The effect of an acidic environment during the hydrothermal carbonization of sewage sludge on solid and liquid products: The fate of heavy metals, phosphorus and other compounds.

The pH of sewage sludge is a crucial factor during the hydrothermal carbonization process that influences the characteristics of the resulting products and migration of certain compounds from the solid to liquid phase. Accordingly, this work is focused on examining the pH impact during the HTC process, in particular, pH equals 2, 3, 4, 5 and 6 on the individual hydrothermally carbonized products generated at 200 °C and 2 h residence time. For this reason, the chemical and physical indicators describing the post-processing liquid and hydrochar were determined. For instance, it was observed that the phosphorus content detected in the liquid, derived at pH2, rose significantly by 80%. Furthermore, decreasing the pH of sewage sludge had a significant impact on the ash content and the calorific value of the hydrochar. Additionally, changes in the specific surface area of hydrochar were noticed: pH = 5 and pH = 6 showed an increase of 20-30%, while for lower pH values a decrease of c.a. 26% was achieved. The distribution of heavy metals between the obtained fractions in the HTC process (solid and liquid) indicated that 92 to almost 100% of the tested heavy metals were transferred to the hydrochar. A significant effect of pH on the distribution between these fractions was observed only for Zn and Ni. For instance, for pH = 2, Zn and Ni in post-processing liquid were 34% and 29%, respectively. In addition, the sequential extraction of heavy metals from hydrochar was also performed in order to identify mobile and non-mobile phases. It was noticed that the acidic environment favours a higher amount of mobile heavy metals in hydrochar. The largest effect was observed for Cd, Pb, Cr and Cu, for which, at pH = 2, their respective amounts in the mobile fraction were 2.7; 3.6; 1.8; 6.2 times higher, compared to the hydrochar without pH correction.

The effect of an acid catalyst on the hydrothermal carbonization of sewage sludge.

This research is focused on the addition of a catalyst, sulphuric acid (VI), to sewage sludge, and its effect on solid and liquid products resulting from the hydrothermal carbonization process. Consequently, for hydrochars, proximate and ultimate analyses, higher heating value and specific surface area were determined. Additionally, Fourier-transform infrared spectrophotometric and thermogravimetric analyses were conducted. The heavy metal contents in the ash composition of hydrochars were identified by X-ray fluorescence spectrometry. It was confirmed that the catalyst addition changed the structure as well as the physical and chemical properties of hydrochars and their ashes. Regarding post-processing water, both pH value and conductivity were determined and the element composition, including heavy metals, was conducted by the inductively coupled plasma optical emission and mass spectrometry analyses. It was found that the addition of the catalyst caused a decrease in heavy metal contents and an increase of phosphorus compound in filtrates.

Workplace bullying: individual hostility, poor work environment or both? Exploring competing explanatory models in a single longitudinal study.

PURPOSE: A central focus of research and literature on workplace bullying is the importance of explanatory factors such as individual dispositions (i.e., the vulnerability hypothesis) and work environment factors (i.e., the work environment hypothesis). Although several studies address the importance of the two approaches, as well as their individual and combined effects, the unique contribution of each of the competing approaches remain unexplored in a single longitudinal study. METHODS: Based on Affective Events Theory, we explore the contribution of work environment and individual hostility in the occurrence of workplace bullying over time, using two-wave survey data, collected with a 6-month time lag among 152 employees from 7 private and public workplaces. RESULTS: Results confirmed that work environment factors predicted later exposure to bullying. Exposure to workplace bullying at T1 was also related to a poor work environment at T2. Results further showed that higher exposure to workplace bullying at T1 and T2 was related to higher levels of almost all aspects of individual hostility over time. Moreover, poor working conditions especially in T1 predicted individual hostility at T2. CONCLUSION: The present study thus documents that a poor work environment fosters bullying, and when bullying exists in a workplace, this elicits interpersonal hostility. Results points to the importance of addressing, through research and practice, work environment factors as predictors of workplace bullying.

A Prospective Study of Employee Response to Bullying in a Workplace Environment: Does Assertiveness Actually Help or Hurt?

