Sorption and displacement of pyrene in soils and sediments

Sorption isotherms of pyrene on soils and sediments were examined to understand its sorption behavior. All systems examined exhibited nonlinear sorption. Sorption nonlinearity was found to be a function of the polarity index of soil/sediment organic matter (SOM), suggesting that the degree of condensation of SOM, characterized by its polarity index, was correlated with the sorption behavior of pyrene. The polarity index of SOM could be a new factor for explaining the sorption nonlinearity. The sorption affinity of two soils and two sediments for pyrene increased with decreasing SOM polarity. A higher sorption affinity in the two soils was associated with a higher degree of condensation of SOM compared to that of the two sediments. A displacement test was performed after pyrene sorption using phenanthrene as a displacer. Pyrene was displaced in all systems examined, and nonlinearity became less pronounced after displacement. Such an increase in isotherm linearity implied that sorption site energies became more homogeneous after displacement. Furthermore, the site energy distribution IE*) derived from the Freundlich model parameters showed that energy reduction of high-energy sites was more significant than that of low-energy sites after displacement. In addition, a decrease in sorption capacity after displacement could be ascribed to the partial depletion of sorption sites by the displacer. The displacement data indicated that the cocontaminant can have potential effects on the fate and bioavailability of anthropogenic organic pollutants sorbed in soils and sediments, thus affecting their exposure risks.     

矿区资源开发与可持续发展

介绍了江苏省淮海盐化有限公司为了实现企业自身可持续发展的经验与做法,依靠科学采矿,采用先进的工艺流程和生产技术,充分挖掘内部潜力,加快技术进步,搞好资源的规模开发与综合利用,促进了企业的健康发展,并提出了存在问题与整改措施。     

Strong sorption of phenanthrene by condensed organic matter in soils and sediments

The nonhydrolyzable carbon (NHC) and black carbon (BC) in three contaminated soils and seven sediments from the Pearl River Delta and Estuary, China, were isolated upon treatments with an acid hydrolysis method and with a combustion method at 375 degrees C, respectively, and their sorption isotherms for phenanthrene (Phen) were established. It was found that NHC is chemically and structurally different from the biopolymer and humic substances and consists mainly of aliphatic and aromatic carbon using elemental analysis, 13C nuclear magnetic resonance spectroscopy (13C NMR), and Fourier transformed infrared spectroscopy (FTIR). All the sorption isotherms are nonlinear and are well fitted by the Freundlich model. The single-point organic carbon-normalized distribution coefficient (K(oc)) measured for the isolated NHC is 1.3-7.7 times higher than that for the bulk samples at the same aqueous concentration of Phen. The NHC fractions play a dominant role to the overall sorption in the bulk samples. The bulk soils and their NHC fractions have lower sorption capacity than the bulk sediments and their NHC fractions, relating to the different source of organic matter between soils and sediments. The Phen sorption capacity in the NHC samples is related significantlyto H/C ratios and aliphatic carbon, but negatively to aromatic carbon, demonstrating the important role of aliphatic carbon to the Phen sorption and the fate in the investigated soils and sediments.     

Biodegradation and attenuation of steroidal hormones and alkylphenols by stream biofilms and sediments

Biodegradation of select endocrine-disrupting compounds (17β-estradiol, estrone, 17α-ethynylestradiol, 4-nonylphenol, 4-nonylphenolmonoexthoylate, and 4-nonylphenoldiethoxylate) was evaluated in stream biofilm, sediment, and water matrices collected from locations upstream and downstream from a wastewater treatment plant effluent discharge. Both biologically mediated transformation to intermediate metabolites and biologically mediated mineralization were evaluated in separate time interval experiments. Initial time intervals (0-7 d) evaluated biodegradation by the microbial community dominant at the time of sampling. Later time intervals (70 and 185 d) evaluated the biodegradation potential as the microbial community adapted to the absence of outside energy sources. The sediment matrix was more effective than the biofilm and water matrices at biodegrading 4-nonylphenol and 17β-estradiol. Biodegradation by the sediment matrix of 17α-ethynylestradiol occurred at later time intervals (70 and 185 d) and was not observed in the biofilm or water matrices. Stream biofilms play an important role in the attenuation of endocrine-disrupting compounds in surface waters due to both biodegradation and sorption processes. Because sorption to stream biofilms and bed sediments occurs on a faster temporal scale (<1 h) than the potential to biodegrade the target compounds (50% mineralization at >185 d), these compounds can accumulate in stream biofilms and sediments.     

