The influence of island generated eddies on the carbon dioxide system, south of the Canary Islands

Measurements of surface partial pressure of CO₂ and water column alkalinity, pH_T, nutrients, oxygen, fluorescence and hydrography were carried out, south of the Canary Islands during September 1998. Cyclonic and anticyclonic eddies were alternatively observed from the northwestern area to the central area of the Canary Islands. Nutrient pumping and vertical uplifting of the deep chlorophyll maximum by cyclonic eddies were also ascertained by upward displacement of dissolved inorganic carbon. A model was applied to determine the net inorganic carbon balance in the cyclonic eddy. The fluxes were determined considering both the diffusive and convective contributions from the upward pumping and the corresponding horizontal transport of water outside the area. An increase in the total inorganic carbon concentration in the upper layers inside the eddy field of 133 mmol C m^− 2 d^− 1 was determined. The upward flux of inorganic carbon decreased the effect of the increased primary production on the carbon dioxide chemistry. The reduced fCO₂ inside the cyclonic eddy, 15 μatm lower than that observed in non-affected surface water, was explained by thermodynamic aspects, biological activity, eddy upward pumping and diffusion and air–sea water exchange effects.     

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%.     

Carbon, sulfur and O2 across the Permian–Triassic boundary

A model for the carbon and sulfur cycles across the Permian–Triassic boundary has been constructed from carbon and sulfur isotopic data. Results indicate a drop in global organic matter burial, the formation of an anoxic deep ocean, and a large drop in atmospheric oxygen over the time span 270 to 240 Ma. Much of these changes were probably due to a drop in terrestrial productivity and preservation and an increase in global aridity.     

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.     

Origin of the Nchanga copper–cobalt deposits of the Zambian Copperbelt

The Zambian Copperbelt forms the southeastern part of the 900-km-long Neoproterozoic Lufilian Arc and contains one of the world’s largest accumulations of sediment-hosted stratiform copper mineralization. The Nchanga deposit is one of the most significant ore systems in the Zambian Copperbelt and contains two major economic concentrations of copper and cobalt, hosted within the Lower Roan Group of the Katangan Supergroup. A Lower Orebody (copper only) and Upper Orebody (copper and cobalt) occur towards the top of arkosic units and within the base of overlying shales. The sulfide mineralogy includes pyrite, bornite, chalcopyrite, and chalcocite, although in the Lower Orebody, sulfide phases are partially or completely replaced by malachite and copper oxides. Carrollite is the major cobalt-bearing phase and is restricted to fault-propagation fold zones within a feldspathic arenite. Hydrothermal alteration minerals include dolomite, phlogophite, sericite, rutile, quartz, tourmaline, and chlorite. Quartz veins from the mine sequence show halite-saturated fluid inclusions, ranging from ~31 to 38 wt% equivalent NaCl, with homogenisation temperatures (Th_TOT) ranging between 140 and 180°C. Diagenetic pyrites in the lower orebody show distinct, relatively low δ ³⁴S, ranging from −1 to −17‰ whereas arenite- and shale-hosted copper and cobalt sulfides reveal distinctly different δ ³⁴S from −1 to +12‰ for the Lower Orebody and +5 to +18‰ for the Upper Orebody. There is also a clear distinction between the δ ³⁴S mean of +12.1±3.3‰ (n=65) for the Upper Orebody compared with +5.2±3.6‰ (n=23) for the Lower Orebody. The δ ¹³C of dolomites from units above the Upper Orebody give δ ¹³C values of +1.4 to +2.5‰ consistent with marine carbon. However, dolomite from the shear-zones and the alteration assemblages within the Upper Orebody show more negative δ ¹³C values: −2.9 to −4.0‰ and −5.6 to −8.3‰, respectively. Similarly, shear zone and Upper Orebody dolomites give a δ ¹⁸O of +11.7 to +16.9‰ compared to Lower Roan Dolomites, which show δ ¹⁸O of +22.4 to +23.0‰_. Two distinct structural regimes are recognized in the Nchanga area: a weakly deformed zone consisting of basement and overlying footwall siliciclastics, and a moderate to tightly folded zone of meta-sediments of the Katangan succession. The fold geometry of the Lower Roan package is controlled by internal thrust fault-propagation folds, which detach at the top of the lowermost arkose or within the base of the overlying stratigraphy and show vergence towards the NE. Faulting and folding are considered to be synchronous, as folding predominantly occurred at the tips of propagating thrust faults, with local thrust breakthrough. The data from Nchanga suggests a strong link between ore formation and the development of structures during basin inversion as part of the Lufilian Orogeny. Sulfides tend to be concentrated within arenites or coarser-grained layers within shale units, suggesting that host-rock porosity and possibly permeability played a role in ore formation. However, sulfides are also commonly orientated along, but not deformed by, a tectonic fabric or hosted within small fractures that suggest a significant role for deformation in the development of the mineralization. The ore mineralogy, hydrothermal alteration, and stable isotope data lend support to models consistent with the thermochemical reduction of a sulfate- (and metal) enriched hydrothermal fluid, at the site of mineralization. There is no evidence at Nchanga for a contribution of bacteriogenic sulfide, produced during sedimentation or early diagenesis, to the ores.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.Editorial handling: H. Frimmel     

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%.     

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.