Durability and chemical resistance of nanoparticles fly ash and silica fume belite cement pastes against sulfate and chloride aggressive media- Part II

The durability (chemical resistence) of the Portland cement (OPC), belite cement (BC) and the optimum belite cement (B4), which their physical and chemo/mechanical properties were perviously investigated in Part I, against 4 % MgSO4 and 4% MgCl2 solutions up to 12 months in terms of compressive strength, total sulfate and total chloride was evaluated and studied. Results showed that the optimum belite cement (B4) containing 15 % High pulverized fly ash (HPFA) and 5 % Silica fume (SF) could be resisted up to 6 months, while that of BC could be withstood only up to 5 months, and the OPC could not resist more than three months of immersion in 4% MgSO4 solution. The compressive strength values exhibited by the samples immesed in sulfate solution at 3, 5 and 6 months of immersion were 83.81, 76.38 and 91.13 MPa, respectively. The same trend was displayed when the same samples were exposed to 4% MgCl2 solution. The compressive strength values exhibited by the same samples exposed to chloride solution at 3, 5 and 6 months of immersion were 84.49, 82.23 and 93.32 MPa, respectively. The total sulfate and chloride contents were enhanced with immesion time up to 12 months, but their values were the minimum with B4 and the maximum with OPC, while with BC were the medium. The optimum cement batch (B4) achieved the highest resistance where it recorded the lowest values for sulfate and chloride ions, but the OPC exhibited the lowest resistance where it recorded the highest values of sulfate and chloride contents at all immersion ages till 12 months.

Cytotoxicity activities and chemical characteristics of exopolysaccharides and intracellular polysaccharides of Physarum polycephalum microplasmodia

Background Microbial polysaccharides have been reported to possess remarkable bioactivities. Physarum polycephalum is a species of slime mold for which the microplasmodia are capable of rapid growth and can produce a significant amount of cell wall-less biomass. There has been a limited understanding of the polysaccharides produced by microplasmodia of slime molds, including P. polycephalum. Thus, the primary objectives of this research were first to chemically characterize the exopolysaccharides (EPS) and intracellular polysaccharides (IPS) of P. polycephalum microplasmodia and then to evaluate their cytotoxicity against several cancer cell lines. Results The yields of the crude EPS (4.43 ± 0.44 g/l) and partially purified (deproteinated) EPS (2.95 ± 0.85 g/l) were comparable (p > 0.05) with the respective crude IPS (3.46 ± 0.36 g/l) and partially purified IPS (2.45 ± 0.36 g/l). The average molecular weight of the EPS and IPS were 14,762 kDa and 1788 kDa. The major monomer of the EPS was galactose (80.22%), while that of the IPS was glucose (84.46%). Both crude and purified IPS samples showed significantly higher cytotoxicity toward Hela cells, especially the purified sample and none of the IPSs inhibited normal cells. Only 38.42 ± 2.84% Hela cells remained viable when treated with the partially purified IPS (1 mg/ml). However, although only 34.76 ± 6.58% MCF-7 cells were viable when exposed to the crude IPS, but the partially purified IPS displayed non-toxicity to MCF-7 cells. This suggested that the cytotoxicity toward MCF-7 would come from some component associated with the crude IPS sample (e.g. proteins, peptides or ion metals) and the purification process would have either completely removed or reduced amount of that component. Cell cycle analysis by flow cytometry suggested that the mechanism of the toxicity of the crude IPS toward MCF-7 and the partially purified IPS toward Hela cells was due to apoptosis. Conclusions The EPS and IPS of P. polycephalum microplasmodia had different chemical properties including carbohydrate, protein and total sulfate group contents, monosaccharide composition and molecular weights, which led to different cytotoxicity activities. The crude and partially purified IPSs would be potential materials for further study relating to cancer treatment.

