Monitoring soil contaminations using a contactless conductivity probe1

In order to investigate the possibility of using low-frequency electromagnetic waves to detect and monitor oil contamination of soils, a series of laboratory measurements were performed. A new measurement system to monitor the resistivities of soil and sand samples while samples are being contaminated by diesel oil is presented. The frequency used in measurements is 100 kHz. Since the measurement system is composed of coil-type transmitters and receivers, there is no need for electrodes to be in contact with samples. The contamination process is simulated using diesel oil dripping on top of soil and sand samples. The conductivity distributions in samples along the sample length are recorded as a function of time. Water-wet sand and soil samples were measured during diesel oil contamination. The measured data show that the conductivities of soil and sand samples change during the contamination process. The change in resistivity for measured samples before and after diesel oil contamination is in the range of 20% to 50%, giving a reflection coefficient change in the low-frequency limit of 4.7% to 7%. This amount of change in the reflection coefficient makes it very challenging to detect and monitor oil contamination based on EM reflection from the contaminants. The results suggest that EM methods based on propagation and induction, such as tomography and borehole induction, could be used for this purpose.     

Evidence that bio-metallic mineral precipitation enhances the complex conductivity response at a hydrocarbon contaminated site

The complex conductivity signatures of a hydrocarbon contaminated site, undergoing biodegradation, near Bemidji, Minnesota were investigated. This site is characterized by a biogeochemical process where iron reduction is coupled with the oxidation of hydrocarbon contaminants. The biogeochemical transformations have resulted in precipitation of different bio-metallic iron mineral precipitates such as magnetite, ferroan calcite, and siderite. Our main objective was to elucidate the major factors controlling the complex conductivity response at the site. We acquired laboratory complex conductivity measurements along four cores retrieved from the site in the frequency range between 0.001 and 1000 Hz. Our results show the following: (1) in general higher imaginary conductivity was observed for samples from contaminated locations compared to samples from the uncontaminated location, (2) the imaginary conductivity for samples contaminated with residual and free phase hydrocarbon (smear zone) was higher compared to samples with dissolved phase hydrocarbon, (3) vadose zone samples located above locations with free phase hydrocarbon show higher imaginary conductivity magnitude compared to vadose zone samples from the dissolved phase and uncontaminated locations, (4) the real conductivity was generally elevated for samples from the contaminated locations, but not as diagnostic to the presence of contamination as the imaginary conductivity; (5) for most of the contaminated samples the imaginary conductivity data show a well-defined peak between 0.001 and 0.01 Hz, and (6) sample locations exhibiting higher imaginary conductivity are concomitant with locations having higher magnetic susceptibility. Controlled experiments indicate that variations in electrolytic conductivity and water content across the site are unlikely to fully account for the higher imaginary conductivity observed within the smear zone of contaminated locations. Instead, using magnetite as an example of the bio-metallic minerals in the contaminated location at the site, we observe a clear increase in the imaginary conductivity response with increasing magnetite content. The presence of bio-metallic mineral phases (e.g., magnetite) within the contaminated location associated with hydrocarbon biodegradation may explain the high imaginary conductivity response. Thus, we postulate that the precipitation of bio-metallic minerals at hydrocarbon contaminated sites impacts their complex conductivity signatures and should be considered in the interpretation of complex conductivity data from oil contaminated sites undergoing intrinsic bioremediation.     

Sources of inherent infiltration variability in postwildfire soils

An automated disc infiltrometer was developed to improve the measurements of soil hydraulic properties (saturated hydraulic conductivity and sorptivity) of soils affected by wildfire. Guidelines are given for interpreting curves showing cumulative infiltration as a function of time measured by the autodisc. The autodisc was used to measure the variability of these soil hydraulic properties in three different sample sets: (a) a reference soil consisting of a nonrepellent, uniform, fine sand; (b) soils with the same soil textural classification derived from the same bedrock geology but having different initial burn severities; and (c) soils from different bedrock geology but having the same burn severity. The autodisc infiltrometer had greater sampling rates and volume resolution when compared with the visual minidisc infiltrometer from previous studies. There was no statistical difference in the mean values measured using the autodisc and visual minidisc, but the variability of the autodisc measurements was significantly less than the visual minidisc for a given set of samples. The greatest variability of soil hydraulic properties in reference samples with uniform particle size was attributed to different pore geometries (coefficient of variation [COV] = 0.28–0.34). Unburned field samples (same soil type) with heterogeneous particle sizes had greater variability (COV = 0.57–0.78) than the reference samples. However, this basic variability decreased or remained constant in these field samples as burn severity increased. Additional sources of variability (COV = 0.53–1.99) were attributed to multiple layers resulting from ash or sediment deposition. Results indicate that resolving differences in soil hydraulic properties from different sites requires more than the common 10 random samples because of the multiple sources of variability.     

