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9060A also offers itself as a recognized authoritative method based on it being an EPA document and it being one of the authoritative sources listed in NR 149 Appendix iii. Note that SW 846 9060 has been retired by the EPA and 9060A is the version that is currently acceptable for use. Although this method may not explicitly be written for solids it can easily be adapted to solids by weighing out a certain portion of sample and placing it in a boat instead of aliquoting a certain volume of sample. The Walkley-Black procedure. We’d call this a procedure, rather than a method, because it has been modified extensively over the years, and includes correction factors. It is over 50 years old and was written as a soil agronomy method used to determine “organic matter” –not TOC– in soils. The Walkley-Black method is a titrimetric procedure that changes from a dull green to a reddish brown color. Note that the endpoint can be very difficult to discern in samples that contain any natural color, particularly sediments laden with tannins or lignins. Besides the multitude of different versions of this procedure being currently utilized (can you say inconsistent analysis) the main problem is that titrimetry is not a TOC technology for which WDNR offers accreditation. Further, Walkley-Black is not recognized as an authoritative method by the EPA and it is not one of the authoritative sources listed in NR 149 Appendix iii. It is well documented that the Walkley-Black method is subject to interferences (chlorides and iron) and does not oxidize all organic carbon and is particularly poor for digesting elemental carbon forms. To overcome the incomplete digestion the method was later modified to include an extensive heating step during the sample digestion which most labs do not utilize. The “Lloyd Kahn” method. This is a method written by a quality assurance chemist for EPA Region II. It has never been sanctioned by the EPA and does not have any official EPA document number. And, in fact, it was originally developed for the determination of TOC in ocean sediments!

Inorganic carbon from carbonates and bicarbonates is removed by acid treatment. The organic compounds are decomposed by pyrolysis in the presence of oxygen or air. The carbon dioxide that is formed is determined by direct non-dispersive infrared detection (NDIR),

flame ionization gas chromatography (GC-FID) after catalytic conversion of the carbon dioxide to methane; or thermal conductivity gas chromatography (GC-TCD), after removal of water.

Lloyd-Kahn’s “procedure” offers several GC technique options for determination, which is not a TOC technology that WI offers accreditation for. It is not recognized as an authoritative method by the EPA or it would have been given an official method number and it is not one of the authoritative sources listed in NR 149 Appendix iii. On top of that, this “method” offers multiple versions or options of itself to users. There is no one official industry standard version of the Lloyd Kahn method recognized so it is hardly certain to even say that a single method exists. The bottom line is that the only accreditation Wisconsin offers for TOC in solid samples is the combustion/oxidation technology. There are many advantages to using this singular method for all TOC analyses in solids. • It is EPA acceptable • It is NR 149 acceptable Finally, using one method to generate TOC results provides consistency to the data users when multiple labs are used. Wisconsin data users have noted TOC results with an order of magnitude of difference in results when different TOC methods are utilized. CRITICAL CAVEAT: Keep in mind that just because our program does not certify TOC methods other than those using oxidation/combustion followed by IR – it does not mean that these alternate procedures cannot be used for agency projects. It just means that accreditation is not offered for them. Certain project sites may prefer other TOC methods for historical purposes, site specific interference purposes, or special data use purposes. That is fine if there is a project specific quality assurance project plan (QAPP) that outlines exactly what method is being performed – version and source - and exactly what elements of the method must be followed if all of the method procedures are not required. NR 149 has an allowance where the QAPP can supersede the requirements of the administrative code as long as they are clearly documented in the QAPP.

PT Provider factoid: The Wisconsin State lab of Hygiene provides PTs for most WI labs, followed closely by ERA and Phenova.

Calculated versus actual phosphorus concentrations.

The relationship between phosphorus concentration and absorbance. Graphic courtesy of North Central Labs.

…pssst…it’s only linear to about 1 ppm!

