On the pH-dependent formation constants of iron(III)-sulfur(IV) transient complexes

An experimental study is described of Fe(III)-S(IV) formation constants measured as a function of pH (1–3), ionic strength (0.2–0.5 M) and [Fe(III)] _T (2.5–5.0×10^–4 M) using a continuous-flow spectrophotometric technique to make observations 160 ms after mixing. Preliminary experiments using pulse-accelerated-flow (PAF) spectrophotometry to measure rate constants on a microsecond timescale are also described. The conditional formation constant at 25 °C can be modeled with the following equation: {ie307-1} where {ie307-2}K ₇ andK ₈ can be interpreted as intrinsic constants for the coordination of HSO ₃ ^– by FeOH²⁺ and Fe³⁺, respectively, but until further evidence is obtained they should be regarded as fitting constants. PAF spectrophotometry showed that the initial reaction of Fe(III) with S(IV) (pH 2.0) is characterized by a second-order rate constant of 4×10⁶ M^–1 s^–1 which is comparable to rate of reaction of FeOH²⁺ with SO ₄ ^2– . However, the PAF results should be regarded as preliminary since unexpected features in the initial data indicate that the reaction may be more complex than expected.     

Seasonal variations of atmospheric sulfur dioxide and dimethylsulfide concentrations at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric sulfur dioxide (SO₂) concentrations were performed from March 1989 to January 1991 at Amsterdam Island (37°50 S–77°30 E), a remote site located in the southern Indian Ocean. Long-range transport of continental air masses was studied using Radon (²²²Rn) as continental tracer. Average monthly SO₂ concentrations range from less than 0.2 to 3.9 nmol m^-3 (annual average = 0.7 nmol m^-3) and present a seasonal cycle with a minimum in winter and a maximum in summer, similar to that described for atmospheric DMS concentrations measured during the same period. Clear diel correlation between atmospheric DMS and SO₂ concentrations is also observed during summer. A photochemical box model using measured atmospheric DMS concentrations as input data reproduces the seasonal variations in the measured atmospheric SO₂ concentrations within ±30%. Comparing between computed and measured SO₂ concentrations allowed us to estimate a yield of SO₂ from DMS oxidation of about 70%.     

The effects of carbon dioxide leakage on fractures, and water quality of potable aquifers during geological sequestration of CO2

Since industrial revolution, the ＂greenhouse effect＂ is one of the most important global environmental issues. Of all the greenhouse gases, CO2 is responsible for about 64% of the enhanced ＂greenhouse effect＂, making it the target for mitigation, so reducing anthropogenic discharge of carbon dioxide attracts more and more attention. Geological sequestration of CO2 in deep saline aquifers is one of the most promising options. But because unknown fractures and faults may exist in the caprock layers which can prevent the leakage of CO2, CO2 will leak upward into upper potable aquifers, and lead to adverse impacts on the shallow potable aquifers. In order to assess the potential effect of CO2 leakage from underground storage reservoirs on fractures and water quality of potable aquifers, this study used the non-isothermal reactive geochemical transport code TOUGHREACT developed by Xu et al to establish a simplified 2-D model of CO2 underground sequestration system, which includes deep saline aquifers, caprock layers, and shallow potable aquifers, and study and analyze the changes of mineral and aqueous components. The simulation results indicated that the minerals of deep saline aquifers and fractures should be mainly composed of aluminosilicate and silicate minerals, which not only enhance the mass of CO2 sequestrated by mineral trapping, but also decrease the porosity and permeability of caprock layers and fractures to prevent and reduce CO2 leakage. The results from deep saline aquifers showed that the mass of carbon dioxide trapped by minerals and solution phases is limited, the rest remained as a supercritical phase, and so once the caprock aquifers have some unknown fractures, the free carbon dioxide phase may leak from CO2 geologic sequestration reservoirs by buoyancy.     

