A chemical ionization mass spectrometer for continuous underway shipboard analysis of dimethylsulfide in near-surface seawater

A compact, low-cost atmospheric pressure, chemical ionization mass spectrometer ("mini-CIMS") has been developed for continuous underway shipboard measurements of dimethylsulfide (DMS) in seawater. The instrument was used to analyze DMS in air equilibrated with flowing seawater across a porous Teflon membrane equilibrator. The equilibrated gas stream was diluted with air containing an isotopically-labeled internal standard. DMS is ionized at atmospheric pressure via proton transfer from water vapor, then declustered, mass filtered via quadrupole mass spectrometry, and detected with an electron multiplier. The instrument described here is based on a low-cost residual gas analyzer (Stanford Research Systems), which has been modified for use as a chemical ionization mass spectrometer. The mini-CIMS has a gas phase detection limit of 220 ppt DMS for a 1 min averaging time, which is roughly equivalent to a seawater DMS concentration of 0.1 nM DMS at 20°C. The mini-CIMS has the sensitivity, selectivity, and time response required for underway measurements of surface ocean DMS over the full range of oceanographic conditions. The simple, robust design and relatively low cost of the instrument are intended to facilitate use in process studies and surveys, with potential for long-term deployment on research vessels, ships of opportunity, and large buoys

Air/Sea Transfer of Highly Soluble Gases Over Coastal Waters

The deposition of soluble trace gases to the sea surface is not well studied due to a lack of flux measurements over the ocean. Here we report simultaneous air/sea eddy covariance flux measurements of water vapor, sulfur dioxide (SO2), and momentum from a coastal North Atlantic pier. Gas transfer velocities were on average about 20% lower for SO2 than for H2O. This difference is attributed to the difference in molecular diffusivity between the two molecules (DSO2/DH2O = 0.5), in reasonable agreement with bulk parameterizations in air/sea gas models. This study demonstrates that it is possible to observe the effect of molecular diffusivity on air-side resistance to gas transfer. The slope of observed relationship between gas transfer velocity and friction velocity is slightly smaller than predicted by gas transfer models, possibly due to wind/wave interactions that are unaccounted for in current models

The Dominion Range Ice Core, Queen Maud Mountains, Antarctica - General Site and Core Characteristics with Implications

The Transantarctic Mountains of East Antarctica provide a new milieu for retrieval of ice-core records. We report here on the initial findings from the first of these records, the Dominion Range ice-core record. Sites such as the Dominion Range are valuable for the recovery of records detailing climate change, volcanic activity, and changes in the chemistry of the atmosphere. The unique geographic location of this site and a relatively low accumulation rate combine to provide a relatively long record of change for this potentially sensitive climatic region. As such, information concerning the site and general core characteristics are presented, including ice surface, ice thickness, bore-hole temperature, mean annual net accumulation, crystal size, crystal fabric, oxygen-isotope composition, and examples of ice chemistry and isotopic composition of trapped gases

Aerosol chemical composition and distribution during the Pacific Exploratory Mission (PEM) Tropics

Distributions of aerosol-associated soluble ions over much of the South Pacific were determined by sampling from the NASA DC-8 as part of the Pacific Exploratory Mission (PEM) Tropics campaign. The mixing ratios of all ionic species were surprisingly low throughout the free troposphere (2-12 km), despite the pervasive influence from biomass burning plumes advecting over the South Pacific from the west during PEM-Tropics. At the same time, the specific activity of 7Be frequently exceeded 1000 fCi m-3 through much of the depth of the troposphere. These distributions indicate that the plumes must have been efficiently scavenged by precipitation (removing the soluble ions), but that the scavenging must have occurred far upwind of the DC-8 sampling regions (otherwise 7Be activities would also have been low). This inference is supported by large enhancements of HNO3 and carboxylic acids in many of the plumes, as these soluble acidic gases would also be readily scavenged in any precipitation events. Decreasing mixing ratios of NH4 + with altitude in all South Pacific regions sampled provide support for recent suggestions that oceanic emissions of NH3 constitute a significant source far from continents. Our sampling below 2 km reaffirms the latitudinal pattern in the methylsulfonate/non-sea-salt sulfate (MSA/nss SO4 =) molar ratio established through surface-based and shipboard sampling, with values increasing from \u3c0.05 in the tropics to nearly 0.6 at 70°S. However, we also found very high values of this ratio (0.2-0.5) at 10 km altitude above the intertropical convergence zone near 10°N. It appears that wet convective pumping of dimethylsulfide from the tropical marine boundary layer is responsible for the high values of the MSA/nss SO4 = ratio in the tropical upper troposphere. This finding complicates use of this ratio to infer the zonal origin of biogenic S transported long distances. Copyright 1999 by the American Geophysical Union