Estimate of heavy metal contamination in soils after a mining accident using reflectance spectroscopy

The possibility to adapt chemometrics approaches for the quantitative estimation of heavy metals in soils polluted by a mining accident was explored. In April 1998, the dam of a mine tailings pond in Aznalcóllar (Spain) collapsed and flooded an area of more than 4000 ha with pyritic sludge contaminated with high concentrations of heavy metals. Six months after the end of the first remediation campaign, soil samples were collected for chemical analysis and measurement of visible to near-infrared reflectance (0.35-2.4 microm). Concentrations for As, Cd, Cu, Fe, Hg, Pb, S, Sb, and Zn were well above background values. Prediction of heavy metals was achieved by stepwise multiple linear regression analysis (MLR) and an artificial neural network (ANN) approach. It was possible to predict six out of nine elements with high accuracy. Best R2 between predicted and chemically analyzed concentrations were As, 0.84; Fe, 0.72; Hg, 0.96; Pb, 0.95; S, 0.87; and Sb, 0.93. Results for Cd (0.51), Cu (0.43), and Zn (0.24) were not significant. MLR and ANN both achieved similar results. Correlation analysis revealed that most wavelengths important for prediction could be attributed to absorptions features of iron and iron oxides. These results indicate that it is feasible to predict heavy metals in soils contaminated by mining residuals using the rapid and cost-effective reflectance spectroscopy.     

Enhancement and inhibition of denitrification by fluid-flow and dissolved oxygen flux to stream sediments

Microscale measurements of nitrate (NO3-) and dissolved oxygen (DO) concentrations in sediments were made in a laboratory channel under turbulent fluid-flow conditions to examine the effects of DO flux on denitrification rates. DO concentrations and flux within sediments increased with increasing velocity in the surface water. Under low fluid-flow conditions (shear stress velocity, u* < 0.23 cm s(-1)), increasing velocity increased NO3- loss from the bulk flow. For high fluid-flow conditions (u* > 0.39 cm s(-1)), increasing velocity inhibited NO3-loss. Sediment cores were collected and sliced to measure the depth distribution of denitrifying biomass in sediments. Quantities of nirK and nirS genes were higher within the surface layer and decreased with depth in the sediments. Microscale concentration profiles of DO and NO3- revealed that denitrification occurs within a thin region just below the oxic-anoxic interface in sediments. The interplay of mass transfer and DO flux generated threshold conditions for NO3- loss by denitrification. These results suggest that for a given sediment and environmental conditions (chemical, physical, microbiological), there exists an optimal range in velocities for enhancing denitrification in aquatic systems.     

Sorption of organic compounds to fresh and field-aged activated carbons in soils and sediments

Activated carbon (AC) amendment to polluted sediment or soil is an emerging in situ treatment technique that reduces freely dissolved porewater concentrations and subsequently reduces the ecological and human health risk of hydrophobic organic compounds (HOCs). An important question is the capacity of the amended AC after prolonged exposure in the field. To address this issue, sorption of freshly spiked and native HOCs to AC aged under natural field conditions and fresh AC amendments was compared for one soil and two sediments. After 12-32 months of field aging, all AC amendments demonstrated effectiveness for reducing pore water concentrations of both native (30-95%) and spiked (10-90%) HOCs compared to unamended sediment or soil. Values of K(AC) for field-aged AC were lower than freshly added AC for spiked HOCs up to a factor of 10, while the effect was less for native HOCs. The different behavior in sorbing native HOCs compared to freshly spiked HOCs was attributed to differences in the sorption kinetics and degree of competition for sorption sites between the contaminants and pore-clogging natural organic matter. The implications of these findings are that amended AC can still be effective in sorbing additional HOCs some years following amendment in the field. Thus, a certain level of long-term sustainability of this remediation approach is observed, but conclusions for decade-long periods cannot be drawn solely based on the present study.     

