Chemical analysis and modes of occurrence of selected trace elements in a coal sample from eastern Kentucky coal bed: White Creek Mine, Martin County, Kentucky

By, Curtis A. Palmer1 , Kristen O. Dennen1 , Allan Kolker1 , Robert B. Finkelman1 , and John H. Bullock, Jr.2

Open-File Report 02-311

2002

Final Technical ReportCRADA AgreementCRADA No. OT8562W with CQ Inc."Prediction of Trace Element Removal from Coal"

This report is preliminary and has not been reviewed for conformity with U.S. Geological Survey editorial standards and stratigraphic nomenclature. Any use of trade names is for descriptive purposes only, and does not imply endorsement by the U.S. Government

U.S. Department of the Interior

U.S. Geological Survey

'U.S. Geological Survey, 956 National Center, Reston, VA 201922U.S. Geological Survey, Denver Federal Center MS 973, Denver, CO 80225

Chemical analysis and modes of occurrence of selected trace elements in a coal sample from eastern Kentucky coal bed: White Creek Mine, Martin County, Kentucky

Curtis A. Palmer, Kris Dennen, Allan Kolker, Robert F. Finkelman, and John I 1 . Bullock, Jr.

"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, expressed 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

upon privately owned rights. Reference herein to any specific commercial product,

process, or service by trade name, trademark, manufacturer, or otherwise do^s 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."

Table of Contents

Abstract............................................................................................................................ 1Introduction....................................................................................................................... 1

Methods...........................................................................................................................^Sequential leaching .....................................................................................................2Scanning electron microscope (SEM) and electron microprobe analysis.................... 3

1 - Coal pellet casting and polishing......................................................................... 32-SEM analysis....................................................................................................... 33 - Electron microprobe analysis .............................................................................. 4

X-ray diffraction analysis.............................................................................................. 4Results and Discussion ....................................................................................................4

SEM and microprobe analysis.....................................................................................41 - SEM analysis of raw coal.................................................................................. 42 - SEM analysis of leached residue..................................................................... 53-Microprobedata............................................................................................... 5

Semi-quantitative mineralogy of low-temperature ash.................................................9Elemental analysis-quality control............................................................................. 10Leaching experiments................................................................................................ 12Semi-quantitative modes of occurrence..................................................................... 20

Conclusions.................................................................................................................... 20

References..................................................................................................................... 24

Appendices

1 Chemical Symbols, mineral names and abbreviations.............................................. 27

2. Quantitative microprobe analyses .............................................................................. 30

3. Data for individual splits.............................................................................................. 34

4. Quality control data..................................................................................................... 38

Abstract

This report provides semi-quantitative data on modes of occurrence of 20 elements in a sample collected from an eastern Kentucky coal from the White Creek Mine, Martin County, Kentucky. The data are in support of the project "Prediction of Trace Element Removal from Coal" -a Cooperative Research and Development Agreement (CRADA) with CQ Inc. The purpose of this CRADA is to apply modes of occurrence information to coal cleaning procedures, specifically a low sulfur central Appalachian coal for this study. Techniques used in this study include sequential selective leaching procedures, scanning electron microscopy, X-ray diffraction analysis, and electron microprobe analysis. Selective leaching results indicate that greate' than 50 percent of the elements Ca, Cd, Mn, Pb, and Zn are associated with HOI- or ammonium acetate-soluble carbonates, iron oxides, or monosulfides; greater than 40 percent of the Al, Be and Cr are associated with HF-soluble silicates; greater than 40 percent of the Co, Cu, Ni, Se, Sb, Th and U are associated with HCI, HF and HNO3 acid-insoluble phases and/or organic matter; and greater than 50 percent of the t- s and Hg is associated with HNCb-soluble pyrite. Due to the high clay content and relatively low pyrite content in this sample, 35 percent of the Fe was associated with th^ HF- soluble silicates while only 25 percent was associated with the pyrite. Thirty-five percent of the Ba is associated with the HF-soluble silicates whereas 40 percent of the B3 was associated with HCI-soluble (and ammonium acetate-soluble) barite. Thirty-five percent of the Mo was associated with the HF soluble clays. The major minerals present in this sample are quartz, kaolinite, and illite, as indicated by scanning electron microscopy and confirmed by X-ray diffraction analysis. The chalcophile elements As, Se, Cu, Ni, Zn, and Cd in most pyrite grains are at or below the detection limit of about 1C 0-200 ppm based on electron microprobe analysis, but two pyrite grains locally showed As concentrations of greater than one weight percent. One of these grains also had over a weight percent of each of the following elements: Co, Cu, Ni, and Se. Lead and Cu were also higher in this grain than in any other grains measured.

The results of this project should aid in the development of models for predicting the response of potentially toxic trace elements in commercial coal cleaning procedures.

Introduction

The United States Geological Survey (USGS) 1 is collaborating with CQ Inc. a coal research laboratory in Homer City Pennsylvania, to better understand how modes of occurrence of elements in coal affect partitioning of elements during physical cc^l cleaning. Previous work (Raleigh and others, 1998; Palmer and others, 1997, 19S3, 2000) describes semi-quantitative methods for determining modes of occurrence of elements in coal or coal-cleaning separates. The eventual goal of this collaborative project is to develop models for predicting the removal efficiency of potentially toxb trace elements from a variety of coals from different US coal basins during commercial coal cleaning operations. Herein, we report on the modes of occurrence of 20 elements in a sample collected from an eastern Kentucky coal bed from the Addington Energy Inc

1 A complete listing of the many abbreviations, chemical symbols, and mineral names used througt out this paper of the is given in Appendix 1.

(AEI)'s White Creek mine in Martin County, in the central Appalachian Basin. Th: "=? coal sample is believed to be a run of mine Broaz Seam coal shipped by barge and collected by personnel at Tennessee Valley Authority's Widow's Creek Fossil Plant barge unloading facilities.

The overall goal of this project is to assess the technical and economic potential for using the most promising advanced coal cleaning technologies to reduce emissions of mercury and other hazardous air pollutants (HAPs) when coal is burned. The objectives included: (1) obtaining semi-quantitative information on trace element modes of occurrence in the sample; and (2) assembling the information in a form that can be used by industry to enhance the potential of coal cleaning technologies for reduc:ng hazardous air pollutants (HAPs). Previous work funded by EPRI and DOE concentrated on understanding the effectiveness of removing Hg and other HAPs-forming elenents from bituminous coal feedstocks that are currently being cleaned (Northern Appalachian Basin, the Southern Appalachian basin, the Illinois basin) (Palmer and others, 1£97a) and the Powder River basin subbituminous coal that is not currently being cleaned. These previous studies included samples of feed stock coal, coal from various coal- cleaning streams and simulated cleaned coal.. This previous work indicated that the success of using physical coal cleaning techniques to reduce the potential HAP'? emissions was highly dependent on: 1) understanding the modes of occurrence of trace elements in coal including what minerals are present and what trace elements are associated with these minerals and applying appropriate cleaning procedures; 2) liberatation of discrete particles of trace element-bearing mineral matter includinp mineral size and associations; and 3) type, amount, and level of intensity of physical treatment. This paper provides data on the modes of occurrence of 20 element?, including all those considered as potential HAPs. This data will be used to develop models to determine the most effective coal cleaning procedures for specific

Methods

Sequential LeachingThe sequential selective leaching procedure used in this study is similar to that

described by Palmer and others (1993), which was modified from that of Finkelrr^n and others (1990). Duplicate 5 g samples were sequentially leached with 35 ml each of 1N ammonium acetate (CH3COONH4), 3N hydrochloric acid (HCI), concentrated hydrofluoric acid (HF; 48 percent), and 2N (1:7) nitric acid (HNOs). Ammonium rcetate removes elements bonded onto exchangeable sites, water-soluble compounds, and some carbonates. HCI dissolves carbonates, iron oxides, monosulfides and sorm chelated organic compounds. HF solublizes silicates, and nitric acid dissolves disulfides, especially pyrite. For the first three leaching stages (CH3COONH4, HCI, and HF), each sample was shaken in conical bottom 50 ml polypropylene tubes for 18 hours on a Burrell2 wrist action shaker. Because of gas formation during some of the leaching steps, it is necessary to enclose each tube in double polyethylene bags each

2Use of trade names and trademarks in this publication is for descriptive purposes only &nd does not constitute endorsement by the U. S. Geological Survey: !

' ' Vi< , ! ' ' ' (.-:

2

closed with plastic coated wire straps. The bags allow gas to escape, but prevent the release of liquid. The HNO3 leach was carried out in an Erlenmeyer flask similar to the method for the determination of pyritic sulfur (ASTM, 2001 a). We have found that this "flask method" is more effective at dissolving pyrite than shaking in tubes, because the partially demineralized coal resulting from the first three leaches has a very low density and forms a protective layer of sediment above the pyrite concentrated at the bottom of the conical tubes. Approximately 0.5 g of residual solid was removed from each t ibe for instrumental neutron activation analysis (INAA) and cold vapor atomic absorption analysis (CVAA) for mercury. Leachate solutions were saved for analyzed by inductively coupled argon plasma-atomic emission spectrometry (ICP-AES) and inductively coupled argon plasma-mass spectrometry (ICP-MS).

Scanning Electron Microscope (SEM) and Microprobe Analysis

1 - Coal pellet casting and polishing

The pellet formation procedure follows the ASTM D2797-85 (ASTM, 2001 b) technique for anthracite and bituminous coal, as modified by Pontolillo and Stanton (1994). The casting procedure impregnates, under pressure, approximately 7-8 g of 20 (850|xm) or 60 mesh (250|xm) crushed sample with Armstrong C4 epoxy. The resultant mold is cured overnight at 60E C. The 2.5 cm diameter circular pellet block is grc'ind and polished using ASTM D2797-85 procedure (ASTM, 2001 b) as modified by Pontolillo and Stanton (1994). The epoxy-coal pellet is first ground with a 15-jxm -diamond platen and then 600-grit SiC paper until flat and smooth. Rough polishing is done with 1 jam alumina and final polishing is completed with 0.06-jam-colloidal silica.

2 - SEM analysis.

A JEOL-840 scanning electron microscope (SEM) equipped with a Princetcn Gamma-Tech, energy-dispersive X-ray analytical system (EDX) and/or an ETEC Autoscan SEM with a Kevex EDX, was used for SEM examination of the coal. Mineral identifications inferred from morphology, and major-element composition of grains. Both secondary electron imaging (SEI) and backscattered electron imaging (BSE) modes were used in coal characterization. The BSE mode is especially sensitive to variation in mean atomic number and is useful for determining within-grain compositional variation. By optimizing the BSE image, the presence of trace phases containing elements with high-atomic number can be revealed. Samples were scanned initially to obtain an overall view of the phases present. This was followed by a series of overlapping traverses in which the relative abundance of the phases was assessed. EDX analysis provides information on elements having concentrations at roughly the tenth-of-percent level or greater. Typically, operating conditions for SEM analysis are: accelerating potential of 10-30 kV, magnifications of ~50-> 10,000 times and working distances ranging from 15 to 20 mm (ETEC Autoscan) and 15, 25, or 39 mm (JEC 1..- 840). The advantage of the conventional SEM methods over automated, computer- controlled SEM is that the operator can select appropriate phases for analysis by EDX

and can apply instantaneous interpretation of the textural relations of the phases being analyzed.

3 - Electron microprobe analysis.A fully-automated, 5 spectrometer microprobe instrument (JEOL JXA 8900R

Superprobe) was used to quantitatively determine element concentrations in pyrite by the wavelength-dispersive technique. In our preliminary microprobe analysis of pyrite the following elements were measured: Fe, S, As, Ni, Cu, Zn, Se, and Co. Natural and synthetic standards were used. A beam current used of 3.0 xlCT8 amps and a voltage of 20 KeV was used in the determinations. The probe diameter was set as a focused beam; the actual working diameter was about 3 micrometers. In this study, the minimum detection limit for microprobe analysis of trace elements was about 100 ppm, using counting times of 60 seconds for peak and 30 seconds for upper and lowe~ background. Counting statistics have a large uncertainty as the detection limit is approached. For Co (only), the detection limit is about 700 ppm (0.07 weight percent) due to an interference with Fe giving a constant background in pyrite of 700-800 ppm. Results for Co shown in Appendix 2 are background-corrected. Microprobe data are shown in Appendix 2.

