Soil Slurry Systems Research Articles

Effects of Autoclaving and Mercuric Chloride Sterilization on PAHs Dissipation in a Two-Liquid-Phase Soil Slurry

A two-liquid-phase (TLP) soil slurry system was employed to quantify the efficiencies of autoclaving and mercuric chloride sterilization in the dissipation of polycyclic aromatic hydrocarbons (PAHs). The fates of 11 PAHs (naphthalene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo( a)anthracene, benzo( a)pyrene, benzo( b)fluoranthene, benzo( k)fluoranthene, dibenzo( a, h)anth-racene) were recorded over 113 days of incubation. No microorganisms were detected in the HgCl 2-sterilized soil slurries during the whole incubation period, indicating very effective sterilization. However, about 2%–36% losses of PAHs were observed in the HgCl 2-sterilized slurry. In contrast to the HgCl 2-sterilized soil slurry, some microorganisms survived in the autoclaved soil slurries. Moreover, significant biodegradation of 6 PAHs (naphthalene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) was observed in the autoclaved soil slurries. This indicated that biodegradation results of PAHs in the soil slurries, calculated on basis of the autoclaved control, would be underestimated. It could be concluded that the sterilization efficiency and effectiveness of HgCl 2 on soil slurry was much higher than those of autoclaving at 121 °C for 45 min.

Reductive Dechlorination of α-, β-, γ-, and δ-Hexachlorocyclohexane Isomers with Hydroxocobalamin, in Soil Slurry Systems

The present study was carried out to test the viability of a method of reductive dehalogenation of α-, β-, γ-, and δ-hexachlorocyclohexane (HCH) in soil slurry systems. The soil slurries were maintained under anaerobic conditions, with titanium(III) citrate as a reducing agent and hydroxocobalamin (vitamin B(12a)) as a catalyzing agent. Experiments were carried out with two soil samples with markedly different characteristics (particularly regarding organic matter content), at a small scale and larger reactor scale. HCH concentration was monitored throughout the 24 h duration of the tests. In the low organic matter soil HCH isomers degraded rapidly, in both the small scale and reactor systems, and undetectable levels (<0.5%) were reached within 5 h. However, complete degradation of HCH isomers was not achieved in soil with high organic matter content, and there were differences between the results obtained in the small scale and reactor systems. In the small scale system, the levels of degradation reached 93, 88, 94, and 91%, for α-, β-, γ-, and δ-HCH, respectively, and the nondegraded HCH was sorbed in the soil. In the reactor system, the reaction stopped after two hours (no more than 65% of any of the isomers was degraded).

Kinetics of Peroxyacetic Acid Formation and Decomposition in Soil-Slurry Systems

In this work, a comprehensive study on the kinetics of formation and decomposition of peroxyacetic acid in soil-slurry systems is presented. A model of peroxyacetic acid formation and decomposition was developed. It includes the kinetics of formation from hydrogen peroxide and acetic acid, peroxyacetic acid decomposition by hydrolysis and hydrogen peroxide and peroxyacetic acid decomposition due to interactions with soil components. The experimental results were properly described by the proposed model, where all kinetic constants were obtained through independent experiments or by fitting of the experimental data. Three application strategies of the process were compared, showing that the highest peroxyacetic concentration in the system is obtained when the soil is added after equilibrium with acetic acid and hydrogen peroxide is achieved.

