Plasma-TiO2 catalytic method for high-efficiency remediation of p-nitrophenol contaminated soil in pulsed discharge

Nonthermal discharge plasma and TiO(2) photocatalysis are two techniques capable of organic pollutants removal in soil. In the present study, a pulsed discharge plasma-TiO(2) catalytic (PDPTC) technique by combining the two means, where catalysis of TiO(2) is driven by the pulsed discharge plasma, is proposed to investigate the remediation of p-nitrophenol (PNP) contaminated soil. The experimental results showed that 88.8% of PNP was removed within 10 min of treatment in PDPTC system and enhancing pulse discharge voltage was favorable for PNP degradation. The mineralization of PNP and intermediates generated during PDPTC treatment was followed by UV-vis spectra, denitrification, total organic carbon (TOC), and CO(x) selectivity analyses. Compared with plasma alone system, the enhancement effects on PNP degradation and mineralization were attributed to more amounts of chemically active species (e.g., O(3) and H(2)O(2)) produced in the PDPTC system. The main intermediates were identified as hydroquinone, benzoquinone, catechol, phenol, benzo[d][1, 2, 3]trioxole, acetic acid, formic acid, NO(2)(-), NO(3)(-), and oxalic acid. The evolution of the main intermediates with treatment time suggested the enhancement effect of the PDPTC system. A possible pathway of PNP degradation in soil in such a system was proposed.     

分析有机物污染土壤修复技术应用

在修复有机物污染土壤时,需要相关人员对有机物污染土壤的危害有所了解,还需要结合各项技术手段强化有机物污染土壤修复效果,降低有机物污染土壤修复难度,确保有机物污染土壤修复水平有所提升。同时还应从多个角度出发分析有机物污染土壤修复过程中涉及的技术,扩展各项技术在有机物污染土壤修复中的应用范围,并在合理技术支持下推进有机物土壤污染修复顺利开展。     

Hydrous ferric oxide incorporated diatomite for remediation of arsenic contaminated groundwater

Two reactive media [zerovalent iron (ZVI, Fisher Fe0) and amorphous hydrous ferric oxide (HFO)-incorporated porous, naturally occurring aluminum silicate diatomite [designated as Fe (25%)-diatomite]], were tested for batch kinetic, pH-controlled differential column batch reactors (DCBRs), in small- and large-scale column tests (about 50 and 900 mL of bed volume) with groundwater from a hazardous waste site containing high concentrations of arsenic (both organic and inorganic species), as well as other toxic or carcinogenic volatile and semivolatile organic compounds (VOC/SVOCs). Granular activated carbon (GAC) was also included as a reactive media since a permeable reactive barrier (PRB) at the subject site would need to address the hazardous VOC/SVOC contamination as well as arsenic. The groundwater contained an extremely high arsenic concentration (341 mg L(-1)) and the results of ion chromatography and inductively coupled plasma mass spectrometry (IC-ICP-MS) analysis showed that the dominant arsenic species were arsenite (45.1%) and monomethyl arsenic acid (MMAA, 22.7%), while dimethyl arsenic acid (DMAA) and arsenate were only 2.4 and 1.3%, respectively. Based on these proportions of arsenic species and the initial As-to-Fe molar ratio (0.15 molAs mole(-1)), batch kinetic tests revealed that the sorption density (0.076 molAs molFe(-1)) for Fe (25%)-diatomite seems to be less than the expected value (0.086 molAs molFe(-1) calculated from the sorption density data reported by Lafferty and Loeppert (Environ. Sci. Technol. 2005, 39, 2120-2127), implying that natural organic matters (NOMs) might play a significant role in reducing arsenic removal efficiency. The results of pH-controlled DCBR tests using different synthetic species of arsenic solution showed that the humic acid inhibited the MMAA removal of Fe (25%)-diatomite more than arsenite. The mixed system of GAC and Fe (25%)-diatomite increased the arsenic sorption speed to more than that of either individual media alone. This increase might be deduced by the fact that the addition of GAC could enhance arsenic removal performance of Fe (25%)-diatomite through removing comparably high portions of NOMs. Small- and large-scale column studies demonstrated that the empty bed contact time (EBCT) significantly affected sorpton capacities at breakthrough (C = 0.5 C0) forthe Fe0/sand (50/50, w/w) mixture, but notfor GAC preloaded Fe (25%)-diatomite. In the large-scale column tests with actual groundwater conditions, the GAC preloaded Fe (25%)-diatomite effectively reduced arsenic to below 50 microg L(-1) for 44 days; additionally, most species of VOC/SVOCs were also simultaneously attenuated to levels below detection.     