X-Ray Diffraction AnalysisTo obtain semi-quantitative information on the minerals present in the coal a split

of the sample was low-temperature (<200° C) ashed. Duplicate samples of low- temperature ash were pressed into pellets and analyzed using an automated X-ray diffractometer. Diffraction of Cu Ka X-rays was measured over the interval from 4° to 60° 20. Counts were collected for 0.5 seconds per step (0.02 degrees). The dat^ were processed using a computer program for semi-quantitative mineral analysis by X-ray diffraction (Hosterman and Dulong, 1985).

Results and Discussion

SEM and Microprobe Analysis

1- SEM Analysis of Raw Coal

SEM analyses show that the major minerals in the eastern Kentucky coal (kaolinite, illrte, and quartz) were generally present as large quartz/clay intergrowths in some cases more than 100 microns in their largest dimension (Table 1). Subhedral and frambodial pyrite, including some particles larger than 10 microns and calcite were present, but not very abundant. A crandelrte group mineral (goyazite?; see appendix 1) was commonly observed, but Fe oxide and barite rare. In addition, rutile or anatese (grains analyzed as Ti only) was found in the raw coal as micron to several micron-sized particles commonly in quartz/clay intergrowths.

2- S

EM

Ana

lysi

s of

Lea

ched

Res

idue

Tw

o hu

ndre

d an

d si

x (2

06)

min

eral

gra

ins

wer

e an

alyz

ed b

y S

EM

. T

hese

gra

ins

rang

ed i

n si

ze fr

om l

ess

than

a

mic

ron

to 1

0 m

icro

ns in

the

lea

ched

res

idue

(m

ater

ial r

emai

ning

afte

r se

quen

tial l

each

ing)

. In

ord

er to

est

imat

e th

e pe

rcen

t of

resi

dual

min

eral

s pr

esen

t, th

e ar

ea o

f the

min

eral

gra

ins

wer

e es

timat

ed b

y as

sum

ing

eith

er a

rec

tang

ular

or

circ

ular

sha

pe.

Thi

s an

alys

is s

how

ed t

hat t

he c

ompo

sitio

n of

85

perc

ent

of th

e m

iner

al g

rain

s an

alyz

ed,

repr

esen

ting

abou

t tw

o th

irds

of th

e to

tal a

rea

of th

ese

min

eral

gra

ins,

wer

e Ti

C>2.

F

igur

e 1

show

s an

are

a of

unu

sual

ly h

igh

conc

entr

atio

n of

min

eral

mat

ter

in o

ne o

f the

lea

ched

res

idue

pel

lets

. E

xcep

t for

two

zirc

on g

rain

s, a

ll pa

rtic

les

on f

igur

e 1

b w

ere

TiO

2 gr

ains

. M

ost o

f the

se w

ere

elon

gate

d gr

ains

, ty

pica

l of

rut

ile.

Bot

h ru

tile

and

zirc

on a

re r

esis

tant

tot

the

leac

hing

pro

cess

. G

ener

ally

, as

can

be

seen

in f

igur

e 1a

the

re is

ver

y lit

tle m

iner

al m

atte

r pr

esen

t in

the

res

idua

l sam

ple.

Fou

r pe

rcen

t of t

he p

artic

les

exam

ined

, ra

ngin

g in

siz

e fr

om s

ub-m

icro

n to

10

mic

rons

(re

pres

entin

g 26

per

cent

of

the

area

) w

ere

pyrit

e co

mpl

etel

y en

caps

ulat

ed b

y or

gani

c m

ater

ial.

In a

dditi

on,

3 pe

rcen

t of t

he p

artic

les

foun

d in

coa

l af

ter

leac

hing

wer

e ch

alco

pyrit

e bu

t all

thes

e pa

rtic

les

wer

e le

ss t

han

2 m

icro

ns in

siz

e an

d re

pres

ente

d on

ly 2

per

cent

of

the

tota

l are

a.

Tra

ce a

mou

nts

of il

lite,

kao

linite

, qu

artz

and

goy

azite

wer

e al

so f

ound

to

be c

ompl

etel

y en

caps

ulat

ed i

n th

e co

al m

atrix

rep

rese

ntin

g th

e re

mai

ning

8

perc

ent o

f the

par

ticle

s an

d 5

perc

ent

of th

e to

tal

min

eral

are

a. E

xcep

t go

yazi

te,

thes

e m

iner

als

are

less

den

se t

han

pyrit

e an

d ru

tile

so th

at th

ey r

epre

sent

eve

n a

smal

ler

perc

enta

ge o

f the

tot

al

min

eral

mat

ter

by w

eigh

t tha

n th

eir

area

sug

gest

s.

3 -M

icro

prob

e D

ata

Mic

ropr

obe

data

for

26

pyrit

e gr

ains

in c

oal s

ampl

e ar

e gi

ven

in A

ppen

dix

2. T

wo

to s

ix d

iffer

ent

poin

ts o

n ea

ch

grai

n w

ere

anal

yzed

. T

he a

vera

ge c

once

ntra

tion

of F

e w

as 4

7 ±

1.4

wei

ght

perc

ent a

nd t

he a

vera

ge w

as 5

3 ±

1.2

wei

ght

perc

ent f

or S

; re

sults

exp

ress

ed o

n an

ato

mic

bas

is g

ive

acce

ptab

le s

oich

iom

etry

for

Fe$2

. C

d is

bel

ow th

e de

tect

ion

limit

for

all a

naly

ses

and

is n

ot s

how

n in

App

endi

x 2.

Zn

is c

onsi

sten

tly le

ss th

an 0

.02

wei

ght

perc

ent f

or a

ll an

alys

es.

The

ot

her

six

elem

ents

(A

s, C

o, C

u, N

i, P

b an

d S

e) s

how

mor

e va

riabi

lity

but

in g

ener

al a

re l

ess

than

0.1

wei

ght

perc

ent.

For

two

pyrit

e gr

ains

, A

s co

ncen

trat

ions

for

one

or m

ore

poin

ts w

ere

one

wei

ght

perc

ent

or h

ighe

r. G

rain

16

(App

endi

x 2)

was

sig

nific

antly

enr

iche

d in

sev

eral

trac

e el

emen

ts.

In a

dditi

on,

As,

Ni,

Se,

and

Co

wer

e al

l fou

nd t

o ha

ve

conc

entr

atio

ns o

f on

e w

eigh

t pe

rcen

t or

mor

e in

spo

t ana

lyse

s.

Pb

conc

entr

atio

ns w

ere

as h

igh

as 0

.48

perc

ent a

nd C

u co

ncen

trat

ions

wer

e 0.

15-0

.18

wei

ght

perc

ent.

Con

cent

ratio

n m

aps

of th

is g

rain

as

wel

l as

the

back

scat

tere

d el

ectr

on

imag

e ar

e sh

own

in f

igur

e 2.

In

bac

ksca

tter

mod

e (fi

g. 2

d) t

he g

rain

loo

ks li

ke a

hal

f of a

fra

mbo

id a

nd i

s cl

early

zon

ed.

Thi

s zo

ning

is a

lso

evid

ent

in t

he e

lem

enta

l m

aps

gene

rate

d fo

r S

e (fi

g. 2

a),

Ni (

fig.

2b)

and

As

(fig.

2c)

alth

ough

the

are

as

of h

ighe

st c

once

ntra

tion

are

diffe

rent

for

each

ele

men

t. H

owev

er,

the

elem

enta

l m

aps

show

the

entir

e fo

rm o

f the

fr

ambo

id,

indi

catin

g th

^st t

he r

emai

ning

por

tion

of th

e fr

srnb

oid

lies

just

be!

o»v

the

surf

ace.

T

hs w

sato

r ba

cksc

atto

r el

ectr

ons

cann

ot p

enet

rate

the

surf

ace

and

ther

efor

e do

not

pro

duce

an

imag

e.

The

str

onge

r x-

rays

use

d to

gen

erat

e th

e el

emen

tal

map

s pe

netr

ate

the

surf

ace

but

are

atte

nuat

ed p

rodu

cing

an

imag

e w

ith a

n ap

pare

nt lo

wer

con

cent

ratio

n fo

r

each of the elements in the upper right hand corner of figures 2a-c w

here the backscatter image of the fram

boid is m

issing.

Table 1. P

hases found in the coal sample and the leached residue using S

EM

analysis

Phases

Quartz

IlliteK

aoliniteFe oxide phase (hem

atite?)P

yriteC

halcopyriteC

alciteB

ariteTi oxide phase (rutile?)Z

irconC

randellite

Raw

Coal

-60 mesh

MMMmmmmmm

Residual

- 60 mesh

mmmmmMmm

M = M

ajor phase (estimated to be

greater than 10 percent of mineral grains

present in the sample)

m = M

inor or trace phase (estim

ated tobe less than 10 percent of the m

ineralgrains present in the sam

ple)blank =none detected

Figure 1. a) SEM micrograph of a coal particle with an unusually high concentration of sub- mircon mineral grains in a relatively small area, b) shows that most particles are elongated rutile (TiO2) grains. The rounded particles are either rutile grains in cross section or anatase (also TiO2 identified by XRD, Table 2) except for two rounded particles labeled as zircon.

Grain 22 (Appendix 2) also showed high As (1.72 weight percent) for one electron mcroprobe analysis point whereas a second point showed an As concentration of only 0.09 weight percent. For this grain, As showed a significant enrichment, so only its elemental map and the corresponding backscattered electron image are shown in figure 3. One area of the grain is clearly high in arsenic whereas the other areas are much lower in concentration. This As-rich zonation appears on the backscattered electron image as a brighter patch in the lower right portion of the grain.

Figure 2. Electron microprobe wavelength-dispersive elemental maps for Se, Ni and As, and backscattered electron image (CP) for a framboidal pyrite in CQ sample CQ-352 (Grain 16 in Appendix 2). Maps show differing regions of enrichment for each of these elements. Scale bar is 10 micrometers; width of field of view is 80 micrometers. Red to orange indicates relatively high concentrations. Yellow to green indicate intermediate concentrations and blue to black indicate low concentrations for figures 2a through 2c. For the backscattered electron image (figure 2d) areas of higher mean atomic number are brighter.

Figure 3. Electron microprobe wavelength-dispersive elemental map for As (3a), and backscattered electron image (CP; 3b) for a subhedral pyrite in CQ sample CQ-352 (Grain 22 in Appendix 2). Arsenic-rich zone corresponds to brighter areas of the backscattered image. Scale bar is 10 micrometers; width of field of view is 100 micrometers.

Semi-Quantitative Mineralogy of Low-Temperature Ash

Table 2 gives semi-quantitative estimates of mineralogy based on X-ray diffraction analysis (XRD) of low-temperature ash (LTA) of duplicate samples of the eastern Kentucky coal sample. About 55 to 60 percent of each LTA sample consists of kaolinite, 15-20 percent of each sample is composed of illite and 15 percent, quartz. Bassanite (CaSO4 V2H2O), likely an artifact of the ashing process, constitutes < 5 percent of the LTA and may be formed from calcite (which was detected by SEM but not by XRD) reacting with organic sulfur in the sample. Siderite, hematite, sphalerite, and pyrite, were detected as trace phases (<5 percent) by XRD. Of these minerals, sphalerite, pyrite and an iron oxide (hematite?) were also detected by SEM. Both rutile and anatase (TiO2) were detected by XRD. Anatase was only detected in one of the duplicate samples, but was detected at the 5 to 10 percent level, whereas rutile was found to be less than 5 percent in both of the duplicate samples. The relatively high percentage of anatase found in one duplicate sample and the non detection of anatase in the other duplicate sample suggests that anatase is not homogeneously distributed in the original coal sample.

