An assessment of natural biotransformation of petroleum hydrocarbons and chlorinated solvents at an aquifer plume transect

Field biogeochemical characterization and laboratory microcosm studies were performed to assess the potential for future biotransformation of trichloroethylene (TCE) and toluene in a plume containing petroleum hydrocarbons and chlorinated solvents at the former Wurtsmith Air Force Base in Oscoda, MI. In situ terminal electron accepting processes (TEAPs), contaminant composition and microbial phylogeny were studied at a plume transect 100 m downgradient of the source. The presence of reduced electron acceptors, relevant microbial communities, and elevated dissolved methane and carbon dioxide concentrations at the transect, as well as downgradient accumulation of BTEX metabolites and dechlorination products, indicated that past or current reductive dechlorination at the transect was likely driven by BTEX biodegradation in the methanogenic zone. However, TCE and toluene mineralization in sediment-groundwater microcosms without added electron acceptors did not exceed 5% during 300 days of incubation and was nearly invariant with original sediment TEAP, even following amendments of nitrogen and phosphorus. Mineralization rates were on the order of 0.0015-0.03 mumol/g day. After 8 months, microcosms showed evidence of methanogenesis, but CH4 and CO2 production arose from the degradation of contaminants other than toluene. Cis-dichloroethylene was observed in only one methanogenic microcosm after more than 500 days. It appears likely that spatially and temporally dynamic redox zonation at the plume transect will prevent future sustained reductive dehalogenation of highly chlorinated solvents, for during the course of a year, the predominant TEAP at the highly contaminated water table shifted from methanogenesis to iron- and sulfate-reduction. It is recommended that biotransformation studies combine considerations of long-term, spatially relevant changes in redox zonation with laboratory-scale studies of electron donor utilization and cometabolic substrate transformation to yield a more accurate assessment of natural bioattenuation of specific pollutants in aquifers contaminated by undefined organic waste mixtures.     

Assessment of biogeochemical natural attenuation and treatment of chlorinated solvents, Altus Air Force Base, Altus, Oklahoma

Biogeochemical reductive dechlorination (BiRD) is a newly recognized method for the remediation or natural attenuation of chlorinated solvents. Chlorinated solvents are rapidly treated by abiotic reaction with reduced mineral iron sulfides. Iron sulfides are formed by naturally occurring sulfate-reducing bacteria when sufficient SO(4)(2-) and organic carbon are present or supplied to sediments containing mineral iron. An example of site characterization focusing on BiRD is presented focusing on mineral phases. Methods demonstrated here may be employed at other sites to evaluate naturally occurring BiRD or to evaluate an engineered BiRD remediation. A field investigation was performed at a TCE contaminated site at Altus AFB with naturally high concentrations of SO(4)(2-) and Fe(III) minerals and where an accidental fuel spill provided organic carbon. In the area of this fuel spill significant mineral iron sulfides were found, sulfate was almost completely removed, and TCE was absent. Only small amounts of daughter products were found, further indicating that the BiRD pathway was operative. Mass balance data indicates all of the remaining TCE (182 kg) could be treated by the remaining FeS (66.5 kg) in the upper aquifer; however, the FeS was not co-located with TCE to enable complete reaction. Laboratory microcosm tests with FeS amended and FeS-rich sediment from Altus AFB also suggest that BiRD is capable of destroying TCE. The results suggest that an engineered BiRD treatment is possible for this site.     

Sorption of chlorinated solvents and degradation products on natural clayey tills

