Formation factor logging by electrical methods. Comparison of formation factor logs obtained in situ and in the laboratory

In this paper, a new in situ method for obtaining the formation factor, which is essential for the matrix diffusion, is described and tested in intrusive igneous rock. The method is based on electrical resistivity measurements in rock where the pore water and rock resistivities are essential parameters. The method is based on electromigration instead of diffusion as in traditional diffusion experiments. In previous works, quantitative formation factors of rock have been obtained by electrical methods in the laboratory. Here, a similar approach is used in situ. An in situ logging campaign was performed by SKB during 2000 in the 1700-m-deep borehole KLX02 in Laxemar, Sweden. The rock resistivity was measured with the slimhole Dual Laterolog from Antares. The groundwater resistivity was measured with the Difference Flow Meter from Posiva. A formation factor log was obtained with the maximum vertical resolution of 10 cm. In order to validate the log, 100 rock samples were taken from the bore core, and a formation factor log was obtained by using electrical methods in the laboratory. Both direct current (DC) and alternating current (AC) were used. The measurements on the core confirmed that the in situ log was quantitative, but with a possible systematic error. The in situ formation factors were on average about 1/3 to 1/5 of the laboratory formation factors, depending on depth.     

Anomalous transport of colloids and solutes in a shear zone

Transport experiments with colloids and radionuclides in a shear zone were conducted during the Colloid and Radionuclide Retardation experiment (CRR) at Nagra's Grimsel Test Site. Breakthrough curves of bentonite colloids and uranine, a non-sorbing solute, were measured in an asymmetric dipole flow field. The colloid breakthrough is earlier than that of uranine. Both breakthrough curves show anomalously long late time tails and the slope of the late time tails for the colloids is slightly higher. Anomalous late time tails are commonly associated with matrix diffusion processes; the diffusive interaction of solutes transported in open channels with the adjacent porous rock matrix or zones of stagnant water. The breakthrough curves for different colloid size classes are very similar and show no signs of fractionation due to their (size-dependent) diffusivity. It is proposed that tailing of the colloids is mainly caused by the structure of the flow field and that for the colloid transport, matrix diffusion is of minor importance. This has consequences for the interpretation of the uranine breakthrough. Comparisons of experimental results with numerical studies and with the evaluation of the colloid breakthrough with continuous time random theory imply that the tailing in the conservative solute breakthrough in this shear zone is not only caused by matrix diffusion. Part of the tailing can be attributed to advective transport in fracture networks and advection in low velocity regions. Models based on the advection-dispersion equation and matrix diffusion do not properly describe the temporal and spatial evolution of colloid and solute transport in such systems with a consistent set of parameters.     

淄博孝妇河流域孔隙水流酸盐污染特征及其形成

分析１９８９～１９９６年孔隙水的化学资料,总结出了研究区孔隙水硫酸盐污染的特点,借助原状土柱试验探明,孔隙水中污染组分来源于农业灌溉污水。农灌的频率与强度及大气降水的特点共同决定了本区孔隙水污染特征的形成。因此,停止或减少污灌量是改善地下水环境的有效且经济的方法。     

Matrix diffusion coefficients in volcanic rocks at the Nevada test site: influence of matrix porosity, matrix permeability, and fracture coating minerals

Diffusion cell experiments were conducted to measure nonsorbing solute matrix diffusion coefficients in forty-seven different volcanic rock matrix samples from eight different locations (with multiple depth intervals represented at several locations) at the Nevada Test Site. The solutes used in the experiments included bromide, iodide, pentafluorobenzoate (PFBA), and tritiated water ((3)HHO). The porosity and saturated permeability of most of the diffusion cell samples were measured to evaluate the correlation of these two variables with tracer matrix diffusion coefficients divided by the free-water diffusion coefficient (D(m)/D*). To investigate the influence of fracture coating minerals on matrix diffusion, ten of the diffusion cells represented paired samples from the same depth interval in which one sample contained a fracture surface with mineral coatings and the other sample consisted of only pure matrix. The log of (D(m)/D*) was found to be positively correlated with both the matrix porosity and the log of matrix permeability. A multiple linear regression analysis indicated that both parameters contributed significantly to the regression at the 95% confidence level. However, the log of the matrix diffusion coefficient was more highly-correlated with the log of matrix permeability than with matrix porosity, which suggests that matrix diffusion coefficients, like matrix permeabilities, have a greater dependence on the interconnectedness of matrix porosity than on the matrix porosity itself. The regression equation for the volcanic rocks was found to provide satisfactory predictions of log(D(m)/D*) for other types of rocks with similar ranges of matrix porosity and permeability as the volcanic rocks, but it did a poorer job predicting log(D(m)/D*) for rocks with lower porosities and/or permeabilities. The presence of mineral coatings on fracture walls did not appear to have a significant effect on matrix diffusion in the ten paired diffusion cell experiments.     

