Instrumental activation analysis of coal and fly ash with thermal and epithermal neutrons and short-lived nuclides

Instrumental neutron activation analysis is applied to the determination of about 25 elements in coals and fly ash by means of nuclides with half-lives of less than 48 h ; thermal and epithermal irradiations are used. The results indicate that epithermal activation is preferable for twelve of the elements (Ga, As, Br, Sr, In, Cs, Ba, La, Sm, Ho, W and U). Data for SRM 1632 (coal) and SRM 1633 (fly ash) compare favorably with the results obtained by other investigators.     

Determination of 30 elements in coal and fly ash by thermal and epithermal neutron-activation analysis

Thirty elements are determined in coal and fly ash by instrumental neutron-activation analysis using both thermal and epithermal irradiation. Gamma-ray spectra were recorded 7 and 20 days after the irradiations. The procedure is applicable to the routine analysis of coals and fly ash. Epithermal irradiation was found preferable for the determination of Ni, Zn, As, Se, Br, Rb, Sr, Mo, Sb, Cs, Ba, Sm, Tb, Hf, Ta, W, Th and U, whereas thermal irradiation was best for Sc, Cr, Fe, Co, La, Ce, Nd, Eu, Yb and Lu. Results for SRM 1632 (coal) and SRM 1633 (fly ash) agree with those of other investigators.     

Determination of cadmium,mercury and lead in coal fly ash by slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

Ultrasonic slurry sampling electrothermal vaporization isotope dilution inductively coupled plasma mass spectrometry (USS-ETV-ID-ICP-MS) has been applied to the determination of Cd, Hg and Pb in coal fly ash samples. Thioacetamide (TAC) was used as the modifier. Since the sensitivities of the elements studied in coal fly ash slurry and aqueous solution were quite different, isotope dilution method was used for the determination of Cd, Hg and Pb in these coal fly ash samples. The isotope ratios of each element were calculated from the peak areas of each injection peak. This method has been applied to the determination of Cd, Hg and Pb in NIST SRM 1633a coal fly ash reference material and a coal fly ash sample collected from Kaohsiung area. Analysis results of reference sample NIST SRM 1633a coal fly ash agreed satisfactorily with the certified values. The other sample determined by isotope dilution and method of standard additions was agreed satisfactorily. Precision was better than 6% for most of the determinations and accuracy was better than 4% with the USS-ETV-ID-ICP-MS method. Detection limits estimated from standard addition curves were in the range of 24–58, 6–28 and 108–110 ng g⁻¹ for Cd, Hg and Pb, respectively.     

The determination of traces of cadmium,lead and thallium in fly ash by potentiometric stripping analysis

The suitability of potentiometric stripping analysis for the determination of cadmium, lead and thallium in fly ash and in waters polluted by leaching of fly ash is assessed. By an appropriate choice of medium and of electrolysis potential and by employing a rotating working electrode, it is possible to eliminate interferences from electroactive species often found in fly ash in high concentrations. The accuracy obtained in a study of a certified coal fly ash (SRM 1633a) is satisfactory.     

Determination of Arsenic and Vanadium in Airborne Related Reference Materials By ICP-MS

This study investigated sample digestion techniques and instrumental interference in determining As and V in airborne related reference materials using inductively coupled plasma mass spectrometry (ICP-MS). Four reference materials, NIST SRM 1648 urban particulate matter,BCR Reference Material No. 176 city waste incineration ash, NIST SRM 2709 San Joaquin soil, and NIST SRM 1633b coal fly ash were dissolved through acid mixture high-pressure bomb digestion.     

Production and separation of no-carrier-added 48V from 16O irradiated chlorine target

The viability of ground coal bottom ash as a potential Portland cement constituent to be used in building materials is assessed. Currently, coal fly ash is used to produce Portland cements and concretes. However, coal bottom ash is mainly landfilled. Gamma spectrometry analysis, compressive strength, physical and chemical testing were performed. The ground coal bottom ash activity concentration index (I = 1.03) was compared to that of the coal fly ash (I = 1.11) provided from the same thermo-electrical power plant. Ground coal bottom ash could be used in building materials in the same way as coal fly ash as a Portland cement constituent.

