Fly Ash Standard Reference Material Research Articles

Simultaneous Determination of 11 Elements in Fly Ash by Inductively Coupled Plasma Orthogonal Acceleration Time-of-Flight Mass Spectrometry After Closed-Vessel Microwave-Assisted Extraction with Ammonium Fluoride

A method for simultaneous multi-element analysis of fly ash samples by inductively coupled plasma orthogonal acceleration time-of-flight mass spectrometry (oaTOF-ICP-MS) after closed-vessel microwave extraction with ammonium fluoride was introduced here. Corrosive and/or toxic acids like HF, HCl or HClO4, as well as HNO3, which are commonly used during sample preparation of the fly ash samples, are avoided in this method. The spectral effects due to the formation of different Cl, Na, K, Ca, Mg-containing polyatomic species interfering with the determination of a number of elements like As, Se or Ni during the oaTOF-ICP-MS analysis are negligible. Under the optimum experimental extraction conditions evaluated using a fractional factorial design (10 mg of the sample extracted with 5 mL of 140 g/L NH4F for 10 min at 200°C), analysis of the resulting supernatant with Rh as an internal standard enabled precise and accurate simultaneous determination of 11 elements (Li, Be, Ni, As, Se, Rb, Sb, Cs, W, Tl and U) at trace and ultratrace levels. The accuracy was assessed by analysing two certified reference materials, namely Fine Fly Ash CTA-FFA-1 and Constituent Elements in Coal Fly Ash Standard Reference Material® 1633b. The precision of the reported method was better than 10%.

Development and Validation of a Sensitive Method for Trace Nickel Determination by Slotted Quartz Tube Flame Atomic Absorption Spectrometry After Dispersive Liquid-Liquid Microextraction.

In this study, dispersive liquid-liquid microextraction was systematically optimized for the preconcentration of nickel after forming a complex with diphenylcarbazone. The measurement output of the flame atomic absorption spectrometer was further enhanced by fitting a custom-cut slotted quartz tube to the flame burner head. The extraction method increased the amount of nickel reaching the flame and the slotted quartz tube increased the residence time of nickel atoms in the flame to record higher absorbance. Two methods combined to give about 90 fold enhancement in sensitivity over the conventional flame atomic absorption spectrometry. The optimized method was applicable over a wide linear concentration range, and it gave a detection limit of 2.1µgL-1. Low relative standard deviations at the lowest concentration in the linear calibration plot indicated high precision for both extraction process and instrumental measurements. A coal fly ash standard reference material (SRM 1633c) was used to determine the accuracy of the method, and experimented results were compatible with the certified value. Spiked recovery tests were also used to validate the applicability of the method.

A novel analytical method for sensitive determination of lead: Hydrogen assisted T-shape slotted quartz tube-atom trap-flame atomic absorption spectrometry

Lead is a toxic metal which affects human health badly due to its high toxicity. The wide application range of lead causes environmental contamination of air, water and soil. Flame atomic absorption spectrometry is one of the simple and economical instrument used for the determination of heavy metals, but it has low sensitivity due to low sample introduction efficiency. In this study, a sensitive analytical method was developed by using T-shaped slotted quartz tube as an atom trap unit to get lower detection limit for lead. The trapped atoms were released using hydrogen gas which supplies reducing environment in T-SQT-AT-FAAS system. Factors such as trapping period, sample and fuel flow rates were optimized to obtain high sensitivity. Under the optimum conditions, limits of detection and quantitation were found to be 0.6 and 2.1μgL−1, respectively. Accuracy of the developed method was checked and results found under the optimum conditions agreed with the certified value of coal fly ash standard reference material. The developed method was applied to water samples to figure out its suitability.

