Enumeration of aromatic oxygenase genes to evaluate biodegradation during multi-phase extraction at a gasoline-contaminated site

Multi-phase extraction (MPE) is commonly used at petroleum-contaminated sites to volatilize and recover hydrocarbons from the vadose and saturated zones in contaminant source areas. Although primarily a physical treatment technology, the induced subsurface air flow can potentially increase oxygen supply and promote aerobic biodegradation of benzene, toluene, ethylbenzene, and xylenes (BTEX), the contaminants of concern at gasoline-contaminated sites. In this study, real-time PCR enumeration of aromatic oxygenase genes and PCR-DGGE profiles were used to elucidate the impact of MPE operation on the aquifer microbial community structure and function at a gasoline-contaminated site. Prior to system activation, ring-hydroxylating toluene monooxygenase (RMO) and naphthalene dioxygenase (NAH) gene copies were on the order of 10(6) to 10(10)copies L(-1) in groundwater samples obtained from BTEX-impacted wells. Aromatic oxygenase genes were not detected in groundwater samples obtained during continuous MPE indicating decreased populations of BTEX-utilizing bacteria. During periods of pulsed MPE, total aromatic oxygenase gene copies were not significantly different than prior to system activation, however, shifts in aromatic catabolic genotypes were noted. The consistent detection of RMO, NAH, and phenol hydroxylase (PHE), which catabolizes further oxidation of hydroxylated BTEX metabolites indicated the potential for aerobic biodegradation of dissolved BTEX during pulsed MPE.     

Applicability of boron-doped diamond electrode to the degradation of chloride-mediated and chloride-free wastewaters

The degradation of diphenylamine (DPA) in aqueous solution by persulfate is investigated. Effects of pH, persulfate concentration, ionic strength, temperature and catalytic ions Fe(3+) and Ag(+) on the degradation efficiency of DPA by persulfate are examined in batch experiments. The degradation of DPA by persulfate is found to follow the pseudo-first-order kinetic model. Increasing the reaction temperature or persulfate concentration may significantly accelerate the DPA degradation. Fe(3+) and Ag(+) ions can enhance the degradation of DPA, and Ag(+) ion is more efficient than Fe(3+) ion. However, the increase of either the pH value or ionic strength will decrease the rate of DPA degradation. N-Phenyl-4-quinoneimine, N-carboxyl-4-quinoneimine, 4-quinoneimine and oxalic acid are identified as the major intermediates of DPA degradation, and a primary pathway for the degradation of DPA is proposed. The degradation of DPA in surface water, groundwater and seawater is also tested by persulfate, and more than 90% of DPA can be degraded at room temperature in 45min at an initial concentration of 20mgL(-1).     

Novel thermally stable poly(vinyl chloride) composites for sulfate removal

The adsorptive and catalytic characteristics of waste-reclaimed adsorbent (WR), which is a calcined mixture of bottom-ash and dredged-soil, was investigated for its application to treating BTEX contamination. BTEX adsorption in WR was 54%, 64%, 62%, and 65%, respectively, for a 72 h reaction time. Moreover, the catalytic characteristics of WR were observed when three types of oxidation systems (i.e., H(2)O(2), persulfate (PS), and H(2)O(2)/Fe(III)/oxalate) were tested, and these catalytic roles of WR could be due to iron oxide on its surface. In PS/WR system, large amounts of metal ions from WR were released because of large drops of solution pH, and the surface area of WR was also greatly reduced. Moreover, the BTEX that was removed per consumed oxidant (ΔC(rem)/ΔOx) increased with increasing PS. In H(2)O(2)/Fe(III)/oxalate with WR system, the highest BTEX degradation rate constants (k(deg)) were calculated as 0.338, 0.365, 0.500 and 0.716 h(-1), respectively, when 500 mM of H(2)O(2) was used, and the sorbed BTEX on the surface of WR was also degraded, which suggests the regeneration of WR. Therefore, the oxidant-injected permeable reactive barrier filled in WR could be an alternative to treating BTEX with both adsorption and catalytic degradation.     

