Air-snow exchange of HNO3 and NOy at Summit, Greenland

Ice core records of NO3− deposition to polar glaciers could provide unrivaled information on past photochemical status and N cycling dynamics of the troposphere, if the ice core records could be inverted to yield concentrations of reactive N oxides in the atmosphere at past times. Limited previous investigations at Summit, Greenland, have suggested that this inversion may be difficult, since the levels of HNO3 and aerosol-associated NO3− over the snow are very low in comparison with those of NO3− in the snow. In addition, it appears that some fraction of the NO3− in snow may be reemitted to the atmosphere after deposition. Here we report on extensive measurements of HNO3, including vertical gradients between 1.5 and 7 m above the snow, made during the summers of 1994 and 1995 at Summit. These HNO3 data are compared with NO3− concentrations in surface snow and the first measurements of the concentrations and fluxes of total reactive nitrogen oxides (Ny) on a polar glacier. Our results confirm that HNO3 concentrations are quite low (mean 0.5 nmol m−3) during the summer, while NO3− is the dominant ion in snow. Daytime peaks in HNO3− appear to be due at least partly to emissions from the snow, an assertion supported by gradients indicating a surface source for HNO3− on many days. Observed short-term increases in NO3− inventory in the snow can be too large to be readily attributed to deposition of HNO3− suggesting that deposition of one or more other N oxides must be considered. We found that the apparent fluxes of HNO3 and NOy were in opposite directions during about half the intervals when both were measured, with more cases of HNO3 leaving the snow, against an NOy flux into the snow, than the reverse. The concentrations of NOy are generally about 2 orders of magnitude greater than those of HNO3; hence deposition of only a small, non-HNO3, fraction of this pool could dominate NO3− in snow, if the depositing species converted to NO3−, either in the snowpack or upon melting for analysis

Concentrations and snow-atmosphere fluxes of reactive nitrogen at Summit, Greenland

Concentrations and fluxes of NOy (total reactive nitrogen), ozone concentrations and fluxes of sensible heat, water vapor, and momentum were measured from May 1 to July 20, 1995 at Summit, Greenland. Median NOy concentrations declined from 947 ppt in May to 444 ppt by July. NOy fluxes were observed into and out of the snow, but the magnitudes were usually below 1 μmol m−2 h−1 because of the low HNO3 concentration and weak turbulence over the snow surface. Some of the highest observed fluxes may be due to temporary storage by equilibrium sorption of peroxyacetylnitrate (PAN) or other organic nitrogen species on ice surfaces in the upper snowpack. Sublimation of snow at the surface or during blowing snow events is associated with efflux of NOy from the snowpack. Because the NOy fluxes during summer at Summit are bidirectional and small in magnitude, the net result of turbulent NOyexchange is insignificant compared to the 2 μmol m−2 d−1 mean input from fresh snow during the summer months. If the arctic NOy reservoir is predominantly PAN (or compounds with similar properties), thermal dissociation of this NOy is sufficient to support the observed flux of nitrate in fresh snow. Very low HNO3 concentrations in the surface layer (1% of total NOy) reflect the poor ventilation of the surface layer over the snowpack combined with the relatively rapid uptake of HNO3 by fog, falling snow, and direct deposition to the snowpack

A major regional air pollution event in the northeastern United States caused by extensive forest fires in Quebec, Canada

During early July 2002, wildfires burned ∼1 × 106 ha of forest in Quebec, Canada. The resultant smoke plume was seen in satellite images blanketing the U.S. east coast. Concurrently, extremely high CO mixing ratios were observed at the Atmospheric Investigation, Regional Modeling, Analysis and Prediction (AIRMAP) network sites in New Hampshire and at the Harvard Forest Environmental Measurement Site (HFEMS) in Massachusetts. The CO enhancements were on the order of 525–1025 ppbv above low mixing ratio conditions on surrounding days. A biomass burning source for the event was confirmed by concomitant enhancements in aerosol K+, NH4+, NO3−, and C2O42− mixing ratios at the AIRMAP sites. Additional data for aerosol K, organic carbon, and elemental carbon from the Interagency Monitoring of Protected Visual Environments network and CO data from Environmental Protection Agency sites indicated that the smoke plume impacted much of the U.S. east coast, from Maine to Virginia. CO mixing ratios and K concentrations at stations with 10-year or longer records suggested that this was the largest biomass burning plume to impact the U.S. east coast in over a decade. Furthermore, CO mixing ratios and aerosol particles with diameters 2.5) mass and scattering coefficients from the AIRMAP network and HFEMS indicated that this event was comparable to the large anthropogenic combustion and haze events which intermittently impact rural New England. The degree of enhancement of O3, NOy, NO3−, NH4+, and SO42− in the biomass plume showed significant variation with elevation and latitude that is attributed to variations in transport and surface depositional processes

Consumer Sensitivity to Interest Rates: An Empirical Study of New Car Buyers and Auto Loans