Aerosol pH indicator and organosulfate detectability from aerosol mass spectrometry measurements

Aerosol sulfate is a major component of submicron particulate matter (PM1). Sulfate can be present as inorganic (mainly ammonium sulfate, AS) or organosulfate (OS). Although OS is thought to be a smaller fraction of total sulfate in most cases, recent literature argues that this may not be the case in more polluted environments. Aerodyne aerosol mass spectrometers (AMSs) measure total submicron sulfate, but it has been difficult to apportion AS vs. OS as the detected ion fragments are similar. Recently, two new methods have been proposed to quantify OS separately from AS with AMS data. We use observations collected during several airborne field campaigns covering a wide range of sources and air mass ages (spanning the continental US, marine remote troposphere, and Korea) and targeted laboratory experiments to investigate the performance and validity of the proposed OS methods. Four chemical regimes are defined to categorize the factors impacting sulfate fragmentation. In polluted areas with high ammonium nitrate concentrations and in remote areas with high aerosol acidity, the decomposition and fragmentation of sulfate in the AMS is influenced by multiple complex effects, and estimation of OS does not seem possible with current methods. In regions with lower acidity (pH > 0) and ammonium nitrate (fraction of total mass < 0.3), the proposed OS methods might be more reliable, although application of these methods often produced nonsensical results. However, the fragmentation of ambient neutralized sulfate varies somewhat within studies, adding uncertainty, possibly due to variations in the effect of organics. Under highly acidic conditions (when calculated pH < 0 and ammonium balance < 0.65), sulfate fragment ratios show a clear relationship with acidity. The measured ammonium balance (and to a lesser extent, the HySOx+ / SOx+ AMS ratio) is a promising indicator of rapid estimation of aerosol pH < 0, including when gas-phase NH3 and HNO3 are not available. These results allow an improved understanding of important intensive properties of ambient aerosols.

Sulfate reduction and anaerobic oxidation of methane in sediments of the South-Western Barents Sea

Anaerobic oxidation of methane (AOM) in marine sediments strongly limits the amount of gas reaching the water column and the atmosphere but its efficiency in counteracting future methane emissions at continental margins remains unclear. Small shifts in methane fluxes due to gas hydrate and submarine permafrost destabilization or enhanced methanogenesis in warming Arctic continental shelves may cause the redox boundary in which AOM occurs, known as Sulfate-Methane Transition Zone (SMTZ), to move closer to seafloor, with potential gas release to bottom waters. Here, we investigated the geochemical composition of pore water (SO42− and DIC concentration, δ13CDIC) and gas (CH4, δ13CCH4) in eight gravity cores collected from Ingøydjupet trough, South-Western Barents Sea. Our results show a remarkable variability in SMTZ depth, ranging from 3.5 m to 29.2 m, and that all methane is efficiently consumed by AOM within the sediment. From linear fitting of the sulfate concentration profiles, we calculated diffusive sulfate fluxes ranging from 1.5 nmol cm−2 d−1 to 12.0 nmol cm−2 d−1. AOM rates obtained for two cores using mixing models are 6.5 nmol cm−2 d−1 and 6.7 nmol cm−2 d−1 and account for only 64 % and 56 % of total sulfate reduction at the SMTZ (SRRtot), respectively. The remaining 36 % and 44 % SRRtot correspond to organoclastic sulfate reduction with rates of 3.7 nmol cm−2 d−1 and 5.3 nmol cm−2 d−1. The shallowest SMTZs ( 20 m. This study provides new insights into the dynamic and biogeochemistry of the SMTZ in marine sediments of continental margins and may help predict the response of the microbial methane filter to future increase in methane fluxes due to ocean warming.

Optimization of the Obtaining of Cellulose Nanocrystals from Agave tequilana Weber Var. Azul Bagasse by Acid Hydrolysis

A multilevel factorial design of 23 with 12 experiments was developed for the preparation of cellulose nanocrystals (CNC) from Agave tequilana Weber var. Azul bagasse, an agro-industrial waste from tequila production. The studied parameters were acid type (H2SO4 and HCl), acid concentration (60 and 65 wt% for H2SO4, 2 and 8N for HCl) temperature (40 and 60 °C for H2SO4, 50 and 90 °C for HCl), and hydrolysis time (40, 55 and 70 min for H2SO4; and 30, 115 and 200 min for HCl). The obtained CNC were physical and chemically characterized using dynamic light scattering (DLS), atomic force microscopy (AFM), Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XDR) techniques. The maximum CNC yield was 90 and 96% for HCL and H2SO4, respectively, and the crystallinity values ranged from 88–91%. The size and morphology of A. tequilana CNC strongly depends on the acid type and hydrolysis time. The shortest CNC obtained with H2SO4 (65 wt%, 40 °C, and 70 min) had a length of 137 ± 68 nm, width 33 ± 7 nm, and height 9.1 nm, whereas the shortest CNC obtained with HCl (2 N, 50 °C and 30 min) had a length of 216 ± 73 nm, width 69 ± 17 nm, and height 8.9 nm. In general, the obtained CNC had an ellipsoidal shape, whereas CNC prepared from H2SO4 were shorter and thinner than those obtained with HCl. The total sulfate group content of CNC obtained with H2SO4 increased with time, temperature, and acid concentration, exhibiting an exponential behavior of CSG=aebt.