Retrieval of stratospheric O3 and NO2 vertical profiles using zenith scattered light observations

Daily zenith scattered light intensity observations were carried out in the morning twilight hours using home-made UV-visible spectrometer over the tropical station Pune (18‡31′, 73‡51′) for the years 2000–2003. These observations are obtained in the spectral range 462–498 nm for the solar zenith angles (SZAs) varying from 87‡ to 91.5‡. An algorithm has been developed to retrieve vertical profiles of ozone (O₃) and nitrogen dioxide (NO₂) from ground-based measurements using the Chahine iteration method. This retrieval method has been checked using measured and recalculated slant column densities (SCDs) and they are found to be well matching. O₃ and NO₂ vertical profiles have been retrieved using a set of their air mass factors (AMFs) and SCDs measured over a range of 87–91.5‡ SZA during the morning. The vertical profiles obtained by this method are compared with Umkehr profiles and ozonesondes and they are found to be in good agreement. The bulk of the column density is found near layer 20–25 km. Daily total column densities (TCDs) of O₃ and NO₂ along with their stratospheric and tropospheric counterparts are derived using their vertical profiles for the period 2000–2003. The total column, stratospheric column and tropospheric column amounts of both trace gases are found to be maximum in summer and minimum in the winter season. Increasing trend is found in column density of NO₂ in stratospheric, tropospheric and surface layers, but no trend is observed in O₃ columns for above layers during the period 2000–2003     

不同涂层的二氧化铅电极催化性能的比较

研究了热分解法和电沉积法制备二氧化铅电极的工艺,通过对苯酚的电解和生成羟基自由基的量,比较了两种方法制得的电极的催化性能,并比较了采用电沉积法制备电极时掺杂铋或镧对电极的催化性能的影响。实验结果表明,这4种电极都具有良好的电催化性能,并且明显降低了槽电压,且对苯酚的降解均符合一级反应动力学,电沉积法制得的电极的催化性能优于热分解法制得的电极,掺镧的电极优于无掺杂和掺铋的电极。     

DMS and SO2 at Baring Head, New Zealand: Implications for the Yield of SO2 from DMS

Atmospheric dimethyl sulfide (DMS) and sulfur dioxide (SO₂) concentrations were measured at Baring Head, New Zealandduring February and March 2000. Anti-correlated DMS and SO₂ diurnalcycles, consistent with the photochemical production of SO₂ from DMS, were observed in clean southerly air off the ocean. The data is used to infer a yield of SO₂ from DMS oxidation. The estimated yields are highly dependent on assumptions about the DMS oxidation rate. Fitting the measured data in a photochemical box model using model-generated OH levels and the Hynes et al. (1986) DMS + OH rate constant suggests that theSO₂ yield is 50–100%, similar to current estimates for the tropical Pacific.However, the observed amplitude of the DMS diurnal cycle suggests that the oxidation rate is higher than that used by the model, and therefore, that theSO₂ yield is lower in the range of 20–40%.     

Genesis of chlorine and sulphur in fumarolic emissions at Vulcano Island (Italy): assessment of pH and redox conditions in the hydrothermal system

Chlorine- and sulphur-bearing compounds in fumarole discharges of the La Fossa crater at Vulcano Island (Italy) can be modelled by a mixing process between magmatic gases and vapour from a boiling hydrothermal system. This allows estimating the compounds in both endmembers. Magma degassing cannot explain the time variation of sulphur and HCl concentrations in the deep endmember, which are more probably linked to reactions of solid phases at depth, before mixing with the hydrothermal vapours. Based on the P–T conditions and speciation of the boiling hydrothermal system below La Fossa, the HCl and S_tot contents in the hydrothermal vapours were used to compute the redox conditions and pH of the aqueous solution. The results suggest that the haematite–magnetite buffer controls the hydrothermal fO₂ values, while the pH has increased since the end of the 1970s. The main processes affecting pH values may be linked to Na–Ca exchanges between evolved seawater, feeding the boiling hydrothermal system, and local rocks. While Na is removed from water, calcium enters the solution, undergoes hydrolysis and produces HCl, lowering the pH of the water. The increasing water–rock ratio within the hydrothermal system lowers the Ca availability, so the aqueous solution becomes less acidic. Seawater flowing towards the boiling hydrothermal brine dissolves a large quantity of pyrite along its path. In the boiling hydrothermal system, dissolved sulphur precipitates as pyrite and anhydrite, and becomes partitioned in vapour phase as H₂S and SO₂. These results are in agreement with the paragenesis of hydrothermal alteration minerals recovered in drilled wells at Vulcano and are also in agreement with the isotopic composition of sulphur emitted by the crater fumaroles.     

