Electron mean free path from angle-dependent photoelectron spectroscopy of aerosol particles

We propose angle-resolved photoelectron spectroscopy of aerosol particles as an alternative way to determine the electron mean free path of low energy electrons in solid and liquid materials. The mean free path is obtained from fits of simulated photoemission images to experimental ones over a broad range of different aerosol particle sizes. The principal advantage of the aerosol approach is twofold. Firstly, aerosol photoemission studies can be performed for many different materials, including liquids. Secondly, the size-dependent anisotropy of the photoelectrons can be exploited in addition to size-dependent changes in their kinetic energy. These finite size effects depend in different ways on the mean free path and thus provide more information on the mean free path than corresponding liquid jet, thin film, or bulk data. The present contribution is a proof of principle employing a simple model for the photoemission of electrons and preliminary experimental data for potassium chloride aerosol particles

Terrestrial groundwater and nutrient discharge along the 240-km-long Aquitanian coast

We collected samples from sea water, runnel water, beach pore waters, water from the unconfined surficial aquifer discharging at the beach face, groundwater, and rainwater from the Aquitanian coast in order to determine the flux of dissolved inorganic nitrogen (DIN), phosphorus and silica from terrestrial submarine groundwater discharge (SGD). The flux of fresh groundwater was obtained from a water balance calculation based on precipitation and evapotranspiration and assessment of the coastal watershed from hydrograph separation. Waters with intermediate salinities between sea water and freshwaters are found all along the 240-km-long coast, indicating that SGD is ubiquitous. The estimated fresh water flux is 2.25 m3 d− 1 m− 1 longshore. Terrestrial SGD provides a DIN flux of 9·106 mol each year to the adjacent coastal zone. This flux is about four times lower than the release of DIN due to tidally driven saline SGD. The freshwater DIN flux is low because the upland land use consists almost exclusively of pine forest. Dissolved organic nitrogen represents more than 60% of the total dissolved nitrogen flux. Dissolved iron, phosphorus and silica have much higher concentrations in the anoxic forest aquifer than in the fresh-water end-member of the subterranean estuary sampled in the upper beach aquifer. This suggests that the salinity gradient of the estuary does not correspond to a redox gradient. The redox front between anoxic groundwater and fresh oxic waters occurs below the soil-depleted foredune/yellow dune. Anoxic P- and Si-rich waters seep directly on the beach face only in the north Gironde, where the foredunes are eroded. This study reveals the role of the sandy foredune aquifer in biogeochemical fluxes from SGD, which is to dilute and oxidize waters from the unconfined surficial upland aquifer

Atomic and Molecular Opacities for Brown Dwarf and Giant Planet Atmospheres

We present a comprehensive description of the theory and practice of opacity calculations from the infrared to the ultraviolet needed to generate models of the atmospheres of brown dwarfs and extrasolar giant planets. Methods for using existing line lists and spectroscopic databases in disparate formats are presented and plots of the resulting absorptive opacities versus wavelength for the most important molecules and atoms at representative temperature/pressure points are provided. Electronic, ro-vibrational, bound-free, bound-bound, free-free, and collision-induced transitions and monochromatic opacities are derived, discussed, and analyzed. The species addressed include the alkali metals, iron, heavy metal oxides, metal hydrides, $H_2$, $H_2O$, $CH_4$, $CO$, $NH_3$, $H_2S$, $PH_3$, and representative grains. [Abridged]Comment: 28 pages of text, plus 22 figures, accepted to the Astrophysical Journal Supplement Series, replaced with more compact emulateapj versio

