Aqueous solubility, effects of salts on aqueous solubility, and partitioning behavior of hexafluorobenzene: experimental results and COSMO-RS predictions

The aqueous solubility of hexafluorobenzene has been determined, at 298.15 K, using a shake-flask method with a spectrophotometric quantification technique. Furthermore, the solubility of hexafluorobenzene in saline aqueous solutions, at distinct salt concentrations, has been measured. Both salting-in and salting-out effects were observed and found to be dependent on the nature of the cationic/anionic composition of the salt. COSMO-RS, the Conductor-like Screening Model for Real Solvents, has been used to predict the corresponding aqueous solubilities at conditions similar to those used experimentally. The prediction results showed that the COSMO-RS approach is suitable for the prediction of salting-in/-out effects. The salting-in/-out phenomena have been rationalized with the support of COSMO-RS σ-profiles. The prediction potential of COSMO-RS regarding aqueous solubilities and octanol-water partition coefficients has been compared with typically used QSPR-based methods. Up to now, the absence of accurate solubility data for hexafluorobenzene hampered the calculation of the respective partition coefficients. Combining available accurate vapor pressure data with the experimentally determined water solubility, a novel air-water partition coefficient has been derived.     

Anthropogenic lead distribution in soils under arable land and permanent grassland estimated by Pb isotopic compositions

The role of land use on fate of metals in soils is poorly understood. In this work, we studied the incorporation of lead in two neighboring soils with comparable pedogenesis but under long-term different agricultural management. Distributions of anthropogenic Pb were assessed from concentrations and isotopic compositions determined on bulk horizon samples, systematical 5-10 cm increment samples, and on 24-h EDTA extracts. Minor amounts of anthropogenic lead were detected until 1-m depth under permanent grassland, linked to high earthworm activity. In arable land, exogenous Pb predominantly accumulated at depths <60 cm. Although the proximity between the two sites ensured comparable exposition regarding atmospheric Pb deposition, the isotopic compositions clearly showed the influence of an unidentified component for the cultivated soil. This work highlights the need for exhaustive information on historical human activities in such anthropized agrosystems when fate of metal pollution is considered.     

磁性壳聚糖改性硅藻土吸附去除水中的铅离子

采用壳聚糖与Fe3O4对硅藻土进行混合改性,制备出一种吸附效果好、且能从液相中磁分离的新型复合吸附剂。通过SEM、XRD、VSM和FTIR等手段对其进行表征,并探究溶液pH、吸附剂投加量以及吸附温度等条件对水溶液中Pb2+吸附效果的影响。结果表明：壳聚糖和Fe3O4都能够负载到硅藻土上面。当溶液pH为5、吸附剂投加量为10 g·L-1、初始浓度为10 mg·L-1时,Pb2+去除率可以达到96.4%。吸附过程较好地符合假二级动力学模型和Langmuir吸附等温模型,热力学数据说明该吸附是吸热、自发的过程。     

Fe3O4／Ag磁性纳米颗粒去除水中的铅离子

采用水相共沉淀法制备小尺寸磁性Fe3O4纳米颗粒,以没食子酸作为还原剂和表面修饰剂,还原Ag[（NH3）2]’制备出Fe3O4／Ag磁性纳米颗粒。研究该磁性纳米颗粒对水溶液中铅离子的吸附行为,研究结果表明,pH为7．0,吸附温度30℃时可得到最好的处理效果,铅的去除率可达99．7％以上,Fe3O4／Ag颗粒吸附行为符合二级动力学模型（R2〉0．99）。该磁性纳米颗粒经过多次再生处理后,仍具有很好的吸附效果,表明Fe3O4／Ag在水处理方面拥有良好的应用前景。     