Solute transport in crystalline rocks at Äspö — I: Geological basis and model calibration

Water-conducting faults and fractures were studied in the granite-hosted Äspö Hard Rock Laboratory (SE Sweden). On a scale of decametres and larger, steeply dipping faults dominate and contain a variety of different fault rocks (mylonites, cataclasites, fault gouges). On a smaller scale, somewhat less regular fracture patterns were found. Conceptual models of the fault and fracture geometries and of the properties of rock types adjacent to fractures were derived and used as input for the modelling of in situ dipole tracer tests that were conducted in the framework of the Tracer Retention Understanding Experiment (TRUE-1) on a scale of metres. After the identification of all relevant transport and retardation processes, blind predictions of the breakthroughs of conservative to moderately sorbing tracers were calculated and then compared with the experimental data. This paper provides the geological basis and model calibration, while the predictive and inverse modelling work is the topic of the companion paper [J. Contam. Hydrol. 61 (2003) 175].The TRUE-1 experimental volume is highly fractured and contains the same types of fault rocks and alterations as on the decametric scale. The experimental flow field was modelled on the basis of a 2D-streamtube formalism with an underlying homogeneous and isotropic transmissivity field. Tracer transport was modelled using the dual porosity medium approach, which is linked to the flow model by the flow porosity. Given the substantial pumping rates in the extraction borehole, the transport domain has a maximum width of a few centimetres only. It is concluded that both the uncertainty with regard to the length of individual fractures and the detailed geometry of the network along the flowpath between injection and extraction boreholes are not critical because flow is largely one-dimensional, whether through a single fracture or a network. Process identification and model calibration were based on a single uranine breakthrough (test PDT3), which clearly showed that matrix diffusion had to be included in the model even over the short experimental time scales, evidenced by a characteristic shape of the trailing edge of the breakthrough curve. Using the geological information and therefore considering limited matrix diffusion into a thin fault gouge horizon resulted in a good fit to the experiment. On the other hand, fresh granite was found not to interact noticeably with the tracers over the time scales of the experiments.While fracture-filling gouge materials are very efficient in retarding tracers over short periods of time (hours–days), their volume is very small and, with time progressing, retardation will be dominated by altered wall rock and, finally, by fresh granite. In such rocks, both porosity (and therefore the effective diffusion coefficient) and sorption K_ds are more than one order of magnitude smaller compared to fault gouge, thus indicating that long-term retardation is expected to occur but to be less pronounced.     

The effect of a biofilm on solute diffusion in fractured porous media

At sites in fractured rock where contamination has been exposed to the rock matrix for extended periods of time, the amount of contaminant mass residing in the matrix can be considerable. Even though it may be possible to diminish concentrations by the advection of clean water through the fracture features, back diffusion from mass held in the matrix will lead to a continuing source of contamination. In such an event, the development of a biofilm (a thin film of microbial mass) on the wall of the fractures may act to limit or prevent the back diffusion process. The objective of this preliminary study is to explore the influence imparted by the presence of a biofilm on the process of matrix diffusion. The investigation was conducted using radial diffusion cells constructed from rock core in which biofilm growth was stimulated in a central reservoir. Once biofilms were developed, forward diffusion experiments were conducted in which a conservative solute migrated from the central reservoir into the intact rock sample. Diffusion experiments were performed in a total of 11 diffusion cell pairs where biofilm growth was stimulated in one member of the pair and inhibited in the other. The effect of the presence of a biofilm on tracer diffusion was determined by comparison of the diffusion curves produced by each cell pair. A semi-analytical model that accounts for the presence of a biofilm was used to investigate the effect of the biofilm on mass transfer due to changes in the effective porosity, effective diffusion coefficient, and the depth of penetration of the biofilm into the intact rock. The results show that the biofilm acted to plug the rock matrix, rather than forming a discrete layer on the reservoir surface. The reduction in effective porosity due to the biofilm ranged from 6% to 52% with the majority of the samples in the 30% to 50% range. Based on the present results, with more efficient biofilm stimulation, it is reasonable to assume that a more complete plugging of the microcrack porosity might be possible, leaving a much thicker and efficient barrier than could be achieved via a surface biofilm.     

