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BOD/CBOD/COD
BY: LAUREN STEWART AND RACHEL YOUNG
HENRICO COUNTY CENTRAL ENVIRONMENTAL LABORATORY
OUTLINE
• MEET THE BOD/CBOD ANALYSIS
• BOD/CBOD SETUP
• COD
• PROBES
• SKALAR
OVERVIEW OF BOD ANALYSIS
• BIOCHEMICAL OXYGEN DEMAND; CARBONACEOUS BOD
• MEASURES OXYGEN CONSUMED BY BACTERIA FROM THE DECOMPOSITION OF
ORGANIC MATTER
• DAY 1: DECHLORINATE AND PH ADJUST IF NECESSARY. DETERMINE DILUTION
SERIES. ADD SEED, NITRIFICATION INHIBITOR IF CBOD, AND DILUTION WATER.
MEASURE INITIAL DO. SAMPLES SHOULD HAVE DO 7-9 mg/L
• INCUBATE AT 20°C FOR 5 DAYS
• DAY 5: READ FINAL DO IN mg/L
THE RESULTS
https://boogersonthewall.com/2014/05/08/bully-fish/
• INITIAL DO SHOULD BE 7-9mg/L
• FINAL DO “TAKE 2, LEAVE 1”
• EACH PERMITTED SAMPLE HAS 4 DILUTIONS,
HOPING THAT AT LEAST 2 WILL BE WITHIN
RANGE
• LOOKING AT DIFFERENTIAL BETWEEN INITIAL
AND FINAL DO. CALCULATION ACCOUNTS
FOR SEED AND mLs OF SAMPLE USED.
• WHY SHOULD WE CARE ABOUT BOD
RESULTS?
FIVE DAYS IS THE
LENGTH OF TIME
IT TOOK FOR
WATER IN RIVER
THAMES TO
FLOW FROM
LONDON TO THE
OCEAN
http://meepandwhatnot.wikia.com/wiki/E.T.
BOD/CBOD SETUP
QC AND BATCH SETUP
• DRIFT CHECKS- CHECK PRECISION OF PROBES
• BLANKS- CHECK DILUTION WATER QUALITY
• SEED- 3 BOTTLES TO CALCULATE SCF (SEED CORRECTION FACTOR)
• GGA- CHECKS ACCURACY OF ANALYSIS
• SAMPLES- ONE DUPLICATE PER BATCH
• SEEDED BLANK- RESULT SHOULD BE SIMILAR TO SCF
SOURCE WATER
• REVERSE OSMOSIS UV DISINFECTION DI SYSTEM
• BIANNUAL MAINTENANCE DONE BY VENDOR
• HIGH HPC RESULTS = FLUSH LINES
• FLUSH LINES WITH DILUTE HYDROGEN
PEROXIDE SOLUTION NOT BLEACH
• HOW TO DETERMINE HOW MUCH DILUTION WATER
NEEDED FOR RUN
• # OF BOTTLES X 300 mLs PER BOTTLE + 2000 mLs
FOR RINSING LINES
• PLACE IN INCUBATOR A DAY BEFORE USE
REVERSE OSMOSIS UV DISINFECTION DI SYSTEM
NUTRIENT PILLOWS
• PURCHASE OR MAKE
• USE 1 mL OF NUTRIENTS PER 1 LITER OF
DI WATER TO MAKE DILUTION WATER
• ADD EXTRA NUTRIENT PILLOW PACK
TO 300 mL BOTTLES
DRIFT CHECK BOTTLES
• BOTTLES FILLED WITH DILUTION WATER – 1 BOTTLE PER PROBE
• FILLED AT BEGINNING OF RUN AND READ AT BEGINNING, EVERY 10 SETS OF
BOTTLES AND AT THE END
• WORKS LIKE A CCV – CHECKS TO MAKE SURE PROBES ARE NOT DRIFTING
THROUGHOUT THE RUN BY RETURNING TO THE SAME BOTTLES
• RECOMMENDED ≤0.2 DIFFERENCE IN INITIAL DO READINGS DURING SETUP
AND FINAL DO READINGS DURING READOFF
NITRIFICATION INHIBITORCBOD: INHIBITS CONVERSION OF AMMONIA (NH3) TO NITRATE (NO3-)
• TCMP
• TRICHLOROMETHYL PYRIDINE
• POWDER NITRIFICATION
• 2 SQUIRTS
• DOESN’T DISSOLVE WELL AND MAY STICK
ON PROBE
• PREFERRED IN SM
Fig 1. http://media.wattswater.com/SS-Nitrification_Inhibitor_literature.pdf
• ATU
• ALLYLTHIOUREA
• LIQUID NITRIFICATION:
300 µLs PER SAMPLE
• 1 G 500 mL DI
• SOLUTION IS STABLE FOR 2
