1. Benefits of On-line Monitoring of Carbon, Nitrogen and Phosphorus
New Jersey Water Environment Association
Hadi Jamehdor
Shimadzu Scientific Instruments
North Central Region, Addison, IL

2. Benefits of On-Line Monitoring
Environment
Consumers
Treatment Facilities

3. Environmental Impact Why Carbon, Nitrogen and Phosphorus?
Because of their environmental impact
These elements are nutrients and can enrich aquatic systems
The problem is when we over enrich: Eutrophication
Potomac River

4. Drinking Water: TOC EPA established two drinking water Regulations:
Stage 1 Disinfection Byproducts Rule (DBPR)1
Protects customers from disinfectants and disinfectant byproducts (DBP)
Enhanced Surface Water Treatment Rule (IESWTR)1
Reduce microbial contamination in drinking water
Federal Register, December 16, 1998, Volume 63, Number 241, or 40 CFR Parts 9, 141, and142

5. Response by EPA: Nitrogen & Phosphorus
States & EPA : issue permits to all wastewater treatment facilities that regulate pollutants such as nitrogen and phosphorus
“Nutrient Criteria Technical Guidance Manual for
Lakes & Reservoir” (EPA-822-B ), released 5/2000
Rivers & Streams” (EPA-822-B ), released 7/2000
Estuarines and Coastal Waters” (EPA-822-B ), released 10/2001

6. Total Organic Carbon TOC (Total Organic Carbon):
Organic carbon bonding with hydrogen or oxygen to form organic compounds
Consists of:
Purgeable Organic Carbon (POC)
Non-purgeable Organic Carbon (NPOC)
i.e TOC = POC + NPOC
Analysis: There are 2 methods,
Difference method : TOC = (TC – IC)
Direct method : TOC  NPOC (if no POC)

7. Total Organic Carbon Measurement
Measure the sample (dilute)
Inorganic Carbon Removal
Hydrochloric Acid Solution
Agitate
Removal of CO2
Decomposition : 680℃ with Pt catalyst
Formation of CO2
Obtain the TOC Result

8. Total Nitrogen TN (Total Nitrogen):
Sum of Both Organic Nitrogen and Inorganic Nitrogen:
Organic Nitrogen (R-N)
(Inorganic) Nitrate (NO3)
(Inorganic) Nitrite (NO2)
(Inorganic) Ammonia (NH3)
Does not include:
Nitrogen Gas (N2)
Chemical unreactive and not very reactive biologically
Not detected by TN Method

9. Total Nitrogen Measurement
Measure the sample (dilute) O2
Decomposition : 720℃ with Pt catalyst
Electricity
Formation of NO
Ozone
Formation of NO2* , -> NO2, Photon Emission
Obtain the TN Result
Relaxation of NO2* to NO2 by emitting light

10. Total Phosphorous Measurement
Measure(dilute) the sample
Sulfuric acid solution
Decomposition : 95℃ with UV irradiation and air
Sodium hydroxide solution for pH control
L-ascorbic acid solution
Color the solution to blue
Sulfuric acid ammonium molybdate
Obtain the TP Result
Measure 880nm absorbance of Phosphomolybdate blue

11. COD, BOD & TOC Permits are usually written on COD, BOD, or TOC
TOC can be used in place of COD or BOD after conversion trends (correlation) have been made.
Running COD or BOD and TOC in parallel

12. COD, BOD & TOC
What is the difference between BOD, COD or TOC? Why do I have to measure them?
All treatment plants are required to measure one of these three items as a measure of the pollution value water.
COD or Chemical Oxygen Demand is the total measurement of all chemicals in the water that can be oxidized.
BOD or Biological Oxygen Demand is supposed to measure the amount of food (or organic carbons) that bacteria can oxidize.
TOC or Total Organic Carbon is the measurement of organic carbons.

13. COD, BOD & TOC
COD -
COD is a chemically chelated/thermal oxidation reaction and can be measured in 2 hours.
False Lows and False Highs
A COD test measures all organic carbon with the exception of certain aromatics (benzene, toluene, phenol, etc.) which are not completely oxidized in the reaction, other reduced substances such as sulfides, sulfites, and ferrous iron will also be oxidized and reported as COD.
NH3-N (ammonia) will NOT be oxidized as COD.
No indication for nitrogen loading

14. COD, BOD & TOC BOD… Two Types C-BOD & BOD
BOD5 measures the oxidation of carbons and possibly nitrogenous compounds present in a water sample. CBOD only measures oxidation of carbons.
5-day test
Need to do Both
Places where the nitrification of ammonia may not be complete (i.e., incomplete conversion of ammonia (NH3) to nitrate (NO3)) or where high levels of amines or ammonia are present, false BOD readings may occur. This can occur in municipal lagoons, wineries and general industry.