On the Hyperbolicity of Lorenz Renormalization

We consider infinitely renormalizable Lorenz maps with real critical exponent $\alpha>1$ and combinatorial type which is monotone and satisfies a long return condition. For these combinatorial types we prove the existence of periodic points of the renormalization operator, and that each map in the limit set of renormalization has an associated unstable manifold. An unstable manifold defines a family of Lorenz maps and we prove that each infinitely renormalizable combinatorial type (satisfying the above conditions) has a unique representative within such a family. We also prove that each infinitely renormalizable map has no wandering intervals and that the closure of the forward orbits of its critical values is a Cantor attractor of measure zero.Comment: 63 pages; 10 figure

Nonlinear rheology of colloidal dispersions

Colloidal dispersions are commonly encountered in everyday life and represent an important class of complex fluid. Of particular significance for many commercial products and industrial processes is the ability to control and manipulate the macroscopic flow response of a dispersion by tuning the microscopic interactions between the constituents. An important step towards attaining this goal is the development of robust theoretical methods for predicting from first-principles the rheology and nonequilibrium microstructure of well defined model systems subject to external flow. In this review we give an overview of some promising theoretical approaches and the phenomena they seek to describe, focusing, for simplicity, on systems for which the colloidal particles interact via strongly repulsive, spherically symmetric interactions. In presenting the various theories, we will consider first low volume fraction systems, for which a number of exact results may be derived, before moving on to consider the intermediate and high volume fraction states which present both the most interesting physics and the most demanding technical challenges. In the high volume fraction regime particular emphasis will be given to the rheology of dynamically arrested states.Comment: Review articl

Earliest land plants created modern levels of atmospheric oxygen

The progressive oxygenation of the Earth’s atmosphere was pivotal to the evolution of life, but the puzzle of when and how atmospheric oxygen (O2) first approached modern levels (~21%) remains unresolved. Redox proxy data indicate the deep oceans were oxygenated during 435-392 Ma, and the appearance of fossil charcoal indicates O2>15-17% by 420-400 Ma. However, existing models have failed to predict oxygenation at this time. Here we show that the earliest plants, which colonized the land surface from ~470 Ma onwards, were responsible for this mid- Paleozoic oxygenation event, through greatly increasing global organic carbon burial – the net long-term source of O2. We use a trait-based ecophysiological model to predict that cryptogamic vegetation cover could have achieved ~30% of today’s global terrestrial net primary productivity by~445 Ma. Data from modern bryophytes suggests this plentiful early plant material had a much higher molar C:P ratio (~2000) than marine biomass (~100), such that a given weathering flux of phosphorus could support more organic carbon burial. Furthermore, recent experiments suggest that early plants selectively increased the flux of phosphorus (relative to alkalinity) weathered from rocks. Combining these effects in a model of long-term biogeochemical cycling, we reproduce a sustained +2‰ increase in the carbonate carbon isotope (δ13C) record by ~445 Ma, and predict a corresponding rise in O2 to present levels by 420-400 Ma, consistent with geochemical data. This oxygen rise represents a permanent shift in regulatory regime to one where fire-mediated negative feedbacks on organic carbon burial stabilise high O2 levels