WEEKS
• MORE ACCURATE WHEN
DISPENSING
COMMERCIAL SEED PREPARATION
• MAKE DILUTION WATER
• USE 1 CAPSULE PER 500 mLs
DILUTION WATER
• AERATE FOR 1 HOUR
• LET SETTLE FOR 5-15 MINS AND
DECANT SUPERNATANT
http://polyseed.com/main/polyseed.php
SEED PREPARATION
• STOPPED USING COMMERCIAL SEED – LOW GGA RECOVERY
• UNPRESERVED PRIMARY EFFLUENT AND INFLUENT SAMPLE
POURED OFF THE DAY BEFORE USE AND PLACED IN
INCUBATOR – 1 L OF EACH
• POUR OFF PE SUPERNATANT –TURBIDITY 40 ± 1 NTU; AT OUR
LAB MUST BE 40 ± 5 NTU
• IF PE HAS A HIGH TURBIDITY, DILUTE WITH DI WATER
• IF PE HAS A LOW TURBIDITY, ADD REMAINING PE SAMPLE OR
USE INFLUENT SAMPLE TO BRING UP TURBIDITY
• SEED VOLUMES CHANGE SEASONALLY
GGA
• PURCHASE OR MAKE
• MUST BE 198 ± 30.5 mg/L PER METHOD
• 3 BOTTLES FOR PERMITTED SAMPLES – 1 BOTTLE FOR NON-
PERMITTED
COD
• CHEMICAL OXYGEN DEMAND (COD) IS A MEASURE OF THE OXIDIZABLE
ORGANIC MATTER CONTENT OF A WASTEWATER SAMPLE. THE SAMPLE IS
REACTED WITH AN ACIDIC SOLUTION OF POTASSIUM DICHROMATE IN THE
PRESENCE OF A CATALYST (SILVER) AND DIGESTED. OXIDIZABLE ORGANIC
COMPOUNDS REDUCE THE DICHROMATE ION (CR2O72-) TO THE CHROMIC ION
(CR3+). THE AMOUNT OF CHROMIC ION PRODUCED IS MEASURED AND
EXPRESSED AS THE NUMBER OF MILLIGRAMS OF OXYGEN CONSUMED PER
LITER OF SAMPLE.
COD
• WE ARE NOT CERTIFIED – USE COD VALUES TO HELP DETERMINE BOD/CBOD
DILUTIONS
• USE Hg FREE VIALS
• TEST FOR CHLORIDE
COD
• MAKE DILUTIONS OF STRONG
SAMPLES THAT WILL FIT IN THE 50
mg/L TO 1000 mg/L CURVE
• ADD 2 mLs OF EACH SAMPLE TO VIAL
• DIGEST FOR 2 HOURS AT 150°C
• READ ON HACH DR4000 SPEC
BOD/CBOD DILUTIONS
• 4 DILUTIONS FOR PERMITTED
SAMPLES
• 3 DILUTIONS FOR NON-
PERMITTED SAMPLES
COD DILUTIONS TO SKALAR
COD DILUTIONS TO SKALAR
COD DILUTIONS TO SKALAR
COD DILUTIONS TO SKALAR
PROBESMEMBRANE AND LUMINESCENT
MEMBRANE PROBE
FIG 1. YSI HTTPS://WWW.YSI.COM/FILE%20LIBRARY/DOCUMENTS/TECHNICAL%20NOTES/T605-ACCURATE-BOD-MEASUREMENTS-WITH-ELECTROCHEMICAL-AND-OPTICAL-PROBES.PDF
• ELECTROCHEMICAL
• TWO METAL ELECTRODES WITH
SUPPORTING ELECTROLYTE
SEPARATED BY GAS PERMEABLE
MEMBRANE. O2 DIFFUSES AND
REDUCED AT CATHODE BY
VOLTAGE
LUMINESCENT PROBE
• FLUORESCENT FILM SENSITIVE TO
O2. CHANGES IN FLUORESCENCE
ACTIVITY PROPORTIONAL TO O2
CONCENTRATION
• O2 NOT CONSUMED
FIG 2. HACH HTTP://WWW.HACH.COM/POWERLDO
THE LDO PROBE
USES THE SAME
TECHNOLOGY AS
A PULSOX METER
http://meepandwhatnot.wikia.com/wiki/E.T.
CALIBRATING
• RINSE WITH DI, BLOT DRY, WAIT 30 MINUTES. MAKE SURE THERE ARE NO
WATER DROPLETS ON THE MEMBRANE.
• MEMBRANE PROBE NEEDS TIME TO POLARIZE
• NO WARMUP PERIOD FOR LDO
Calibration Verification:
8.83 @ 21.5oC
8.83 x 0.999 = 8.82
ZERO SOLUTION
• IMMERSE THE PROBE IN SODIUM SULFITE SOLUTION OR WATER
THAT HAS INERT GAS (N, AR) BUBBLING THROUGH IT. METER
SHOULD READ <1% DO.
