respectively, was observed, after which the rate of degradation increased rapidly. Mineralization of exposed CA DS-1.7 and DS-2.5 powders reported as the percentage theoretical CO₂ recovered reached 72.4 and 77.6% in 24 and 60 days, respectively. The results of this study demonstrated that microbial degradation of CA films exposed to aerobic thermophilic laboratory-scale compost reactors not only results in film weight loss but also causes severe film pitting and a corresponding decrease in chainM _n and degree of substitution for the residual material. Furthermore, conversions to greater than 70% of the theoretical recovered CO₂ for CA (DS 1.7 and 2.5) substrates indicate high degrees of CA mineralization.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Feasibility of greenhouse gas emissions offsets for natural source zone depletion of petroleum hydrocarbons

Hydrocarbon biodegradation is an important process for remediating petroleum hydrocarbons and managing large sites. However, this biodegradation results in what are essentially unavoidable CO₂ emissions to the atmosphere. A feasibility assessment was conducted to quantitatively consider reuse options for petroleum brownfields that would offset contaminant respiration emissions rates in the 2 to 10 micromoles CO₂ per meters squared per second (μmol CO₂ m^?2 s^?1) typically observed. Under a wide range of solar resource scenarios, placement of solar panels over only a fraction (no more than 35%) of the site footprint is estimated as necessary to achieve an emissions offset. Similarly, placement of one 30‐meter tall wind turbine of moderate rating (approximately 30 to 50 kW) is sufficient to provide an offset for a nominal 1,000 square meters site. For spreading of spent calcium‐rich construction materials, under even a high emissions scenario, the required footprint for the offset is less than the site footprint. While these approaches appear feasible, revegetation as forestland is estimated as sufficient only at contaminant respiration rates up to 2 μmol CO₂ m^?2 s^?1. Revegetation as rangeland and cropland, which sequesters CO₂ mainly in soil organic carbon, is estimated as requiring more than the site footprint under many contaminant respiration rates. Revegetation as a wetland fares slightly better from a carbon storage perspective, but it also has the potential for N₂O and CH₄ emissions that may largely undo the benefit from sequestration in soil organic matter. Overall, the results indicate several methods that are viable for achieving emissions offsets and a quantitation method that can be honed with site‐specific input parameters as appropriate.     

Chemical Oxidation Performance in High Temperature,Saline Groundwater Impacted With Hydrocarbons

A series of laboratory microcosm experiments and a field pilot test were performed to evaluate the potential for in situ chemical oxidation (ISCO) of aromatic hydrocarbons and methyl tertiary butyl ether (MTBE), a common oxygenate additive in gasoline, in saline, high temperature (more than 30 °C) groundwater. Groundwater samples from a site in Saudi Arabia were amended in the laboratory portion of the study with the chemical oxidants, sodium persulfate (Na₂S₂O₈) and sodium percarbonate (Na₂(CO₃)₂), to evaluate the changes in select hydrocarbon and MTBE concentrations with time. Almost complete degradation of the aromatic hydrocarbons, naphthalene and trimethylbenzenes (TMBs), was found in the groundwater sample amended with persulfate, whereas the percarbonate‐amended sample showed little to no degradation of the target hydrocarbon compounds in the laboratory. Isotopic analyses of the persulfate‐amended samples suggested that C‐isotope fractionation for xylenes occurred after approximately 30 percent reduction in concentration with a decline of about 1 percent in the δ¹³C values of xylenes. Based on the laboratory results, pilot‐scale testing at the Saudi Arabian field site was carried out to evaluate the effectiveness of chemical oxidation using nonactivated persulfate on a high temperature, saline petroleum hydrocarbon plume. Approximately 1,750 kg of Na₂S₂O₈ was delivered to the subsurface using a series of injection wells over three injection events. Results obtained from the pilot test indicated that all the target compounds decreased with removal percentages varying between 86 percent for naphthalene and more than 99 percent for the MTBE and TMBs. The benzene, toluene, ethylbenzene, and xylene compounds decreased to 98 percent on average. Examination of the microbial population upgradient and downgradient of the ISCO reactive zone suggested that a bacteria population was present following the ISCO injections with sulfate‐reducing bacteria (SRB) being the dominant bacteria present. Measurements of inorganic parameters during injection and postinjection indicated that the pH of the groundwater remained neutral following injections, whereas the oxidation–reduction potential remained anaerobic throughout the injection zone with time. Nitrate concentrations decreased within the injection zone, suggesting that the nitrate may have been consumed by denitrification reactions, whereas sulfate concentrations increased as expected within the reactive zone, suggesting that the persulfate produced sulfate. Overall, the injection of the oxidant persulfate was shown to be an effective approach to treat dissolved aromatic and associated hydrocarbons within the groundwater. In addition, the generation of sulfate as a byproduct was an added benefit, as the sulfate could be utilized by SRBs present within the subsurface to further biodegrade any remaining hydrocarbons. ©2015 Wiley Periodicals, Inc.     

