The Determination of the Level of Bicarbonate,Carbonate, or Carbon Dioxide in Aqueous Solutions

Abstract

A rapid and convenient method for the measurement of bicarbonate, carbonate, or carbon dioxide in water was developed using fourier transform infrared spectroscopy (FTIR). Bicarbonate and carbonate are converted to carbon dioxide by lowering the pH of the solution, then the absorbance of the dissolved carbon dioxide at 2345 wavenumbers is measured using a liquid sample cell. If the measurement of dissolved carbon dioxide is the objective, the pH is not adjusted, and the carbon dioxide in the free form can be measured without interference from low levels of carbonates. The method is linear from 10.48 ppm to a minimum of 366.8 ppm carbon dioxide (r squared = 0.9996). The coefficient of variation at 10.48 ppm (LOD 3 signal/noise), 52.4 ppm, and 262 ppm is 45.6, 4.0, and 3.9, respectively. The average percent recovery at 10.48 ppm, 52.4 ppm, and 262 ppm is 74.5, 104.2, and 104.0, respectively.     

A system for the direct determination of the nonvolatile organic carbon,dissolved organic carbon,and inorganic carbon in water samples through inductively coupled plasma atomic emission spectrometry

A new system has been developed for the determination of total organic carbon (TOC) and inorganic carbon (IC) or total inorganic carbon (TIC) in waters. Only nonvolatile organic compounds can be detected through the present method. The system presented in this work is based on the measurement of the carbon atomic emission intensity in inductively coupled plasma atomic emission spectrometry (ICP-AES). This way, the organic matter does not undergo any preoxidation step. A semiautomatic accessory connected to the spectrometer separates the different carbon fractions (i.e., organic and inorganic). Because most of the solutions used in the present work did not contain suspended solid particles, the actual parameter that was determined was the dissolved organic carbon (DOC). The present system exhibits good sensitivities compared to those provided by conventional TOC and IC determination methods. The limits of detection obtained in the present work have been 0.07 and 0.0007 mg/L C in terms of TOC and IC, respectively. Furthermore, the system is able to handle high-salt-content solutions. This fact suggests that it would be possible to analyze seawater samples, avoiding some of the problems encountered with conventional methods, such as system blocking or interferences. The TOC and IC values found for natural samples are very close to those measured using conventional methods. The ICP-AES method has been successfully used in two interesting applications: (i) monitoring the efficiency of a water treatment plant and (ii) determining the contents of dissolved carbon dioxide, on one hand, and that of carbonate and bicarbonate, on the other, in the same sample.     

Photoelectrochemical oxygen sensor using copper-plated screen-printed carbon electrodes

We report here an efficient photocatalytic amperometric sensor for the determination of dissolved oxygen (DO) in phosphate buffer solution using a disposable copper-plated screen-printed carbon electrode (CuSPE). The photoelectrochemical activity toward DO of the CuSPE was related to the formation of a p-type semiconductor Cu(I)2O. The solution pH and biased potential (E(bias)) were systematically optimized as pH 8 PBS and -0.7 V vs Ag/AgCl, respectively. Under optimized conditions, the calibration plot was linear in the range of 1-8 ppm with sensitivity and regression coefficient of 23.51 (microA cm2)(-1) ppm(-1) and 0.9982, respectively. The reproducibility of the system was good with seven successive measurements of DO yielding a RSD value of 1.87%. Real sample assays for groundwater and tap water were also consistent with those measured by a commercial DO meter. The principle used in DO measurement has an opportunity to extend into various research fields.     