Potential for activated persulfate degradation of BTEX contamination

The present study focused on evaluation of activated persulfate (PS) anion (S 2O 8 2−) oxidative degradation of benzene, toluene, ethylbenzene, and xylene (constituents of gasoline and known collectively as BTEX) contamination. The results indicated that BTEX were effectively oxidized by PS in aqueous and soil slurry systems at 20 °C. PS can be activated thermally, or chemically activated with Fe 2+ to form the sulfate radical (SO 4 − ) with a redox potential of 2.4 V. The degradation rate constants of BTEX were found to increase with increased persulfate concentrations. For two PS/BTEX molar ratios of 20/1 and 100/1 experiments, the observed aqueous phase BTEX degradation half-lives ranged from 3.0 to 23.1 days and 1.5 to 20.3 days in aqueous and soil slurry systems, respectively. In the interest of accelerating contaminant degradation, Fe 2+ and chelated Fe 2+ activated persulfate oxidations were investigated. For all iron activation experiments, BTEX and persulfate degradations appear to occur almost instantaneously and result in partial BTEX removals. It is speculated that the incomplete degradation reaction may be due to the cannibalization of SO 4 − in the presence of excess Fe 2+. Furthermore, the effects of various chelating agents including, hydroxylpropyl-β-cyclodextrin (HPCD), ethylenediaminetetraacetic acid (EDTA), and citric acid (CA) on maintaining available Fe 2+ and activating PS for the degradation of benzene were studied. The results indicated that HPCD and EDTA may be less susceptible to chelated Fe 2+. In contrast, CA is a more suitable chelating agent in the iron activated persulfate system and with a PS/CA/Fe 2+/B molar ratio of 20/5/5/1 benzene can be completely degraded within a 70-min period.

Enhanced abiotic reduction of Cr(VI) in a soil slurry system by natural biomaterial addition

Among various plant-based natural biomaterials, pine bark was chosen as an efficient biomaterial capable of removing toxic Cr(VI) from aqueous solution. XPS spectra indicated that Cr(VI) was abiotically reduced to Cr(III) in both liquid and solid phases. The Cr(VI)-reducing capacity of pine bark was determined as 545 (±1.3) mg-Cr(VI) g −1 of it, which was 8.7 times higher than that of a common chemical Cr(VI)-reductant, FeSO 4·7H 2O. Because pine bark could completely reduce toxic Cr(VI) to less toxic or nontoxic Cr(III) even at neutral pH, it was used as an organic reductant to remediate Cr(VI)-contaminated soil in this study. Soil slurry system using a bottle roller was applied to ex situ slurry-phase remediation experiments. In the soil slurry system, pine bark completely reduced Cr(VI) to Cr(III) and adsorbed the reduced-Cr(III) on its surface. Abiotic remediation rate of Cr(VI)-contaminated soil increased with the increase of pine bark dosage and with the decreases of Cr(VI) and water contents. In conclusion, pine bark can be used to remediate Cr(VI)-contaminated soil efficiently and environmentally friendly.

Pyrene fate affected by humic acid amendment in soil slurry systems

BackgroundHumic acid (HA) has been found to affect the solubility, mineralization, and bound residue formation of polycyclic aromatic hydrocarbons (PAHs). However, most of the studies on the interaction between HA and PAH concentrated on one or two of the three phases. Few studies have provided a simple protocol to demonstrate the overall effects of HA on PAH distribution in soil systems for all three phases.MethodsIn this study, three doses of standard Elliott soil HA (ESHA), 15, 187.5, and 1,875 μg ESHA/g soil slurry, were amended to soil slurry systems. 14C-pyrene was added to the systems along with non-radiolabeled pyrene; 14C and 14CO2 were monitored for each system for a period of 120 days.ResultsThe highest amendment dose significantly increased the 14C fraction in the aqueous phase within 24 h, but not after that time. Pyrene mineralization was significantly inhibited by the highest dose over the 120-day study. While organic solvent extractable 14C decreased with time in all systems, non-extractable or bound 14C was significantly enhanced with the highest dose of ESHA addition.ConclusionAmendment of the highest dose of ESHA to pyrene contaminated soil was observed to have two major functions. The first was to mitigate CO2 production significantly by reducing 14CO2 from 14C pyrene mineralization. The second was to significantly increase stable bound 14C formation, which may serve as a remediation end point. Overall, this study demonstrated a practical approach for decontamination of PAH contaminated soil. This approach may be applicable to other organic contaminated environments where active bioremediation is taking place.

