Coal Fly Ash Reference Material Research Articles

Determination of Lead Elemental Concentration and Isotopic Ratios in Coal Ash and Coal Fly Ash Reference Materials Using Isotope Dilution Thermal Ionization Mass Spectrometry.

The rapid expansion of coal-fired power plants around the world has produced a huge volume of toxic elements associated with combustion residues such as coal fly ash (CFA) and coal ash (CA), which pose great threats to the global environment. It is therefore crucial for environmental science to monitor the migration and emission pathway of toxic elements such as CFA and CA. Lead isotopes have proved to be powerful tracers capable of dealing with this issue. Unfortunately, up to now, few high precision lead isotope data of CFA and CA certified reference materials (CRMs) determined by using the double spike technique have been reported. Hence, to facilitate the application of lead isotopes in environmental science, it is indispensable and urgent to determine a suite of high precision Pb isotope ratios and Pb elemental contents for CFA and CA CRMs. Here, we measured lead isotope ratios from four CFA and CA CRMs using thermal ionization mass spectrometry (TIMS) combined with the 204Pb–207Pb double spike method. Lead isotope ratios values of CRMs (GBW11124, GBW08401, GBW11125d, and JCFA-1) covered wide variation ranges from 17.993 to 19.228 for 206Pb/204Pb, from 15.513 to 15.675 for 207Pb/204Pb, and from 38.184 to 39.067 for 208Pb/204Pb. Lead isotope ratios of these CRMs, except for GBW11124, show good external reproducibility (2 RSD, n = 8), which is better than 0.05% for 206Pb/204Pb and 207Pb/204Pb, 0.07% for 208Pb/204Pb, 0.04% for 206Pb/207Pb, and 0.05% for 208Pb/206Pb. The Pb concentrations of these CRMs were determined using 207Pb single spike method. The reproducibility (1 RSD, n = 4) of Pb elemental content was <0.60%. This indicates the distribution of Pb elements in these CRMs is homogeneous. With the exception of GBW11124, the suite of CRMs can be used for determining CFA and CA matrix composition for quality control of Pb isotope analyses.

Determination of trace elements in medicinal activated charcoal using slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry with low vaporization temperature

The determination of Cd, Sb, Te, Hg, Tl and Pb in medicinal activated charcoal by ultrasonic slurry sampling electrothermal vaporization inductively coupled plasma mass spectrometry (USS-ETV-ICP-MS) was described. EDTA was used as the modifier to enhance the volatility of elements studied. The influences of instrument operating conditions and slurry preparation on the ion signals were studied. A relatively low vaporization temperature of 1000°C was used, which separated the analyte from the major matrix components that improved ion signals. The method has been applied to determine Cd, Sb, Te, Hg, Tl and Pb in an NIST SRM 1633b Coal Fly Ash reference material and three brands of medicinal activated charcoal capsules using isotope dilution and standard addition calibration methods. The concentrations that are in ngg−1 levels were in good agreement between different calibration methods. The precision between sample replicates was better than 7% with USS-ETV-ICP-MS technique. The method detection limit estimated from standard addition curves was 0.4, 0.3, 0.3, 0.3, 0.04 and 0.9ngg−1 for Cd, Sb, Te, Hg, Tl and Pb, respectively, in original medicinal activated charcoal.

Fractionation of trace elements in total atmospheric deposition by filtrating-bulk passive sampling

We have developed and validated a new simple and effective methodology for fractionation of soluble and insoluble forms of trace elements in total atmospheric deposition. The proposed methodology is based on the modification of a standard total deposition passive sampler by integrating a quartz fiber filter that retains the insoluble material, allowing the soluble fraction to pass through and flow to a receiving bottle. The quartz filter containing the insoluble fraction and the liquid containing the soluble fraction are then separately assayed by standardized ICP–MS protocols. The proposed atmospheric elemental fractionation sampler (AEFS) was validated by analyzing a Coal Fly Ash reference material with proper recoveries, and tested for field fractionation of a set of 10 key trace elements in total atmospheric deposition at the industrial area of Puchuncaví–Ventanas, Chile. The AEFS was proven useful for pollution assessment and also to identify variability of the soluble and insoluble fractions of the selected elements within the study area, improving the analytical information attainable by standard passive samplers for total deposition without the need of using sophisticated and high cost wet-only/dry only collectors.

Optical emission spectrometric determination of arsenic and antimony by continuous flow chemical hydride generation and a miniaturized microwave microstrip argon plasma operated inside a capillary channel in a sapphire wafer

Continuous flow chemical hydride generation coupled directly to a 40 W, atmospheric pressure, 2.45 GHz microwave microstrip Ar plasma operated inside a capillary channel in a sapphire wafer has been optimized for the emission spectrometric determination of As and Sb. The effect of the NaBH 4 concentration, the concentration of HCl, HNO 3 and H 2SO 4 used for sample acidification, the Ar flow rate, the reagent flow rates, the liquid volume in the separator as well as the presence of interfering metals such as Fe, Cu, Ni, Co, Zn, Cd, Mn, Pb and Cr, was investigated in detail. A considerable influence of Fe(III) (enhancement of up to 50 %) for As(V) and of Fe(III), Cu(II) and Cr(III) (suppression of up to 75%) as well as of Cd(II) and Mn(II) (suppression by up to 25%) for Sb(III) was found to occur, which did not change by more than a factor of 2 in the concentration range of 2–20 μg ml − 1 . The microstrip plasma tolerated the introduction of 4.2 ml min − 1 of H 2 in the Ar working gas, which corresponded to an H 2/Ar ratio of 28%. Under these conditions, the excitation temperature as measured with Ar atom lines and the electron number density as determined from the Stark broadening of the H β line was of the order of 5500 K and 1.50 · 10 14 cm − 3 , respectively. Detection limits (3σ) of 18 ng ml − 1 for As and 31 ng ml − 1 for Sb were found and the calibration curves were linear over 2 orders of magnitude. With the procedure developed As and Sb could be determined at the 45 and 6.4 μg ml − 1 level in a galvanic bath solution containing 2.5% of NiSO 4. Additionally, As was determined in a coal fly ash reference material (NIST SRM 1633a) with a certified concentration of As of 145 ± 15 μg g − 1 and a value of 144 ± 4 μg g − 1 was found.

