Application of diffusive gradient in thin films probes to monitor trace levels of labile methylmercury in freshwaters.

This study aimed to optimize the methods for sampling and analyzing methylmercury (MeHg) concentrated within diffusive gradients in thin films (DGT) and its application to different water bodies. We explored the elution solution for MeHg, comprised of 1.13 mM thiourea and 0.1M HCl, optimizing its volume to 50 mL. In addition, we found that it is necessary to analyze the entire extraction solution after adjusting its pH, to ensure completion of the ethylation reaction. The DGT samplers were deployed in two distinct aquatic environments (i.e., Okjeong Lake and Nakdong River) for up to 6 weeks, and this study demonstrated to predict the time-weighted average concentration with a diffusion coefficient of 7.65 × 10-6 cm2 s-1 for MeHg in the diffusive gel. To assess the diffusive boundary layer (DBL) effects, the DGT samplers with different agarose diffusive gel thickness were deployed. The mass of MeHg accumulated in the DGT resin at a given time decreased with increasing diffusive gel thickness, because of creating longer diffusion pathways within thicker gels. The labile MeHg concentration estimated by the DGT in Okjeong Lake and Nakdong River are found in the range of 61-111 and 55-105 pg L-1, respectively, which were found to be similar to the grab sampling data. Additionally, this study evaluated depth-dependent MeHg in Okjeong Lake. The vertical profile results showed that the concentration of MeHg at the depth of 2.3 and 15.7 m are about 1.5 and 4.6 times of the DGT installed at 0.3 m of the surface layer, respectively, suggesting potential mercury methylation in deep waters. These findings have practical implications for predicting bioavailability, assessing risks, and formulating strategies for water body management and contamination remediation.

The release, degradation, and distribution of PVC microplastic-originated phthalate and non-phthalate plasticizers in sediments.

This study investigated the leaching of phthalate and non-phthalate plasticizers from polyvinyl chloride microplastics (MPs) into sediment and their degradation over a 30-d period via abiotic and biotic processes. The results showed that 3579% of plasticizers were released into the sediment from the MPs and > 99.9% degradation was achieved. Although a significantly higher degradation was found in plasticizer-added microcosms under biotic processes (overall, 94%), there was a noticeable abiotic loss (72%), suggesting that abiotic processes also play a role in plasticizer degradation. Interestingly, when compared with the initial sediment-water partitioning for plasticizers, the partition constants for low-molecular-weight compounds decreased in both microcosms, whereas those for high-molecular-weight compounds increased after abiotic degradation. Furthermore, changes in the bacterial community, abundance of plasticizer-degrading bacterial populations, and functional gene profiles were assessed. In all the microcosms, a decrease in bacterial community diversity and a notable shift in bacterial composition were observed. The enriched potential plasticizer-degrading bacteria were Arthrobacter, Bacillus, Desulfovibrio, Desulfuromonas, Devosia, Gordonia, Mycobacterium, and Sphingomonas, among which Bacillus was recognized as the key plasticizer degrader. Overall, these findings shed light on the factors affecting plasticizer degradation, the microbial communities potentially involved in biodegradation, and the fate of plasticizers in the environment.

Field application of bio-foam spray to reduce ammonia emission from ammonia-rich swine manure piles.

In this study, the first field-scale application of a bio-foam spray (a mixture of microbes and a surfactant) for the reduction of ammonia emitted from manure was investigated on six field swine manure piles. The objective of this study was to evaluate the odor suppression ability of bio-foam and odor degradation ability of odor-degrading bacteria loaded in the surfactant foam after covering manure piles. The size of field manure piles tested in this study ranged from 27 to 300 m3. Bio-foam spraying completely suppressed the release of the major odor component, ammonia (NH3), and odor-degrading bacteria in the bio-foam aided in the degradation of NH3 in field swine manure piles. On average, 85.7-100% of NH3 was reduced after 24-48 h of serial bio-foam spray application on the swine manure surface, while the control showed 25-42%. The reduction efficiency of NH3 by the bio-foam application was affected by the bio-foam spray frequency, ambient temperature, ventilation of the field facility, and upward airflow to the pile. The reduction in surface emission of NH3 also reduced the ambient air concentration of NH3 at the gate of the compost facility. NH3 gas measurements at a depth of 50 cm indicated that NH3-degrading bacteria infiltrated the manure and were active in biodegradation. Finally, the measured effectiveness of bio-foam application as shown by this study indicates that sprinkling bio-foam via specialized rotating sprinklers may be an efficient and uniform method for the delivery of bio-foam to wide field areas within composting facilities.

