Removal of polycyclic aromatic hydrocarbons from aqueous solution on soybean stalk-based carbon

Soybean [ (L.) Merr.] stalk-based carbons were prepared by phosphoric acid activation at different carbonization temperatures. Characteristics of the prepared carbon, including specific surface area, iodine number, and amount of methylene blue sorption, were determined. Experiments on phenanthrene, naphthalene, and acenaphthene, as representatives of polycyclic aromatic hydrocarbons (PAHs), removal from aqueous solution by the prepared carbon were conducted at different levels of carbon addition. The results indicated that the specific surface area, iodine number, and amount of methylene blue sorption increased with an increase of carbonization temperature. The maximum values were observed at 700°C and were 287.63 m g, 508.99 mg g, and 90.14 mg g, respectively. The removal efficiencies of phenanthrene, naphthalene, and acenaphthene tended to increase with increasing carbon amounts and carbonization temperature. The optimal removal performance was obtained under the experimental conditions of carbon concentrations of 0.04 g 32 mL and carbonization temperature of 700°C, and the removal efficiencies of phenanthrene, naphthalene, and acenaphthene were 99.89, 100, and 95.64%, respectively. The performance of the prepared carbon was superior to that of commercial activated carbon. Additionally, for the same carbon concentrations, the removal efficiency of PAHs on prepared carbons followed the order: phenanthrene > naphthalene > acenaphthene. Results obtained from this work provide some insight into the reuse of an agricultural residue, and also provide a new application for the treatment of PAHs in contaminated water utilizing activated carbon prepared from agricultural residues.     

Degradation of polycyclic aromatic hydrocarbons by combined chemical pre-oxidation and bioremediation in creosote contaminated soil

The ability of pre-oxidation to overcome polycyclic aromatic hydrocarbons (PAH) recalcitrance to biodegradation was investigated in creosote contaminated soil. Sand and peat artificially spiked with creosote (quality WEI C) were used as model systems. Ozonation and Fenton-like treatment were proved to be feasible technologies for PAH degradation in soil. The efficiency of ozonation was strongly dependent on the water content of treated soil samples. The removal of PAH by Fenton-like treatment depended on the applied H2O2/soil weight ratio and ferrous ions addition. It was determined that the application of chemical oxidation in sand resulted in a higher PAH removal and required lower oxidant (ozone, hydrogen peroxide) doses. The enhancement of PAH biodegradability by different pre-treatment technologies also depended on the soil matrix. It was ascertained that combined chemical and biological treatment was more efficient in PAH elimination in creosote contaminated soil than either one alone. Thus, the combination of Fenton-like and the subsequent biological treatment resulted in the highest removal of PAH in creosote contaminated sand, and biodegradation with pre-ozonation was found to be the most effective technology for PAH elimination in peat.     

IN SITU MEASUREMENT OF ADSORPTION AND BIOTRANSFORMATION AT A HAZARDOUS WASTE SITE1

ABSTRACT: A three well injection-production test was performed at the United Creosoting Company (UCC) site in Conroe, Texas, to estimate the effective in situ retardation factors for adsorption and to evaluate the significance of biotransformation in limiting the transport of polycydic aromatics present in the shallow aquifer. The field test was also used as a model to determine if this type of testing would be feasible at other hazardous waste sites. During the test, chloride, a non-reactive tracer and two organic compounds, naphthalene and paradichlorobenzene (pDCB), were injected into a center well for 24 hours followed by clean ground water for six days. Ground water was continuously produced from two adjoining wells and monitored to observe the breakthrough of these compounds. Data from the test were analyzed by comparing the statistical moments of the chloride and organics distributions. Retardation factors for naphthalene and pDCB were estimated to be 1.03 and 0.97 by comparison of the statistical moments. A significant loss of naphthalene and pDCB was also observed during the three well test, apparently due to biotransformation. These results suggest that biotransformation is the major process limiting the transport of naphthalene and similar compounds at the UCC site.     

