Experimental investigation of wellbore integrity and CO2–brine flow along the casing–cement microannulus

Wellbore integrity is one of the key performance criteria in the geological storage of CO₂. It is significant in any proposed storage site but may be critical to the suitability of depleted oil and gas reservoirs that may have 10’s to 1000’s of abandoned wells. Much previous work has focused on Portland cement which is the primary material used to seal wellbore systems. This work has emphasized the potential dissolution of Portland cement. However, an increasing number of field studies (e.g., Carey et al., 2007), experimental studies (e.g., Kutchko et al., 2006) and theoretical considerations indicate that the most significant leakage mechanism is likely to be flow of CO₂ along the casing–cement microannulus, cement–cement fractures, or the cement–caprock interface.In this study, we investigate the casing–cement microannulus through core-flood experiments. The experiments were conducted on a synthetic wellbore system consisting of a 5-cm diameter sample of cement that was cured with an embedded rectangular length of steel casing that had grooves to accommodate fluid flow. The experiments were conducted at 40 $°$ C and 14 MPa pore pressure for 394 h. During the experiment, 6.2 l of a 50:50 mixture of supercritical CO₂ and 30,000 ppm NaCl-rich brine flowed through 10-cm of limestone before flowing through the 6-cm length cement–casing wellbore system. Approximately 59,000 pore volumes of fluid moved through the casing–cement grooves. Scanning electron microscopy revealed that the CO₂–brine mixture impacted both the casing and the cement. The Portland cement was carbonated to depths of 50–250 $\mu$m by a diffusion-dominated process. There was very little evidence for mass loss or erosion of the Portland cement. By contrast, the steel casing reacted to form abundant precipitates of mixed calcium and iron carbonate that lined the channels and in one case almost completely filled a channel. The depth of steel corroded was estimated at 25– $30\mu$m and was similar in value to results obtained with a simplified corrosion model.The experimental results were applied to field observations of carbonated wellbore cement by Carey et al. (2007) and Crow et al. (2009) to show that carbonation of the field samples was not accompanied by significant CO₂–brine flow at the casing–cement interface. The sensitivity of standard-grade steel casing to corrosion suggests that relatively straight-forward wireline logging of external casing corrosion could be used as a useful indicator of flow behind casing. These experiments also reinforce other studies that indicate rates of Portland cement deterioration are slow, even in the high-flux CO₂–brine experiments reported here.     

Aquatic leeches (Hirudinea) as bioindicators of organic chemical contaminants in freshwater ecosystems

Freshwater leeches from an industrially polluted creek were found to contain very high residues of chlorophenols, when compared with fish, tadpoles and most other benthic invertebrates. Leeches are recommended as possible bioindicators of aquatic organic contamination.     

WATER QUALITY IN THE PAWTUXET RIVER: METAL MONITORING AND GEOCHEMISTRY1

ABSTRACT: The Pawtuxet River flows from a relatively rural area through some of the more highly industrialized sections of Rhode Island. During its journey, the river receives many municipal, industrial, and ground water sources of metal constituents. The present report is the first in a two part series in which the water quality of this urban river was evaluated by a chemical monitoring study of the sources, transport mechanisms, and fate of cadmium, chromium, copper, lead, and nickel in the river. The second paper will use the chemical data to derive and calibrate a steady-state water quality model for this river. The metal concentrations In the river tended to increase from the headwaters to the mouth with river stations nearest to point source outfalls showing elevated values. In some sections of the river, levels of a few of the metals could not be explained by the point sources; and other inputs, including sediment resuspension, axe proposed to make up this apparent unbalance. The ability of a municipal secondary treatment plant to remove metals was demonstrated, and the tie-in of the effluent from a major chemical company to the plant did not cause any observable deterioration in treatment efficiency.     

夏季长三角地区臭氧非线性响应曲面模型的建立及应用

2013年8月上旬,长三角地区发生了一次大范围高浓度臭氧污染事件.本研究基于WRF-CMAQ空气质量模型系统,结合长三角地区大气污染物排放清单,构建了臭氧与其前体物之间的非线性响应曲面模型(Response surface modeling,RSM).基于RSM探讨了长三角地区O_3化学的敏感性特征,分析了上海市O_3的来源并预测不同情景下O_3的变化,提出O_3污染的最优控制方案.研究结果表明,长三角地区夏季O3主控因素区域差别较大,上海环科院、杭州卧龙桥、南京玄武湖等城区点位属于VOC控制型;徐州铜山、合肥肥西、丽水青田等郊区属于NOx控制型.O_3的敏感性特征在不同浓度水平下也呈现较大差异,随着O_3浓度水平的升高,各地区NOx敏感性均有所增加.从区域来源来看,远距离传输对平日上海O_3贡献较大,占50%以上;而在O_3污染日,本地及区域贡献为72.1%,而远距离传输贡献下降至27.9%.快速预测了110组减排情景,表明在本地及区域前体物均减排70%的情况下,2013年8月上海O_3浓度能完全达标.     