Depth-dependent microbial communities potentially mediating mercury methylation and various geochemical processes in anthropogenically affected sediments.

Metal contamination and other geochemical alterations affect microbial composition and functional activities, disturbing natural biogeochemical cycles. Therefore, it is essential to understand the influences of multi-metal and geochemical interactions on microbial communities. This work investigated the distributions of total mercury (THg), methylmercury (MeHg), and trace metals in the anthropogenically affected sediment. The microbial communities and functional genes profiles were further determined to explore their association with Hg-methylation and geochemical features. The levels of THg and MeHg in sediment cores ranged between 10 and 40 mg/kg and 0.01-0.16 mg/kg, respectively, with an increasing trend toward bottom horizons. The major metals present at all depths were Al, Fe, Mn, and Zn. The enrichment and contamination indices confirmed that the trace metals were highly enriched in the anthropogenically affected sediment. Various functional genes were detected in all strata, indicating the presence of active microbial metabolic processes. The microbial community profiles revealed that the phyla Proteobacteria, Bacteroidetes, Bathyarchaeota, and Euryarchaeota, and the genera Thauera, Woeseia, Methanomethylovorans, and Methanosarcina were the dominant microbes. Correlating major taxa with geochemical variables inferred that sediment geochemistry substantially affects microbial community and biogeochemical cycles. Furthermore, archaeal methanogens and the bacterial phyla Chloroflexi and Firmicutes may play crucial roles in enhancing MeHg levels. Overall, these findings shed new light on the microbial communities potentially involved in Hg-methylation process and other biogeochemical cycles.

Enhanced migration of plasticizers from polyvinyl chloride consumer products through artificial sebum.

In the present study, the migration of plasticizers from modeled and commercial polyvinyl chloride (mPVC and cPVC, respectively) to poly(dimethylsiloxane) via artificial sebum was assessed to mimic the dermal migration of plasticizers. In addition, the various factors affecting migration of phthalic acid esters (PAEs) from diverse PVC products were investigated. The migrated mass and migration ratio of PAEs increased but the migration rate decreased over time. The migration rate increased with sebum mass, contact time, and temperature but decreased under higher pressure. Low-molecular-weight PAEs (dimethyl phthalate and diethyl phthalate) migrated in higher amounts than high-molecular-weight PAEs (dicyclohexyl phthalate [DCHP] and diisononyl phthalate [DINP]). Diffusion of all PAEs in mPVC increased with temperature, with diffusion coefficients ranging from 10-13 to 10-15, 10-12 to 10-14, and 10-10 to 10-12 cm2·s-1 at 25 °C, 40 °C, and 60 °C, respectively; the enthalpy of activation ranged between 127 and 194 kJ·mol-1. Moreover, migration depended on total PAE content of the product, as the diffusion coefficient for DINP in cPVC (softer PVC) was approximately three orders of magnitude higher than that for DINP in mPVC (harder PVC); this may be due to the increase in free volume with increasing plasticizer content. Finally, the daily exposure doses of the plasticizers were estimated. These findings will be helpful for estimating dermal exposure risk.

Determination of partition coefficients of phthalic acid esters between polydimethylsiloxane and water and its field application to surface waters.

Phthalic acid esters (PAEs) or phthalates are endocrine-disrupting chemicals and among the most frequently detected hydrophobic organic pollutants, which can be gradually released from consumer products into the environment (e.g., water). This study measured the equilibrium partition coefficients for 10 selected PAEs, with a wide range of logarithms of the octanol-water partition coefficient (log Kow) from 1.60 to 9.37, between poly(dimethylsiloxane) (PDMS) and water (KPDMSw) using the kinetic permeation method. The desorption rate constant (kd) and KPDMSw for each PAEs were calculated from kinetic data. The experimental log KPDMSw for the PAEs ranges from 0.8 to 5.9, which is linearly correlated with log Kow values up to 8 from the literature (R2 > 0.94); however, it slightly deviated for the PAEs with log Kow values greater than 8. In addition, KPDMSw decreased with the temperature and enthalpy for PAEs partitioning in PDMS-water in an exothermic manner. Furthermore, the effects of dissolved organic matter and ionic strength on the partitioning of PAEs in PDMS were investigated. PDMS was used as a passive sampler to determine the aqueous concentration of plasticizers in river surface water. The results of this study can be used to evaluate the bioavailability and risk of phthalates in real environmental samples.

