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The hydroxyl radical (OH) reacts with thousands of chemical species in the atmosphere, initiating their removal and the chemical reaction sequences that produce ozone, secondary aerosols, and gas-phase acids. OH reactivity, which is the inverse of OH lifetime,influences the OH abundance and the ability of OH to cleanse the atmosphere. The NASA Atmospheric Tomography (ATom) campaign used instruments on the NASA DC-8 aircraft to measure OH reactivity and more than 100 trace chemical species. ATom presented a unique opportunity to test the completeness of the OH reactivity calculated from the chemical species measurements by comparing it to the measured OH reactivity over two oceans across four seasons. Although, throughout much of the free troposphere, the calculated OH reactivity was below the limit-of-detection for the ATom instrument used to measure OH reactivity, the instrument was able to measure the OH reactivity in and just above the marine boundary layer. The mean measured value of OH reactivity in the marine boundary layer across all latitudes and all ATom deployments was 1.9 s-1, which is 0.5 s-1larger than the mean calculated OH reactivity. The missing OH reactivity, the difference between the measured and calculated OH reactivity, varied between 0 s-1to 3.5 s-1, with the highest values over the Northern Hemisphere Pacific Ocean. Correlations of missing OH reactivity with formaldehyde, dimethyl sulfide, butanal, and sea surface temperature suggest the presence of unmeasured or unknown volatile organic compounds or oxygenated volatile organic compounds associated with ocean emissions.
Lester and coworkers have experimentally characterized complexes of OH in the X and A states with H2 and N2. Recently, we have carried out ab initio calculations of relevant portions of the ground state and excited state potential energy surfaces for these systems, including the conical intersection regions, which are responsible for electronic quenching of the A state of OH by H2 and N2. Both of these systems have weakly bound complexes in the X state and strongly bound complexes in the A state. The OH-H2 complex is T-shaped, while the OH-N2 complex is collinear. In both cases the H end of OH is oriented toward the H2 or N2 molecule, respectively. Rotation of the OH about its center of mass involves only a small barrier and rotation by 1800 so that the 0 end of OH is oriented toward the H2 or N2 molecule leads to conical intersections with the ground state surface. Since there is about 95 kcal/mol of available energy after crossing to the ground state surface, chemical reactions on the ground state surface are possible, in addition to electronic quenching. In the case of OH-H2, the conical intersection is much lower in energy than the OH (A state) + H2 asymptotic energy and the A state complex can be characterized as a hanging well on the upper cone of the conical intersection. Passage through the conical intersection places the system on the ground state potential energy surface with the possibility of going to OH (X state) + H2 (i.e. electronic quenching) or to H2O + H (reaction). For OH-N2, the A state complex is also a hanging well on the upper cone of the conical intersection, but the conical intersection is only slightly below the OH (A state) + H2 asymptotic energy. Passage through the conical intersection can lead to OH (X state) + N2 (i.e. electronic quenching), but so far reactive pathways have not been found.
Brucite [Mg(OH) 2 ] is a promising sorbent for carbon dioxide removal (CDR) due to its availability and low calcination temperatures. However, natural and synthetic brucites tend to contain metal impurities, such as iron or manganese, and how these impurities affect the interfacial chemical reactivity is uncertain. Here, in this study, the impact of low concentrations of iron and manganese impurities on the carbonation efficiency of Mg(OH) 2 was examined. Mg(OH) 2 with small amounts (1–5 mol %) of Fe and Mn was synthesized. The increasing substitution of Fe into Mg(OH) 2 was accompanied by the oxidation of Fe. The phase transformation sequence during the carbonation was found to be brucite [Mg(OH) 2 ] → amorphous magnesium carbonate (MgCO 3 ·nH 2 O) → nesquehonite (MgCO 3 ·3H 2 O), regardless of impurity concentration. Both the Fe- and Mn-doped Mg(OH) 2 samples were more reactive than endmember Mg(OH) 2 , possibly due to their higher surface areas and lower stabilities. During carbonation, 3 mol % Fe- and Mn-doped Mg(OH) 2 showed the highest reactivity. The variance in reactivity for Mn-doped Mg(OH) 2 was less than that of Fe-doped Mg(OH) 2 . These results suggest that natural or industrial waste Mg(OH) 2 with less than 5 mol % Fe and Mn impurities may be targeted as more effective CDR sorbents than endmember Mg(OH) 2 .
