Micellar solubilization of naphthalene and phenanthrene from nonaqueous-phase liquids

The equilibrium partitioning of the polycyclic aromatic hydrocarbon (PAH) compounds naphthalene and phenanthrene, from nonaqueous-phase liquids (NAPLs) into micellar solutions of five different nonionic polyethoxylated surfactants, is evaluated in this study. A series of synthesized NAPLs, comprised of naphthalene and/or phenanthrene dissolved in hexadecane at varying concentrations, were equilibrated with surfactant solutions in well-mixed batch systems. It was observed that the extent of micellar partitioning of PAH compounds increases linearly with their relative abundance in the NAPLs. A theoretical liquid-liquid partitioning framework that describes PAH equilibrium partitioning between the NAPL, aqueous, and the liquid-like micellar phases is presented. Although the maximum solubilization capacity of micelles is generally higher for naphthalene as compared to phenanthrene, results indicate that with certain NAPLs phenanthrene may be solubilized to a similar extent as naphthalene, even when equal mole fractions of the compounds are present in the NAPLs. Selective solubilization of naphthalene over phenanthrene into micellar solutions of Brij 35 was observed in systems where naphthalene and phenanthrene were both present. The extent of micellar partitioning of phenanthrene was decreased by approximately 18% in the presence of naphthalene, while naphthalene partitioning was unaffected by the presence of phenanthrene.     

Effect of interface fertilization on biodegradation of polycyclic aromatic hydrocarbons present in nonaqueous-phase liquids

The main goal of this study was to use an oleophilic biostimulant (S-200) to target possible nutritional limitations for biodegradation of polycyclic aromatic hydrocarbons (PAHs) at the interface between nonaqueous-phase liquids (NAPLs) and the water phase. Biodegradation of PAHs present in fuel-containing NAPLs was slow and followed zero-order kinetics, indicating bioavailability restrictions. The biostimulant enhanced the biodegradation, producing logistic (S-shaped) kinetics and 10-fold increases in the rate of mineralization of phenanthrene, fluoranthene, and pyrene. Chemical analysis of residual fuel oil also evidenced an enhanced biodegradation of the alkyl-PAHs and n-alkanes. The enhancement was not the result of an increase in the rate of partitioning of PAHs into the aqueous phase, nor was it caused by the compensation of any nutritional deficiency in the medium. We suggest that biodegradation of PAH by bacteria attached to NAPLs can be limited by nutrient availability due to the simultaneous consumption of NAPL components, but this limitation can be overcome by interface fertilization.     

Biosurfactant- and biodegradation-enhanced partitioning of polycyclic aromatic hydrocarbons from nonaqueous-phase liquids

A study was conducted on the effect of two different biological factors, microbial surfactants and biodegradation, on the kinetics of partitioning of polycyclic aromatic hydrocarbons (PAHs) from nonaqueous-phase liquids (NAPLs). The effect of rhamnolipid biosurfactants on partitioning into the aqueous phase of naphthalene, fluorene, phenanthrene, and pyrene, initially dissolved in di-2-ethylhexyl phthalate (DEHP) or 2,2,4,4,6,8,8-heptamethylnonane (HMN), was determined in multiple-solute experiments. Biosurfactants at a concentration above the CMC enhanced the partitioning rate of fluorene, phenanthrene, and pyrene but were ineffective with naphthalene. Enhancement of partitioning was also observed in the presence of suspended humic acid-clay complexes, which simulated the solids often present in the subsurface. Biosurfactants sorbed to the complexes modified PAH partitioning between the NAPL and these solids, increasing the fraction of solid-phase PAH. Biodegradation-driven partitioning was estimated in mineralization experiments with phenanthrene initially present in HMN and three representative soil bacterial strains, differing in their potential adherence to the NAPL. In the three cases, the rates of mineralization were very similar and significantly higher than the abiotic rate of partitioning. Our study suggests that in NAPL-polluted sites, partitioning of PAH may be efficiently enhanced by in situ treatments involving the use of biosurfactants and biodegradation.     

Cyclodextrin enhanced biodegradation of polycyclic aromatic hydrocarbons and phenols in contaminated soil slurries