Fenton-like oxidation of 2,4,6-trinitrotoluene using different iron minerals

Degradation of 2,4,6-trinitrotoluene (TNT) was investigated in presence of different oxidants (Fenton's reagent, sodium persulfate, peroxymonosulfate and potassium permanganate) and different iron minerals (ferrihydrite, hematite, goethite, lepidocrocite, magnetite and pyrite) either in aqueous solution or in soil slurry systems. Fenton's reagent was the only oxidant able to degrade TNT in solution (k(app)=0.0348 min(-1)). When using iron oxide as heterogeneous catalyst at pH 3, specific reaction rate constants per surface area were k(surf)=1.47.10(-3) L min(-1) m(-2) and k(surf)=0.177 L min(-1) m(-2) for magnetite and pyrite, respectively while ferric iron minerals were inefficient for TNT degradation. The major asset of iron mineral catalyzed Fenton-like treatment has been the complete oxidation of the pollutant avoiding the accumulation of possible toxic by-products. In soil slurry systems, 38% abatement of the initial TNT concentration (2 g/kg) was reached after 24 h treatment time at neutral pH. Rate limiting steps were the availability of soluble iron at neutral pH together with desorption of the TNT fraction sorbed on the clay mineral surfaces.

Trinitrotoluene removal in a soil slurry and soil box systems by an oil-degrading mixed bacterial culture

Bioremediation of trinitrotoluene (TNT)-contaminated soil has proven difficult due to the low bioavailability of the contaminant and its resistance to biocatalytic attack, causing slow rates of biodegradation. We have previously described a mixed bacterial culture acclimated and maintained on crude oil-containing medium that is capable of high rates of TNT biotransformation activity with low production of metabolites. We investigated the ability of this culture to bioremediate TNT-spiked soil and artificially weathered soil slurry systems, as well as a soil box system. The culture was able to remove up to 302 ppm (mg/l) of TNT within 24 h in a spiked-soil slurry system, which is among the highest rates of TNT removal reported to date. The toxicity of artificially weathered TNT-spiked soil to Vibrio fischeri decreased over a period of 39 h from a 15-min EC50 of 15.7 to 32.5 ppm. Preliminary results of a soil box system, in which no agitation was used, showed similar TNT removal to the soil slurry system, with 100 ppm TNT being removed within 24 h.

Enhanced Fenton’s destruction of non-aqueous phase perchloroethylene in soil systems

The Fenton’s system is applied to the destruction of perchloroethylene (PCE) present as a dense non-aqueous phase liquid (DNAPL) in soil slurry systems; the initial concentration of PCE was 45 times higher than its aqueous solubility. Studies were conducted in two matrices: Ottawa sand and soil from Warsaw, IN. In Ottawa sand, a 60–62% decrease in PCE concentration was observed, and Cl − recovery was 47–58%, whereas in Warsaw soil, a 44–49% decrease in PCE concentration and a Cl − recovery of 40–42% were observed after the addition of 600 mM H 2O 2 and 10 mM dissolved iron. Significantly enhanced destruction resulted during application of N-(2-hydroxyethyl) iminodiacetic acid (HEIDA) to Warsaw soil. For example, in the absence of HEIDA in Warsaw soil, 36% PCE loss and 33% Cl − release were observed at 600 mM H 2O 2 and 5 mM Fe(III), while 74% PCE loss and 63% Cl − release were achieved at 600 mM H 2O 2 and 5 mM Fe(III)-HEIDA. For both soils, the catalytic activities of Fe(II) and Fe(III) were nearly equivalent. These findings clearly demonstrate that system design can be optimized with regard to process variables in Fenton’s treatment of DNAPL in soils.

Anaerobic degradation of hexachlorocyclohexane isomers in liquid and soil slurry systems

Gamma-hexachlorocyclohexane (γ-HCH or lindane), one of the most commonly used insecticides, has been mainly used in agriculture. Organochloride compounds are known to be highly toxic and persistent, causing serious water and soil pollution. The objective of the present study is the evaluation of the anaerobic degradation of α-, β-, γ-, δ-HCH in liquid and slurry cultures. The slurry system with anaerobic sludge appears as an effective alternative in the detoxification of polluted soils with HCH, as total degradation of the four isomers was attained. While α- and γ-HCH disappeared after 20–40 d, the most recalcitrant isomers: β- and δ-HCH were only degraded after 102 d. Intermediate metabolites of HCH degradation as pentachlorocyclohexane (PCCH), tetrachlorocyclohexene (TCCH), tri-, di- and mono-chlorobenzenes were observed during degradation time.

