Effects of geosorbent and solution properties on sorption and desorption of PAHs

Characteristics of phenanthrene and pyrene’s sorption and desorption on two local soils in solutions of simulated groundwater, simulated lung fluid, and simulated saliva were studied with batch equilibrium experiments to understand the fate of PAHs in the karst region of southwestern China and to assess the environmental exposure and the health risk of PAHs. The results showed that the sorption and desorption isotherms of phenanthrene and pyrene on two target soils in the three solution systems could be adequately described by the Freundlich model, while the fitted isotherm parameters for the simulated groundwater solution distinguished notably from those for the simulated body fluid solutions. For the sorption experiments, in the simulated groundwater, the n values were 0.722 and 0.672 for phenanthrene and were 0.724 and 0.663 for pyrene, respectively, on the yellow soil and the limestone soil; The log K_F values were 3.118 and 3.323 for phenanthrene and were 3.648 and 3.846 for pyrene, respectively, on the yellow soil and the limestone soil. In the simulated body fluids, the n values for phenanthrene and pyrene ranged from 0.622 to 0.836 and from 0.590 to 0.865, respectively, and the log K_F values of phenanthrene and pyrene ranged from 2.845 to 3.327 and from 3.344 to 3.779, respectively. For the desorption experiments, in the simulated groundwater, the n values were 0.662 and 0.744 for phenanthrene and were 0.702 and 0.647 for pyrene, respectively, on the yellow soil and the limestone soil. The log K_F values were 3.666 and 3.686 for phenanthrene and were 4.128 and 4.225 for pyrene, respectively, on the yellow soil and the limestone soil. In the simulated body fluids, the n values for phenanthrene and pyrene ranged from 0.612 to 0.668 and from 0.631 to 0.819, respectively, and the log K_F values of phenanthrene and pyrene ranged from 3.134 to 3.407 and from 3.533 to 3.839, respectively. The limestone soil had relatively higher log K_F values but lower K_OC values compared to those of the yellow soil, indicated that the nature of sorbent soils played the dominant role in sorption and desorption behaviors of PAHs. The experimental results showed a remarkable differences in sorption and desorption behaviors of PAHs in simulated body fluids and groundwater. The nonlinearities of measured isotherms and the measured sorption capacities of soils in simulated body fluids were significantly lower than corresponding those in the simulated groundwater, and HI values for simulated body fluids systems were significantly smaller than corresponding those for the simulated groundwater systems. The results underscore cautions in assessing environmental exposure and health risks of PAHs based on their sorption–desorption data in simulated groundwater as this is traditionally done.

     

Pollution characteristics of polycyclic aromatic hydrocarbons （PAHs） in oily sludge from the Zhongyuan Oilfield and its peripheral soils

The purpose of this study is to determine the degree of contamination caused by polycyclic aromatic hydrocarbons (PAHs) in oily sludge and soils around it in the Zhongyuan Oilfield. The contents of polycyclic aromatic hydrocarbons in oily sludge samples were determined with HPLC. The contents of PAHs of oily sludge from three different oil production plants vary from high to low in the order of the Wenming oily sludge dumping site of No. 3 Oil Production Plant (3W)>the Mazhai oily sludge dumping site of No. 3 Oil Production Plant (3M)>the Wen’er oily sludge dumping site of No. 4 Oil Production Plant (4W). Naphthalene, acenaphthylene, acenaphthene, fluorine and phenanthrene are the major pollutants of PAHs in oily sludge. The contents of PAHs in soil samples around the oily sludge dumping sites vary widely from 434.49 to 2408.8 ng/g. Naphthalene, acenaphthene, fluorine, phenanthrene and pyrene are the characteristic factors of PAHs in soil samples of 3M and 3W, and naphthalene, acenaphthene, fluorine and phenanthrene are the characteristic factors of PAHs in soil samples of 4W. According to these data and the ratios of Fl/Py, PAHs in oily sludge samples come mainly from petrogenic sources, and soil samples are divided into petrogenic soil samples and mixed-source soil samples, and both petrogenic and pyrogenic soil samples in terms of the sources of PAHs. The classification by Nemero index P indicates that soils around the oily sludge dumping sites have been seriously polluted.     

