In situ laser-induced fluorescence (LIF) analysis of petroleum product-contaminated soil samples

General considerations of the calibrations of in situ measurements are presented and the concept of using an "average oil" with average analysability for calibration purposes is introduced. The in situ analysis of 30 petroleum product-contaminated soil samples with laser-induced fluorescence (LIF) spectroscopy was performed. Compared to an uncontaminated laboratory reference (LR) soil, 23 soil samples exhibited significantly higher LIF signals, so that these soil samples were classified as contaminated. The repeatability and reproducibility of the in situ LIF analysis were investigated. For the calibration of the LIF data, two LR oils (a fuel oil and a crude oil) were employed. The degree of soil contamination with petroleum products ranged from the limit of detection (LOD) for LIF analysis (ca. 100 ppm), or below, to more than 10,000 ppm. The petroleum product concentrations determined with in situ LIF analysis reveal a reasonable correlation with the results of standard IR analysis after extraction of the contaminated soils.     

Estimates of total polychlorinated biphenyl (PCB) compounds in soils/sediments by hydrogenolysis to dicyclohexyl

A method to determine the total PCB content by hydrogenolysis (hydrodechlorination and hydrogenation) of chlorinated biphenyl compounds was extended to natural particulate matrices (soil and sediment). The contaminated soil was suspended in hexane in the presence of Pd/gamma-Al2O3 in a hydrogen atmosphere then permitted to react for one hour at 65 degrees C. Dicyclohexyl, recovered in the hexane, was quantified by gas chromatography mass spectrometry. The reaction was very efficient for soil/sediment in hexane suspension and virtually complete provided that excess catalyst was added to samples that were burdened with higher PCB loadings prior to reaction otherwise some partial hydrogenation of biphenyl was also observed. The proposed method was validated with the analysis of five certified reference materials.     

Assessment of metal contamination using X-ray fluorescence spectrometry and the toxicity characteristic leaching procedure (TCLP) during remediation of a waste disposal site in Antarctica

The remediation of the Thala Valley landfill, Casey Station, East Antarctica, is part of efforts to clean-up contaminated sites associated with the Australian Antarctic Program. These sites, ranging from abandoned rubbish dumps to fuel spills, are contaminated principally with metals and petroleum hydrocarbons. Remediation success depends on accurate, cost-effective and timely--fit-for-purpose--chemical analysis of soil and water samples from the site, which is required to guide excavation, the in situ or off-site treatment and disposal of contaminated material, and to validate satisfactory remediation. Owing to the remote location of Antarctica, it is necessary to carry out chemical analyses on-site. Waste and soil contaminated with Pb, Zn, Cd, and Cu were excavated from Thala Valley for removal to Australia, treatment and disposal. Analysis of total metal concentrations in soil was performed at Casey Station with a transportable energy dispersive X-ray fluorescence (EDXRF) spectrometer. Soil samples were prepared using a simple size-fractionation method to expedite sample throughput. A method for assessing contaminant mobility in solid waste (toxicity characteristic leaching procedure, TCLP) was also used to characterise soil. Although this was more labour-intensive and time-consuming than the total metals analysis, it was of great utility because leachable metals were often significant determinants in the assessment of contaminated soil. The combined data helped managers during remediation, directing excavation and allowing waste to be classified for treatment and disposal before its return to Australia.     

Fingerprinting of petroleum hydrocarbons (PHC) and other biogenic organic compounds (BOC) in oil-contaminated and background soil samples

