Kinetics of the low-temperature pyrolysis of polyethene, polypropene and polystyrene modeling, experimental determination and comparison with literature models and data

The pyrolysis kinetics of low-density polyethylene, high-density polyethylene, polypropylene, and polystyrene has been studied at temperatures below 450 C. In addition, a literature review on the low-temperature pyrolysis of these polymers has been conducted and has revealed that the scatter in the reported kinetic data is significant, which is most probably due to the use of simple first-order kinetic models to interpret the experimental data. This model type is only applicable in a small conversion range, but was used by many authors over a much wider conversion range. In this investigation the pyrolysis kinetics of the forementioned polymers and a mixture of polymers has been studied at temperatures below 450 C by performing isothermal thermogravimetric analysis (TGA) experiments. The TGA experimental data was used to determine the kinetic parameters on the basis of a simple first-order model for high conversions (70-90%) and a model developed in the present study, termed the random chain dissociation (RCD) model, for the entire conversion range. The influence of important parameters, such as molecular weight, extent of branching and -scission on the pyrolysis kinetics was studied with the RCD model. This model was also used to calculate the primary product spectrum of the pyrolysis process. The effect of the extent of branching and the initial molecular weight on the pyrolysis process was also studied experimentally. The effect of the extent of branching was found to be quite significant, but the effect of the initial molecular weight was minor. These results were found to agree quite well with the predictions obtained from the RCD model. Finally, the behavior of mixtures of the aforementioned polymers was studied and it was found that the pyrolysis kinetics of the polymers in the mixture remains unaltered in comparison with the pyrolysis kinetics of the pure polymers

The Effect of the Bentonite Clay Constituents in a Flocculent of FeCl3 and CaMg.2(OH)2 during AMD Treatment Ntwampe OI1, Waanders FB2 and Bunt JR2

Abstract: Two sets of experiments were conducted by pouring 200 mL of the acid mine drainage (AMD) decant from Krugersdorp (South Africa) into five 500 mL beakers (mixing) and Erlenmeyer flasks (shaking) and dosed with 20- 60 mL of FeCl3, Fe2(SO4)3, CaMg.2(OH)2 and a combination of FeCl3 with CaMg.2(OH)2 (af-PFCl) respectively. The samples were placed in a flocculator and a shaker and stirred at 250 rpm for 2 minutes respectively, settled for 1 hour and the pH, conductivity and turbidity were measured. A third similar set of experiments was conducted without mixing settled for 1 hour and the same measurement taken. The fourth and fifth sets of experiments were conducted with CaMg.2(OH)2 and afPFCl flocculent respectively. The novelty of this study is to determine the turbidity removal efficiency using FeCl3 and CaMg.2(OH)2 in a form of unprocessed polymers. The results showed that the pH and residual turbidity in the samples with Fe3+ salts, CaMg.2(OH)2 is relatively identical to those in the samples with af-PFCl dosages. The turbidity removal efficiencies exhibited by the Fe salts, CaMg.2(OH)2 and af-PFCl were optimal. The pH and residual turbidity in the AMD samples with mixing, shaking and without mixing indicate that destabilization-hydrolysis is influenced by the physico-chemical properties of the solution, whereas mechanical agitation mainly disperses the reagent(s). Optimal turbidity removal of the samples without mixing also indicates that perikinetic flocculation is a predominant process during aggregation/flocs formation

Bayesian reconstruction of binary media with unresolved fine-scale spatial structures

We present a Bayesian technique to estimate the fine-scale properties of a binary medium from multiscale observations. The binary medium of interest consists of spatially varying proportions of low and high permeability material with an isotropic structure. Inclusions of one material within the other are far smaller than the domain sizes of interest, and thus are never explicitly resolved. We consider the problem of estimating the spatial distribution of the inclusion proportion, F(x), and a characteristic length-scale of the inclusions, δ, from sparse multiscale measurements. The observations consist of coarse-scale (of the order of the domain size) measurements of the effective permeability of the medium (i.e., static data) and tracer breakthrough times (i.e., dynamic data), which interrogate the fine scale, at a sparsely distributed set of locations. This ill-posed problem is regularized by specifying a Gaussian process model for the unknown field F(x) and expressing it as a superposition of Karhunen–Loève modes. The effect of the fine-scale structures on the coarse-scale effective permeability i.e., upscaling, is performed using a subgrid-model which includes δ as one of its parameters. A statistical inverse problem is posed to infer the weights of the Karhunen–Loève modes and δ, which is then solved using an adaptive Markov Chain Monte Carlo method. The solution yields non-parametric distributions for the objects of interest, thus providing most probable estimates and uncertainty bounds on latent structures at coarse and fine scales. The technique is tested using synthetic data. The individual contributions of the static and dynamic data to the inference are also analyzed.United States. Dept. of Energy. National Nuclear Security Administration (Contract DE-AC04_94AL85000