Table 2. Semi-quantitative determination of minerals by X-ray diffraction (XPD) of low-temperature ash (LTA; values in weight percent on an LTA basis)

Sample KOL ILL QTZ PY SIP RUT ANA HEM SPH BAS BOE CHL FLD APADuplicate analysis

CQ353A1 60 20 15 <5 <:5 <5 <5<5<5 ? <5 CQ352B2 55 15 15 < 5 < 5 <5 >5<10 <5 <5<5 ? <5<5 QTZ = quartz; KOL = kaolinite; ILL = illite; BAS = bassanite; SID = siderite; ANA= anatase; HEM = hematite; PY = pyrite; SPH = sphalerite; FLD= feldsbar; CHL= chlorite; BOE= boehmite. ? =Trace constituent (< 5 %) that could not be resolved with certainty. Blank entry = not detected. Weight percentages listed are on a low-temperature ash basis. Frank T. Dulong, analyst.

Elemental Analysis Quality Control

in addition to the eastern Kentucky coal sample, CQ, Inc. submitted five b'ind standards for quality control purposes. The Eastern Kentucky coal was chemicall analyzed by multiple techniques. Concentrations of 30 elements were determined by INAA, using techniques described by Palmer (1997) on duplicate sample splits. Results were also obtained by ICP-AES (sinter and acid dissolution procedures; Pnggs, 1997) ICP-MS (Meier, 1997), hydride generation AA (Se), cold vapor AA (Hg; O'Leary, 1997) and ion chromatography (1C; Gent and Wilson, 1985) on triplicate sample splits at the USGS laboratories in Denver, Colorado. Table 3 shows the average results for 53 elements in the Eastern Kentucky coal sample.

The elemental concentrations of a series of 5 "blind" samples were submitted by CQ, Inc. to various laboratories to determine the comparability of data among laboratories. These samples were determined only by INAA because the limited quantity of sample provided did not allow for our standard ICP-AES and ICP-MS analysis. The first two samples, labeled CQO11202 and CQO111208 appear to be duplicates. There was no significant difference between the samples for any of tt 3 30 elements determined by INAA. The next two samples CQO111211 and CQO111214 are probably different splits of the same sample. The only element that differs frcm the first two samples is Br. The average concentration of Br was determined to be 5^.9 ±1.3 ppm for CQO11202 and 54.6±1.3 ppm for CQO11208 compared to 21.1 ±0.53 for CQO111211 and 21.0±0.53 for CQO111214. All of these samples appear to be snlrts of the eastern Kentucky coal sample analyzed in this study. The Br concentration ir the sample used for this study was 21.0±0.53: the same as CQO111211 and CQO11214. The final blind sample CQO111218 is significantly different than the other four control samples. However, it is not significantly different than the 1632C control sample tvat was run with all of the samples in this study. Certified, recommended, and informational values are given in Appendix 4-2 for each reference sample.

10

Table 3. Average Values for 53 Elements in the Eastern Kentucky coal sample (CQ352)

Variables:units:CQ352

Variables:units:CQ352

Variables:units:CQ352

Variables:units:CQ352

Variables:units:CQ352

Variables:units:CQ352

Variables:units:CQ352wt.=weight

HgPpm0.15

BePpm

2.0

Alwt. %

2.4

LiPpm

31

SePpm

6.2

LaPpm

14

HfPpm

1.1

Aspprn6.4

Cdppm

0.058

CaWt. %0.095

Bppm

43

Brppm

21

Ceppm

26

Tappm0.32

Crppm

22

Cuppm

17

Fewt. %

0.48

Pppm

76

Rbppm

20

Ndppm<5

Wppm0.86

Pbppm

9.2

Moppm

1.8

Nawt. %0.023

Clppm610

Srppm

71

Smppm

2.8

Auppm

< 0.002

Coppm

9.8

Znppm

18

MgWt. %0.080

Scppm

5.2

Yppm

9.3

Euppm0.52

Tlppm0.07

Nippm

17

Sbppm0.63

Siwt. %

3.8

Vppm

35

Zrppm

31

Tbppm

0.075

Mnppm

14

Thppm

3.7

Kwt. %

0.31

Gappm

5.9

Snppm

1.5

Ybppm0.12

Bappm130

Uppm

1.3

TiWt. %

0.12

Geppm

2.1

Csppm

1.4

Luppm0.04

These values typically represent the average of values determined by all techniques for a given element. Individual determinations, average values for each technique, and the overall values (which may be weighted averages depending on the reliability of the different techniques for a given element) for each sample are given in Appendix 3, which is color-coded to show the type of analysis for each determina*ion.

11

Leaching Experiments

Leachate solutions were analyzed by ICP-AES and ICP-MS, and solid residues were analyzed by CVAA (Hg) and INAA. Chemical data for the leachates and the solid residues have been processed to derive the mean percentages of each element leached by each of the four solvents. The calculated percentages were then used as an indirect estimate of the mode of occurrence of individual trace elements in the cot»l sample. The analytical errors were estimated to be ± 2 to ± 25 percent for these data, but errors are generally within ±5 percent, absolute.

Results for the Kentucky coal sample were determined in duplicate leaching experiments. Reproducibility is generally within the expected analytical errors, and is generally better within a given technique than among techniques. Figure 4 shows an example of the duplicate analyses of Co, determined by INAA, ICP-AES, and ICP-MS. Cobalt was not determined by ICP-MS on the whole coal fractions, therefore, the percent leached by ICP-MS is compared to ICP-AES whole coal, which might explain some of the differences of ICP-AES and ICP-MS. The results for each leached fraction agree within 10 percent absolute, but the ICP-MS is consistently higher than the other two techniques. The total amount leached is about 15 percent higher (or the unleached Co is 15 percent lower) as determined by ICP-MS. By averaging the various data for the duplicate individual analysis and rounding to the nearest 5, percent b^st values for each technique are determined. These results are then combined into a single stacked bar by further averaging, giving more weight to more accurate numbers and rounding to the nearest 5 percent to give the "overall best values".

Figure 5 shows the overall values for Ca, Mn, Cd, Zn, Pb, Cu and Ba. Th^se results are grouped together because the combined amounts of each of these elements leached by ammonium acetate and HCI are greater than the amount leached by any other solvent. Palmer and others, (1998) have shown that calcite (found in this rample by SEM; table 1) is partially soluble in ammonium acetate as well as being soluble in HCI. They also suggest that other carbonates, especially siderite, may be soluble in ammonium acetate. Mn and Ca have been shown to be primarily associated with carbonates (Palmer and others, 1998). Mn is also associated with silicates, particularly clays, as 30 percent of the Mn is HF teachable. These results are consistent witr our previous leaching experiments (Palmer and others, 1998).Forty to fifty percent of the Cd, Zn and Pb are leached by HCI with small amount? of Cd and Zn leached by ammonium acetate. Generally, these elements are associate'! with the monosulfides (galena and sphalerite). We did not identify either of these minerals by SEM in this sample. However, the concentrations of Cd, Zn and Pb are very bw in this sample. Twenty to twenty-five percent of these elements are leached by HNO3 suggesting that these elements also have an association with pyrite. Thirty percent of the Zn was leached by HF; consistent with Zn concentrations in illite and kaolinite found in coal. (Palmer and Lyons, 1996).

12

100

ICP-AES individual

Best ICP-AES

ICP-MS individual

Best ICP-MS

INAA individual

CH3 COOI\IH4 HCI HF a H

Figure 4. Percent cobalt (rounded to ± 5 percent) leached by selected solvents for two "individual" sample splits and "Best" (average values rounded to ± 5 percent) for ICP-AES,ICP-MS and INAA as well as "Best Overall" (weighted average of all values for all techniques rounded to ± 5 percent.)

13

100

Orig

inal

Co

ncen

tratio

nCa

95

00 p

pmM

n 14

ppm

Cd

0.58

ppm

Zn

17.5

ppm

Pb

9.2

ppm

Cu

17 p

pmBa

9.

8 pp

m

CH

3CO

ON

H4

HC

IH

FH

N0

3

Figu

re 5

. Le

achi

ng r

esul

ts fo

r el

emen

ts le

ache

d pr

imar

ily w

ith a

mm

oniu

m a

ceta

te a

nd H

CI.

Barite (BaSO4) was detected with the SEM. Barite is only partially soluble with HCI, and at most, only about 20 percent of the total Ba dissolved in the HCI coulcf be due to barite, according to solubility data given by Linke (1958). The remaining H~l- leachable Ba could be due to Ba in carbonate minerals. The ammonium acetate- soluble Ba also suggests that some Ba may be in carbonate minerals. Thirty-five percent of the barium is associated with the silicates (HF soluble), most likely clays (Palmer and others, 1996) and twenty percent is unleached which may be insolub'e barite or organically associated Ba.

The modes of occurrence of Cu are less certain than other elements in this group. Fifteen percent of the Cu is associated with pyrite and and an equal percentage associated with the silicates. Twenty-five percent of the copper is HCI soluble. This copper could exist as copper sulfate minerals many of which are HCI soluble, or copper oxides that are also HCI soluble.

HF leached a greater percentage of the elements shown in figure 6 (Al, Be Cr, Sb, U, Mo, and Co) than any other single solvent, suggesting a silicate association. However, except for Al, 35 to 55 percent of these elements remain unleached suggesting an organic association. In addition, all of these elements (except Al) have small, but significant HCI-soluble fractions. In rocks, Be is generally associated wi "i Al minerals (Goldschmidt, 1954) such as boehmite found to be present in trace amounts by XRD. In previous leaching experiments, Palmer and others, (1998) found that Be is leached mainly by HF in bituminous coal, with significant organic (unleached) Be, whereas, in lower rank coal some Be is also soluble in HCI with much smaller percentage of organic Be.

In the sample investigated in this study, 50 percent of the Be and 100 percent of the Al is HF soluble. Abundant kaolinite and Illite account for the majority of the Al. The presence of HF-soluble Be indicates significant association with the silicates (prot ^bly clays) but the large unleached fraction (45 percent) indicates a significant organic association as well. Palmer and others (2000) suggest that some HCI soluble Be may also be also be organically associated. Data for bituminous coal reported by Palrmr and others (1998) show that 20-65 percent of the Be was insoluble and therefore organically-associated, and less than 20 percent of the Be was soluble in HCI. Querol and Heurta (1998) found nearly all of the Be was organically-associated (based on float- sink procedures) even for samples jointly analyzed by their group and the USGS, which were shown by USGS techniques to have significant silicate association. To date the exact modes of occurrence of Be are unresolved.

Forty-five percent of the Cr in each sample is leached by HF and this Cr is probably associated with illite and mixed-layer clays (fig. 6; Palmer and others, 19^8). Only 10 percent of the Cr is HCI-soluble and may be associated with Cr oxy-hydrcxides (Huffman and others, 1994). Thirty-five percent of the Cr is not leached. Some of this may be organically associated, but some may be present in insoluble trace phase." such as chromite.

15

100

Orig

inal

Co

ncen

tratio

nAl

2.

38 w

t. pe

tBe

2.

0 pp

mCr

21

.8 p

pmSb

0.

63 p

pmM

o 1.

8 pp

m

CH

3CO

ON

H4

HC

IH

F D

H

N0

3

Co

9.8

ppm

Figu

re 6

. Le

achi

ng r

esul

ts fo

r ele

men

ts le

ache

d pr

imar

ily w

ith H

F. E

xcep

t for

Al t

hese

ele

men

ts h

ave

sign

ifica

nt u

nlea

ched

por

tions

.

16

Thirty-five percent of the Sb and U in the eastern Kentucky coal sample is leached by HF indicating a silicate association (clay minerals and zircon). Fifty percent of the Sb and 55 percent of the U is unleached, suggesting that it is organically bound. The percentage of HF leached Sb is higher than in bituminous coal studied previously (10-20 percent), but the portion of unleached Sb is remarkably similar to results from previous studies (Palmer and others, 1998). The high percentage of organically-bound U is not surprising considering its uptake into the organic matrix in peat swamps (Zielinski and Meier, 1988), however some of the unleached U may be due to the presence of insoluble zircon in the sample (fig. 1)

Five percent of the Sb and U is HCI-soluble in both samples, perhaps due to Sb and U present in carbonates, iron oxides or chelates. Some of the HCI- soluble U may be in organic chelates increasing the total percentage of organically associated U.

