DMS oxidation and turbulent transport in the marine boundary layer: A numerical study

DMS oxidation in the marine boundary layer has been simulated with a mesoscale meteorological model including detailed physical parameterizations. The impact of vertical turbulent transport on the DMS and SO₂ diurnal cycles with and without in-cloud SO₂ oxidation has been studied in a one-dimensional version of the model and compared to results obtained with a zero-dimensional box model. Initialisation has been done using balanced values issued from the imposed sea-air fluxes, dry deposition fluxes and chemical source/sink terms. Particular emphasis has been put on the important role played by evolving vertical mixing in the marine boundary layer.     

Aircraft Measurements of Dimethyl Sulfide (DMS) Using a Whole Air Sampling Technique

We present a technique for the measurement of dimethyl sulfide (DMS) from airborne and ground-based platforms, using whole air sampling followed by gas chromatography with mass spectrometer and flame ionization detection. DMS measurements that were obtained during the 1999 NASA Pacific Exploratory Mission-Tropics B showed excellent agreement with independent in-flight DMS measurements, over a wide range of concentrations. The intercomparison supports two key results from this study, first that DMS can be accurately quantified based on ethane and propane per-carbon-response-factors (PCRFs), and second that DMS is stable in water-doped electropolished stainless steel canisters for at least several weeks. In addition, our sampling frequency and duration are flexible and allow detail in the vertical structure of DMS to be well captured. Sampling times as fast as 8 s were achieved and these data are suitable for DMS flux calculations using the mixed-layer gradient technique. Correlations between DMS and other marine tracers can also be readily investigated by this whole air sampling technique, because DMS is analyzed together with more than 50 simultaneously sampled hydrocarbons, halocarbons, and alkyl nitrates. The detection limit of the DMS measurements is 1 part per trillion by volume (pptv), and we conservatively estimate the accuracy to be ±20% or 3 pptv, whichever is larger. The measurement precision (1 ) is 2–4% at high mixing ratios (> 25 pptv), and 1 pptv or 15%, whichever is larger, at low mixing ratios (<10 pptv).     

Effects of inorganic seed aerosols on the growth and chemical composition of secondary organic aerosol formed from OH-initiated oxidation of toluene

(NH₄)₂SO₄, CaCl₂, Na₂SiO₃ and NaNO₃ were selected as surrogates of inorganic seed aerosols of ambient atmosphere of Chinese urban areas, respectively, to study their effects on the formation of secondary organic aerosol (SOA) in the toluene/CH₃ONO/NO_x photooxidation system. The SMPS and aerosol laser time-of-flight mass spectrometer (ALTOFMS) was used to measure the aerodynamic size and chemical composition of individual SOA particles in real-time. Experimental results indicate that either the growth or products of SOA is affected by the presence of inorganic seed aerosol. Inorganic seed aerosols would promote growth rates of SOA formation at the start of the reaction and inhibits its formation rate with prolonging the reaction time. In the case of about 100 μg m^?3 seed aerosol load, the addition of Na₂SiO₃ induced a same growth rate of SOA formation as NaNO₃. The influence of four individual seed aerosols on the generation of SOA decreased in the order of CaCl₂ > (NH₄)₂SO₄ > NaNO₃, Na₂SiO₃. The presence of Na₂SiO₃ or NaNO₃ has no obvious effect on the growth rates of SOA formation, but it does increase the yield of organic acid and nitrogen-containing organic compounds, respectively. Besides the significantly effect on the growth rate of SOA formation, the presence of CaCl₂ or (NH₄)₂SO₄ can lead to the formation of high-molecular weight species which is found to be positively correlated with the hygroscopic behavior of seed aerosols. The CaCl₂ shows the strongest hygroscopic behavior among the four individual seed aerosols, and the most significant promotion effect on the formation of the high-molecular weight species. It is proposed that the SOA generation enhancement and high-molecular weight products are achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of CaCl₂ and (NH₄)₂SO₄ seed aerosols.     

