Solar Photocatalytic Decolorization and Detoxification of Industrial Batik Dye Wastewater Using P(3HB)‐TiO2 Nanocomposite Films

Solar photocatalytic decolorization and detoxification of batik dye wastewater using titanium dioxide (TiO₂) immobilized on poly‐3‐hydroxybutyrate (P(3HB)) film was studied. The effects of initial dye concentration, catalyst concentration, P(3HB) film thickness, and fabrication methods of the nanocomposite films were evaluated against methylene blue, a standard organic dye. It was observed that 0.4 g of P(3HB)‐40 wt% TiO₂ removed 96% of the color under solar irradiation. P(3HB) and TiO₂, mixed concurrently in chloroform followed by stirring for 24 h showed a more even distribution of the photocatalyst on the polymer surface and yielded almost 100% color removal. The photocatalytic films were able to completely decolorize real industrial batik dye wastewater in 3 h and induced a chemical oxygen demand (COD) reduction of 80%. Reusability of the 0.4 g P(3HB)‐40 wt% TiO₂ film in decolorizing the batik dye wastewater was also possible as it gave a high consistent value of decolorization percentage (>80%) even after the sixth repeated usage. Recovery step of the photocatalysts was also not required in this simple treatment system. The decolorized batik dye wastewater had less/no toxic effects on mosquito larvae, Aedes aegypti, and microalgae, Scenedesmus quadricauda indicating simultaneous detoxification process along with the decolorization process.     

Multi-proxy approach (H/H, O/O, C/C and Sr/Sr) for the evolution of carbonate-rich groundwater in basalt dominated aquifer of Axum area, northern Ethiopia

Isotopic and chemical composition of groundwater from wells and springs, and surface water from the basalt-dominated Axum area (northern Ethiopia) provides evidence for the origin of water and dissolved species. Shallow (depth < 40 m) and deep groundwater are distinguished by both chemical and isotopic composition. Deep groundwater is significantly enriched in dissolved inorganic carbon up to 40 mmol l⁻¹ and in concentrations of Ca²⁺, Mg²⁺, Na⁺ and Si(OH)₄ compared to the shallow type.The δ²H and δ¹⁸O values of all solutions clearly indicate meteoric origin. Shifts from the local meteoric water line are attributed to evaporation of surface and spring water, and to strong water–rock interaction. The δ¹³C_DIC values of shallow groundwater between −12 and −7‰ (VPDB) display the uptake of CO₂ from local soil horizons, whereas δ¹³C_DIC of deep groundwater ranges from −5 to +1‰. Considering open system conditions with respect to gaseous CO₂, δ¹³C_DIC = +1‰ of the deep groundwater with highest PCO₂ = 10^−0.9 atm yields δ¹³C_CO2(gas) ≈ −5‰, which is close to the stable carbon isotopic composition of magmatic CO₂. Accordingly, stable carbon isotope ratios within the above range are referred to individual proportions of CO₂ from soil and magmatic origin. The uptake of magmatic CO₂ results in elevated cations and Si(OH)₄ concentrations. Weathering of local basalts is documented by ⁸⁷Sr/⁸⁶Sr ratios of the groundwater from 0.7038 to 0.7059. Highest values indicate Sr release from the basement rocks. Besides weathering of silicates, neoformation of solids has to be considered, which results in the formation of, e.g., kaolinite and montmorillonite. In several solutions supersaturation with respect to calcite is reached by outgassing of CO₂ from the solution leading to secondary calcite formation.     

Contact angles in CO2-water-coal systems at elevated pressures

Injection of carbon dioxide into coal seams is considered to be a potential method for its sequestration away from the atmosphere. However, water present in coals may retard injection: especially if carbon dioxide does not wet the coal as well as water. Thus contact angles in the coal-water-CO₂ system were measured using CO₂ bubbles in water/coal systems at 40 °C and pressures up to 15 MPa using five bituminous coals. At low pressures, in this CO₂/water/coal system, receding contact angles for the coals ranged between 80° to 100°; except for one coal that had both high ash yield and low rank, with a contact angle of 115°, indicating that it was hydrophilic. With increasing pressure, the receding contact angles for the different coals decreased, indicating that they became more CO₂-wetting. The relationship between contact angle and pressure was approximately linear. For low ash or high rank coals, at high pressure the contact angle was reduced to 30-50°, indicating the coals became strongly CO₂-wetting; that is CO₂ fluids will spontaneously penetrate these wet coals. In the case of the coal that was both high ash and hydrophilic, the contact angle did not drop to 90° even at the highest pressures used. These results suggest that CO₂ will not be efficiently adsorbed by all wet coals equally well, even at high pressure. It was found that at high pressures (> 2 MPa) the rate of penetration of carbon dioxide into the coals increased rapidly with decreasing contact angle, independently of pressure. Injecting CO₂ into wet coals that have both low rank and high ash will not trap CO₂ as well as injecting it into high rank or low ash coals.     

