Demonstration of combined zero-valent iron and electrical resistance heating for in situ trichloroethene remediation.

The effectiveness of in situ treatment using zero-valent iron (ZVI) for nonaqueous phase or significant sediment-associated contaminant mass can be limited by relatively low rates of mass transfer to bring contaminants in contact with the reactive media. For a field test in a trichloroethene (TCE) source area, combining moderate-temperature subsurface electrical resistance heating with in situ ZVI treatment was shown to accelerate TCE treatment by a factor of about 4 based on organic daughter products and a factor about 8 based on chloride concentrations. A mass-discharge-based analysis was used to evaluate reaction, dissolution, and volatilization processes at ambient groundwater temperature (~10 °C) and as temperature was increased up to about 50 °C. Increased reaction and contaminant dissolution were observed with increased temperature, but vapor- or aqueous-phase migration of TCE out of the treatment zone was minimal during the test because reactions maintained low aqueous-phase TCE concentrations.

Mass-removal and mass-flux-reduction behavior for idealized source zones with hydraulically poorly-accessible immiscible liquid.

A series of flow-cell experiments was conducted to investigate aqueous dissolution and mass-removal behavior for systems wherein immiscible liquid was non-uniformly distributed in physically heterogeneous source zones. The study focused specifically on characterizing the relationship between mass flux reduction and mass removal for systems for which immiscible liquid is poorly accessible to flowing water. Two idealized scenarios were examined, one wherein immiscible liquid at residual saturation exists within a lower-permeability unit residing in a higher-permeability matrix, and one wherein immiscible liquid at higher saturation (a pool) exists within a higher-permeability unit adjacent to a lower-permeability unit. The results showed that significant reductions in mass flux occurred at relatively moderate mass-removal fractions for all systems. Conversely, minimal mass flux reduction occurred until a relatively large fraction of mass (>80%) was removed for the control experiment, which was designed to exhibit ideal mass removal. In general, mass flux reduction was observed to follow an approximately one-to-one relationship with mass removal. Two methods for estimating mass-flux-reduction/mass-removal behavior, one based on system-indicator parameters (ganglia-to-pool ratio) and the other a simple mass-removal function, were used to evaluate the measured data. The results of this study illustrate the impact of poorly accessible immiscible liquid on mass-removal and mass-flux processes, and the difficulties posed for estimating mass-flux-reduction/mass-removal behavior.

Enhanced remedial amendment delivery through fluid viscosity modifications: experiments and numerical simulations.

Low-permeability zones are typically bypassed when remedial fluids are injected into subsurface heterogeneous aquifer systems. Therefore, contaminants in the bypassed areas may not be contacted by the amendments in the remedial fluid, which may significantly prolong remediation operations. Laboratory experiments and numerical studies have been conducted to investigate the use of a shear-thinning polymer (Xanthan gum) to improve access to low-permeability zones in heterogeneous systems. The chemicals sodium mono-phosphate and the surfactant MA-80 were used as the remedial amendments. The impact of polymer concentration, fluid injection rate, and permeability contrast in the heterogeneous systems has been studied in a series of eleven two-dimensional flow cell experiments. The Subsurface Transport over Multiple Phases (STOMP) simulator was modified to include polymer-induced shear-thinning effects. The experimental and simulation results clearly show that using the polymer leads to an enhanced delivery of remedial amendments to lower-permeability zones and an increased sweeping efficiency. An added benefit of using the polymer is the stabilization of the displacing front when density differences exist between displaced and displacing fluids. The modified STOMP simulator was able to predict the experimental observed fluid displacing behavior well and might be used to predict subsurface remediation performance when a shear-thinning fluid is used to remediate a heterogeneous system at larger scales.

An experimental investigation of nitrogen gas produced during denitrification.