Direct determination of carbon dioxide in aqueous solution using mid-infrared quantum cascade lasers

A method for the direct determination of carbon dioxide in aqueous solutions using a room-temperature mid-infrared (MIR) quantum cascade laser at 2330 cm(-1) is reported. The absorption values of different carbon dioxide concentrations were measured in a 119 microm CaF2 flow-through cell. An optical system made of parabolic mirrors was used to probe the flow cell and to focus the laser beam on the mercury cadmium telluride (MCT) detector. Aqueous carbon dioxide standards were prepared by feeding different mixtures of gaseous N2 and CO2 through wash bottles at controlled temperature. The concentration of the dissolved CO2 was calculated according to Henry's law, taking into account the temperature and the partial pressure of CO2. The carbon dioxide standards were connected via a selection valve to a peristaltic pump for subsequent, automated measurement in the flow-through cell. A calibration curve was obtained in the range of 0.338 to 1.350 g/L CO2 with a standard deviation of the method sxo equal to 19.4 mg/L CO2. The limit of detection was calculated as three times the baseline noise over time and was determined to be 39 mg/L.     

Synthesis, characterization and capacitive performance of hydrous manganese dioxide nanostructures

Hydrous manganese dioxide nanostructures were synthesized via a catalytic oxidation reaction mechanism at mild temperatures. It was found that the morphology of the manganese dioxide nanostructures was significantly influenced by the pH of the reaction system. With increasing pH the morphology of manganese dioxide nanostructures changed from urchin-like structures to nanobelts. The capacitive performance was investigated by using cycle voltammetry and galvanostatic charge/discharge techniques. Hydrous manganese dioxide nanostructures obtained from a basic solution exhibited a capacitance of 262 F g(-1) at a current density of 250 mA g(-1) and a capacitive retention of 75% after 1200 cycles, suggesting that this is a promising electrode material for supercapacitors. The high specific capacitance is attributed to the hydrous nature coupled with a high surface area (181 m(2) g(-1)) of the manganese dioxide nanostructure.     

The chemical effects of storing hydrazine containing carbon dioxide impurity in stainless steel systems

The effect of low concentrations (<250 ppm) of dissolved carbon dioxide (carbazic acid) on the rate of decomposition of hydrazine, in both stainless steel and glass vessels, has been investigated. In a stainless steel vessel at 60°C the rate of hydrazine decomposition was found to be directly proportional to the total concentration of added carbon dioxide (above about 20 ppm) while for a glass vessel at 51°C the relationship between concentration of added carbazic acid and hydrazine decomposition rate is best interpreted in terms of a Langmuir isotherm equation. The preparation of some carbazato-complexes of iron, chromium and nickel, such as may be formed during the hydrazine/carbon dioxide corrosion of stainless steel, is also reported. Additions of small amounts of dicarbazatodihydrazineiron (II) to hydrazine in a glass vessel had no measurable effect on the decomposition rate at 43°C. Tricarbazatochromium (III) dihydrate was found to be similarly inactive while the principal nickel carbazato- complex is completely insoluble in hydrazine.     

Enhanced Serum Carbon Dioxide Measurements with a Silicone Rubber-Based Carbonate Ion-Selective Electrode and a High-pH Dilution Buffer

A new silicone rubber matrix carbonate-selective membrane and a high-pH buffer diluent are used to enhance the performance of the electrode measurements for serum carbon dioxide. The proposed membrane employs one-component silicone rubber as the matrix and trifluoroacetyl-p-decylbenzene as the neutral ionophore. The optimized membrane formulation incorporates as high as 21.9 wt % plasticizer (e.g., bis(2-ethylhexyl) adipate). The highly plasticized silicone rubber membranes not only function equivalently, in terms of the carbonate response, to the conventional PVC matrix membranes, but they also exhibit substantially reduced interfering response toward salicylate. Furthermore, the silicone rubber membrane exhibits better adhesion to the solid surface than do PVC or PU membranes. The use of higher pH buffers (e.g., 2-amino-2-methyl-1-propanol (AMP)-H(2)SO(4), pH 9.5-10.5) further enhances the selectivity of the carbonate electrode measurement system for total CO(2) species over other anions. It is shown that the combined use of the silicone rubber matrix membrane and the high-pH AMP buffer provides a carbonate sensor system that is substantially less subject to interference from salicylate and chloride than is the conventional measurement system employing the PVC-based electrode with the lower pH (8.4-8.8) buffer diluent.     