Five percent of the U and 10 percent of the Sb is HNOs soluble. The HNOs soluble U may indicate dissolution of U-bearing phosphates, which may be exposed following HF dissolution of encapsulating silicates. The concentration of U in pyrite is very low (about 1 ppm; Palmer and others, 1996) and U has been found to be HCI soluble after the HF leach (see discussion of Th below). The total Sb concentration is very low, 0.63 ppm, and it is possible that even with the low pyrite concentration in this sample (less than 1 percent), 10 percent of the Sb could be in the pyrite.

Thirty-five percent of the Mo is in HF-soluble silicates, most likely clay minerals. The 35 percent of unleached Mo indicates a significant organic association. Twenty percent of the Mo has a pyrite association and 15 percent was leached by HCI.

Cobalt appears to have mixed modes of occurrence. Results for Co are included in figure 6 because the 20 percent of the Co leached by HF is greater than that leached by HCI (15 percent) or that leached by either HNO3 or Ammonium Acetate (5 percent each). The HF soluble Co is associated with the silicates, probably clay minerals, HCI- and ammonium acetate-soluble Co is probably associated with carbonates, Fe-oxides and/or HCI-soluble monosulfides and the nitric acid soluble Co is associated with pyrite. This leaves 55 percent of the Co unleached, presumably associated with organic matter.

At least 25 percent of each element in figure 7 ( Fe, As, Hg, Ni, Se, and Th) was leached by nitric acid indicating a pyrite association. However, pyrite is not the primary mode of occurrence of all of these elements. This is partly because the total concentration of pyrite is small (on the order of about 0.25 weight percent). Thirty-five percent of the Fe is leached by HF indicating a silicate association. Table 1 shows that illitic clays are abundant with large quartz/clay intergrowths in some cases over 100 mircons in their longest dimension. Energy dispersive analyses of illitic clay particles by SEM show Fe to be a major component of these clays.

17

Fe oxides identified in SEM pellets (table 1) account for the 20 percent fraction of the Fe dissolved by HCI. Some of this Fe oxide may be due to the oxidation of pyrite. In addition, about 20 percent of the Fe was unleached. SEM examination of the leached solid residue found eight pyrite grains of the 206 grains analyzed (4 submicron framboids, 2-1 micron framboids, 1 subhedral grain 3X5 micrometers in size and 1-10 micrometer framboid, always completely surrounded by organic material). In addition, four particles of chalcopyrite were found ranging from 0.3 microns to 2 microns in their longest dimension. If one assumes that all of the unleached Ti is due to rutile and or anatase then (based on the area of other unleached minerals and appropriate density corrections) approximately 25 percent of the unleached Fe is due to pyrite or 5 percent of the total Fe in the sample and the amount of Fe due to unleached chalcopyrite and kaolinite is much less than 1 percent of the total Fe.

A larger percentage of the As (50 percent) than Fe (25 percent) is leached by nitric acid, indicating that much of the As is in pyrite. About the same percentage of Arsenic as iron was dissolved by HCI. This is consistent with the observation above that some of the Fe oxide may be due to pyrite oxidation. About 15 percent of the original As is in the silicates as determined by the leaching of As by HF. This is consistent with As found in illite (2.35 ppm) and kaolinite (0.52 ppm) by Palmer and others, (1996). Fifteen percent of the As was unleached suggesting an organic association. However, we calculate that most of the unleached As is due to unleached pyrite or about 5 percent of the total As, so that the remaining unleached (organically associated As) is less than 5 percent.

Seventy percent of the Hg was leached by nitric acid suggesting a strong pyrite association in this coal. Assuming that Hg is homogeneously distributed throughout the pyrite and calculating the amount of unleached pyrite, we calculate that 17 percent of the unleached Hg or about 15 percent of the total Hg is due to unleached pyrite. The remaining 15 percent of the unleached Hg may be organically associated. The total concentration of Hg was 0.15 ppm (table 3).

Equal percentages (25 percent) of Ni were associated with silicates and pyrite. However, as silicates represent a much larger percentage of the whole coal, the average concentration of Ni in the pyrite is much larger than the concentration in the clays. Ten percent of the Ni is HCI-soluble and may be associated with the Fe-oxides, or associated with carbonates. About 5 percent of the Ni is due to unleached pyrite using the assumptions above, and the remaining 35 percent of the Ni is unleached and is likely organically bound.

Twenty-five percent of the Se was nitric acid soluble and therefore associated with pyrite. An additional 5 percent of the Se may be due to unleached pyrite but the remaining 50 percent of the unleached Se is probably organically associated. Ten percent of the Se was leached by HF (silicate associated; probably clays) and by HCI (may be due to oxidized pyrite).

Thirty percent of the Th is leached by HNC>3 suggesting a pyrite association. However, the HNC>3 leachable Th may be from phosphates shielded by silicates, rather than in pyrite, as the samples in this study have very little pyrite, and concentrations of Th in pyrite have been found to be less than 0.5 ppm (Palmer et al. 1996). Thorium-bearing minerals such as monazite are detrital, and

18

100

Orig

inal

C

once

ntra

tion

Fe

4800

ppm

As

6.4

ppm

Hg

0.15

ppm

Ni

17 p

pmSe

6.

2 pp

m

CH

3CO

ON

H4

EE

HC

I

HF

D

HN

03

Th

3.69

ppm

Figu

re 7

. Le

achi

ng r

esul

ts fo

r se

lect

ed e

lem

ents

leac

hed

to a

sig

nific

ant d

egre

e by

19

are commonly associated with silicates. Experiments on a high pyrite coal (Palmar et al., 1999) show that 40 percent of the Th was removed by HCI, whereas an addit:onal 20 percent was released by a second HCI leach, conducted following the HF step instead of leaching with nitric acid.

The result of the second HCI leaching for this coal is equal to the 20 percent Th leached by nitric acid using the standard leaching protocol, again suggesting tha* nitric acid leachable Th does not necessarily reside in pyrite. Similar results were found for U, but elements generally associated with pyrite such as As and Hg, were not found to be HCI-soluble after the HF leach. The 15 percent of the Th leached by HF, is probably associated with the clays, although some HF leachable Th may be from zircon (detected by SEM). HCI-soluble Th (15 percent) is probably derived from trace amounts of apatite or monazite. Forty percent of the Th remains unleached. Some of this unleached Th could reside in insoluble or partially soluble minerals such as zircon (table 1), or may be organically bound.

Semi-quantitative Modes of Occurrence

Semi-quantitative assessments of each trace-element's modes of occurrence have been determined by combining all of the information available. This include." leaching results, electron microprobe analysis, scanning electron microscopy, X-^ay diffraction analysis and chemical analyses, as well as knowledge of the geocherrical characteristics of each element. Table 4 shows the percentage of 20 elements in each of three or four major phases or minerals. In cases where there is supporting direct evidence for a particular mode of occurrence, the host form of the mineral is given, such as As in pyrite, Zn in sphalerite or Cr in illite. In cases where there is strong geochemical evidence and strong indirect evidence, classes of minerals are given, such as sulfides, silicates, oxides or arsenates. In the remaining cases a descriptor is used, such as HCI-soluble.

Conclusions

The sample of eastern Kentucky coal in this study is lower in pyrite than rrost eastern US bituminous coal. Most of the 14 percent ash yield is due to quartz and clay minerals particularly kaolinite and illite. This leads to higher percentages of elements that are normally chalcophilic associated with the silicates. Greater than 15 percent of 15 of the 20 elements presented in this study were associated with silicates. Only Hg and As were primarily (greater than 50 percent) associated with pyrite.

For 9 of the 20 elements, greater than 40 percent of the original material was unleached. Although some of the unleached material can be accounted for by unleached pyrite, chalcopyrite and other minerals, except for Cu and Ti (not included in this study), the residual minerals represented only a small amount of the unleached element and most of the unleached elements were assumed to be organically associated. Except for Al, all elements had multiple modes of occurrence, although Hg and Ca had only two modes of occurrence.

20

Table 4. Modes of Occurrence of Trace Elements the Eastern Kentucky Coal Sample

Calcium

CQ352AExchangeable/Carbonates Organics

55% 45%

CQ352A

CQ352A

ManganeseCarbonates

60%

Pyrite 25%

Silicates 30%

Cadmium

Sphalerite 40%

Organics 10%

Silicates 5%

Organics 30%

CQ352APyrite 20%

Zinc

Sphalerite 50%

Silicates 30%

Organics 5%

CQ352APyrite 20%

Lead

Galena 50%

Silicates 5%

Organics 25%

CQ352A

Copper

Chalcopyrite/pyrite Oxides/Carbonates Silicates 60% 25% 15%

Barium

CQ352ABarite 35%

Silicates HNO3- Soluble Organics 35% 5% 25%

Aluminum

CQ352ASilicates 100%

21

Table 4. Modes of Occurrence of Trace Elements the Eastern Kentucky Coal Sample (Continued).

CQ352A

Beryllium

Oxides/Hydroxides Silicates 5% 50%

Chromium

Organ ics 45%

CQ352APyrite Oxyhydroxides Illite Organics

10% 10% 45% 35%

CQ352AHCI-soluble

5%

Antimony

Pyrite 10%

Silicates 35%

Organics 50%

Uranium

Oxides/Phosphates/Chelates Silicates Organics CQ352A 10% 35% 55%

CQ352AOxides

15%

Molybdenum

Silicates 30%

Pyrite 20%

Organics 35%

CQ352A

Cobalt

Pyrite HCI Soluble 5% 15%

Iron

Silicates20%

Organics 60%

CQ352A

CQ352A

Pyrite Oxides/Carbonates Silicates Organics 30% 20% 35% 15%

Arsenic

Pyrite Arsenates Silicates Organics 55% 20% 15% 10%

22

Table 4. Modes of Occurrence of Trace Elements the Eastern Kentucky Coal Sample (Continued)

CQ352A

CQ352A

CQ352A

Mercury

CQ352A

Pyrite 80%

Sulfides 25%

Sulfides 25%

hosphates45%

Nickel

Ni oxides 10%

Selenium

HCI-Soluble 10%

Thorium

Silicates15%

Organic 20%

Silicates Orgarvcs 65% 40%

Silicates Organic.? 10% 55%

Insoluble40%

23

References

ASTM (American Society for Testing and Materials), 2001, D2492-90 Standard Test Method for Forms of Sulfur in Coal: in Annual book of ASTM standards. Vol. 5.05 Gaseous fuels, coal and coke. Philadelphia, , p. 262-267

ASTM (American Society for Testing and Minerals), 2001, D2797-95 Standard practice for preparing coal samples for microscopical analysis by reflected light: in Annual book of ASTM standards. Vol. 5.05 Gaseous fuels, coal and coke. Philad3lphia, Pennsylvania, p. 282-285.

Briggs, P.M.,1997 Determination of 25 elements in coal ash from 8 Argonne Prerrium Coal samples by inductively coupled argon plasma-atomic emission spectrometry, in Palmer, C.A. ed., The chemical analysis of Argonne Prerrrjm Coal samples. U.S. Geological Survey Bulletin 2144, p 39-44.

Finkelman, R.B. Palmer, C.A., Krasnow, M.R., Aruscavage, P.J. Sellers,G.A., anc1Dulong, FT., 1990, Combustion and leaching behavior of elements in Argonne Premium Coal samples: Energy and Fuels v. 4 no. 5, p. 755-766.

Gent, C.A., and Wilson, S.A., 1985, The determination of sulfur and chlorine in coalsand oil shales using Ion chromatography: Analytical Letters, v. 18 No. A6, p. 729- 740.

Goldschmidt, V.M.,1954, Geochemistry, Oxford Press, London, 730 p.

Hosterman, J.W., and Dulong, FT., 1985, A computer program for semi-quantitative mineral analysis by X-ray diffraction: In Pevear, D.R., and Mumpton, F.A., eds., Qualitative mineral analysis of clays: CMS Workshop, Lectures, vol. 1, The Clay Minerals Society, Evergreen Colorado, p. 38-50.

Huffman, G.P., Muggins, F.E., Shah, N.,Zhao, J.,1994, Speciation of arsenic and chromium in coal combustion ash by XAFS spectroscopy: Fuel Processing Technology v. 39 no. 1/3. p. 47-62.

