Hach Company IntelliCAL™ Probes for Superior Measurement Performance for LDO® Dissolved OxygenDon F. Harrington, Robbin A. Crane, and Cary B. Jackson, Ph.D. • Hach Company • Loveland, Colorado
INTRODUCTION
Hach’s IntelliCAL LDO probes deliver a number of benefits, which help to en-
sure the highest degree of accuracy. Some of these product features include:
• Calibration Alerts
• Automatic Probe Recognition
• Automatic Prompts for Calibration Protocol
• Automatic Storage of Calibration History
• No Membranes
• No electrodes to polish or maintain
• No electrolyte solution to refill
• Easy Stable Calibration
• Superior Accuracy and Precision
• No Polarization
• Fast Measurement Readings
• No Chemical Interferences
• Compact and Field Portable
The United States Environmental Protection Agency (USEPA) has recom-
mended that each EPA Region grant interim approval of ASTM International
Standard D 888-05 Standard Test Methods for the Measurement of Dissolved
Oxygen in Water for measurement of DO in wastewater and in for use in mea-
suring DO in methods approved at Title 40 of the Code of Federal Regula-
tions Part 136.3 (40 CFR Part 136.3) for measuring Biological Oxygen De-
mand (BOD5). EPA has reviewed the method and supporting validation data
and determined that the method, includ-
ing Test Method C (Luminescence-Based
Sensor Procedure) meets all requirements
for approval in compliance monitoring. In
response, many EPA Regions and States
have begun to authorize use of LDO in DO
effluent monitoring as well as in BOD de-
terminations.
EPA RECOMMENDSLDO METHOD
COMPARATIVE PERFORMANCE
CONCLUSIONS:
Accuracy and Precision
Summary of Bias and Precision
Method Reference Water POTW Wastewater % Biasavg %Precisionavg % Biasavg %Precisionavg Winkler 2.5 5.0 5.0 4.4Membrane 2.5 3.8 3.3 2.9 LDO 0.0 2.5 0.0 2.5
Hach’s HQd Series of Meters and IntelliCAL Probes offer a superior solution for
measuring dissolved oxygen for water quality assessments, compliance moni-
toring, and for process control.
LDO® is first in accuracy
LDO® is first in precision
LDO® is the first choice in DO measurement
A summary of validation results, including data collected from 12 participating
wastewater facilities nationwide, from both influent to treatment and final ef-
fluent samples are shown below. Each of the facilities performed independent
accuracy and precision of DO, and BOD5 determinations. Measurements
were performed in parallel with Winkler, Membrane Electrode, and LDO meth-
ods. Below are charts demonstrating the comparative performance:
R es ults by M etho d C o mpa red to T heo retic a l D is s o lv ed O xygen
1.50
2.50
3.50
4.50
5.50
6.50
7.50
8.50
9.50
10.50
1.50 3.50 5.50 7.50 9.50
Theoretical DO (mg/L)
Met
ho
d D
O (
mg
/L)
Theoret ic al
Winkler
Membrane
Luminesc enc e
Linear ( Theoret ic al)
air - saturated w ater
BOD5 Demonstration
Quality Control Acceptance Criteria for LDOIPR Range IPR Conc. 97.5% Lower 97.5% Upper 96% Upper (mg/L) Limit of Limit of Limit of Recovery(%) Recovery(%) Precision (%)
Low 1.72 – 1.74 95.4 104 1.75 High 7.22 – 9.23 96.2 104 1.10
APPLICATIONS
Hach’s HQd Series of Meters and IntelliCAL Probes, along with LDO Technol-
ogy, offer the premier solution for your application needs, including:
• Process control
• Effluent discharge compliance monitoring
• Biological Oxygen Demand compliance reporting
• Biological nutrient removal
• TMDL development in receiving water
Dissolved oxygen (DO) concentration is one of the most important parameters
monitored in surface water and wastewater. When used to access water qual-
ity and derive the biological oxygen demand (BOD5), it becomes a regulatory
compliance and process control tool. Thus, accuracy and precision for the de-
termination of DO becomes critical for establishing and measuring water qual-
ity criteria in surface water and wastewater facilities, as well as for calculating
loading costs for industrial discharges to municipal wastewater treatment facili-
ties.
With the recent EPA recommendation for interim approval of ASTM D888-05:
Method C – Luminescence Based Procedure, there are now three compliance
methods for the measurement of DO. These are the Winkler Titration, Mem-
brane Electrode (e.g., Clark Cell), and luminescence dissolved oxygen (e.g.,
LDO®). The Winkler Titration was first proposed in 1888 and the Patent for the
Clark Cell was originally awarded in 1959. Hach launched its breakthrough
LDO technology (Patent # 6,912,050) in early 2003 and has been delighting
customers from various industries ever since.
Hach’s new HQd series of meters and IntelliCAL™ probes offer a number of
advantages for DO measurement over traditional compliance methods. Un-
like Winkler and membrane electrode methods, LDO is free of chemical inter-
ferences, maintenance free, and nearly unaffected by sample flow across the
luminescence sensor. LDO also offers superior accuracy and precision com-
pared to alternative methods.
Hach’s IntelliCAL probes offer additional benefits beyond the LDO technolo-
gy to further insure accuracy and to make the end users job easier. IntelliCAL
probes store the calibration history, allowing easy change-over of probes with-
out the need to recalibrate. Additionally, the IntelliCAL probes are automatically
recognized by the meter, prompting the user through the appropriate Calibra-
tion Protocol.
How Does LDO Work
LDO is a patented breakthrough technology that measures the quenching of
a particular luminescent dye embedded in a hard plastic, oxygen permeable
cap. The luminescent dye is excited by a flash of light from a blue LED. A de-
tector positioned close to the sensor measures the emitted red luminescence.
The higher the measured luminescence, the lower the oxygen concentration
and vice versa.