Valorization Strategies in CO2 Capture: A New Life for Exhausted Silica-Polyethylenimine.

The search for alternative ways to give a second life to materials paved the way for detailed investigation into three silica-polyethylenimine (Si-PEI) materials for the purpose of CO2 adsorption in carbon capture and storage. A solvent extraction procedure was investigated to recover degraded PEIs and silica, and concomitantly, pyrolysis was evaluated to obtain valuable chemicals such as alkylated pyrazines. An array of thermal (TGA, Py-GC-MS), mechanical (rheology), and spectroscopical (ATR-FTIR, 1H-13C-NMR) methods were applied to PEIs extracted with methanol to determine the relevant physico-chemical features of these polymers when subjected to degradation after use in CO2 capture. Proxies of degradation associated with the plausible formation of urea/carbamate moieties were revealed by Py-GC-MS, NMR, and ATR-FTIR. The yield of alkylpyrazines estimated by Py-GC-MS highlighted the potential of exhausted PEIs as possibly valuable materials in other applications.

Determination of polyurethanes within microplastics in complex environmental samples by analytical pyrolysis.

Polyurethanes (PUR) are a group of polymers synthesized from different diisocyanate and polyol monomers resulting in a countless number of possible structures. However, the large market demand, and the variety of application fields justify the inclusion of PUR in microplastic (MP) investigation. This study aimed at providing comprehensive information on PUR within MP analysis by pyrolysis-gas chromatography-mass spectrometry to clarify whether (i) it is possible to make a reliable statement on the PUR content of environmental samples based on a few pyrolysis products and (ii) which restrictions are required in this context. PUR were managed as subclasses defined by the diisocyanates employed for polymer synthesis. Methylene diphenyl diisocyanate (MDI)- and toluene diisocyanate (TDI)-based PUR were selected as subclasses of greatest relevance. Different PUR were pyrolyzed directly and under thermochemolytic conditions with tetramethylammonium hydroxide (TMAH). Distinct pyrolytic indicators were identified. The study supported that the use of TMAH greatly reduced the interactions of pyrolytic MP analytes with the remaining organic matrix of environmental samples and the associated negative effects on analytical results. Improvements of chromatographic behavior of PUR was evidenced. Regressions (1-20 µg) showed good correlations and parallelism tests underlined that quantitation behavior of different MDI-PUR could be represented by the calibration of just one representative with sufficient accuracy, entailing a good estimation of the entire subclass if thermochemolysis were used. The method was exemplary applied to road dusts and spider webs sampled around a plastic processing plant to evaluate the environmental spread of PUR in an urban context. The environmental occurrence of MDI-PUR as MP was highly influenced by the proximity to a potential source, while TDI markers were not observed.

Bioplastic leachates characterization and impacts on early larval stages and adult mussel cellular, biochemical and physiological responses.

Bioplastics are promoted as safer alternatives to tackle the long-term persistence of conventional plastics. However, information on the potential release of additives and non-intentionally added substances (NIAS) in the surrounding environment is limited, and biological effects of the leachates have been little studied. Leachates produced from three bioplastics, i.e. compostable bags (CB), bio-polyethylene terephthalate bottles (bioPET) and polylactic acid cups (PLA), and a control polymeric material, i.e. rubber tire (TR), were examined. The chemical nature of bioplastic polyesters PET, PLA and poly (butylene adipate-co-terephthalate) (PBAT) in CB, was confirmed by analytical pyrolysis. Fragments were incubated in artificial sea water for 14 days at 20 °C in darkness and leachate contents examined by GC-MS and HPLC-MS/MS. Catalysts and stabilizers represented the majority of chemicals in TR, while NIAS (e.g. 1,6-dioxacyclododecane-7,12-dione) were the main components of CB. Bisphenol A occurred in all leachates at a concentration range 0.3-4.8 µg/L. Trace metals at concentrations higher than control water were found in all leachates, albeit more represented in leachates from CB and TR. A dose response to 11 dilutions of leachates (in the range 0.6-100%) was tested for biological effects on early embryo stages of Mytilus galloprovincialis. Embryotoxicity was observed in the whole range of tested concentrations, the magnitude of effect depending on the polymers. The highest concentrations caused reduction of egg fertilization (CB, bioPET, TR) and of larvae motility (CB, PLA, TR). TR leachates also provoked larvae mortality in the range 10-100%. Effects on adult mussel physiology were evaluated after a 7-day in vivo exposure to the different leachates at 0.6% concentration. Nine biomarkers concerning lysosomal functionality, neurotransmission, antioxidant and immune responses were assessed. All lysosomal parameters were affected, and serum lysozyme activity inhibited. Harmonized chemical and biological approaches are recommended to assess bioplastic safety and support production of sustainable bioplastics.