Polycyclic aromatic hydrocarbon behavior in bioactive soil slurry reactors amended with a nonionic surfactant

The effects of an ethoxylated sorbitan fatty ester nonionic surfactant (Tween 80) on the bioavailability of polycyclic aromatic hydrocarbons (PAHs) were examined by using soil-free and dense-slurry (67% solids content, by wt) systems containing a creosote-contaminated field soil. The dispersed-micelle-phase PAHs in soil-free systems were not readily bioavailable to the mixed consortium of microbes indigenous to the creosote-contaminated soil. Instead, the microbes partially and preferentially utilized readily available portions of the surfactant as carbon sources (16-18% of the initial surfactant dose). This selective microbial attack resulted in destabilization of dispersed-phase micelles and significant decreases in molar solubilization ratio and micelle-water partition coefficient values. Remarkably high dosages (>20 g/L) of Tween 80 were required to enhance mobilization of the sorbed PAHs via micelle association because of the sorption of Tween 80 to the soil employed. The PAHs released from the destabilized micelles in soil-slurry systems either associated with sorbed-phase surfactants or readsorbed to soil organic matter too rapidly to be biologically accessed, even by the acclimated PAH-degrading microbes present. The work provides important new information and practical insights to surfactant solubilization and mobilization technology applications for the bioremediation of PAH-contaminated soils and sediments.

Biodegradation of phenanthrene in soil-slurry systems with different mass transfer regimes and soil contents

The effect of soil contents and mass transfer rates on soil bioremediation was investigated. Phenanthrene, a 3-ring polycyclic aromatic hydrocarbon (PAH), was chosen as a model target compound. The biodegradation tests were performed in soil-slurry systems at two distinct mass transfer rates: fast in flasks tests at 150 rpm and slow in roller-bottle tests at 2 rpm. The rate of phenanthrene biodegradation was similar at low soil content (2 wt.%) in both slurry systems, but the rates at high soil contents (6 and 18 wt.%) were higher in the roller-bottle tests. The maximum utilization rate constant for sorbed-phase biodegradation obtained from curve fitting using a mathematical model was decreased in the flask tests with increasing soil content, while not decreased in the roller-bottle tests.

Biodegradation of phenanthrene in soil-slurry systems with different mass transfer regimes and soil contents

The effect of soil contents and mass transfer rates on soil bioremediation was investigated. Phenanthrene, a 3-ring polycyclic aromatic hydrocarbon (PAH), was chosen as a model target compound. The biodegradation tests were performed in soil-slurry systems at two distinct mass transfer rates: fast in flasks tests at 150 rpm and slow in roller-bottle tests at 2 rpm. The rate of phenanthrene biodegradation was similar at low soil content (2 wt.%) in both slurry systems, but the rates at high soil contents (6 and 18 wt.%) were higher in the roller-bottle tests. The maximum utilization rate constant for sorbed-phase biodegradation obtained from curve fitting using a mathematical model was decreased in the flask tests with increasing soil content, while not decreased in the roller-bottle tests.

Persulfate oxidation for in situ remediation of TCE. II. Activated by chelated ferrous ion

In situ chemical oxidation (ISCO) is a technique used to remediate contaminated soil and groundwater systems. It has been postulated that sodium persulfate (Na 2S 2O 8) can be activated by transition metal ions such as ferrous ion (Fe 2+) to produce a powerful oxidant known as the sulfate free radical (SO 4 − ) with a redox potential of 2.6 V, which can potentially destroy organic contaminants. In this laboratory study persulfate oxidation of dissolved trichloroethylene (TCE) was investigated in aqueous and soil slurry systems under a variety of experimental conditions. A chelating agent (i.e., citric acid) was used in attempt to manipulate the quantity of ferrous ion in solution by providing an appropriate chelate/Fe 2+ molar ratio. In an aqueous system a chelate/Fe 2+ molar ratio of 1/5 (e.g., S 2O 8 2−/chelate/Fe 2+/TCE ratio of 20/2/10/1) was found to be the lowest acceptable ratio to maintain sufficient quantities of Fe 2+ activator in solution resulting in nearly complete TCE destruction after only 20 min. The availability of Fe 2+ appeared to be controlled by adjusting the molar ratio of chelate/Fe 2+. In general, high levels of chelated ferrous ion concentrations resulted in faster TCE degradation and more persulfate decomposition. However, if initial ferrous ion contents are relatively low, sufficient quantities of chelate must be provided to ensure the chelation of a greater percentage of the limited ferrous ion present. Citric acid chelated ferrous ion appeared effective for TCE degradation within soil slurries but required longer reaction times. Additionally, the use of citric acid without the addition of supplemental Fe 2+ in soil slurries, where the citric acid apparently extracted native metals from the soil, appeared to be somewhat effective at enhancing persulfate oxidation of TCE over extended reaction times. A comparison of different chelating agents revealed that citric acid was the most effective.

