Deliquescence Relative Humidity Research Articles

Design, synthesis and characterization of linear unnatural amino acids for skin moisturization.

ObjectivesThis work aimed to design, synthesize and characterize replacement natural moisturizing factor (NMF) composed of modified hygroscopic linear amino acids to pre‐empt or repair skin barrier dysfunction.MethodsFollowing synthesis and characterization, thermo‐gravimetric analysis and quantum mechanics molecular modelling quantified and depicted water binding to the new compounds. Deliquescence relative humidity demonstrated the water‐scavenging ability of the compounds, whereas snake skin moisturizing studies showed they increased water uptake into snake skin.ResultsFrom thermal analysis, N‐hydroxyglycine showed greatest water‐holding capacity followed by N‐hydroxyserine, l‐homoserine and α‐hydroxyglycine; coupled with quantum mechanics molecular modelling, between 8 and 12 molecules of water could associate with each molecule of either N‐hydroxyglycine, N‐hydroxyserine or l‐homoserine. All of our modified amino acids were efficacious and induced similar or greater water uptake compared with the established moisturizing compounds hyaluronic acid, glycerine and urea in snake skin. Incorporated at 10% in Oilatum, N‐hydroxyserine induced >200% greater moisture uptake into dry snake skin compared to treatment with water alone, with efficacy related to the molecule structure and ability to bind to 12 water molecules. Oilatum cream spiked with all our unnatural amino acid hydrotropes increased water uptake into snake skin compared with Oilatum alone.The compound series was designed to elucidate some structure – efficacy relationships. Amino acid chirality did not affect the water‐holding capacity but did affect uptake into skin. Compounds with high melting points and bond energies tended to decrease water‐holding capacity. With isosteric replacement, the more electronegative atoms gave greater water‐holding capacities.ConclusionsThis work demonstrates the potential of unnatural amino acid hydrotropes as skin moisturizers and has developed some predictive ‘rules’ for further design and refinement of chemical structures.

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.

Optical and Physicochemical Properties of Brown Carbon Aerosol: Light Scattering, FTIR Extinction Spectroscopy, and Hygroscopic Growth.

A great deal of attention has been paid to brown carbon aerosol in the troposphere because it can both scatter and absorb solar radiation, thus affecting the Earth's climate. However, knowledge of the optical and chemical properties of brown carbon aerosol is still limited. In this study, we have investigated different aspects of the optical properties of brown carbon aerosol that have not been previously explored. These properties include extinction spectroscopy in the mid-infrared region and light scattering at two different visible wavelengths, 532 and 402 nm. A proxy for atmospheric brown carbon aerosol was formed from the aqueous reaction of ammonium sulfate with methylglyoxal. The different optical properties were measured as a function of reaction time for a period of up to 19 days. UV/vis absorption experiments of bulk solutions showed that the optical absorption of aqueous brown carbon solution significantly increases as a function of reaction time in the spectral range from 200 to 700 nm. The analysis of the light scattering data, however, showed no significant differences between ammonium sulfate and brown carbon aerosol particles in the measured scattering phase functions, linear polarization profiles, or the derived real parts of the refractive indices at either 532 or 402 nm, even for the longest reaction times with greatest visible extinction. The light scattering experiments are relatively insensitive to the imaginary part of the refractive index, and it was only possible to place an upper limit of k ≤ 0.01 on the imaginary index values. These results suggest that after the reaction with methylglyoxal the single scattering albedo of ammonium sulfate aerosol is significantly reduced but that the light scattering properties including the scattering asymmetry parameter, which is a measure of the relative amount of forward-to-backward scattering, remain essentially unchanged from that of unprocessed ammonium sulfate. The optical extinction properties in the mid-IR range (800 to 7000 cm(-1)) also showed no significant changes in either the real or the imaginary parts of the refractive indices for brown carbon aerosol particles when compared to ammonium sulfate. Therefore, changes in the optical properties of ammonium sulfate in the mid-IR spectral range due to reaction with methylglyoxal appear to be insignificant. In addition to these measurements, we have characterized additional physicochemical properties of the brown carbon aerosol particles including hygroscopic growth using a tandem-differential mobility analyzer. Compared to ammonium sulfate, brown carbon aerosol particles are found to have lower deliquescence relative humidity (DRH), efflorescence relative humidity (ERH), and hygroscopic growth at the same relative humidities. Overall, our study provides new details of the optical and physicochemical properties of a class of secondary organic aerosol which may have important implications for atmospheric chemistry and climate.