Application of multiphase transport models to field remediation by air sparging and soil vapor extraction

The design and operation of air sparging and soil vapor extraction (AS/SVE) remediation systems remains in large an art due to the absence of reliable physically based models that can utilize the limited available field data. In this paper, a numerical model developed for the design and operation of air sparging and soil vapor extractions systems was used to simulate two field case studies. The first-order mass transfer kinetics were incorporated into the model to account for contaminant mass transfer between the water and air (stripping), NAPL and water (dissolution), NAPL and air (volatilization), and water and soil (sorption/desorption), the model also accounted for soil heterogeneity. Benzene, toluene, ethyl benzene and xylenes (BTEX) were the contaminants of concern in both case studies. In the second case study, the model was used to evaluate the effect of pulsed sparging on the removal rate of BTEX compounds. The pulsed sparging operation was approximated assuming uniform contaminant redistribution at the beginning of the shut-off period. The close comparison between the observed and simulated contaminant concentration in the aqueous phase showed that the approximation of the pulsed sparging operation yielded reasonable prediction of the removal process. Field heterogeneity was simulated using Monte Carlo analysis. The model predicted about 80-85% of the contaminant mass was removed by air-water mass transfer, which was similar to the average removal obtained by Monte Carlo analysis. The analysis of the removal/rebound cycles demonstrated that removal rate was controlled by the organic-aqueous distribution coefficient K(oc). Due to the lack of site-specific data, the aerobic first-order biodegradation coefficients (k(bio)) were obtained from a literature survey, therefore, uncertainty analysis of the k(bio) was conducted to evaluate the contribution of the aerobic biodegradation to total contaminant removal. Results of both case studies showed that biodegradation played a major role in the remediation of the contaminated sites.     

Pilot plant experiences using physical and biological treatment steps for the remediation of groundwater from a former MGP site

The production of manufactured gas at a site in Vienna, Austria led to the contamination of soil and groundwater with various pollutants including PAHs, hydrocarbons, phenols, BTEX, and cyanide. The site needs to be remediated to alleviate potential impacts to the environment. The chosen remediation concept includes the excavation of the core contaminated site and the setup of a hydraulic barrier to protect the surrounding aquifer. The extracted groundwater will be treated on-site. To design the foreseen pump-and-treat system, a pilot-scale plant was built and operated for 6 months. The scope of the present study was to test the effectiveness of different process steps, which included an aerated sedimentation basin, a submerged fixed film reactor (SFFR), a multi-media filter, and an activated carbon filter. The hydraulic retention time (HRT) was 7.0 h during normal flow conditions and 3.5h during high flow conditions. The treatment system was effective in reducing the various organic and inorganic pollutants in the pumped groundwater. However, it was also demonstrated that appropriate pre-treatment was essential to overcome problems with clogging due to precipitation of tar and sulfur compounds. The reduction of the typical contaminants, PAHs and BTEX, was more than 99.8%. All water quality parameters after treatment were below the Austrian legal requirements for discharge into public water bodies.     

Comparison of reductive dechlorination of p-chlorophenol using Fe0 and nanosized Fe0

Chlorophenols, as a kind of important contaminants in groundwater, are toxic and difficult to biodegrade. Laboratory tests were conducted to examine zero-valent iron as an enhancing agent in the dechlorination of chlorinated organic compounds. Nanoscale iron particles were synthesized from common precursors KBH(4) and FeSO(4). Batch experiments were performed to investigate the reduction of p-chlorophenol (4-CP) by both common Fe(0) and nanoscale Fe(0). Comparison of 300 mesh/100 mesh/commercial reductive iron powders showed that size of iron particles played an important role in reduction process. Initial concentration and pretreatment of iron particles also influenced the chlorination rate. Nanoscale Fe(0) offered much more advantages for treatment of 4-CP compared with common iron particles, such as stability and durability. And they can be used to treat contaminants in groundwater over a long time. Among different parts of synthesized nanoscale iron particle solution, the very fine particles were the major agent for treatment of pollutants. As for preservation of nanoscale Fe(0), ethanol was recommended.     