In situ denitrification relies on indigenous microorganisms to reduce nitrate to N(2) gas. However, when initial nitrate concentrations are large, produced gas volumes also can be very large, potentially resulting in reduced water saturation and hydraulic conductivity in the treatment zone. In this study, we investigated the fate of N(2) and other gases produced during denitrification in a laboratory flow cell containing packed sediment. Denitrifying activity was stimulated by additions of nitrate and ethanol. Microbial activity was monitored by measuring nitrate, nitrite, and ethanol concentrations; gas saturations were measured during the experiment using a gamma imaging system. Biomass was measured using phospholipid fatty acid analysis of sediment samples. Bioenergetic calculations calibrated to measured nitrate consumed and biomass produced predicted that 1.2 L N(2) gas/L water should have been produced following the addition of 100 mM nitrate. However, the maximum measured gas saturation was only 23%, indicating substantial gas loss from the sediment pack. Temporal gamma images and visual observations confirm that small gas bubbles formed in the sediment pack coalesced into larger bubbles and migrated upward through gas-filled channels to the sediment pack surface. Although gas saturations increased, there was no significant change in sediment pack hydraulic conductivity. These results suggest that in permeable reactive barriers used for in situ denitrification, gas production will not necessarily lead to unlimited gas accumulation in the pore space and that the effects of gas production on water saturation and hydraulic conductivity may be relatively minor.

Injectable silica-permanganate gel as a slow-release MnO4(-) source for groundwater remediation: rheological properties and release dynamics.

Injectable slow-release permanganate gels (ISRPGs), formed by mixing aqueous KMnO4 solution with fumed silica powders, may have potential applications in remediating chlorinated solvent plumes in groundwater. A series of batch, column, and two-dimensional (2-D) flow cell experiments has been completed to characterize the ISRPG and study the release of permanganate (MnO4(-)) under a variety of conditions. The experiments have provided information on ISRPG rheology, MnO4(-) release dynamics and distribution in porous media, and trichloroethene (TCE) destruction by the ISRPG-released oxidant. The gel possesses shear thinning characteristics, resulting in a relatively low viscosity during mixing, and facilitating subsurface injection and distribution. Batch tests clearly showed that MnO4(-) diffused out from the ISRPG into water. During this process, the gel did not dissolve or disperse into water, but rather maintained its initial shape. Column experiments demonstrated that MnO4(-) release from the ISRPG lasted considerably longer than that from an aqueous solution. In addition, due to the longer release duration, TCE destruction by ISRPG-released MnO4(-) was considerably more effective than that when MnO4(-) was delivered using aqueous solution injection. In the 2-D flow cell experiments, it was demonstrated that ISRPGs released a long-lasting, low-concentration MnO4(-) plume potentially sufficient for sustainable remediation in aquifers.

Evaluation of deep vadose zone contaminant flux into groundwater: Approach and case study.

For sites with a contaminant source located in the vadose zone, the nature and extent of groundwater contaminant plumes are a function of the contaminant flux from the vadose zone to groundwater. Especially for thick vadose zones, transport may be relatively slow making it difficult to directly measure contaminant flux. An integrated assessment approach, supported by site characterization and monitoring data, is presented to explain current vadose zone contaminant distributions and to estimate future contaminant flux to groundwater in support of remediation decisions. The U.S. Department of Energy Hanford Site (WA, USA) SX Tank Farm was used as a case study because of a large existing contaminant inventory in its deep vadose zone, the presence of a limited-extent groundwater plume, and the relatively large amount of available data for the site. A predictive quantitative analysis was applied to refine a baseline conceptual model through the completion of a series of targeted simulations. The analysis revealed that site recharge is the most important flux-controlling process for future contaminant flux. Tank leak characteristics and subsurface heterogeneities appear to have a limited effect on long-term contaminant flux into groundwater. The occurrence of the current technetium-99 groundwater plume was explained by taking into account a considerable historical water-line leak adjacent to one of the tanks. The analysis further indicates that the vast majority of technetium-99 is expected to migrate into the groundwater during the next century. The approach provides a template for use in evaluating contaminant flux to groundwater using existing site data and has elements that are relevant to other disposal sites with a thick vadose zone.

Changes in major risk factors for cardiovascular diseases over 25 years in the Serbian cohorts of the Seven Countries Study.