Very high-frequency and seasonal cave atmosphere PCO2 variability: Implications for stalagmite growth and oxygen isotope-based paleoclimate records

Cave air P_CO2 at two Irish sites varied dramatically on daily to seasonal timescales, potentially affecting the timing of calcite deposition and consequently climate proxy records derived from stalagmites collected at the same sites. Temperature-dependent biochemical processes in the soil control CO₂ production, resulting in high summer P_CO2 values and low winter values at both sites. Large Large-amplitude, high-frequency variations superimposed on this seasonal cycle reflect cave air circulation. Here we model stalagmite growth rates, which are controlled partly by CO₂ degassing rates from drip water, by considering both the seasonal and high-frequency cave air P_CO2 variations. Modeled hourly growth rates for stalagmite CC-Bil from Crag Cave in SW Ireland reach maxima in late December (0.063 μm h^− 1) and minima in late June/early July (0.033 μm h^− 1). For well-mixed ‘diffuse flow’ cave drips such as those that feed CC-Bil, high summer cave air P_CO2 depresses summer calcite deposition, while low winter P_CO2 promotes degassing and enhances deposition rates. In stalagmites fed by well-mixed drips lacking seasonal variations in δ¹⁸O, integrated annual stalagmite calcite δ¹⁸O is unaffected; however, seasonality in cave air P_CO2 may influence non-conservative geochemical climate proxies (e.g., δ¹³C, Sr/Ca). Stalagmites fed by ‘seasonal’ drips whose hydrochemical properties vary in response to seasonality may have higher growth rates in summer because soil air P_CO2 may increase relative to cave air P_CO2 due to higher soil temperatures. This in turn may bias stalagmite calcite δ¹⁸O records towards isotopically heavier summer drip water δ¹⁸O values, resulting in elevated calcite δ¹⁸O values compared to the ‘equilibrium’ values predicted by calcite–water isotope fractionation equations. Interpretations of stalagmite-based paleoclimate proxies should therefore consider the consequences of cave air P_CO2 variability and the resulting intra-annual variability in calcite deposition rates.     

Comparison of two different equations of state for application of carbon dioxide sequestration

We suggest that different equations of state (EOS) algorithms can and frequently will provide very different predictions of CO₂ migration following injection for sequestration. Rather than carry out an exhaustive examination of all EOS algorithms available, we elected to evaluate this general hypothesis by making detailed comparisons of simulation results of two very common EOS algorithms. We simulated and compared CO₂ migration patterns using two fundamentally different EOS algorithms – Modified Redlich-Kwong EOS (MRKEOS) and Span and Wagner EOS (SWEOS). In general, the predictions of thermophysical properties for both algorithms are close, except for a contrast in the predicted fugacity coefficient of CO₂, which subsequently propagates to a contrast in predicted solubility in water/brine. Typically, MRKEOS underestimates solubility of CO₂ compared to both SWEOS and experimental solubility data. In simulations of CO₂ migration, dissolution rates of separate-phase CO₂ predicted from the two EOS algorithms were significantly different, even for small contrasts in predicted fluid properties from EOS algorithms, resulting in markedly different migration patterns.     

Volatile emissions and gas geochemistry of Hot Spring Basin,Yellowstone National Park,USA

We characterize and quantify volatile emissions at Hot Spring Basin (HSB), a large acid-sulfate region that lies just outside the northeastern edge of the 640 ka Yellowstone Caldera. Relative to other thermal areas in Yellowstone, HSB gases are rich in He and H₂, and mildly enriched in CH₄ and H₂S. Gas compositions are consistent with boiling directly off a deep geothermal liquid at depth as it migrates toward the surface. This fluid, and the gases evolved from it, carries geochemical signatures of magmatic volatiles and water–rock reactions with multiple crustal sources, including limestones or quartz-rich sediments with low K/U (or ^40?Ar/^4?He). Variations in gas chemistry across the region reflect reservoir heterogeneity and variable degrees of boiling. Gas-geothermometer temperatures approach 300 °C and suggest that the reservoir feeding HSB is one of the hottest at Yellowstone. Diffuse CO₂ flux in the western basin of HSB, as measured by accumulation-chamber methods, is similar in magnitude to other acid-sulfate areas of Yellowstone and is well correlated to shallow soil temperatures. The extrapolation of diffuse CO₂ fluxes across all the thermal/altered area suggests that 410 ± 140 t d^− 1 CO₂ are emitted at HSB (vent emissions not included). Diffuse fluxes of H₂S were measured in Yellowstone for the first time and likely exceed 2.4 t d^− 1 at HSB. Comparing estimates of the total estimated diffuse H₂S emission to the amount of sulfur as SO₄²⁻ in streams indicates ~ 50% of the original H₂S in the gas emission is lost into shallow groundwater, precipitated as native sulfur, or vented through fumaroles. We estimate the heat output of HSB as ~ 140–370 MW using CO₂ as a tracer for steam condensate, but not including the contribution from fumaroles and hydrothermal vents. Overall, the diffuse heat and volatile fluxes of HSB are as great as some active volcanoes, but they are a small fraction (1–3% for CO₂, 2–8% for heat) of that estimated for the entire Yellowstone system.     

