This presentation discusses continuous monitoring and why a new method is needed that measures total nitrogen (TN) as a single result. High temperature catalytic oxidation (HTCO) is also presented as an method for monitoring TN. For more information, go to ssi.shimadzu.com or follow Shiamdzu on Twitter @shimadzussi. Thanks for viewing.

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Continuous Total Nitrogen
Measurement in Aqueous Samples
William Lipps
Analytical & Measuring Instrument Division
Shimadzu Scientific Instruments, Columbia, MD.

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Why Continuous Monitoring?
Laboratory sampling
is only a “snapshot”
of the sample on a
good day.

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Sampling at the “Pipe” Does Not Sample
Storm Water or Irrigation Water

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Sources of Nutrient Pollution Outside
“The Pipe”

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Rarely Do We Sample When Rivers are
Flooding
Just one more bottle

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So Why Monitor for Nutrients?

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Algae: It Might be Good for Alcohol,
But No Fun For Skiing

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TN is Bad - What is it and How Can We
Measure it Continuously?

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The Current EPA Definition for Total
Nitrogen Cannot be Readily Automated
Measure
TKN
Measure
NO3/
NO2-N
TN

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EPA Defined TN Requires 2 Methods
and One is TKN
TKN includes:
l Organic Nitrogen
l Ammonia Nitrogen (NH3-N)
TKN does not include:
l Nitrate Nitrogen (NO3-N)
l Nitrite Nitrogen (NO2-N)

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A New Method is Needed That Measures
Total Nitrogen as a Single Result
Organic
Nitrogen!
NH3-N! NOx-N! TN!
This method can be automated and measured online

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Any New “Method” for Continuous
Online Monitoring of TN Should:
• Obtain equivalent results to TKN and other TN methods
• Be “rugged”
• Use few reagents
• Have a large dynamic range
• Sample/handle a complex matrix
• Calibrate with multiple points
• Require periodic check samples compared to lab

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High Temperature Catalytic Oxidation is a
Simple Method Requiring Few Reagents
Oxidation
• 2(NH2)2CO +5O2 + catalyst à 4NO + 4H2O + 2CO2
Formation of NO2*
• NO + O3à NO2* + O2
• NO + O3à NO2 + O2
Measurement
• NO2* à NO2 + hv

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HTCO Methods Obtain Near Equal
Results with TKN on QC Samples

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HTCO Methods Obtain Near Equal
Results with TN on Unknown Samples
0
20
40
60
80
100
120
Sample
1
Sample
2
Sample
3
Sample
4
Sample
5
%Recovery
TN TNb

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The Online HTCO Methods Obtains Near
Equal Results to TKN Continuously
0
10
20
30
40
50
11/19/04 11/29/04 12/9/04 12/19/04 12/29/04 1/8/05
AverageTotalNitrogen
(mg/L/day)
Date
TKN vs TN TKN
TN

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The Online Total Nitrogen Measurement is
Rugged and Uses Few Reagents
Measure the sample (dilute)
Decomposition : 720℃ with Pt
catalyst
O2 from air
Ozone
Obtain the TN Result (every 5 minutes)
Formation of NO2
* , -> NO2, Photon
Emission
Formation of NO
Electricity

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The Online HTCO Total Nitrogen Analyzer (TNA)
is Rugged Enough for Field & Plant Use

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The Online Total Nitrogen Method Has a
Large Dynamic Range
Method Detection Limit (MDL) Multiple point calibration range Maximum concentration by
automatic dilution
0.05 mg/L N 2 – 100 mg/L N (user defined) 4000 mg/L N

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The Online TNA is Capable of Sampling
Multiple Streams
Multi-Stream Sample Switching Unit

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The Online TNA is Capable of Handling TSS
Multiple Stream TSS Unit

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Back Flush Capability for Low TN and Highly
Variable Samples
Backwash Strainer Sampling Unit

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The Online TNA is Capable of Multiple Point
Calibrations and Check Standards
Automatic dilution capability:
- Reduces maintenance
- Reduces interferences
- Enables the use of one
standard to prepare
different calibration curves

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Placement in a Wastewater Treatment
Facility for Process Control

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Continuous Monitoring Provides More
Information & Trends With Less Labor
TOC/TN/TP Relative mg/L/day
0
30
60
90
120
150
180
7:34 18:34 5:34
Time (hrs)
RelativeConcentration
(mg/L/day)
TOC
TN
TP

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Benefits of Online Monitoring
Automatic
• Sampling
• Pretreatment
• Digestion
• Analysis
• Report
Flexibility of Sampling
• Hourly
• Daily
• Weekly
• Monthly
Reduce
• Labor
• Time
• Money
Achieve Maximum Efficiency
• Faster Response
• Better Treatment
• Cost Reduction

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