cyanide chemistry, methodology, interferences, … uv to liberate hcn from fe descriptive name...
TRANSCRIPT
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Cyanide Analysis: Cyanide Chemistry,
Methodology, Interferences,
Sample Handling and
Regulatory Updates
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Distribution of the Industrial Uses of CN
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Who is measuring cyanide?
•NPDES
• Pretreatment
• SDWA
• Industrial hygiene
• Foods
•Beverages
•Mining
•Manufacturing
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A generalized summary of cyanide and it’s metal
– cyanide species
• Transition metals - strong bonds
• Alkali metals - ionic bonds :C≡N
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Free Cyanide is the CN ion and HCN, generate
HCN at pH 6
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Metal Complexes require acid to generate HCN
Zn, Cd, Cu, Ni, Ag
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Strong Metal Complexes are stable in acid
solution
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Iron Cyanide Complexes are very stable in the
environment
[Fe(CN)6]-3 + H+
6 HCN + Fe+3
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Toxicity of Cyanide Complexes is related to its
ability to produce HCN
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Cyanide methods measure the various
cyanide “species”
Total
CN
Strong Metal Complexes
Fe, Co, Pt, Au
Available
CN
Weak to Moderately
Strong Metal Complexes
Ag, Cd, Cu, Hg, Ni, Zn
Free
CN
HCN
CN-
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Cyanide methods measure the various cyanide
“species”
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How Do You Measure Cyanide?
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Gas diffusion - Amperometry
HCN
CN-
Membrane
Sulfide > 50 ppm
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Titration by silver ion
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Ion Selective Electrode (ISE)
S-2
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Colorimetric methods
Turbidity
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Manual “distillation” is used to dissociate as
HCN
Macro Distillation MIDI
Distillations
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Distillation can be automated on a continuous
flow analyzer
Distillate
Distillation and
condenser
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Cyanide Methods
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Cyanide methods require separation
of CN from matrix
• Separated from interferences,
cyanide measurement is no different
than running standards.
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APPROVED METHODS
Free CN GD-
Amperometry
ASTM D7237
WAD CN Distillation/
Colorimetry
ASTM D2036 or
SM4500
CATC Distillation/
Colorimetry
ASTM D2036 or
SM4500
Available CN GD-
Amperometry
OIA 1677 or
ASTM D6888
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Unlike colorimetry, GD amperometry
is easy to visualize
• CN- + H+ HCN
• HCN + OH- CN- + H2O
• Ag + 2CN- Ag(CN)2
- + e-
measure
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Aquatic Free Cyanide Analysis
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ASTM D7237-06 can be run on a
OIA1677 CNSolution analyzer
Buffer
Same Cartridge as OIA 1677
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WAD Cyanide methods measure “available
cyanide”
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Available Cyanide Analysis
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WAD Cyanide methods measure “available
cyanide”
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Ligand Exchange methods measure
available cyanide
Method
Number Description Measurement
OIA 1677
Ligand
Exchange / Flow
Injection
Analysis
Gas Diffusion -
Amperometry
ASTM D 6888
Ligand
Exchange / Flow
Injection
Analysis
Gas Diffusion -
Amperometry
GD-amperometry methods do not
require distillation
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OIA 1677 or ASTM D6888 flow diagram
Acid Reagent
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Ligand Exchange GD-amperometry
methods have fewer interferences
CATC WAD OIA 1677
N-organics Excessive
Iron Cyanide None
SCN,NH3,NO2
Concentration
Dependent —
S2O3, H2O2 — —
Concentration
Dependent — —
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Ligand Exchange GD-amperometry
methods provide the best benefits
• No distillation (eliminates 1 – 4 hours
preliminary sample treatment)
• Low MDL (0.5 ppb)
• No Interferences
• High Throughput
(up to 90 samples per hour)
• Ease of Operation, very simple
chemistry.
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Total Cyanide Methods
Automated gas diffusion distillation and non-
distillation methods
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Total Cyanide Methods – Manual Distillation
Method Number Description Measurement
SM 4500-CN C Manual Macro Distillation –
Mg Cl2
Manual colorimetry /
ISE
ASTM D 2036 Manual Macro Distillation –
MgCl2
Manual colorimetry,
ISE, GD-amperometry,
IC
EPA 335.4 Midi Distillation – MgCl2 Automated
Colorimetry
ASTM D 7284 Midi / Micro Distillation –
MgCl2
Gas Diffusion -
Amperometry
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Automated total cyanide methods use UV to liberate HCN from Fe
Descriptive
Name
Method
Number Description Measurement
Total Cyanide
ASTM D4374
(Kelada 01)
High power UV-
Auto distillation
Alkaline pH
Automated
colorimetry
EPA 335.3
Low power UV-
Auto distillation
pH <2
Automated
Colorimetry
OIA
1678/ASTM
D7511
Low power UV-
pH <2
Gas Diffusion -
Amperometry
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Comparison of Kelada and OIA 1678
Kelada 01 ASTM D7511
Pump Tubes 15 5
Reagents Pyridine No Pyridine
Distillation Yes No
SCN
Interaction 0.25 – 0.5 % 0.01 – 0.03 %
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Comparison of Total CN methods
335.4 ASTM
D7284
ASTM
D7511
Sample
Preparation
2 – 3 hour
distillatio
n
1 – 3 hour
distillation
No
distillation
Analysis 1 – 2
minutes
1 – 2
minutes
1 – 2
minutes
Total Time 3 – 4
hours
2 – 4 hours 1 – 2
minutes
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Advantages - CNSolution 3100
Total Cyanide
Distillation/
Colorimetry EPA 335.4
Distillation / GD-
Amperometry ASTM D7284
No Distillation /
GD-
Amperometry
OIA 1678
(ASTM D7511-09)
One Instrument – multiple methods
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How do you solve interference problems caused
by distillation?
