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Mobilizing particles in a saturated zone during air sparging.

The mobilization of soil particles changes the porosity of saturated zone during air sparging. Soil porosity is shown to be correlated with soil electrical resistivity. This study performs porosity-resistivity tests to establish the relationship between porosity and resistivity of quartz sand. Experiments, involving a large sandbox to simulate the saturated zone, are then performed to compare the resistivity of compacted sand before air injection with that after air injection. The relevant data enable the mobilization of quartz sand particles to be quantified. Results of the experiments indicate the mobilization of sand particles and an increase in porosity directly proportional to the rate at which air is injected. Besides, a layer of fine-grained particles covered the compacted sand at the upper boundary of sandbox after each air injection experiment. This is direct evidence that finer particles were transported upward during air sparging. Two methods were applied to verify the results of this study. The first verification method indicated that changes in porosity increased directly proportional to the air injection rate, which is consistent with shear theory. The other validation method indicated that the mass of sand in the tank did not change after air sparging, which indicates that the resistivity-porosity method is unbiased.

Air↗

Predicting fracture of the femoral neck.

A prediction of the probability of safe loading of the femoral neck, based on queueing theory, is presented. The following methods have been applied: (I) criterion of bone fracture was formulated, taking into consideration the complex state of stress-strain in the porosity zones of the bone; (II) tensile stresses around pores in the stretched zone of the bone were evaluated; (III) the influence of random events of the critical regimes of loading was modeled. The evaluation of the probability of safe loading of bones was obtained based on the levels of the tensile stresses, Young's moduli and ultimate tensile stresses which are affected by the increase in bone porosity and the distribution of the pores. Examples of analysis involving typical mechanical properties of bone in areas of vascular and lacunar-canalicular porosity are demonstrated. The ranges of initial average values of effective Young's moduli and ultimate tensile strengths were taken as 15.8-17.5GPa and 83-95MPa, respectively. The present analysis discovers the existence of three levels of safe loading: (1) a relatively safe level of the nominal tensile stresses (smaller than (2.8-3.2)MPa) where the probability of safe loading is of the order of 0.95 for the bone porosity which is less than 0.15; (2) an intermediate level of safety where the nominal tensile stresses are below (4.2-4.8)MPa and the probability of safe loading is 0.89 or higher, for the same level of bone porosity; (3) a critical level of safe loading where the nominal tensile stresses are about (8.3-9.5)MPa; they lead to sharp drop of probabilities of safe loading to 0.85-0.8 if the porosity is about 0.10 and to probabilities of 0.41-0.4 if the porosity is about 0.15.

Algorithms↗

Prediction of strength of cortical bone in vitro by microcomputed tomography.

OBJECTIVE: The aim of this study was to evaluate the predictive value of bone mineral density and intracortical porosity measured by microcomputed tomography for the strength of cortical bone biopsies. DESIGN: Experimental study comparing the predictive value of bone mineral density and of intracortical porosity determined in vitro by microcomputed tomography for the mechanical properties of cortical bone cylinders. BACKGROUND: The assessment of cortical bone strength might be relevant for the prediction of fracture risk or the choice of suitable therapy strategies in orthopaedic surgery. The predictive value of cortical density for the mechanical properties is discussed controversially. The relevance of intracortical porosity measured by histomorphometry has been established, but the predictive value of porosity determined by microcomputed tomography remains to be explored. METHODS: Femoral cortical bone specimens from the mid diaphysis of 24 patients were harvested during total hip replacement procedure at the location, where a diaphyseal hole (diameter 4.5 mm) was drilled in order to reduce the intramedullary pressure. In vitro intracortical porosity and bone mineral density measurements by microcomputed tomography were compared with strength and elastic modulus assessed by a compression test transverse to the Haversian systems of the same specimens. RESULTS: Significant negative correlations were found between porosity measured by microcomputed tomography scans and yield stress, stiffness and elastic modulus (P<0.001), however, the positive correlations between bone mineral density and mechanical parameters were stronger (P<0.0001). The mechanical parameter best predicted by mineral density as well as by porosity was yield stress (r=0.72,P<0.0001;r=-0.64,P<0.001). CONCLUSIONS: Bone mineral density determined by microcomputed tomography imaging in vitro may be a potent method to predict mechanical properties of cortical bone non-destructively. The application in vivo remains to be explored.