Dissolved organic matter in pore water of freshwater sediments: effects of separation procedure on quantity, quality and functionality

Pore water was separated either with or without water extraction prior to centrifugation (7600 or 20 000 × g) in order to investigate the effects of separation procedure on the amount and properties of dissolved organic matter (DOM i.e. the material passing through a 0.45-μm filter) in three freshwater sediments. On the basis of solubility in alkaline, organic matter was concluded to compose of humic substances in two (S1 and S3) and of humin (S2) in one of the sediments. DOM in the samples was quantified by total organic carbon measurement. Specific UV-absorption (SUVA) and high performance size exclusion chromatography (HPSEC) analyses were used to characterize DOM. Sorption of pyrene was used as a measure for functionality of DOM. Both water extraction and centrifugation speed were shown to affect the properties of DOM; however, the effects were sediment dependent. Water extraction increased the amount of DOM separated from the two sediments that had humic character (S1 and S3). In most cases water extraction increased SUVA and shifted the molecular size distribution of DOM towards larger sizes. The separation procedure had also an effect on the functionality of DOM. In water extracted samples of S2 and S3 the sorption of pyrene was higher than in the corresponding samples separated without water extraction, whereas in S1 similar effect was not found. Generally, centrifugation speed had smaller effects on the properties of DOM than water extraction. The fact that the effects of separation procedure on DOM depend on the sediment characteristics complicates the comparison between samples and evaluation of functionality in field conditions.     

Interpretation of injection-withdrawal tracer experiments conducted between two wells in a large single fracture

Tracer experiments conducted using a flow field established by injecting water into one borehole and withdrawing water from another are often used to establish connections and investigate dispersion in fractured rock. As a result of uncertainty in the uniqueness of existing models used for interpretation, this method has not been widely used to investigate more general transport processes including matrix diffusion or advective solute exchange between mobile and immobile zones of fluid. To explore the utility of the injection-withdrawal method as a general investigative tool and with the intent to resolve the transport processes in a discrete fracture, two tracer experiments were conducted using the injection-withdrawal configuration. The experiments were conducted in a fracture which has a large aperture (>500 microm) and horizontally pervades a dolostone formation. One experiment was conducted in the direction of the hydraulic gradient and the other in the direction opposite to the natural gradient. Two tracers having significantly different values of the free-water diffusion coefficient were used. To interpret the experiments, a hybrid numerical-analytical model was developed which accounts for the arcuate shape of the flow field, advection-dispersion in the fracture, diffusion into the matrix adjacent to the fracture, and the presence of natural flow in the fracture. The model was verified by comparison to a fully analytical solution and to a well-known finite-element model. Interpretation of the tracer experiments showed that when only one tracer, advection-dispersion, and matrix diffusion are considered, non-unique results were obtained. However, by using multiple tracers and by accounting for the presence of natural flow in the fracture, unique interpretations were obtained in which a single value of matrix porosity was estimated from the results of both experiments. The estimate of porosity agrees well with independent measurements of porosity obtained from core samples. This suggests that: (i) the injection-withdrawal method is a viable tool for the investigation of general transport processes provided all relevant experimental conditions are considered and multiple conservative tracers are used; and (ii) for the conditions of the experiments conducted in this study, the dominant mechanism for exchange of solute between the fracture and surrounding medium is matrix diffusion.     

