Rethinking reactive halogen budgets in the midlatitude lower stratosphere

Current stratospheric models have difficulties in fully explaining the observed midlatitude ozone depletion in the lowermost stratosphere, particularly near the tropopause. Such models assume that only long-lived source gases provide significant contributions to the stratospheric halogen budget, while all the short-lived compounds are removed in the troposphere, the products being rained out. Here we show this assumption to be flawed. Using bromine species as an example, we show that in the lowermost stratosphere, where the observed midlatitude ozone trend maximizes, bromoform (CHBr3) alone likely contributes more inorganic bromine than all the conventional long-lived sources (halons and methyl bromide) combined. Copyright 1999 by the American Geophysical Union

Effects of atmospheric sphericity on stratospheric chemistry and dynamics over Antarctica

Atmospheric sphericity is an important factor that must be considered in order to evaluate an accurate ozone loss rate in the polar stratosphere. The built-in plane-parallel radiative transfer scheme of a nudging chemical transport model (CTM) and an atmospheric general circulation model (AGCM) with coupled chemistry is modified by a pseudospherical approximation. The plane-parallel atmosphere radiative transfer version (PPA version) is compared with the pseudospherical atmosphere radiative transfer version (SA version) for both the nudging CTM and AGCM. The nudging CTM can isolate the chemical effects for a given dynamical field, while the interaction among the chemical, radiative, and dynamical processes can be studied with the AGCM. The present analysis focuses on Antarctica during an ozone hole period. In the ozone loss period over Antarctica, ozone starts to decrease earlier and minimum value of total ozone becomes lower in the SA versions of both the nudging CTM and the AGCM than in the corresponding PPA versions. The ozone mixing ratio decreases earlier in the SA version because of an earlier increase of ClO concentration initiated by the upward actinic flux at solar zenith angles greater than 90°. Dynamics plays an important role as well as the chemical processes. During the ozone recovery period, the ozone distribution becomes almost the same in the SA and PPA versions of the nudging CTM, while in the AGCM the ozone amount in the SA version remains at lower values compared to those of the PPA version. In the AGCM, a decrease of ozone over Antarctica enhances the latitudinal gradient of temperature and thus strengthens the polar vortex in the SA version. A resultant delay of the polar vortex breakup causes the delay of the ozone recovery. For the AGCM, ensemble runs are performed. The ensemble experiment exhibits large ozone variances after the middle of December, when the ozone recovery is dynamically controlled. Most ensemble members of the AGCM show a delay of the polar vortex breakup in the SA version, while a few members show opposite results. In the latter members, the polar vortex breakup is strongly affected by the enhanced EP flux from the troposphere around 100 hPa, which causes the variances in the ozone recovery period. Most members, however, do not show large statistical variances; that justifies the conclusions from the ensemble means

Bromoform and dibromomethane above the Mauritanian upwelling: Atmospheric distributions and oceanic emissions

Natural sources of bromoform (CHBr3) and dibromomethane (CH2Br2), including oceanic emissions, contribute to stratospheric and tropospheric O3 depletion. Convective transport over tropical oceans could deliver large amounts of these short-lived organic bromine species to the upper atmosphere. High mixing ratios of atmospheric CHBr3 in air masses from the northwest African coast have been hypothesized to originate from the biologically active Mauritanian upwelling. During a cruise into the upwelling source region in spring 2005 the atmospheric mixing ratios of the brominated compounds CHBr3 and CH2Br2 were found to be elevated above the marine background and comparable to measurements in other coastal regions. The shelf waters were identified as a source of both compounds for the atmosphere. The calculated sea-to-air emissions support the hypothesis of a strong upwelling source for reactive organic bromine. However, calculated emissions were not sufficient to explain the elevated concentrations observed in the coastal atmosphere. Other strong sources that could contribute to the large atmospheric mixing ratios previously observed over the Atlantic Ocean must exist within or near West Africa

Assimilation of photochemically active species and a case analysis of UARS data

We present a short overview of applications of estimation theory in atmospheric chemistry and discuss some common methods of gridding and mapping of irregular satellite observations of chemical constituents. It is shown that these methods are unable to produce truly synoptic maps of short-lived photochemically active species due to insufficient temporal and spatial density of satellite observations. The only way to overcome this limitation is to supplement observations with prior independent information given, for instance, by atmospheric numerical models and/or climatologies. Objective approaches to combining such prior information with observations are commonly referred to as data assimilation. Mathematical basis of data assimilation known as optimal estimation equations is presented following Lorenc [1986]. Two particular techniques of data assimilation, the variational method and the extended Kalman filter, are briefly described, and their applications to time-dependent numerical photochemical models are discussed. We investigate validity of the linear approximation which is utilized in both methods, present time evolution of the linearization and covariance matrices, and discuss some of their properties. On the basis of ideas of Fisher and Lary [1995] we then employ a trajectory model and a photochemical box model for assimilation and mapping of the Upper Atmosphere Research Satellite (UARS) measurements of chemical species. The assimilation is performed using the variational technique and the extended Kalman filter, and results of bo th methods are presented and discussed

Tropopause and hygropause variability over the equatorial Indian Ocean during February and March 1999.