Total petroleum hydrocarbons (TPH) or petroleum hydrocarbons (PHC) are one of the most widespread soil contaminants in Canada, the United States and many other countries worldwide. Clean-up of PHC-contaminated soils costs the Canadian economy hundreds of millions of dollars annually. In Canada, most PHC-contaminated site evaluations are based on the methods developed by the Canadian Council of the Ministers of the Environment (CCME). However, the CCME method does not differentiate PHC from BOC (the naturally occurring biogenic organic compounds), which are co-extracted with petroleum hydrocarbons in soil samples. Consequently, this could lead to overestimation of PHC levels in soil samples. In some cases, biogenic interferences can even exceed regulatory levels (300 μg g(-1) for coarse soils and 1300 μg g(-1) for fine soils for Fraction 3, C(16)-C(34) range, in the CCME Soil Quality Level). Resulting false exceedances can trigger unnecessary and costly cleanup or remediation measures. Therefore, it is critically important to develop new protocols to characterize and quantitatively differentiate PHC and BOC in contaminated soils. The ultimate objective of this PERD (Program of Energy Research and Development) project is to correct the misconception that all detectable hydrocarbons should be regulated as toxic petroleum hydrocarbons. During 2009-2010, soil and plant samples were collected from over forty oil-contaminated and paired background sites in various provinces. The silica gel column cleanup procedure was applied to effectively remove all target BOC from the oil-contaminated sample extracts. Furthermore, a reliable GC-MS method in combination with the derivatization technique, developed in this laboratory, was used for identification and characterization of various biogenic sterols and other major biogenic compounds in these oil-contaminated samples. Both PHC and BOC in these samples were quantitatively determined. This paper reports the characterization results of this set of 21 samples. In general, the presence of petroleum-characteristic alkylated PAH homologues and biomarkers can be used as unambiguous indicators of the contamination of oil and petroleum product hydrocarbons; while the absence of petroleum-characteristic alkylated PAH homologues and biomarkers and the presence of abundant BOC can be used as unambiguous indicators of the predominance of natural organic compounds in soil samples.     

Ecotoxicological and microbiological characterization of soils from heavy-metal- and hydrocarbon-contaminated sites

The aims of this study were to characterize soils from industrial sites by combining physicochemical, microbiological, and ecotoxicological parameters and to assess the suitability of these assays for evaluation of contaminated sites and ecological risk assessment. The soil samples were taken from long-term contaminated sites containing high amounts of heavy metals (sites 1 and 2) or petroleum hydrocarbons (site 3) located in the upper Silesia Industrial Region in southern Poland. Due to soil heterogeneity, large differences between all investigated parameters were measured. Microbiological properties revealed the presence of high numbers of viable hetrotrophic microorganisms. Soil enzyme activities were considerably reduced or could not be detected in contaminated soils. Activities involved in N turnover (N mineralization and nitrification) were significantly (P?<?0.05) higher in samples from the metal-contaminated sites than in samples from the hydrocarbon-contaminated site, whereas the opposite was observed for phosphatase activity. The Microtox test system appeared to be the most appropriate to detect toxicity and significant differences in toxicity between the three sites. The Ostracodtoxkit test was the most appropriate test system to detect toxicity in the hydrocarbon-contaminated soil samples. Correlation analysis between principal components (obtained from factor analysis) determined for physicochemical, microbiological, and ecotoxicological soil properties demonstrated the impact of total and water-extractable contents of heavy metals on toxicity.     

Assessing soil and groundwater contamination in a metropolitan redevelopment project

The purpose of this study was to assess contaminated soil and groundwater for the urban redevelopment of a rapid transit railway and a new mega-shopping area. Contaminated soil and groundwater may interfere with the progress of this project, and residents and shoppers may be exposed to human health risks. The study area has been remediated after application of first remediation technologies. Of the entire area, several sites were still contaminated by waste materials and petroleum. For zinc (Zn) contamination, high Zn concentrations were detected because waste materials were disposed in the entire area. For petroleum contamination, high total petroleum hydrocarbon (TPH) and hydrocarbon degrading microbe concentrations were observed at the depth of 7 m because the underground petroleum storage tank had previously been located at this site. Correlation results suggest that TPH (soil) concentration is still related with TPH (groundwater) concentration. The relationship is taken into account in the Spearman coefficient (α).     