Assessing Changes in Phosphorus Concentrations in Relation to In-Stream Plant Ecology in Lowland Permeable Catchments: Bringing Ecosystem Functioning Into Water Quality Monitoring

Changes in concentrations of soluble reactive phosphorus (SRP), excess partial pressure of carbon dioxide (EpCO₂), and chlorophyll-a were examined for two rivers in the in the upper Thames catchment: the main river Thames at Wallingford and a chalk stream tributary, the River Kennet. Sampling began in the spring of 1997 and has covered extremes in river flow conditions. During the sampling period there was a dramatic reduction in phosphorus (P) inputs from the introduction of effluent P-treatment at sewage treatment works, as a result of the EU Urban Wastewater Treatment Directive. Despite major reductions in baseflow SRP concentrations in the River Kennet, from around 700 μg-P L^-1 to around 100 μg-P L^-1, observations of aquatic plant communities indicate overall degradation in ecological quality since effluent P-treatment was introduced. The degradation was associated with a spring and summer decline in growth of Ranunculus, a macrophyte of high conservation value in chalk streams, particularly from 2000 onwards, linked to shading by epiphytic algae. Although the EpCO₂ records indicate a reduction in primary productivity since effluent P-treatment, the River Kennet may have become more sensitive to epiphyte blooms. Episodes of epiphyte proliferation appear to be linked temporally to small increases in SRP concentrations (typicallyabove a 100 μg-P L^-1 threshold) under summer baseflow conditions. The in-stream system is highly complex and individual processes and causality are difficult to resolve, particularly given changes in river flows linked to background climatic variability and limited availability of biological data. This study demonstrates the need for integrated long-term biological and chemical monitoring of river systems subject to major perturbations to assess timescales required to produce new dynamic equilibria in ecosystem response.     

Microbial biomass yield and turnover in soil biodegradation tests: carbon substrate effects

Most of the standardized biodegradation tests used to assess the ultimate biodegradation of environmentally degradable polymers are based solely on the determination of net evolved carbon dioxide. However, under aerobic conditions, it has to be considered that heterotrophic microbial consortia metabolize carbon substrates both to carbon dioxide and in the production of new cell biomass. It is generally accepted that in the relatively short term, 50% of the carbon content of most organic substrates is converted to CO₂, with the remaining carbon being assimilated as biomass or incorporated into humus. The latter is particularly important when the metabolism of the organic matter occurs in a soil environment. A straightforward relationship between the free-energy content of a carbon substrate (expressed as the standard free-energy of combustion) and its propensity for conversion to new microbial biomass rather than mineralization to CO₂ has been established. This can potentially lead to underestimation of biodegradation levels of test compounds, especially when they consist of carbon in a fairly low formal oxidation state and relatively high free-energy content. In the present work, the metabolism of different kind of carbon substrates, especially in soil, is reviewed and compared with our own experimental results from respirometric tests. The results show that conversion of highly oxidized materials, such as the commonly used reference materials, cellulose or starch, to CO₂ may be significantly overestimated. The addition of glucosidic material to soil leads to greatly increased respiration and is accompanied by a very low conversion to biomass or humic substances. In contrast, relatively less oxidized substrates metabolize more slowly to give both CO₂ and biomass to an extent which may be significantly underestimated if glucosidic materials are used as the reference. The need for an overall carbon balance taking into account both the carbon immobilized as biomass and that volatized as CO₂ must be considered in standard respirometric procedures for assessing the biodegradability of slowly degrading macromolecules.