Modeling in situ ozonation for the remediation of nonvolatile PAH-contaminated unsaturated soils

Mathematical models were developed to investigate the characteristics of gaseous ozone transport under various soil conditions and the feasibility of in situ ozone venting for the remediation of unsaturated soils contaminated with phenanthrene. On the basis of assumptions for the mass transfer and reactions of ozone, three approaches were considered: equilibrium, kinetic, and lump models. Water-saturation-dependent reactions of gaseous ozone with soil organic matter (SOM) and phenanthrene were employed. The models were solved numerically by using the finite-difference method, and the model parameters were determined by using the experimental data of Hsu [The use of gaseous ozone to remediate the organic contaminants in the unsaturated soils, PhD Thesis, Michigan State Univ., East Lansing, MI, 1995]. The transport of gas-phase ozone is significantly retarded by ozone consumption due to reactions with SOM and phenanthrene, in addition to dissolution. An operation time of 156 h was required to completely remove phenanthrene in a 5-m natural soil column. In actual situations, however, the operation time is likely to be longer than the ideal time because of unknown factors including heterogeneity of the porous medium and the distribution of SOM and contaminant. The ozone transport front length was found to be very limited (< 1 m). The sensitivity analysis indicated that SOM is the single most important factor affecting in situ ozonation for the remediation of unsaturated soil contaminated with phenanthrene. Models were found to be insensitive to the reaction mechanisms of phenathrene with either gas-phase ozone or dissolved ozone. More study is required to quantify the effect of OH* formation on the removal of contaminant and on ozone transport in the subsurface.     

Modelling of diffusion-limited retardation of contaminants in hydraulically and lithologically nonuniform media

A new reactive transport modelling approach and examples of its application are presented, dealing with the impact of sorption/desorption kinetics on the spreading of solutes, e.g. organic contaminants, in groundwater. Slow sorption/desorption is known from the literature to be strongly responsible for the retardation of organic contaminants. The modelling concept applied in this paper quantifies sorption/desorption kinetics by an intra-particle diffusion approach. According to this idea, solute uptake by or release from the aquifer material is modelled at small scale by a "slow" diffusion process where the diffusion coefficient is reduced as compared to the aqueous diffusion coefficient due to (i) the size and shape of intra-particle pores and (ii) retarded transport of solutes within intra-particle pores governed by a nonlinear sorption isotherm. This process-based concept has the advantage of requiring only measurable model parameters, thus avoiding fitting parameters like first-order rate coefficients.In addition, the approach presented here allows for modelling of slow sorption/desorption in lithologically nonuniform media. Therefore, it accounts for well-known experimental findings indicating that sorptive properties depend on (i) the grain size distribution of the aquifer material and (ii) the lithological composition (e.g. percentage of quartz, sandstone, limestone, etc.) of each grain size fraction. The small-scale physico-chemical model describing sorption/desorption is coupled to a large-scale model of groundwater flow and solute transport. Consequently, hydraulic heterogeneities may also be considered by the overall model. This coupling is regarded as an essential prerequisite for simulating field-scale scenarios which will be addressed by a forthcoming publication.This paper focuses on mathematical model formulation, implementation of the numerical code and lab-scale model applications highlighting the sorption and desorption behavior of an organic contaminant (Phenanthrene) with regard to three lithocomponents exhibiting different sorptive properties. In particular, it is shown that breakthrough curves (BTCs) for lithologically nonuniform media cannot be obtained via simple arithmetic averaging of breakthrough curves for lithologically uniform media. In addition, as no analytical solutions are available for model validation purposes, simulation results are compared to measurements from lab-scale column experiments. The model results indicate that the new code can be regarded as a valuable tool for predicting long-term contaminant uptake or release, which may last for several hundreds of years for some lithocomponents. In particular, breakthrough curves simulated by pure forward modelling reproduce experimental data much better than a calibrated standard first-order kinetics reactive transport model, thus indicating that the new approach is of high quality and may be advantageously used for supporting the design of remediation strategies at contaminated sites where some lithocomponents and/or grain size classes may provide a long-term pollutant source.     

