A Two-Phase Box Model to Study Mercury Atmospheric Mechanisms

2005 ◽  
Vol 2 (3) ◽  
pp. 205 ◽  
Author(s):  
Li Pan ◽  
Gregory R. Carmichael

Environmental Context. Elemental mercury (Hg0) is converted to divalent mercury (Hg2+) in the atmosphere, largely in water droplets. The wet deposition of Hg2+ is a major concern to human health. Because it is bio-accumulated through the food chain, consumption of contaminated fish can be particularly dangerous. Currently the budgets of mercury in the atmosphere are poorly understood, due in part to uncertainties in the chemical pathways controlling the speciated forms of mercury. Improved mercury chemistry models are needed to better predict Hg2+ levels in water droplets and to estimate wet deposition of Hg2+ in order to help assess the potential health risks of mercury. Abstract. A box model designed to investigate mercury chemical mechanisms in the atmosphere is presented. Aqueous-phase mercury oxidation–reduction, sulfite, and oxygen reactions, along with gas-phase mercury reactions are included in the model. The model is used to evaluate the key reaction steps under several atmospheric conditions. The sensitivity of the results to parameters, initial conditions, and assumptions regarding chemical mechanisms are investigated. Model simulations were performed in closed (liquid only) and two-phase (liquid/gas) systems. In the liquid phase, elemental mercury is oxidized to divalent mercury by ozone at night and by hydroxide radical and ozone during the day. Ozone is shown to play a significant role in mercury mechanisms by oxidizing elemental mercury directly and producing hydroxyl and hydroperoxyl radicals. The effects of sulfite on mercury aqueous chemistry were found to be limited due to its rapid conversion to sulfate. The results of two-phase simulations show that Hg2+ concentrations exhibit a diurnal cycle, increasing before the sunrise and decreasing before the sunset due to the aqueous-phase hydrogen–oxygen photochemistry that produces hydroxyl and hydroperoxyl radicals. Gas-phase mercury oxidation reactions significantly enhance the levels of Hg2+ in the aqueous phase, and reactions with ozone and hydroxyl radicals play the leading role. The effect of reactive chlorine on mercury chemistry can be important.

2008 ◽  
Vol 8 (23) ◽  
pp. 7165-7180 ◽  
Author(s):  
Z.-Q. Xie ◽  
R. Sander ◽  
U. Pöschl ◽  
F. Slemr

Abstract. Atmospheric mercury depletion events (AMDEs) during polar springtime are closely correlated with bromine-catalyzed tropospheric ozone depletion events (ODEs). To study gas- and aqueous-phase reaction kinetics and speciation of mercury during AMDEs, we have included mercury chemistry into the box model MECCA (Module Efficiently Calculating the Chemistry of the Atmosphere), which enables dynamic simulation of bromine activation and ODEs. We found that the reaction of Hg with Br atoms dominates the loss of gaseous elemental mercury (GEM). To explain the experimentally observed synchronous depletion of GEM and O3, the reaction rate of Hg+BrO has to be much lower than that of Hg+Br. The synchronicity is best reproduced with rate coefficients at the lower limit of the literature values for both reactions, i.e. kHg+Br≈3×10−13 and kHg+BrO≤1×10−15 cm3 molecule−1 s−1, respectively. Throughout the simulated AMDEs, BrHgOBr was the most abundant reactive mercury species, both in the gas phase and in the aqueous phase. The aqueous-phase concentrations of BrHgOBr, HgBr2, and HgCl2 were several orders of magnitude larger than that of Hg(SO3)22−. Considering chlorine chemistry outside depletion events (i.e. without bromine activation), the concentration of total divalent mercury in sea-salt aerosol particles (mostly HgCl42−) was much higher than in dilute aqueous droplets (mostly Hg(SO3)22−), and did not exhibit a diurnal cycle (no correlation with HO2 radicals).


