Gas-Phase Formation of Sulfurous Acid (H2SO3) in the Atmosphere.

Sulfurous acid (H2SO3) is known to be thermodynamically instable decomposing into SO2 and H2O. All attempts to detect this elusive acid in solution failed up to now. Reported H2SO3 formation from an experiment carried out in a mass spectrometer as well as results from theoretical calculations, however, indicated a possible kinetic stability in the gas phase. Here, it is shown experimentally that H2SO3 is formed in the OH radical-initiated gas-phase oxidation of methanesulfinic acid (CH3S(O)OH) at 295±0.5 K and 1 bar of air with a molar yield of 53 - 17 + 7 ${{53}_{-17}^{+\ 7}}$ %. Further main products are SO2, SO3 and methanesulfonic acid. CH3S(O)OH represents an important intermediate product of dimethyl sulfide oxidation in the atmosphere. Global modeling predicts an annual H2SO3 production of ∼8 million metric tons from the OH+CH3S(O)OH reaction. The investigated H2SO3 depletion in the presence of water vapor results in k(H2O+H2SO3) <3×10-18 cm3 molecule-1 s-1, which indicates a lifetime of at least one second for atmospheric humidity. This work provides experimental evidence that H2SO3, once formed in the gas phase, is kinetically stable enough to allow its characterization and subsequent reactions.

Daytime Atmospheric Halogen Cycling through Aqueous-Phase Oxygen Atom Chemistry.

Halogen atoms are important atmospheric oxidants that have unidentified daytime sources from photochemical halide oxidation in sea salt aerosols. Here, we show that the photolysis of nitrate in aqueous chloride solutions generates nitryl chloride (ClNO2) in addition to Cl2 and HOCl. Experimental and modeling evidence suggests that O(3P) formed in the minor photolysis channel from nitrate oxidizes chloride to Cl2 and HOCl, which reacts with nitrite to form ClNO2. This chemistry is different than currently accepted mechanisms involving chloride oxidation by OH and could shift our understanding of daytime halogen cycling in the lower atmosphere.

Temperature-Dependent Oxidation of Hydroxylated Aldehydes by •OH, SO4•-, and NO3• Radicals in the Atmospheric Aqueous Phase.

T-dependent aqueous-phase rate constants were determined for the oxidation of the hydroxy aldehydes, glyceraldehyde, glycolaldehyde, and lactaldehyde, by the hydroxyl radicals (•OH), the sulfate radicals (SO4•-), and the nitrate radicals (NO3•). The obtained Arrhenius expressions for the oxidation by the •OH radical are: k(T,GLYCERALDEHYDE+OH•) = (3.3 ± 0.1) × 1010 × exp((-960 ± 80 K)/T)/L mol-1 s-1, k(T,GLYCOLALDEHYDE+OH•) = (4.3 ± 0.1) × 1011 × exp((-1740 ± 50 K)/T)/L mol-1 s-1, k(T,LACTALDEHYDE+OH•) = (1.6 ± 0.1) × 1011 × exp((-1410 ± 180 K)/T)/L mol-1 s-1; for the SO4•- radical: k(T,GLYCERALDEHYDE+SO4•-) = (4.3 ± 0.1) × 109 × exp((-1400 ± 50 K)/T)/L mol-1 s-1, k(T,GLYCOLALDEHYDE+SO4•-) = (10.3 ± 0.3) × 109 × exp((-1730 ± 190 K)/T)/L mol-1 s-1, k(T,LACTALDEHYDE+SO4•-) = (2.2 ± 0.1) × 109 × exp((-1030 ± 230 K)/T)/L mol-1 s-1; and for the NO3• radical: k(T,GLYCERALDEHYDE+NO3•) = (3.4 ± 0.2) × 1011 × exp((-3470 ± 460 K)/T)/L mol-1 s-1, k(T,GLYCOLALDEHYDE+NO3•) = (7.8 ± 0.2) × 1011 × exp((-3820 ± 240 K)/T)/L mol-1 s-1, k(T,LACTALDEHYDE+NO3•) = (4.3 ± 0.2) × 1010 × exp((-2750 ± 340 K)/T)/L mol-1 s-1, respectively. Targeted simulations of multiphase chemistry reveal that the oxidation by OH radicals in cloud droplets is important under remote and wildfire influenced continental conditions due to enhanced partitioning. There, the modeled average aqueous •OH concentration is 2.6 × 10-14 and 1.8 × 10-14 mol L-1, whereas it is 7.9 × 10-14 and 3.5 × 10-14 mol L-1 under wet particle conditions. During cloud periods, the aqueous-phase reactions by •OH contribute to the oxidation of glycolaldehyde, lactaldehyde, and glyceraldehyde by about 35 and 29%, 3 and 3%, and 47 and 37%, respectively.

