Oxidation of Elemental Mercury in the Atmosphere; Constraints Imposed by Global Scale Modelling

We use the global mercury model published by Bergan et al. (1999) to evaluate the potential role of ozone and the hydroxyl radical as gas phase oxidants for the oxidation of elemental mercury in the atmosphere. The magnitude of natural and man-made mercury emissions are taken from recent literature estimates. We consider only two mercury reservoirs, elemental mercury, Hg⁰, and the more soluble divalent form, HgII. Wet and dry deposition of HgII is explicitly treated.Applying monthly mean fields of ozone for the oxidation of gas phase Hg⁰ and using the reaction rate by Hall (1995) yields a global transformation of Hg⁰ to HgII which is too slow to keep the simulated concentration of Hg⁰ near observed values. This shows that there must be additional important removal processes for Hg⁰ or that the reaction rate proposed by Hall (1995) is too slow. A simulation in which the oxidation rate was artificially increased, so that the global turn-over time of Hg⁰ is one year and the simulated average concentration of Hg⁰ realistic, produces latitudinal and seasonal variations in Hg⁰ that do not support the hypothesis that gas phase reaction with O₃ is the major oxidation process for Hg⁰.Recent studies indicate that OH may be an important gas phase oxidant for Hg⁰ (Sommar et al., 2001). Using OH as the sole oxidantand applying the oxidation rate by Sommar et al., we calculate aconcentration of Hg⁰ well below (about a factor of three) the observations. By prescribing a slower rate, corresponding to a turn-over time of Hg⁰ of one year, we calculate concentrations of both Hg⁰ in surface air and HgII in precipitation which correspond reasonably well, both in magnitude and temporal variation, with seasonal observations in Europe and North America. This result supports the suggestion that the oxidation by OH is an important pathway for the removal of Hg⁰. In view of the uncertainties associated with our calculations, this conclusion should still be regarded as tentative.     

Experimental investigation of the scavenging of gaseous mercury by sea salt aerosol

Sea salt aerosol may be an important sink for reactive gaseous mercury (RGM) in the marine boundary layer, reducing ambient RGM concentrations and transferring the mercury (Hg) to the oceans and coastal ecosystems. The goal of this study was to determine the affinity of gaseous mercury for sea salt aerosol (SSA) by conducting adsorption experiments with sea salt-coated sampling denuders. In the first set of experiments, ambient outdoor air was passed through denuders coated with either KCl, as in the widely accepted method to sample RGM, or with NaCl, a primary component of sea salt aerosols. On the one sampling day in which RGM was above the MDL, the NaCl coated denuders removed Hg from the ambient air, equivalent to 87% of the RGM in the air (as determined by KCl denuders). For the second set of experiments HgCl₂ generated in the laboratory was passed through denuders coated with KCl and either NaCl or sea salt. The NaCl denuders collected an average of 99 ± 16% of the mercury that the KCl denuders collected. Newly coated sea salt denuders collected 88 ± 17% of the amount of mercury that the KCl denuders collected, but interestingly the sea salt denuders capacity decreased with repeated use. These experiments demonstrate that HgCl₂, a major component of RGM has a strong affinity for NaCl and sea salt and is therefore likely to be scavenged by SSA. This study adds to the growing evidence that RGM is scavenged by sea salt aerosols and therefore more quickly deposited to the ocean and coastal environment.     

Chlorine-hydrocarbon photochemistry in the marine troposphere and lower stratosphere

A one-dimensional photochemical model was used to explore the role of chlorine atoms in oxidizing methane and other nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere. Where appropriate, the model predictions were compared with available measurements. Cl atoms are predicted to be present in the marine troposphere at concentrations of approximately 10³ cm^-3, mostly as a consequence of the reaction of OH with HCl released from sea spray. Despite this low abundance, our results indicate that 20 to 40% of NMHC oxidation in the troposphere (0–10 km) and 40 to 90% of NMHC oxidation in the lower stratosphere (10–20 km) is caused by Cl atoms. At 15 km, NMHC-Cl reactions account for nearly 80% of the PAN produced.The model was also used to test the longstanding hypothesis that NOCl is an intermediate to HCl formation from sea salt aerosols. It was found that the NOCl concentration required (10 ppt) would be incompatible with field observations of reactive nitrogen and ozone abundance. Chlorine nitrate (ClONO₂) and methyl nitrate (CH₃ONO₂) were shown to be minor components of the total NO _y abundance. Heterogeneous reactions that might enhance photolysis of halocarbons or convert ClONO₂ to HOCl or Cl₂ were determined to be relatively unimportant sources of Cl atoms. Specific and reliable measurements of HCl and other reactive chlorine species are needed to better assess their role in tropospheric chemistry.     

