Treatment system for solid matrix contaminated with fluoranthene. II--Recirculating photodegradation technique.

A laboratory-scale solar reactor and photodegradation technique were developed to enhance the degradation process of fluoranthene. Fluoranthene was used in this study to represent toxic polycyclic aromatic hydrocarbons (PAHs) that are persistent in the environment. The extracted fluoranthene from soil in organic solvent (EFOS) and hydrogen peroxide (H2O2) were pumped from a 100 ml vessel into a solar glass cell coated with titanium dioxide (TiO2) at 80 microl min(-1). This work compares the efficiency of the developed photocatalytic degradation technique with the conventional batch process. The degradation efficiency of the developed technique was assessed at different initial concentrations of fluoranthene and percentages of H2O2 in the extract using different flow rates. Preliminary results indicated that the developed technique degraded 99% of fluoranthene from EFOS in the presence of H2O2 and 83% without H2O2. There was no significant difference between fluoranthene degradation rates by the developed technique and the batch method. The developed technique however, treated double the volume of solution that was treated by the batch reactor method which was time consuming and required continuous attention.     

Remediation of soil contaminated with dioxins by subcritical water extraction

The effectiveness of subcritical water extraction (SCWE) was examined for removing dioxins from contaminated soil. Most dioxins in the soil sample were reduced at 300 degrees C or more, but decreased dioxin concentrations were also observed at 150 degrees C. After 4 h of extraction, 99.4%, 94.5% and 60% of PCDDs were removed from samples at 350, 300 and 150 degrees C, respectively. It was also determined that degradation of dioxins had occurred, since the sum of dioxins in the soil plus water extracts after the experiments had considerably decreased. This study revealed that pressurizing is not essential for the removal of dioxins. Reduction was complete within 30 min at 350 degrees C; however, it took a much longer time at lower temperatures. The results of addition experiments in which OCDDs were added to different types of soil samples have shown that dechlorination is one of the major reaction pathways. After addition of OCDD to soil samples, experiments were carried out to examine in detail the degradation pathways of PCDDs. The removal rates and congener profiles varied among soil types. Although it was previously assumed that removal rates and congener profiles depended on the chemical components in soil, nonparametric statistical analysis revealed no significant relationship between the rate of reduction and elements present in the soil. It was confirmed from isomer patterns that dechlorination of the 2,3,7,8-positions in PCDDs takes place somewhat faster than for the 1,4,6,9-positions.     

水溶性巯基壳聚糖对污染土壤吸附态汞的解吸作用研究

用两种巯基化试剂半胱氨酸(Cys)和硫代乙醇酸(Thi)与壳聚糖(CTS)反应,制备了两种水溶性巯基壳聚糖,即Cys-CTS和Thi-CTS,对比研究了这两种巯基壳聚糖与CTS对被染毒土壤中吸附态汞的提取能力.结果表明,Thi-CTS在pH=3、质量浓度为0.5g/L、用量为20 mL的条件下.对汞的提取率为59.44%,相同条件下CTS和cys-CTS对汞的最高提取率只有31.81%和10.15%.     

Solvent extraction for heavy crude oil removal from contaminated soils

A new strategy of heavy crude oil removal from contaminated soils was studied. The hexane-acetone solvent mixture was used to investigate the ability of solvent extraction technique for cleaning up soils under various extraction conditions. The mixtures of hexane and acetone (25 vol%) were demonstrated to be the most effective in removing petroleum hydrocarbons from contaminated soils and approx 90% of saturates, naphthene aromatics, polar aromatics, and 60% of nC₇-asphaltenes were removed. Kinetic experiments demonstrated that the equilibrium was reached in 5 min and the majority of the oil pollutants were removed within 0.5 min. The effect of the ratio between solvent and soil on the extraction efficiency was also studied and results showed that the efficiency would increase following the higher solvent soil ratio. Then the multistage continuous extraction was considered to enhance the removal efficiency of oil pollutants. Three stages crosscurrent and countercurrent solvent extraction with the solvent soil ratio 6:1 removed 97% oil contaminants from soil. Clearly the results showed that the mixed-solvent of hexane and acetone (25 vol%) with character of low-toxic, acceptable cost and high efficiency was promising in solvent extraction to remove heavy oil fractions as well as petroleum hydrocarbons from contaminated soils.     