Sorption kinetics of naphthalene and phenanthrene in loess soils

A laboratory study was executed to investigate the effect of surfactants to enhance sorption of polycyclic aromatic hydrocarbon (PAH) contaminants in loess soil. Phenanthrene and naphthalene were chosen as organic contaminant indicators in loess soil modified by the cation surfactant hexadecyltrimethylammonium (HDTMA) bromide. The kinetic behavior of sorption during transport in natural and modified loess soil was studied. The results indicated that sorption rate in the cation surfactant modified loess soils was at least 3 times faster than that of the natural soil. A first-order kinetics model fitted the sorption data well for both soils. The sorption rates of the two organic compounds were related to their primary residual quantity on the soils. The experiments showed that sorption amounts approached constant values approximately within 30 and 90 min for naphthalene and phenanthrene at 298–318 K, respectively. The rate constants, however, displayed negative correlation with increasing temperature. With changing temperature, the activation energy was calculated at –6.196–1.172 kJ/mol for naphthalene and –28.86–15.70 kJ/mol for phenanthrene at 298–318 K. The results can be used to predict the sorption kinetics of phenanthrene and naphthalene in loess soils, and in a wider perspective, be used to better understand the transport of petroleum contaminants in the soil environment.     

Polycyclic aromatic hydrocarbons in the soils of technogenic landscapes

An integrated study of qualitative and quantitative composition of polycyclic aromatic hydrocarbons (PAH) in the atmospheric precipitation-soil-lysimetric water system of aerotechnogenic polluted landscapes was conducted using high-performance liquid chromatography in a gradient mode. Only low-molecular weight polyarenes (phenanthrene, anthracene, fluoranthene, pyrene, benz(a)anthracene, and chrysene) were found in the atmospheric precipitation and lysimetric waters. The growth of PAHs in soils is provided by the input of phenanthrene, fluoranthene, and pyrene with atmospheric precipitation. The absence of heavy PAHs (benzfluoranthenes, benz(a)pyrene, dibenz(a,h)anthracene, benz(ghi) perylene, and indeno[1,2,3-cd]pyrene) in the atmospheric precipitation and their identification in soil give grounds to state that their accumulation was caused mainly by transformation of organic matter during pedogenesis. The technogenic impact was estimated and criterion of the degree of soil pollution by PAH was proposed.     

大气干湿沉降: 地下河多环芳烃的重要来源——以广西清水泉地下河为例

为证实大气干湿沉降物是岩溶地下河中多环芳烃(PAHs)的来源,研究选择了某城市典型的岩溶地下河水源地作为研究地点,采用大气干湿采样器、聚氨酯泡沫(PUF)大气被动采样器分别采集大气及其干湿沉降物样品,同时采集地下河水样和分层采集流域土壤,利用气相色谱-质谱联用仪(GC-MS)测定了16种PAHs优先控制污染物。结果表明,地下河流域大气干湿沉降中PAHs的干湿沉降通量为147.26 ng·(m2·d)-1,流域PAHs沉降量为1943.8 g;大气中的PAHs浓度为45.33 ng·m-3;地下河水中PAHs浓度平均值为220.98 ng·L-1;土壤中PAHs浓度为38.72 ng·g-1;大气、降雨和土壤中PAHs组成以2~3环的萘、芴、菲、荧蒽、芘5种为主,地下河水中以芴、菲、荧蒽、芘、苯并[a]蒽、苯并[a]芘6种为主。利用地下河多介质中的16种PAHs成分谱、特征比值结合它们的物理化学性质进行PAHs的源解析,研究显示大气干湿沉降是岩溶地下河水中多环芳烃的主要污染源之一,这归因于岩溶地区防污性能的脆弱性。     

Dissipation of polycyclic aromatic hydrocarbons in crop soils amended with oily sludge