On the Gas Phase Reactions Between Volatile Biogenic Mercury Species and the Nitrate Radical

Tropospheric mercury is dominated by gas phase species. In this paper, the gas phase reactions between the nitrate radical and volatile biogenic mercury species have been investigated. An upper limit for the gas phase rate coefficient for reaction between elemental mercury and NO₃-radicals was determined to 4 × 10^–15 cm³ molecule^–1 s^–1 by using the fast flow-discharge technique. The reaction between dimethyl mercury and NO₃, previously shown to be rapid, has also been studied in the laboratory with respect to product distribution using FT-IR. The result from the product study is consistent with a transformation of dimethyl mercury into inorganic, divalent mercury. All carbon delivered as dimethyl mercury was transformed into formaldehyde, methanol and methyl peroxynitrate. Hg was observed as a minor (2%) product. By exclusion, HgO is proposed as the mercury-containing product. Thus, the reaction between dimethyl mercury and the nitrate radical is excluded as a source of monomethyl mercury species in the atmosphere.     

An Examination of the Atmospheric Chemistry of Mercury Using 210Pb and 7Be

Measurements of Hg (total gas-phase, precipitation-phase andparticulate-phase), aerosol mass, particulate ²¹⁰Pb and⁷Be and precipitation ²¹⁰Pb were made at an atmosphericcollection station located in a near remote area of northcentral Wisconsin,U.S.A. (46°10N, 89°50W) during the summers of 1993, 1994and 1995. Total Hg and ²¹⁰Pb were observed to correlate strongly(slope = 0.06 ± 0.03 ng mBq^-1; r ² =0.72) in rainwater. Mercury to ²¹⁰Pb ratios in particulate matter(0.03 ± 0.02 ng mBq^-1; r ² = 0.06) wereconsistent with the ratio in rain. Enrichment of the Hg/mass ratio (approx.5–50×) relative to soil and primary pollutant aerosols indicatedthat gas-to-particle conversion had taken place during transport. Comparisonof these results with models for the incorporation of Hg into precipitationindicates that atmospheric particles deliver more Hg to precipitation than canbe explained by the presence of soot. A lack of correlation between totalgas-phase Hg (TGM) and a ⁷Be/²¹⁰Pb function suggests novertical concentration gradient within the troposphere, and allows an estimateof TGM residence time of 1.5 ± 0.6 yr be made based on surface airsamples.     

Sorption Characteristics of Inorganic, Methyl and Elemental Mercury on Lichens and Mosses: Implication in Biogeochemical Cycling of Mercury

The sorption studies of Hg²⁺, CH₃Hg⁺ and elemental mercury (Hg⁰) were carried out on lichen (Parmelia sulcata) and moss (Funaria hygrometrica) samples under laboratory conditions. Desorption studies with HCl indicate that inorganic mercury (Hg⁺²) and methyl mercury could be completely desorbed with 1 M HCl and 0.5 M HCl, respectively. Samples loaded with elemental mercury, however, needed 4–5 M HCl concentration for complete desorption of the adsorbed elemental mercury. When similar desorption studies were carried out with field samples collected around a thermometer factory with elevated levels of mercury (8 mg/kg), it was found that only about 10–15% of total mercury was desorbed with 1M HCl, while 4–5 M acid was required for complete desorption. We have tried to correlate this information to understand the transformations of mercury species that may occur either in the atmosphere or on the biomonitors. The results indicated that the elemental mercury, the principal form of mercury contamination around the thermometer factory, is converted into a strongly held form by some chemical binding agents on the surface of lichen/moss, or elemental mercury could diffuse into the cells of the lichen/moss, which then needs the stronger acid to release it. Sorption capacity studies suggest that the lichens and mosses can also be used as sorbent material for the decontamination of inorganic and methyl mercury from aqueous solutions.     

