USGS Bulletin 1823 - APPENDIX: Reference Materials for Coal Analysis

METHODS FOR SAMPLING AND INORGANIC ANALYSIS OF COAL
U.S. Geological Survey Bulletin 1823

The following tabulations list some of the reference materials available for use in the chemical analysis of coal. Data given in these tables are intended only to illustrate the degree to which the individual materials have been characterized. The analyst should always refer to specific certificates of analysis or other data provided directly by the supplier of the reference materials used.

Several coal standards now are being (or only recently have been) prepared by different laboratories; plans for preparation of these materials and available data are included in this section to alert the reader to these developments. The most significant program underway for the preparation and distribution of new coal standards is the Premium Coal Sample Program at Argonne National Laboratory. This program, described later, has produced eight new coal standards collected, analyzed, processed, and maintained for distribution to the coal research community. Important new coal and coal-ash standard reference materials for trace elements and radioactivity are expected to be available from the International Atomic Energy Agency in 1988. Also, the U.S. Geological Survey is preparing a new trace-element coal standard; preliminary data for this sample are included in this appendix.

These SRMs are intended primarily for use as analytical standards for the determination of total sulfur in coal, ash content, and calorific value. Semiquantitative data for these SRMs are available from NBS on 32 elements, including carbon, hydrogen, and nitrogen.

Source: National Bureau of Standards (NBS) certificate of analysis for standard reference materials 2682, 2683, 2684, and 2685, February 25, 1985.

	Concentration, m g/g^b
Element or Property	1632b	1635	1633a
Al(%)	0.855	(0.32)	14.3
As	3.72	0.42	145
Ba	67.5	-	(0.15)
Be	-	-	(12)
Br	(17)	-	-
C(total, %)	78.11	-	-
Ca	0.204	-	1.11
Cd	0.0573	0.03	1.0
Ce	(9)	(3.6)	(180)
Cl	(1260)	-	-
Co	2.29	(0.65)	(46)
Cr	(11)	2.5	196
Cs	(0.44)	-	(11)
Cu	6.28	3.6	118
Eu	(0.17)	(0.06)	(4)
Fe(%)	0.759	0.239	9.4
Ga	-	(1.05)	(58)
H(%)	5.07	-	-
Hf	(0.43)	(0.29)	(8)
Hg	-	-	0.16
K(%)	0.0748	-	1.88
La	(5.1)	-	-
Li	(10)	-	-
Mg(%)	0.0383	-	0.455
Mn	12.4	21.4	179
Mo	(0.9)	-	(29)
N(%)	1.56	-	-
Na(%)	0.0515	(0.24)	0.17
Ni	6.10	1.74	127
Pb	3.67	1.9	72.4
Rb	5.05	-	131
S(%)	1.89	0.33	(0.18)
Sb	(0.24)	(0.14)	6.8
Sc	(1.9)	(0.63)	(40)
Se	1.29	0.9	10.3
Si(%)	(1.4)	-	22.8
Sm	(0.87)	-	-
Sr	(102)	-	830
Th	1.34	0.62	24.7
Ti(%)	0.0454	(0.02)	(0.8)
Tl	-	-	5.7
U	0.436	0.24	10.2
V	(14)	5.2	297
W	(0.48)	-	-
Zn	11.9	4.7	220
Ash(%)	6.79	-	-
Calorific Value
(MJ/kg)	32.57	-	-
^a Source: National Bureau of Standards (NBS) certified values and information values, in parentheses, are from the following certificates of analysis: 1632b - Bituminous coal from Osage, W. Va, June 20, 1985. 1635 - Subbituminous coal from Erie, Colo., August 22, 1979. 1633a - Coal fly ash from Pennsylvania and West Virginia coals, January 5, 1985. Further information and data on NBS standards are available from the following sources: Gladney, E.S.,and others, 1984, standard reference materials: 1982 compilation of elemental concentration data for NBS biological, geological, and environmental standard reference materials: NBS Special Publication 260-88, Washington, D.C., U.S. Government Printing Office, 221 pp. Taylor, J.K., 1985, Standard reference materials: handbook for SRM users: NBS Special Publication 260-100, Washington, D.C., U.S. Government Printing Office, 85 pp. National Bureau of Standards, 1984 Standard reference materials catalog 1984-85: NBS Special Publication 260, Washington, D.C., U.S. Government Printing Office. Office of Standard Reference Materials, Room B311, Chemistry Building, National Bureau of Standards, Gaithersburg, MD 20899, telephone 301-921-2045. ^b Concentration units are percent, that is, centigrams per gram, for the elements Al, C, Fe, H, K, Mg, N, Na, S, Si, and Ti and for ash.