The Serbian cohorts of the Seven Countries Study were examined four times during a 25-year period. Large changes were observed in average serum cholesterol, blood pressure and the prevalence of smoking in these ageing cohorts. Comparison of men of the same age strata e.g. men aged 50-59 examined at baseline and after 10 years of follow-up and of men aged 65-69 examined after 10 and 25 years of follow-up showed that serum cholesterol increased by about 45% in Zrenjanin, 35% in Velika Krsna and 15% in Belgrade over the last 25 years. Systolic blood pressure increased by 9% in Zrenjanin and 7% in Velika Krsna. No significant increase in systolic blood pressure was observed in Belgrade. There was no major secular trend in smoking and the changes observed during 25 years were mainly due to ageing. No major change was observed in body mass index. The increases in serum cholesterol and blood pressure observed in the Serbian cohorts during the last 25 years are compatible with the increase in cardiovascular disease mortality observed in Yugoslavian men aged 30-69 during the period 1970-1984.

A measurement of social support in epidemiological research: the social experiences checklist tested in a general population in The Netherlands.

STUDY OBJECTIVE: This study aimed to examine in a general population the psychometric qualities of an instrument designed to measure positive and negative social experiences that had been developed in a clinical setting. DESIGN: The Netherlands monitoring project on cardiovascular disease risk factors, a large scale population based study (comprising 36,588 men and women aged 20 to 59 years) carried out in three Dutch towns (Amsterdam, Doetinchem, and Maastricht) offered the possibility of testing the strength of this instrument cross sectionally. MEASUREMENTS AND MAIN RESULTS: The social experiences checklist (SEC) which resulted from a research project on the quality of life of cancer patients was used. The independence of positive and negative experiences was confirmed. The reliability of both the positive and negative experiences dimension was good (Cronbach's alpha = 0.82 and 0.72 respectively). In accordance with the results of a study on cancer patients, the theoretically derived four dimensions in the experience of social support did not seem to be independent. The validity of the SEC was confirmed by Pearson correlations with neuroticism and coping styles. Neuroticism seemed to be negatively correlated with positive social experiences and was positively correlated with negative social experiences. The coping style of seeking information and direct action was positively correlated with positive social experiences. Coping by withdrawal was negatively correlated with negative social experiences. Women and highly educated people seemed to have more positive and fewer negative social experiences than men and people with less education. Younger people had more positive social experiences than older people. The oldest group in the study, those aged 50 to 59, reported fewer negative social experiences than any other age group. CONCLUSIONS: Similar results were found in a study of cancer patients. This underlines the usefulness of the instrument not only for cancer patients but also in survey research in a general population.

The effect of radical and conserving surgery on the quality of life of early breast cancer patients.

In a randomized trial at the Leiden University Hospital, comparing (modified) radical mastectomy with tumorectomy followed by radiotherapy, all patients have been studied with respect to the quality of their lives 11 months and 18 months after surgery. The body image of women was more severely impaired after mastectomy than it was after breast conserving treatment (P less than 0.01). This was true for both younger and older women. Fear of recurrence of cancer was not related to the type of treatment. Thus, from a psychological point of view, breast conserving treatment is to be preferred in women of all ages. The overall quality of life improved and the suffering from psychological and physical complaints decreased with time in both groups of patients. This change may, therefore, have to be attributed to getting over the experience of having had cancer, and not to the treatment schedule.

A constitutive model for air-NAPL-water flow in the vadose zone accounting for immobile, non-occluded (residual) NAPL in strongly water-wet porous media.

A hysteretic constitutive model describing relations among relative permeabilities, saturations, and pressures in fluid systems consisting of air, nonaqueous-phase liquid (NAPL), and water is modified to account for NAPL that is postulated to be immobile in small pores and pore wedges and as films or lenses on water surfaces. A direct outcome of the model is prediction of the NAPL saturation that remains in the vadose zone after long drainage periods (residual NAPL). Using the modified model, water and NAPL (free, entrapped by water, and residual) saturations can be predicted from the capillary pressures and the water and total-liquid saturation-path histories. Relations between relative permeabilities and saturations are modified to account for the residual NAPL by adjusting the limits of integration in the integral expression used for predicting the NAPL relative permeability. When all of the NAPL is either residual or entrapped (i.e., no free NAPL), then the NAPL relative permeability will be zero. We model residual NAPL using concepts similar to those used to model residual water. As an initial test of the constitutive model, we compare predictions to published measurements of residual NAPL. Furthermore, we present results using the modified constitutive theory for a scenario involving NAPL imbibition and drainage.

