Method

Free Cyanide by ASTM D 7237-10

Document #41550415

Flow Solution™ FS 3700 Automated Chemistry Analyzer

Free Cyanide by Gas Diffusion and Amperometric Detection
ASTM D 7237-10, Flow Injection Analysis
Cartridge Part Number 330356CT

Scope and Application

This method is used for determining the concentration of free cyanide in aqueous wastewater effluent by flow injection
analysis and amperometric detection according to ASTM D 7237-10.13 This method is used in the USEPA’s data
gathering and monitoring programs associated with the Clean Water Act and NPDES permit compliance reporting.
Free cyanide is defined as HCN, CN-, and cyanide bound in metal-cyanide complexes that are easily dissociable
into free CN- ions at the pH of the aquatic environment ranging from pH 6 to pH 8.
Method Performance
Range 2.0–500 μg/L
Rate 30 samples/hour
Precision 3% RSD
Method Detection Limit (MDL) 0.5 μg/L

The range may be extended to analyze other concentrations by changing the size of the sample loop.

Figure 1. General flow diagram for Free Cyanide by ASTM D 7237-10 (see Figure 2 for a detailed flow diagram).

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 Free Cyanide by ASTM D 7237-10

Reagents and Calibrants

Chemical Name CAS # Chemical Formula Part Number

Cadmium potassium cyanide 14402-75-6 K2Cd(CN)4
Potassium cyanide 151-50-8 KCN
Sodium acetate 127-09-3 C2H3O2Na
Sodium hydroxide 1310-73-2 NaOH A001103
Sodium phosphate, dibasic 7558-79-4 Na2HPO4
Sodium phosphate, monobasic 7558-80-7 NaH2PO4
Sulfuric acid, concentrated 7664-93-9 H2SO4
Water, deionized H 2O
Zinc Potassium Cyanide 14244-62-3 K2Zn(CN)4
Additionally, the following chemicals may be needed for sample preservation or treatment.
Acetic acid, glacial 64-19-7 C2H4O2
Acetone 67-64-1 C 3H 6O
Ascorbic acid 50-81-7 C6H8O6
5-[4-Dimethylaminobenzylidene]rhodanine 536-17-4 C12H12N2OS2
Ethylenediamine 107-15-3 C 2H 8N 2
Silver nitrate 7761-88-8 AgNO3
Sodium arsenite 7784-46-5 NaAsO

Summary of ASTM D 7237-10

Method

 Aquatic free cyanide by gas diffusion amperometry (ASTM D 7237-10) is based on the instrumentation and
technology detailed in ASTM D 6888, but employs milder conditions (pH 6-8 buffer versus HCl or H2SO4), and
does not use ligand displacement reagents.

 A sample is injected into a carrier stream and mixed with a phosphate buffer at pH 6 to measure free cyanide
(or pH 6 to 8 to measure aquatic free cyanide). Hydrogen cyanide gas (HCN) that is present diffuses across a
hydrophobic membrane into an alkaline acceptor solution, where it converts back to ionic cyanide (CN-). Cyanide
is then carried into an amperometric flow cell where cyanide ions react with a silver working electrode, silver/
silver chloride reference electrode, and platinum/stainless steel counter electrode at an applied potential of zero
volts. The current generated is proportional to the cyanide concentration of the measured sample. The detector
response is displayed as a peak. The resulting peak height is proportional to the cyanide concentration present
in the sample.

Interferences

 Method interferences can be caused by contaminants in the reagents, reagent water, and glassware, which may
bias the results. Take care to keep all such items free of contaminants.

 High levels of carbonate can release CO2 into the acceptor stream and cause an interference with the amperometric
detector that results in a slight masking effect (15% negative bias with 20 ppb cyanide in 1500 ppm carbonate).2

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 Sulfide above 50 mg/L will diffuse through the gas diffusion membrane and can be detected in the amperometric
flowcell. Oxidized products of sulfide can also rapidly convert CN- to SCN- at high pH.2

 Oxidizing agents such as chlorine decompose most cyanides. Remove oxidizing agents that decompose
cyanides by adding ascorbic acid if analysis is to be within 24 hours, otherwise use sodium arsenite. Sample
treatment is described in Sample Handling and Preservation.