2013 ◽  
Vol 13 (10) ◽  
pp. 5117-5135 ◽  
Author(s):  
B. Ervens ◽  
Y. Wang ◽  
J. Eagar ◽  
W. R. Leaitch ◽  
A. M. Macdonald ◽  
...  

Abstract. Cloud and fog droplets efficiently scavenge and process water-soluble compounds and, thus, modify the chemical composition of the gas and particle phases. The concentrations of dissolved organic carbon (DOC) in the aqueous phase reach concentrations on the order of ~ 10 mgC L−1 which is typically on the same order of magnitude as the sum of inorganic anions. Aldehydes and carboxylic acids typically comprise a large fraction of DOC because of their high solubility. The dissolution of species in the aqueous phase can lead to (i) the removal of species from the gas phase preventing their processing by gas phase reactions (e.g., photolysis of aldehydes) and (ii) the formation of unique products that do not have any efficient gas phase sources (e.g., dicarboxylic acids). We present measurements of DOC and select aldehydes in fog water at high elevation and intercepted clouds at a biogenically-impacted location (Whistler, Canada) and in fog water in a more polluted area (Davis, CA). Concentrations of formaldehyde, glyoxal and methylglyoxal were in the micromolar range and comprised ≤ 2% each individually of the DOC. Comparison of the DOC and aldehyde concentrations to those at other locations shows good agreement and reveals highest levels for both in anthropogenically impacted regions. Based on this overview, we conclude that the fraction of organic carbon (dissolved and insoluble inclusions) in the aqueous phase of clouds or fogs, respectively, comprises 2–~ 40% of total organic carbon. Higher values are observed to be associated with aged air masses where organics are expected to be more highly oxidised and, thus, more soluble. Accordingly, the aqueous/gas partitioning ratio expressed here as an effective Henry's law constant for DOC (KH*DOC) increases by an order of magnitude from 7 × 103 M atm−1 to 7 × 104 M atm−1 during the ageing of air masses. The measurements are accompanied by photochemical box model simulations. These simulations are used to contrast two scenarios, i.e., an anthropogenically vs. a more biogenically impacted one as being representative for Davis and Whistler, respectively. Since the simplicity of the box model prevents a fully quantitative prediction of the observed aldehyde concentrations, we rather use the model results to compare trends in aldehyde partitioning and ratios. They suggest that the scavenging of aldehydes by the aqueous phase can reduce HO2 gas phase levels significantly by two orders of magnitude due to a weaker net source of HO2 production from aldehyde photolysis in the gas phase. Despite the high solubility of dicarbonyl compounds (glyoxal, methylglyoxal), their impact on the HO2 budget by scavenging is < 10% of that of formaldehyde. The overview of DOC and aldehyde measurements presented here reveals that clouds and fogs can be efficient sinks for organics, with increasing importance in aged air masses. Even though aldehydes, specifically formaldehyde, only comprise ~ 1% of DOC, their scavenging and processing in the aqueous phase might translate into significant effects in the oxidation capacity of the atmosphere.


2021 ◽  
Author(s):  
Simon Rosanka ◽  
Rolf Sander ◽  
Bruno Franco ◽  
Catherine Wespes ◽  
Andreas Wahner ◽  
...  