Genotoxicity is unrelated to total concentration of priority carcinogenic polycyclic aromatic hydrocarbons in soils undergoing biological treatment

A solid-phase microbiological assay was used to determine the changes in genotoxicity associated with sequestration or biodegradation of carcinogenic compounds in contaminated soils. The concentration of six carcinogenic polycyclic aromatic hydrocarbons (PAHs) did not change in 59 d in sterile soil, but the genotoxicity declined markedly. In a soil undergoing bioremediation in the field for 147 d or biodegradation in the laboratory for 180 d, the concentrations either changed little or declined at different rates, but the genotoxicity increased followed by a decline. The genotoxicity of a second soil declined as a result of biological treatment. The data show that genotoxicity of contaminated soils may be unrelated to the concentration of carcinogenic PAHs because of aging or new mutagens formed during biological treatment.     

Isolation of a novel yeast strain Candida digboiensis TERI ASN6 capable of degrading petroleum hydrocarbons in acidic conditions

A novel yeast species Candida digboiensis TERI ASN6 was isolated from soil samples contaminated with acidic oily sludge (pH 1–3) from the Digboi refinery (Northeast India). The strain TERI ASN6 could degrade 73% of the total petroleum hydrocarbons present in the medium at pH 3 in a week. This strain presents a dimorphic behaviour and showed mycelia morphology when grown under stressed conditions such as low pH and in a medium containing petroleum hydrocarbons. The C. digboiensis strain could efficiently degrade the aliphatic and aromatic fractions of the acidic oily sludge at pH 3 as confirmed by gas chromatography. During the growth of TERI ASN6 in dibenzothiophene (DBT), DBT-sulfone and biphenyl-2-ol were detected. An active cytochrome P450 system, implicated in hydrocarbon oxidation, was also detected in this yeast using degenerated primers based on its conserved regions. This yeast is a potential candidate for petroleum bioremediation treatment of hydrocarbon contaminated acidic soils. Its physiological behaviour allows the strain to work efficiently where other hydrocarbon-degrading bacteria may not survive.     

Sorption of MS2 bacteriophage to layered double hydroxides: effects of reaction time, pH, and competing anions

Batch sorption and column breakthrough studies were conducted to investigate the potential of layered double hydroxides (LDHs) to remove bacteriophage MS2 from contaminated waters. All four of the LDHs evaluated in this study had very high retention capacities for MS2. Sorption results showed that MS2 could be completely removed from 5.2 x 10(2) plaque-forming units (pfu)/mL solution by Mg-Al LDH 2 (i.e., 2:1 Mg to Al ratio LDH), with the highest sorption capacity observed in this study of 1.51 x 10(10) pfu/g. Attachment of MS2 to LDHs was a rapid process and reached quasi-equilibrium after a 1-h reaction time. Within the pH range studied (pH 4-9), Mg-Al LDH 2 showed high sorption potential for MS2 at all pH values but sorption decreased slightly with increasing solution pH. Background solution anions influenced virus sorption, with SO4(2-) and HPO4(2-) decreasing sorption significantly whereas the presence of NO3- had little effect on the attachment of MS2 to Mg-Al LDH 2. The addition of another virus (phiX174) only caused a slight decrease in the retention of MS2 by Mg-Al LDH 2, suggesting that there was insignificant competitive sorption between MS2 and phiX174 on LDH surfaces. Results from column experiments indicate that there was no MS2 breakthrough from columns packed with Mg-Al LDH 2-coated sand, suggesting complete MS2 retention at the virus concentration tested. The high mass recovery by beef extract solution revealed that the removal of viruses by the LDH was due to sorption of MS2 to LDH surfaces, rather than inactivation.     