A constitutive model for air-NAPL-water flow in the vadose zone accounting for immobile, non-occluded (residual) NAPL in strongly water-wet porous media.

A hysteretic constitutive model describing relations among relative permeabilities, saturations, and pressures in fluid systems consisting of air, nonaqueous-phase liquid (NAPL), and water is modified to account for NAPL that is postulated to be immobile in small pores and pore wedges and as films or lenses on water surfaces. A direct outcome of the model is prediction of the NAPL saturation that remains in the vadose zone after long drainage periods (residual NAPL). Using the modified model, water and NAPL (free, entrapped by water, and residual) saturations can be predicted from the capillary pressures and the water and total-liquid saturation-path histories. Relations between relative permeabilities and saturations are modified to account for the residual NAPL by adjusting the limits of integration in the integral expression used for predicting the NAPL relative permeability. When all of the NAPL is either residual or entrapped (i.e., no free NAPL), then the NAPL relative permeability will be zero. We model residual NAPL using concepts similar to those used to model residual water. As an initial test of the constitutive model, we compare predictions to published measurements of residual NAPL. Furthermore, we present results using the modified constitutive theory for a scenario involving NAPL imbibition and drainage.

Flow behavior and residual saturation formation of liquid carbon tetrachloride in unsaturated heterogeneous porous media.

The formation of residual, discontinuous nonaqueous phase liquids (NAPLs) in the vadose zone is a process that is not well understood. To obtain data that can be used to study the development of a residual NAPL saturation in the vadose zone and to test current corresponding models, detailed transient experiments were conducted in intermediate-scale columns and flow cell. The column experiments were conducted to determine residual carbon tetrachloride (CCl(4)) saturations of two sands and to evaluate the effect of CCl(4) vapors on the water distribution. In the intermediate-scale flow cell experiment, a rectangular zone of the fine-grained sand was packed in an otherwise medium-grained matrix. A limited amount of CCl(4) was injected from a small source and allowed to redistribute until a pseudo steady state situation had developed. A dual-energy gamma radiation system was used to determine fluid saturations at numerous locations. The experiments clearly demonstrated the formation of residual CCl(4) saturations in both sands. Simulations with an established multifluid flow simulator show the shortcomings of current relative permeability-saturation-capillary pressure (k-S-P) models. The results indicate that nonspreading behavior of NAPLs should be implemented in simulators to account for the formation of residual saturations.

In-situ oxidation of trichloroethene by permanganate: effects on porous medium hydraulic properties.

In-situ oxidation of dense nonaqueous-phase liquids (DNAPLs) by strong oxidants such as potassium permanganate (KMnO4) has been proposed as a possible DNAPL remediation strategy. In this study, we investigated the effects of in-situ trichloroethene (TCE) oxidation by KMnO4 on porous medium hydraulic properties. In particular, we wanted to determine the overall effects of concurrent solid phase (MnO2) precipitation, gas (CO2) evolution and TCE dissolution resulting from the oxidation reaction on the porous medium's aqueous-phase relative permeability, krw. Three TCE removal experiments were conducted in a 95-cm long, 5.1-cm i.d. glass column, which was homogeneously packed with well-characterized 30/40-mesh silica sand. TCE was emplaced in the sand-pack in residual, entrapped form through a sequence of water/TCE imbibition and drainage steps. The column was then flushed under constant aqueous flux conditions for up to 104 h with either deionized water (reference experiment), deionized water containing 5 mM KMnO4 or deionized water containing 5 mM KMnO4 and 300 mM Na2HPO4. Aqueous-phase relative permeabilities were computed from measured flow rates and measurements of aqueous-phase pressure head, h obtained using pressure transducers connected to tensiometers distributed along the column length. A dual-energy gamma radiation system was used to monitor changes in fluid saturation that occurred during each experiment. In addition, column effluent samples were collected for chemical analyses. Dissolution of TCE during deionized water flushing led to an increase in krw by approximately 22% and a local reduction in h. On the other hand, vigorous CO2 gas production and precipitation of MnO2 was visually observed during flushing with deionized water that contained 5 mM KMnO4. As a consequence, krw declined by approximately 96% and h increased locally by more than 1000 cm H2O during the first 24 h of the experiment, causing sand-pack ruptures and pump failure. Conversely, less CO2 gas production and MnO2 precipitation was visually observed during flushing with deionized water that contained 5 mM KMnO4 and 300 mM Na2HPO4. Consequently, only small increases in h (< 15 cm H2O) were observed in this experiment due to a reduction in krw of approximately 53%. While we must attribute changes in h due to variations in krw to our specific experimental design (constant aqueous flux, one-dimensional flow experiments), these experiments nevertheless confirm that successful application of in situ chemical oxidation of TCE requires consideration of detrimental processes such as MnO2 precipitation and CO2 gas formation. In addition, our results indicate that utilization of a buffered oxidant solution may improve the effectiveness of in-situ oxidation of TCE by KMnO4 in otherwise weakly buffered porous media.

