Regulation 85

Navigating Regulation 85 Part IILab Methods and Data Submission

Presented By:Colorado Water Quality Monitoring Council (CWQMC)

andColorado Monitoring Framework (CMF)

rk (CMF)

Presenters

Phil Russell – LEWWTP

Sherry Scaggiari – City of Aurora

Linda Chynoweth – City of Aurora

Julie Stahli – Metro Wastewater

What Are We Sampling?

Phosphorus

Nitrogen

Flow

Effluent SamplingALL Dischargers

Phosphorus: Total Phosphorus

Nitrogen: Total Nitrogen (TN) andTotal Inorganic Nitrogen (TIN)

Flow: Total daily flow (in gallons or MGD) on the day that nitrogen and phosphorus samples are collected. Typically the same value as in permit.

Stream SamplingDischargers > 1 MGD

Phosphorus: Total Phosphorus

Nitrogen: Total Nitrogen (TN)

Flow: Daily average flow (cfs, typically from a downstream gaging station).

Total Nitrogen (TN) = TIN + TONOr

Total Inorganic Nitrogen (TIN) = NH3 + NO3 + NO2

Total Organic Nitrogen (TON) = TKN – NH3

So, TN = NO3 + NO2 + TKN

Bottom Line

Detection Limits & Sample TypeUpstream & Downstream (mdl)

Total Phosphorous 0.01 mg/LNitrate + Nitrite (N) 0.02 mg/LTKN 0.1 mg/LTN 0.1 mg/L

Effluent (PQL)

Total Phosphorous 0.01 mg/LNitrate + Nitrite (N) 0.5 mg/LTKN 0.5 mg/LTN 0.5 mg/LNH3 0.05 mg/L

Regulation 85

QUESTIONS?

MDLs and PQLsand    

Choosing a Lab

MDLMethod Detection Limit

40CFR136, Appendix B, definition of MDL:

“The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the analyte concentration is greater than zero and is determined from analysis of a sample in a given matrix containing the analyte.”

What does that mean?

A result greater than the MDL means the sample has a concentration greater than zero.

NOT that the concentration is greater than the MDL.

The method to calculate MDLs is specified in 40 CFR Part 136 Appendix B

MDL is detection, not quantitation

Reg 85 MDLs

Required MDLs are specified in Reg85 for all stream analytes

(refer to previous section)

PQL

Practical Quantitation Limit

“The lowest level that can be reliably achieved within specified limits of precision and accuracy during routine laboratory operating conditions”

EPA.gov NPDES Glossaryhttp://cfpub.epa.gov/npdes/glossary.cfm?program_id=0

PQL

PQL is set by the state as the level that your

chosen method must be able to

meet.

PQLs were listed in the previous section.

RL – Reporting Limit

“The lowest quantified level within an analytical method’s operational range deemed

reliable enough, and therefore appropriate, for reporting by a laboratory”

Standard Methods 22nd Edition, 1010C

RL – Reporting Limit

Reporting Limit is Quantitation

The level that we can quantitatively say the analyte

exists at that concentration.

RLIt comes down to what concentration the laboratory feels comfortable saying they can quantify, confidently, on a daily basis.

The final arbiter of the RL is the concentration of the lowest standard analyzed for that sample set.

Laboratories almost universally have set their RL to the concentration of that lowest standard.

Region III Quality Assurance MDL Fact Sheet http://www.epa.gov/region3/esc/qa/pdf/whatthel.pdf

PQL and RL

If the PQL is set at 0.5mg/L:

• Case 1: the lab reports an RL = 0.5 mg/L that will work

• Case 2: the lab reports an RL at 0.4mg/L that will work, but you could ask them to report your data at 0.5 mg/L.

• Case 3: the lab reports an RL at 0.6 mg/L that method or lab MAY not work. You could consult with the lab and find out if it is possible for them to lower their RL. They have to set up a special method for you and run standards at the 0.5 mg/L level.