Linke, W.F., 1958, Solubilities of Inorganic and Metal Organic Compounds. 4th edition. D. Van Nostrand Company, Inc. Princeton. 1487 pp.

Meier, A. L., 1997, Determination of 33 elements in coal ash from 8 Argonne Prenfum Coal samples by inductively coupled argon plasma-mass spectrometry, in Palmer, C.A. ed., The chemical analysis of Argonne Premium Coal samples: U.S. Geological Survey Bulletin 2144, p. 45-50.

O'Leary, R.M., 1997, Determination of mercury and selenium in eight Argonne Premium Coal samples by cold-vapor and hydride-generation atomic absorption

24

spectrometry, in Palmer, C.A. ed., The chemical analysis of Argonne Premium Coal samples: U.S. Geological Survey Bulletin 2144, p. 51-56.

Palmer, C.A., 1997, The determination of 29 elements in eight Argonne Premium Coal samples by instrumental neutron activation analysis, in Palmer, C.A. ed., The chemical analysis of Argonne Premium Coal samples: U.S. Geological Survey Bulletin 2144, p.25-32.

Palmer, C.A., Krasnow, M.R., Finkelman, R.B., and D'Angelo, W.M., 1993, An evaluation of leaching to determine modes of occurrence of selected toxic elements in coal: Journal of Coal Quality v. 12, no. 4, 135-141.

Palmer C.A., and Lyons P.C., 1996, Selected elements in major minerals from bituminous coal determined as by INAA: Implications for removal of environmentally sensitive elements from coal. International Journal of Coal Geology, v. 32, p. 151-166.

Palmer, C. A., Kolker, Allan, Finkelman, R. B., Kolb, K. C., Mroczkowski, S. J., C'owley, S. S., Belkin, H. E., Bullock, J. H., Jr., and Motooka, J. M., 1997a, U.S. Geological Survey report to CQ, Inc. on data related to HAP'sRx Project: A technical report by the U.S. Geological Survey for CQ, Inc.: [Published as a chapter in: Akers, D. J., Raleigh, C. E., Lebowitz, H. E., Ekechukwu, Kenneth, Aluko, M. E., Arnold, B. J., Palmer, C. A., Kolker, Allan, and Finkelman, R. B., 1997, HAPs-Rx : Precombustion removal of hazardous air pollutant precursors: Final Report, DOE Contract DE-AC22-95PC95153, U.S. Department of Energy]. 115+p.

Palmer, C.A., Kolker, Allan, Finkelman, R.B., Kolb, K.C., Mroczkowski, S.J., Crowley, S.S., Belkin, H.E., Bullock, J.H., Jr., and Motooka, J.M., 1997b, Modes of occurrence of trace elements from a coal cleaning plant: Final technical contract report to CQ, Inc, U.S. Geological Survey Open-File report 97-732, 97p.

Palmer, C.A., Mroczkowski, S.J., Finkelman, R.B., Crowley, S.S., and Bullock, J.H., Jr., 1998, The use of sequential leaching to quantify the modes of occurrence of elements in coal: Fifteenth Annual International Pittsburgh Coal Conference Proceedings, CD-ROM, PDF166, 28 p.

Palmer, C.A., Mroczkowski, S.J., Finkelman, R., Bullock, J.H., Jr., 1999, Quantifying the modes of occurrence of trace elements in coal: Proceedings of the 24th International Technical Conference on coal utilization and fuel systems, p. 369- 380.

Palmer, C. A., Mroczkowski, S. J., Kolker, Allan, Finkelman, R. B., and Bullock, Jr., J. H., 2000, Chemical analyis and modes of occurrence of selected trace elements in a Powder River Basin coal and its corresponding simulated cleaned coal. U.S. Geological Survey Open-File Report 00-323. 52 p.

25

Pontolillo, J. and Stanton, R.W., 1994, Coal petrographic laboratory procedures and safety manual II: U. S. Geological Survey Open-File Report 94-631, 69 p.

Querol, X. and Heurta, A., 1998, Determination of the occurrence and distribution of trace-elements in coal: An inter-laboratory comparison- Determination of trace element affinities by density fractionation of bulk coal samples: Internationa 1 Energy Agency, Interim Project Report, 16 p.

Querol, X., Finkelman, R. B., Alastuey, A., Palmer, C. A., Mroczkowski, S. J., and Kolker, A., 1998, Quantitative determination of modes of occurrence of major, minor, and trace elements in coal: A comparison of results from different methods: Proceedings of the Eighth Australian Coal Conference, December, 1998, p. 51-56.

Raleigh, C.E., Jr., Akers, D.J., and Arnold, B.J., 1998, Precombustion control of trace metals in coal: Empire State Electric Energy Research Report EP 96-07, 57 p.

Zielinski, R.A., Meier, A.L., 1988, The association of uranium with organic matter in Holocene peat: an experimental study. Applied Geochemistry v. 3, p.631-6^3.

26

Appendix 1. Chemical symbols, mineral names, and abbreviations used in this report

Chemical symbols

AtAsAu BBaBe BrCCaCdCeClCoCrCs

Cu EuF

Fe *differs

aluminumarsenicgold boronbariumberyllium brominecarboncalciumcadniumceriumchlorinecobaltchromiumcesiumcopper europium fluorineiron

from abbreviation

GaGeHHgKLaLiMgMn

MoN*

NaNdNiOPPbRb

GalliumGeraniumHydrogenMercuryPotassiumLanthanumLithiumMagnesiumManganeseMolybdenumnitrogenSodiumNeodymiumNickeloxygenphosphorusLeadrubidium

sSbScSeSiSmSn

SrTbThTiTl

UVW

YZn

Zr

SulfurantimonyscandiumseleniumSiliconsamariumTinstrontiumterbiumthoriumtitaniumthalliumuraniumvanadiumtungstenYttriumZinc

zirconium

for normal (see below) because it is part of a chemical formula

Major Minerals

Quartz SiO2Kaolinite AI2(Si2O15)(OH)4Illite A group of mica-clay minerals with the general formula:

(K,H30)(AI, Mg, Fe)2(Si,AI)4O10[(OH)2 H2O]

Trace Minerals

AnataseApatiteBariteBassaniteBoehmiteCalciteChalcopyriteChromiteChloriteCrandelite

TiO2Ca5((F,CI,OH)(PO4)3BaSO4CaSO49 1/2 H2OAIO(OH)CaCO3CuFeS2FeCr2O4

CaAI3(PO4)2(OH)5eH2O

,2+i, Mg, Mn2+ ,Ni; Z=AI, Fe3+ ,Si

Feldspar XR4O8***Galena PbSGoyazite SrAI3(PO4)2(OH)5 H2C

Hematite Fe2O3 Molybdite MoO3 Monazite (Ce.La.Y, Th)PO4 Pyrite FeS2 Rutile TiO2 Siderite FeCO3 Sphalerite ZnS Zircon ZrSiO4 ***X=Ba,Ca,K,Na,NH4,Sr;R=AI,B,Si

27

Appendix 1. Chemical symbols, mineral names, and abbreviations used in this report

(continued)

Abbreviations

-60 KV urn <1:7°C o 22

AAampANAASTMBASBOEBSECVAACHLCRADACH3COONH4EDXETEC AutoscanFLD9HAPsHCIHEMHFHN031CICP-AESICP-MSILLINAAJEOL-840JEOL JXA 8900RKeVKOLmlMm

less than 60K alpha (line intensities for X-rays)micrometerless than(one part acid and 7 parts water)degrees Centigrade (refers to temperature)degrees 2 theta (measurement of angle of x-ray peaks in XRD)atomic absorptionampereanatase (See mineral list above)American Society for Testing Materialsbassanite (See mineral list above)boehmite (See mineral list above)backscattered electron imagingcold vapor atomic absorptionchlorite (See mineral list above)Cooperative research and development agreementammonium acetateEnergy Dispersive X-raymodel of a scanning electron microscope used in this studyfeldspar (See mineral list above)gramshazardous air pollutantshydrochloric acidhematite (See mineral list above)hydrofluoric acidnitric acidion chromotography: used to analyze for Clinductively coupled argon plasma- atomic emission spectrometryinductively coupled argon plasma- mass spectrometryillite (See mineral list above)instrumental neutron activation analysismodel number of a scanning electron microscope used in this stuc'vmodel number of microprobe used in this studykilo-electron volt (unit of energy)kaolinite (See mineral list above)millilitersmajor phaseminor or trace phase

28

Appendix 1. Chemical symbols, mineral names, and abbreviations used in this report

(continued)

N****

ppmPYQTZRUTSIDSEISEMSPHSiCU.S.USGSXRD

normalityparts per millionpyrite (see mineral list above)quartz (See mineral list above)rutile (see mineral list above)siderite (See mineral list above)secondary electron imagingscanning electron microscopesphalerite (see mineral list above)silicon carbideUnited StatesUnited States Geological SurveyX-ray diffraction

' Concentration of a solution in equivalents per liter; differs from the chemical symbol for nitre gen in that it is proceeded by a number and followed by a chemical formula or chemical name.

29

Appendix 2: Quantitative microprobe analyses of 26 pyrite grains

Where possible, pyrite classifications having genetic significance are used such as cleat or framboidal pyrite. In many cases, the genesis of the pyrite is uncertain and descriptive terms are used. These include: irregular- an irregular mass consisting of smaller, generally well-formed crystals. For individual crystals, descriptive terms include euhedral- referring to a complete crystal form defined by well-formed crystal facer; subhedra\ an approximate crystal form that may include some well-formed faces; and anhedral- a grain that lacks obvious crystal form. d.l.=detection limit.

30

Appendix 2: Q

uantitative microprobe analyses of 26 pyrite grains

in sample C

Q352

(values in weight percent;d.l.=detection lim

it)Form

(size) G

rain Se

Ni

Co

Cu

Zn A

s Pb

Fe S

Total C

omm

ent (m

icrons)

112223334567788891010111111

0.160.13

d.l.d.l.d.l.

d.l.d.l.d.l.

d.l.d.l.0.01

d.l.d.l.

d.l.d.l.

0.01

d.l.

d.l.d.l.

d.l.d.l.d.l.

0.03d.l.

0.010.010.06

d.l.d.l.0.01

0.020.050.03

d.l.0.01

0.030.03

0.03

d.l.

0.030.02

d.l.d.l.

0.01

0.040.01

0.01d.l.

0.01

0.010.010.02

0.040.040.03

0.01

0.01

0.010.010.02

0.01

d.l.0.02

0.02

0.020.02

0.510.59

0.010.020.03

0.010.010.01

0.010.010.01

0.010.01

d.l.d.l.d.l.

d.l.

0.010.01

d.l.0.01d.l.

0.d0.d0. 01.1.01.1.02

0.020.dddddddddddd

02.1..1..1..1..1..1..I.LI..1..1..I..1.

0.020.0. 0101

0.250.27

0.010.010.02

d.l.0.020.02

0.020.070.04

0.070.04

0.010.020.01

0.02

0.080.07

0.01d.l.

0.05

d.l.d.l.

d.l.d.l.d.l.

d.l.d.l.d.l.

d.l.d.l.d.l.

0.320.20

d.l.d.l.d.l.

d.l.

d.l.d.l.

d.l.d.l.d.l.

