Carbon dioxide sequestration in cement kiln dust through miner carbonation

The feasibility of carbon sequestration in cement kiln dust (CKD) was investigated in a series of batch and column experiments conducted under ambient temperature and pressure conditions. The significance of this work is the demonstration that alkaline wastes, such as CKD, are highly reactive with carbon dioxide (CO2). In the presence of water, CKD can sequester greater than 80% of its theoretical capacity for carbon without any amendments or modifications to the waste. Other mineral carbonation technologies for carbon sequestration rely on the use of mined mineral feedstocks as the source of oxides. The mining, pre-processing and reaction conditions needed to create favorable carbonation kinetics all require significant additions of energy to the system. Therefore, their actual net reduction in CO2 is uncertain. Many suitable alkaline wastes are produced at sites that also generate significant quantities of CO2. While independently, the reduction in CO2 emissions from mineral carbonation in CKD is small (~13% of process related emissions), when this technology is applied to similar wastes of other industries, the collective net reduction in emissions may be significant. The technical investigations presented in this dissertation progress from proof of feasibility through examination of the extent of sequestration in core samples taken from an aged CKD waste pile, to more fundamental batch and microscopy studies which analyze the rates and mechanisms controlling mineral carbonation reactions in a variety of fresh CKD types. Finally, the scale of the system was increased to assess the sequestration efficiency under more pilot or field-scale conditions and to clarify the importance of particle-scale processes under more dynamic (flowing gas) conditions. A comprehensive set of material characterization methods, including thermal analysis, Xray diffraction, and X-ray fluorescence, were used to confirm extents of carbonation and to better elucidate those compositional factors controlling the reactions. The results of these studies show that the rate of carbonation in CKD is controlled by the extent of carbonation. With increased degrees of conversion, particle-scale processes such as intraparticle diffusion and CaCO3 micropore precipitation patterns begin to limit the rate and possibly the extent of the reactions. Rates may also be influenced by the nature of the oxides participating in the reaction, slowing when the free or unbound oxides are consumed and reaction conditions shift towards the consumption of less reactive Ca species. While microscale processes and composition affects appear to be important at later times, the overall degrees of carbonation observed in the wastes were significant (> 80%), a majority of which occurs within the first 2 days of reaction. Under the operational conditions applied in this study, the degree of carbonation in CKD achieved in column-scale systems was comparable to those observed under ideal batch conditions. In addition, the similarity in sequestration performance among several different CKD waste types indicates that, aside from available oxide content, no compositional factors significantly hinder the ability of the waste to sequester CO2.

Effects of carbonation on the mineral composition of cement kiln dust

Due to their relatively high calcium oxide content, industrial mineral oxide wastes are potential candidates for mineral sequestration of carbon dioxide (CO2). Cement kiln dust (CKD), a byproduct of cement manufacturing contains 20-60% CaO making it a possible candidate for CO2 sequestration. In this study, three types of CKD are characterized, before and after carbonation, using environmental scanning electron microscopy and energy dispersive x-ray microanalysis to determine the mineralogical and morphological changes occurring due to carbonation. The reactants, products, and precipitation mechanisms were investigated to enhance understanding of the governing processes and allow better utilization of CKD for CO2 sequestration. The results of multiple independent analyses confirmed the formation of CaCO3 during carbonation. Examinations of the reaction pathways found that CaO and calcium hydroxide (Ca(OH)2) were the major reactants. Three types of CaCO3 precipitation mechanisms were observed: (1) diffusion of CO2 into Ca(OH)2 particles causing precipitation in the pores of the particle and the growth of a CaCO3 ring from the outside inward, (2) precipitation onto existing particles, and (3) precipitation from aqueous solution. The growth of a CaCO3 ring on the outside of a particle may slow further diffusion of CO2 into a particle slowing iv the overall sequestration rate. Additionally, changes caused by carbonation in the solubility of trace metals were studied by mixing pre- and post-carbonated CKD with water and analyzing the solution using inductively coupled plasma mass spectrometry. Decreases in the leaching of chromium, lead, and copper were observed, and is an incentive for use of CKD for CO2 sequestration. Equilibrium modeling using PHREEQC confirmed that CaO and Ca(OH)2 would carbonate readily and form CaCO3.

