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.     

Diurnal variability in turbidity and coral fluorescence on a fringing reef flat: Southern Molokai,Hawaii

Terrigenous sediment in the nearshore environment can pose both acute and chronic stresses to coral reefs. The reef flat off southern Molokai, Hawaii, typically experiences daily turbidity events, in which trade winds and tides combine to resuspend terrigenous sediment and transport it alongshore. These chronic turbidity events could play a role in restricting coral distribution on the reef flat by reducing the light available for photosynthesis. This study describes the effects of these turbidity events on the Hawaiian reef coral Montipora capitata using in situ diurnal measurements of turbidity, light levels, and chlorophyll fluorescence yield via pulse-amplitude-modulated (PAM) fluorometry. Average surface irradiance was similar in the morning and the afternoon, while increased afternoon turbidity resulted in lower subsurface irradiance, higher fluorescence yield (ΔF/F_m^′), and lower relative electron transport rates (rETR). Model calculations based on observed light extinction coeffecients suggest that in the absence of turbidity events, afternoon subsurface irradiances would be 1.43 times higher than observed, resulting in rETR for M. capitata that are 1.40 times higher.     

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.     

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.     

鄱阳湖湿地溶解性有机质的光化学属性对水体光活性中间体(PPRIs)季节性变化的影响

湿地的水文和水化学在时空尺度上会呈现显著差异,进而会引发光化学反应的变化,光活性中间体(PPRIs)是水体间接光反应的产物,具有极强的氧化性,对水环境中有机物和污染物的归驱具有重要的影响,因此迫切需要探究湿地中PPRIs的产生过程。本研究通过捕获剂法监测了鄱阳湖湿地4个季节水体中3种PPRIs(¹O₂、·OH及³CDOM^*)的产生速率和稳态浓度的变化,并通过紫外吸收光谱、三维荧光光谱、以及傅立叶变换离子回旋共振质谱等技术对水体中可溶性有机质(DOM)组分的化学特征进行分析,揭示了鄱阳湖湿地不同季节水体中的DOM的光化学反应特性及与PPRIs产生的相关性。结果发现:鄱阳湖夏季和秋季水体的pH值、溶解有机碳(DOC)浓度较高,相反,硝酸盐、亚硝酸盐浓度在夏季和秋季较低。夏季和秋季的DOM中芳香族化合物丰度较高,并且木质素丰度明显高于冬季和春季。不同季节鄱阳湖水体有色可溶性有机物产生能力依次为秋季>夏季>冬季>春季。夏季和秋季水体中¹O₂和·OH产生速率和稳态浓度显著高于春季和冬季水体。pH、DOC、E2/E3、脂类、蛋白类及木质素类与PPRIs产生速率展现出了良好的正相关关系,尤其是其中的DOC与木质素类组分;另外在三维荧光指标结果中,荧光指数(FI)和新鲜度指数(β/α)与PPRIs呈现负相关关系,证明FI值越低即DOM陆源性越高、非新生DOM比例越高,则PPRIs产生速率越高。综上,PPRIs的光化学产生与植物源DOM密切相关。与春季和冬季相比,夏季和秋季鄱阳湖水体的有机质高,而其中DOM组分中芳香族化合物丰度较高,主要来自陆生植物和土壤有机质,其有机质的腐殖化水平较高,而在春季和冬季水体有机质主要来自湖泊本身和微生物产生的有机质,属于内源。淹水植物残体降解过程释放的有机组分,对夏、秋季DOM的来源和组成有着极易被忽视的影响和作用,而其中光化学活性较强的有机组分如木质素是造成其PPRIs产率更高的主要原因。