Application of laser-based ion mobility (IM) spectrometry for the analysis of polycyclic aromatic compounds (PAC) and petroleum products in soils

The capability of laser-based IM spectrometry to detect PAC and petroleum products (oils) in model matrices, laboratory reference (LR) materials and in real-world contaminated soil samples was demonstrated. Quantitative IM investigations of PAC-doped PVC films yielded detection limits in the ppm range for single PAC. The potential of IM spectrometry for in situ analysis was demonstrated by the analysis of PAC-containing certified reference (CR) material, and of petroleum product-containing LR materials and real-world soil samples. The calibration of IM signals obtained from oil-doped LR materials was also possible, and detection of oils with concentrations below 100 mg kg(-1) was achieved. The in situ analysis of real-world contaminated soils with the IM and LIF techniques was in good accordance with ex situ reference investigations.     

Total petroleum hydrocarbon distribution in soils and groundwater in Songyuan oilfield, Northeast China

In order to investigate the distribution of the total petroleum hydrocarbons (TPH) in groundwater and soil, a total of 71 groundwater samples (26 unconfined groundwater samples, 37 confined groundwater samples, and 8 deeper confined groundwater samples) and 80 soil samples were collected in the Songyuan oilfield, Northeast China, and the vertical variation and spatial variability of TPH in groundwater and soil were assessed. For the groundwater from the unconfined aquifer, petroleum hydrocarbons were not detected in three samples, and for the other 23 samples, concentrations were in the range 0.01–1.74 mg/l. In the groundwater from the confined aquifer, petroleum hydrocarbons were not detected in two samples, and in the other 35 samples, the concentrations were 0.04–0.82 mg/l. The TPH concentration in unconfined aquifer may be influenced by polluted surface water and polluted soil; for confined aquifer, the injection wells leakage and left open hole wells may be mainly responsible for the pollution. For soils, the concentrations of TPH varied with sampling depth and were 0–15 cm (average concentration, 0.63 mg/g), >40–55 cm (average concentration, 0.36 mg/g), >100–115 cm (average concentration, 0.29 mg/g), and >500–515 cm (average concentration, 0.26 mg/g). The results showed that oil spillage and losses were possibly the main sources of TPH in soil. The consequences concluded here suggested that counter measures such as remediation and long-term monitoring should be commenced in the near future, and effective measures should be taken to assure that the oilfields area would not be a threat to human health.     

Effects of an oil spill on soil physico-chemical properties of a spill site in the Niger Delta Area of Nigeria

Physico-chemical analysis of soil samples at an oil spill site in the Niger Delta Area of Nigeria showed that the total hydrocarbon content of top soil layers ranged from 0.8 to 12.4 ppm in the heavy impact zone and the oil had penetrated to a depth of 7.2 m. Hydrocarbon concentration in the medium impact zone ranged from 0.02 to 0.40 ppm while hydrocarbons were not detected in 75% of samples from the unimpacted reference zone. Measurement of heavy metal concentrations in the soils revealed a significant build-up (p<0.05) of lead, iron and zinc in the heavy impact zone. Other parameters including electrical conductivity, exchangeable cations, available phosphorus and total nitrogen in impacted soils were comparatively low while the total organic carbon was high, compared with the reference site. Textural class of soil from the different depths showed a predominantly brown sand at the top soil, loamy sand at medium depths and grey coarse sand at greater depths.     

Effects of an Oil Spill on Soil Physico-Chemical Properties of a Spill Site in a Typic Udipsamment of the Niger Delta Basin of Nigeria

Physico-chemical analysis of soil samples at an oil spill site in a Typic Udipsamment of the Niger Delta Basin of Nigeria showed that the total hydrocarbon content of top soil layers ranged from 18.6 to 23.6 ppm in the heavy impact zone and the oil had penetrated to a depth op 8.4 m. The concentration of hydrocarbons in the medium impact zone ranged from 10.04 to 10.38 ppm while hydrocarbons were not detected in 85% of samples from the unimpacted reference zone. Heavy metal concentration measurements in the soil revealed a significant build-up (P < 0.05) of lead, copper and zinc in the heavy impact zone. Other quality parameters including electrical conductity, exchangeable cations, total nitrogen and available phosphorus in impacted soils were relatively low, while the total organic carbon was high compared with the reference site. Textural class of soil from the different depths showed a predominantly brown sand at the topsoil, loamy sand and grey coarse sand at medium depths, and grey coarse sand and greyish sandy clay at greater depths.     