基于探地雷达回波信号获取污染土壤中污染物含量的研究进展

从探地雷达GPR(Ground Penetrating Radar)在土壤污染探测中的应用、污染土壤介电常数模型的演化和土壤介电常数求取三方面综述了目前国内外学者利用探地雷达技术开展的土壤污染探测研究.研究认为以土壤介电常数为纽带,采用适宜的方法从雷达回波信号求得介电常数,基于合理的土壤介电常数模型,通过神经网络技术,可驯化建立介电常数和污染土壤多个参数之间联系,从而实现污染土壤中多种污染物含量的监测.     

Estimation of clay content in soil based on resistivity modelling and laboratory measurements

The determination of clay content in near‐surface formations is crucial for geotechnical, hydrogeological and oil‐contamination studies. We have developed a technique for estimating clay content that consists of the minimization of the difference between the theoretically calculated and measured soil resistivities as a function of water salinity. To calculate the resistivity, we used a model that takes into account the electrochemical processes in the clay micropores. The experimental measurements of soil resistivity were performed on soil samples, completely saturated by brines at different concentrations of NaCl salt in the range 0.6–100 g/l, to obtain the resistivity versus salinity curve. The parameters obtained with this curve inversion are the clay content, the total porosity and the cation exchange capacity. To verify the new technique, we determined clay concentrations of artificial mixtures of calibrated sand and clay. The relative mean error in the clay content does not exceed 20% for a 5% fitting error of the resistivity versus salinity curves. Such evaluations allow the correct separation of the main lithological groups (sand, sandy loam, loam, and light, medium and heavy clay). We applied this technique to estimate the petrophysical parameters of soils (clay content, porosity and cation exchange capacity) at various sites in Mexico. The results improved the interpretation of the vertical electrical soundings, the lithological soil characterization and the delineation of oil‐contaminated areas.     

Laboratory technique for measurement of spectral induced polarization response of soil sampies1

Laboratory measurements of soil samples are necessary to assess the effect of mineralogy, grain size distribution, moisture content, and electrolyte composition on the resistivity spectrum of soil material. Laboratory results are also required for the interpretation of field data. Induced polarization phenomena in glacial soils are poorly understood and so far no convenient laboratory techniques are available for its measurement. Coarse grain size and the need to measure unsaturated samples and to monitor the homogeneity of the sample require a sample holder–electrode construction that differs from those presented in Clay mineral Studies. This study presents a spectral induced polarization laboratory system that is suitable for measuring fine- and coarse-grained and both saturated and unsaturated soil samples. The noise caused by the electrode–electrolyte interface is studied in detail. It is shown that easy-to-use platinum or acid-free steel potential electrodes are convenient over a broad frequency band ranging from 0.016Hz up to more than 1000 Hz. The laboratory experiments and comparisons between laboratory and field results also indicate that sampling and sample packing procedures have only a minor influence on the phase spectrum of glacial soils.     

A radiomagnetotelluric survey on an oil-contaminated area near the Brazi Refinery, Romania

Scalar radiomagnetotelluric measurements were carried out on a contaminated test area close to the Brazi Refinery in Romania in order to detect and to monitor a 1 m thick oil layer expected at 5 m depth. Radio transmitters broadcasting in a frequency range from 10 kHz to 300 kHz were selected to observe the apparent resistivity and the phase data associated with the E‐ and B‐polarizations. They were located parallel and perpendicular to the assumed strike direction of the contamination plume. The data were interpreted by a 2D inversion technique from which the conductivity structure of the area was derived. The 2D inversion models of all profiles on the contaminated area show a poor‐conductivity zone above the groundwater table which could be associated with the oil contamination. A first attempt was also made to monitor the contaminated layer: the radiomagnetotelluric measurements were repeated on the same profiles a year later, but this time in a dry period, not in a rainy one. The 2D inversion results of the measurements in the dry period indicate that the high‐resistivity layer moved closer to the surface. Additional reference measurements were then carried out on a non‐contaminated area situated at a distance from the refinery, in the opposite direction to the flow of the groundwater. These reference measurements were used for the derivation of the unperturbed geology and they were also compared with the measurements of the contaminated test area. There is a significant difference in the frequency dependences of the apparent resistivities of the reference and contaminated areas, which could indicate a contamination at shallow depth. The 2D inversion results show the increase of resistivity at a depth of about 5 m beneath the contaminated area where the oil contamination is expected according to the information from the boreholes.     