Treatment of PAHs in contaminated soil by extraction with aqueous DNA followed by biodegradation with a pure culture of Sphingomonas sp

The biodegradation of polycyclic aromatic hydrocarbons (PAHs) in aqueous deoxyribonucleic acid (DNA) solution from contaminated soil washing was investigated. Initial data with a model effluent consisting of anthracene, phenanthrene, pyrene and benzo[a]pyrene that were individually dissolved in 1% aqueous DNA solution confirmed their positive degradation by Sphingomonas sp. at around 10(8)CFU mL(-1) initial cell loading. For anthracene and phenanthrene, complete removal was achieved within 1h treatment. Degradation of pyrene and benzo[a]pyrene took a relatively longer time of a few days and weeks, respectively. DNA-dissolved PAHs were also degraded relatively faster than PAH crystals in aqueous medium to suggest that the binding of the PAHs in the polymer does not pose serious constraint to bacterial uptake. The DNA was stable against the PAH-degrading bacteria. Parallel experiments with actual DNA solutions obtained during pyrene extraction from an artificially spiked soil also showed similar results. Close to 100% pyrene degradation was achieved after 1d treatment. With its chemical stability, the cell-treated DNA was re-used up to four cycles without a considerable decline in extraction performance.     

Combined treatment of PAHs contaminated soils using the sequence extraction with surfactant-electrochemical degradation

Polycyclic aromatic hydrocarbons (PAHs) cause a high environmental impact when released into the environment. The objective of this study was to evaluate the capacity of decontamination of polluted soils with PAHs using the sequence extraction-electrochemical treatment: extraction of PAHs from the soil with surfactant followed by electrochemical degradation of the liquid collected. Several PAHs (anthracene, benzo[a]pyrene, and phenanthrene) have been used as model compounds since such PAHs are found in high concentrations in contaminated environmental samples. Due to their hydrophobic nature, soil extraction has been limited. In this work, the use of six surfactants, Brij 35, Merpol, Tergitol, Tween 20, Tween 80 and Tyloxapol, has been evaluated on the PAH extraction from a model soil such as kaolin. Furthermore, the electrochemical degradation of PAHs with the surfactant that gave the best result was investigated working with neat solutions. The electrochemical treatment of these solutions was carried out in two electrochemical cells with different working volumes, 0.4 and 1.5l, and electrode material (graphite or titanium). Near complete degradation was reached for all the experiments in both cells.     

交换电极法强化电动修复铬污染土壤

pH值是影响污染土壤电动修复的主要因素。为此提出了交换电极法强化电动修复,并对该技术进行了实验研究。实验土壤Cr污染浓度为506.36 mg/kg,工作电压为1 V/cm,结果显示,固定电极方向运行模式下,运行2 d,产生聚焦效应,运行8 d,碱性区Cr(III)残留量和酸性区Cr(VI)残留量较大,分别是97.88 mg/kg和328 mg/kg,总铬去除率为59.04%。采用交换电极法,交换频率为4 d,运行8 d,总铬去除率为70.18%;交换频率为2 d,运行8 d,总铬去除率高达86.10%,土壤中总铬平均含量从506.36 mg/kg降至73.56 mg/kg,达到酸性土壤环境质量一级标准。该技术可控制土壤pH值在中性范围,电流密度高,不添加化学试剂,操作简单。     