Albedo and Reflection Spectra of Extrasolar Giant Planets

We generate theoretical albedo and reflection spectra for a full range of extrasolar giant planet (EGP) models, from Jovian to 51-Pegasi class objects. Our albedo modeling utilizes the latest atomic and molecular cross sections, a Mie theory treatment of extinction by condensates, a variety of particle size distributions, and an extension of the Feautrier radiative transfer method which allows for a general treatment of the scattering phase function. We find that due to qualitative similarities in the compositions and spectra of objects within each of five broad effective temperature ranges, it is natural to establish five representative EGP albedo classes: a ``Jovian'' class (T$_{\rm eff} \lesssim 150$ K; Class I) with tropospheric ammonia clouds, a ``water cloud'' class (T$_{\rm eff} \sim 250$ K; Class II) primarily affected by condensed H$_2$O, a ``clear'' class (T$_{\rm eff} \gtrsim 350$ K; Class III) which lacks clouds, and two high-temperature classes: Class IV (900 K $\lesssim$ T$_{\rm{eff}}$ $\lesssim$ 1500 K) for which alkali metal absorption predominates, and Class V (T$_{\rm{eff}}$ $\gtrsim$ 1500 K and/or low surface gravity ($\lesssim$ 10$^3$ cm s$^{-2}$)) for which a high silicate layer shields a significant fraction of the incident radiation from alkali metal and molecular absorption. The resonance lines of sodium and potassium are expected to be salient features in the reflection spectra of Class III, IV, and V objects. We derive Bond albedos and effective temperatures for the full set of known EGPs and explore the possible effects of non-equilibrium condensed products of photolysis above or within principal cloud decks. As in Jupiter, such species can lower the UV/blue albedo substantially, even if present in relatively small mixing ratios.Comment: revised LaTeX manuscript accepted to Ap.J.; also available at http://jupiter.as.arizona.edu/~burrows/paper

Sources and sinks of dissolved inorganic carbon in an urban tropical coastal bay revealed by delta C-13-DIC signals

Dissolved inorganic carbon (DIC), its stable isotope composition (delta C-13-DIC) and ancillary parameters of the water column were investigated in a eutrophic tropical marine-dominated estuary surrounded by a large urban area (Guanabara Bay, Rio de Janeiro, Brazil). Most negative delta C-13-DIC signatures (down to -6.1 parts per thousand) were found in polluted regions affected by direct sewage discharges where net heterotrophy induces high partial pressure of CO2 (pCO(2)) and DIC concentrations. Keeling plot was applied to this polluted region and determined the delta C-13-DIC sewage signature source of -12.2 parts per thousand, which is very consistent with isotopic signature found in wastewater treatment plans. These negative delta C-13-DIC signatures (i.e., DIC depleted in C-13) were restricted to the vicinity of urban outlets, whereas in the largest area of the bay delta C-13-DIC signatures were more positive (i.e., DIC enriched in C-13). The most positive delta C-13-DIC signatures (up to 4.6 parts per thousand) were found in surface waters dominated by large phytoplankton blooms, with positive correlation with chlorophyll a (Chl a). In the largest area of the bay, the preferential uptake of the lighter stable carbon isotope (C-12) during photosynthesis followed the Rayleigh distillation, and appeared as the most important driver of delta C-13-DIC variations. This reveals an important isotopic fractionation (epsilon) by phytoplankton due to successive algal blooms that has turned the remaining DIC pool enriched with the heavier stable carbon isotope (C-13). The calculated diel apparent epsilon showed higher values in the morning (18.7 parts per thousand-21.6 parts per thousand) and decreasing in the afternoon (6.8 parts per thousand-11.1 parts per thousand). epsilon was positively correlated to the pCO(2) (R-2 = 0.88, p = 0.005) and DIC concentrations (R-2 = 0.73, p = 0.02), suggesting a decline in carbon assimilation efficiency and decreasing uptake of the lighter carbon under CO2 limiting conditions. The eutrophic coastal waters of Guanabara Bay have delta C-13-DIC signatures well above that found in estuaries, shelf and ocean waters worldwide

Hydro-ecological controls on dissolved carbon dynamics in groundwater and export to streams in a temperate pine forest