This work aimed to evaluate the relative contribution of soil catabolic activity, contaminant bioaccessibility, and nutrient levels on the biodegradation of field-aged polycyclic aromatic hydrocarbons and phenolic compounds in three municipal gas plant site soils. Extents of biodegradation achieved, in 6 week-long soil slurry assays, under the following conditions were compared: (i) with inoculation of catabolically active PAH and phenol-degrading microorganisms, (ii) with and without hydroxypropyl-beta-cyclodextrin supplementation (HPCD; 100 g L(-1)), and finally (iii) with the provision of additional inorganic nutrients in combination with HPCD. Results indicated no significant (p < 0.05) differences between biodegradation endpoints attained in treatments inoculated with catabolically active microorganisms as compared with the uninoculated control. Amendments with HPCD significantly (p < 0.05) lowered biodegradation endpoints for most PAHs and phenolic compounds. Only in one soil did the combination of HPCD and nutrients consistently achieve better bioremediation endpoints with respect to the HPCD-only treatments. Thus, for most compounds, biodegradation was not limited by the catabolic activity of the indigenous microorganisms but rather by processes resulting in limited availability of contaminants to degraders. It is therefore suggested that the bioremediation of PAH and phenol impacted soils could be enhanced through HPCD amendments. In addition, the biodegradability of in situ and spiked (deuterated analogues) PAHs following 120 days aging of the soils suggested that this contact time was not sufficient to obtain similar partitions to that observed for field-aged contaminants; with the spiked compounds being significantly (p < 0.05) more available for biodegradation.     

Effect of fungal hyphae on the access of bacteria to phenanthrene in soil

The effect of fungal hyphae on the mobilization of soil-dwelling bacteria and their access to hydrophobic phenanthrene in soil was tested in columns containing air-filled agricultural soil. The experimental design included a spatial separation between zones of bacterial inoculation and contamination. Motile Pseudomonas putida PpG7 (NAH7) and fast-growing, hydrophilic Pythium ultimum were used as the model phenanthrene-degrading and vector organisms, respectively. Efficient translocation of strain PpG7 in the range of centimetres in presence of P. ultimum indicated that the fungal mycelia bridged air-filled pores and thereby provided a continuous network of water-paths that enabled bacteria to spread in the soil. Biodegradation of the soil-associated phenanthrene was found only in the presence of the fungal mycelia, hence proving that the fungal network facilitated the access of the bacteria to the contaminant. Our data suggest that the specific stimulation of indigenous fungi is a promising method to mobilize pollutant degrading bacteria and thereby improve soil bioremediation in-situ.     

施用生物炭对Cd污染土壤生物学特性及土壤呼吸速率的影响

[目的]为研究施用生物炭对Cd污染土壤生物学特性及土壤呼吸速率的影响。[方法]于2016年采用盆栽试验（每盆装土25 kg）,外源添加Cd 0 mg/kg （G0）、30 mg/kg （G1）、60 mg/kg （G2）,分别添加生物炭0 g/kg （T0）、10 g/kg （T1）、20 g/kg （T2）,二因素试验共计9个处理,分别为:G0T0、G0T1、G0T2、G1T0、G1T1、G1T2、G2T0、G2T1、G2T2。测定不同时期的土壤微生物数量,土壤微生物生物量碳、氮,土壤酶活性及土壤呼吸速率。[结果]土壤脲酶活性、土壤细菌、放线菌数量和土壤微生物生物量碳、微生物生物量氮含量和土壤呼吸速率均随施加Cd浓度的升高呈现降低的趋势,随生物炭的施用而显著增加,且均在移栽后55 d达到较高水平。土壤呼吸速率随生育期的延长呈升高的趋势,在Cd污染严重的土壤中,土壤呼吸速率随生物炭施用量的增加显著提高。[结论]施用生物炭能明显改善Cd污染土壤的生物学特性,提高土壤呼吸速率,从而达到改善Cd污染土壤质量的目的。      

Impact of black carbon in the extraction and mineralization of phenanthrene in soil

During the past century, increased biomass burning and fossil fuel consumption have drastically increased the input of black carbon (BC) into the environment, and that has been shown to influence the behavior of organic contaminants in soil. A study was conducted to investigate the effects of BC on the relationship between aqueous hydroxypropyl-beta-cyclodextrin (HPCD) extraction and microbial mineralization (bioaccessibility) of 14C-phenanthrene (10 mg kg(-1)) in four soils amended with 0, 0.1, 0.5, 1, 2.5, and 5% (% dry wt soil) activated charcoal, a type of BC. Mineralisation was monitored over 20 d incubation, within respirometric assays, using an inoculum containing a phenanthrene-degrading pseudomonad and compared to HPCD extraction (24 h) using 50 mM aqueous solution; analyses were conducted after 1, 25, 50, and 100 d soil-phenanthrene contact time. Statistical analyses revealed that for each soil the addition of BC led to significant (P < 0.001) reductions in both HPCD extractability and microbial mineralization. Linear correlations for BC concentrations of 0% (r2 = 0.95; slope = 0.89) and 0.1% (r2 = 0.67; slope = 0.95) revealed a highly significant (P < 0.01) relationship between HPCD extractability and total mineralization (20 d), indicating a direct prediction of phenanthrene bioaccessibility by HPCD. However, in soils amended with 0.5, 1, 2.5, and 5% BC exhibited r2 values ranging 0.51-0.13 and slopes of 2.19-12.73. This study has shown that BC strongly sorbs phenanthrene causing reductions in extractability and, to a lesser extent, bioaccessibility to degrading microorganisms.     