Deliquescence-induced wetting and RSL-like darkening of a Mars analogue soil containing various perchlorate and chloride salts.

Recurring slope lineae (RSL) are flow‐like features on Mars characterized by a local darkening of the soil thought to be generated by the formation and flow of liquid brines. One possible mechanism responsible for forming these brines could be the deliquescence of salts present in the Martian soil. We show that the JSC Mars‐1a analogue soil undergoes a darkening process when salts dispersed in the soil deliquesce, but forming continuous liquid films and larger droplets takes much longer than previously assumed. Thus, RSL may not necessarily require concurrent flowing liquid water/brine or a salt‐recharge mechanism, and their association with gullies may be the result of previously flowing water and deposited salts during an earlier warmer and wetter period. In addition, our results show that electrical conductivity measurements correlate well with the deliquescence rates and provide better overall characterization than either Raman spectroscopy or estimates based on deliquescence relative humidity.

A modified thermodynamic insight to deliquescence of a void‐containing nanocrystal confirmed by MD simulation

Existence of voids in crystalline structures can affect their physical and chemical properties considerably. When the size of the crystal reaches to nanoscale, experimental determination of its void fraction is difficult. In this work, a molecular dynamics approach is introduced to find equilibrium void fractions of a simple cubic (CsCl) and fcc (KCl) nanocrystals by determination of their deliquescence relative humidity (DRH) for different sizes and void fractions and extrapolation of the results to the bulk limit. To confirm the simulation results, the size dependency of DRH to the nanoparticle size was studied thermodynamically by inclusion of size‐dependent density of water nanodroplet which leads to a simple homographic equation. This method proposes the equilibrium void percents of CsCl and KCl nanoparticles to be 10 and 15%, respectively, which are obtained by extrapolation of the results to the bulk limit. The success of obtained Möbius function was also confirmed by fitting it to experimental data for deliquescence of NaCl nanoparticles which implies the importance of considering density of water nanodroplet as a size dependent quantity. Also, using the mentioned thermodynamic approach, void dependency of deliquescence for the nanoparticles was found to be as a quasi‐linear trend which is compatible with the simulation results. It is noticeable that the approach used this work for determination of equilibrium void fraction is only valid if the utilized force fields are accurate. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4066–4077, 2016

Mole Ratio Dependence of the Mutual Deliquescence Relative Humidity of Aqueous Salts of Atmospheric Importance.

The response of the mutual deliquescence relative humidity (MDRH) of several mixed salt systems to changes in mole ratio is presented here. The MDRH values of NH4Cl-NaCl, NH4Cl-(NH4)2SO4, and, for the first time, the NaCl-NaBr systems were acquired as a function of mole ratio. These changes were studied using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy. The MDRH values of 1:1 salt mixtures were consistently found to be lower than the values of the individual deliquescence relative humidity (iDRH) of NH4Cl-NaCl and NH4Cl-(NH4)2SO4. The exception was the MDRH of the NaCl-NaBr system, which was found to be higher than the iDRH of NaBr particles, but lower than the iDRH of NaCl particles. When the mole ratio of the mixed system was varied, the MDRH of the mixtures showed a slight dependence on the mole ratio.

Aqueous film formation on irregularly shaped inorganic nanoparticles before deliquescence, as revealed by a hygroscopic differential mobility analyzer–Aerosol particle mass system

ABSTRACTA hygroscopic tandem differential mobility analyzer (H-TDMA) and a hygroscopic coupled DMA and aerosol particle mass (H-DMA-APM) were coupled to examine aqueous film formation and the deliquescence behavior of inorganic nanoparticles. The two systems complement each other because H-DMA-APM measures mass change, while H-TDMA measures mobility diameter (volume) change of nanoparticles upon water uptake. The former mass change was, in particular, more capable to discern minute particle phase changes than the latter size change at moderate RHs. The mass and diameter changes were used to derive the particle effective density for evaluation of aqueous film formation on the nanoparticle surface before and after deliquescence transition. The measurements further showed that approximately 3–5 and 12–20 monolayer equivalents of water molecules formed on the respective surface of 50- and 100-nm inorganic aerosols (ammonium sulfate and sodium chloride) before deliquescence relative humidity (DRH). These findi...