Uncertainties in measuring trace amounts of cobalt and europium with low-flux neutron activation analysis

Neutron activation analysis is widely used for identification of elements and their quantities even in trace amounts in the samples of almost any type. The challenges in detecting trace amounts of particular elements are often associated with the neutron flux produced at the research reactors. Low-flux neutron activation analysis usually presents the biggest challenge when analyzing trace quantities of elements with lower magnitude of radiative capture cross-sections. In this paper, we present the methodology and the quantified uncertainties associated with the detection of trace amounts of cobalt and europium, using as an example concrete aggregates. Recent growing interest is in improving structural concrete (increasing its strength but reducing its activation in nuclear power plant environments). Aside from buildings, structural concrete is also used as a biological shield in nuclear power plant that become radioactive after exposure to neutron flux. Due to radiative capture interactions, artificial radionuclides are generated to high enough concentrations that classify concrete as low-level radioactive waste at the time of the plant's decommissioning. Disposal of this concrete adds to the expense of nuclear power plant financing and its construction. Three radionuclides, 60Co, 152Eu, and 154Eu, account for 99 % of total residual radioactivity of nuclear power plant decommissioned concrete. IAEA document RS-G-1.7, Application of the Concepts of Exclusion, Exemption, and Clearance, specifies clearance levels of radionuclides specific activities: a specific activity lower than 0.1 Bqg-1 for 60Co and 152Eu, and 154Eu allows for a concrete to be recycled after decommissioning of the nuclear power plant. Therefore, low-flux neutron activation analysis is used to test the detection limits of trace elements in samples of cement, coarse, and fine concrete aggregates. These samples are irradiated at the University of Utah's 100 kW TRIGA Reactor at power levels of 10 kW, 30 kW, and 90 kW, with the corresponding thermal neutron flux values of 1.5?108, 7.3?109, and 3.76?1011 cm-2s-1.The samples are irradiated for time periods of 1, 3, 30, 60, and 120 minutes. Different power levels and different irradiation times are used to find if there is a threshold set of neutron activation analysis parameters in detecting trace amounts of these isotopes. Each of the samples is counted on a Canberra BEGe high purity germanium detector. Cement samples are concurrently irradiated with a National Institute of Standards and Technology coal fly ash standard reference material and coarse and fine aggregates with Montana soil standard reference material to accurately quantify the mass concentration of the isotopes in concrete samples. Final results show that reactor power, irradiation, and detector measurement times are heavily correlated to finding the optimum combination for a low-flux neutron activation analysis approach in detecting trace contents of elements, specifically cobalt and europium.

Determination of Inorganic Thallium Compounds in the Particulate Matter of Emissions and Workplace Air by Sequential Dissolution

Inorganic thallium compounds in the atmospheric particulate matter of emissions and in the workplace air of specific industrial production can be determined through selective sequential extractions: Tl(I) is separated from Tl(0) and Tl(III) in the first step, Tl(0) in the second one, while in the final extraction both Tl(III) soluble and insoluble compounds are determined. The procedure has been tested on 1633a Coal Fly Ash standard reference material. The thallium recovery was in the range 91 - 98%.

Investigation of electrochemical hydride generation coupled to microwave plasma torch optical emission spectrometry for the determination of arsenic: analytical figures of merit, interference studies and applications to environmentally relevant samples

A continuous flow thin layer electrolysis cell with a Pt cathode in combination with a microwave plasma torch operated with Ar as working gas was used for the optical emission spectrometric determination of As with the hydride technique. Under the optimised conditions the limit of detection (3σ) in the case of the As(I) 228.81 nm emission line was 81 ng mL−1. Especially the influence of the transition metals Cu(II), Fe(III) and Ni(II), of the hydride forming elements Sb(III), Se(IV) and Sn(II) and of Na on the determination of As was studied. Cu(II) was found to be the strongest interferent, as in the presence of 100 µg mL−1 of Cu(II) the signal for 3 µg mL−1 of As was reduced to 4% of the signal without interferent. Sn(II) and Sb(III) were found to yield an increase of the signal for As. L-cysteine and KI/ascorbic acid (1 : 1) at a concentration of 2% were found effective to reduce the interferences of Cu(II), Fe(III) and Ni(II). For a solution containing 3 µg mL−1 of As and 100 µg mL−1 of Ni(II) it was shown that in the presence of L-cysteine or KI/ascorbic acid the signal for As was 99% and 94% of the one without interferent, whereas it was only 43% without masking reagents. The procedure could be used for the determination of As in a digested coal fly ash standard reference material (NIST SRM 1633a®) with a certified value of 145 ± 15 µg g−1 for As. A concentration of 131 ± 15 µg g−1 was found. Additionally, As could be determined in two process water samples from a copper refinery. It was found that the amount of As determined with ECHG-MPT-OES agrees well with the values determined by FAAS and ICP-OES at the 0.02 and 1.6 g L−1 level, respectively.

