Supercritical Fluid Extraction for Forensic Analysis of Hydrocarbons in Soil

Supercritical fluid extraction (SFE) was investigated to evaluate its potential for obtaining high quality chromatographic fingerprints from soils encountered in environmental investigations. While the volatile and semivolatile fractions of light nonaqueous phase liquid (LNAPL) samples can be “fingerprinted” in a single chromatographic run, it is commonly not possible to obtain samples of LNAPL in the locations of interest. For this and other reasons, it was desirable to develop this method (SFE) of soil extraction, which allows chromatographic fingerprinting of the same quality routinely obtained with LNAPL so that environmental forensic investigations could be extended to areas beyond those containing LNAPL in monitoring wells. In this study, SFE was compared to conventional dichloromethane extraction. Both artificially spiked soil and soil from petroleum release sites were tested. Since water can be a problem when using the SFE method, particular attention was given to handling soils with high moisture contents. The SFE extracts showed excellent retention of low molecular components, including pentanes. Gas chromatography of SFE extracts yielded molecular distributions that showed no significant bias toward either low or high molecular weight components. These results show that SFE can be used to obtain an unbiased, single-run chromatographic “fingerprint” of both volatile and semivolatile hydrocarbons in contaminated soil samples.     

固定化微生物修复石油污染土壤影响因素研究

针对石油污染土壤修复,利用实验室已筛选的高效石油降解单菌SM-3,以天然有机材料为载体,吸附法制备固定化微生物。将游离与固定化微生物应用于室内花盆模拟修复石油污染土壤,对C/N/P、微生物投加量、石油含量、氧化剂和表面活性剂设计5因素4水平正交实验,探讨不同修复时期各影响因素的重要性顺序,最佳条件下各菌株的修复效果。结果表明,不同微生物在不同降解时期,各影响因素的重要性会发生变化;经过21 d的修复,固定化单菌SM-3石油降解率为22.77%,修复过程中,接种量是最重要的影响因素,营养元素N、P投加影响较大,表面活性剂和氧化剂影响次之。     

生物强化修复石油污染土壤

筛选高效石油降解菌,考察菌株的降解性能及降解机理,进行花盆模拟高效外源菌强化修复石油污染土壤实验,在降解后期添加激活剂H2O2以及木屑来试图改善微生物的修复环境,减缓微生物的衰亡,并考察修复效果。结果表明,菌株L-1的降解效果较好,其对pH和温度有较大范围的适应性,能分泌较多的表面活性物质,细胞疏水性较强。将其应用于土壤修复中,经过50 d的修复,石油残留率达到50.6%左右,生物强化比自然修复残留率降低了8%左右。在第45天添加激活剂能有效改善修复效果,70 d时添加外源菌的土样最小石油残留率达到37.9%。     

NiO-CuO/ZSM-5催化剂对催化裂化烟气的脱硫脱硝性能

采用浸渍法制备了不同NiO和CuO质量分数的NiO-CuO/ZSM-5催化剂,并以CH4为还原剂研究了NiO-CuO/ZSM-5催化剂对催化裂化烟气的脱硫脱硝活性。XRD分析结果表明,NiO质量分数为4%、CuO质量分数为6%的催化剂4%NiO-6%CuO/ZSM-5中的ZSM-5结构完好,CuO和NiO高度分散在ZSM-5骨架中,表明具有较好的催化活性。4%NiO-6%CuO/ZSM-5的脱硫脱硝起活温度均较低,无氧条件下最高NO转化率和SO2转化率分别为94.7%和95.9%,O2体积分数为1.0%时的NO转化率和SO2转化率分别为97.7%和89.0%。     

Speciation and transport of arsenic in an acid sulfate soil-dominated catchment, eastern Australia