Oil fields present a potential ecological risk to nearby farmland soil. Here we present a new method designed to evaluate the ability of winter wheat (Triticum aestivum) to contribute to the dissipation of polycyclic aromatic hydrocarbons (PAHs), which are priority pollutants in soils contaminated by oily sludge. The influence of different doses of oily sludge on the dissipation of PAHs was studied along with individual PAH profiles in soils after different periods of plant growth. Five soil samples were artificially contaminated with different percentages of oily sludge (0 %, 5 %, 10 %, 15 % and 20 %). Winter wheat grew in the oily sludge–amended soils for 265 days. PAH content in the soils was monitored over the course of the study. The rate of PAH dissipation is related to the properties of different PAHs, period of winter wheat growth, and oily sludge application dose. Analysis for treated soils indicates that the dissipation of PAHs increased significantly over the first 212 days, followed by minimal changes over the final 53 days of treatment. In contrast, PAH dissipation slowed with increasing oily sludge application. For each PAH, the experimental results showed a significant compound-dependent trend. Winter wheat in the present study significantly enhanced the dissipation of PAHs in oily sludge–contaminated soil.     

Geomorphic controls on mercury accumulation in soils from a historically mined watershed, Central California Coast Range, USA

Historic Hg mining in the Cache Creek watershed in the Central California Coast Range has contributed to the downstream transport of Hg to the San Francisco Bay-Delta. Different aspects of Hg mobilization in soils, including pedogenesis, fluvial redistribution of sediment, volatilization and eolian transport were considered. The greatest soil concentrations (>30 mg Hg kg⁻¹) in Cache Creek are associated with mineralized serpentinite, the host rock for Hg deposits. Upland soils with non-mineralized serpentine and sedimentary parent material also had elevated concentrations (0.9–3.7 mg Hg kg⁻¹) relative to the average concentration in the region and throughout the conterminous United States (0.06 mg kg⁻¹). Erosion of soil and destabilized rock and mobilization of tailings and calcines into surrounding streams have contributed to Hg-rich alluvial soil forming in wetlands and floodplains. The concentration of Hg in floodplain sediment shows sediment dispersion from low-order catchments (5.6–9.6 mg Hg kg⁻¹ in Sulphur Creek; 0.5–61 mg Hg kg⁻¹ in Davis Creek) to Cache Creek (0.1–0.4 mg Hg kg⁻¹). These sediments, deposited onto the floodplain during high-flow storm events, yield elevated Hg concentrations (0.2–55 mg Hg kg⁻¹) in alluvial soils in upland watersheds. Alluvial soils within the Cache Creek watershed accumulate Hg from upstream mining areas, with concentrations between 0.06 and 0.22 mg Hg kg⁻¹ measured in soils 90 km downstream from Hg mining areas. Alluvial soils have accumulated Hg released through historic mining activities, remobilizing this Hg to streams as the soils erode.     

Rapid transport of anthropogenic lead through soils in southeast Missouri

To investigate Pb transport and cycling, soils from the forest floor and cores from White Oaks (Quercus alba L.) were collected near a Pb smelter in SE Missouri at varying depths from the surface and varying distances. Lead concentrations in soil samples at the surface drop dramatically with distance from approximately 1500 mg/kg at less than 2 km from the smelter to around 100 mg/kg at localities greater than 2 km from the smelter. Lead contents in tree rings are below 0.5 mg/kg in samples dated prior to 1970, and rapidly increase in 1975–1990 samples. Isotopic compositions of soils and tree rings exhibit systematic variations of Pb isotopic compositions with depth and tree ring age. Distinguishable isotopic signatures for Pb sources allowed quantification of the contribution of smelter Pb to the soils. At depths where Pb concentrations decreased and approached constant values (10–25 cm, 10–30 mg/kg), 50–90%, 40–50% and 10–50% of the Pb could be derived from the smelter for the samples at locations less than 2, 2–4 and over 4 km from the smelter, respectively. The remaining portion was attributable to automobile emission and bedrock sources. Because the smelter operated from 1963 to 2003 and samples were collected in 1999, it is estimated that smelter Pb infiltrates at rates of 1 cm/yr (30 cm in 30 yr). At distances less than 1.5 km from the smelter, even though Pb concentrations become asymptotic at a depth of 30 cm, isotopic evidence suggests that Pb has migrated below this depth, presumably through exchange with naturally occurring Pb in the soil matrix. This implies that soils heavily polluted by Pb can exceed their Pb carrying capacity, which could have potential impacts on shallow groundwater systems and risk further exposure to human and ecological receptors.     