EFFECTS OF AN OIL SPILL ON SOIL PHYSICO-CHEMICAL PROPERTIES OF A SPILL SITE IN A TYPIC PALEUDULT OF MIDWESTERN NIGERIA

Physico-chemical analysis of soil samples at an oil spill sitein a Typic Paleudult of midwestern Nigeria showed that thetotal hydrocarbon content of top soil layers ranged from 0.6to 12.6 ppm in the heavy impact zone and the oil hadpenetrated to a depth of 9.2 m. Hydrocarbon concentration inthe medium impact zone ranged from 0.36 ppm while hydrocarbonswere not detected in 80% of samples from the unimpactedreference zone. Measurement of heavy metal concentrations inthe soil revealed a significant build-up (p< 0.05) of lead,iron and zinc in the heavy impact zone. Other parametersincluding electrical conductivity, exchangeable cations,available phosphorus and total nitrogen in impacted soils werecomparatively low while the total organic carbon was high,compared with the reference site. Textural class of soil fromthe different depths showed a predominantly brown sand at thetopsoil, loamy sand and grey fine sand at medium depths andred sandy clay at greater depths.     

环境中总石油烃的气相色谱分析测定

将总石油烃划分为挥发性汽油类(C6～C10)、可萃取柴油和重油类(C10～C40)两部分,分别建立了通过吹扫捕集、液液萃取和超声溶剂萃取分离富集,气相色谱-火焰离子化检测器(GC-FID)测定环境水体和土壤中总石油烃的分析方法。以汽油、柴油、润滑油标准溶液进行外标校正,以色谱出峰总面积进行定量。汽油类(C6～C10)的检出限分别为0.04mg/L和0.42mg/kg,柴油和重油类(C10～C40)的检出限分别为0.06mg/L和4.9mg/kg。方法的精密度和准确度均良好。     

Environmental and Biological Assessment of Exposure to Benzene in Petroleum Workers

Occupational exposure to benzene was measured in two gasoline marketing terminals and five major refineries in Singapore. A total of 280 workers were monitored over two years. This assessment was carried out with two primary objectives: (1) To find out the extent of occupational exposure to benzene in the petroleum industry in Singapore, (2) To identify suitable biomarkers for monitoring of low levels of benzene exposure. The exposure was measured in five different categories of petroleum and petrochemical workers, i.e., truck drivers, despatch assistant, process operators, oil movements operators and laboratory technicians. The results revealed wide variations in exposure, from 0.01 to 13.6 ppm for personal time weighted average (TWA) exposure over the whole workshift. The exposure of truck drivers appeared to be the highest, with geometric mean (GM) of 1.98 ppm (ranged from 0.25 to 13.6 ppm). The average benzene exposure for process operators was relative low with a GM of 0.04 ppm. Lowest benzene exposure was found in the laboratory technicians, with a GM of 0.02 ppm. As cigarette smoking is known to affect metabolism of benzene, data analyses on the relationships with environmental exposure were conducted only on the 190 nonsmokers. The results showed that urinary trans, trans-muconic acid (ttMA), unmetabolized benzene in urine (UBZ) and benzene in blood (BBZ) were better biomarkers for low level benzene exposure as compared to urinary phenolic metabolites in urine, such as hydroquinone, phenol and catechol.     