Each year, hunters sight-in (re-calibrate) their rifles prior to deer season. You might call this a 3-point calibration: zero, 25 or 50, and 100 yards. For most of us who hunt woodlots or northern Wisconsin cedar swamps, this calibration is just fine. But what if this year, you’re taking that big trip out west to try your luck at elk or mule deer. Your calibration out to 100 yards isn’t going to work out so well in Big Sky Country where 300-plus yard shots are common. Your 30-06, sighted in at 100 yards, will drop about 12 inches at 300 yards. Best know your calibration range before you take that shot! While we don’t have gravity working against us, the same concept applies to total phosphorus. Due to the nature of the chemistry of colorimetric phosphorus analysis, instrument response becomes non-linear past about 1 ppm. If you calibrate up to 1 ppm and the absorbance of your sample is greater than the absorbance of your 1 mg/L standard, then your total phosphorus result will be biased low.

So, if you do not dilute your sample such that the absorbance is below that of your high standard (typically 1.0 ppm or less) you will under-report the actual concentration of phosphorus in your sample.

The more you go beyond the linear portion of the curve, the more inaccurate your results will become. This is important in reporting accurate and defensible compliance data. Many facilities measure the phosphorus in their influent to gauge the level of required phosphorus removal. If you do not sufficiently dilute your sample to within the linear range of the curve (as close to the middle as you can is the best for the most accurate results) you will be underestimating how much actual phosphorus is coming into your plant. This, in turn, could grossly underestimate the percent removal you are achieving. In summary, do not extend your calibration like you would for your rifle. Instead, bring your phosphorous target within range and DILUTE!

Are You Calibrating Your Total Phosphorus Within Range?

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If the water utility adds phosphate, consider treating the water used for glassware and sample containers with reverse osmosis followed by anion exchange.

Consider purchasing a laboratory grade dishwasher for glassware and sample container cleaning. Most washers designed for laboratory use are equipped with a pump to allow the laboratory to feed the washer with water that has been treated to remove phosphate. Lab grade dishwashers can also be setup to include a wash cycle using a mild acid such as sulfamic or citric acid. Joe Panek from the Bristol Wastewater Treatment Plant has successfully used this approach for many years. He installed a 20 gallon polyethylene reservoir which he feeds with deionized water. The washer draws all water used for washing and rinsing from this reservoir.

If hand washing, use distilled or deionized (anion and cation exchange) treated water for washing and rinsing.

Instead of washing the sampler carboys consider using a food grade polyethylene bag as a liner for carboys. Mike Suha from the City of Appleton Wastewater Treatment Facility uses a relatively inexpensive food grade polyethylene bag as a liner. Mike says they cost $0.15 each so he has them changed daily. Contact the LabCert program for more information.

If a facility has a discharge permit for metals and requires monthly sampling, consider using the food grade polyethylene bag and changing the sampler line and pump tubing immediately before sampling for metals. Sam Warp and Ted Bratton from the City of Marshfield Wastewater Utility began using Clavies plastic bags as carboy liners in 2014 to address copper and phosphorus contamination issues. They found copper levels in their effluent samples decreased significantly after switching to the carboy liners. They determined prior samples were elevated due to sample contamination during the sampling process.

Finally, a word about acid washing. Don’t go crazy using strong acid to wash glassware and sample containers. Use dilute hydrochloric acid; limit it to 1%. DO NOT USE stronger acid. Remember, strong acids pose an increased safety hazard and do not improve cleaning efficiency. When it comes to acid, less is more.

From little known secret sources of contamination (phosphates used in the water supply) to carboy liners

to using too much acid, there are many things that detract from an operator’s ability to do the job well. Always feel free to contact your auditor for assistance as needed. …Not everything goes!

They say that a picture tells 1000 words, but when it comes to approved methods to be used for compliance testing, pictures don’t cut it. In their desire to be customer friendly, Hach has developed quick “picture” versions of its methods. Unfortunately, these “picture” methods are NOT approved for compliance. You must actually have (and use) a paper or electronic copy of an approved Hach Method in EPA format when using and citing Hach Methods for any compliance monitoring. The “EPA Format” method version of methods can be found on the Hach website or contact a Hach representative. The Hach Co. has developed a number of test kit methods that have been approved outright (as standalone methods) by the EPA. These EPA approved methods will appear in 40 CFR Parts 136 [wastewater] or 141 [drinking water]. These methods are acceptable for compliance testing under the programs that approved them. Other Hach (and similar vendors’ test kits) methods have been deemed “equivalent” to approved methods under those federal programs.