 Tests conducted on samples containing large amounts of colloids indicate rapid cyanide losses. Filter turbid or
colloidal samples.

 Nitrate and nitrite do not interfere in this method.

 Thiocyanate, sulfite, and thiosulfate do not interfere with this method.

Safety

WARNING: Cyanide ion, hydrocyanic acid, all cyanide salts, and most metal-cyanide complexes are extremely
dangerous. As a contact poison, cyanide does not need to be ingested to produce toxicity. Also, cyanide
solutions produce fatally toxic hydrogen cyanide gas when acidified. For these reasons,
any method involving cyanide in a sample or reagent should only be performed by properly
trained personnel wearing adequate personal protective equipment.

1. The toxicity or carcinogenicity of each compound or reagent used in this method has not been fully established.
Each chemical should be treated as a potential health hazard. Exposure to these chemicals should be reduced
to the lowest possible level.

2. For reference purposes, a file of Safety Data Sheets (SDS) for each chemical used in this method should be
available to all personnel involved in this chemical analysis. The preparation of a formal safety plan is also
advisable.

3. Chemicals used in this method may be highly toxic or hazardous and should be handled with extreme caution
at all times. Consult the appropriate SDS before handling.

4. Unknown samples may be potentially hazardous and should be handled with extreme caution at all times.

5. Proper personal protective equipment (PPE) should be used when handling or working in the presence of
chemicals.

6. This method does not address all safety issues associated with its use. The laboratory is responsible for
maintaining a safe work environment and a current awareness file of OSHA regulations regarding the safe
handling of the chemicals specified in this method.

Sample Handling and Preservation

1. Collect samples in amber glass bottles with minimal headspace that have been thoroughly cleaned and rinsed
with reagent water.

2. Ensure the volume of sample collected is sufficient to obtain a representative sample, analyze replicates, and
minimize waste disposal. 40 mL amber VOA vials are sufficient.

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3. Add NaOH solution to pH 11 and cool samples to 2-6 °C.

4. Do not add NaOH if the cyanide concentration would change as a result of the addition.

5. Treat samples containing sulfide ion.

a. Test samples with lead acetate test paper to determine the presence or absence of sulfide ions. Note
that the lead acetate test paper can be unreliable and is typically not usable for sulfide concentrations
below approximately 50 ppm.
i. If sulfide is detected by the lead acetate test strip (sulfide > 50 ppm), dilute sample so that sulfide
is below the amount detected by test strips. Record dilution factor on chain of custody/
sample bottle.
ii. Lead acetate test paper should be tested for minimum level of sulfide detection by spiking reagent
water aliquots with decreasing levels of sulfide. The spiked samples are tested with lead acetate
test paper moistened with acetate buffer. Test each new batch of test paper or acetate buffer
to determine the lowest level of sulfide ion detection prior to use.
iii. Sulfide is removed by treating the sample with small increments of powdered lead carbonate or
with dropwise addition of lead acetate solution. Black lead sulfide precipitates in samples
containing sulfide. Repeat operation until no more lead sulfate forms. Immediately
(within 15 minutes) filter with coarse filter paper (5 μm). Stabilize by adding 1 mL of
1M NaOH per liter of sample. pH must be > 10. Samples that are known or suspected
to contain sulfides should be analyzed as soon as possible to avoid cyanide degradation.
b. If the sample contains particulate matter that would be removed with filtration, filter the sample.
Particulate matter need not be analyzed.

6. Treat samples containing or suspected to contain formaldehyde, acetaldehyde, or other water-soluble

aldehydes with 20 mL of 3.5% ethylenediamine solution per liter of sample.

NOTE: Samples that have been disinfected by UV irradiation are likely to contain aldehydes.

7. Oxidizing agents such as chlorine can destroy most of the cyanide during storage and manipulation. Destroy
the oxidizing agent at the time of sample collection so the test result reflects an accurate cyanide concentration
in the source at the time of collection. Treat samples containing chlorine, hypochlorite, or sulfite with 0.6 g
sodium arsenite per 100 mL sample. Sodium thiosulfate may be used in place of sodium arsenite.

a. Using a plastic pipette, place a drop of sample on a strip of potassium iodide-starch test paper.
b. If observing a bluish discoloration on the paper, add a few crystals of sodium arsenite to the sample
with a spatula. Continue to add crystals and testing a drop of sample on the test paper until color is no
longer produced on the test paper.