Sources and contamination characteristics of PAHs in environmental media in a karst underground river system (southern China)

The aim of this study was to determine the sources and contamination characteristics of polycyclic aromatic hydrocarbons (PAHs) in various environmental media in a karst underground river system. For this purpose, air, underground river water, sediment, and soil samples were collected from a typical underground river in southern China in the dry and wet seasons of 2013–2014, and the compositional spectra, distribution, and ratio characteristics of 16 PAHs were determined for comparative analysis. The results show that three 2–3-ring PAHs (naphthalene, phenanthrene, and fluoranthene) mainly occur in air and underground river water. In sediments and soils, 4–6-ring PAHs are the main components. The PAH concentrations in the air in the wet season are clearly greater than those in the dry season, while it is the opposite in the underground water. Seasonal differences in the concentration of PAHs in the sediments and soils are minor. The concentrations of PAHs in the environmental media overall showed variation in the following order: upstream < midstream < downstream, and this is related to pollutant discharge, adsorption, etc. The main source of PAHs in the upstream area is the combustion of grass, wood, and coal, while it is petroleum in the midstream area, and combustion of grass, wood, coal, and petroleum near the outlet of the underground river. It is necessary to change the energy structure in the study area, improve the efficiency of environmental protection facilities, reduce the emission in vehicle exhaust, and control pollution by PAHs at their sources.     

Polycyclic aromatic hydrocarbons in Niger Delta soil: contamination sources and profiles

The distribution and sources of PAHs in soil as well as PAHs profiles have been investigated in areas with anthropogenic pollution in the Niger Delta (Nigeria) such as Warri and Ughelli. PAHs were identified in 21 soil samples (0–10cm upper layer) collected in May, 2003. The typical total PAHs level in Niger Delta soil ranged from 182 ± 112 - to - 433 ±256 íg/kg dw. PAH concentrations in soil samples from Warri Refinery, Tanker Loading point and Ugboko via Rapele oil field were quite high ( the mean ÓPAH concentrations were 433, 402 and 384 íg/kg dry weight respectively). The dominant PAHs in soil samples were pyrene, naphthalene and benzo[k]fluoranthene. The soil total PAHs (PAH_tot.) concentration, normalized to organic carbon content (OC), ranged from 11.4 to 47.2 mg PAH_tot. /kg OC; and showed that organic matter of the soil samples from Quality Control Centre, Ugelli West is highly contaminated with PAHs and had a value of 47.2 ± 31.2 mg PAH_tot./kg OC. Two and three ring aromatic hydrocarbons predominated in soil samples from Ughelli West, Tanker Loading point and Delta Steel Company, which is indicative of petrogenic origin.     

污染土壤中多环芳烃的微生物降解及其机理研究进展

多环芳烃(PAHs)是一类普遍存在于环境中的难降解危险性“三致”有机污染物。微生物对多环芳烃的降解是去除土壤中多环芳烃的主要途径。研究表明，对于土壤中低分子量多环芳烃类化合物，微生物一般以唯一碳源方式代谢；而大多数细菌和真菌对四环或四环以上的多环芳烃的降解作用一般以共代谢方式开始。本文重点论述了高分子量多环芳烃：芘和苯并(a)芘的微生物降解及其机理。并介绍了多环芳烃污染的微生物—植物联合修复机制，最后展望了污染土壤中多环芳烃的研究趋势。     

Vertical distribution and source identification of polycyclic aromatic hydrocarbons in anoxic sediment cores of Chini Lake, Malaysia: Perylene as indicator of land plant-derived hydrocarbons