Fast Oxidation Reaction of Nitrite by Dissolved Oxygen in the Freezing Process in the Tropospheric Aqueous Phase

Nitrite oxidation in the tropospheric aqueous phase by freezing was evaluated by freezing a field sample. Nitrite oxidation by dissolved oxygen in the freezing process is much faster than by other oxidation processes, such as reactions with ozone, hydrogen peroxide or dissolved oxygen in an aqueous solution at pHs 3 to –6. At pH 4.5 and 25°C, the lifetime of nitrite in the aqueous phase is ca. 1 hr in oxidation by ozone (6×10^-10 mol dm^-3), ca. 10 hr in oxidation by H₂O₂ (2×10^-4 mol dm^-3), and 7.5 hr (Fischer and Warneck, 1996) in photodissociation at midday in summer. Under the same conditions at a temperature below 0°C, the lifetime of nitrite in the freezing process is estimated as ca. 2 sec when the droplets are frozen within a second. The reaction by freezing is affected by the presence of salts, such as NaCl or KCl, or orgnaic compounds, such as methanol or acetone. The results of freezing a field rain or fog sample showed that nitrite oxidation proceeds below pH 6, and the conversion ratio of nitrate from nitrite increases with decreasing pH. The oxidation of nitrite by freezing was also observed in freezing fog particles generated by an ultrasonic humidifier. The ratios of the concentrations of ions in the winter sample to those in the summer sample (or those in the fog sample) were almost the same values. However, the concentration of nitrite in the winter sample was lower than that estimated by the ratios of other ions. From the present study, it seems that the freezing process plays an important role in the nitrite sink process in the tropospheric aqueous phase.     

The sources and composition of mercury in Pacific Ocean rain

Here we report measurements of total Hg (Hg_T), reactive Hg (Hg_R), and methylmercury (MMHg) in precipitation from the equatorial Pacific Ocean, collected during a cruise in January and February 1990, and from a mid-continental location in the rural temperate lacustrine northcentral Wisconsin environs. The concentrations of Hg_T (14.4±6.5 pM), Hg_R (8.9±4.5 pM) and MMHg (<50 fM) found in equatorial Pacific rain were less than the average concentrations found in Wisconsin. In general, the results indicate that although particulate Hg is a small fraction of the total atmospheric Hg burden, it is the major contributor to Hg in precipitation. Furthermore, deposition could be an important source of Hg_R to the equatorial Pacific Ocean. In contrast, deposition is not a significant source of MMHg to either the equatorial Pacific Ocean or the remote seepage lakes of Wisconsin. This implies that methylated mercury is formedin situ in these systems.     

Modelling multiphase chemistry in deliquescent aerosols and clouds using CAPRAM3.0i

Modelling studies were performed with the multiphase mechanism RACM-MIM2ext/CAPRAM 3.0i to investigate the tropospheric multiphase chemistry in deliquesced particles and non-precipitating clouds using the SPACCIM model framework. Simulations using a non-permanent cloud scenario were carried out for two different environmental conditions focusing on the multiphase chemistry of oxidants and other linked chemical subsystems. Model results were analysed by time-resolved reaction flux analyses allowing advanced interpretations. The model shows significant effects of multiphase chemical interactions on the tropospheric budget of gas-phase oxidants and organic compounds. In-cloud gas-phase OH radical concentration reductions of about 90 % and 75 % were modelled for urban and remote conditions, respectively. The reduced in-cloud gas-phase oxidation budget increases the tropospheric residence time of organic trace gases by up to about 30 %. Aqueous-phase oxidations of methylglyoxal and 1,4-butenedial were identified as important OH radical sinks under polluted conditions. The model revealed that the organic C₃ and C₄ chemistry contributes with about 38 %/48 % and 8 %/9 % considerably to the urban and remote cloud / aqueous particle OH sinks. Furthermore, the simulations clearly implicate the potential role of deliquescent particles to operate as a reactive chemical medium due to an efficient TMI/HO_x,y chemical processing including e.g. an effective in-situ formation of OH radicals. Considerable chemical differences between deliquescent particles and cloud droplets, e.g. a circa 2 times more efficient daytime iron processing in the urban deliquescent particles, were identified. The in-cloud oxidation of methylglyoxal and its oxidation products is identified as efficient sink for NO₃ radicals in the aqueous phase.     

