Relative importance of ozone energy transfer processes in the middle and upper atmosphere

The relative importance of different processes and transitions in the appearance of non-LTE populations for the fundamental levels of ozone was studied by quantifying the kinetic law of every process and transition that affect each level population. The vibrational temperatures and the relative contribution of every transition are presented as a function of altitude. The results show that the appearance of non-LTE populations for the fundamental levels is not produced by a direct imbalance between absorption and emission but as a consequence of imbalanced collisional transitions provoked by the overpopulation of O₃(0 v₂ 0) levels. This fact confirms that the relaxation cascade drives through the bending mode ν₂.     

Size and elemental distributions of nano- to micro-particulates in the geochemically-stratified Great Salt Lake

The characterization of trace elements in terms of their apportionment among dissolved, macromolecular, nano- and micro-particulate phases in the water column of the Great Salt Lake carries implications for the potential entry of toxins into the food web of the lake. Samples from the anoxic deep and oxic shallow brine layers of the lake were fractionated using asymmetric flow field-flow fractionation (AF4). The associated trace elements were measured via online collision cell inductively-coupled plasma mass spectrometry (CC-ICP-MS). Results showed that of the total (dissolved + particulate) trace element mass, the percent associated with particulates varied from negligible (e.g. Sb), to greater than 50% (e.g. Al, Fe, Pb). Elements such as Cu, Zn, Mn, Co, Au, Hg, and U were associated with nanoparticles, as well as being present as dissolved species. Particulate-associated trace elements were predominantly associated with particulates larger than 450 nm in size. Among the smaller nanoparticulates (<450 nm), some trace elements (Ni, Zn, Au and Pb) showed higher percent mass (associated with nanoparticles) in the 0.9–7.5 nm size range relative to the 10–250 nm size range. The apparent nanoparticle size distributions were similar between the two brine layers; whereas, important differences in elemental associations to nanoparticles were discerned between the two layers. Elements such as Zn, Cu, Pb and Mo showed increasing signal intensities from oxic shallow to anoxic deep brine, suggesting the formation of sulfide nanoparticles, although this may also reflect association with dissolved organic matter. Aluminum and Fe showed greatly increased concentration with depth and equivalent size distributions that differed from those of Zn, Cu, Pb and Mo. Other elements (e.g. Mn, Ni, and Co) showed no significant change in signal intensity with depth. Arsenic was associated with <2 nm nanoparticles, and showed no increase in concentration with depth, possibly indicating dissolved arsenite. Mercury was associated with <2 nm nanoparticles, and showed greatly increased concentration with depth, possibly indicating association with dissolved organic matter.     

Evolution of fluid geochemistry at the Turrialba volcano (Costa Rica) from 1998 to 2008

Turrialba (10°02′N, 83°45′W) is a 3,349-m high stratovolcano belonging to the Holocene “Cordillera Central” volcanic belt of Costa Rica. The summit consists of three EW-oriented craters (East, Central, and West). Since its last eruptive phase (1864–1866), the Central and West craters have displayed modest fumarolic activity, with outlet temperatures clustering around 90°C. In 2001, seismic swarms, ground deformation, and increasing fumarolic activity occurred. From 2005 to 2008, new fumarolic vents opened between and within the Central and West craters, and along the western and southwestern outer flanks of the volcanic edifice. These physical changes were accompanied by a drastic modification in the gas chemistry that can be divided in three stages: (1) hydrothermal (from 1998 to autumn 2001), characterized by the presence of H₂O, CO₂, H₂S, and, to a very minor extent, HCl and HF; (2) hydrothermal/magmatic (autumn 2001–2007), with the appearance of SO₂ and a significant increase of HCl and HF; and (3) magmatic-dominated (2007–2008), characterized by increased SO₂ content, SO₂/H₂S > 100, and temperatures up to 282°C. Accordingly, gas equilibrium in the CO₂-CH₄-H₂ system suggests a progressive evolution of the deep fluid reservoir toward higher temperatures and more oxidizing conditions. The chemical–physical modifications of Turrialba in the last decade can be interpreted as part of a cyclic mechanism controlling the balance between the hydrothermal and the magmatic systems. Nevertheless, the risk of rejuvenation of the volcanic activity cannot be excluded, and an appropriate seismic, ground deformation, and geochemical monitoring program is highly recommended. Turrialba lies at a distance of 35 and 15 km from San José and Cartago, respectively, the two largest cities in Costa Rica.     