Observation of DMSO and CH3S(O)OH from the gas phase reaction between DMS and OH

Products and mechanisms have been investigated for the reactions between dimethylsulfide (DMS) and dimethylsulfoxide (DMSO) and the hydroxyl radical (OH) in the presence of NO_x. All of the experiments were performed in a 480 L reaction chamber, applying Fourier transform infrared spectroscopy (FT-IR) and ion chromatography as the analytical techniques.In addition to the sulfur containing products that are known to be produced from the gas phase reaction between DMS and OH (SO₂, dimethylsulfone, methylsulfonyl peroxynitrate, methanesulfonic acid, H₂SO₄), DMSO and methanesulfinic acid (CH₃S(O)OH) were also observed as products. Only SO₂, DMSO₂ and methylsulfonyl peroxynitrate were found as sulfur containing products in the reaction between DMSO and OH. Based on these new results we propose a mechanism for the atmospheric oxidation of DMS and DMSO by OH radical.     

Uncertainty analysis for estimation of landfill emissions and data sensitivity for the input variation

Results of research and practical experience confirm that stabilization of GHG concentrations will require a tremendous effort. One of the sectors identified as a significant source of methane (CH₄) emissions are solid waste disposal sites (SWDS). Landfills are the key source of CH₄ emissions in the emissions inventory of Slovakia, and the actual emission factors are estimated with a high uncertainty level. The calculation of emission uncertainty of the landfills using the more sophisticated Tier 2 Monte Carlo method is evaluated in this article. The software package that works with the probabilistic distributions and their combination was developed with this purpose in mind. The results, sensitivity analysis, and computational methodology of the CH₄ emissions from SWDS are presented in this paper.     

DMS and SO2 at Baring Head, New Zealand: Implications for the Yield of SO2 from DMS

Atmospheric dimethyl sulfide (DMS) and sulfur dioxide (SO₂) concentrations were measured at Baring Head, New Zealandduring February and March 2000. Anti-correlated DMS and SO₂ diurnalcycles, consistent with the photochemical production of SO₂ from DMS, were observed in clean southerly air off the ocean. The data is used to infer a yield of SO₂ from DMS oxidation. The estimated yields are highly dependent on assumptions about the DMS oxidation rate. Fitting the measured data in a photochemical box model using model-generated OH levels and the Hynes et al. (1986) DMS + OH rate constant suggests that theSO₂ yield is 50–100%, similar to current estimates for the tropical Pacific.However, the observed amplitude of the DMS diurnal cycle suggests that the oxidation rate is higher than that used by the model, and therefore, that theSO₂ yield is lower in the range of 20–40%.     

Photooxidation of dimethyl sulfide and dimethyl disulfide. II: Mechanism evaluation

The mechanisms for atmospheric photooxidation of CH₃SCH₃ and CH₃SSCH₃ developed in Part I are evaluated by a series of outdoor smog chamber experiments. Measured product yields, including SO₂, H₂SO₄, CH₃SO₃H and HCHO, are reported. The predictions of the mechanisms developed in Part I are found to be in substantial agreement with the measured concentrations from the smog chamber. By comparison of mechanism predictions and observations, critical uncertainties in the mechanism are identified.     

Photooxidation of dimethyl sulfide and dimethyl disulfide. I: Mechanism development

Detailed theoretical (Part I, this article) and experimental (Part II) investigations are presented for the mechanism of the atmospheric photooxidation of dimethyl sulfide (CH₃SCH₃) and dimethyl disulfide (CH₃SSCH₃). In this paper, comprehensive mechanisms for the atmospheric chemistry of CH₃SCH₃ and CH₃SSCH₃ are developed based on fundamental considerations of all available kinetic and mechanistic information.     

The oxidation of S(IV) during riming by cloud droplets

Experiments have been performed to investigate whether the process of freezing during riming in clouds may induce oxidation of dissolved SO₂ to SO ₄ ^2– . The experiments were conducted in a cold room at varying temperatures between –6 and –15 °C. Solutions containing dissolved SO₂ and NH₄OH in various proportions, in the range of concentrations between 3×10^–5 and 10^–3 M, were sprayed. Rime was collected on a rotating cylinder and analyzed. Absorption of oxygen from laboratory air was prevented, except in the spray, to avoid spurious oxidation. Blank experiments were made at +3 to +6 °C. The results indicate clearly that, as the dominant cation becomes NH ₄ ⁺ rather than H⁺, substantial oxidation of S(IV) occurs during riming. This is consistent with redox reactions taking place as a result of charge separation at the ice-water interface during freezing.     