MEMBRANE PROBE MAINTENANCE
• ELECTROLYTE REPLACEMENT: ABOUT 2-4 WEEKS
• MEMBRANE LIFE: AVG REPLACEMENT IS 2-4 WEEKS
• REMOVE MEMBRANE AND RINSE OFF PROBE EVERY 1-3MTH. EACH
CLEANING REMOVES MATERIALS SO AVOID EXCESSIVE CLEANING
• AS NEEDED: SOAK IN 14% AMMONIUM HYDROXIDE 2-3MIN OR
OVERNIGHT IN 3%. RINSE WITH DI WATER, RECHARGE WITH ELECTROLYTE,
AND INSTALL A NEW MEMBRANE.
• AS NEEDED: POLISH DISK FOR DULL FINISHES.
• TURN OFF OVERNIGHT
POLISHING
SILVER ANODE, FROM WHERE CURRENT IS SENT OUT, SHOULD BE SILVER-LOOKING
Silver
Anode
Gold
cathode
YSI https://www.ysi.com/File%20Library/Documents/Technical%20Notes/T605-Accurate-BOD-Measurements-with-Electrochemical-and-Optical-Probes.pdf
LDO MAINTENANCE
• CLEANING SENSOR CAP: USE DI AND KIMWIPE.
RINSE WITH 3% HYDROGEN PEROXIDE TO DISINFECT AND MILD DISH
DETERGENT TO CLEAN AS NEEDED; RINSE WITH DI WATER.
• SENSOR CAP WILL NEED TO BE REPLACED ABOUT ONCE PER YEAR
TROUBLESHOOTING
Issues Membrane LDO
Calibration
difficulty
Wait up to 30 minutes to allow
membrane to polarize
Make sure there aren’t water droplets
Change membrane & solution
Clean probe
Verify calibration coefficients were entered
correctly
Make sure there aren’t water droplets
Clean sensor cap
Rehydrate sensor cap
Replace sensor cap (ensure cavity is dry)
Unstable readings Allow sufficient time for
stabilization (at least 1 min)
Change membrane & solution
Clean probe
Clean sensor cap
Rehydrate sensor cap
Replace sensor cap
Erroneous readings
(jumpy readings,
drifting)
Ensure stir paddle is working correctly
Change membrane & solution
Clean probe
Remove sensor cap and inspect for cracks or
damage
Inspect O-Ring and gasket for damage
Rehydrate sensor cap
Replace sensor cap
SHORT TERM STORAGE
• LDO STORAGE:
• BOD BOTTLE CONTAINING ~ 80 mL OF WATER.
• MEMBRANE STORAGE:
• BOD BOTTLE CONTAINING AT LEAST 1 INCH OF WATER.
LONG TERM STORAGE
MEMBRANE STORAGE:
• REMOVE MEMBRANE CAP, RINSE WITH DI, INSTALL DRY
MEMBRANE (NO ELECTROLYTE SOLUTION)
LDO STORAGE:
• MOISTEN THE SPONGE IN CAP THAT WAS PROVIDED WITH
THE PROBE AND PLACE IT OVER THE SENSOR WITH THE
SENSOR CAP INSTALLED.
• OR PLACE PROBE WITH SENSOR CAP DIRECTLY IN BEAKER
NEW SENSOR CAP. SAVE SPONGE AND SLEEVE.