4746.00.91

46.7046464645464547464446484547454747474847

.91.60

.10.83.06

.19.43.83

.61.13

.02.75

.94

.90

.47.54

.80.02.79

53.6753.85

52.2752.0752.00

51.4851.4651.84

50.1352.6652.55

50.4352.76

53.8152.1353.81

51.02

53.5853.51

53.8353.7753.96

10

1.7

4C

Q#

1A

p1

.1

101.8

3C

Q#1A

p1.2

99

.10

CQ

#1

Ap

2.1

99.08 C

Q#1A

p2.2 98.79 C

Q#

1A

p2

.3

97.69 CQ

#1Ap3.1

97.41 CQ

#1

Ap

3.2

98.03 C

Q#

1A

p3

.3

Subhedral (20x20)

Subhedral (30x40)

Subhedral (30x30)

95.48 CQ

#1 Ap5.1 Fram

boid (15)100.32 C

Q#1A

p5.2 Fram

boid (15)99.56 C

Q#1A

p5.3 Fram

boid (15)

95.52 CQ

#1Ap6.1

Subhedral (30x40)

99.23 CQ

#1Ap6.2

101.94CQ

#1Ap7.1

Subhedral (30x40)

98.02 CQ

#1Ap7.2

101.8

9C

Q#1A

p7.3

97.02 CQ

#1Ap8.2

Fram

boid (20)

10

1.2

3C

Q#

1A

p9

.1

Subhedral (25x40)

101

.24C

Q#1A

p9.2

101.75CQ

#1Ap10.1 S

ubhedral (25x40)1

01

.90

CQ

#1

Ap

10

.2101.92 C

Q#1A

p10.3

31

App

endi

x 2

(con

tinue

d):

Qua

ntita

tive

mic

ropr

obe

anal

yses

of 2

6 py

rite

grai

ns f

or s

ampl

e C

Q35

2 (v

alue

s in

wei

ght

perc

ent;

d.l.=

det

ectio

n lim

it

No.

Se

Ni

Co

Cu

Zn

As

Pb

FeTo

tal

Com

men

t

12

0.01

12

d.l.

12

d.l.

13

0.01

13

0.03

13

0.02

14

d.l.

14

d.l.

15

d.l.

15

0.01

15

0.01

16

0.52

16

0.66

16

1.24

17

d.l.

17

d.l.

17

d.l.

17

d.l.

18

d.l.

18

d.l.

18

d.l.

19

0.02

19

0.02

0.05

0.03

0.05

0.04

0.03

0.03 d.l.

0.01 d.l.

d.l.

d.l.

1.52

1.54

1.25 d.l.

0.01 d.l.

d.l.

d.l.

0.01 d.l.

0.04

0.03

0.02

0.02

0.03

0.04

0.04

0.02

0.01

0.01

0.02

0.02

0.01

0.40

0.51

1.30

0.02 d.l.

0.01

0.01

0.02

0.03

0.03

0.02

0.01

0.02

0.01

0.02

0.03

0.05

0.03

0.02

0.01 d.l.

d.l.

d.l.

0.16

0.18

0.15 d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

0.06

0.06

0.02 d.l.

0.02

0.02 d.l.

0.01

0.01

0.01 d.l.

d.l.

d.l.

0.01 d.l.

0.01 d.l.

0.01 d.l.

0.01 d.l.

d.l.

d.l.

d.l.

d.l.

0.30

0.17

0.20

0.05

0.05

0.04

0.04

0.06

0.03

0.02

0.01

1.00

0.61

0.82

0.03

0.08

0.07

0.05

0.02 d.l.

0.02

0.08

0.06

0.01 d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

0.36

0.48 d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

d.l.

46.2

647

.90

47.2

4

47.8

547

.64

47.7

4

46.4

246

.66

47.9

348

.21

48.0

8

43.3

843

.52

38.8

6

48.7

048

.29

48.1

348

.12

47.0

847

.00

46.8

6

46.6

146

.38

51.4

753

.27

52.5

4

53.8

052

.90

53.1

6

51.9

252

.26

53.2

354

.18

54.6

8

51.5

452

.04

46.8

3

53.8

253

.67

53.4

253

.26

52.3

751

.37

51.4

1

52.7

452

.33

98.

101

22 .47

100.

17

101

100

101

98.

99.

101

102

102

98.

99.

91.

102

102

101

101

99.

98.

98..9

0.8

0.1

2

48 09 .28

.51

.87

59 48 02 .65

.13

.70

.52

55 49 38

99.6

298

.97

CQ

#1A

p11.

1C

Q#1

Ap1

1.2

CQ

#1A

p11.

3

CQ

#1A

p12.

1C

Q#1

Ap1

2.2

CQ

#1A

p12.

3

CQ

#1A

p13.

1C

Q#1

Ap1

3.2

CQ

#1A

p14.

1C

Q#1

Ap1

4.2

CQ

#1A

p14.

3

CQ

#1A

p15.

1C

Q#1

Ap1

5.2

CQ

#1A

p15.

3

CQ

#1B

p1.1

CQ

#1B

p1.2

CQ

#1B

p1.3

CQ

#1B

p1.4

CQ

#1B

p2.1

CQ

#1B

p2.2

CQ

#1B

p2.3

CQ

#1B

p3.1

CQ

#1B

p3.2

Form

(si

ze)

(mic

rons

)

Fram

boid

(20

)

Fram

boid

(20

)

Sub

hedr

al (

20x2

0)

Sub

hedr

al (

30x5

0)

Hal

ffram

boid

(25)

Sub

hedr

al (

25x7

0)

Fram

boid

(25

)

32

Appendix 2 (continued): Q

uantitative microprobe analyses of 26 pyrite grains for sam

ple CQ

352 (values in w

eight percent; d.l.= detection limit)

No.20202020

202021212121222223232324242525252526262626

Se

0.02d.l.d.l.d.l.d.l.d.l.

d.l.0.01d.l.d.l.

0.010.01

0.02d.l.d.l.

d.l.d.l.

d.l.d.ld.l.d.l

d.l.d.l.d.l.

0.01

Ni

d.l.d.l.d.l.d.l.d.l.d.l.

d.l.d.l.

0.01d.l.

0.04d.l.

d.l.0.010.01

d.l.d.l.

d.l.dl

0.01rtl

0.01d.l.

0.01d.l.

Co

0.010.010.020.020.01d.l.

0.010.020.020.02

0.010.02

0.01d.l.

0.01

0.010.02

0.01dl

d.l.dl

0.020.020.010.01

Cu

d.l.0.01d.l.d.l.

0.010.01

d.l.d.l.d.l.d.l.

0.010.01

d.l.d.l.d.l.

d.l.d.l.

0.030040.01001

d.l.d.l.d.l.

0.01

Zn

d.l.0.01d.l.d.l.d.l.d.l.

d.l.0.01d.l.d.l.

d.l.d.l.

0.01d.l.d.l.

d.l.d.l.

d.l.d.l.d.l.d.l.

d.l.d.l.d.l.

0.01

Mb

0.270.200.120.040.110.12

0.110.070.100.08

0.091.72

0.01d.l.

0.04

0.090.03

0.010.020.030.03

0.310.270.480.32

Pb

d.l.d.l.d.l.d.l.d.l.d.l.

d.l.d.l.d.l.d.l.

d.l.d.l.

d.l.d.l.d.l.

d.l.d.l.

d.l.d.l.d.l.d.l.

d.l.d.l.d.l.d.l.

f-e

48.0348.3348.2647.5748.0047.85

47.4847.8747.4347.02

46.4547.55

47.3348.2147.75

47.2947.79

46.7546.8646.2946.44

47.3947.1446.8546.07

S54.0754.4553.9853.77

53.5352.90

53.4553.1353.0553.53

52.5452.94

53.6653.8553.62

52.8252.60

52.1852.2951.9752.01

53.6353.8853.1553.30

Total

102.47103.09102.45101.47101.74100.94

101.12101.17100.66100.73

99.22102.31

101.10102.15101.49

100.27100.50

99.0599.2898.3898.56

101.44101.38100.5799.79

Com

ment

CQ

#1Bp4.1

CQ

#1Bp4.2

CQ

#1Bp4.3

CQ

#1 Bp4.4

CQ

#1Bp4.5

CQ

#1Bp4.6

CQ

#1Bp5.1

CQ

#1

Bp

5.2

CQ

#1Bp5.3

CQ

#1Bp5.4

CQ

#2AP

1.1C

Q#2A

P1 .3

CQ

#2AP

2.2C

Q#2A

P2.3

CQ

#2AP

2.4

CQ

#2AP

3.1C

Q#

2A

P3

.2

CQ

#2AP

4.1C

Q#

2A

P4

.2C

Q#2A

P4.3

CQ

#2AP

4.4

CQ

#2AP

5.1C

Q#2A

P5.2

CQ

#2AP

5.3C

Q#2A

P5.4

Form (size)

(miu

lons)

Subhedral (60x80)

Subhedral (60x90)

Subhedral (35x50)

Subhedral (45x100)

Subhedral (40x70)

Subhedral (45x45)

Subhedral (20x40)

33

App

endi

x 3:

Dat

a fro

m in

divi

dual

spl

its

The

"be

st o

vera

ll va

lues

" in

App

endi

x 3

are

also

rep

orte

d in

Tab

le 3

. A

ppen

dix

3 al

so g

ives

sep

arat

e "b

est v

alue

s"

for

INA

A a

nd fo

r "o

ther

tech

niqu

es"

beca

use

som

e el

emen

ts d

eter

min

ed b

y IN

AA

wer

e al

so d

eter

min

ed b

y ot

her

tech

niqu

es b

ut th

ere

is n

o du

plic

atio

n of

resu

lts b

etw

een

the

othe

r te

chni

ques

.A

ll IN

AA

val

ues

wer

e de

term

ined

in th

e sa

me

irrad

iatio

n w

ith q

ualit

y co

ntro

l sam

ples

sub

mitt

ed b

y C

Q (

App

endi

x 4-

1) a

nd

qual

ity c

ontr

ol s

tand

ards

: U

SG

S s

tand

ard

refe

renc

e m

ater

ial C

LB-1

and

Nat

iona

l Ins

titut

e fo

r S

tand

ards

and

Tec

hnol

ogy

(NIS

T) c

ertif

ied

refe

renc

e m

ater

ial 1

632C

(A

ppen

dix

4-2)

. Th

e qu

ality

con

trol

sta

ndar

ds fo

r "o

ther

tech

niqu

es"

(App

endi

x 4-

2) w

ere

also

run

tog

ethe

r with

the

sam

ple

split

s in

App

endi

x 3.

Sam

ples

CQ

353A

and

CQ

352B

wer

e su

bmitt

ed a

s bl

ind

dupl

icat

es.

CQ

352B

A w

as a

lab

dupl

icat

e of

CQ

352B

.

34

App

endi

x 3.

D

ata

for

indi

vidu

al s

plits

in

ppm

exc

ept a

s no

ted.

Si (

%)

Al

(%)

Fe (

%)

Mg

(%)

Ca

(%)

Na

(%)

K (

%)

Ti (

%)

P (%

) C

l (%

)C

Q35

2Arr

or A

C

Q35

2B

i_rr

or B

B

est

INA

AF

stim

ate^

IN

AA

err

ror

CQ

352A

(23

3)

CQ

352B

(23

3)

CQ

352B

A (

233)

B

est V

alue

oth

er te

chni

ques

F

chni

ques

err

or

Bes

t ove

rall

valu

e E

stim

ated

ove

rall

erro

r

CQ

352A

rroi

C

Q35

2Brr

or B

B

est

INA

Ast

imat

ed I

NA

A e

rrro

r C

Q35

2A

CQ

352B

C

Q35

2BA

B

est V

alue

oth

er te

chni

ques

.siii

,. ^u

oth

er te

chni

ques

err

or

Bes

t ov

eral

l val

ue

Est

imat

ed o

vera

ll er

ror

Key

: N

D=N

ot D

eter

min

ed;

INA

A=i

nstru

men

tal

neut

ron

activ

atio

n an

alyi

s.O

ther

tech

niqu

es in

clud

e:in

duct

ivly

cou

pled

pla

sma

(ICP

) at

omic

em

isso

n sp

ectro

scop

y (A

ES

)-ac

id d

IC

P-A

ES

sin

ter

dige

st,

ICP

-mas

s sp

ectro

scop

y-ac

id d

iges

t; hy

drid

e ge

nera

tion

(HG

) at

omic

abs

orpt

ion

(AA

); C

old

vapo

r A

A;

ion

chro

mot

ogra

phy

Err

or «

> gi

ey

35

ND 3.

863.

723.

613.

730.

193.

730.

19

Li ND 31 31 31 311.

531

1.5

ND 2.

422.

352.

272.

350.

122.

350.

12

Be

ND 2.

02.

02.

02.

00.

102.

00.

10

0.46

2 0.

009

0.45

90.