Organic Contamination of Ground Water at Gas Works Park, Seattle, Washington

Gas Works Park, in Seattle, Washington, is located on the site of a coal and oil gasification plant that ceased operation in 1956. During operation, many types of wastes, including coal, tar, and oil, accumulated on-site. The park soil is currently (1986) contaminated with compounds such as polynuclear aromatic hydrocarbons, volatile organic compounds, trace metals, and cyanide. Analyses of water samples from a network of observation wells in the park indicate that these compounds are also present in the ground water.
Polynuclear aromatic hydrocarbons and volatile organic compounds were identified in ground water samples in concentrations as large as 200 mg/L. Concentrations of organic compounds were largest where ground water was in contact with a non-aqueous phase liquid in the soil. Where no non-aqueous phase liquid was present, concentrations were much smaller, even if the ground water was in contact with contaminated soils. This condition is attributed to weathering processes in which soluble, low-molecular-weight organic compounds are preferentially dissolved from the non-aqueous phase liquid into the ground water. Where no non-aqueous phase liquid is present, only stained soils containing relatively insoluble, high-molecular-weight compounds remain. Concentrations of organic contaminants in the soils may still remain large.     

Magnetic signature of hydrocarbon-contaminated soils and sediments at the former oil field H?nigsen, Germany

Magnetic properties of hydrocarbon (HC) containing soils and sediments from two sites (Site A and B) of the former oil-field H?nigsen were analyzed in order to determine whether magnetic methods can be employed to delineate HC contamination of soils and sediments. Magnetic parameters such as magnetic susceptibility and induced isothermal remanent magnetizations, as well as soil and sediment properties such as pH, iron content and water content, HC content and most probable number counts of iron-metabolizing microorganisms were determined. The magnetic concentration-dependent parameters for HC contaminated samples were 25 times higher in soils from Site A than in sediment samples from Site B. However, at Site B the magnetic susceptibility was still four times higher in comparison to lithologically similar non-contaminated sediment samples from a third Site C. Newly formed magnetite containing mainly single domain particles was responsible for the magnetic enhancement, whereas superparamagnetic grains represented only a minor component. Site A had an acidic pH compared to neutral pH at Site B, and a higher crystalline and bioavailable total iron content. Nevertheless, Site B samples contained significant numbers of both iron(II)-oxidizing and iron(III)-reducing microorganisms indicating that microbial iron cycling might have taken place at this site and potentially played a role for iron mineral transformation, including magnetite (trans)formation. The content of total non-polar hydrocarbons (TNPH) at Site A was one order of magnitude higher than at Site B. Only at Site A magnetic susceptibility correlated well with TNPH. Our results demonstrate that HC contaminated samples had an enhanced magnetite content compared to non-contaminated soils and sediments. Therefore, magnetic methods may provide a quick and cost-effective way to assess HC contamination in soils and sediments. However, more field sites and laboratory investigations are needed to reveal the complex nature of the processes involved.     

Electrical properties and geochemistry of carbonate rocks from the Qasr El‐Sagha Formation,El‐Faiyum,Egypt

Understanding petrographical, geochemical and electrical properties of rocks is essential for investigating minerals. This paper presents a study of the petrographical, geochemical and A.C. electrical properties of carbonate rock samples. The samples collected show six lithostratigraphic rock units. Electrical properties were measured using a non‐polarizing electrode at room temperature (～20°C) and a relative atmospheric humidity of ～50% by weight in the frequency range from 42 Hz to 5 MHz. The difference in electrical properties between the samples was attributed to the change in composition and texture between the samples. Electrical properties generally change with many factors (grain size, chemical composition, grain shape and facies). The dielectric constant decreases with frequency and increases with conductor composition. The conductivity increases with the increase of conductor paths between electrodes. Many parameters can contribute to the same result of the electrical properties. The main objective of the present study is to shed more light on the relation between the texture and geochemical composition of measured samples (carbonates that contain clays and quartz grains) through electrical laboratory measurements (conductivity and dielectric constant as a function of frequency).     

