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Article

Coal Feed-Dependent Variation in Fly Ash Chemistry in a Single Pulverized-Combustion Unit

1
Center for Applied Energy Research, University of Kentucky, 2540 Research Park Drive, Lexington, KY 40511, USA
2
Department of Earth & Environmental Sciences, University of Kentucky, Lexington, KY 40506, USA
3
Department of Mining Engineering, University of Kentucky, Lexington, KY 40506, USA
4
Department of Civil & Environmental Engineering, Duke University, Durham, NC 27708, USA
*
Author to whom correspondence should be addressed.
Submission received: 1 August 2022 / Revised: 19 August 2022 / Accepted: 23 August 2022 / Published: 24 August 2022

Abstract

:
Four suites of fly ash, all generated at the same power plant, were selected for the study of the distribution of rare earth elements (REE). The fly ashes represented two runs of single-seam/single-mine coals and two runs of run-of-mine coals representing several coal seams from several mines. Plots of the upper continental crust-normalized REE, other parameters derived from the normalization, and the principal components analysis of the derived REE parameters (including the sum of the lanthanides plus yttrium and the ratio of the light to heavy REE) all demonstrated that the relatively rare earth-rich Fire Clay coal-derived fly ashes have a different REE distribution, with a greater concentration of REE with a relative dominance of the heavy REE, than the other fly ashes. Particularly with the Fire Clay coal-derived fly ashes, there is a systematic partitioning of the overall amount and distribution of the REE in the passage from the mechanical fly ash collection through to the last row of the electrostatic precipitator hoppers.

1. Introduction

The concentration of the lanthanide—also known as the rare earth elements (REE)—and other critical elements during coal combustion has made fly ash a potential target for the extraction of metals. Whether through the incidental use of fly ash produced in the routine utility combustion of coal [1,2,3,4,5] or of fly ash produced for the secondary or even express purpose of recovering critical elements [6,7,8,9], the latter being a novel addition to the typical power-generation uses of the region’s coals, fly ash has some advantages compared to coal in terms of the removal of most of the carbon, the fine size of the material, and the potential availability of decades of fly ash production in landfills at or near the power plants.
The chemistry of the feed coal influences the chemistry of the fly ash. In consideration of Meij’s [10] Venn diagram of element partitioning from the feed coal to the ash products, particularly for the low volatility trace elements that tend to concentrate in the fly ash and bottom ash, it is noted that the concentrations of the REE do not vary substantially from the feed coal ash to the combustion fly ash. Some partitioning may occur because of the redistribution of REE-bearing minerals [11]. In this study, we discuss the differences in rare earth elements inherent in the differences between the coal sources fed into a single 100-MW boiler with an unchanging ash-collection system through the years of our studies.

2. Methods

2.1. Sample Sources

All fly ash samples were collected from the series of ash collection units for boiler unit 1 of Kentucky power plant I (letters were assigned to Kentucky power plants to anonymize their identity). Ash Series 1 (92645 to 92647) was collected as an exclusive run of the Manchester coal from a single mine [12]; series 2 (93855 to 93859) was part of the Center for Applied Energy Research’s (CAER) 2012 sampling of the coal-fired utility power plants in Kentucky [13]; series 3 (93953 to 93960) was collected as an exclusive run of the Fire Clay coal from a single mine [14]; and series 4 (94012 to 94019) was from a previously unpublished 2016 collection. The 2012 and 2016 fuels were the routine run-of-mine coal feeds typically used at the power plant.

2.2. Basic Chemistry and X-ray Fluorescence

For the basic analyses performed at the CAER, total sulfur analyses followed ASTM Standard D4239-18e1 [15], and the ultimate analysis was performed based on ASTM Standards D3176-15 [16]. Major oxide and non-REE minor element—including Se—chemistry at the CAER was analyzed by X-ray fluorescence on a Philips PW2404 X-ray spectrometer (Philips, Amsterdam, The Netherlands), following procedures originally outlined by Hower and Bland [17] and modified as needed for newer generations of XRF units. Mercury was analyzed on a LECO AMA254 Advanced Mercury Analyzer (St. Joseph, MI, USA).