Use of sequential extraction to assess metal partitioning in soils

The state of heavy metal pollution and the mobility of Cd, Cu, Ni, Cr, Pb and Zn were studied in three texturally different agricultural soil profiles near a Cu-Ni smelter in Harjavalta, Finland. The pseudo-total concentrations were determined by an aqua regia procedure. Metals were also determined after division into four fractions by sequential extraction with (1) acetic acid (exchangeable and specifically adsorbed metals), (2) a reducing agent (bound to Fe/Mn hydroxides), (3) an oxidizing agent (bound to soil organic matter) and (4) aqua regia (bound to mineral structures). Fallout from the smelter has increased the concentrations of Cd, Cu and Ni in the topsoil, where 75-90% of Cd, 49-72% of Cu and 22-52% of Ni occurred in the first two fractions. Slight Pb and Zn pollution was evident as well. High proportions of mobile Cd, Cu and Ni also deeper in the sandy soil, closest to the smelter, indicated some downward movement of metals. The hydroxide-bound fraction of Pb dominated in almost all soils and horizons, while Ni, Cr and Zn mostly occurred in mineral structures. Aqua regia extraction is usefully supplemented with sequential extraction, particularly in less polluted soils and in soils that exhibit substantial textural differences within the profiles.     

Adsorption of Pb(II) on variable charge soils amended with rice-straw derived biochar

Two Ultisols and one Oxisol from tropical regions of southern China were incubated with rice straw biochar to investigate the effect of biochar on their surface charge and Pb(II) adsorption using batch methods. The incorporation of biochar induced a remarkable increase in soil cation exchange capacity after 30 d of incubation. The incorporation of biochar significantly increased the adsorption of Pb(II) by these variable charge soils; the enhancement of adsorption of Pb(II) by these soils increased with the addition level of biochar. Adsorption of Pb(II) involved both electrostatic and non-electrostatic mechanisms; however, biochar mainly increased Pb(II) adsorption through the non-electrostatic mechanism via the formation of surface complexes between Pb²⁺ and functional groups on biochar. There was greater enhancement of biochar on the non-electrostatic adsorption of Pb(II) by the variable charge soils at relatively low pH. Therefore, the incorporation of biochar decreased the activity and availability of Pb(II) to plants through increased non-electrostatic adsorption of Pb(II) by acidic variable charge soils.     

Long-term nitrate increases in two oligotrophic lakes, due to the leaching of atmospherically-deposited N from moorland ranker soils

During the last 50 years nitrate concentrations in Buttermere and Wastwater (Cumbria, UK) have risen significantly, by 70 and 100%, respectively. By estimating contemporary nitrate fluxes in the lakes' catchments and in sub-catchments and comparing them with the fractional areas of different soil types, it is deduced that the surface water nitrate is derived almost entirely from organic-rich ranker soils that have a limited ability to retain atmospherically-deposited nitrogen. Little or no nitrate leaches from the other major soil type, a brown podzol, despite it having a lower C:N ratio (12.0 g g(-1)) than the ranker (17.0 g g(-1)), nor is there much contribution from the small areas of improved (chemically fertilised) grassland within the catchments. Although some nitrate leaching is occurring, total N losses are appreciably smaller than atmospheric inputs, so the catchment soils are currently accumulating between 3 and 4 g N m(-2) a(-1).     

Dissipation of oxytetracycline in soils under different redox conditions

This study investigated the dissipation kinetics of oxytetracycline in soils under aerobic and anoxic conditions. Laboratory experiments showed that the dissipation of oxytetracycline in soil followed first-order reaction kinetics and its dissipation rates decreased with increasing concentration. Oxytetracycline dissipated faster in soil under aerobic conditions than under anoxic conditions. The half-lives for oxytetracycline in soil under aerobic conditions ranged between 29 and 56 days for non-sterile treatments and 99-120 days for sterile treatments, while under anoxic conditions the half-lives of oxytetracycline ranged between 43 and 62 days in the non-sterile soil and between 69 and 104 days in the sterile soil. This suggests microbes can degrade oxytetracycline in agricultural soil. Abiotic factors such as strong sorption onto soil components also played a role in the dissipation of oxytetracycline in soil.     

