ARSENIC DETERMINATION ON PROCESS
MATERIALS FROM ASARCO'S COPPER
SMELTER IN TACOMA, WASHINGTON
Prepared for
U.S. Environmental Protection Agency
Emission Measurement Branch
Research Triangle Park, North Carolina 27711
Contract No. 68-02-2812
Work Assignment No. 66
August 1980
Prepared by
D. Ringwald
TRW
ENVIRONMENTAL ENGINEERING DIVISION
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CONTENTS
SECTION PAGE
1 Introduction 1
2 Summary of Results 1
3 Analysis Procedure 1
4 Quality Assurance 4
5 Calculations 8
6 Appendix 9
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TABLES
NUMBER PAGE
1 Arsenic Composition of Process Samples 2
2 Arsenic Composition of Secondary Standards 4
3 Percent Recovery of 1.00 mg Arsenic Spike 5
4 Results of Determination of 1.02% Arsenic 7
Secondary Standard Under Various Conditions
11
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I. INTRODUCTION
This work assignment consists of determination of the percent arsenic
in thirty-nine process samples from various stages of the smelting operation
at the Asarco.copper smelter in Tacoma, Washington. Three secondary standard
arsenic samples were supplied by Asarco to aid in investigation of matrix
effects and accuracy of the analytical method.
II. SUMMARY OF RESULTS
The results of the analysis of the process samples is summarized in
Table I. It includes a sample description, date of collection, results
of the duplicate determinations and the average arsenic composition in
percent.
III. ANALYSIS PROCEDURE
Sample dissolution was accomplished by weighing an appropriate
amount (0.5 gms to 0.05 gms) to the nearest 0.1 milligram into the teflon
cup of an acid digestion bomb. Two milliliters each of nitric acid (HNO-)
and hydrofluoric acid (HF) were added to the digestion cup and it was
immediately sealed in stainless steel bombs. The samples were then heated
in an oven to 105°C for two hours.
When cool the dissolved samples were filtered through Whatman #4 filter
paper that was pre-extracted with 0.5N HNO- into 50 ml polypropylene
volumetric flasks. The flasks were brought to volume with 0.5N HNO.,
washing of the filter.
The prepared samples were screened using an Instrumentation Laboratory
Model 551 Atomic Absorption Spectrophotometer with a nitrous oxide/acetylene
flame and 2.0 nm bandpass. Deuterium arc background correction was used at
all times. Appropriate dilutions were made to high arsenic samples.
Arsenic determinations were made using the method of standard additions
to eliminate chemical interferences and with one percent potassium chloride
to inhibit ionization of the arsenic in the flame. A three point least
squares best fit calculation was applied to the data obtained by the
standard additions and the arsenic concentration was caluculated using
the applicable dilution factors and original sample weight.
1
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TABLE I.
ARSENIC COMPOSITION OF PROCESS SAMPLES
SAMPLE DESCRIPTION
Arsenic Baghouse Dust
#1 Roaster Baghouse Dust
#1 Plate Treater
San Luis Arsenic
Godfrey Charge
Godfrey Charge
Godfrey Calcine
Godfrey Calcine
Pot #1 FCE
Pot #1 Dump
Pot #2 FCE
Pot ..#2 Dump
Pot #3 FCE
Pot #3 Dump
Pot #3 Top
Pot #3 Bottom
Pot #4 FCE
Pot #4 Dump
Reverb Matte
Reverb Matte
Reverb Matte
Reverb Slag
Reverb Slag
Reverb Slag
Roaster Charge
Roaster Charge
Roaster Charge
Roaster Charge
Roaster Charge
DATE COLLECTED
9/13-9/24
9/13-9/24
9/13-9/24
9/24-9/25
9/24
9/25
9/24
9/25
9/19
9/19
9/20
9/21
9/21
9/22
9/22
9/22
9/22
9/23
9/19
9/20
9/21
9/19
9/20
9/21
9/15
9/16
9/18
9/19
9/20
1
76.8%
2.94%
30.6%
72.2%
5.35%
5,. 73%
2.63%
6.01%
0.45%
0.61%
0.59%
0.82%
0.66%
0.30%
0.44%
0. 78%
0.54%
0.64%
0.38%
0.40%
0.40%
0.68%
0.56%
0.58%
0.92%
1.37%
1.17%
1.28%
1.25%
72.7%
3.55%
37.3%
74.9%
6.02%
5.56%
3.31%
6.03%
0.75%
0.61%
0.72%
0.73%
0.68%
0.48%
0.57%
0.59%
0.72%
0.71%
0.34%
0.45%
0.41%
0.77%
0.60%
0.51%
0.99%
1.46%
1.05%
1.21%
1.30%
AVG.
74.8%
3.25%
34.0%
73.6%
5.69%
5.65%
2.97%
6.02%
0.60%
0.61%
0.66%
0.78%
0.67%
0.39%
0.51%
0.69%
0.63%
0.68%
0.36%
0.43%
0.41%
0.73%
0.58%
0.55%
0.96%
1.42%
1.11%
1.25%
1.28%
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TABLE 1. CONTINUED
SAMPLE DESCRIPTION DATE COLLECTED
Roaster Charge
Roaster Charge
Roaster Calcine
Roaster Calcine
Roaster Calcine
Roaster Calcine
Roaster Calcine
Roaster Calcine
Roaster Calcine
Converter Slag
Converter Slag
Converter Slag
9/21
9/22
9/15
9/16
9/18
9/19
9/20
9/21
9/22
9/19
9/20
9/21
1.44%
1.02%
1.43%
1.26%
1.31%
1.05%
1.33%
1.05%
1.12%
0.32%
0.35%
0.39%
1.21%
0.93%
1.14%
1.42%
1.48%
1.18%
1.17%
1.49%
1.01%
0.32%
0.25%
0.36%
1.33%
0.98%
1.29%
1.34%
1.40%
1.12%
1.25%
1.27%
1.07%
0.32%
0.30%
0.38%
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IV. QUALITY ASSURANCE
In order to evaluate the accuracy and precision of the analytical
method employed, the arsenic composition of the three secondary
standard process materials supplied by ASARCO' s chemical laboratory
in Tacoma were determined in triplicate using the method described
above. Despite the difference in analytical methods (ASARCO uses
a volumetric determination with potassium bromate), the results,
summarized in Table 2, are within two standard deviations of ASARCO's
results. The standard deviations also show good precision is achieved
by this method, even in the reverberatory slag, the most complicated
of the matrices.
