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.     

Availability of polycyclic aromatic hydrocarbons in aging soils

Purpose  

The soil contamination by hydrophobic organic contaminants (HOCs), such as polycyclic aromatic hydrocarbons (PAHs), poses great threats to human health and ecological security and attracts worldwide concerns. The total HOC concentrations overestimate its available fraction to the soil biota. Increased understanding of the availabilities of PAHs in soil environment will have considerable benefits for their risk assessment and be very instructive to food safety and remediation strategies in contaminated sites. However, the availability of PAHs in aging soils and particularly the correlations of the availabilities with their forms in soils have yet to be elucidated. In this work, the availabilities of PAHs in aging soils were evaluated using a sequential mild extraction technique.     

Sorption of heavy metals by iron-manganic nodules in soils of Primorskii region

The accumulation and deactivation (detoxification) of heavy metals in soils and in soil iron-manganic nodules have been studied. Data on the relative distribution of the total and mobile compounds of heavy metals in soils and nodules upon different rates of technogenic loads are obtained. It is shown that iron-manganic nodules play the role of specific depositors in the soil system, affect the redistribution of heavy metals in the soil cover, and control their migration in the soil profiles.     

Comparison of direct benthic flux to ebullition-facilitated flux of polycyclic aromatic hydrocarbons and heavy metals measured in the field

Journal of Soils and Sediments - No studies to date have compared directly the ebullition-facilitated organic and metal contaminant fluxes to direct benthic contaminant fluxes measured in the...     

Formation of polycyclic aromatic hydrocarbons in northern and middle taiga soils

An integrated study of the qualitative and quantitative composition of polycyclic aromatic hydrocarbons (PAHs) in the atmospheric precipitation-soil-lysimetric water system was performed using high performance liquid chromatography. It was shown that the accumulation of low-molecular PAHs (phenanthrene, anthracene, fluoranthene, pyrene, benz[a]anthracene, and chrysene) in soils is due to the transformation of organic matter and the regional transport and deposition of PAHs with atmospheric precipitation on the underlying surface. High-molecular polyarenes (benz[b]fluoranthene, benz[k]fluoranthene, benz[a]pyrene, dibenz[a,h]anthracene, benzo[ghi]perylene, and indeno[1,2,3-cd]pyrene) mainly result from the decomposition of soil organic matter.     

多环芳烃污染土壤的植物-微生物联合修复初探

在温室盆栽条件下,通过种植紫花苜蓿单独或联合接种菌根真菌(Glomus caledonium L.)(AM)和多环芳烃专性降解菌(DB),研究了利用植物-微生物强化修复多环芳烃(PAHs)长期污染土壤的效果。试验结果表明,接种菌根真菌和PAHs专性降解菌能促进紫花苜蓿的生长和土壤中PAHs的降解。经过90天修复试验,种植紫花苜蓿接种AM、DB和DB+AM处理的PAHs的降解率分别为47.9%、49.6%、60.1%,均高于只种植紫花苜蓿的对照处理(CK)(21.7%)。另外,随着PAHs苯环数的增加,其平均降解率逐渐降低,但是接种PAHs专性降解菌能够提高4环和5环PAHs的降解率。同时也发现土壤中脱氢酶活性和PAHs降解菌数量越高的处理,土壤PAHs的降解率也越高,这也是种植紫花苜蓿接种微生物能够有效促进土壤PAHs降解的原因。     

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.     

Contamination of soils in the urbanized areas of Belarus with polycyclic aromatic hydrocarbons

The content of polycyclic aromatic hydrocarbons (PAHs) in the soils of urbanized areas, including the impact zones of Belarus, were studied. The concentrations of 16 PAHs in the soils were determined for individual and high-rise building zones, forests, and forest parks of Belarus. The levels of the PAH accumulation in the soils of different industrial enterprises and boiler stations were analyzed. Possible sources of soil contamination with PAHs were considered, and the structure of the PAHs in the soils was shown. The levels of the soil contamination were determined from the regulated parameters for individual compounds and the sum of 16 PAHs.     

