Abstract. HONO formation has been proposed as an important OH radical source in simulation chambers for more than two decades. Besides the heterogeneous HONO formation by the dark reaction of NO 2 and adsorbed water, a photolytic source has been proposed to explain the elevated reactivity in simulation chamber experiments. However, the mechanism of the photolytic process is not well understood so far. As expected, production of HONO and NO x was also observed inside the new atmospheric simulation chamber SAPHIR under solar irradiation. This photolytic HONO and NO x formation was studied with a sensitive HONO instrument under reproducible controlled conditions at atmospheric concentrations of other trace gases. It is shown that the photolytic HONO source in the SAPHIR chamber is not caused by NO 2 reactions and that it is the only direct NO y source under illuminated conditions. In addition, the photolysis of nitrate which was recently postulated for the observed photolytic HONO formation on snow, ground, and glass surfaces, can be excluded in the chamber. A photolytic HONO source at the surface of the chamber is proposed which is strongly dependent on humidity, on light intensity, and on temperature. An empirical function describes these dependencies and reproduces the observed HONO formation rates to within 10 %. It is shown that the photolysis of HONO represents the dominant radical source in the SAPHIR chamber for typical tropospheric O 3 /H 2 O concentrations. For these conditions, the HONO concentrations inside SAPHIR are similar to recent observations in ambient air.
Abstract. The influence of chemical precursors and sunlight on the atmospheric OH abundance is investigated by a comparison of locally measured tropospheric OH with model calculations. The latter are based on the gas phase reaction mechanism of the regional acid deposition model (RADM2) which incorporates an explicit inorganic and a comprehensive organic chemistry. The experimental data were obtained in the planetary boundary layer during two sets of campaigns. In Deuselbach (1983) and Schauinsland (1984), rural conditions were encountered with NOx concentrations on the average of 2.2 and 0.9 ppb, respectively. This data set was already compared with model calculations based upon an older and less detailed chemical reaction scheme (Perner et al., 1987). Since then the experimental data were reanalyzed leading to modified measured OH concentrations and also to modified precursor concentrations.
Over 7.8 meters of seafloor subsidence has occurred at the Ekofisk Field in the Norwegian sector of the North Sea since the start of production in 1971. Full field water injection was initiated at Ekofisk on a limited scale in 1987. The surface subsidence is a result of reservoir compaction, which is considered primarily to be due to pressure depletion until the early 1990's and water weakening thereafter. Rock compressibility was input as a function of initial porosity and increasing net effective stress (i.e. declining reservoir pressure) in earlier Ekofisk studies. In 1994, under a voidage balancing reservoir management program, water injection was increased sufficiently to stabilize reservoir pressure. However, no reduction in surface subsidence rate was seen. This, in combination with other field and lab observations, led to the conclusion that water was weakening the reservoir chalk and necessitated revising the rock compressibility functions at Ekofisk to include the effect of additional compaction due to the water weakening. The development and implementation of the water induced compaction functions at Ekofisk is presented in this paper. Rock compressibility is now input into the model as a function of initial porosity, net effective stress, and water saturation. As water saturation increases in a model cell due to water injection or water influx, the model cell transitions to a weaker stress-strain curve. The effect of increasing water saturation, and the resulting water weakening of the chalk, is that compaction and subsidence may continue in spite of stable or increasing reservoir pressure. Both laboratory and field data are presented which support the use of the water weakening functions. The development and calibration of these curves is presented, which includes the effects of fracturing, creep, water dispersion effects, hysteresis logic, and strain hardening. A comparison of the calculated and measured compaction and subsidence bowls is also presented.
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