Mixture Of Ammonium Sulfate Research Articles

Solubility of neodymium and dysprosium sulfates at different pH and temperature and the effect of yttrium sulfate, sodium sulfate, and ammonium sulfate mixtures: Strengthening the predictive capacities of the OLI software

This study focuses on investigating the solubilities of two rare earth element (REE) sulfate salts, Nd2(SO4)3 (representing light REEs) and Dy2(SO4)3 (representing heavy REEs), under various conditions. Four different systems are studied: 1) binary REE2(SO4)3–H2O system at natural pH and temperatures of 25, 46, 65, and 80 °C, 2) ternary REE2(SO4)3–NaOH–H2O system, covering a pH range from 7 down to neutral, at temperatures of 25, 46, 65, and 80 °C, 3) ternary REE2(SO4)3–Y2(SO4)3–H2O system, involving Y2(SO4)3 concentrations ranging from 0 to 20 g/L, pH values of 3 and 7, all at 25 °C, and 4) quaternary REE2(SO4)3–Na2SO4–(NH4)2SO4–H2O system, encompassing Na2SO4 and (NH4)2SO4 concentrations varying from 0 to 20 g/L, pH values of 3 and 7, and at 25 °C. Solubilities of Nd2(SO4)3 and Dy2(SO4)3 decrease as temperature rises, attributed to the exothermic dissolution reactions. Within pH 2 to 5, solubilities remain relatively constant, but at higher pH, they decrease due to the formation of REE2(SO4)(OH)4(H2O)2 (rare earth sulfate hydroxide hydrate). Addition of Y2(SO4)3 does not significantly affect solubilities because of the relatively low Y2(SO4)3 concentration range (below 0.03 mol/kg of water), but solubilities are lower at pH 7 due to REE2SO4OH4H2O2 formation. For Nd2(SO4)3, solubility decreases with increasing Na2SO4 and (NH4)2SO4 concentrations, especially at pH 3 due to the formation of NaNd(SO4)2(H2O) (sodium neodymium bis(sulfate) hydrate) which is also confirmed by the decrease in Na2SO4 concentration compared with the target value. However, at pH 7, the concentration of Na2SO4 is much closer to the target range. This suggests that the formation of NaNd(SO4)2(H2O) is less significant at pH 7 and most of Nd precipitates as Nd2SO4OH4H2O2. For Dy2(SO4)3, solubility increases with increasing sulfate concentrations again due to the to the formation of REESO4+ and REE(SO4)2− complexes but the solubility is lower at pH 7 due to Dy2SO4OH4H2O2 and DySO4OH formation. The outcomes of this investigation represent a notable augmentation to the existing repository of solubility data for Nd2(SO4)3 and Dy2(SO4)3. These particular systems were deliberately chosen to emulate the process of extracting rare earth elements (REEs) from ion-adsorbed clays. Nonetheless, the implications of this research extend beyond this context and hold relevance for various procedures that involve the handling of REEs in sulfate-based environments. One prominent application of these findings lies in the augmentation of thermodynamic models, notably the MSE model integrated into the OLI software. Through the incorporation of this new dataset, the OLI software is poised to become a more potent tool for forecasting and simulating the chemistry of rare earth sulfate systems. This advancement bears significant promise for forthcoming research endeavors and industrial applications where precise modeling of REE behavior is of paramount importance.

Band Phosphorus and Sulfur Fertilization as Drivers of Efficient Management of Nitrogen of Maize (Zea mays L.).