Determination of trace multi-elements in coal fly ash by inductively coupled plasma mass spectrometry

The contents of Cr, Cu, Ni, As, Cd and Pb in coal fly ash were determined by a high resolution inductively coupled plasma mass spectrometry method. The sample digestions were performed in closed microwave vessels with HNO3, NClO4 and HF. The optimum conditions for the determination were obtained. The applicability of the proposed method was validated by the analysis of coal fly ash reference material (NIST SRM 1633a). The results show that most of the spectral interferences can be avoided by measuring in the high resolution mode (maximum mass resolution R=9 000). The detection limit is from 0.05 to 0.21 μg/g, and the precision is fine with relative standard deviation less than 4.3%.

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.

Determination of copper in coal fly ash in the presence of excess titanium by dynamic reaction cell inductively coupled plasma mass spectrometry.

Inductively coupled plasma quadrupole mass spectrometry (ICP-QMS) was used for the accurate determination of copper in coal fly ash samples in the presence of excess titanium, using the reaction of Cu(+) ions with NH(3) in the cell. The method eliminated the effect of polyatomic isobaric interferences at m/z 63 and 65 caused by the formation of (47)Ti(16)O(+), (49)Ti(16)O(+) and (47)Ti(18)O(+) on (63)Cu(+) and (65)Cu(+) by detecting Cu(+) as the product cluster ion Cu(NH(3))(2)(+). As the signal of (63)Cu(NH(3))(2)(+) overlapped with that of (97)Mo(+) which existed in the samples, (65)Cu(NH(3))(2)(+) was detected at m/z 99. The effect of the operating conditions of DRC system was studied in order to obtain the best signal to noise ratio for Cu(NH(3))(2)(+) at m/z 99. The formation of Cu(NH(3))(2)(+) was through the clustering reaction Cu(+)+2NH(3)-->Cu(NH(3))(2)(+) which resulted in the separation of analyte from the interfering oxide. The detection limit for Cu(NH(3))(2)(+) was 0.015 ng mL(-1) as Cu. The method was applied to the determination of copper in NIST SRM 1633a and 1633b coal fly ash reference materials. The precision between sample replicates was better than 2.0% and the analysis results were in good agreement with the certified values.

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.

Palladium nitrate—magnesium nitrate modifier for electrothermal atomic absorption spectrometry. Part 3. Determination of mercury in environmental standard reference materials

A single addition of 15 µg of palladium is sufficient for 40–60 determinations of mercury if the graphite tube is not heated to temperatures higher than 1500 °C in the cleaning step. A pyrolysis temperature of 400 °C can be used without any loss of mercury, and a characteristic mass of 0.1 ng of mercury was obtained for an atomization temperature of 1000 °C. Interferences caused by high sodium chloride concentrations could be eliminated by using a mixture of 95% argon and 5% hydrogen as the purge gas. Mercury could be determined accurately in Aquatic Plant, Albacore Tuna, River Sediment and Coal Fly Ash reference materials.

Homogeneity tests and certification analyses of the IRANT coal fly ash reference material ECO by instrumental neutron activation analysis

The instrumental neutron activation analysis technique (INAA) was used for homogeneity tests and certification analyses of the coal fly ash reference material ECO prepared at the Institute of Radioecology and Applied Nuclear Techniques (IRANT), Kosice, Czechoslovakia. The relative standard deviations due to inhomogeneity were found to be <3% for 19 elements including for sample weights about 50 mg. The results of determination of the elements Al, As, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Ga, Hf, In, K, La, Mn, Mo, Na, Nd, Ni, Rb, Sb, Sc, Sm, Sr, Ta, Th, Ti, U, V, W, and Zn, were compared with the IRANT certified or information values. Inference was made on the reliability of the IRANT specified values for the element contents.

Homogeneity tests and certification analyses of coal fly ash reference materials by instrumental neutron activation analysis

The instrumental neutron activation analysis technique (INAA) was used for homogeneity tests and certification analyses of coal fly ash reference materials ENO, ECH, and EOP prepared at the Institute of Radioecology and Nuclear Techniques (IRANT), Kosice, Czechoslovakia. Quantitative estimation of a degree of inhomogeneity was suggested. The relative standard deviations due to inhomogeneity were found to be <1% for macroconstituents and <3% for minor and trace elements for sample weights about 25 mg. The results of determination of the elements Al, As, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Ga, Hf, In, K, La, Mn, Na, Nd, Ni, Rb, Sb, Sc, Sm, Sr, Ta, Th, Ti, U, V, W, and Zn were compared with the IRANT certified or information values. NBS SRM 1633a Trace Elements in Coal Fly Ash was also analyzed as a control sample and the results for the above elements were compared with the NBS certified, information or literature available values. From these comparisons, inference was made on the quality of the IRANT specified values for the element contents.