Optimization and comparison of chemical and electrochemical hydride generation for optical emission spectrometric determination of arsenic and antimony using a novel miniaturized microwave induced argon plasma exiting the microstrip wafer

Continuous flow (CF) chemical hydride generation (CHG) and electrochemical hydride generation (ECHG) directly coupled to a novel 40 W, atmospheric pressure, 2.45 GHz microwave microstrip Ar plasma exiting a microstrip wafer has been developed for the emission spectrometric determination of As and Sb using a miniaturized optical fiber spectrometer and a CCD-array detector. The experimental conditions for both procedures were optimized with respect to the relative net intensities of the As I 228.8 nm and Sb I 252.8 nm lines and their signal-to-background intensity ratios. Additionally, the susceptibility to interferences from Cd, Co, Cr, Cu, Fe, Ni, Pb and Zn and other hydride-forming elements in the determination of As and Sb using the CHG and ECHG techniques was investigated in detail. Under the optimized conditions, it was found that ECHG is more prone to interferences compared to CHG. The detection limits (3 σ) of As (6 ng mL −1) and Sb (7 ng mL −1) obtained for the ECHG–MSP–OES method are about three times lower than in the case of the CHG–MSP–OES method due to a two-fold lower amount of H 2 introduced into the MSP in case of the ECHG, resulting in a better plasma stability and reduced background level. The linearity ranges for both calibration curves to a concentration of up to 5 μg mL −1 and a precision between 2% and 7% (2 μg mL −1 and 0.050 μg mL −1 of As and Sb, respectively) were found for both methods. The developed ECHG–MSP–OES method was validated for As through the analysis of a certified coal fly ash standard reference material (NIST SRM 1633a) after sample dissolution. The derived concentration (140 ± 8 μg g −1) was found to agree well with the certified data (145 ± 15 μg g −1). The method was also successfully applied to the analysis of both a galvanic bath sample, which contained Sb and was spiked with As, and a tap water sample spiked with both analytes. Recovery rates of 99–101% and a Sb concentration of 6.6 μg mL −1 in the galvanic bath sample were revealed. The latter value showed a good agreement with the data obtained from ICP-OES analysis, which was also used for validation purpose.

Rietveld quantitative X-ray diffraction analysis of NIST fly ash standard reference materials

Rietveld quantitative X-ray diffraction analysis of the fly ash Standard Reference Materials (SRMs) issued by the National Institute of Standards and Technologies was performed. A rutile (TiO2) internal standard was used to enable quantitation of the glass content, which ranged from 65% to 78% by weight. TheGSASRietveld code was employed. Precision was obtained by performing six replicates of an analysis, and accuracy was estimated using mixtures of fly ash crystalline phases and an amorphous phase. The three low-calcium (ASTM Class F) fly ashes (SRM 1633b, 2689 and 2690) contained four crystalline phases: quartz, mullite, hematite, and magnetite. SRM 1633b also contained a detectable level of gypsum, which is not common for this type of fly ash. The high-calcium (ASTM Class C) fly ash, SRM 2691, had eleven crystalline phases and presented a challenge for the version ofGSASemployed, which permits refinement of only nine crystalline phases. A method of analyzing different groups of nine phases and averaging the results was developed, and tested satisfactorily with an eleven-phase simulated fly ash. The results were compared to reference intensity ratio method semiquantitative analyses reported for most of these SRMs a decade ago.