Effect of biochar amendment on organic matter and dissolved organic matter composition of agricultural soils from a two-year field experiment.

Dissolved organic matter (DOM) is an important organic matter fraction that plays a key role in many biological and chemical processes in soil. The effect of biochar addition on the content and composition of soil organic matter (SOM) and DOM in an agricultural soil in Italy was investigated within a two-year period. UV-Vis spectroscopy and analytical pyrolysis have been applied to study complex components in DOM soil samples. Additionally, analytical pyrolysis was used to provide qualitative information of SOM at molecular level and the properties of biochar before and one year after amendment. A method was developed to quantify biochar levels by thermogravimetric analysis that enabled to identify deviations from the amendment rate. The water-soluble organic carbon (WSOC) concentrations in the amended soils were significantly lower than those in the control soils, indicating that biochar decreased the leaching of DOM. DOM in treated soils was characterized by a higher aromatic character according to analytical pyrolysis and UV-Vis spectroscopy. Moreover, a relatively high abundance of compounds with N was observed in pyrolysates of treated soils, suggesting that biochar increased the proportion of microbial DOM. The results from thermal and spectroscopy techniques are consistent in highlighting significant changes in DOM levels and composition due to biochar application with important effects on soil carbon storage and cycling.

Outcome of surgical treatment of 54 Periprosthetic femoral fractures after total hip arthroplasty at mid term follow-up.

PURPOSE: The aim of the present study was to review the outcome of the surgical treatment of 54 periprosthetic femoral fractures (PFF) after total hip arthroplasty at a mean follow-up of 45 months. At final follow-up, the clinical outcome was measured using the Harris Hip score (HHS), the Karnofsky score (KS), while, the radiographic results were evaluated using the Beals and Tower's criteria. RESULTS: There were 13 post-operative complications that occurred in 10 patients with an overall re-operation rate of 11%. At final follow-up the mean HHS was 64 (range 20-100) and the mean KS was 66 (range 30-100). The radiological results were excellent in 89%, good in 9% and poor 2% of patients. The mortality rate was 0% at 3 months and 3.7% at one year post-operatively. The mean last HHS and KS of patients older than 75 years or with comorbidities were lower than that of patients younger than 75 years or without comorbidities. CONCLUSIONS: Although this study have shown that the surgical treatment of PFF was associated with a low re-operative rate, a good to excellent radiological results and a low mortality rate at 3 months and 1 year postoperatively, there was a marked functional deterioration in many patients. This decline of function could be attributed to the advanced age of patients and the presence of comorbidities.

Management of a Lumbar Burst Fracture Occurring After a Sneeze in a Patient Affected by Systemic Mastocytosis: A Case Report.

CASE: We present a 36-year-old man with L1 burst fracture after a sneeze. He was in follow-up for indolent systemic mastocytosis (ISM), and osteoporosis was treated with bisphosphonate. Owing to neurologic impairment, posterior decompressive laminectomy and thoraco-lumbar fusion with cemented screws were performed. CONCLUSION: Vertebral fractures in young patients affected by ISM required a multidisciplinary approach and a careful preoperative planning to achieve acceptable results. These fractures are so rare that even an experienced spine surgeon may not come across them during his whole career. Nevertheless, diagnostic tool improvement makes its diagnosis more frequent, that is why every spine surgeon should know this disease.

A Selective Ratiometric Fluorescent Probe for No-Wash Detection of PVC Microplastic.