Heterogeneous Chemistry of Nitryl Halides in Relation to Tropospheric Halogen Activation

The heterogeneous chemistry of nitryl chloride and nitryl bromide by salt containing solutions was studied as a function of temperature in the range from 275 to 293 K with the wetted-wall flowtube combined with FTIR and mass spectrometry detection. Uptake coefficients and values of the product Hk^1/2 on these saline solutions have been determined. For nitryl halides interacting with NaI and NaBr solutions, the values of the product Hk^1/2 are respectively 4384.7±326.7 and 103.1±18.7 M atm^-1 s^-1/2 for nitryl chloride at 275 K and 544.2±94.7 and 47.7±15.2 M atm^-1 s^-1/2 for nitryl bromide at 278 K. When reacting with NaI or NaBr solutions, these heterogeneous reactions release, as major products, the molecular forms of the halogen i.e., respectively I₂ and Br₂. A simplified reaction scheme explaining the formation of these products is presented and is inserted into a model simulating the chemistry in the marine boundary layer. The modelling effort showed Cl and BrO atoms concentrations up to 5×10⁴ and 1.8×10⁶ molecules cm^-3 respectively, which are comparable to values actually measured in field campaigns.     

Mechanism development and modelling of tropospheric multiphase halogen chemistry: The CAPRAM Halogen Module 2.0 (HM2)

A new detailed multiphase halogen mechanism, the CAPRAM Halogen Module 2.0 (HM2), has been developed and coupled to the multiphase chemistry mechanism RACM-MIM2ext/CAPRAM 3.0n. The overall mechanism comprises 1,705 reactions including 595 reactions of the HM2. Halogen chemistry box model studies have been, for the first time, performed with a non-permanent cloud scenario for pristine open ocean regions in mid-latitudes. Moreover, detailed time-resolved reaction flux analysis has been used to investigate the multiphase halogen reaction cycles in more detail. Clouds significantly change the multiphase halogen chemical system and new reaction cycles are proposed for in-cloud conditions. While most gas phase concentrations are decreased for chlorine and iodine species, they are increased for bromine. Flux analyses determined the relative contributions of the methylene dihalides CH₂IX (X = Cl, Br, I) as the main I atom source with a contribution of about 80 % to the total iodocarbon sources. Furthermore, HOI was confirmed to be important for chlorine activation. It is shown that 25 % of the ozone loss can be attributed to halogens. VOC oxidation by halogens is important as halogens account for about 20 % of the methane oxidation and up to 80 % of the oxidation of other VOCs. In other cases, enhanced VOC and VOC oxidation product concentration levels were found. For example, 15 % of the methyl peroxyl radicals are formed after the reaction of chlorine atoms with methane or methyl hydroperoxide. In the aqueous phase, changes in the oxidation of organics do only occur for highly oxidised organics without a C-H bond. For example, over 80 % of oxalic acid are oxidised by electron transfer with Cl₂ ^? in deliquescent particles during non-cloud periods.     

Uptake of the NO <Subscript>3</Subscript> Radical on Aqueous Surfaces

Using a single drop experiment, the uptake of NO₃ radicals on aqueous solutions of the dye Alizarin Red S and NaCl was measured at 293 K. Uptake coefficients in the range (1.7–3.1) ⋅ 10^{− 3} were measured on Alizarin Red S solutions. The uptake coefficients measured on NaCl solutions were in the range of (1.1–2.0) ⋅ 10⁻³ depending on the salt concentration. Both experiments lead to a consistent result for the mass accommodation coefficient of α_NO3 = (4.2_{− 1.7}^+2.2)⋅ 10⁻³. The product H(D_l k_Cl−^II)^0.5 for the NO₃ radical was determined to be (1.9 ± 0.2) M atm^{− 1} cm s^−0.5 M^−0.5 s^−0.5 by fitting the uptake data for the NaCl solutions to the so-called resistance model. The yield of the chemical NO₃ radical source was characterized using UV-VIS and FT-IR spectroscopy. The amount of gas-phase NO₃ radicals measured at elevated humidities was less than expected. Instead, a rise of the gas-phase HNO₃ concentration was found indicating a conversion of gas-phase NO₃ radicals to gas-phase HNO₃ on the moist reactor walls.     

Experimental study of the heterogeneous reactivity between atomic chlorine and palmitic acid films

The present study focuses on the heterogeneous reaction between gaseous atomic chlorine and solid palmitic acid films, used as a proxy of the fatty acids detected in atmospheric airborne particles. This reaction is investigated in a coated wall flow tube reactor coupled to a molecular beam mass spectrometer. The reactive surfaces were prepared by coating the inner surface of the reactor. The initial Cl˙ and Cl₂ uptake coefficient measured for these heterogeneous reactions is found to be fast: γ_o ^Cl?=?0.07. The rapid formation of hydrogen chloride corresponding with the disappearance of atomic chlorine is highlighted. Furthermore, the formation of new chlorinated species on the solid substrate has been detected by TOF SIMS analysis leading to an ageing process of the surface. A heterogeneous recombination of Cl atoms to Cl₂ molecules was observed for aged surfaces.     