Obtaining the porewater composition of a clay rock by modeling the in- and out-diffusion of anions and cations from an in-situ experiment

A borehole in the Callovo–Oxfordian clay rock in ANDRA's underground research facility was sampled during 1 year and chemically analyzed. Diffusion between porewater and the borehole solution resulted in concentration changes which were modeled with PHREEQC's multicomponent diffusion module. In the model, the clay rock's pore space is divided in free porewater (electrically neutral) and diffuse double layer water (devoid of anions). Diffusion is calculated separately for the two domains, and individually for all the solute species while a zero-charge flux is maintained. We explain how the finite difference formulas for radial diffusion can be translated into mixing factors for solutions. Operator splitting is used to calculate advective flow and chemical reactions such as ion exchange and calcite dissolution and precipitation. The ion exchange reaction is formulated in the form of surface complexation, which allows distributing charge over the fixed sites and the diffuse double layer. The charge distribution affects pH when calcite dissolves, and modeling of the experimental data shows that about 7% of the cation exchange capacity resides in the diffuse double layer. The model calculates the observed concentration changes very well and provides an estimate of the pristine porewater composition in the clay rock.     

Ultraviolet degradation of methyltins: elucidating the mechanism by identification of a detected new intermediary product and investigating the kinetics at various environmental conditions

The photodegradation of methyltins, as environmental pollutants, has scarcely been studied so far because of the shortage of rapid and sensitive speciation methods, even though they have very simple structures. The photodegradation of monomethyltin trichloride (MMT), dimethyltin dichloride (DMT) and trimethyltin chloride (TMT) was studied with our new developed HPLC-FPD hyphenated system, which enables rapid and sensitive detection of methyltins. The half-life times and kinetic rate constants of their degradation at different pH were calculated. The results suggest that MMT, DMT and TMT can be degraded under the UV irradiation rapidly at different pH, with a degradation rate sequence of TMT相似文献   

Influencing factors of carbon emissions and their trends in China and India: a machine learning method

China and India are the largest coal consumers and the most populated countries in the world. With industrial and population growth, the need for energy has increased, which has inevitably led to an increase in carbon dioxide (CO₂) emissions because both countries depend on fossil fuel consumption. This paper investigates the impact of energy consumption, financial development (FD), gross domestic product (GDP), population, and renewable energy on CO₂ emissions. The study applies the long short-term memory (LSTM) method, a novel machine learning (ML) approach, to examine which influencing driver has the greatest and smallest impact on CO₂ emissions; correspondingly, this study builds a model for CO₂ emission reduction. Data collected between 1990 and 2014 were analyzed, and the results indicated that energy consumption had the greatest effect and renewable energy had the smallest impact on CO₂ emissions in both countries. Subsequently, we increased the renewable energy coefficient by one and decreased the energy consumption coefficient by one while keeping all other factors constant, and the results predicted with the LSTM model confirmed the significant reduction in CO₂ emissions. Finally, this study forecasted a CO₂ emission trend, with a slowdown predicted in China by 2022; however, CO₂ emission’s reduction is not possible in India until 2023. These results suggest that shifting from nonrenewable to renewable sources and lowering coal consumption can reduce CO₂ emissions without harming economic development.

     

The effects of scale and spatial heterogeneities on diffusion in volcanic breccias and basalts: Amchitka Island, Alaska

Knowledge of the factors that influence the diffusion of contaminants, such as the diffusivity and the connected porosity, is crucial to modeling the long-term fate and transport of contaminants in subsurface systems with small or negligible advective flow, such as in fractured crystalline rock. Fractured rock is naturally heterogeneous, and hence, understanding the diffusivity of a molecule through this material (or the formation factor of the medium) becomes a complex problem, with critical concerns about the scale of laboratory measurements and about the spatial variability of these measurements relative to the scale needed for fate and transport modeling. This study employed both electrical and tracer-based laboratory methods to investigate the effects of scale and pore system connectivity on the diffusivity for volcanic matrix rock derived from the study site, a former underground nuclear test site at Amchitka Island, Alaska. The results of these investigations indicate a relatively well-connected pore system with scale effects generally limited to approximately 6 cm lengths and well-correlated to observed heterogeneous features. An important conclusion resulting from this study, however, is that there is a potential for the estimated diffusivity to be misrepresented by an order of magnitude if multiple samples or longer sample lengths are not used. Given the relatively large number of measurements resulting from these investigations, an analysis of the probability density function (PDF) of the diffusivity was possible. The PDF of the diffusivity was shown to generally follow a normal distribution for individual geologic layers. However, when all of the geologic layers are considered together, the distribution of the subsurface as a whole was shown to follow a lognormal distribution due to the order of magnitude differences amongst the layers. An understanding of these distributions is essential for future stochastic modeling efforts.     