Four anoxic sediment cores were collected from Chini Lake, Malaysia in order to investigate the variability of polycyclic aromatic hydrocarbon (PAH) and perylene concentrations. The study also determined significant differences of perylene concentrations in different sediment layers. Total PAH concentrations ranged from 248 to 8098 ng g⁻¹ in the samples. Diagnostic PAH ratios such as methylphenanthrenes/phenanthrene (MP/P), phenanthrene/anthracene (P/A) and fluoranthene/(fluoranthene + pyrene) (Fl/(Fl + Py) revealed a dominance of pyrogenic influences and partial petrogenic inputs to the top sediment layers. Perylene concentrations were high in the top layers (<12 cm) and increased with increasing depth. There is a significant positive correlation (r = 0.705, p = 0.01) between perylene concentrations and TOC. Analysis of variance (ANOVA) and LSD revealed significant differences (p < 0.05) in TOC-normalized perylene concentrations between the upper (<12 cm) and bottom layers (>12 cm). The average perylene concentrations accounted for 26–50% (0–12 cm) and 50–77% (12–36 cm) of pentacyclic-aromatic hydrocarbon isomers (PAI) present whereas it made up 10–34% (0–12 cm) and 46–66% (12–36 cm) of the total PAH. The average pyrene concentrations decreased with increasing depth and accounted for 62% (0–3 cm), 20–23% (3–12 cm) and 3–1.4% (12–36 cm) of perylene present. The results of hierarchical cluster analysis based on these ratios suggested different input sources for the top and bottom layers. It is concluded that the activity of termites on woody plants produced perylene which is supplied to the lake by run-off from the heavy and frequent rains in this Asian tropical climate. In addition, there was also in situ formation of perylene in the bottom layers due to diagenetic processes.     

Compositional fractionation of polyaromatic hydrocarbons in the karst soils, South China

This study aims to explore the condensation and fractionation trends of persistent organic pollutants (POPs) in the karst soils. The tiankeng is a karst surface expression that can act as a focal point for introduction of contaminants to a karst aquifer, which may serve both as condenser for vapor phase POPs and as barrier/sink for particulate associated less volatile POPs. The fractionation of POPs in soils from the upper rim and floor of tiankeng is of interest in understanding the role of tiankeng in the long-distance transport of POPs. In the present study, polycyclic aromatic hydrocarbons (PAHs) in the surface soils from the upper rim and floor of Dashiwei tiankeng in Southern China were analyzed. The total PAH concentrations in soils were 23.40–190 ng g⁻¹, with phenanthrene being the most abundant. The distribution patterns of PAH compounds in the soil samples matched well with their properties. It indicated the heavy PAHs were susceptible to retention by the floor soils of tiankeng than light PAHs. A plot of Cfloor/Crim against PAH molecular weight gave a good positive relationship in the molecular weight range of 152–276. It is suggested that the floor soils can be focal points of more concentrated PAH and deserve attention. The concentrations of total PAHs in the floor soils (43.40–190 ng g⁻¹, mean 87.76 ng g⁻¹) were higher than those in the upper rim (23.40–88.94 ng g⁻¹, mean 57.74 ng g⁻¹). In addition, there was a shift in compound pattern with an increase in the proportion of light PAHs (2–3 rings), a decrease in heavy PAHs (5–6 rings) and a relatively stable content of 4-ring PAHs. A combination of particulate scavenging and cold condensation is proposed as the major mechanism for the compositional fractionation of PAHs in the soils from the upper rim and floor of tiankeng.     

Indications for pedogenic formation of perylene in a terrestrial soil profile: Depth distribution and first results from stable carbon isotope ratios

Concentrations and isotope compositions of polycyclic aromatic hydrocarbons (PAHs) were determined in natural soils of Southern Germany. In selected profiles perylene concentrations increased with soil depth when compared to the other PAH compounds present. However, its low solubility made vertical transport by seepage water unlikely. Therefore two mechanisms are discussed that could have caused the unusual distribution of perylene in these soils:

(a) Atmospheric deposition of combustion-derived (i.e. pyrogenic) perylene in the top-soil and

(b) in situ generation in the sub-soil of these specific terrestrial environments. This could have been caused by microbial activities or other catalytic processes yet unknown.

