Relationship between Urban and Rural Sulfate Levels

Abstract

The topic of global warming as a result of increased atmospheric CO₂ concentration is arguably the most important environmental issue that the world faces today. It is a global problem that will need to be solved on a global level. The link between anthropogenic emissions of CO₂ with increased atmospheric CO₂ levels and, in turn, with increased global temperatures has been well established and accepted by the world. International organizations such as the United Nations Framework Convention on Climate Change (UNFCCC) and the Intergovernmental Panel on Climate Change (IPCC) have been formed to address this issue. Three options are being explored to stabilize atmospheric levels of greenhouse gases (GHGs) and global temperatures without severely and negatively impacting standard of living: (1) increasing energy efficiency, (2) switching to less carbon-intensive sources of energy, and (3) carbon sequestration. To be successful, all three options must be used in concert. The third option is the subject of this review. Specifically, this review will cover the capture and geologic sequestration of CO₂ generated from large point sources, namely fossil-fuel-fired power gasification plants. Sequestration of CO₂ in geological formations is necessary to meet the President’s Global Climate Change Initiative target of an 18% reduction in GHG intensity by 2012. Further, the best strategy to stabilize the atmospheric concentration of CO₂ results from a multifaceted approach where sequestration of CO₂ into geological formations is combined with increased efficiency in electric power generation and utilization, increased conservation, increased use of lower carbonintensity fuels, and increased use of nuclear energy and renewables.

This review covers the separation and capture of CO₂ from both flue gas and fuel gas using wet scrubbing technologies, dry regenerable sorbents, membranes, cryogenics, pressure and temperature swing adsorption, and other advanced concepts. Existing commercial CO₂ capture facilities at electric power-generating stations based on the use of monoethanolamine are described, as is the Rectisol process used by Dakota Gasification to separate and capture CO₂ from a coal gasifier.

Two technologies for storage of the captured CO₂ are reviewed—sequestration in deep unmineable coalbeds with concomitant recovery of CH4 and sequestration in deep saline aquifers. Key issues for both of these techniques include estimating the potential storage capacity, the storage integrity, and the physical and chemical processes that are initiated by injecting CO₂ underground. Recent studies using computer modeling as well as laboratory and field experimentation are presented here. In addition, several projects have been initiated in which CO₂ is injected into a deep coal seam or saline aquifer. The current status of several such projects is discussed. Included is a commercial-scale project in which a million tons of CO₂ are injected annually into an aquifer under the North Sea in Norway. The review makes the case that this can all be accomplished safely with off-the-shelf technologies. However, substantial research and development must be performed to reduce the cost, decrease the risks, and increase the safety of sequestration technologies.

This review also includes discussion of possible problems related to deep injection of CO₂ . There are safety concerns that need to be addressed because of the possibilities of leakage to the surface and induced seismic activity. These issues are presented along with a case study of a similar incident in the past. It is clear that monitoring and verification of storage will be a crucial part of all geological sequestration practices so that such problems may be avoided. Available techniques include direct measurement of CO₂ and CH4 surface soil fluxes, the use of chemical tracers, and underground 4-D seismic monitoring.

Ten new hypotheses were formulated to describe what happens when CO₂ is pumped into a coal seam. These hypotheses provide significant insight into the fundamental chemical, physical, and thermodynamic phenomena that occur during coal seam sequestration of CO₂ .     

Accelerated carbonation of wood combustion ash for CO<Subscript>2</Subscript> removal from gaseous streams and storage in solid form

In this work, ash generated by the combustion of wood in a central heating plant was used to remove and permanently store by accelerated carbonation CO₂ contained in a gas mixture simulating biogas. The process was studied as an alternative treatment to the ones currently available on the market for biogas upgrading. The process was investigated at laboratory scale by setting up a facility for directly contacting the wood ash and the synthetic biogas in a fixed bed reactor. The process was able to completely remove CO₂ during its initial phase. After about 30 h, CO₂ started to appear again in the outlet stream and its concentration rapidly increased. The specific CO₂ uptake achieved in solid carbonate form was of about 200 g/kg of dry wood ash. This value is an order of magnitude higher than the ones found for waste incineration bottom ash carrying out similar experiments. The difference was ascribed to the physicochemical properties of the ash, characterized by a fine particle size (d₅₀ <?0.2 mm) and high content of reactive phases with CO₂ (e.g., Ca hydroxides). The leaching behavior of the wood ash was examined before and after the accelerated carbonation process showing that the release of several elements was lower after the treatment; Ba leaching in particular decreased by over two orders of magnitude. However, the release of the critical elements for the management of this type of residues (especially Cr and sulfates) appeared not to be significantly affected, while V leaching increased.     