Vertebroplasty: experimental characterization of polymethylmethacrylate bone cement spreading as a function of viscosity, bone porosity, and flow rate

STUDY DESIGN: This is an experimental study on an artificial vertebra model and human cadaveric spine. OBJECTIVE: Characterization of polymethylmethacrylate (PMMA) bone cement distribution in the vertebral body as a function of cement viscosity, bone porosity, and injection speed. Identification of relevant parameters for improved cement flow predictability and leak prevention in vertebroplasty. SUMMARY OF BACKGROUND DATA: Vertebroplasty is an efficient procedure to treat vertebral fractures and stabilize osteoporotic bone in the spine. Severe complications result from bone cement leakage into the spinal canal or the vascular system. Cement viscosity has been identified as an important parameter for leak prevention but the influence of bone structure and injection speed remain obscure. METHODS: An artificial vertebra model based on open porous aluminum foam was used to simulate bone of known porosity. Fifty-six vertebroplasties with 4 different starting viscosity levels and 2 different injection speeds were performed on artificial vertebrae of 3 different porosities. A validation on a human cadaveric spine was executed. The experiments were radiographically monitored and the shape of the cement clouds quantitatively described with the 2 indicators circularity and mean cement spreading distance. RESULTS: An increase in circularity and a decrease in mean cement spreading distance was observed with increasing viscosity, with the most striking change occurring between 50 and 100 Pas. Larger pores resulted in significantly reduced circularity and increased mean cement spreading distance whereas the effect of injection speed on the 2 indicators was not significant. CONCLUSION: Viscosity is the key factor for reducing the risk of PMMA cement leakage and it should be adapted to the degree of osteoporosis encountered in each patient. It may be advisable to opt for a higher starting viscosity but to inject the material at a faster rate.

Characterization of a Coal Fly Ash-Cement Slurry by the Absolute Foam Index

This dissertation established a standard foam index: the absolute foam index test. This test characterized a wide range of coal fly ash by the absolute volume of air-entraining admixture (AEA) necessary to produce a 15-second metastable foam in a coal fly ash-cement slurry in a specified time. The absolute foam index test was used to characterize fly ash samples having loss on ignition (LOI) values that ranged from 0.17 to 23.3 %wt. The absolute foam index characterized the fly ash samples by absolute volume of AEA, defined as the amount of undiluted AEA solution added to obtain a 15-minute endpoint signified by 15-second metastable foam. Results were compared from several foam index test time trials that used different initial test concentrations to reach termination at selected times. Based on the coefficient of variation (CV), a 15-minute endpoint, with limits of 12 to 18 minutes was chosen. Various initial test concentrations were used to accomplish consistent contact times and concentration gradients for the 15-minute test endpoint for the fly ash samples. A set of four standard concentrations for the absolute foam index test were defined by regression analyses and a procedure simplifying the test process. The set of standard concentrations for the absolute foam index test was determined by analyzing experimental results of 80 tests on coal fly ashes with loss on ignition (LOI) values ranging from 0.39 to 23.3 wt.%. A regression analysis informed selection of four concentrations (2, 6, 10, and 15 vol.% AEA) that are expected to accommodate fly ashes with 0.39 to 23.3 wt.% LOI, depending on the AEA type. Higher concentrations should be used for high-LOI fly ash when necessary. A procedure developed using these standard concentrations is expected to require only 1-3 trials to meet specified endpoint criteria for most fly ashes. The AEA solution concentration that achieved the metastable foam in the foam index test was compared to the AEA equilibrium concentration obtained from the direct adsorption isotherm test with the same fly ash. The results showed that the AEA concentration that satisfied the absolute foam index test was much less than the equilibrium concentration. This indicated that the absolute foam index test was not at or near equilibrium. Rather, it was a dynamic test where the time of the test played an important role in the results. Even though the absolute foam index was not an equilibrium condition, a correlation was made between the absolute foam index and adsorption isotherms. Equilibrium isotherm equations obtained from direct isotherm tests were used to calculate the equilibrium concentrations and capacities of fly ash from 0.17 to 10.5% LOI. The results showed that the calculated fly ash capacity was much less than capacities obtained from isotherm tests that were conducted with higher initial concentrations. This indicated that the absolute foam index was not equilibrium. Rather, the test is dynamic where the time of the test played an important role in the results. Even though the absolute foam index was not an equilibrium condition, a correlation was made between the absolute foam index and adsorption isotherms for fly ash of 0.17 to 10.5% LOI. Several batches of mortars were mixed for the same fly ash type increasing only the AEA concentration (dosage) in each subsequent batch. Mortar air test results for each batch showed for each increase in AEA concentration, air contents increased until a point where the next increase in AEA concentration resulted in no increase in air content. This was maximum air content that could be achieved by the particular mortar system; the system reached its air capacity at the saturation limit. This concentration of AEA was compared to the critical micelle concentration (CMC) for the AEA and the absolute foam index.