Digestion methods for analysis of fly ash samples by atomic absorption spectrometry

The efficiency of different digestion methods (six microwave decomposition methods and a wet acid digestion method) in the solubilisation of six metals (Cr, Ni, Cu, Pb, Cd, Zn), for their determination in fly ashes, was compared. Five different mineral acid mixtures and two different microwave systems were tested. The study was carried out by analyzing two highly homogenised fly ash samples (from sewage sludge and city waste incineration) provided by the Joint Research Centre of Ispra. Determinations were performed by atomic absorption spectrometry and by inductively coupled plasma atomic emission spectrometry. The analytical performance of the laboratory was evaluated using the 1633a Coal Fly Ash Standard Reference Material of National Bureau of Standards (NBS SRM 1633a). Results showed that a HNO 3 microwave treatment was strong enough to solubilise metals from the considered fly ashes. Moreover, microwave methods generally provided higher release than the classical aqua regia method, whereas no significant advantage was observed using a high performance microwave unit.

Ko method of quantification in neutron activation analysis as applied to environmental samples

The Ko factor method in neutron activation analysis adopts all the principles of comparator method and can be used for the rapid determination of elemental comcentrations during routine monitoring of environmental samples. The method necessiates the use of same in-pile conditions, such as irradiation time, irradiation position and the type of neutron spectrum, for which the factors have been generated. The K_o factors were estimated for various elements of environmental importance for three irradiation positions of Apsara Reactor at Bhabha Atomic Research Centre. Standard reference materials of soil and coal were used for all the elements except for Hg for which HgCl2 was used. The concentration of the elements determined using these factors in a flyash standard reference material revealed good agreement within 10% of the certified values. The efficacy of the method compared well with that of specific element comparator method as revealed by the elemental concentrations obtained by both the techniques.

96/05643 Characterization of polycyclic aromatic hydrocarbons in a coal fly ash standard reference material

Most commercial buildings do not perform as well in practice as intended by the design and their performances often deteriorate over time. Reasons include faulty construction, malfunctioning equipment, incorrectly configured control systems and inappropriate operating procedures. One approach to addressing this problems is to compare the predictions of an energy simulation model of the building to the measured performance and analyze significant differences to infer the presence and location of faults. This paper presents a framework that allows a comparison of building actual performance and expected performance in real time. The realization of the framework utilized the EnergyPlus, the Building Controls Virtual Test Bed (BCVTB) and the Energy Management and Control System (EMCS) was developed. An EnergyPlus model that represents expected performance of a building runs in real time and reports the predicted building performance at each time step. The BCVTB is used as the software platform to acquire relevant inputs from the EMCS through a BACnet interface and send them to the EnergyPlus and to a database for archiving. A proof-of-concept demonstration is also presented.

X-Ray Powder Diffraction Study of NBS Fly Ash Standard Reference Materials

AbstractThe fly ash Standard Reference Materials (SRMs) issued by the U.S. National Bureau of Standards have been studied by X-ray powder diffraction (XRD). Based on observations of large diffuse scattering maxima in their X-ray diffractograms, it was evident that all of the ashes had a high glass content. SRM 1633a and 2689, derived from the combustion of bituminous coal, contained different amounts of quartz, mullite, hematite and ferrite spinel (magnetite). SRM 2891, derived from subbituminous coal had quite a different chemical composition and a more complex crystalline phase assemblage, that included these four phases plus anhydrite, tricalcium aluminate, lime, periclase and minor phases. SRM 2690, also derived from subbituminous coal, had only quartz, mullite and ferrite spinel as detectable phases in its diffractogram. Analytical CaO is an important factor in determining the phase assemblage; SRM 2691 had 25.8 wt%, SRM-2690 had 8.0%, and the ash derived from bituminous coals had only 1.6-3.0%. The changing composition of the glass phases in the SRMs is detected in a shift in the position and shape of the diffuse scattering maximum in the diffractograms. Use of an internal intensity standard permitted quantitative comparisons of the relative amounts of crystalline phases among the four fly ash SRMs.

Semi-Quantitative X-Ray Diffraction Analysis of Fly Ash by the Reference Intensity Ratio Method

ABSTRACTA protocol for relatively inexpensive and rapid semi-quantitative x-ray diffraction analysis of fly ash mineralogy by the Reference Intensity Ratio (RIR) method is described. RIR's for the common crystalline phases in fly ashes derived from low rank and bituminous coal are given. The method is semi-quantitative for some phases because of unavoidable overlaps of the stronger peaks suitable for quantitation. Use of the protocol is illustrated with the four fly ash Standard Reference Materials supplied by the National Institute of Standards and Technology. Recommendations for implementation of this protocol in other laboratories and for improvements in quantitation of fly ash mineralogy are given.