2.3. Inductively Coupled Plasma-Mass Spectroscopy

Gallium, Ge, As, Sc, Y, and the lanthanides were analyzed using an Agilent 7900 Inductively coupled plasma-mass spectroscopy (ICP-MS) (Agilent Technologies, Santa Clara, CA, USA) at the CAER. Samples were digested following the ASTM D6357-21b [18] digestion method, utilizing heating the sample with a combination of nitric, hydrochloric, and hydrofluoric acids. The method was modified to include an additional nitric acid step at the end to handle any potential solid residue that might be present, and a sample weight of 0.1 g was utilized. The available standards were the certified reference material NIST 1633b, the primary method control sample, and the U.S. Geological Survey Brush Creek Shale (SBC-1) [19]; LGC Standards (https://www.lgcstandards.com/US/en; accessed on 24 August 2022) Brown Coal Ash (BF BE1); and available round-robin certified samples. The reference standards are digested in parallel with the samples to ensure that the digestion is complete. The certified values of the reference standard were in good agreement with the measured results. Instrument integrity is routinely monitored with random blanks and analytical standards throughout each sequence. The analysis signal for 153Eu via ICP-MS overlapped with the signals for barium oxide polyatomic species (137Ba16O, 136Ba17O, 135Ba18O, and 134Ba18OH) [20]. If samples with Ba/Eu > 1000 (mass basis), slightly more than 3× the world average for Ba/Eu [21], are flagged as unreliable, as suggested by Dai et al. [20] for the interpretation of Eu anomalies, then most of the samples in this study would have suspect Eu values.
The REE in the series 3 samples were analyzed by ICP-MS at Duke University using techniques described in Taggart et al. [14].

2.4. Notes on the Comparison of ICP Methods

One suite of series 4 samples (94012–94014, 94017–94019) was originally run on an inductively coupled plasma-optical emission spectroscopy (ICP-OES) instrument at the CAER (samples were digested following the ASTM D6357-11 [22] digestion method, which utilizes heating the sample with a combination of nitric, hydrochloric, and hydrofluoric acids). The method was modified to include an additional nitric acid step at the end to handle any potential solid residue that might be present, and a sample weight of 0.1 g was utilized. The certified reference material NIST 1633b was utilized as the primary method control sample). The samples were re-examined with ICP-MS for this study. In consideration of the known issues with the comparisons between ICP-OES and ICP-MS, studies have been made of the results from the two methods [3,23] and between ASTM D6357-11 22 (mixed acid digestion with heat); ASTM D4503 [23] (lithium borate fusion); and the ASTM D6357-11 [22] method, and with the addition of boric acid to neutralize the HF [24]. For these six fly ashes, except for five fly ashes for the Nd analysis and one ash for the La analysis, the comparison of the analyses of the light REE vs. the cluster of the heavier REE (including Pr and Sm) gave the impression of a reasonable correlation between the two techniques (Figure 1A). A closer examination of the results for Pr, Sm, and the heavy REE illustrated the uncertainties in the comparison of those elements (Figure 1B). Given the problems with high Tm analyses on the CAER’s ICP-OES, the non-detection of Ho, and the general wider range of ICP-OES analyses than the corresponding ICP-MS analyses, with Ce being an exception (Figure 1A), ICP-OES is generally considered to be a less reliable technique than ICP-MS.

2.5. Notes on Rare Earth Nomenclature, Normalization, and the Expressions of Normalized Data

In this study, we used REE to describe the lanthanide elements, REY for REE + Y, and REYSc for REY + Sc. The light REE (LREE) are defined as La through Sm and the heavy REE (HREE) are defined as Eu through Lu [25,26]. Following the normalization of REE abundances to crustal averages (indicated by the suffix “N”) [27], the normalized distribution can be divided into L-type (light type; LaN/LuN > 1); M-type (medium type; LaN/SmN < 1, GdN/LuN > 1); and H-type (heavy type; LaN/LuN < 1) enrichment patterns [28]. Ratios based on the upper continental crust (UCC) corrections after Taylor and McLennan [27] are used to decouple Ce, Eu, and Gd from the other REE in the distribution patterns [20,29,30,31]:
EuN/EuN* = EuN/(0.67SmN + 0.33TbN)
CeN/CeN* = CeN/(0.5LaN + 0.5PrN)
GdN/GdN* = GdN/(0.33SmN + 0.67TbN)

3. Results and Discussion

3.1. Basic Element Trends

The chemistry of the four series of fly ashes is shown in Table 1, Table 2, Table 3, Table 4, Table 5 and Table 6. Among the non-REE, the general trend for an increase in volatile elements towards the last rows of the electrostatic precipitator (ESP) array, a function of both the decreasing particle size and the cooler flue gas temperatures in the back rows, has been noted by Sakulpitakphon et al. [12], Mardon and Hower [32], Hower et al. [33], and Hood et al. [34], among others. In these samples, As, V, Mo, Zn, Cu, Ge, Ga, and Pb generally exhibit an increase in concentration toward the last ESP rows. Selenium also increases toward the third-row ESP in the series 3 fly ashes. Mercury concentration also increases towards the cooler end of the ash-collection system, but Hg capture is complicated by Hg’s dependence upon the amount and form of carbon for efficient capture [35,36].