Mercury and other trace elements distribution and profiling of microbial community in the surface sediments of East Siberian Sea.

In this study, total mercury (THg), methylmercury (MeHg), various trace elements, and microbial communities were measured in surface sediments of the East Siberian Sea (ESS). The results showed that the average values of THg and MeHg were 58.8 ± 15.21 µg/kg and 0.50 ± 0.22 µg/kg, respectively. The notable levels of trace elements present in both surface sediment and porewater were Al, Fe, and Mn. The enrichment factor and geoaccumulation index analyses found that both natural phenomena and anthropogenic activities contributed to elevated concentrations of metals in the ESS. The redox proxy metals, pH, and SO42- were the major factors influencing the THg and MeHg distributions. Microbial profiles were substantially affected by metals and other abiotic factors. Proteobacteria and Thaumarchaeota were the most abundant phyla. Overall, the findings presented here facilitate the understanding of the current status of metal contamination, its influencing factors, and metal-microbiota-interactions in ESS.

Insights into the biodegradation of diesel oil and changes in bacterial communities in diesel-contaminated soil as a consequence of various soil amendments.

Soil amendment is a promising strategy to enhance biodegradation capacity of indigenous bacteria. To assess the consequences of various soil amendments before large-scale implementation, a microcosm study was employed to investigate the effects of nutrients (TN), surfactants (TS), oxidants (TO), biochar (TB), and zero-valent iron nanoparticles (nZVI; TNP) on diesel degradation, bacterial communities, and community-level physiological profiles (CLPPs) of legacy field contaminated soil. The results showed that the TN, TB, TNP, TS, and TO, reduced 75.8%, 63.9%, 62.8%, 49.3%, and 40.1% of total petroleum hydrocarbons (TPH), respectively, within 120 days, while control (TW) reduced only 33.8%. In all soil amendments, TPH reduction was positively correlated with oxidation-reduction potential and heterotrophic and TPH-degrading bacteria, while negatively correlated with total nitrogen and available phosphate. Furthermore, in TW, TB, and TNP microcosms, TPH reduction showed positive association with pH, whereas in TN, TS, and TO, TPH reduction was negatively associated with pH. The bacterial diversity was reduced in all treatments as a function of the soil amendment and remediation time: the enriched potential TPH-degrading bacteria were Dyella, Paraburkholderia, Clavibacter, Arthrobacter, Rhodanobacter, Methylobacterium, and Pandoraea. The average well colour development (AWCD) values in CLPPs were higher in TB, sustained and improved in TN, and markedly lower in TNP, TS, and TO microcosms. Overall, these data demonstrate that nutrients and biochar amendments may be helpful in boosting biodegradation, increasing diesel-degrading bacteria, and improving soil physiological functions. In conclusion, diesel degradation efficiency and bacterial communities are widely affected by both type and duration of soil amendments.

Effect of consortium bioaugmentation and biostimulation on remediation efficiency and bacterial diversity of diesel-contaminated aged soil.

This study aimed to evaluate the effects of consortium bioaugmentation (CB) and various biostimulation options on the remediation efficiency and bacterial diversity of diesel-contaminated aged soil. The bacterial consortium was prepared using strains D-46, D-99, D134-1, MSM-2-10-13, and Oil-4, isolated from oil-contaminated soil. The effects of CB and biostimulation were evaluated in various soil microcosms: CT (water), T1 (CB only), T2 (CB + NH4NO3 and KH2PO4, nutrients), T3 (CB + activated charcoal, AC), T4 (CB + nutrients + AC), T5 (AC + water), T6 (CB + nutrients + zero-valent iron nanoparticles, nZVI), T7 (CB + nutrients + AC + nZVI), T8 (CB + activated peroxidase, oxidant), T9 (AC + nZVI), and T10 (CB + nZVI + AC + oxidant). Preliminary evaluation of the bacterial consortium revealed 81.9% diesel degradation in liquid media. After 60 days of treatment, T6 demonstrated the highest total petroleum hydrocarbon (TPH) degradation (99.0%), followed by T1 (97.4%), T2 (97.9%), T4 (96.0%), T7 (96.0%), T8 (94.8%), T3 (93.6%), and T10 (86.2%). The lowest TPH degradation was found in T5 (24.2%), T9 (17.2%), and CT (11.7%). Application of CB and biostimulation to the soil microcosms decreased bacterial diversity, leading to selective enrichment of bacterial communities. T2, T6, and T10 contained Firmicutes (50.06%), Proteobacteria (64.69%), and Actinobacteria (54.36%) as the predominant phyla, respectively. The initial soil exhibited the lowest metabolic activity, which improved after treatment. The study results indicated that biostimulation alone is inadequate for remediation of contaminated soil that lacks indigenous oil degraders, suggesting the need for a holistic approach that includes both CB and biostimulation. Graphical Abstract.