Influence of soil geochemical and physical properties on the sorption and bioaccessibility of chromium(III)

There are numerous Cr(III)-contaminated sites on Department of Defense (DoD) and Department of Energy (DOE) lands that are awaiting possible clean up and closure. Ingestion of contaminated soil by children is the risk driver that generally motivates the likelihood of site remediation. The purpose of this study was to develop a simple statistical model based on common soil properties to estimate the hioaccessibility of Cr(III)-contaminated soil upon ingestion. Thirty-five uncontaminated soils from seven major soil orders, whose properties were similar to numerous U.S. DoD contaminated sites, were treated with Cr(III) and aged. Statistical analysis revealed that Cr(III) sorption (e.g., adsorption and surface precipitation) by the soils was strongly correlated with the clay content, total inorganic C, pH, and the cation exchange capacity of the soils. Soils with higher quantities of clay, inorganic C (i.e., carbonates), higher pH, and higher cation exchange capacity generally sequestered more Cr(III). The amount of Cr(III) bioaccessible from the treated soils was determined with a physiologically based extraction test (PBET) that was designed to simulate the digestive process of the stomach. The bioaccessibility of Cr(III) varied widely as a function of soil type with most soils limiting bioaccessibility to <45 and <30% after I and 100 d soil-Cr aging, respectively. Statistical analysis showed the bioaccessibility of Cr(III) on soil was again related to the clay and total inorganic carbon (TIC) content of the soil. Bioaccessibility decreased as the soil TIC content increased and as the clay content decreased. The model yielded an equation based on common soil properties that could be used to predict the Cr(III) bioaccessibility in soils with a reasonable level of confidence.     

Kriging method evaluation for assessing the spatial distribution of urban soil lead contamination

Describing contaminant spatial distribution is an integral component of risk assessment. Application of geostatistical techniques for this purpose has been demonstrated previously. These techniques may provide both an estimate of the concentration at a given unsampled location, as well as the probability that the concentration at that location will exceed a critical threshold concentration. This research is a comparative study between multiple indicator kriging and kriging with the cumulative distribution function of order statistics, with both local and global variograms. The aim was to determine which of the four methods is best able to delineate between "contaminated" and "clean" soil. The four methods were validated with a subset of data values that were not used in the prediction. Method performance was assessed by calculating the root mean square error (RMSE), analysis of variance, the proportion of sites misclassified by each method as either "clean" when they were actually "contaminated" or vice versa, and the expected loss for each misclassification type. The data used for the comparison were 807 topsoil Pb concentrations from the inner-Sydney suburbs of Glebe and Camperdown, Australia. While there was very little difference between the four methods, multiple indicator kriging was found to produce the most accurate predictions for delineating "clean" from "contaminated" soil.     

Development of a bioremediation process by biostimulation of native microbial consortium through the heap leaching technique

Heap leaching is an effective and widely used method of recovering metals from low-grade ores. However, the heap leaching technique has not yet been used in other biotechnological processes such as bioremediation. This work describes biostimulation of the native microbial consortium as a novel application of the heap leaching technique to bioremediate mining soils contaminated with hydrocarbons. Microorganisms present in the polluted soil were isolated in a liquid mineral solution using diesel fuel as the sole energy and carbon source. Biodegradation activity was evaluated and two genera, Flavobacterium and Aspergillus, were identified as the primary microorganisms that degraded hydrocarbons in the polluted soil. In order to simulate the heap leaching process on a laboratory scale, using both columns and piles, the contaminated soil was mixed with different sand concentrations and was agglomerated before it was used. Three flow rates, of the mineral solution, were evaluated. Of the rates tested, biodegradation was most efficient at a flow rate of 200 ml h(-1). The heap leaching technique demonstrated good efficiency in the column and pile, with a 2% soil-sand mixture lowering the TPH concentration from 61,000 to 1800 mg kg(-1) (98.5%) in 15 d.     

Sydney tar ponds: some problems in quantifying toxic waste

Information on the type and amount of hazardous and toxic waste is required to develop a meaningful strategy and estimate a realistic cost for clean up of the Sydney Tar Pond site which is located on Cape Breton, in the province of Nova Scotia, Canada. The site covers the area of the decommissioned Sysco (Sydney Steel Corporation) plant. The materials of concern include BTEX (benzene, toluene, ethylbenzene, and xylenes), PAH (polycyclic aromatic hydrocarbons), PCB (polychlorinated biphenyl), and particulates laden with toxic metals, such as arsenic, lead, and others. The originally nontoxic materials such as soil, blast furnace slag, and vegetation, as well as surface and ground waters, which were subsequently contaminated, must also be included if they fail tests prescribed by environmental regulations. An extensive sampling program must be undertaken to obtain data for an accurate estimate of the waste to be cleaned and disposed of. Apparently, 700,000 tons of toxic waste, which is believed to be present on the site, may represent only a fraction of the actual amount. The clean-up of the site is only part of the solution. Toxic waste has to be disposed of in accordance with environmental regulations.     