The hydroxyl radical (OH) plays a vital role in tropospheric chemistry, as it provides the dominant sink for a multitude of pollutants and climate-relevant gases such as methane. Observational constraints on the global distribution and temporal variability of OH are limited, and models simulate a wide range of OH distributions. While OH itself has a short atmospheric lifetime, OH is photochemically coupled to longer-lived species that undergo atmospheric transport. Here, we investigate how much of the OH variability within and between models can be explained by differences in observable species to develop diagnostics for OH differences. We find that NO 2 and water vapor together explain much of the spatial and temporal variability in simulated OH, and we use satellite observations to identify biases in these variables. The OH response to ENSO also differs between models, and we investigate potential causes of these differences such as differences in convection or lightning NOx. We also explore the potential of idealized tracers to represent the OH distribution. Within a single model, meteorological variables such as humidity and idealized tracers of transport can explain a significant portion of the OH spatial variability. We use a Gradient Boosted Regression Trees, a type of machine learning, to account for non-linear relationships between OH and the input variables.
Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to relative humidity (RH) and external OH reactivity (OHRext), as both non-OH reactants and OH scale roughly proportional to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D), O(3P), and O3 have relative contributions to VOC consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. Under pathological OFR conditions of low RH and/or high OHRext, the importance of non-OH reactants is enhanced because OH is suppressed. Some biogenics can have substantial destructions by O3, and photolysis at non-tropospheric wavelengths (185 and 254 nm) may also play a significant role in the degradation of some aromatics under pathological conditions. Working under low O2 with the OFR185 mode allows OH to completely dominate over O3 reactions even for the biogenic species most reactive with O3. Non-tropospheric VOC photolysis may have been a problem in some laboratory and source studies, but can be avoided or lessened in future studies by diluting source emissions and working at lower precursor concentrations in lab studies, and by humidification. SOA photolysis is shown to be insignificant for most functional groups, except for nitrates and especially aromatics, which may be photolyzed at high UV flux settings. Our work further establishes the OFR's usefulness as a tool to study atmospheric chemistry and enables better experiment design and interpretation, as well as improved future reactor design.
Oxidation flow reactors (OFRs) using low-pressure Hg lamp emission at 185 and 254 nm produce OH radicals efficiently and are widely used in atmospheric chemistry and other fields. However, knowledge of detailed OFR chemistry is limited, allowing speculation in the literature about whether some non-OH reactants, including several not relevant for tropospheric chemistry, may play an important role in these OFRs. These non-OH reactants are UV radiation, O(1D), O(3P), and O3. In this study, we investigate the relative importance of other reactants to OH for the fate of reactant species in OFR under a wide range of conditions via box modeling. The relative importance of non-OH species is less sensitive to UV light intensity than to relative humidity (RH) and external OH reactivity (OHRext), as both non-OH reactants and OH scale roughly proportional to UV intensity. We show that for field studies in forested regions and also the urban area of Los Angeles, reactants of atmospheric interest are predominantly consumed by OH. We find that O(1D), O(3P), and O3 have relative contributions to VOC consumption that are similar or lower than in the troposphere. The impact of O atoms can be neglected under most conditions in both OFR and troposphere. Under pathological OFR conditions of low RH and/or high OHRext, the importance of non-OH reactants is enhanced because OH is suppressed. Some biogenics can have substantial destructions by O3, and photolysis at non-tropospheric wavelengths (185 and 254 nm) may also play a significant role in the degradation of some aromatics under pathological conditions. Working under low O2 with the OFR185 mode allows OH to completely dominate over O3 reactions even for the biogenic species most reactive with O3. Non-tropospheric VOC photolysis may have been a problem in some laboratory and source studies, but can be avoided or lessened in future studies by diluting source emissions and working at lower precursor concentrations in lab studies, and by humidification. SOA photolysis is shown to be insignificant for most functional groups, except for nitrates and especially aromatics, which may be photolyzed at high UV flux settings. Our work further establishes the OFR's usefulness as a tool to study atmospheric chemistry and enables better experiment design and interpretation, as well as improved future reactor design.
Results from simulations performed for the Atmospheric Chemistry and Climate Modeling Intercomparison Project (ACCMIP) are analysed to examine how OH and methane lifetime may change from present day to the future, under different climate and emissions scenarios. Present day (2000) mean tropospheric chemical lifetime derived from the ACCMIP multi-model mean is 9.8+/-1.6 yr (9.3+/-0.9 yr when only including selected models), lower than a recent observationally-based estimate, but with a similar range to previous multi-model estimates. Future model projections are based on the four Representative Concentration Pathways (RCPs), and the results also exhibit a large range. Decreases in global methane lifetime of 4.5 +/- 9.1% are simulated for the scenario with lowest radiative forcing by 2100 (RCP 2.6), while increases of 8.5+/-10.4% are simulated for the scenario with highest radiative forcing (RCP 8.5). In this scenario, the key driver of the evolution of OH and methane lifetime is methane itself, since its concentration more than doubles by 2100 and it consumes much of the OH that exists in the troposphere. Stratospheric ozone recovery, which drives tropospheric OH decreases through photolysis modifications, also plays a partial role. In the other scenarios, where methane changes are less drastic, the interplay between various competing drivers leads to smaller and more diverse OH and methane lifetime responses, which are difficult to attribute. For all scenarios, regional OH changes are even more variable, with the most robust feature being the large decreases over the remote oceans in RCP8.5. Through a regression analysis, we suggest that differences in emissions of non-methane volatile organic compounds and in the simulation of photolysis rates may be the main factors causing the differences in simulated present day OH and methane lifetime. Diversity in predicted changes between present day and future OH was found to be associated more strongly with differences in modelled temperature and stratospheric ozone changes. Finally, through perturbation experiments we calculated an OH feedback factor (F) of 1.24 from present day conditions (1.50 from 2100 RCP8.5 conditions) and a climate feedback on methane lifetime of 0.33+-0.13 yr/K, on average. Models that did not include interactive stratospheric ozone effects on photolysis showed a stronger sensitivity to climate, as they did not account for negative effects of climate-driven stratospheric ozone recovery on tropospheric OH, which would have partly offset the overall OH/methane lifetime response to climate change.