Trends in ambient concentrations of agrochemicals in humans and the environment of the United States

Uses of pesticides and related agrochemicals have been regulated in the United States since 1948. The United States government has supported human and environmental monitoring for pesticides and selected toxic chemicals for the past 15 yr. The initial ambient monitoring systems were designed to determine average concentrations of pesticides and related chemicals in human and environmental media on a nationwide basis and determine changes in these concentrations over time. The results of these surveys showed that almost all of the general human population and various environmental components contained low concentrations of chlorinated pesticides. As the Environmental Protection Agency (EPA) restricted many uses of the chlorinated pesticides, the organophosphorous and carbamate pesticides which replaced them were not as easily monitored by ambient surveys. Special monitoring studies had to be done more frequently to produce data on these compounds which were not as persistent or accumulative in the environment. Currently, a re-evalution has begun to determine pesticide monitoring data needs for the next 5 to 10 yr, modify existing ambient surveys, and plan needed short-term studies to efficiently meet regulatory data needs. Ambient monitoring for trends in chemical levels in humans and the environment will continue in the United States at a reduced level, and many exposure data needs will be met with use-specific monitoring studies.Presented at the International Conference on Environmental Hazards of Agrochemicals in Developing Countries, 8–12 November, 1983 in Alexandria, Egypt.     

Mechanisms of electron acceptor utilization: implications for simulating anaerobic biodegradation

Simulation of biodegradation reactions within a reactive transport framework requires information on mechanisms of terminal electron acceptor processes (TEAPs). In initial modeling efforts, TEAPs were approximated as occurring sequentially, with the highest energy-yielding electron acceptors (e.g. oxygen) consumed before those that yield less energy (e.g., sulfate). Within this framework in a steady state plume, sequential electron acceptor utilization would theoretically produce methane at an organic-rich source and Fe(II) further downgradient, resulting in a limited zone of Fe(II) and methane overlap. However, contaminant plumes often display much more extensive zones of overlapping Fe(II) and methane. The extensive overlap could be caused by several abiotic and biotic processes including vertical mixing of byproducts in long-screened monitoring wells, adsorption of Fe(II) onto aquifer solids, or microscale heterogeneity in Fe(III) concentrations. Alternatively, the overlap could be due to simultaneous utilization of terminal electron acceptors. Because biodegradation rates are controlled by TEAPs, evaluating the mechanisms of electron acceptor utilization is critical for improving prediction of contaminant mass losses due to biodegradation. Using BioRedox-MT3DMS, a three-dimensional, multi-species reactive transport code, we simulated the current configurations of a BTEX plume and TEAP zones at a petroleum-contaminated field site in Wisconsin. Simulation results suggest that BTEX mass loss due to biodegradation is greatest under oxygen-reducing conditions, with smaller but similar contributions to mass loss from biodegradation under Fe(III)-reducing, sulfate-reducing, and methanogenic conditions. Results of sensitivity calculations document that BTEX losses due to biodegradation are most sensitive to the age of the plume, while the shape of the BTEX plume is most sensitive to effective porosity and rate constants for biodegradation under Fe(III)-reducing and methanogenic conditions. Using this transport model, we had limited success in simulating overlap of redox products using reasonable ranges of parameters within a strictly sequential electron acceptor utilization framework. Simulation results indicate that overlap of redox products cannot be accurately simulated using the constructed model, suggesting either that Fe(III) reduction and methanogenesis are occurring simultaneously in the source area, or that heterogeneities in Fe(III) concentration and/or mineral type cause the observed overlap. Additional field, experimental, and modeling studies will be needed to address these questions.     

Prenatal diagnosis of zellweger's syndrome by chorionic villus sampling-and a caveat

At 7·5 weeks gestation, two small chorionic villous biopsies were obtained from a woman at risk for Zellweger's cerebro-hepato-renal syndrome, and were separately established in culture. After 3 weeks, dihydroxyacetone phosphate acyltransferase (DHAP-AT) activity was measured in both cultures. The enzyme was markedly deficient in one cell strain and this was subsequently shown to have a male karyotype. However, the second culture had normal enzyme activity and a female karyotype. The pregnancy was terminated at 11·5 weeks gestation, and follow-up studies on fetal tissues confirmed a male fetus with markedly deficient DHAP-AT activity.     

Application of an Adapted Version of MT3DMS for Modeling Back‐Diffusion Remediation Timeframes