Effect of sintering parameters on the density and microstructure of carbonate hydroxyapatite

This work documents an investigation into the effect of water on the density and microstructure of carbonate hydroxyapatite in carbon dioxide sintering atmospheres. Carbonate apatites with carbonate contents of between 3.2 and 7.8 wt % were precipitated and the precipitates were formed into dry gels. Isothermal and isochronal sintering experiments were performed under dry carbon dioxide and wet carbon dioxide (containing 3 wt % water) atmospheres. The effect of carbonate content was studied by using two gels both with a green density of 37% and with carbonate contents of 5.8 and 7.8 wt %. Both isothermal and isochronal experiments demonstrated that bloating of the apatite occurred and this behavior was associated with the loss of carbonate from the apatite. It was found that only in wet carbon dioxide atmospheres fully dense translucent carbonate apatite could be formed. 93% dense carbonate apatite was formed after 4 h sintering at temperatures as low as 700 °C. © 2000 Kluwer Academic Publishers     

点排放源中二氧化碳浓度的测量研究

大气中温室气体浓度的增加引起的全球气候变化是世界关注的焦点问题。在所有的排放源中,固定排放源排放的二氧化碳气体是温室效应的主要因素。政府间气候变化专门委员会(IPCC)将直接测量排放量方法列为温室气体排放清单统计的最高等级,以提高数据统计精度。为了实现排放量的精确测量,固定排放源浓度直接测量至关重要。基于分析吸收光谱建立了相对于纯气体的测量方法,通过多次反射直接吸收光谱技术,建立了精确测量二氧化碳浓度的相对法装置,测量了293 K和0~13 kPa下二氧化碳在6 362.5 cm^-1的(30012)←(00001)R20e跃迁谱线,通过与纯二氧化碳吸收面积的比较得到15%,35%,50%和75%二氧化碳混合物的浓度。结果表明与天平称重法得到的结果具有很好的一致性,相对扩展测量不确定度在0.7%以下(k=2)。     

Direct optical carbon dioxide sensing based on a polymeric film doped with a selective molecular tweezer-type ionophore

A novel optical method for the determination of CO(2) concentration in aqueous and gaseous samples of plasticized PVC film is presented. The detection principle makes use of a direct molecular recognition of the carbonate ion by a molecular tweezer-type ionophore, which has previously been demonstrated to exhibit excellent carbonate selectivity. The carbonate ion is extracted together with hydrogen ions into a polymeric film that contains the anion exchanger tridodecylmethylammonium chloride, a lipophilic, electrically charged, and highly basic pH indicator, which is used for the readout in absorbance mode, in addition to the lipophilic carbonate ionophore. According to known bulk optode principles, such an optical sensor responds to the product of the carbonate ion activity and the square of hydrogen ion activity. This quantity is thermodynamically linked to the activity of carbon dioxide. This allows one to realize a direct carbon dioxide sensor that does not make use of the traditional Severinghaus sensing principle of measuring a pH change upon CO(2) equilibration across a membrane. A selectivity analysis shows that common ions such as chloride are sufficiently suppressed for direct PCO(2) measurements in freshwater samples at pH 8. Chloride interference, however, is too severe for direct seawater measurements at the same pH. This may be overcome by placing a gas-permeable membrane over the optode sensing film. This is conceptually confirmed by establishing that the sensor is equally useful for gas-phase PCO(2) measurements. As expected, humid air samples are required for proper sensor functioning, as dry CO(2) gas will not cause any signal change. The sensor showed acceptable response times and good reproducibility under both conditions.     

基于多次反射直接吸收精确测量二氧化碳浓度的研究

二氧化碳气体排放过多是造成温室效应的主要原因,对全球环境及生态系统产生了深远影响。企业燃料燃烧产生的二氧化碳是城市区域碳排放的主要来源。为了通过碳排放交易来实现企业减排,就必须对企业烟囱排放二氧化碳进行精确的计量,而企业烟囱排放的二氧化碳含量一般在20%以下,需要建立高准确度的现场测量方法。通过多次反射吸收光谱技术精确获得二氧化碳在6 361. 25 cm^-1的(30012)←(00001) R18e跃迁谱线信息,进一步结合理想气体方程来精确获得15%,10%,5%和1%二氧化碳/氮气(氮气为平衡气体)混合物的浓度。结果表明所建立的装置和方法能够快速精确地测量待测气体的浓度,测量结果与基于天平的称重法相当,扩展相对不确定度小于0. 65%(k=2)。     

