Single-well, gas-sparging tests for evaluating the in situ aerobic cometabolism of cis-1,2-dichloroethene and trichloroethene

This study developed single-well, gas-sparging tests for assessing the feasibility of in situ aerobic cometabolism of trichloroethene (TCE) and cis-1,2-dichloroethene (cis-DCE) using propane and methane as growth substrates. Tests were performed in groundwater contaminated with TCE (100-400 microg l(-1)) and cis-DCE (20-60 microg l(-1)). A series of gas-sparging tests was performed by first sparging ("bubbling") gas mixtures in a well fitted with a "straddle" packer and then periodically sampling groundwater from the same well to develop concentration profiles and to estimate transformation rate coefficients. Evidence that gas-sparging of propane (or methane) and oxygen had stimulated organisms expressing a propane (or methane) monooxygenase enzyme system and the capability to transform TCE and cis-DCE included: (1) the transformation of sparged ethylene and propylene to their corresponding cometabolic by-products, ethylene oxide and propylene oxide, (2) the transformation of both cis-DCE and TCE in the propane-sparged well, (3) the transformation of cis-DCE in the methane-sparged well, and (4) the inhibition of ethylene and propylene transformations in the presence of acetylene, a known monooxygenase inactivator. At a well sparged with propane, first-order rate coefficients for propane utilization and ethylene and propylene transformation were similar, ranging from 0.007 to 0.010 h(-1). At the well sparged with methane, the propylene first-order transformation rate coefficient was 0.028 h(-1), a factor of 1.8 and 1.6 greater than methane and ethylene, respectively. The results demonstrated that gas-sparging tests are a rapid, low-cost means of assessing the potential for the in situ aerobic cometabolism of cis-DCE and TCE.     

Cometabolic degradation kinetics of TCE and phenol by Pseudomonas putida

Modeling of cometabolic kinetics is important for better understanding of degradation reaction and in situ application of bio-remediation. In this study, a model incorporated cell growth and decay, loss of transformation activity, competitive inhibition between growth substrate and non-growth substrate and self-inhibition of non-growth substrate was proposed to simulate the degradation kinetics of phenol and trichloroethylene (TCE) by Pseudomonas putida. All the intrinsic parameters employed in this study were measured independently, and were then used for predicting the batch experimental data. The model predictions conformed well to the observed data at different phenol and TCE concentrations. At low TCE concentrations (<2 mg l(-1)), the models with or without self-inhibition of non-growth substrate both simulated the experimental data well. However, at higher TCE concentrations (>6 mg l(-1)), only the model considering self-inhibition can describe the experimental data, suggesting that a self-inhibition of TCE was present in the system. The proposed model was also employed in predicting the experimental data conducted in a repeated batch reactor, and good agreements were observed between model predictions and experimental data. The results also indicated that the biomass loss in the degradation of TCE below 2 mg l(-1) can be totally recovered in the absence of TCE for the next cycle, and it could be used for the next batch experiment for the degradation of phenol and TCE. However, for higher concentration of TCE (>6 mg l(-1)), the recovery of biomass may not be as good as that at lower TCE concentrations.     

Competitive sorption of cis-DCE and TCE in silica gel as a model porous mineral solid

The competitive sorption of 1,2-cis-dichloroethene (cis-DCE) and trichloroethene (TCE) was investigated by means of column experiments using a model porous mineral solid represented by silica gel. The experimental isotherms were obtained by employing a chromatographic method. The competitive sorption isotherms were modelled with the extended Freundlich and extended Langmuir isotherms, using the parameters from single-solute experiments. The breakthrough curves were modelled with the advection-dispersion transport equation coupled with the lumped pore diffusion model. The best results were obtained when the extended Freundlich isotherm was employed. The competitive sorption was revealed with the presence of an overshoot in the breakthrough curve of cis-DCE and a decrease in the degree of sorption of cis-DCE (20%) and TCE (12%). A linear dependency of the overshoot with an increase in the concentration of cis-DCE at a fixed concentration of TCE was observed, between 16% and 20%, and at least at concentrations <6 mg L(-1) in the liquid phase. The displaced molecules of cis-DCE by TCE were accumulated through the column causing its overshoot; thus short columns may hinder its observation. Thermodynamic analysis shows an exothermic adsorption process of -34 to -41 kJ mol(-1), which is enhanced by sorption in micropores. The Gibbs free energy is positive for cis-DCE in the multi-component case, due to its displacement by TCE.     