Effective parameters for two-phase flow in a porous medium with periodic heterogeneities.

Computational simulations of two-phase flow in porous media are used to investigate the feasibility of replacing a porous medium containing heterogeneities with an equivalent homogeneous medium. Simulations are performed for the case of infiltration of a dense nonaqueous phase liquid (DNAPL) in a water-saturated, heterogeneous porous medium. For two specific porous media, with periodic and rather simple heterogeneity patterns, the existence of a representative elementary volume (REV) is studied. Upscaled intrinsic permeabilities and upscaled nonlinear constitutive relationships for two-phase flow systems are numerically calculated and the effects of heterogeneities are evaluated. Upscaled capillary pressure-saturation curves for drainage are found to be distinctly different from the lower-scale curves for individual regions of heterogeneity. Irreducible water saturation for the homogenized medium is found to be much larger than the corresponding lower-scale values. Numerical simulations for both heterogeneous and homogeneous representations of the considered porous media are carried out. Although the homogenized model simulates the spreading behavior of DNAPL reasonably well, it still fails to match completely the results form the heterogeneous simulations. This seems to be due, in part, to the nonlinearities inherent to multiphase flow systems. Although we have focussed on a periodic heterogeneous medium in this study, our methodology is applicable to other forms of heterogeneous media. In particular, the procedure for identification of a REV, and associated upscaled constitutive relations, can be used for randomly heterogeneous or layered media as well.

A practical model for mobile, residual, and entrapped NAPL in water-wet porous media.

Flow of nonvolatile nonaqueous phase liquid (NAPL) and aqueous phases that account for mobile, entrapped, and residual NAPL in variably saturated water-wet porous media is modeled and compared against results from detailed laboratory experiments. Residual saturation formation in the vadose zone is a process that is often ignored in multifluid flow simulators, which might cause an overestimation of the volume of NAPL that reaches the ground water. Mobile NAPL is defined as being continuous in the pore space and flows under a pressure gradient or gravitational body force. Entrapped NAPL is defined as being occluded by the aqueous phase, occurring as immobile ganglia surrounded by aqueous phase in the pore space and formed when NAPL is replaced by the aqueous phase. Residual NAPL is defined as immobile, nonwater entrapped NAPL that does not drain from the pore spaces and is conceptualized as being either continuous or discontinuous. Free NAPL comprises mobile and residual NAPL. The numerical model is formulated on mass conservation equations for oil and water, transported via NAPL and aqueous phases through variably saturated porous media. To account for phase transitions, a primary variable switching scheme is implemented for the oil-mass conservation equation over three phase conditions: (1) aqueous or aqueous-gas with dissolved oil, (2) aqueous or aqueous-gas with entrapped NAPL, and (3) aqueous or aqueous gas with free NAPL. Two laboratory-scale column experiments are modeled to verify the numerical model. Comparisons between the numerical simulations and experiments demonstrate the necessity to include the residual NAPL formation process in multifluid flow simulators.

Measuring spatial variability of vapor flux to characterize vadose-zone VOC sources: flow-cell experiments.