Phytoremediation of aged petroleum sludge: effect of irrigation techniques and scheduling

The use of higher plants to accelerate the remediation of petroleum contaminants in soil is limited by, among other factors, rooting depth and the delivery of nutrients to the microsites at which remediation occurs. The objective of this study was to test methods of enhancing root growth and remediation in the subsurface of a contaminated petroleum sludge. The phytoremediation of highly contaminated petroleum sludge (total petroleum hydrocarbons >35 g kg(-1) was tested in the greenhouse as a function of the frequency and the depth of irrigation and fertilization. Water and dissolved plant nutrients were added to the soil surface or at a depth of 30 cm, either daily or weekly. Equivalent quantities of water and nutrients were added in all cases. Daily irrigation at a depth of 30 cm invoked greater root growth and enhanced contaminant degradation relative to all other treatments. In the absence of plants, residual concentrations of petroleum hydrocarbons after 7 mo were higher than with plants. The presence of plant roots clearly improved the physical structure of the soil and increased microbial populations. Thus, the plant roots in conjunction with daily additions of soluble N and P appeared to enhance oxygen transport to greater depths in the soil, stimulate petroleum-degrading microorganisms, and provide microbial access to soil micropores. Subsurface irrigation with frequent, small amounts of water and nutrients could significantly accelerate phytoremediation of field soils contaminated with petroleum hydrocarbons.     

The effect of flow path and mixing layer on phosphorus release: physical mechanisms and temperature effects

Soil phosphorus (P) concentrations typically are greater in surface soils compared with subsurface soils. Surface soils have a greater chance to interact with runoff leading to P transport to streams. The thin surface layer where P concentrates is referred to as the mixing layer denoting where water and chemicals mix during transport. The objective of this study was to evaluate the effect of hydrologic flow paths on soluble reactive phosphorus (SRP) loss at two temperatures. Laboratory flumes were built to simulate infiltration, return flow, saturation excess, and interflow, and subsequent interaction with the mixing layer. The sandy loam soil in the flumes was kept at saturation throughout all experiments, so that biochemical effects were normalized. Flow through the flumes was maintained at 3.6 mm/h for 24 to 99 h (at 6 and 25 degrees C) with water entering and exiting the flumes at different ports (to simulate different flow paths) or as low intensity rainfall. Experiments were performed with and without an artificially created P-enriched surface layer (5 mm thick, total P increased from 1010 mg/kg in the original soil to 2310 mg/kg by addition of dissolved phosphate). Results indicated that (i) SRP release was greater in soil with a mixing layer than in soil without a mixing layer; (ii) SRP release was greater during experiments at 25 degrees C than at 6 degrees C; (iii) at 25 degrees C, SRP release was greatest when water traversed the mixing layer in the upward direction (i.e., in return flow), and by flow parallel to the mixing layer (i.e., surface runoff); and (iv) at 6 degrees C, SRP release in subsurface flow following rainfall was slightly greater than in return flow and infiltration. Our results confirmed the presence of a variable, temperature-dependent desorption process when runoff water interacted with the mixing layer. Our findings have important implications for how different water flow paths in and over the soil interact with P in the soil, and what the ultimate concentration will be in runoff and interflow.     