Mesozoic-Cenozoic evolution of the Xining-Minhe and Dangchang basins, northeastern Tibetan Plateau: Magnetostratigraphic and biostratigraphic results

Accurate stratigraphic ages are crucial to understanding the deformation history of the Tibetan Plateau prior to and during the Indo-Asian collision. Efforts to quantify Mesozoic-Cenozoic ages are hindered by limited fossils and a paucity of volcanic horizons and regionally correlative strata. Magnetostratigraphic and biostratigraphic results from the Xining-Minhe-Longzhong basin complex and Dangchang basin provide an improved chronology of nonmarine basin development over a large region of the northeastern Tibetan Plateau (34–37°N, 101–105°E). Analyses of 171 magnetostratigraphic levels and 24 palynological assemblages (\u3e120 species) indicate Late Jurassic-Early Cretaceous to mid-Tertiary deposition. Although magnetic polarity zonation is incomplete, independent palynological age control partially restricts possible correlations to the Geomagnetic Polarity Timescale. The sediment accumulation record, basin provenance, structural geology, and published thermochronological data support a history of Jurassic exhumation, Late Jurassic-Early Cretaceous fault-related basin initiation, and Cretaceous-Paleogene reduced accumulation. These patterns, which are compatible with Late Jurassic-Early Cretaceous extension and Cretaceous-Paleogene postrift thermal subsidence, were disrupted at about 40–30 Ma, when shortening related to the Indo-Asian collision induced localized range uplift, vertical axis rotation, and amplified subsidence

Human phosphodiesterase 4D7 (PDE4D7) expression is increased in TMPRSS2-ERG positive primary prostate cancer and independently adds to a reduced risk of post-surgical disease progression

background: There is an acute need to uncover biomarkers that reflect the molecular pathologies, underpinning prostate cancer progression and poor patient outcome. We have previously demonstrated that in prostate cancer cell lines PDE4D7 is downregulated in advanced cases of the disease. To investigate further the prognostic power of PDE4D7 expression during prostate cancer progression and assess how downregulation of this PDE isoform may affect disease outcome, we have examined PDE4D7 expression in physiologically relevant primary human samples. methods: About 1405 patient samples across 8 publically available qPCR, Affymetrix Exon 1.0 ST arrays and RNA sequencing data sets were screened for PDE4D7 expression. The TMPRSS2-ERG gene rearrangement status of patient samples was determined by transformation of the exon array and RNA seq expression data to robust z-scores followed by the application of a threshold >3 to define a positive TMPRSS2-ERG gene fusion event in a tumour sample. results: We demonstrate that PDE4D7 expression positively correlates with primary tumour development. We also show a positive association with the highly prostate cancer-specific gene rearrangement between TMPRSS2 and the ETS transcription factor family member ERG. In addition, we find that in primary TMPRSS2-ERG-positive tumours PDE4D7 expression is significantly positively correlated with low-grade disease and a reduced likelihood of progression after primary treatment. Conversely, PDE4D7 transcript levels become significantly decreased in castration resistant prostate cancer (CRPC). conclusions: We further characterise and add physiological relevance to PDE4D7 as a novel marker that is associated with the development and progression of prostate tumours. We propose that the assessment of PDE4D7 levels may provide a novel, independent predictor of post-surgical disease progression

Hypomagnesaemia and its determinants in a contemporary primary care cohort of persons with type 2 diabetes

