Quantum yield for the photochemical production of dissolved inorganic carbon in seawater

The direct photooxidation of coloured dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) may provide a significant sink for organic carbon in the ocean. To calculate the rate of this reaction on a global scale, it is essential to know its quantum yield, or photochemical efficiency. We have determined quantum yield spectra, φ(λ), (moles DIC/mole photons absorbed) for 14 samples of seawater from environments ranging from a turbid, eutrophic bay to the Gulf Stream. The spectra vary among locations, but can be represented quite well by three pooled spectra for zones defined by location and salinity: inshore φ(λ)=e^{−(6.66+0.0285(λ−290))}; coastal φ(λ)=e^{−(6.36+0.0140(λ−290))}; and open ocean φ(λ)=e^{−(5.53+0.00914(λ−290))}. Production efficiency increases offshore, which suggests that the most highly absorbing and quickly faded terrestrial chromophores are not those directly responsible for DIC photoproduction.     

Amino acid nitrogen in atmospheric aerosols: Occurrence,sources and photochemical modification

The presence of amino acids in atmospheric precipitation and aerosols has been noted for many years, yet relatively little is known about these or other nitrogen containing organic compounds in the atmosphere. Marine and continental rainwater analyses indicate that atmospheric aerosols, and subsequently atmospheric precipitation, may contain substantial levels of free and combined amino acids. The most likely source of amino N in the remote marine atmosphere appears to be the injection of proteinaceous material through the action of bursting bubbles at the sea-air interface or the long range transport from terrestrial sources. The capacity of these substrates to undergo photooxidation and photodegradation in the atmosphere to simpler species, such as ammonium ions, carboxylic acids, and for the S containing amino acids, oxidized forms of sulfur, has received little attention from atmospheric chemists. The photochemistry of covalently bound amino groups, particularly as found in peptides and amino acids, is discussed here with the purpose of summarizing what is known of their occurrence and their possible importance to atmospheric chemistry.     

The role of clouds in tropospheric photochemistry

We show that photochemical processes in the lower half of the troposphere are strongly affected by the presence of liquid water clouds. Especially CH₂O, an important intermediate of CH₄ (and of other hydrocarbon) oxidation, is subject to enhanced breakdown in the aqueous phase. This reduces the formation of HO _x -radicals via photodissociation of CH₂O in the gas phase. In the droplets, the hydrated form of CH₂O, its oxidation product HCO₂ ^–, and H₂O₂ recycle O₂ ^– radicals which, in turn, react with ozone. We show that the latter reaction is a significant sink for O₃. Further O₃ concentrations are reduced as a result of decreased formation of O₃ during periods with clouds. Additionally, NO _x , which acts as a catalyst in the photochemical formation of O₃, is depleted by clouds during the night via scavenging of N₂O₅. This significantly reduces NO _x -concentrations during subsequent daylight hours, so that less NO _x is available for O₃ production. Clouds thus directly reduce the concentrations of O₃, CH₂O, NO _x , and HO _x . Indirectly, this also affects the budgets of other trace gases, such as H₂O₂, CO, and H₂.     

Measurement of the photodissociation coefficient of NO2 in the atmosphere: II,stratospheric measurements

The photodissociation coefficient of NO₂, J _{NO 2}, has been measured from a balloon platform in the stratosphere. Results from two balloon flights are reported. High Sun values of J _{NO 2} measured were 10.5±0.3 and 10.3±0.3×10^-3 s^-1 at 24 and 32 km respectively. The decrease in J _{NO 2} at sunset was monitored in both flights. The measurements are found to be in good agreement with calculations of J _{NO 2} using a simplified isotropic multiple scattering computer routine.     

A study of ozone in the Colorado mountains

The seasonal and diurnal variations of ozone mixing ratios have been observed at Niwot Ridge. Colorado. The ozone mixing ratios have been correlated with the NO _x (NO+NO₂) mixing ratios measured concurrently at the site. The seasonal and diurnal variations in O₃ can be reasonably well understood by considering photochemistry and transport. In the winter there is no apparent systematic diurnal variation in the O₃ mixing ratio because there is little diurnal change of transport and a slow photochemistry. In the summer, the O₃ levels at the site are suppressed at night due to the presence of a nocturnal inversion layer that isolated ozone near the surface, where it is destroyed. Ozone is observed to increase in the summer during the day. The increases in ozone correlate with increasing NO _x levels, as well as with the levels of other compounds of anthropogenic origin. We interpret this correlation as in-situ or in-transit photochemical production of ozone from these precursors that are transported to our site. The levels of ozone recorded approach 100 ppbv at NO _x mixing ratios of approximately 3 ppbv. Calculations made using a simple clean tropospheric chemical model are consistent with the NO _x -related trend observed for the daytime ozone mixing ratio. However, the chemistry, which does not include nonmethane hydrocarbon photochemistry, underestimates the observed O₃ production.     

The action of chlorine on the ozone layer as given by a zonally averaged two-dimensional model

In order to study the behavior of stratospheric minor constituents related to aeronomic processes and atmospheric transport in the meridional plane, a numerical two-dimensional model is established.This model is applied to the study of chlorine compounds in the stratosphere. A special attention is devoted to the effect in the ozonosphere of an increase of CIX due to anthropogenic activities.     

A two-dimensional photochemical model of the stratosphere with Rayleigh scattering

Computations of concentrations of minor stratospheric gases using a two-dimensional model of the stratosphere are reported. The model includes Rayleigh scattering. This results in an increase in the photodissociation rate computation time by a factor of 1.5. The effect of ground albedo is assessed by comparing our results with a calculation of photolysis rates for a constant albedo with latitude. Comparison of results with a reference model including only molecular absorption are also made. The largest differences (50%) occur in NO and OH. An approximate expression for including the effects of Rayleigh scattering and surface reflectance in multi-dimensional models is suggested.     

UV Photopolarimetric Imaging of C/1995 O1 (Hale-Bopp) with the Wide Field Imaging Survey Polarimeter (WISP)

We report on the reduction and analysis of UVpolarimetric images of CI (λ1657 Å) and dust continuum (2696 Å emissions from C/1995 O1 (Hale-Bopp) taken using the Wide Field Imaging Survey Polarimeter (WISP) sounding rocket on 8 April, 1997. These observations represent the first imaging polarimetry of comets in the UV, and were performed in consort with ground based measurements of gas and dust polarization and distribution. The continuum results show 9% polarization across the image field with a polarization phase angle close to the 129° prediction. Comparison with ground based data implies minimal color dependence for Hale-Bopp in either the degree of polarization and in the position angle. The carbon polarimetry implies that most production occurs in the dense inner coma, and that it leaves that area in thermodynamic equilibrium. Its radial profile further constrains the carbon outflow speed to be sufficient to travel ≥5 × 10⁶ km without photoionization.