Laboratory Determination of the Carbon Kinetic Isotope Effects (KIEs) for Reactions of Methyl Halides with Various Nucleophiles in Solution

Large carbon kinetic isotope effects (KIEs) were measured for reactions of methyl bromide (MeBr), methyl chloride (MeCl), and methyl iodide (MeI) with various nucleophiles at 287 and 306 K in aqueous solutions. Rates of reaction of MeBr and MeI with H₂O (neutral hydrolysis) or Cl⁻ (halide substitution) were consistent with previous measurements. Hydrolysis rates increased with increasing temperature or pH (base hydrolysis). KIEs for hydrolysis were 51 ± 6%₀ for MeBr and 38 ± 8%₀ for MeI. Rates of halide substitution increased with increasing temperature and greater reactivity of the attacking nucleophile, with the fastest reaction being that of MeI with Br⁻. KIEs for halide substitution were independent of temperature but varied with the reactant methyl halide and the attacking nucleophile. KIEs were similar for MeBr substitution with Cl⁻ and MeCl substitution with Br⁻ (57 ± 5 and 60 ± 9%₀, respectively). The KIE for halide exchange of MeI was lower overall (33 ± 8%₀) and was greater for substitution with Br⁻ (46 ± 6%₀) than with Cl⁻ (29 ± 6%₀).     

Henry's law and hydrolysis-rate constants for peroxyacyl nitrates (PANs) using a homogeneous gas-phase source

The solubilities and hydrolysis rates of PAN (peroxyacetyl nitrate) and its homologues PPN (peroxypropionyl nitrate), PnBN (peroxy-n-butyl nitrate), PiBN (peroxy-isobutyl nitrate) and MPAN (peroxymethacryloyl nitrate) in liquid water have been studied at 20 °C. Temperature dependencies were measured for PAN and PPN. The solubilities of peroxyacyl nitrates decrease smoothly with increasing carbon-chain length fromH (293 K)=4.1 M atm^–1 (PAN) toH (293 K)=1.0 M atm^–1 (PiBN). Hydrolysis-rate constants, which cover the range fromk _h (293 K)=(2.4–7.4)×10^–4 s^–1, do not show a systematic chain-length dependency. Solubilities of PAN and PPN in solutions which mimic the composition and ionic strength of sea water are 15% and 20% lower than in pure water. The hydrolysis rate constants are not affected.     

Global Modelling of the Atmospheric Methyl Bromide Budget

A global three-dimensional chemical transport model has been used to identify and evaluate possible candidates for the `missing' surface source required to balance the atmospheric budget of methyl bromide. Both natural and anthropogenic emissions of methyl bromide are `coloured' in the model, thus allowing the global CH₃Br distribution to be broken-down into its source components. These coloured CH₃Br tracers are then combined in various ways to create one base-line emission scenario and five further plausible scenarios. The additional emission scenarios are specifically designed to test whether the geographical distribution and seasonal cycles of additional vegetation and/or increased biomass burning emissions are consistent with atmospheric observations of methyl bromide mixing ratios. Due to an imbalance in our current understanding of the methyl bromide budget, simulated CH₃Br mixing ratios from the base-line emission scenario are significantly lower than atmospheric measurements. Both the inclusion of a vegetation source in the tropics and a double strength biomass burning source substantially improve the agreement between model simulations and atmospheric measurements compared with the base-line emission scenario. While measurement data provides useful information on global fluxes and regional CH₃Br seasonal cycles, small differences between the simulated seasonal cycles of different emission scenarios makes it difficult to distinguish between the relative likelihoods of model scenarios containing a tropical vegetation source or an increased biomass burning source. Further measurements performed in continental mid-to-high northern latitudes, central-southern Africa and South America would be of particular benefit in future attempts to constrain the location and magnitude of the natural terrestrial sources of methyl bromide.     

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.     

Future emissions of marine halogenated very-short lived substances under climate change