International audienceWe studied the export of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) from forested shallow groundwater to first-order streams, based on groundwater and surface water sampling and hydrological data. The selected watershed was particularly convenient for such study, with a very low slope, with pine forest growing on sandy permeable podzol and with hydrology occurring exclusively through drainage of shallow groundwater (no surface runoff). A forest plot was instrumented for continuous eddy covariance measurements of precipitation, evapotran-spiration, and net ecosystem exchanges of sensible and latent heat fluxes as well as CO 2 fluxes. Shallow groundwater was sampled with three piezometers located in different plots, and surface waters were sampled in six first-order streams; river discharge and drainage were modeled based on four gauging stations. On a monthly basis and on the plot scale, we found a good consistency between precipitation on the one hand and the sum of evapotranspiration, shallow groundwater storage and drainage on the other hand. DOC and DIC stocks in groundwater and exports to first-order streams varied drastically during the hydrological cycle, in relation with water table depth and amplitude. In the groundwater, DOC concentrations were maximal in winter when the water table reached the superficial organic-rich layer of the soil. In contrast , DIC (in majority excess CO 2) in groundwater showed maximum concentrations at low water table during late summer , concomitant with heterotrophic conditions of the forest plot. Our data also suggest that a large part of the DOC mobilized at high water table was mineralized to DIC during the following months within the groundwater itself. In first-order streams, DOC and DIC followed an opposed seasonal trend similar to groundwater but with lower concentrations. On an annual basis, leaching of carbon to streams occurred as DIC and DOC in similar proportion, but DOC export occurred in majority during short periods of the highest water table, whereas DIC export was more constant throughout the year. Leaching of forest carbon to first-order streams represented a small portion (approximately 2 %) of the net land CO 2 sink at the plot. In addition, approximately 75 % of the DIC exported from groundwater was not found in streams, as it returned very fast to the atmosphere through CO 2 de-gassing

Technical Note: Large overestimation of pCO2 calculated from pH and alkalinity in acidic, organic-rich freshwaters

© 2015 Author(s). Inland waters have been recognized as a significant source of carbon dioxide (CO 2 ) to the atmosphere at the global scale. Fluxes of CO 2 between aquatic systems and the atmosphere are calculated from the gas transfer velocity and the water-air gradient of the partial pressure of CO 2 (pCO 2 ). Currently, direct measurements of water pCO 2 remain scarce in freshwaters, and most published pCO 2 data are calculated from temperature, pH and total alkalinity (TA). Here, we compare calculated (pH and TA) and measured (equilibrator and headspace) water pCO 2 in a large array of temperate and tropical freshwaters. The 761 data points cover a wide range of values for TA (0 to 14 200 μmol L -1 ), pH (3.94 to 9.17), measured pCO 2 (36 to 23 000 ppmv), and dissolved organic carbon (DOC) (29 to 3970 μmol L -1 ). Calculated pCO 2 were >10% higher than measured pCO 2 in 60% of the samples (with a median overestimation of calculated pCO 2 compared to measured pCO 2 of 2560 ppmv) and were >100% higher in the 25% most organic-rich and acidic samples (with a median overestimation of 9080 ppmv). We suggest these large overestimations of calculated pCO 2 with respect to measured pCO 2 are due to the combination of two cumulative effects: (1) a more significant contribution of organic acids anions to TA in waters with low carbonate alkalinity and high DOC concentrations; (2) a lower buffering capacity of the carbonate system at low pH, which increases the sensitivity of calculated pCO 2 to TA in acidic and organic-rich waters. No empirical relationship could be derived from our data set in order to correct calculated pCO 2 for this bias. Owing to the widespread distribution of acidic, organic-rich freshwaters, we conclude that regional and global estimates of CO 2 outgassing from freshwaters based on pH and TA data only are most likely overestimated, although the magnitude of the overestimation needs further quantitative analysis. Direct measurements of pCO 2 are recommended in inland waters in general, and in particular in acidic, poorly buffered freshwaters.status: publishe