Aged↗

Fractal dimension of trabecular bone projection texture is related to three-dimensional microarchitecture.

The purpose of this work was to understand how fractal dimension of two-dimensional (2D) trabecular bone projection images could be related to three-dimensional (3D) trabecular bone properties such as porosity or connectivity. Two alteration processes were applied to trabecular bone images obtained by magnetic resonance imaging: a trabeculae dilation process and a trabeculae removal process. The trabeculae dilation process was applied from the 3D skeleton graph to the 3D initial structure with constant connectivity. The trabeculae removal process was applied from the initial structure to an altered structure having 99% of porosity, in which both porosity and connectivity were modified during this second process. Gray-level projection images of each of the altered structures were simply obtained by summation of voxels, and fractal dimension (Df) was calculated. Porosity (phi) and connectivity per unit volume (Cv) were calculated from the 3D structure. Significant relationships were found between Df, phi, and Cv. Df values increased when porosity increased (dilation and removal processes) and when connectivity decreased (only removal process). These variations were in accordance with all previous clinical studies, suggesting that fractal evaluation of trabecular bone projection has real meaning in terms of porosity and connectivity of the 3D architecture. Furthermore, there was a statistically significant linear dependence between Df and Cv when phi remained constant. Porosity is directly related to bone mineral density and fractal dimension can be easily evaluated in clinical routine. These two parameters could be associated to evaluate the connectivity of the structure.

Femur Head↗

The effect of heat treatment on the morphology of D-Gun sprayed hydroxyapatite coatings.

In this study, the morphology of the Hydroxyapatite (HA) coatings sprayed on Ti alloy samples by Detonation Gun Spray (D-Gun) and the effect of aging before and after heat treatment in physiological solution were observed. Cross-sectional porosity and percentages of amorphous and crystal phase were measured using optical, electron microscopy, and X-ray diffraction analysis. Differential Thermogravimetric Analysis (DTA) was performed to estimate the glass-crystalline phase transformation temperatures. Heat-treatment at 300, 500, 700, 800 and 1200 degrees C were carried out to confirm DTA results. As a final analysis, the aging effect using Ringer's solution for 1 week on heat-treated and non-heat-treated samples was measured. It was observed that, in D-Gun sprayed samples, the cross-sectional porosity stayed in the accepted 5% range as reported for other spraying techniques.(1-5) On the other hand, surface porosity measured using the water immersion method remained in the conventional porosity limit of 15% for non-heat-treated samples. Heat-treatment had a small influence on the porosity while the crystallinity increased considerably; in addition, aging had little effect on HA crystallinity for heat treated samples. This work showed that D-gun sprayed HA coatings had lower porosity and better integrity than other coatings, due to which we can expect better performance during in vivo applications.

Alloys↗

Effect of varying physical properties of porous, surface modified bioactive glass 45S5 on osteoblast proliferation and maturation.