Field column study using zerovalent iron for mercury removal from contaminated groundwater

Passive in situ remediation technologies, for example, permeable reactive barriers, PRBs, are an attractive and less expensive alternative compared to conventional pump and treat systems for groundwater remediation. Field column experiments were conducted to evaluate the removal of dissolved mercury from groundwater using zerovalent iron as the reactive media. Two column tests were conducted over a 6-week period, which simulated 2 and 10 years of groundwater flow through a potential full-scale treatment system. The influent groundwater pH was 7.8-9.5. The groundwater was reduced with an Eh, corrected to the standard hydrogen electrode, ranging from 0 to 120 mV over the trial period. Prior to treatment the total mercury concentration of the groundwater was approximately 40 microg L(-1). Effluent from the 10-year simulation contained approximately 0.5 microg/L of mercury during the first 3 weeks and increased to as much as 4 microg L(-1) by the end of the testing period. Effluent from the 2-year simulation was generally < 0.1 microg L(-1). Profile sampling of the 2-year simulation suggests that most of the mercury removal occurred in the initial 50% of the 20 cm column. Mineralogical studies, conducted using SEM/EDS and X-ray absorption spectroscopy (XAS), confirm the accumulation of mercury onto a zerovalent iron surface in this 20-cm zone. These analyses indicate that mercury accumulated as a mercury sulfide with a stoichiometery similar to those of cinnabar and metacinnabar (HgS).     

污染场地土壤环境的管理与修复对策初探

工业革命的完成使得世界各国开始大力发展工业生产,工业生产规模的大幅度扩大,加剧了各国在生产过程中的环境污染,而持续产生的环境污染也对各国社会以及经济的发展造成了极大的危害。本文是关于污染场地土壤环境的管理以及修复的相关对策探讨,希望能够为改善环境污染提供参考。     

Dual biomarkers of anaerobic hydrocarbon degradation in historically contaminated groundwater

This study reports that ongoing in situ anaerobic hydrocarbon biodegradation at a manufactured gas plant impacted site is occurring, 9 years after the initial investigation. Groundwater samples from the site monitoring wells (MW) were analyzed for biomarkers by GC-MS, end-point PCR, and quantitative PCR (qPCR). Metabolic biomarkers included specific intermediates of anaerobic naphthalene and/or 2-methylnaphthalene degradation: 2-naphthoic acid (2-NA); 5,6,7,8-tetrahydro-2-NA (TH-2-NA); hexahydro-2-NA (HH-2-NA); and carboxylated-2-methylnaphthalene (MNA). The analogues of gene bssA, encoding alpha subunit of enzyme benzylsuccinate synthase, were used as a genetic biomarker. Results indicate 1-2 orders of magnitude higher abundance of total bacteria in the impacted wells than in the unimpacted wells. End-point PCR analysis of bssA gene, with degenerate primers, indicated the presence of hydrocarbon degrading bacteria within the plume. In qPCR analysis, using primers based on toluene-degrading denitrifying or sulfate-reducing/methanogenic bacteria, bssA genes were detected only in MW-24, located downstream from the source. Metabolic biomarkers were detected in multiple wells. The highest abundance of 2-NA (6.7 μg/L), TH-2-NA (2.6 μg/L), HH-2-NA, and MNA was also detected in MW-24. The distribution of two independent biomarkers indicates that the site is enriched for anaerobic hydrocarbon biodegradation and provides strong evidence in support of natural attenuation.     