A model for the effect of rhizodeposition on the fate of phenanthrene in aged contaminated soil

Microcosm data were used to develop a deterministic model to describe how rhizodeposition affects the fate of phenanthrene in aged contaminated soil. Microbial mineralization and soil sequestration of 14C-phenanthrene were compared in microcosms amended weekly with phenolic-rich mulberry root extracts versus unamended controls. Mineralization was higher in the amended soils simulating the rhizosphere (57.7 +/- 0.9%) than in controls simulating bulk (unplanted) soils (53.2 +/- 0.7%) after 201 days (p < 0.05). Humin was the main soil sink for the residual 14C-label. Whereas the total 14C-label associated with humin remained constant in biologically active soils (at about 30%), it increased up to 80% after 201 days in sterile controls. The initial phenanthrene extraction with n-butanol (commonly used to assess bioavailability) slightly underestimated the fraction thatwas mineralized (assessed by 14CO2 recovery). Changes in the unextractable fraction (determined by combustion in a biological oxidizer) suggested the presence of two soil sequestration domains: (1) irreversibly bound residue, and (2) an intermediate transition phase that is unextractable by solvents at a given point in time but could become bioavailable due to physicochemical or biological transformations of the binding matrix. The fate of phenanthrene was accurately modeled by considering the transfer of the 14C label between different soil compartments as first-order kinetic processes. Model simulations suggested that the system was approaching a stable end-point after 201 days of simulated rhizoremediation, and corroborated that microorganisms have a significant impact on the fate of phenanthrene in soil.     

Chemical extractions affect the structure and phenanthrene sorption of soil humin

Humin is a major fraction of soil organic matter and strongly affects the sorption behavior and fate of organic contaminants in soils and sediments. This study evaluated four different extraction methods for soil humins in terms of their organic carbon structural changes and the consequent effects on phenanthrene sorption. Solid-state 13C NMR demonstrated that 0.1 M NaOH exhaustively extracted humin and humin extracted with 6 M HF/HCl at 60 degrees C had a relatively high amount of aliphatic components as compared with 1 M HF-extracted humin. The treatment of 6 M HF/HCl at 60 degrees C greatly reduced carbohydrate components (50-108 ppm) from humin samples, i.e., more than 50% reduction. In addition, the humin from this 6 M HF/HCl treatment contained relatively more amorphous poly(methylene) domains than the humins extracted by other methods. With the respect to phenanthrene sorption, the linearity of sorption isotherm (N) and sorption affinity (Koc) varied markedly among the humin samples extracted by different methods. The NaOH exhaustively extracted humin had the most nonlinear sorption isotherm and the HF-extracted humin had the lowest Koc. It is concluded that humin samples from different extraction procedures exhibited substantial differences in their organic carbon structure and sorption characteristics, even though they were from the same soil. Therefore, one needs to be cautious when comparing the structural and sorption features of soil humins, especially when they are extracted differently. The 6 M HCl/HF extraction at elevated temperature is not encouraged, due to the modifications of chemical structure and physical conformation of organic matter.     

Novel chamber to measure equilibrium soil-air partitioning coefficients of low-volatility organic chemicals under conditions of varying temperature and soil moisture

The need to determine soil-air partitioning coefficients (K(SA)) of low-volatility organic chemicals as a measure of their distribution in the soil surface after release into the environment resulted in the development of a novel chamber system, which has been filed for patent. A major advantage of this pseudo-static system is that sufficient time can be factored into the experiment to ensure that the system has achieved equilibrium. In a highly precise method, the air is collected in adsorption tubes and subsequently liberated in a thermodesorption system for the quantitation of the adsorbed compound. The precision of the method is great enough that even the effects of temperature and soil moisture on the soil-air partitioning of very low-volatility compounds can be quantified. Because of analytical detection limits, quantitation of these influences has not been possible to date. Functionality of the setup was illustrated by measurements on the fungicide fenpropimorph. K(SA) values of fenpropimorph displayed a negative relationship with temperature and soil moisture. The type of application (spraying or incorporation) and the use of formulated compounds was shown to have a major impact on the measured K(SA) values. Comparison with calculations using an estimation method revealed that the use of experimentally determined K(SA) values will facilitate a more adequate consideration of volatilization in recent model approaches.     

