92

TRACE IMPURITIES IN COAL

E. N. Pollock
Introduction

A; trace i m p u r i t i e s in the environment become of increasing concern,

those rna:eriai5 that can have important impact on t h e environment a r e coming = > d e r c a r e f u l scrutiny.

f Coal, along with the other s o u r c e s o

T h e F e d e r a l Environmental

energy, is a m a t e r i a l of m a j o r i n t e r e s t .

Protectfor! Agency is developing a growing l i s t of environmental contarnL?zn:s that will have to be monitored i n t h e e n e r g y sources. These

include s l s r c u r y , b e r y l l i u m and a s b e s t o s presently, but other elements t h a t have a n d e s i r a b l e physiological effects on plant and animal life such a s cadmium, a r s e n i c , l e a d and fluorine will r e c e i v e i n c r e a s i n g attention.

The determination of potentially toxic elements in coal has received

l i t t l e effort'in the p a s t . In many c a s e s e a r l y information w a s unreliable because of poor methodology. Coal is a complex m a t e r i a l containing both

o r g a n i c and i i o r g a n i c p h a s e s and analyses in the p a s t have suffered from both l o s s e s and contaminations in dissolution. Beyond the elemental

analysis. :he determination of elemental form,whether inorganic or organicall>- bound,will condition t h e e n v i r o F e n t a l impact.
' .

T h e investigators

in the determination of m e r c u r y in coal have experienced a l l . t h e s e p r o b l e m s

in attemptizg t o follow the mass balance of m e r c u r y i n the combusfion of coal.'

T h i s paper i s s t i l l only concerned with elemental analyses. However,
, ' ,

methods .;:-ere investigated for most elements that could be potential environmental
'

po1luten;s.
Tvvo different general analytical techniques w e r e employed: m a s s

spectror-e:rj- and wet chemical methods.

Six e l e m e n t s w e r e determined by

. m a s s s p z t r o r n e t r y and seventeen elements w e r e determined by a v a r i e t y

of r e t c h e x i c a l methods.

93

T r a c e Elements b y Spark Source M a s s Spectrometry

T h e s p a r k s o u r c e m a s s s p e c t r o m e t r i c (SSMS) technique is one of t h e most sensitive instrumental methods f o r determining inorganic i m p u r i t i e s i n a variety of m a t e r i a l s ? Since the advent of e l e c t r i c a l detection. t h i s 2 A method h a s been method h a s become much m o r e rapid and reliable

developed f o r the determination of six elements of toxicological i n t e r e s t and correlation between these impurities i n the original coal and the coal ash, will be shown. Since no p r i m a r y standards a r e available at t h i s

t i m e for coal, all m a s s s p e c t r o m e t r i c data is compared to a t o m i c absorption spectrophotometry (AAS) values determined on t h e s a m e s a m p l e s . Relative standard deviations a r e on the o r d e r of 6 to 15% f o r t h e m a s s s p e c t r o m e t r i c data and 2 t o 3% f o r the atomic absorpticn values.

Experimental An AEI MS-7 s p a r k source m a s s s p e c t r o m e t e r equipped with e l e c t r i c a l detection w a s used in this study.

A description of this a p p a r a t u s complete

2

with manufacturers a c c e s s o r i e s and modifications has been d e s c r i b e d previously and will not be detailed h e r e

The instrument w a s used i n the The i n s t r u m e n t

peak- switching mode only to provide m o r e p r e c i s e analyses.

operating p a r a m e t e r s a r e given i n Table I. The integrated multiplier c u r r e n t

for each p r e s e t position on the peak switches (each position corresponding

t o a different isotope to be determined) w a s displayed on a digital voltmeter. T h e s e intensity values w e r e then used to calculate the actual concentration.

Standard and Sample P r e p a r a t i o n Since no p r i m a r y s t a n d a r d s were available at the t i m e of t h i s investigation, A A S mas used t o provide analyses on s e v e r a l different coals

s o that they could b e used as secondary standards.

Representative portions of

94

each sample and s t a n d a r d w e r e obtained by grinding and splitting.