Increasing the efficiency of nitrogen use (NUE) from mineral fertilizers is one of the most important priorities of modern agriculture. The objectives of the present study were to assess the role of different nitrogen (N), phosphorus (P) and sulfur (S) rates on maize grain yield (GY), crop residue biomass, NUE indices, N concentration in plants during the growing season, N management indices and to select the most suitable set of NUE indicators. The following factors were tested: band application of di-ammonium phosphate and ammonium sulphate mixture (NPS fertilizer at rates 0, 8.7, 17.4, 26.2 kg ha−1 of P) and different total N rates (0, 60, 120, 180 kg ha−1 of N). In each year of the study, a clear trend of increased GY after NP(S) band application was observed. A particularly positive influence of that factor was confirmed at the lowest level of N fertilization. On average, the highest GY values were obtained for N2P3 and N3P1 treatments. The total N uptake and NUE indices also increased after the band application. In addition, a trend of improved N remobilization efficiency and the N contribution of remobilized N to grain as a result of band application of NP(S) was observed. Among various NUE indices, internal N utilization efficiency (IE) exhibited the strongest, yet negative, correlation with GY, whereas IE was a function of the N harvest index.

Hygroscopicity and cloud condensation nucleation activities of hydroxyalkylsulfonates

Hydroxyalkylsulfonates may contribute significantly to atmospheric particles; however, their hygroscopic properties and cloud condensation nuclei (CCN) activities remain unknown. In this study, three complementary techniques were utilized to examine the hygroscopicity of sodium hydroxymethanesulfonate (NaHMS), sodium 2-hydroxyethylsulfonate (NaHES), and ammonium 2-hydroxyethylsulfonate (NH4HES) under subsaturated and supersaturated environments. The mass changes in the three hydroxyalkylsulfonates at different relative humidities at 25 °C were examined by a vapor sorption analyzer, and the mass growth factors were measured to be 3.25 ± 0.01 for NaHMS, 3.32 ± 0.02 for NaHES, and 3.34 ± 0.04 for NH4HES at 90% RH. Their hygroscopic growth was investigated by a humidity tandem differential mobility analyzer, and hygroscopic growth factors were 1.78 ± 0.02 for NaHMS, 1.71 ± 0.02 for NaHES, and 1.68 ± 0.03 for NH4HES at 90% RH. Furthermore, the CCN activities of NaHMS, NaHES, and NH4HES were explored, and their single hygroscopicity parameters (κccn) were measured to be 0.649 ± 0.097 for NaHMS, 0.559 ± 0.069 for NaHES, and 0.434 ± 0.073 for NH4HES. In addition, the hygroscopic growth and CCN activities of binary mixtures of ammonium sulfate with one of the three hydroxyalkylsulfonates were also examined.

Efficient bioethanol production from date palm (Phoenix dactylifera L.) sap by a newly isolated Saccharomyces cerevisiae X19G2

In this research, 54 newly isolated strains of yeast from various microhabitats were screened in order to explore their potential for bioethanol production through bioconversion of date palm sap (DPS), as a renewable raw material. The highest ethanol concentration of 58.7 ± 0.23 g/L was achieved by the newly selected Saccharomyces cerevisiae strain X19G2 under anaerobic conditions. The effects of nitrogen supplementation, inoculum size and incubation temperature on bioethanol production from DPS by this strain were investigated. Bioethanol yield (0.43 ± 0.01 g/g consumed sugars) and ethanol productivity (1.49 ± 0.11 g/L/h) increased significantly when a mixture of ammonium sulfate and yeast extract (1:1) were used as nitrogen sources at 30 °C. Subsequently, batch and fed-batch (FB) fermentation were performed in a 2 L bioreactor. The highest ethanol yield was achieved in the FB experiment, reaching 0.48 g/g consumed sugars, which corresponded to over 90 % of the maximum theoretical yield. Based on these findings, the minimum bioethanol production potential using DPS was estimated to be approximately 11000 L per hectare of palm trees. This study indicated that DPS is a highly promising feedstock for bioethanol production by the yeast S. cerevisiae strain X19G2 with economic benefits for industrial scale production.