Persulfate oxidation for in situ remediation of TCE. I. Activated by ferrous ion with and without a persulfate–thiosulfate redox couple

The objective of the laboratory study is to examine the conditions under which transition metal ions (e.g., ferrous ion, Fe 2+) could activate the persulfate anion (S 2O 8 2−) to produce a powerful oxidant known as the sulfate free radical (SO 4 − ) with a standard redox potential of 2.6 V. The SO 4 − is capable of destroying groundwater contaminants in situ such as trichloroethylene (TCE). Experiments using Fe 2+ as an activator under various molar ratios of S 2O 8 2−/Fe 2+/TCE in an aqueous system indicated that partial TCE degradation occurred almost instantaneously and then the reaction stalled. Either destruction of SO 4 − in the presence of excess Fe 2+ or the rapid conversion of all Fe 2+ to Fe 3+ limited the ultimate oxidizing capability of the system. Sequential addition of Fe 2+ in small increments resulted in an increased TCE removal efficiency. Therefore, it appeared that Fe 2+ played an important role in generating SO 4 − . An observation of oxidation–reduction potential (ORP) variations revealed that the addition of sodium thiosulfate (Na 2S 2O 3) to the ferrous ion activated persulfate system could significantly decrease the strong oxidizing conditions. It was hypothesized that the thiosulfate induced reducing conditions might convert Fe 3+ to a lower valence state of Fe 2+, making the Fe 2+ available to activate persulfate decomposition. The sequential addition of thiosulfate (S 2O 3 2−), after the initial stalling of ferrous ion activated persulfate oxidation of TCE, resulted in an improvement in TCE removal. The ferrous ion activated persulfate–thiosulfate redox couple resulted in fairly complete TCE degradation in aqueous systems in a short time frame. In soil slurry systems, TCE degradation was slower in comparison to aqueous systems.

Phenanthrene biodegradation in soil slurry systems: Influence of salicylate and triton X-100

The effects of a nonionic surfactant (Triton X-100) and a metabolic inducer (salicylate) were investigated in order to enhance the biodegradation rate of phenanthrene in soil slurry systems. The addition of salicylate reduced the time for the complete degradation of phenanthrene up to about 3 times (12.9 mg/L-d) even at highly concentrated soils of 650 mg/kg. The inducer was beneficial not only by increasing metabolic activity of existing cells, but also by increasing cell mass since it was utilized as an additional carbon source. The fraction of fast growing bacteria in total with salicylate addition was much higher compared to that without salicylate. The addition of Triton X-100 ranging from 0 to 10 g/L increased the apparent solubility of phenanthrene in soil slurry, but significantly inhibited the phenanthrene degradation in both slurry and pure liquid systems without any inhibition to cell growth. The phenanthrene degradation was inhibited much more with increasing the surfactant concentration. The inhibition by surfactant addition might be due to the prevention of bacterial adhesion to phenanthrene sorbed to soil and/or decrease of micellar-phase bioavailability

Quantification of gene expression in methanotrophs by competitive reverse transcription-polymerase chain reaction.