NOTE: Do not add an excess of reducing agent.

8. High concentrations of carbonate can result in a negative response in the amperometric detector when carbon
dioxide diffuses across the membrane into the alkaline acceptor reagent, reducing its pH. The high
buffer capacity of the acceptor reagent largely eliminates sensitivity to carbonate. Nevertheless, Standard
Methods recommend using hydrated lime to stabilize samples such as effluents from coal gasification wastes,
atmospheric emission scrub waters, and other high carbonate-containing wastes.

a. Slowly add hydrated lime while stirring to raise the pH of the sample to 12.0–12.5.
b. Decant the sample after the precipitate settles.

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Configuration and Start-Up

Refer to the Flow Solution™ 3700 Operator Manual and/or the FlowView Quick Start Reference Guide
for assistance configuring the FS 3700 and FlowView.2,9

1. Build Method - Set Up the Method

a. Verify that the cartridge is configured as illustrated in the cartridge schematic shown in Figure 2.
b. Connect the appropriate pump tubes to the cartridge and to their appropriate reagent containers
according to the flow diagram.
c. Create and Save Method in FlowView, as follows:
i. In the Build Method screen, press the Add button. Type the desired name in the data entry
field near the top of the screen.
ii. Use the following tables to specify method parameters on the Method Settings, Signals/Peak
Marking, and Calibration Table screens.
iii. Press the Save button.

Method Settings on next page.

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Method Settings
Analysis Settings Mode FIA
Load Time 35 seconds

Cycle Duration 120 seconds

Heater Setpoint (°C) Not Used

Sample Pump Run Speed 40%

Detector Settings Mode Amperometric

Polarity Normal

Detector Applied Potential 0.0V

Gain 1x-4x typical

Signals/Peak Marking
Peak Measurement Measure Peaks by Height
Baseline Value for Peak-marking Sync Peak Start as Baseline (default)
Apply Carryover Correction to all No
Samples
Minimum Peak Height 400
Minimum Peak Width 60

Sync Peak Marking Recognize Peak Start by a rise of 100 counts

...total counts within 5 seconds
Sync Peak Ignore Time 50 seconds
Use Return to Baseline ✓
Return-to-Baseline % 99%
Use D1V ✓
Minimum Return-to-Baseline 90
Cutoff Counter Value for End of Peak 4

Smoothing Savitzky-Golay 7 points

Calibration Table (suggested)

Enable Target Concentration (μg/L)
✓ STD1 0
✓ STD2 2
✓ STD3 5
✓ STD4 10

✓ STD5 20
✓ STD6 50
✓ STD7 100
✓ STD8 200
✓ STD9 500
Calibration Curve Fitting Method 2nd Order
Calibrant Units ppb

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2. Configure Analyzer - Load Method into Configuration

a. Set pump speed for each chassis.

b. Set detector performance parameters (gain, lamp intensity, applied potential).

3. Instrument Stabilization

a. Start the pump, allowing the solution to flow through the entire system.
b. Make sure that the flow cell of each detector is purged of all bubbles and the flow is stable and free from surging.
c. For trace level analysis, OI Analytical recommends calibrating from 2.00-100 μg/L.

4. Amperometric Cell Conditioning

Perform the following after servicing the amperometric cell, or as needed.

a. Load a 5 mg/L cyanide standard into the autosampler and inject it into the system.
b. Continue to inject 5 mg/L cyanide standard until three successive peak heights or area results are within 5%
RSD, indicating a stable electrode system.
c. Following stabilization, or to demonstrate stability of the electrode system, inject the 0.5 mg/L cyanide calibrant
until three successive peak heights or area results are within 3% RSD.

5. Start the Run

a. Select Sample Table and specify Result File and Operator ID prior to starting the run. For help on creating
a Sample Table, refer to the FlowView Software Quick Start Guide.12
b. Press Start to begin to collecting baseline data. Verify that the baseline does not drift and is free from large
fluctuations. When ready, click Run.