Evaluation of natural attenuation rate at a gasoline spill site

Contamination of groundwater by gasoline and other petroleum-derived hydrocarbons released from underground storage tanks (USTs) is a serious and widespread environmental problem. Natural attenuation is a passive remedial approach that depends upon natural processes to degrade and dissipate contaminants in soil and groundwater. Currently, in situ column technique, microcosm, and computer modeling have been applied for the natural attenuation rate calculation. However, the subsurface heterogeneity reduces the applicability of these techniques. In this study, a mass flux approach was used to calculate the contaminant mass reduction and field-scale decay rate at a gasoline spill site. The mass flux technique is a simplified mass balance procedure, which is accomplished using the differences in total contaminant mass flux across two cross-sections of the contaminant plume. The mass flux calculation shows that up to 87% of the dissolved total benzene, toluene, ethylbenzene, and xylene (BTEX) isomers removal was observed via natural attenuation at this site. The efficiency of natural biodegradation was evaluated by the in situ tracer method, and the first-order decay model was applied for the natural attenuation/biodegradation rate calculation. Results reveal that natural biodegradation was the major cause of the BTEX mass reduction among the natural attenuation processes, and approximately 88% of the BTEX removal was due to the natural biodegradation process. The calculated total BTEX first-order attenuation and biodegradation rates were 0.036 and 0.025% per day, respectively. Results suggest that the natural attenuation mechanisms can effectively contain the plume, and the mass flux method is useful in assessing the occurrence and efficiency of the natural attenuation process.     

Application of persulfate to remediate petroleum hydrocarbon-contaminated soil: feasibility and comparison with common oxidants

In this study, batch experiments were conducted to evaluate the feasibility of petroleum-hydrocarbon contaminated soil remediation using persulfate oxidation. Various controlling factors including different persulfate and ferrous ion concentrations, different oxidants (persulfate, hydrogen peroxide, and permanganate), and different contaminants (diesel and fuel oil) were considered. Results show that persulfate oxidation is capable of treating diesel and fuel oil contaminated soil. Higher persulfate and ferrous ion concentrations resulted in higher diesel degrading rates within the applied persulfate/ferrous ion molar ratios. A two-stage diesel degradation was observed in the batch experiments. In addition, treatment of diesel-contaminated soil using in situ metal mineral activation under ambient temperature (e.g., 25°C) may be a feasible option for site remediation. Results also reveal that persulfate anions could persist in the system for more than five months. Thus, sequential injections of ferrous ion to generate sulfate free radicals might be a feasible way to enhance contaminant oxidation. Diesel oxidation efficiency and rates by the three oxidants followed the sequence of hydrogen peroxide>permanganate>persulfate in the limited timeframes. Results of this study indicate that the application of persulfate oxidation is a feasible method to treat soil contaminated by diesel and fuel oil.     

Oxidation of polyvinyl alcohol by persulfate activated with heat,Fe, and zero-valent iron

The oxidation of polyvinyl alcohol (PVA) by persulfate (S₂O₈²⁻) activated with heat, Fe²⁺, and zero-valent iron (Fe(0)) was investigated via batch experiments. It was hypothesized that elevated temperature and the addition of Fe²⁺ or Fe(0) into a persulfate-water system could enhance the oxidation of PVA by activated persulfate. Increasing the temperature from 20 to 60 °C or 80 °C accelerated the oxidation rate of PVA, which achieved complete oxidation in 30 and 10 min, respectively. At 20 °C, the addition of Fe²⁺ or Fe(0) to the persulfate-water system significantly enhanced the oxidation of PVA. The optimal persulfate-to-Fe²⁺ or Fe(0) molar ratio was found to be 1:1. Complete oxidation of PVA was obtained by Fe(0)-activated persulfate in 2 h. Synergistic activation of persulfate by heat and Fe²⁺ or Fe(0) was also shown to enhance the oxidation of PVA in the persulfate-water system. By using GC–MS analysis, an oxidation product of PVA was identified as vinyl acetic acid (C₄H₆O₂), which is readily biodegradable. Our results suggest that the oxidative treatment of PVA by activated persulfate is a viable option for the pretreatment of PVA-laden wastewater to enhance its biodegradability.     