Optimization of the Obtaining of Cellulose Nanocrystals from Agave Tequilana Weber Var. Azul Bagasse by Acid Hydrolysis

A multilevel factorial design of 23 with 12 experiments was developed for the preparation of cellulose nanocrystals (CNC) from Agave tequilana Weber var. Azul bagasse. The studied parameters were acid type (H2SO4 and HCl), acid concentration (60 and 65 wt% for H2SO4, 2 and 8N for HCl) temperature (40 and 60&deg;C for H2SO4, 50 and 90&deg;C for HCl), and hydrolysis time (40, 55 and 70 min for H2SO4, 30, 115 and 200 min for HCl). The obtained CNC were physical and chemically characterized using dynamic light scattering (DLS), atomic force microscopy (AFM), Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XDR) techniques. The size and morphology of A. tequilana CNC strongly depend on the acid type and hydrolysis parameters. The shortest CNC were obtained with H2SO4 (65 wt%, 40 &deg;C, and 70 min) had a length of 137 &plusmn; 68 nm, width 33 &plusmn; 7 nm, and height 9.1 nm, whereas the shortest CNC obtained with HCl (2 N, 50 &deg;C and 30 min) had a length of 216 &plusmn; 73 nm, width 69 &plusmn; 17 nm, and height 8.9 nm. CNC prepared from H2SO4 resulted shorter and thinner than those obtained with HCl. The total sulfate groups content in CNC obtained with H2SO4 increase with time agree to CSG=aebt, and increases with temperature and acid concentration.

Over-sulfated soils and sediments treatment: A brief discussion on performance disparities of biological and non-biological methods throughout the literature

High sulfate concentrations in industrial effluents as well as solid materials (excavated soils, dredged sediments, etc.) are a major hindrance for circular economy outlooks. SO42- acceptability standards are indeed increasingly restrictive, given the potential outcomes for public health and ecosystems. This literature review deals with the treatment pathways relying on precipitation, adsorption and microbial redox principles. Although satisfactory removal performances can be achieved with each of them, significant yield differences are displayed throughout the bibliography. The challenge here was to identify the parameters leading to this variability and to assess their impact. The precipitation pathway is based on the formation of two main minerals (ettringite and barite). It can lead to total sulfate removal but can also be limited by aqueous wastes chemistry. Stabilizer kinetics of formation and equilibrium are highly constrained by background properties such as pH, Eh, SO42- saturation state and inhibiting metal occurrences. Regarding the adsorption route, sorbents’ intrinsic features such as the qmax parameter govern removal yields. Concerning the microbial pathway, the chemical oxygen demand/SO42- ratio and the hydraulic retention time, which are classically evoked as yield variation factors, appear here to be weakly influential. The effect of these parameters seems to be overridden by the influence of electron donors, which constitute a first order factor of variability. A second order variability can be read according to the nature of these electron donors. Approaches using simple monomers (ethanol lactates, etc.) perform better than those using predominantly ligneous organic matter.

Aerosol pH Indicator and Organosulfate Detectability from Aerosol Mass Spectrometry Measurements