NOTE: Very sharp fluctuations in the baseline and/or consistent drifting are typically signs of bubbles in the flowcell.
The flowcell must be free of bubbles prior to beginning analysis.

6. Operating Notes

a. Sensitivity and performance at the low end may be enhanced by:

i. Increasing the size of the sample loop.
ii. Decreasing the range of calibrants to closer fit the concentration of the samples being run.
b. Performance may be enhanced and the range extended on the high end by:
i. Decreasing the size of the sample loop.
ii. Making the shortest possible connection between the cartridge and the detector.
iii. Increasing the cycle duration time in “Cartridge configuration”.
iv. Moving the calibrant range up so that the calibrants are closer to the concentration of the actual samples.

7. After the Run

a. Disconnect the lead from the working electrode.

b. Place acid reagent pump tubes into reagent water and pump reagent water through the system for at least
10–15 minutes. Do not pump reagent water in place of base reagent.
c. Stop the pump, and wait for flow to stop.
d. Release tension on all pump tubes.
e. Store the Gel Polymer Reference Electrode (PN 329513) in electrode storage solution when not in use with
Reference Electrode Storage Kit (PN 326133).
f. Power off the system.

NOTE: For short-term and overnight shutdowns, simply turn off the pump and release tension on the pump tubes.

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References
1. Wilmont, J.C.; Solujic, L.; Milosavljevic, E. B.; Hendrix, J.L.; Rader, W.S. Formation of Thiocyanate During
Removal of Sulfide as Lead Sulfide Prior to Cyanide Determination. Analyst 1996, 121, 799–801.

2. ASTM D7237-10 Free Cyanide with Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and
Amperometric Detection, ASTM International, West Conshohocken, PA, www.astm.org.

3. Flow Solution™ 3700 Operator’s Manual (part number 329998). Available from OI Analytical, P.O. Box 9010,
College Station, TX, 77842–9010.

4. Milosavljevic, E.B.; Solujic, L. How to Analyze for Cyanide. Cyanide: Social Industrial and Economic Aspects. The
Minerals, Metals, and Materials Society. 2001, 125–128.

5. Ingersol, D.; Harris, W.R.; Bomberger, D.C.; Coulson, D.M. Development and Evaluation Procedures for the
Analysis of Simple Cyanides, Total Cyanides, and Thiocyanate in Water and Waste Water: 1983; EPA-600/4-83-
054; U.S. Environmental Protection Agency, Environmental Monitoring Systems Laboratory, U.S. Government
Printing Office: Washington, DC, 1983.

6. Milosavljevic, E.B.; Solujic, L.; Hendrix, J.L. Environ. Sci. Technol. 1995, 29 (No. 2), 426–430.

7. Federal Register, CFR Title 40, Part 136, Appendix B, U.S. Government Printing Office: Washington, DC, 1994.

8. Guide to Method Flexibility and Approval of EPA Water Methods. Available from the National Technical
Information Service (PB97-117766).

9. Handbook for Analytical Quality Control in Water and Wastewater Laboratories: 1979; EPA-600/4-79-019; U.S.
Environmental Protection Agency, Environmental Monitoring Systems Laboratory, U.S. Government Printing
Office: Washington, DC, 1979.

10. Less is Better: Laboratory Chemical Management for Waste Reduction. Available from the American Chemical
Society, Department of Government Regulations and Science Policy, 1155 16th Street, NW, Washington, DC
20036.

11. ASTM D 7365-09a Standard Practice for Sampling, Preservation and Mitigating Interferences in Water Samples
for Analysis of Cyanide.

12. Flow Solution™ 3700 ACA Flow Analyzer Software Quick Start Guide (part number 327069). Available from OI
Analytical, P.O. Box 9010, College Station, TX, 77842–9010.

13. ASTM D 7237-10 Free Cyanide with Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and
Amperometric Detection.

14. Solujic, Ljiljana and Milosavljevic, Emil, “Flow Injection Based Method for Determination of Aquatic Free
Cyanide,” prepared for Newmont Mining Corporation, Charles Bucknam, 10101 East Dry Creek Road,
Englewood, CO 80513, July 18, 2003.