In order to distinguish between pyrogenic and natural generation compound-specific ¹³C/¹²C ratios (δ¹³C) were compared between perylene and other PAHs in samples from the top-soil and sub-soil. Despite successful clean-up of the extracts, low perylene concentrations and peak overlaps with benzo(e)pyrene and benzo(a)pyrene prevented determination of a unique δ¹³C value for perylene in the upper horizon. However, the δ¹³C value of perylene in the sub-soil was 5.7 permille more negative than other equal-mass PAHs (with m/z of 252) in the top-soil, which rather supports in situ generation of perylene in the sub-soil.     

Polycyclic aromatic hydrocarbon concentrations in urban soils representing different land use categories in Shanghai

An extensive soil survey was carried out in Shanghai to investigate the spatial distribution and possible sources of polycyclic aromatic hydrocarbons (PAHs) in urban soils. Soil samples were collected from highways, iron-smelting plants, steel-smelting plants, shipbuilding yards, coking plants, power plants, chemical plants, urban parks, university campuses and residential areas and were analyzed for 16 PAHs by gas chromatography with mass detection. High PAH concentrations were found in all locations investigated, with mean values of soil total PAH concentrations in the range 3,279–38,868 μg/kg DM, and the PAH concentrations were significantly influenced by soil organic matter content. Soil PAH profiles in all districts were dominated by PAHs with 4–6 rings. Principal components analysis and diagnostic ratios of PAHs indicate that they were mainly derived from coal combustion and petroleum but in soils from highways the PAHs were derived largely from vehicle exhaust emissions. The high concentrations of PAHs found indicate that many urban soils in Shanghai represent a potential hazard to public health.     

水体悬浮颗粒物的扫描电镜与X射线能谱显微分析

通过对湖州地区74个土壤样品多环芳烃含量的测定,分析了湖州市不同土地利用类型土壤中多环芳烃(PAHs)的含量特征及污染水平。结果表明,湖州地区PAHs各组分的含量均有检出,各种土地利用类型表层土壤均受到一定程度的PAHs污染,但均小于荷兰土壤修复标准;湖州市区耕地中PAHs的含量最高;从PAHs低环/高环比值小于1以及芘/苯并(a)芘比值小于2,反映了湖州地区土壤中PAHs主要是由燃煤和生活污染产生的。     

Garnet lherzolites from the Hanaus-I and Louwrensia kimberlites of Namibia

The Gibeon cluster of Namibian kimberlites is emplaced into the Orange River Belt which has accreted to the Kaapvaal Craton. These offcraton kimberlites lack diamonds and are younger than the diamondiferous on-craton kimberlites. The Hanaus-I and Louwrensia kimberlites each contain a bimodal suite of upper-mantle-derived garnet lherzolite xenoliths characterized by a coarse granular or mosaic porphyroclastic texture. The Louwrensia pipe in addition contains garnet harzburgites. Deformed lherzolites are not iron-enriched relative to the coarse types. Conditions of equilibration calculated by the Wells-Wood method are 841–1,013° C at 25.6–36.3 kbars, and 869–1,195° C at 23.9–39.4 kbars, for coarse lherzolites from Louwrensia and Hanaus respectively, and from 1,080–1,112° C at 31.6–34.5 kbars, and 983–1,228° C at 24.7–35.2 kbars, for mosaic porphyroclastic types from Louwrensia and Hanaus respectively. The coarse varieties from both localities have similar equilibration conditions to coarse lherzolites from on-craton kimberlites and define the lower limb of a perturbed geotherm. The upper high temperature limb of the Namibian geotherm is considered to be an apparent geotherm generated by the deformation and metasomatism of the upper mantle by a rising diapir. Such geotherms, being the result of kimberlite-xenolith interactions, provide no stratigraphic or thermal information concerning the site of kimberlite or diamond formation.     