Degradation of petroleum hydrocarbons in soil via advanced oxidation process using peroxymonosulfate activated by nanoscale zero-valent iron.

Recently, the use of nanoscale zero-valent iron (nZVI) for removal of organic contaminants from aqueous and soil system has increased. In this study, we employ nZVI to activate peroxymonosulfate (PMS) for the degradation of total petroleum hydrocarbons (TPHs) in aged diesel-contaminated soil. Upon PMS activation by nZVI, PMS produces more highly reactive oxygen species (ROS) in both aqueous solution and soil compared to other compounds (PMS/Co(II)), as determined by electron paramagnetic resonance spectroscopy. Thus, nZVI is an effective catalyst for PMS activation, leading to the efficient degradation of diesel oil in soil compared to other catalysts and oxidants. The optimal concentrations of PMS and nZVI were found to be 3 and 0.2%, respectively, showing the best degradation efficiency (61.2% in 2 h). The observed TPH degradation was retarded (up to 19.1-37% efficiency) in the presence of radical scavengers, such as tert-butyl alcohol, nitrobenzene, ethyl alcohol, and isopropyl alcohol. These results also demonstrate that ROS (hydroxyl and sulfate free radicals) are generated via PMS activation by nZVI. Moreover, more than 96% of TPH can be degraded by sequential applications of PMS/nZVI. Factors affecting TPH degradation, namely PMS/nZVI concentration, soil:solution ratio, soil pH, activators, and oxidants, are also analyzed. The results demonstrate that TPH is degraded to below the residential soil quality limit using PMS/nZVI based on the advanced oxidation process (AOP), which is therefore an effective option for chemical remediation of diesel-contaminated soils over a wide range of pH.

Biodegradation and post-oxidation of fuel-weathered field soil.

Owing to the less volatile and less biodegradable nature of weathered fuel-contaminated soil, it cannot be easily remediated using conventional bioremediation approaches. Therefore, this study was aimed to enhance the landfarming bioremediation process by introducing post-oxidation for the degradation of the residual total petroleum hydrocarbons (TPH) in fuel-contaminated field soil. A laboratory-scale landfarming bioaugmentation process was performed by using oil-degrading microbes, nutrients, and surfactants, followed by chemical oxidation as a post treatment. The results demonstrated that the addition of microbes and nutrients gradually decreased the TPH concentration of the soil (initial TPH = 5932 ± 267 mg/kg) with a removal efficiency of 70-72% (TPH > 800 mg/kg; Korean limit for non-residential sites). However, the use of post-oxidation treatments with 5% KMnO4 decreased the TPH to approximately 401-453 mg/kg (TPH below 500 mg/kg; residential site limit) with an overall efficiency of 92-93% compared to the corresponding value of 13% for the control (water treatment). Performing landfarming through biodegradation followed by chemical oxidation as a post treatment could successfully remove the weathered TPH in soil below the regulatory limits. Furthermore, the post-oxidation treatment may oxidize the less biodegradable portions only after biodegradation, thereby minimizing the oxidant demand and enhancing the soil properties such as the pH, amount of natural substrates and microbial population.

Combined effects of soil particle size with washing time and soil-to-water ratio on removal of total petroleum hydrocarbon from fuel contaminated soil.