The Mechanism of Reactive NO3 Uptake on Dry NaX (X=Cl, Br)

A simple kinetic mechanism of nitrate radicals uptake on dry sea-salt NaCl, NaBr surfaces is proposed. The mechanism includes adsorption/desorption equilibrium and unimolecular decomposition of the adsorbed complex: NO₃(g) + NaX(s) (NO₃-NaX)(s); (NO₃-NaX)(s) NaNO₃ + X(s) Two techniques were used: the matrix isolation ESR and mass spectrometry. The uptake coefficient () is found to be dependent on exposure time of salt to NO₃ for raw coating. The initial (t0) is higher than the observable steady-state _obs. At room temperature _obs is independent of [NO₃] at low [NO₃] = 3 × 10⁹ - 10¹¹ cm^-3, but it is inversely proportional to [NO₃] at concentrations higher than 10¹² cm^-3. At temperatures above 100 °C, _obs becomes independent of [NO₃] in a wider range of [NO₃]. An increased number of dislocations is supposed to exist in the case of raw coating. Due to a wide spread of the surface sites binding energy with the ionic lattice near dislocations, the part of surface complexes has lower binding energy and "burns" more rapidly. That burning determines the transition from (t0) down to _obs.The kinetic parameters and elementary rate coefficients are obtained. The recommended for low atmospheric NO₃ concentration are in the range of 0.002 ± 0.04 for NaCl and 0.1-0.3 for NaBr depending on a mechanism of the (t) relaxation.     

Degradation of Isoprene in the Presence of Sulphoxy Radical Anions

Autoxidation of S(IV) initiated by manganese sulphate or potassium peroxydisulphate in alkaline aqueous solutions was significantly slowed down by dissolved isoprene, which decayed in the process. The laboratory experiments were carried out in a batch, perfectly mixed reactor, which had no gas space. The concentration–time profiles of oxygen were measured with a Clark-type electrode. The profiles of sulphite species and of isoprene were evaluated from the UV spectra of solutions. The kinetic analysis indicated that isoprene reacted directly with sulphate radical anions produced during the S(IV) autoxidation. A relative second-order rate constant of (2.12 ± 0.37) × 10⁹ M^–1 s^–1 was determined for this reaction at 25 °C, pH (8.0–8.5) and ionic strength of (1.7–4.9) × 10^–3 M (the reference rate constant of the reaction of sulphate radical anions with sulphite ions equalled 3.4 × 10⁸ M^–1 s^–1). A tentative mechanism of isoprene oxidation during S(IV) autoxidation, which included formation of isoprene – SO^– ₄ adduct, was based on the analogy to the gas-phase reactions of isoprene and to the liquid-phase reactions of sulphate radical anions with other compounds. Atmospheric significance of the aqueous-phase reaction of isoprene with sulphate radicals was discussed. Approximate analysis showed the reaction is a potential sink for isoprene in the aqueous phase and in the gas–liquid systems of high liquid water content (LWC > 10^–5 m³ m^–3). The aqueous-phase oxidation of isoprene can produce secondary pollutants, and influence transformation and the long-range transport of SO₂ in the atmosphere.     

Mn(II)-catalysed S(IV) oxidation and its inhibition by acetic acid in acidic aqueous solutions

The kinetics of the S(IV) oxidation by oxygen in the presence of Mn(II) ions and acetic acid has been studied. Experiments were carried out at 25°C, 3.5?≤?pH?≤?5.0, [S(IV)]≈1?×?10^?3 mol/dm³, 1?×?10^?6 mol/dm³?≤?[Mn(II)]?≤?1?×?10^?5 mol/dm³, 1?×?10^?6 mol/dm³?≤?[CH₃COOH]?≤?1?×?10^?4 mol/dm³. Based on the experimental results, rate constants and orders of the reactions were determined. Depending on the reaction conditions, the observed rate constants for the Mn(II)-catalysed S(IV) oxidation ranged between 3.91?×?10^?8 and 8.89?×?10^?7 (mol/dm³) s^?1, and in the presence of acetic acid they ranged between 2.95?×?10^?8 and 7.45?×?10^?7 (mol/dm³) s^?1. The reaction order in S(IV) was zero for both reactions. The effect of Mn(II) ion and acetic acid concentrations as well as an initial pH of the solution on the S(IV) oxidation rate was discussed. It was found that the rate of the S(IV) oxidation depends on the initial pH of the solution but it is independent of the pH change during the reaction. Acetic acid has a weak inhibiting effect on the Mn(II)-catalysed S(IV) oxidation. Under the experimental conditions the S(IV) oxidation rate decreased no more than twice.     