Reporting resultsPQL is 0.5 mg/L, MDL is 0.1 mg/L

Case 1: result is 0.60 mg/L report 0.6 mg/L

Case 2: result is 0.50 mg/L report 0.5 mg/L

Case 3: result is 0.42mg/L report 0.4 mg/L, J

Case 4: result is 0.09 mg/L report <0.1 mg/L, BDL

This result is above the PQL

This result is at the PQL, but not less than the PQL

This result is less than the PQL but greater than the MDL

This result less than the MDL

Choosing a Lab or method

• Large list of methods (see SAP)– Title 40, Part 136, Section 136.3 

• Laboratory Choice:– Internal Abilities– Many contract labs

Method Choice• The method must be followed according to its

reference (EPA, Standard Methods, etc)• The method must be capable of meeting the MDL

requirements. (40 CFR Part 136 Appendix B)• All QC for the method must be followed. This is not

bench or operational testing.– Generally blanks, spikes (a sample made up with

a known quantity) and duplicates are required.– If a calibration curve is needed for the method, it

must adhere to the requirements for number of standards and correlation coefficients.

Internal Abilities• Assess whether or not your personnel have the skills, time, space and equipment to analyze these parameters.

• Compare costs with a contract lab.

• MDL studies must be done in accordance with CFR

Questions for the Lab• Which Method Numbers are run?• What are their MDLs and PQLs?• Are they using 40 CFR Part 136 Appendix B

to determine their MDLs? If not, then how are they being calculated?

• While there is no official certification, labs should be doing blind performance testing (i.e. USGS Round Robin, DMRQA). – Ask them for the most recent results for the

parameters you are requesting.

Questions for the Lab

• What is the procedure for ordering bottles or sample kits? – How much lead time is needed?– Is there a preservative?– Is the preservative added by the lab or the

sampler?– Do the samples need to remain at a given

temperature?– What is the sample holding time?

Questions for the Lab

• When is the best time to sample?– If you have to ship samples – can the lab

accept on Saturdays?

– If you sample late in the day, can you still get samples to the lab? How late can they accept them?

Grab vs Composite

• Grab Samples:  upstream and downstream samples  ‐ could also be effluent sample.

• Composite Samples:  effluent samples are usually going to be composite samples.

Grab Samples

• Typically one bottle for each parameter.• Preservative

– If preservative is already in the bottle – DO NOT RINSE

– If not, then rinse the bottle with sample three times before filling the bottle.

– Observe all requirements for chilling and transporting samples.

Composite samples

• Can be a mechanical compositor or timed grab samples.

• Can be used on Effluent• Must collect sufficient

volume for all tests.• Evenly spaced samples

Composite Samples• If using grab samples, pour each grab into one main

container or carboy.

• Keep good records of time, amount and flow

• Once all grab samples have been combined, mix the composite sample thoroughly and pour into bottles for required analyses.

• Preserve samples– If pre-preserved bottles do not overflow

– If not preserved – leave room for preservative.

• Observe all requirements for chilling and transporting samples.

Sample Preservation• The stability of a sample depends on how

well it is preserved. • Proper preservation includes the use of the

correct containers, pH control, protection from light, absence of head space, chemical addition, and temperature control.

• The chemistry of all analytes must be considered, recognizing that certain reactions may still occur under recommended preservation conditions.

Sample Preservation

• The objective is to provide the lab with a set of samples that closely represents the aquatic environment from which they were taken.

• To ensure consistency and efficiency, sample handling, preservation, storage, and transportation procedures must be followed and documented.

Holding Time

Holding time is the length of time a sample can be stored after collection and preservation, and before preparation and analysis, without significantly affecting the analytical results.

Holding times vary with the analyte, preservation technique, and analytical method.

• Field duplicates and field blanks

• one each for every 20 samples (10% of samples) collected

• the field duplicate is collected immediately after the primary sample is collected at the site.  

• Field blanks are taken by pouring reagent water from the laboratory into sample bottles at the site. 

• Reagent water would need to be requested from the laboratory.  

• Field duplicates/blanks are labeled as separate samples to avoid confusion and to provide an unbiased blind evaluation.

Recommended Field QA/QC

The ability to trace possession and handling of the sample from the time of collection to laboratory

testing and then to final disposition.

Chain of Custody

Regulation 85

QUESTIONS?

Data Submission 

Minimum Data Elements

• Typically a minimum set of elements for your data in four categories:– Organization information– Information on your monitoring project– Monitoring locations– Results

Data Template

• An excel spreadsheet can be used for the minimum data elements. The tabs on your excel spreadsheet will be the four categories.