15. Reference Material Sm-990-011 is available from High Purity Standards, Charleston, SC.

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 Free Cyanide
Valve Detector
B
Figures
A001309
B D
1
A 2 1 D 2
8
329513

Part Number 327070

3 S 10 S
3 7
4 9 A B
B

Flow Solution™ 3700 Method

5
C 6
10-port valve configuration
10-port tubing kit (330121)
X8 4 6
Cyanide Waste
X 5
7 E To waste line
C assembly
(A001415)
8-port valve configuration
8-port tubing kit (330398) 330001

329040
330252 (Membrane 5 pk: A001520)
Valve B

Sample Pull

Carrier
Valve C

330356TK
Base
E
Buffer

Valve D
To Acid Waste
330251 329498 A001488 330022
Figure 2. Diagram of 330356CT (Free Cyanide cartridge) and 330355 (Free Cyanide channel)

NOTES:
Pump speed: 40%
Sample Loop: 200 μL
Bypass Loop: 200 μL
A Autosampler transfer line
Free Cyanide by ASTM D 7237-10

9
 Free Cyanide by ASTM D 7237-10
Figure 3. Free Cyanide Calibration Series

Figure 4. Calibration curve and statistics

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Figure 5. Method MDL, Accuracy & Precision

2 ppb 5 ppb 50 ppb
Replicate 1 2.0825 5.5382 54.4865
Replicate 2 2.0776 5.6372 54.8737
Replicate 3 2.0803 5.6558 55.2183
Replicate 4 2.1415 5.6658 55.3389
Replicate 5 2.0309 5.6868 55.3552
Replicate 6 2.0473 5.6799 55.1593
Replicate 7 2.0039 5.6952 55.0648
Replicate 8 2.0121 5.6811 55.5072
Replicate 9 2.0333 5.6554 55.3583
Replicate 10 2.0015 5.648 54.9034
Mean 2.051 5.6543 55.1266
Standard Deviation 0.044299 0.044783 0.304170
%RSD 2.16% 0.79% 0.55%
%Accuracy 102.6% 113.1% 110.3%
MDL 0.125 ppb — —

Method performance was obtained by repetitive analyses of (undistilled) standard

solutions, and represent results operating under optimal conditions. A higher MDL may
result using distilled samples.

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Appendix A - Prep Guide

Reagent Preparation

WARNING: Do not add surfactants to reagents as their presence could severely hinder or impede proper
diffusion of cyanide through the gas diffusion membrane.

NOTE: For best results, filter and degas all reagents prior to use.

Reagent Water
1. Prepare degassed and deionized reagent water using one of the following methods.
2. Place distilled/deionized water under a strong vacuum for 15–20 minutes. Magnetic stirring or sonication aids
in the degassing process.
3. Purge distilled/deionized water with nitrogen gas (or other inert gas) through a glass frit for approximately
5 minutes.
4. Boil distilled/deionized water in an Erlenmeyer flask for 15–20 minutes. Remove the flask from the heat source,
cover it with an inverted beaker, and allow it to cool to room temperature. After preparing degassed reagent
water, store it in a tightly-sealed container to protect it from reabsorbing atmospheric gases. For best results,
store degassed reagent water under a slight vacuum when not used.

Stock Solution – Base Reagent, 10 M sodium hydroxide

1. While stirring, carefully add 400 g of sodium hydroxide in 700 mL of reagent water in a 1 L volumetric flask.
2. Cool to room temperature.
3. Dilute to volume with reagent water and mix well.
4. Store in an amber bottle at room temperature.

NOTE: CO2 from atmosphere absorbs into NaOH solution. Do not shake or mix stock reagent prior to pipeting.
Always pipet from top.

Stock Solution – Buffer Solution A, 2 M Sodium phosphate monobasic

1. Weigh 276 g sodium phosphate monobasic monohydrate (NaH2PO4) in a 1 L volumetric flask.
2. Dissolve and dilute to volume with reagent water.

Stock Solution – Buffer Solution B, 2 M Sodium phosphate dibasic

1. Weigh 284 g sodium phosphate dibasic, anhydrous (Na2HPO4) in a 1 L volumetric flask.
2. Dissolve and dilute to volume with reagent water.
3. If necessary, warm to 40 °C on a hot plate to aid in dissolving the sodium phosphate dibasic into water. Cool
before use.