3.2. Principal Components Analysis on REY and Selected Major Oxides and Minor Elements

A principal components analysis (PCA; JMP® Pro 16.0.0, SAS Institute, Cary, NC, USA) was implemented to further understand the distributions of the major oxides and minor elements. The elements and combinations of selected elements and oxides were REY, LREE/HREE, and K2O/(SiO2 + Al2O3) as an indicator of clay minerals, and Zr and TiO2/(TiO2 + Al2O3) as indicators of detrital minerals. The results, shown in Figure 2 with details on the statistics on the PCA tab in Table S1, demonstrate that the Zr and REY axes are in close proximity to each other, opposite the K2O/(SiO2 + Al2O3) axis, and orthogonal to the opposing LREE/HREE and TiO2/(TiO2 + Al2O3) axes. The first principal component, with nearly co-equal contributions from Zr, REY, and, in the opposite direction, K2O/(SiO2 + Al2O3), accounts for 62.51% of the variation. The first three principal components account for 96.80% of the variation. All of the eigenvectors make sense geologically. While not always specifically for REE or in the context of PCA, the nature of geochemical associations in eastern Kentucky and other coals has been discussed elsewhere [17,20,26,30,32,37,38,39]. For example, Y is an accessory element in zircons; therefore, Zr and REY are related. The nature of the REY associations with clays is different from the association in detrital minerals. Moreover, clays can act as a diluent of the REY-bearing clastic minerals, and TiO2/(TiO2 + Al2O3) indicates a strictly clastic source in contrast to the broader array of sources encompassed by the LREE/HREE.
The PCA analysis, as shown in Figure 2, also demonstrates that the series-3 Fire Clay-derived ashes are distinct from the other series, a function of their higher concentrations of Zr and REY than the other three series of fly ashes. Further, the mechanical ashes occupy a distinct area from the ESP ashes with the ESP rows showing a sequential distribution (Figure 2 inset). In the first case, the differentiation is a function of the higher LREE/HREE and lower TiO2/(TiO2 + Al2O3) in the mechanical ashes vs. the ESP ashes. A similar differentiation drives the partition between the ESP rows. While this seems to contradict the inference of subtle, if any, REY variations between ashes from the same source [11], the differentiation in the amount and nature of the mineral inclusions seems to be sufficient to segregate the ashes. Of course, Liu et al. [11] focused on REY distributions, not a wider spectrum of major oxides and minor elements. They also examined the size fractions of a few single series-1 ashes with less emphasis on the discrete nature of the ashes from individual mechanical and ESP hoppers, as in this study. The nature of the ashes with respect to REY is further discussed below.