煤层处置CO2 的二元气- 固耦合数值模拟

利用不可开采煤层处置二氧化碳可以有效控制温室气体的排放量并可驱动和增加煤层气资源的开采量。二氧化碳注入煤层处置后引入一个复杂的CH4-CO2二元气体与煤体的气固耦合问题,耦合了二元气体竞争吸附、竞争扩散,气体渗流以及煤体变形过程。基于COMSOL Multiphysics建立了二元气固耦合的有限元数值模型,并应用数值模拟实验对二元气固耦合进行了机理分析。模拟结果表明,CO2注入煤层后不断驱替CH4,CH4组分明显减少;气体吸附引起的煤层膨胀量可以抵消部分有效应力引起的压缩变形,由于CH4-CO2二元气体较单一CH4引起的煤层吸附膨胀量大,二氧化碳注入煤层后可以缓解煤层的压缩变形;不同孔隙压力条件下,吸附膨胀与孔隙压力两者竞争作用引起的煤层净变形不同,而净变形也控制着煤层孔隙压力和渗流率的变化,煤层渗透整体呈现先降后升,模拟进行到4.66×107 s时煤层渗透率发生反弹。     

中国对外贸易产生的CO_2排放区位转移分析

减缓以CO2为主的温室气体排放所引起的全球气候变化问题越来越为国际社会所瞩目.目前有关的国际协定主要以国家本土温室气体排放为基准核算国家的碳排放责任和减排成效,忽略了国际商品贸易流引起的排放区位与产品消费区位的空间分离.本文利用2000～2006年中国海关货物进出口商品分类数据,采用投入产出法,分析了中国货物进出口贸易产生的CO2排放区位向中国的转移效应.结果表明,中国出口商品内涵的CO2排放量从2000年的9.6亿t增加到2006年的19.1亿t,每年占全国总排放的比重基本在30%-35%.扣除进口商品使我国避免在本土排放的CO2,货物进出口贸易使净转移到我国的CO2排放量至少从2.3亿t增加到7.2亿t,中美贸易顺差、中国与欧盟贸易顺差是产生净转移的主要原因.结论主张相关国际协定从排放区位与消费区位相结合的角度制定温室气体减排政策.     

A Study of DMS Oxidation in the Tropics: Comparison of Christmas Island Field Observations of DMS, SO2, and DMSO with Model Simulations

This study reports comparisonsbetween model simulations, based on current sulfurmechanisms, with the DMS, SO₂ and DMSOobservational data reported by Bandy et al.(1996) in their 1994 Christmas Island field study. For both DMS and SO₂, the model results werefound to be in excellent agreement with theobservations when the observations were filtered so asto establish a common meteorological environment. Thisfiltered DMS and SO₂ data encompassedapproximately half of the total sampled days. Basedon these composite profiles, it was shown thatoxidation of DMS via OH was the dominant pathway withno more than 5 to 15% proceeding through Cl atoms andless than 3% through NO₃. This analysis wasbased on an estimated DMS sea-to-air flux of 3.4 ×10⁹ molecs cm^-2 s^-1. The dominant sourceof BL SO₂ was oxidation of DMS, the overallconversion efficiency being evaluated at 0.65 ± 0.15. The major loss of SO₂ was deposition to theocean's surface and scavenging by aerosol. Theresulting combined first order k value was estimated at 1.6 × 10^-5 s^-1. In contrast to the DMSand SO₂ simulations, the model under-predictedthe observed DMSO levels by nearly a factor of 50. Although DMSO instrument measurement problems can notbe totally ruled out, the possibility of DMSO sourcesother than gas phase oxidation of DMS must beseriously considered and should be explored in futurestudies.