Revised IR spectrum, radiative efficiency and global warming potential of nitrogen trifluoride

Nitrogen trifluoride (NF3) is an industrial gas used in the semiconductor industry as a plasma etchant and chamber cleaning gas. NF3 is an alternative to other potent greenhouse gases and its usage has increased markedly over the last decade. In recognition of its increased relevance and to aid planning of future usage we report an updated radiative efficiency and global warming potentials for NF3. Laboratory measurements give an integrated absorption cross section of 7.04 x 10(-17) cm(2) molecule(-1) cm(-1) over the spectral region 200 2000 cm(-1). The radiative efficiency is calculated to be 0.21 Wm(-2) ppbv(-1) and the 100 year GWP, relative to carbon dioxide, is 17200. These values are approximately 60% higher than previously published estimates, primarily reflecting the higher infrared absorption cross-sections reported here.

Multidecadal modulation of El Nino-Southern Oscillation (ENSO) variance by Atlantic Ocean sea surface temperatures

Observations suggest a possible link between the Atlantic Multidecadal Oscillation (AMO) and El Nino Southern Oscillation (ENSO) variability, with the warm AMO phase being related to weaker ENSO variability. A coupled ocean-atmosphere model is used to investigate this relationship and to elucidate mechanisms responsible for it. Anomalous sea surface temperatures (SSTs) associated with the positive AMO lead to change in the basic state in the tropical Pacific Ocean. This basic state change is associated with a deepened thermocline and reduced vertical stratification of the equatorial Pacific ocean, which in turn leads to weakened ENSO variability. We suggest a role for an atmospheric bridge that rapidly conveys the influence of the Atlantic Ocean to the tropical Pacific. The results suggest a non-local mechanism for changes in ENSO statistics and imply that anomalous Atlantic ocean SSTs can modulate both mean climate and climate variability over the Pacific.

Cone model-based SEP event calculations for applications to multipoint observations

The problem of modeling solar energetic particle (SEP) events is important to both space weather research and forecasting, and yet it has seen relatively little progress. Most important SEP events are associated with coronal mass ejections (CMEs) that drive coronal and interplanetary shocks. These shocks can continuously produce accelerated particles from the ambient medium to well beyond 1 AU. This paper describes an effort to model real SEP events using a Center for Integrated Space weather Modeling (CISM) MHD solar wind simulation including a cone model of CMEs to initiate the related shocks. In addition to providing observation-inspired shock geometry and characteristics, this MHD simulation describes the time-dependent observer field line connections to the shock source. As a first approximation, we assume a shock jump-parameterized source strength and spectrum, and that scatter-free transport occurs outside of the shock source, thus emphasizing the role the shock evolution plays in determining the modeled SEP event profile. Three halo CME events on May 12, 1997, November 4, 1997 and December 13, 2006 are used to test the modeling approach. While challenges arise in the identification and characterization of the shocks in the MHD model results, this approach illustrates the importance to SEP event modeling of globally simulating the underlying heliospheric event. The results also suggest the potential utility of such a model for forcasting and for interpretation of separated multipoint measurements such as those expected from the STEREO mission.

An event-based approach to validating solar wind speed predictions: high-speed enhancements in the Wang-Sheeley-Arge model

One of the primary goals of the Center for Integrated Space Weather Modeling (CISM) effort is to assess and improve prediction of the solar wind conditions in near‐Earth space, arising from both quasi‐steady and transient structures. We compare 8 years of L1 in situ observations to predictions of the solar wind speed made by the Wang‐Sheeley‐Arge (WSA) empirical model. The mean‐square error (MSE) between the observed and model predictions is used to reach a number of useful conclusions: there is no systematic lag in the WSA predictions, the MSE is found to be highest at solar minimum and lowest during the rise to solar maximum, and the optimal lead time for 1 AU solar wind speed predictions is found to be 3 days. However, MSE is shown to frequently be an inadequate “figure of merit” for assessing solar wind speed predictions. A complementary, event‐based analysis technique is developed in which high‐speed enhancements (HSEs) are systematically selected and associated from observed and model time series. WSA model is validated using comparisons of the number of hit, missed, and false HSEs, along with the timing and speed magnitude errors between the forecasted and observed events. Morphological differences between the different HSE populations are investigated to aid interpretation of the results and improvements to the model. Finally, by defining discrete events in the time series, model predictions from above and below the ecliptic plane can be used to estimate an uncertainty in the predicted HSE arrival times.