Effect of mixing structure on the water uptake of mixtures of ammonium sulfate and phthalic acid particles

Abstract. Aerosol mixing state regulates the interactions between water molecules and particles and thus controls aerosol activation and hygroscopic growth, which thereby influences visibility degradation, cloud formation, and its radiative forcing. There are, however, few current studies on the mixing structure effects on aerosol hygroscopicity. Here, we investigated the hygroscopicity of ammonium sulfate / phthalic acid (AS / PA) aerosol particles with different mass fractions of PA in different mixing states in terms of initial particle generation. Firstly, the effect of PA coatings on the hygroscopic behavior of the core-shell-generated mixtures of AS with PA was studied using a coating hygroscopicity tandem differential mobility analyzer (coating HTDMA). The slow increase in the hygroscopic growth factor of core-shell-generated particles is observed with increasing thickness of the coating PA prior to the deliquescence relative humidity (DRH) of AS. At relative humidity (RH) above 80 %, a decrease in the hygroscopic growth factor of particles occurs as the thickness of the PA shell increases, which indicates that the increase of PA mass fractions leads to a reduction of the overall core-shell-generated particle hygroscopicity. In addition, the use of the Zdanovskii–Stokes–Robinson (ZSR) relation leads to the underestimation of the measured growth factors of core-shell-generated particles without consideration of the morphological effect of core-shell-generated particles, especially at higher RH. Secondly, in the case of the AS / PA initially well-mixed particles, a shift of the DRH of AS (∼80 %, Tang and Munkelwitz, 1994) to lower RH is observed due to the presence of PA in the initially well-mixed particles. The predicted hygroscopic growth factor using the ZSR relation is consistent with the measured hygroscopic growth factor of the initially well-mixed particles. Moreover, we compared and discussed the influence of mixing states on the water uptake of AS / PA aerosol particles. It is found that the hygroscopic growth factor of the core-shell-generated particles is slightly higher than that of the initially well-mixed particles with the same mass fractions of PA at RH above 80 %. The observation of AS / PA particles may contribute to a growing field of knowledge regarding the influence of coating properties and mixing structure on water uptake.

Liquid-Liquid Phase Separation in Supermicrometer and Submicrometer Aerosol Particles.

ConspectusThe interactions of aerosol particles with light and clouds are among the most uncertain aspects of anthropogenic climate forcings. The effects of aerosol particles on climate depend on their optical properties, heterogeneous chemistry, water uptake behavior, and ice nucleation activity. These properties in turn depend on aerosol physics and chemistry including composition, size, shape, internal structure (morphology), and phase state. The greatest numbers of particles are found at small, submicrometer sizes, and the properties of aerosol particles can differ on the nanoscale compared with measurements of bulk materials. As a result, our focus has been on characterizing the phase transitions of aerosol particles in both supermicrometer and submicrometer particles. The phase transition of particular interest for us has been liquid-liquid phase separation (LLPS), which occurs when components of a solution phase separate due to a difference in solubilities. For example, organic compounds can have limited solubility in salt solutions especially as the water content decreases, increasing the concentration of the salt solution, and causing phase separation between organic-rich and inorganic-rich phases. To characterize the systems of interest, we primarily use optical microscopy for supermicrometer particles and cryogenic-transmission microscopy for submicrometer particles.This Account details our main results to date for the phase transitions of supermicrometer particles and the morphology of submicrometer aerosol. We have found that the relative humidity (RH) at which LLPS occurs (separation RH; SRH) is highly sensitive to the composition of the particles. For supermicrometer particles, SRH decreases as the pH is lowered to atmospherically relevant values. SRH also decreases when non-phase-separating organic compounds are added to the particles. For submicrometer particles, a size dependence of morphology is observed in systems that undergo LLPS in supermicrometer particles. In the limit of slow drying rates, particles <30 nm are homogeneous and larger particles are phase-separated. This size dependence of aerosol morphology arises because small particles cannot overcome the activation barrier needed to form a new phase when phase separation occurs by a nucleation and growth mechanism. The inhibition of LLPS in small particles is observed for mixtures of ammonium sulfate with single organic compounds as well as complex organics like α-pinene secondary organic matter. The morphology of particles affects activation diameters for the formation of cloud condensation nuclei. These results more generally have implications for aerosol properties that affect the climate system. In addition, LLPS is also widely studied in materials and biological chemistry, and our results could potentially translate to implications for these fields.