Halogenated Very Short-lived Substances (VSLS), such as bromoform, dibromomethane and methyl iodide, are naturally produced in the oceans and are involved in ozone depletion in the troposphere and the stratosphere. The effect of climate change on the oceanic emissions of these compounds is not well quantified. Based on present-day observed global oceanic and atmospheric concentrations, and historic and future data from three CMIP5 models, past and future sea-to-air fluxes of these VSLS are calculated. The simulations are used to infer possible effects of projected changes of physical forcing on emissions in different oceanic regimes. CMIP5 model output for 1979–2100 from the historical scenario and the RCP scenarios 2.6 and 8.5 are used as input data for the emission calculations. Of the parameters that have the main influence on the sea-to-air fluxes, the global sea surface temperatures show a steady increase during the twenty-first century, while the projected changes of sea surface wind speed is very small. The calculated emissions based on the historical CMIP5 model runs (1979–2005) increased over the 26 year period and agree well with the emissions based on ERA-Interim data. The future sea-to-air fluxes of VSLS generally increase during the twenty-first century under the assumption of constant concentration fields in the ocean and atmosphere. The multi-model mean global emissions of bromoform increase by 29.4% (9.0%) between 1986 and 2005 and 2081–2100 under RCP 8.5 (2.6) and dibromomethane and methyl iodide emissions increase by 23.3% (6.4%) and 5.5% (1.5%), respectively. Uncertainties of the future emission estimates, driven by ongoing environmental changes such as changing oceanic productivity (not considered in this study) are discussed.     

海洋表层流模式和月尺度海气耦合试验

本文第一部分设计了一个海洋表层流模式，较成功地模拟出冬夏季海表层中的大尺度洋流和海面高度第二部分是月时间尺度的海气耦合试验，将海表层洋流模式和球带范围的大气模式相耦合，用数值试验讨论了洋流和海气耦合方式对模拟结果的影响。     

Latitude versus Depth Simulations of Ecodynamics and Dissolved Gas Chemistry Relationships in the Central Pacific

Nutrient ecology and trace gas processing are intimately coupled in the surface ocean and participate in key linkages through the Earth biogeochemical system. We have added water column photochemistry for volatile sulfur and organic compounds to large scale nutrient cycle modules, in order to create a one dimensional, open ocean ecochemistry simulator. Phyto- and zooplankton, recyclers and biological waste products are represented through N and Fe densities. Dimethyl sulfide, carbonyl sulfide and the methyl halides are tracked individually along with certain precursors and nonmethane hydrocarbons. The model is applied along the 180 degree meridian in the Northern Hemisphere. Ecodynamics are validated against satellite ocean color maps. Biological/photochemical production terms are then iterated upon to match measured distributions for the trace gases. Data are most complete for dimethyl sulfide. Major patterns in its climatology are captured within individual ecological provinces. However, at the basin scale reduced sulfur release must be varied over almost an order of magnitude because the mechanism developed contains only one plant taxon. Based on sparser data, first order rate constants are estimated for phytoplanktonic exudation of the methyl halides. Parameters are also established for photolytic injection of carbonyl sulfide and propylene from the dissolved organics. Ocean general circulation models and interactive ocean-atmosphere transport simulations are discussed as frameworks for future application.     

南海暖池初步研究

观测事实表明,南海有暖池存在。本文主要采用南海２０ｍ层的水温分布资料,讨论了南海暖池的时空演变特征,并结合地转流和海洋环流数值模拟的结果探讨了暖池的形成机制。结果南海暖池有显著的季节张年际变化;暖池的发展除有太阳辐射有关外,还与海洋中涡旋活动及从印度洋输入的暖水有密切关系。     

THE CLIMATE FEATURES OF THE SOUTH CHINA SEA WARM POOL

There exists a warm pool in the South China Sea (SCS). The temporal and spatial distribution and evolution of SCS warm pool is investigated using water temperatures at a depth of 20 min the sea. The formation of the warm pool is discussed by combining water temperatures with geostrophic currents and simulated oceanic circulation. It is found that there are significant seasonal and interannual changes in the warm pool and in association with the general circulation of the atmosphere. The development of SCS warm pool is also closely related to the gyre activities in the sea and imported warm water from Indian Ocean (Java Sea) besides radiative warming.     

The evolution of temperature extremes in the Gaspé Peninsula,Quebec, Canada (1974–2013)

The majority of natural hazards that affect Canadian territory are the result of extreme climate and weather conditions. Among these weather hazards, some can be calculated from the application of thresholds for minimum and maximum temperatures at a daily or monthly timescale. These thermal indices allowed the prediction of extreme conditions that may have an impact on the human population by affecting, for example, health, agriculture, and water resources. In this article, we discuss the methods used (RHtestsV4, SPLIDHOM, ClimPACT) then describe the steps followed to calculate the indices, including how we dealt with the problem of missing data and the necessity to identify a common methodology to analyze the time series. We also present possible solutions for ensuring the quality of meteorological data. We then present an overview of the results, namely the main trends and variability of extreme temperature for seven stations located in the Gaspé Peninsula from 1974 to 2013. Our results indicate some break points in time series and positive trends for most indices related to the rise of the temperatures but indicate a negative trend for the indices related to low temperatures for most stations during the study period.     