Toxicity assessment for petroleum-contaminated soil using terrestrial invertebrates and plant bioassays

The assessment of soil quality after a chemical or oil spill and/or remediation effort may be measured by evaluating the toxicity of soil organisms. To enhance our understanding of the soil quality resulting from laboratory and oil field spill remediation, we assessed toxicity levels by using earthworms and springtails testing and plant growth experiments. Total petroleum hydrocarbons (TPH)-contaminated soil samples were collected from an oilfield in Sfax, Tunisia. Two types of bioassays were performed. The first assessed the toxicity of spiked crude oil (API gravity 32) in Organization for Economic Co-operation and Development artificial soil. The second evaluated the habitat function through the avoidance responses of earthworms and springtails and the ability of Avena sativa to grow in TPH-contaminated soils diluted with farmland soil. The EC₅₀ of petroleum-contaminated soil for earthworms was 644 mg of TPH/kg of soil at 14 days, with 67 % of the earthworms dying after 14 days when the TPH content reached 1,000 mg/kg. The average germination rate, calculated 8 days after sowing, varied between 64 and 74 % in low contaminated soils and less than 50 % in highly contaminated soils.     

Thermogenic hydrocarbons in seawater of the Gippsland Shelf,southeast Australia

An offshore survey measured the concentration of thermogenic hydrocarbons (THCs) in samples extracted from seawater at 718 locations along 22 traverse lines across the Gippsland Shelf, southeast Australia, and recorded compounds typical of subsurface crude oil and natural gas (petroleum) accumulations. Background concentrations of 8 ppm, with isolated peak levels of 20 to 52 ppm, were detected in samples extracted from seawater at depths of 30 to 50 m over distances of 10 km. Two sources have been suggested — seepage of THCs from subsurface accumulations of petroleum, or THCs in waste-water discharged by several offshore petroleum production facilities which are present on the shelf. A waste-water source is favoured because of the transitory nature of the concentrations, and changes in composition consistent with plume drift away from the point(s) of discharge. Overall, however, the concentration of THCs in waters of the Gippsland Shelf compare favourably with levels in waters affected by urban runoff. The concentration of THCs in other coastal waters from urban and onshore sources is low, equivalent to the background concentration in the major oceans of the world.     

An Assessment of the Effects of Crude Oil Pollution on Soil Properties, Germination and Growth of Maize (Zea Mays) using Two Crude Types – Forcados Light and Escravos Light

The effect of crude oil pollution on soil properties, germination and height of maize (Zea mays) was investigated under natural environment in three separate pot experiments. Two crude oil types--Forcados light and Escravos light were used. In Experiment 1, the effect of crude oil application on germination using high pollution levels of 5, 15, 25 and 40 mL kg(-1) of soil was assessed. In Experiment 2, the effect of crude oil application on maize plant height using the same pollution levels was assessed. The last experiment (Experiment 3) was used to test for the effects of crude oil application on maize plant height using lower levels of pollution (1.0, 1.5, 2.0 and 2.5 mL kg(-1) of soil). Soil samples were collected before, during and after the experiment and analyzed for some physical and chemical properties. Results obtained showed variation in chemical properties of soil. % organic matter increased from 1.34 to 2.62% in polluted soils. Available P decreased from 15.00 ppm in control to between 7.34 and 5.42 in soils polluted with 'high' levels of crude oil. Statistical analysis of height data showed that crude oil inhibited the growth of maize at high pollution levels. High levels of pollution also inhibited germination and for Escravos light there was no germination at 40 mL kg(-1) soil level of crude oil pollution.     

Risk assessment and remediation suggestion of impacted soil by produced water associated with oil production

Produced water is water trapped in underground formations that is brought to the surface along with oil or gas production. Oilfield impacted soil is the most common environmental problem associated with oil production. The produced water associated with oil-production contaminates the soil and causes the outright death of plants, and the subsequent erosion of topsoil. Also, impacted soil serves to contaminate surface waters and shallow aquifers. This paper is intended to provide an approach for full characterization of contaminated soil by produced water, by means of analysis of both the produced water and the impacted soil using several recommended analytical techniques and then identify and assay the main constituents that cause contamination of the soil. Gialo-59 oilfield (29N, 21E), Libya, has been chosen as the case study of this work. The field has a long history of petroleum production since 1959, where about 300,000 bbl of produced water be discharged into open pit. Test samples of contaminated soil were collected from one of the disposal pits. Samples of produced water were collected from different points throughout the oil production process, and the analyses were carried out at the labs of Libyan Petroleum Institute, Tripoli, Libya. The results are compared with the local environmental limiting constituents in order to prepare for a plan of soil remediation. The results showed that the main constituents (pollutants) that impact the soil are salts and hydrocarbon compounds. Accordingly; an action of soil remediation has been proposed to remove the salts and degradation of hydrocarbons.     