Environmental applications of poly(amic acid)-based nanomaterials

Nanoscale materials offer new possibilities for the development of novel remediation and environmental monitoring technologies. Different nanoscale materials have been exploited for preventing environmental degradation and pollutant transformation. However, the rapid self-aggregation of nanoparticles or their association with suspended solids or sediments where they could bioaccumulate supports the need for polymeric coatings to improve mobility, allows faster site cleanups and reduces remediation cost. The ideal material must be able to coordinate different nanomaterials functionalities and exhibit the potential for reusability. We hereby describe two novel environmental applications of nanostructured poly (amic acid)-based (nPAA) materials. In the first application, nPAA was used as both reductant and stabilizer during the in situ chemical reduction of chromium(vi) to chromium(iii). Results showed that Cr(vi) species were rapidly reduced within the concentration range of 10(-1) to 10(2) mM with efficiency of 99.9% at 40 °C in water samples and 90% at 40 °C in soil samples respectively. Furthermore, the presence of PdNPs on the PAA-Au electrode was found to significantly enhance the rate of reduction. In the second application, nPAA membranes were tested as filters to capture, isolate and detect nanosilver. Preliminary results demonstrate the capability of the nPAA membranes to quantitatively capture nanoparticles from suspension and quantify their abundance on the membranes. Silver nanoparticles detection at concentrations near the toxic threshold of silver was also demonstrated.     

Dissipation and residue of MCPA (4-chloro-2-ethylphenoxyacetate) in wheat and soil

A rapid and simple HPLC method has been developed for the quantitation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in both wheat and soil samples. Samples were extracted in acidic media and cleaned up by solid-phase extraction with C(18) cartridges before HPLC-DAD detection. The limits of detection and quantification of MCPA were 0.02 ng and 0.01 mg/kg for both wheat and soil. The mean recoveries ranged from 87.1% to 98.2%, and the RSDs ranged from 0.604% to 3.44% for the three spiked levels (0.01, 0.1, 0.5 mg/kg). The proposed method was successfully applied to the analysis of MCPA residues in wheat and soil samples from an experimental field. The dissipation half-lives in soil were calculated to be 3.22 days (Beijing) and 3.10 days (Tianjin), respectively. Direct confirmation of the analytes in real samples was achieved by gas chromatography-mass spectrometry. The results indicated that at harvest time, the residues of MCPA in wheat were well below the maximum residue levels and were safe to apply in wheat.     

Petroleum contaminated soil in Oman: Evaluation of bioremediation treatment and potential for reuse in hot asphalt mix concrete

This paper presents a study that aims at evaluating the leaching characteristics of petroleum contaminated soils as well as their application in hot mix asphalt concrete. Soil samples are environmentally characterized in terms of their total heavy metals and hydrocarbon compounds and leachability. The total petroleum hydrocarbon (TPH) present in the PCS before and after treatment was determined to be 6.8% and 5.3% by dry weight, indicating a reduction of 1% in the TPH of PCS due to the current treatment employed. Results of the total heavy metal analysis on soils indicate that the concentrations of heavy metals are lower when extraction of the soil samples is carried out using hexane in comparison to TCE. The results show that the clean soils present in the vicinity of contaminated sites contain heavy metals in the following decreasing order: nickel (Ni), followed by chromium (Cr), zinc (Zn), copper (Cu), lead (Pb), and vanadium (V). The current treatment practice employed for remediation of the contaminated soil reduces the concentrations of nickel and chromium, but increases the concentrations of all remaining heavy metals.     

我国污染场地土壤石油烃环境质量标准体系的现状与趋势

石油烃污染场地已经成为国内外重点关注的工业污染场地类型之一。国内基于人体健康风险的污染场地管理模式及分层次评估方法已经展现雏形,为风险管理者提供了基于人体健康的土壤石油烃风险筛选值和管制值,也为污染场地的防治与修复工作提供了决策支持。在前人研究的基础上,梳理了国内土壤环境质量标准体系的建立与发展历程,分析了石油烃类污染物检测方法的现状与未来发展趋势,并着重对比与分析了各标准制订的石油烃及其指示化合物的风险评估筛选值。目前面临的关键问题:①完善石油烃监测指标体系及分析方法是精准获得风险评估结果的前提。现有石油烃馏分指标划分较为宽泛,有必要参考国外先进标准体系,逐渐完善石油烃馏分指标划分及其配套的定量分析方法。②新颁布的国家建设用地土壤污染风险管控标准在前期场地调查中具有一定的普遍适用性,但是考虑到地域建筑物参数、人群暴露参数等的差异性,在后期场地调查中还需要因地制宜地制定适合污染场地的具体修复目标值,并针对关键性参数作定量化解析。     