&lt;p&gt;Large parts of the troposphere are affected by clouds, whose aqueous-phase chemistry differs significantly from gas-phase chemistry. Box-model studies have demonstrated that clouds influence the tropospheric oxidation capacity. However, most global atmospheric models do not represent this chemistry reasonably well and are largely limited to sulfur oxidation. Therefore, we have developed the J&amp;#252;lich Aqueous-phase Mechanism of Organic Chemistry (JAMOC), making a detailed in-cloud oxidation model of oxygenated volatile organic compounds (OVOCs) readily available for box as well as for regional and global simulations that are affordable with modern supercomputers. JAMOC includes the phase transfer of species containing up to ten carbon atoms, and the aqueous-phase reactions of a selection of species containing up to four carbon atoms, e.g., ethanol, acetaldehyde, glyoxal. The impact of in-cloud chemistry on tropospheric composition is assessed on a regional and global scale by performing a combination of box-model studies using the Chemistry As A Boxmodel Application (CAABA) and the global atmospheric model ECHAM/MESSy (EMAC). These models are capable to represent the described processes explicitly and integrate the corresponding ODE system with a Rosenbrock solver.&amp;#160;&lt;/p&gt;&lt;p&gt;Overall, the explicit in-cloud oxidation leads to a reduction of predicted OVOCs levels. By comparing EMAC's prediction of methanol abundance to spaceborne retrievals from the Infrared Atmospheric Sounding Interferometer (IASI), a reduction in EMAC's overestimation is observed in the tropics. Further, the in-cloud OVOC oxidation shifts the hydroperoxyl radicals (HO&lt;sub&gt;2&lt;/sub&gt;) production from the gas- to the aqueous-phase. As a result, the in-cloud destruction (scavenging) of ozone (O&lt;sub&gt;3&lt;/sub&gt;) by the superoxide anion (O&lt;sub&gt;2&lt;/sub&gt;&lt;sup&gt;-&lt;/sup&gt;) is enhanced and accompanied by a reduction in both sources and sinks of tropospheric O&lt;sub&gt;3&lt;/sub&gt; in the gas phase. By considering only the in-cloud sulfur oxidation by O&lt;sub&gt;3&lt;/sub&gt;, about 13 Tg a&lt;sup&gt;-1&lt;/sup&gt; of O&lt;sub&gt;3&lt;/sub&gt; are scavenged, which increases to 336 Tg a&lt;sup&gt;-1&lt;/sup&gt; when JAMOC is used. With the full oxidation scheme, the highest O&lt;sub&gt;3&lt;/sub&gt; reduction of 12 % is predicted in the upper troposphere/lower stratosphere (UTLS). Based on the IASI O&lt;sub&gt;3&lt;/sub&gt; retrievals, it is demonstrated that these changes in the free troposphere significantly reduce the modelled tropospheric O&lt;sub&gt;3&lt;/sub&gt; columns, which are known to be generally overestimated by global atmospheric models. Finally, the relevance of aqueous-phase oxidation of organics for ozone in hazy polluted regions will be presented. &amp;#160;&lt;/p&gt;


2001 ◽  
Vol 4 (04) ◽  
pp. 289-296
Author(s):  
Holger F. Thern ◽  
Songhua Chen