Decadal trends and interannual variations in the hydroxyl radical (OH), while poorly constrained at present, are critical for understanding the observed evolution of atmospheric methane (CH4). Through analyzing the OH fields simulated by the model ensemble of the Chemistry-Climate Model Initiative (CCMI), we find (1) the negative OH anomalies during the El Niño years mainly corresponding to the enhanced carbon monoxide (CO) emissions from biomass burning and (2) a positive OH trend during 1980-2010 dominated by the elevated primary production and the reduced loss of OH due to decreasing CO after 2000. Both two-box model inversions and variational 4D inversions suggest that ignoring the negative anomaly of OH during the El Niño years leads to a large overestimation of the increase in global CH4 emissions by up to10±3Tg yr-1to match the observed CH4 increase over these years. Not accounting for the increasing OH trends given by the CCMI models leads to an underestimation of the CH4 emission increase by 23±9Tg yr-1from 1986 to 2010. The variational inversion estimated CH4 emissions show that the tropical regions contribute most to the uncertainties related to OH. This study highlights the significant impact of climate and chemical feedbacks related to OH on the top-down estimates of the global CH4 budget.
Large-aperture photometric observations of comet Hale-Bopp (C/1995 O1) in the forbidden red line of neutral oxygen ([O I] 6300 angstroms) with the 150 mm dual-etalon Fabry-Perot spectrometer that comprises the Wisconsin H-alpha Mapper and a 50 mm dual-etalon Fabry-Perot spectrometer at the McMath-Pierce main telescope from 1997 late February to mid April yield a total metastable O((sup 1)D) production rate of (2.3-5.9) x 10(exp 30)/s. Applying the standard H2O and OH photodissociation branching ratios, we derive a water production rate, Q(H2O), of (2.6-6.1) x 10(exp 31)/s, which disagrees with Q(H2O = 1x10(exp 31)/s determined by independent H2O, OH, and H measurements. Furthermore, our own [O I] 6300 observations of the inner coma (< 30,000 km) using the 3.5 m Wisconsin-Indiana-Yale-NOAO telescope Hydra and Densepak multi-object spectrographs yield Q(H2O) = 1 x 10(exp 31)/s. Using our [O I] 6300 data, which cover spatial scales ranging from 2,000 to 1x10(exp 6) km, and a complementary set of wide-field ground-based OH images, we can constrain the sources of the apparent excess O((sup 1)D) emission to the outer coma, where photodissociation of OH is assumed to be the dominant O((sup 1)D) production mechanism. From production rates of other oxygen-bearing volatiles (e.g., CO and CO2), we can account for at most 30% of the observed excess O((sup 1)D) emission. Since even less O((sup 1)D) should be coming from other sources (e.g., electron excitation of neutral O and distributed nonnuclear sources of H2O), we hypothesize that the bulk of the excess O((sup 1)D) is likely coming from photodissociating OH. Using the experimental OH photo-dissociation cross section of Nee and Lee at Ly-alpha as a guide in modifying the theoretical OH cross sections of van Dishoeck and Dalgarno, we can account for approximately 60% of the observed O((sup 1)D) excess without requiring major modifications to the other OH branching ratios or the total OH photodissociation lifetime.