Site environmental assessment to an old paint factory in China

High ethyl-benzene and total petroleum hydrocarbons (TPHs) were found in the soil samples and groundwater samples during a site environmental assessment for an old paint factory in the city Changchun, Jilin province of China. The target old paint plant had been in operation for near 30 years by manufacturing resin and house paint. Driving force for this study was to identify potential environmental contamination existing in this paint factory which is located next to a new resident area under construction. The assessment result would be used as baseline environmental data input for remediation plan when the factory site will be changed into potential resident area in near future. The analytical data from the soil samples from different area of the factory which had high exposure to operation showed that solid waster storage area was contaminated with high heavy metals (Cd, Pb, and Zn) and waster paint storage areas were contaminated with ethyl-benzene, xylene and C9-C30 aromatic hydrocarbon solvent. The analytical data from the groundwater samples from different area of the factory showed that resin plant area and waster paint storage areas were contaminated with high concentration of naphthalene, ethyl-benzene and xylene which exceed the reference standard. Remediation action is recommended.     

Simultaneous analysis of endosulfan, chlorpyrifos, and their metabolites in natural soil and water samples using gas chromatography-tandem mass spectrometry

Analysis of endosulfan, chlorpyrifos, and their nonpolar metabolites in extracts from environmental aqueous and soil samples was performed using a gas chromatography-tandem mass spectrometry (GC–MS/MS) technique. Full-scan GC–MS analysis showed poor sensitivity for some of the metabolites (endodiol and endosulfan ether). A multisegment MS/MS method was developed and MS/MS parameter isolation time, excitation time, excitation voltage, and maximum excitation energy were optimized for chosen precursor ions to enhance selectivity and sensitivity of the analysis. The use of MS/MS with optimized parameters quantified analytes with significantly higher accuracy, and detection limits were lowered to ~1/6th compared with the full-scan method. Co-eluting compounds, chlorpyrifos and chlorpyrifos oxon, were also analyzed successfully in the MS/MS mode by choosing exclusive precursor ions. Analysis of soil and water phase samples from contaminated soil slurry bioreactors showed that the MS/MS method could provide more reliable estimates of these pesticide and metabolites (especially those present in low concentrations) by annulling interferences from soil organic matter.     

Fast simultaneous determination of traces of Cu(II) and Co(II) in soils and sediments with the luminol/perborate chemiluminescent system

A flow injection analysis method based on ion chromatography and luminol chemiluminescence detection was used for the simultaneous determination of copper (II) and cobalt (II) trace levels in soils and sediments following microwave-assisted acid digestion. Detection was based on chemiluminescence (CL) of the luminol–perborate system in an alkaline medium, which is catalyzed by both transition metals. The concentration and pH of the eluent (oxalic acid) was found to affect CL intensities and retention times, both of which were inversely proportional to the oxalic acid concentration. The calibration curves for both metal ions were linear and allowed a limit of detection of 0.003 μg l^?1 for cobalt (II) and 0.014 μg l^?1 for cooper (II) to be calculated. The proposed method was successfully used to determine both metal ions in certified reference materials of stream and river sediments and soil samples. Based on the results, the determination is free of interferences from the usual concomitant ions.     

X射线荧光光谱法测定土壤样品中铅的不确定度评定

用实例对X射线荧光光谱法测定土壤样品中铅的不确定度进行了评定.测量结果的不确定度由仪器综合稳定性、制样、标准物质、回归工作曲线、重复测量等所引入的不确定度分量组成.在对各个不确定度分量进行量化的基础上,通过合成得到测量结果的标准不确定度,再乘以95%置信概率下的扩展因子2,得到测量结果的扩展不确定度.     

超声波萃取-红外分光光度法测定土壤中石油类

采用超声波萃取-红外分光光度法测定土壤中石油类,并对超声波机的功率、水浴温度和萃取时间进行优化.试验表明：方法在0mg/L～80.0mg/L范围内线性良好,相关系数r为0.9997;方法检出限为6.00μg/L,当取土壤样品10.0g时,方法检出限为0.03mg/kg;空白土壤的加标回收率为97.4% ～103%;测定实际土壤样品的RSD为3.0% ～3.9%.通过比较超声波萃取、四氯化碳热浸法和快速溶剂萃取法的前处理效果,显示出超声波萃取法的优越性.     