In situ remediation of groundwater contaminated by heavy- and transition-metal ions by selective ion-exchange methods

Laboratory studies were conducted to investigate the feasibility of using ion-exchange resins in permeable reactive barriers (PRBs) for the remediation of groundwater contaminated by heavy and transition metals. Ion-exchange resins represent an essentially neglected class of materials which may, in addition to iron, activated carbon, and zeolites, prove effective for use in PRBs. Four resins were considered: two commercially available resins, Duolite GT-73 (Rohm and Haas) and Amberlite IRC-748 (Rohm and Haas), and two solvent-impregnated resins (SIRs). The SIRs were prepared from Amberlite IRA-96 (Rohm and Haas) and two different thiophosphoric extractants. All four resins are able to reduce cadmium, lead, and copper concentrations from 1000 microg/L (typical for contaminated groundwaters) to below 5 microg/L. Significantly, all of the resins are effective for the capture of cadmium, copper, and lead, even in the presence of CaCl2 and clay. Because of their high hydraulic conductivity, the use of these resins in clusters of wells, as an alternative to continuous walls, is considered in the design of effective PRBs. Numerical solution of the groundwater flow equations shows that, depending on the well configuration, most (or all) of the contaminated groundwater can pass through the resins. These results demonstrate the possibility of using selective ion-exchange resins as an effective, active material in PRBs for in situ groundwater remediation.     

Application of waves for remediation of contaminated aquifers

A theory developed suggested that significant displacement of solute in saturated porous media results from the propagation of compression waves. Four independent one-dimensional experimental setups and a variety of laboratory methods were used to confirm the predictions of the theory, specifically aimed at developing a novel method of inducing compression waves for use in remediation of contaminated aquifers. Compaction and shock waves were emitted through granular porous media saturated with saline water. The changes in solute concentration at observation points along the propagating wave were used to verify the validity of theory. The first setup was designed mainly to provide a qualitative assessment (i.e., changes in pressure due to the propagating wave were not recorded). In situ quantitative measurements of the pressure and electrical conductivity profiles along a sand column were done with the second and third experimental setups, respectively, to short and long shock waves. In the fourth setup, solute displacement was visualized by X-ray absorption. The findings were consistent with the theory in all experimental setups.     

CO2-efflux measurements for evaluating source zone natural attenuation rates in a petroleum hydrocarbon contaminated aquifer

In order to gain regulatory approval for source zone natural attenuation (SZNA) at hydrocarbon-contaminated sites, knowledge regarding the extent of the contamination, its tendency to spread, and its longevity is required. However, reliable quantification of biodegradation rates, an important component of SZNA, remains a challenge. If the rate of CO(2) gas generation associated with contaminant degradation can be determined, it may be used as a proxy for the overall rate of subsurface biodegradation. Here, the CO(2)-efflux at the ground surface is measured using a dynamic closed chamber (DCC) method to evaluate whether this technique can be used to assess the areal extent of the contaminant source zone and the depth-integrated rate of contaminant mineralization. To this end, a field test was conducted at the Bemidji, MN, crude oil spill site. Results indicate that at the Bemidji site the CO(2)-efflux method is able to both delineate the source zone and distinguish between the rates of natural soil respiration and contaminant mineralization. The average CO(2)-efflux associated with contaminant degradation in the source zone is estimated at 2.6 μmol m(-2) s(-1), corresponding to a total petroleum hydrocarbon mineralization rate (expressed as C(10)H(22)) of 3.3 g m(-2) day(-1).     

Hydrogen isotopic enrichment: an indicator of biodegradation at a petroleum hydrocarbon contaminated field site

Compound-specific carbon and hydrogen isotope analysis was used to investigate biodegradation of benzene and ethylbenzene in contaminated groundwater at Dow Benelux BV industrial site. delta13C values for dissolved benzene and ethylbenzene in downgradient samples were enriched by up to 2+/-0.5 per thousand, in 13C, compared to the delta13C value of the source area samples. delta2H values for dissolved benzene and ethylbenzene in downgradient samples exhibited larger isotopic enrichments of up to 27+/-5 per thousand for benzene and up to 50+/-5 per thousand for ethylbenzene relative to the source area. The observed carbon and hydrogen isotopic fractionation in downgradient samples provides evidence of biodegradation of both benzene and ethylbenzene within the study area at Dow Benelux BV. The estimated extents of biodegradation of benzene derived from carbon and hydrogen isotopic compositions for each sample are in agreement, supporting the conclusion that biodegradation is the primary control on the observed differences in carbon and hydrogen isotope values. Combined carbon and hydrogen isotope analyses provides the ability to compare biodegradation in the field based on two different parameters, and hence provides a stronger basis for assessment of biodegradation of petroleum hydrocarbon contaminants.     