The objective of this study was to determine the effect of porous bioactive glass (45S5) substrate characteristics on the expression and maintenance of the osteoblastic phenotype. We cultured ROS 17/2. 8 cells on substrates with different pore size and porosity for periods up to 14 days and analyzed the characteristics of the cells and extracellular matrix. Results of the study show that the glass substrates supported the proliferation and growth of osteoblast-like cells. Although the morphologies of the cells differed on the various substrates, their shape and the extent of membrane ruffling suggested that they maintained high levels of metabolic activity. Cells on all substrates expressed high levels of alkaline phosphatase activity and produced extracellular matrices that mineralized to form nonstoichiometric, carbonated, calcium-deficient apatites. An important finding was that at a given porosity of 44%, the pore size neither directed nor modulated the in vitro expression of the osteoblastic phenotype. In contrast, porosity did affect cellular function. We noted that at an average pore size of 92 microm, as the porosity increased from 35 to 59%, osteoblast activity was reduced. As designed in this experiment, an increase in the porosity led to a corresponding increase in total surface area of the specimens. With increasing porosity and surface area, glass reactions in the media may persist for longer durations at higher intensities, thereby affecting local media composition. As such, we suggest that extensive conditioning treatments before cell seeding can reduce this effect. Our results also revealed that the expression of the osteoblastic phenotype is enhanced by the ongoing glass dissolution. The reaction pathway at the origin of this effect still needs to be elucidated. Taken together, the findings support the overall hypothesis that in vitro cell activity can be controlled by a careful selection of substrate properties.

Alkaline Phosphatase↗

Effect of WOW process parameters on morphology and burst release of FITC-dextran loaded PLGA microspheres.

Using fluorescein isothiocyanate labeled dextran (FITC-dextran 40, FD40) as a hydrophilic model compound, microspheres were prepared by a WOW double emulsion technique. Influence of process parameters on microsphere morphology and burst release of FD40 from PLGA microspheres was studied. Internal morphology of microspheres was investigated by stereological method via cryo-cutting technique and scanning electron microscopy (SEM). Drug distribution in microspheres was observed with confocal laser scanning microscopy (CLSM). Polymer nature (RG503 and RG503H) had significant influence on the micro-morphology of microspheres. Increase in continuous water phase volume (W2) led to increased surface porosity but decreased internal porosity. By increasing PVA concentration in the continuous phase from 0.1 to 1%, particle size changed marginally but burst release decreased from 12.2 to 5.9%. Internal porosity of microspheres decreased considerably with increasing polymer concentration. Increase in homogenization speed during the primary emulsion preparation led to decreased internal porosity. Burst release decreased with increasing drug loading but increased with drug molecular weight. Drug distribution in microspheres depended on preparation method. The porosity of microspheres decreased with time in the diffusion stage, but internal morphology had no influence on the release behavior in the bioerosion stage. In summary, surface porosity and internal morphology play a significant role in the release of hydrophilic macromolecules from biodegradable microspheres in the initial release phase characterized by pore diffusion.

Calorimetry, Differential Scanning↗

Nutrients adsorption from seawater by new porous carrier made from zeolitized fly ash and slag.

This study investigated the adsorption and precipitation of phosphate by blast furnace slag (BFS) separately. In order to evaluate the adsorption capacity of BFS, BFS was treated before its use by acid. The authors aim to develop a new porous carrier to adsorb simultaneously ammonium and phosphate from seawater under eutrophic conditions. The current paper deals with a promising new approach to improve the utilization of some industrial solid wastes such as BFS and zeolite synthesized from fly ash [ZFA(Fe)] by their solidification to cylindrical porous carriers using a hydrothermal hot-pressing (HHP) method. Attempts to produce porous carriers using an arranged HHP method with different porosities (24%, 40% and 52% (v/v)) were carried out. Physical properties of carriers such as porosity, compressive strength and height have been investigated. Laboratory studies showed strong evidence that the porous carrier was very selective towards phosphate and ammonium. The results demonstrated the role of porosity in enhancing phosphate and ammonium adsorption by the increase of the surface area per weight. The estimates of the parameters and the correlation coefficients according to the Freundlich equations revealed that adsorption was related to the porosity of carriers and phosphate and ammonium were adsorbed well on the carriers having large porosity. The results suggested that developing carrier with high porosity was a promising way to enhance nutrients adsorption.

Adsorption↗

Hydroxyapatite fiber reinforced poly(alpha-hydroxy ester) foams for bone regeneration.