3.3. Lanthanide Elements

Apart from two fly ashes in the Manchester coal-derived series 1, all of the fly ashes have more than 390-ppm REE. The series-3 Fire Clay coal-derived ashes are all in the 604- to 638-ppm REE range. The series-3 Fire Clay-derived mechanical-collection fly ashes are the only ones in the study to show an L-type (normalized La > Lu) distribution (“dist.” column in Table 6). The LREE/HREE distributions differ, with the mechanical ashes from the latter series having an LREE/HREE from 6.80 to 6.93, while the ashes from the 1st- to 3rd-row ESPs steadily decrease from 5.92–5.95 to 5.81 to 5.59–5.60. The mechanical ashes from series 2 and 4 also have higher LREE/HREE than the ESP ashes in those series. The overall order mimics the trend seen for the series-3 Fire Clay principal components (Figure 2), demonstrating the influence of the LREE/HREE on the trends and emphasizing the importance of REE distributions as a tool in understanding their behavior in combustion systems.
The upper continental crust-normalized REE distribution after Taylor and McLennan (1985) (Figure 3; Table 5) is cluttered. In consideration of the two single-source-coal-feed sets (Figure 4), it is evident that the trends seen in the PCA plots are also clearly seen in the normalized data. While both the ESP and mechanical ashes from the Fire Clay coal-derived series show negative Eu and positive Gd anomalies, the ESP ashes have a higher Tb through Lu distribution. Note that, while some of the lithotypes contributing to the Manchester coal-derived ash have high ash-basis REE contents, the ash contents of those lithotypes are low, therefore, they are not major contributors to the overall REE concentration of the fly ash [37,38].
The distribution of the decoupled CeN/CeN*, EuN/EuN*, and GdN/GdN* distributions (Figure 5, Figure 6 and Figure 7) all show the segregation of the Fire Clay-derived mechanical and ESP fly ashes both from each other and, particularly, for the GdN/GdN* vs. EuN/EuN* (Figure 6) and GdN/GdN* vs. CeN/CeN* (Figure 7) distributions from the other three series. The latter trends are largely driven by the high GdN/GdN* in the Fire Clay-derived ashes, an indicator of their high HREE concentration, compared to the other fly ashes. Series 2 is separated from the Manchester-coal-derived fly ashes and from the series 4 fly ashes in the CeN/CeN* vs. EuN/EuN* (Figure 5) and GdN/GdN* vs. EuN/EuN* (Figure 6) distributions, owing to their low EuN/EuN*.

3.4. Discussion

By focusing on a single 100-MW unit at a power plant, we were able to focus on variations in fly ash chemistry, as they are influenced by variations in the feed coal. From the PCA of several parameters, plots of the decoupled CeN/CeN*, EuN/EuN*, and GdN/GdN* distributions, and spider plots of the upper continental crust-normalized REE values, we observed that the Fire Clay coal-derived fly ashes were distinctive in composition compared to the other three series. (Although, note that the spider-plot contrast is only evident in the comparison of the Fire Clay- and Manchester-derived fly ashes). Largely, this contrast is a function of the increased presence of REY-bearing minerals in the Fire Clay coal [26,32,38,39] compared to other coals in the region. The other coals are not necessarily depleted of REY. For example, the Manchester coal in the mine supplying the coal for Sakulpitakphon et al.’s [12] study of the series-1 fly ash has several benches with >1600-ppm REY (ash basis) [38]. Nevertheless, none of them have the lateral continuity of the Fire Clay coal.
Using the Fire Clay-derived fly ashes as an example, it was noted above that the LREE/HREE ratio decreases from the mechanical rows through to the third-ESP row. The PCA analysis demonstrated a subtle partitioning between the three ESP rows. This is confirmed for CeN/CeN* vs. EuN/EuN* (Figure 5) and GdN/GdN* vs. EuN/EuN* (Figure 6), owing to the EuN/EuN* increases from the first to the third ESP rows. Further, the EuN/EuN* for the mechanical fly ash is lower than for the ESP ashes. As with Liu et al.’s [11] examination of REY partitioning in fly ashes from the Series 1 fly ashes point towards the variations in LREE/HREE and the decoupled element distributions being a function of (1) petrographic variations between the samples from the individual collection times; (2) partitioning of the REY-bearing minerals; (3) variations in the chemistry of certain minerals.