资源、环境、生态的关系探讨及对自然资源管理的建议

资源、环境和生态是我国生态文明建设的三个关键词,也是地球系统科学的重要组成,但目前学术研究和政策制定上仍存在模棱两可的问题,给自然资源领域的科学发展和贯彻落实生态文明发展理念带来了潜在不利影响,明晰其各自概念边界具有重要理论价值和现实意义。本文在分析自然资源、自然环境和生态环境三者内涵的基础上,对比了国内外关注视角、问题和需求的差异,并根据各自特征属性尝试构建了三者关系及判别图解模型。主要结论为:(1)国内外对自然资源、自然环境和生态环境的关注视角、问题和需求存在显著差异,其关注视角分别为数量、质量和平衡状态,关注问题分别为枯竭、退化和破坏,而关注需求分别为节约、保护和恢复;(2)三个概念的相互关系可通过是否自然、是否有价值和是否生物相关三个属性进行判别,自然资源的本质为有价值的自然环境,与自然环境是包含与被包含的关系,生物相关的自然资源即是生态环境;(3)对自然资源管理提出了拓展调查研究内容、采用"资源环境"表述和对生态治理工程进行以生物多样性为重点的负面影响评价三方面的建议。     

Hydrophobicity of soil colloids and heavy metal mobilization: effects of drying

Drying of soil may increase the hydrophobicity of soil and affect the mobilization of colloids after re-wetting. Results of previous research suggest that colloid hydrophobicity is an important parameter in controlling the retention of colloids and colloid-associated substances in soils. We tested the hypothesis that air-drying of soil samples increases the hydrophobicity of water-dispersible colloids and whether air-drying affects the mobilization of colloid-associated heavy metals. We performed batch experiments with field-moist and air-dried (25 degrees C) soils from a former sewage farm (sandy loam), a municipal park (loamy sand), and a shooting range site (loamy sand with 25% C(org)). The filtered suspensions (<1.2 microm) were analyzed for concentrations of dissolved and colloidal organic C and heavy metals (Cu, Cd, Pb, Zn), average colloid size, zeta potential, and turbidity. The hydrophobicity of colloids was determined by their partitioning between a hydrophobic solid and a hydrophilic aqueous phase. Drying increased hydrophobicity of the solid phase but did not affect the hydrophobicity of the dispersed colloids. Drying decreased the amount of mobilized mineral and (organo-)mineral colloids in the sewage farm soils but increased the mobilization of organic colloids in the C-rich shooting range soil. Dried samples released less colloid-bound Cd and Zn than field-moist samples. Drying-induced mobilization of dissolved organic C caused a redistribution of Cu from the colloidal to the dissolved phase. We conclude that drying-induced colloid mobilization is not caused by a change in the physicochemical properties of the colloids. Therefore, it is likely that the mobilization of colloids in the field is caused by increasing shear forces or the disintegration of aggregates.     

Use of modified hydroxy-aluminum bentonites for chromium(III) removal from solutions

The retention of chromium(III) from a 2000ppm chromium basic sulfate and tannery waste solution at pH 4.5 using modified hydroxy-aluminum bentonites (OH-Al bentonites) as adsorbents was studied. OH-Al bentonite was prepared by mixing clay with a hydrolyzed commercial chlorohydroxy Al solution. The modified Al bentonites were obtained by (a) a treatment with 0.5M sodium chloride and (b) a treatment with a Na-hexametaphosphate solution (HMP) after adding sodium chloride. The effect of heating the adsorbents at 100, 500, 700 and 800 degrees C on Cr retention as a function of time was also analyzed. Cr retention by modified OH-Al bentonite with HMP increased with time (up to 100mgCr/g) where modified OH-Al bentonite was twice that of untreated bentonite. The relatively high uptake of metal from the salt solution by modified OH-Al bentonite treated at 800 degrees C, in which a complete interlayer collapse occurred, indicated the importance of the contribution of external surface sites to the retention capacity. The maximum Cr uptake from a water waste was 24mg/g, due to interferences and different chromium species in the industrial solution.     