The sorption of chlorinated solvents and degradation products on seven natural clayey till samples from three contaminated sites was investigated by laboratory batch experiments in order to obtain reliable sorption coefficients (K_d values). The sorption isotherms for all compounds were nearly linear, but fitted by Freundlich isotherms slightly better over the entire concentration range. For chloroethylenes, tetrachloroethylene (PCE) was most strongly sorbed to the clayey till samples (K_d = 0.84-2.45 L kg⁻¹), followed by trichloroethylene (TCE, K_d = 0.62-0.96 L kg⁻¹), cis-dichloroethylene (cis-DCE, K_d = 0.17-0.82 L kg⁻¹) and vinyl chloride (VC, K_d = 0.12-0.36 L kg⁻¹). For chloroethanes, 1,1,1-trichloroethane (1,1,1-TCA) was most strongly sorbed (K_d = 0.2-0.45 L kg⁻¹), followed by 1,1-dichloroethane (1,1-DCA, K_d = 0.16-0.24 L kg⁻¹) and chloroethane (CA, K_d = 0.12-0.18 L kg⁻¹). This is consistent with the order of hydrophobicity of the compounds. The octanol-water coefficient (log K_ow) correlated slightly better with log K_d values than log K_oc values indicating that the K_d values may be independent of the actual organic carbon content (f_oc). The estimated log K_oc or log K_d for chlorinated solvents and degradation products determined by regression of data in this study were significantly higher than values determined by previously published empirical relationships. The site specific K_d values as well as the new empirical relationship compared well with calculations on water and soil core concentration for cis-DCE and VC from the Rugårdsvej site. In conclusion, this study with a wide range of chlorinated ethenes and ethanes - in line with previous studies on PCE and TCE - suggest that sorption in clayey tills could be higher than typically expected.     

Integrative approach to delineate natural attenuation of chlorinated benzenes in anoxic aquifers

Biodegradation of chlorobenzenes was assessed at an anoxic aquifer by combining hydrogeochemistry and stable isotope analyses. In situ microcosm analysis evidenced microbial assimilation of chlorobenzene (MCB) derived carbon and laboratory investigations asserted mineralization of MCB at low rates. Sequential dehalogenation of chlorinated benzenes may affect the isotope signature of single chlorobenzene species due to simultaneous depletion and enrichment of ¹³C, which complicates the evaluation of degradation. Therefore, the compound-specific isotope analysis was interpreted based on an isotope balance. The enrichment of the cumulative isotope composition of all chlorobenzenes indicated in situ biodegradation. Additionally, the relationship between hydrogeochemistry and degradation activity was investigated by principal component analysis underlining variable hydrogeochemical conditions associated with degradation activity at the plume scale. Although the complexity of the field site did not allow straightforward assessment of natural attenuation processes, the application of an integrative approach appeared relevant to characterize the in situ biodegradation potential.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/ aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally atteuated by a combination of active anaerobic and aerobic biotransformation processes.     

Anaerobic transformations and bioremediation of chlorinated solvents

Chlorinated aliphatic compounds, notably the chlorinated solvents, are common contaminants in soil and groundwater at hazardous waste sites. While these compounds are often recalcitrant, under favorable conditions they can be transformed and degraded through microbially mediated processes. There is great interest in understanding the transformations that are observed at contaminated sites and in manipulating these systems to achieve remediation. An important class of transformations occurs in anaerobic environments. Many of the transformations are reductive, and many yield useful energy to specific anaerobic bacteria. They include reductive dechlorination, dehydrochlorination and dichloroelemination. Of these, reductive dechlorination is often a growth-supporting reaction, while the others may be abiological or catalyzed by biological molecules. The reactions may result in chlorinated products, but there are often reaction sequences leading to completely dechlorinated products. The behavior of carbon tetrachloride (CT), 1,1,2,2-tetrachloroethane (TeCA) and the chloroethenes, perchloroethylene (PCE) and trichloroethylene (TCE), illustrate the range of anaerobic transformations that are possible, as well as the limited transformation that often is seen in the environment. CT undergoes reductive and substitutive reactions that are catalyzed by biological molecules but do not support bacterial growth. The anaerobic degradation of TeCA, which is a major contaminant at a site near Tacoma, WA, USA, provides examples of each type of transformation, and the products formed are consistent with the chlorinated compounds that are found in groundwater extraction wells. A laboratory study, using anaerobic sludge that had been fed chlorinated compounds, a cell-free extract from the sludge, and killed controls, showed that TeCA was transformed to four products and that these were further transformed, suggesting that it might be possible to degrade TeCA to innocuous products. Reductive dechlorination of PCE and TCE has been studied in many laboratories. Studies with mixed anaerobic consortia and with several dehalogenating bacteria, including strain 195 (. Isolation of a bacterium that reductively dechlorinates tetrachloroethane to ethane. Science 276, 1568-1571) that transforms PCE to ethene, have demonstrated that reductive dechlorination supports growth of the novel bacteria that carry out the reactions. Hydrogen has been shown to be an electron donor for the bacterial dehalogenation reactions, and kinetic and thermodynamic considerations indicate that dehalogenators can compete in some, but not all, anaerobic environments, pointing to applications of in situ bioremediation and to its limitations. Selected field studies of anaerobic transformations help delineate the applications of this type of bioremediation.     

