Electrode Log # Electrode Log # Electrode Log # Electrode Log # 33

Parameter
Cyanide

Sample Type
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
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.

References
1. 4500-CN
-
C, F. Standard Methods for the Examination of
Water and Wastewater, 20
th
Edition, 1998. APHA, AWWA,
& 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.
www.astm.org

Result Statistics
# Trials Average %CV %Recovery
4 0.301 mg/L* 4.2% 120.4%
*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.

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.

Solutions Preparation (See on page 2)

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



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

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

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.

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.

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.

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

Calibration
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.

Analysis
Place electrode and stirrer in the prepared sample. Press
STIRRER key to turn on stirrer. The ISE:mg/L icon will flash
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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Electrode Log # Electrode Log # Electrode Log # Electrode Log # 33
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
Log concentration (mg/L)
E
l
e
c
t
r
o
d
e

p
o
t
e
n
t
i
a
l

(
m
V
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