Factors controlling the transport of geogenically-derived arsenic from a coastal acid sulfate soil into downstream sediments are identified in this study with both solid-phase associations and aqueous speciation clearly critical to the mobility and toxicity of arsenic. The data from both sequential extractions and X-ray adsorption spectroscopy indicate that arsenic in the unoxidised Holocene acid sulfate soils is essentially non-labile in the absence of prolonged oxidation, existing primarily as arsenopyrite or as an arsenopyrite-like species, likely arsenian pyrite. Anthropogenically-accelerated pedogenic processes, which have oxidised this material over time, have greatly enhanced the potential bioavailability of arsenic, with solid-phase arsenic almost solely present as As(V) associated with secondary Fe(III) minerals present. Analyses of downstream sediments reveal that a portion of the arsenic is retained as a mixed As(III)/As(V) solid-phase, though not at levels considered to be environmentally deleterious. Determination of arsenic speciation in pore waters using high performance liquid chromatography/Inductively Coupled Plasma-Mass Spectrometry shows a dominance of As(III) in upstream pore waters whilst an unidentified As species reaches comparative levels within the downstream, estuarine locations. Pore water As(V) was detected at trace concentrations only. The results demonstrate the importance of landscape processes to arsenic transport and availability within acid sulfate soil environments.     

Molecular characterization of conjugative plasmids in pesticide tolerant and multi-resistant bacterial isolates from contaminated alluvial soil

A total of 35 bacteria from contaminated soil (cultivated fields) near pesticide industry from Chinhat, Lucknow, (India) were isolated and tested for their tolerance/resistance to pesticides, heavy metals and antibiotics. Bacterial isolates were identified by 16S rDNA sequencing. Gas Chromatography analysis of the soil samples revealed the presence of lindane at a concentration of 547 ng g⁻¹ and α-endosulfan and β-endosulfan of 422 ng g⁻¹ and 421 ng g⁻¹ respectively. Atomic Absorption Spectrophotometry analysis of the test sample was done and Cr, Zn, Ni, Fe, Cu and Cd were detected at concentrations of 36.2, 42.5, 43.2, 241, 13.3 and 11.20 mg kg⁻¹ respectively. Minimum inhibitory concentrations of all the isolates were determined for pesticides and heavy metals. All the multi-resistant/tolerant bacterial isolates were also tested for the presence of incompatibility (Inc) group IncP, IncN, IncW, IncQ plasmids and for rolling circle plasmids of the pMV158-family by PCR. Total community DNA was extracted from pesticide contaminated soil. PCR amplification of the bacterial isolates and soil DNA revealed the presence of IncP-specific sequences (trfA2 and oriT) which was confirmed by dot blot hybridization with RP4-derived DIG-labelled probes. Plasmids belonging to IncN, IncW and IncQ group were neither detected in the bacterial isolates nor in total soil DNA. The presence of conjugative or mobilizable IncP plasmids in the isolates indicate that these bacteria have gene transfer capacity with implications for dissemination of heavy metal and antibiotic resistance genes. We propose that IncP plasmids are mainly responsible for the spread of multi-resistant bacteria in the contaminated soils.     

Polychlorinated dibenzo-p-dioxins, dibenzofurans, and dioxin-like polychlorinated biphenyls in rice straw smoke and their origins in Japan

Polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) contained in the smoke generated from rice straw burning in post-harvest paddy fields in Japan were analyzed to determine their congener profiles. Both the apportionment of toxic equivalent (TEQ) by using indicative congeners and the comparison of the homolog profiles showed that the PCDDs/PCDFs/DL-PCBs present in the rice-straw smoke were greatly influenced by those present as impurities in pentachlorophenol (PCP) and chlornitrofen (CNP, 4-nitrophenyl-2,4,6-trichlorophenyl ether) formulations that had been widely used as herbicides in paddy fields in Japan. Further, in order to investigate the effects of paddy-field soil on the PCDDs/PCDFs/DL-PCBs present in rice-straw smoke, PCDD/PCDF/DL-PCB homolog profiles of rice straw, rice-straw smoke and paddy-field soil were compared. Rice-straw smoke was generated by burning rice straw on a stainless-steel tray in a laboratory. The results suggested that the herbicides-originated PCDDs/PCDFs/DL-PCBs and the atmospheric PCDDs/PCDFs/DL-PCBs contributed predominantly to the presence of PCDDs/PCDFs/DL-PCBs in the rice-straw smoke while the contribution of PCDDs/PCDFs/DL-PCBs formed during rice straw burning was relatively minimal. The major sources of the PCDDs/PCDFs/DL-PCBs found in the rice-straw smoke were attributed primarily to the paddy-field soil adhered to the rice straw surface and secondarily to the air taken by the rice straw. The principal component analysis supported these conclusions. It is concluded that rice straw burning at paddy fields acts as a driving force in the transfer of PCDDs/PCDFs/DL-PCBs from paddy-field soil to the atmosphere.     