Effect of salinity on community structure and naphthalene dioxygenase gene diversity of a halophilic bacterial consortium

The aim of this study is to analyze the effect of salinity on polycyclic aromatic hydrocarbons (PAHs) biodegradation, community structure and naphthalene dioxygenase gene (ndo) diversity of a halophilic bacterial consortium with the denaturing gradient gel electrophoresis (DGGE) approach. The consortium was developed from oil-contaminated saline soil after enrichment for six times, using phenanthrene as the substrate. The prominent species in the bacterial consortium at all salinities were identified as halophilic bacteria Halomonas, Alcanivorax, Marinobacter, Idiomarina, Martelella and uncultured bacteria. The predominant microbes gradually changed associating with the saline concentration fluctuations ranging from 0.1% to 25% (w/v). Two ndo alpha subunits were dominant at salinities ranging from 0.1% to 20%, while not been clearly detected at 25% salinity. Consistently, the biodegradation occurred at salinities ranging from 0.1% to 20%, while no at 25% salinity, suggesting the two ndo genes played an important role in the degradation. The phylogenetic analysis revealed that both of the two ndo alpha subunits were related to the classic nah-like gene from Pseudomonas stutzeri AN10 and Pseudomonas aeruginosa PaK1, while one with identity of about 82% and the other one with identity of 90% at amino acid sequence level. We concluded that salinity greatly affected halophilic bacterial community structure and also the functional genes which were more related to biodegradation.

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多环芳烃化合物菲分解菌的分离鉴定及分解特性研究

利用2，3-二差劲基联苯喷雾技术，从石油污染土壤中分离到2株菲降解菌。它们可以菲为惟一的碳源和能源良好地生长。在生理生化试验的基础上，利用16SrRNA（小核糖亚单位RNA序列）的方法鉴定这株菌为鞘氨醇单胞菌属细菌，这些菌对菲的降解性是通过在液体培养基内菌体的增加及底物的减少来证实的，静止细胞反应试验表明，这些菌除了菲以外还可降解其它芳烃化合物。     

Cell size dependent toxicity thresholds of polycyclic aromatic hydrocarbons to natural and cultured phytoplankton populations

The toxicity of pyrene and phenanthrene to phytoplankton was studied by analyzing the effect on the growth, abundance and cell viability of cultured species and natural communities of the Atlantic Ocean and the Mediterranean Sea. A decrease in cell abundance, and growth rate was observed as concentration of PAHs increased, with catastrophic cell mortality induced at the highest PAH concentration tested. A strong positive linear relationship was observed between the LC50 (the PAH concentration at which cell population will decline by a half), and the species cell volume, for both phenanthrene and pyrene. Natural communities were however significantly more sensitive to PAHs than cultured phytoplankton, as indicated by the lower slope (e.g. 0.23 and 0.65, respectively, for pyrene) of the relationship LC50 vs. cell volume. The results highlight the importance of cell size in determining the phytoplankton sensitivity to PAHs identifying the communities from the oligotrophic ocean to be more vulnerable.     

Assessing the bioavailability of phenanthrene to soil microorganisms using the Tenax extraction method

The Tenax TA extraction technique followed by gas chromatography mass spectrometry (GC-MS) determinations was used to assess the actually bioavailable fraction of phenanthrene (ABF-Phe) in three different soils freshly contaminated with this compound at levels of 10, 100, and 1,000 mg kg⁻¹. The results were related to the ecotoxic effect of phenanthrene on soil nitrifying bacteria. Nitrification potential measurements were applied as an ecotoxicity end point. A strong positive linear relationship (r ² = 0.95) was obtained between the content of the actually bioavailable phenanthrene fraction and the inhibition of nitrifying bacteria activity.     