Mineralogical evolution of salt over nine years, after removal of efflorescence and saline crusts from Elche’s Old Bridge (Spain)

The Old Bridge Elche’s showed abundant efflorescence and salt crusts that were eliminated in an intervention in 2005. We have followed the development of efflorescence after the intervention. And nine years later the efflorescence mineralogy was quite similar to the mineralogy of the pre-restoration efflorescence.The efflorescence on Elche’s Old Bridge (Puente Viejo) shows a wide mineralogical variation in the vertical profile, which is the result of a balance between two diffusive processes: the evaporation–condensation of atmospheric water vapor on/inside the wall, and the capillary flow of saline groundwater. Diurnal variations in atmospheric relative humidity (RH) and the low deliquescence relative humidity (DRH) values of some saline minerals (nitrate & chloride) play an important role in the vertical distribution of minerals.The mineral composition of efflorescence and saline crusts prior to cleaning the monument was similar to that identified nine years later.The chemical composition of groundwater, with a high sodium chloride component and much lower concentrations of sulfate and bicarbonate, explained the presence of halite, while the presence of demolition waste of a gypsiferous nature near the bridge explained the presence of sulfate salts, thenardite, konyaite, aphthitalite, and arcanite. The dissolution of airborne particles in condensation water probably contributed to the genesis of nitrate-rich minerals such as nitratine, darapskite, and especially humberstonite.

A case study of single hygroscopicity parameter and its link to the functional groups and phase transition for urban aerosols in Taipei City

The hygroscopicity, functional groups and phase transitions of urban aerosol particles in Taipei City were studied using a cloud condensation nuclei counter (CCNc) with a scanning mobility particle sizer (SMPS) and an attenuated total reflectance with infrared (ATR-IR) detection technique. With the assumption of larger particles being activated first, the derived single hygroscopicity parameter (κ) exhibited an increasing trend with particle size, i.e., from 0.022 ± 0.01 at 87 ± 10 nm to 0.13 ± 0.03 at 240 ± 20 nm. The collected size-selected particles were characterized using ATR-IR for the functional groups of alkyl, carbonyl, ammonium, sulfate and nitrate, which showed various size dependence patterns, linked to different formation mechanisms. The hygroscopic response based on the ratio (xW_solute) for sample film of absorption by the enhanced water-stretching peak to that by the selected solute showed a better consistency with pure ammonium sulfate for sub-micron size particles. Based on the derived ammonium sulfate volume fraction from IR analysis, the κ received from CCNc measurements was concluded mainly contributed by ammonium sulfate for sub-micrometer particles. The increasing trend of sodium nitrate absorbance at aerosol diameter ≥1 μm was due to a reaction of nitric acid with sea salt particles. The micrometer sized particles were apparent not only in a significantly higher xW_solute than pure sodium nitrate but also had a deliquescence RH of 69 ± 1%, similar to that of sodium nitrate-sodium chloride mixtures. Overall, the organic species in this study exhibited a low hygroscopicity with less than 0.036 of contribution for the overall κ, and the major hygroscopic material of urban aerosols consisted primarily of ammonium sulfate in the sub-micrometer particles and sodium nitrate with sea salt in the coarse particles.

Gas–particle partitioning and hydrolysis of organic nitrates formed from the oxidation of <i>α</i>-pinene in environmental chamber experiments

Abstract. Gas–particle partitioning and hydrolysis of organic nitrates (ON) influences their role as sinks and sources of NOx and their effects on the formation of tropospheric ozone and organic aerosol (OA). In this work, organic nitrates were formed from the photo-oxidation of α-pinene in environmental chamber experiments under different conditions. Particle-phase ON hydrolysis rates, consistent with observed ON decay, exhibited a nonlinear dependence on relative humidity (RH): an ON decay rate of 2 day−1 was observed when the RH ranged between 20 and 60 %, and no significant ON decay was observed at RH lower than 20 %. In experiments when the highest observed RH exceeded the deliquescence RH of the ammonium sulfate seed aerosol, the particle-phase ON decay rate was as high as 7 day−1 and more variable. The ON gas–particle partitioning was dependent on total OA concentration and temperature, consistent with absorptive partitioning theory. In a volatility basis set, the ON partitioning was consistent with mass fractions of [0 0.11 0.03 0.86] at saturation mass concentrations (C*) of [1 10 100 1000] µg m−3.