Effectiveness of zerovalent iron and nickel catalysts for degrading chlorinated solvents and n-nitrosodimethylamine in natural groundwater.

Laboratory batch experiments were performed to evaluate the effectiveness of nickel catalysts, nanoscale zerovalent iron (nZVI) doped with palladium, and microscale ZVI for treatment of tetrachloroethene, trichloroethene, and n-nitrosodimethylamine (NDMA) in soil-groundwater slurries. Results indicated that the presence of NDMA inhibited degradation of chlorinated solvents. Although both the nickel catalyst and nZVI were able to degrade NDMA in deionized water, neither of these metals was effective at degrading NDMA in the soil-groundwater system evaluated in this study. The effectiveness of the nickel catalyst and nZVI, with respect to treatment of the chlorinated solvents, also appeared to be highly dependent on the groundwater geochemical conditions. Overall results of this study suggest that the degradation mechanisms involving nickel catalysts and nZVI in natural soil/groundwater systems are not well-understood, and addition of metal catalysts to ZVI may not necessarily enhance observed degradation rates in natural systems.     

The variability and intrinsic remediation of a BTEX plume in anaerobic sulphate-rich groundwater

Data from long-term groundwater sampling, limited coring, and associated studies are synthesised to assess the variability and intrinsic remediation/natural attenuation of a dissolved hydrocarbon plume in sulphate-rich anaerobic groundwater. Fine vertical scale (0.25- and 0.5-m depth intervals) and horizontal plume-scale (>400 m) characteristics of the plume were mapped over a 5-year period from 1991 to 1996. The plume of dissolved BTEX (benzene, toluene, ethylbenzene, xylene) and other organic compounds originated from leakage of gasoline from a subsurface fuel storage tank. The plume was up to 420 m long, less than 50 m wide and 3 m thick. In the first few years of monitoring, BTEX concentrations near the point of leakage were in approximate equilibrium with non-aqueous phase liquid (NAPL) gasoline. NAPL composition of core material and long-term trends in ratios of BTEX concentrations in groundwater indicated significant depletion (water washing, volatilisation and possibly biodegradation) of benzene from residual NAPL after 1992. Large fluctuations in BTEX concentrations in individual boreholes were shown to be largely attributable to seasonal groundwater flow variations. A combination of temporal and spatial groundwater quality data was required to adequately assess the stationarity of plumes, so as to allow inference of intrinsic remediation. Contoured concentration data for the period 1991 to 1996 indicated that plumes of toluene and o-xylene were, at best, only partially steady state (pseudo-steady state) due to seasonal groundwater flow changes. From this analysis, it was inferred that significant remediation by natural biodegradation was occurring for BTEX component plumes such as toluene and o-xylene, but provided no conclusive evidence of benzene biodegradation. Issues associated with field quantification of intrinsic remediation from groundwater sampling are highlighted. Preferential intrinsic biodegradation of selected organic compounds within the BTEX plume was shown to be occurring, in parallel with sulphate reduction and bicarbonate production. Ratios of average hydrocarbon concentrations to benzene for the period 1991 to 1992 were used to estimate degradation rates (half-lives) at various distances along the plume. The estimates varied with distance, the narrowest range being, for toluene, 110 to 260 days. These estimates were comparable to rates determined previously from an in situ tracer test and from plume-scale modelling.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: characterization of microbial community structure