Microplastics (MP) are micrometric plastic particles present in drinking water, food and the environment that constitute an emerging pollutant and pose a menace to human health. Novel methods for the fast detection of these new contaminants are needed. Fluorescence-based detection exploits the use of specific probes to label the MP particles. This method can be environmentally friendly, low-cost, easily scalable but also very sensitive and specific. Here, we present the synthesis and application of a new probe based on perylene-diimide (PDI), which can be prepared in a few minutes by a one-pot reaction using a conventional microwave oven and can be used for the direct detection of MP in water without any further treatment of the sample. The green fluorescence is strongly quenched in water at neutral pH because of the formation dimers. The ability of the probe to label MP was tested for polyvinyl chloride (PVC), polyethylene (PE), polyethylene terephthalate (PET), polypropylene (PP), polystyrene (PS), poly methyl methacrylate (PMMA) and polytetrafluoroethylene (PTFE). The probe showed considerable selectivity to PVC MP, which presented an intense red emission after staining. Interestingly, the fluorescence of the MP after labeling could be detected, under excitation with a blue diode, with a conventional CMOS color camera. Good selectivity was achieved analyzing the red to green fluorescence intensity ratio. UV-Vis absorption, steady-state and time-resolved fluorescence spectroscopy, fluorescence anisotropy, fluorescence wide-field and confocal laser scanning microscopy allowed elucidating the mechanism of the staining in detail.

Biomarkers of Low-Level Environmental Exposure to Benzene and Oxidative DNA Damage in Primary School Children in Sardinia, Italy.

BACKGROUND: The main anthropic sources of exposure to airborne benzene include vehicular traffic, cigarette smoke, and industrial emissions. METHODS: To detect early genotoxic effects of environmental exposure to benzene, we monitored environmental, personal, and indoor airborne benzene in children living in an urban area and an area near a petrochemical plant. We also used urinary benzene and S-phenylmercapturic acid (S-PMA) as biomarkers of benzene exposure and urinary 8-hydroxydeoxyguanosine (8-OHdG) as a biomarker of early genotoxic effects. RESULTS: Although always below the European Union limit of 5 µg/m3, airborne benzene levels were more elevated in the indoor, outdoor, and personal samples from the industrial surroundings compared to the urban area (p = 0.026, p = 0.005, and p = 0.001, respectively). Children living in the surroundings of the petrochemical plant had urinary benzene values significantly higher than those from the urban area in both the morning and evening samples (p = 0.01 and p = 0.02, respectively). Results of multiple regression modelling showed that age was a significant predictor of 8-OHdG excretion, independent of the sampling hour. Moreover, at the low exposure level experienced by the children participating in this study, neither personal or indoor airborne benzene level, nor personal monitoring data, affected 8-OHdG excretion. CONCLUSIONS: Our results suggest the importance of biological monitoring of low-level environmental exposure and its relation to risk of genotoxic effects among children.

Worldwide Survey of COVID-19-Associated Arrhythmias.

[Figure: see text].

Manual handling of patients: role of kinesiophobia and catastrophizing in health workers with chronic low back pain.

BACKGROUND: Biomechanical overload due to patients' manual handling represents a relevant contributor to chronic low back pain (LBP). Fear of movement (also known as kinesiophobia) and catastrophising may influence the development of chronic complaints and lower performances also in working environments, despite these issues are poorly investigated. AIM: The aim of this study is twofold: 1) to evaluate the levels of kinesiophobia and catastrophizing in a sample of health personnel with chronic LBP and employed in activities specifically requiring patients' manual handling; 2) to appraise the influence of these factors on disability. DESIGN: Cross-sectional observational study. SETTING: Four Italian hospitals. POPULATION: Sixty-four healthcare workers suffering from nonspecific low back pain, exposed to the spinal risk of biomechanical overload due to patients' manual handling. METHODS: We assessed kinesiophobia, catastrophizing and disability by means of validated questionnaires (the Tampa Scale of Kinesiophobia [TSK], the Pain Catastrophizing Scale [PCS], and the Oswestry Disability Index [ODI], respectively). Values of central tendency and dispersion of the variable of interest were calculated, along with the association among variables through multiple linear regression analysis. RESULTS: The results showed presence of kinesiophobia (TSK=34.0; IQR=28.2-42.09), catastrophizing (PCS=20.5; IQR=10.2-29.0) and disability (ODI=28.8; IQR=13.5-40.0) in the population enrolled. Disability was significantly predicted by kinesiophobia and catastrophizing (R2=0.529 P=0.00003). CONCLUSIONS: Kinesiophobia and catastrophizing are present in health workers with chronic LBP involved in patients' manual handling and are linked to disability. Further investigations in this field are recommended to investigate a role for cognitive-behavioral strategies aimed at managing catastrophizing and kinesiophobia to increase working abilities. CLINICAL REHABILITATION IMPACT: The assessment of catastrophizing and kinesiophobia is crucial in health workers engaged with patients' manual handling and suffering from chronic LBP.