生物表面活性剂强化微生物修复多环芳烃污染土壤的初探

通过温室盆栽实验,单独或联合接种多环芳烃专性降解菌(DB)和添加生物表面活性剂-鼠李糖脂(RH),研究了生物表面活性剂强化微生物修复多环芳烃(PAHs)长期污染土壤的效果。结果表明,添加RH和接种DB能明显促进土壤中PAHs总量和各组分PAHs的降解。经过90 d培养后,添加RH、DB和RH+DB处理的PAHs的降解率分别为21.3%、32.6%、36.0%,较对照分别提高了333.0%、563.3%、633.0%。此外,随着苯环数的增加,土壤中15种PAHs平均降解率逐渐降低。同时也发现DB、RH+DB处理土壤中脱氢酶活性、多酚氧化酶活性和PAHs降解菌数量显著高于CK、RH处理,但是CK与RH处理没有显著差异,说明DB、RH在促进土壤中PAHs的降解方面有不同的机制。     

Microtox技术检测多环芳烃生物毒性的研究

利用Microtox技术检测 5种多环芳烃化合物生物毒性结果表明 ,二甲亚砜配制的测试液中萘、菲及荧蒽均对发光细菌具有一定生物毒性 ,且随浓度的增大而增强 ,相同浓度下毒性菲 >萘 ;测试液中当萘浓度小于其溶解度时即产生 10 0 %的抑光率 ,萘EC50 为 4 .32mg/L ,而菲及荧蒽浓度近其溶解度时所产生的最大抑光率分别为 <5 0 %和15 %左右 ;芘及蒽最大浓度时则对发光细菌无生物毒性显示。表明Microtox技术可有效检测低环化合物萘的生物毒性 ,但对高环化合物 (≥ 3环 )的检测因受其低水溶性的限制而灵敏度降低 ,利用二甲亚砜获取多环芳烃污染物提取液的生物毒性主要与低分子化合物萘及菲有关     

Determination of high molecular mass polycyclic aromatic hydrocarbons in a typical Italian smoked cheese by HPLC-FL

High-performance liquid chromatography with fluorescence detection was used for the analysis of polycyclic aromatic hydrocarbons (PAHs), in "Diavoletto" smoked cheese. Such cheese is typically produced in the Sorrento peninsula, and it is smoked commonly with different materials of vegetable origin. The importance of the smoking generation material is proven by the attention that the EU is paying in indicating the list of wood that may be used to produce smoking flavor agents. The PAHs considered are classified as "probable human carcinogens" by the U.S. Environmental Protection Agency for sufficient data from animal bioassays. The smoked samples contained high molecular mass PAHs with different levels ranging from 0.12 to 6.21 microg/kg. The determination was carried out also on liquid smoking flavor agents, smoke-flavored cheese, and nonsmoked cheese to measure the level of contamination before the treatment.     

城市土壤多环芳烃的特征和来源解析研究进展

Polycyclic aromatic hydrocarbons (PAHs) are mainly produced by combustion processes and consist of a number of toxic compounds.They are always emitted as a mixture and have become a major type of pollutants in urban areas.The degree of soil contamination by PAHs is of special concern in areas immediately in proximity to cities with heavy traffic,factories,older buildings,and infrastructure.The accumulation of soil PAHs is also affected by non-anthropogenic factors,such as climate,vegetation,and soil property.This paper reviews three typical source identification techniques,including diagnostic ratios,positive matrix factorization,and principle conrponents analysis.The advantages or disadvantages of these techniques are analyzed.It is recommended that multiple identification techniques be used to determine the sources in order to minimize the weaknesses inherent in each method and thereby to strengthen the conclusions for PAH source identification.     

Dissipation and sorption processes of polycyclic aromatic hydrocarbons (PAHs) to organic matter in soils amended by exogenous rich-carbon material

Purpose

The aim of the research was to assess the effect of biochar addition on aging, degradation, and sorption processes of polycyclic aromatic hydrocarbons (PAHs) to soil organic matter. The study was carried out as a sorption experiment in strictly controlled water and air conditions, which allowed for the accurate observation and prediction of PAH behavior in soils.

Materials and methods

Four soils were fortified with a PAH mixture (Fluorene-Flu, Anthracene-Ant, Phenanthrene-Phe, Pyrene-Pyr, Chrysene-Chry) at 20 mg kg^?1 of single-compound concentration level. The experiment was carried out in two trials: soils?+?5PAHs amended with biochar and soil?+?5PAHs without biochar addition with incubation times of 0, 1, 3, 6, and 9 months. After each interval time, the extractable (E-SOM) and stable organic matter (S-SOM) were measured as well as PAHs determined in two forms: total concentration (PAH-tot) and residual concentration (PAH-rest) after E-SOM extraction. The PAH loss and half-life times were estimated according to pseudo first-order kinetics equation.