A polyphasic approach based on cultivation and direct recovery of 16S rRNA gene sequences was utilized for microbial characterization of an aquifer contaminated with chlorinated ethenes. This work was conducted in order to support the evaluation of natural attenuation of chlorinated ethenes in groundwater at Area 6 at Dover Air Force Base (Dover, DE). Results from these studies demonstrated the aquifer contained relatively low biomass (e.g. direct microscopic counts of < 10(7) bacteria/g of sediment) comprised of a physiologically diverse group of microorganisms including iron reducers, acetogens, sulfate reducers, denitrifiers, aerobic and anaerobic heterotrophs. Laboratory microcosms prepared with authentic sediment and groundwater provided direct microbiological evidence that the mineralization of vinyl chloride and cis-dichloroethene as well as each step in the complete reductive dechlorination of tetracloroethene to ethene can occur in the Area 6 aquifer. Enrichment cultures capable of the oxidative degradation of cis-1,2-dichloroethene (cis-DCE) and vinyl chloride (VC) were obtained from groundwater across the aquifer demonstrating the possible importance of direct, non-cometabolic oxidation of cis-DCE and VC in natural attenuation. Culture-independent analyses based upon recovery of 16S rRNA gene sequences revealed the presence of anaerobic organisms distributed primarily between two major bacterial divisions: the delta subdivision of the Proteobacteria and low-G + C gram positive. Recovery of sequences affiliated with phylogenetic groups containing known anaerobic-halorespiring organisms such as Desulfitobacterium, Dehalobacter, and certain groups of iron reducers provided qualitative support for a role of reductive dechlorination processes in the aquifer. This molecular data is suggestive of a functional linkage between the microbiology of the site and the apparent natural attenuation process. The presence and distribution of microorganisms were found to be consistent with a microbially driven attenuation of chlorinated ethenes within the aquifer and in accord with a conceptual model of aquifer geochemistry which suggest that both reductive and oxidative mechanisms are involved in heterogeneous, spatially distributed processes across the aquifer.     

Processes controlling the distribution and natural attenuation of dissolved phenolic compounds in a deep sandstone aquifer

Processes controlling the distribution and natural attenuation (NA) of phenol, cresols and xylenols released from a former coal-tar distillation plant in a deep Triassic sandstone aquifer are evaluated from vertical profiles along the plume centerline at 130 and 350 m from the site. Up to four groups of contaminants (phenols, mineral acids, NaOH, NaCl) form discrete and overlapping plumes in the aquifer. Their distribution reflects changing source history with releases of contaminants from different locations. Organic contaminant distribution in the aquifer is determined more by site source history than degradation. Contaminant degradation at total organic carbon (TOC) concentrations up to 6500 mg l(-1) (7500 mg l(-1) total phenolics) is occurring by aerobic respiration NO3-reduction, Mn(IV)-/Fe(III)-reduction, SO4-reduction, methanogenesis and fermentation, with the accumulation of inorganic carbon, organic metabolites (4-hydroxybenzaldehyde, 4-hydroxybenzoic acid), acetate, Mn(II), Fe(II), S(-II), CH4 and H2 in the plume. Aerobic and NO3-reducing processes are restricted to a 2-m-thick plume fringe but Mn(IV)-/Fe(II)-reduction, SO4-reduction, methanogenesis and fermentation occur concomitantly in the plume. Dissolved H2 concentrations in the plume vary from 0.7 to 110 nM and acetate concentrations reach 200 mg l(-1). The occurrence of a mixed redox system and concomitant terminal electron accepting processes (TEAPs) could be explained with a partial equilibrium model based on the potential in situ free energy (deltaGr) yield for oxidation of H2 by specific TEAPs. Respiratory processes rather than fermentation are rate limiting in determining the distribution of H2 and TEAPs and H2 dynamics in this system. Most (min. 90%) contaminant degradation has occurred by aerobic and NO3-reducing processes at the plume fringe. This potential is determined by the supply of aqueous O2 and NO3 from uncontaminated groundwater, as controlled by transverse mixing, which is limited in this aquifer by low dispersion. Consumption to date of mineral oxides and SO4 is, respectively, <0.15% and 0.4% of the available aquifer capacity, and degradation using these oxidants is <10%. Fermentation is a significant process in contaminant turnover, accounting for 21% of degradation products present in the plume, and indicating that microbial respiration rates are slow in comparison with fermentation. Under present conditions, the potential for degradation in the plume is very low due to inhibitory effects of the contaminant matrix. Degradation products correspond to <22% mass loss over the life of the plume, providing a first-order plume scale half-life >140 years. The phenolic compounds are biodegradable under the range of redox conditions in the aquifer and the aquifer is not oxidant limited, but the plume is likely to be long-lived and to expand. Degradation is likely to increase only after contaminant concentrations are reduced and aqueous oxidant inputs are increased by dispersion of the plume. The results imply that transport processes may exert a greater control on the natural attenuation of this plume than aquifer oxidant availability.     