Nitrogen oxides (NO(x) = NO + NO2) produced by lightning make a major contribution to the production of the dominant tropospheric oxidants (OH and ozone). These oxidants control the lifetime of many trace gases including long-lived greenhouse gases, and control the source-receptor relationship of inter-hemispheric pollutant transport. Lightning is affected by meteorological variability, and therefore represents a potentially important tropospheric chemistry-climate feedback. Understanding how interannual variability (IAV) in lightning affects IAV in ozone and OH in the recent past is important if we are to predict how oxidant levels may change in a future warmer climate. However, lightning parameterizations for chemical transport models (CTMs) show low skill in reproducing even climatological distributions of flash rates from the Lightning Imaging Sensor (LIS) and the Optical Transient Detector (OTD) satellite instruments. We present an optimized regional scaling algorithm for CTMs that enables sufficient sampling of spatiotemporally sparse satellite lightning data from LIS to constrain the spatial, seasonal, and interannual variability of tropical lightning. We construct a monthly time series of lightning flash rates for 1998-2010 and 35degS-35degN, and find a correlation of IAV in total tropical lightning with El Nino. We use the IAV-constraint to drive a 9-year hindcast (1998-2006) of the GEOS-Chem 3D chemical transport model, and find the increased IAV in LNO(x) drives increased IAV in ozone and OH, improving the model fs ability to simulate both. Although lightning contributes more than any other emission source to IAV in ozone, we find ozone more sensitive to meteorology, particularly convective transport. However, we find IAV in OH to be highly sensitive to lightning NO(x), and the constraint improves the ability of the model to capture the temporal behavior of OH anomalies inferred from observations of methyl chloroform and other gases. The sensitivity of OH is explained using photochemical reaction rates which show a "magnification" effect of the initial lightning NO perturbation on OH primary production, HO(x) recycling, and OH loss frequencies. This influence on OH may represent a negative feedback, if lightning increases in a warming world..
The mineral apatite is present in a wide range of planetary materials. The presence of volatiles (F, Cl, and OH) within its crystal structure (X-site) have motivated numerous studies to investigate the partitioning behavior of F, Cl, and OH between apatite and silicate melt with the end goal of using apatite to constrain the volatile contents of planetary magmas and mantle sources. A number of recent experimental studies have investigated the apatite-melt partitioning behavior of F, Cl, and OH in magmatic systems. Apatite-melt partitioning of volatiles are best described as exchange equilibria similar to Fe-Mg partitioning between olivine and silicate melt. However, the partitioning behavior is likely to change as a function of temperature, pressure, oxygen fugacity, apatite composition, and melt composition. In the present study, we have conducted experiments to assess the partitioning behavior of F, Cl, and OH between apatite and silicate melt over a pressure range of 0-6 gigapascals, a temperature range of 950-1500 degrees Centigrade, and a wide range of apatite ternary compositions. All of the experiments were conducted between iron-wustite oxidation potentials IW minus 1 and IW plus 2 in a basaltic melt composition. The experimental run products were analyzed by a combination of electron probe microanalysis and secondary ion mass spectrometry (NanoSIMS). Temperature, apatite crystal chemistry, and pressure all play important roles in the partitioning behavior of F, Cl, and OH between apatite and silicate melt. In portions of apatite ternary space that undergo ideal mixing of F, Cl, and OH, exchange coefficients remain constant at constant temperature and pressure. However, exchange coefficients vary at constant temperature (T) and pressure (P) in portions of apatite compositional space where F, Cl, and OH do not mix ideally in apatite. The variation in exchange coefficients exhibited by apatite that does not undergo ideal mixing far exceeds the variations induced by changes in temperature (T) or pressure (P) . In regions where apatite undergoes ideal mixing of F, Cl, and OH, temperature has a stronger effect than pressure on the partitioning behavior, but both are important. Furthermore, fluorine becomes less compatible in apatite with increasing pressure and temperature. We are still in the process of analyzing our experimental run products, but we plan to quantify the effects of P and T on apatite-melt partitioning of F, Cl, and OH.
Planar laser-induced fluorescence (LIF) was employed to measure the absolute density of hydroxyl radicals (OH) in the effluent of the COST Reference Microplasma Jet for two feed gas mixtures: He/H 2 O and He/O 2 . Experiments were conducted with the effluent propagating into air and N 2 environments. For the He/H 2 O case, measurements were also performed with the effluent impinging on a solid target at varying distances from the jet nozzle. Calibration of the OH-LIF signal from the COST-Jet was achieved by comparing it to a reference signal generated by the photofragmentation of H 2 O 2 . Results demonstrated that OH densities were sustained longer when the effluent propagates in a nitrogen environment compared to air, particularly with water added to the feed gas. The broader OH distribution in N 2 suggests slower consumption due to the absence of oxygen, which accelerates OH depletion in air via reactions involving O 2 and HO 2 . Even when water was not added to the feed, as in the He/O 2 case, appreciable OH densities were observed, due to gas impurities and reactive species interactions with atmospheric humidity, forming reaction fronts that delineate the gas flow. Two-dimensional fluid dynamics simulations elucidated the influence of atmospheric gas entrainment and solid targets on the OH distribution. Experimental trends were further compared with a zero-dimensional chemistry model to explore OH production and consumption mechanisms in air and nitrogen environments.