Simulation of back‐diffusion remediation timeframe for thin silt/clay layers, or when contaminant degradation is occurring, typically requires the use of a numerical model. Given the centimeter‐scale vertical grid spacing required to represent diffusion‐dominated transport, simulation of back‐diffusion in a 3‐D model may be computationally prohibitive. Use of a local 1‐D model domain approach for simulating back‐diffusion is demonstrated to have advantages but is limited to only some applications. Incorporation of a local domain approach for simulating back‐diffusion in a new model, In Situ Remediation‐MT3DMS (ISR‐MT3DMS) is validated based on a benchmark with MT3DMS and comparisons with a highly discretized finite difference numerical model. The approach used to estimate the vertical hydrodynamic dispersion coefficient is shown to have a significant influence on the simulated flux into and out of silt/clay layers in early time periods. Previously documented back‐diffusion at a Florida site is modeled for the purpose of evaluating the sensitivity of the back‐diffusion controlled remediation timeframe to various site characteristics. A base case simulation with a clay lens having a thickness of 0.2 m and a length of 100 m indicates that even after 99.96 percent aqueous TCE removal from the clay lens, the down‐gradient concentrations still exceed the MCL in groundwater monitoring wells. This shows that partial mass reduction from a NAPL source zone via in situ treatment may have little benefit for the long‐term management of contaminated sites, given that back‐diffusion will sustain a groundwater plume for a long period of time. Back‐diffusion model input parameters that have the greatest influence on remediation timeframe and thus may warrant more attention during field investigations, include the thickness of silt/clay lenses, retardation coefficient representing sorbed mass in silt/clay, and the groundwater velocity in adjacent higher permeability zones. Therefore, pump‐and‐treat systems implemented for the purpose of providing containment may have an additional benefit of reducing back‐diffusion remediation timeframe due to enhanced transverse advective fluxes at the sand/clay interface. Remediation timeframes are also moderately sensitive to the length of the silt/clay layers and transverse vertical dispersivity, but are less sensitive to degradation rates within silt/clay, contaminant solubility, contact time, tortuosity coefficient, and monitoring well‐screen length for the scenarios examined. ©2015 Wiley Periodicals, Inc.     

Evaluating the longevity of a PFAS in situ colloidal activated carbon remedy

The remediation of per‐ and polyfluoroalkyl substances by injection of colloidal activated carbon (CAC) at a contaminated site in Central Canada was evaluated using various visualization and modeling methods. Radial diagrams were used to illustrate spatial and temporal trends in perfluoroalkyl acid (PFAA) concentrations, as well as various redox indicators. To assess the CAC adsorption capacity for perfluorooctane sulfonate (PFOS), laboratory Freundlich isotherms were derived for PFOS mixed with CAC in two solutions: (1) PFOS in a pH 7.5 synthetic water that was buffered by 1 millimolar NaHCO₃ (K_f = 142,800 mg^1‐a L^a/kg and a = 0.59); and (2) a groundwater sample (pH = 7.4) containing PFOS among other PFAS from a former fire‐training area in the United States (K_f = 4,900 mg^1‐a L^a/kg and a = 0.24). A mass balance approach was derived to facilitate the numerical modeling of mass redistribution after CAC injection, when mass transitions from a two‐phase system (aqueous and sorbed to organic matter) to a three‐phase system that also includes mass sorbed to CAC. An equilibrium mixing model of mass accumulation over time was developed using a finite‐difference solution and was verified by intermodel comparison for prediction of CAC longevity in the center of a source area. A three‐dimensional reactive transport model (ISR‐MT3DMS) was used to indicate that the CAC remedy implemented at the site is likely to be effective for PFOS remediation for decades. Model results are used to recommend remedial design and monitoring alternatives that account for the uncertainty in long‐term performance predictions.     

DNAPL Source Depletion: 2. Attainable Goals and Cost–Benefit Analyses

It is difficult to quantify the range in source strength reduction (MdR) that may be attainable from in situ remediation of a dense nonaqueous‐phase liquid (DNAPL) site given that available studies typically report only the median MdR without providing insights into site complexity, which is often a governing factor. An empirical study of the performance of in situ remediation at a wide range of DNAPL‐contaminated sites determined MdRs for in situ bioremediation (EISB), in situ chemical oxidation (ISCO), and thermal treatment remedies. Median MdR, geometric mean MdR, and lower/upper 95 percent confidence interval for the mean were: 49x, 105x, 20x/556x, respectively, for EISB; 9x, 21x, and 4x/110x for ISCO; and 19x, 31x, and 6x/150x for thermal treatment. Lower MdR values were determined for large, complex sites and for sites with DNAPL pool‐dominated source zones. A feasibility analysis of partial DNAPL depletion is described for a pool‐dominated source zone. Back‐diffusion from low‐hydraulic conductivity units within a pool‐dominated source zone is shown to potentially sustain a secondary source for more than 1,000 years, indicating that aggressive source treatment may not reduce the remediation timeframe. Estimated plume response demonstrates there may be no reduction in cost associated with aggressive treatment, and little difference in risk reduction associated with the various alternatives. Monitored natural attenuation (MNA) for the source zone is shown to be a reasonable alternative for the pool‐dominated source zone considered in this example. It is demonstrated that pool‐dominated source zones with a large range in initial DNAPL mass (250 to 1,500 kg) may correspond to a narrow range in source strength (20 to 30 kg/year). This demonstrates that measured source strength is nonunique with respect to DNAPL mass in the subsurface and, thus, source strength should not be used as the sole basis for predicting how much DNAPL mass remains or must be removed to achieve a target goal. If aggressive source zone treatment is to be implemented due to regulatory requirements, strategic pump‐and‐treat is shown to be most cost effective. These remedial decisions are shown to be insensitive to a range of possible DNAPL pool conditions. At sites with an existing pump‐and‐treat system, a significant increase in mass removal and source strength reduction may be achieved for a low incremental cost by strategic placement of extraction wells and pumping rate selection. © 2014 Wiley Periodicals, Inc.