Multi-component reactive transport modeling of natural attenuation of an acid groundwater plume at a uranium mill tailings site

Natural attenuation of an acidic plume in the aquifer underneath a uranium mill tailings pond in Wyoming, USA was simulated using the multi-component reactive transport code PHREEQC. A one-dimensional model was constructed for the site and the model included advective-dispersive transport, aqueous speciation of 11 components, and precipitation-dissolution of six minerals. Transport simulation was performed for a reclamation scenario in which the source of acidic seepage will be terminated after 5 years and the plume will then be flushed by uncontaminated upgradient groundwater. Simulations show that successive pH buffer reactions with calcite, Al(OH)3(a), and Fe(OH)3(a) create distinct geochemical zones and most reactions occur at the boundaries of geochemical zones. The complex interplay of physical transport processes and chemical reactions produce multiple concentration waves. For SO4(2-) transport, the concentration waves are related to advection-dispersion, and gypsum precipitation and dissolution. Wave speeds from numerical simulations compare well to an analytical solution for wave propagation.     

Cost-effective sampling network design for contaminant plume monitoring under general hydrogeological conditions

A new simulation-optimization methodology is developed for cost-effective sampling network design associated with long-term monitoring of large-scale contaminant plumes. The new methodology is similar in concept to the one presented by Reed et al. (Reed, P.M., Minsker, B.S., Valocchi, A.J., 2000a. Cost-effective long-term groundwater monitoring design using a genetic algorithm and global mass interpolation. Water Resour. Res. 36 (12), 3731-3741) in that an optimization model based on a genetic algorithm is coupled with a flow and transport simulator and a global mass estimator to search for optimal sampling strategies. However, this study introduces the first and second moments of a three-dimensional contaminant plume as new constraints in the optimization formulation, and demonstrates the proposed methodology through a real-world application. The new moment constraints significantly increase the accuracy of the plume interpolated from the sampled data relative to the plume simulated by the transport model. The plume interpolation approaches employed in this study are ordinary kriging (OK) and inverse distance weighting (IDW). The proposed methodology is applied to the monitoring of plume evolution during a pump-and-treat operation at a large field site. It is shown that potential cost savings up to 65.6% may be achieved without any significant loss of accuracy in mass and moment estimations. The IDW-based interpolation method is computationally more efficient than the OK-based method and results in more potential cost savings. However, the OK-based method leads to more accurate mass and moment estimations. A comparison of the sampling designs obtained with and without the moment constraints points to their importance in ensuring a robust long-term monitoring design that is both cost-effective and accurate in mass and moment estimations. Additional analysis demonstrates the sensitivity of the optimal sampling design to the various coefficients included in the objective function of the optimization model.     

Progression of natural attenuation processes at a crude-oil spill site: I. Geochemical evolution of the plume

A 16-year study of a hydrocarbon plume shows that the extent of contaminant migration and compound-specific behavior have changed as redox reactions, most notably iron reduction, have progressed over time. Concentration changes at a small scale, determined from analysis of pore-water samples drained from aquifer cores, are compared with concentration changes at the plume scale, determined from analysis of water samples from an observation well network. The small-scale data show clearly that the hydrocarbon plume is growing slowly as sediment iron oxides are depleted. Contaminants, such as ortho-xylene that appeared not to be moving downgradient from the oil on the basis of observation well data, are migrating in thin layers as the aquifer evolves to methanogenic conditions. However, the plume-scale observation well data show that the downgradient extent of the Fe2+ and BTEX plume did not change between 1992 and 1995. Instead, depletion of the unstable Fe (III) oxides near the subsurface crude-oil source has caused the maximum dissolved iron concentration zone within the plume to spread at a rate of approximately 3 m/year. The zone of maximum concentrations of benzene, toluene, ethylbenzene and xylene (BTEX) has also spread within the anoxic plume. In monitoring the remediation of hydrocarbon-contaminated ground water by natural attenuation, subtle concentration changes in observation well data from the anoxic zone may be diagnostic of depletion of the intrinsic electron-accepting capacity of the aquifer. Recognition of these subtle patterns may allow early prediction of growth of the hydrocarbon plume.     