Considerations when using Hach methodologies

A listing of Hach EPA compliant methods, by program, is available at: http://www.hach.com/cms/documents/pdf/EPA/HachEPACompliantMethods.pdf

A. For drinking water you may only use methods that appear in 40 CFR Part 141 or the methods that are “EPA-approved” for the Drinking Water program.

B. For all other environmental programs you may use methods that are “Approved”, “Accepted” or “Equivalent”.

C. If you’re unsure…contact your auditor or the program general contact.

There are a number of other considerations when using Hach methods: What method should I report with my results? For wastewater compliance monitoring (WPDES) labs must report the authoritative method (the approved reference method listed in the Hach method). Do not cite the Hach method unless it is approved as a standalone method in the Federal Register. The reference method is provided in the table on the [http://www.hach.com/cms/documents/pdf/EPA/HachEPACompliantMethods.pdf] link. For example, if a lab is using the TNT Plus 843, Hach Method 10210 for Total Phosphorus, the method to be reported is EPA 365.1 [automated] or EPA 365.3 [manual]. Note that this approach will also help when reporting PT sample results.

How do I indicate I’m using a Hach method for testing if my reference is something else? If you are using a Hach Method, that information must be included in your SOP. There are method numbers and product numbers for Hach. For instance, for Total Phosphorus the product numbers are TNT843, TNT844, and TNT845 but the Hach Method number is 10210  for all of these. Use the Hach Method number in your SOP, but also be sure to include the product number used under the consumables section of your SOP. What quality control is required? Labs must perform the required quality control samples listed in the approved reference method – not what is in the Hach method. If there are no required QC samples in the reference method then defer to NR 149 for required QC. My vendor says I can use the pre-programmed calibration on my DR-xxx. Is that true? Sorry, but no. No matter what any vendor representative or method may proclaim, WI does not allow the use of pre-programmed calibration curves. Each lab must generate their own calibration curve, at the frequency required by NR 149, using their own equipment, standards, reagents, and lab conditions.

My vendor says I never have to calibrate my new LDO probe for BOD. Is that true? Again, no. This is not true in Wisconsin. DO/BOD probes must be calibrated daily.

Is there anything else I need to be concerned about? Even some of the allowable Hach versions have errors and here are TWO common ones that you need to be aware of.

A. Total Phosphorus method 10210 contains two clear errors. Samples must be digested for 30 minutes

at 150 ºC at a minimum. (Many versions indicate to heat for 60 minutes at 100 ºC).

Samples must be neutralized before digesting. (All versions indicate that a pH between 2 and 10 is acceptable).

B. Ammonia by method 10205 contains an error as well. Samples must be preserved with sulfuric

acid --not hydrochloric acid (HCl), as many Hach versions indicate).

…is ACME Labs certified for tetramethyltoast? Many regulatory agencies drill down and certify to the analyte level. We find these Scopes of Accreditation to be decidedly user UNfriendly. The average client procuring lab services would be hard pressed to wade through scores of analytes for different regulatory programs and analytical methods to determine that a lab is capable of providing its testing needs. While the Wisconsin Laboratory Certification and Registration Program can provide accreditation on the analyte level for those analytes we offer accreditation for; we also provide an array of discrete “Analyte Group” offerings in the aqueous and solid matrices to make your life easier. These offerings are as follows:

• PAH group (lists for GC, GCMS, & HPLC) • BNA group (GCMS) • VOC group (lists for GC & GCMS) • Organochlorine Pesticides group (lists for GC &

GCMS) • PCB as Aroclors group (lists for GC & GCMS) • PCB Congeners group (lists for GC, GCMS, &

HRMS) • Dioxin & Furans group (lists for GCMS, & HRMS)

The benefits of utilizing the analyte group accreditation, instead of individual analytes are: • Your certification scope is more concise and easier

to read • Proficiency testing (PT) samples are not required

for each analyte in the group – instead we only require the analysis of a standard (VOC/BNA/PAH/ Organochlorine pesticide/PCB/Dioxins-Furans] PT sample from an approved Provider. Note, however, that: Our program does not assess PTs as the

NELAC program does,

Our program has established minimum numbers of analytes which must have non-zero assigned values,

Only analytes with non-zero assigned values “count”,

At least 80% of non-zero analytes must have acceptable results,

False positive and false negatives will adversely affect your score.