Occurrence of MTBE in Heating Oil and Diesel Fuel in Connecticut

The objective of this study was to confirm if MTBE, which is not intentionally added to fuels other than gasoline, is a contaminant in heating oil and diesel fuel. The study entailed conducting a statewide sampling program of heating oil and diesel fuel in Connecticut. An analytical method was developed to conduct analyses of heating oil and diesel fuel for MTBE in the milligram per liter (mg/L) range. The method involved equilibrating product with water to extract MTBE followed by static head-space analysis on aliquots of the water. Analyses were conducted using a gas chromatograph with a MTBE specific column. The statewide sampling program confirmed the widespread occurrence of MTBE in heating oil and diesel fuel. MTBE was detected in all samples collected during our sampling program at concentrations ranging from 9.7 to 906 mg/L in heating oil (26 samples), and from 74 to 120 mg/L in diesel fuel (five samples). Based on these ranges. MTBE concentrations in ground water in the vicinity of heating oil and diesel fuel releases could exceed thousands of micrograms per liter. Our analysis would suggest that the levels of heating oil and diesel fuel contamination observed could result from the commingling of only a few parts gasoline with thousands of parts of these fuels. The extent to which MTBE occurs in heating oil and diesel fuel nationwide is not known, but our data suggests that it may be widespread.     

Microbial Degradation of Tar Oil Compounds under Different Redox Conditions

The microbial transformation of typical tar oil compounds such as acridine, benzo(b)thiophene, dibenzofuran, indane, and indene under different redox conditions was investigated in microcosm studies. Under aerobic conditions the inherent contamination in polluted soil as well as the added N‐, S‐, O‐ heterocyclic and homocyclic compounds were transformed predominantly apart from thiophene. 1‐Indanone was detected by RP‐HPLC‐DAD and GC‐MS as an intermediate metabolite from indane and indene. Under nitrate and sulfate reducing conditions indane, benzo(b)thiophene, and dibenzofuran were transformed in assays with the polluted soil samples from well B 65 and B 66 within 426 days, whereas they were persistent in assays with the highly polluted soil B 67. All heterocyclic and homocyclic compounds added to the non‐contaminated soil from well B 85 were not degraded under nitrate and sulfate reducing conditions, too. The results indicate that for the decision, wether natural attenuation can be implemented in the remediation of contaminated site, in addition to BTEX and PAHs especially the fate of further tar oil compounds in anoxic aquifers has to be considered.     

Saturation effect on electrical properties of hematitic sandstone in the audio frequency range using non-polarizing electrodes

This paper is devoted to study the effect of saturation, with distilled water, on AC electrical conductivity and dielectric constant of a fully and partially saturated hematitic sandstone sample (Aswan area, Egypt). The saturation of the sample was changed from full saturation to partial saturation by air drying. Complex resistivity measurements at room temperature (∼16° C) were performed in the frequency range from 10 Hz to 100 kHz. We used non-polarizing Cu/CuSO₄ gel electrodes. Experimental electrical spectra indicate, generally, that the electrical conductivity and dielectric constant vary strongly with water saturation and frequency. The low-frequency electrical conductivity and dielectric constant are supposed to be mainly controlled by surface conduction and polarization of the electrical double layer. Power law behaviours with frequency were noticed. The change in electrical conductivity and dielectric constant with increasing water content is fast at low saturations and slow at high saturations. The behaviour of the electrical conductivity and dielectric constant, with increasing water content, was argued to be the orientational polarization of bound water for very low saturations, displacement of the excess surface charges for relatively low saturations and free exchange of excess ions in double layer with the bulk electrolyte and generation of transient diffusional potentials, which lag behind the applied field for high saturations in addition to membrane polarization on clay and at inter-grain and grain surface water throats having selective charge transport properties. Also, from the data a semi-percolation behaviour was found that has a peak of dielectric constant at a certain concentration and an abrupt change in conductivity at another saturation.     

Field Application of the Combined Membrane‐Interface Probe and Hydraulic Profiling Tool (MiHpt)

The Membrane‐Interface Probe and Hydraulic Profiling Tool (MiHpt) is a direct push probe that includes both the membrane interface probe (MIP) and hydraulic profiling tool (HPT) sensors. These direct push logging tools were previously operated as separate logging systems for subsurface investigation in unconsolidated formations. By combining these two probes into one logging system the field operator obtains useful data about the distribution of both volatile organic contaminants (VOCs) and relative formation permeability in a single boring. MiHpt logging was conducted at a chlorinated VOC contaminated site in Skuldelev, Denmark, to evaluate performance of the system. Formation cores and discrete interval slug tests are used to assess use of the HPT and electrical conductivity (EC) logs for lithologic and hydrostratigraphic interpretation. Results of soil and groundwater sample analyses are compared to the adjacent MiHpt halogen specific detector (XSD) logs to evaluate performance of the system to define contaminant distribution and relative concentrations for the observed VOCs. Groundwater profile results at moderate to highly contaminated locations were found to correlate well with the MiHpt‐XSD detector responses. In general, soil sample results corresponded with detector responses. However, the analyses of saturated coarse‐grained soils at the site proved to be unreliable as demonstrated by high RPDs for duplicate samples. The authors believe that this is due to pore water drainage observed from these cores during sampling. Additionally, a cross section of HPT pressure and MiHpt‐XSD detector logs provides insight into local hydrostratigraphy and formation control on contaminant migration.     