A process has been developed to manufacture biodegradable composite foams of poly(DL-lactic-co-glycolic acid) (PLGA) and hydroxyapatite short fibers for use in bone regeneration. The processing technique allows the manufacture of three-dimensional foam scaffolds and involves the formation of a composite material consisting of a porogen material (either gelatin microspheres or salt particles) and hydroxyapatite short fibers embedded in a PLGA matrix. After the porogen is leached out, an open-cell composite foam remains which has a pore size and morphology defined by the porogen. By changing the weight fraction of the leachable component it was possible to produce composite foams with controlled porosities ranging from 0.47 +/- 0.02 to 0.85 +/- 0.01 (n = 3). Up to a polymer:fiber ratio of 7:6, short hydroxyapatite fibers served to reinforce low-porosity PLGA foams manufactured using gelatin microspheres as a porogen. Foams with a compressive yield strength up to 2.82 +/- 0.63 MPa (n = 3) and a porosity of 0.47 +/- 0.02 (n = 3) were manufactured using a polymer:fiber weight ratio of 7:6. In contrast, high-porosity composite foams (up to 0.81 +/- 0.02, n = 3) suitable for cell seeding were not reinforced by the introduction of increasing quantities of hydroxyapatite short fibers. We were therefore able to manufacture high-porosity foams which may be seeded with cells but which have minimal compressive yield strength, or low porosity foams with enhanced osteoconductivity and compressive yield strength.

Biocompatible Materials↗

Plasticisation of amylodextrin by moisture: consequences for drug release from tablets.

Moisture influences the consolidation behaviour of amylodextrin powders and the porosity and mechanical strength of compacts thereof. The aim of this study is to relate moisture content and compact properties to drug release characteristics of amylodextrin tablets. Therefore, amylodextrin tablets containing theophylline monohydrate were prepared and their release characteristics were studied as a function of moisture content and initial porosity. Drug release from amylodextrin tablets occurs through a leaching mechanism in which cracks are progressively formed in the hydrated part of the matrix leading to almost constant release rates. Small variations in moisture content resulted in large changes of the release rate. A unique relationship between porosity and release rate, which was independent on moisture content and compaction pressure, was observed. Above a critical porosity of 0.075 crack formation was followed by disintegration and fast release. Below this critical porosity, tablets stayed intact despite of the formation of cracks, and sustained release was observed. It is concluded that control over moisture content is essential for the production of amylodextrin tablets with reproducible release characteristics. Using amylodextrin containing 10-17%, moisture, tablets with a constant release behaviour can be obtained if sufficient compaction pressure ( > 300 MPa) is applied. Lubrication of amylodextrin powders reduces the effect of porosity significantly and improves the robustness of amylodextrin tablets as a release controlling excipient in tablets largely.

Bronchodilator Agents↗

Microvascular A-V shunts and the growth of autologous tissue flaps in Millipore chambers.

An animal model was developed using the male Sprague-Dawley rat to establish a protocol and design criteria for the growth of autologous tissue based on a microvascular pedicle. It became apparent that growth within the chamber depended heavily on membrane porosity and the presence of the microarteriovenous shunt. Different membrane porosities ranging from 0.0, 0.25, 1.2, to 8.0 microns were evaluated (n = 48). Optimal growth occurred with the 1.2-microns and the 8.0-microns micropore Millipore. Growth within the chamber consisted of a radial deposition of collagen and neovascularization originating from the arteriovenous (A-V) anastomosis. In contrast, control chambers (no A-V anastomosis), with the preceding range in membrane porosity, experienced little to no cell growth. In addition, the majority of A-V shunts did not remain patent in chambers having 0.0-microns porosity or 0.25-microns porosity. Thus it is apparent that a strong relationship exists between membrane porosity, patency, and in situ vascularization allowing for the proliferation of cells and collagen.

Animals↗

Effect of pressure difference on the quality of titanium casting.