Effect of global climatic change on carbonation progress of concrete

In the recent years, global warming has dramatically increased the atmospheric carbon-dioxide (CO₂) concentration and temperature. As a consequence of this, carbonation has become one of the most critical durability issues for concrete structures in urban environment.In this study, the climate scenario IS92a recommended by Intergovernmental Panel on Climate Change (IPCC) is used for evaluating the effect of CO₂ concentration on carbonation of concrete. A modified mathematical equation, based on Fick's 1st law of diffusion, is used to evaluate CO₂ diffusion coefficient of concrete. The required cover depth of concrete is estimated by using the applicative methods of reliability and stochastic concepts to take microclimatic conditions into consideration.The tolerance of cover depth should be considered in order to prevent carbonation-induced corrosion. From the relationship between the weight loss of reinforcement and corrosion current density for a given time, the tolerance of cover depth to prevent carbonation-induced corrosion is suggested. It was observed that corrosion occurs when the distance between carbonation front and reinforcement bar surface (the uncarbonated depth) is <5 mm.     

Continuous CO2 capture and MSWI fly ash stabilization, utilizing novel dynamic equipment

Novel dynamic equipment with gas in and out continuously was developed to study the capture capacity of CO₂. Municipal solid waste incineration (MSWI) fly ash has a high capture rate of CO₂ in CO₂-rich gas. Fly ash can sequester pure CO₂ rapidly, and its capacity is 16.3 g CO₂/100 g fly ash with no water added and 21.4 g CO₂/100 g fly ash with 20% water added. For simulated incineration gas containing 12% CO₂, the capture rate decreased and the capacity was 13.2 g CO₂/100 g fly ash with no water added and 18.5 g CO₂/100 g fly ash with 20% water added. After accelerated carbonation, the C and O contents increased, indicating CO₂ capture in the fly ash; CO₂ combines with Ca(OH)₂ to form CaCO₃, which increased the CaCO₃ content from 12.5 to 54.3%. The leaching of Pb markedly decreased from 24.48 to 0.111 mg/L.     

Determination of lipid peroxidation and cytotoxicity in calcium, magnesium, titanium and hectorite (SHCa-1) suspensions

This paper reports data on the relative ability of CaO, CaCl₂, MgO, MgCl₂, TiO₂, and hectorite (SHCa-1) to induce oxidative stress (as determined by lipid peroxidation, LP) in biological matrices. The effectiveness of structural (oxide form) versus soluble Ca and Mg to induce LP is compared. An assessment on cytotoxicity as affected by soluble and structural Ca, Mg, TiO₂ and SHCa-1 is also addressed. LP was screened and monitored using the Thiobarbituric Acid Reactive Substances (TBARS). The extent of TBARS production was found to vary with the type and initial concentration of the soluble or structural cation, Ca or Mg respectively. Obtained results showed higher magnitude values for the latter set of experiments. In the presence of TiO₂ no significant TBARS production was detected pointing out a negligible effect of TiO₂ on LP. At solid concentrations ca. 100 ppm, CaO appears to be more effective than SHCa-1 to induce LP. By contrast at ca. 25 ppm, MgO appears to be more effective than the clay mineral. The SHCa-1 LP-inducing activity has been proven to closely relate to structural Ca. The prevalence of mechanisms that may induce LP but not cytotoxicity (as determined by cell growth inhibition) was also addressed. Results on cell growth inhibition as affected by soluble and structural Ca, Mg, TiO₂ and hectorite provide evidence to support that structural Ca or Mg brings about significantly higher variations than soluble Ca.     

