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.     

Trace metal exposure of soil bacteria depends on their position in the soil matrix

Micropores and biofilms of soils may protect bacteria against chemical stress, predation, and competition phenomena, explaining the great diversity and robustness of soil microbial communities and functions. We used sequential dispersion/density gradient centrifugation to separate free and loosely attached cells (FLA) from strongly attached cells (SA). The two fractions of the soils communities were investigated along a Zn and Cd pollution gradient, and the pollution-induced trace metal community tolerance (PICT) for SA and FLA was analyzed. FLA had developed a strong PICT in response to the 80 years of Zn and Cd pollution, whereas SA was virtually unaffected. It appears that the position of SA in biofilms and micropores has effectively protected them against toxic metal concentrations. The estimated free ion activity showed that the Cd activity was too low to reach toxic levels (PICT(cd) was probably caused by Zn). In contrast, the estimated Zn ion activity was close to a critical level, and could have caused the observed PICT(Zn) in FLA, at least if temporal/ spatial fluctuations of soil pH are taken into account. Such fluctuations could also explain the protection of SA as a result of diffusion constraints; which would be of little help under constant conditions because chemical equilibrium would be reached throughout.     

Taking the fungal highway: mobilization of pollutant-degrading bacteria by fungi

The capacity of fungi to serve as vectors for the dispersion of pollutant-degrading bacteria was analyzed in laboratory model systems mimicking water-saturated (agar surfaces) and unsaturated soil environments (glass-bead-filled columns). Two common soil fungi (Fusarium oxysporum and Rhexocercosporidium sp.) forming hydrophilic and hydrophobic mycelia, respectively, and three polycyclic aromatic hydrocarbon degrading bacteria (Achromobacter sp. SK1, Mycobacterium frederiksbergense LB501TG, and Sphingomonas sp. L138) were selected based on the absence of mutual antagonistic effects. It was shown that fungal hyphae act as vectors for bacterial transport with mobilization strongly depending on the specific microorganisms chosen: The motile strain Achromobacter sp. SK1 was most efficiently spread along hyphae of hydrophilic F. oxysporum in both model systems with transport velocities of up to 1 cm d(-1), whereas no dispersion of the two nonmotile strains was observed in the presence of F. oxysporum. By contrast, none of the bacteria was mobilized along the hydrophobic mycelia of Rhexocercosporidium sp. growing on agar surfaces. In column experiments however, strain SK1 was mobilized by Rhexocercosporidium sp. It is hypothesized that bacteria may move by their intrinsic motilitythrough continuous (physiological) liquid films forming around fungal hyphae. The results of this study suggest that the specific stimulation of indigenous fungi may be a strategy to mobilize pollutant-degrading bacteria leading to their homogenization in polluted soil thereby improving bioremediation.     

Enhancing phenanthrene biomineralization in a polluted soil using gaseous toluene as a cosubstrate

Laboratory experiments were conducted to study the potential of adding gaseous toluene, as a readily degradable carbon source, to enhance phenanthrene mineralization in polluted soil (1,000 mg/kg(dry soil)) aged for 400 days. Experiments were conducted in 0.5-L column reactors packed with a mixture of (80:20 w(wet)/w(wet)) spiked soil and vermiculite and fed with 1 g m(-3)reactor h(-1) toluene load in air. Removal efficiencies of 100% for toluene and greater than 95% for phenanthrene were obtained in 190 h. Evolved CO2 showed that phenanthrene mineralization increased from 39% to 86% in columns treated with gaseous toluene. Phthalic acid was identified as the principal soluble intermediate, which accumulated when no toluene was added. Increased phenanthrene uptake and mineralization with toluene can be attributed to increased biomass and the induction of enzymes involved in the intermediate mineralization. In microcosm experiments, phthalic acid mineralization increased from 19% to 81% within 50 h in the presence of toluene. Experiments with 14C-labeled phenanthrene confirmed the enhancement of phenanthrene mineralization from 45% to 83% in 385 h with toluene as a second carbon source. The results indicate thatthe addition of an appropriate gaseous cosubstrate could be an adequate strategy to enhance mineralization of PAHs in soil.     