Flexibility of a simple tropospheric gas phase reaction mechanism: investigations of a simulated experiment by inverse modelling

Inverse modelling was applied to computer simulated time series of trace gas concentrations as a means to design real experiments and to explore the potential of their real counterparts to deduce rate constants of a simplified reaction mechanism of tropospheric chemistry. Two cases were examined: As a first case, the model to be fitted was complete, but its rate constants were modified within the constraints from prior knowledge. For this case, we got a good fit and significantly improved the modified parameters. As a second case, an incomplete model, where an important reaction was omitted from the model, was fitted to the simulated experiment. For the incomplete model, we also got an apparently good fit, showing the flexibility of the mechanism. However, the hypothesis “mechanism is correct” had to be rejected because it is not consistent with the prior knowledge. The rejection was further confirmed by a simulated control experiment with different experimental constraints.     

BCC_CSM1.1对10年尺度全球及区域温度的预测研究

近期10～30年时间尺度的年代际预测是第五次耦合模式国际比较计划(CMIP5)重要内容之一。按照CMIP5试验要求, 国家气候中心利用气候系统模式BCC_CSM1.1完成并提交了年代际试验结果。本文评估了该模式年代际试验对10年尺度全球及区域地表温度的预测能力, 并通过与20世纪历史气候模拟试验的对比分析, 研究模式模拟对海洋初始观测状态的依赖程度。分析结果表明:(1)在有、无海洋初始化条件下, 模式均能模拟出1960～2005年间全球10年平均实测地表温度的变暖趋势, 但在有海洋初始化条件下, 可以明显减小BCC_CSM1.1模式模拟的全球升温趋势, 使得年代际试验比历史试验的结果更接近观测值。这一特点在观测资料相对丰富的南北纬50°以内地区更为显著。(2)在年代际试验预测前期, 通过Nudging方法, 利用SODA再分析海洋温度资料对模式进行初始化, 经过前期8～12月的协调后, 模式预测的第1年南北纬50°范围海洋、陆面的平均地表气温接近于观测值(CRUTEM3, HadSST2)。由于模式初值SODA再分析SST资料与HadSST2观测值存在明显的全球大洋系统暖偏差以及模式本身系统偏差的影响, 年代际试验模拟的地表气温在2～7年之内, 从观测SST状态逐渐恢复到模式系统本身状态。在同组Decadal试验中, 陆面和海洋恢复调整的时间长度几乎一致。(3) 从10年平均气候异常在区域尺度上的预报技巧来看, 有、无海洋初始同化对预测结果影响不大, 高预测技巧区主要分布在南半球印度洋中高纬度、热带西太平洋以及热带大西洋区域。(4)SST变化与下垫面热通量密切相关, 在热带和副热带海洋区域, 长波辐射和感热通量是影响10年时间尺度SST变化较大的物理量, 在中高纬度海洋, 洋面温度变化主要受潜热通量的影响相对较大。     

Reactions of Cl Atoms with Selected VOCs: Kinetics, Products and Mechanisms

The reactions of isoprene, MBO (2-methyl-3-buten-2-ol) and toluene with chlorine atoms have been studied at 298 ± 5 K and 740 ± 5 Torr with the use of FTIR spectroscopy. Major products of the isoprene-Cl reaction and of the MBO-Cl reaction have been identified and quantified, and reaction mechanisms have been tentatively proposed in order to explain the products formed. The reaction between isoprene and Cl atoms yields mainly HCl, formyl chloride, formic acid, methylglyoxal (pyruvic aldehyde), CO and CO2, while the MBO-Cl reaction forms acetone, HCl, formyl chloride, formic acid, CO, CO2. As products from the reaction between toluene and Cl we identified and quantified HCl and benzaldehyde. The rate constants for the reactions of isoprene and toluene with Cl atoms have also been determined using a relative rate method. The measured values are: kisoprene = (5.5 ± 1.0) × 10–10 cm3 molecule–1 s–1 and ktoluene = (5.6 ± 1.3) × 10–11 cm3 molecule–1 s–1. Atmospheric lifetimes have been estimated from these values.     

Simulations of warm tropical conditions with application to middle Pliocene atmospheres

During the early and mid-Pliocene, the period from 5 to 3 million years ago, approximately, the Earth is believed to have been significantly warmer than it is today, but the reasons for the higher temperatures are unclear. This paper explores the impact of recent findings that suggest that, at that time, cold surface waters were absent from the tropical and subtropical oceanic upwelling zones. El Niño was in effect a perennial rather than intermittent phenomenon, and sea surface temperatures in low latitudes were essentially independent of longitude. When these conditions are specified as the lower boundary condition for an atmospheric GCM, we find that the trade winds along the equator, and hence the Walker Circulation, collapse. The low-level stratus clouds in low latitudes diminish greatly, thus reducing the albedo of the Earth. The atmospheric concentration of water vapor increases, and enhanced latent heat release due to stronger evaporation warms up the tropical atmosphere, particularly between 40°S and 20°N. Moreover, teleconnection patterns from the Pacific induce a warming over North America that is enhanced by surface albedo feedback, a process that may have helped to maintain this region ice-free before 3 Ma. The results presented here indicate that the suggested absence of cold surface waters from the tropical and subtropical oceanic upwelling zones could have contributed significantly to the Pliocene warmth.     