Seasonal behavior of PM2.5 deliquescence, crystallization, and hygroscopic growth in the Po Valley (Milan): Implications for remote sensing applications

Atmospheric aerosols deliquescence and crystallization relative humidity (DRH and CRH) are rarely measured compared to the worldwide number of hygroscopicity measurements; this feature comes from the lack of an efficient method able to capture the whole complexity of chemical composition of aerosols. Despite this, the knowledge of both DRH and CRH are crucial for a correct parameterization of the aerosol hygroscopic growth used in different applications, among which the remote sensing is very important.In this paper, a newly developed technique (direct current conductance method) was applied in an aerosol chamber to Milan PM2.5 samples, to identify aerosol DRH and CRH both during winter and summer. These results were compared with those independently obtained by gravimetric measurements conducted in the chamber using a microbalance. Microbalance data allowed also the determination of the mass hygroscopic growth factor on the collected PM2.5 samples.Results evidenced first a good agreement between the two methods (RMSE=2.7% and 2.3% for DRH and CRH, respectively). Collected data evidenced the hysteresis behavior of ambient particles and variability in both DRH and CRH between the two seasons. Summer samples showed higher DRH and CRH (on average 71.4±1.0% RH and 62.6±1.2% RH, respectively) than the winter ones (on average 55.2±0.7% RH and 46.9±0.6% RH). This behavior was related to the higher content of sulfates during the summer season. Conversely, the mass hygroscopic growth factor at 90% RH was higher for winter samples (2.76±0.06) with respect to the summer ones (1.91±0.11).Since hysteresis behavior affects optical properties of aerosols, when RH conditions are within the loop, the hygroscopic growth factor could be assigned in a wrong way. Thus, the growth factor was calculated within the hysteresis loop for both upper and lower branches: results showed that difference in hygroscopic growth factor could reach up the 24%.

Contact efflorescence as a pathway for crystallization of atmospherically relevant particles

Inadequate knowledge of the phase state of atmospheric particles represents a source of uncertainty in global climate and air quality models. Hygroscopic aqueous inorganic particles are often assumed to remain liquid throughout their atmospheric lifetime or only (re)crystallize at low relative humidity (RH) due to the kinetic limitations of efflorescence (salt crystal nucleation and growth from an aqueous solution). Here we present experimental observations of a previously unexplored heterogeneous nucleation pathway that we have termed "contact efflorescence," which describes efflorescence initiated by an externally located solid particle coming into contact with the surface of a metastable aqueous microdroplet. This study demonstrates that upon a single collision, contact efflorescence is a pathway for crystallization of atmospherically relevant aqueous particles at high ambient RH (≤80%). Soluble inorganic crystalline particles were used as contact nuclei to induce efflorescence of aqueous ammonium sulfate [(NH4)2SO4], sodium chloride (NaCl), and ammonium nitrate (NH4NO3), with efflorescence being observed in several cases close to their deliquescence RH values (80%, 75%, and 62%, respectively). To our knowledge, these observations represent the highest reported efflorescence RH values for microdroplets of these salts. These results are particularly important for considering the phase state of NH4NO3, where the contact efflorescence RH (∼20-60%) is in stark contrast to the observation that NH4NO3 microdroplets do not homogeneously effloresce, even when exposed to extremely arid conditions (<1% RH). Considering the occurrence of particle collisions in the atmosphere (i.e., coagulation), these observations of contact efflorescence challenge many assumptions made about the phase state of inorganic aerosol.

Hygroscopic behavior of NaCl–MgCl&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; mixture particles as nascent sea-spray aerosol surrogates and observation of efflorescence during humidification