Decomposition of benzene and toluene in air streams in fixed-film photoreactors coated with TiO2 catalyst

The decomposition of benzene and toluene in air streams by UV/TiO2 process was studied in different annular photoreactors under various operating conditions. The shells of reactors used in this research are made of stainless steel, Pyrex glass, or titanium. The TiO2 film was coated to the inner surface of the reactors by either rotating coating or sol-gel techniques. The TiO2 films coated by sol-gel technique were found to be smoother and more uniform than those coated by rotating coating. However, experimental results indicated that the photocatalysis of benzene or toluene in a glass reactor with rotating-coated TiO2 film delivered higher decompositions in air streams than that with sol-gel coated reactors. Benzene and toluene were decomposed more effectively in a coated glass reactor than in a coated stainless steel reactor under the same operating conditions. The presence of water vapor in air-stream plays an important role in the decomposition of benzene and toluene, and a relative humidity of approximately 5-6% was found to be adequate. The presence of excessive amounts of humidity retarded the decomposition to certain extents possibly results from the competitive adsorption of water molecules on the active sites of TiO2.     

Multiple microbial activities for volatile organic compounds reduction by biofiltration

In the northeast of Italy, high volatile organic carbon (VOC) emissions originate from small-medium companies producing furniture. In these conditions it is difficult to propose a single, efficient, and economic system to reduce pollution. Among the various choices, the biofiltration method could be a good solution, because microbial populations possess multiple VOC degradation potentials used to oxidize these compounds to CO2. Starting from the air emissions of a typical industrial wood-painting plant, a series of experiments studied in vitro microbial degradation of each individual VOC. Isolated strains were then added to a laboratory-scale biofiltration apparatus filled with an organic matrix, and the different VOC behavior demonstrated the potential of single and/or synergic microbial removal actions. When a single substrate was fed, the removal efficiency of a Pseudomonas aeruginosa inoculated reactor was 1.1, 1.17, and 0.33 g m(-3) hr(-1), respectively, for xylene, toluene, and ethoxy propyl acetate. A VOC mixture composed of butyl acetate, ethyl acetate, diacetin alcohol, ethoxy propanol acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, and xylene was then fed into a 2-m(3) reactor treating 100 m3 hr(-1) of contaminated air. The reactor was filled with the same mixture of organic matrix, enriched with all of the isolated strains together. During reactor study, different VOC loading rates were used, and the behavior was evaluated continuously. After a short acclimation period, the removal efficiency was > 65% at VOC load of 150-200 g m(-3) hr(-1). Quantification of removal efficiencies and VOC speciation confirmed the relationship among removal efficiencies, compound biodegradability, and the dynamic transport of each mixture component within the organic matrix. Samples of the fixed bed were withdrawn at different intervals and the heterogeneous microbial community evaluated for both total and differential compound counts.     

Competing TCE and cis-DCE degradation kinetics by zero-valent iron-experimental results and numerical simulation