4. Summary

The chemistry of four series of fly ashes generated in the same boiler but with different feed coal—either single-mine/single-seam coals in two cases or run-of-mine blends of coals from multiple mines and multiple seams—was examined with special attention to the concentration and distribution of the rare earth elements.
1/The principal components analysis demonstrated that series 3, the fly ashes derived from the combustion of the Fire Clay coal, were (1) distinctly partitioned from the other fly ash series; (2) internally divided between the mechanical hoppers and the three rows of ESP hoppers; (3) the ESP rows showed a subtle separation. The separation of the series-3 Fire Clay-derived ashes from the other series was driven by the higher Zr and REY in the series 3 ashes and the partitioning between the mechanical and ESP fly ashes, and among the ESP ashes is a function of the variations in the LREE/HREE and the TiO2/(TiO2 + Al2O3) ratios.
2/Upper continental crust normalization [27], particularly the plot of just the two single-mine/single-seam-coal-derived fly ashes, demonstrated the differentiation of (1) the Manchester coal-derived ash from the Fire Clay coal-derived ash; (2) in the REE abundances and distributions between ESP rows (Manchester coal source, series 1 fly ashes), and between the mechanical and ESP rows (Fire Clay coal source, series 3).
3/The decoupled CeN/CeN*, EuN/EuN*, and GdN/GdN* distributions are complicated due to the Ba interferences with Eu. Nevertheless, the CeN/CeN* vs. EuN/EuN* and, in particular, the GdN/GdN* vs. EuN/EuN* distributions confirm the distinction between the Fire Clay coal-derived ashes and the remainder of the fly ashes, and the Fire Clay coal-derived mechanical and ESP ashes from each other. Both trends are also evident in the plot of GdN/GdN* vs. CeN/CeN*, although the differentiation between the ESP rows is not as distinct as in the CeN/CeN* vs. EuN/EuN* and the GdN/GdN* vs. EuN/EuN* plots.
4/The chemistry of the feed coal, while not specifically addressed here, is an obvious factor in the concentration and distribution of REE in the fly ash. Specifically, the Fire Clay coal-derived series 3 fly ash has distinctly different distribution patterns than the other single-seam or coal blend series. In addition, there is evidence that the distribution of REE progressively changes from the mechanical ash collection system through the ESP rows. While this might seem to differ from the conclusions of Liu et al. [11], it is noted that this study focused on sized fractions of single fly ashes, not the differentiation associated with the temperature and particle size gradients in the passage from the mechanical hoppers to the third row of the ESP array.

Supplementary Materials

The following supporting information can be downloaded at: www.mdpi.com/article/10.3390/min12091071/s1, Table S1: Supporting information for PCA test.

Author Contributions

Conceptualization, J.C.H. and H.H.-K.; Data curation, J.C.H. and R.K.T.; Formal analysis, J.C.H., J.G.G., S.D.H., T.D.M., H.H.-K. and R.K.T.; Funding acquisition, J.C.H., J.G.G. and H.H.-K.; Investigation, J.C.H., J.G.G., H.H.-K. and R.K.T.; Methodology, J.C.H., H.H.-K. and R.K.T.; Project administration, J.G.G. and H.H.-K.; Resources, J.G.G.; Writing—original draft, J.C.H.; Writing—review and editing, J.C.H., J.G.G., S.D.H., T.D.M., H.H.-K. and R.K.T. All authors have read and agreed to the published version of the manuscript.

Funding

The current study is based upon work supported by the Department of Energy, Office of Fossil Energy and Carbon Management under Award Number DE-FE0032054. The 1999 and 2012 collections were funded by grants from the Commonwealth of Kentucky to the Center for Applied Energy Research. The collection and the original analyses of the 2014 and 2016 samples sets were completed as part of U.S. Department of Energy contract DE-FE0026952 and National Science Foundation grants CBET-1510965 and CBET-1510861 to Duke University and the University of Kentucky, respectively.

Acknowledgments

We thank our editor and the reviewers for their constructive comments.

Conflicts of Interest

The authors declare no conflict of interest.

Disclaimer

This report was prepared as an account of work sponsored by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof.