Sodium Hydroxide, 1 M
1. While stirring, carefully add 40 g of sodium hydroxide in 700 mL of reagent water in a 1 L volumetric flask.
2. Cool to room temperature.
3. Dilute to volume with reagent water and mix well.
4. Store in an amber bottle at room temperature.

Stock Solution – 1 M Phosphate Buffer Solution, pH 6

1. Add 219.25 mL buffer solution A and 30.75 mL of buffer solution B to a 500 mL volumetric flask.
2. Dilute to volume with reagent water.

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Sample Preservation Reagents

Acetate Buffer
1. Dissolve 146 g of sodium acetate in 400 mL of reagent water in a 1 L volumetric flask.
2. Add 480 g of glacial acetic acid.
3. Dilute to volume with reagent water and mix well.

Ethylenediamine Solution, 3.5% (v/v)

1. Add 3.5 mL of ethylenediamine to a 100 mL volumetric flask.
2. Dilute to volume with reagent water and mix well.
Ascorbic Acid—Crystals

Sodium Arsenite—Crystals

Flow Solutions

Carrier – Reagent Water

Phosphate Buffer – 0.2 M phosphate buffer pH 6.0

1. Add 200 mL of 1M phosphate buffer solution, pH 6 to a 1 L volumetric flask.
2. The pH should be pH 6.0 ± 0.1. Verify pH and adjust if necessary with dilute sodium hydroxide or sulfuric acid.

Base reagent, 0.1 M sodium hydroxide

1. Dilute 10 mL of 10 M NaOH stock solution to 1 L in a volumetric flask and mix well.
2. Dilute to volume with reagent water and mix well.
3. Store in an amber bottle at room temperature.

Calibrant Preparation

Stock Solutions

Standard Silver Nitrate Solution, 0.0192 N

1. Dissolve 3.27 g of silver nitrate in 700 mL of reagent water in a 1 L volumetric flask.
2. Dilute to volume with reagent water and mix well.
3. Store in an amber bottle at room temperature.

Rhodanine Solution, 0.2 mg/mL in Acetone

1. Dissolve 20 mg of 5-[4-(dimethylamino)benzylidene]rhodanine in 80 mL of acetone in a 100 mL volumetric flask.
2. Dilute to volume with acetone and mix well.

Potassium Cyanide Stock Solution, 1,000 mg/L

1. Dissolve 2 g of sodium hydroxide in 500 mL of reagent water in a 1 L volumetric flask.
2. Add 2.51 g of potassium cyanide.
3. Dilute to volume with reagent water and mix well.
4. Store in an amber bottle at 4 °C. If stored properly, this reagent is typically stable for two months.

NOTE: This stock solution can be purchased from OI Analytical or another reputable supplier.

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Standardized Potassium Cyanide Stock Solution

1. Add 0.5 mL of rhodanine solution to 25 mL of potassium cyanide stock solution.
2. Titrate with silver nitrate solution until the color changes from canary yellow to a salmon hue.
3. Based on the determined potassium cyanide concentration, dilute the potassium cyanide stock solution to
a final concentration of 1.00 g/L. If the concentration is not 1.00 g/L, correct the intermediate and working
calibration concentrations accordingly.
4. Store in an amber bottle at 4 °C. If stored properly, this reagent is typically stable for two months.

Cadmium (II) cyanide stock solution, 1,000 mg/L cyanide

1. Dissolve 0.567 g of cadmium potassium cyanide and 0.2 g sodium hydroxide in 25 mL of reagent water in a
100 mL volumetric flask.
2. Dilute to volume with reagent water and mix well.
3. Store in an amber bottle at 4 °C. If stored properly, this reagent is typically stable for two months.

Zinc(II) cyanide stock solution, 1,000 mg/L cyanide

1. Dissolve 0.477 g of zinc potassium cyanide and 0.2 g sodium hydroxide in 25 mL of reagent water in a
100 mL volumetric flask.
2. Dilute to volume with reagent water and mix well.
3. Store in an amber bottle at 4 °C. If stored properly, this reagent is typically stable for two months.