Characterization of carbonic anhydrase II from Chlorella vulgaris in bio-CO2 capture

Carbonic anhydrase II (CA II) can catalyze the reversible hydration reaction of CO₂ at a maximum of 1.4?×?10⁶ molecules of CO₂ per second. The crude intracellular enzyme extract containing CA II was derived from Chlorella vulgaris. A successful CO₂ capture experiment with the presence of calcium had been conducted on the premise that the temperature was conditioned at a scope of 30?C40?°C, that the biocatalyst-nurtured algal growth period lasted 3?days, and that pH ranged from7.5 to 8.5. Ions of K⁺, Na⁺, Ca²⁺, Co²⁺, Cu²⁺, Fe³⁺, Mg²⁺, Mn²⁺, and Zn²⁺ at 0.01, 0.1, and 0.5?M were found to exhibit no more than 30?% inhibition on the residual activity of the biocatalyst. It is reasonable to expect that calcification catalyzed by microalgae presents an alternative to geological carbon capture and sequestration through a chain of fundamental researches carried on under the guidance of sequestration technology.     

Pilot project at Hazira,India, for capture of carbon dioxide and its biofixation using microalgae

The objective of the present study was to set up a small-scale pilot reactor at ONGC Hazira, Surat, for capturing CO₂ from vent gas. The studies were carried out for CO₂ capture by either using microalgae Chlorella sp. or a consortium of microalgae (Scenedesmus quadricauda, Chlorella vulgaris and Chlorococcum humicola). The biomass harvested was used for anaerobic digestion to produce biogas. The carbonation column was able to decrease the average 34 vol.% of CO₂ in vent gas to 15 vol.% of CO₂ in the outlet gas of the carbonation column. The yield of Chlorella sp. was found to be 18 g/m²/day. The methane yield was 386 l CH₄/kg VS_fed of Chlorella sp. whereas 228 l CH₄/kg VS_fed of the consortium of algae.     

不同Ca/P比下碳酸根对磷酸钙沉淀反应回收磷的影响

以模拟污水处理厂污泥厌氧消化液为处理对象,进行磷酸钙沉淀除磷小试实验,考察了不同Ca/P物质的量比下碳酸根(CO2-3)对磷酸钙沉淀反应回收磷的影响;利用扫描电镜(SEM)、X射线衍射仪(XRD)和傅里叶变换红外光谱(FTIR)对沉淀产物进行表征。结果表明,磷酸钙沉淀反应是一个快速过程,CO2-3的存在并未改变这一显著特征。磷酸钙沉淀反应过程中,CO2-3的存在降低了磷的去除率,改变了沉淀物形貌、结构和组分;实验设定范围内,磷酸钙的过饱和度越高,越难形成晶体态羟基磷灰石((Ca5(PO4)3OH,HAP);当pH值为9.0,Ca/P比为1.67时,CO2-3取代HAP晶格中的PO3-4,形成碳磷灰石(CHAP);当pH值为9.0,Ca/P比为3.33和5.01时,CO2-3和PO3-4之间竞争,形成碳酸钙(CaCO3);增大Ca/P能有效提高磷的去除率,降低CO2-3对磷酸钙沉淀反应的抑制作用,但综合考虑实际效果,选择Ca/P比为3.33作为适宜的反应条件。     

Aqueous mineral carbonation of ultramafic material: a pre-requisite to integrate into mineral extraction and tailings management operation

Environmental Science and Pollution Research - Ex situ aqueous mineral carbonation of ultramafic mining waste is an evolving technology for the CO2 sequestration from small- to medium-scale...     