Polycyclic aromatic hydrocarbons (PAHs) in particle-size fractions of urban topsoils

Polycyclic aromatic hydrocarbons’ (PAHs) concentrations in bulk samples are commonly used to assess contamination but PAHs are unevenly distributed among particle-size fractions. Seventeen urban surface soil samples from the city of Xuzhou, China, were collected and then fractionated into five size fractions (2,000–300, 300–150, 150–75, 75–28, and <28 μm). The concentrations of 12 US EPA PAHs were measured using gas chromatograph/mass spectrometry in various fractions, and the bulk soil samples and distribution patterns of PAHs in different particle-size fractions were investigated. The mean concentration of total PAHs in bulk soil samples was 1,879 ng/g. The median concentrations for all individual PAH were higher for the 75–2,000 μm fraction than for the <75 μm fraction. The distribution factors for various PAHs in <28 μm soil fraction were closely correlated (r = ?0.661, p < 0.019) to bulk soil fugacity capacity. The values of PAH isomer indicated that traffic emissions might be the major origin of PAHs in Xuzhou surface soils. Spearman correlation analysis was performed and the result suggested that soil organic carbon might be a factor controlling the concentrations of PAHs in soils.     

Adsorption of phenanthrene and pyrene by biochar produced from the excess sludge: experimental studies and theoretical analysis

A biochar derived from the pyrolysis of excess sludge of sewage treatment plant at 700 °C was used to remove phenanthrene and pyrene from aqueous solution. The adsorption equilibrium for phenanthrene and pyrene was achieved within 7.5 and 15 h, respectively. The adsorption kinetics of phenanthrene and pyrene were well fitted to pseudo-second-order model, and the isotherms were well fitted to Freundlich adsorption isotherm model (R ² > 0.96). The effect of variation of pH on the adsorption of the biochar was observed to be insignificant. The hydrophobic action and pore filling might be the main mechanisms of the adsorption of phenanthrene and pyrene on the biochar. The density functional theory calculations confirmed that the adsorption depended mainly on the biochar structure and the molecular volumes of phenanthrene and pyrene. Phenanthrene molecule is smaller than the pyrene molecule and therefore showed better adsorption characteristics with the biochar than the pyrene molecule.     

Geochemical coupling of uranium and phosphorous in soils overlying an unmined uranium deposit: Coles Hill, Virginia

The mineralogy and geochemistry of soils developed over the unmined Coles Hill uranium deposit (Virginia) were studied to determine how phosphorous influences the speciation of uranium in oxidizing soil/saprolite systems typical of the eastern US. Results from this study have implications for both uranium remediation (e.g. in situ stabilization) and uranium resource exploration (e.g. near-surface geochemical sampling). The primary uranium ore (coffinite and uraninite hosted in quartzo-feldspathic gneiss) weathers to saprolites containing the same uranium concentration as the underlying ore (approximately 1000 mg U/kg saprolites). In these water saturated (below water table) saprolites the uranium is retained as uranyl phosphates of the meta-autunite group (mainly meta-uranocircite). Above the water table the soils overlying the deposit contain approximately 200 mg uranium per kg soil (20 times higher than uranium concentrations in similar soils formed from unmineralized rocks adjacent to the deposit). In these unsaturated zone soils uranium is retained by two processes: (1) incorporation into barium–strontium–calcium aluminum phosphate minerals of the crandallite group (mainly gorceixite), and (2) sorption of uranium with phosphorous onto iron oxides that coat the surfaces of other soil minerals.Thermodynamic calculations suggest that the meta-autunite group minerals present in the saprolites below the water table are not stable in the unsaturated zone soils overlying the deposit due to the drop in soil pH from  6.0 down to  4.5. Mineralogical observations suggest that, once exposed to the unsaturated environment, the meta-autunite group minerals react to form U(VI)-bearing aluminum phosphates and U(VI) surface complexes or nano-precipitates associated with ferric oxides. These results therefore indicate that models predicting U(VI) speciation in phosphate amended soils must simultaneously account for variations in pH, ion activities (aluminum appears to be particularly important) and surface complexation with iron oxide mineral surfaces.