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Figure 1. (A) Comparison of ICP-OES and ICM-MS analyses for rare earth element contents in samples 94012–94019 (series 4). (B) A subset of the data, within blue outline in panel (A), focused on the lower abundance (and heavier) REE. Note that La, Ce, and Nd do not appear in this portion of the graph.
Figure 1. (A) Comparison of ICP-OES and ICM-MS analyses for rare earth element contents in samples 94012–94019 (series 4). (B) A subset of the data, within blue outline in panel (A), focused on the lower abundance (and heavier) REE. Note that La, Ce, and Nd do not appear in this portion of the graph.
Minerals 12 01071 g001
Figure 2. Plot of principal component analysis axes (right) and individual points (left). The inset shows the detail of the Fire Clay source (93953–93960) series 3 ESP data. The detailed key to the symbols is on Table S1.
Figure 2. Plot of principal component analysis axes (right) and individual points (left). The inset shows the detail of the Fire Clay source (93953–93960) series 3 ESP data. The detailed key to the symbols is on Table S1.
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Figure 3. Upper continental crust-normalized REE distribution after Taylor and McLennan [27]. All of the fly ash series are shown on this graph.
Figure 3. Upper continental crust-normalized REE distribution after Taylor and McLennan [27]. All of the fly ash series are shown on this graph.
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Figure 4. Upper continental crust-normalized REE distribution after Taylor and McLennan [27] for the Fire Clay- and Manchester-coal-derived fly ashes.
Figure 4. Upper continental crust-normalized REE distribution after Taylor and McLennan [27] for the Fire Clay- and Manchester-coal-derived fly ashes.
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Figure 5. EuN/EuN* vs. CeN/CeN* for all of the samples.
Figure 5. EuN/EuN* vs. CeN/CeN* for all of the samples.
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Figure 6. EuN/EuN* vs. GdN/GdN* for all of the samples.
Figure 6. EuN/EuN* vs. GdN/GdN* for all of the samples.
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Figure 7. CeN/CeN* vs. GdN/GdN* for all of the samples.
Figure 7. CeN/CeN* vs. GdN/GdN* for all of the samples.
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Table 1. Series, sample type, collection date, coal seam, ultimate analysis. dl—detection limit.
Table 1. Series, sample type, collection date, coal seam, ultimate analysis. dl—detection limit.
%; Mois—As-Rec., Others—Dry Basis
SeriesSampleTypeRowDateCoalAshMois.CHNSO
192645ESP2May-99Manchester90.01 6.93
192646ESP3May-99 92.25 5.96
192647ESP3May-99 91.05 6.53
293855mech1Dec-12blend93.750.101.830.11dl0.104.21
293856mech1Dec-12 92.410.129.740.620.730.12dl
293857ESP1Dec-12 94.710.206.160.240.050.26dl
293858ESP2Dec-12 94.570.326.030.240.010.36dl
293859ESP3Dec-12 94.850.763.830.22dl1.050.05
393953mech1Oct-14Fire Clay94.460.098.230.30dl1.09dl
393954mech1Oct-14 93.190.089.850.25dl1.09dl
393955ESP1Oct-14 93.340.228.110.27dl1.49dl
393956ESP1Oct-14 92.390.239.350.29dl1.36dl
393957ESP2Oct-14 94.000.267.820.35dl1.47dl
393958ESP2Oct-14 92.570.208.520.27dl1.63dl
393959ESP3Oct-14 91.980.558.260.34dl1.92dl
393960ESP3Oct-14 94.270.356.050.33dl1.94dl
494017mech1Dec-16blend94.56dl5.940.09dl0.04dl
494018mech1Dec-16 92.61dl8.110.10.010.1dl
494019mech1Dec-16 91.29dl8.830.09dl0.09dl
494012ESP1Dec-16 92.87dl6.480.13dl0.370.15
494013ESP1Dec-16 92.59dl6.580.10.010.180.54
494014ESP2Dec-16 85.051.246.660.17dl1.616.51
Table 2. Major oxides. dl—detection limit.
Table 2. Major oxides. dl—detection limit.
%; Ash Basis
SampleTypeRowNa2OMgOAl2O3SiO2P2O5K2OCaOTiO2Fe2O3SO3
92645ESP20.780.2325.5047.400.332.451.881.4313.670.13
92646ESP30.630.2025.9948.130.262.501.871.4514.390.14
92647ESP30.720.1524.9946.490.592.393.821.4014.260.07
93855mech10.141.1428.5653.080.132.570.981.1713.35dl
