Duke Energy Corporation

526 South Church Street
Charlotte, NC 28202

Mailing Address:

EC13K / P.O. Box 1006

Charlotte, NC 28201-1006

May 15, 2012

Via Electronic Mail

Ronald P. Jordan U. S. EPA Headquarters Engineering & Analysi s Division (4303T) Ariel Rios Building 1200 Pennsylvania Avenue, N.W. Washington, DC 20460

RE: Miami Fort Data: Monthly Sampling Events

Dear Mr. Jordan:

Thank you for the opportunity to comment on the draft data from t he samples taken at the Duke Energy Miami Fort Station in September, November , and December 2010, and January 2011. We have done our best, gi ven the amount of data provided and the relatively short time frame for review, to thoroughly review the data. These comments should be considered pr eliminary, as we may, upon furt her consideration of the data,

have additional comments.

I. General Comments

Data Usability

Duke Energy agrees with EPA’s efforts to identify and flag pot entially erroneous (outlier) data points in the Miami Fort data set. If a value is an outlier, howev er, then it should be

discarded from the data set and not used for any purpose. Also, t here is no discussion of how flagged data points will be used (or excluded) from consideration in calculating the new steam electric effluent limitations guid elines. For example, data points flagged B, Est, F and T indicate potentially significant inaccuracy (bias) in the associated data.

Duke Energy also questions the validity an d use of the 4-set averages EPA calculated using the four monthly data sets (see Tables C5-1 - C5-3). The use of averages in some cases may obscure important differenc es among data points. EPA should explain how it intends to use the averages.

Also, the EPA uses the following approach when calculating averages: “If at least one result was above the quantitation limit, then 1⁄2 the quantitation limit was used in the average calculation for all resu lts that were less than the quant itation limit and the result is reported with a less than si gn (“<”)”. This approach is not justified because it2 introduces arbitrarily estimated data into the ca lculations. A more consistent, justifiable and conservative approach would be to use the quantitation limit in t he calculations as

is done when all results are below the quantitation limit.

II. Inadequate Treatment System Desi gn and Operational Descriptions and Data

We noted several instances of inadequate treatment system des ign and operational descriptions and data in our earlier comment s on the draft Sampling Episode Report (SER) for Miami Fort. All of those comm ents also apply to the additional data set.

However, we reiterate here an essential point:

• EPA’s study plan should have included a comprehensive study of the coal feed
stock during each sampling event. It is clea r that coal characteristics have a very significant impact on FGD chemistry and wastewater treat ment. While EPA
gathered some information about coal consti tuents during the sampling events, it

should have collected full information about levels of sulfur, metals, and chlorides
in the coal, as well as the heating va lue of the coal being burned during the
relevant period for the sampling event.

III. Analytical Methods Descriptions

Also, as we stated in our ear lier comments, the analytical descriptions in the SER and the analytical narratives omit some basic information that should be included and would be helpful in making data evaluations and co mparisons. We reiterate our request for basic analytical information, as follows:

1. How were the trace metals samples digested? Was a heated strong acid leach digestion patterned after EPA method 200.2 used or some other alternative digestion? Were the metals samples pres erved to pH < 2 at least 24 hours prior to digestion (total recoverable) or analysis (dissolved)? Would EPA provide a description of the diges tion procedure used for metals samples analyzed by

Method 200.7 and 200.8?

2. How were the Hg sample s digested? Was the bromi ne monochloride digestion done at room temperature, heated, by Method 1631E Appendix A, etc.? If heated BrCl digestions were used, what temperature and duration were used? Were the same digestion procedures us ed for samples collected at SP-1, SP-2

and SP-3?

3. Was a bubbler system or a flow-injec tion analytical system used for the Method 1631E analyses?3 4. Were individual grab samples for Hg flow-proportion composited? If so, was the compositing done physically prior to ana lysis or was the “c ompositing” done arithmetically after the indi vidual analysis of each sample?

5. What type of 0.45 micron f ilter was used to filter the dissolved Hg samples (e.g., capsule, flat membrane with pre-filter, fl at membrane with no pr e-filter, etc.)? Were the samples allowed to settle and the supernatant filtered or were the whole samples shaken and filtered directly without settling? What was the range of elapsed times after collection that the dissolved Hg samples were filtered?

6. How are known interferences in FGD matrices controlled? For example, chloride

is a known interferent in the COD method and the concentration must be carefully controlled to achieve accurate results.