Test system for exposing fish to resuspended, contaminated sediment

We describe a new test system for exposing fish to resuspended sediments and associated contaminants. Test sediments were resuspended by revolving test chambers on rotating shafts driven by an electric motor. The timing, speed, and duration of test-chamber revolution were controlled by a rheostat and electronic timer. Each chamber held 45 litres of water and accommodated about 49 g of test fish. The system described had three water baths, each holding six test chambers. We illustrate the performance of this system with results from a 28-day test in which juvenile bluegills Lepomis macrochirus were exposed to resuspended, riverine sediments differing in texture and cadmium content. The test had one sediment-free control and five sediment treatments, with three replicates (chambers) per treatment and 25 fish per replicate. Two-thirds (30 litres) of the test water and sediment in each chamber was renewed weekly. The mean concentration of total suspended solids (TSS) did not vary among treatments; the grand-mean TSS in the five sediment treatments was 975 mg litre(-1), similar to the target TSS of 1000 mg litre(-1). At the end of the test, an average of 50% of the introduced cadmium was associated with the suspended sediment compartment, whereas the filtered (0.45 microm) water contained 0.4% and bluegills 1.8% of the cadmium.     

Determination of hydrocarbons in old creosote contaminated soil using headspace solid phase microextraction and GC-MS.

Headspace solid phase microextraction (HS-SPME) has been used together with GC-MS to analyze organic substances directly in a soil, heavily contaminated with PAHs/creosote (approximately 300 mg/kg soil), from an old gaswork site in Stockholm, Sweden. The HS-SPME results, both qualitative and quantitative, were compared with traditional liquid extraction using ethyl acetate/hexane (20:80). It was shown that the concentrations determined with HS-SPME at 60 degrees C correlated well, for compounds containing up to two and three aromatic rings (naphthalenes, acenaphthene, acenaphthylene and fluorenes, while a lower concentration was obtained for phenanthrene, anthracene, fluoranthene and pyrene. The total concentrations for each compound determined with HS-SPME ranged from 2 to 25 microg/g soil. Quantification was done using standard addition of compounds directly to the soil samples. The bioavailable fraction of the compounds in the contaminated soil at 20 degrees C was analyzed using external calibration by spiking sterile uncontaminated sand (same texture and particle size as the contaminated soil but without a heavily sorbed organic fraction) with hydrocarbon standards in different concentrations. Storage of exposed fibers at 20 degrees C showed that analysis should be done within two days to make qualitative measurements and earlier (as soon as possible) for quantitative determinations.     

Improved extraction procedures for polychlorinated biphenyls in solid samples with aqueous sodium hydroxide under autoclave conditions

The efficacy of the extraction of polychlorinated biphenyls (PCBs) from varnish-infiltrated insulating papers as a model of solid materials with an aqueous sodium hydroxide (NaOH) by autoclaving at 121 degrees C for 30 min was compared with those for the conventional procedures, i.e., saponification with 1 N ethanolic NaOH in a boiling water bath for 60 min and extraction with benzene in a Soxhlet apparatus. The newly invented autoclaving method was found to be superior to the conventional ones, yielding approximately 5- to 6-fold cumulative PCB congeners without being accompanied by extended decomposition. Therefore, the autoclave-based sample treatment is recommended for more accurate determination of PCBs in the case of PCB-impregnated solid materials such as hardened oils and resin-coated or -infiltrated papers instead of being treated conventionally.     

萃取法预处理间二硝基苯生产废水

间二硝基苯生产废水中含有邻硝基苯磺酸和对硝基横酸，采用三辛胺－煤油作萃取剂对其进行萃取处理，在最佳工艺条件下，经过三级萃取，废水的COD去除率达95％以上，硝基物去除率达98％以上，萃取剂用NaOH水溶液处理后可循环使用。     

Comparative study of extraction methods for the determination of PAHs from contaminated soils and sediments