ALTHOUGH it has never been clear whether the consumer needs to be protected from his own folly or from the rapaciousness of those who feed on him, consumer protection is a topic of intense current interest in the courts, in the legislatures, and in the law schools. A number of recent court decisions have attempted to attack problems confronting the consumer; unfortunately, these judicial efforts have succeeded primarily in disclosing the limitations in the courts\u27 ability to deal with such problems. State and federal legislative bodies have pursued more carefully designed remedies. Congress has passed the Truth-in-Lending Act; the National Conference of Commissioners on Uniform State Laws has proposed the Uniform Consumer Credit Code; and many states have enacted retail installment sales acts to update and supplement their long-standing usury laws. These legisJative and judicial acts have always relied, at best, on anecdotal knowledge of consumer behavior. In this Article we offer the results of an empirical study of a small slice of consumer behavior in the use of installment credit

Interannual, seasonal, and diel variation in soil respiration relative to ecosystem respiration at a wetland to upland slope at Harvard Forest

Soil carbon dioxide efflux (soil respiration, SR) was measured with eight autochambers at two locations along a wetland to upland slope at Harvard Forest over a 4 year period, 2003–2007. SR was consistently higher in the upland plots than at the wetland margin during the late summer/early fall. Seasonal and diel hystereses with respect to soil temperatures were of sufficient magnitude to prevent quantification of the influence of soil moisture, although apparent short‐term responses of SR to precipitation occurred. Calculations of annual cumulative SR illustrated a decreasing trend in SR over the 5 year period, which were correlated with decreasing springtime mean soil temperatures. Spring soil temperatures decreased despite rising air temperatures over the same period, possibly as an effect of earlier leaf expansion and shading. The synchronous decrease in spring soil temperatures and SR during regional warming of air temperatures may represent a negative feedback on a warming climate by reducing CO2 production from soils. SR reached a maximum later in the year than total ecosystem respiration (ER) measured at a nearby eddy covariance flux tower, and the seasonality of their temperature response patterns were roughly opposite. SR, particularly in the upland, exceeded ER in the late summer/early fall in each year, suggesting that areas of lower efflux such as the wetland may be significant in the flux tower footprint or that long‐term bias in either estimate may create a mismatch. Annual estimates of ER decreased over the same period and were highly correlated with SR

Characterization of Reactants Reaction Mechanisms and Reaction Products Leading to Extreme Acid Rain and Acid Aerosol Conditions in Southern California

Analyses of fogwater collected by inertial impaction in the Los Angeles basin and the San Joaquin Valley indicated unusually high concentrations of major and minor ions. The dominant ions measured were NO_3^-, SO_4^(2-), NH_4^+ and H^+ Nitrate exceeded sulfate on an equivalent basis by a factor of 2.5 in the central and coastal regions of the Los Angeles basin, but was approximately equal in the eastern Los Angeles basin and the San Joaquin Valley. Maximum observed values for NH_4^+, NO_3^- and SO_4^(2-) were 10., 12., and 5. meq L^(-1), while the lowest pH observed was 2.2. Iron and lead concentrations over 0.1 mM and 0.01 mM, respectively, were observed. High concentrations of chemical components in fog appeared to correlate well with the occurrence of smog events. Concentrations in fogwater were also affected by the physical processes of condensation and evaporation. Light, dissipating fogs routinely showed the highest concentrations. The chemistry of urban fog has been modelled using a hybrid kinetic and equilibrium computer code. Extreme acidity found in Southern California fog may be due either to condensation and growth on acidic condensation nuclei or in situ S(IV) oxidation. Important oxidants of S(IV) were found to be O_2 as catalyzed by Fe(III) and Mn(II), H_2)_2 and 0_3. formation of hydroxymethane sulfonate ion (HMSA) via the nucleophilic addition of HSO_3^-to CH_2 CH_2O(ℓ) significantly increased the droplet capacity for S(IV) but did not slow down the net S(IV) oxidation rate leading to fog acidification. Gas phase nitric acid, ammonia and hydrogen peroxide were scavenged efficiently, although aqueous phase hydrogen peroxide was depleted rapidly by reduction with S(IV). Nitrate production in the aqueous phase was found to be dominated by HNO_3 gas phase scavenging. Major aqueous-phase species concentrations were controlled primarily by condensation, evaporation, and pH

What can tracer observations in the continental boundary layer tell us about surface-atmosphere fluxes?

