Photochemistry in the Arctic Free Troposphere: Ozone Budget and Its Dependence on Nitrogen Oxides and the Production Rate of Free Radicals

Local ozone production and loss rates for the arctic free troposphere (58–85° N, 1–6 km, February–May) during the TroposphericOzone Production about the Spring Equinox (TOPSE) campaign were calculated using a constrained photochemical box model. Estimates were made to assess the importance of local photochemical ozone production relative to transport in accounting for the springtime maximum in arctic free tropospheric ozone. Ozone production and loss rates from our diel steady-state box model constrained by median observations were first compared to two point box models, one run to instantaneous steady-state and the other run to diel steady-state. A consistent picture of local ozone photochemistry was derived by all three box models suggesting that differences between the approaches were not critical. Our model-derived ozone production rates increased by a factor of 28 in the 1–3 km layer and a factor of 7 in the 3–6 kmlayer between February and May. The arctic ozone budget required net import of ozone into the arctic free troposphere throughout the campaign; however, the transport term exceeded the photochemical production only in the lower free troposphere (1–3 km) between February and March. Gross ozone production rates were calculated to increase linearly with NO_x mixing ratiosup to 300 pptv in February and for NO_x mixing ratios up to 500 pptv in May. These NO_x limits are an order of magnitude higher thanmedian NO_x levels observed, illustrating the strong dependence ofgross ozone production rates on NO_x mixing ratios for the majority of theobservations. The threshold NO_x mixing ratio needed for netpositive ozone production was also calculated to increase from NO_x 10pptv in February to 25 pptv in May, suggesting that the NO_x levels needed to sustain net ozone production are lower in winter than spring. This lower NO_x threshold explains how wintertime photochemical ozone production can impact the build-up of ozone over winter and early spring. There is also an altitude dependence as the threshold NO_x neededto produce net ozone shifts to higher values at lower altitudes. This partly explains the calculation of net ozone destruction for the 1–3 km layerand net ozone production for the 3–6 km layer throughout the campaign.     

On the Role of Lightning NOx in the Formation of Tropospheric Ozone Plumes: A Global Model Perspective

A series of ozone transects measured each year from 1987 to 1990 over thewestern Pacific and eastern Indian oceans between mid-November andmid-Decembershows a prominent ozone maximum reaching 50–80 ppbv between 5 and 10 kmin the 20° S–40° S latitude band. This maximum contrasts with ozonemixing ratios lower than20 ppbv measured at the same altitudes in equatorial regions. Analyses witha globalchemical transport model suggest that these elevated ozone values are part ofa large-scale tropospheric ozone plume extending from Africa to the western Pacific acrosstheIndian ocean. These plumes occur several months after the peak in biomassburninginfluence and during a period of high lightning activity in the SouthernHemispheretropical belt. The composition and geographical extent of these plumes aresimilar to theozone layers previously encountered during the biomass burning season in thisregion.Our model results suggest that production of nitrogen oxides from lightningstrokes sustains the NO_x (= NO+NO₂) levels and the ozonephotochemical productionrequired in the upper troposphere to form these persistent elevated ozonelayers emanating from biomass burning regions.     

Active Nitrogen in Surface Ozone Depletion Events at Alert during Spring 1998

Measurements of NO_x,y were made at Alert, Nunavut, Canada (82.5° N, 62.3° W) during surface layer ozone depletion events. In spring 1998, depletion events were rare and occurred under variable actinic flux, ice fog, and snowfall conditions. NO_y changed by less than 10% between normal, partially depleted, and nearly completely depleted ozone air masses. The observation of a diurnal variation in NO_x under continuous sunlight supports a source from the snowpack but with rapid conversion to nitrogen reservoirs that are primarily deposited to the surface or airborne ice crystals. It was unclear whether NO_x was reduced or enhanced in different stages of the ozone depletion chemistry because of variations in solar and ambient conditions. Because ozone was depleted from 15–20 ppbv to less than 1 ppbv in just over a day in one event it is apparent that the surface source of NO_x did not grossly inhibit the removal of ozone. In another case ozone was shown to be destroyed to less than the 0.5 ppbv detection limit of the instrument. However, simple model calculations show that the rate of depletion of ozone and its final steady-state abundance depend sensitively on the strength of the surface source of NO_x due to competition from ozone production involving NO_x and peroxy radicals. The behavior of the NO/NO₂ ratio was qualitatively consistent with enhanced BrO during the period of active ozone destruction. The model is also used to emphasize that the diurnal partitioning of BrO_x during ozone depletion events is sensitive to even sub ppbv variations in O₃.     

