Prediction of Thermogravimetric Data in Bromine Captured from Brominated Flame Retardants (BFRs) in e-Waste Treatment Using Machine Learning Approaches.

The principal objective in the treatment of e-waste is to capture the bromine released from the brominated flame retardants (BFRs) added to the polymeric constituents of printed circuits boards (PCBs) and to produce pure bromine-free hydrocarbons. Metal oxides such as calcium hydroxide (Ca(OH)2) have been shown to exhibit high debromination capacity when added to BFRs in e-waste and capturing the released HBr. Tetrabromobisphenol A (TBBA) is the most commonly utilized model compound as a representative for BFRs. Our coauthors had previously studied the pyrolytic and oxidative decomposition of the TBBA:Ca(OH)2 mixture at four different heating rates, 5, 10, 15, and 20 °C/min, using a thermogravimetric (TGA) analyzer and reported the mass loss data between room temperature and 800 °C. However, in the current work, we applied different machine learning (ML) and chemometric techniques involving regression models to predict the TGA data at different heating rates. The motivation of this work was to reproduce the TGA data with high accuracy in order to eliminate the physical need of the instrument itself, so that this could save significant experimental time involving sample preparation and subsequently minimizing human errors. The novelty of our work lies in the application of ML techniques to predict the TGA data from e-waste pyrolysis since this has not been conducted previously. The significance of our work lies in the fact that e-waste is ever increasing, and predicting the mass loss curves faster will enable better compositional analysis of the e-waste samples in the industry. Three ML models were employed in our work, namely Linear, random forest (RF), and support vector regression (SVR), out of which the RF method exhibited the highest coefficient of determination (R2) of 0.999 and least error of prediction as estimated by the root mean squared error (RMSEP) at all 4 heating rates for both pyrolysis and oxidation conditions. An 80:20 split was used for calibration and validation data sets. Furthermore, for showing versatility and robustness of the best-predicting RF model, it was also trained using all the data points in the lower heating rates of 5 and 10 °C/min and predicted on all the data points for the higher heating rates of 15 and 20 °C/min to again obtain a high R2 of 0.999. The excellent performance of the RF model showed that ML techniques can be used to eliminate the physical use of TGA equipment, thus saving experimental time and potential human errors, and can further be applied in other real-time e-waste recycling scenarios.

Computed tomography-derived skeletal muscle index: A novel predictor of frailty and hospital length of stay after transcatheter aortic valve replacement.

To determine the prevalence of low skeletal muscle mass in patients undergoing transcatheter aortic valve replacement (TAVR) and whether skeletal muscle mass measured from preoperative computed tomography (CT) images provides value in predicting postoperative length of stay (LOS). BACKGROUND: There are limited data on the use of body composition as a frailty measure in TAVR patients and no studies have determined if this measure predicts LOS. METHODS: We studied 104 consecutive patients who underwent TAVR at Tallahassee Memorial Hospital from 2012 to 2016. Patient demographics, standard frailty measures (hand grip, albumin, and 5-m walk test), clinical comorbidities, echocardiographic data, and Valve Academic Research Consortium II major complications were recorded prospectively. Skeletal muscle index (SMI) [skeletal muscle mass cross-sectional area at L3/height2] was measured from CT images using Slice-O-Matic software (Tomovision, Montreal, Quebec, Canada). Clinical outcomes were assessed and multivariate methods used to determine predictors of LOS. RESULTS: Sarcopenia was prevalent in men (83%) and women (56%). Patients who suffered from a major complication had significantly longer length of stay (13 vs 4.6days, P<.0001). Skeletal muscle index correlated with age, sex, body mass index, handgrip strength, and previous coronary artery bypass graft surgery, but not major complications. A multivariate model including all univariate predictors of LOS showed SMI, major complications, transapical access, atrial fibrillation, and chronic obstructive pulmonary syndrome as independent predictors of LOS. For every 14-cm2/m2 increase in SMI, there was a 1-day reduction in LOS. None of the standard measures of frailty predicted LOS. CONCLUSIONS: Skeletal muscle index, a measure of sarcopenia readily determined from pre-TAVR CT scans, independently predicts TAVR LOS better than standard frailty testing. Further evaluation of SMI as a frailty measure after TAVR and other cardiovascular procedures is warranted.

