APPLICATION REPORT

DMA-80 evo | COAL

DETERMINATION OF TOTAL
MERCURY IN COAL SAMPLES

Determination of Total Mercury in Coal Utilizing Direct Combustion for Mercury

Analysis for coal and fly ash samples
| INTRODUCTION
A 2005 EPA study showed that coal-fired Absorption (CVAA) and ICP-MS both
power plants emit approximately 50 tons of require sample preparation prior to analysis.
mercury every year. This mercury is This results in both techniques being costly,
ultimately redistributed and accumulates in labor-intensive and subsequently, having a
lakes and rivers where it is converted, by long turnaround time.
anaerobic organisms, to methylmercury – Direct mercury analysis, as described in
its most toxic form. EPA Method 7473 and ASTM Method
This prompted the EPA, in March 2005, 6722-01, is a cost-effective, proven
to initiate the Clean Air Interstate Rule alternative to these labor-intensive, wet
(CAIR) and the Clean Air Mercury Rule chemistry techniques.
(CAMR) with the goal of reducing mercury Direct analysis affords the laboratory many
emissions from coal-fired utilities by almost benefits including:
70% by 2018. • Reduced Sample Turnaround
These initiatives have driven many facilities (6 Minutes)
to investigate ways in which to test their • No Sample Preparation
mercury emissions. • Reduced Hazardous Waste Generation
Several methods exist for the determination • Reduction of Analytical Errors
of mercury in coal. Traditional analytical • General Cost Savings (70% versus
methods such as Cold Vapor Atomic CVAA)
 APPLICATION REPORT
DMA-80 evo | COAL

| EXPERIMENTAL stages are implemented to first dry and then

INSTRUMENT thermally decompose a sample introduced
The DMA-80 evo from Milestone, as into a quartz tube. A continuous flow of
referenced in EPA Method 7473, was used oxygen carries the decomposition products
in this study. through a hot catalyst bed where halogens,
nitrogen, and sulfuric oxides are trapped. All
mercury species are reduced to Hg(0) and
are then carried along with reaction gases
to a gold amalgamator where the mercury
is selectively trapped. All non-mercury
vapors and decomposition products are
Figure 1 Milestone's DMA-80 evo Direct Mercury flushed from the system by the continuous
Analyzer
flow of gas. The amalgamator is
The DMA-80 evo features a circular, subsequently heated and releases all
stainless steel, interchangeable 40-position trapped mercury to the double beam, fixed
autosampler for virtually limitless throughput wavelength atomic absorption
and can accommodate both nickel (500 spectrophotometer. Absorbance is
mg) and quartz boats (1500 µL) depending measured at 253.7 nm as a function of
on the requirements of the application. It mercury content.
operates from a single phase 110/220V,
50/60 Hz power supply and requires regular
grade oxygen as a carrier gas. As the
process does not require the conversion of
mercury to mercuric ions, both solid and
liquid matrices can be analyzed without the
need for acid digestion or other sample
preparation. The fact that zero sample
preparation is required also eliminates all
hazardous waste generation. Figure 2 An Internal Schematic of Milestone’s
DMA-80 evo.
All results, instrument parameters including
furnace temperatures, are controlled and EXPERIMENTAL DISCUSSION
saved with easy export capabilities to Excel For this study, a power-generating
or LIMS. company provided eight unknown coal
samples. Prior to analysis, all samples were
PRINCIPLE OF OPERATION ground to a 60-mesh particle size. Sample
Direct mercury analysis incorporates the weights ranged from 0.09 g - 0.26 g and
following operating sequence: Thermal were placed inside the nickel sample boats
Decomposition, Catalytic Conversion, (500 mg) for analysis on the DMA-80. In
Amalgamation, and Atomic Absorption addition, NIST 1633b Coal Fly Ash and
Spectrophotometry. Controlled heating SARM 20 Coal, in weights ranging from

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 APPLICATION REPORT
DMA-80 evo | COAL