?
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Replace distillation with gas diffusion
HCN
CN-
Membrane
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Distillation most common technique
to remove interference
Macro Distillation MIDI
Distillations
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Many cyanide interferences result from
distillation
• Destroy CN • Create CN • UV distillation colorimetry - worst
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Distillation actually creates CN
interferences
• Boiling acid
• Automated UV-Distillation – Boiling acid
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Interferences –
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Thiosulfate reacts with cyanide
during distillation
• 0.200 mg/L CN- + 200 mg/L S2O3-2
– Cyanide Found = 0.160 mg/L
– Recovery = 80%*
– * Double Chloramine T added, or
recovery would be lower.
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These compounds are in almost every sample
and interfere significantly
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Thiocyanate + Nitrate results in
positive bias
• The addition of Sulfamic acid
does not sufficiently reduce this
interference.
– A real POTW sample with 0.1 mg/L SCN-
and 63.5 mg/L NO3- detected total CN- at
0.10 mg/L even after the addition of
Sulfamic Acid
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Interferences – Thiocyanate
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Interferences – Thiocyanate and Nitrate
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Sulfite reacts rapidly with CN in
basic solutions
• 0.200 mg/L CN- + 200 mg/L SO3-2
– Cyanide Found = 0.000 mg/L
– Recovery = 0%
• This reaction occurs in absorber solution, or in
preserved sample
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Interferences – Thiosulfate
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Interferences – Sulfite
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Interferences – Sulfur Compounds
• No Spot Tests
• Dechlorination
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Sulfur compounds react rapidly with
CN
• Elemental Sulfur – 8CN- + S8 SCN-
• Metal Sulfides – Cu2S, FeS, PbS, CuFeS2, CdS,
ZnS, etc.
– S reacts with CN- to form SCN-
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Holding Time Study – Sulfide Bearing Samples
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Cannot use Cadmium to Treat Sulfide
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Headspace to Treat Sulfide
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Bismuth to Treat Sulfide then distillation
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Oxidizers destroy cyanide before or
during distillation
• Hypochlorite
• Peroxide
• Caro’s Acid
• Chloramines
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Oxidizer Removal
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Ligand Exchange GD-amperometry
methods get better recovery
OIA 1677 CATC WAD
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Cyanide methods that utilize distillation
have significant disadvantages
• Time Consuming
– One hour long distillation (does not take
into account setup and teardown)
– CATC requires two, one hour
distillations
• Bulky and Relatively Expensive Glassware
• Operator-dependent results (technique)
• Multiple Interferences
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GD-amperometry provides the safest,
easiest, and most accurate technique
Acid Reagent
ASTM D7284-08 is a “green” chemistry
No pyridine
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CNSolution 3100
• Rapidly Analyze Cyanide with Confidence in Results
– Free Cyanide
– Available Cyanide
– Total Cyanide
• Eliminate Time Consuming, Error Causing Distillations
• Expand Capability to Colorimetric FIA and SFA
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Gas diffusion eliminates distillation
and associated cost
0
2000
4000
6000
8000
10000
12000
Dollars per
Year
Consumables + labor
per year
MicroDist
Midi Dist
CNSolution
Lowest cost
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Eliminating distillation increases
laboratory capacity
0
100
200
300
400
500
600
700
800Sa
mp
les
per
8 h
ou
r Sh
ift
Midi Dist
Micro Dist
CNSolution
Highest sample
capacity
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Ligand Exchange GD-amperometry
methods give you results in minutes
CATC WAD OIA 1677
Sample
Preparation
2
distillations
2 – 3 hours
1 distillation
2 – 3 hours
No
distillation
Analysis 1 – 2
minutes 1 – 2 minutes 1 – 2 minutes
Total Time 3 – 4 hours 3 – 4 hours 1 – 2 minutes
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Ligand Exchange GD-amperometry
methods means more samples
0
20
40
60
80
100
Sa
mp
les p
er h
ou
r
Distillation
Diffusion
90 samples per
hour
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The CNSolution is your solution to
cyanide analysis
• Gas diffusion amperometry methods: – Save time
– Save money
– Are more accurate
– Have fewer interferences
– Are “green”
• The CNSolution = the FS3100
– Change to a photometric detector and run any
colorimetric chemistry
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The CNSolution 3100 available cyanide
system
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The CNSolution 3100 total cyanide
system
UV irradiation
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OIA 1677 - CNSolution
Gas Diffusion and Mixing
Detector
Flow-cell
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Flow Solution 3100
• Flow Injection Analyzer
– Colorimetric detector added it becomes
the FS 3100 FIA analyzer
– All FS 3100 methods
• NO3-N
• NH3-N
• PO4
• TKN
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A high quality peristaltic pump
Separate module, individual channels, long
pump tube life.