Zementaugmentation bei Wirbelmetastasen (Vertebro- und Kyphoplasie) [Cement injection for spinal metastases (vertebroplasty and kyphoplasty)]

Osteolytic lesions of the spine (metastasis, myeloma) can be treated extremely efficiently by percutaneous cement injection. The treatment should be restricted to osteolytic lesions of the vertebral body, and only if a relevant mechanical deterioration is present. If the pedicles and/or the lamina are involved and if there is compression of the spinal canal, the treatment is no longer appropriate. The surgical technique is similar to the treatment of osteoporotic fractures; however, there is definitely a higher risk for cement leakage and the clinical outcome is not as predictable as in osteoporotic fracture treatment. It is important to realize that cement injection per se has no impact on the tumor itself, but provides stability to the vertebral body. An osteolytic lesion without mechanical compromise does not need a vertebroplasty. Patients with tumorous lesions of the spine should be followed by an interdisciplinary team of spine surgeon, oncologist and radio-oncologist.

The effect of pulsed jet lavage in vertebroplasty on injection forces of PMMA bone cement: an animal study

Percutaneous vertebroplasty, comprising of the injection of polymethylmethacrylate (PMMA) into vertebral bodies, is an efficient procedure to stabilize osteoporotic compression fractures as well as other weakening lesions. Besides fat embolism, cement leakage is considered to be one of the major and most severe complications during percutaneous vertebroplasty. The viscosity of the PMMA during injection plays a key role in this context. It was shown in vitro that the best way to lower the risk of cement leakage is to inject the cement at higher viscosity, which is requires high injection forces. Injection forces can be reduced by applying a newly developed lavage technique as it was shown in vitro using human cadaver vertebrae. The purpose of this study was to prove the in vitro results in an in vivo model. The investigation was incorporated in an animal study that was performed to evaluate the cardiovascular reaction on cement augmentation using the lavage technique. Injection forces were measured with instrumentation for 1 cc syringes, additionally acquiring plunger displacement. Averaged injection forces measured, ranged from 12 to 130 N and from 28 to 140 N for the lavage group and the control group, respectively. Normalized injection forces (by viscosity and injection speed) showed a trend to be lower for the lavage group in comparison to the control group (P = 0.073). In conclusion, the clinical relevance on the investigated lavage technique concerning lowering injection forces was only shown by trend in the performed animal study. However, it might well be that the effect is more pronounced for osteoporotic vertebral bodies.

Clinical investigations of polymethylmethacrylate cement viscosity during vertebroplasty and related in vitro measurements

Percutaneous vertebroplasty, comprising an injection of polymethylmethacrylate (PMMA) into vertebral bodies, is a practical procedure for the stabilization of osteoporotic compression fractures as well as other weakening lesions. Cement leakage is considered to be one of the major and most severe complications during percutaneous vertebroplasty. The viscosity of the material plays a key role in this context. In order to enhance the safety for the patient, a rheometer system was developed to measure the cement viscosity intraoperatively. For this development, it is of great importance to know the proper viscosity to start the procedure determined by experienced surgeons and the relation between the time period when different injection devices are used and the cement viscosity. The purpose of the study was to investigate the viscosity ranges for different injection systems during conventional vertebroplasty. Clinically observed viscosity values and related time periods showed high scattering. In order to get a better understanding of the clinical observations, cement viscosity during hardening at different ambient temperatures and by simulation of the body temperature was investigated in vitro. It could be concluded, that the direct viscosity assessment with a rheometer during vertebroplasty can help clinicians to define a lower threshold viscosity and thereby decrease the risk of leakage and make adjustments to their injection technique in real time. Secondly, the acceleration in hardening of PMMA-based cements at body temperature can be useful in minimizing leakages by addressing them with a short injection break.