基于Herriott吸收池的固定源二氧化碳浓度测量研究

准确的碳排放计量是实现“碳峰化、碳中和”目标的重要一步。在所有碳排放源中,固定排放源排放的CO2是温室效应的主要因素。因此,精确测量固定排放源CO2的浓度尤为重要。基于近红外分子吸收光谱原理并结合多次反射直接吸收光谱技术,利用35% CO2/N;2混合物,建立了精确测量CO2浓度的方法,测量了293K和0,4.1,8.1,13.3kPa下,CO2在6359.97cm-1的(30012)←(00001)R16e和6361.25cm-1的(30012)←(00001)R18e跃迁谱线,计算了R18e的谱线强度,通过比较35% CO2/N2混合物和其它CO2/N;2混合物的吸收面积,可以得到15%,10%,5%的CO2/N;2混合物的浓度。结果表明所建立的理论方法和实验结果能够较好地表征待测气体的浓度,测量不确定度与基于天平的称重法相当。     

Trace detection of dissolved hydrogen gas in oil using a palladium nanowire array

The electrical resistance, R, of an array of 30 palladium nanowires is used to detect the concentration of dissolved hydrogen gas (H(2)) in transformer oil over the temperature range from 21 to 70 °C. The palladium nanowire array (PdNWA), consisting of Pd nanowires ～100 nm (width), ～20 nm (height), and 100 μm (length), was prepared using the lithographically patterned nanowire electrodeposition (LPNE) method. The R of the PdNWA increased by up to 8% upon exposure to dissolved H(2) at concentrations above 1.0 ppm and up to 2940 ppm at 21 °C. The measured limit-of-detection for dissolved H(2) was 1.0 ppm at 21 °C and 1.6 ppm at 70 °C. The increase in resistance induced by exposure to H(2) was linear with [H(2)](oil)(1/2) across this concentration range. A PdNWA sensor operating in flowing transformer oil has functioned continuously for 150 days.     

Biodegradability of packaging materials using a respirometric method

To measure the biodegradability of packaging materials, a scientific and methodological approach is proposed, using the results obtained with cellulosic materials as models. Their degradation was evaluated using a respirometric method based on the measurement of CO₂ released by microorganisms (Pseudomonas fluorescens and a mixture of cellulolytic bacteria). Our study was conducted in confined conditions, and the CO₂ released was detected by gas chromatography (GC). Glucose was used as a reference compound because of its complete bioassimilation by the strains studied. The percentage of carbon converted into carbon dioxide was the parameter used to classify materials according to their potential biodegradability. With both inocula, the percentage of absolute conversion of glucose to CO₂ reached about 36% compared with 24% and 13% for the hydrated crystalline cellulose and the paraffin waxed paper, respectively. Measurements of the percentage of absolute conversion of glucose to CO₂, of the dissolved carbon in the culture medium, of the biomass carbon and of the residual glucose permitted the calculation of an approximate carbon balance with Pseudomonas fluorescens. The percentages of absolute and relative conversion of packaging materials into CO₂ were calculated and the growth rates evaluated. It was shown that to evaluate the biodegradation of insoluble substrates, the biomass produced and the dissolved carbon must be taken into account.     

Biofiltration of volatile ethanol using sugar cane bagasse inoculated with Candida utilis.