Results and discussion

The amounts of PAH-tot in the soils without biochar decreased by an average of 92%, while in soil with biochar, this was 41% after 9 months of aging. The amount of PAHs-rest bounded with S-SOM after 9 months of incubation varied from 0.9 to 3.5% and 0.2 to 1.3% of the initial PAH concentration, respectively, for soils non-induced and induced by biochar. In soils without biochar, Flu, Ant, Phe, and Pyr exhibited similar T_1/2 (43–59 days), but Chry was characterized by a much higher and broader T_1/2 than other hydrocarbons (67–280 days). Biochar addition to the soils significantly influenced the half-life changes for all PAHs. The highest changes were noted for Phe (14-fold increase), and the lowest was for Flu (7-fold increase).

Conclusions

The addition of exogenous-rich carbon material such as biochar to the soil significantly changes the behavior and sorption potential of PAHs in the soil. Soils enriched with biochar are characterized by a higher persistence of PAHs, longer aging time, and lower affinity for sorption by native organic matter structures. Soils freshly polluted by PAH are mainly sorbed by E-SOM, which significantly increases their accessibility and reduces formation of bound-residues in the soil.

     

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.     

Pyrogenic polycyclic aromatic hydrocarbons in soils of reserved and anthropogenically modified areas: Factors and features of accumulation

The accumulation features of pyrogenic polycyclic aromatic hydrocarbons (PAHs) in soils were analyzed depending on the type of burning material and the combustion conditions (the temperature, oxygen access, and dispersion of the combustion products). The PAH accumulation features in the soils of three reserved areas of forest, steppe, and peat fires were revealed. The distribution features of the PAHs resulting from the anthropogenic pyrogenic processes (the household combustion of wood and the inflammation of coal dumps) in soils were established. The differences in the qualitative composition of the PAHs arriving to the soils from the different pyrogenic sources were shown.     

多环芳烃微生物降解机理研究进展

主要阐述了微生物降解PAHs的机理,比较了典型微生物种类芽孢杆菌(Bacillus)和分支杆菌(M.vanbaalenii PYR-1)对同种PAHs菲的代谢过程不同之处,并分析了分支杆菌(M.vanbaalenii PYR-1)对菲和芘的代谢机理,指出微生物氧化降解PAHs主要从其K区和湾区开始,而K区氧化是有毒PAHs降解的主要可能途径,资料显示真菌比细菌对苯并[a]芘的降解能力更强,同时给出了微生物代谢菲、芘和苯并[a]芘的降解图,以便做进一步研究。     

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.     

Concentrations and composition of polycyclic aromatic hydrocarbons in the granulodensimetric fractions of soils in Moscow parks

A comprehensive study of the contents and composition of 15 compounds from the group of polycyclic aromatic hydrocarbons in granulodensimetric fractions of soddy-podzolic soils was performed. The specificity of the accumulation of these substances in the clay (heavy-weight) and light-weight soil fractions was investigated. The levels of the soil contamination in Moscow parks with polyarenes were determined, and the assessment of changes in the degree of the soil contamination over a long period of time was made.     

湛江市区不同利用类型土壤的PAHs污染特征和来源

首次对湛江市表层土壤PAHs污染进行研究,并根据利用类型对其进行分类讨论。虽然湛江市的环境质量在全国名列前茅,但研究显示随着重化工业的快速发展,湛江市土壤已受到一定程度的PAHs污染,∑PAHs的平均含量达491.1ng.g-1,低于珠三角的发达城市,而高于中等城市,特别是某些工业区污染严重,超过荷兰相关标准;与其它城市一样,湛江市土壤PAHs的组分构成以4环和5环为主,占∑PAHs的65.1%。∑PAHs的变化趋势为旧厂址>市区工业区>交通>郊区工业区>休闲>农业,市区>郊区;3环组分比重随市中心距离的增大而增加,4环和5环则相反,6环差异较小。农业和郊区工业高比重的3环组分可能与市区石油源PAHs的大气输送有关。已搬迁工厂高含量∑PAHs表明PAHs在土壤的积累影响是长期的,而休闲区178.7 ng.g-1的∑PAHs则表明解决PAHs的污染问题必须解决污染源问题。利用4种PAHs比值判断湛江市土壤PAHs的来源主要是石油源、石化燃烧和煤、柴等生物燃烧源的混合源,与湛江市社会经济情况相符。