溶解性富里酸对土壤中多环芳烃迁移的影响

多数多环芳烃（PAHs）因其水溶性低,且易被土壤有机质固持,曾经被认为其迁移能力十分微弱。但土壤中溶解性有机质可能影响PAHs的溶解、吸附等环境过程,进而影响其迁移性。本文旨在研究富里酸提取的溶解性有机质（FDOM）对PAHs在土－水间迁移的影响及其可能机制。溶液化学稳定性研究结果显示,FDOM在溶液pH 2.0～7.0、CaCl₂浓度0～1 500 mmol L^-1范围内均能保持较好的分散性,未发生絮凝沉淀。室内土柱淋溶试验结果表明,FDOM在土壤中具有较强的迁移能力,在FDOM持续淋溶条件下,菲、芘以及苯并[a]芘在淋出液中的浓度明显提高,并有少量二苯并[a, h]蒽淋出。FDOM淋溶处理的土柱表层土壤中菲、芘、苯并[a]芘和二苯并[a, h]蒽的淋失率分别为92.06%、92.07%、84.52%和23.27%,显著高于对照组（p<0.05）。以上研究结果表明,FDOM可作为载体提高PAHs在土壤中的迁移性,增加PAHs向深层土壤和地下水迁移的可能性。     

Extraction of polycyclic aromatic hydrocarbons from spiked soil

A homogenization method was evaluated for extracting polycyclic aromatic hydrocarbons (PAHs) from soils. Fifteen PAHs were spiked and recovered from 2 soils at concentrations ranging from 1 to 1000 micrograms/g, using the homogenization method and a Soxhlet extraction method. Each extraction method performed well in removing the 15 PAHs from both soils over a broad range of concentrations. In general, Soxhlet extraction yielded slightly but significantly (P less than 0.05) higher recoveries than did the homogenization method. The homogenization method, however, was easy to use, and the extraction step turnaround time was less than 15 min/sample. The method should be suitable for other applications requiring the extraction of hydrophobic organic compounds from soils.     

The maps of soil tolerance toward pollution with oil products and polycyclic aromatic hydrocarbons: Methodological aspects

Natural factors ensuring soil tolerance toward pollution with technogenic hydrocarbons, particularly, oil products and polycyclic aromatic hydrocarbons, are considered. The maps of the self-purification capacity of the soils of Russia and its particular humid and arid regions with respect to their contamination with technogenic hydrocarbons are analyzed. The principles lying in the basis of these maps are discussed. It is argued that the cartographic assessment of soil tolerance toward pollution with technogenic hydrocarbons is necessary for setting the values of maximum permissible concentrations of hydrocarbons in soils, for the choice of adequate soil rehabilitation procedures, and for the organization of soil monitoring.     

Enhanced sorption of polycyclic aromatic hydrocarbons by soil amended with biochar

Purpose  

Polycyclic aromatic hydrocarbon (PAHs) are ubiquitous pollutants in agricultural soils in China. Biochar is the charred product of biomass pyrolysis, which is widely applied to soils to sequestrate atmospheric carbon dioxide and guarantees a long-term benefit for soil fertility. Knowledge about the impacts of various biochars on soil sorption affinity remains obscure. In this study, we evaluated the effects of various biochars on PAHs sorption to biochar-amended agricultural soil.     

Effect of soil pH on the sorption capacity of soil organic matter for polycyclic aromatic hydrocarbons in unsaturated soils

Sorption by soil organic matter (SOM) is considered the most important process affecting the bioavailability of hydrophobic organic chemicals (HOCs)in soil.The sorption capacity of SOM for HOCs is affected by many environmental factors.In this study,we investigated the effects of soil pH and water saturation level on HOC sorption capacity of SOM using batch sorption experiments.Values of soil organic carbon-water partition coefficient (K_OC) of six selected polycyclic aromatic hydrocar...     

多环芳烃菲对淹水土壤微生物动态变化的影响

本文研究了多环芳烃菲对土壤微生物的动态影响。通过利用生物反应器,观察了淹水条件下太湖流域微碱性粘质乌栅水稻土和红壤地区酸性砂质旱地红砂土中,在加与不加菲后土壤微生物数量的动态变化。试验结果表明,菲对2种土壤中细菌有刺激作用,在旱地红砂土中细菌增加了一个数量级,达1.63 ?107 cfu/g(干土计)。在一定时间范围内,菲对真菌和放线菌有明显的抑制作用。菲对这2种土壤中微生物数量的影响与土壤性质、反应时间和微生物种类有关。这些观察结果为多环芳烃菲污染土壤的微生物学影响评价和潜在有效降解菌的筛选提供了有用的信息。     

Selenium enhances Conyza canadensis phytoremediation of polycyclic aromatic hydrocarbons in soil

Journal of Soils and Sediments - To determine whether supplemental selenium (Se) enhances the tolerance of Conyza canadensis (C. canadensis) to polycyclic aromatic hydrocarbons (PAHs) and thereby...     

