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Parameter

top line. For other Orion ISE meters, see meter instruction manual.

Cyanide

Sample Type

Electrode Setup See the electrode manual for preparation of the electrode.

Wastewater

Introduction The ion-selective electrode method is an EPA-approved test procedure. The total cyanide in wastewater is determined by direct measurement with the Orion 9606BNWP Sure-Flow® Combination Cyanide Electrode on the Orion Star meter. The method has no turbidity or color interferences. Pre-distillation

References

Electrode Performance Check Check slope daily according to the electrode manual. Drift may be checked by comparing a 1 minute to a 2 minute reading of 0.25mg/L std. Results should agree with desired criteria. If there is slope or drift problem, polish the electrode as it described in troubleshooting section of manual and equilibrate for 30 min. in 1mg/L CN std before use.

of the sample is required for EPA reporting purposes. Refer to Part 4500-CN - C in Standard Methods or ASTM D2036 Test Method A (Section 16.1) for sample distillation procedures.

Electrode Storage, Soaking, and Rinsing See electrode manual for storage 1) between measurements, 2) overnight, and 3) for long periods of time. Between measurements, rinse the electrode with DI water.

1. 4500-CN - C, F. Standard Methods for the Examination of

Water and Wastewater, 20 th Edition, 1998. APHA, AWWA,

Water and Wastewater, 20 t h Edition, 1998. APHA, AWWA,
& WEF, Washington, D.C. www.standardmethods.org

& WEF, Washington, D.C. www.standardmethods.org

2.

D 2036-98,(A),16.4. Annual Book of ASTM Standards,

Section 11, Water and Environmental Technology, Volume 11.01, 2005. ASTM International, West Conshohocken, PA.

Section 11, Water and Environmental Technology, Volume 11.01, 2005. ASTM International, West Conshohocken, PA.

www.astm.org

www.astm.org
Result Statistics

Result Statistics

Sample Preservation If sample can be analyzed within 48 hours and sulfide is not present, adjust pH to >12 with NaOH and refrigerate at less than or equal to 6 deg C. To extend the holding time to 14 days, treat samples to mitigate interferences, adjust pH to >12 with NaOH, and refrigerate at less than or equal to 6 deg C. Refer to references and/or EPA 40 CFR Part 136.3 for details.

with NaOH, and refrigerate at less than or equal to 6 deg C. Refer to references
with NaOH, and refrigerate at less than or equal to 6 deg C. Refer to references
with NaOH, and refrigerate at less than or equal to 6 deg C. Refer to references
with NaOH, and refrigerate at less than or equal to 6 deg C. Refer to references
with NaOH, and refrigerate at less than or equal to 6 deg C. Refer to references

# Trials

Average

%CV

%Recovery

Sample Preparation

Calibration

Analysis

4

0.301 mg/L*

4.2%

120.4%

Distill sample. Concentrated samples (>25ppm) should be

*Note: Cyanide was not detected in wastewater sample; standard was spiked into the distilled sample at 0.25mg/L and the above results were obtained.

diluted before measurement. For precise measurements, allow all the standards and the samples to reach the same temperature before analysis. Measure 30 mL of distilled

Recommended Equipment 5 Star-Benchtop pH/ISE/Cond/DO Meter (Orion 1119000) or other Orion ISE meter; Sure-Flow® Combination Cyanide Electrode (Orion 9606BNWP); benchtop stirrer (Orion 096019). Optional: printer (Orion 1010006); Star Navigator Software (Orion 1010007).

Required Solutions 1000mg/L Cyanide Stock Standard; Cyanide calibration standards (0.025, 0.125, 0.25, and 2.5mg/L); ISA (Orion 951011); Optimum Results B fill solution (Orion 900062); 0.01 N Silver Nitrate; Deionized water.

sample in 0.04N NaOH into a 50-mL beaker. Add 0.18 mL of ISA to adjust sodium hydroxide concentration in sample to 0.1N. A larger sample size can be used if desired as long as ISA is added in a 100:1 ratio or to 0.1N final NaOH concentration.

Perform four point calibration using 0.025, 0.125, 0.25, and 2.5mg/L cyanide standards. After calibration, the electrode slope will be displayed and should be above 54mV/decade. Analyze a mid-range standard to verify the calibration.

Place electrode and stirrer in the prepared sample. Press

Solutions Preparation (See on page 2)

STIRRER key to turn on stirrer. The “ISE:mg/L” icon will flash

Meter Setup Connect the electrode and stirrer to the meter. Set measurement mode to ISE. In Setup mode, set resolution to 3, units to mg/L, range to high, read type to continuous. If all steps were followed correctly, the meter display will show three digits in the top line and "ISE: mg/L” to the right of the

until the reading is stable. Press the MEASURE key to print and log the result. Press STIRRER key to turn off stirrer. Alternately, set read type to “auto” for automatic print and data log.

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Quality Control (QC). Recommended QC procedures include: calibration and calibration verification, initial demonstration of laboratory capability and method detection limit determination, laboratory control samples (LCS), method blanks, matrix spikes (MS), sample duplicates, and independent reference materials. See references for details.

Solutions Preparation 1000 mg/L (ppm) cyanide stock standard: dissolve 2.50 g potassium cyanide and 10 mL ISA with DI water in 1L volumetric flask. Standardize weekly (see note below). 2.5mg/L CN: dilute a calculated volume of stock solution, based on the determined concentration, and 1 mL ISA to 100 mL with DI water. Prepare daily. 0.25mg/L: dilute 10mL 2.5mg/L std and 1mL ISA with DI water in 100-mL volumetric flask. Prepare daily. 0.125mg/L: dilute 5mL 2.5mg/L std and 1mL ISA with DI water in 100-mL volumetric flask. Prepare daily. 0.025mg/L: dilute 1mL 2.5mg/L std and 1mL ISA with DI water in 100-mL volumetric flask. Prepare daily.

Note: Standardize cyanide stock solution: Titrate 1 mL of cyanide stock solution (diluted to about 50 mL in a 100-mL beaker) with 0.01N silver nitrate using Orion 9616 silver/sulfide electrode (or indicator solution per SM 4500-CN - D.4) to determine the endpoint.

Waste Water*

ppm (mg/L)

Cyanide

Sample 1

0.309

Sample 2

0.290

Sample 3

0.315

Sample 4

0.291

Mean

0.301

Standard Deviation

0.013

%CV

4.2%

Average spike

 

recovery, %

120.4%

*Note: Results are from a spike of 0.25mg/L Cyanide Standard in waste water samples as no cyanide was found in the waste water alone.

Typical CN Electrode Calibration Curve

-250 -200 -150 -100 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0 0.5 1.0 Electrode potential
-250
-200
-150
-100
-3.0
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
Electrode potential (mV)

Log concentration (mg/L)