93856mech10.111.1428.8451.880.132.570.981.1813.15dl
93857ESP10.201.2730.5852.460.272.911.091.2510.22dl
93858ESP20.211.3229.8350.420.323.011.121.2310.710.08
93859ESP30.191.2430.0349.540.502.851.291.4010.340.89
93953mech10.180.7830.1054.210.261.751.461.689.27dl
93954mech10.180.7730.0254.600.251.721.511.669.30dl
93955ESP10.250.9430.7652.810.521.901.721.757.540.12
93956ESP10.240.9330.7455.960.521.961.761.787.580.06
93957ESP20.260.9830.6052.590.671.991.841.818.310.27
93958ESP20.260.9930.6553.320.692.011.871.818.220.22
93959ESP30.271.0130.2251.290.771.991.921.839.180.51
93960ESP30.281.0429.5650.120.892.022.011.789.870.96
94017mech10.231.0728.8055.540.582.371.681.489.620.08
94018mech10.231.0829.0455.560.602.351.721.499.500.09
94019mech10.231.0628.8755.200.602.321.741.499.630.09
94012ESP10.291.1629.8952.641.362.442.041.598.410.22
94013ESP10.281.1529.6752.491.222.442.011.568.340.38
94014ESP20.240.9323.4643.260.672.041.501.2926.051.69
Table 3. Minor elements (ash basis with the exception of Se and Hg on the whole-sample basis). dl—detection limit.
Table 3. Minor elements (ash basis with the exception of Se and Hg on the whole-sample basis). dl—detection limit.
ppm; Ash Basis
SampleTypeRowVCrMnCoNiCuZnGaGeAsRbSrZr
92645ESP2471266322168328284 124118576 196
92646ESP3 8273361 140
92647ESP3456258325176339253 10290420 157
93855mech132213320048110120182531911246911313
93856mech13311352004711012019044169641954269
93857ESP1416160227441341613537435284131211229
93858ESP24481682784614416141710051463131147246
93859ESP35571912435218043141013464491141352207
93953mech146114911145881787451 57369964365
93954mech1440151108411211606445 45390928366
93955ESP162220313275147271183143 218dl1035327
93956ESP163920613174149282174136 212dl1261391
93957ESP271323314990173331236179 325dl1297381
93958ESP272323414890179322234180 325dl1312384
93959ESP381425917596196392289223 550dl1359403
93960ESP3831265196103210398333215 582dl1254359
94017mech1374137130449211681339643801500198
94018mech13751361274589115794414813761550277
94019mech13721361274589119793510664121507210
94012ESP1496182149671421902067222270dl1767185
94013ESP1480180148661351852028627312dl1560214
94014ESP24332141086671802482338431249dl910179
ppm; Ash Basis ppm; Whole Sample
SampleTypeRowNbMoCdSbBaPbThU Se Hg
92645ESP229 16 461 391 0.45
92646ESP321 0.52
92647ESP325 17 460 400 0.92
93855mech136351388574
93856mech128371287575
93857ESP12863111029173
93858ESP22963111107218
93859ESP32867111349262
93953mech1 140dl61139824416 13 0.27
93954mech1 142dl61113794515 13 0.24
93955ESP1 122dldl15731494931 61 1.36
93956ESP1 188dl616011354629 59 1.82
93957ESP2 1931619131964736 67 1.42
93958ESP2 1951619081984837 76 1.90
93959ESP3 2091725022475046 110 2.31
93960ESP3 1681425832244344 215 0.94
94017mech126120dl9172677
94018mech140118dl9173478
94019mech129110dl8173573
94012ESP125117dl62112183
94013ESP129103dl42010172
94014ESP225dl281634150
Table 4. Sc, Y, rare earth elements.
Table 4. Sc, Y, rare earth elements.
ppm; Ash Basis
SampleTypeRow550 AshScYLaCePrNdSmEuGdTbDyHoErTmYbLu
92645ESP290.742665771682081173.4162.4152.97.91.16.80.9
92646ESP393.291021481121458122.3111.6101.95.20.74.30.6
92647ESP391.671425511261562122.5111.6101.95.30.74.40.6
93855mech193.43398112126531122254.2233.4224.212.01.711.01.5
93856mech192.441729701621978152.5131.9122.36.50.95.70.8
93857ESP194.893065821752183183.2172.6173.39.31.38.91.2
93858ESP294.503881932042396203.7203193.811.01.610.01.4
93859ESP395.283266761681978173.3172.6173.39.61.48.71.2
93953mech1 4010611726128110223.6253.4193.911.01.69.91.5
93954mech1 3910211726128110233.5253.4193.810.71.69.51.5
93955ESP1 5312911926529113244.2274.0234.813.42.012.31.8
93956ESP1 5212711425228109224.0263.7224.512.91.911.41.7
93957ESP2 5513011325228109234.3263.9224.613.21.911.71.8
93958ESP2 5513311625728111234.3273.9234.713.42.012.21.8
93959ESP3 5713811725929113244.6284.1245.014.22.112.71.9
93960ESP3 5413211024627106234.5263.9234.713.52.012.01.8