     

Development of a slurry-extraction procedure for direct determination of cobalt by electrothermal atomic absorption spectrometry in complex environmental samples

A new procedure for Co determination in a complex matrix (coal fly ash) by slurry extraction-electrothermal atomic absorption spectrometry (ETAAS) is presented. Fractional experimental designs were applied to find the most important variables affecting Co extraction. Two liquid media (HCl + HNO₃ and HF) and three agitation modes (ultrasonic probe, ultrasonic bath and manual shaking) were assayed. HF revealed as the most suitable medium for Co extraction, being its concentration and time of contact the most significant variables. Quantitative extraction was obtained after their optimisation (16%, v/v HF; 5 min), with good accuracy (coal fly ash SRM 1633a and SRM 1633b) and precision (R.S.D. < 11.5%). The limit of detection of the method was 0.02 μg g⁻¹ (100 mg mL⁻¹ slurry), and the characteristic mass was 15 ± 1 pg. The ‘slurry-extraction procedure’ established is simple, fast, cheap and was also validated for soil and sediment analysis. As far as we know, a slurry-extraction procedure has not yet been applied to quantify cobalt by ETAAS in such matrices. Moreover, nine coal fly ashes, 12 sediments and 18 soils were analysed by the proposed method and also by a direct slurry sampling-ETAAS procedure in order to compare their performance. In general, the HF-extraction slurry procedure revealed superior.     

Establishing a basis for nuclear archaeometry in Australia using the 20 MW OPAL research reactor

The k ₀-method of standardisation for instrumental neutron activation analysis (INAA) has been used at the OPAL research reactor to determine the elemental composition of three certified reference materials: coal fly ash (SRM 1633b), brick clay (SRM 679) and Montana soil (SRM 2711). Of the 41 certified elements in the three materials, 88 percent were within five percent of the certified values and all determinations were within 15 percent of the certified values. The average difference between the measured and certified values was 0.1 percent, with a standard deviation of 4.1 percent. Since these reference materials are widely used as standards in the analysis of archaeological ceramics by INAA, it has been concluded that the INAA facility in Australia is particularly well-suited for nuclear archaeometry.     

Composition and morphology of stack emissions from coal and oil fuelled boilers

Instrumental neutron activation analysis (INAA) together with scanning electron microscopy (SEM) have been used in the study of fly ash from large electric power and heating plants. Two basic kinds of fly ash originating either from brown coal or heavy-oil combustion can be characterized both by morphology and trace element composition. INAA technique used consisted of both short (1 min) and long (2 h) activations to ensure the determination of 30–40 elements in each fly ash sample. The average composition and determination limits obtained by INAA for coal fly ash produced in several electric power plants burning two kinds of brown coal have been compared with those obtained for fly ash originating from heating plants burning heavy-oil. Coal fly ash showed much higher concentrations of many elements especially of Sc. La, Th, Cs, Ce, Sm, Rb and Al in comparison with oil fly ash. On the other hand, the latter contained relatively high concentrations of V and Ni. The results of INAA of fly ash samples can be used for the projection of efficient separating devices and for the evaluation and prediction of contamination levels in the vicinity of large emission sources.     

Determination of total mercury in coal fly ash by gold amalgamation cold vapour atomic absorption spectrometry

A method for the determination of total mercury in coal fly ash by gold amalgamation cold vapour atomic absorption spectrometry (CV-AAS) was optimized. Most of the experiments were performed on NBS SRM 1633a Coal Fly Ash with a certified value of 160 ± 10 ng Hg g^?1. The main attention was focused on the decomposition of the sample. The efficacy of pressure decompositions in closed silica and sealed Pyrex tubes using various combinations of acids (HNO₃, HCl, HClO₄) was compared with oxidative combustion of the coal fly ash. Notwithstanding the incomplete mineralization of the sample in sealed tubes, the results obtained showed good agreement with the certified value and results obtained by neutron activation analysis (NAA), which suggests that mercury is quantitatively released from the sample into solution. Lower results were obtained using decomposition in closed (but not hermetically sealed) silica tubes owing to losses of mercury by volatilization during decomposition. Interferences from some metal ions (nickel, lead, copper, silver, palladium, zinc and antimony) were also examined. The results showed a serious depression of the mercury signal only when gold, palladium and platinum were present at higher concentrations, which never or very seldom occur in fly ash matrices, and therefore do not represent a limitation of the method.     