The crystallisation trends of spinels in tertiary basalts from Rhum and Muck and their petrogenetic significance

Spinels are commonly observed in alkali olivine basalts and olivine basalts that form the Plateau Magma Series of the British Tertiary Province. The spinels are either partly or wholly enclosed within olivine or may have adhered to olivine surfaces, and have undergone cation exchange and reaction with the cooling basaltic melt. Detailed microprobe traverses indicate complex exchanges involving Fe-Mg, Cr-Al, Fe³⁺-R³⁺ and Fe²⁺ Ti-R³⁺ substitutions. Some of these changes are due to a reaction with liquid that produced plagioclase and resulted in Al depletion in the spinel. A complex series of solid solutions between hercynite-magnesioferrite-chromite and Al-Cr-titomomagnetite, is indicated in a combination that precludes the disappearance of spinel by a simple peritetic reaction with the melt. The initial spinels are compositionally distinct from the chromites found in the Rhum layered series and underline the great compositional variability of liquidus spinels that can crystallise from basaltic liquid. Some of this variability may relate to the changing solubility of Cr, which behaves as a trace element, in basaltic liquids in response to slight changes in the structure of the melt.LDGO Contribution no. 2575     

The variability of chemical analyses as a function of sample heterogeneity,and the implications to the analyses of rock standards

The errors in the chemical analyses of a granodiorite rock powder for 6 constituents (K ₂O, Na₂O, CaO,∑Fe₂O₃, MgO, and MnO) have been determined by replicate analyses of the whole rock and of a series of different sieved fractions. Sample inhomogeneity is indicated. This is confirmed by analyses of the fused rock powder. Fusion to a glass is therefore recommended for the preparation of geochemical rock standards.     

Meso-scale surface wind changes associated with the passage of cold fronts along the eastern side of the Southern Alps,New Zealand

Summary The movement of cold fronts along the eastern side of the Southern Alps has been studied in detail during the Southerly Change Experiment (SOUCHEX). An enhanced network of surface wind monitoring stations was established in the Canterbury region of the South Island to allow detailed study of meso-scale wind fields during the passage of fronts. Fivesoutherly changes occurred during the experiment, one of which failed to produce a clear wind change over much of the area. The often erratic movement of these fronts along the eastern side of the mountains is illustrated by isochrone maps of the onset of the wind change. Other general characteristics of these events include their shallowness (1000–1500 m deep) and in most cases their abrupt onset. Detailed analysis of anemograph data collected during SOUCHEX indicates great variability in the surface wind field associated with passage of the fronts. Maps of the meso-scale wind field plotted for the first southerly change of the 14 January 1988 illustrate the complexity of the wind changes experienced over the eastern South Island in particular. The arrival of the cold fronts at individual sites provided features of air mass interaction which appear to relate to time of day, and regional and local site factors. Variations, in wind, temperature and relative humidity provide clear examples of both single and double air mass changes. However, nocturnal changes seem to be less distinct due to lower ambient temperatures and increased boundary layer stability.With 9 Figures     

Petrologic constraints on rift-zone processes

The Puu Oo eruption in the middle of Kilauea volcano's east rift zone provides an excellent opportunity to utilize petrologic constraints to interpret rift-zone processes. Emplacement of a dike began 24 hours before the start of the eruption on 3 January 1983. Seismic and geodetic evidence indicates that the dike collided with a magma body in the rift zone. Most of the lava produced during the initial episode of the Puu Oo eruption is of hybrid composition, with petrographic and geochemical evidence of mixing magmas of highly evllved and more mafic compositions. Some olivine and plagioclase grains in the hybrid lavas show reverse zoning. Whole-rock compositional variations are linear even for normally compatible elements like Ni and Cr. Leastsquares mixing calculations yield good residuals for major and trace element analyses for magma mixing. Crystal fractionation calculations yield unsatisfactory residuals. The highly evolved magma is similar in composition to the lava from the 1977 eruption and, at one point, vents for these two eruptions are only 200 m apart. Possibly both the 1977 lava and the highly evolved component of the episode 1 Puu Oo lava were derived from a common body of rift-zone-stored magma. The more mafic mixing component may be represented by the most mafic lava from the January 1983 eruption; it shows no evidence of magma mixing. The dike that was intruded just prior to the start of the Puu Oo eruption may have acted as a hydraulic plunger causing mixing of the two rift-zone-stored magmas.     

Hydrogen isotope fractionation factors between hydrous minerals and ore fluids at low temperatures: evidence from the Granny Smith gold deposit,Western Australia

There are no reported experimental data on hydrogen isotope fractionation between muscovite and water at low temperatures (< 400 °C). A fractionation curve derived from extrapolation of the high temperature calibration of Suzuoki and Epstein (1976) yields 20 to 40%. higher D values than the empirical graphical calibration of Bowers and Taylor (1985) at temperatures of about 300 °C. Data from natural hydrothermal systems formed at approximately 300 °C, where D analyses are available both from fluid inclusions and alteration muscovite/sericite, support the Bowers and Taylor (1985) calibration, thus indicating smaller fractionation factors at these temperatures than suggested by extrapolations from high-temperature experimental results.