94017mech194.412562881922187183.6172.5163.08.61.28.01.1
94018mech193.8739951062182599204192.8183.49.51.49.01.2
94019mech192.922459931982290183.7182.6163.18.91.38.31.1
94012ESP192.502861841802081173.4172.5163.18.71.28.01.1
94013ESP192.183475952072395204.1202.9193.710.01.59.61.3
94014ESP287.692654761561872153.2152.2142.87.91.17.21.0
Table 5. Upper continental crust-normalized rare earth elements.
Table 5. Upper continental crust-normalized rare earth elements.
UCC-Normalized REE
LaCePrNdSmEuGdTbDyHoErTmYbLu
SampleTypeRow30647.1264.50.93.80.63.50.82.30.32.20.32
92645ESP22.572.632.823.123.783.864.214.004.293.633.433.673.093.00
92646ESP31.601.751.972.232.672.612.892.672.862.382.262.331.952.00
92647ESP31.701.972.112.382.672.842.892.672.862.382.302.332.002.00
93855mech14.034.144.374.695.564.776.055.676.295.255.225.675.005.00
93856mech12.332.532.683.003.332.843.423.173.432.882.833.002.592.67
93857ESP12.732.732.963.194.003.644.474.334.864.134.044.334.054.00
93858ESP23.103.193.243.694.444.205.265.005.434.754.785.334.554.67
93859ESP32.532.632.683.003.783.754.474.334.864.134.174.673.954.00
93953mech13.904.073.974.234.964.096.545.345.534.934.784.834.493.42
93954mech13.894.083.984.235.034.006.535.235.444.754.654.704.313.40
93955ESP13.974.144.084.365.274.757.176.196.625.965.825.965.604.21
93956ESP13.793.943.904.184.994.516.945.856.225.625.595.625.164.03
93957ESP23.773.943.924.205.124.876.976.026.425.775.755.865.324.08
93958ESP23.864.013.994.285.164.937.146.086.525.905.835.965.534.18
93959ESP33.894.044.064.345.275.237.356.406.916.256.196.295.764.41
93960ESP33.673.853.824.095.025.106.966.056.525.905.865.945.474.23
94017mech12.933.002.963.354.004.094.474.174.573.753.744.003.643.67
94018mech13.533.413.523.814.444.555.004.675.144.254.134.674.094.00
94019mech13.103.093.103.464.004.204.744.334.573.883.874.333.773.67
94012ESP12.802.812.823.123.783.864.474.174.573.883.784.003.643.67
94013ESP13.173.233.243.654.444.665.264.835.434.634.355.004.364.33
94014ESP22.532.442.542.773.333.643.953.674.003.503.433.673.273.33
Table 6. Rare earth-related parameters.
Table 6. Rare earth-related parameters.
SampleTypeRowEuN/EuN*CeN/CeN*GdN/GdN*dist.REEREYREYScLREE/HREE
92645ESP21.000.981.07H4194845106.44
92646ESP30.980.981.09H2823033136.49
92647ESP31.071.031.09H3043293437.00
93855mech10.850.991.08H6477287676.80
93856mech10.871.011.06H3904194367.54
93857ESP10.880.961.06H4435085385.94
93858ESP20.911.011.09H5105916295.93
93859ESP30.951.011.08H4224885205.59
93953mech10.801.041.25L6177237636.80
93954mech10.791.041.26L6167197586.93
93955ESP10.851.031.22H6437728255.92
93956ESP10.861.031.25H6137407925.95
93957ESP20.901.031.22H6167468005.81
93958ESP20.901.021.24H6287618165.81
93959ESP30.931.021.22H6387758335.60
93960ESP30.951.031.22H6047377915.59
94017mech11.011.021.09H4675295546.66
94018mech11.010.971.09H5366316706.85
94019mech11.021.001.12H4845435676.68
94012ESP10.991.001.11H4435045326.26
94013ESP11.021.011.12H5125876216.10
94014ESP21.060.961.11H3914454716.19
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Hower, J.C.; Groppo, J.G.; Hopps, S.D.; Morgan, T.D.; Hsu-Kim, H.; Taggart, R.K. Coal Feed-Dependent Variation in Fly Ash Chemistry in a Single Pulverized-Combustion Unit. Minerals 2022, 12, 1071. https://0-doi-org.brum.beds.ac.uk/10.3390/min12091071

AMA Style

Hower JC, Groppo JG, Hopps SD, Morgan TD, Hsu-Kim H, Taggart RK. Coal Feed-Dependent Variation in Fly Ash Chemistry in a Single Pulverized-Combustion Unit. Minerals. 2022; 12(9):1071. https://0-doi-org.brum.beds.ac.uk/10.3390/min12091071

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Hower, James C., John G. Groppo, Shelley D. Hopps, Tonya D. Morgan, Heileen Hsu-Kim, and Ross K. Taggart. 2022. "Coal Feed-Dependent Variation in Fly Ash Chemistry in a Single Pulverized-Combustion Unit" Minerals 12, no. 9: 1071. https://0-doi-org.brum.beds.ac.uk/10.3390/min12091071

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