David S. Sayres

Bio: David S. Sayres is an academic researcher from Harvard University. The author has contributed to research in topics: Water vapor & Stratosphere. The author has an hindex of 19, co-authored 42 publications receiving 1568 citations.

Process-evaluation of tropospheric humidity simulated by general circulation models using water vapor isotopologues: 1. Comparison between models and observations

Abstract: The goal of this study is to determine how H2O and HDO measurements in water vapor can be used to detect and diagnose biases in the representation of processes controlling tropospheric humidity in atmospheric general circulation models (GCMs). We analyze a large number of isotopic data sets (four satellite, sixteen ground-based remote-sensing, five surface in situ and three aircraft data sets) that are sensitive to different altitudes throughout the free troposphere. Despite significant differences between data sets, we identify some observed HDO/H2O characteristics that are robust across data sets and that can be used to evaluate models. We evaluate the isotopic GCM LMDZ, accounting for the effects of spatiotemporal sampling and instrument sensitivity. We find that LMDZ reproduces the spatial patterns in the lower and mid troposphere remarkably well. However, it underestimates the amplitude of seasonal variations in isotopic composition at all levels in the subtropics and in midlatitudes, and this bias is consistent across all data sets. LMDZ also underestimates the observed meridional isotopic gradient and the contrast between dry and convective tropical regions compared to satellite data sets. Comparison with six other isotope-enabled GCMs from the SWING2 project shows that biases exhibited by LMDZ are common to all models. The SWING2 GCMs show a very large spread in isotopic behavior that is not obviously related to that of humidity, suggesting water vapor isotopic measurements could be used to expose model shortcomings. In a companion paper, the isotopic differences between models are interpreted in terms of biases in the representation of processes controlling humidity. Copyright © 2012 by the American Geophysical Union.

UV Dosage Levels in Summer: Increased Risk of Ozone Loss from Convectively Injected Water Vapor

Abstract: The observed presence of water vapor convectively injected deep into the stratosphere over the United States can fundamentally change the catalytic chlorine/bromine free-radical chemistry of the lower stratosphere by shifting total available inorganic chlorine into the catalytically active free-radical form, ClO. This chemical shift markedly affects total ozone loss rates and makes the catalytic system extraordinarily sensitive to convective injection into the mid-latitude lower stratosphere in summer. Were the intensity and frequency of convective injection to increase as a result of climate forcing by the continued addition of CO2 and CH4 to the atmosphere, increased risk of ozone loss and associated increases in ultraviolet dosage would follow.

Observations of deep convective influence on stratospheric water vapor and its isotopic composition

Abstract: [1] In situ observations of H2O and HDO in the midlatitude stratosphere are used to evaluate the role of convection in determining the stratospheric water budget. The observations show that water vapor in the overworld stratosphere (potential temperature > 380 K) is isotopically heavier than expected. Measurements in an airmass with anomalously high concentrations of water vapor show isotopic water signatures that are characteristic of evaporated ice lofted from the troposphere during convective storms. Observed H2O and HDO concentrations in the plume of enhanced water and in the background stratosphere suggest that extratropical convection can account for a significant fraction of the observed water vapor in the summertime overworld stratosphere above the mid-North American continent.

Ice supersaturations exceeding 100% at the cold tropical tropopause: implications for cirrus formation and dehydration

Abstract: Recent in situ measurements at tropical tropopause temperatures as low as 187 K indicate supersaturations with respect to ice exceeding 100% with little or no ice present. In contrast, models used to simulate cloud formation near the tropopause assume a supersaturation threshold for ice nucleation of about 65% based on laboratory measurements of aqueous aerosol freezing. The high supersaturations reported here, along with cloud simulations assuming a plausible range of temperature histories in the sampled air mass, indicate that the vast majority of aerosols in the air sampled on this flight must have had supersaturation thresholds for ice nucleation exceeding 100% (i.e. near liquid water saturation at these temperatures). Possible explanations for this high threshold are that (1) the expressions used for calculating vapor pressure over supercooled water at low temperatures give values are at least 20% too low, (2) organic films on the aerosol surfaces reduce their accommodation coefficient for uptake of water, resulting in aerosols with more concentrated solutions when moderate-rapid cooling occurs and correspondingly inhibited homogeneous freezing, and (3) if surface freezing dominates, organic coatings may increase the surface energy of the ice embryo/vapor interface resulting in suppressed ice nucleation. Simulations of in situ cloud formation in the tropical tropopause layer (TTL) throughout the tropics indicate that if decreased accommodation coefficients and resulting high thresholds for ice nucleation prevailed throughout the tropics, then the calculated occurrence frequency and areal coverage of TTL cirrus would be significantly suppressed. However, the simulations also show that even if in situ TTL cirrus form only over a very small fraction of the tropics in the western Pacific, enough air passes through them due to rapid horizontal transport such that they can still effectively freeze-dry air entering the stratosphere. The TTL cirrus simulations show that even if very large supersaturations are required for ice nucleation, these large supersaturations should occur very rarely.