Comparing aerosol refractive indices retrieved from full distribution and size- and mass-selected measurements

Refractive index retrievals (also termed inverse Mie methods or optical closure) have seen considerable use as a method to extract the refractive index of aerosol particles from measured optical properties. Retrievals of an aerosol refractive index use one of two primary methods: 1) measurements of the extinction, absorption and/or scattering cross-sections or efficiencies of size- (and mass-) selected particles for mass-mobility refractive index retrievals (MM-RIR) or 2) measurements of aerosol size distributions and a combination of the extinction, absorption and/or scattering coefficients for full distribution refractive index retrievals (FD-RIR). These two methods were compared in this study using pure and mixtures of ammonium sulfate (AS) and nigrosin aerosol, which constitute a non-absorbing and absorbing material, respectively. The results indicate that the retrieved complex refractive index values are correlated to the amount of nigrosin in the aerosol but can be highly variable with differences in the real and imaginary components that range between –0.002 and 0.216 and –0.013 and 0.086; the average and standard deviation of the differences are 0.046 ± 0.046 and 0.023 ± 0.033, respectively. Forward calculation of the optical properties yielded average absolute values of the relative deviation of ≈ 15% and ≈ 26% for FD-RIR data using the MM-RIR values and contrariwise. The range of retrieved refractive indices were used to calculate the normalized global average aerosol radiative forcing of a model accumulation mode remote continental aerosol. Deviations using the refractive indices of the pure materials range from 9% to 32% for AS and 27% to 45% for nigrosin. For mixtures of nigrosin and AS, deviations were all > 100% and not always able to capture the correct direction of the forcing; i.e., positive versus negative.

Evidence for pyrazine-based chromophores in cloud water mimics containing methylglyoxal and ammonium sulfate

Abstract. Simulating aqueous brown carbon (aqBrC) formation from small molecule amines and aldehydes in cloud water mimics provides insight into potential humic-like substance (HULIS) contributors and their effect on local and global aerosol radiative forcing. Previous work has shown that these (Maillard type) reactions generate products that are chemically, physically, and optically similar to atmospheric HULIS in many significant ways, including in their complexity. Despite numerous characterization studies, attribution of the intense brown color of many aqBrC systems to specific compounds remains incomplete. In this work, we present evidence of novel pyrazine-based chromophores (PBCs) in the product mixture of aqueous solutions containing methylglyoxal and ammonium sulfate. PBCs observed here include 2,5-dimethyl pyrazine (DMP) and products of methylglyoxal addition to the pyrazine ring. This finding is significant as the literature of Maillard reactions in food chemistry tightly links the formation of pyrazine (and related compounds) to browning in foods. We investigated the roles of both cloud processing (by bulk evaporation) and pH in absorptivity and product distribution in microliter samples to understand the contribution of these PBCs to aqBrC properties. In agreement with previous work, we observed elevated absorptivity across the entire UV–visible spectrum following simulated cloud processing as well as higher absorptivity in more basic samples. Absorptivity of the pH 2 sample, following evaporation over a period of days, exceeded that of the unevaporated pH 9 sample. In addition, mixtures of ammonium sulfate and methylglyoxal at pH 5 that were dried in under 1 h and analyzed 24 h later were as absorptive as pH 9 samples allowed to react for 7 days, indicating that evaporation occurring during cloud processing may provide a reaction pathway favorable for carbonyl–ammonia chemistry even under acidic conditions of aerosol and cloud water. The fraction of pyrazine compounds in the product mixture increased by up to a factor of 4 in response to drying with a maximum observed contribution of 16 % at pH 5. Therefore, cloud processing under acidic conditions may produce PBCs at the expense of imine- and imidazole-derived compounds. This finding has implications for further BrC reactivity and degradation pathways.

Kinetic Limitation to Inorganic Ion Diffusivity and to Coalescence of Inorganic Inclusions in Viscous Liquid-Liquid Phase-Separated Particles.