Uptake of organic pollutants by silica--polycation-Immobilized micelles for groundwater remediation

Interest has grown in designing new materials for groundwater treatment via "permeable reactive barriers". In the present case, a model siliceous surface, controlled pore glass (CPG), was treated with a polycation (quaternized polyvinyl pyridine, QPVP) which immobilizes anionic/nonionic mixed micelles, in order to solubilize a variety of hydrophobic pollutants. Polymer adsorption on CPG showed atypically slow kinetics and linear adsorption isotherms, which may be a consequence of the substrate porosity. The highest toluene solubilization efficiency was achieved for the silica-polycation-immobilized micelles (SPIM) with the highest polymer loading and lowest micelle binding, a result discussed in terms of the configuration of the bound polymer and the corresponding state of the bound micelles. The ability of SPIM to treat simultaneously a wide range of pollutants and reduce their concentration in solution by 20-90% was demonstrated. Optimization of SPIM systems for remediation calls for a better understanding of both the local environment of the bound micelles and their intrinsic affinities for different hydrophobic pollutants.     

Mechanisms of uranium interactions with hydroxyapatite: implications for groundwater remediation

The speciation of U(VI) sorbed to synthetic hydroxyapatite was investigated using a combination of U LIII-edge XAS, synchrotron XRD, batch uptake measurements, and SEM-EDS. The mechanisms of U(VI) removal by apatite were determined in order to evaluate the feasibility of apatite-based in-situ permeable reactive barriers (PRBs). In batch U(VI) uptake experiments with synthetic hydroxyapatite (HA), near complete removal of dissolved uranium (>99.5%) to <0.05 microM was observed over a range of total U(VI) concentrations up to equimolar of the total P in the suspension. XRD and XAS analyses of U(VI)-reacted HA at sorbed concentrations < or = 4,700 ppm U(VI) suggested that uranium(VI) phosphate, hydroxide, and carbonate solids were not present at these concentrations. Fits to EXAFS spectra indicate the presence of Ca neighbors at 3.81 A. U-Ca separation, suggesting that U(VI) adsorbs to the HA surfaces as an inner-sphere complex. Uranium(VI) phosphate solid phases were not detected in HA with 4700 ppm sorbed U(VI) by backscatter SEM or EDS, in agreement with the surface complexation process. In contrast, U(VI) speciation in samples that exceeded 7000 ppm sorbed U(VI) included a crystalline uranium(VI) phosphate solid phase, identified as chernikovite by XRD. At these higher concentrations, a secondary, uranium(VI) phosphate solid was detected by SEM-EDS, consistent with chernikovite precipitation. Autunite formation occurred at total U:P molar ratios > or = 0.2. Our findings provide a basis for evaluating U(VI) sorption mechanisms by commercially available natural apatites for use in development of PRBs for groundwater U(VI) remediation.     

Evaluation of gastrointestinal solubilization of petroleum hydrocarbon residues in soil using an in vitro physiologically based model

Petroleum hydrocarbon residues in weathered soils may pose risks to humans through the ingestion pathway. To understand the factors controlling their gastrointestinal (GI) absorption, a newly developed experimental extraction protocol was used to model the GI solubility of total petroleum hydrocarbon (TPH) residues in highly weathered soils from different sites. The GI solubility of TPH residues was significantly higher for soil contaminated with diesel than with crude oil. Compared to the solubility of TPH residues during fasted state,the solubility of TPH residues during fat digestion was much greater. Diesel solubility increased from an average of 8% during the "gallbladder empty" phase of fasting (and less than 0.2% during the otherfasting phase) to an average of 16% during fat digestion. For crude oil, the solubility increased from an average of 1.2% during the gallbladder empty phase of fasting (and undetectable during the other fasting phase) to an average of 4.5% during fat digestion. Increasing the concentration of bile salts also increased GI solubility. GI solubility was reduced by soil organic carbon but enhanced by the TPH content.     