The successful dechlorination of mixtures of chlorinated hydrocarbons with zero-valent metals requires information concerning the kinetics of simultaneous degradation of different contaminants. This includes intraspecies competitive effects (loading of the reactive iron surface by a single contaminant) as well as interspecies competition of several contaminants for the reactive sites available. In columns packed with zero-valent iron, the degradation behaviour of trichloroethylene (TCE), cis-dichloroethylene (DCE) and mixtures of both was measured in order to investigate interspecies competition. Although a decreasing rate of dechlorination is to be expected, when several degradable substances compete for the reactive sites on the iron surface, TCE degradation is nearly unaffected by the presence of cis-DCE. In contrast, cis-DCE degradation rates decrease significantly when TCE is added. A new modelling approach is developed in order to identify and quantify the observed competitive effects. The numerical model TBC (Transport, Biochemistry and Chemistry, Sch?fer et al., 1998a) is used to describe adsorption, desorption and dechlorination in a mechanistic way. Adsorption and degradation of a contaminant based on a limited number of reactive sites leads to a combined zero- and first-order degradation kinetics for high and low concentrations, respectively. The adsorption of several contaminants with different sorption parameters to a limited reactive surface causes interspecies competition. The reaction scheme and the parameters required are successfully transferred from Arnold and Roberts (2000b) to the model TBC. The degradation behaviour of the mixed contamination observed in the column experiments can be related to the adsorption properties of TCE and cis-DCE. By predicting the degradation of the single substances TCE and cis-DCE as well as mixtures of both, the calibrated model is used to investigate the effects of interspecies competition on the design of permeable reactive iron barriers. Even if TCE is present in only small concentrations (>3% of molar cis-DCE concentration) it is the contaminant limiting the residence time and the required thickness of the iron barrier.     

Microbial activity in a combined UASB-activated sludge reactor system

A combined upflow anaerobic sludge bed-activated sludge (UASB-AS) reactor system with consistently wasting of excess biomass was used to treat suspended-solids pre-settled piggery wastewater (COD=2000 mg l(-1), total Kjeldahl nitrogen TKN=400 mg l(-1), suspended solids=250-400 mg l(-1)). Thus, the activity of nitrogen-related microbial groups in each individual bioreactor was investigated. When the granules retention time (GRT) of 20-50 d in the UASB reactor, the solids retention time (SRT) of 10-25 d in the AS reactor and the recycle-to-influent ratio (Re) of 1 were maintained, the combined system removed 95-97% of chemical oxygen demand (COD), 100% of TKN and 54-55% of total nitrogen (TN). Denitrification and methanogenesis occurred in the UASB reactor so that both biochemical processes contributed to most of the COD removal and, complete nitrification (most of the TKN removal) occurred in the AS reactor. Compact granules with good settling abilities developed in the UASB reactor, and rapid rates of granulation of break-up granules in the UASB reactor were confirmed by experiments. The activity of nitrifiers and denitrifiers (an=0.68-0.87; adn=0.55-0.70) and the calculated specific nitrification and denitrification rates (qn=0.26-0.47 mg NH4+ -N mg VSS(-1)d(-1); qdn=0.046-0.076 mg NOx- -N mg VSS(-1)d(-1)) significantly increased with decreasing SRT and GRT, respectively. Accordingly, the combined UASB-AS reactor system should be regarded a promising alternative for the removal of organic carbon and nitrogen from piggery wastewater.     

T-RFLP detection of nitrifying bacteria in a fluidized bed reactor of achieving simultaneous nitrification-denitrification

Steady simultaneous nitrification-denitrification (SND) was achieved in a fluidized bed reactor (FBR) by the control of DO concentration without physical separation of the aerobic and anoxic zones. The performance and composition of nitrifying bacteria were examined in this study. The ammonium removal efficiency was higher than 80% and the DO concentration (1-5 mg l(-1)) had little influence on it. More than 50% total nitrogen (TN) removal efficiency was achieved when DO was less than 3 mg l(-1) and in many cases the removal efficiency varied between 60-70%. The volumetric loading of TN varied between 0.12 and 0.20 kg Nm(-3)d(-1). 16S rRNA-based terminal restriction fragment length polymorphism analysis was used to characterize the diversity and distribution of the ammonia oxidizing bacteria (AOB) and nitrite-oxidizing bacteria (NOB) in the FBR. The results indicated that, the composition and number of both AOB and NOB changed with position in the reactor and operating time. Nitrosomonas sp. was found to be dominant species of the AOB community, and Nitrobacter sp. also existed in the system. The SND mechanism in the FBR was proved to be the vertical stratification of active populations; however, the presence of microenvironments within the biofilm cannot be ruled out.     