• Less PT requirements means less money and time spent on the annual requirement. While certifying by analyte groups is a great bonus for labs, labs need to remember that there is a specific list of analytes associated with each analyte group and that those are the only analytes you are certified for – not every possible analyte that can fall under the description of a PAH, BNA, VOC, etc. analyte. So how does a lab know which analytes fall under each analyte group? We provide a list of those analytes on our website (http://dnr.wi.gov/regulations/labcert/info.html#tabx2) Each analyte group that we offer accreditation for is listed along with the technologies that are associated with them. Click on any of those groups and a pdf that is downloadable is available that lists all of the analytes covered by the “analyte group” accreditation. So when a laboratory is checking to verify proper WI accreditations they need to review these analyte group lists versus their project lists to make sure they are not performing any work without certification.

Analyte Groups – a flexible option

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This document is intended solely as guidance and does not include any mandatory requirements except where requirements found in statute or administrative rule are referenced. This guidance does not establish or affect legal rights or obligations and is not finally determinative of any of the issues addressed. This guidance

does not create any rights enforceable by any party in litigation with the State of Wisconsin or the Department of Natural Resources. Any regulatory decisions made by the Department of Natural Resources in any manner addressed by this guidance will be made by applying the governing statutes and administrative rules

to the relevant facts.

NR 149 indicates the following

NR 149.46 (4) SAMPLE PRESERVATION AND HOLDING TIME. (a) Laboratories shall follow the sample preservation procedures and holding times required by state and federal regulations. NR 149.46 (2) SAMPLE ACCEPTANCE POLICY. (a) The laboratory shall have and follow a written policy that clearly outlines the conditions under which samples will be accepted or rejected for analysis, or under which associated reported results will be qualified.

1. Drinking water samples received beyond holding time, improperly preserved, in inappropriate containers or showing evidence that they have not been collected according to approved or accepted protocols shall be rejected for analysis, unless the laboratory can document that it has been instructed by the client to proceed with analyses, and all associated results are accompanied by a disclaimer attesting that results may not be used to determine or evaluate compliance with the safe drinking water act.

So the laboratory must have a written sample acceptance policy and include in that policy the criteria the laboratory is using to determine whether drinking water samples will be rejected or accepted. This is a decision that the laboratory makes based on the law – neither the client nor the water system can indicate that a rejected sample is acceptable for compliance analysis. The following elements, at a minimum, must be assessed and addressed in the sample acceptance policy: improper temperature preservation, improper chemical preservation, improper containers, expired holding time, and unsecure receipt. The sample acceptance policy must also discuss the action the laboratory takes for communicating the rejected samples to the client and how this communication is documented.

The client can request that the rejected samples be analyzed by the laboratory for informational purposes

if that instruction is received in writing and if the results are qualified with a “not

to be used for compliance purposes” qualifier.

If it is discovered that the laboratory is not rejecting drinking water samples appropriately and they are not qualifying the results appropriately the consequence is a likely Notice of Non-compliance enforcement action from Wisconsin. Repeat offenses will result in escalation to a Notice of Violation. If any laboratory would like assistance in explaining this requirement to a client, contact us and we would be glad to intervene. We need only look to Flint, Michigan to be reminded of our collective responsibility in protecting public health.

LabNotes Newsletter of the Laboratory Certification Program

LabNotes is published by the Wisconsin DNR Laboratory Certification and Registration Program.

Bureau of Science Services

(608) 267-9753

Steve Geis, Chief Environmental Science Services Section

(608) 266-0245

Rick Mealy LabNotes Editor (608) 264-6006