Modelling the risk of Pb and PAH intervention value exceedance in allotment soils by robust logistic regression

Soils of allotments are often contaminated by heavy metals and persistent organic pollutants. In particular, lead (Pb) and polycyclic aromatic hydrocarbons (PAHs) frequently exceed legal intervention values (IVs). Allotments are popular in European countries; cities may own and let several thousand allotment plots. Assessing soil contamination for all the plots would be very costly. Soil contamination in allotments is often linked to gardening practice and historic land use. Hence, we predict the risk of IV exceedance from attributes that characterize the history and management of allotment areas (age, nearby presence of pollutant sources, prior land use). Robust logistic regression analyses of data of Swiss allotments demonstrate that the risk of IV exceedance can be predicted quite precisely without costly soil analyses. Thus, the new method allows screening many allotments at small costs, and it helps to deploy the resources available for soil contamination surveying more efficiently.     

Sequestration of organochlorine pesticides in soils of distinct organic carbon content

In the present study, five soil samples with organic carbon contents ranging from 0.23% to 7.1% and aged with technical dichlorodiphenyltrichloroethane (DDT) and hexachlorocyclohexane (HCH) for 15 months were incubated in a sealed chamber to investigate the dynamic changes of the OCP residues. The residues in the soils decreased over the incubation period and finally reached a plateau. Regression analysis showed that degradable fractions of OCPs were negatively correlated with soil organic carbon (SOC) except for α-HCH, while no correlation was found between degradation rate and SOC, which demonstrated that SOC content determines the OCP sequestration fraction in soil. Analysis of the ratio of DDT and its primary metabolites showed that, since it depends on differential sequestration among them, magnitude of (p,p′-DDE + p,p′-DDD)/p,p′-DDT is not a reliable criterion for the identification of new DDT sources.     

Distribution of polycyclic aromatic hydrocarbons in agricultural soils in South Korea

The content and type of polycyclic aromatic hydrocarbons (PAH) in soils from paddy fields and upland areas in South Korea were determined using gas chromatography linked to mass spectrometry (GC–MS). The distribution map of total PAH content was obtained as a contour plot using a geographical information system. The overall distribution of PAH was found to be closely related to the pollution sources, the size of city and the type of industry. The average content of total PAH in all samples was 236 μg kg⁻¹, and the range was from 23.3 to 2834 μg kg⁻¹. The highest concentrations were found in soils sampled near iron processing plants. The concentration of PAH decreased in the order fluoroanthene>benzo(b)fluoroanthene>pyrene. Special PAH compound ratios, such as phenanthrene/anthracene and fluoroanthene/pyrene, were calculated to evaluate the origin. The collected data suggested that the pyrogenic origins such as motor vehicle exhaust and heavy industry emission were the dominant source of PAH in Korean soils.     

Contamination and source differentiation of Pb in park soils along an urban-rural gradient in Shanghai

Urban soil Pb contamination is a great human health risk. Lead distribution and source in topsoils from 14 parks in Shanghai, China were investigated along an urban-rural gradient. Topsoils were contaminated averagely with 65 mg Pb kg⁻¹, 2.5 times higher than local soil background concentrations. HCl-extracts contained more anthropogenic Pb signatures than total sample digests as revealed by the higher ^207/206Pb and ^208/206Pb ratios in extracts (0.8613 ± 0.0094 and 2.1085 ± 0.0121 versus total digests 0.8575 ± 0.0098 and 2.0959 ± 0.0116). This suggests a higher sensitivity of HCl-extraction than total digestion in identifying anthropogenic Pb sources. Coal combustion emission was identified as the major anthropogenic Pb source (averagely 47%) while leaded gasoline emission contributed 12% overall. Urbanization effects were observed by total Pb content and anthropogenic Pb contribution. This study suggests that to reduce Pb contamination, Shanghai might have to change its energy composition to clean energy.     