Effect of NAPL entrapment conditions on air sparging remediation efficiency

The effect of soil heterogeneity and the entrapment condition of NAPL source on the mass removal efficiency of air sparging coupled with soil vapour extraction (AS/SVE) was investigated using an intermediate scale two-dimensional laboratory soil tank. Four different NAPL entrapments were created by varying the height of the water table in heterogeneous soil models. Different mass removal efficiencies were achieved for different NAPL entrapment conditions, which were governed by soil heterogeneity and water table height before and during AS/SVE operation. Remobilization and redistribution of toluene and water improved the mass removal. Overall results suggested that it was difficult to achieve the complete remediation of NAPL source due to complex entrapment in heterogeneous soil system. In order to assess the potential contamination in the post-remediation stage, gas and dissolved concentrations of toluene were measured after the AS/SVE operation. The results showed that gas concentration close to remaining NAPL source zone increased rapidly and reached to steady state values, which were much smaller than the vapour pressure, whereas the aqueous phase concentrations increased continuously toward the solubility limit.     

Preparation of bismuth substituted dysprosium iron garnet film by a sol-gel process

Garnet films of Bi1Dy2Fe5O12 were prepared by a sol-gel process, the so called modified Pechini process, in which ethylene diamine tetraacetic acid (EDTA) rather than citric acid (CA) acted as a chelating agent. The results of analysis on crystallization characteristics for sol-gel derived films showed that efficient removal of organic compounds and carbon residuals before the firing process was vital to forming a single phase garnet within the films. © 1998 Kluwer Academic Publishers     

Adsorption of BTEX from aqueous solution by macroreticular resins

Theoretical and experimental investigations were conducted on the adsorption of benzene, toluene, ethylbenzene and xylene (BTEX) by macroreticular resins. A mass transfer model based on the squared-driving force principle is presented for describing the BTEX transfer between the aqueous and solid phases. Also proposed is a theoretical model for describing the BTEX breakthrough curves of the adsorption column. While the mass transfer model involves only an overall mass transfer coefficient, the column adsorption model has two model parameters. Those parameters are conveniently estimated using the observed mass transfer and breakthrough data. The predictions using the proposed models were found to compare well with the experimental data of batch and column BTEX adsorption tests.     

Stabilization of heavy metals in municipal solid waste incineration ash using mixed ferrous/ferric sulfate solution

The purpose of this study is to test the effectiveness of mixing FeSO4 and Fe2(SO4)(3) solutions with municipal solid waste incineration (MSWI) ash at room temperature to prevent heavy metals in treated ash from being dissolved. After conducting toxicity characteristic leaching procedure (TCLP) tests nine times, the accumulation of extracted lead from treated scrubber ash was lower than regulated limits by the sixth test. X-ray diffraction (XRD) and scanning electron microscopy/energy dispersive spectrometer (SEM/EDS) studies of the ash revealed that the mixed solution reacted with the scrubber ash to form Ca4Fe9O17, which coated the surface of ash particles.     

The effect of Fe0/Fe2+/Fe3+ on nitrobenzene degradation in the anaerobic sludge

The influence of Fe(0)/Fe(2+)/Fe(3+) on the nitrobenzene (NB) degradation in the anaerobic granular sludge was studied and the results demonstrated that: adding iron powder into the anaerobic sludge could exert an accelerative effect on the NB degradation and the degradation rate was faster than that by using iron or the anaerobic sludge alone. The external addition of Fe(2+)/Fe(3+) exhibited different influences on the NB degradation depending on the concentrations of Fe(2+)/Fe(3+) and the solution's pH. When Fe(2+)/Fe(3+) are less than 100 mg/L at pH 6, Fe(2+)/Fe(3+) inhibited the NB degradation slightly, and when Fe(2+)/Fe(3+) was 100-200 mg/L, the NB degradation was enhanced. When pH was shifted to 9, Fe(2+) of lower than 100 mg/L promoted the NB degradation, and 200 mg/L Fe(2+) inhibit the NB degradation. The synergism of combined use of iron and the anaerobic sludge in treating NB wastewater was proposed, and adjusting the concentrations of Fe(2+)/Fe(3+) in the anaerobic sludge according to the pH of the wastewater could be an effective method to obtain a high removal rate of NB.     