To improve the monitoring of methanotrophic activity, a competitive reverse transcription-polymerase chain reaction (RT-PCR) methodology was developed. Homologous internal RNA standards were created for mmoX and pmoA, genes encoding polypeptides of sMMO and pMMO, respectively. Using specific primer sets, expression of sMMO and pMMO could be quantified by means of competitive RT-PCR and capillary electrophoresis with uncoated bare-fused silica columns and UV detection. Using this technique, it was discovered that the amount of mRNA transcript for both mmoX and pmoA correlated well with whole-cell sMMO and pMMO activity respectively. A method for soil RNA extraction was also developed to utilize this RNA quantification technique for the monitoring of methanotrophic activity in situ. In a model soil slurry system with a background concentration of 2.9 micro M copper, it was found that only pmoA was transcribed by cells capable of expressing both forms of MMO. As pMMO and sMMO have very different substrate ranges and kinetics, this methodology may prove useful for optimizing in situ bioremediation by methanotrophs. Provided sufficient sequence information is available to create specific primer sets, these techniques can be applied for monitoring and measuring the activity of other microbial communities in situ.

Influence of peanut oil on microbial degradation of polycyclic aromatic hydrocarbons.

Peanut oil amendment (0.1%-0.2% (v/v)) increased the biodegradation of various polycyclic aromatic hydrocarbons (PAHs) by 15%-80% with a mixed bacterial culture and a pure culture of Comamonas testosteroni in aqueous media and in PAH-contaminated weathered soil slurry systems. The stimulatory effect on biodegradation was more pronounced with the high molecular weight PAHs (e.g., >3 rings). The presence of peanut oil also accelerated the biodegradation of PAHs sorbed onto activated carbon, indicating its potential application in the bioregeneration of activated carbon.

Enhanced degradation of carbazole and 2,3-dichlorodibenzo-p-dioxin in soils by Pseudomonas resinovorans strain CA10.

We studied the degradation of carbazole (CAR) and 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD) in soils inoculated with carbazole- and dioxin-degrader Pseudomonas resinovorans strain CA10. By using Tn5-based transposon delivery systems, this bacterium was chromosomally marked with a tandem green fluorescent protein (gfp) gene. Real-time competitive PCR and direct counting using the (gfp) marker were employed to monitor the total number of carbazole 1,9a-dioxygenase gene (carAa) and survival of CA10 cells in the soil and soil slurry microcosms. Bioaugmentation studies indicated that the survival of the marked CA10 cells in soil microcosms was strongly influenced by pH and organic matter. While the number of the marked CA10 cells decreased rapidly in pH 6 with low organic matter, a high cell density was maintained in pH 7.3 with 2.5% organic matters up to 21 days after inoculation. In pH 7.3 soil, the period needed for complete degradation of CAR (100 microg kg(-1)) was markedly shortened from 21 to 7 days by the inoculation with the CA10 cells. Single inoculation of CA10 cells into the soil slurry system of 2,3-DCDD-contaminated soil enhanced the degradation of 2,3-DCDD from 25.0% to 37.0%. In this system, the population density of CA10 cells and the total number of carAa gene were maintained up to 14 days after inoculation. By repeated inoculation (every 2 days) with CA10 cells each at a density of 10(9) CFU g(-1) of soil, almost all of the 2,3-DCDD (1 microg kg(-1)) was degraded within 14 days. Results of these experiments suggest that P. resinovorans strain CA10 may be an important resource for bioremediation of CAR and chlorinated dibenzo-p-dioxin in contaminated soils.

Feasibility of metal recovery from soil using DTPA and its biostability

Removal of heavy metals from contaminated soil by chelation can be a valid remediation method. Important properties of the chelating agent used are: strength of the chelation bonding, reusability, and biostability during the remediation operation. This work tested the extraction, recovery, and biostability of diethylenetriaminepentaacetate (DTPA) as a remediation agent for soils contaminated with metals. Reported here are effects of parameters such as DTPA concentration, precipitant type and concentration, and pH relative to extraction and recovery efficiencies of the chelator, as well as workable recovery conditions. The assessment of biostability was determined at different DTPA concentrations, in aqueous and soil slurry systems, and in presence of lead using acclimated and unacclimated activated sludge cultures. The results showed that DTPA was capable of extracting lead from the tested contaminated soils and could be recovered by the use of cationic and anionic precipitants in alkaline pH conditions. It was biostable to some extent especially with unacclimated cultures. Thus, DTPA proved to be a strong and reusable chelating agent for some metals in soils, and it was relatively biostable, which makes it a valid remediation agent for soil metal extraction.