Abstract. As Na+, Mg2+, and Cl− are major ionic constituents of seawater, NaCl–MgCl2 mixture particles might represent sea-spray aerosols (SSAs) better than pure NaCl. However, there have been very few hygroscopic studies of pure MgCl2 and NaCl–MgCl2 mixture aerosol particles despite the MgCl2 moiety playing a major role in the hygroscopic behavior of nascent SSAs. Laboratory-generated pure MgCl2 and NaCl–MgCl2 mixture aerosol particles with 12 mixing ratios (0.01 ≤ mole fraction of NaCl (XNaCl) ≤ 0.9) were examined systematically by optical microscopy (OM), in situ Raman micro-spectrometry (RMS), and scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDX) elemental X-ray mapping to observe their hygroscopic behavior, derive the experimental phase diagrams, and obtain the chemical micro-structures. Dry-deposited MgCl2 ⋅ 6H2O particles exhibited a deliquescence relative humidity (DRH) of ~ 33.0 % and an efflorescence RH (ERH) of 10.8–9.1 %, whereas the nebulized pure MgCl2 and MgCl2-dominant particles of XNaCl = 0.026 (eutonic) and 0.01 showed single-stage transitions at DRH of ~ 15.9 % and ERH of 10.1–3.2 %. The characteristic OH-stretching Raman signatures indicated the crystallization of MgCl2 ⋅ 4H2O at low relative humidities (RHs), suggesting that the kinetic barrier to MgCl2 ⋅ 6H2O crystallization is not overcome in the timescale of the dehydration measurements. The NaCl–MgCl2 mixture particles of 0.05 ≤ XNaCl ≤ 0.9 generally showed two-stage deliquescence: first at the mutual DRH (MDRH) of ~ 15.9 %; and second with the complete dissolution of NaCl at the second DRHs depending on the mixing ratios, resulting in a phase diagram composed of three distinct phases. During dehydration, most particles of 0.05 ≤ XNaCl ≤ 0.9 exhibited two-stage efflorescence: first, by the homogeneous nucleation of NaCl; and second, at mutual ERH (MERH) of ~ 10.4–2.9 %, by the crystallization of the MgCl2 ⋅ 4H2O moiety, also resulting in three distinct phases. Interestingly, particles of XNaCl = 0.1 and 0.2 frequently showed three different types of mutual deliquescence behaviors. The first type exhibited an MDRH at ~ 15.9 %. The second exhibited the first MDRH at ~ 15.9 %, efflorescence to MgCl2 ⋅ 6H2O (confirmed by in situ RMS) at RH of ~ 16.1–25.0 %, and a second MDRH at ~ 33.0 %. The third showed an MDRH at ~ 33.0 %. Some particles of XNaCl = 0.1 and 0.2 also exhibited higher MERHs = 15.2–11.9 % and 23.7–15.3 %, respectively, forming MgCl2 ⋅ 6H2O. These observations suggest that the presence of sufficient condensed water and optimally sized crystalline NaCl (XNaCl = 0.1 and 0.2) acting as heterogeneous nucleation seeds helps overcome the kinetic barrier, leading to the structural growth and crystallization of MgCl2 ⋅ 6H2O. SEM/EDX elemental X-ray mapping showed that the effloresced NaCl-rich particles contain homogeneously crystallized NaCl in the center, surrounded by MgCl2 ⋅ 4H2O. The observation of an aqueous phase over a wider RH range for NaCl–MgCl2 mixture particles indicates their more probable heterogeneous chemistry compared to pure NaCl particles as a nascent SSA surrogate.

Relative effect of solder flux chemistry on the humidity related failures in electronics

Purpose – This paper aims to investigate the effect of no-clean flux chemistry with various weak organic acids (WOAs) as activators on the corrosion reliability of electronics with emphasis on the hygroscopic nature of the residue. Design/methodology/approach – The hygroscopicity of flux residue was studied by quartz crystal microbalance, while corrosive effects were studied by leakage current and impedance measurements on standard test boards. The measurements were performed as a function of relative humidity (RH) in the range from 60 to ∼99 per cent at 25°C. The corrosiveness of solder flux systems was visualized by the ex situ analysis using a gel with tin ion indicator. Findings – The results showed that the solder flux residues are characterized by different threshold RH, above which a sudden increase in direct current leakage by 2–4 orders of magnitude and a significant reduction in surface resistance in the impedance measurements were observed. Practical implications – The findings are attributed to the deliquescence RH of the WOA(s) in the flux and chemistry of water-layer formation. The results show the importance of WOA type in relation to its solubility and deliquescence RH on the corrosion reliability of printed circuit boards under humid conditions. Originality/value – The classification of solder flux systems according to IPC J-STD-004 standard does not specify the WOAs in the flux; however, ranking of the flux systems based on the hygroscopic property of activators would be useful information when selecting no-clean flux systems for electronics with applications in humid conditions.