Intermediate Standard – 10 mg/L

1. Using a volumetric pipette, transfer 10 mL of standardized potassium cyanide stock standard to a 1 L
volumetric flask that contains 10 mL of 1 M sodium hydroxide and 40 mL of reagent water.
2. Dilute to volume with reagent water and mix well.
3. Store in an amber bottle at 4 °C. If stored properly, this reagent is typically stable for one month.

Calibration series
1. A calibration series may be prepared by using 100 mL volumetric flasks containing 1 mL of 1 M sodium
hydroxide using the table below.
2. Transfer the prescribed amount of 10 mg/L Intermediate Standard.
3. Dilute to volume with reagent water and mix well.
4. Store in an amber bottle at 4 °C.
5. Prepare fresh calibrants daily.

Final Concentration (ppb) 2 5 10 50 100 250 500

Volume of Intermediate 20 50 100 500 1000 2500 5000
Standard to Transfer (μL)

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Appendix B - Additional Data

Figure 6 summarizes data obtained from single laboratory testing of the method. Recoveries and reproducibility for
“free” forms of cyanide are shown, including the recovery and reproducibility of cadmium and zinc species.

Figure 6. Species-dependent Cyanide Recoveries Using Method ASTM D 7237-10

0.20 mg/L CN- 2.0 mg/L CN-
Species
Recovery (%) Precision (% RSD) Recovery (%) Precision (% RSD)
[Zn(CN)4] 2-
97.4 (0.7) 98.5 (0.7)
[Cd(CN)4] 2-
100.0 (0.8) 100.0 (0.2)
[Cu(CN)4] 2-
100.9 (1.3) 99.0 (0.6)

This method is based on Test Method D6888 and is expected to have similar performance.This method was
evaluated and validated in a single laboratory with synthetic samples, treated gold leaching effluent, and receiving
water samples.14 Portions of the data from this study are shown in Tables 6 and 7.

Precision and bias were determined as described in Standard Practice D 2777. The samples were evaluated
at pH 6 at room temperature with Standard Material 990-011, which is a synthetic precious metals processing
wastewater.15 The sample matrix is described in Table 8.

Figure 7. The Effect of the Reagent Stream pH on the species Dependent Cyanide Recoveries from Various
Metal-cyano Complexes at 0.250 ppm (μg/mL) CN- Level

pH6
Species CN found (ppm) % Recovery
[Zn(CN)4]2- 0.253 (0.54) 101.2
[Cd(CN)4] 2-
0.256 (1.2) 102.4
[Hg(CN)4] 2-
0.125 (2.0) 50.0
[Cu(CN)4] 3-
0.150 (1.2) 60.0
[Ag(CN)2] -
0.058 (1.0) 23.2

Figure 8. Spike Recoveries in a Precious Metals Leaching Process Sample (R: pH 6 Buffer); All Concentrations are
in ppm (μg/mL) CN-

CN- Found in the Spiked Sample

Spike Concentration Spiking Species Rep. 1 Rep. 2 Mean RPD(%) Spike Recovery (%)
0.050 CN -
NaCN 0.048 (0.44) 0.048 (0.32) 0.048 0.00 96.0
0.050 CN -
[Cu(CN)4] 3-
0.041 (0.15) 0.041 (1.6) 0.041 0.00 82.0
0.500 CN -
NaCN 0.498 (1.0) 0.499 (0.20) 0.4985 0.20 99.7
0.500 CN- [Zn(CN)4]2- 0.500 (2.9) 0.479 (2.3) 0.4895 4.29 97.9
0.500 CN -
[Cu(CN)4] 3-
0.313 (0.96) 0.309 (0.64) 0.311 1.29 62.2

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Figure 9. Cyanide recoveries from various aqueous matrices

Analyte Concentration, mg/L

Al 0.2
Ca 250
Mg 1
Mn 0.05
Mo 0.2
K 15
Se 0.04
Zn 0.1
NH3 as N 25
NO3 as N 25
F 0.2
SO4 475
Cl 250
SCN 15
OCN 25
SO4 475
Cl 250
SCN 15
OCN 25

Cyano-complexes of platinum and iron were added to the POTW and petroleum refinery effluents, respectively.
Thiocyanate was added to the metals finishing effluent to demonstrate that the FI/LE system does not determine
these cyanide forms.

Flow Soution™ 3700 Method

Part Number 327070 16