The aim of the present two-wave prospective study was twofold: (1) to identify the role of assertiveness in exposure to workplace bullying and (2) to determine causal and reverse causal long-term associations between workplace bullying exposure, working conditions and assertiveness. In the present two-wave panel design study (N = 128), with a six-month lag, high assertiveness predicted exposure to bullying. Furthermore, in line with the work environment hypothesis, the results indicate that negative workplace conditions in the first wave led to workplace bullying exposure. The findings suggest that assertive communication may be inappropriate in the case of workplace bullying. As such, we argue that functional assertiveness could be useful.

Assessment of selected carbohydrate parameters in children exposed to gestational diabetes in utero.

OBJECTIVES: The study was undertaken to assess the selected carbohydrate parameters in children exposed to gestational diabetes in utero. METHODS: 50 children exposed to gestational diabetes were compared with 46 control subjects. Anthropometric parameters of a newborn were obtained from the medical records. In all participants height, body mass, waist and hip circumferences were measured; BMI, WHR and WHtR were calculated. Values of fasting glucose, insulin, C-peptide and HbA1c were measured and HOMA2-IR, HOMA2-S, HOMA2-B were calculated. In obese children (BMI ≥95th percentile) OGTT was performed. RESULTS: The prevalence of overweight/obesity in the study group was 38%, in the control group 41% (p=0.19). Higher fasting glucose level (p=0.02) and HbA1c (p=0.00004) were found in the study group comparing to the control. In children exposed to GDM in utero a positive correlation of fasting insulin and WHR (Rs=0.31, p=0.028) as well as significantly lower HOMA2-B (p=0.03) were observed. In the study group higher HOMA2-IR (p=0.0002) and HOMA2-B (p=0.0000039) and also lower HOMA2-S (p=0.0002) were observed among participants with overweight/obesity comparing to children with normal body weight. In the study group a correlation of HOMA2-IR and SD of the birth weight was found (Rs=0.28, p=0.049). CONCLUSIONS: Children exposed to gestational diabetes in utero, in spite of similar prevalence of overweight/obesity comparing to their non-exposed peers, could have higher risk of glucose intolerance and diabetes mellitus in future. Towards observed decreased insulin sensitivity and compensatory increase in insulin secretion, prevention of overweight and obesity in this group seems to be essential.

The treatment of post-processing liquid from the hydrothermal carbonization of sewage sludge.

The liquid phase, being a major product of the hydrothermal carbonization of sewage sludge, is highly problematic due to numerous toxic compounds that make it impossible to dispose of without adequate purification. Therefore, this study is focused on the two groups of selected advanced methods of post-processing water derived from the hydrothermal carbonization process of sewage sludge. The first group included membrane processes, namely ultrafiltration, nanofiltration and double nanofiltration. The second included coagulation, ultrasonication and chlorination. Chemical and physical indicators were determined to confirm the validity of these treatment methods. The highest reduction values were found for double nanofiltration, which showed a spectacular decrease in the Chemical Oxygen Demand by 84.9 %, specific conductivity by 71.3 %, nitrate nitrogen by 92.4 %, phosphate phosphorus by 97.1 %, total organic carbon by 83.3 %, total carbon by 83.6 %, and inorganic carbon by 88.5 %, as compared to the liquid phase after hydrothermal carbonization. In the second group, for the largest number of parameters, the greatest reduction was achieved when 10 cm3/L of iron coagulant was added to the permeate from ultrafiltration. Additionally, COD decreased by 41 %, P-PO43- content by 78 %, phenol content by 34 %, TOC content by 97 %, TC content by 95 % and IC content by 40 %.

Life cycle assessment of the hydrothermal carbonization process applied to the wet fraction mechanically separated from municipal mixed waste.