Simulating the effect of aerobic biodegradation on soil vapor intrusion into buildings: influence of degradation rate, source concentration, and depth

Steady-state vapor intrusion scenarios involving aerobically biodegradable chemicals are studied using a three-dimensional multicomponent numerical model. In these scenarios, sources of aerobically biodegradable chemical vapors are placed at depths of 1-14 m beneath a 10 m x 10 m basement or slab-on-grade construction building, and the simultaneous transport and reaction of hydrocarbon and oxygen vapors are simulated. The results are presented as Johnson and Ettinger attenuation factors alpha (predicted indoor air hydrocarbon concentration/source vapor concentration), and normalized contour plots of hydrocarbon and oxygen concentrations. In addition to varying the vapor source depth, the effects of source concentration (2-200 mg chemical/L vapor) and oxygen-limited first-order reaction rates (0.018-1.8 h(-1)) are studied. Hydrocarbon inputs were specific to benzene, although the relevant properties are similar to those for a range of hydrocarbons of interest. Overall, the results suggest that aerobic biodegradation could play a significant role in reducing vapor intrusion into buildings (decreased alpha-values) relative to the no-biodegradation case, with the significance of aerobic biodegradation increasing with increasing vapor source depth, decreasing vapor source concentration, and increasing first-order biodegradation rate. In contrast to the no-biodegradation case, differences in foundation construction can be significant in some settings. The significance of aerobic biodegradation is directly related to the extent to which oxygen is capable of migrating beneath the foundation. For example, in the case of a basement scenario with a 200 mg/L vapor source located at 3 m bgs, oxygen is consumed before it can migrate beneath the foundation, so the attenuation factors for simulations with and without aerobic biodegradation are similar for all first-order rates studied. For the case of a 2 mg/L vapor source located at 8 m bgs, the oxygen is widely distributed beneath the foundation, and the attenuation factor for the biodegradation case ranges from about 3 to 18 orders-of-magnitude less than that for the no-biodegradation case.     

Enhanced anaerobic biodegradation of polychlorinated biphenyls in burnt soil culture

Anaerobic microbial degradation of polychlorinated biphenyls (PCBs) in Kanechlors-300 and -400 was enhanced significantly by adding burnt soil originally obtained from an uncontaminated paddy soil to the microbial culture. The maximum PCB-degrading activity was 0.49 nmol-Cl/ml-culture/day (238 ng-total-PCBs/ml-culture/day), where the degradation was observed in most of the congeners in Kanechlors-300 and -400: not only in meta- and para-substituted congeners but also ortho-substituted congeners. The degradation of PCBs occurred during the increase in the microbial population with acetate as the main electron donor. The ratio between the consumption of electron donors and the dechlorination of PCBs was revealed to be 93.9 nmol-Cl/mmol-e-donor, which is also the dechlorination efficiency over 56 d of incubation. The addition of acetate and lactate several times into the culture rejuvenated the activity.     

褐土区不同钾肥施用量对烟株钾含量的影响

采用盆栽和大田试验研究了褐土区不同钾肥施用量对烟株钾含量的影响。结果表明,随着钾肥施用量的增加,根、茎、叶钾含量增加;随着烟株生育进程的推进,根、茎、叶钾含量下降,但随着烟株的生长根、茎、叶中钾积累量均呈增长趋势;钾在烟株中的分配比例为叶> 茎> 根。盆栽烟髓部钾含量随着钾肥施用量的增加在增加,变化范围为2.40%~3.99%;钾肥用量对烤烟花中钾含量没有影响。盆栽和大田的叶片及叶脉钾含量随钾肥施用量的增加而增加。供钾充足时,由下至上烟叶含钾量逐渐降低;供钾不足时,随叶位的上升钾含量也上升。      

Implications of alcohol partitioning behavior for in situ density modification of entrapped dense nonaqueous phase liquids

Surfactant-based remediation techniques have the potential to be very effective for removing dense nonaqueous-phase liquids (DNAPLs) from contaminated sites. However, a risk associated with surfactant-based remediation of DNAPLs is the potential for unwanted downward mobilization of the DNAPL contaminants, making them more difficult to remove from the subsurface. The work described here examines the use of hydrophobic alcohol solutions to reduce the densities of entrapped DNAPLs, converting them to light nonaqueous-phase liquids (LNAPLs). Results of partitioning studies are presented for alcohol-DNAPL systems, in the absence and presence of surfactants. Results indicate that alcohol concentrations near saturation are necessary for conversion of DNAPLs to LNAPLs--particularly for high-density DNAPLs such as trichloroethylene (TCE) and tetrachloroethylene (PCE). Although surfactants can increase the mass of alcohol that can be delivered to a contaminated zone, they appear to change the partitioning equilibrium such that higher alcohol concentrations are required to achieve the same result. Results of this work indicate the importance of minimizing dilution during density modification applications and suggest the concept of using an alcohol macroemulsion flood for density conversion. Implications of the results of this work for remediation system design are discussed.