The Microstructure of National Bureau of Standards Reference Fly Ashes

ABSTRACTA suite of three fly ashes, National Bureau of Standards* Standard Reference Materials (SRMs) 2689, 2690 and 2691, was studied by transmission electron microscopy and by analytical electron microscopy (aem): sample preparation techniques are described. The chemical compositions of the glassy phase, analyzed by aem, showed a wide dispersion of values although the mean composition of the glass remained close to that of the whole fly ash.The microstructure of these materials is complex: besides crystalline inclusions, the aluminasilica glasses have undergone phase separation on a nanometer scale, and consist of two glassy phases. Since liquid-liquid phase separation has also been found in British fly ashes, it appears to be a characteristic feature of the glassy phase in Class F ashes and is also encountered in occasional Al-Si rich particles in Class C ashes. High iron content glass was found in fly ash SRM 2689, and its phase separation and crystallization were investigated.

X-Ray Powder Diffraction For Studying the Mineralogy of fly ash

ABSTRACTA brief summary of the use of x-ray powder diffraction for studying the mineralogy of fly ash is presented. Mineralogies of low-, intermediate- and high-calcium fly ashes are discussed and illustrated by results from XRD characterization of U.S. National Bureau of Standards fly ash Standard Reference Materials.

Elemental determinations in NBS 1633A Fly Ash Standard Reference Material using INAA and PGNAA

Instrumental neutron activation analysis (INAA) was used for the determination of 23 elements and prompt gamma neutron activation analysis (PGNAA) was used for the determination of 10 elements in U.S. National Bureau of Standards (NBS) 1633A Fly Ash Standard Reference Material (SRM). The results are in excellent agreement with the limited number of NBS certified values available.

Preparation and Characterization of Three New NBS Fly Ash Standard Reference Materials

Three new fly ash standard reference materials (SRM's) have been produced by CTL under contract with the U.S. National Bureau of Standards (NBS). Each unit of the SRM's consists of approximately ten grams of well-blended fly ash hermetically sealed in a glass vial. Twenty-thousand vials of each SRM were produced. The SRM's will be certified for major and minor chemical elements, loss on ignition, and for the percentage residue on the No. 325 standard sieve. The SRM's are suitable for use in developing new methods of chemical and physical analysis, for checking the performance of instruments and analysts, and for research into the composition and properties of fly ash.

Development of EDXRF techniques for the quantitative multielement analysis of urban dust samples

The investigation and monitoring of suspended particulate matter in air require accurate and sensitive multielement analysis of large numbers of samples. In the work described, airborne particles and settled urban dusts were examined by energy dispersive X-ray fluorescence spectrometry with secondary-target excitation. The practical requirements of trace-element determinations in dusts are reasonably satisfied by two techniques. Deposition of fine particles (under 3.5μm) on Nucleopore membrane filters provides thin-film samples, for which absorption and particle-size effects are usually negligible. Calibration is achieved by sputtering of certified NBS standard glasses onto membrane filters. In the destructive “fusion and direct solidification” technique, sample inhomogeneities and particle-size effects are eliminated by fusing the sample with lithium borate in a Pt/Au alloy crucible. La2O3 or WO3, added as heavy absorbers, can reduce the interelement-effects of the thick specimens to a certain extent. A newly developed computer program, based on a modified mathematical expression for the intensity, compensates for absorption and secondary fluorescence effects. It is demonstrated that for some trace elements the background can be easily predicted as a linear function of the incomplete charge-collection of the Si(Li) detector. An intermethod comparison with atomic-absorption results is presented; the results are verified with the NBS Fly Ash standard reference material.

Elemental concentrations in the National Bureau of Standards' environmental coal and fly ash Standard Reference Materials

Elemental concentrations in the National Bureau of Standards' environmental coal and fly ash Standard Reference Materials