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DMA-80
Direct Mercury Analyzer
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Introduction
Mercury in the atmosphere can
be from manmade sources
(coal-fired power plants,
municipal incinerators,
industrial boilers) or from
natural sources (forest fires,
geologic formations,volcanoes)
Precipitation is the primary
mechanism for transporting
airborne gaseous or particulatemercury from the atmosphere
to surface water and land
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Mercury Analysis
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Aqueous samples
and extractsASV7472
Solid or semi-solid
wasteCV-AAS7471A
Liquid wasteCV-AAS7470A
Sample typeTechniqueMethod
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CV-AAS
Cold Vapor-Atomic Absorption Spectroscopy
Samples are digested or dissolved
Mercury is reduced to free atomic state by using tin
(II) chloride or sodium boro-hydride in a closed
reaction vessel Mercury is measured by atomic absorption
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CV-AAS
Few minutesAASAnalysis
Mercury reduction
1 hour
Interference removal
Wet chemistry
20 minutes- 1 hourClosed vessel
microwave
2 hours- 2 daysHot plate
Sample acid digestion
TimeDescriptionStep
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CV-AAS and ASV
Both methods require sample digestion and
further wet chemistry Sample digestion can be problematic because
of Hg volatility
Sample preparation is the bottleneck for higheranalytical productivity
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DMA-80
Direct Mercury Analyzer
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DMA-80 Advantages
Direct Hg determination at trace level on solid
and liquid samples No sample digestion step
No wet chemistry pre-treatment step
Fast, approximately 6 minutes per sample
Eliminates waste disposal
Validated results (US EPA method 7473) forsolid and liquid matrices
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DMA-80
Principle of operation
Solid or liquid samples are weighed and introduced in
the DMA-80 The sample is initially dried and then thermally
decomposed in a oxygen flow
Combustion products are carried off and further
decomposed in a hot catalyst bed
Mercury vapors are trapped on a gold amalgamator and
subsequently desorbed for quantitation
The mercury content is determined using atomicabsorption spectrophotometry at 254 nm
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DMA-80
Major components
Sample dosing system Thermal process furnaces
Atomic absorption spectrophotometer
System controller
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Sample Dosing System
Built-in 40 position auto-sampler for high
throughput unattended operation, for solid andliquid samples
Maximum sample weight 500 mg
Maximum sample volume 500 l
Possibility of multiple sample dosing for Hg pre-
concentration on amalgamator
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Sample Introduction
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Fully Loaded Autosampler
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Pipetting Liquid Samples
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Thermal process
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Thermal Process
12 s0-30 s900C850-950CAmalgam
600C550-650CCatalysis
180 s0-420 s
850C800-1.000CDecomposition
60 s0-300 s300C20-300CDrying
Typical timeTime rangeTypical
temperature
Temperature
rangeStep
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Oxygen
Research grade
(O2 > 99,95%)Purity
200 ml/minuteFlow rate
4 bar (60 psig)Inlet pressure
Carrier and decomposition
gasFunction
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Atomic Absorption
Spectrophotometer
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AAS Technical Data
Si-photodiode sensorDetector
254 nm, 9 nm bandwidthInterference filter
253,65 nmWavelength
Low pressure mercury lampLight source
Single beam spectrophotometer
with sequential flow through of
measurement cells
Instrument optics
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Typical Absorbance Profile
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DMA-80
Performance Specifications
(1)Sample weight 100 mg(2)Automatic switching when absorbance 0,8
0,20,02Detection limit
(1st) 0,2-350
(2nd) 350-6.000
(1st) 0,02-35
(2nd) 35-600Working range(2)
Hg concentration(1)
(g/kg)Total Hg (ng)Data
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DMA-80
Performance Specifications
6 minutesTypical analysis time
< 1,5%Typical reproducibility
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System controller
Lab TERMINAL
Touch-screen Pentium-based controller, 266 MHz, 64MB Ram, Windows 98, Color 12,1 TFT SVGA
monitor, CD-ROM, FD, Smart Card Reader, 2 COM,
1 USB, LAN ports
Standard bench-top computer with similar
specifications
Dedicated Terminal 1024
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EasyControl Software
Evolution of previous Windows based DMA-80
software Selectable calibration algorithm
Virtually unlimited memory for programs and
actual data storage Built-in service and diagnosis functions
CFR-21 part 11 compliant
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System Status
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1st
Cell Linear Calibration
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1st
Cell Square Calibration
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Measurement/Graphic
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Balance Setup
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History Trail CFR 21 Part 11
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Mercury Trap
Optional mercury trap tobe located at DMA-80
outlet
Activated charcoal Safe operation
Easy and ready to install
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DMA-80Analytical Performance
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Getting Started Oxygen cylinder with gas regulator stable at 4 bar (60
psig)
Power 115-230 V/50-60 Hz
Analytical balance with serial interface
Windows compatible printer
Standard reference materials
Aqueous standards
Precision pipettes
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DMA-80 Calibration
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DMA-80 Calibration Liquid standards
Different concentrations, same volume Same concentration, different volumes
Use fresh standards, stabilized with HNO3 orHCl/K2Cr2O7