	Concentration,m g/g^b
Element	SARM 18	SARM 19	SARM 20
Al(%)	1.36	4.24	5.96
As	-	7	4.7
B	(30)	(90)	(90)
Ba	78	304	372
Be	4.1	2.8	2.5
Br	(3)	(2)	(2)
Ca(%)	0.13	0.99	1.34
Ce	22	56	87
Cl	-	(32)	-
Co	6.7	5.6	8.3
Cr	16	50	(67)
Cs	(1)	1.4	(2)
Cu	5.9	13	18
Eu	(0.3)	(0.7)	(1)
Fe(%)	0.20	1.22	0.82
Ga	(8)	14	16
Ge	(8)	13	-
Hf	1.7	5.4	4.8
Hg	(0.04)	(0.2)	(0.25)
K(%)	0.12	0.20	0.12
La	10	27	43
Li	(11)	(37)	(90)
Mg(%)	0.066	0.12	0.26
Mn	22	157	80
Mo	(1)	(2)	-
Na(%)	0.0130	0.22	0.20
Nb	(6)	(10)	(16)
Ni	10.8	16	25
P	30	130	610
Pb	(5)	20	26
Rb	8.1	9	10
S(%)	0.56	1.49	0.51
Sb	(0.3)	(0.3)	(0.4)
Sc	4.3	7.6	10
Se	-	(1)	0.8
Si(%)	2.90	7.01	8.26
Sm	2.0	4.9	6.3
Sn	(1.0)	(3)	(4)
Sr	44	126	330
Ta	(0.3)	(0.8)	1.2
Tb	(0.3)	(0.7)	(0.9)
Th	3.4	12	18
Ti(%)	0.0683	0.204	0.38
U	1.5	5	4
V	23	35	47
W	(2)	(2)	(3)
Y	(12)	(20)	29
Yb	-	(2)	(2)
Zn	5.5	12	17
Zr	67	351	(180)
L.O.I.(%)^c	90.11	71.28	64.66
^a SARM: South African reference material. ^bConcentration units are micrograms per gram, unless indicated otherwise. ^cL.O.I.: Loss on ignition. SARM 18 is a high-volatile, low-rank bituminous coal with a rank in the vitrinite category V₇. SARM 19 is a subbituminous to bituminous coal and is of generally very low rank (average V₄). SARM 20 is a subbituminous to bituminous coal and is of generally low rank (average V₆). Petrographic information is provided by Ring and Hansen (1984) on each SARM. Source: Ring, E.J. and Hansen, R.G., 1984, The preparation of three South African coals for use as reference materials: MINTEK Report No. M169, 130 p. Council for Mineral Technology, 200 Hans Strijdom Road, Randburg, South Africa.

This program was established to provide a suite of eight different premium coal samples to serve as standards for comparison. Coal samples designated "premium" have been selected, collected, transported, processed, and stored, while the original conditions were closely maintained. The coals selected represent a range of coalification, maceral content, mineral composition, and commercial significance. Each sample is kept in an inert atmosphere during transportation and in all processing steps. Prepared samples are sealed in glass ampoules and carboys. Each coal has been characterized by physical and chemical methods. The analyses planned include proximate, ultimate, calorific value, sulfur forms, Gieseler plasticity, and others. Information is available from the manager of the Premium Coal Sample Program: Dr. Karl S. Vorres, Chemistry Division, Building 211, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439, telephone 312-972-7374.

Reference materials for trace elements and radioactivity will be available in 1988. Information is available through Dr. R. Schelenz, Head, Chemistry Unit, Analytical Quality Control Services, International Atomic Energy Agency, P.O. Box 100, A-1400 Vienna, Austria.