Determination of Ga, Ge, As, Se and Sb in fly ash samples by ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry

Ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) has been applied to determine Ga, Ge, As, Se and Sb in fly ash samples. The influences of instrument operating conditions and slurry preparation on the ion signals were reported. Pd and ascorbic acid were used as the mixed modifiers to enhance the ion signals. This method has been applied to determine Ga, Ge, As, Se and Sb in NIST SRM 1633a and 1633b coal fly ash reference materials and a fly ash sample collected locally. Since the sensitivities of the elements studied in slurry solution and aqueous solution were different slightly, analyte addition technique was used for the determination of Ga, Ge, As, Se and Sb in these samples. The As and Se analysis results of the reference materials agreed with the certified values. The results for which no certified value was available were also found to be in good agreement between the ETV-ICP-MS results and the reference values. The reference value was obtained by digesting the samples and analyzing the digested sample solutions by pneumatic nebulization Dynamic Reaction Cell™ (DRC) ICP-MS. The method detection limits estimated from analyte addition curves were about 0.23, 0.13, 0.17, 0.25 and 0.11 μg g⁻¹ for Ga, Ge, As, Se and Sb, respectively, in original fly ash samples.     

Nuclear activation methods for the characterization of fossil fuels

A review is presented on the use of neutron activation analysis (NAA) for the analyses of coal, oil shale, tar sands and petroleum. Fast NAA has been widely used for the determination of oxygen, and to a limited extent, of other elements such as nitrogen and silicon. Reactor NAA followed by instrumental counting, and in specific cases, after radiochemical separations is discussed. Thermal and epithermal neutrons are both used. Limited use of the²⁵²Cf source has been made in fuel analysis. A complementary technique to NAA is the photon-activation analysis with linear accelerator. It can determine over thirty elements, many of them not possible to do by NAA. Round-robin analyses of standard coal, fly ash, or oil shale samples indicate nuclear activation methods are comparable in accuracy and precision to X-ray fluorescence or atomic spectrometric methods for most elements.     

Determination of Ga,Th, and U in Bauxite and Coal Ash by Epithermal Neutron Activation Analysis

Neutron activation analysis is applied to the determination of Ga, Th and U in Bauxite and coal ash; thermal and epithermal irradiations are used. The other analytical methods are also quantitatively surveyed for gallium. The results indicate that epithermal neutron activation is prefered for those trace elements because the former method is more simple and quick.     

Determination of sulfur in coal and ash slurry by high-resolution continuum source electrothermal molecular absorption spectrometry

We propose a procedure for the determination of sulfur in coal slurries by high resolution continuum source electrothermal molecular absorption spectrometry. The slurry, whose concentration is 1 mg mL^− 1, was prepared by mixing 50 mg of the sample with 5% v/v nitric acid and 0.04% m/v Triton X-100 and was homogenized manually. It sustained good stability. The determination was performed via CS molecular absorption at 257.592 nm, and the optimized vaporization temperature was 2500 °C. The accuracy of the method was ensured by analysis of certified reference materials SRM 1632b (trace elements in coal) and SRM 1633b (coal fly ash) from the National Institute of Standards and Technology, using external calibration with aqueous standards prepared in the same medium and used as slurry. We achieved good agreement with the certified reference materials within 95% confidence interval, LOD of 0.01% w/w, and RSD of 6%, which confirms the potential of the proposed method.     

燃烧福建无烟煤的循环流化床锅炉飞灰及其未燃炭分析

以三个燃烧福建无烟煤的商业CFB锅炉电厂飞灰为研究对象，分析飞灰的粒径和含碳量分布；观察并区分了飞灰中煤炭、烟怠、半焦和灰渣等颗粒的表面形貌；测定了飞灰炭的反应活性并与入炉煤作比较；并研究了飞灰炭的来源。结果表明，采用单级分离装置的CFB锅炉，粒径在0.0385mm～0.0500mm的飞灰质量最多，未燃炭份额也最高；而采用双级分离装置的CFB锅炉，飞灰质量分布和飞灰炭份额的峰值则出现在粒径为0.0500mm~0.0750mm处。飞灰主要由三种形貌的颗粒组成，颗粒状的未燃炭、絮团状的灰渣、和介于两者之间的半焦。与入炉煤相比，飞灰炭的反应活性较高，主要来源于入炉煤中的细粉和燃烧早期因破碎和磨蚀而产生的、来不及在炉膛中燃尽的细小含炭颗粒。入炉煤中易破碎、反应性较高的亮煤是构成电厂CFB锅炉飞灰炭的主要成分。     