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A random access xyz sampler
• Integrated
circulating wash
station
• 90 or 360 positions
• Separate standard
and QC vials
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Winflow software provide accurate
quantitation of CN results
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The CNSolution 3100 is accurate,
and cost effective
• Rapidly analyze cyanide
• Eliminate time consuming error
causing distillations
• Expand capability to colorimetric FIA
and SFA
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ASTM D7511 is easy to understand
and operate and does not distill.
“Green” Chemistry
No pyridine
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GD-Amperometry Equivalent to Colorimetry
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Estimated Reagent and Consumable Cost
per Analysis for Distillation (US Dollars)
0
1
2
3
4
5
6
7
8D
ollars
Midi-Dist MICRO DIST CNSolution
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Estimated Labor (in minutes) Required to
Distill 20 Samples for Analysis
0
50
100
150
200
250
Midi-dist MICRO DIST CNSolution
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Estimated Annual Labor Cost to Distill and Analyze
40 Samples per Month (Including Overhead)
$0.00
$1,000.00
$2,000.00
$3,000.00
$4,000.00
$5,000.00
$6,000.00
$7,000.00
Midi Dist MICRO DIST CNSolution
Assume tech pay at
$15/hour
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Estimated Annual Cost for Consumables to
Distill and Analyze 40 Samples per Month
$0.00
$500.00
$1,000.00
$1,500.00
$2,000.00
$2,500.00
$3,000.00
$3,500.00
$4,000.00
Midi Dist MICRO DIST CNSolution
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Estimated Annual Cost for Reagents to
Distill and Analyze 40 Samples per Month
$0.00
$500.00
$1,000.00
$1,500.00
$2,000.00
$2,500.00
Midi Dist MICRO DIST CNSolution
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Annual Cost for Distillation vs. Non-
Distillation Techniques
$0.00
$5,000.00
$10,000.00
$15,000.00
$20,000.00
$25,000.00
Mid
i D
ist
MIC
RO
DIS
T
CN
So
luti
on
40 /month
100 / month
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Comparison of Cost per Sample
by Cyanide Species and Method
$0.00
$5.00
$10.00
$15.00
$20.00
$25.00
$30.00
$35.00
Mid
i D
ist
MIC
RO
DIS
T
CN
So
luti
on
Available
Total
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Profit per Sample by Cyanide Species
at $40 per Test
$0.00
$5.00
$10.00
$15.00
$20.00
$25.00
$30.00
$35.00
$40.00
Mid
i D
ist
MIC
RO
DIS
T
CN
So
luti
on
Available
Total
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Profit per Month by Cyanide Species
at $40 per Test and 40 Samples per Month
$0.00
$200.00
$400.00
$600.00
$800.00
$1,000.00
$1,200.00
$1,400.00
$1,600.00
Mid
i D
ist
MIC
RO
DIS
T
CN
So
luti
on
Available
Total
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Profit per Shift by Cyanide Species at $40
per Test Based on Maximum Capacity
$0.00$2,000.00$4,000.00$6,000.00$8,000.00
$10,000.00$12,000.00$14,000.00$16,000.00$18,000.00$20,000.00
Mid
i D
ist
MIC
RO
DIS
T
CN
So
luti
on
Available
Total
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Estimated Profit by Number of Samples
Analyzed at Maximum Capacity
$0
$100,000
$200,000
$300,000
$400,000
$500,000
$600,000
$700,000
$800,000
40 100 200 400 800 1600
Samples per Month
Pro
fit
pe
r Y
ea
r
MICRO DIST
Midi Dist
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Thoughts Regarding “Break Even” Analysis
• Manual distillation and manual
spectrometer versus CNSolution
– Manual equipment costs 3 x less
– CNSolution profit 3 x higher per test
• Break Even = 1000 samples for both!
• That’s 20 samples per week regardless
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Benefits
Distillation / Colorimetry
GD-Amperometry
In summary, distillation/colorimetry should be replaced
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Thank You
Questions?
www.oico.com
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