The following four methods were compared on the extraction efficiency of 16 EPA (US Environmental Protection Agency) polycyclic aromatic hydrocarbons (PAHs): German method of the Verband Deutscher Landwirtschaftlicher Untersuchungs und Forschungsanstalten (VDLUFA), two methods of the International Organization for Standardization using shaking (ISO A) and Soxhlet extraction (ISO B) and an ultrasonic method. Recovery rates of 16 PAHs were determined in two soils. Extraction efficiency was evaluated in five soils and three sediments. Effect of drying soils and sediments on extraction efficiency was tested using the VDLUFA and the ultrasonic methods. Our study shows that the number of aromatic rings, rather than extraction procedures, significantly influenced recovery rates of individual PAHs. No significant differences in extraction efficiency of the four methods were observed for less polluted samples. For highly polluted soils, extraction efficiency decreased in the following order: VDLUFA method > ISO A > ultrasonic method > ISO B. Influence of soil moisture on extraction efficiency depended to some extent on both solvent used and content of PAHs in samples. A mixture of dichloromethane/acetone (5:1) is recommended for PAH extraction from moist samples when the ultrasonic method is used.     

中原油田石油污染土壤原位生物修复技术实验研究

通过实验室选择性富集培养,从中原油田石油污染土壤中获得了能以中原原油为碳源快速生长的石油降解菌群。结合黑麦草（Ryegrass）和苜蓿（Alfalfa）,采用该降解菌群对原油污染土壤进行了原位生物联合修复实验。接入降解菌的实验区分种植黑麦草、种植苜蓿、未种植区,另设黑麦草区和空白区。经过99 d的生物修复,石油烃累计降...     

Development of supercritical carbon dioxide extraction with a solid phase trap for dioxins in soils and sediments

A method involving supercritical fluid extraction (SFE) with a solid phase trap containing activated alumina was investigated for the rapid analysis of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin like polychlorinated biphenyls (DL-PCBs) in soils and sediments. The samples were extracted by using supercritical carbon dioxide with water (2% versus CO(2) flow velocity) being used as an entrainer at a pressure of 30 MPa and a temperature of 130 degrees C for 50 min. The extracts were adsorbed on an activated alumina trap that was maintained at a temperature of 150 degrees C, and then, PCDD/DFs and DL-PCBs were eluted with 20 ml of hexane at 60 degrees C. After concentration, they were measured with a high-resolution gas chromatograph interfaced to a high-resolution mass spectrometric detector. The average concentrations of PCDD/DFs and DL-PCBs corresponded to the results obtained by the conventional method, and the reproducibility of this SFE method was below 21% of the relative standard deviations for all samples. The total time required for the analysis of the pretreatment of this method was only 2 h.     

Methodology for management of endosulfan contaminated eluent.

Management of Endosulfan contaminated eluent (24 mg/l) resulting from a treatment process to remove Endosulfan from water with wood charcoal, was attempted using various methods viz. volatilisation, hydrolysis and sorption by viable cell bacteria with and without acclimatisation. Volatilisation failed in giving better result, as Endosulfan was not considerably volatile. It could achieve a removal efficiency of 1.4-2%. Hydrolysis resulted in 28.4% and 17.9% removal of Endosulfan in acidic and alkaline media, respectively. Viable cell bacteria (aerobic) without prior acclimatization showed efficiency of 89.7% and after prior acclimatisation showed 96% removal efficiency. Sorption by the acclimatized biomass was found a suitable method for the removal of Endosulfan at a concentration of 24 mg/l.     