Water interaction with MgCl<Subscript>2</Subscript>×6H<Subscript>2</Subscript>O and NaCl surfaces: measurements of the uptake coefficient

The uptake of water vapor on MgCl₂×6H₂O and NaCl salt dry solid films was studied over the temperature range 240 to 340 K and at 1 Torr pressure of helium using a flow reactor coupled to a modulated molecular beam mass spectrometer. The H₂O to salt uptake data were obtained from the kinetics of H₂O loss on salt coated Pyrex rods. The following Arrhenius expression was obtained for the initial uptake coefficient of H₂O on MgCl₂×6H₂O films: γ ₀ (MgCl₂) = (6.5 ± 1.0) × 10⁻⁶ exp[(470 ± 40)/T] (calculated with specific BET surface area, quoted uncertainties are 1σ statistical). The rate of H₂O adsorption on NaCl was found to be much lower than on MgCl₂×6H₂O, and only an upper limit was determined for the corresponding uptake coefficient: γ (NaCl) ≤ 5.6 × 10⁻⁶ at T = 300 K. The results show that the rate of H₂O adsorption to salt surfaces is drastically dependent on the salt sample composition.     

Variations of atomic mercury concentration in atmospheric surface layer over the Ussuri Bay of the Sea of Japan during the typhoon Bolaven passage in 2012

Presented are the results of measuring the concentration of atomic mercury Hg⁰ on August 28–30, 2012 in the atmospheric surface layer over the Ussuri Bay in the Sea of Japan during the typhoon Bolaven passage. It is revealed that the Hg⁰ concentration during this period varied from 1.7 to 3.3 ng/m³. The maximum values were observed at the coming of mercury-enriched air masses from the Yellow Sea area at the simultaneous decrease in the air pressure and increase in the wind speed.     

Speciation and Photochemistry of Mercury in Rainwater

Mercury speciation was determined in rainwater from 76 storms in southeastern North Carolina between September 1, 2003 and September 30, 2005. Volume-weighted average concentrations of total Hg (THg), total dissolved Hg (TDHg), particulate Hg (Hg_part) and dissolved monomethyl Hg (MMHg) were 45.5 pM, 34.8 pM, 12.0 pM and 1.1 pM respectively. TDHg accounted for 77% of THg in precipitation which is similar to Cu but significantly higher than Cr or Fe. Concentrations of the various Hg species were very similar during summer and winter indicating that there was not a dominant seasonal influence on Hg speciation in rainwater at this location. THg, TDHg, and MMHg concentrations were also not significantly impacted by storm origin suggesting that they are relatively well mixed regionally and that air mass back trajectory is not the dominant factor controlling their concentration at this location. Concentrations of TDHg and Hg_part were inversely correlated in rainwater samples subjected to irradiation with simulated sunlight, suggesting the distribution between dissolved and particulate Hg may be controlled by photochemical transformations. Unlike TDHg and Hg_part, no significant changes in MMHg were observed upon photolysis of rainwater indicating that its distribution is not significantly driven by sunlight-mediated reactions, in contrast to what has been observed in surface waters. Results presented in this study indicate that the speciation of Hg in rainwater is dynamic and is driven by a complex combination of natural and anthropogenic processes as well as interactions with sunlight.     

An experimental technique for studying heterogeneous reactions of polyaromatic hydrocarbons on particle surfaces

An experimental technique for studying atmospheric heterogeneous reactions of polyaromatic hydrocarbons (PAH) on particle surfaces is reported. Particle bound organics were reacted in a 200 liter Teflon continuous stirred tank reactor (CSTR), with vapor phase oxidants. To provide a source of chemically stable particles for the CSTR, soot particles from a residential wood stove were first introduced during under darkness into a 25 m³ outdoor Teflon chamber. Air containing the particles was then added at a constant flow to the CSTR. The rates of heterogeneous reactions were obtained by comparing reacted particle samples with unreacted ones. The derivation of rate expressions for heterogeneous reactions in the CSTR is described. The use of the technique for a study of the nitration of selected soot particle bound PAH species by NO₂ and HNO₃ is demonstrated.