Reply to Comment on Lecca, L.I.; Portoghese, I.; Mucci, N.; Galletta, M.; Meloni, F.; Pilia, I.; Marcias, G.; Fabbri, D.; Fostinelli, J.; Lucchini, R.G.; Cocco, P.; Campagna, M. Association between Work-Related Stress and QT Prolongation in Male Workers.

We appreciate the interest raised by our paper on the association between conditions linked to work-related stress and the prolongation of the QT interval on the electrocardiogram [...].

Association between Work-Related Stress and QT Prolongation in Male Workers.

: Background: Work-related stress is a potential cardiovascular risk factor, but the underlying mechanism is not fully explained. The autonomic nervous system control of cardiac function might play a specific role; therefore, monitoring the QT interval in the electrocardiogram can highlight an autonomic imbalance induced by occupational stressors. The aim of our study was to explore the QT interval parameters as early indicators of imbalance of the autonomic cardiac function in relation to work-related stress. METHODS: During 2015-2016 annual workplace health surveillance, we measured work-related stress in 484 workers of a logistic support company using the Health and Safety Executive (HSE) tool. We assessed the frequency-corrected QT (QTc) interval and the QT index (QTi) on the electrocardiogram of each participant, and collected demographic and clinical data. We compared the QTc values by the four Karasek's categories (active/passive jobs, low/high strain job), and by job support (present/lacking), and conducted multivariate analysis to adjust for possible confounders. RESULTS: The results of the multivariate regression analysis showed that QTc was prolonged among workers operating at a specific site where stress level was found to be elevated. Regular physical activity showed a beneficial effect against QTc prolongation. We did not observe an effect on QTc length by the cross-combined Karasek's categories of job control, job demand, and job support. CONCLUSIONS: Our study suggests subclinical effects of conditions associated with work-related stress on the autonomic regulation of cardiac function. Further research is warranted to elucidate the combined effect of work organization and lifestyle factors on autonomic cardiac function.

Determination of linear and cyclic volatile methyl siloxanes in biogas and biomethane by solid-phase microextraction and gas chromatography-mass spectrometry.

A new method based on solid-phase microextraction (SPME) followed by gas chromatography-mass spectrometry (GC-MS) was developed for the analysis of seven linear (L2 - L5) and cyclic (D3 - D5) volatile methyl siloxanes (VMS) in biogas and biomethane, directly collected into Tedlar® bags (Tedlar SPME) from anaerobic digesters and wastewater treatment plants. The method was employed to monitor VMS content in biomethane produced by biogas upgrading with a pilot-plant membrane unit and provided adequate limits of quantification (< 0.05 mg m-3) to detect trace siloxane impurities. Tedlar SPME was validated against a standard procedure based on indirect sampling of gas streams with sorbent tubes followed by solvent extraction and GC-MS. Method precision (RSD) on total and individual VMS concentrations was lower than 10%, while RSD values of the standard procedure were higher than 20%. Tedlar SPME suitably revealed high VMS levels, expressed as total volatile silicon (> 1 mgSim-3), in wastewater biogas and provided a more efficient sampling of heavier VMS in comparison to the sorbent tubes method. At low values (< 0.1 mgSim-3) typical of wood waste biogas and biomethane, no statistically significant differences were observed between the two methods. Overall, Tedlar SPME simplified the analytical procedure by reducing the procedural steps, avoiding the use of solvents and demonstrated its applicability for testing the quality of biomethane as advanced biofuel.