Rapid prediction of long-term rates of contaminant desorption from soils and sediments

A method using heated and superheated (subcritical) water is described for rapid prediction of long-term desorption rates from contaminated geosorbents. Rates of contaminant release are measured at temperatures between 75 and 150 degrees C using a dynamic water desorption technique. The subcritical desorption rate data are then modeled to calculate apparent activation energies, and these activation energies are used to predict desorption behaviors at any desired ambient temperature. Predictions of long-term release rates based on this methodology were found to correlate well with experimental 25 degrees C desorption data measured over periods of up to 640 days, even though the 25 degrees C desorption rates were observed to vary by up to 2 orders of magnitude for different geosorbent types and initial solid phase contaminant loading levels. Desorption profiles measured under elevated temperature and pressure conditions closely matched those at 25 degrees C and ambient pressure, but the time scales associated with the high-temperature measurements were up to 3 orders of magnitude lower. The subcritical water technique rapidly estimates rates of desorption-resistant contaminant release as well as those for more labile substances. The practical implications of the methodology are significant because desorption observed under field conditions and ambient temperatures typically proceeds over periods of months or years, while the high temperature experiments used for prediction of such field desorption phenomena can be completed within periods of only hours or days.     

Low-temperature, mineral-catalyzed air oxidation: a possible new pathway for PAH stabilization in sediments and soils

Reactivity of polycyclic aromatic hydrocarbons (PAHs) in the subsurface is of importance to environmental assessment, as they constitute a highly toxic hazard. Understanding their reactivity in the long term in natural recovering systems is thus a key issue. This article describes an experimental investigation on the air oxidation of fluoranthene (a PAH abundant in natural systems polluted by industrial coal use) at 100°C on different mineral substrates commonly found in soils and sediments (quartz sand, limestone, and clay). Results demonstrate that fluoranthene is readily oxidized in the presence of limestone and clay, leading to the formation of high molecular weight compounds and a carbonaceous residue as end product especially for clay experiments. As demonstrated elsewhere, the experimental conditions used permitted the reproduction of the geochemical pathway of organic matter observed under natural conditions. It is therefore suggested that low-temperature, mineral-catalyzed air oxidation is a mechanism relevant to the stabilization of PAHs in sediments and soils.     

Black carbon and kerogen in soils and sediments. 1. Quantification and characterization

A comprehensive wet chemical procedure was developed by combining acid demineralization, base extraction, and dichromate oxidation for fractionation and quantitative isolation of soil/sediment organic matter (SOM) into four fractions: (1) humic acids + kerogen + BC (HKB); (2) kerogen + BC (KB); (3) humic acid (HA); and (4) BC. The soil/sediment samples tested were collected from the suburban areas of Guangzhou, a rapidly developing city of China. The results show that BC and kerogen constitute 57.8-80.6% of the total organic carbon (TOC) and that the relative content of BC ranges from 18.3% to 41.0% of the TOC, indicating that both BC and kerogen are major organic components in soils and sediments from this industrialized region. Systematic characterization of the isolated SOMs shows that both BC and kerogen have sizes ranging from a few microns to above 100 microm, relatively low O/C and H/C atomic ratios, and low contents of oxygen-containing functional groups. The isolated BC has unique fusinite and semifusinite macerals, highly porous nature, and structures indicative of its possible origins. The study indicates that SOM is highly heterogeneous and that humin, the nonextractable humus fraction, consists mainly of kerogen and BC materials in the tested soil/sediment samples. The presence of these materials in soils and sediments may have significant impacts on pollutant mass transfer and transformation processes such as desorption and bioavailability of less polar organic chemicals in surface aquatic and groundwater environments.     