Mixed organic/inorganic aerosols may undergo liquid-liquid phase separation (LLPS) when the relative humidity drops in the atmosphere. Phase-separated particles adopt different morphologies, which will have different consequences for atmospheric chemistry and climate. Recent laboratory studies on submicron particles led to speculation whether LLPS observed for larger drops might actually be suppressed in smaller droplets. Here, we report on micron-sized droplets of a ternary mixture of ammonium sulfate (AS), carminic acid, and water at different temperatures, which were exposed to typical atmospheric drying rates ranging from 0.34 to 5.0% RH min-1. Our results reveal that increasing the drying rate and lowering the temperature results in different morphologies after LLPS and may suppress the growth and coalescence of the inorganic-rich phase inclusions due to kinetic limitations in a viscous matrix. The coalescence time was used to estimate the viscosity of the organic-rich phase within a factor of 20, and based on the Stokes-Einstein relationship, we estimated AS diffusivity. Furthermore, we evaluated the initial growth of inclusions to quantitatively determine the AS diffusivity in the organic-rich phase, which is about 10-8 cm2 s-1 at room temperature. Extrapolation of diffusivity to lower temperatures using estimations for the diffusion activation energy leads us to conclude that the growth of the inorganic phase is not kinetically impeded for tropospheric submicron particles larger than 100 nm.

Sulfur-containing air pollutants as draw solution for fertilizer drawn forward osmosis desalination process for irrigation use

This study investigated suitability and performance of the sulfur-based seed solution (SBSS) as a draw solution (DS), a byproduct taken from the photoelectrochemical (PEC) process where the SBSS is used as an electrolyte for H2 production. This SBSS DS is composed of a mixture of ammonium sulfate ((NH4)2SO4) and ammonium sulfite ((NH4)2SO3), and it can be utilized as fertilizer for fertilizer drawn forward osmosis (FDFO) desalination of saline water. The FDFO process employed with thin-film composite (TFC) membrane and showed that the process performance (i.e. water flux and reverse salt flux) is better than that with cellulose triacetate (CTA) membrane. In addition, it produced high water flux of 19LMH using SBSS as DS at equivalent concentration at 1M and 5g/L NaCl of feed solution (model saline water). Experimental results showed that the reverse salt flux of SBSS increased with the increase in pH of the DS and that lowering the concentration of ammonium sulfite in the SBSS led to the higher water flux of feed solution. The result also demonstrated that this SBSS is practically suitable for the FDFO process toward development of water-energy-food nexus technology using sulfur chemicals-containing air pollutant.

Copper Recovery from Yulong Complex Copper Oxide Ore by Flotation and Magnetic Separation

A combined process of flotation and high-gradient magnetic separation was proposed to utilize Yulong complex copper oxide ore. The effects of particle size, activators, Na2S dosage, LA (a mixture of ammonium sulfate and ethylenediamine) dosage, activating time, collectors, COC (a combination collector of modified hydroxyl oxime acid and xanthate) dosage, and magnetic intensity on the copper recovery were investigated. The results showed that 74.08% Cu was recovered by flotation, while the average grade of the copper concentrates was 21.68%. Another 17.34% Cu was further recovered from the flotation tailing by magnetic separation at 0.8 T. The cumulative recovery of copper reached 91.42%. The modifier LA played a positive role in facilitating the sulfidation of copper oxide with Na2S, and the combined collector COC was better than other collectors for the copper flotation. This technology has been successfully applied to industrial production, and the results are consistent with the laboratory data.

Deliquescence Relative Humidities of Organic and Inorganic Salts Important in the Atmosphere.

The deliquescence relative humidities (DRH) as a function of temperature have been determined for several salts of atmospheric importance using humidity controlled thermogravimetric analysis (HTGA): sodium hydrogen oxalate monohydrate (NaHC2O4·H2O), sodium oxalate (Na2C2O4), sodium ammonium sulfate dihydrate (NaNH4SO4·2H2O, lecontite), sodium hydrogen malonate monohydrate (NaHC3H2O4·H2O), sodium malonate monohydrate (Na2C3H2O4·H2O), and ammonium hydrogen malonate (NH4HC3H2O4). The temperature-dependent onset DRH values (where a dry mixture begins to take up water) were also determined for mixtures of ammonium sulfate with malonic acid, and ammonium sulfate with sodium oxalates and sodium malonates, respectively. We demonstrate that the onset DRH is independent of the ratio of solids in the mixture. In general, onset DRH values were always lower than the pure component DRH values.