A Study of DMS Oxidation in the Tropics: Comparison of Christmas Island Field Observations of DMS, SO2, and DMSO with Model Simulations

This study reports comparisonsbetween model simulations, based on current sulfurmechanisms, with the DMS, SO₂ and DMSOobservational data reported by Bandy et al.(1996) in their 1994 Christmas Island field study. For both DMS and SO₂, the model results werefound to be in excellent agreement with theobservations when the observations were filtered so asto establish a common meteorological environment. Thisfiltered DMS and SO₂ data encompassedapproximately half of the total sampled days. Basedon these composite profiles, it was shown thatoxidation of DMS via OH was the dominant pathway withno more than 5 to 15% proceeding through Cl atoms andless than 3% through NO₃. This analysis wasbased on an estimated DMS sea-to-air flux of 3.4 ×10⁹ molecs cm^-2 s^-1. The dominant sourceof BL SO₂ was oxidation of DMS, the overallconversion efficiency being evaluated at 0.65 ± 0.15. The major loss of SO₂ was deposition to theocean's surface and scavenging by aerosol. Theresulting combined first order k value was estimated at 1.6 × 10^-5 s^-1. In contrast to the DMSand SO₂ simulations, the model under-predictedthe observed DMSO levels by nearly a factor of 50. Although DMSO instrument measurement problems can notbe totally ruled out, the possibility of DMSO sourcesother than gas phase oxidation of DMS must beseriously considered and should be explored in futurestudies.     

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.     

Covariations in oceanic dimethyl sulfide,its oxidation products and rain acidity at Amsterdam Island in the Southern Indian Ocean

Simultaneous measurements of rain acidity and dimethyl sulfide (DMS) at the ocean surface and in the atmosphere were performed at Amsterdam Island over a 4 year period. During the last 2 years, measurements of sulfur dioxide (SO₂) in the atmosphere and of methane sulfonic acid (MSA) and non-sea-salt-sulfate (nss-SO₄ ^2-) in rainwater were also performed. Covariations are observed between the oceanic and atmospheric DMS concentrations, atmospheric SO₂ concentrations, wet deposition of MSA, nss-SO₄ ^2-, and rain acidity. A comparable summer to winter ratio of DMS and SO₂ in the atmosphere and MSA in precipitation were also observed. From the chemical composition of precipitation we estimate that DMS oxidation products contribute approximately 40% of the rain acidity. If we consider the acidity in excess, then DMS oxidation products contribute about 55%.     

Uncertainty in Carbon Capture and Storage (CCS) deployment projections: a cross-model comparison exercise

Carbon Capture and Storage (CCS) can be a valuable CO₂ mitigation option, but what role CCS will play in the future is uncertain. In this paper we analyze the results of different integrated assessment models (IAMs) taking part in the 27th round of the Energy Modeling Forum (EMF) with respect to the role of CCS in long term mitigation scenarios. Specifically we look into the use of CCS as a function of time, mitigation targets, availability of renewables and its use with different fuels. Furthermore, we explore the possibility to relate model results to general and CCS specific model assumptions. The results show a wide range of cumulative capture in the 2010–2100 period (600–3050 GtCO₂), but the fact that no model projects less than 600 GtCO₂ indicates that CCS is considered to be important by all these models. Interestingly, CCS storage rates are often projected to be still increasing in the second half of this century. Depending on the scenario, at least six out of eight, up to all models show higher storage rates in 2100 than in 2050. CCS shares in cumulative primary energy use are in most models increasing with the stringency of the target or under conservative availability of renewables. The strong variations of CCS deployment projection rates could not be related to the reported differences in the assumptions of the models by means of a cross-model comparison in this sample.     