Heavy metals mobilization from harbour sediments using EDTA and citric acid as chelating agents

In this paper experimental tests of heavy metals mobilization from sediments collected from an Italian harbour are presented and discussed. Batch tests of washing with an aqueous solution of chelating agent were performed at selected liquid/solid (L/S) ratios and chelant concentration (0.01, 0.05 and 0.1M). Two chelating agents were chosen: EDTA and citric acid. The objective of the tests was to investigate metal mobilization and soil mineral dissolution promoted by the washing treatment. The study was focused on the mobilization of Pb, Zn, and Cu: their concentrations in the contact solution, together with Fe and Ca concentration, were monitored along time for 144h. Results of experimental tests performed at different chelant concentration and L/S ratio show EDTA effectiveness in mobilizing metals bond to the sediment. The overall amount of the three selected metals (Cu, Pb and Zn) extracted in the tests with EDTA varied in a quite narrow range (from 2.262 to 2.724mmol), while the higher was the EDTA concentration in the washing solution, the higher the dissolution of other competitive cations, such as Ca and Fe. In addition, a general difficulty in copper extraction from the organic fraction of the sediment was observed, due to the high stability of copper humate. The mechanism of metals extraction was found to involve the initial metals salts dissolution, that was pH-dependant, followed by the development of exchange reactions between the metal-EDTA complexes previously formed. Depending upon the pH of the washing solution an initial high Ca dissolution was observed, followed by dramatic reduction in Ca(2+) content, mainly determined by calcium carbonate precipitation, as a result of the increase of pH during mixing. Metal mobilization was evaluated performing sequential extraction tests: the dissolution of Cu, Pb and Zn from the carbonate fraction of the sediment was almost total, as the mobilization of Pb and Zn from the Fe-Mn oxides and hydroxides fraction. On the contrary, as a consequence of the mobilization induced by washing treatment, about 17% of the remaining Cu and 10% of the remaining Zn resulted in the exchangeable fraction. At the investigated operating conditions, citric acid was unable to extract Pb and Cu from the sediment, while at the strong acidic conditions maintained during the extractions with citric acid, a Zn mobilization up to the 80% of the initial amount was observed, depending upon the operating conditions in the extractions. In addition, because of the great affinity between citric acid and Fe, and the strong acidic conditions maintained during extraction, a high Fe dissolution was observed (up to about the 39% of the total Fe content in the sediment).     

Proposal of a sequential treatment methodology for the safe reuse of oil sludge-contaminated soil

In this study sequential steps were used to treat and immobilize oil constituents of an oil sludge-contaminated soil. Initially, the contaminated soil was oxidized by a Fenton type reaction (13 wt% for H(2)O(2); 10mM for Fe(2+)). The oxidative treatment period of 80 h was carried out under three different pH conditions: 20 h at pH 6.5, 20 h at pH 4.5, and 40 h at pH 3.0. The oxidized contaminated sample (3 kg) was stabilized and solidified for 2h with clay (1 kg) and lime (2 kg). Finally, this mixture was solidified by sand (2 kg) and Portland cement (4 kg). In order to evaluate the efficiency of different processes to treat and immobilize oil contaminants of the oil sludge-contaminated soil, leachability and solubility tests were performed and extracts were analyzed according to the current Brazilian waste regulations. Results showed that the Fenton oxidative process was partially efficient in degrading the oil contaminants in the soil, since residual concentrations were found for the PAH and BTEX compounds. Leachability tests showed that clay-lime stabilization/solidification followed by Portland cement stabilization/solidification was efficient in immobilizing the recalcitrant and hazardous constituents of the contaminated soil. These two steps stabilization/solidification processes are necessary to enhance environmental protection (minimal leachability) and to render final product economically profitable. The treated waste is safe enough to be used on environmental applications, like roadbeds blocks.     