Aerosol water parameterisation: a single parameter framework

Abstract. We introduce a framework to efficiently parameterise the aerosol water uptake for mixtures of semi-volatile and non-volatile compounds, based on the coefficient, νi. This solute-specific coefficient was introduced in Metzger et al. (2012) to accurately parameterise the single solution hygroscopic growth, considering the Kelvin effect – accounting for the water uptake of concentrated nanometer-sized particles up to dilute solutions, i.e. from the compounds relative humidity of deliquescence (RHD) up to supersaturation (Köhler theory). Here we extend the νi parameterisation from single to mixed solutions. We evaluate our framework at various levels of complexity, by considering the full gas–liquid–solid partitioning for a comprehensive comparison with reference calculations using the E-AIM, EQUISOLV II and ISORROPIA II models as well as textbook examples. We apply our parameterisation in the EQuilibrium Simplified Aerosol Model V4 (EQSAM4clim) for climate simulations, implemented in a box model and in the global chemistry–climate model EMAC. Our results show (i) that the νi approach enables one to analytically solve the entire gas–liquid–solid partitioning and the mixed solution water uptake with sufficient accuracy, (ii) that ammonium sulfate mixtures can be solved with a simple method, e.g. pure ammonium nitrate and mixed ammonium nitrate and (iii) that the aerosol optical depth (AOD) simulations are in close agreement with remote sensing observations for the year 2005. Long-term evaluation of the EMAC results based on EQSAM4clim and ISORROPIA II will be presented separately.

Two dimensional size–mass distribution function inversion from differential mobility analyzer–aerosol particle mass analyzer (DMA–APM) measurements

We developed and applied a data inversion routine to determine the number based size–mass distribution function (the two dimensional distribution function) from tandem differential mobility analyzer–aerosol particle mass analyzer (DMA–APM) measurements. The two dimensional distribution function is expressed in units of particle number concentration per unit mobility diameter per unit particle mass. It can be used to directly calculate the number based size distribution (commonly determined using DMA measurements) or the mass based size distribution (commonly inferred from impactor measurements). The inversion routine utilizes the Twomey–Markowski algorithm and is applied in this study to DMA–APM measurements of sodium chloride, cesium iodide, and ammonium sulfate particles in the 30–200nm mobility diameter range, as well as acetylene flame generated soot aggregates in the 40–350nm range. To utilize the inversion routine, the APM transfer function must be known a priori. Here it is computed using a modified version of the Ehara (uniform flow) model, with a transmission correction factor inferred from measurements. For the three examined salt particle types, visual representation of the two dimensional distribution function reveals that at a given mobility diameter, particles have very narrow mass distributions, with the peak masses in good agreement with predictions based on bulk salt densities. However, for soot particles, extremely broad distributions are observed. Soot measurements are compared to predictions for quasifractal aggregates in the transition regime; this comparison suggests that aggregates with fractal dimensions ranging from 1.4 to 2.5 are all generated in the same system. Finally, we determine the two-dimensional distribution function for a mixture of ammonium sulfate and soot particles, demonstrating that these two particle populations are separable from one another via mobility-mass analysis.

Atmospheric oxidation of isoprene and 1,3-butadiene: influence of aerosol acidity and relative humidity on secondary organic aerosol