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.     

Excrement from Heron colonies for environmental assessment of toxic elements

Excrement cast from Great Blue Heron nests was collected during the nesting period of 1978 from four colonies in Washington and Idaho. Cheesecloth strips placed on the ground beneath the nests served as excrement collecting devices. Chemical analysis for lead, mercury and cadmium were performed on dried samples. Lead was the most abundant trace metal found in heron debris. The Idaho colony at Lake Chatcolet had an average concentration of 46 ppm in the beneath-nest samples and 6 ppm in control samples. A heron colony near Tacoma, Washington had beneath-nest samples averaging 28 ppm and control samples averaging 20 ppm. Two colonies located in the interior region of Washington had substantially lower concentrations of lead. The difference observed between colonies was attributed to their associations with a polluted watershed (Chatcolet colony) an interstate highway (Tacoma colony) and an unpopulated largely agricultural area (inland Washington).     

Screening of brick-kiln area soil for determination of heavy metal Pb using LIBS

Rapid measurement of heavy metals in soil is an important factor in modeling the effect of industrial pollution on agricultural soil. Conventional methods of heavy metal analysis are relatively slow in terms of measurement/analysis time and sample preparation time with the requirement of skilled manpower. Our results highlight the quantitative analysis of toxic metal lead (Pb), for the first time, in an Indian agricultural soil, in the vicinity of brick-kiln area, Phaphamau, near Allahabad, India, by using a novel technique named as Laser-induced breakdown spectroscopy (LIBS). LIBS spectra of soil has been recorded in the wavelength range from ultraviolet (UV) to infrared region (200-1,100 nm). The suitability of Pb lines for drawing the calibration curve is checked and realized, for the first time, that 220.3 nm, which is observed in the UV region of LIBS spectra, is completely interference free and best suited for the quantification of trace amount of Pb in soil instead of any other Pb lines, because it has best linear regression coefficient and smallest standard deviation of the background signal. In the present work the detection limit for Pb in soil is found to be 45 ppm. Based on the present work the concentration of Pb in agricultural soil of brick-kiln area in Phaphamau is found to be congruent with 570 ppm, which is more than the regulatory standards imposed by US Environmental Protection Agency (400 ppm) for the presence of lead in soil, therefore, it is of great concern to us.     

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.     

Remediation of hydrocarbons in crude oil-contaminated soils using Fenton’s reagent

Sandy soil samples spiked with Bonny light crude oil were subsequently treated with Fenton's reagent at acidic, neutral, and basic pH ranges. Oil extracts from these samples including an untreated one were analyzed 1?week later with a gas chromatograph to provide evidence of hydrocarbon depletion by the oxidant. The reduction of three broad hydrocarbon groups-total petroleum hydrocarbon (TPH); benzene, toluene, ethylbenzene, and xylene (BTEX); and polycyclic aromatic hydrocarbon (PAH) were investigated at various pHs. Hydrocarbon removal was efficient, with treatment at the acidic pH giving the highest removal of about 96% for PAH, 99% for BTEX, and some TPH components experiencing complete disappearance. The four-ringed PAHs were depleted more than their three-ringed counterparts at the studied pH ranges.     