In casting titanium using a two-compartment casting machine, Herø et al. (1993) reported that the pressure difference between the melting chamber and the mold chamber affected the soundness of the castings. This study tested the hypothesis that differences in pressure produce castings with various amounts of porosity and different mechanical properties values. Plastic dumbbell-shaped patterns were invested with an alumina-based, phosphate-bonded investment material. Both chambers of the casting machine were evacuated to 6 x 10(-2) torr; the argon pressure difference was then adjusted to either 50, 150, 300, or 450 torr. The porosity of the cast specimens was determined by x-ray radiography and quantitative image analysis. Tensile strength and elongation were measured by means of a universal testing machine at a strain rate of 1.7 x 10(-4)/s. The fractured surfaces were examined by SEM. Changes in Vickers hardness with depth from the cast surface were measured on polished cross-sections of the specimens. Raising the argon pressure difference to 300 and 450 torr caused a significant increase in internal porosity and a resultant decrease in the engineering tensile strength and elongation. The highest tensile strength (approximately 540 MPa), elongation (approximately 10%), bulk hardness (HV50g 209), and lowest porosity level (approximately 0.8%) occurred in the specimens cast at 150 torr. Turbulence of the metal during casting was thought to be responsible for the increase in porosity levels with the increase in argon pressure difference. By choosing an argon pressure difference (around 150 torr) suitable for this geometry, we could produce castings which have adequate mechanical properties and low porosity levels.

Analysis of Variance↗

Alterations in bone remodeling in the femur after medullary reaming and cemented hip arthroplasty in dogs.

OBJECTIVE: To determine whether medullary reaming alone, or followed by cemented hemiarthroplasty, influenced porosity, vascularity, and new bone formation in the proximal portion of the femur in dogs. ANIMALS: 12 adult mixed-breed dogs. PROCEDURE: Unilateral femoral head and neck excisions were performed, followed by femoral medullary reaming in 6 dogs and femoral medullary reaming and cemented hemiarthroplasty in 6 dogs; the contralateral femur was used as a control. All dogs were euthanatized 28 days after surgery, and femurs were harvested. Vascularity, porosity, and new bone formation were quantified for all femurs of dogs from both groups at 3 proximal-to-distal levels, 3 regions (periosteal, midcortical, and endosteal), and 4 quadrants (cranial, caudal, medial, and lateral) of the femur. RESULTS: Medullary reamed and cemented hemiarthroplasty femurs had significant increases in vascularity and porosity at all levels and in new bone formation at levels 2 and 3. Porosity was increased significantly in the periosteal region of the cemented hemiarthroplasty (9.7+/-0.7%), compared with control (2.3+/-0.2%) and medullary reamed (8.4+/-0.7%) femurs. Porosity was increased in the caudal and medial quadrants in the medullary reamed and cemented hemiarthroplasty femurs; vascularity results were similar. CONCLUSION: Increased porosity, vascularity, and new bone formation in reamed and cemented hemiarthroplasty-treated femurs supports the theory that surgical trauma associated with medullary reaming is an important factor in early cortical bone loss after hip arthroplasty. CLINICAL RELEVANCE: Femoral remodeling associated with reaming and broaching is appreciable but may be only a temporary response, whereas other factors may be responsible for chronic cortical bone loss.

Analgesics, Opioid↗

Three-dimensional printing and porous metallic surfaces: a new orthopedic application.