Treatment of groundwater contaminated with gasoline components by an ozone/UV process

In this paper, the treatment of real groundwater samples contaminated with gasoline components, such as benzene, toluene, ethylbenzene, and xylene (BTEX), methyl tert-butyl ether (MTBE), tert-butyl alcohol (TBA), and other gasoline constituents in terms of total petroleum hydrocarbons as gasoline (TPHg) by an ozone/UV process was investigated. The treatment was conducted in a semi-batch reactor under different experimental conditions by varying ozone gas dosage and incident UV light intensity. The groundwater samples contained BTEX compounds, MTBE, TBA, and TPHg in the ranges of 5-10000, 3000-5500, 80-1400, and 2400-20000mugl(-1), respectively. The ozone/UV process was very effective compared to ozonation in the removal of the gasoline components from the groundwater samples. For the various gasoline constituents, more than 99% removal efficiency was achieved for the ozone/UV process and the removal efficiency for ozonation was as low as 27%. The net ozone consumed per mol of organic carbon (from BTEX, MTBE, and TBA) oxidized varied in the range of 5-60 for different types of groundwater samples treated by the ozone/UV process. In ozonation experiments, it was observed that the presence of sufficient amount of iron in groundwater samples improved the removal of BTEX, MTBE, TBA, and TPHg.     

应用籽粒苋修复镉污染农田土壤的潜力

针对农田土壤镉污染问题,采用超富集植物籽粒苋并配施不同组合的外源活化剂进行盆栽实验和田间实验,并测定籽粒苋及根系土壤中镉含量并计算富集系数。结果表明,在盆栽实验的不同处理组中,施加磷酸二氢钾(0.74 mmol·kg^-1)、EDTA(2 mmol·kg^-1)和柠檬酸(4 mmol·kg^-1)最有助于提高籽粒苋对Cd的提取修复效率。田间实验中添加活化剂(EDTA和柠檬酸)后籽粒苋的根、茎和叶组织对Cd的富集能力分别是不添加活化剂处理组的2.10、1.84和2.76倍;与对照组相比,籽粒苋的根、茎和叶部分的Cd含量都显著提高(P < 0.05),这说明外源活化剂促进了籽粒苋对土壤中Cd的吸收,提高了修复效率。每年种植两茬籽粒苋并添加活化剂,Cd的去除率可达4%~10%。种植超富集植物并配施活化剂既可以提高修复效率,又可以节约修复成本。     

An approach for arsenic in a contaminated soil: Speciation, fractionation, extraction and effluent decontamination

The fractionation and speciation of As in a contaminated soil were investigated, and a remediation strategy was tested. Regarding speciation, we found that As(V) prevails over As(III) whereas more than 40% of total arsenic is in organic form. The fractionation of As was investigated with two sequential extraction methods: a low mobility was found. Then we tested the possibility of using phosphoric acid to extract As from the soil and cleaning the washing effluents by sorption onto montmorillonite. The efficiency of the extraction and of the adsorption onto the clay were also investigated for Cr, Cu, Fe, Mn, Ni, Pb and Zn, whose total concentrations and fractionation in the soil are reported here. The extraction percentages for As and metals ranged from 30 to 65%; the residual proportions in the soil are presumably in very unreactive forms. Montmorillonite showed a good uptake capacity towards the investigated pollutants.     

Remediation of DDTs contaminated soil in a novel Fenton-like system with zero-valent iron

Application of a novel Fenton-like system with zero-valent iron, EDTA and Air (ZVI/EDTA/Air) was investigated to degrade dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethane, and dichlorodiphenyldichloroethylene (DDE) in the actual contaminated soil from an organochlorine pesticide site. It was found DDTs in the soil were effectively degraded by the system at room temperature, ambient atmosphere pressure and near neutral pH. The dosages of EDTA and ZVI were the dominant factors influencing the removal of contaminants. An increase of EDTA from 0.05 to 0.2 mM and ZVI from 1 to 5 g L^?1 improved the removal of the contaminants significantly. However, excessive amount of EDTA led to a negative effect on the degradation process. Meanwhile, EDTA was simultaneously degraded so as to avoid the secondary pollution risk on soil remediation. Only a small amount of 4,4′-DDE and 2,2-bis(4-chlorophenyl)-1-chloroethylene (4,4′-DDMU) generated as the intermediates of DDT degradation during the process. Our investigation suggests that the Fenton-like system is a promising alternative for remediation of organochlorine pesticides contaminated soils.