AIMS: Among persons with type 2 diabetes mellitus (T2DM) hypomagnesaemia has been reported in 14-48% of patients. This may be of significance given the emerging associations of hypomagnesaemia with glucometabolic disturbances and possibly even complications. We assessed the prevalence of hypomagnesaemia and its determinants, in a well-defined cohort of persons with T2DM treated in primary care. METHODS: Observational cohort study among persons with T2DM treated in primary care in the Northeast of the Netherlands. Magnesium was measured using a colorimetric endpoint assay (Roche). Hypomagnesaemia was defined as a serum magnesium level <0.70 mmol/L. Pearson correlations were performed to correlate variables with serum magnesium. Next, a stepwise backward regression model was made. RESULTS: Data of 929 persons (55% male) with a mean age of 65 (± 10) years, diabetes duration 6.5 [3.0-10.1] years, and HbA1c concentration 6.7 (± 0.7)% (50 (± 9) mmol/mol) were analysed. Serum magnesium was 0.79 (± 0.08) mmol/L. The percentage of persons with magnesium deficiency was 9.6%. Age, diabetes duration, BMI, HbA1c, use of metformin, sulfonylurea derivatives, and DPP4 inhibitors were negatively associated with magnesium concentrations. In contrast, LDL cholesterol and serum creatinine were positively associated serum magnesium. CONCLUSIONS: Hypomagnesaemia was present in 9.6% of T2DM patients treated in primary care. This percentage is remarkably lower than reported previously, possibly due to the unselected nature of our population. Concerning T2DM-related factors, only BMI, HbA1c and the use of metformin, sulfonylurea derivatives and DPP4 inhibitors correlated negatively with magnesium concentrations

Different routes of insulin administration do not influence serum free thiols in type 1 diabetes mellitus

Aims: Intraperitoneal (IP) insulin administration is a last-resort treatment option for selected patients with type 1 diabetes mellitus (T1DM). As the IP route of insulin administration mimics the physiology more closely than the subcutaneous (SC) route, we hypothesized that IP insulin would result in less oxidative stress (expressed as systemic level of free sulphydryl (R-SH) content) compared to SC insulin in subjects with T1DM.Materials and methods: Prospective, observational case-control study. Serum thiol measurements were performed at baseline and at 26 weeks in age- and gender-matched patients with T1DM. Serum-free thiols, compounds with a R-SH group that are readily oxidized by reactive oxygen species, are considered to be a marker of systemic redox status.Results: A total of 176 patients, 39 of which used IP and 141 SC insulin therapy were analysed. Mean baseline R-SH concentration was 248 (31) μmol/L. In multivariable analysis, the route of insulin therapy had no impact on baseline R-SH levels. The estimated geometric mean concentrations of R-SH did not differ significantly between both groups: 264 (95% CI 257, 270) for the IP group and 258 (95% CI 254, 261) for the SC group with a difference of 6 (95% CI -2, 14) μmol/L.Conclusions: Based on R-SH as a marker of systemic oxidative stress, these findings demonstrate that the route of insulin administration, IP or SC, does not influence systemic redox status in patients with T1DM.</p

Hypomagnesemia in persons with type 1 diabetes:associations with clinical parameters and oxidative stress

Background: Among persons with type 1 diabetes mellitus (T1DM) low concentrations of magnesium have been reported. Previous (small) studies also suggested a relation of hypomagnesemia with (poor) glycaemic control and complications. We aimed to investigate the magnitude of hypomagnesemia and the associations between magnesium with parameters of routine T1DM care in a population of unselected outpatients. Methods: As part of a prospective cohort study, initially designed to measure quality of life and oxidative stress, data from 207 patients with a mean age of 45 [standard deviation (SD) 12] years, 58% male, diabetes duration 22 [interquartile range (IQR) 16, 31] years and glycated haemoglobin (HbA1c) of 60 (SD 11) mmol/mol [7.6 (SD 1.0)%] were examined. Hypomagnesemia was defined as a concentration below Results: Mean magnesium concentration was 0.78 (SD 0.05) mmol/l. A deficiency was present in 4.3% of participants. Among these persons, mean concentration was 0.66 (SD 0.03) mmol/l. There was no correlation between magnesium and HbA1c at baseline (r = -0.014, p = 0.843). In multivariable analysis, free thiols (reflecting the degree of oxidative stress) were significantly and negatively associated with magnesium concentrations. Conclusion: In this cohort of T1DM outpatients, the presence of hypomagnesemia was infrequent and, if present, relative mild. Magnesium was not associated with glycaemic control nor with presence of micro- and macrovascular complications. Although these results need confirmation, in particular the negative association of magnesium with free thiols, this suggests that hypomagnesemia is not a relevant topic in routine care for people with T1DM