As-cast, porous surfaced CoCr implants were tested for bone interfacial shear strength in a canine transcortical model. Three-dimensional printing (3DP) was used to create complex molds with a dimensional resolution of 175 microm. 3DP is a solid freeform fabrication technique that can generate ceramic pieces by printing binder onto a bed of ceramic powder. A printhead is rastered across the powder, building a monolithic mold, layer by layer. Using these 3DP molds, surfaces can be textured "as-cast," eliminating the need for additional processing as with commercially available sintered beads or wire mesh surfaces. Three experimental textures were fabricated, each consisting of a surface layer and deep layer with distinct individual porosities. The surface layer ranged from a porosity of 38% (Surface Y) to 67% (Surface Z), whereas the deep layer ranged from 39% (Surface Z) to 63% (Surface Y). An intermediate texture was fabricated that consisted of 43% porosity in both surface and deep layers (Surface X). Control surfaces were commercial sintered beaded coatings with a nominal porosity of 37%. A well-documented canine transcortical implant model was utilized to evaluate these experimental surfaces. In this model, five cylindrical implants were placed in transverse bicortical defects in each femur of purpose bred coonhounds. A Latin Square technique was used to randomize the experimental implants left to right and proximal to distal within a given animal and among animals. Each experimental site was paired with a porous coated control site located at the same level in the contralateral limb. Thus, for each of the three time periods (6, 12, and 26 weeks) five dogs were utilized, yielding a total of 24 experimental sites and 24 matched pair control sites. At each time period, mechanical push-out tests were used to evaluate interfacial shear strength. Other specimens were subjected to histomorphometric analysis. Macrotexture Z, with the highest surface porosity, failed at a significantly higher shear stress (p = 0.05) than the porous coated controls at 26 weeks. It is postulated that an increased volume of ingrown bone, resulting from a combination of high surface porosity and a high percentage of ingrowth, was responsible for the observed improvement in strength. Macrotextures X and Y also had significantly greater bone ingrowth than the controls (p = 0.05 at 26 weeks), and displayed, on average, greater interfacial shear strengths than controls, although they were not statistically significant.

Animals↗

Transient response of a solid-liquid model biological fluidised bed to a step change in fluid superficial velocity.

The evolution of a solid-liquid model biological fluidised bed under a step change in fluid superficial velocity is described. During a transient step change, the fluidised bed divides into a top zone which remains at the initial porosity and a bottom zone which settles at the final porosity. The interface of discontinuity in porosity moves progressively upwards through the fluidised bed. The velocity at which the top of the fluidised bed expands or contracts and the upward velocity of the porosity transition interface depend only upon the initial and final states of the bed porosity and the fluid superficial velocity. This results in a linear evolution with time of the total bed height and the height of porosity transition interface. The proposed model is well suited to describe the transient response of low-density particles in a fluidised bed, such as encountered in biological systems, to a sudden change of liquid superficial velocity. The model was validated experimentally.

Biomedical Engineering↗

Canine cortical bone autograft remodeling in two simultaneous skeletal sites.

The morphological and physical aspects of cortical bone autografts implanted in dogs for 1-9 months in two differently located skeletal defects are reported with a twofold aim: to provide a reference system for further comparison with various allografts and to delineate a general pattern of cortical bone graft healing. A 3-cm osteoperiosteal gap was created in the diaphyseal segment of the ulna and fibula of mature dogs. The grafts, freed from periosteum and bone marrow, were then inverted and replaced for the autografts in the left limb bone without internal fixation or external splints. On the right side, different allografts were tested. A group of three animals also had an unfilled segmental resection on the right as control. Dogs were observed for 1, 2, 3, 6, and 9 months and were able to bear weight within 3 days. Twenty-eight ulnae and 27 fibulae were available for this autograft study. Fluorochromes were injected at mid-term and at the end of the observation. All the grafts were assessed morphologically by cross-section microradiographs and ultraviolet light microscopy, and a morphometric analysis for porosity and fluorescence was done. To evaluate the physical aspects of graft healing, the recovered ulnar autografts, when available, were submitted to photon absorptiometry and to torsional loading. Morphologically, resorption was found to invade the cortical bone graft transversely through radial tunnels, and in addition to the host-bone-graft junction, the entire transplant surface provided another way for revascularization. The highest porosity level was achieved 2 months after surgery for both ulna and fibula, while new bone formation, as assessed by fluorochromes, was most important at 3 months. At 9 months, porosity remained above the normal range as determined in a set of five nongrafted dogs. While the lack of correlation for porosity between the two grafts suggests that local factors are more important in graft resorption, the observed correlation for fluorescence indicates that new bone deposition is more dependent upon skeletal metabolic activity. Within each graft, porosity and new bone formation were not well correlated. In the ulna, the bone mineral content (BMC) reflected the graft volumetric variations during the remodeling, with the lowest mean value at 3 months. For each graft, BMC was well correlated with the torsional stiffness. When torsionally loaded, the maximal tangential shear stress at failure of the graft was negatively related to its cortical porosity.(ABSTRACT TRUNCATED AT 400 WORDS)