Groundwater-surface water interaction and its role on TCE groundwater plume attenuation

A field investigation of a TCE plume in a surficial sand aquifer shows that groundwater-surface water interactions strongly influence apparent plume attenuation. At the site, a former industrial facility in Connecticut, depth-discrete monitoring along three cross-sections (transects) perpendicular to groundwater flow shows a persistent VOC plume extending 700 m from the DNAPL source zone to a mid-size river. Maximum TCE concentrations along a transect 280 m from the source were in the 1000s of microg/L with minimal degradation products. Beyond this, the land surface drops abruptly to a lower terrace where a shallow pond and small streams occur. Two transects along the lower terrace, one midway between the facility and river just downgradient of the pond and one along the edge of the river, give the appearance that the plume has strongly attenuated. At the river, maximum TCE concentrations in the 10s of microg/L and similar levels of its degradation product cis-DCE show direct plume discharge from groundwater to the river is negligible. Although degradation plays a role in the strong plume attenuation, the major attenuation factor is partial groundwater plume discharge to surface water (i.e. the pond and small streams), where some mass loss occurs via water-air exchange. Groundwater and stream mass discharge estimates show that more than half of the plume mass discharge crossing the first transect, before surface water interactions occur, reaches the river directly via streamflow, although river concentrations were below detection due to dilution. This study shows that groundwater and surface water concentration measurements together provide greater confidence in identifying and quantifying natural attenuation processes at this site, rather than groundwater measurements alone.     

Factors controlling natural VOC emissions in a southeastern US pine forest

A one-year field study was conducted to investigate the control factors of the monoterpene emissions from slash and loblolly pine saplings at the Austin Cary Forest site in Florida. The α-pinene, camphene, β-pinene, myrcene, d-limonene, and β-phellandrene were identified in the emission samples collected from native pine trees. The α-pinene was the principal (>60%) monoterpene emitted by both slash and loblolly pine saplings. Terpene emission rates in spring were the highest and most volatile for slash pine trees, possibly due to the influences of bud formation and elongation. Loblolly pine emissions, under a similar environmental temperature range, revealed different seasonal patterns of emissions when compared to those for slash pines. Emission rates of monoterpenes from slash and loblolly pine trees were found to depend on temperature, season's change (e.g., bud emissions), tree age, needle surface wetness, and rough handling. It is suggested that the emission control factors besides the environmental temperature should also be taken into account in assessing regional biogenic emissions for compling a worldwide hydrocarbon emission inventory. It is also found that monoterpene emission rates could easily change over a long period of time (e.g., years), and so it is desirable to analyze the emission data based on the short term (e.g., season, month) for reasonable temperature-emission algorithm.     

Treatment of chlorinated solvents by TiO2 photocatalysis and photo-Fenton: influence of operating conditions in a solar pilot plant

Titanium dioxide photocatalysis (using 20 0mg l(-1) of TiO2), under aerobic and anaerobic conditions, and photo-Fenton (2 and 56 mg l(-1) iron) were applied to the treatment of different NBCS (non-biodegradable chlorinated solvents), such as dichloroethane, dichloromethane and trichloromethane dissolved in water at 50 mg l(-1). All the tests were performed in a 35-l solar pilot plant with compound parabolic collectors (CPCs) under natural illumination. The two solar treatments were compared with attention to chloride release and TOC mineralisation, as the main parameters. Photo-Fenton was found to be the more appropriate treatment for these compounds, assuming volatilisation as a drawback of photocatalytic degradation of NBCS dissolved in water. In this context, several operating parameters related to NBCS degradation, e.g., treatment time, temperature, hydrogen peroxide consumption and volatility of parent compounds are discussed. The correct choice of operating conditions can very often diminish the problem of volatilisation during treatment.     