Measurements of temperature, water vapor, total water, ozone, and cloud properties were made above the western equatorial Indian Ocean in February and March 1999. The cold-point tropopause was at a mean pressure-altitude of 17 km, equivalent to a potential temperature of 380 K, and had a mean temperature of 190 K. Total water mixing ratios at the hygropause varied between 1.4 and 4.1 ppmv. The mean saturation water vapor mixing ratio at the cold point was 3.0 ppmv. This does not accurately represent the mean of the measured total water mixing ratios because the air was unsaturated at the cold point for about 40% of the measurements. As well as unsaturation at the cold point, saturation was observed above the cold point on almost 30% of the profiles. In such profiles the air was saturated with respect to water ice but was free of clouds (i.e., backscatter ratio <2) at potential temperatures more than 5 K above the tropopause and hygropause. Individual profiles show a great deal of variability in the potential temperatures of the cold point and hygropause. We attribute this to short timescale and space-scale perturbations superimposed on the seasonal cycle. There is neither a clear and consistent “setting” of the tropopause and hygropause to the same altitude by dehydration processes nor a clear and consistent separation of tropopause and hygropause by the Brewer-Dobson circulation. Similarly, neither the tropopause nor the hygropause provides a location where conditions consistently approach those implied by a simple “tropopause freeze drying” or “stratospheric fountain” hypothesis

Multimodel projections of stratospheric ozone in the 21st century

Simulations from eleven coupled chemistry-climate models (CCMs) employing nearly identical forcings have been used to project the evolution of stratospheric ozone throughout the 21st century. The model-to-model agreement in projected temperature trends is good, and all CCMs predict continued, global mean cooling of the stratosphere over the next 5 decades, increasing from around 0.25 K/decade at 50 hPa to around 1 K/ decade at 1 hPa under the Intergovernmental Panel on Climate Change (IPCC) Special Report on Emissions Scenarios (SRES) A1B scenario. In general, the simulated ozone evolution is mainly determined by decreases in halogen concentrations and continued cooling of the global stratosphere due to increases in greenhouse gases (GHGs). Column ozone is projected to increase as stratospheric halogen concentrations return to 1980s levels. Because of ozone increases in the middle and upper stratosphere due to GHGinduced cooling, total ozone averaged over midlatitudes, outside the polar regions, and globally, is projected to increase to 1980 values between 2035 and 2050 and before lower stratospheric halogen amounts decrease to 1980 values. In the polar regions the CCMs simulate small temperature trends in the first and second half of the 21st century in midwinter. Differences in stratospheric inorganic chlorine (Cly) among the CCMs are key to diagnosing the intermodel differences in simulated ozone recovery, in particular in the Antarctic. It is found that there are substantial quantitative differences in the simulated Cly, with the October mean Antarctic Cly peak value varying from less than 2 ppb to over 3.5 ppb in the CCMs, and the date at which the Cly returns to 1980 values varying from before 2030 to after 2050. There is a similar variation in the timing of recovery of Antarctic springtime column ozone back to 1980 values. As most models underestimate peak Cly near 2000, ozone recovery in the Antarctic could occur even later, between 2060 and 2070. In the Arctic the column ozone increase in spring does not follow halogen decreases as closely as in the Antarctic, reaching 1980 values before Arctic halogen amounts decrease to 1980 values and before the Antarctic. None of the CCMs predict future large decreases in the Arctic column ozone. By 2100, total column ozone is projected to be substantially above 1980 values in all regions except in the tropics

Deciphering ligand specificity of a Clostridium thermocellum family 35 carbohydrate binding module (CtCBM35) for Gluco- and Galacto- Substituted mannans and Its calcium induced stability