Laboratory longitudinal diffusion tests: 1. Dimensionless formulations and validity of simplified solutions

To obtain reliable diffusion parameters for diffusion testing, multiple experiments should not only be cross-checked but the internal consistency of each experiment should also be verified. In the through- and in-diffusion tests with solution reservoirs, test interpretation of different phases often makes use of simplified analytical solutions. This study explores the feasibility of steady, quasi-steady, equilibrium and transient-state analyses using simplified analytical solutions with respect to (i) valid conditions for each analytical solution, (ii) potential error, and (iii) experimental time. For increased generality, a series of numerical analyses are performed using unified dimensionless parameters and the results are all related to dimensionless reservoir volume (DRV) which includes only the sorptive parameter as an unknown. This means the above factors can be investigated on the basis of the sorption properties of the testing material and/or tracer. The main findings are that steady, quasi-steady and equilibrium-state analyses are applicable when the tracer is not highly sorptive. However, quasi-steady and equilibrium-state analyses become inefficient or impractical compared to steady state analysis when the tracer is non-sorbing and material porosity is significantly low. Systematic and comprehensive reformulation of analytical models enables the comparison of experimental times between different test methods. The applicability and potential error of each test interpretation can also be studied. These can be applied in designing, performing, and interpreting diffusion experiments by deducing DRV from the available information for the target material and tracer, combined with the results of this study.     

Influencing factors and improvement paths of green water use efficiency in the Yellow River Basin: a new perspective based on ecogeographical divisions

Environmental Science and Pollution Research - Exploring the influencing factors and improvement paths of green water use efficiency (GWUE) based on different regions is very important for the...     

Analysis of PCDD/Fs and dioxin-like PCBs in atmospheric deposition samples from the Flemish measurement network: Optimization and validation of a new CALUX bioassay method

Since the CALUX (Chemically Activated LUciferase gene eXpression) bioassay is a fast, sensitive and inexpensive tool for the analysis of a high number of samples, validation of new methods is urgently needed. In this study, a new method for the analysis of PCDD/Fs and dioxin-like PCBs in atmospheric deposition samples with the CALUX bioassay was developed, optimized and validated. The method consists of 4 steps: filtration, extraction, clean up and bioassay analysis. To avoid the use of large amounts of toxic solvents, new techniques were used for filtration and extraction: a C18 filter was used instead of a liquid/liquid extraction and an Accelerated Solvent Extractor (ASE) was used instead of the traditional soxhlet extraction. After pre-oxidation of the sample extract, clean up was done using a multi-layer silica gel column coupled to a carbon column. The PCDD/F and PCB fractions were finally analyzed with the H1L7.5c1 and/or the H1L6.1c3 mouse hepatoma cell lines. The limit of quantification was 1.4 pg CALUX-BEQ m⁻² d⁻¹ for the PCBs and 5.6 pg CALUX-BEQ m⁻² d⁻¹ for the PCDD/Fs, when using the new sensitive H1L7.5c1 cell line. The GC-HRMS recovery for all PCDD/F congeners was between 55% and 112%, with a mean recovery of 90%. CALUX recoveries of spiked procedural blanks were between the accepted ranges of 80-120%. Repeatability and reproducibility were satisfactory and no interferences from metals were detected. The first results from the Flemish measurement program showed good correlation between CALUX and GC-HRMS.     

Dioxin concentration in human milk in Hebei province in China and Tokyo, Japan: potential dietary risk factors and determination of possible sources

Very limited information is available on body burdens and environmental levels of dioxins and dioxin-like PCBs (dl-PCBs) in mainland China. In the current studies, human milk samples were collected from 30 breastfeeding mothers in Shijiazhuang city (industrialized) and 11 in the Tanshan countryside (agricultural) of Hebei Province in northern China. An additional 20 samples were obtained from mothers in Tokyo, Japan. PCDDs, PCDFs, and dl-PCBs in human milk were analyzed by high-resolution gas chromatography/high-resolution mass spectrometry. Our results show that arithmetic means for body burdens of PCDDs/Fs and dl-PCBs in Hebei were 3.6 and 1.9 pg TEQ g⁻¹ fat, respectively, which were only about one fourth of the levels in Japan. In addition, no difference was found in the chemical levels except dl-PCBs between the urban and rural areas. Based on the results of an in-person interview of the Chinese mothers using a 59-item questionnaire, freshwater fish consumption was found to correlate with the body burden of dioxins. Principal component analysis of dioxin congeners revealed that the patterns of dioxins in the Hebei urban and rural areas are quite similar; however, they are clearly different from those in Japan. Collectively, our results suggest that the lower body burdens of dioxin in Hebei may be due in part to the relatively slow industrialization and a lower consumption of marine foods. Finally, the results indicate that comprehensive monitoring of dioxins and dl-PCBs in humans as well as in the environment and foods is necessary in China.     