Aerosol sulfate is a major component of submicron particulate matter (PM1). Sulfate can be present as inorganic (mainly ammonium sulfate, AS) or organic sulfate (OS). Although OS are thought to be a smaller fraction of total sulfate in most cases, recent literature argues that this may not be the case in more polluted environments. Aerodyne Aerosol Mass Spectrometers (AMS) measure total submicron sulfate, but it has been difficult to apportion AS vs. OS as the detected ion fragments are similar. Recently, two new methods have been proposed to quantify OS separately from AS with AMS data. We use observations collected during several airborne field campaigns covering a wide range of sources and airmass ages (spanning the continental US, marine remote troposphere, and Korea) and targeted laboratory experiments to investigate the performance and validity of the proposed OS methods. Four chemical regimes are defined to categorize the factors impacting sulfate fragmentation (Fig. shown in abstract). In polluted areas with high ammonium nitrate concentrations and in remote areas with high aerosol acidity, the decomposition and fragmentation of sulfate in the AMS is influenced by multiple complex effects, and estimation of OS does not seem possible with current methods. In regions with lower acidity (pH>0) and ammonium nitrate (fraction<0.3), the proposed OS methods might be more reliable, although application of these methods often produced nonsensical results. However, the fragmentation of ambient neutralized sulfate varies somewhat within studies, adding uncertainty, possibly due to variations in the effect of organics. Under highly acidic conditions, sulfate fragment ratios show a clear relationship with acidity (pH and ammonium balance). The measured ammonium balance (and to a lesser extent, the HySOx+/SOx+ AMS ratio) is a promising indicator for rapid estimation of aerosol pH < 0, including when gas-phase NH3 and HNO3 are not available. These results allow an improved understanding of important intensive properties of ambient aerosols.

On the relationship between cloud water composition and cloud droplet number concentration

Aerosol–cloud interactions are the largest source of uncertainty in quantifying anthropogenic radiative forcing. The large uncertainty is, in part, due to the difficulty of predicting cloud microphysical parameters, such as the cloud droplet number concentration (Nd). Even though rigorous first-principle approaches exist to calculate Nd, the cloud and aerosol research community also relies on empirical approaches such as relating Nd to aerosol mass concentration. Here we analyze relationships between Nd and cloud water chemical composition, in addition to the effect of environmental factors on the degree of the relationships. Warm, marine, stratocumulus clouds off the California coast were sampled throughout four summer campaigns between 2011 and 2016. A total of 385 cloud water samples were collected and analyzed for 80 chemical species. Single- and multispecies log–log linear regressions were performed to predict Nd using chemical composition. Single-species regressions reveal that the species that best predicts Nd is total sulfate (Radj2=0.40). Multispecies regressions reveal that adding more species does not necessarily produce a better model, as six or more species yield regressions that are statistically insignificant. A commonality among the multispecies regressions that produce the highest correlation with Nd was that most included sulfate (either total or non-sea-salt), an ocean emissions tracer (such as sodium), and an organic tracer (such as oxalate). Binning the data according to turbulence, smoke influence, and in-cloud height allowed for examination of the effect of these environmental factors on the composition–Nd correlation. Accounting for turbulence, quantified as the standard deviation of vertical wind speed, showed that the correlation between Nd with both total sulfate and sodium increased at higher turbulence conditions, consistent with turbulence promoting the mixing between ocean surface and cloud base. Considering the influence of smoke significantly improved the correlation with Nd for two biomass burning tracer species in the study region, specifically oxalate and iron. When binning by in-cloud height, non-sea-salt sulfate and sodium correlated best with Nd at cloud top, whereas iron and oxalate correlated best with Nd at cloud base.

Crude Fucoidan Activity Extracted from Sargassum sp. as Mycotoxin (T-2) Binder

Fucoidan is a sulfated polysaccharide which is mainly found in brown seaweed like Sargassum sp. In this study, fucoidan was extracted with two distinct methods, one was using 0.1 N HCl (Fucoidan A) and the other 0.1 N H3PO4 (Fucoidan B). The yield of HCl extraction was respectively 7.50% and H3PO4 extraction 7.02%. Characterization of crude fucoidan was carried out through fourier-transform infrared spectroscopy (FTIR), followed by total carbohydrate and total sulfate level measurement. Crude fucoidan was then used to determine its binding activity against Trichothecenes T-2 toxin. Quantitative analysis of 50 ug/ml T-2 toxin binding capacity shows an efficiency of 59.52% at pH 3.0 and 58.37% at pH 6.8 for crude fucoidan A. As for crude fucoidan B, efficiency of T-2 toxin binding capacity has value of 58.12% at pH 3.0 and 57.33% at pH 6.8. Meanwhile, Commercial crude fucoidan extract from Fucus vesiculosus sp. was used as control for T-2 toxin binding capacity analysis with efficiency of 57.31% at pH 3.0 and 56.64% at pH 6.8. Therefore, fucoidan from Sargassum sp. can be utilized better as mycotoxin especially T-2 toxin binder than from Fucus vesiculosus sp. through efficiency result of fucoidan binding capacity.