Debromination of novel brominated flame retardants using Zn-based additives: A viable thermochemical approach in the mitigation of toxic effects during e-waste recycling.

Brominated flame retardants (BFRs) are bromine-bearing additives added to the polymeric fraction in various applications to impede fire ignition. The Stockholm Convention and various other legislations abolished legacy BFRs usage and hence, the so-called novel BFRs (NBFRs) were introduced into the market. Recent studies spotlighted their existence in household dust, aquifers and aquatic/aerial species. Co-pyrolysis of BFRs with metal oxides has emerged as a potent chemical recycling approach that produces a bromine-free stream of hydrocarbon. Herein, we investigate the debromination of two prominent two NBFRs; namely tetrabromobisphenol A 2,3-dibromopropyl ether (TD) and tetrabromobisphenol A diallyl ether (TAE) through their co-pyrolysis with zinc oxide (ZnO) and franklinite (ZnFe2O4). Most of the zinc content in electrical arc furnace dust (EAFD) exists in the form of these two metal oxides. Conversion of these metal oxides into their respective bromides could also assist in the selective extraction of the valuable zinc content in EAFD. The debromination potential of both oxides was unveiled via a multitude of characterization studies to analyze products (char, gas and condensates). The thermogravimetric analysis suggested a pyrolytic run up to 500 °C and the TAE treatment with ZnO produced only a trivial amount of brominated compounds (relative area, 0.83%). Phenol was the sole common compound in condensable products; potentially formed by the ß-scission debromination reaction from the parental molecular skeleton. Inorganic compounds and methane were the major constituents in the gaseous products. The pyrochar analyses confirmed the presence of metal bromides retained in the residue, averting the bromine release into the atmosphere. The ion chromatography analysis portrayed <8% of HBr gas release into the atmosphere upon pyrolysis with ZnO. The ZnO dominance herein envisaged further probes into other spinel ferrites in combating brominated polymers.

Combating toxic emissions from thermal recycling of polymeric fractions laden with novel brominated flame retardants (NBFRs) in e-waste: an in-situ approach using Ca(OH)2.

Legacy brominated flame retardants (BFRs) in printed circuit boards are gradually being replaced by novel BFRs (NBFRs). Safe disposal and recycling of polymeric constituents in the polymeric fractions of e-waste necessitate the removal of their toxic and corrosive bromine content. This is currently acquired through thermal recycling operations involving the pyrolysis of BFRs-containing materials with metal oxides. Nonetheless, the debromination capacity toward NBFRs is yet to be established. Thus, this study aims to address these two crucial gaps in the current knowledge pertaining to the plausible formation of brominated toxicants from the thermal decomposition of NBFRs and their thermal recycling potential. Herein, we investigate the pyrolysis of a mixture of 2,4,6-tribromophenol (TBP), allyl 2,4,6-tribromophenyl ether (ATE) and Tetrabromobisphenol A-bis (2,3-dibromo propyl ether) (TBBPA-DBPE) in the presence of acrylonitrile butadiene styrene (ABS) polymers at various loads. To demonstrate a viable debromination route, pyrolysis of NBFRs-ABS mixture with Ca(OH)2 was also investigated. The latter is a potent debromination agent for legacy BFRs. Upon pyrolysis with Ca(OH)2, the bromine content in the collected oil was reduced up to 80.49% between 25-500 °C. Products of the co-pyrolysis process generally feature non-brominated aromatic and aliphatic compounds; a finding that indicates an effective thermal recycling approach. As evident by IC measurements, no HBr emission could be detected when Ca(OH)2 is added to the mixture. As XRD patterns show, Ca(OH)2 is partially converted into CaBr2. DFT calculations provide pathways for the observed surface debromination characterized by surface-assisted fission of aromatic C-Br bonds and the formation of CaBr sites. Outcomes reported herein are instrumental to designing and operating a thermal recycling facility of polymeric materials contaminated with high loads of bromine, i.e., most notably during scenarios encountered in the thermal recycling of e-waste.