Utilization of waste bittern from saltern as a source for magnesium and an absorbent for carbon dioxide capture

During solar salt production, large quantities of bittern, a liquid by-product containing high inorganic substance concentrations, are produced. The purpose of this research was to examine the utilization of waste bittern generated from salterns as a source for Mg production and as an absorbent for carbon dioxide (CO₂) capture. The study was conducted in a sequential two-step process. At NaOH/Mg molar ratios of 2.70–2.75 and pH 9.5–10.0, > 99% Mg precipitation from the bittern was achieved. After washing with water, 100–120 g/L of precipitate containing 94% Mg(OH)₂ was recovered from the bittern. At the optimum NH₄OH concentration of 5%, 120 g of sodium bicarbonate precipitate per liter of bittern were recovered, which was equivalent to 63 g CO₂ captured per liter of bittern. These results can be used to support the use of bittern as a resource and reduce economic losses during solar salt production.     

Electricity from Fossil Fuels without CO2 Emissions: Assessing the Costs of Carbon Dioxide Capture and Sequestration in U.S. Electricity Markets

ABSTRACT

The decoupling of fossil-fueled electricity production from atmospheric CO₂ emissions via CO₂ capture and sequestration (CCS) is increasingly regarded as an important means of mitigating climate change at a reasonable cost. Engineering analyses of CO₂ mitigation typically compare the cost of electricity for a base generation technology to that for a similar plant with CO₂ capture and then compute the carbon emissions mitigated per unit of cost. It can be hard to interpret mitigation cost estimates from this plant-level approach when a consistent base technology cannot be identified. In addition, neither engineering analyses nor general equilibrium models can capture the economics of plant dispatch. A realistic assessment of the costs of carbon sequestration as an emissions abatement strategy in the electric sector therefore requires a systems-level analysis. We discuss various frameworks for computing mitigation costs and introduce a simplified model of electric sector planning. Results from a “bottom-up” engineering-economic analysis for a representative U.S. North American Electric Reliability Council (NERC) region illustrate how the penetration of CCS technologies and the dispatch of generating units vary with the price of carbon emissions and thereby determine the relationship between mitigation cost and emissions reduction.     

Mineral aerosols from western India: Temporal variability of coarse and fine atmospheric dust and elemental characteristics

Size-segregated aerosol samples (PM_2.5 and PM₁₀) were collected during Jan–Dec-2007 from a high-altitude site located in a semi-arid region (Mt. Abu, 24.6 °N, 72.7 °E, 1680 m asl) in order to asses the temporal variability in the abundance of atmospheric mineral dust and its elemental composition over western India. The mass concentrations of fine (PM_2.5) and coarse (PM_10–2.5) mode aerosols varied from 1.6 to 46.1 and 2.3 to 102 μg m^?3 respectively over the annual seasonal cycle; with dominant and uniform contribution of mineral dust (60–80%) in the coarse mode relative to large temporal variability (11–75%) observed in the fine mode. The coarse mass fraction shows a characteristic increase with the wind speed during summer months (Mar to Jun); whereas fine aerosol mass and its elemental composition exhibit conspicuous temporal pattern associated with north-easterlies during wintertime (Oct–Feb). The Fe/Al weight ratio in PM_2.5 ranges from 0.5 to 1.0 during winter months. The relative enrichment of Fe in fine mode, compared to the crustal ratio of 0.44, is attributed to the down-wind advective transport of combustion products derived from large-scale biomass burning, industrial and automobile emission sources located in the Indo-Gangetic Plain (northern India). In contrast, Ca/Al and Mg/Al weight ratios show relative enrichment of Ca and Mg in the coarse mode; indicating their dominant contribution from carbonate minerals. This has implication to efficient neutralization of atmospheric acidic species (SO₄^2? and NO₃^?) by mineral dust over western India.     

Olivine dissolution from Indian dunite in saline water

The rate and mechanism of olivine dissolution was studied using naturally weathered dunite FO_98.21(Mg_1.884Fe_0.391SiO₄) from an Indian source, that also contains serpentine mineral lizardite. A series of batch dissolution experiments were carried out to check the influence of temperature (30–75 ^°C), initial dunite concentration (0.5 and 20 g/L), and salinity (0–35 g/L NaCl) under fixed head space CO₂ pressure (P\(_{\text {CO}_{2}}\) = 1 barg) on dunite dissolution. Dissolved Mg, Si, and Fe concentrations were determined by inductive coupled plasma atomic emission spectroscopy. End-product solids were characterized by scanning electron microscopy and X-ray diffraction. Initially, rates of dissolution of Si and Mg were observed to be in stoichiometric proportion. After 8 h, the dissolution rate was observed to decline. At the end of the experiment (504 h), an amorphous silica-rich layer was observed over the dunite surface. This results in decay of the dissolution rate. The operating conditions (i.e., salinity, temperature, and mineral loading) affect the dissolution kinetics in a very complex manner because of which the observed experimental trends do not exhibit a direct trend.     