	Concentration^a, m g/g				Method^b
Element	AR-l800	AR-1801	AR-1802	AR-1803
Ag	0.3^a	0.3^a	0.3^a	0.3^a	C
As	5.0	6.1	52.0	4.8	A
B	129	118	131	60	B
Be	3.9	3.3	3.9	0.3	C
Cd	0.2^a	0.2^a	0.2^a	0.2^a	C
Co	15	11	7	1	C
Cr	25	20	19	4	C
Cu	24	18	19	10	C
F	83	68	62	46	D
Ga	15^a	15^a	15^a	15^a	C
Ge	15	15	13	-	C
Hg	0.03	0.04	0.32	0.05	E
Li	32	17	13	4	C
Mn	15	14	33	11	C
Mo	2	2	3	l^a	C
Ni	82	58	22	5	C
Pb	8	8	64	4	C
Sb	0.9	0.9	0.8	1.2	A
Se	2.4	2.6	3.0	0.5	F
Sr	92	127	114	558	G
Tl	3^a	3^a	3^a	3^a	C
V	53	28	36	11	C
Zn	51	109	23	3	C
^aConcentration reported is at or below detection limit formethod. ^bMethod: A. HF-HCl digestion; gaseous hydride generation atomic absorption spectrometry (AAS). B. Na₂CO₃ fusion of ash; curcumin colorimetric. C. ASTM D3683-78-AAS. D. ASTM D3761-79 oxygen-bomb combustion; ion-selective electrode. E. ASTM D3684-78; oxygen-bomb combustion. F. Oxygen-bomb combustion; gaseous hydride generation AAS. G. HF-HCl dissolution; flame emission. Alpha Resources, Inc., also has available coal standards for sulfur, with concentrations of sulfur that range from 0.2 to 6 percent sulfur, and 11 coal standards for sulfur forms (pyritic, sulfate, organic, and total sulfur). The latter standards have been characterized for proximate analysis (ash, volatile matter, fixed carbon, and calorific value), for ultimate analysis (carbon, hydrogen, nitrogen, chlorine, and ash), and for oxides (P₂O₅, SiO₂, Fe₂O₃, A1₂O₃, TiO₂, CaO, MgO, SO₃, K₂O, Na₂O). Alpha Resources, Inc., Box 199, Stevensville, MI 49127.

Element	Concentration, m g/g^b
As	20
Ba	<90
Br	61
Ce	8
Co	4.1
Cr	8.2
Cs	0.2
Eu	0.19
Fe(%)	0.73
Hf	0.3
Hg	0.14
K(%)	<0.30
La	5
Lu	0.07
Na(%)	0.02
Nd	<20
Rb	<20
Sb	0.9
Sc	1.5
Se	1.9
Sm	0.7
Sr	38
Ta	0.13
Tb	0.14
Th	1.2
U	0.4
W	<2
Yb	0.5
Zn	43
^aPreliminary data are from instrumental neutron activation analysis of whole coal, September 1983; S. Mee, analyst. ^bConcentration units are percent, that is, centigrams per gram, for the elements Fe, K, and Na.

		Sulfur	Furnace Ash	Higher Heating
SRM^a	Coal Type	%	%	Value^b MJ/kg
2682	Subbituminous	0.47	6.37	27.08
2683	Bituminous	1.85	6.85	32.58
2684	Bituminous	3.00	11.09	29.21
2685	Bituminous	4.62	16.53	27.61
^aSRM: Standard Reference Material. ^bMoisture free.

Property	Certified Value	95% Conf. Interval
Ash	39.1 mg/g	0.6 mg/g
Sulfur	8.3 mg/g	0.2 mg/g
Calorific Value	34.915 kJ/g	0.070 kJ/g
Source: Catalogue of BCR Reference Materials, Commission of the European Communities, Community Bureau of Reference, Brussels, 1982.

Element	Certified Concentration m g/g	95 % Confidence Limit, m g/g
As	48.0	2.3
Cd	4.6	0.3
Co	53.8	1.9
Cu	176	9
Fe	338.10	7.10
Hg	2.10	0.15
Mn	479	16
Na	374.10	15.10
Pb	262	11
Zn	581	29
Particle size = 0.5 to 10 m m. Source: Addendum to the Catalogue of BCR Reference Materials .