扎龙湿地土壤中抗性菌株对Pb和Cd去除率与其生理生化特性的相关性及通径分析

利用相关性和通径分析研究了从扎龙湿地土壤中筛选的抗性菌株对Pb、Cd的去除率与其生理生化特性之间的关系。相关性分析表明:细胞长宽比与Pb去除率呈显著负相关性;淀粉酶水解、过氧化氢酶和甲基红与Pb去除率均呈极显著或显著的正相关性;V-P与Cd去除率呈显著负相关性。通径分析表明:细胞长宽比、淀粉酶水解、甲基红对Pb去除率有明显的直接作用,但总的间接作用不明显;酪蛋白和过氧化氢酶对Pb去除率有明显的负向直接作用,但总的正向间接作用很大;淀粉酶水解对Cd去除率有明显的正向直接作用;V-P对Cd去除率有明显的负向直接作用,间接作用不明显。     

The solid-solution partitioning of heavy metals (Cu,Zn, Cd,Pb) in upland soils of England and Wales

Ninety-eight surface soils were sampled from the uplands of England and Wales, and analysed for loss-on-ignition (LOI), and total and dissolved base cations, Al, Fe, and trace heavy metals (Cu, Zn, Cd, Pb). The samples covered wide ranges of pH (3.4-8.3) and LOI (9-98%). Soil metal contents measured by extraction with 0.43 mol l-1 HNO3 and 0.1 mol l-1 EDTA were very similar, and generally lower than values obtained by extraction with a mixture of concentrated nitric and perchloric acids. Total heavy metal concentrations in soil solution depend positively upon soil metal content and [DOC], and negatively upon pH and LOI, values of r2 ranging from 0.39 (Cu) to 0.81 (Pb). Stronger correlations (r2=0.76-0.95) were obtained by multiple regression analysis involving free metal ion (Cu2+, Zn2+, Cd2+, Pb2+) concentrations calculated with the equilibrium speciation model WHAM/Model VI. The free metal ion concentrations depend positively upon MHNO3 and negatively upon pH and LOI. The data were also analysed by using WHAM/Model VI to describe solid-solution interactions as well as solution speciation; this involved calibrating each soil sample by adjusting the content of "active" humic matter to match the observed soil pH. The calibrated model provided fair predictions of total heavy metal concentrations in soil solution, and predicted free metal ion concentrations were in reasonable agreement with the values obtained from solution-only speciation calculations.     

两相分配式生物反应器处理高盐废水中的苯酚

采用新型两相分配式生物反应器(TPPB)和前期研究得到的高效苯酚降解菌对高盐废水中苯酚的降解进行研究,研究中确定煤油为反应系统的最佳有机溶剂,并考察了废水苯酚含量、废水盐度以及搅拌器搅拌速度对苯酚降解的影响。结果表明,反应系统能正常降解苯酚含量为1 000～2 500 mg/L的高盐苯酚废水;反应系统在含盐量为100 g NaCl/L、搅拌速度为50 r/min的运行工况条件下,降解时间缩短为52 h,总酚去除率为20.58 mg/(L.h)。     

Heavy metal solubility in podzolic soils exposed to the alkalizing effect of air pollutants

The heavy metal content of pine forest soil was studied near the boundary between Russia and Estonia, an area characterized by large amounts of acidic and basic air pollutants, mainly sulfur dioxide and calcium. Alkalization dominates the processes in soil, since sulfur is adsorbed only in small quantities, and calcium is much better adsorbed. In addition to Ca, great amounts of Al, Fe, K, and Mg are accumulated in the humus layer due to air pollution. The heavy metal content has increased. The exchangeable content of heavy metals was in many cases much higher in polluted alkaline soils than in non-polluted acidic soils, even the ratio of exchangeable to total metal content being higher in alkaline plots. To avoid a dangerous increase in soluble heavy metal content, it is important to decrease not only the large sulfur emissions of local pollutant sources, but also the alkaline pollutants. A similar concern must be taken into account when liming of acidic forest soils is planned.     

Impact of redox conditions on metolachlor and metribuzin degradation in mississippi flood plain soils

Abstract

The effect of soil redox conditions on the degradation of metolachlor and metribuzin in two Mississippi soils (Forrestdale silty clay loam and Loring silt loam) were examined in the laboratory. Herbicides were added to soil in microcosms and incubated either under oxidized (aerobic) or reduced (anaerobic) conditions. Metolachlor and metribuzin degradation under aerobic condition in the Forrestdale soil proceeded at rates of 8.83 ngd^‐1 and 25 ngd^‐1, respectively. Anaerobic degradation rates for the two herbicides in the Forestdale soil were 8.44 ngd^‐1 and 32.5 ngd^‐1, respectively. Degradation rates for the Loring soil under aerobic condition were 24.8 ngd^‐1 and 12.0 ngd^‐1 for metolachlor and metribuzin, respectively. Metolachlor and metribuzin degradation rates under anaerobic conditions in the Loring soil were 20.9 ngd^‐1 and 5.35 ngd^‐1. Metribuzin degraded faster (12.0 ngd^‐1) in the Loring soil under aerobic conditions as compared to anaerobic conditions (5.35 ngd^‐1).     