In this study, total petroleum hydrocarbon (TPH) removal from fuel-contaminated field soil was investigated. The influence of the washing method (washing before/after sieving), washing time, soil-to-water ratio, and soil particle size on TPH removal efficiency was evaluated under constant stirring speed. Washing the whole contaminated soil is more efficient than separating the soils into particle size fractions and separately washing the fractions. Particles with differing diameters would be more in contact with each other resulting in detachment of contaminants from the soil particle surface. Effects of soil washing time and soil-to-water ratio on TPH removal were not significant in coarse soil particles (greater than 0.15 mm diameter) but significantly affected TPH removal in fine particles (less than 0.15 mm diameter). This study suggests a threshold washing time of 1 h and a threshold soil-to-water ratio of 1:6 for the whole soil in soil washing. However, soil particles less than 0.075 mm (<75 µm) should be separated after washing to meet the Korean soil TPH limit of less than 500 mg/kg. This study demonstrates the importance of finer soils as debrading media and particle size fraction composition of fuel-contaminated soil in soil washing.

Degradation of petroleum hydrocarbons in unsaturated soil and effects on subsequent biodegradation by potassium permanganate.

To date, the oxidation of petroleum hydrocarbons using permanganate has been investigated rarely. Only a few studies on the remediation of unsaturated soil using permanganate can be found in the literature. This is, to the best of our knowledge, the first study conducted using permanganate pretreatment to degrade petroleum hydrocarbons in unsaturated soil in combination with subsequent bioaugmentation. The pretreatment of diesel-contaminated unsaturated soil with 0.5-pore-volume (5%) potassium permanganate (PP) by solution pouring and foam spraying (with a surfactant) achieved the total petroleum hydrocarbon (TPH) removal efficiencies of 37% and 72.1%, respectively. The PP foam, when coupled with bioaugmentation foam, further degraded the TPH to a final concentration of 438 mg/kg (92.1% total reduction). The experiment was conducted without soil mixing or disturbance. The relatively high TPH removal efficiency achieved by the PP-bioaugmentation serial foam application may be attributed to an increase in soil pH caused by the PP and effective infiltration of the remediation agent by foaming. The applied PP foam increased the pH of the acidic soil, thus enhancing microbial activity. The first-order biodegradation rate after PP oxidation was calculated to be 0.068 d-1. Furthermore, 94% of the group of relatively persistent hydrocarbons (C18-C22) was removed by PP-bioaugmentation, as verified by chromatogram peaks. Some physicochemical parameters related to contaminant removal efficiency were also evaluated. The results reveal that PP can degrade soil TPH and significantly enhance the biodegradation rate in unsaturated diesel-contaminated soil when combined with bioaugmentation foam.

Soil infiltration capacity of chemical oxidants used for risk reduction of soil contamination.

Chemical oxidation has been applied to remove soil contaminants and thereby reduce human and ecological risks from contaminated sites. However, few studies have been conducted on the natural infiltration of oxidant solutions into unsaturated soil. Moreover, the infiltration capacity of oxidant solutions at various concentrations in unsaturated soil has not yet been studied. This study investigated the natural infiltration tendency of oxidant solutions like hydrogen peroxide (H2O2), potassium permanganate (KMnO4), and sodium persulfate (Na2S2O8), in sand and sandy loam. Cumulative infiltration was recorded from a soil column equipped with a Mariotte reservoir. The infiltration rate, sorptivity, and unsaturated hydraulic conductivity were obtained from the cumulative infiltration results. Na2S2O8 showed the highest infiltration rate in both sand and sandy loam, and the infiltration of Na2S2O8 increased as the concentration was increased from 0.05 to 1%. However, the infiltration of KMnO4 and H2O2 solutions was governed more by chemical reaction behavior than by liquid physical properties or soil hydraulic properties. The production of oxides and gas due to reaction induced clogging in flow paths, resulting in less infiltration. Infiltration of H2O2 at concentrations greater than 0.5% was not observed in sand or sandy loam due to gas formation and swelling.

Development of a bacterial consortium comprising oil-degraders and diazotrophic bacteria for elimination of exogenous nitrogen requirement in bioremediation of diesel-contaminated soil.

The purpose of this study was to develop an effective bacterial consortium and determine their ability to overcome nitrogen limitation for the enhanced remediation of diesel-contaminated soils. Towards this, various bacterial consortia were constructed using oil-degrading and nitrogen-fixing microbes. The diesel removal efficiency of various developed consortia was evaluated by delivering the bacterial consortia to the diesel-contaminated soils. The consortium Acinetobacter sp. K-6 + Rhodococcus sp. Y2-2 + NH4NO3 resulted in the highest removal (85.3%) of diesel from the contaminated soil. The consortium containing two different oil-degrading microbes (K-6 + Y2-2) and one nitrogen-fixing microbe Azotobacter vinelandii KCTC 2426 removed 83.1% of the diesel from the soil after 40 days of treatment. The total nitrogen content analysis revealed higher amounts of nitrogen in soil treated with the nitrogen-fixing microbe when compared with that of the soil supplemented with exogenous inorganic nitrogen. The findings in this present study reveal that the consortium containing the nitrogen-fixing microbe degraded similar amounts of diesel to that degraded by the consortium supplemented with exogenous inorganic nitrogen. This suggests that the developed consortium K-6 + Y2-2 + KCTC 2426 compensated for the nitrogen limitation and eliminated the need for exogenous nitrogen in bioremediation of diesel-contaminated soils.