Experimental investigation on effect of an absorber plate covered by a layer of sand on the efficiency of passive solar air collector

A passive flat-plate solar air collector was constructed in the laboratory of New and Renewable Energy in Arid Zones, Ouargla University, South East Algeria. The absorber of the passive flat-plate solar air collector was laminated with a thin layer of local sand. This acted as a thermal packed bed with a collecting area of 0.5 m² (1 m × 0.5 m). Three series of experiments were performed. The first consisted of choosing the best sand brought from three different places of the Algerian desert. The second consisted of studying the effect of the thickness of the sand layer on the daily efficacy of the collector. The influence of the sand diameter was investigated in the third series. The experimental results showed that: All collectors covered with sand had higher efficiency than those without. It was noticed that, for a fixed mass of sand (given thickness of the sand layer), the improvement of the collector was inversely proportional to the sand particle diameters. The maximum efficiency approximates 62.1% for a particle diameter 0.063 mm, compared to 41.71% for a diameter 0.250 mm.The efficiency of the collector for a fixed particle diameter increases with the increase in the thickness of the sand layer. The collector with thickness sand layer 0.84 mm gave the best efficiency of 46.14% compared to 27.8% for 0.28 mm of thickness sand layer.     

搅拌棒吸附萃取气相色谱法测定地表水中多环芳烃

建立了新型的搅拌棒吸附萃取（SBSE）和热脱附系统（TDU）结合的气相色谱（GC）测定地表水中多环芳烃的方法。考察了萃取时间、搅拌条件及萃取温度对实验的影响,对7种多环芳烃（萘、荧蒽、苯并[b]荧蒽、苯并[k]荧蒽、苯并[ghi]苝、茚并[1,2,3-cd]芘和苯并[a]芘）的加标回收率为89.17%～99.38%,相对标准偏差（RSD）为1.6%～5.6%（n=3）。通过实际样品中PAHs的分析表明,该法快速、灵敏、简单,能满足痕量分析的需求。     

Pyrene mineralization by Mycobacterium sp. strain KMS in a barley rhizosphere

To determine whether the soil Mycobacterium isolate KMS would mineralize pyrene under rhizosphere conditions, a microcosm system was established to collect radioactive carbon dioxide released from the labeled polycyclic aromatic hydrocarbon. Microcosms were designed as sealed, flow-through systems that allowed the growth of plants. Experiments were conducted to evaluate mineralization of 14C-labeled pyrene in a sand amended with the polycyclic aromatic hydrocarbons degrading Mycobacterium isolate KMS, barley plants, or barley plants with roots colonized by isolate KMS. Mineralization was quantified by collecting the 14CO2 produced from 14C-labeled pyrene at intervals during the 10-d incubation period. Roots and foliar tissues were examined for 14C incorporation. Mass balances for microcosms were determined through combustion of sand samples and collection and quantification of 14CO2 evolved from radiolabeled pyrene. No pyrene mineralization was observed in the sterile control systems. Greater release of 14CO2 was observed in the system with barley colonized by KMS than in microcosms containing just the bacterium inoculum or sterile barley plants. These findings suggest that phytostimulation of polycyclic aromatic hydrocarbons mineralization could be applied in remediation schemes.     

Fire effects on stable isotopes in a Sierran forested watershed

This study tested the hypothesis that stable C and N isotope values in surface soil and litter would be increased by fire due to volatilization of lighter isotopes. The hypothesis was tested by: (1) performing experimental laboratory burns of organic and mineral soil materials from a watershed at combinations of temperature ranging 100 to 600 degrees C and duration ranging from 1 to 60 min; (2) testing field samples of upland soils before, shortly after, and 1 yr following a wildfire in the same watershed; and (3) testing field soil samples from a down-gradient ash/sediment depositional area in a riparian zone following a runoff event after the wildfire. Muffle furnace results indicated the most effective temperature range for using stable isotopes for tracing fire impacts is 200 to 400 degrees C because lower burn temperatures may not produce strong isotopic shifts, and at temperatures>or=600 degrees C, N and C content of residual material is too low. Analyses of field soil samples were inconclusive: there was a slightly significant effect of the wildfire on delta15N values in upland watershed analyses 1 yr postburn, while riparian zone analyses results indicated that delta13C values significantly decreased approximately 0.71 per thousand over a 9 mo post-fire period (p=0.015), and ash/sediment layer delta13C values were approximately 0.65 per thousand higher than those in the A horizon. The lack of field confirmation may have been due to overall wildfire burn temperatures being <200 degrees C and/or microbial recovery and vegetative growth in the field. Thus, the muffle furnace experiment supported the hypothesis, but it is as yet unconfirmed by actual wildfire field data.