Differential partitioning and speciation of Hg in wet FGD facilities of two Spanish PCC power plants

This paper evaluates the speciation and partitioning of mercury in two Spanish pulverised coal combustion power plants (PP1 and PP2), equipped with wet limestone-based flue gas desulphurisation facilities (FGD) operating with forced oxidation and re-circulation of FGD water streams. These plants are fed with coal (PP1) and coal/pet-coke blends (PP2) with different mercury contents. The behaviour, partitioning and speciation of Hg were found to be similar during the combustion processes but different in the FGD systems of the two power plants. A high proportion (86-88%) of Hg escaped the electrostatic precipitator in gaseous form, Hg²⁺ being the predominant mercury species (68-86%) to enter the FGD. At this point, a relatively high total Hg retention (72% and 65%) was achieved in the PP1 and PP2 (2007) FGD facilities respectively. However, during the second sampling campaign for PP2 (2008), the mercury removal achieved by the FGD was much lower (26%). Lab-scale tests point to liquid/gas ratio as the main parameter affecting oxidised mercury capture in the scrubber. The partitioning of the gaseous mercury reaching the FGD system in the wastes and by-products differed. In the low mercury input power plant (PP1) most of the mercury (67%) was associated with the FGD gypsum. Moreover in PP2 a significant proportion of the gaseous mercury reaching the FGD system remained in the aqueous phase (45%) in the 2007 sampling campaign while most of it escaped in 2008 (74%). This may be attributed to the scrubber operating conditions and the different composition and chemistry of the scrubber solution probably due to the use of an additive.     

Equilibrium partitioning theory to predict the sediment toxicity of the anionic surfactant C(12)-2-LAS to Corophium volutator

The study of the effect of the sorption of linear alkylbenzene sulfonates (LAS) on the bioavailability to marine benthic organisms is essential to refine the environmental risk assessment of these compounds. According to the equilibrium partitioning theory (EqP), the effect concentration in water-only exposure will be similar to the effect concentration in the sediment pore water. In this work, sorption and desorption experiments with two marine sediments were carried out using the compound C₁₂-2-LAS. The effect of the sediment sorption on the toxicity of benthic organisms was studied in water-only and in sediment bioassays with the marine mud shrimp Corophium volutator. In addition, three common spiking methods were tested for its application in the toxicity tests, as well as the stability of the surfactant during the water-only and sediment-water test duration. LC50 values obtained from water-only exposure showed a good correspondence with the pore water concentrations calculated from the sorption and desorption isotherms in the spiked sediments.     

Kinetic extractions to assess mobilization of Zn, Pb, Cu, and Cd in a metal-contaminated soil: EDTA vs. citrate

Kinetic EDTA and citrate extractions were used to mimic metal mobilization in a soil contaminated by metallurgical fallout. Modeling of metal removal rates vs. time distinguished two metal pools: readily labile (QM1) and less labile (QM2). In citrate extractions, total extractability (QM1+QM2) of Zn and Cd was proportionally higher than for Pb and Cu. Proportions of Pb and Cu extracted with EDTA were three times higher than when using citrate. We observed similar QM1/QM2 ratios for Zn and Cu regardless of the extractant, suggesting comparable binding energies to soil constituents. However, for Pb and Cd, more heterogeneous binding energies were hypothesized to explain different kinetic extraction behaviors. Proportions of citrate-labile metals were found consistent with their short-term, in-situ mobility assessed in the studied soil, i.e., metal amount released in the soil solution or extracted by cultivated plants. Kinetic EDTA extractions were hypothesized to be more predictive for long-term metal migration with depth.