Kinetics and Mechanisms of Aqueous-Phase Reactions of Triplet-State Imidazole-2-carboxaldehyde and 3,4-Dimethoxybenzaldehyde with α,ß-Unsaturated Carbonyl Compounds.

Reactions in the atmospheric aqueous phase are an important source of secondary organic aerosols (SOA). Within the present study, the reactions of triplet-state imidazole-2-carboxaldehyde (32-IC*) with methyl vinyl ketone (MVK, R1), methacrolein (MACR, R2), and methacrylic acid (MAA, R3), as well as the reaction of triplet-state 3,4-dimethoxybenzaldehyde (3DMB*) with the unsaturated compounds (MVK, R4), (MACR, R5), and (MAA, R6), in the aqueous phase were investigated using laser flash excitation-laser long path absorption and ultraperformance liquid chromatography coupled with high definition electrospray ionization spectrometry. The second-order reaction constants for 32-IC* were determined to be k1 = (1.0 ± 0.1) × 109 L mol-1 s-1 at pH 4-5 and 9, k2 = (1.4 ± 0.4) × 109 L mol-1 s-1 and (1.5 ± 0.1) × 109 L mol-1 s-1 at pH 4-5 and 9, and k3 = (1.4 ± 0.4) × 109 L mol-1 s-1 and (1.1 ± 0.4) × 108 L mol-1 s-1 at pH 4-5 and 9, respectively. The main products of the [2 + 2] photocycloaddition reactions of 32-IC* with both monomer and dimer of MVK as well as MACR were characterized. Similarly, the [2 + 2] photocycloaddition of the carbonyl of the excited triplet state of 3,4-dimethoxybenzaldehyde (3DMB*) with MVK was observed. The second order rate constants for the reactions of 3DMB* were determined: k4 = (1.5 ± 0.2) × 108 L mol-1 s-1, k5 = (2.8 ± 0.5) × 108 L mol-1 s-1, and k6 = (5.2 ± 1.2) × 106 L mol-1 s-1 at pH 9. The studied reactions show that different triplet photosensitizers react with strongly varying rate constants. Advanced CAPRAM process model studies show that active photosensitizers such as 3DMB* can quickly react with unsaturated organic compounds under deliquesced aerosol conditions modifying SOA, while the quenching with oxygen dominates the excited photosensitizer loss under cloud conditions.

Particle-Phase Photoreactions of HULIS and TMIs Establish a Strong Source of H2O2 and Particulate Sulfate in the Winter North China Plain.

During haze periods in the North China Plain, extremely high NO concentrations have been observed, commonly exceeding 1 ppbv, preventing the classical gas-phase H2O2 formation through HO2 recombination. Surprisingly, H2O2 mixing ratios of about 1 ppbv were observed repeatedly in winter 2017. Combined field observations and chamber experiments reveal a photochemical in-particle formation of H2O2, driven by transition metal ions (TMIs) and humic-like substances (HULIS). In chamber experiments, steady-state H2O2 mixing ratios of 116 ± 83 pptv were observed upon the irradiation of TMI- and HULIS-containing particles. Correspondingly, H2O2 formation rates of about 0.2 ppbv h-1 during the initial irradiation periods are consistent with the H2O2 rates observed in the field. A novel chemical mechanism was developed explaining the in-particle H2O2 formation through a sequence of elementary photochemical reactions involving HULIS and TMIs. Dedicated box model studies of measurement periods with relative humidity >50% and PM2.5 ≥ 75 µg m-3 agree with the observed H2O2 concentrations and time courses. The modeling results suggest about 90% of the particulate sulfate to be produced from the SO2 reaction with OH and HSO3- oxidation by H2O2. Overall, under high pollution, the H2O2-caused sulfate formation rate is above 250 ng m-3 h-1, contributing to the sulfate formation by more than 70%.