Candida utilis (C. utilis) growing on sugar cane bagasse complemented with a mineral salt solution was studied for gaseous ethanol removal in a biofilter. Ethanol loads from 93.7 to 511.9 g/h m(3) were used, by varying both inlet ethanol concentration (9.72 to 52.4 g/m(3)) and air flow rate (1.59 x 10(-3) to 2.86 x 10(-3) m(3)/h). At a loading rate of 93.7 g/h m(3), a steady-state was maintained for 300 h. Ethanol removal was complete, and 76.3% of the carbon consumed was found in carbon dioxide. At an higher aeration rate (ethanol load=153.8 g/h m(3)), the biofilter displayed an average removal efficiency (RE) of 70%, and an elimination capacity (EC) of 107.7 g/h m(3). Only 64.4% of the carbon consumed was used for CO(2) production. Acetaldehyde and ethyl acetate in the outlet gas attained 7.86 and 20.4% in terms of carbon balance, respectively. In both cases, the transient phase was less than one day. At a high inlet ethanol concentration (52.4 g/m(3)), no steady-state was observed and the process stopped during the third day. In the three cases, final biomass was poor, ranging from 10.5 to 14.8 mg/g dm. Final pH 4.0-4.6, indicated that acidifying non-volatile metabolites, such as acetate, accumulated in the reactor.     

Thermal decomposition of synthesised carbonate hydroxyapatite

Heat treatments are used when sintering hydroxyapatite to make porous blocks and granules and during plasma spraying of coatings. Calcium : phosphorus ratio is known to affect the thermal decomposition behavior of hydroxyapatite. Hydroxyapatite with carbonate ions substituted for phosphate ions is more similar in composition to bone mineral. While it has been shown that carbonate apatite may be sintered, relatively little is known about its high temperature stability. Various atmospheres have been used in investigations into the thermal stability of hydroxyapatites and carbonate hydroxyapatites, including nitrogen, wet carbon dioxide air, water vapor and wet oxygen, but few of these studies were directly comparable. Previous work has shown that loss of carbonate from CHA at high temperature is time dependent, which suggests that rapid high temperature treatment may prevent carbonate loss during processing. This study investigated the effect of dry carbon dioxide, carbon dioxide containing 3% water, nitrogen and nitrogen containing 3% water on the phase composition of hydroxyapatite containing between 1.0 and 11.5 wt % carbonate rapidly heated to temperatures of between 700 and 1400 °C. Carbonate ion substitution was observed to decrease the temperature at which crystallisation occurred to a minimum of 700 °C for 11.8 wt % carbonate apatite heated in wet atmospheres. Atmosphere was found to appreciably affect the crystallization temperature and phase transformations of carbonate apatite containing 7.8 wt % carbonate. In wet and dry carbon dioxide atmospheres, crystallisation began in this material at 1100 and 900 °C, TCP was formed at 1500 and 1300 °C respectively. The high temperature decomposition of carbonate hydroxyapatite would appear to depend on the composition of the apatite and the atmosphere in which it is heated.     

Characterization of inorganic fraction of spent potliners: evaluation of the cyanides and fluorides content.

Spent potliner (SPL) is a solid waste generated by the aluminum industry during the manufacture of aluminum metal in electrolytic cells. Initially the electrolityc cell liners comprise of graphite and carbonaceous materials, but after several years of operation, the liner materials deteriorate and must be removed from the cells. Because of the presence of fluoride and cyanide in the SPL, the US Environmental Protection Agency (USEPA) has listed the materials as a hazardous waste. The purpose of this work was to characterize the extent of leaching of cyanides and fluorides from SPL, as a function of the number of years the material was present in an operating electrolytic cell. At Alumínio Brasileiro S.A. (ALBRAS) plant, SPL was separated into two fractions: a carbon component and an inorganic part. Inorganic materials from nine pots, about 28 tonnes per pot, were examined in this study. When placed in water at a ratio of 20 g solid to 20 ml of water, the pH for all samples varied from 10 to 11.8. The total measured fluoride content of the solid samples varied from 5.13 to 11.41%. However, when leached at a pH of 5, the dissolved fluoride was equivalent to only 0.26-3.46%. With a pH of 12 in the leachate solution, the dissolved fluoride was equivalent to 6.45-9.39%. The data show that the fluorides of the waste are more soluble in basic solutions, and when leached at a pH of 12 are much closer to the actual fluorides content. For the same samples, the dissolved quantity of cyanide was equivalent to 4.34-27.33 ppm, with an average of 13.26 ppm. For all the samples studied, there did not appear to be a correlation between the fractions of fluoride and cyanide leached from the samples and the operating life of the potliner materials.     