Space- and Time-Dependent Probabilities for Earthquake Fault Systems from Numerical Simulations: Feasibility Study and First Results

In weather forecasting, current and past observational data are routinely assimilated into numerical simulations to produce ensemble forecasts of future events in a process termed “model steering”. Here we describe a similar approach that is motivated by analyses of previous forecasts of the Working Group on California Earthquake Probabilities (WGCEP). Our approach is adapted to the problem of earthquake forecasting using topologically realistic numerical simulations for the strike-slip fault system in California. By systematically comparing simulation data to observed paleoseismic data, a series of spatial probability density functions (PDFs) can be computed that describe the probable locations of future large earthquakes. We develop this approach and show examples of PDFs associated with magnitude M > 6.5 and M > 7.0 earthquakes in California.     

Trends in total ozone and the effect of the equatorial zonal wind QBO

Trends in total column ozone have been analyzed in terms of the equatorial zonal wind. We used zonal monthly mean total ozone from Total Ozone Mapping Spectrometer (TOMS) and monthly mean zonal wind in the equatorial stratosphere at 30 hPa to define the phases of the quasi-biennial oscillation (QBO). Total column ozone trends have been assessed during the period 1979–2004, for both Hemispheres, and for each month, under three conditions considering, all the ozone dataset, ozone values during easterly phase and ozone values during westerly phase of the QBO. When the whole dataset is considered, negative trends are observed. From low to midlatitudes a zonal pattern is noticed with increasing negative values toward higher latitudes. When the data is filtered according to the QBO phase, statistically significant positive trends appear in the westerly case during January to May at low latitudes .The trend pattern in the case of the easterly phase presents more negative values.     

Accumulation and effects of benzo(a)pyrene on cytochrome P450 1A in waterborne exposed and intraperitoneal injected juvenile turbot (Scophthalmus maximus)

Juvenile turbot (Scophthalmus maximus) were exposed to benzo(a)pyrene (BaP) for 14 d using a glass bead generator flow-through system. Exposure was followed by a recovery period of 16 d. The highest BaP concentration in the edible portion of the fish, 16.5 ± 4.3 μg BaP/kg, was observed on the first day. Then concentrations dropped following first-order kinetics. BaP was below detection level at the end of the experiment. A statistically significant increase in bile fluorescence was observed from day 9 until the end of the experiment, suggesting the elimination of BaP metabolites by this route. No significant differences between control and exposed fish in EROD activity and CYP1A concentration, measured by immunodetection method, were observed. Intraperitoneal injection of 2.5 mg BaP/kg in juvenile turbot induced EROD activity. Under waterborne experimental conditions, bile fluorescence was observed to be a more sensitive biomarker of BaP exposure than EROD activity and CYP1A measurement.     

Development of a Field Preconcentration/Elution Unit for Routine Determination of Dissolved Metal Concentrations by ICP-OES in Marine Waters: Application for Monitoring of the New Caledonia Lagoon

An iminodiacetate chelating resin was optimised for the rapid determination of Co, Cu, Fe, Mn and Ni in seawater. Using inexpensive, high-capacity, reusable cartridges allowed high flow rates of up to 25 ml min⁻¹. High preconcentration factors, of up to 500, were obtained in order to analyse samples using an ICP-OES. The requirement for a buffer was eliminated due to the high tolerance of the ICP-OES to interfering matrix elements, thereby further reducing the potential for contamination. Quantification limits in seawater were: Co = 6 ng l⁻¹, Cu = 8 ng l⁻¹, Fe = 6 ng l⁻¹, Mn = 5 ng l⁻¹ and Ni = 6 ng l⁻¹. The method was verified by the analysis of near shore seawater (CASS-4) and open ocean seawater (NASS-5) reference materials. In order to satisfy the high sampling demands using the iminodiacetate cartridges, a portable off-line preconcentration unit was developed for routine analysis. The multi-channel preconcentration unit, was capable of treating up to eight samples simultaneously with concentrating times as little as 30 minutes. The technique was also used to determine dissolved metals in fresh and interstitial waters. The technique has been successfully used in a number of environmental studies and impact assessments to evaluate the effects of mining on the New Caledonian lagoon.