Elliptical Instability and Multiple-Roll Flow Modes of the Large-Scale Circulation in Confined Turbulent Rayleigh-Bénard Convection.

The large-scale circulation (LSC) of fluid is one of the main concepts in turbulent thermal convection as it is known to be important in global heat and mass transport in the system. In turbulent Rayleigh-Bénard convection (RBC) in slender containers, the LSC is formed of several dynamically changing convective rolls that are stacked on top of each other. The present study reveals the following two important facts: (i) the mechanism which causes the twisting and breaking of a single-roll LSC into multiple rolls is the elliptical instability and (ii) the heat and momentum transport in RBC, represented by the Nusselt (Nu) and Reynolds (Re) numbers, is always stronger (weaker) for smaller (larger) number n of the rolls in the LSC structure. Direct numerical simulations support the findings for n=1,…,4 and the diameter-to-height aspect ratio of the cylindrical container Γ=1/5, the Prandtl number Pr=0.1 and Rayleigh number Ra=5×10^{5}. Thus, Nu and Re are, respectively, 2.5 and 1.5 times larger for a single-roll LSC (n=1) than for a LSC with n=4 rolls.

Organosulfates in Ambient Aerosol: State of Knowledge and Future Research Directions on Formation, Abundance, Fate, and Importance.

Organosulfates (OSs), also referred to as organic sulfate esters, are well-known and ubiquitous constituents of atmospheric aerosol particles. Commonly, they are assumed to form upon mixing of air masses of biogenic and anthropogenic origin, that is, through multiphase reactions between organic compounds and acidic sulfate particles. However, in contrast to this simplified picture, recent studies suggest that OSs may also originate from purely anthropogenic precursors or even directly from biomass and fossil fuel burning. Moreover, besides classical OS formation pathways, several alternative routes have been discovered, suggesting that OS formation possibly occurs through a wider variety of formation mechanisms in the atmosphere than initially expected. During the past decade, OSs have reached a constantly growing attention within the atmospheric science community with evermore studies reporting on large numbers of OS species in ambient aerosol. Nonetheless, estimates on OS concentrations and implications on atmospheric physicochemical processes are still connected to large uncertainties, calling for combined field, laboratory, and modeling studies. In this Critical Review, we summarize the current state of knowledge in atmospheric OS research, discuss unresolved questions, and outline future research needs, also in view of reductions of anthropogenic sulfur dioxide (SO2) emissions. Particularly, we focus on (1) field measurements of OSs and measurement techniques, (2) formation pathways of OSs and their atmospheric relevance, (3) transformation, reactivity, and fate of OSs in atmospheric particles, and (4) modeling efforts of OS formation and their global abundance.

Enhanced Chlorine and Bromine Atom Activation by Hydrolysis of Halogen Nitrates from Marine Aerosols at Polluted Coastal Areas.

Detailed multiphase chemistry box model studies are carried out, investigating halogen radical activation at polluted coastal areas. Simulations are performed for a nonpermanent cloud and a cloud-free scenario and reveal that ClNO2 photolysis and ICl photolysis are crucial for gas-phase Cl atom activation. In the cloud scenario, the integrated ClNO2 and ICl photolysis rates are 3.7 × 107 and 3.1 × 107 molecules cm-3 s-1. In the cloud-free scenario, the integrated ClNO2 and ICl photolysis rates are 8.1 × 107 and 3.6 × 107 molecules cm-3 s-1. The simulations show larger contributions of ClNO2 photolysis in the morning and higher ones of ICl photolysis during afternoon. Throughout the simulation, average contributions to Cl atom activation in the cloud and cloud-free scenarios by ClNO2 photolysis are 42% and 62% and by ICl photolysis 35% and 28%, respectively. ICl is formed through an aqueous-phase reaction of HOI with chloride. Two thirds of the formed ICl is released into the gas phase. The residual third reacts with bromide, creating IBr. Overall, the simulations emphasize the crucial role of INO3 hydrolysis for Cl and Br atom activation in polluted coastal areas. Therefore, it needs to be considered in chemical transport models to improve air quality predictions.

An advanced modeling study on the impacts and atmospheric implications of multiphase dimethyl sulfide chemistry.

Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO42-) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueous-phase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO42- aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions.

Oxidation of substituted aromatic hydrocarbons in the tropospheric aqueous phase: kinetic mechanism development and modelling.