(Corrosion Division Morris Cohen Student Award) Impact of Salt Deliquescence on the Humidity-Dependence of Atmospheric Corrosion

In atmospheric environments, corrosion is often approximated as a discontinuous process reliant on the availability of electrolyte to provide ionic conduction between cathodic and anodic sites. A critical question in atmospheric corrosion is when can a surface be considered wet enough for corrosion to occur at a considerable rate? For surfaces contaminated with hygroscopic salts, such as those which comprise atmospheric sea salt particles, the relative humidity (RH) associated with the deliquescence of these salts is often assumed to serve as the wet/dry threshold in this regard. Deliquescence is the bulk phase transformation whereby solid salt spontaneously absorbs water to form an aqueous electrolyte at and above a specific RH, the deliquescence RH (DRH). In this work, we examined the relationship between the hygroscopic phase transitions of NaCl, MgCl2 and ASTM artificial seawater (ASW) and the response of mild steel contaminated with these sea salt simulants at the initial stage of corrosion. The hygroscopic behavior of salt microparticles of each composition, similar in size to natural atmospheric aerosol, was characterized by impedance measurements across an interdigitated electrode sensor. The corrosion behavior of mild steel loaded these microparticles was investigated as a function of RH under isohumidity, room temperature conditions. Both the attack morphology and volume loss rates were quantified using optical profilometry. Ex-situ characterization of the dried salts on the corroded steel and sensor were carried out using SEM/EDS and Raman spectroscopy. Trends in corrosion loss versus RH were not directly reflective of the deliquescence phase transitions observed or predicted for the salts examined. Considerable corrosion was observed below the DRH of the salts and attributed to (1) the presence of non-equilibrium electrolyte due to kinetic limitations during drying, (2) alteration of the deliquescence behavior by the corrosion chemistry and (3) adsorbed electrolyte at the solid salt/metal interface. For NaCl, sustained corrosion was observed down to 33% RH for up to 300 days. At 53% RH and above, attack proceeded at rates comparable to that observed above the DRH (76%) due to the development of hygroscopic corrosion chemistry. There was no significant difference in attack depth and volume loss trends between samples that were originally loaded with droplets and those loaded with NaCl crystals prior to isohumidity exposure. The initiation of corrosion under NaCl deposits well below the DRH can be explained in terms of the presence of adsorbed water associated with the salt crystals in contact with the steel. For MgCl2 and ASW, sustained corrosion was detectable down to 11% and 23% RH, respectively, for up to 30 days. This is well below the DRH of MgCl2 (33%), which is often considered the active component of sea salt mixtures at low humidity levels. Significant admittance was measured across ASW and MgCl2 deposits on the electrode sensors at < 2% RH after 24 hours, likely due to trapping of supersaturated MgCl2 fluid under solid salt crusts. Trends in attack morphology and volume loss above 33% RH of ASW-loaded samples were similar to those loaded with NaCl alone. This may be explained by the similar corrosion chemistry that developed on the NaCl and ASW samples. Together, these results show that DRH of an individual salt contaminant for the systems under study did not serve as the delineation between a wet and a dry surface, nor as the boundary between significant and insignificant corrosion attack. The impact of these findings on humidity-dependent atmospheric corrosion models along with translation to understanding atmospheric corrosion of other alloy systems will be discussed.

Determination of interfacial parameters of a soluble particle in a nonideal solution from measured deliquescence and efflorescence humidities