Changes in the pattern of polycyclic aromatic hydrocarbons in soil treated with biochar from a multiyear field experiment.

The influence of biochar added to an agricultural soil on polycyclic aromatic hydrocarbon (PAH) levels, PAH diagnostic ratios and soil properties was investigated in a five-year field experiment. The experiment was carried out in an Italian vineyard and included two biochar treatments: 16.5 t ha-1 of biochar applied in 2009 (soil B); 16.5 t ha-1 in 2009 and further 16.5 t ha-1 in 2010 (soil BB). A set of 75 samples that included five replicates and a control soil (untreated) was characterized in terms of organic carbon, pH, cation exchange capacity (CEC), bulk density and concentration of PAHs. Biochar addition to soil caused an increase in organic carbon, pH and CEC, and a decrease of bulk density. After almost two years the first application of biochar, PAH concentrations were higher in soil B (56 ng g-1) and BB (153 ng g-1) in comparison to control soil (24 ng g-1). Thereafter, PAH concentrations decreased significantly, but the original PAHs levels were reached only in soil B after five years. The naphthalene/(naphthalene + phenanthrene) ratios were higher in the treated soils in accordance to the dominance of naphthalene in the original biochar. The cross plots naphthalene/(naphthalene + phenanthrene) vs. fluoranthene/(fluoranthene + pyrene) enabled to trace the signature of biochar PAHs up to five years after its first application. Diagnostic ratios can be a useful tool to study the persistence of PAHs introduced in soil by biochar when the pattern of these contaminants in biochar and original soil are different.

Getting to the root of the matter: Water-soluble and volatile components in thermally-treated biosolids and biochar differentially regulate maize (Zea mays) seedling growth.

The use of thermally treated biomass, including biochar, as soil amendments can improve soil fertility by providing nutrients, stable C and improving soil water-holding capacity. However, if the degree of carbonization is low, these soil amendments can lower crop productivity as a result of high salinity or organic compounds. The overall effect of these soil amendments is mediated by complex relationships between production conditions, soil properties and environmental conditions. This study aimed to 1) characterize the physiochemical properties and organic compounds released by three soil amendments (softwood biochar or pyrogenic carbonaceous biosolids), 2) determine the effects of these amendments on maize (Zea mays) seedling productivity, and 3) relate properties of these amendments to effects on maize seedling productivity under controlled environment conditions. Physicochemical properties and mobile organic compounds (water-soluble and volatile organic compounds were determined. The amendments were tested in maize germination and greenhouse experiments. Chemical fingerprinting of volatile and water-soluble compounds revealed over 100 mobile organic species. Increasing treatment temperature from 270 to 320°C reduces phytotoxicity of pyrogenic carbonaceous biosolids soil amendments. Water-soluble components of pyrogenic carbonaceous biosolids produced at 270°C (inorganic N, Na and/or organic compounds) were associated with reduced maize seedling productivity. Volatile components of pyrogenic carbonaceous biosolids produced at 320°C were associated with improved maize seedling productivity; nitrogen uptake was increased in spite of smaller root systems as a result of increased mineralization of soil or amendment N and/or uptake of organic N compounds. These results suggest that pyrogenic carbonaceous biosolids have potential benefits to provide plant nutrients when the amount of organic and inorganic species are limited during early growth stages, under greenhouse conditions. Future studies should examine these effects under field conditions to confirm whether controlled environment results translate into effects on yield.

Determination of volatile fatty acids in digestate by solvent extraction with dimethyl carbonate and gas chromatography-mass spectrometry.