The Role of Multiphase Chemistry in the Oxidation of Dimethylsulphide (DMS). A Latitude Dependent Analysis

A kinetic model for the OH-initiated homogeneous gas phase oxidation of dimethylsulfide (DMS) in the atmosphere (Saltelli and Hjorth, 1995), has been extended here to include the liquid phase chemistry. The updated model has then been employed to predict the temperature dependency of the MSA/nss-SO42- ratio. Model predictions have been compared with observational data reported in Bates et al. (1992). Sensitivity and uncertainty analysis has been performed in a Monte Carlo fashion to identify which are the important uncertainties on the input parameters and which are the possible combinations of parameter values that could explain the field observations. Results of the analysis have indicated that the temperature dependencies of the interactions between gas phase and liquid phase chemistry may to a large extent explain the observed T-dependence of the MSA/nss- SO42- ratio. The potential role of multi-phase atmospheric chemistry, not only in the case of SO2 but also of other oxidation products of DMS and, particularly, of DMS itself, has been highlighted.     

气候变化背景下欧洲中部水资源供给的不稳定性评估——以易北河流域为例

 欧洲中部的易北河流域是典型的湿润半湿润地区。夏季的水资源供给是限制农业生产的因素之一,特别是在具有较高农业生产力水平,而年降水量只有500 mm的黄土地区。通过总结气候变化与水文循环（GLOWA-Elbe）项目第一阶段的成果,根据气候和土地利用变化的各种情景并考虑其不确定性,对未来50 a德国易北河流域水资源供给稳定性作出综合评估。研究表明,欧洲中部必须从自然和社会角度应对未来气候变化情景下产生水资源供给短缺的可能情况。     

The atmospheric chemistry of dimethylsulfoxide (DMSO) kinetics and mechanism of the OH+DMSO reaction

We have employed a pulsed laser photolysis-pulsed laser induced fluorescence technique to study the kinetics and mechanism of the reaction of OH with dimethylsulfoxide and its deuterated analogue. A rate coefficient of (1.0±0.3)×10^-10 cm³ molecule^-1 s^-1 was obtained ar room temperature. The rate coefficient was independent of pressure over the range 25–700 Torr, showed no dependence on the nature of the buffer gas and showed no kinetic isotope effect. A limited study of the temperature dependence indicated that the reaction displays a negative activation energy. The gas phase ultraviolet absorption spectrum was obtained at room temperature and showed a strong absorption feature in the far ultraviolet. The absolute absorption cross-section at 205 nm, the absorption peak, is (1.0±0.3)×10^-17 cm², where the large uncertainty results from experimental difficulties associated with the low vapor pressure and stickiness of DMSO.     

集合预报对台风天鹅(2015)远距离暴雨的不确定性研究

2015年8月23—24日期间台风天鹅引发华东中部沿海地区出现暴雨或大暴雨天气。基于欧洲中期天气预报中心的集合预报分析导致此次远距离暴雨预报不确定的关键原因,并利用集合敏感性分析方法研究影响此次暴雨过程的主要天气系统的敏感区域,此外对暴雨发生发展的热动力机制展开探讨,主要结论包括:集合预报对此次台风天鹅引起的远距离暴雨的可预报性明显偏低,仅在暴雨发生前24 h才做出较大调整。在不同起报时次下,当台风路径的系统性偏差最小时,台风降水集合预报也最接近实况,但是进一步的分析表明,台风路径误差与降水量级之间的对应关系并不确定。不同雨量成员组间中低层环流场的对比分析表明:高空槽的预报差异是集合预报不确定的主要原因,高空槽东移加深有利于增加暴雨区的斜压不稳定,也有利于增强对流层低层的水汽输送急流带。500 hPa高度场的敏感性分析表明无论是初始场还是预报场,暴雨区平均降雨量均与高空槽的东移和加深显著相关,且随着预报时次的临近,显著相关区域向低槽下游明显扩大。此外还发现高空槽的东移有利于增强(减弱)暴雨区左(右)侧低层冷空气的强度,使得台风右侧更多暖湿气流向暴雨区输送。