009

0.46

00.

009

0.51

0.49

0.46

0.48

0.02

0.47

0.02

B

ND 47 39 39 412.

141

2.1

ND 0.

081

0.08

00.

076

0.07

90004

0.07

90.

004

Sc 5.

210.

076

5.20

0.07

65.

210.

076

5.3

5.1

5.2

5.2

02

65.

20.

3

ND 0.

100.

090.

090.

090.

005

0.09

0.00

5

V

ND 35 35 35 35 2 35 2

0 0 0 0 0 0 0 0 0 0 0 0 0

Cr

221

22 0 22 0 22 21 21 211

221.0

24

.001

.0

24.0

01.0

24.0

01.0

22.0

22.0

22.0

22I

M

.023 001

.4 .0 .3 .7 .3 .8 .07

0.31

2 0.

013

0.30

50.

014

0.30

80013

0.32

0.30

0.30

0.31

0.02

0.31

0.02 Mn

ND 14 14 15 14 0.

7214

.45

0.72

ND 0.

130.

120.

120.

120.

010.

120.

01 Co

9.93

0.19

9.84

0.29

9.88

0.24

9.4

9.9

9.6

9.6

0.48

10 0.48

ND 0. 0. 0. 0. 0. 0. 0. Ni

18. 3 13. 2. 16. 2. 17 18 16 17 0. 17 3.

0080

0073

0067

0074

0004

01 0004

9 1 3 6 1 840

85 5

ND 0

.06'

0.07

J

0.06

EO.

OOG

0.06

£o.

oo:

Cu

ND 18 17 17 17 0.

8617 0.

86

App

endi

x 3.

D

ata

for

indi

vidu

al s

plits

in p

pm (

cont

inue

d)

Zn

Ga

Ge

As

Se

Br

Rb

Sr

CQ

352A

Eriu

, M

CQ

352B

Err

or B

Bes

t IN

AA

Est

imat

ed I

NA

Aer

rror

CQ

352A

CQ

352B

CQ

352B

AB

est V

alue

oth

er te

chni

ques

stim

ated

oth

er te

chni

ques

err

or

Bes

t ove

rall

valu

e E

stim

ated

ove

rall

erro

r

CQ

352A

Err

or A

C

Q35

2B

Err

or B

B

est

INA

Ast

imat

ed I

NA

Aer

rror

C

Q35

2A

CQ

352B

C

Q35

2BA

B

est V

alue

oth

er te

chni

ques

?d o

ther

tec

hniq

ues

erro

r B

est o

vera

ll va

lue

Est

imat

ed o

vera

ll er

ror

Key:

ND

=Not

Det

erm

ined

; IN

AA

=ins

trum

enta

l ne

utro

n ac

tivat

ion

anal

yis.

othe

r tec

hniq

ues

incl

ude:

indu

ctiv

ly c

oupl

ed p

lasm

a (IC

P) a

tom

ic e

mis

son

spec

trosc

opy

(AE

S)-

acid

d

ICP

-nE

S s

inte

r di

gest

, IC

P-m

ass

spec

trosc

opy-

acid

dig

est;

hydr

ide

gene

ratio

n (H

G)

atom

ic a

bsor

ptio

n (A

A);

Col

d va

por A

A; I

on c

hrom

otog

raph

y F

i n

grey

36

18 1 18 1 18 1 16 17 17 17 084

171 Zr

ND 33 30 28 30

1 5

30.3 1.5

ND 43 42 43 43 2

143

2.1

Nb

ND 3.

22.

72.

82.

90

142.

880.

14

ND 15 15 15 15 0

75

15 0.75

Mo 2.

50.

61.

30.

41.

90.

51.

61.

61.

61.

60

-.£

1.6

0.5

6.7

02

6.5

0.2

6.6

0.2

6.4

6.4

6.3

6.4

03

26.

50.

3 Cd

ND

0.06

20.

055

0.06

00.

059

0 0'

.0.

060.

003

6.2

05

5.9

04

6.1

05

6.0

6.8 ND

6.4

03

26.

30.

5

Sn

ND

1.7

1.2

1.4

1.5

L'07

1.45

0.07

20.9 0.5

21.3 0.5

21.1 0.5 N

D

21.1 0.5 S

b0.

612

0.02

30.

598

0.02

30.

605

0.02

30.

680.

640.

630.

650

03

0.61

0.05

20.9 1.6

21.0 1 6

21.0 1.6

20 19 20 20 0.96

20.5 1.5 Cs

1.43

0.07

1.42

00

51.

430.

061.

41.

31.

41.

40

07

1.4

0.07

72 13 77 12 74

ND

13 67

9.4

67

9.1

69

9.3

68

9.3

;9

0.46

69

9.28

7 0.

46

Ba

124 12 128 13

126 12

138

132

131

133 6

67

130 8

La 14.1 0.3

14.1 0.3

14.1

0342

Ce

26.1 0.6

25.7 0.8

25.9 0.71

0

Sm

2.76

0.07

2.76

00

72.

70.

066

Eu

0.52

50.

017

0.51

00.

016

0.51

80.

017

Tb 0.34

00

10.

350.

020.

344

00

15

Yb

1.28

00

71.

220.

081.

251

0.07

5

Lu 0.17

0.01

0.17

0.01

0.17

0.01

2

Hf

1.02

00

81.

01004

1.01

0.05

7

App

endi

x 3.

D

ata

for

indi

vidu

al s

plits

in p

pm (

cont

inue

d)

CQ

352A

A

CQ

352B

ror

B B

est

INA

Ast

imat

ed I

NA

A e

rrro

r C

Q35

2A

CQ

352B

C

Q35

2BA

Bes

t Val

ue o

ther

tech

niqu

es

ND

N

D

ND

N

D

ND

N

D

ND

N

D

r.stim

ateu

oth

er te

chni

ques

err

orB

est

over

all v

alue

14

.1

25.9

2.

8 0.

52

0.34

1.

25

0.17

1.

01

Est

imat

ed o

vera

ll er

ror

0.3

0.7

0.1

0.01

7 0.

015

,075

0.

012

06

Ta

W

Tl

Hg

Pb

Bi

Th

UC

Q352A

0.

32

1.0

3.75

1.

4E

rror

A

0.01

0.

1 0

08

0.

1C

Q35

2B

0.32

0.

73

3.63

1.

3rr

orB

0.

03

0.07

008

0.1

Bes

t IN

AA

0.

32

0.86

N

D

ND

N

D

ND

3.

69

1.35

2st

imat

ed I

NA

A e

rrro

r 0.

021

0.07

4 0.

080

0105

CQ

352A

0.

75

0.15

9.

4 0.

18

3.6

1.4

CQ

352B

0.

70

0.14

8.

8 0.

17

3.5

1.3

CQ

352B

A

0.71

0.

15

9.2

0.17

3.

4 1.

3B

est V

alue

oth

er te

chni

ques

N

D

ND

0.

72

0.15

9.

1 0.

17

3.5

1.3

isti'

;L

othe

r te

chni

ques

err

or

0.04

0.

008

0.46

0.

01

0.18

0.

07B

est o

vera

ll va

lue

0.32

0.

86

0.72

0.

15

9.14

0.

17

3.6

1.4

Est

imat

ed o

vera

ll er

ror

0.02

0.

07

0.04

0.

008

0.46

0.

01

0.18

0.

10K

ey:

ND

=Not

Det

erm

ined

; IN

AA

=ins

trum

enta

l ne

utro

n ac

tivat

ion

anal

yis.

othe

r te

chni

ques

incl

ude:

indu

ctiv

ly c

oupl

ed p

lasm

a (IC

P)

atom

ic e

mis

son

spec

trosc

opy

(AE

S)-

acid

d

iCP

-AE

S s

inte

r di

gest

, IC

P-m

ass

spec

trosc

opy-

acid

dig

est;

hydr

ide

gene

ratio

n (H

G)

atom

ic a

bsor

ptio

n (A

A);

Col

d va

por

AA

; Io

n ch

rom

otog

raph

y E

rror

in g

rey

37

Appendix 4. Quality Control Data

Control samples in Appendix 4-1 were submitted as blind samples. Due to limited sample size elemental concentrations in these samples were determined only by INAA. Elemental concentrations of standard reference material USGS CLEM and certified reference material NIST 1632C (Appendix 4-2) were determined with the samples in Appendix 3 for all techniques. Elemental concentrations of certified reference materials, NIST 1633b and NIST 1632b, were also determined for selected techniques (Appendix 4-2).

38

Tabl

e A

4-1.

C

Q "

Blin

d" q

ualit

y co

ntro

l sa

mpl

es. V

alue

s in

ppm

exc

ept

as n

oted

.

varia

bles

:C

Q01

1120

2Er

ror:

CQ

01 1

1202

Err

or:

Ave

rage

Aver

age

Erro

r

CQ

O11

1208

Erro

r:C

Q01

1120

8E

rror

:A

vera

geA

vera

ge E

rror

CQ

0111

211

Err

or:

CQ

0111

211

Erro

r:A

vera

geA

vera

ge E

rror

CQ

O11

1214

Erro

r:C

Q01

1121

4Er

ror:

Ave

rage

Ave

rage

Erro

r

CQ

O11

1218

Err

or:

CQ

0111

218

Err

or:

Ave

rage

Ave

rage

Erro

r

Sc

5.26

0.08

5.27

0.08

5.26

0.07

7

5.26

0.08

5.30

0.08

5.28

0.07

7

5.19

0.08

5.17

0.08

5.18

0.07

5

5.18

0.07

55.

120.

079

5.15

0.07

7

2.80

0.04

32.

790.

042

2.80

0.04

3

Se 5.

700.

576.

240.

325.

970.

445

5.67

0.88

6.02

0.56

5.84

10.

719

5.32

0.92

5.59

0.65

5.45

20.

788

5.89

50.

551

5.44

70.

838

5.67

10.

694

1.20

60.

143

1.08

50.

205

1.14

50.

174

Sr

82.8

11.7

96.1 9.67

89.5

10.7

89.8

17.1

82.3

10.9

86.0

14.0

78.4

10.9

82.4

13.0

80.4

12.0

66.9

10.0

73.2 8.6

70.1 9.3

68.8

11.0

65.3

10.9

67.0

10.9

Ta 0.

350.

010.

350.

020.

352

0.01

9

0.34

0.01

0.35

0.02

0.34

30.

016

0.34

0.02

0.32

0.01

0.32

70.

019

0.34

70.

015

0.32

90.

015

0.33

80.

015

0.14

20.

011

0.13

30.

009

0.13

70.

010

Th 3.89

0.08

3.95

0.10

3.92

0.09

1

3.96

0.08

3.88

0.08

3.92

0.08

3

3.74

0.08

3.74

0.08

3.74

0.07

9

3.73

60.

089

3.76

0.08

33.

750.

09

1.35

0.04

01.

350.

048

1.35

0.04

4

U 1.20

0.10

1.35

0.11

1.28

0.11

1.47

0.13

1.25

0.10

1.36

0.11

3

1.35

0.10

1.37

0.11

1.36

0.10

5

1.30

0.10

1.39

0.11

1.34

0.10

0.53

80.

071

0.47

40.

062

0.50

60.

066

W 0.73

0.06

0.80

0.07

0.76

50.

070

0.71

0.06

0.99

0.11

0.84

70.

088

0.83

0.09

0.86

0.08

0.84

40.

084

0.71

30.

064

0.83

60.

077

0.77

50.

070

0.42

10.

061

0.24

40.

047

0.33

30.

054

Zn 32.4 1.7

32.6 1.9

32.5 1.8

30.9 1.6

33.7 1.6

32.3 1.6

19.2 1.3

20.3 1.4

19.7 1.3

19.0 1.5

16.8 2.4

17.9 1.9

10.9

0.85

10.2

0.90

10.5

0.88

La 14.7 0.35

14.6 0.36

14.6

0.35

4

14.5 0.35

14.7 0.36

14.6 0.35

14.0 0.34

14.1 0.34

14.0 0.34

14.1 0.34

14.1 0.34

14.1 0.34

6.50

0.17

6.49

0.17

6.50

0.17

Ce

27.0 0.58

27.4 0.62

27.2 0.60

27.1 0.59

27.3 0.61

27.2 0.60

26.0 0.57

26.3 0.60

26.2 0.58

25.6 0.65

26.2 0.58

25.9 0.62

11.4 0.52

11.6 0.35

11.5 0.43

Sm 2.80

0.06

62.