The Production of Methanol by Flowering Plants and the Global Cycle of Methanol

Methanol has been recognised as an important constituent of the background atmosphere, but little is known about its overall cycle in the biosphere/atmosphere system. A model is proposed for the production and emission to the atmosphere of methanol by flowering plants based on plant structure and metabolic properties, particularly the demethylation of pectin in the primary cell walls. This model provides a framework to extend seven sets of measurements of methanol emission rates to the global terrestrial biosphere. A global rate of release of methanol from plants to the atmosphere of 100 Tg y^–1 is calculated. A separate model of the global cycle of methanol is constructed involving emissions from plant growth and decay, atmospheric and oceanic chemical production, biomass burning and industrial production. Removal processes occur through hydroxyl radical attack in the atmosphere, in clouds and oceans, and wet and dry deposition. The model successfully reproduces the methanol concentrations in the continental boundary-layer and the free atmosphere, including the inter-hemispheric gradient in the free atmosphere. The model demonstrates a new concept in global biogeochemistry, the coupling of plant cell growth with the global atmospheric concentration of methanol. The model indicates that the ocean provides a storage reservoir capable of holding at least 66 times more methanol than the atmosphere. The ocean surface layer reservoir essentially buffers the atmospheric concentration of methanol, providing a physically based smoothing mechanism with a time constant of the order of one year.     

Kinetics of the Gas-Phase Reactions of OH and NO3 Radicals and O3 with the Monoterpene Reaction Products Pinonaldehyde, Caronaldehyde, and Sabinaketone

Using a relative rate method, rate constants have been measured for the gas-phase reactions of OH and NO3 radicals with pinonaldehyde, caronaldehyde and sabinaketone at 296 ± 2 K. The OH radical reaction rate constants obtained are (in units of 10–12 cm3 molecule–1 s–1): pinonaldehyde, 48 ± 8; caronaldehyde, 48 ± 8; and sabinaketone, 5.1 ± 1.4, and the NO3 radical reaction rate constants are (in units of 10–14 cm3 molecule–1 s–1): pinonaldehyde, 2.0 ± 0.9; caronaldehyde, 2.5 ± 1.1; and sabinaketone, 0.036 ± 0.023, where the error limits include the estimated overall uncertainties in the rate constants for the reference compounds. Upper limits to the O3 reaction rate constants were also obtained, of <2 × 10–20 cm3 molecule–1 s–1 for pinonaldehyde and caronaldehyde, and <5 × 10–20 cm3 molecule–1 s–1 for sabinaketone. These reaction rate constants are combined with estimated ambient tropospheric concentrations of OH radicals, NO3 radicals and O3 to calculate tropospheric lifetimes and dominant transformation process(es) of these and other monoterpene reaction products.     

A predictability study of simulated North Atlantic multidecadal variability

 The North Atlantic is one of the few places on the globe where the atmosphere is linked to the deep ocean through air–sea interaction. While the internal variability of the atmosphere by itself is only predictable over a period of one to two weeks, climate variations are potentially predictable for much longer periods of months or even years because of coupling with the ocean. This work presents details from the first study to quantify the predictability for simulated multidecadal climate variability over the North Atlantic. The model used for this purpose is the GFDL coupled ocean-atmosphere climate model used extensively for studies of global warming and natural climate variability. This model contains fluctuations of the North Atlantic and high-latitude oceanic circulation with variability concentrated in the 40–60 year range. Oceanic predictability is quantified through analysis of the time-dependent behavior of large-scale empirical orthogonal function (EOF) patterns for the meridional stream function, dynamic topography, 170 m temperature, surface temperature and surface salinity. The results indicate that predictability in the North Atlantic depends on three main physical mechanisms. The first involves the oceanic deep convection in the subpolar region which acts to integrate atmospheric fluctuations, thus providing for a red noise oceanic response as elaborated by Hasselmann. The second involves the large-scale dynamics of the thermohaline circulation, which can cause the oceanic variations to have an oscillatory character on the multidecadal time scale. The third involves nonlocal effects on the North Atlantic arising from periodic anomalous fresh water transport advecting southward from the polar regions in the East Greenland Current. When the multidecadal oscillatory variations of the thermohaline circulation are active, the first and second EOF patterns for the North Atlantic dynamic topography have predictability time scales on the order of 10–20 y, whereas EOF-1 of SST has predictability time scales of 5–7 y. When the thermohaline variability has weak multidecadal power, the Hasselmann mechanism is dominant and the predictability is reduced by at least a factor of two. When the third mechanism is in an extreme phase, the North Atlantic dynamic topography patterns realize a 10–20 year predictability time scale. Additional analysis of SST in the Greenland Sea, in a region associated with the southward propagating fresh water anomalies, indicates the potential for decadal scale predictability for this high latitude region as well. The model calculations also allow insight into regional variations of predictability, which might be useful information for the design of a monitoring system for the North Atlantic. Predictability appears to break down most rapidly in regions of active convection in the high-latitude regions of the North Atlantic. Received: 28 October 1996 / Accepted: 21 March 1997     