The

s a m p l e s thus obtained (e100 mesh) w e r e then weighed into porcelain crucibles and placed into a vented cold furnace and t h e t e m p e r a t u r e i s elevated to 300 C in one-half hour.
0 0

The t e m p e r a t u r e w a s then r a i s e d t o The

550 C for one-half h o u r and then to 85OoC f o r a n additional hour.

crucibles w e r e then removed f r o m the furnace and the a s h d r y mixed with

a g l a s s s t i r r i n g rod.
0

T h e crucibles w e r e then r e t u r n e d to the furnace at

850 -C without venting until ashing was completed (usually one additional.
hour). Samples f o r SSMS w e r e reground with a boron carbide m o r t a r and The s a m p l e s with

pestle and diluted with two p a r t s of high purity graphite.

graphite were placed in polystyrene vials with two or t h r e e 1/8" d i a m e t e r polystyrene beads a n d mixed i n a spex m i l l f o r twenty minutes. Electrode's

w e r e prepared f r o m the powtlers using t h e AEI briquetting die and polyethylene. slugs. Once the e l e c t r o d e s had been prepared, they w e r e placed in the s o u r c e .. of t h e instrument using a standardized mounting procedure.
. .

Repetitive

exposures w e r e then r e c o r d e d f o r each element of i n t e r e s t in the standards and unknowns'. relationship: T h e concentrations w e r e calculated f r o m t h e following

m-he r e

C and C a r e the concentrations, the s u b s c r i p t s s and x

X

r e f e r to the standard and unknown, respectively:

I and I a r e the intensities (integrated multiplier currents).

X

R e s u l t s and Discussions One of the questions posed by the d r y ashing of coal is whether or not s o m e of the e l e m e n t s may b e l o s t through volitilization during t h e combustion p r o c e s s . ,A c o m p a r i s o n of wet ashing and d r y ashing of s o m e of the elements analyzed in t h i s study i s given i n Table 11. T h i s data i s based

95

solely on atomic absorption analyses.

As can b e s e e n f r o m the table, the

T h i s would
~

agreement between the two s e t s of data is generally v e r y good.

s e e m to indicate that none of t h e s e particular elements a r e l o s t during the d r y ashing of coal. This data does not, however, allow one to make t h i s

s a m e generalization f o r all elements since t h e s e are the only elements determined by both ashing techniques during t h i s investigation. Kometani,

et. al.

have indicated that the p r e s e n c e of sulfates prevents the loss of

m a n y elements during d r y ashing; and since coal contains appreciable amounts of sulfates, this may help to explain the agreement between the two methods

of ashing.

Vapor p r e s s u r e data a l s o imply. that these m e t a l s could possibly Since a s h contents of the coals studied

b e present a s oxides o r silicates.

varied f r o m 5 to 25% according t o the geographical location, the s t a n d a r d s

f o r the SSMS analysis w e r e chosen so a s to coincide with the approximate

a r e a from which the actual samples w e r e taken.

1 Table 1 1 i s a comparison

of the AAS and SSMS data obtained on ten different coal s a m p l e s f r o m t h r e e

or four different geographical a r e a s .

These values a r e based'upon the m e t a l

concentration in the whole coal w h e r e a s the analysis w a s performed on the ash. Again, t h e r e i s generally v e r y good agreement between the two different methods used. This data a l s o shows that hydrocarbon interference
A v e r y volatile element s u c h

is not a problem at t h e s e concentration levels.

as m e r c u r y could n o t be analyzed u s i n g t h i s method a s it h a s been postulated

that it i s pumped away during heating caused by the excitation process, depending upon the p a r a m e t e r s selected. The validity of SSMS with electrical detection h a s proven to b e an acceptable method of analysis. Another important aspect of this study w a s the time involved p e r sample. Sample

and standard preparation (including ashing), electrode preparation, instrument preparation (setting peaks). running of ten s a m p l e s and four standards, data reduction and conversion to concentration in the whole coal required only fifteen hours. T h i s r e p r e s e n t s 84 separate analyses. T h i s fifteen

96

hours a l s o includes sample turn-around t i m e and five s e p a r a t e 0.3nC monitor e x p o s u r e s f o r each element in each s a m p l e and standard.
p'"cision e SSMS iPchRic;Ue 6 t9 l!y& datz fsr t h is re?.-ti.-,p.