Solid standards Certified mercury content
Vary by weight
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0 ng
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10 ng
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20 ng
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30 ng
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100 ng
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200 ng
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500 ng
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Calibration 1st
Cell
0,6%0,722330 ng
1,2%0,499620 ng
2,2%0,254910 ng
1,5%0,12725 ng
16,7%0,0012Blank
RSD (n=3)AbsorbanceSolution
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Calibration 2nd
Cell
0,9%0,7285500 ng
1,9%0,3117200 ng
2,2%0,1546100 ng
RSD (n=3)AbsorbanceSolution
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Calibration Curves
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DMA-80 Accuracy
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Certified Reference Materials
6.250 190NIST 2711 Soil
1.400 80NIST 2709 Soil
141 19NIST 1633b Fly Ash
93,8 3,7NIST 1630a Coal
34 4NIST 1573a Tomato Leaves
5,8 0,5NIST 1568a Rice Flour
Hg content (g/kg)Sample
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NIST 1568a Rice Flour
2,0
3,0
4,0
5,0
6,0
7,08,0
Hg(g/kg)
Certified DMA-80
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NIST 1573a Tomato Leaves
24,0
28,0
32,0
36,0
40,0
Hg(g/kg)
Certified DMA-80
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NIST 1630a Coal
80,0
85,0
90,0
95,0
100,0
Hg(g/kg)
Certified DMA-80
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NIST 1633b Fly Ash
100,0
120,0
140,0
160,0
180,0
Hg(g/kg)
Certified DMA-80
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NIST 2709 Soil
1,0
1,2
1,4
1,6
1,8
Hg(mg/kg
Certified DMA-80
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NIST 2711 Soil
5,8
6,0
6,2
6,4
6,6
Hg(
mg/kg)
Certified DMA-80
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DMA-80 Precision
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Fresh Salmon
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Collecting Sample
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Weighing
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Loading Autosampler
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Loading Furnace
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After Analysis
Fresh Salmon
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Fresh Salmon
56,20,29925
58,00,34044
57,80,23303
54,10,22962
55,40,28491
Hg (g/kg)Weight (g)Run
Fresh Salmon
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Fresh Salmon
5N
1,6Sd (g/kg)
56,3Average (g/kg)
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DMA-80 Detection Limit
Detection Limit
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Detection Limit
The detection limit is defined as the concentration which
will give an absorbance signal of two (sometimes three)
times the magnitude of the baseline noise. The baseline
noise may be statistically quantified typically by making
ten or more replicate measurements of the baseline
absorbance signal observed for an analytical blank, anddetermining the standard deviation of the
measurements. The detection limit is then defined as the
concentration which will produce an absorbance signal
twice (or three times) the standard deviation
Detection Limit
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Detection Limit
0,0006100,00075
0,000890,00084
0,001080,00063
0,000870,00102
0,001060,00071
AbsorbanceRunAbsorbanceRun
Detection Limit
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Detection Limit
0,02 ngDL
0,0004683*Sd
0,000156Sd
0,0008Average
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DMA-80 Memory Effect
DMA-80 Memory Effect
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DMA-80 Memory Effect
0,40,0097 (1st)Blank 2
1,50,0374 (1st)Blank 1
500 (set)0,7285 (2nd)Standard 500 ng
Mercury content (ng)AbsorbanceSample
DMA-80 Memory Effect
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DMA 80 Memory Effect
Quartz Boats
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Quartz Boats
Analysis of liquids with
DMA-80 autosampler
Improved performance
Lower memory effect
Better reproducibility
Longer life time
Quartz vs. Metal Boats
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Quartz vs. Metal Boats
0
0,1
0,2
0,3
0,4
1 2 3 4 5 6 7 8 9 10Run
Signal
Metal Quartz
Memory Effect
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Memory Effect
0,010,000,0000,1001
0,450,050,00110,1001
1.106,01110,600,14740,1001
Result
(g/kg)Hg (ng)HeightWeight (g)Sample ID
Reproducibility at Low
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Concentrations
AVG 8,55SD 0,09 g/kgRSD 1,01%Statistics
8,500,850,02170,100
8,490,850,02160,100
8,510,850,02170,100
8,530,850,02180,100
8,720,870,02220,100
Results (g/kg)Hg (ng)HeightWeight (g)
Reproducibility at High
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Concentrations
AVG 1.143,7RSD 0,69%SD 7,88 g/kgStatistics
1.143,4114,340,15230,100
1.158,7115,870,15430,100
1.141,3114,130,15200,100
1.136,2113,620,15140,100
1.138,8113,880,15170,100
Results (g/kg)Hg (ng)HeightWeight (g)
Lifetime
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US EPA method 7473 Mercury in solids and solutions by thermal
decomposition amalgamation and atomic absorption
spectrophotometry
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ComparisonDMA-80 vs. CV-AAS
Comparison
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DMA-80 vs. CV-AAS
YesMinimalWaste generation
Yes, to eliminate
interferencesNot requiredWet chemistry
ElevatedModerateRunning cost
Limited to low rangeUp to 600 ngWorking range
100 ml solutionUp to 500 mg sampleSample size
AqueousLiquid and solidsSample type
Acid digestionNot requiredSample preparation
CV-AASDMA-80Technique
Time Comparison
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DMA-80 vs. CV-AAS
0
60
120
180
240
DMA-80 CV-AAS
Tim
e(minutes
Sample preparation Analysis
DMA-80 Major Applications
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Biological Blood, urine, hair, tissue, plankton
Liquids Waste water, crude oil, heavy oil, detergents, paints
Solids Coal, fly ash, soil, sediment, sludge, minerals, food, feed, plastic,
wood, vegetables, leaves, waxes Medicinal
Pharmaceuticals, gelatin capsules, lipstick, lotions
DMA-80
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Direct Mercury Analyzer
Recommended