Monocyclic aromatic compounds are ubiquitous in the polluted troposphere and contribute to the formation of tropospheric ozone and anthropogenic secondary organic aerosol, including brown carbon. Currently available physico-chemical data including aqueous-phase kinetic and mechanistic data, as well as phase-transfer parameters have been compiled and reviewed, to construct a novel aqueous-phase oxidation mechanism for monocyclic aromatic compounds. The performed chemical mechanism development results in a comprehensive aqueous-phase oxidation mechanism (addressed as CAPRAM-AM1.0), which includes 292 processes considering the oxidation of different aromatic compounds. Detailed numerical simulations with the air parcel model SPACCIM are carried out for different urban environmental and seasonal conditions. Results show that the aqueous-phase chemistry of aromatic compounds, particularly in clouds, increases the organic aerosol mass by up to 10% in total. The absolute contribution to aqSOA in summertime is modelled to be 260 ng m-3 and 1.2 µg m-3 under moderate and strongly polluted conditions, respectively. Aqueous-phase oxidations of aromatic compounds are important not only for the degradation, but also for the formation of nitrated aromatic compounds. In-cloud chemistry contributes up to 54% to the nitrocatechol oxidation and up to 37% to its formation under polluted tropospheric conditions. Besides, nitrated aromatic compounds contribute up to 5.4 µg m-3 to modelled brown carbon concentration in cloud droplets and 140 ng m-3 in aerosol particles. Further, the model simulations indicate that besides OH radical oxidations, aromatic compounds with two hydroxyl groups are also strongly oxidised by O3 and HO2. O3 contributes with 49% to 68% and HO2 with 19% to 22% to the aqueous-phase oxidation of catechol under moderate and strong polluted environmental conditions studied.

Modeling the impact of iron-carboxylate photochemistry on radical budget and carboxylate degradation in cloud droplets and particles.

To quantify the effects of an advanced iron photochemistry scheme, the chemical aqueous-phase radical mechanism (CAPRAM 3.0i) has been updated with several new Fe(III)-carboxylate complex photolysis reactions. Newly introduced ligands are malonate, succinate, tartrate, tartronate, pyruvate, and glyoxalate. Model simulations show that more than 50% of the total Fe(III) is coordinated by oxalate and up to 20% of total Fe(III) is bound in the newly implemented 1:1 complexes with tartronate, malonate, and pyruvate. Up to 20% of the total Fe(III) is found in hydroxo and sulfato complexes. The fraction of [Fe(oxalate)2](-) and [Fe(pyruvate)](2+) is significantly higher during nighttime than during daytime, which points toward a strong influence of photochemistry on these species. Fe(III) complex photolysis is an important additional sink for tartronate, pyruvate, and oxalate, with a complex photolysis contribution to overall degradation of 46, 40, and 99%, respectively, compared to all possible sink reactions with atmospheric aqueous-phase radicals, such as (•)OH, NO3(•), and SO4(•) (-). Simulated aerosol particles have a much lower liquid water content than cloud droplets, thus leading to high concentrations of species and, consequently, an enhancement of the photolysis sink reactions in the aerosol particles. The simulations showed that Fe(III) photochemistry should not be neglected when considering the fate of carboxylic acids, which constitute a major part of aqueous secondary organic aerosol (aqSOA) in tropospheric cloud droplets and aqueous particles. Failure to consider this loss pathway has the potential to result in a significant overestimate of aqSOA production.

Atmospheric peroxides in a polluted subtropical environment: seasonal variation, sources and sinks, and importance of heterogeneous processes.

Hydrogen peroxide (H2O2) and organic peroxides play an important role in atmospheric chemistry, but knowledge of their abundances, sources, and sinks from heterogeneous processes remains incomplete. Here we report the measurement results obtained in four seasons during 2011-2012 at a suburban site and a background site in Hong Kong. Organic peroxides were found to be more abundant than H2O2, which is in contrast to most previous observations. Model calculations with a multiphase chemical mechanism suggest important contributions from heterogeneous processes (primarily transition metal ion [TMI]-HOx reactions) to the H2O2 budget, accounting for about one-third and more than half of total production rate and loss rate, respectively. In comparison, they contribute much less to organic peroxides. The fast removal of H2O2 by these heterogeneous reactions explains the observed high organic peroxide fractions. Sensitivity analysis reveals that the role of heterogeneous processes depends on the abundance of soluble metals in aerosol, serving as a net H2O2 source at low metal concentrations, but as a net sink with high metal loading. The findings of this study suggest the need to consider the chemical processes in the aerosol aqueous phase when examining the chemical budget of gas-phase H2O2.