Optimizing nutrient supply in a rotatory-switching biofilter for toluene vapor treatment

The influence of nutrient conditions on the degradation of toluene vapor in a rotatory-switching biofilter (RSB) was investigated. The biofilter consists of four segments connected in series, each with a packing layer made of polyvinyl formal. The influent airstreams including toluene vapors were passed through segments 1-3 as up-flow with a toluene concentration of 0.9-1.2 g m(-3) and with an empty-bed retention time of 26-52 sec. Nutrient solutions were fed to all packed segments once a day by means of immersion. The nutrient solution was used repeatedly and replenished by the addition of (NH4)2SO4. The result at 155 days showed nitrogen depletion was particularly obvious and the lack of nitrogen affected toluene removal. By adding 161 g of nitrogen solution per volumetric cubic meter of reactor, toluene removal efficiency was immediately increased to greater than 99%. With long-term biofilter operation, 21%-32% of ammonium was utilized for nitrification because of the growth of nitrifying bacteria such as Nitrosomonas sp. Based on the carbon-nitrogen balance, the daily nitrogen demand for toluene removal was estimated 2.1 g day(-1) at a toluene load of 70 g m(-3) hr(-1).     

Coupled solar photo-Fenton and biological treatment for the degradation of diuron and linuron herbicides at pilot scale

A coupled solar photo-Fenton (chemical) and biological treatment has been used to remove biorecalcitrant diuron (42 mg l(-1)) and linuron (75 mg l(-1)) herbicides from water at pilot plant scale. The chemical process has been carried out in a 82 l solar pilot plant made up by four compound parabolic collector units, and it was followed by a biological treatment performed in a 40 l sequencing batch reactor. Two Fe(II) doses (2 and 5 mg l(-1)) and sequential additions of H2O2 (20 mg l(-1)) have been used to chemically degrade the initially polluted effluent. Next, biodegradability at different oxidation states has been assessed by means of BOD/COD ratio. A reagent dose of Fe=5 mg l(-1) and H2O2=100 mg l(-1) has been required to obtain a biodegradable effluent after 100 min of irradiation time. Finally, the organic content of the photo-treated solution has been completely assimilated by a biomass consortium in the sequencing batch reactor using a total suspended solids concentration of 0.2 g l(-1) and a hydraulic retention time of 24h. Comparison between the data obtained at pilot plant scale (specially the one corresponding to the chemical step) and previously published data from a similar system performing at laboratory scale, has been carried out.     

Comparison of bio-dissolution of spent Ni-Cd batteries by sewage sludge using ferrous ions and elemental sulfur as substrate

Bioleaching of spent Ni-Cd batteries using acidified sewage sludge was carried out in a continuous flow two-step leaching system including an acidifying reactor and a leaching reactor. Two systems operated about 30d to achieve almost complete dissolution of heavy metals Ni, Cd and Co in four Ni-Cd batteries. Ferrous sulphate and elemental sulfur were used as two different substrates to culture indigenous thiobacilli in sewage sludge. pH and ORP of the acidifying reactor was stabilized around 2.3 and 334mV for the iron-oxidizing system and 1.2 and 390mV for the sulfur-oxidizing system. It was opposite to the acidifying reactor, the pH/ORP in the leaching reactor of the iron-oxidizing system was relatively lower/higher than that of the sulphur-oxidizing system in the first 17d. The metal dissolution, in the first 12-16d, was faster in the iron-oxidizing system than in the sulphur-oxidizing system due to the lower pH. In the iron-oxidizing system, the maximum solubilization of cadmium (2500mg l(-1)) and cobalt (260mg l(-1)) can be reached at day 6-8 and the most of metal nickel was leached in the first 16d. But in the sulphur-oxidizing system there was a lag period of 4-8d to reach the maximum solubilization of cadmium and cobalt. The maximum dissolution of nickel hydroxide (1400mg l(-1)) and metallic nickel (2300mg l(-1)) occurred at about day 12 and day 20, respectively.     