Summary Accurate estimates of porosity, fluid saturations, and in-situ gas properties are critical for the evaluation of a gas reservoir. By combining data from a dual wait-time (DTW) nuclear magnetic resonance (NMR) log and a density log, these properties can be determined more reliably than by either of the data alone. The density and NMR dual wait-time (DDTW) technique, introduced in this paper, is applicable to reservoirs where the pore-filling fluid consists of a liquid phase and a gas phase. The low proton density of the gas phase causes a reduction in the NMR signal strength resulting in underestimation of the apparent porosity. The polarization for different wait-times depends on the spin-lattice relaxation time of each fluid and may cause additional NMR porosity underestimation. The density log, on the other hand, delivers a porosity that is overestimated because of the presence of a gas phase. These data, together with known correlations for gas properties, yield a robust approach for the gas-zone porosity, f, and the flushed zone gas saturation, Sg, xo. DDTW also derives gas properties including the in-situ gas density, ?g, as well as the two NMR-related properties, hydrogen index, IH, g, and spin-lattice relaxation time, T1g. Two field examples illustrate the method, and an error propagation study shows the reliability of the technique. Introduction NMR well logging yields information about fluid and rock properties. Depending on the goal of the investigation, various NMR measurement procedures are employed. Differences in the acquisition pulse sequence - including the wait-time (tw) between the echo-train measurements - characterize these procedures. Common evaluation techniques estimate different petrophysical properties, such as incremental and total porosities or movable (fm, NMR) and irreducible (fir, NMR) fluid fractions. More sophisticated methods separate the response of multiple fluids for hydrocarbon typing and saturation estimation. DTW NMR Log. Water as the wetting phase is dominated by surface relaxation and usually has a shorter T1 than hydrocarbons. DTW NMR uses the T1 contrast between aqueous fluid and hydrocarbon phases to achieve partial or full polarization for different fluid phases. The DTW log acquires two echo trains with a long (tw, L) and a short (tw, S) wait-time in a single pass; tw, L is chosen to fully polarize both water and hydrocarbon, and tw, S is sufficiently long to fully polarize the water fraction, while the hydrocarbon fraction is only partially polarized, causing porosity underestimation. An interpretation technique for DTW NMR data - used mainly qualitatively - is the differential spectrum method (DSM).1 A successful quantitative evaluation technique is the time domain analysis (TDA).2 Both techniques require the calculation of either differential echo signals or differential T2 spectra, where the spectra are derived from echo-train data by inversion. The differential signals are significantly weaker than the original signal, and the noise level increases because the incoherent noise of the echo trains is added. Differential data, therefore, are unfavorable in terms of their signal-to-noise ratio (SNR). SNR often limits the applicability of evaluation techniques that are based solely on NMR data. Particularly when coupled with low hydrocarbon saturation and the low proton density of a gas phase, poor SNR is the limiting factor in estimating accurate reservoir properties. Density Log. The density log provides a bulk density, ?b, of the investigated formation. Additional information about the density of the rock matrix and formation fluids determines the density porosity fr. An established method to evaluate gas-bearing formations combines the apparent porosities provided by the density and the neutron logging tools. For many data sets, however, this method yields only semiquantitative results because of the strong influence of rock mineralogy on the neutron measurement. Theory The porosity of clean formations bearing only liquid-phase components can be accurately quantified by either the NMR or the density logging tool. However, the tool's responses are significantly altered by the presence of a gas phase, causing the estimated porosities to deviate from the formation porosity. Three main effects cause the deviation.Low IH, g decreases the NMR porosity.Partial polarization Pg&lt;1 decreases the NMR-derived porosity, if the wait-time between the NMR measurements is insufficiently long.Low ?g increases the density porosity. The characterization of a hydrocarbon gas by three key properties, ?g, IH, g, and T1g, effectively quantifies these effects. DTW NMR Log. In a two-phase system with one gas and one liquid phase, the total NMR porosity ft, NMR is expressed byEquation 1 where the first term on the right side describes the contribution of the gas phase and the second term describes the contribution of the liquid phase. The polarization P (with P?[0,1]) quantifies the reduction of the NMR signal caused by underpolarization. The termsEquation 2Equation 3 describe the polarization of the liquid and gas phases, respectively. Some approximations can be made for common reservoir conditions.IH, l is close to 1 for an aqueous-phase liquid and most oleic-phase liquids. In the presence of a light liquid hydrocarbon, its value can be slightly smaller (IH, l =0.8-1).If tw 3T1, the polarization is nearly unity. Typical tw values range from 1 to several seconds, whereas typical T1 values for formation water range from a few milliseconds to a few seconds. However, in a porous medium saturated with two fluid phases, the wetting phase (i.e., water) saturates smaller pores, and the maximum T1 of the aqueous-phase liquid usually reduces to values less than several hundreds of milliseconds.3 Thus, Pl is unity for aqueous-phase liquids in a two-phase system, when data are acquired with typical wait-time parameters in an MRIL®* DTW acquisition (i.e., tw, S,˜1–2 seconds and tw, L,˜6–10 seconds).