0.059 g – 0.075 g, were analyzed Parameter Setting

periodically throughout the sequence to
Drying Temp/Time 90 seconds to 200 °C
evaluate the instrument’s performance on
120 seconds to 750
standard reference materials (SRM’s). Decomposition Ramp
°C
Decomposition Hold 90 seconds at 750 °C
CALIBRATION
Calibration standards were prepared using Catalyst Temp 565 °C
a NIST traceable stock solution of 1000 Purge Time 60 seconds
ppm Hg preserved in 5 % HNO3. Working Amalgamation Time 12 seconds at 900 °C
standards of 100 ppb and 1 ppm were
Recording Time 30 seconds
prepared and preserved in 0.37% HCl and
stored in amber glass vials. By injecting Oxygen Flow 120 mL/min
increasing sample volumes of standard into Table 1 Analysis Operating Parameters
the quartz sample boats calibration graphs
of 0 – 1500 ng of mercury were created RESULTS
using aqueous standards. The results of the SRM’s are shown in
Table 2. All results were within 10% of the
certified value. Table 3 shows all data for
the unknown coal analyses.
Concentration Certified
Sample
(ppm) (ppm)
SARM 20 0.249 0.25
SARM 20 0.260 0.25
SARM 20 0.250 0.25
Figure 3 0 ng – 20 ng Calibration Graph for ultra-
low level SARM 20 0.228 0.25
SARM 20 0.258 0.25

Table 2 Summary of results of QA/QC analysis

(SARM 20 Coal)

Concentratio Certified
Sample
n(ppm) (ppm)
NIST 1633b 0.142 0.14±0.02
NIST 1633b 0.142 0.14±0.02
Figure 4 20 ng – 1000 ng Calibration Graph for low
to mid-level analysis (ppb, ppm) NIST1633b 0.139 0.14±0.02
NIST 1633b 0.135 0.14±0.02
| OPERATING CONDITIONS
The DMA-80 evo’s operating conditions for NIST 1633b 0.140 0.14±0.02
all analyses are shown in Table 1. Table 3 Summary of results of QA/QC analysis (Coal
Fly Ash)

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 APPLICATION REPORT
DMA-80 evo | COAL

A B C D E FURTHER READING
To learn more about mercury and other
0.160 0.153 0.040 0.11 0.094 related topics, feel free to visit these
0.135 0.144 0.043 0.102 0.109 websites.
EPA Method 7473
0.155 0.144 0.039 0.096 0.090 http://www.epa.gov/waste/hazard/testmet
0.143 0.153 0.036 0.092 0.094 hods/sw846/pdfs/7473.pdf

Table 4 Data from unknown coal analysis. All results ASTM Method D6722-01
are noted in ppm http://www.astm.org/Standards/D6722.ht
m
Sampl Mean concentration
SD
e (ppm) EPA Mercury
A 0.148 0.009
http://www.epa.gov/mercury/
B 0.148 0.005 Methylmercury
C 0.039 0.003 http://en.wikipedia.org/wiki/Methylmercury
D 0.100 0.008
Mercury in Fish
E 0.097 0.008
http://www.epa.gov/waterscience/fish/advi
ce/mercupd.pdf
Table 5 Summary of results of unknown coal
analysis
Mercury in Coal
| CONCLUSION http://energy.er.usgs.gov/health_environm
The results of the SRM’s shown in Table 2 ent/mercury/
indicate that direct mercury analysis is an
Mercury Analysis
effective technique for the determination of
http://www.milestonesci.com
mercury in coal and similar products.
Table 3 shows that the reproducibility of
the technique is comparable to wet
chemistry techniques, keeping in mind | ABOUT MILESTONE
that coal samples are notorious for not At Milestone we help chemists by providing the
being homogeneous in their chemical most innovative technology for metals analysis,
composition. The DMA-80 evo does not direct mercury analysis and the application of
require any sample preparation which microwave technology to extraction, ashing and
results in lower detection level capabilities synthesis. Since 1988 Milestone has helped
chemists in their work to enhance food,
when compared to traditional techniques.
pharmaceutical and consumer product safety,
and to improve our world by controlling pollutants
in the environment.

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