Volatile fatty acids (VFAs) are among the most important parameters in process monitoring of anaerobic digestion plants for biogas production. The concentration of single VFA species is typically determined by direct injection of the acidified aqueous phase of digestate samples into GC-FID. Analysis of dimethyl carbonate extracts was investigated as an alternative method consisting of a simple and rapid in-vial procedure of acidification and solvent extraction of the sample, followed by centrifugation and GC-MS analysis. The principal figures of merit resulting from internal standard calibration were comparable to those proposed for the direct analysis of aqueous digestate, while the analysis of real samples did not provide statistically significant differences between the two methods according to parametric and non-parametric tests. Procedural aspects including sample amount and solid removal improved with dimethyl carbonate, while GC contamination was reduced. The method was applied to seventeen samples from fully operating anaerobic digesters fed with various feedstocks and enabled the individuation of high probability of system stress through the values of total VFA, propanoic acid, longer chained VFA concentrations and the ratio between acetic and propanoic acid concentrations. The use of dimethyl carbonate allowed the detection of alicyclic and aromatic acids that could represent new molecular markers in assessing the origin of feed and process conditions.

Stress Fracture of Proximal Femur after Hip Resurfacing Treated with Cannulated Screw.

Stress fractures of the proximal femur are described in athletes and military personnel. In most cases, they are not treated surgically, except when they are at the top of the femoral neck and with cortical involvement. The return to sports is not recommended in patients with hip replacement, especially for the high rate of revision of implants in the younger patients. One of the major complications of hip resurfacing (HR) is the medial fracture of the femoral neck, which usually occurs within 9 weeks after surgery. The causes have to be attributed to a malposition of the femoral component or to an insufficient bone density. The case reported herein is unique because it describes a stress fracture on patient operated with HR, treated with screw fixation. Two years after surgery, the patient returned to his normal life, practicing sports, without progression of varus angulation of the stem.

Composition of Metallic Elements and Size Distribution of Fine and Ultrafine Particles in a Steelmaking Factory.

BACKGROUND: The characteristics of aerosol, in particular particle size and chemical composition, can have an impact on human health. Particle size distribution and chemical composition is a necessary parameter in occupational exposure assessment conducted in order to understand possible health effects. The aim of this study was to characterize workplace airborne particulate matter in a metallurgical setting by synergistically using two different approaches; Methodology: Analysis of inhalable fraction concentrations through traditional sampling equipment and ultrafine particles (UFP) concentrations and size distribution was conducted by an Electric Low-Pressure Impactor (ELPI+™). The determination of metallic elements (ME) in particles was carried out by inductively coupled plasma mass spectrometry; Results: Inhalable fraction and ME concentrations were below the limits set by Italian legislation and the American Conference of Governmental Industrial Hygienists (ACGIH, 2017). The median of UFP was between 4.00 × 104 and 2.92 × 105 particles/cm³. ME concentrations determined in the particles collected by ELPI show differences in size range distribution; Conclusions: The adopted synergistic approach enabled a qualitative and quantitative assessment of the particles in steelmaking factories. The results could lead to a better knowledge of occupational exposure characterization, in turn affording a better understanding of occupational health issues due to metal fumes exposure.

Source and Biological Response of Biochar Organic Compounds Released into Water; Relationships with Bio-Oil Composition and Carbonization Degree.

Water-soluble organic compounds (WSOCs) were extracted from corn stalk biochar produced at increasing pyrolysis temperatures (350-650 °C) and from the corresponding vapors, collected as bio-oil. WSOCs were characterized by gas chromatography (semivolatile fraction), negative electron spray ionization high resolution mass spectrometry (hydrophilic fraction) and fluorescence spectroscopy. The pattern of semivolatile WSOCs in bio-oil was dominated by aromatic products from lignocellulose, while in biochar was featured by saturated carboxylic acids from hemi/cellulose and lipids with concentrations decreasing with decreasing H/C ratios. Hydrophilic species in poorly carbonized biochar resembled those in bio-oil, but the increasing charring intensity caused a marked reduction in the molecular complexity and degree of aromaticity. Differences in the fluorescence spectra were attributed to the predominance of fulvic acid-like structures in biochar and lignin-like moieties in bio-oil. The divergence between pyrolysis vapors and biochar in the distribution of WSOCs with increasing carbonization was explained by the hydrophobic carbonaceous matrix acting like a filter favoring the release into water of carboxylic and fulvic acid-like components. The formation of these structures was confirmed in biochar produced by pilot plant pyrolysis units. Biochar affected differently shoot and root length of cress seedlings in germination tests highlighting its complex role on plant growth.