Animals↗

Influence of the packing heterogeneity on the performance of liquid chromatography supports.

We report on a series of plate height and flow resistance data obtained via computational fluid dynamics simulations in a simplified two-dimensional (2D) mimic of real packed bed and monolithic columns. By varying the external porosity (0.4 < epsilon < 0.8) and the degree of packing randomness, a good qualitative insight in the relationship between the packing porosity and heterogeneity and the general chromatographic performance parameters is obtained, unbiased by any differences in phase retention factor k', mobile phase diffusivity or viscosity or intra-skeleton porosity. The results provide a quantitative support for the use of domain size reduced plate heights as a means to compare the performance of chromatographic beds with a different porosity, as it was found that packings with a similar degree of packing heterogeneity yield very similar domain size reduced h(min)-values, nearly completely independent of the porosity. The study also clearly shows that the presence of preferential flow paths (inevitably accompanied by the presence of more clustered regions) leads to a decrease of the flow resistance, but also leads to a strong increase of the band broadening if supports with the same porosity epsilon and the same radial width are compared. For the presently considered 2D system, the flow resistance reduction is too small to overcome the corresponding strong increase in band broadening, such that the presence of preferential flow paths always leads to an overall increase of the separation impedance.

Chromatography, Liquid↗

Longevity of granular iron in groundwater treatment processes: changes in solute transport properties over time.

Although progress has been made toward understanding the surface chemistry of granular iron and the mechanisms through which it attenuates groundwater contaminants, potential long-term changes in the solute transport properties of granular iron media have until now received relatively little attention. As part of column investigations of alterations in the reactivity of granular iron, studies using tritiated water (3H(2)O) as a conservative and non-partitioning tracer were periodically conducted to independently isolate transport-related effects on performance from those more directly related to surface reactivity. Hydraulic residence time distributions (HRTDs) within each of six 39-cm columns exposed to bicarbonate solutions were obtained over the course of 1100 days of operation. First moment analyses of the data revealed generally modest increases in mean pore water velocity (v) over time, indicative of decreasing water-filled porosity. Gravimetric measurements provided independent estimates of water-filled porosity that were initially consistent with those obtained from 3H(2)O tracer tests, although at later times, porosities derived from gravimetric measurements deviated from the tracer test results owing to mineral precipitation. The combination of gravimetric measurements and 3H(2)O tracer studies furnished estimates of precipitated mineral mass; depending on the assumed identity of the predominant mineral phase(s), the porosity decrease associated with solute precipitation amounted to 6-24% of the initial porosity. The accumulation of mineral and gas phases led to the formation of regions of immobile water and increased spreading of the tracer pulse. Application of a dual-region transport model to the 3H(2)O breakthrough curves revealed that the immobile water-filled region increased from initially negligible values to amounts ranging between 3% and 14% of the total porosity in later periods of operation. For the aged columns, mobile-immobile mass transfer coefficients (k(mt)) were generally in the range of 0.1-1.0 day(-1) and reflected a slow exchange of 3H(2)O between the two regions. Additional model calculations incorporating sorption and reaction suggest that although changes in HRTD can have an appreciable effect on trichloroethylene (TCE) transformation, the effect is likely to be minor relative to that stemming from passivation of the granular iron surface.

Chemical Precipitation↗