The impact of global warming on the tropical Pacific Ocean and El Niño

The El Niño–Southern Oscillation (ENSO) is a naturally occurring fluctuation that originates in the tropical Pacific region and affects ecosystems, agriculture, freshwater supplies, hurricanes and other severe weather events worldwide. Under the influence of global warming, the mean climate of the Pacific region will probably undergo significant changes. The tropical easterly trade winds are expected to weaken; surface ocean temperatures are expected to warm fastest near the equator and more slowly farther away; the equatorial thermocline that marks the transition between the wind-mixed upper ocean and deeper layers is expected to shoal; and the temperature gradients across the thermocline are expected to become steeper. Year-to-year ENSO variability is controlled by a delicate balance of amplifying and damping feedbacks, and one or more of the physical processes that are responsible for determining the characteristics of ENSO will probably be modified by climate change. Therefore, despite considerable progress in our understanding of the impact of climate change on many of the processes that contribute to El Niño variability, it is not yet possible to say whether ENSO activity will be enhanced or damped, or if the frequency of events will change.

A model study of oceanic mechanisms affecting Equatorial Pacific sea surface temperature during the 1997-98 El Niño

In this study, the processes affecting sea surface temperature variability over the 1992–98 period, encompassing the very strong 1997–98 El Niño event, are analyzed. A tropical Pacific Ocean general circulation model, forced by a combination of weekly ERS1–2 and TAO wind stresses, and climatological heat and freshwater fluxes, is first validated against observations. The model reproduces the main features of the tropical Pacific mean state, despite a weaker than observed thermal stratification, a 0.1 m s−1 too strong (weak) South Equatorial Current (North Equatorial Countercurrent), and a slight underestimate of the Equatorial Undercurrent. Good agreement is found between the model dynamic height and TOPEX/Poseidon sea level variability, with correlation/rms differences of 0.80/4.7 cm on average in the 10°N–10°S band. The model sea surface temperature variability is a bit weak, but reproduces the main features of interannual variability during the 1992–98 period. The model compares well with the TAO current variability at the equator, with correlation/rms differences of 0.81/0.23 m s−1 for surface currents. The model therefore reproduces well the observed interannual variability, with wind stress as the only interannually varying forcing. This good agreement with observations provides confidence in the comprehensive three-dimensional circulation and thermal structure of the model. A close examination of mixed layer heat balance is thus undertaken, contrasting the mean seasonal cycle of the 1993–96 period and the 1997–98 El Niño. In the eastern Pacific, cooling by exchanges with the subsurface (vertical advection, mixing, and entrainment), the atmospheric forcing, and the eddies (mainly the tropical instability waves) are the three main contributors to the heat budget. In the central–western Pacific, the zonal advection by low-frequency currents becomes the main contributor. Westerly wind bursts (in December 1996 and March and June 1997) were found to play a decisive role in the onset of the 1997–98 El Niño. They contributed to the early warming in the eastern Pacific because the downwelling Kelvin waves that they excited diminished subsurface cooling there. But it is mainly through eastward advection of the warm pool that they generated temperature anomalies in the central Pacific. The end of El Niño can be linked to the large-scale easterly anomalies that developed in the western Pacific and spread eastward, from the end of 1997 onward. In the far-western Pacific, because of the shallower than normal thermocline, these easterlies cooled the SST by vertical processes. In the central Pacific, easterlies pushed the warm pool back to the west. In the east, they led to a shallower thermocline, which ultimately allowed subsurface cooling to resume and to quickly cool the surface layer.