Numerical model for biological fluidized-bed reactor treatment of perchlorate contaminated groundwater

Biological fluidized-bed reactor (BFBR) treatment with 1.3 mm granular activated carbon as support medium is being used for removal of 2.6 mg/L perchlorate from contaminated groundwater in California. The California drinking-water action level of 4 microg/L for perchlorate requires 99.9% perchlorate removal. Sufficient ethanol, the electron donor, is added to remove oxygen and nitrate as well as perchlorate, as all three serve as electron acceptors, but with biological preference for oxygen and nitrate. A numerical BFBR model based upon basic physical, chemical, and biological processes including reaction stoichiometry, biofilm kinetics, and sequential electron acceptor usage was developed and evaluated with the full-scale treatment results. A key fitting parameter was bacterial detachment rate, which impacts reaction stoichiometry. For best model fit this was found to vary between 0.062 and 0.31 d(-1), with an average of 0.22 d(-1). The model indicates that GAC particle size, reactor diameter, and perchlorate concentration affect BFBR performance. While empty-bed detention time might be decreased somewhat below 10 min by an increase in either GAC particle size or reactor diameter, the current design provides a good factor of safety in operation. With a 10 min detention time, the effluent goal of 4 microg/L should be achievable even with influent perchlorate concentration as high as 10 mg/L.     

Probabilistic approach to estimating indoor air concentrations of chlorinated volatile organic compounds from contaminated groundwater: a case study in San Antonio, Texas

This paper describes a probabilistic model, based on the Johnson-Ettinger algorithm, developed to characterize the current and historic exposure to tricholorethylene (TCE) and tetrachlorethylene (PCE) in indoor air from plumes of groundwater contamination emanating from the former Kelly Air Force Base in San Antonio, Texas. We estimate indoor air concentration, house by house, in 30?101 homes and compare the estimated concentrations with measured values in a small subset of homes. We also compare two versions of the Johnson-Ettinger model: one used by the Environmental Protection Agency (EPA) and another based on an alternative parametrization. The modeled mean predicted PCE concentration historically exceeded PCE screening levels (0.41 ug/m(3)) in 5.5% of houses, and the 95th percentile of the predicted concentration exceeded screening levels in 85.3% of houses. For TCE, the mean concentration exceeded the screening level (0.25 ug/m(3)) in 49% of homes, and the 95th percentile of the predicted concentration exceeded the screening level in 99% of homes. The EPA model predicts slightly lower indoor concentrations than the alternative parametrization. Comparison with measured samples suggests both models, with the inputs selected, underestimate indoor concentrations and that the 95th percentiles of the predicted concentrations are closer to measured concentrations than predicted mean values.     

Selective remediation of contaminated sites using a two-level multiphase strategy and geostatistics

Selective soil remediation aims to reduce costs by cleaning only the fraction of an exposure unit (EU) necessary to lower the average concentration below the regulatory threshold. This approach requires a prior stratification of each EU into smaller remediation units (RU) which are then selected according to various criteria. This paper presents a geostatistical framework to account for uncertainties attached to both RU and EU average concentrations in selective remediation. The selection of RUs is based on their impact on the postremediation probability for the EU average concentration to exceed the regulatory threshold, which is assessed using geostatistical stochastic simulation. Application of the technique to a set of 600 dioxin concentrations collected at Piazza Road EPA Superfund site in Missouri shows a substantial decrease in the number of RU remediated compared with single phase remediation. The lower remediation costs achieved by the new strategy are obtained to the detriment of a higher risk of false negatives, yet for this data set this risk remains below the 5% rate set by EPA region 7.     

Results of field tests on radio-wave heating for soil remediation

After developing the radio-wave technique for various conditions in laboratory-scale and technical plant-scale experiments, field tests in combination with biodegradation and soil vapor extraction were carried out at three sites: (i) a bioremediation facility for ex situ cleaning of soil, (ii) in situ remediation of contamination at a former storage facility for organic solvents, and (iii) a polluted soil under a former petrol station. Various electrode arrangements such as parallel plates, rod arrays, and coaxial antenna were applied in order to meet the site-specific requirements optimally. Soil temperatures between 35 and 100 degrees C were established. The successful tests gave much insight into the engineering, physical, biological, and chemical aspects of radio-wave application. General conclusions on the appropriateness and competitiveness of the radio-wave method as well as on preferred application fields are drawn.