Low‐molecular‐weight organic acids enhance desorption of polycyclic aromatic hydrocarbons from soil

The impact of low‐molecular‐weight organic acids (LMWOAs) on desorption of phenanthrene and pyrene as representative polycyclic aromatic hydrocarbons (PAHs) from a contaminated soil was investigated by using a laboratory batch experiment. Three LMWOAs were used in this study and were citric, oxalic and malic acids. The LMWOAs in aqueous solution promoted desorption of PAHs from soil significantly and demonstrated an increasing trend as the concentration of LMWOAs increased. When compared with desorption of phenanthrene and pyrene from soil to water, the addition of LMWOAs enhanced desorption of test PAHs by up to 285 and 299%, respectively. Among the three LMWOAs studied, citric acid demonstrated the greatest efficiency in promoting PAH desorption from soil. Solutions of LMWOA continuously promoted PAH removal from soil during the multiple cycles of desorption. Overall, the experimental results suggest that LMWOAs in aqueous solution could disrupt soil organic matter (SOM)–metal cation–mineral linkages in soils, resulting in the release of SOM from soil and simultaneous increase of dissolved organic carbon (DOC) in solution. The loss of SOM from soil and increase of DOC in solution are responsible for the enhanced PAH desorption from soil. The positive correlation between DOC in solution and desorbed PAHs from soil suggests that the loss of SOM from soil plays an important role in LMWOA‐enhanced desorption of PAHs from soil.     

多环芳烃在土壤中的环境行为研究进展

综述了土壤环境中多环芳烃(PAHs)来源及其进入环境后的行为和归宿,并提出多环芳烃污染土壤的修复对策。     

Partitioning of polycyclic aromatic hydrocarbons (PAH) to water-soluble soil organic matter

The mobility of polycyclic aromatic hydrocarbons (PAH) in soils can be influenced by the presence of dissolved organic matter. Partition coefficients of selected polycyclic aromatic hydrocarbons, ranging from 3-ring to 6-ring compounds, to water-soluble soil organic matter (WSSOM) were determined. Partition coefficients were determined for WSSOM obtained from two soils under agricultural use and forest and for commercially available humic acid (Aldrich), taking advantage of a reversed phase (C₁₈) separation method. The WSSOM was characterised with regard to charge and hydrophilic/hydrophobic properties with a dissolved organic matter (DOM) fractionation method. No sorption to WSSOM was found for the tri- and tetracyclic PAH, whereas the penta- and hexacyclic PAH showed a significant binding to both types of WSSOM and to Aldrich humic acid. The affinity of penta- and hexacyclic PAH to WSSOM was considerably lower compared to the affinity to Aldrich humic acid. This is suggested to be due to the lower amount of hydrophobic fractions, c. 30%, in the natural WSSOM as compared to Aldrich humic acid. Effective partition coefficients (Koc_eff) for the sorption of PAH to bulk soil calculated from K_DOC and DOM in the naturally occurring concentration range were only 60–70% of the K_oc values in pure water. The impact of DOM on pollutant transport is further influenced by non-equilibrium behaviour of PAH in soils and by sorption of DOM to the solid-soil matrix. Several scenarios are described in which the effect of DOM on pollutant transport may become important.     

甜菜与牧草间作对多环芳烃污染土壤的修复作用

通过盆栽试验方法,选择经济作物甜菜和牧草类黑麦草、苏丹草、香根草为供试植物,研究了甜菜与3种牧草分别间作及各自单作对多环芳烃（PAHs）菲、荧蒽、芘和苯并[a]芘污染土壤修复作用。结果显示：经6个月连续两茬种植试验后,所有种植植物的处理中土壤PAHs的去除率均高于无植物种植组,间作种植土壤PAHs的去除率高于单作,黑麦草、苏丹草、香根草与甜菜间作对土壤PAHs的去除率分别达到84.85%、79.96%、84.11%;在土壤污染条件下,间作模式更有利于甜菜生长;种植植物增强了土壤中多酚氧化酶和过氧化氢酶的活性,间作模式下二者活性高于单作4.37%~43.07%,过氧化氢酶较多酚氧化酶对PAHs土壤污染更敏感,可作为关键酶用于评价土壤PAHs污染状况。在不影响农业生产的前提下,修复植物牧草和经济作物甜菜间作种植模式显著提高了土壤PAHs的降解率。     

Dissipation of polycyclic aromatic hydrocarbons (PAHs) in soil microcosms amended with mushroom cultivation substrate