H(2) production through anaerobic mixed culture: effect of batch S(0)/X(0) and shock loading in CSTR

Biological production of H(2) has received considerable attention lately. The present study was undertaken to observe the effects of substrate/seeding ratios (S(0)/X(0)) on batch H(2) generation. The H(2)-producing seeding spores were obtained from the heat treatment (88 degrees C for 12h) of the compost from a grass composting facility. A dehydrated brewery mixture was used as feed substrate. The results indicate that the pattern of the cumulative H(2) production with time is similar to the growth curve with a typical lag, exponential and stationary phase; the results were successfully modeled with a modified Gompertz equation. It appears that maximum H(2) yield potential (27ml g(-1)COD(added)) occurs at an S(0)/X(0) ratio of about 4, whereas the maximum specific H(2) yield (205ml g(-1) VSSd(-1)) occurs at approximately S(0)/X(0)=3. The S(0)/X(0) ratios higher than 4 would inhibit H(2) production. An attempt was made to waste a certain amount of reactor content and replaced it with fresh substrate in order to enhance H(2) production. After this medium replacement, the H(2) production was initially inhibited and the system then exhibited a long lag before it reached an active H(2) production stage. For a continuous-stirred tank-reactor (CSTR) system, the results of replacing 25% of the reactor content indicate that there is still a lag time before a sudden increase in H(2) production after the addition of the new substrate feed. The major low molecular weight acids identified are HAc and HBu with total volatile acids of about 6000-8000mg l(-1). The ratio of HAc/HBu in the present study is relatively constant (about 5) and appears not significantly affected by the medium replacement. The concentration of total alcohols is about 2000mg l(-1). All in all, the CSTR system is able to recover to its previous performance after such a dramatic 25% medium replacement.     

Effect of recycle-to-influent ratio on activities of nitrifiers and denitrifiers in a combined UASB-activated sludge reactor system

A laboratory study using a combined upflow anaerobic sludge bed (UASB)-activated sludge (AS) reactor system was undertaken to explore the effect of recycle-to-influent ratio (R(e)=1, 2, and 3) on the activities of nitrifiers and denitrifiers. Suspended-solids pre-settled piggery wastewater was used as the substrate-feed wastewater. At the R(e) of 1-3, the combined reactor system achieved efficient removal of COD (96-97%), TKN (100%) and total nitrogen TN (54-77%). Methanogenesis occurred with nearly-complete denitrification in the UASB reactor, whereas complete nitrification took place in the AS reactor. A higher R(e) (i.e., accompanied with a shorter solids retention time) resulted in a larger amount of high-activity denitrifiers and thereby achieved a higher TN removal efficiency. Compact granules and a high biomass concentration in the UASB reactor were observed. At the R(e) of 1-3, the maximum specific reaction rate of nitrifiers (0.45-0.49 NH(4)(+)-NmgVSS(-1)d(-1)) and the specific nitrification rates of mixed culture (0.18-0.22mg NH(4)(+)-NmgVSS(-1)d(-1)) in the AS reactor varied slightly; whereas the maximum specific reaction rate of denitrifiers (0.18-0.27mg NO(x)(-)-NmgVSS(-1)d(-1)) and the specific denitrification and COD removal rates of mixed culture (0.025-0.050mg NO(x)(-)-NmgVSS(-1)d(-1); 0.24-0.31mgCODmgVSS(-1)d(-1)) in the UASB reactor increased with increasing R(e). The primary finding of the study is that the combined UASB-AS reactor system should be operated at a higher R(e) to maintain high-activity denitrifiers to remove organic materials and nitrogen from piggery wastewater.     

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature,pH, and air-flow

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO(2) (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 gl(-1); while the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure oxygen, an optimal flow rate was observed at 300 ml min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 (+/-0.6) kJ mol(-1).     

Heap leaching of Pb and Zn contaminated soil using ozone/UV treatment of EDTA extractants