• Example:

Characteristic Name Method SpeciationResult Sample 

FractionResult Value Result Unit

Ammonia‐nitrogenas N

Total mg/l

Nitrate as N Total 7.2 mg/l

Nitrite as N Total 5.46 mg/l

Kjeldahl nitrogen as N Total 12.3 mg/l

Phosphorus as P Total 0.81 mg/l

Pay attention when you enter data!

• When putting data into your spreadsheet you have to make sure that you put the correct information into the correct column. This becomes crucial when conducting queries and sorts on the database.

• For instance you don’t want your low ammonia number in your nitrate row and the nitrate number in your ammonia row or it will appear that you have an serious ammonia problem.

Flagging of data

• The State recognizes that there is a greater uncertainty in any value reported for individual data points between the PQL and the MDL level.

• This is regarded as “J data”. This “J data” can provide important and useful information about the nutrient conditions at that location.

Flagging of data

Characteristic Name Method Speciation

Result Measure Qualifier

Result Sample Fraction Result Value Result Unit Reporting Limit 

MeasureReporting Level 

Unit

Ammonia‐nitrogen

as N

J Total 0.09 mg/l 0.15 mg/l

Nitrateas N

Total 7.2 mg/l0.02

mg/l

Nitriteas N

Total 5.46 mg/l0.02

mg/l

Kjeldahl nitrogenas N

Total 12.3 mg/l0.1

mg/l

Phosphorus as PTotal 0.81

mg/l 0.01 mg/l

Regulation 85

QUESTIONS?

Why share data?

• The regulatory problems that we are dealing with today are more complicated than they have ever been.

• Gathering data in a common way and in a common place can give us the tools to evaluate water quality on a massive scale.

• Models developed off of robust datasets can lead to regulations that are scientifically sound.

• A robust dataset can show spatial and temporal patterns that can help determine appropriate regulations (not over or under regulation).

• You are required to share with the State – why not share with each other?

Intro to the Colorado Data Sharing Network

A project of the CWQMC for the past 10 years.

A single repository for all water quality monitoring data collected in the State.

We recommend that Reg 85 data is uploaded through the CDSN.

AWQMS Portal

• Storage of all Colorado DSN data

• Can filter based on org, site, data and compounds

• Public Login– http://www.coloradow

aterquality.org/cdsn– Login: cdsnpublic– Password:

cdsnpublic

Google Map Interface

A single visual indication of data

Data availability changes at different

scales

Data downloads are available by location

only

Now has Exceedancefeature

Providing a Public GoodProviding a Public Resource

• Data in the Interactive Google-map utility and in the database are public resources to help facilitate understanding of water quality throughout Colorado

• We operate on a nonprofit basis – relying on donations and grants to fund the majority of our services.

Phosphorus: gaging station).

What the DSN can do for you…Data submitted to the DSN can be easily

transferred to the State in accordance with Reg 85 requirements.

Submitted data can be seen by everyone, which gives all of us a more complete picture of nutrient concentrations around the state.

If you are working with a group, data for downstream gages only has to be submitted

once, and can be seen by all participants.

How can I participate with CDSN?

A one time set up fee of $250 is required to develop your account

You will get a unique username and password.

You can request that all/part of your data be submitted to CDPHE as part of the required

submission every year.

We have tutorials and webinars available to help you learn the system.

Phosphorus: gaging station).

Data and Data Management

Fee for Service Packages

The CWQMC is developing packages to serve the needs of those

regulated by Reg 85.

Developing a fee for service program allows us to diversify our funding

sources to keep our program alive while providing a useful service to

people monitoring around the state.

Fee for Service Packages• We are developing options that range from one‐on‐

one upload assistance, to uploading data in the provided template, to collecting information from your bench sheets.

• All of these options bring support to help you make sure that your data is uploaded correctly and completely.• We will ensure you have all the required minimum data 

elements.• Upon your request, we will submit that data to CDPHE.• You still have the control/responsibility of verifying that the 

data submitted is accurate.

Fee for Service Packages

We should have these packages fully developed by Summer 2013.

If you would be interested in these services, feel free to email us at

board@coloradowaterquality.orgto start the conversation.

simplify, unite, empower, educate, confirm, defend, discover, predict, 

Data Sharing can help. 

www.coloradowaterdata.org

www.coloradowaterquality.org