The potential of mushroom cultivation substrate (MCS) in bioremediation was examined in polycyclic aromatic hydrocarbon (PAH)-contaminated soil. After a 60-day incubation, 32.9% dissipation of the 15 studied PAHs was observed in MCS-amended microcosms, with anthracene, benzo(a)pyrene and benzo(a)anthracene being the most degradable PAHs. MCS significantly increased the abundance and changed the community compositions of bacteria, fungi and aromatic hydrocarbon degraders. Two species belonging to the Sordariomycetes of the Ascomycota were enriched in all MCS-treated soil samples, and coupled with the unique changes in the PAH profile, this implies the involvement of laccase-like enzymes. Limited improvement was observed after adding Pleurotus ostreatus, possibly because of its poor colonization of the soil. In addition, alfalfa appeared to antagonize the bioremediation effects of MCS. The results of this study suggest that MCS can be a cost-effective and green biostimulation agent, thereby providing support for the development of MCS-based biostimulation of PAH-contaminated soil.     

Distribution of polycyclic aromatic hydrocarbons in the soil-plant system

The content and composition of the polycyclic aromatic hydrocarbons (PAHs) in the conjugated systems of [arable soil]-[above-ground plant organs] in background (reference) and contaminated regions were studied. The coefficients of the biological uptake of PAHs by plants (K _bPAH) were determined for different PAH concentrations in the soil. Correlations of the PAH accumulation rate in plants with the physicochemical properties of the PAHs—the solubility, hydrophobicity, volatility, and chemical activity (polarizability and ionization potential)—were revealed. The high accuracy, sensitivity, and information value of the standardized parameters K _b were shown (with K _bPAH as an example) for the quantitative study of the accumulation mechanisms of substances by plants compared to the average arithmetic values of their concentrations in the plants.     

Chemical studies on soil humic acids

Seventeen samples of soil humic acids, two fractions of soil fulvic acid sample, and several related compounds such as lignin, tannin, flavonoid and artificial humic substances were decomposed in conc. KOH solution at 180°C. Succinic acid, glutaric acid, phloroglucin, p-hydroxybenzoic acid, vanillic acid, protocatechuic acid, 3,4-dihydroxy-5-methoxybenzoic acid, and gallic acid were detected in the degradation products of humic acids. The amounts of these degradation products were discussed in relation to the degree of humification or the sources of the humic acid samples. Succinic acid also resulted from glucose, polymaleic acid, and the humic acid and humin prepared from glucose, but glutaric acid resulted only from glucose humic acid and glucose humin but not from glucose and polymaleic acid. Succinic acid and glutaric acid were supposed to result from the same structural portions in humic acids because of the very significant positive linear correlation between their amounts. p-Hydroxybenzoic, vanillic, protocatechuic, and 3,4-dihydroxy-S-methoxybenzoic acids were presumed to result mainly from lignin structure in humic acids. Soil humic acids yielded small amounts of gallic acid although the yields by hydrolysable tannins were in large amounts. The yields of above-mentioned degradation products from humic acids decreased with increasing degree of humification. Phloroglucin resulting from ftavonoids including condensed tannins were also found in the degradation products of humic substances. Its yield showed no linear correlation with RF value of humic acid, and is presumed to be rather related to the vegetation at the sites of soil sampling.     

Chemical studies on soil humic acids

The levels of alcoholic and phenolic hydroxyl, methoxyl, carboxyl, and carbonyl groups of 33 to 38 humic acids obtained from various types of soils were determined to analyze the relationships between the amounts of these functional groups and the degree of humification or the types of soils. The amounts of various oxygen-containing functional groups examined were all proven to be significantly different among the various types of humic acids by analyses of variance. During humification. generally, the carboxyl and carbonyl groups increased while alcoholic and phenolic hydroxyl and methoxyl groups decreased. Linear and logarithmic regression analyses of carboxyl group contents on RF values (optical density of the alkaline solution of humic acids at 600 nm) gave very significant positive correlations. The carboxyl group contents of Rp type humic acids and humic acids from calcareous soils were largely distributed in the upper side of the regression curve. The carbonyl group contents showed a very significant linear positive correlation with carboxyl group contents. and both of them showed high linear positive correlation with RF values. Phenolic hydroxyl group contents decreased with humification in Rp(l). B. and A type humic acids. Alcoholic hydroxyl group contents showed a significant negative linear association with _RF values. Methoxyl group contents decreased rapidly with increasing humification in low humified humic acids, and their negative correlation with _RF values were proven to be very significant by logarithmic regression analysis. The complicated relationship between oxygen content and RF value which was reported previously (7) has been accounted for by the results obtained in the experiments conducted here.     

Assessment of polycyclic aromatic hydrocarbons in biochar and biochar-amended agricultural soil from Southern Spain

Journal of Soils and Sediments - The goal of this study was to determine if the application of four biochars produced from different feedstock leads to soil contamination with the 16 US...     