Biomineralization-based conversion of carbon dioxide to calcium carbonate using recombinant carbonic anhydrase

Recently, as a mimic of the natural biomineralization process, the use of carbonic anhydrase (CA), which is an enzyme catalyzing fast reversible hydration of carbon dioxide to bicarbonate, has been suggested for biological conversion of CO₂ to valuable chemicals. While purified bovine CA (BCA) has been used in previous studies, its practical utilization in CO₂ conversion has been limited due to the expense of BCA preparation. In the present work, we investigated conversion of CO₂ into calcium carbonate as a target carbonate mineral by using a more economical, recombinant CA. To our knowledge, this is the first report of the usage of recombinant CA for biological CO₂ conversion. Recombinant α-type CA originating in Neisseria gonorrhoeae (NCA) was highly expressed as a soluble form in Escherichia coli. We found that purified recombinant NCA which showed comparable CO₂ hydration activity to commercial BCA significantly promoted formation of solid CaCO₃ through the acceleration of CO₂ hydration rate, which is naturally slow. In addition, the rate of calcite crystal formation was also accelerated using recombinant NCA. Moreover, non-purified crude recombinant NCA also showed relatively significant ability. Therefore, recombinant CA could be an effective, economical biocatalyst in practical CO₂ conversion system.     

Exploratory study of some potential environmental impacts of CO2 sequestration in unmineable coal seams

An initial investigation into the potential environmental impacts of CO₂ sequestration in unmineable coal seams has been conducted, focusing on changes in the produced water during enhanced coalbed methane (ECBM) production, using a CO₂ injection process (CO₂-ECBM). A high volatile bituminous coal, Pittsburgh No. 8, was reacted with synthetic produced water and gaseous carbon dioxide at 40°C and 50 bar to evaluate the potential for mobilisation of toxic metals during CO₂-ECBM/sequestration. Microscopic and X-ray diffraction analysis of the post-reaction coal samples clearly show evidence of chemical reaction and chemical analysis of the synthetic produced water shows substantial changes in composition. These results suggest that changes to the produced water chemistry and the potential for mobilising toxic trace elements from coal beds are important factors to be considered when evaluating deep, unmineable coal seams for CO₂ sequestration.     

高硬度富锶地下水的软化沉淀-超滤膜联用工艺

针对一种高硬度富锶地下水,分别采用石灰和石灰-碳酸钠两种方法,利用药剂软化/超滤膜工艺对其进行软化处理,同时考察了药剂投量对出水锶含量的影响。结果表明,采用石灰软化/超滤膜法,Ca(OH)2最佳投加量为270 mg/L时,出水总硬度(以CaCO3计)由287.12 mg/L降低到96.44 mg/L,硬度去除率为66.41%,出水锶含量也由原水中的0.37 mg/L下降为0.21 mg/L;而采用石灰-碳酸钠软化/超滤膜法,Ca(OH)2和Na2CO3最佳投加量分别为270 mg/L、160mg/L时,出水总硬度降低到60.34 mg/L,硬度去除率达78.98%,锶含量仅为0.02 mg/L。2种处理方法出水总硬度均达到预期目标,石灰软化/超滤膜法可使出水锶含量满足富锶水的要求,而石灰-碳酸钠软化/超滤膜法则造成了对人体有益微量元素锶的大量损失。     

Effects of high dose copper on plant growth and mineral nutrient (Zn,Fe, Mg,K, Ca) uptake in spinach