800.

067

2.80

0.06

6

2.79

0.07

2.81

0.07

2.80

0.06

7

2.75

0.06

2.76

0.07

2.75

0.06

5

2.76

0.06

52.

770.

066

2.77

0.06

6

1.10

0.02

91.

090.

028

1.10

0.02

8

Eu 0.

510.

018

0.53

0.01

70.

522

0.01

8

0.53

0.02

0.55

0.02

0.54

00.

020

0.53

0.02

0.52

0.02

0.52

80.

017

0.54

60.

017

0.53

20.

017

0.53

90.

017

0.22

10.

011

0.20

80.

009

0.21

50.

010

Tb 0.

360.

013

0.36

0.01

40.

361

0.01

3

0.34

0.01

0.36

0.01

0.35

30.

013

0.36

0.01

0.35

0.01

0.35

60.

013

0.34

60.

020

0.36

10.

014

0.35

30.

017

0.13

50.

012

0.12

80.

007

0.13

10.

009

Yb 1.

320.

083

1.28

0.07

81.

300.

080

1.31

0.08

1.16

0.08

1 24

0.07

7

1.30

0.12

1.16

0.14

1.23

0.12

8

1.33

0.12

41.

280.

076

1.31

0.10

0

0.49

20.

056

0.55

20.

066

0.52

20.

061

40

1.20

1.17

0.09

8

1.61

1.65

40.

0034

231

23.0

20.

08

0.79

0.79

90.

021

0.91

0.91

50.

0013

7

15.1

15.0

50.

27

0.89

50

02

20.

860.

874

0.35

0.75

50

01

20.

740.

735

0.11

6.5

7.78

0.23

0.03

0.02

830.

0018

0.03

0.03

840.

0032

0.5

0.48

20.

008

015

0.16

0.00

71

0.14

0.14

50.

030

1.6

1.51

0.06

0.01

98O

.OO

OSf

0.02

390.

017

0.00

2

0.03

1O

.OO

OSf

!0.

0292

0.02

988

0.00

048

0.19

0.20

10.

003

0.06

40.

0040

0.06

0.06

30.

004

0.10

60.

0057

0.11

0.11

000.

0033

2 1.95

0.03

0.05

0.04

70.

0018

0.05

0.05

170.

0032

07

70.

791

0.01

4

0.03

0.03

10.

004

0.01

0.01

5

0.24

0.23

01

13

0.11

40.

1139

0.00

41

ND

ND

8 8 8 8

173

Tabl

e A

4-2

US

GS

Qua

lity

Con

trol

Sta

ndar

ds V

alue

s in

ppm

exc

ept a

s no

ted

Si(%

) A

l(%

) F

e(%

) M

g(%

) C

a (%

) N

a (%

) K

(%

) Ti

(%

) P

(%)

Cl (

%)

IC

LB-1

Err

orC

LB-1

Rec

omm

ende

d/In

form

atio

nE

rror

(R

ecom

men

ded

and

info

rmat

ion)

1632

-C

Err

or16

32-C

Cer

tifie

d/R

efer

ence

/lnfo

rmat

iona

l E

rror

(C

ertif

ied

and

Ref

eren

ce v

alue

s)

1633

-BC

ertif

ied/

Non

certi

fied

Err

or (

Cer

tifie

d va

lues

)

1632

-B

0.10

7 C

ertif

ied/

Non

certi

fied

0.12

6 Er

ror

(Cer

tifie

d va

lues

)

Be

B

Sc

V

Cr

Mn

Co

Ni

Cu

ZnC

LB-1

Err

orC

LB-1

Rec

omm

ende

d/I n

form

atio

nE

rror

(R

ecom

men

ded

and

info

rmat

ion)

1632

-C

Erro

r16

32-C

Cer

tifie

d/R

efer

ence

/Info

rmat

iona

l E

rror

(Cer

tifie

d an

d R

efer

ence

val

ues)

1633

-B (

233)

C

ertif

ied/

Non

certi

fied

Err

or (

Cer

tifie

d va

lues

) 3.

6 4.

7 1.

7 1.

8 2.

6 Ke

y:N

D=N

ot D

eter

min

ed;

INAA

=ins

trum

enta

l neu

tron

activ

atio

n an

alyi

s.ot

her t

echn

ique

s in

clud

e:in

duct

ivly

cou

pled

pla

sma

(ICP)

ato

mic

em

isso

n sp

ectro

scop

y (A

ES)-a

cid

dige

st;

ICP-

AES

sint

er d

iges

', IC

P-m

ass

spec

trosc

opy-

acid

dig

est;

hydr

ide

gene

ratio

n (H

G)

atom

ic a

bsor

ptio

n (A

A); C

old

vapo

r AA;

Ion

cnr

umot

ogra

phy.

41

1.17

1.17

1.01

1.0

12.6

441

2 0 2.04

.029

.12

2.0

61.72

62 2 61.9

0 2 0 2 2 0 41 41

.1 .83

.039

.86

.905

.036

.8

12 12 1 22.4

23.72

0.51

288

295.

7

10.2 0.41

10.5 9.7

1.2

13.9 0.79

14.4

13.73

0.2

182

198.2

8.95

8 13.0

13.04

0.53

129

131.8

6.97

0.14

6.74

7.0

0.7

3.43

0.18

3.79

3.48

0.20

50.0

50

13.6 3.4

19.0

18 2 10.7 2.9

10.1

09.

320.

51

108

120.6

11.1

10 5.93

6.01

0.25

108

112.8

5C 3.5

44.4

48.0

10.5 0.92

13.6

12.1 1.3

192

210

2 3 3 3 51

Tabl

e A

4-2

US

GS

Qua

lity

Con

trol

Sta

ndar

ds V

alue

s in

ppm

exc

ept a

s no

ted,

(co

ntin

ued)

CLB

-1E

rror

CLB

-1R

ecom

men

ded/

Info

rmat

ion

Err

or (

Rec

omm

ende

d an

d in

form

atio

n)

1632

-C

Err

or16

32-C

Cer

tifie

d/R

efer

ence

/Info

rmat

iona

l E

rror

(C

ertif

ied

and

Ref

eren

ce v

alue

s)

1633

-BC

ertif

ied/

Non

certi

fied

Err

or (C

ertif

ied

valu

es)

1632

-6(2

33)

Cer

tifie

d/N

once

rtifie

d E

rror

(C

ertif

ied

valu

es)

CLB

-1 (

71)

Err

orC

LB-1

(23

3)Re

com

men

ded/

Info

rmat

ion

Err

or (

Rec

omm

ende

d an

d in

form

atio

n)

1632

-C (

71)

Err

or16

32-C

(23

3)C

ertif

ied/

Ref

eren

ce/In

form

atio

nal

Err

or (C

ertif

ied

and

Ref

eren

ce v

alue

s)

1633

-6(2

33)

Cer

tifie

d/N

once

rtifie

d E

rror

(C

ertif

ied

valu

es)

27K

ey:N

D=N

ot D

eter

min

ed;

INA

A=i

nstru

men

tal n

eutro

n ac

tivat

ion

anal

yis.

Oth

er te

chni

ques

incl

ude:

indu

ctiv

ly c

oupl

ed p

lasm

a (IC

P) a

tom

ic e

mis

son

spec

trosc

opy

(AE

S)-

acid

dig

est;

iCP

-AE

S s

inte

r dig

est,

ICP

-mas

s sp

ectro

scop

y-ac

id d

iges

t; hy

drid

e ge

nera

tion

(HG

) aw

mic

abs

orpt

ion

(AA)

; C

old

vapo

r AA;

Ion

chr

omot

ogra

phy.

42

Ge

13.8

4.7

5 17.0 Sn

0.75

1.04

1.00

12.1

As

13.7 : 5°

13.9

13 5.93

0 1

4

6.16

6.18

0.27

128

136.

22.

6 Sb

1.55

0.08

91.

601.

5

0.42

60.

016

0.47

0.46

10.

029

5.6

6

Se

2.2

04

32.

552.

10.

39

1.31

0 1.32

1.32

60.

071

1.25

1.29

0.11 C

s0.

359

0.02

30.

32

0.60

80.

029

0.62

0.59

40.

01

10.5

11

Br

75.4 4.41

24.4 044

18.7 0.4 Ba

42.0 7.0

35.0

345

46.5 7.1

38.2

41.1 1.6

688

709

Rb

6.7

C:

5.25

5.2

0.9

7.47

1 '

7,37

7.52

0.33

140

140 La 5.94

0.11

5 6.59

0.12

Sr

Y

Zr

Nb

Mo

87.6

12

.0P

7

P^G

70.6

4.

93

10.9

6 1.

07

9.89

67.1

1

9

67.1

<

1 2

10 64.7

3.

95

16.2

5 1

23

0.77

63.8

4

16

1 0.

81.

4

1040

85

.9

193

20.4

14

.610

4114

Ce

Sm

E

u Tb

Y

b10

.6

1.17

0.

225

0.15

6 0.

557

0.78

0.

028

0.01

5 0.

0086

0.

035

101.

6

11.5

1.

103

0.20

3 0.

136

0.53

10.

32

0.02

1 0.

0085

0.

0079

11.9

1.

078

0.12

380.

2 0.

028

0.00

3

Cd

0.08

8

0.07

20.

072

0.00

7

0.75

0.78

40.

006

Lu0.

075

0.00

89

0.07

0

Tabl

e A

4-2

US

GS

Qua

lity

Con

trol

Sta

ndar

ds V

alue

s in

ppm

exc

ept

as n

oted

, (c

ontin

ued)

Hf

Ta

W

Tl

Hg

Pb

Bi

Th

UC

LB-1

(71

) 0.

445

0.10

6 0.

691

1.40

0.

580

Err

or

0055

0023

00

59

0

05

7

0.07

4C

LB-1

(23

3)

08

3

0.15

4 5.

25

0,09

1.

39

0.53

CLB

-1 (

248)

0.

163

Rec

omm

ende

d/In

form

atio

n 0.

2 5

1.4

0.55

E

rror

(R

ecom

men

ded

and

info

rmat

ion)

1632

-C(7

1)

Err

or

1632

-C (

233)

1632

-C (

248)

Cer

tifie

d/R

efer

ence

/Info

rmat

iona

l Er

ror (

Cer

tifie

d an

d R

efer

ence

val

ues)

1633

-B (

233)

16

33-B

(24

8)

Cer

tifie

d/N

once

rtifi

ed

Err

or (

Cer

tifie

d va

lues

)

1632

-B (

233)

1632

-B (

248)

C

ertif

ied/

Non

cert

ified

E

rror

(C

ertif

ied

valu

es)

0.49

50

04

0

0.58

50.

1

0.12

3 0.

418

00

17

0

04

50.

38

0.09

40.

087

0.4

0.09

380.

0037

6.3

0.13

10.

135

5.9

0.14

10.

019

0.07

5

0.06

9

3.83

3.79

0.07

64.0

68.2 1.1

1.40 1 0

590.

12

1.42

0.1

1.40

0.03

1.1

25.8

25.7 1.3

0.52

00

0 -

0.52

0.51

30.

012

9.5

8.79

0.36

Key:

ND

=Not

Det

erm

ined

; IN

AA=i

nstru

men

tal n

eutro

n ac

tivat

ion

anal

yis.

Oth

er te

chni

ques

incl

ude:

indu

ctiv

ly c

oupl

ed p

lasm

a (IC

P) a

tom

ic e

mis

son

spec

trosc

opy

(AES

)-aci

d di

gest

; iC

P-AE

S si

nter

dig

est,

ICP-

mas

s sp

ectro

scop

y-ac

id d

iges

t; hy

drid

e ge

nera

tion

(HG

) at

omic

abs

orpt

ion

(AA)

; C

oid

vapo

r AA;

Ion

rhr

omot

ogra

phv.

43