Responses of wild small mammals to a pollution gradient: Host factors influence metal and metallothionein levels

We investigated how host factors (species, age, gender) modulated Cd, Pb, Zn, and Cu concentrations, metallothionein levels (MTs) and their relationships in 7 sympatric small mammal species along a pollution gradient. Cd concentrations in liver and kidneys increased with age in all species. Age effect on other metals and MTs differs among species. Gender did not influence metal and MT levels except in the bank vole. Three patterns linking internal metal concentrations and MTs were observed along the gradient: a low metal accumulation with a (i) high (wood mouse) or (ii) low (bank vole) level of MTs accompanied by a slight or no increase of MTs with Cd accumulation; (iii) an elevated metal accumulation with a sharp increase of MTs (common and pygmy shrews). In risk assessment and biomonitoring perspectives, we conclude that measurements of MTs and metals might be associated because they cannot be interpreted properly when considered separately.     

Large outdoor chamber experiments and computer simulations: (I) Secondary organic aerosol formation from the oxidation of a mixture of d-limonene and α-pinene

This work merges kinetic models for α-pinene and d-limonene which were individually developed to predict secondary organic aerosol (SOA) formation from these compounds. Three major changes in the d-limonene and α-pinene combined mechanism were made. First, radical–radical reactions were integrated so that radicals formed from both individual mechanisms all reacted with each other. Second, all SOA model species from both compounds were used to calculate semi-volatile partitioning for new semi-volatiles formed in the gas phase. Third particle phase reactions for particle phase α-pinene and d-limonene aldehydes, carboxylic acids, etc. were integrated. Experiments with mixtures of α-pinene and d-limonene, nitric oxide (NO), nitrogen dioxide (NO₂), and diurnal natural sunlight were carried out in a dual 270 m³ outdoor Teflon film chamber located in Pittsboro, NC. The model closely simulated the behavior and timing for α-pinene, d-limonene, NO, NO₂, O₃ and SOA. Model sensitivities were tested with respect to effects of d-limonene/α-pinene ratios, initial hydrocarbon to NO_x (HC₀/NO_x) ratios, temperature, and light intensity. The results showed that SOA yield (Y_SOA) was very sensitive to initial d-limonene/α-pinene ratio and temperature. The model was also used to simulate remote atmospheric SOA conditions that hypothetically could result from diurnal emissions of α-pinene, d-limonene and NO_x. We observed that the volatility of the simulated SOA material on the aging aerosol decreased with time, and this was consistent with chamber observations. Of additional importance was that our simulation did not show a loss of SOA during the daytime and this was consistent with observed measurements.     

Influence of environmental factors on the response of a natural population of Daphnia magna (Crustacea: Cladocera) to spinosad and Bacillus thuringiensis israelensis in Mediterranean coastal wetlands

The present study was undertaken to assess the impact of a candidate mosquito larvicide, spinosad (8, 17 and 33 μg L⁻¹) on a field population of Daphnia magna under natural variations of water temperature and salinity, using Bti (0.16 and 0.50 μL L⁻¹) as the reference larvicide. Microcosms (125 L) were placed in a shallow temporary marsh where D. magna was naturally present. The peak of salinity observed during the 21-day observation period may have been partly responsible for the decrease of daphnid population density in all the microcosms. It is also probably responsible for the absence of recovery in the microcosms treated with spinosad which caused a sharp decrease of D. magna abundance within the first two days following treatment whereas Bti had no effect. These results suggest that it may be difficult for a field population of daphnids to cope simultaneously with natural (water salinity and temperature) and anthropogenic (larvicides) stressors.