The

The detectien
This is not

l i m i t s fa- the e l e m e n t s studied a r e on the o r d e r of 1 to 2 ppmw in the \:.noie csal usir,g rne previously mentioned p a r a m e t e r s .

necessarily the l o w e r l i m i t s a s such i t e m s a s exposure (nC), multiplier gain and s a m p l e dilution may i n c r e a s e o r d e c r e a s e t h i s lwel. F r o m the

intensity values obtained during this investigation, absolute detection l i m i t s ranging between 0 . 1 and 0. 3 ppm b y weight with whole coal would b e a r e a l i s t i c estimate. T h e s e lower values w e r e not actually determined.

The a v e r a g e deviation f r o m t h e AAS r e s u l t s is 29.2%.

Trace Elements by Wet Chemical Methods

The determination of t r a c e impurities by wet chemical methods can immediately be s e p a r a t e d into two m a j o r divisions. First, those elements that can b e d r y ashed, leached in acid and the analysis completed by conventional AAS. These elements a r e Li, Be, V. C r , Mn, Ni, Cu. Zn,

Ag. Cd and Pb. Second, those that r e q u i r e specialized techniques.

1. 2.

H g - 0 2 bomb combustion followed by f l a m e l e s s AAS.

As, Bi and

3.

deteryLinationof their hydrides using AAS. 7 Se-combustion and cold trapping followed by determination a s i t s hydride using A.4S.

SS - d r y ashing and acid dissolution followed by 5. 6

4.

0 bomb combustion followed by specific ion analysis

2

5. B - d r y ashing followed by N a 2 C 0 3 fusion, dissolution in dilute

H2S04, then followed by colorimetric determination with 10 c a r m i n i c acid

97

Determination of Li, Be, V. C r , Mn. Ni; Co. Cu, Zn, Ag, Cd and P b Coal samples are p r e p a r e d and ashed a s described in the procedure employed f o r SShIS. F i v e g r a m samples of coal a r e u s e d . The ash is

placed in 100 m l reflon beakcr containing 5 m l of H F (conc.) and 15 ml of H N 0 3 (conc). IYarm to dissolve the ash, then evaporate the solution just to dryness. Add u-ater and a few d r o p s of HN03, then t r a n s f e r to a 100 m l AIake t o volume with water and mix. Immediately t r a n s f e r

volumetric flask.

to a plastic bottle to p r e s e r v e as a stock solution for t h e conventional AAS determinations of Li, Be, V, C r . Mn. Ni. Co, Cu. An, Ag, Cd and Pb. Samples w e r e a l s o prepared f o r conventional AAS determination by wet ashing approximately 5 . 0 g r a m s of coal in a mixture of HNO 3 H2S04 and (NH4)2 S208. The Determination of M e r c u r y

A coal sample is decomposed by burning a combustion bomb containing

a dilute nitric acid solution under 24 atmospheres of oxygen p r e s s u r e . After

combustion, the bomb washings a r e diluted to a known volume and m e r c u r y

is determined by atomic absorption spectrophotometry using a f l a m e l e s s

cold vapor technique.

ProcedureT r a n s f e r approximately 1 g r a m of 60 mesh X 0 coal to a clean combustion crucible and weigh to the nearest 0.1 milligram. T r a n s f e r 10 m l of 10%

n i t r i c acid to the bomb, place the crucible in the electrode support of the bomb, and attach the fuse F i r e . Assemble the bomb and add oxygen to a p r e s s u r e

of 24 atornospheres (gauge). P l a c e the bomb i n the calorimeter (a cold

water bath in, a l a r g e stainless s t e e l beaker i s a l s o satisfactory) and ignite t h e sample using appropriate safety precautions.ordinarily employed in bomb c a l o r i m e t r y work.

98

After combustion. the bomb should be left undistrubed f o r 10 minutes

to allow t e m p e r a t u r e equilibration and the absorption of soluble vapors.

Reknae thc prcssiirc s?ow!y and tisiisfei t h e coiltenis oi ihe bomb iarri crsiboiej

t o the m e r c u r y reduction v e s s e l by washing with 10% n i t r i c acid.

Rinse

t h e bomb, electrodes, and crucible thoroughly with s e v e r a l small washings of 10% n i t r i c acid, then dilute the contents of the reduction v e s s e l with 10% n i t r i c acid to a total volume of 50 ml. described under Standardization. Proceed with the determination a s

Determine the amount of m e r c u r y in

m i c r o g r a m s and divide by the s a m p l e weight in g r a m s to obtain the m e r c u r y

value i n p a r t s p e r million.