Articles in International JournalsThis study investigated the role of CBM35 from Clostridium thermocellum (CtCBM35) in polysaccharide recognition. CtCBM35 was cloned into pET28a (+) vector with an engineered His6 tag and expressed in Escherichia coli BL21 (DE3) cells. A homogenous 15 kDa protein was purified by immobilized metal ion chromatography (IMAC). Ligand binding analysis of CtCBM35 was carried out by affinity electrophoresis using various soluble ligands. CtCBM35 showed a manno-configured ligand specific binding displaying significant association with konjac glucomannan (Ka = 14.3×104 M−1), carob galactomannan (Ka = 12.4×104 M−1) and negligible association (Ka = 12 µM−1) with insoluble mannan. Binding of CtCBM35 with polysaccharides which was calcium dependent exhibited two fold higher association in presence of 10 mM Ca2+ ion with konjac glucomannan (Ka = 41×104 M−1) and carob galactomannan (Ka = 30×104 M−1). The polysaccharide binding was further investigated by fluorescence spectrophotometric studies. On binding with carob galactomannan and konjac glucomannan the conformation of CtCBM35 changed significantly with regular 21 nm peak shifts towards lower quantum yield. The degree of association (Ka) with konjac glucomannan and carob galactomannan, 14.3×104 M−1 and 11.4×104 M−1, respectively, corroborated the findings from affinity electrophoresis. The association of CtCBM35with konjac glucomannan led to higher free energy of binding (ΔG) −25 kJ mole−1 as compared to carob galactomannan (ΔG) −22 kJ mole−1. On binding CtCBM35 with konjac glucomannan and carob galactomannan the hydrodynamic radius (RH) as analysed by dynamic light scattering (DLS) study, increased to 8 nm and 6 nm, respectively, from 4.25 nm in absence of ligand. The presence of 10 mM Ca2+ ions imparted stiffer orientation of CtCBM35 particles with increased RH of 4.52 nm. Due to such stiffer orientation CtCBM35 became more thermostable and its melting temperature was shifted to 70°C from initial 50°C

A novel a-L-Arabinofuranosidase of Family 43 Glycoside Hydrolase (Ct43Araf ) from Clostridium thermocellum

Articles in International JournalsThe study describes a comparative analysis of biochemical, structural and functional properties of two recombinant derivatives from Clostridium thermocellum ATCC 27405 belonging to family 43 glycoside hydrolase. The family 43 glycoside hydrolase encoding a-L-arabinofuranosidase (Ct43Araf) displayed an N-terminal catalytic module CtGH43 (903 bp) followed by two carbohydrate binding modules CtCBM6A (405 bp) and CtCBM6B (402 bp) towards the C-terminal. Ct43Araf and its truncated derivative CtGH43 were cloned in pET-vectors, expressed in Escherichia coli and functionally characterized. The recombinant proteins displayed molecular sizes of 63 kDa (Ct43Araf) and 34 kDa (CtGH43) on SDS-PAGE analysis. Ct43Araf and CtGH43 showed optimal enzyme activities at pH 5.7 and 5.4 and the optimal temperature for both was 50uC. Ct43Araf and CtGH43 showed maximum activity with rye arabinoxylan 4.7 Umg21 and 5.0 Umg21, respectively, which increased by more than 2-fold in presence of Ca2+ and Mg2+ salts. This indicated that the presence of CBMs (CtCBM6A and CtCBM6B) did not have any effect on the enzyme activity. The thin layer chromatography and high pressure anion exchange chromatography analysis of Ct43Araf hydrolysed arabinoxylans (rye and wheat) and oat spelt xylan confirmed the release of L-arabinose. This is the first report of a-L-arabinofuranosidase from C. thermocellum having the capacity to degrade both pnitrophenol- a-L-arabinofuranoside and p-nitrophenol-a-L-arabinopyranoside. The protein melting curves of Ct43Araf and CtGH43 demonstrated that CtGH43 and CBMs melt independently. The presence of Ca2+ ions imparted thermal stability to both the enzymes. The circular dichroism analysis of CtGH43 showed 48% b-sheets, 49% random coils but only 3% a-helices

Oceanic bromoform sources for the tropical atmosphere

Oceanic bromoform (CHBr3) is the major source of organic Br to the atmosphere and may be significant for ozone depletion through the contribution of reactive bromine to the upper troposphere and lower stratosphere of the midlatitudes and tropics. We report the first analyses of boundary layer air, surface and deep ocean waters from the tropical Atlantic. The data provide evidence of a source of CHBr3 throughout the tropical open ocean associated with the deep chlorophyll maximum within the tropical thermocline. Equatorial upwelling carries the CHBr3 to the surface, adding to increased concentrations in the equatorial mixed layer and driving oceanic emissions that support locally elevated atmospheric concentrations. In air masses that had crossed the coastal upwelling region off NW Africa even higher atmospheric mixing ratios were measured. The observations suggest a link between climate, wind-driven upwelling, and the supply of Br to the upper atmosphere of the tropics