咖啡豆残渣有机肥对德阳雪茄根际土壤肥力及真菌群落的影响

【目的】咖啡豆残渣作为农业废弃物具有一定的资源化利用价值,为研究咖啡豆残渣有机肥在雪茄烟叶生产中的应用效果。【方法】以咖啡豆残渣有机肥为主设计3种配方有机肥、作基肥穴施,分析各处理对雪茄烟株生长、植烟土壤肥力及根际土壤真菌群落结构的影响。【结果】（1）3种配方有机肥处理下雪茄烟的株高、叶长和叶宽均有显著提升,其中“菜籽粕+酒糟+咖啡豆残渣”的配方有机肥处理（T2）效果最好。（2）各处理下的土壤有机质、富里酸、全氮、有效磷和速效钾含量较对照均增加。团棵期土壤的有效磷、速效钾、全氮、有机质、胡敏酸和富里酸含量,以及成熟期的土壤速效钾和碱解氮含量都显著影响根际真菌群落结构。（3）3种配方有机肥均可改变雪茄烟根际真菌的优势种群,降低α多样性,且各处理下团棵期α多样性均大于成熟期。T2处理可显著降低根际土壤中明梭孢属和镰刀菌属的相对丰度,显著提高圆酵母属、曲霉属和被孢霉属的相对丰度。LEfSe分析表明,在门水平下处理间差异物种为子囊菌门和被孢霉门;在属水平下处理间差异物种为镰刀菌属、曲霉属、明梭孢属和被孢霉属。【结论】咖啡豆残渣有机肥可提高雪茄植烟土壤肥力、影响根际土壤真菌群落和促进雪茄生长。本...     

Effect of the application of cow slurry to grassland on nitrate levels in soil and soil water contents

The effect of a single heavy dressing of unamended cow slurry, applied to grassland in early spring (March), on nitrate levels and moisture contents in the soil profile have been examined for a 12 month period after the application. The slurry was allowed to remain on the soil surface until late autumn, when it was cultivated and a pasture re-established. Nitrate accumulated in the slurry and surface soil over spring, summer and autumn: the amount found in the slurry and 0–20 cm depth of soil in October (172 kg N/ha) accounted for 9% of the total-N originally added in the slurry. Significant leaching of nitrate into the subsoil did not occur until the soil was subsequently rewetted to field capacity in late autumn and winter. The layer of slurry on the soil surface restricted moisture losses from the soil during summer to less than one half of those under untreated grassland. Restricted aeration under the slurry is considered to be an important factor in delaying nitrification and stimulating anaerobic activity in the soil so that deep leaching of nitrate may not be likely for several months after a heavy application.     

Enhanced soil washing of phenanthrene by mixed solutions of TX100 and SDBS

Increased desorption of hydrophobic organic compounds (HOCs) from soils and sediments is a key to the remediation of contaminated soils and groundwater. In this study, phenanthrene desorption from a contaminated soil by mixed solutions of a nonionic surfactant(octylphenol polyethoxylate, TX100) and an anionic surfactant (sodium dodecylbenzenesulfonate, SDBS) was investigated. Phenanthrene desorption depended on not only aqueous surfactant concentrations and phenanthrene solubility enhancement but also the soil-sorbed surfactant amount and the corresponding sorption capacity of sorbed surfactants. The added surfactant critical desorption concentrations (CDCs) for phenanthrene from soil depended on both sorbed concentrations of surfactants and their critical micelle concentrations (CMCs). Phenanthrene desorption by mixed solutions was more efficient than individual surfactants due to the low sorption loss of mixed surfactants to soil. Among the tested surfactant systems, mixed TX100 and SDBS with a 1:9 mass ratio exhibited the highest phenanthrene desorption. Mixed micelle formation, showing negative deviation of CMCs from the ones predicted by the ideal mixing theory, was primarily responsible for the significant reduction of soil-sorbed amounts of TX100 and SDBS in their mixed systems. Therefore, mixed anionic-nonionic surfactants had great potential in the area of enhanced soil and groundwater remediation.     