2008 ◽  
Vol 8 (4) ◽  
pp. 13197-13232 ◽  
Author(s):  
Z.-Q. Xie ◽  
R. Sander ◽  
U. Pöschl ◽  
F. Slemr

Abstract. Atmospheric mercury depletion events (AMDEs) during polar springtime are closely correlated with bromine-catalyzed tropospheric ozone depletion events (ODEs). To study gas- and aqueous-phase reaction kinetics and speciation of mercury during AMDEs, we have included mercury chemistry into the box model MECCA (Module Efficiently Calculating the Chemistry of the Atmosphere), which enables dynamic simulation of bromine activation and ODEs. We found that the reaction of Hg with Br atoms dominates the loss of gaseous elemental mercury (GEM). To explain the experimentally observed synchronous destruction of Hg and O3, the reaction rate of Hg+BrO has to be much lower than that of Hg+Br. The synchronicity is best reproduced with rate coefficients at the lower limit of the literature values for both reactions, i.e. kHg+Br≈3×10-13 and kHg+BrO≤1×10-15cm3 mol-1 s-1, respectively. Throughout the simulated AMDEs, BrHgOBr was the most abundant reactive mercury species, both in the gas phase and in the aqueous phase. The aqueous phase concentrations of BrHgOBr, HgBr2, and HgCl2 were several orders of magnitude larger than that of Hg(SO3)2-2. Considering chlorine chemistry outside depletion events (i.e. without bromine activation), the concentration of total divalent mercury in sea-salt aerosol particles (mostly HgCl2) was much higher than in dilute aqueous droplets (mostly Hg(SO3)2-2), and did not exhibit a diurnal cycle (no correlation with HO2 radicals).


2021 ◽  
Author(s):  
Erik Hans Hoffmann ◽  
Tao Li ◽  
Andreas Tilgner ◽  
Yan Wang ◽  
Hartmut Herrmann

&lt;p&gt;Mercury is a neurotoxic element emitted predominantly in its less-reactive form as gaseous elemental mercury (GEM) into the atmosphere by various natural and anthropogenic processes. Once emitted it undergoes chemical processing in the atmospheric gas and aqueous phase. There, GEM is oxidised into gaseous oxidised mercury (GOM), which partitions into aerosol particles residing there as particulate bounded mercury (PBM) due to its much higher solubility. The faster deposition of GOM and PBM compared to GEM is of special environmental importance, because they can be converted into more toxic organic mercury in aquatic environments and then take serious place in the food web. Thus, it is crucial for models to understand the transformation of GEM into GOM and PBM and vice versa. To date, numerous gas-phase chemistry simulations were performed, but reveal missing oxidation and reduction processes. However, only few models exist that investigate the multiphase mercury chemistry in a detailed manner.&lt;/p&gt;&lt;p&gt;Therefore, a comprehensive multiphase mercury chemistry mechanism, the CAPRAM HG module 1.0 (CAPRAM-HG1.0), has been developed. The CAPRAM-HG1.0 includes 74 gas-phase reactions, 22 phase transfers and 77 aqueous-phase reactions. It was coupled to the multiphase chemistry mechanism MCMv3.2/CAPRAM4.0 and the extended CAPRAM halogen module 3.0 (CAPRAM-HM3.0) for investigations of multiphase Hg redox under Chinese polluted conditions. Simulations were performed for summer conditions in 2014 using the air parcel model SPACCIM to investigate the performance of the model to simulate typical concentrations and patterns of GEM, GOM and PBM.&lt;/p&gt;&lt;p&gt;Under non-cloud conditions, model results reveal good coincides with concentrations and patterns for GEM, GOM and PBM measured in China. However, the simulations also show that there are still high uncertainties in atmospheric mercury chemistry. Especially, the complexation with HULIS within aerosol particles needs evaluation as the simulations indicate this process as key process driving concentrations and patterns of both GOM and PBM. Further, the present study demonstrates the need of a better understanding of continental concentrations of reactive halogen species and particle bounded halides as well as their link to the multiphase chemistry and atmospheric cycling of mercury.&lt;/p&gt;


2014 ◽  
Vol 7 (5) ◽  
pp. 6949-6996
Author(s):  
H. S. Chen ◽  
Z. F. Wang ◽  
J. Li ◽  
X. Tang ◽  
B. Z. Ge ◽  
...  