不同土壤中含油污水污染区的电性变化研究及污染区探测

本文利用室内电阻率测试的方法研究了研究了饱和土和不饱和土两类土中含油污水的侵入量对其导电性的影响.测试结果表明,对于不饱和土,含油污水的侵入会改变土的饱和度从而引起其电阻率的降低,侵入量越大其电阻率越低;而饱和土的电阻率随含油污水侵入量的增大而增大直到趋于稳定.基于此,通过室内模拟土层污染和野外实地观测污染土层的方式研究了含油污水污染不同饱和度土层的电剖面异常特征,在不饱和土层中污染区域表现为相对低阻异常区而在饱和土层中表现为相对高阻异常区.通过对比不同时期的监测结果显示异常区的范围随污染区的变化而变化,并可反映出污染区的实际分布.文章分析了利用电阻率法进行含油污水污染地下介质调查的几个模糊点,对提高探测效果具有指导意义.     

Using neural networks for calibration of time-domain reflectometry measurements

Abstract

Time-domain reflectometry (TDR) is an electromagnetic technique for measurements of water and solute transport in soils. The relationship between the TDR-measured dielectric constant (K_a ) and bulk soil electrical conductivity ([sgrave]_a) to water content (θ_W) and solute concentration is difficult to describe physically due to the complex dielectric response of wet soil. This has led to the development of mostly empirical calibration models. In the present study, artificial neural networks (ANNs) are utilized for calculations of θ_w and soil solution electrical conductivity ([sgrave]_w) from TDR-measured K_a and [sgrave]_a in sand. The ANN model performance is compared to other existing models. The results show that the ANN performs consistently better than all other models, suggesting the suitability of ANNs for accurate TDR calibrations.     

Biodegradation of petroleum products in experimental plots in Antarctic marine sediments is location dependent

Clean sediment collected from O'Brien Bay, East Antarctica, was artificially contaminated with a mix of Special Antarctic Blend diesel fuel and lubricating oil and deployed in two uncontaminated locations (O'Brien and Sparkes Bays) and a previously contaminated bay (Brown Bay) to evaluate whether a history of prior contamination would influence the biodegradation process. Detailed analysis of the hydrocarbon composition in the sediment after 11 weeks revealed different patterns of degradation in each bay. Biodegradation indices showed that hydrocarbon biodegradation occurred in all three bays but was most extensive in Brown Bay. This study shows that even within a relatively small geographical area, the longevity of hydrocarbons in Antarctic marine sediments can be variable. Our results are consistent with faster natural attenuation of spilt oil at sites with previous exposure to oil but further work is needed to confirm this. Such information would be useful when evaluating the true risk and longevity of oils spills.     

Limitations of Monitoring Wells for the Detection and Quantification of Petroleum Products in Soils and Aquifers

Theoretical analysis and laboratory column experiments were carried out to investigate the conditions required for petroleum products (oil) to flow into a well installed through a sandy porous medium contaminated with the oil. The results indicated that oil would flow into a well only after a layer of "free oil" is formed in the adjacent porous medium. Because significant quantities of oil could be stored in the porous medium under the influence of capillary suction prior to the formation of the zone of free oil, the presence of oil in a well would indicate an advanced stage of oil contamination of the subsurface. While monitoring wells could be used to delineate the extent of the free-oil plume and the plume of dissolved petroleum constituents, they are not useful for delineating the extent of capillary held oil.
The experimental results also indicated that the ratio of the oil-layer thickness in the well to that in the porous medium is not a constant as is sometimes assumed in practice. Further, estimates of the oil thickness in the medium based on the oil thickness in wells and on capillary properties measured in the laboratory were sensitive to the values of the parameters used in these estimates. The measured thickness of the oil layer in a monitoring well alone may not yield reliable estimates of the amount of oil in the subsurface, and assuming that the oil-thickness ratio is a constant can lead to inadequate site assessments and inappropriate remedial plans.     

甚高频时岩石介电常数的测试方法和特性

本文讨论20-200MHz频率范围内平行板电容法测量岩石介电常数和电导率的方法,指出常用的静电场公式的局限性,给出较精确的似稳场动态公式,并讨论20-50MHz频率范围内的岩石介电特性。     

甚高频时岩石介电常数的测试方法和特性

本文讨论20—200MHz频率范围内平行板电容法测量岩石介电常数和电导率的方法,指出常用的静电场公式的局限性,给出较精确的似稳场动态公式,并讨论20—50MHz频率范围内的岩石介电特性。