Abstract. The effects of acidic seed aerosols on the formation of secondary organic aerosol (SOA) have been examined in a number of previous studies, several of which have observed strong linear correlations between the aerosol acidity (measured as nmol H+ m−3 air sample volume) and the percent change in secondary organic carbon (SOC). The measurements have used several precursor compounds representative of different classes of biogenic hydrocarbons including isoprene, monoterpenes, and sesquiterpenes. To date, isoprene has displayed the most pronounced increase in SOC, although few measurements have been conducted with anthropogenic hydrocarbons. In the present study, we examine several aspects of the effect of aerosol acidity on the secondary organic carbon formation from the photooxidation of 1,3-butadiene, and extend the previous analysis of isoprene. The photooxidation products measured in the absence and presence of acidic sulfate aerosols were generated either through photochemical oxidation of SO2 or by nebulizing mixtures of ammonium sulfate and sulfuric acid into a 14.5 m3 smog chamber system. The results showed that, like isoprene and β-caryophyllene, 1,3-butadiene SOC yields linearly correlate with increasing acidic sulfate aerosol. The observed acid sensitivity of 0.11% SOC increase per nmol m−3 increase in H+ was approximately a factor of 3 less than that measured for isoprene. The results also showed that the aerosol yield decreased with increasing humidity for both isoprene and 1,3-butadiene, although to different degrees. Increasing the absolute humidity from 2 to 12 g m−3 reduced the 1,3-butadiene yield by 45% and the isoprene yield by 85%.

Hygroscopicity of organic compounds from biomass burning and their influence on the water uptake of mixed organic ammonium sulfate aerosols

Abstract. Hygroscopic behavior of organic compounds, including levoglucosan, 4-hydroxybenzoic acid, and humic acid, as well as their effects on the hygroscopic properties of ammonium sulfate (AS) in internally mixed particles are studied by a hygroscopicity tandem differential mobility analyzer (HTDMA). The organic compounds used represent pyrolysis products of wood that are emitted from biomass burning sources. It is found that humic acid aerosol particles only slightly take up water, starting at RH (relative humidity) above ~70%. This is contrasted by the continuous water absorption of levoglucosan aerosol particles in the range 5–90% RH. However, no hygroscopic growth is observed for 4-hydroxybenzoic acid aerosol particles. Predicted water uptake using the ideal solution theory, the AIOMFAC model and the E-AIM (with UNIFAC) model are consistent with measured hygroscopic growth factors of levoglucosan. However, the use of these models without consideration of crystalline organic phases is not appropriate to describe the hygroscopicity of organics that do not exhibit continuous water uptake, such as 4-hydroxybenzoic acid and humic acid. Mixed aerosol particles consisting of ammonium sulfate and levoglucosan, 4-hydroxybenzoic acid, or humic acid with different organic mass fractions, take up a reduced amount of water above 80% RH (above AS deliquescence) relative to pure ammonium sulfate aerosol particles of the same mass. Hygroscopic growth of mixtures of ammonium sulfate and levoglucosan with different organic mass fractions agree well with the predictions of the thermodynamic models. Use of the Zdanovskii–Stokes–Robinson (ZSR) relation and AIOMFAC model lead to good agreement with measured growth factors of mixtures of ammonium sulfate with 4-hydroxybenzoic acid assuming an insoluble organic phase. Deviations of model predictions from the HTDMA measurement are mainly due to the occurrence of a microscopical solid phase restructuring at increased humidity (morphology effects), which are not considered in the models. Hygroscopic growth factors of mixed particles containing humic acid are well reproduced by the ZSR relation. Lastly, the organic surrogate compounds represent a selection of some of the most abundant pyrolysis products of biomass burning. The hygroscopic growths of mixtures of the organic surrogate compounds with ammonium sulfate with increasing organics mass fraction representing ambient conditions from the wet to the dry seasonal period in the Amazon basin, exhibit significant water uptake prior to the deliquescence of ammonium sulfate. The measured water absorptions of mixtures of several organic surrogate compounds (including levoglucosan) with ammonium sulfate are close to those of binary mixtures of levoglucosan with ammonium sulfate, indicating that levoglucosan constitutes a major contribution to the aerosol water uptake prior to (and beyond) the deliquescence of ammonium sulfate. Hence, certain hygroscopic organic surrogate compounds can substantially affect the deliquescence point of ammonium sulfate and overall particle water uptake.