Assessment of the impact of petroleum and petrochemical industries to the surrounding areas in Malaysia using mosses as bioindicator supported by multivariate analysis

Biomonitoring of multi-element atmospheric deposition using terrestrial moss is a well-established technique in Europe. Although the technique is widely known, there were very limited records of using this technique to study atmospheric air pollution in Malaysia. In this present study, the deposition of 11 trace metals surrounding the main petroleum refinery plant in Kerteh Terengganu (eastern part of peninsular Malaysia) has been evaluated using two local moss species, namely Hypnum plumaeforme and Taxithelium instratum as bioindicators. The study was also done by means of observing whether these metals are attributed to work related to oil exploration in this area. The moss samples have been collected at 30 sampling stations in the vicinity of the petrochemical industrial area covering up to 15 km to the south, north, and west in radius. The contents of heavy metal in moss samples were analyzed by energy dispersive x-ray fluorescence technique. Distribution of heavy metal content in all mosses is portrayed using Surfer software. Areas of the highest level of contaminations are highlighted. The results obtained using the principal components analysis revealed that the elements can be grouped into three different components that indirectly reflected three different sources namely anthropogenic factor, vegetation factor, and natural sources (soil dust or substrate) factor. Heavy metals deposited mostly in the distance after 9 km onward to the western part (the average direction of wind blow). V, Cr, Cu, and Hg are believed to have originated from local petrochemical-based industries operated around petroleum industrial area.     

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.     

The use of sensory perception indicators for improving the characterization and modelling of total petroleum hydrocarbon (TPH) grade in soils

This paper proposes a multistep approach for creating a 3D stochastic model of total petroleum hydrocarbon (TPH) grade in potentially polluted soils of a deactivated oil storage site by using chemical analysis results as primary or hard data and classes of sensory perception variables as secondary or soft data. First, the statistical relationship between the sensory perception variables (e.g. colour, odour and oil–water reaction) and TPH grade is analysed, after which the sensory perception variable exhibiting the highest correlation is selected (oil–water reaction in this case study). The probabilities of cells belonging to classes of oil–water reaction are then estimated for the entire soil volume using indicator kriging. Next, local histograms of TPH grade for each grid cell are computed, combining the probabilities of belonging to a specific sensory perception indicator class and conditional to the simulated values of TPH grade. Finally, simulated images of TPH grade are generated by using the P-field simulation algorithm, utilising the local histograms of TPH grade for each grid cell. The set of simulated TPH values allows several calculations to be performed, such as average values, local uncertainties and the probability of the TPH grade of the soil exceeding a specific threshold value.     

Optimization of extractants, purifying packings, and eluents for analytical extraction of organochlorine pesticides in Hydragric Acrisols

In this study, we screened for an economic, rapid, and efficient hypotoxic pretreatment method for organochlorine pesticides in soil samples for gas chromatography (GC) analysis. The analytical extraction efficiencies of 11 different extractants, nine types of solid-phase purification (SPP) cartridge packings, and three types of eluents for 13 organochlorine pesticides (OCPs) in spiked and natural Chinese red soil (Hydragric Acrisols) were evaluated using an ultrasonic extraction and solid-phase purification method. High percent recoveries (85-106%) were obtained for the 13 organochlorine pesticides in soil when petroleum ether/acetone/water (10:5:2, v/v) was used an extractant. They were purified using celite SPP cartridge packing and eluted with 9 mL of dichloromethane/petroleum ether (1:9, v/v). The OCPs purification pretreatment of Hydragric Acrisols, using the above method, meets the GC analysis requirements. Compared with other traditional pretreatment methods for OCPs in soil samples, this method has several advantages, such as a short extraction time, reducing the amount of solvent, having no emulsion phenomenon, and hypotoxicity to the laboratory technicians. The concentrations of 1,1,1,-trichloro-2(p-chlorophenyl)-2-(o-chlorophenyl) ethane (DDTs; 3.42-8.08 ng g(-1)) in field soils were higher than the hexachlorocyclohexane concentration (2.94-6.12 ng g(-1)). The 1,1-dichloro-2,2-bis(p-chlorophenyl) ethylene (p,p'-DDE)?+?1,1-dichloro-2,2-bis(p-chlorophenyl)-ethane (p,p'-DDD)/p,p'-DDT ratio in this field soil was approximately 2.7, suggesting that no new DDT pollution source was introduced into the sampling site.