Prediction of Thermogravimetric Data in the Thermal Recycling of e-waste Using Machine Learning Techniques: A Data-driven Approach.

The release of bromine-free hydrocarbons and gases is a major challenge faced in the thermal recycling of e-waste due to the corrosive effects of produced HBr. Metal oxides such as Fe2O3 (hematite) are excellent debrominating agents, and they are copyrolyzed along with tetrabromophenol (TBP), a lesser used brominated flame retardant that is a constituent of printed circuit boards in electronic equipment. The pyrolytic (N2) and oxidative (O2) decomposition of TBP with Fe2O3 has been previously investigated with thermogravimetric analysis (TGA) at four different heating rates of 5, 10, 15, and 20 °C/min, and the mass loss data between room temperature and 800 °C were reported. The objective of our paper is to study the effectiveness of machine learning (ML) techniques to reproduce these TGA data so that the use of the instrument can be eliminated to enhance the potential of online monitoring of copyrolysis in e-waste treatment. This will reduce experimental and human errors as well as improve process time significantly. TGA data are both nonlinear and multidimensional, and hence, nonlinear regression techniques such as random forest (RF) and gradient boosting regression (GBR) showed the highest prediction accuracies of 0.999 and lowest prediction errors among all the ML models employed in this work. The large data sets allowed us to explore three different scenarios of model training and validation, where the number of training samples were varied from 10,000 to 40,000 for both TBP and TBP + hematite samples under N2 (pyrolysis) and O2 (combustion) environments. The novelty of our study is that ML techniques have not been employed for the copyrolysis of these compounds, while the significance is the excellent potential of enhanced online monitoring of e-waste treatment and extension to other characterization techniques such as spectroscopy and chromatography. Lastly, e-waste recycling could greatly benefit from ML applications since it has the potential to reduce total and operational costs and improve overall process time and efficiency, thereby encouraging more treatment plants to adopt these techniques, resulting in reducing the increasing environmental footprint of e-waste.

Degradation of tetrabromobisphenol A (TBBA) with calcium hydroxide: a thermo-kinetic analysis.

Thermal treatment of bromine-contaminated polymers (i.e., as in e-waste) with metal oxides is currently deployed as a mainstream strategy in recycling and resources recovery from these objects. The underlying aim is to capture the bromine content and to produce pure bromine-free hydrocarbons. Bromine originates from the added brominated flame retardants (BFRs) to the polymeric fractions in printed circuits boards, where tetrabromobisphenol A (TBBA) is the most utilized BFR. Among notable deployed metal oxides is calcium hydroxide, i.e., Ca(OH)2 that often displays high debromination capacity. Comprehending thermo-kinetic parameters that account for the BFRs:Ca(OH)2 interaction is instrumental to optimize the operation at an industrial scale. Herein, we report comprehensive kinetics and thermodynamics studies into the pyrolytic and oxidative decomposition of a TBBA:Ca(OH)2 mixture at four different heating rates, 5, 10, 15, and 20 °C min-1, carried out using a thermogravimetric analyser. Fourier Transform Infrared Spectroscopy (FTIR) and a carbon, hydrogen, nitrogen, and sulphur (CHNS) elemental analyser established the vibrations of the molecules and carbon content of the sample. From the thermogravimetric analyser (TGA) data, the kinetic and thermodynamic parameters were evaluated using iso-conversional methods (KAS, FWO, and Starink), which were further validated by the Coats-Redfern method. The computed activation energies for the pyrolytic decomposition of pure TBBA and its mixture with Ca(OH)2 reside in the narrow ranges of 111.7-112.1 kJ mol-1 and 62.8-63.4 kJ mol-1, respectively (considering the various models). Obtained negative ΔS values suggest the formation of stable products. The synergic effects of the blend exhibited positive values in the low-temperature ranges (200-300 °C) due to the emission of HBr from TBBA and the solid-liquid bromination process occurring between TBBA and Ca(OH)2. From a practical point of view, data provided herein are useful in efforts that aim to fine-tune operational conditions encountered in real recycling scenarios, i.e., in co-pyrolysis of e-waste with Ca(OH)2 in rotary kilns.