Abstract. In order to study the growth/shrinking of a hygroscopic nanoparticle during hydration/dehydration in an atmosphere of water vapour, we have employed a thermodynamic approach proposed by Shchekin et al. (2008). This approach uses the mechanic and thermodynamic concept of disjoining pressure of thin films and allows, among others, the prediction of the humidity growth factor of both (i) a homogeneous solution droplet with completely dissolved residual core and (ii) a heterogeneous solution droplet with partially dissolved residual core as a function of the ambient relative humidity. For application to a nanometric sodium chloride particle we have extended the original approach by (i) considering the nonideality of the solution through the dependence of molecular volumes of the solvent and solute molecules and the solute and solvent activities on the solution concentration, (ii) deriving an equation for the estimation of the efflorescence properties of a homogeneous solution droplet, and (iii) combining the empirical power law fittings for the size dependence of the deliquescence and efflorescence relative humidity values by Biskos et al. (2006a). It was demonstrated how the solution/solute interface energy and the correlation length of a thin solution film can be determined from a combination of experimentally determinable efflorescence and deliquescence humidities with the present calculus. The solution/solute interface energy was found to be in close agreement with some previous values reported in the literature, while it strongly differs from data of some other sources. The calculated deliquescence humidity shows a low sensitivity to the choice of the numerical value for the film correlation length. The estimated film correlation length of 1 nm for a nanometric sodium chloride particle with dry particle radius of 5 nm was found to be reconcilable with available a priori estimates of the correlation length from the literature when the measurement uncertainty of the deliquescence humidity is considered. Considering the combination of an extensive calculus, a comprehensive set of thermophysical constraints, and independent measurements of the deliquescence and efflorescence humidities as functions of dry particle radius, the obtained values of the solution/solute interface energy and the correlation length are in close agreement with previous estimations. The humidification of sodium chloride particles in the initial hydration stages was found to be very sensitive to the specification of the disjoining pressure. The enhancement of the wettability of the particle surface leads to an earlier onset of hygroscopic growth.

Hygroscopic properties of NaCl and NaNO&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt; mixture particles as reacted inorganic sea-salt aerosol surrogates

Abstract. NaCl in fresh sea-salt aerosol (SSA) particles can partially or fully react with atmospheric NOx/HNO3, so internally mixed NaCl and NaNO3 aerosol particles can co-exist over a wide range of mixing ratios. Laboratory-generated, micrometer-sized NaCl and NaNO3 mixture particles at 10 mixing ratios (mole fractions of NaCl (XNaCl) = 0.1 to 0.9) were examined systematically to observe their hygroscopic behavior, derive experimental phase diagrams for deliquescence and efflorescence, and understand the efflorescence mechanism. During the humidifying process, aerosol particles with the eutonic composition (XNaCl = 0.38) showed only one phase transition at their mutual deliquescence relative humidity (MDRH) of 67.9 (±0.5)% On the other hand, particles with other mixing ratios showed two distinct deliquescence transitions; i.e., the eutonic component dissolved at MDRH, and the remainder in the solid phase dissolved completely at their DRHs depending on the mixing ratios, resulting in a phase diagram composed of four different phases, as predicted thermodynamically. During the dehydration process, NaCl-rich particles (XNaCl &gt; 0.38) showed a two stage efflorescence transition: the first stage was purely driven by the homogeneous nucleation of NaCl and the second stage at the mutual efflorescence RH (MERH) of the eutonic components, with values in the range of 30.0–35.5%. Interestingly, aerosol particles with the eutonic composition (XNaCl = 0.38) also showed two-stage efflorescence, with NaCl crystallizing first followed by heterogeneous nucleation of the remaining NaNO3 on the NaCl seeds. NaNO3-rich particles (XNaCl ≤ 0.3) underwent single-stage efflorescence transitions at ERHs progressively lower than the MERH because of the homogeneous nucleation of NaCl and the almost simultaneous heterogeneous nucleation of NaNO3 on the NaCl seeds. SEM/EDX elemental mapping indicated that the effloresced NaCl–NaNO3 particles at all mixing ratios were composed of a homogeneously crystallized NaCl moiety in the center, surrounded either by the eutonic component (for XNaCl &gt; 0.38) or NaNO3 (for XNaCl ≤ 0.38). During the humidifying or dehydration process, the amount of eutonic composed part drives particle/droplet growth or shrinkage at the MDRH or MERH (second ERH), respectively, and the amount of pure salts (NaCl or NaNO3 in NaCl- or NaNO3-rich particles, respectively) drives the second DRHs or first ERHs, respectively. Therefore, their behavior can be a precursor to the optical properties and direct radiative forcing for these atmospherically relevant mixture particles representing the coarse, reacted inorganic SSAs. In addition, the NaCl–NaNO3 mixture aerosol particles can maintain an aqueous phase over a wider RH range than pure NaCl particles as SSA surrogate, making their heterogeneous chemistry more probable.