Standardization Add a n aliquot of a standard m e r c u r y solution to contain 0.1 m i c r o g r a m s of m e r c u r y to the m e r c u r y reduction flask. Add KMnO
4

(3%) dropwise until

the pink color p e r s i s t s . Adjust the volume to 100 ml, then add in o r d e r 5 ml

of HNO3 (1:2), H2S04 ( l j l ) and hydroxylamine hydrochloride.

When the pink

color fades, add 5 m l of the SnCl (10%) and immediately connect into t h e 2 system. Start the pump which circulates t h e m e r c u r y in the vapor phase
I

through the optical cell in the atomic absorption spectrophotometer with t h e m e r c u r y l a m p optimized a t 253.7 n m and normal operating conditions a s established b y the AA instrument manufacturer. Samples are r u n by taking

all or an aliquot f r o m the 0 bomb combustion stock solution. 2

.

l'he Uetermination of Arsenic, Antimony and Bismuth

As. Sb and B i can be determined by AAS after generation and evolution

of their hydrides.

The hydrides a r e formed by t h e reaction of nascent

hydrogen generated by magnesium inetal in a TiCl -HCl solutiqn. A 3 modified P e r k i n - E l m e r High Sensitivity Arsenic-Selenium Sampling System can b e u s e d with a n y atomic absorption spectrophotometer.

IJ

99

Coal s a m p l e s for the determination of A s , Sb and Bi c a n be ashed by the method previously described for Li, Be, etc. leached in H F and HCl.
3

However, t h e a s h should b e

C a r e must be taken in warming not to l o s e volatile

2

chlorides. If HNO, is used in place of HCl. a mixed K I and SnCl

must be

used in place of TiCl t o generate nascent hydrogen; however, the HC1 s y s t e m 3 is p r e f e r r e d .

A s e p a r a t e aliquot of I-ICl-HF s a m p l e containing up t o 0. 3 m i c r o g r a m s

of A s o r up to 0.6 m i c r o g r a m s of Sb o r E i is placed in the hydride generation

flask. Add 1 0 m l of TiC13 (1% in HC1) and adjust the volume t o 25 m l with water. After flushing the s y s t e m with a r g o n f o r fifteen seconds, add a one

inch length of 1/8 inch d i a m e t e r magnesium r o d . t o the flask through the pinch damp.
Allow one minute f o r collection time in the expansion v e s s e l .

Then

r e l e a s e g a s e s into the argon-hydrogen entrained air f l a m e using a t r i p l e slottype b u r n e r and the AAS manufacturers standard practices. appropriate standards a r e run f o r each of the elements. Blank and

The Determination of Selenium T h e p r i o r separation of selenium f r o m the bulk of the coal s a m p l e u s e s the combustion technique a s described by H. L. Rook i n a neutron activation analysis.
7

It w a s originally u s e d

The equipment w a s modified t o use a quartz

combustion tube 5 112 inches long connected by a ground g l a s s joint to a second section 3 112 inches long. The section ends with a U-tube which can

be i m m e r s e d in a Dewar F l a s k containing liquid N2 or s o m e other suitable

coolant.
t

F o r analyses, an 0 . 5 g r a m s a m p l e is weighed into a porcelain boat

2

and inserted into the combustion tube with an 0 flow of -30 cc/min.

With the

cold t r a p in place, the sample is ignited by heating the combustion tube with
a m e k e r burner.

The coal s a m p l e is allowed to burn freely, the t e m p e r a t u r e The combustion The

is then raised to the maximum of the b u r n e r f o r five minutes.

tube is cooled f o r five minutes and separated f r o m the condenser section, condenser i s removed f r o m the cold t r a p and allowed to w a r m t o ambient

100

temperature.

Add 10 m l of HC1 to the condenser and flush into a 50 ml Wash condenser with water and add rinsings to the volumetric Take a n aliquot of 15 ml o r l e s s

volumetric flask. flask.

Make t o volume with water and mix.

containing up to 0.3 m i c r o g r a m s of Se and proceed a s in the method f o r As. Sb, and Bi b y AAS a s previously described.