Estrogen receptor mediated activity in bankside groundwater, with flood suspended particulate matter and floodplain soil - an approach combining tracer substance, bioassay and target analysis

Bankside groundwater is widely used as drinking water resource and, therefore, contamination has to be avoided. In the European Union groundwater protection is explicit subject to Water Framework Directive. While groundwater pollution may originate from different sources, this study investigated on impacts via flood events.Groundwater was sampled with increasing distance to the river Rhine near Karlsruhe, Germany. Samples were HPLC-MS-MS analyzed for the river contaminant carbamazepine to indicate river water infiltration, giving permanent presence in 250 m distance to the river (14-47 μg L⁻¹). Following a flood event, concentrations of about 16-20 μg L⁻¹ could also be detected in a distance of 750 m to the river. Furthermore, estrogenic activity as determined with the Yeast Estrogen Screen assay was determined to increase up to a 17β-ethinylestradiol equivalent concentration (E-EQ) = 2.9 ng L⁻¹ near the river, while activity was initially measured following the flood with up to E-EQ = 2.6 ng L⁻¹ in 750 m distance. Detections were delayed with increasing distance to the river indicating river water expansion into the aquifer.Flood suspended matter and floodplain soil were fractionated and analyzed for estrogenic activity in parallel giving up to 1.4 ng g⁻¹ and up to 0.7 ng g⁻¹, respectively. Target analysis focusing on known estrogenic active substances only explained <1% of measured activities.Nevertheless, river water infiltration was shown deep into bankside groundwater, thus, impacting groundwater quality. Therefore, flood events have to be in the focus when aiming for groundwater and drinking water protection as well as for implementation of Water Framework Directive.     

上海城市样带土壤有机碳空间变异性研究

为揭示城市化、工业化等人为活动对土壤有机碳的影响,选择能反映上海城郊乡梯度差异的城市样带,采用地统计学方法对表层土壤样品土壤有机碳的空间变异结构和分布格局进行了分析。结果表明：城市表层土壤有机碳含量均属中等变异,徐汇区土壤有机碳含量呈正态分布,奉贤区、闵行区和所研究样带土壤有机碳含量呈对数正态分布。半方差函数模型拟合结果显示徐汇和闵行区土壤有机碳符合指数模型,奉贤和所研究样带土壤有机碳符合球状模型。通过泛克里格插值得到城市表层土壤有机碳含量空间分布图,发现徐汇、闵行区土壤有机碳呈岛状,奉贤区呈条带状,而所研究样带呈条带和岛状分布相结合的特点。土壤有机碳含量城郊乡梯度差异明显,工业化、城市化、肥料投入与管理等人为因素对城市土壤有机碳空间分布密切相关     

城乡交错带土地利用方式对土壤理化性质的影响

以长沙市南郊山地丘陵区为研究对象,选择7种不同土地利用方式（次生林地、经济林地、杉木人工林、采伐迹地、撂荒地、苗圃地、坡耕地）研究了城乡交错带不同土地利用方式对土壤理化性质的影响。结果表明：7种土地利用方式下,土壤颗粒组成主要集中在1～0.05 mm和＜0.001 mm两个粒级范围内,土壤质地以重壤土和轻粘土为主。随着人为干扰程度的减弱,土壤砂粒（1.0～0.05 mm）、土壤粉粒（0.05～0.01 mm）百分率逐渐下降,＜0.01 mm的土壤物理性粘粒百分率增加。自然、半自然状态利用方式的林地（次生林地、经济林地、杉木人工林地）土壤总孔隙度、含水量普遍较高,土壤密度低于坡耕地、苗圃地、撂荒地、采伐迹地,而土壤pH值、有机质含量及氮、磷、钾含量普遍高于坡耕地、苗圃地、撂荒地、采伐迹地