The under-sieve fraction (USF), obtained as one of the output streams from the mechanical pretreatment of mixed municipal solid waste, is usually aerobically biologically stabilized before being landfilled. For its characteristics (i.e., moisture and organic content), the USF can be alternatively processed by hydrothermal carbonization (HTC), producing hydrochar to be used for energy production. Based on previous results obtained from laboratory HTC tests of the USF, this work is aimed at evaluating the sustainability of the proposed process from an environmental point of view by applying the Life Cycle Assessment. Various combinations of process parameters (temperature, time, and dry solid-to-water ratios) and two different utilization pathways for hydrochar (the whole amount produced in external lignite power plants or part of it used internally) are compared. The results indicate that environmental performances are mainly connected with process energy consumption: in general, the cases operating at the lowest dilution ratio and the highest temperature provide improved environmental indicators. Co-combusting all the produced hydrochar in external power plants provides better environmental performances than feeding a portion of it to the HTC itself: the avoided effects by displacing lignite are higher than the additional burdens from natural gas use. Then, alternative process water treatments are compared, showing that the burdens added by the process water treatments do not offset the benefits generated by the main HTC process for the major part of the considered environmental indicators. Finally, the proposed process indicates better environmental performances when compared to the conventional method of treating the USF, based on aerobic biostabilization and landfilling.

NGS analysis of collagen type I genes in Polish patients with Osteogenesis imperfecta: a nationwide multicenter study.

Osteogenesis imperfecta (OI) is a rare genetic disorder of the connective tissue. It presents with a wide spectrum of skeletal and extraskeletal features, and ranges in severity from mild to perinatal lethal. The disease is characterized by a heterogeneous genetic background, where approximately 85%-90% of cases have dominantly inherited heterozygous pathogenic variants located in the COL1A1 and COL1A2 genes. This paper presents the results of the first nationwide study, performed on a large cohort of 197 Polish OI patients. Variants were identified using a next-generation sequencing (NGS) custom gene panel and multiplex ligation probe amplification (MLPA) assay. The following OI types were observed: 1 (42%), 2 (3%), 3 (35%), and 4 (20%). Collagen type I pathogenic variants were reported in 108 families. Alterations were observed in α1 and α2 in 70% and 30% of cases, respectively. The presented paper reports 97 distinct causative variants and expands the OI database with 38 novel pathogenic changes. It also enabled the identification of the first glycine-to-tryptophan substitution in the COL1A1 gene and brought new insights into the clinical severity associated with variants localized in "lethal regions". Our results contribute to a better understanding of the clinical and genetic aspects of OI.

New approach for amino acid profiling in human plasma by selective fluorescence derivatization.

A new approach for the separation of 6-aminoquinolyl-carbamyl (AQC)-derivatized amino acids has been proposed. The chromatography used ion-pairing mechanism to increase the method selectivity. Mobile phase was based on triethylamine buffer containing N,N-dimethyloctylamine as a modifier. A number of factors, buffer composition and pH, counterion concentration, temperature and acetonitrile gradient profile, were optimized to achieve final chromatographic conditions. With the presented analytical method, the separation and identification of 34 AQC-amino acids and amino compounds present in human plasma is possible. The results of validation proved the applicability of the method for quantification of 27 amino acids in biological samples. The ultrafiltration proposed as deproteinization procedure gave repeatable and reliable results for the amino acids under investigation. This method introduced in routine testing can be a suitable tool for amino acid profiling in plasma including all aspects of clinical application.

Analysis of biologically active peptides using two-dimensional HPLC-CE.

High-performance liquid chromatography (HPLC) is a technique most frequently used for the assessment of biologically active peptides. Owing to the ionic character of these compounds, they may also be separated and assayed using capillary electrophoresis (CE), which offers very high efficiency, short analysis time and low consumption of reagents, and is used increasingly more often. The paper describes the combination of HPLC and CE in order to increase the efficiency of the separation of complex mixture of peptides (active substance and its related impurities). The developed two-dimensional HPLC-CE technique was employed for the analysis of the impurities of octreotide, a cyclic octapeptide used in therapy. Because distinct separation mechanisms are used, the two-dimensional technique ensures higher separation efficiency and a more comprehensive impurity profile of the medicinal product than either of the techniques used separately.

Effect of SWCNT-Tuball Paper on the Lightning Strike Protection of CFRPs and Their Selected Mechanical Properties.