The effect of ENSO (El Nino Southern Oscillation) on Ashes series results in Australia

An analysis of the results of those "Ashes" cricket test matches between England and Australia which are played in Australia suggests a correlation between these results and the El-Niño Southern Oscillation, or ENSO. In those years with a positive ENSO, results favour Australia, whereas in those years with a negative ENSO, results are more even. A potential mechanism is presented for this apparent correlation.

A new perspective on warming of the global oceans

Changes in ocean circulation associated with internal climate variability have a major influence on upper ocean temperatures, particularly in regions such as the North Atlantic, which are relatively well-observed and therefore over-represented in the observational record. As a result, global estimates of upper ocean heat content can give misleading estimates of the roles of natural and anthropogenic factors in causing oceanic warming. We present a method to quantify ocean warming that filters out the natural internal variability from both observations and climate simulations and better isolates externally forced air-sea heat flux changes. We obtain a much clearer picture of the drivers of oceanic temperature changes, being able to detect the effects of both anthropogenic and volcanic influences simultaneously in the observed record. Our results show that climate models are capable of capturing in remarkable detail the externally forced component of ocean temperature evolution over the last five decades.

Transient teleconnection event at the onset of a planet-encircling dust storm on Mars

We use proper orthogonal decomposition (POD) to study a transient teleconnection event at the onset of the 2001 planet-encircling dust storm on Mars, in terms of empirical orthogonal functions (EOFs). There are several differences between this and previous studies of atmospheric events using EOFs. First, instead of using a single variable such as surface pressure or geopotential height on a given pressure surface, we use a dataset describing the evolution in time of global and fully three-dimensional atmospheric fields such as horizontal velocity and temperature. These fields are produced by assimilating Thermal Emission Spectrometer observations from NASA's Mars Global Surveyor spacecraft into a Mars general circulation model. We use total atmospheric energy (TE) as a physically meaningful quantity which weights the state variables. Second, instead of adopting the EOFs to define teleconnection patterns as planetary-scale correlations that explain a large portion of long time-scale variability, we use EOFs to understand transient processes due to localised heating perturbations that have implications for the atmospheric circulation over distant regions. The localised perturbation is given by anomalous heating due to the enhanced presence of dust around the northern edge of the Hellas Planitia basin on Mars. We show that the localised disturbance is seemingly restricted to a small number (a few tens) of EOFs. These can be classified as low-order, transitional, or high-order EOFs according to the TE amount they explain throughout the event. Despite the global character of the EOFs, they show the capability of accounting for the localised effects of the perturbation via the presence of specific centres of action. We finally discuss possible applications for the study of terrestrial phenomena with similar characteristics.

Atmospheric chemistry of C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH: temperature dependence of the kinetics of their reactions with OH radicals, atmospheric lifetimes and global warming potentials

The atmospheric chemistry of several gases used in industrial applications, C4F9OC2H5 (HFE-7200), C4F9OCH3 (HFE-7100), C3F7OCH3 (HFE-7000) and C3F7CH2OH, has been studied. The discharge flow technique coupled with mass-spectrometric detection has been used to study the kinetics of their reactions with OH radicals as a function of temperature. The infrared spectra of the compounds have also been measured. The following Arrhenius expressions for the reactions were determined (in units of cm3 molecule-1 s-1): k(OH + HFE-7200) = (6.9+2.3-1.7) × 10-11 exp(-(2030 ± 190)/T); k(OH + HFE-7100) = (2.8+3.2-1.5) × 10-11 exp(-(2200 ± 490)/T); k(OH + HFE-7000) = (2.0+1.2-0.7) × 10-11 exp(-(2130 ± 290)/T); and k(OH + C3F7CH2OH) = (1.4+0.3-0.2) × 10-11 exp(-(1460 ± 120)/T). From the infrared spectra, radiative forcing efficiencies were determined and compared with earlier estimates in the literature. These were combined with the kinetic data to estimate 100-year time horizon global warming potentials relative to CO2 of 69, 337, 499 and 36 for HFE-7200, HFE-7100, HFE-7000 and CF3CF2CF2CH2OH, respectively.