Determination of petroleum hydrocarbons and polycyclic aromatic hydrocarbons in sludge from wastewater treatment basins

Screening by gas chromatography with flame ionization detection and gas chromatography-mass spectrometry has been carried out on sludge extracts of wastewater treatment basins. Soxhlet extraction with trichlorotrifluoroethane was applied. The yields for petroleum hydrocarbons and PAH recovery were high, usually in excess of 90%. The proposed investigations permit a quick assessment of petroleum pollutants in the environment.     

Evaluation of Pb, Cu, Zn, Cd, Ni and Fe levels in Rosmarinus officinalis labaiatae (Rosemary) medicinal plant and soils in selected zones in Jordan

The concentration of heavy metals including Pb, Cu, Zn, Cd, Ni and Fe in different parts of Rosmarinus officinalis medicinal plant grown in Jordan were evaluated. Medicinal plant samples and soil samples were collected from three different zones in Jordan (Irbid, Al-Mafraq and Ma’an). Samples were analyzed by atomic absorption spectrometry (AAS) after chemical treatments using acid digestion procedures. Heavy metal levels in washed and unwashed in each part of R. officinalis were analyzed and compared statistically. Results show that concentrations of investigated heavy metals were varied from plant part to another part of R. officinalis. For example, Pb, Zn, Cu and Cd in most parts of R. officinalis in the three zones were concentrated in the following order: flowers, leaves, stems, whereas Pb, Ni and Fe were concentrated in order as follows: leaves, flowers and stems. Heavy metal concentrations in soil samples was evaluated and correlated with their levels in R. officinalis. Two standard reference materials of plant (SRM 1790a; spinach leaves and CRM 281; rye grass) and one standard reference materials of soil (GBW 07406) were examined to validate the method used. Results show that high recoveries were obtained.     

Development of an Expert System for the Remediation of Petroleum-Contaminated Sites

Groundwater and soil contamination caused by light nonaqueous phase liquids (LNAPLs) spills and leakage in petroleum industry is currently one of the major environmental concerns in North America. Numerous site remediation technologies, generally classified as ex situ and in situ remediation techniques, have been developed and implemented to clean up the contaminated sites in the last two decades. One of the problems associated with ex situ remediation is the cost of operation. In recent years, in situ techniques have acquired popularity. However, the selection process of the desired techniques needs a large amount of knowledge. Insufficient expertise in the process may result in unnecessary inflation of expenses. In this study, petroleum waste management experts and Artificial Intelligence (AI) researchers worked together to develop an expert system (ES) for the management of petroleum contaminated sites. Various AI techniques were used to construct a useful tool for site remediation decision-making. This paper presents the knowledge engineering processes of knowledge acquisition, conceptual design, and system implementation in the project. The expert system was applied to a real-world case study and the results show that the expert system can generate desired remediation alternatives to assist decision-makers. The application case study constitutes partial validation of the prototype expert system.     

Optimization of the Microwave-Assisted Solvent Extraction of Petroleum Hydrocarbons in Marine Sediment and Soil

A microwave-assisted solvent extraction (MASE) technique was developed for the quantitative extraction of gasoline- and diesel-range petroleum hydrocarbons (PHs) from soil and marine sediment samples. The influence of different extracting solvents, extraction temperature and duration of extraction on the recoveries of PHs was evaluated using a two-level orthogonal array design (OAD) with a OA8(27) matrix. Gas chromatographic-mass spectrometry (GC-MS) in multiple selective ion monitoring (MSIM) mode was used for the analysis of the PHs in environmental samples. The spiking range of the PHs in the environmental samples was between 1 to 1000 g/g. Good recoveries (>80%) could be obtained for most of the PHs using the optimum MASE conditions. The limit of detection (LOD) achieved by the GC-MS-MSIM was 0.02 g/g. A preliminary survey for the levels of PHs in marine sediment and soil samples from different parts of Singapore was carried out using the method.     

红外分光光度法测定水中油类物质吸附方法的比较

吸附处理是红外法测定石油类的一个重要环节.通过实验对吸附柱法和振荡吸附法进行对较,结果表明动植物油质量浓度为0.560 mg/L～145 mg/L的水样,振荡吸附法吸附效率高于吸附柱法.振荡吸附法还具有操作时间短、硅酸镁耗量低、对操作人员危害性小、样品可批量分析的优点.