Reactive transport modeling of processes controlling the distribution and natural attenuation of phenolic compounds in a deep sandstone aquifer

Reactive solute transport modeling was utilized to evaluate the potential for natural attenuation of a contaminant plume containing phenolic compounds at a chemical producer in the West Midlands, UK. The reactive transport simulations consider microbially mediated biodegradation of the phenolic compounds (phenols, cresols, and xylenols) by multiple electron acceptors. Inorganic reactions including hydrolysis, aqueous complexation, dissolution of primary minerals, formation of secondary mineral phases, and ion exchange are considered. One-dimensional (1D) and three-dimensional (3D) simulations were conducted. Mass balance calculations indicate that biodegradation in the saturated zone has degraded approximately 1-5% of the organic contaminant plume over a time period of 47 years. Simulations indicate that denitrification is the most significant degradation process, accounting for approximately 50% of the organic contaminant removal, followed by sulfate reduction and fermentation reactions, each contributing 15-20%. Aerobic respiration accounts for less than 10% of the observed contaminant removal in the saturated zone. Although concentrations of Fe(III) and Mn(IV) mineral phases are high in the aquifer sediment, reductive dissolution is limited, producing only 5% of the observed mass loss. Mass balance calculations suggest that no more than 20-25% of the observed total inorganic carbon (TIC) was generated from biodegradation reactions in the saturated zone. Simulations indicate that aerobic biodegradation in the unsaturated zone, before the contaminant entered the aquifer, may have produced the majority of the TIC observed in the plume. Because long-term degradation is limited to processes within the saturated zone, use of observed TIC concentrations to predict the future natural attenuation may overestimate contaminant degradation by a factor of 4-5.     

Migration and natural fate of a coal tar creosote plume: 1. Overview and plume development

A volume of sand containing coal tar creosote was emplaced below the water table at CFB Borden to investigate natural attenuation processes for complex biodegradable mixtures. Coal tar creosote is a mixture of more than 200 polycyclic aromatic hydrocarbons, heterocyclic compounds and phenolic compounds. A representative group of seven compounds was selected for detailed study: phenol, m-xylene, naphthalene, phenanthrene, 1-methylnaphthalene, dibenzofuran and carbazole. Movement of groundwater through the source led to the development of a dissolved organic plume, which was studied over a 4-year period. Qualitative plume observations and mass balance calculations indicated two key conclusions: (1) compounds from the same source can display distinctly different patterns of plume development and (2) mass transformation was a major influence on plume behaviour for all observed compounds.     

Dissipation of DDT in natural water under field conditions

Abstract

¹⁴C‐DDT dissipated gradually from natural water under outdoor conditions and declined to 40% of the applied radioactivity after 5 months. The losses are due to adsorption to particulates and volatilization from the water surface. In natural water DDT undergoes gradual conversion to DDE as the major degradation product and to a lesser extent to DDD. It may be concluded that DDT dissipates and degrades fairly rapidly in subtropical natural waters. Adsorption to particulate matter contributes to partial “removal” of DDT.     

Modelling of physical and reactive processes during biodegradation of a hydrocarbon plume under transient groundwater flow conditions

Numerical experiments of non-reactive and reactive transport were carried out to quantify the influence of a seasonally varying, transient flow field on transport and natural attenuation at a hydrocarbon-contaminated field site. Different numerical schemes for solving advective transport were compared to assess their capability to model low transversal dispersivities in transient flow fields. For the field site, it is shown that vertical plume spreading is largely inhibited, particularly if sorption is taken into account. For the reactive simulations, a biodegradation reaction module for the geochemical transport model PHT3D was developed. Results of the reactive transport simulations show that under the site-specific conditions the temporal variations in groundwater flow do, to a modest extent, affect average biodegradation rates and average total (dissolved) contaminant mass in the aquifer. The model simulations demonstrate that the seasonal variability in groundwater flow only results in significantly enhanced biodegradation rates when a differential sorption of electron donor (toluene) and electron acceptor (sulfate) is assumed.