Design considerations in high-sensitivity off-axis integrated cavity output spectroscopy

Abstract: Off-axis integrated cavity output spectroscopy (OA-ICOS) has generated much interest because it potentially allows highly sensitive field measurements with robust optical alignment. We discuss here design choices involved in design of an OA-ICOS instrument and how these choices impact instrument sensitivity, using as our example the design of the Harvard ICOS isotope instrument, which demonstrates the highest reported sensitivity for mid-IR OA-ICOS (2.4×10-11 cm-1Hz-1/2 at 6.7 μm, obtained during measurements of water vapor isotopologues H2O, HDO, and H2 18O in the laboratory and onboard NASA’s WB-57 high-altitude research aircraft). We compare the sensitivity of several OA-ICOS instruments with differing design parameters, show how comparisons are hindered by differing definitions of instrument performance metrics, and suggest a common metric of MDAmeas, the fractional absorption equivalent to 1σ uncertainty in an actual measurement, normalized to 1 s integration. We also note that despite an emphasis on sensitivity in the literature, in the Harvard ICOS isotope instrument and likely also similar instruments, systematic errors associated with fitting of the baseline laser power are of equal importance to total measurement uncertainty.

The formation, properties and impact of secondary organic aerosol: current and emerging issues

Abstract: Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

Atmospheric aerosols: composition, transformation, climate and health effects.

Abstract: Aerosols are of central importance for atmospheric chemistry and physics, the biosphere, climate, and public health. The airborne solid and liquid particles in the nanometer to micrometer size range influence the energy balance of the Earth, the hydrological cycle, atmospheric circulation, and the abundance of greenhouse and reactive trace gases. Moreover, they play important roles in the reproduction of biological organisms and can cause or enhance diseases. The primary parameters that determine the environmental and health effects of aerosol particles are their concentration, size, structure, and chemical composition. These parameters, however, are spatially and temporally highly variable. The quantification and identification of biological particles and carbonaceous components of fine particulate matter in the air (organic compounds and black or elemental carbon, respectively) represent demanding analytical challenges. This Review outlines the current state of knowledge, major open questions, and research perspectives on the properties and interactions of atmospheric aerosols and their effects on climate and human health.

Optical gas sensing: a review

Abstract: The detection and measurement of gas concentrations using the characteristic optical absorption of the gas species is important for both understanding and monitoring a variety of phenomena from industrial processes to environmental change. This study reviews the field, covering several individual gas detection techniques including non-dispersive infrared, spectrophotometry, tunable diode laser spectroscopy and photoacoustic spectroscopy. We present the basis for each technique, recent developments in methods and performance limitations. The technology available to support this field, in terms of key components such as light sources and gas cells, has advanced rapidly in recent years and we discuss these new developments. Finally, we present a performance comparison of different techniques, taking data reported over the preceding decade, and draw conclusions from this benchmarking.

Tropical tropopause layer

Abstract: [1] Observations of temperature, winds, and atmospheric trace gases suggest that the transition from troposphere to stratosphere occurs in a layer, rather than at a sharp “tropopause.” In the tropics, this layer is often called the “tropical tropopause layer” (TTL). We present an overview of observations in the TTL and discuss the radiative, dynamical, and chemical processes that lead to its time-varying, three-dimensional structure. We present a synthesis definition with a bottom at 150 hPa, 355 K, 14 km (pressure, potential temperature, and altitude) and a top at 70 hPa, 425 K, 18.5 km. Laterally, the TTL is bounded by the position of the subtropical jets. We highlight recent progress in understanding of the TTL but emphasize that a number of processes, notably deep, possibly overshooting convection, remain not well understood. The TTL acts in many ways as a “gate” to the stratosphere, and understanding all relevant processes is of great importance for reliable predictions of future stratospheric ozone and climate.