The main aim of this work was the investigation of the possibility of replacing the heavy metallic meshes applied onto the composite structure in airplanes for lightning strike protection with a thin film of Tuball single-wall carbon nanotubes in the form of ultra-light, conductive paper. The Tuball paper studied contained 75 wt.% or 90 wt.% of carbon nanotubes and was applied on the top of carbon fibre reinforced polymer before fabrication of flat panels. First, the electrical conductivity, impact resistance and thermo-mechanical properties of modified laminates were measured and compared with the reference values. Then, flat panels with selected Tuball paper, expanded copper foil and reference panels were fabricated for lightning strike tests. The effectiveness of lightning strike protection was evaluated by using the ultrasonic phased-array technique. It was found that the introduction of Tuball paper on the laminates surface improved both the surface and the volume electrical conductivity by 8800% and 300%, respectively. The impact resistance was tested in two directions, perpendicular and parallel to the carbon fibres, and the values increased by 9.8% and 44%, respectively. The dynamic thermo-mechanical analysis showed higher stiffness and a slight increase in glass transition temperature of the modified laminates. Ultrasonic investigation after lightning strike tests showed that the effectiveness of Tuball paper is comparable to expanded copper foil.

The Utilisation of Solid Fuels Derived from Waste Pistachio Shells in Direct Carbon Solid Oxide Fuel Cells.

The comprehensive results regarding the physicochemical properties of carbonaceous materials that are obtained from pistachio shells support their usage as solid fuels to supply direct carbon solid oxide fuel cells (DC-SOFCs). The influence of preparation conditions on variations in the chemical composition, morphology of the biochar powders, and degree of graphitization of carbonaceous materials were investigated. Based on structural investigations (X-ray diffraction analysis and Raman spectroscopy), it was observed that disordered carbon particles developed during the application of thermal treatments. The use of X-ray fluorescence enabled a comparative analysis of the chemical composition of the inorganic matter in biocarbon-based samples. Additionally, the gasification of carbonaceous-based samples vs. time at a temperature of 850 °C was investigated in a H2O or CO2 gas atmosphere. The analysis demonstrated the conversion rate of biochar obtained from pistachio shells to H2, CH4 and CO during steam gasification. The electrochemical investigations of the DC-SOFCs that were supplied with biochars obtained from pistachio shells were characterized by satisfactory values for the current and power densities at a temperature range of 700-850 °C. However, a higher power output of the DC-SOFCs was observed when CO2 was introduced to the anode chamber. Therefore, the impact of the Boudouard reaction on the performance of DC-SOFCs was confirmed. The chars that were prepared from pistachio shells were adequate for solid fuels for utilization in DC-SOFCs.

The Foot-in-the-Door Phenomenon 40 and 50 Years Later: A Direct Replication of the Original Freedman and Fraser Study in Poland and in Ukraine.

Since the original Freedman and Fraser studies were published, a great amount of research using the foot-in-the-door tactic has revealed its effectiveness. Nevertheless, the effect sizes reported in meta-analysis studies tend to be low and the effect size obtained by Freedman and Fraser in their studies has never been obtained again. We conducted a direct replication of the original foot-in-the-door experiment in two time intervals and in two countries. The results indicate a drop of compliance over time. The results reveal that, while in 2003 the foot-in-the-door strategy was effective in Ukraine and ineffective in Poland, in 2013, the effect was insignificant in both Ukraine and Poland. The results are explained by high ecological validity of the foot-in-the-door procedure.

Effects of Nordic walking training on exercise capacity and fitness in men participating in early, short-term inpatient cardiac rehabilitation after an acute coronary syndrome--a controlled trial.