Development of candidate gene-based markers and map-based cloning of a dominant rust resistance gene in cultivated groundnut (Arachis hypogaea L.).

A dominant rust resistance gene, VG 9514-Rgene was isolated through map-based cloning. Sequence analysis revealed non-synonymous mutations in the TIR, NBS and LRR region of the R-protein. Candidate gene-based markers from these SNPs revealed complete co-segregation of the isolated VG 9514-Rgene with rust resistance in a RIL population and confirmed their map position in between FRS 72 and SSR_GO340445 markers in arahy03 chromosome. Blastp search of VG 9514-Rprotein detected Arahy.T6DCA5 with >80.0% identity that localized at 142,544,745.0.142,549,184 in arahy03 chromosome. Ka/Ks calculation revealed that VG 9514-Rgene had undergone positive selection compared to four homologous genes in the groundnut genome. Homology based structure modelling of this R-protein revealed a typical consensus three-dimensional folding of TIR-NBS-LRR protein. Non-synonymous mutations in susceptible version of R-protein were mapped and found E268Q mutation in hhGRExE motif, Y309F in RNBS-A motif and I579T in MHD motif of NB-ARC domain are probable candidates for loss of function.

Anorectal Cancer with Bone Marrow and Leptomeningeal Metastases.

This is an interesting case of anorectal signet ring carcinoma with first presentation of an early stage disease, showing the aggressive disease and the undetectable behavior of this type of histology which can mislead diagnosis. Brain/CNS metastasis from colorectal cancer (CRC) is rare occurring in 3% of cases, and leptomeningeal carcinomatosis (LMC) is extremely rare in CRC (<0.02%). Symptoms and signs of LMC are pleomorphic and may be localized to three compartments: cerebral hemispheres, cranial nerves, and spinal cords and roots. Treatment of metastatic rectal cancer has been improving over the last few years with a lot of changes toward longer survival and improvement in quality of life and to change the disease into a chronic condition. However, in our case, the overall survival from the onset of LMC was 3 weeks only. Revising the evidence in the treatment of signet ring histology of rectal cancer, there is no specific treatment recommendation that is for this histology and for such very aggressive behavior which could be considered as a separate entity to the classic adenocarcinoma histology.

A severely displaced metaphyseal fracture of the proximal humerus with dislocation of the shoulder in a child / 中华创伤杂志(英文版)

Fracture of the proximal humerus metaphysis with coexistent dislocation of the shoulder in children is a rare injury. The injury often occurs as a consequence of high velocity trauma. Most fractures of the proximal humerus commonly associated with the epiphysis in children can be treated with closed reduction. We presented a case of 5-year-old girl who sustained this type of fracture- dislocation of the shoulder. Open reduction and internal fixation with multiple smooth K-wires was performed. At two years follow-up, the patient was pain free and regained full range of motion.

Correlations of cerebrospinal fluid pressure with hemodynamic parameters during thoracoabdominal aortic aneurysm repair.