SELENIUM CONBUSTlOW APPARATUS

The Determination of Fluorine

A coai sample

IS

aecomposed by ignition in a combustion bomb containing

Na CO solution under 24 atmospheres of oxygen p r e s s u r e . After combustion, 3 3 the bomb washings a r e diluted to a known volume and an aliquot is taken to determine F by the standard Orion specific ion procedure.
1

T r a n s f e r approximately 1 g r a m of coal to a combustion crucible and weigh to n e a r e s t 1.0 mg. T r a n s f e r 5 m l of Na CO solution (5%) to the bomb, 2 3 place crucible in the electrode support and attach the fuse wire. Assemble the Place the bomb in a cold water

bomb and add oxygen to a p r e s s u r e of 24 atmos.

101

bath and ignite the sample using appropriate safety precautions. After combustion, t h e bomb should b e left undisturbed f o r t e n minutes to allow t e m p e r a t u r e equilibration and absorption of the soluble vapors. Release

the p r e s s u r e s l o v ~ l y and t r a n s f e r contents of the bomb (and crucible) into a 25 ml volumetric flask. Make s e v e r a l s m a l l washings with w a t e r and add Make to volume with water and r e s e r v e the

rinsings to the volumetric flask. stock solution in a plastic bottle.

Using an expanded scale pH meter, such as the Orion 801, pipet 1 0 ml of the stock solution into a s m a l l beaker and add 10 m l of T i s a b (Orion Cat. No. 94-09-09), determine the electrode potential using a fluoride electrode Orion 94-09. Comparison is m a d e by bracketing with fluoride standards

p r e p a r e d similarly.

T h e Determinaticn of Boron After d r y ashing in the manner used in the Li, Be, etc. procedure, the

ash is fused with Na C o g . leached in water and acidified with H SO The 2 2 4' 6 . colorimetric c a r m i n i c acid method is then used f o r the determination of boron.
Weigh approximately 1 g r a m of coal into a platinum crucible and carefully ignite in a vented oven. maintain for one hour. fuse f o r ten minutes. Gradually i n c r e a s e the temperature to 850 C and
0

Remove f r o m oven and add 2 g r a m s of Na CO and 2 3 Leach in 25 ml of w a r m water in a teflon beaker: When

volumetric flask.

dissolution is complete, add 10 m l of H SO carefully. T r a n s f e r to a 50 m l 2 4 Make to volume with water and r e s e r v e in a plastic bottle. P l a c e a 5 ml aliquot o r less in a 50 m l volumetric flask, make to 5 m l volume

with H SO ( 3 . 6IW if less than 5 m l aliquot was used. Aliquot should contain 2 4 0 t o 100 m i c r o g r a m s of B. Then add 20 m l of chilled H2S04 (18M) and s w i r l . Then add by pipet 20 m l of c a r m i n i c acid (0.92 g r a m s in H SO 18M). Make 2 4 to volume with H SO (18M) and determine absorbance in 1 c m cells in a 2 4 spectrophotometer a t 605 n m with a reagent blank in the r e f e r e n c e cell. Compare to a standard c u r v e containing 0 to 100 m i c r o g r a m s .

102

TABLE I Operating Parameters Spark Variac Pulse Repetition Rate (pps) Pulse Length (psec) Source Slit Multiplier Slit Moniter Expo sure Multiplier and Amplifier Gains Electrodes Vibrated
35%
100 100

0.002" ,002"

0.3nC Variable according to sample elements and concentratiorl

103

104

. .. . -

- . ..

. ..

105

REFERENCES

1.

A. J. Ahearn. Ed., T r a c e Analysis by M a s s Spectrometry, Academic (1972). C. A. Evans, Jr.. R . J. Guidoboni, and F. D. Leipziger. 85 (1970). Apply Spect.

2.

2 .

3.

T. Y . Kometani. et. al. Environmental Science Technology, 617 (1972).

4.

W. W. H a r r i s o n and D. L. Donohue. Twentieth Annual Conference on M a s s Spectrometry and Allied Topics, Dallas (1972).
E. N. Pollock and S. J. West, At. Abs. Newsletter, Vol. 11, No. 5. September - October, 1972. E. N. Pollock and S. J. West, At. Abs. Newsletter, 1973. H. L. Rook, Anal. Chem. Vol. 44, No. 7, June 1972, p. 1276. ASTM D808 Part 17. Orion Bulletin. No. 5 (1968).

5.

6. 7. 8. 9. 10.

E. N. Pollock and L . P. Zopatti. Talanta, Vol. 10, 118 (1963).