Numerical simulation of the 12 May 1997 CME Event: The role of magnetic reconnection

We perform a numerical study of the evolution of a Coronal Mass Ejection (CME) and its interaction with the coronal magnetic field based on the 12 May 1997, CME event using a global MagnetoHydroDynamic (MHD) model for the solar corona. The ambient solar wind steady-state solution is driven by photospheric magnetic field data, while the solar eruption is obtained by superimposing an unstable flux rope onto the steady-state solution. During the initial stage of CME expansion, the core flux rope reconnects with the neighboring field, which facilitates lateral expansion of the CME footprint in the low corona. The flux rope field also reconnects with the oppositely orientated overlying magnetic field in the manner of the breakout model. During this stage of the eruption, the simulated CME rotates counter-clockwise to achieve an orientation that is in agreement with the interplanetary flux rope observed at 1 AU. A significant component of the CME that expands into interplanetary space comprises one of the side lobes created mainly as a result of reconnection with the overlying field. Within 3 hours, reconnection effectively modifies the CME connectivity from the initial condition where both footpoints are rooted in the active region to a situation where one footpoint is displaced into the quiet Sun, at a significant distance (≈1R ) from the original source region. The expansion and rotation due to interaction with the overlying magnetic field stops when the CME reaches the outer edge of the helmet streamer belt, where the field is organized on a global scale. The simulation thus offers a new view of the role reconnection plays in rotating a CME flux rope and transporting its footpoints while preserving its core structure.

Action following the discovery of a global association between the whole genome and adverse event risk in a clinical drug-development programme

Observation of adverse drug reactions during drug development can cause closure of the whole programme. However, if association between the genotype and the risk of an adverse event is discovered, then it might suffice to exclude patients of certain genotypes from future recruitment. Various sequential and non-sequential procedures are available to identify an association between the whole genome, or at least a portion of it, and the incidence of adverse events. In this paper we start with a suspected association between the genotype and the risk of an adverse event and suppose that the genetic subgroups with elevated risk can be identified. Our focus is determination of whether the patients identified as being at risk should be excluded from further studies of the drug. We propose using a utility function to? determine the appropriate action, taking into account the relative costs of suffering an adverse reaction and of failing to alleviate the patient's disease. Two illustrative examples are presented, one comparing patients who suffer from an adverse event with contemporary patients who do not, and the other making use of a reference control group. We also illustrate two classification methods, LASSO and CART, for identifying patients at risk, but we stress that any appropriate classification method could be used in conjunction with the proposed utility function. Our emphasis is on determining the action to take rather than on providing definitive evidence of an association. Copyright (C) 2008 John Wiley & Sons, Ltd.

Perfluorodecalin: global warming potential and first detection in the atmosphere

Perfluorodecalin (C10F18) has a range of medical uses that have led to small releases. Recently, it has been proposed as a carrier of vaccines, which could lead to significantly larger emissions. Since its emissions are controlled under the Kyoto Protocol, it is important that values for the global warming potential (GWP) are available. For a 50:50 mixture of the two isomers of perfluorodecalin, laboratory measurements, supplemented by theoretical calculations, give an integrated absorption cross-section of 3.91 x 10(-16) cm(2) molecule(-1) cm(-1) over the spectral region 0-1500 cm(-1); calculations yield a radiative efficiency of 0.56 W m(-2) ppbv(-1) and a 100-year GWP, relative to carbon dioxide, of 7200 assuming a lifetime of 1000 years. We report the first atmospheric measurements of perfluorodecalin, at Bristol, UK and Mace Head, Ireland, where volume mixing ratios are about 1.5 x 10(-15). At these concentrations, it makes a trivial contribution to climate change, but on a per molecule basis it is a potent greenhouse gas, indicating the need for careful assessment of its possible future usage. (c) 2005 Elsevier Ltd. All rights reserved.