Changes in soil properties after remediation influence the performance and survival of soil algae and earthworm.

Previous research on soil remediation focused on soil properties and not on its effects on soil ecosystems. The present study investigated the adverse effects of soil physicochemical changes due to remediation on the biological indicators Chlorococcum infusionum and Chlamydomonas reinhardtii (algae) and Eisenia andrei (earthworm). Soil physicochemical properties, concentrations of total, bioavailable, and water-soluble heavy metals in soil were measured before and after remediation. Changes in soil pH, electrical conductivity, total nitrogen, and total phosphorous immediately after soil remediation were the primary causes of the biomass and photosynthetic activity inhibition observed in C. infusionum and C. reinhardtii, and the survival, normality, and burrowing behavior decrease observed in E. andrei in remediated soils showing dramatic changes in those properties. These findings suggest that remediated soils need some time to recover before restoring their functions, although heavy metals are no longer contaminating the soil.

Feasibility of oxidation-biodegradation serial foam spraying for total petroleum hydrocarbon removal without soil disturbance.

This study evaluated surface foam spraying technology, which avoids disturbing the soil, to deliver chemical oxidant and oil-degrading microbes to unsaturated soil for 30 days. Hydrogen peroxide foam was sprayed once onto diesel contaminated soil for oxidation of soil total petroleum hydrocarbon (TPH). Periodic bioaugmentation foam was sprayed every three days for biodegradation of soil TPH. Foam spraying employing oxidation-bioaugmentation serial application significantly reduced soil TPH concentrations to 550 mg·kg-1 from an initial 7470 mg·kg-1. This study selected an optimal hydrogen peroxide concentration of 5%, which is capable of treating diesel oil contaminated soil following biodegradation without supplementary iron. Application of hydrogen peroxide by foam spraying increased the infiltration of hydrogen peroxide into the unsaturated soil. Surface foam spraying provided the aqueous phase of remediation agents evenly to the unsaturated soil and resulted in relatively similar soil water content throughout the soil. The easy and even infiltration of remediation reagents increased their contact with contaminants, resulting in enhanced oxidation and biodegradation. Fractional analysis of TPH showed C18-C22 present in diesel as biodegradation recalcitrant hydrocarbons. Recalcitrant hydrocarbons were reduced by 92% using oxidation-biodegradation serial foam, while biodegradation alone only reduced the recalcitrant fraction by 25%.

Application of persulfate-oxidation foam spraying as a bioremediation pretreatment for diesel oil-contaminated soil.

This study investigated a persulfate-bioaugmentation serial foam spraying technique to remove total petroleum hydrocarbons (TPHs) present in diesel-contaminated unsaturated soil. Feeding of remedial agents by foam spraying increased the infiltration/unsaturated hydraulic conductivity of reagents into the unsaturated soil. Persulfate mixed with a surfactant solution infiltrated the soil faster than peroxide, resulting in relatively even soil moisture content. Persulfate had a higher soil infiltration tendency, which would facilitate its distribution over a wide soil area, thereby enhancing subsequent biodegradation efficiency. Nearly 80% of soil-TPHs were degraded by combined persulfate-bioaugmentation foam spraying, while bioaugmentation foam spraying alone removed 52%. TPH fraction analysis revealed that the removal rate for the biodegradation recalcitrant fraction (C18 to C22) in deeper soil regions was higher for persulfate-bioaugmentation serial foam application than for peroxide-bioaugmentation foam application. Persulfate-foam spraying may be superior to peroxide for TPH removal even at a low concentration (50 mN) because persulfate-foam is more permeable, persistent, and does not change soil pH in the subsurface. Although the number of soil microbes declines by oxidation pretreatment, bioaugmentation-foam alters the microbial population exponentially.