Monitoring volcanic hazard using eddy covariance at Solfatara volcano, Naples, Italy

An eddy covariance (EC) station was deployed at Solfatara crater, Italy, June 8–25, 2001 to assess if EC could reliably monitor CO₂ fluxes continuously at this site. Deployment at six different locations within the crater allowed areas of focused gas venting to be variably included in the measured flux. Turbulent (EC) fluxes calculated in 30-min averages varied between 950 and 4460 g CO₂ m⁻² d⁻¹; the highest measurements were made downwind of degassing pools. Comparing turbulent fluxes with chamber measurements of surface fluxes using footprint models in diffuse degassing regions yielded an average difference of 0% (±4%), indicating that EC measurements are representative of surface fluxes at this volcanic site. Similar comparisons made downwind of degassing pools yielded emission rates from 12 to 27 t CO₂ d⁻¹ for these features. Reliable EC measurements (i.e. measurements with sufficient and stationary turbulence) were obtained primarily during daytime hours (08:00 and 20:00 local time) when the wind speed exceeded 2 m s⁻¹. Daily average EC fluxes varied by ±50% and variations were likely correlated to changes in atmospheric pressure. Variations in CO₂ emissions due to volcanic processes at depth would have to be on the same order of magnitude as the measured diurnal variability in order to be useful in predicting volcanic hazard. First-order models of magma emplacement suggest that emissions could exceed this rate for reasonable assumptions of magma movement. EC therefore provides a useful method of monitoring volcanic hazard at Solfatara. Further, EC can monitor significantly larger areas than can be monitored by previous methods.     

A Laboratory and Theoretical Study on the Uptake of SO2 Gas by Large and Small Water Drops Containing Heavy Metal Ions

Laboratory experiments have been carried out to investigate the uptake of sulfur dioxide by water drops containing heavy metal ions where the metal ions serve as catalysts to oxidise the taken up S(IV) into S(VI). During the gas uptake the drops were freely suspended at their terminal velocity in the airstream of the Mainz vertical wind tunnel. Two series of experiments were carried out, one with large millimeter size water drops containing manganese or iron ions, and the other with small water drops containing manganese ions and having radii in hundreds of micron size range. The experimental results were compared against model computations using the Kronig–Brink model and the fully mixed model, modified for the case that heavy metal ions present in the liquid phase act as catalysts for the oxidising process. The results of the model calculations show that there are only small differences between the predicted gas uptake according to the two models. In addition it was found that the experimental obtained results from the uptake of SO₂ by water drops containing heavy metal ions for both, large and small water drops did agree with the model results.     

Measurement of Carbon Dioxide Emissions Plumes from Prudhoe Bay, Alaska Oil Fields

Large carbon dioxide plumes with concentrations up to 45 ppm aboveambient levels were measured about 15 km downwind of the Prudhoe Bay, Alaskamajor oil production facilities, located at 70° N Lat. above the ArcticCircle. The measured emissions were 1.3 × 10³ metrictons (C) hour^-1 (11.4× 10⁶ metric tons(C) year^-1), six times greater than the combustion emissionsassumed by Jaffe and coworkers in J. Atmos. Chem. 20 (1995), 213–227,based on 1989 reported Prudhoe Bay oil facility fuel consumption data, andfour times greater than the total C emissions reported by the oil facilitiesfor the same months as the measurement time periods. Variations in theemissions were estimated by extrapolating the observed emissions at a singlealtitude for all tundra research transect flights conducted downwind of theoil fields. These 30 flights yielded an average emission rate of1.02 × 10³ metric tons (C) hour^-1 with astandard deviation of 0.33 × 10³. These quantity ofemissions are roughly equivalent to the carbon dioxide emissions of7–10 million hectares of arctic tussock tundra (Oechel and Vourlitis,Trends in Ecol. Evolution 9 (1994), 324–329).