TABLE 2
ARSENIC COMPOSITION OF SECONDARY STANDARDS
SECONDARD
STANDARD
REVERBERATORY
SLAG
BLISTER
COPPER
ANODE
COPPER
ASARCO
% As
1.02
0.30
0.10
TRW
% As
0,91
0.34
0.12
STANDARD
DEVIATION
0.04
0.05
< 0.01
A wide range of matrices are encountered in materials from
various stages of the smelting process. To evaluate the applicability
of the analytical method to the variety of process samples to be
analyzed, the five major sample types were spiked with 1.00 mg of
arsenic before dissolution and the percent recovery of the spike was
calculated. The recovery data, summarized in Table 3, shows that an
average recovery of 96% was obtained.
4
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TABLE 3
PERCENT RECOVERY OF 1.00 mg ARSENIC SPIKE
Sample
Reverb slag (9/19)
Roaster Charge (9/15)
Converter Slag (9/21)
Acid Blank (7/29)
Pot #1 FCE (9/19)
Godfrey Charge
(9/24)
1
98%
95%
93%
93%
85%
93%
2
104%
93%
3
100%
107%
Avg.
96%
98%
Std.
Deviation
10%
8%
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To ascertain the influences of several important analytical variables
such as method of digestion, flame conditions, and potential chemical and
spectral interferences, the reverberatory slag secondary standard was analyzed
under a variety of conditions.
One potential source of loss of arsenic is as the As?3 which is a
volatile compound. An alternate digestion precedure was carried out in
which the secondary standard slag was first subjected to two milliliters
each of HN03 and HCL04, sealed in the acid digestion bombs and heated.
This initial oxidation step was intended to convert all the arsenic to the
As(V) oxidation state. Two milliliters of HF were added to the cooled
digest and the bombs re-sealed and heated.
The HN03/HF digested samples and the HN03/HCL04)/HF digested samples
were analyzed using both air/acetylene and nitrous oxide/acetylene flames
and using 2.0 nm, 1.0 nm and 0.5 nm spectral band passes. The method of
standard additions was used with all sample solutions to minimize chemical
interference. Sample size, and standard spikes were carefully chosen to
keep the arsenic levels within the linear absorbance range of arsenic (up
to about 0.250 absorbance units). The results of the determination under
these varying conditions are summarized in Table 4.
The Air/acetylene flame produced several problems including decreased
energy throughout to the detector and an increase in noise levels. It
also gave high results in arsenic levels independent of digestion technique
and bandpass used. These high results suggest some background interference
which is uncorrected by the deuterium arc background system.
The Nitrous oxide/acetylene flame gave low results in arsenic levels.
This suppression of arsenic absorbance was later found to be inhibited by
making analyte solutions up in one percent potassium chloride. This suggests
that in the much hotter nitrous oxide/acetylene flame the arsenic undergoes
considerable ionization thus decreasing the absorbing population in the
flame. This condition was relieved by the addition of a large amount of
the much more easily ionizable potassium.
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Table 4
Results of Determination of 1.02% Arsenic
Secondary Standard Under Various Conditions
Digestion
Technique
HN03/HF
avg.
HNO,/HC104/
(HF
avg.
Nitrous Oxide/ Acetylene
Spectral Bandpass
2. Onm
0.80
0.80
0.78
0.73
0.78
0.69
0.77
0.80
0.94
0.80
1 .Onm
0.52
0.58
0.61
0.57
0.57
O.Snm
0.60
0.53
0.54
0.55
0.56
0.80
0.77
0.85
0.97
0.85
Air/ Acetylene
Spectral Bandpass
2. Onm
1.40
1.32
1.31
1.40
1.36
1.37
1.25
1.31
1.21
1.29
0 .5nm
0.97
1.29
1.30
1.20
1.19
1.50
1.36
1.40
1.50
1.44
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V. CALCULATIONS
The thirty-nine process samples were run in duplicate and the
resulting arsenic percentages and the average of the duplicate samples
are reported in Table 3.
In calculating the percent recovery of the 1.00 mg arsenic spike
the percent arsenic in an unspiked sample was calculated by solving the
equation of the least squares best fit for the X-intercept, which
corresponds to the concentration of. the arsenic in solution in ug/ml.
%AS= (ug/ml) (50ml) (A) (B) fEouation n
• ..™—, _ _—. .A. JLUVJ i-CjCnjciCXOri j.j
UOOO ug/Mg) (nig of sample) ^
A = dilution factor used in making up standard addition solutions
B = intermediate dilution factor necessary to reduce original
solution to 20-40 ug/ml
The spike recovery calculation is completed by obtaining the
concentration of arsenic in the spiked sample and applying Equation 2.
(total mg As) - (mg As From Sample) , nn
mg As of Spike
(ug/ml) (50 ml) (A) (B) - (% As) (mg of sample) (Equation 2.)
(1000 ug/Mg) 100 J
1.00 mg
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