15. COD, BOD & TOC BOD Uses and Limitations
BOD testing has its widest application in measuring waste loadings of treatment plants, and in evaluating the efficiency of treatment processes.
The hard to degrade organics found in some of these systems also may take longer than five days to break down, so a BOD test will give an inaccurate measurement.

16. COD, BOD & TOC What is Total Organic Carbon?
Organic matter content is typically measured as total organic carbon and dissolved organic carbon, which components of the carbon cycle.
The Total Organic Carbon test measures all organic carbon as CO2
TOC does not differentiate between the source of organic carbon, which can be metabolized (assimilated).
Total organic carbon is a more accurate indication of pollutants that cause problems with BOD testing.

17. Sampling Scheme Collection Analysis Reporting Sampling Preserving
Storage
Analysis
Physical Treatment
Chemical Treatment
Batch
Measurement
Reporting
Report Generation
Review/React

18. Sampling Scheme Collection Analysis Reporting Sampling Preserving
Storage
Analysis
Physical Treatment
Chemical Treatment
Measurement
Reporting
Report Generation
Review/React

19. On-Line Sampling Considerations
When selecting a sampling device Consider:
Particulates
Are there a lot of particulates?
Do I need to include them in my reading?
Concentration of Analyte
Are there special precautions based on level?
Do I need to consider environmental influences?
Number of Sampling Points
Can I monitor all necessary points?

20. On-Line Sampling Considerations
Particulates can add to the complexities of collecting and analyzing samples.
Do you have particulates?
If yes will they interfere with the analysis
Do I need to consider them in my analysis?
Do they contribute to your analysis?

21. On-Line Sampling Considerations
Performing low level analysis can be influenced by environmental influences such as contact with air or water used in the process.

22. Multi-Stream Suspended Solids Unit
Sample flows in the top and drains out the bottom
Actuators move the sampling arm into the stream
Sample flows down into the sampling chamber through the strainer removing larger particles
Mixing blades homogenizes the sample
System back flushes then washes
Movie

23. Multi-Stream Sample Switching Unit
Sample flows in the bottom and out the top
Some sample flows in lower chamber on the outside of the sample collection cup
Actuators move the stream to the sample collection chamber.
Reduces Sample-Air Contact
Eliminates need for washing

24. Backwash Strainer Sampling Unit
Sample flows in the bottom and out the top
Air pressure prevents sample from entering inner chamber until sampling
Air is turned off and sample is filtered as it enters chamber
Sample flow dynamics self clean the sample mechanism
Movie

25. Field Application: Waste Water Facility

26. Onsite Installation

27. Water Treatment Utility
WATER SOURCE
MONITORING
TECHNIQUE
AUTOMATIC TECHNIQUE
MANUAL TECHNIQUE
CHEMICALS COST
(per Analysis)
AUTOMATIC ADDITION
REDUCE ERROR
LAST LONGER
Labor
(per Analysis)
Time
(per Analysis)
Variability
Frequency
Hourly/Weekly/ Monthly
Biweekly
TREATMENT

28. Manual vs Automatic Total Nitrogen
Comparable Data

29. Manual vs Automatic Total Phosphorus
Comparable Data

30. Monitoring Why Biweekly vs. Hourly ?
Manual:
To reduce cost
To reduce labor
To reduce time
Automatic:
Reduces labor
Reduces time
Reduces cost
HOURLY/DAILY/WEEKLY/
MONTHLY
REDUCES COST OF POST
TREATMENT
FASTER RESPONSE
IMPROVE WATER QUALITY
BIWEEKLY

31. Manual vs Automatic Total Phosphorus
Hourly :
More information
Less labor
Better quality
Biweekly
Hourly

32. Hourly vs Biweekly…..Allows FASTER RESPONSE
TPK
Sudden Changes
Hourly TP

33. Benefits of On-Line 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

34. Thank You!
Special Thanks to