Chemical studies on soil humic acids

Abstract

Relationships between elementary compositions and types of humic acids or the "degrees of humification were studied statistically using 39 humic acids prepared from various types of soils. Mean values of C%. H%. N%, 0%, H/C, N/C, and O/C of the different types of humic acids (A. B. Rp(l), Rp(2). and Po) were compared. The elementary compositions of various types of humic acids were proven by variance analyses to be significantly distinct. Linear regression analyses of C%, H%, N%. 0%, H/C, N/C, or O/C on RF or AlogK values were also carried out on 35 humic acids excluding the P_+~+++ type humic acids. The linear associations were found to be significant between C%-RF (5% level), H%-RF, H%-?logK, H/C-RF and HIC-?logK (0.1% level), N/C-RF(O.1% level). N%-RF(l% level), N%-?logK N/C-?logK(5% level), and ?logK (1% level), while no significant relationship was found with regard to C%;-?logK, 0%-?logK (both 5% level) and O/C-RF and O/C-?logK (l0% level). Carbon and oxygen contents of humic acids may be apt to reflect the different conditions of soils. The deeper the visible light absorption of humic acids and so the higher the degrees of humification, the lower the hydrogen contents of humic acids were. Though nitrogen content showed a trend similar to the trend of hydrogen content against RF values as a whole. the nitrogen content of less humified humic acids (Rp type) varied from very low to very high values. suggesting the enrichment of nitrogen into humic acid molecules in the early stage of humification. In the H/C versus O/C diagram, humic acids occupied an area reserved for the oxydation products of lignins. The area was fairly wide and “J”-shaped, that is, in the early to the middle stage of humification humic acids were arranged in the direction of dehydrogenation or demethanation, and in the later stage they were arranged in the direction of dehydration.     

Phytotoxicity of polycyclic aromatic hydrocarbons to willow trees

The toxicity of PAH to willow trees(Salix alba, S. viminalis, S. viminalis x schwerinii) was investigated. Willow cuttings were grown in PH-saturated hydroponic solution (naphthalene NAP, phenanthrene PHEN and benzo(a)pyrene BaP). Toxicity was related to aqueous solubility and was highest for NAP. PHEN did not show significant effects, except in one case. Exposure of trees to BaP showed no effect in two cases, but increased transpiration and growth in two others. High dosages of NAP were fatal for the trees, the lowest dosage significantly stimulated growth. Soil samples were taken from several PAH contaminated sites, among them gas works sites and a former sludge basin. The PAH contents ranged from 1.76 mg/kg to 1451 mg/kg. None of the soils was lethally toxic to the trees, and difference between growth in control soils and growth in PAH contaminated soils was not apparent. Growth and water use efficiency were positively, but not significantly correlated to the PAH content of the soils. Outdoor growth of willows and poplars on the former sludge basin in Valby was monitored, with willows growing faster than poplars(Fopulus trichocarpa). Phytotoxic effects could be observed at some willows at the Valby sludge basin, but it is not sure whether these effects can be contributed to PAH.     

Sorption of polycyclic aromatic hydrocarbons to mineral surfaces

Minerals contribute crucially to the retention of polycyclic aromatic hydrocarbons (PAHs) in subsurface environments. To investigate the sorption behaviour to mineral surfaces batch sorption experiments were conducted using three PAHs (phenanthrene, pyrene, benzo(a)pyrene) and three mineral sorbents that were representative of subsurface materials (quartz, goethite‐coated quartz, quartz‐montmorillonite mixture). Sorption kinetics showed an instantaneous, considerable PAH sorption to all minerals, except for phenanthrene sorption to quartz at small aqueous‐phase concentrations. Apparent sorption equilibrium was achieved after 4 hours of contact time. The sorption characteristics were fitted to six isotherm models by applying Monte Carlo simulation and nonlinear regression. Best‐fit models were obtained by a model discrimination approach. Phenanthrene and pyrene sorption were best described by the Freundlich isotherm model, with the exception of phenanthrene sorption to quartz (linear isotherm). Good fit results for quartz were also obtained for the combined linear‐Freundlich isotherm. Benzo(a)pyrene sorption to all minerals followed linear high‐affinity isotherms. In the case of phenanthrene and pyrene, the Monte Carlo simulations resulted in mean values with small standard deviations for the isotherm parameters, indicating a negligible influence of the experimental uncertainties on the accuracy of the fitted parameters. For phenanthrene, (i) linear isotherms to quartz and goethite‐coated quartz and (ii) a nonlinear concave‐shaped isotherm to quartz–montmorillonite, assuming a pore‐filling process to micropores formed by clay aggregates, were confirmed. For pyrene, nonlinear convex‐shaped isotherms to the mineral surfaces were assessed. A specific sorption affinity of pyrene to the goethite surface indicated a non‐covalent cation‐π interaction. Small sorption affinities to quartz–montmorillonite support an unfavourable partitioning into the adjacent water.