Differences in endplate deformation of the adjacent and augmented vertebra following cement augmentation

Vertebral cement augmentation can restore the stiffness and strength of a fractured vertebra and relieve chronic pain. Previous finite element analysis, biomechanical tests and clinical studies have indirectly associated new adjacent vertebral fractures following augmentation to altered loading. The aim of this repeated measures in situ biomechanical study was to determine the changes in the adjacent and augmented endplate deformation following cement augmentation of human cadaveric functional spine units (FSU) using micro-computed tomography (micro-CT). The surrounding soft tissue and posterior elements of 22 cadaveric human FSU were removed. FSU were assigned to two groups, control (n = 8) (loaded on day 1 and day 2) and augmented (n = 14) (loaded on day 1, augmented 20% cement fill, and loaded on day 2). The augmented group was further subdivided into a prophylactic augmentation group (n = 9), and vertebrae which spontaneously fractured during loading on day 1 (n = 5). The FSU were axially loaded (200, 1,000, 1,500-2,000 N) within a custom made radiolucent, saline filled loading device. At each loading step, FSUs were scanned using the micro-CT. Endplate heights were determined using custom software. No significant increase in endplate deformation following cement augmentation was noted for the adjacent endplate (P > 0.05). The deformation of the augmented endplate was significantly reduced following cement augmentation for both the prophylactic and fracture group (P < 0.05, P < 0.01, respectively). Endplate deformation of the controls showed no statistically significant differences between loading on day 1 and day 2. A linear relationship was noted between the applied compressive load and endplate deflection (R (2) = 0.58). Evidence of significant endplate deformation differences between unaugmented and augmented FSU, while evident for the augmented endplate, was not present for the adjacent endplate. This non-invasive micro-CT method may also be useful to investigate endplate failure, and parameters that predict vertebral failure.

Temporary zinc oxide-eugenol cement: eugenol quantity in dentin and bond strength of resin composite

Uptake of eugenol from eugenol-containing temporary materials may reduce the adhesion of subsequent resin-based restorations. This study investigated the effect of duration of exposure to zinc oxide–eugenol (ZOE) cement on the quantity of eugenol retained in dentin and on the microtensile bond strength (μTBS) of the resin composite. The ZOE cement (IRM Caps) was applied onto the dentin of human molars (21 per group) for 1, 7, or 28 d. One half of each molar was used to determine the quantity of eugenol (by spectrofluorimetry) and the other half was used for μTBS testing. The ZOE-exposed dentin was treated with either OptiBond FL using phosphoric acid (H3PO4) or with Gluma Classic using ethylenediaminetetraacetic acid (EDTA) conditioning. One group without conditioning (for eugenol quantity) and two groups not exposed to ZOE (for eugenol quantity and μTBS testing) served as controls. The quantity of eugenol ranged between 0.33 and 2.9 nmol mg−1 of dentin (median values). No effect of the duration of exposure to ZOE was found. Conditioning with H3PO4 or EDTA significantly reduced the quantity of eugenol in dentin. Nevertheless, for OptiBond FL, exposure to ZOE significantly decreased the μTBS, regardless of the duration of exposure. For Gluma Classic, the μTBS decreased after exposure to ZOE for 7 and 28 d. OptiBond FL yielded a significantly higher μTBS than did Gluma Classic. Thus, ZOE should be avoided in cavities later to be restored with resin-based materials.

Percutaneous cement augmentation techniques for osteoporotic spinal fractures

Minimally invasive vertebral augmentation-based techniques have been used for the treatment of spinal fractures (osteoporotic and malignant) for approximately 25 years. In this review, we try to give an overview of the current spectrum of percutaneous augmentation techniques, safety aspects and indications. Crucial factors for success are careful patient selection, proper technique and choice of the ideal cement augmentation option. Most compression fractures present a favourable natural course, with reduction of pain and regainment of mobility after a few days to several weeks, whereas other patients experience a progressive collapse and persisting pain. In this situation, percutaneous cement augmentation is an effective treatment option with regards to pain and disability reduction, improvement of quality of life and ambulatory and pulmonary function.

Cement-augmented anterior screw fixation of Type II odontoid fractures in elderly patients with osteoporosis