Loessal soil is one of the main cultivated soils in northwest China. Part of its distribution area was irrigated with industrial wastewater in past three decades. This caused heavy metal contamination in the soil. It had induced toxicity on crops and also threatened local human health for now. Based on a field plot experiment, effects of different Cu concentrations (from 45 to 2000 mg kg^?1) in loessal soil on spinach plant growth and uptake of mineral nutrients (Zn, Fe, Mg, K, and Ca) by spinach were investigated. The Cu addition increased available concentrations of mineral nutrients in loessal soil and concentrations of Cu, Zn, Mg, and Ca in roots. The translocation of mineral nutrients from roots to leaves was inhibited under Cu addition, inducing their decrease in leaves. The EC₁₀ and EC₅₀ of soil Cu in relative dry weights of leaves were 240.33 mg kg^?1 and 1205.04 mg kg^?1, respectively. The PLS-PM analysis showed that available concentrations of nutrients in soil were only affected by Cu in soil positively, nutrients in roots were mainly affected by Cu in soil and Cu in leaves positively, nutrients in leaves were mainly affected by Cu in roots negatively, translocation of nutrients in spinach and plant growth were principally affected by Cu in leaves negatively, and the total effect of Cu in leaves on nutrients in roots and leaves, translocation of nutrients in spinach, and plant growth was the highest. Our results indicated that the phytotoxicity of Cu including spinach growth inhibition and mineral disorder in spinach was mainly affected by the Cu concentrations in leaves.

     

Sorption of SO2 on Ground Nahcolite Ore

Large quantities of nahcolite ore, a naturally occurring mineral containing between 70 and 90% sodium bicarbonate are known to occur in the Green River Formation of the Piceance Creek Basin of northwestern Colorado.¹ Deposits occur in two major forms, as either bedded or disseminated ore. In the latter case, the host rock is oil shale, a dolomitic marlstone containing kerogen material. Bench and pilot scale studies have shown finely divided nahcolite ore to be an effective SO₂ sorbent in baghouse filters.² These studies form the basis of the nahcolite ore injection process as a means for controlling SO₂ emissions to the environment.³ Although there have been published investigations of reactions of SO₂ with Na₂CO₃and NaHCO_3, ⁴ no reference could be found to a systematic study of nahcolite ore reacting with SO₂.     

脱硫灰与钾矿石复合生产钾钙硅镁硫肥料研究

对脱硫灰与钾矿石复合生产钾钙硅镁硫肥的研究意义、反应原理、生产流程、环境安全性能以及施肥方法等进行了介绍和评估,并对其应用前景进行了展望。研究结果表明:利用脱硫灰与钾矿石复合生产钾钙硅镁硫肥在理论上可行;生产出的产品中硫酸钾的含量达10.34%～12.0%,枸溶氧化钙19.06%～32.28%,枸溶二氧化硅10.98%～14.46%,枸溶氧化镁1.46%～1.82%。产品的pH值从原脱硫灰的10.65下降到9.60。重金属含量低于农用粉煤灰国家标准,生产过程中不会产生SO2等有害气体污染。肥料的生产成本低于350元/t,该肥料不但可以增加土壤中钾、钙、硅、镁和硫等中微量元素的含量,而且可以提高或改善农作物的产量和品质。达到变废为宝,促进循环经济发展之目的。     

Soil nitrogen transformations under elevated atmospheric CO₂ and O₃ during the soybean growing season

We investigated the influence of elevated CO₂ and O₃ on soil N cycling within the soybean growing season and across soil environments (i.e., rhizosphere and bulk soil) at the Soybean Free Air Concentration Enrichment (SoyFACE) experiment in Illinois, USA. Elevated O₃ decreased soil mineral N likely through a reduction in plant material input and increased denitrification, which was evidenced by the greater abundance of the denitrifier gene nosZ. Elevated CO₂ did not alter the parameters evaluated and both elevated CO₂ and O₃ showed no interactive effects on nitrifier and denitrifier abundance, nor on total and mineral N concentrations. These results indicate that elevated CO₂ may have limited effects on N transformations in soybean agroecosystems. However, elevated O₃ can lead to a decrease in soil N availability in both bulk and rhizosphere soils, and this likely also affects ecosystem productivity by reducing the mineralization rates of plant-derived residues.