An electrochemical impedance study of bare and anodized AZ31 Mg alloy in dilute Harrison solution

Anodic oxides were grown on AZ31 Mg alloy by micro-arc anodic oxidation in phosphate-based alkaline solutions with and without silicate and aluminate ions. The anodic oxides were characterized by SEM and XRD. Impedance spectra were recorded before and after single cycle anodic polarization in dilute Harrison solution (DHS), which is constituted by a mixture of ammonium sulfate and sodium chloride. Addition of silicate and aluminate oxyanions to the phosphate-based anodizing solution provided anodic oxides with improved morphology and thickness. Nevertheless, the protection performance in DHS is relatively poor due to the high reactivity of Mg in the presence of NH4+. The dissociation of this species into NH3 and H+ as local pH increases promotes further metal corrosion and hinders precipitation of Mg(OH)2. The likely better protection indicated only silicate-rich oxide results from favored film compaction and blocking effect of Mg(OH)2 due to interactions between the oxide bulk phase and NH4+.

Diferentes suplementos associados à palma forrageira em dietas para ovinos: consumo, digestibilidade aparente e parâmetros ruminais

Objetivou-se avaliar o consumo, a digestibilidade aparente dos nutrientes e os parâmetros ruminais de ovinos alimentados com dietas à base de palma forrageira, bagaço de cana-de-açúcar e ureia associados a diferentes suplementos. Foram utilizados cinco ovinos sem padrão racial definido, machos, não-castrados, fistulados no rúmen. Os animais foram distribuídos aleatoriamente em quadrado latino 5 x 5, com cinco animais (linhas) e cinco períodos (colunas). Cada período teve duração de 13 dias. A ração sem suplemento foi composta de 67,6% de palma forrageira, 27,7% de bagaço de cana-de-açúcar in natura, 2,7% de mistura ureia:sulfato de amônio (9:1) e 2,0% de mistura mineral, em base da matéria seca (MS). Os demais tratamentos consistiram na adição de um suplemento à ração ao nível de 0,4% do peso corporal, composta por: farelo de trigo, farelo de soja, farelo de algodão ou caroço de algodão. Não foram observados efeitos da associação dos suplementos sobre os parâmetros avaliados, sendo: 3,29%, 60,61%, 76,37%, 6,51 e 11,85mg/100mL os valores médios observados para o consumo de MS em função do peso corporal, digestibilidades da MS e da PB, pH e amônia ruminal, respectivamente. A escolha do suplemento deve estar associada à disponibilidade e ao custo.

Mixed electrolytes in hydrophobic interaction chromatography†

An essential part of the modulation of protein-binding capacity in hydrophobic interaction chromatography is the buffer-salt system. Besides using "single" electrolytes, multicomponent electrolyte mixtures may be used as an additional tool. Both the protein solubility and the binding capacity depend on the position of a salt in the so-called Hofmeister series. Specific interactions are observed for an individual protein-salt combination. For salt mixtures, selectivity, recovery, and binding capacity do not behave like for the single salts that are positioned in between the two mixed components in the Hofmeister series, as the continuous correlation would suggest. Thus, finding strategies for mixed salts could potentially lead to improved capacities in hydrophobic interaction chromatography. Mixtures of ammonium sulfate, sodium citrate, sodium sulfate, sodium chloride, sodium acetate, and glycine were used to investigate the binding capacities for lysozyme and a monoclonal antibody on various hydrophobic resins. Resin capacity for two investigated proteins increases when mixtures consisting of a chaotropic and a kosmotropic salt are applied. It seems to be related to the rather basic isoelectric points of the proteins.

Preparation and characterization of zinc oxide nanoflakes using anodization method and their photodegradation activity on methylene blue

In this work, we report the formation of leaf-like ZnO nanoflakes by anodization of zinc foil in a mixture of ammonium sulfate and sodium hydroxide electrolytes under various applied voltage and concentration of sodium hydroxide. The morphology and structure of ZnO nanoflakes were investigated by field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction analysis. In addition, the photocatalytic activity of the prepared nanoflakes zinc oxide was evaluated in the photodegradation of organic dye methylene blue (MB) solution under UV irradiation. It was found that zinc oxide prepared under high concentration of sodium hydroxide and high voltage showed better performance in the photodegradation of methylene blue.