Experimental Measurements of Particulate Matter Deliquescence and Crystallization Relative Humidity: Application in Heritage Climatology

Climate and pollution can lead to materials weathering. In this study, an innovative method is employed to evaluate the hazard for heritage stone substrates induced by the synergic effect of particulate matter (PM) and climate. In this respect, two hazard indicators for stone materials were determined: the time of wetness and the number of dissolution and crystallization cycles. The two indicators were computed by coupling experimental measurements of the PM deliquescence and crystallization relative humidity with climatic data. For the first time, these indicators were estimated based on the PM hygroscopic properties, considering its whole hysteresis loop and its consequent hydration level. The proposed method was applied to PM samples collected in the polluted Po Valley (Milan): the experimental measurements of both PM deliquescence and crystallization relative humidity were performed in an environmental-controlled chamber using an electrical conductivity method. The time of wetness and the number of dissolution and crystallization cycles were then calculated by coupling the PM deliquescence and crystallization relative humidity with climatic data of Milan over the last decade (2003–2013). Results point out that, depending on the seasons, different hazards were identified. In winter, high time of wetness (89 ± 11%) and low number of cycles (3 ± 3 cycles/month) were found. Conversely, summer was characterized by low time of wetness (20 ± 13%) and high number of cycles (11 ± 5 cycles/month). Interestingly, spring and fall resulted the most dangerous seasons for outdoor-exposed stones, since they presented both high time of wetness and number of cycles. Since the two indicators are calculated considering PM properties and climatic data, their values are site-specific, while the method used for their determination is of general application and it can be used for an efficient hazard assessment in a heritage climatology perspective.

The effect of low solubility organic acids on the hygroscopicity of sodium halide aerosols

Abstract. In order to accurately assess the influence of fatty acids on the hygroscopic and other physicochemical properties of sea salt aerosols, hexanoic, octanoic or lauric acid together with sodium halide salts (NaCl, NaBr and NaI) have been chosen to be investigated in this study. The hygroscopic properties of sodium halide sub-micrometre particles covered with organic acids have been examined by Fourier-transform infrared spectroscopy in an aerosol flow cell. Covered particles were generated by flowing atomized sodium halide particles (either dry or aqueous) through a heated oven containing the gaseous acid. The obtained results indicate that gaseous organic acids easily nucleate onto dry and aqueous sodium halide particles. On the other hand, scanning electron microscopy (SEM) images indicate that lauric acid coating on NaCl particles makes them to aggregate in small clusters. The hygroscopic behaviour of covered sodium halide particles in deliquescence mode shows different features with the exchange of the halide ion, whereas the organic surfactant has little effect in NaBr particles, NaCl and NaI covered particles experience appreciable shifts in their deliquescence relative humidities, with different trends observed for each of the acids studied. In efflorescence mode, the overall effect of the organic covering is to retard the loss of water in the particles. It has been observed that the presence of gaseous water in heterogeneously nucleated particles tends to displace the cover of hexanoic acid to energetically stabilize the system.

Determination of aerosol deliquescence and crystallization relative humidity for energy saving in free-cooled data centers

This study examines an innovative application of the aerosol deliquescence and crystallization determination, for corrosion prevention and energy-saving strategies in free-cooled data centers. Aerosol deliquescence and crystallization were investigated by combining standardized aerosol sampling techniques (i.e. EN-14907) with the assessment of the electrical effects of aerosol, while varying relative humidity within a specially designed aerosol exposure chamber. Aerosol samples collected in the Po Valley (Northern Italy) were analysed; a clearly defined hysteresis cycle (deliquescence and crystallization at 60.5 ± 0.8 and 47.9 ± 0.7 % of RH, respectively) was found. Results were applied to a data center designed for the Italian National Oil and Gas Company, making it possible to identify a critical area for direct free cooling at this data center. As a result, aerosol hydration was avoided (thus preventing aerosol from damaging electrical components) and a large amount of energy saved (using free cooling instead of air-conditioning); the potential energy saving achieved in this way was 79 % (compared to the energy consumption of a traditional air-conditioning system): 215 GWh of energy was saved, and 78 fewer kt of equivalent CO2 was emitted per year. Moreover, in order to evaluate whether a real-time estimation of the aerosol hydration state within a data center could be performed, measured deliquescence and crystallization were compared through simulations performed using three different models: two thermodynamic models for deliquescence and a parametric model for crystallization. The results obtained tend to converge in terms of deliquescence, whereas in the case of crystallization, they failed to effectively simulate experimental aerosol behaviour.