Testing carbon sequestration site monitor instruments using a controlled carbon dioxide release facility

Two laser-based instruments for carbon sequestration site monitoring have been developed and tested at a controlled carbon dioxide (CO(2)) release facility. The first instrument uses a temperature tunable distributed feedback (DFB) diode laser capable of accessing the 2.0027-2.0042 microm spectral region that contains three CO(2) absorption lines and is used for aboveground atmospheric CO(2) concentration measurements. The second instrument also uses a temperature tunable DFB diode laser capable of accessing the 2.0032-2.0055 mum spectral region that contains five CO(2) absorption lines for underground CO(2) soil gas concentration measurements. The performance of these instruments for carbon sequestration site monitoring was studied using a newly developed controlled CO(2) release facility. A 0.3 ton CO(2)/day injection experiment was performed from 3-10 August 2007. The aboveground differential absorption instrument measured an average atmospheric CO(2) concentration of 618 parts per million (ppm) over the CO(2) injection site compared with an average background atmospheric CO(2) concentration of 448 ppm demonstrating this instrument's capability for carbon sequestration site monitoring. The underground differential absorption instrument measured a CO(2) soil gas concentration of 100,000 ppm during the CO(2) injection, a factor of 25 greater than the measured background CO(2) soil gas concentration of 4000 ppm demonstrating this instrument's capability for carbon sequestration site monitoring.     

Detection of copper in water using on-line plasma-excited atomic absorption spectroscopy (AAS)

A measurement method and apparatus was developed to measure continuously toxic metal compounds in industrial water samples. The method was demonstrated by using copper as a sample metal. Water was injected into the sample line and subsequently into a nitrogen plasma jet, in which the samples comprising the metal compound dissolved in water were decomposed. The transmitted monochromatic light was detected and the absorbance caused by copper atoms was measured. The absorbance and metal concentration were used to calculate sensitivity and detection limits for the studied metal. The sensitivity, limit of detection, and quantification for copper were 0.45 ± 0.02, 0.25 ± 0.01, and 0.85 ± 0.04 ppm, respectively.     

A hybrid model of the CO2 geochemical cycle and its application to large impact events

A hybrid model of the carbonate-silicate geochemical cycle is presented which is capable of calculating the partitioning of carbon dioxide between the atmosphere, ocean, and sedimentary rocks. The ocean is subdivided into a shallow, mixed layer, which remains in equilibrium with the atmosphere, and a massive, deep layer which does not. Gradients in dissolved carbon content are established between the mixed layer and the deep ocean as a consequence of downward fluxes of fecal matter and of dead planktonic organisms. The dissolved carbon content and alkalinity of the ocean as a whole are controlled by weathering and metamorphism of sedimentary rocks. Equilibrium solutions are derived for the preindustrial atmosphere/ocean system and for a system that may be similar to that existing during the Late Cretaceous Period. The model is then used to determine how the modern and ancient marine biospheres might be affected by an oceanic impact of a large asteroid or comet. Such an event could perturb the carbon cycle in several different ways. Global darkening caused by stratospheric dust veil could destroy most of the existing phytoplankton in a period of several weeks to several months. At the same time, dissolution of atmospheric NOx compounds synthesized during the impact would lower the pH of ocean surface waters and release CO2 into the atmosphere. Both effects might be enhanced by an influx of CO2 released from upwelling of deep ocean water near the hot impact site, from oxidation of dead organic matter, and from the comet itself. The net result could be to raise surface temperatures by several degrees and to make the surface ocean uninhabitable by calcareous organisms for as much as 20 yrs (the time scale for mixing with deep ocean). It appears unlikely, however, that an impact could create a "Strangelove ocean," in which surface waters remained corrosive to calcium carbonate for thousands or tens of thousands of years. Thus, disruption of the carbon cycle by an impact event cannot by itself explain the scarcity of calcium carbonate in sediments found within the first few centimeters above the K/T boundary.