Microfluidic device for airborne BTEX detection

We fabricated a microfluidic device for the optical detection of airborne benzene, toluene, ethylbenzene and xylenes (BTEX). The device consists of concentration and detection cells formed of 3 cm x 1 cm Pyrex plates. The concentration cell is composed of an adsorbent to concentrate the BTEX gases and a thin-film heater todesorb the concentrated gases from the adsorbent thermally. The collected gases are introduced into the detection cell, which is connected to optical fibers, to measure their absorption spectra. We optimized the device's operating conditions by studying the thermal characteristics of the concentration cell and the time profile of the gas concentration flowing in the detection cell. We used the device under optimized operating conditions to detect toluene gas as a typical example BTEX. The gas concentration amplification rate was approximately 2 orders of magnitude, and we successfully measured parts-per-million levels of toluene gas with this device.     

A pilot study for the selection of a bioreactor for remediation of groundwater from a coal tar contaminated site.

Coal tars in soil at a gasworks site in South Eastern Australia led to groundwater contamination with polycyclic aromatic hydrocarbons (PAHs), mono-aromatic compounds (BTEX) and phenols. The scope of the study included testwork in laboratory scale bioreactors and evaluation of available commercial groundwater treatment units. Two bioreactor configurations, a submerged fixed film reactor (SFFR) and a fluidized bed bioreactor (FBR) were effective, with high efficiencies of contaminant removal (typically >90%) over a range of hydraulic retention times (HRT) (3-29 h). Specifically, concentrations of total PAH, naphthalene, pyrene and total phenols in the feedstock and effluent of the SFFR were 123, 60, 51, 1.38 and 0.004, 0.001, 0.004, 0.1mg/l, respectively. The FBR was only marginally less effective than the SFFR for the same groundwater contaminants. Discharge to sewer was the most appropriate end use for the effluent. SFFRs are regarded as being simpler in design and operation, and a commercially available unit has been identified which would be suitable for treating small volumes (<10 m(3) per day) of contaminated water collected at an interception trench at the site.     

Decolourization and mineralization of commercial reactive dyes by using homogeneous and heterogeneous Fenton and UV/Fenton processes

The oxidative decolourization and mineralization of three reactive dyes in separately prepared aqueous solutions C.I. Reactive Yellow 3 (RY3), C.I. Reactive Blue 2 (RB2) and C.I. Reactive Violet 2 (RV2) by using homogeneous and heterogeneous Fenton and UV/Fenton processes have been investigated. The effects of H(2)O(2), Fe(2+) and Fe(0) concentrations, Fe(2+)/H(2)O(2) and Fe(0)/H(2)O(2) molar ratios at pH 3 and T=23+/-1 degrees C have been studied. Optimal operational conditions for the efficient degradation of all three dye solutions (100 mg L(-1)) were found to be Fe(2+)/H(2)O(2)=0.5mM/20mM and Fe(0)/H(2)O(2)=2mM/1mM. The experimental results showed that the homogeneous Fenton process employing UV irradiation was the most effective. By using this process, the high levels of mineralization (78-84%) and decolourization (95-100%) were achieved. Pseudo-first-order degradation rate constants were obtained from the batch experimental data.     

Application of persulfate-releasing barrier to remediate MTBE and benzene contaminated groundwater

The objective of this study was to assess the potential of using an in situ oxidation barrier system to remediate gasoline-contaminated groundwater. The passive remedial system included a persulfate-releasing barrier containing persulfate-releasing materials to release persulfate for contaminant oxidation. Bench experiments were performed to determine the components and persulfate-releasing rate of the persulfate-releasing materials. Column experiments were conducted to evaluate the effectiveness of the designed persulfate-releasing materials on the control of petroleum-hydrocarbon plume. In this study, methyl tert-butyl ether (MTBE) and benzene were used as the target compounds. The optimal persulfate releasing rate was obtained when the mass ratio of persulfate/cement/sand/water was 1/1/0.16/0.5, and the rate varied from 31 to 8 mg persulfate per day per g of material. Significant amounts of MTBE and benzene were removed through the oxidation process due to the release of persulfate, and the produced tert-butyl formate (TBF) and tert-butyl alcohol (TBA), byproducts of MTBE, were further oxidized in the system. Results suggest that the oxidation rate would be affected by the oxidant reduction potential and concentrations of ferrous iron and persulfate.