Climate sensitivity to tropical land surface changes with coupled versus prescribed SSTs

Tropical land cover change experiments with fixed sea-surface temperatures (SSTs) and with an interactive ocean are compared to assess the relevance of including the ocean system in sensitivity studies to land surface conditions. The results show that the local response to deforestation is similar with fixed and simulated SSTs. Over Amazonia, all experiments simulate a comparable decrease in precipitation and no change in moisture convergence, implying that there is only a change in local water recycling. Over Africa, the impact on precipitation is not identical for all experiments; however, the signal is smaller than over Amazonia and simulations of more than 50 years would be necessary to statistically discriminate the precipitation change. We observe small but significant changes in SSTs in the coupled simulation in the tropical oceans surrounding the deforested regions. Impacts on mid and high latitudes SSTs are also possible. As remote impacts to deforestation are weak, it has not been possible to establish possible oceanic feedbacks to the atmosphere. Overall, this study indicates that the oceanic feedback to land surface sensitivity studies is of second importance, and that the inclusion of the oceanic system will require ensembles of long climate simulations to properly take into account the low frequency variability of the ocean.     

氨基酸离子液体[bmin]Gly的合成探索及表征

探索两步法合成1-丁基-3-甲基咪唑甘氨酸离子液体([bmim]Gly)的反应条件.第一步,采用阴离子树脂静态交换法由1-丁基-3-甲基咪唑溴盐([bmim]Br)与强碱性阴离子树脂生成中间产物1-丁基-3-甲基咪唑氢氧化物([bmim]OH),通过单因素实验获得其最佳交换条件;第二步,[bmim]OH与甘氨酸(Gly)反应,经脱水、洗涤后得目标产物.对产物进行核磁(¹H NMR)和红外(IR)表征,结果表明产品纯度较高.与动态合成法相比,静态法合成[bmim]Gly操作简便,节水省时,有助于实现氨基酸离子液体合成过程的绿色化和工业化.     

The circulation and residence time of the strait of Georgia using a simple mixing‐box approach

Abstract

New observations in the Strait of Georgia, British Columbia, Canada show that temperature and dissolved oxygen have a pronounced seasonal cycle, with a spatially varying phase. Phase lags in oscillating systems arise due to internal time scales which can be interpreted in fluid systems as residence times. Exploiting phase we construct a quantitative and internally consistent circulation scheme for this body of water after dividing it into four regions: the Fraser River plume, the surface waters down to 50 m, the intermediate waters down to 200 m, and the deep water. In this scheme the intermediate water, the largest region by volume, is continually renewed, and its characteristics change in response to continuous changes in the characteristics of source waters. The dependence of the estuarine circulation on variations in fresh inflow is weak. The deep water is volumetrically less important, but seasonal changes in the density of oceanic source waters can produce a variation in the overall circulation by driving an additional inflow which leads to both deep renewal and increased upwelling. In turn, this increased upwelling results in lower surface temperatures than might otherwise be expected. Intermediate water residence times are about 160 days. Deep water is renewed once per year in summer and is affected only by vertical diffusion during the rest of the year. Surface water residence times for the entire Strait are a few months at most, but the Fraser River plume has a freshwater residence time of approximately 1 day. In addition, we find that the residence time of oceanic source waters in the Strait is 1.7 years due to a substantial recirculation in Haro Strait. Other consequences of this scheme are consistent with independent estimates of horizontal transports, air‐sea heat fluxes, subsurface oxygen (O₂) utilization, and primary production. Finally, analysis of the spatial phase variations suggests that the intermediate inflow enters the Strait as a boundary current along the slopes of the Fraser delta.