A method termed vapor-phase tomography has recently been proposed to characterize the distribution of volatile organic contaminant mass in vadose-zone source areas, and to measure associated three-dimensional distributions of local contaminant mass discharge. The method is based on measuring the spatial variability of vapor flux, and thus inherent to its effectiveness is the premise that the magnitudes and temporal variability of vapor concentrations measured at different monitoring points within the interrogated area will be a function of the geospatial positions of the points relative to the source location. A series of flow-cell experiments was conducted to evaluate this premise. A well-defined source zone was created by injection and extraction of a non-reactive gas (SF6). Spatial and temporal concentration distributions obtained from the tests were compared to simulations produced with a mathematical model describing advective and diffusive transport. Tests were conducted to characterize both areal and vertical components of the application. Decreases in concentration over time were observed for monitoring points located on the opposite side of the source zone from the local-extraction point, whereas increases were observed for monitoring points located between the local-extraction point and the source zone. The results illustrate that comparison of temporal concentration profiles obtained at various monitoring points gives a general indication of the source location with respect to the extraction and monitoring points.

Effect of aspirin intake at bedtime versus on awakening on circadian rhythm of platelet reactivity. A randomised cross-over trial.

The risk of acute cardiovascular events is highest during morning hours, and platelet activity peaks during morning hours. The effect of timing of aspirin intake on circadian rhythm and morning peak of platelet reactivity is not known. It was our objective to evaluate the effect of timing of aspirin intake on circadian rhythm and morning peak of platelet reactivity. A randomised open-label cross-over trial in healthy subjects (n=14) was conducted. Participants used acetylsalicylic acid (80 mg) on awakening or at bedtime for two periods of two weeks, separated by a four-week wash-out period. At the end of both periods blood was drawn every 3 hours to measure COX-1-dependent (VerifyNow-Aspirin; Serum Thromboxane B2 [STxB2]) and COX-1-independent (flow cytometry surface CD62p expression; microaggregation) platelet activity. VerifyNow platelet reactivity over the whole day was similar with intake on awakening and at bedtime (mean difference: -9 [95 % confidence interval (CI) -21 to 4]). However, the morning increase in COX-1-dependent platelet activity was reduced by intake of aspirin at bedtime compared with on awakening (mean difference VerifyNow: -23 Aspirin Reaction Units [CI -50 to 4]; STxB2: -1.7 ng/ml [CI -2.7 to -0.8]). COX-1-independent assays were not affected by aspirin intake or its timing. Low-dose aspirin taken at bedtime compared with intake on awakening reduces COX-1-dependent platelet reactivity during morning hours in healthy subjects. Future clinical trials are required to investigate whether simply switching to aspirin intake at bedtime reduces the risk of cardiovascular events during the high risk morning hours.

Rheological behavior of xanthan gum solution related to shear thinning fluid delivery for subsurface remediation.

Xanthan gum solutions are shear thinning fluids which can be used as delivery media to improve the distribution of remedial amendments injected into heterogeneous subsurface environments. The rheological behavior of the shear thinning solution needs to be known to develop an appropriate design for field injection. In this study, the rheological properties of xanthan gum solutions were obtained under various chemical and environmental conditions relevant to delivery of remedial amendments to groundwater. Higher xanthan concentration raised the absolute solution viscosity and increased the degree of shear thinning. Addition of remedial amendments (e.g., phosphate, sodium lactate, ethyl lactate) caused the dynamic viscosity of xanthan solutions to decrease, but they maintained shear-thinning properties. Use of mono- and divalent salts (e.g., Na(+), Ca(2+)) to increase the solution ionic strength also decreased the dynamic viscosity of xanthan and the degree of shear thinning, although the effect reversed at high xanthan concentrations. A power law analysis showed that the consistency index is a linear function of the xanthan concentration. The degree of shear thinning, however, is best described using a logarithmic function. Mechanisms to describe the observed empiricism have been discussed. In the absence of sediments, xanthan solutions maintained their viscosity for months. However, the solutions lost their viscosity over a period of days to weeks when in contact with site sediment. Loss of viscosity is attributed to physical and biodegradation processes.