生物泥浆反应器中微生物数量变化与PAHs降解

分别以浓度、温度、接种量、通气量和表面活性剂为降解调控因子,采用平板记数法进行了生物泥浆反应器中微生物数量变化与ＰＡＨｓ降解的关系研究。结果表明：土壤中细菌数量与ＰＨＥ、ＰＹ投加浓度呈显著正相关。ＰＨＥ、ＰＹ初始浓度越高,细菌数量越大。此外,反应器的温度对微生物生长速度和数量有重要影响。反应器温度为３０℃时对细菌迅速繁殖有利,反应器温度为２０℃时对真菌生长繁殖有利。接种量为５％即可明显提高ＰＨＥ和     

Microbial degradation of dissolved organic matter (DOM) and its influence on phenanthrene-DOM interactions

Microbial degradation-induced changes in the characteristics of dissolved organic matter (DOM), and the subsequent effects on phenanthrene-DOM interactions were investigated based on the microbial incubation of DOM collected from four different sources for 28 d. Partially biodegraded DOM presented higher specific UV absorbance (SUVA), lower protein-like fluorescence, higher humic-like fluorescence, lower aliphatic carbon fraction, and higher hydrophobic neutral fractions compared to the original DOM. Microbial changes in DOM led to an increase in the isotherm nonlinearity as well as the extent of phenanthrene binding. A negative relationship between SUVA and the Freundlich n values was established for the original and the biodegraded DOM, suggesting that aromatic condensed structures may play important roles in providing nonlinear strong binding sites irrespective of microbial degradation. In contrast, there were two separate slopes of the correlations between the percentage of hydrophobic acid (HoA) fraction and the n values for the original and the biodegraded DOM with a higher slope exhibited for the latter, implying that the microbial utilization of oxygen-containing structures in the HoA fractions may contribute to enhancing the associated isotherm nonlinearity.     

Interactions of arsenic and phenanthrene on their uptake and antioxidative response in Pteris vittata L

The interactions of arsenic and phenanthrene on plant uptake and antioxidative response of Pteris vitatta L. were studied hydroponically. The combination of arsenic and phenanthrene decreased arsenic contents in fronds by 30-51%, whereas increased arsenic concentrations 1.2-1.6 times in roots, demonstrating the suppression of arsenic translocation compared to the corresponding treatment without phenanthrene. Under the co-exposure, As(III) concentrations in fronds deceased by 12-73%, and at higher arsenic exposure level (≥10 mg/L), As(V) in fronds and As(III) in roots increased compared to the single arsenic treatment. Arsenic exposure elevated phenanthrene concentrations in root by 39-164%. The co-existence of arsenic and phenanthrene had little impact on plant arsenic accumulation, although synergistic effect on antioxidants was observed, suggesting the special physiological process of P. vitatta in the co-exposure and application potential of P. vitatta in phytoremediation of arsenic and PAHs co-contamination.     

Sorption of phenanthrene to biochar modified by base

Biochar (BC) is a potential material for removal of polycyclic aromatic hydrocarbons from soil and water, and base modification is a promising method for improving its sorption ability. In this study, we synthesized a series of base-modified biochars, and evaluated their sorption of phenanthrene. Original biochars were produced by pyrolysis of three feedstocks (rice straw, wood and bamboo) at five temperatures (300°C, 350°C, 400°C, 500°C and 700°C). Base-modified biochars were further obtained by washing of biochars with base solution. The base soluble carbon (SC) was extracted from the supernatant, which were only obtained from biochars pyrolyzed at low temperatures (<500°C) and the content was decreased with the increase of pyrolysis temperature. The SC content between different feedstocks followed the trend of rice straw>wood>bamboo when same pyrolysis conditions were applied. It was found that base modification improved the sorption of phenanthrene on biochars that SC could be extracted from (extractable-BCs). However, base treatment but had limited effects for biochars that no SC could be extracted from. It suggested that base modification improved the sorption of phenanthrene to extractable-BCs by removing the SC and thus increasing the surface area and hydrophobicity. Therefore, base modification was suggested to be used in modifying extractable-BCs.

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