The feasibility of a novel EDTA-based soil heap leaching method with treatment and reuse of extractants in a closed process loop was evaluated on a laboratory scale. Ozone and UV irradiation were used for oxidative decomposition of EDTA-metal complexes in extractants from Pb (1243 mg kg(-1)) and Zn (1190 mg kg(-1)) contaminated soil. Released metals were absorbed in a commercial metal absorbent Slovakite. Six-consecutive additions of 2.5 mmol kg(-1) EDTA (total 15 mmol kg(-1) EDTA) removed 49.6 +/- 0.6% and 19.7 +/- 1.7% of initial total Pb and Zn from soil (4.6 kg) packed in 22 cm high columns. The efficiency of extraction was similar to small-scale simulations of heap leaching (15 0 g of soil), where EDTA used in the same manner removed 49.7 +/- 1.0% and 13.7 +/- 0.4% of Pb and Zn. The new heap leaching method produced discharge extractant with fairly low final concentrations of Pb, Zn and EDTA (1.98 +/- 2.17 mg l(-1), 4.55 +/- 2.36 mg l(-1), and 0.05 +/- 0.04 mM, respectively), which could presumably be reduced even further with continuation of treatment. The results of our study indicate that for soils contaminated primarily with Pb, treating the EDTA extractants with ozone/UV and reuse of extractants enables efficient soil heap leaching with very little or no wastewater generation, easy control over emissions, and lowers the requirements for process water.     

A kinetic study of anaerobic digestion of olive mill wastewater at mesophilic and thermophilic temperatures

The kinetics of the anaerobic digestion of olive mill wastewater (OMW) was studied in the mesophilic and thermophilic ranges of temperature. Two completely mixed continuous flow bioreactors operating at 35 degrees C and 55 degrees C and with an average biomass concentration of 5.45 g VSS litre(-1) were used. The thermophilic reactor worked satisfactorily between hydraulic retention times (HRT) of 10 to 40 days, removing between 94.6 and 84.4% of the initial chemical oxygen demand (COD). In contrast, the mesophilic reactor showed a marked decrease in substrate utilization and methane production at a HRT of 10 days. TVFA levels and the TVFA/alkalinity ratio were higher and close to the suggested limits for digester failure. The yield coefficient for methane production (1 CH(4) STP g(-1) COD(added)) was 28% higher in the thermophilic process than in the mesophilic one. Macroenergetic parameters, calculated using Guiot's kinetic model, gave yield coefficients for the biomass (Y) of 0.18 (mesophilic) and 0.06 g VSS g(-1) COD (thermophilic) and specific rates of substrate uptake for cell maintenance (m) of 0.12 (mesophilic) and 0.27 g COD g(-1) VSS.day(-1) (thermophilic). The experimental results showed the rate of substrate uptake (R(s); g COD g(-1) VSS.day(-1)), correlated with the concentration of biodegradable substrate (S(b); g COD litre(-1)), through an equation of the Michaelis-Menten type for the two temperatures used.     

Mechanistics of trichloroethylene mineralization by the white-rot fungus Trametes versicolor

The white-rot fungus Trametes versicolor degraded trichloroethylene (TCE), a highly oxidized chloroethene, and produced 2,2,2-trichloroethanol and carbon dioxide as the main products of degradation, based on the results obtained using [13C]-TCE as the substrate. For a range of concentrations of TCE between 2 and 20 mg l(-1), 53% of the theoretical maximum chloride expected from complete degradation of TCE was observed. Laccase was shown to be induced by TCE, but did not appear to play a role in TCE degradation. Cytochrome P-450 appears to be involved in TCE degradation, as evidenced by marked inhibition of degradation of TCE in the presence of 1-aminobenzotriazole, a known inhibitor of cytochrome P-450. Our results suggested that chloral (trichloroacetaldehyde) was an intermediate of the TCE degradation pathway. The results indicate that the TCE degradation pathway in T. versicolor appears to be similar to that previously reported in mammals and is mechanistically quite different from bacterial TCE degradation.     

Microbial in situ degradation of aromatic hydrocarbons in a contaminated aquifer monitored by carbon isotope fractionation