SKALAR SP1000
MANUAL VS. INSTRUMENT
Manual Instrument
1 probe 1 or more probes
Pour sample, seed, NI, dilution water, GGA Pour samples and GGA – Skalar does the
rest
Wait for each sample to stabilize Instrument has settings to stabilize – analyst
can walk away (can stabilize for up to 3
mins)
Room for error when recording DO values Records DO values directly from probes
Manually record and track changes or
issues throughout the run
Automatically keeps track of changes and
errors throughout the run
SKALAR MAINTENANCE
PROBE MAINTENANCE• DAILY
• RINSE WITH DI AND BLOT DRY
• CALIBRATE WITH 1 POINT CALIBRATION
• QUARTERLY
• VERIFY BAROMETRIC PRESSURE WITH RIC
(AS NEEDED)
• CHECK PROBE ALIGNMENT
• YEARLY
• CALIBRATE TEMPERATURE (AS NEEDED)
• CHANGE SENSOR CAPS
• AS NEEDED
• CLEAN CAPS WITH MILD SOAP
DETERGENT
BAROMETRIC PRESSURE
• BAROMETRIC PRESSURE (ATMOSPHERIC PRESSURE) IS THE PRESSURE EXERTED BY
THE WEIGHT OF THE AIR IN THE ATMOSPHERE OF EARTH
• VARIES WITH ALTITUDE AND MOISTURE
• DECREASES WITH INCREASING ELEVATION
• WEBSITE TO FIND BAROMETRIC PRESSURE AT RIC
• HTTP://VDEM-RICHMONDVA.ALERTEAGLE.COM/HISTORYBAROMETER.ASPX
PUMP MAINTENANCE
• 6 MONTHS
• CHANGE PUMP TUBING
POSITION
• YEARLY
• REPLACE PUMP TUBING
RINSE WELL MAINTENANCE
• DAILY
• EMPTY
• WEEKLY
• CLEAN RINSE WELLS
SEED LINE MAINTENANCE
• DAILY
• RINSE ALL LINES WITH HOT TAP WATER, DI
WATER AND AIR
• 6 MONTHS
• CLEAN SEED LINES WITH 1-2% BLEACH
SOLUTION AND RINSE WITH SODIUM
THIOSULFATE SOLUTION (AS NEEDED)
• YEARLY
• REPLACE LINES (AS NEEDED)
CLEAN SEED LINES
• REMOVE SEED LINES AND PROBES FROM SKALAR
• PREPARE 1-2% BLEACH SOLUTION
• ADD BLEACH SOLUTION TO LINES AND ALLOW TO SIT FOR 15
MINS; REPEAT UNTIL LINES ARE CLEAR
• RINSE LINES WITH DI AND A SODIUM THIOSULFATE SOLUTION
• ATTACH LINES TO SKALAR AND RINSE WITH DI
• CHECK TRC – REPEAT SODIUM THIOSULFATE RINSE AND DI RINSE
UNTIL TRC IS <0.05 mg/L
SYRINGE MAINTENANCE
• DAILY
• VERIFY SYRINGES ARE WORKING
PROPERLY
• YEARLY
• VERIFY SYRINGE DISPENSE VOLUMES
FOR SEED AND ATU
• AS NEEDED
• REPLACE/REPAIR SYRINGES (EX.
GASKET/PLUNGER)
ERROR CODES
• DO1U UNSTABLE DO READING DAY1
• DO5U UNSTABLE DO READING DAY5
• RECHECK CALIBRATION CHECK HAS FAILED THE FIRST TIME
• CALFAIL CALIBRATION CHECK HAS FAILED THE SECOND TIME, ABORTING RUN
• FE FILL ERROR - BOTTLE NOT FULL AFTER ALLOWED TIME.
• SATE SATURATION ERROR, DO>120%
TROUBLESHOOTING
• DO NOT WRITE SEQUENCES
WHILE THE SKALAR IS SETTING UP
A RUN OR READING OFF A RUN
• MAKE TEMPLATES
• KEEP RINSE WELLS CLEAN
• KEEP SEED LINES CLEAN
http://dnr.wi.gov/regulations/labce
rt/BODAbout.html
CALCULATIONS• SEED CORRECTION FACTOR:
INDIVIDUAL SEED CORRECTION FACTOR = ______(INITIAL D.O. – FINAL D.O.)_____
(mL OF SEED IN SEED CORRECTION BOTTLE)
• AVERAGE THE VALUES FROM THE EQUATION ABOVE FOR THE THREE SEED CORRECTION SAMPLES RUN. DETERMINE THE
SEED CORRECTION AS FOLLOWS:
SEED CORRECTION FACTOR = AVERAGE × (mL OF SEED ADDED TO SAMPLE BOTTLES)
• UNSEEDED BLANKS:
BOD5 = INITIAL D.O. – FINAL D.O.
• GGA STANDARD (ASSUMING 6 mL OF GGA USED):
[(INITIAL DO – FINAL DO) – (SEED CORRECTION FACTOR)] X 50 = GGA VALUE
• SEEDED SAMPLES:
BOD5 = ((INITIAL DO – FINAL DO) – SEED CORRECTION FACTOR) X 300
(mL SAMPLE USED)
• IF ANY SAMPLES HAVE A SEED CORRECTED DIFFERENCE <1 mg/L, EXCLUDE THIS RESULT FROM FURTHER CALCULATIONS
FOR NOT MEETING CRITERIA.
REFERENCES
• STANDARD METHODS 5210B-2011
• HENRICO COUNTY SOP #16 BOD-CBOD REV 2.0
• YSI PRO-ODO USER MANUAL
• YSI MEMBRANE PROBE INSTRUCTION MANUAL
• HTTP://WWW.POLYSEED.COM/USERS/APPLICATION_PROCEDURES.PHP
• SKALAR MANUAL
• “A BIRDS-EYE VIEW OF THE BOD TEST” BY PERRY BLAKE, JANUARY 2007
QUESTIONS??
www.examprofessor.com
www.stevehackman.net