BACKGROUND CONTEXT: Closed reduction and internal fixation by an anterior approach is an established option for operative treatment of displaced Type II odontoid fractures. In elderly patients, however, inadequate screw purchase in osteoporotic bone can result in severe procedure-related complications. PURPOSE: To improve the stability of odontoid fracture screw fixation in the elderly using a new technique that includes injection of polymethylmethacrylat (PMMA) cement into the C2 body. STUDY DESIGN: Retrospective review of hospital and outpatient records as well as radiographs of elderly patients treated in a university hospital department of orthopedic surgery. PATIENT SAMPLE: Twenty-four elderly patients (8 males and 16 females; mean age, 81 years; range, 62-98 years) with Type II fractures of the dens. OUTCOME MEASURES: Complications, cement leakage (symptomatic/asymptomatic), operation time, loss of reduction, pseudarthrosis and revision surgery, patient complaints, return to normal activities, and signs of neurologic complications were all documented. METHODS: After closed reduction and anterior approach to the inferior border of C2, a guide wire is advanced to the tip of the odontoid under biplanar fluoroscopic control. Before the insertion of one cannulated, self-drilling, short thread screws, a 12 gauge Yamshidi cannula is inserted from anterior and 1 to 3 mL of high-viscosity PMMA cement is injected into the anteroinferior portion of the C2 body. During polymerization of the cement, the screws are further inserted using a lag-screw compression technique. The cervical spine then is immobilized with a soft collar for 8 weeks postoperatively. RESULTS: Anatomical reduction of the dens was achieved in all 24 patients. Mean operative time was 64 minutes (40-90 minutes). Early loss of reduction occurred in three patients, but revision surgery was indicated in only one patient 2 days after primary surgery. One patient died within the first eight postoperative weeks, one within 3 months after surgery. In five patients, asymptomatic cement leakage was observed (into the C1-C2 joint in three patients, into the fracture in two). Conventional radiologic follow-up at 2 and 6 months confirmed anatomical healing in 16 of the19 patients with complete follow-up. In two patients, the fractures healed in slight dorsal angulation; one patient developed a asymptomatic pseudarthrosis. All patients were able to resume their pretrauma level of activity. CONCLUSIONS: Cement augmentation of the screw in Type II odontoid fractures in elderly patients is technically feasible in a clinical setting with a low complication rate. This technique may improve screw purchase, especially in the osteoporotic C2 body.

The cement prosthesis-like spacer: an intermediate halt on the road to healing.

BACKGROUND Periprosthetic infections remain a devastating problem in the field of joint arthroplasty. In the following study, the results of a two-stage treatment protocol for chronic periprosthetic infections using an intraoperatively molded cement prosthesis-like spacer (CPLS) are presented. METHODS Seventy-five patients with chronically infected knee prosthesis received a two-stage revision procedure with the newly developed CPLS between June 2006 and June 2011. Based on the microorganism involved, patients were grouped into either easy to treat (ETT) or difficult to treat (DTT) and treated accordingly. Range of motion (ROM) and the knee society score (KSS) were utilized for functional assessment. RESULTS Mean duration of the CPLS implant in the DTT group was 3.6 months (range 3-5 months) and in the ETT group 1.3 months (range 0.7-2.5 months). Reinfection rates of the final prosthesis were 9.6% in the ETT and 8.3% in the DTT group with no significant difference between both groups regarding ROM or KSS (P = 0.87, 0.64, resp.). CONCLUSION The results show that ETT patients do not necessitate the same treatment protocol as DTT patients to achieve the same goal, emphasizing the need to differentiate between therapeutic regimes. We also highlight the feasibility of CLPS in two-stage protocols.

In vitro temperature evaluation during cement augmentation of proximal humerus plate screw tips

BACKGROUND The treatment of proximal humerus fractures in patients with poor bone quality remains a challenge in trauma surgery. Augmentation with polymethylmethacrylate (PMMA) cement is a possible method to strengthen the implant anchorage in osteoporotic bone and to avoid loss of reduction and reduce the cut-out risk. The polymerisation of PMMA during cement setting leads, however, to an exothermic reaction and the development of supraphysiological temperatures may harm the bone and cartilage. This study addresses the issue of heat development during augmentation of subchondrally placed proximal humerus plate screws with PMMA and the possible risk of bone and cartilage necrosis and apoptosis. METHODS Seven fresh frozen humeri from geriatric female donors were instrumented with the proximal humerus interlocking system (PHILOS) plate and placed in a 37°C water bath. Thereafter, four proximal perforated screws were augmented with 0.5 ml PMMA each. During augmentation, the temperatures in the subchondral bone and on the articular surface were recorded with K-type thermocouples. The measured temperatures were compared to threshold values for necrosis and apoptosis of bone and cartilage reported in the literature. RESULTS The heat development was highest around the augmented tips of the perforated screws and diminished with growing distance from the cement cloud. The highest temperature recorded in the subchondral bone reached 43.5°C and the longest exposure time above 42°C was 86s. The highest temperature measured on the articular surface amounted to 38.6°C and the longest exposure time above 38°C was 5 min and 32s. CONCLUSION The study shows that augmentation of the proximal screws of the PHILOS plate with PMMA leads to a locally limited development of supraphysiological temperatures in the cement cloud and closely around it. The critical threshold values for necrosis and apoptosis of cartilage and subchondral bone reported in the literature, however, are not reached. In order to avoid cement extravasation, special care should be taken in detecting perforations or intra-articular cracks in the humeral head.