氧含量对还原法检测原料乳细菌总数的影响

以还原法理论为基础,以刃天青作为氧化还原试剂,研制原料乳细菌总数快速检测仪器.原料乳中一些成分影响刃天青的颜色变化速度,干扰测定结果.对溶解氧的影响程度进行了判定,结果表明其影响程度较大,不容忽视.     

Effect of pesticides on the seed-borne fungi and fungal succession on rice in Malaysia

Three fungicides (thiophanate methyl, thiram and 2-methoxyethyl mercury chloride) and two insecticides (carbaryl and malathion) were used to study the effects of each of the pesticides on the seed-borne fungi of rice. A total of over 40 species in 23 genera of fungi, including several pathogenic forms was isolated from the untreated flowers and seeds. Fewer fungi were encountered on flowers still enclosed within the sheaths and the largest number of fungi was isolated from seeds just before harvest. Storage of the seeds for 6 months eliminated a large number of field fungi that was originally present on freshly harvested rice seeds. The fungi that persisted on the stored seeds, however, were species reported to be capable of grain deterioration and mycotoxin production. With the pesticide-treated seeds, fewer fungi were isolated from those treated with thiram or 2-methoxyethyl mercury chloride than with any of the other chemicals. Species of Curvularia were isolated as the principal fungi on seeds treated with any of the chemicals.     

益生菌对黄曲霉毒素的作用

益生菌的功能性引起了广泛的关注。介绍益生菌对强致癌物黄曲霉毒素作用的研究情况,包括益生菌对黄曲霉毒素产生的抑制作用及对黄曲霉毒素的去除作用。     

Adsorption of phenanthrene on natural snow

The snowpack is a reservoir for semivolatile organic compounds (SVOCs) and, in particular, for persistent organic pollutants (POPs), which are sequestered in winter and released to the atmosphere or hydrosphere in the spring. Modeling these processes usually assumes that SVOCs are incorporated into the snowpack by adsorption to snow surfaces, but this has never been proven because the specific surface area (SSA) of snow has never been measured together with snow composition. Here we expose natural snow to phenanthrene vapors (one of the more volatile POPs) and measure for the first time both the SSA and the chemical composition of the snow. The results are consistent with an adsorption equilibrium. The measured Henry's law constant is H(Phen)(T) = 2.88 x 10(22) exp(-10660/7) Pa m2 mol(-1), with Tin Kelvin. The adsorption enthalpy is delta H(ads) = -89 +/- 18 kJ mol(-1). We also perform molecular dynamics calculations of phenanthrene adsorption to ice and obtain AHads = -85 +/- 8 kJ mol(-1), close to the experimental value. Results are applied to the adsorption of phenanthrene to the Arctic and subarctic snowpacks. The subarctic snowpack, with a low snow area index (SAI = 1000), is a negligible reservoir of phenanthrene, butthe colder Arctic snowpack, with SAI = 2500, sequesters most of the phenanthrene present in the (snow + boundary layer) system.     