7. More information is needed in the analytical narratives for matrix spikes and matrix spike duplicates (MS/MSD) that fail. For example, if failed recoveries are close to the acceptance range (87% when the limit is 90 to 100%) then the data can be used with qualification. However, if the recoveries are significantly below the method acceptance criteria then the data should not be used.

8. For the FGD influent (SP-1) samples, were whole, shaken samples used to determine classical analytes (except TD S and TSS) or were the FGD samples allowed to settle and the clearer super natant used for any of the classical analysis

Duke Energy urges EPA to make this informa tion available so that the data can be reviewed in the context of full laboratory QA/QC information and a full understanding of the analytical methods used.

IV. Quality Assurance/Quality Control Issues

Problems with ICV, CCV, ICB, CCB, ISA, ISB, CRI or MR L Standard (indicated by a “^”)— This “catch all” mark appears to have been used by EPA to indicate a multitude of possible QC problems that would only be evident from an examination of the raw laboratory data. For ICP/MS, problems with the ICV (initial calibration verification) are supposed to be resolved before analysis proc eeds. Also, the CCV analyses (continuing calibration verification, per formed once every ten samples) are supposed to be corrected by recalibration and re-analysis. It is unclear why any of the samples would be qualified for either ICV or CCV outliers.

Also, continuing calibration blanks (CCBs) are a very important QC check when the laboratory is reporting values down to the MD L as J qualified results, as is being done here. ERG stated that they app lied “method specific criteria” in determining whether the CCBs (and other criteria qualified with a “^”, see above) were acceptable. However, for

both the ICP and ICP-MS met hods, the CCB acceptability is based on the reporting limit, not the MDL. For exam ple, Method 200.7 requires only that the CCB be less than4 the minimum (reporting) level. The ML is defi ned in Section 1.12 of the method: “The ML for each analyte can be calculated by mult iplying the MDL by 3.18 and rounding to the nearest (2, 5, or 10 X 10n) where n is an integer.” If the method criteria are applied,

then the data review would not qualify data until a continui ng calibration blank exceeded the reporting limit. This means that values reported below the r eporting limit can be highly inaccurate even without any data qualifier (other than “J”).

More on Continuing Calibration Blanks (CCB)— This is a very important QC check when the laboratory is reporting values down to the MDL as J qualified results, as is being done here. ERG st ated that they applied “method spec ific criteria” in determining whether the CCBs (and other crit eria qualified with a “^”, see above) were acceptable. However, for both the ICP and ICP-MS methods , the CCB acceptability as based on the reporting limit, not the MDL. For example, Method 200.7 r equires only that the CCB be less than the minimum (reporting) level. T he ML is defined in Section 1.12 of the method: “The ML for each analyte can be calc ulated by multiplying the MDL by 3.18 and rounding to the nearest (2, 5, or 10 X 10n) where n is an int eger.” If the method criteria are applied, then the data re view would not qualify data until a CCB exceeded the reporting limit. This means that values re ported below the report ing limit can be highly inaccurate even without any dat a qualifier (other than “J”).

MS/MSD QC Excursions (“F”)— Any “F” qualified results should be considered

estimated values and excluded from the EPA dataset. The “F” flag appears on the following Miami Fort FGD effluent data (Table C5-3):

Set 1 Barium, Silver Set 2 Ammonia, Nitrate/Nitri te, COD, Cyanide, Silver

Set 4 COD

V. EPA Requested Information

As requested, please find below the mercury sp lit sample results from the effluent of the FGD wastewater treatment system (SP2) fr om Miami Fort Generating Station for sample sets 1, 2, 3 and 4. Split sample s were not collected from the influent to the wastewater treatment system (SP1) at Miami Fort G enerating Station during the monthly sampling events.

Miami Fort Split Sample Results - Total Recoverable Hg Data for SP-2

Sampling Date SP-2, Total Rec. Hg, μg/L

09/28/2010 0.242

11/02/2010 0.343

12/07/2010 0.155

01/14/2011 0.1295 VI. Summary

In summary, Duke Energy reserves the right to comment on these data as EPA

continues its work on the st eam electric effluent guidelines rulemaking. In order to assess the data fully, EPA should provide comprehensive laboratory data for all samples. Duke Energy requests that EPA provide the actual laboratory reports from its contract laboratories for both the 4-day sa mpling episode and the monthly samples in order for Duke Energy to further ev aluate the data and the QA/QC results.