Direct sulfuric acid formation from the gas-phase oxidation of reduced-sulfur compounds.

Sulfuric acid represents a fundamental precursor for new nanometre-sized atmospheric aerosol particles. These particles, after subsequent growth, may influence Earth´s radiative forcing directly, or indirectly through affecting the microphysical and radiative properties of clouds. Currently considered formation routes yielding sulfuric acid in the atmosphere are the gas-phase oxidation of SO2 initiated by OH radicals and by Criegee intermediates, the latter being of little relevance. Here we report the observation of immediate sulfuric acid production from the OH reaction of emitted organic reduced-sulfur compounds, which was speculated about in the literature for decades. Key intermediates are the methylsulfonyl radical, CH3SO2, and, even more interestingly, its corresponding peroxy compound, CH3SO2OO. Results of modelling for pristine marine conditions show that oxidation of reduced-sulfur compounds could be responsible for up to ∼50% of formed gas-phase sulfuric acid in these areas. Our findings provide a more complete understanding of the atmospheric reduced-sulfur oxidation.

Rapid growth of Aitken-mode particles during Arctic summer by fog chemical processing and its implication.

In the Arctic, new particle formation (NPF) and subsequent growth processes are the keys to produce Aitken-mode particles, which under certain conditions can act as cloud condensation nuclei (CCNs). The activation of Aitken-mode particles increases the CCN budget of Arctic low-level clouds and, accordingly, affects Arctic climate forcing. However, the growth mechanism of Aitken-mode particles from NPF into CCN range in the summertime Arctic boundary layer remains a subject of current research. In this combined Arctic cruise field and modeling study, we investigated Aitken-mode particle growth to sizes above 80 nm. A mechanism is suggested that explains how Aitken-mode particles can become CCN without requiring high water vapor supersaturation. Model simulations suggest the formation of semivolatile compounds, such as methanesulfonic acid (MSA) in fog droplets. When the fog droplets evaporate, these compounds repartition from CCNs into the gas phase and into the condensed phase of nonactivated Aitken-mode particles. For MSA, a mass increase factor of 18 is modeled. The postfog redistribution mechanism of semivolatile acidic and basic compounds could explain the observed growth of >20 nm h-1 for 60-nm particles to sizes above 100 nm. Overall, this study implies that the increasing frequency of NPF and fog-related particle processing can affect Arctic cloud properties in the summertime boundary layer.

Hydrotrioxide (ROOOH) formation in the atmosphere.

Organic hydrotrioxides (ROOOH) are known to be strong oxidants used in organic synthesis. Previously, it has been speculated that they are formed in the atmosphere through the gas-phase reaction of organic peroxy radicals (RO2) with hydroxyl radicals (OH). Here, we report direct observation of ROOOH formation from several atmospherically relevant RO2 radicals. Kinetic analysis confirmed rapid RO2 + OH reactions forming ROOOH, with rate coefficients close to the collision limit. For the OH-initiated degradation of isoprene, global modeling predicts molar hydrotrioxide formation yields of up to 1%, which represents an annual ROOOH formation of about 10 million metric tons. The atmospheric lifetime of ROOOH is estimated to be minutes to hours. Hydrotrioxides represent a previously omitted substance class in the atmosphere, the impact of which needs to be examined.

Acidity and the multiphase chemistry of atmospheric aqueous particles and clouds.

The acidity of aqueous atmospheric solutions is a key parameter driving both the partitioning of semi-volatile acidic and basic trace gases and their aqueous-phase chemistry. In addition, the acidity of atmospheric aqueous phases, e.g., deliquesced aerosol particles, cloud, and fog droplets, is also dictated by aqueous-phase chemistry. These feedbacks between acidity and chemistry have crucial implications for the tropospheric lifetime of air pollutants, atmospheric composition, deposition to terrestrial and oceanic ecosystems, visibility, climate, and human health. Atmospheric research has made substantial progress in understanding feedbacks between acidity and multiphase chemistry during recent decades. This paper reviews the current state of knowledge on these feedbacks with a focus on aerosol and cloud systems, which involve both inorganic and organic aqueous-phase chemistry. Here, we describe the impacts of acidity on the phase partitioning of acidic and basic gases and buffering phenomena. Next, we review feedbacks of different acidity regimes on key chemical reaction mechanisms and kinetics, as well as uncertainties and chemical subsystems with incomplete information. Finally, we discuss atmospheric implications and highlight the need for future investigations, particularly with respect to reducing emissions of key acid precursors in a changing world, and the need for advancements in field and laboratory measurements and model tools.