OBJECTIVE: To investigate the effects of Nordic Walking training supplemental to a standard, early rehabilitation programme on exercise capacity and physical fitness in men after an acute coronary syndrome. DESIGN: A controlled trial. SETTING: Cardiac rehabilitation service of a provincial hospital. SUBJECTS: Eighty men 2-3 weeks after an acute coronary syndrome, with good exercise tolerance. INTERVENTIONS: Three-week, inpatient cardiac rehabilitation programme (control group) supplemented with Nordic Walking (Nordic Walking group), or with traditional walking training (walking training group). MAIN MEASURES: Exercise capacity was assessed as peak energy cost (in metabolic equivalents) in symptom-limited treadmill exercise test, and physical fitness with the Fullerton Functional Fitness Test. RESULTS: Exercise capacity after the rehabilitation programme was higher in the Nordic Walking group than in the control group (10.8 +/- 1.8 versus 9.2 +/- 2.2 metabolic equivalents, P =0.025). The improvement in exercise capacity in the Nordic Walking group was higher than in the control group (1.8 +/- 1.5 versus 0.7 +/- 1.4 metabolic equivalents, P =0.002). In contrast to the control group, the results of all components of the Fullerton test improved in the Nordic Walking and walking training groups. After the programme, lower body endurance, and dynamic balance were significantly better in the Nordic Walking group in comparison with the walking training and control groups, and upper body endurance was significantly better in the Nordic Walking and walking training groups than in the control group. CONCLUSIONS: Nordic Walking may improve exercise capacity, lower body endurance and coordination of movements in patients with good exercise tolerance participating in early, short-term rehabilitation after an acute coronary syndrome.

Why patients after acute coronary syndromes do not participate in an early outpatient rehabilitation programme?

BACKGROUND: The value of cardiac rehabilitation in patients with coronary artery disease has been well established. The main problem is a low attendance of patients qualified for rehabilitation. AIM: To assess differences between subjects attending outpatient cardiac rehabilitation (OutCR) after completing an early inpatient programme (InCR), and patients refusing participation in OutCR; to investigate factors determining patients' decisions. METHODS: Seventy-two patients (mean age 57 +/- 9.4 years; 53 men) 2-3 weeks after an acute coronary syndrome (ACS) treated with primary PCI were enrolled. On admission to the cardiac rehabilitation ward, the following parameters were assessed: quality of life (EuroQol-5D questionnaire), psychological status (Beck's, SOPER and STAI questionnaires), marital status, education, economic status, employment, place of living, smoking status, and comorbidities (a questionnaire prepared by the authors). Additionally, patients' opinions on outpatient and inpatient cardiac rehabilitation were noted. The inpatient programme lasted 2-3 weeks. At discharge, the assessment was repeated, and patients were proposed to enrol in a 12-week outpatient programme. In the case of refusal, patients were asked to give the reason. RESULTS: Two men failed to complete the inpatient program. Of the remaining 70 subjects, 16 attended and completed the outpatient programme. In the group participating in OutCR, there were fewer patients with depression before InCR (12 vs. 39% in the group without OutCR, p = 0.0484). Subjects in the OutCR group had a higher score for mood after InCR (7.7 +/- 1.25 vs. 6.7 +/- 1.69, p = 0.0365), lower score for emotional stress before and after InCR (before InCR: 4.4 +/- 1.09 vs. 5.3 +/- 1.34, p = 0.0188; after InCR: 3.8 +/- 1.51 vs. 4.8 +/- 1.4, p = 0.0262), and lower score for anxiety before InCR (3.1 +/- 1.75 vs. 4.4 +/- 2.12, p = 0.0426). Patients in the two groups differed with regard to employment (p = 0.0256) and smoking status (p = 0.0517). In both groups, most patients (l 80%) preferred inpatient rehabilitation. Continuous medical care, lack of commuting problems, and convenience were the most frequently given advantages of inpatient rehabilitation, while commuting problems and conflict with job were the most frequently perceived barriers to outpatient rehabilitation. CONCLUSIONS: Only a small proportion of patients after an ACS decides to participate in outpatient rehabilitation after completing a short-term inpatient programme. Psychological status, employment and smoking status are among the factors that differentiate OutCR attenders and non-attenders. Continuous medical care, lack of commuting problems, and convenience were the most frequently given advantages of inpatient rehabilitation, while commuting problems and conflict with job were the most frequently perceived barriers to outpatient rehabilitation.

Mindfulness and Compliance: The Way We Make Requests Influences Compliance With the Foot-in-the-Door Strategy.