International audienceWe analyze the potential for inferring spatially resolved surface fluxes from atmospheric tracer observations within the mixed layer, such as from monitoring towers, using a receptor oriented transport model (Stochastic Time-Inverted Lagrangian Transport model ? STILT) coupled to a simple biosphere in which CO2 fluxes are represented as functional responses to environmental drivers (radiation and temperature). Transport and biospheric fluxes are coupled on a dynamic grid using a polar projection with high horizontal resolution (~20 km) in near field, and low resolution far away (as coarse as 2000 km), reducing the number of surface pixels without significant loss of information. To test the system, and to evaluate the errors associated with the retrieval of fluxes from atmospheric observations, a pseudo data experiment was performed. A large number of realizations of measurements (pseudo data) and a priori fluxes were generated, and for each case spatially resolved fluxes were retrieved. Results indicate strong potential for high resolution retrievals based on a network of tall towers, subject to the requirement of correctly specifying the a priori uncertainty covariance, especially the off diagonal elements that control spatial correlations. False assumptions about the degree to which the uncertainties in the a priori fluxes are spatially correlated may lead to a strong underestimation of uncertainties in the retrieved fluxes, or, equivalently, to biased retrievals. The framework presented here, however, allows a conservative choice of the off diagonal elements that avoids biasing the retrievals

Seasonal cycles of isoprene concentrations in the Amazonian rainforest

International audienceTropical forests are an important global source of volatile organic compounds (VOCs) and other atmospheric trace gases. The high biodiversity in tropical rainforests complicates the extrapolation of biogenic volatile organic compound (BVOC) emissions from leaf-level measurements to landscape and regional or global scales. In Amazônia, a significant fraction of the carbon emitted from the biosphere to the atmosphere is emitted in the form of BVOCs, and the knowledge of these emissions is important to our understanding of tropical and global atmospheric chemistry and carbon cycling. As part of the Large scale Biosphere-atmosphere experiment in Amazônia (LBA). VOC concentrations were measured at two sites near Santarém, Para State, Brazil. The two sites are located in the National Forest of Tapajós, the first corresponding to primary forest and the second to a forest, that was selectively logged. The samples were collected simultaneously at heights of 65 and 55 m (20 and 10 m above forest canopy, respectively). The average isoprene mixing ratio was 2.2?2.5 ppb at the two sites and the standard deviations within a site ranged from 1 to 1.2 ppb. A strong seasonality of isoprene mixing ratio was observed and associated with the wet and dry seasons. The lowest mixing ratios were found during the transition between the wet to dry season, while at the start of the biomass burning season the mixing ratios increase. A qualitative analysis of a one dimensional model demonstrates that the seasonal cycle in concentrations reflects changes in isoprene production by the ecosystem, not changes in boundary layer dynamics or chemistry. The magnitude of the cycle indicates that the physiological capacity of the ecosystem to emit isoprene may depend on water availability although phenological changes could also contribute to the observed variations. A simple 1-D model that assumes mean daytime isoprene fluxes of 1.5 mg m?2h?1 and 0.9 mg m?2h?1 scaled by an algorithm depending on precipitation at the primary forest and selectively logged sites, respectively, is able to reproduce the observed vertical gradients

Electron electric dipole moment experiment using electric-field quantized slow cesium atoms

A proof-of-principle electron electric dipole moment (e-EDM) experiment using slow cesium atoms, nulled magnetic fields, and electric field quantization has been performed. With the ambient magnetic fields seen by the atoms reduced to less than 200 pT, an electric field of 6 MV/m lifts the degeneracy between states of unequal mF and, along with the low (approximately 3 m/s) velocity, suppresses the systematic effect from the motional magnetic field. The low velocity and small residual magnetic field have made it possible to induce transitions between states and to perform state preparation, analysis, and detection in regions free of applied static magnetic and electric fields. This experiment demonstrates techniques that may be used to improve the e-EDM limit by two orders of magnitude, but it is not in itself a sensitive e-EDM search, mostly due to limitations of the laser system.Comment: 9 pages, 8 figures, accepted for publication in Phys. Rev.

Formaldehyde, glyoxal, and methylglyoxal in air and cloudwater at a rural mountain site in central Virginia

As part of the Shenandoah Cloud and Photochemistry Experiment (SCAPE), we measured formaldehyde (HCHO), glyoxal (CHOCHO), and methylglyoxal (CH3C(O)CHO) concentrations in air and cloudwater at Pinnacles (elevation 1037 m) in Shenandoah National Park during September 1990. Mean gas‐phase concentrations of HCHO and CHOCHO were 980 and 44 pptv, respectively. The concentration of CH3C(O)CHO rarely exceeded the detection limit of 50 pptv. Mean cloudwater concentrations of HCHO and CHOCHO were 9 and 2 μM, respectively; the mean CH3C(O)CHO concentration was below its detection limit of 0.3 μM. The maximum carbonyl concentrations were observed during stagnation events with high O3, peroxides, and CO. Outside of these events the carbonyls did not correlate significantly with O3, CO, or NOy. Carbonyl concentrations and concentration ratios were consistent with a major source for the carbonyls from isoprene oxidation. Oxidation of CH4 supplies a significant background of HCHO. The carbonyl concentrations were indistinguishable in two size fractions of cloudwater having a cut at d=18 μm. Gas‐ and aqueous‐phase concentrations of HCHO from samples collected during a nighttime cloud event agree with thermodynamic equilibria within a factor of 2. Samples collected during a daytime cloud event show HCHO supersaturation by up to a factor of 4. Positive artifacts in the cloudwater samples due to hydrolysis of hydroxymethylhydroperoxide (HOCH2OOH) could perhaps account for this discrepancy