Tropospheric aqueous-phase free-radical chemistry: radical sources, spectra, reaction kinetics and prediction tools.

The most important radicals which need to be considered for the description of chemical conversion processes in tropospheric aqueous systems are the hydroxyl radical (OH), the nitrate radical (NO(3)) and sulphur-containing radicals such as the sulphate radical (SO(4)(-)). For each of the three radicals their generation and their properties are discussed first in the corresponding sections. The main focus herein is to summarize newly published aqueous-phase kinetic data on OH, NO(3) and SO(4)(-) radical reactions relevant for the description of multiphase tropospheric chemistry. The data compilation builds up on earlier datasets published in the literature. Since the last review in 2003 (H. Herrmann, Chem. Rev. 2003, 103, 4691-4716) more than hundred new rate constants are available from literature. In case of larger discrepancies between novel and already published rate constants the available kinetic data for these reactions are discussed and recommendations are provided when possible. As many OH kinetic data are obtained by means of the thiocyanate (SCN(-)) system in competition kinetic measurements of OH radical reactions this system is reviewed in a subchapter of this review. Available rate constants for the reaction sequence following the reaction of OH+SCN(-) are summarized. Newly published data since 2003 have been considered and averaged rate constants are calculated. Applying competition kinetics measurements usually the formation of the radical anion (SCN)(2)(-) is monitored directly by absorption measurements. Within this subchapter available absorption spectra of the (SCN)(2)(-) radical anion from the last five decades are presented. Based on these spectra an averaged (SCN)(2)(-) spectrum was calculated. In the last years different estimation methods for aqueous phase kinetic data of radical reactions have been developed and published. Such methods are often essential to estimate kinetic data which are not accessible from the literature. Approaches for rate constant prediction include empirical correlations as well as structure activity relationships (SAR) either with or without the usage of quantum chemical descriptors. Recently published estimation methods for OH, NO(3) and SO(4)(-) radical reactions in aqueous solution are finally summarized, compared and discussed.

Power requirement of the geodynamo from ohmic losses in numerical and laboratory dynamos.

In the Earth's fluid outer core, a dynamo process converts thermal and gravitational energy into magnetic energy. The power needed to sustain the geomagnetic field is set by the ohmic losses (dissipation due to electrical resistance). Recent estimates of ohmic losses cover a wide range, from 0.1 to 3.5 TW, or roughly 0.3-10% of the Earth's surface heat flow. The energy requirement of the dynamo puts constraints on the thermal budget and evolution of the core through Earth's history. Here we use a set of numerical dynamo models to derive scaling relations between the core's characteristic dissipation time and the core's magnetic and hydrodynamic Reynolds numbers--dimensionless numbers that measure the ratio of advective transport to magnetic and viscous diffusion, respectively. The ohmic dissipation of the Karlsruhe dynamo experiment supports a simple dependence on the magnetic Reynolds number alone, indicating that flow turbulence in the experiment and in the Earth's core has little influence on its characteristic dissipation time. We use these results to predict moderate ohmic dissipation in the range of 0.2-0.5 TW, which removes the need for strong radioactive heating in the core and allows the age of the solid inner core to exceed 2.5 billion years.

SO2 formation and peroxy radical isomerization in the atmospheric reaction of OH radicals with dimethyl disulfide.

The atmospheric reaction of OH radicals with dimethyl disulfide, CH3SSCH3, proceeds primarily via OH addition forming CH3S and CH3SOH as reactive intermediates, and to a lesser extent via H-abstraction resulting in the peroxy radical CH3SSCH2OO in the presence of O2. The latter undergoes a fast two-step isomerization process leading to HOOCH2SSCHO. CH3S and CH3SOH are both converted to SO2 and CH3O2 with near unity yields under atmospheric conditions.