Biotransformation of 8:2 fluorotelomer alcohol in soil and by soil bacteria isolates

The microbial transformation of 8:2 fluorotelomer alcohol (FTOH) to perfluorocarboxylic acids, including the globally detected perfluorooctanoic acid (PFOA), has recently been confirmed to occur in mixed bacteria cultures, activated sludge, and soil. However, little is known to date about the microbes involved in the transformation. In the present study, the effect of three carrier solvents (ethanol, octanol, and 1,4-dioxane), which may serve as carbon sources, on the aerobic degradation rate of 8:2 FTOH and metabolite distribution was evaluated both in a clay loam soil and in two pure soil bacterial cultures. Biodegradation pathways appeared similar regardless of the solvent; however, significant differences in 8:2 FTOH degradation rates were observed: 1,4-dioxane > ethanol > octanol. In the presence of 1,4-dioxane, which is not easily biodegraded, 8:2 FTOH degradation was the fastest With octanol, which is a structural analogue of 8:2 FTOH, the transformation was inhibited, but upon depletion of octanol, 8:2 FTOH was biodegraded. In the pure culture study, two soil bacterial strains, Pseudomonas species OCY4 and OCW4, enriched from soil using octanol as a sole carbon source, also transformed 8:2 FTOH without prior exposure or acclimation to 8:2 FTOH. Increased biomass resulting from octanol metabolism did increase 8:2 FTOH transformation rates; however, 8:2 FTOH could not support bacterial growth, indicating the transformation by pure cultures was via cometabolic processes.     

Effect of catechins on the growth of oxygen-sensitive probiotic bacteria

Oxygen plays a major role in the loss of viability of oxygen-sensitive bacteria. Antioxidant compounds, such as catechins, could be used to limit negative effects of oxygen exposure on bacteria during their growth and storage in food products. The objective of the present study was to measure the effects of different concentrations of (+)-catechin hydrate, green tea epigallocatechin gallate and green tea extracts (GTE) on the growth of probiotic strains with different oxygen sensitivities: Bifidobacterium longum ATCC 15708, B. longum subsp infantis ATCC 15697 and Lactobacillus helveticus R0052. Redox potential (ORP) measurements of the culture medium as well as Fourier-transform infrared (FTIR) spectroscopy analyses on bacterial cells were carried out to evaluate the effects of GTE supplementation. Results obtained showed that medium enrichment with catechins did not stimulate the growth of the two bifidobacteria. However, the growth of L. helveticus was greatly enhanced, under aerobic conditions, by supplementation of the medium with GTE. This growth-promoting effect could be due, in part, by the reduction of the initial ORP value of the medium following addition of GTE. Moreover, the differences in the FTIR spectral region corresponding to fatty acids observed suggest an effect of GTE also on the lipids of the bacterial cell membrane. Thus, GTE supplementation could be used to limit oxygen toxicity on specific probiotic strains but the growth-promoting effect seems to be strain-dependent.     

Sorption of ionic surfactants to estuarine sediment and their influence on the sequestration of phenanthrene

The sorption of an anionic surfactant (sodium dodecyl sulfate; SDS) and a cationic surfactant (hexadecyl trimethylammonium bromide; HDTMA) to estuarine sediment has been studied in river water and seawater. Sorption isotherms for SDS were essentially linear in both waters, suggesting a nonspecific, hydrophobic interaction between the SDS tail and particle surface. Sorption of HDTMA was considerably greater, more nonlinear, and more sensitive to water composition. These observations were attributed to a combination of both electrostatic and hydrophobic interactions between the surfactant and particle surface, the formation of admicelles, and salinity-induced structural alteration of the hydrophobic tail of the HDTMA molecule. Presence of SDS caused a reduction in the sorption of phenanthrene to estuarine sediment because of the competitive effects of the surfactant tail for hydrophobic sorption sites on the particle surface. Conversely, the presence of HDTMA caused significant enhancement in phenanthrene sequestration because of head-on sorption of surfactant molecules and a resulting, more hydrophobic particle surface. The most persistent feature of our results was an inverse dependence of unit sorption on particle concentration, and an empirical algorithm defining the effect was used to calculate the sediment-water fractionation of realistic concentrations of reactants in the estuarine water column. The results of these calculations, and the more general findings of this study, significantly improve our understanding of both the transport and fate of ionic surfactants in the estuarine environment, and the effects that these surfactants have on the partitioning of hydrophobic organic micropollutants.