Abstract. Atmospheric mercury (Hg) is a toxic pollutant and can be transported over the whole globe due to its long lifetime in the atmosphere. For the purpose of assessing Hg hemispheric transport and better characterizing regional Hg pollution, a global nested atmospheric Hg transport model (GNAQPMS-Hg) has been developed. In GNAQPMS-Hg, the gas and aqueous phase Hg chemistry representing the transformation among three forms of Hg: elemental mercury (Hg(0)), divalent mercury (Hg(II)), and primary particulate mercury (Hg(P)) are calculated. A detailed description of the model, including mercury emissions, gas and aqueous phase chemistry, and dry and wet deposition is given in this study. Worldwide observations including extensive data in China have been collected for model evaluation. Comparison results show that the model reasonably simulates the global mercury budget and the spatial–temporal variation of surface mercury concentrations and deposition. Overall, model predictions of annual total gaseous mercury (TGM) and wet deposition agree with observations within a factor of two, and within a factor of five for oxidized mercury and dry deposition. The model performs significantly better in North America and Europe than in East Asia. This can probably be attributed to the large uncertainties in emission inventories, coarse model resolution and to the inconsistency between the simulation and observation periods in East Asia. Compared to the global simulation, the nested simulation shows improved skill at capturing the high spatial variability of Hg concentrations and deposition over East Asia. In particular, the root mean square error (RMSE) of simulated Hg wet deposition over East Asia is reduced by 24% in the nested simulation. Model sensitivity studies indicate that Chinese primary anthropogenic emissions account for 30 and 62% of surface mercury concentrations and deposition over China, respectively. Along the rim of the western Pacific, the contributions from Chinese sources are 11 and 15.2% over the Korean Peninsula, 10.4 and 8.2% over Southeast Asia, and 5.7 and 5.9% over Japan. But for North America, Europe and West Asia, the contributions from China are all below 5%.


2016 ◽  
Vol 149 ◽  
pp. 23-28 ◽  
Author(s):  
Wen-Jun Huang ◽  
Hao-Miao Xu ◽  
Zan Qu ◽  
Song-Jian Zhao ◽  
Wan-Miao Chen ◽  
...  

2012 ◽  
Vol 9 (1) ◽  
pp. 131-135
Author(s):  
M.A. Pakhomov

The paper presents the results of modeling the dynamics of flow, friction and heat transfer in a descending gas-liquid flow in the pipe. The mathematical model is based on the use of the Eulerian description for both phases. The effect of a change in the degree of dispersion of the gas phase at the input, flow rate, initial liquid temperature and its friction and heat transfer rate in a two-phase flow. Addition of the gas phase causes an increase in heat transfer and friction on the wall, and these effects become more noticeable with increasing gas content and bubble diameter.


Author(s):  
A. Navarro-Sempere ◽  
M. García ◽  
A. S. Rodrigues ◽  
P. V. Garcia ◽  
R. Camarinho ◽  
...  

AbstractMercury accumulation has been proposed as a toxic factor that causes neurodegenerative diseases. However, the hazardous health effects of gaseous elemental mercury exposure on the spinal cord in volcanic areas have not been reported previously in the literature. To evaluate the presence of volcanogenic inorganic mercury in the spinal cord, a study was carried out in São Miguel island (Azores, Portugal) by comparing the spinal cord of mice exposed chronically to an active volcanic environment (Furnas village) with individuals not exposed (Rabo de Peixe village), through the autometallographic silver enhancement histochemical method. Moreover, a morphometric and quantification analysis of the axons was carried out. Results exhibited mercury deposits at the lumbar level of the spinal cord in the specimens captured at the site with volcanic activity (Furnas village). A decrease in axon calibre and axonal atrophy was also observed in these specimens. Given that these are relevant hallmarks in the neurodegenerative pathologies, our results highlight the importance of the surveillance of the health of populations chronically exposed to active volcanic environments.


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