We present an approach for characterizing in situ microbial degradation using the 13C/12C isotope fractionation of contaminants as an indicator of biodegradation. The 13C/12C isotope fractionation of aromatic hydrocarbons was studied in anoxic laboratory soil percolation columns with toluene or o-xylene as the sole carbon and electron source, and sulfate as electron acceptor. After approximately 2 months' of incubation, the soil microbial community degraded 32 mg toluene l(-1) and 44 mg o-xylene l(-1) to less than 0.05 mg l(-1), generating a stable concentration gradient in the column. The 13C/12C isotope ratio in the residual non-degraded fraction of toluene and o-xylene increased significantly, corresponding to isotope fractionation factors (alphaC) of 1.0015 and 1.0011, respectively. When the extent of biodegradation in the soil column was calculated based on the measured isotope ratios (R(t)) and an isotope fractionation factor (alphaC=1.0017) obtained from a sulfate-reducing batch culture the theoretical residual substrate concentrations (C(t)) matched the measured toluene concentrations in the column. This indicated that a calculation of biodegradation based on isotope fractionation could work in systems like soil columns. In a field study, a polluted, anoxic aquifer was analyzed for BTEX and PAH contaminants. These compounds were found to exhibit a significant concentration gradient along an 800-m groundwater flow path downstream of the source of contamination. A distinct increase in the carbon isotope ratio (delta13C) was observed for the residual non-degraded toluene (7.2 per thousand ), o-xylene (8.1 per thousand ) and naphthalene fractions (1.2 per thousand ). Based on the isotope values and the laboratory-derived isotope fractionation factors for toluene and o-xylene, the extent to which the residual substrate fraction in the monitoring wells had been degraded by microorganisms was calculated. The results revealed significant biodegradation along the groundwater flow path. In the wells at the end of the plume, the bioavailable toluene and o-xylene fractions had been almost completely reduced by in situ microbial degradation. Although indane and indene showed decreasing concentrations downstream of the groundwater flow path, suggesting microbial degradation, their carbon isotope ratios remained constant. As the physical properties of these compounds are similar to those of BTEX compounds, the constant isotope values of indane and indene indicated that microbial degradation did not lead to isotope fractionation of all aromatic hydrocarbons. In addition, physical interaction with the aquifer material during the groundwater passage did not significantly alter the carbon isotope composition of aromatic hydrocarbons.     

Comparison of polyurethane foam and biodegradable polymer as carriers in moving bed biofilm reactor for treating wastewater with a low C/N ratio

This paper presents a comparison between two different materials used as carriers: inert polyurethane (PU) foam and biodegradable polymer polycaprolactone (PCL) particles for the removal of organics and nitrogen from wastewater with a low C/N ratio using moving bed biofilm reactors. The results, during a monitoring period of four months, showed that TOC and ammonium removal efficiency was higher in reactor 2 filled with PU carriers than in reactor 1 filled with PCL carriers (90% and 65% in the former, compared with 72% and 56% in the latter at an hydraulic retention time of 14 h). Reactor 1 showed good behavior in terms of total nitrogen removal as the biodegradable polymer was an effective substrate providing reducing power for denitrification. From three-dimensional excitation-emission matrix analysis, it was shown that the effluent from reactor 1 contained mainly protein-like and soluble microbial product-like substances.     

Influence of pH on persulfate oxidation of TCE at ambient temperatures

In situ chemical oxidation (ISCO) is a technology used for groundwater remediation. This laboratory study investigated the use of the oxidant sodium persulfate for the chemical oxidation of trichloroethylene (TCE) at near ambient temperatures (10, 20 and 30 degrees C) to determine the influence of pH (pH=4, 7 and 9) on the reaction rate (i.e., pseudo-first-order rate constants) over the range of temperatures utilized. TCE solutions (60 mg l(-1); 0.46 mM) were prepared in phosphate buffered RO water and a fixed persulfate/TCE molar ratio of 50/1 was employed in all tests. Half-lives of TCE degradation at 10, 20 and 30 degrees C (pH 7) were 115.5, 35.0 and 5.5h, respectively. Maximum TCE degradation occurred at pH 7. Lowering system pH resulted in a greater decrease in TCE degradation rates than increasing system pH. Radical scavenging tests used to identify predominant radical species suggested that the sulfate radical (SO(4)(.-)) predominates under acidic conditions and the hydroxyl radical (.OH) predominates under basic conditions. In a side by side comparison of TCE degradation in a groundwater vs. unbuffered RO water it was demonstrated that when the system pH is buffered to near neutral pH conditions due to the presence of natural occurring groundwater constituents that the TCE degradation rate is higher than in unbuffered RO water where the system pH dropped from 5.9 to 2.8. The results of this study suggest that in a field application of ISCO, pH should be monitored and adjusted to near neutral if necessary.