Geostatistical approach for assessing soil volumes requiring remediation: validation using lead-polluted soils underlying a former smelting works

Assessing the volume of soil requiring remediation and the accuracy of this assessment constitutes an essential step in polluted site management. If this remediation volume is not properly assessed, misclassification may lead both to environmental risks (polluted soils may not be remediated) and financial risks (unexpected discovery of polluted soils may generate additional remediation costs). To minimize such risks, this paper proposes a geostatistical methodology based on stochastic simulations that allows the remediation volume and the uncertainty to be assessed using investigation data. The methodology thoroughly reproduces the conditions in which the soils are classified and extracted at the remediation stage. The validity of the approach is tested by applying it on the data collected during the investigation phase of a former lead smelting works and by comparing the results with the volume that has actually been remediated. This real remediated volume was composed of all the remediation units that were classified as polluted after systematic sampling and analysis during clean-up stage. The volume estimated from the 75 samples collected during site investigation slightly overestimates (5.3% relative error) the remediated volume deduced from 212 remediation units. Furthermore, the real volume falls within the range of uncertainty predicted using the proposed methodology.     

Nonsingular adsorption/desorption of chlorpyrifos in soils and sediments: experimental results and modeling

At environmentally relevant concentrations in soils and sediments, chlorpyrifos, a hydrophobic organic insecticide, showed strong adsorption that correlated significantly with organic matter content. Chlorpyrifos desorption followed a nonsingular falling desorption isotherm that was estimated using a memory-dependent mathematical model. Desorption of chlorpyrifos was biphasic in nature, with a labile and nonlabile component. The labile component comprised 18-28% of the original solid-phase concentration, and the residue was predicted to slowly partition to the aqueous phase, implying long-term desorption from contaminated soils or sediments. The newly proposed mechanism to explain sorption/desorption hysteresis and biphasic desorption is the unfavorable thermodynamic energy landscape arising from limitation of diffusivity of water molecules through the strongly hydrophobic domain of soils and sediments. Modeling results suggest that contaminated soils and sediments could be secondary long-term sources of pollution. Long-term desorption may explain the detection of chlorpyrifos and other hydrophobic organic compounds in aquatic systems far from application sites, an observation that contradicts conventional transport predictions.     

矿区生态环境评价及环境保护探讨

我国矿山种类丰富,在矿山开采领域具有较先进的水平,但在矿区的生态环境保护方面存在着一些问题.本文首先分析了矿区开发对周围环境造成的影响,然后分析了如何进行矿区的生态环境评价,最后研究了矿区的生态治理方法.希望通过本研究有效改善矿区的生态治理水平,确保矿区生态协调发展.     

高海拔矿区用金刚石钻头的研制与应用效果

根据高海拔矿区的施工特点和岩层情况,有针对性地研制专用的金刚石钻头和采用新的钻进工艺方法,克服了高寒矿区的各种影响因素,使国产金刚石钻头在高海拔矿区的施工中,取得比较好的效果。     

Evaluating competitive sorption mechanisms of volatile organic compounds in soils and sediments using polymers and zeolites

The competitive sorption of trichloroethene (TCE) and tetrachloroethene (PCE) was investigated in three natural solids, two polymers, and four zeolites. Competition was observed in natural solids with high contents of recalcitrant organic carbon, in the glassy polymer, and in zeolites with strongly and moderately hydrophobic micropores of large (7.5 x 10 A) and small pore widths (approximately 5.4 A), respectively. Isotherm results and recalcitrant OC% values for natural solids indicate that the extent of competition between TCE and PCE is related to the amount of hard organic carbon. Gas adsorption results and the variability in C/H values suggest that natural organic matter contains micropores with varying width and polarity. Isotherm results for zeolites indicate that competition between TCE and PCE increases with increasing hydrophobicity and decreasing micropore width. We suggest that competition between volatile organic contaminants in the subsurface is controlled by competition for hydrophobic micropores in hard organic matter and that smaller more hydrophobic micropores result in stronger competition.     

Thallium in foods and the diet

Sources of thallium in food and normal levels of thallium in food are discussed. Information on dietary intakes of thallium in the UK is presented, current intakes are estimated to be about 0.005 mg/day. The dietary intake and published data on urinary excretion are consistent. It is considered that brassicae are likely to be the main source of dietary exposure to thallium in food produced on contaminated land.