The foot-in-the-door effect is considered more effective when a time lapse occurs between performing an initial, smaller request and being asked a second request. It has been hypothesized that mindfulness moderates the effectiveness of two versions of the strategy - time-delay and no-delay foot-in-the-door. The greater magnitude of time-delay foot-in-the-door is considered to be connected with increased mindfulness. The aim of this study was to verify the assumption concerning mindfulness as a state triggering time-delay foot-in-the-door. In a field experiment ( N = 249), we manipulated the time lapse and kind of reason (real, placebic, and no reason) accompanying a difficult or less difficult target request. This extended Langer et al. replication indicates that time-delay foot-in-the-door is indeed greater after mindfulness activation.

Combustion and kinetic parameters estimation of torrefied pine, acacia and Miscanthus giganteus using experimental and modelling techniques.

A novel approach, linking both experiments and modelling, was applied to obtain a better understanding of combustion characteristics of torrefied biomass. Therefore, Pine, Acacia and Miscanthus giganteus have been investigated under 260°C, 1h residence time and argon atmosphere. A higher heating value and carbon content corresponding to a higher fixed carbon, lower volatile matter, moisture content, and ratio O/C were obtained for all torrefied biomass. TGA analysis was used in order to proceed with the kinetics study and Chemkin calculations. The kinetics analysis demonstrated that the torrefaction process led to a decrease in Ea compared to raw biomass. The average Ea of pine using the KAS method changed from 169.42 to 122.88kJ/mol. The changes in gaseous products of combustion were calculated by Chemkin, which corresponded with the TGA results. The general conclusion based on these investigations is that torrefaction improves the physical and chemical properties of biomass.

Assessment of selected lipid parameters in in children exposed to gestational diabetes (GDM) in utero.

INTRODUCTION: The assessment of maternal hyperglycemia during pregnancy and lipid profile in the offspring is recently highlighted. AIM: The study was undertaken to assess the selected lipid parameters in children exposed to gestational diabetes (GDM) in utero. MATERIAL AND METHODS: 50 children, 7-15 years of age, exposed to GDM were compared with 46 control subjects (7-16 years old). In all participants anthropometric parameters (height, weight, waist and hip circumferences) and values of total cholesterol, LDL-, HDL-cholesterol and triglycerides (TG) were measured. BMI, waist-to-hip ratio (WHR) and TG to HDL-cholesterol ratio were calculated. RESULTS: The prevalence of overweight/obesity in the study cohort was 38% and 41% in the control (p=0.19). Higher total cholesterol level (p=0.002) and LDL-cholesterol (p=0.007) were found in the study group. In children exposed to GDM significantly higher values of LDL-cholesterol (p=0.02), triglycerides (p=0.02), TG to HDL-cholesterol ratio (p=0.007) and lower HDL-cholesterol (p=0.02) were observed in overweight/obese children compared to slim participants. In the control group, similar results were not noted. In the study group, a positive correlations of TG to HDL-cholesterol ratio and BMI SDS (RS=0.47, p=0.0006), WHR (RS =0.31, p=0.03), SDS of birth weight (RS =0.47, p=0.0006) were found. CONCLUSION: Children exposed to GDM in utero could have a higher risk of dyslipidemia with its cardiovascular complications. Towards observed worse lipid parameters in children with excessive body mass born from pregnancies with GDM, prevention of overweight and obesity in this group seems to be essential.

Separation of synthetic food colourants in the mixed micellar system. Application to pharmaceutical analysis.

The paper presents a rapid method for the determination of commonly used synthetic food dyes by micellar electrokinetic capillary chromatography. Detection and separation conditions allowing complete resolution of 15 synthetic food colourants were investigated. The effect of different surfactants on the analytes mobility in relation to their structure was tested. After optimization procedure a dual micellar system was selected. All food dyes were separated in less then 20 min using a fused silica capillary in the borate/dodecylsulfate/deoxycholate buffer containing acetonitrile as organic modifier. The detection wavelength was set at 210nm. The method was successfully validated by determination of linearity ranges, detection limits, precision and repeatability for all colourants tested. In order to apply the method for pharmaceutical analysis a sample pretreatment procedures were found. Liquid pharmaceuticals were used as it or just after dilution with water. From tablets or capsules the colourants were isolated by adsorption on acidic aluminium oxide. The method was used for identification and if possible for quantification the synthetic food dyes in pharmaceuticals. The analytes are detectable at a concentration level 0.3-0.8 microg ml(-1).