Central venous pressure (CVP) has long been thought to correlate with cerebrospinal fluid (CSF) pressure during thoracoabdominal aortic aneurysm repair. We examined hemodynamic factors during thoracoabdominal aortic aneurysm surgery to determine their relationship with CSF pressure and aortic cross-clamping. Hemodynamic parameters and CSF pressure were measured in 124 patients at six different stages during repair of descending thoracic or thoracoabdominal aortic aneurysms: skin incision, left lung collapse, pump on, aortic clamp on, aortic clamp off, and pump off. Stepwise multiple regression analysis was used for statistical analysis. CVP was a weak predictor for CSF pressure at the beginning of surgery and when the pump was initiated. At the onset of left lung collapse, cardiac output correlated with CSF pressure. There were no predictors during aortic cross-clamping. Model r2 values were low, ranging 0.03-0.15. We found no hemodynamic predictors of CSF pressure throughout the period of aortic cross-clamping during descending thoracic or thoracoabdominal aortic aneurysm surgery. Model r2 values were low, indicating generally poor prediction of CSF pressure.

Determinants of early and late outcome for reoperations of the proximal aorta.

BACKGROUND: The purpose of this study was to investigate the cause of ascending aorta and aortic arch reoperations and to identify determinants of early and late outcome. METHODS: Between January 1991 and March 2003 we repaired aneurysms of the proximal aorta in 597 patients. Of these patients, 104 had reoperations for replacement of the ascending aorta, aortic root, or transverse aortic arch. Previous surgery was defined as any previous cardiac or proximal aortic repair. Median age was 60 years, and 29 of the patients (28%) were female. Indications for reoperation and replacement of the proximal aorta included acute type A dissection in 6 patients (5.8%), aneurysm with chronic dissection in 60 (57.7%), progression of aneurysm in 23 (22.1%), infection in 12 (1.5%), inflammatory disease in 2 (1.9%), and atheromatous disease in 1 (1.0%). Reoperations included aortic root replacement in 20 patients (19.2%), total arch replacement with elephant trunk in 28 (26.7%), ascending and proximal arch in 39 (37.5%), and ascending aorta in 27 (26.0%). The median interval between operations was 69 months. Retrograde cerebral perfusion was used in 80 (77%) cases. RESULTS: Chronic dissection was the most common indicator for reoperation in our population, followed by progression of aneurysm and infection. Thirty-day and in-hospital mortality was 13.5% (14 of 104) and 15.4% (16 of 104), respectively. Chronic obstructive pulmonary disease, renal dysfunction, and increased pump time were risk factors for mortality. Median follow-up was 5.02 years. Eight patients died during that period. Estimated survival at 1, 5, and 10 years was 83%, 80%, and 62%, respectively. Freedom from second proximal reoperations was 97.1% (10 of 104). Freedom from subsequent distal thoracic aortic repair was 84.6% (8 of 104). CONCLUSIONS: Reoperations of the ascending aorta and aortic arch can be performed safely with good long-term results. Patients with previous proximal aortic dissection repair need long-term surveillance. Renal dysfunction and chronic obstructive pulmonary disease must be carefully considered before reoperations of the proximal aorta.

Trans-Scaphoid Perilunate Dislocation with Fractured Carpal Bones in a Child: A Case Report / 대한정형외과학회잡지

Transcarpal fractures and dislocations in children are rarely reported in the orthopedics literature. This is a case report of a 10-year-old boy who sustained a trans-scaphoid perilunate dislocation with fractures across the carpal structure: these included injuries to the capitate and triquetrum bones. Treatment consists of a closed reduction for the dislocation and using the dorsal approach, an open reduction with internal fixation of the fractures. The injury healed well with a full return of good wrist function. This unusual pattern of injury is described so that it may be more readily appreciated in the future.

Tumoral Calcinosis of the Foot: MRI & Histologic Findings; Two Cases Report / 대한족부족관절학회지

Tumoral calcinosis is rarely encountered disease, and most of reported cases involved large joints such as hip or elbow. We report two patients with tumoral calcinosis in the foot. In the 1st case, the lesion was observed at the 1st MP joint of foot, and in the 2nd case it was found at the DIP joint of 5th toe area with bony erosion which is rare in other tumoral calcinosis. They all needed evaluation with MRI, and eventually surgical excision.