石嘴山电厂煤中微量元素的迁移释放行为

应用电感耦合等离子体质谱（ICP-MS）和原子荧光光谱（AFS）对中国西北部石嘴山电厂的原煤、底灰和飞灰中Hg、As、Se、Pb、Cr、Cd、Mo、Ni、Co、U和Th 11种微量元素的含量进行了测定。根据底灰和飞灰的产率, 结合微量元素在底灰和飞灰中的含量计算了电厂燃煤过程中微量元素的挥发性。结果表明, Hg、Cd、Se、As四种元素在燃煤过程的挥发率均在50%以上, 最高可达70%。通过对底灰和飞灰在酸性介质下的柱淋滤实验研究了底灰和飞灰中微量元素在60h内的迁移释放行为。Mn、Ni、Co、As四种元素的最大淋出率均超过2.0%, 最高接近10.0%, 并且还未达到淋滤平衡。根据微量元素的挥发和淋滤释放特性建立了电厂煤中有害微量元素在燃烧和淋滤过程中的释放分配模型。结果显示, 燃煤过程中的挥发是微量元素释放的主要形式, 部分元素的淋滤释放也可对周围水环境造成污染。
     

Characterization and quantification of persistent organic pollutants in fly ash from coal fueled thermal power stations in India

The burning of pulverized coal to produce energy for generation of electricity in thermal power plants results in huge quantity of coal ash of varying properties. In India the coal based thermal power plants have been the major source of power generation in the past and would continue for decades to come. Because of the increase in electricity production, the amount of ash produced will increase proportionally. Very few studies on characterization of organic constituents in fly ash from Indian thermal power plants have been reported in the literature. In the present study, the fly ashes generated from five thermal power stations from different parts of India were investigated regarding the elaboration of distribution pattern of persistent organic pollutants (POPs) such as PAHs and PCBs in them. The PAHs in the fly ash samples were identified and quantified using high pressure liquid chromatography (HPLC-UV) whereas the estimation of PCB congeners was carried out using gas chromatography (GC-ECD). Lower molecular weight (MW) PAHs, were found to be predominant in fly ash samples. The concentration of Benzo(a)Pyrene which is the most potent carcinogenic PAH, varied between 0.82 ng/g and 18.14 ng/g with a mean concentration of 9.02 ng/g. Among the PCB congeners, CB-77 is having higher toxicity value, the concentrations of which in the fly ash samples were in the range of 4.58 ng/g to 104.98 ng/g with a mean value of 62.53 ng/g.     

Certification of a new NIST fly ash standard reference material

In June 1993 the National Institute of Standards and Technology (NIST) released the third version of Constituent Elements in Coal Fly Ash Standard Reference Material (SRM 1633b). This material is intended for quality assurance purposes in evaluating the analytical methods used for the determination of constituent elements in coal fly ash or in materials with similar matrices. It has been certified for 23 major, minor and trace elements using ten different analytical techniques. For an element to be certified in a NIST SRM, its concentration is usually determined by at least two independent analytical techniques. The concentrations of additional 24 elements are provided for information only purposes in the new fly ash. Current plans are to certify the concentrations of a number of rare earths upon completion of additional analytical work now in progress. Homogeneity testing was accomplished using instrumental neutron activation analysis and X-ray fluorescence. This presentation summarizes the preparation of this new material and the analytical results used for certification.     

The determination of antimony and arsenic concentrations in fly ash by hydride generation inductively coupled plasma optical emission spectrometry

Hydride generation inductively coupled plasma optical emission spectrometry (HG-ICP-OES) was used in the determination of As and Sb concentrations in fly ash samples. The effect of sample pre-treatment reagents and measurement parameters used for hydride generation was evaluated. Due to memory effects observed, the appropriate read delay time was adjusted to 60 s resulting in RSDs 0.6% and 2.3% for As and Sb, respectively. The most suitable volumes of pre-reduction reagents for 10 mL of sample were 4 mL of KI/ascorbic acid (5%) and 6 mL of HCl (conc.). The determination of Sb was significantly interfered by HF, but the interference could be eliminated by adding 2 mL of saturated boric acid and heating the samples to 60 °C at least 45 min. The accuracy of the method was studied by analyses of SRM 1633b and two fly ash samples with the recovery test of added As and Sb. As high a recovery as 96% for SRM 1633b was reached for As using 193.696 nm with two-step ultrasound-assisted digestion. A recovery rate of 103% was obtained for Sb using 217.582 nm and the pre-reduction method with the addition of 2 mL of saturated boric acid and heating. The quantification limits for the determination of As and Sb in the fly ash samples using two-step ultrasound-assisted digestion followed with HG-ICP-OES were 0.89 and 1.37 mg kg⁻¹, respectively.     

煤中15种微量元素在燃烧产物中的分配

建立了燃煤中１５种向量元素在悄灰和底灰中含量分布的经验公式，该公式可以估算煤中微量元素在燃烧产物中的分配及传输通量。煤中非挥发性元素大部分存在于底灰和飞灰中，挥发性元素进入大气的量较高。