### Date: November 6 , 2014

To: Jeff Telander, EPA/OAQPS/SPPD

From: Gabrielle Raymond and Kristin Sroka

, RTI International

Subject: Determination of “Non

- Detect” Test Data for C lay C eramics Proposed Rule

I. I ntroduction

In accordance with section 112 of the Clean Air Act (CAA), the U.S. Environmental Protection Agency (EPA) established national emission standards for hazardous air pollutants (NESHAP) on May 16, 2003 for the clay ceramics manufacturing industry, specifical ly the sanitaryware and ceramic tile industry sectors. Sanitaryware includes plumbing and bathroom

fixtures such as toilets and sinks. Ceramic tile is used to cover floors and walls. The NESHAP regulated emissions of hydrogen fluoride (HF), hydrogen chlori de (HCl), and particulate matter (PM)

— a surrogate for hazardous air pollutant ( HAP ) metals

— from new and reconstructed kilns located at clay ceramics facilities

. On March 13, 2007, the D.C. Circuit Court vacated the emission standards for clay ceramics man ufacturing due to issues associated with the methodology used to determine the minimum regulatory “floors” for new and existing units. 1


### Therefore, the EPA is proposing new standards for clay ceramics manufacturing, including standards for HF, HCl, mercury (Hg), non

- Hg HAP metals (specifically, the PM surrogate), and

dioxins/furans (D/F)

.

The list of affected sources to be regulated has been expanded to include new and existing kilns, spray dryers (ceramic tile only), press dryers (floor tile only), and spr ay glaze operations (sanitaryware and floor tile only)

. The facilities currently subject to the proposed NESHAP include all three sanitaryware facilities and one wall tile facility. The other ceramic tile facilities (all floor tile facilities) have taken t he necessary steps to become synthetic area sources (i.e., have obtained a federally enforceable limit reducing emissions below major source thresholds), and would not be subject to the major source clay ceramics NESHAP. The objective

of this memo randum is to describe the determination of “non

- detect” EPA Method 29 (multi

metals) and EPA Method 23 (dioxin/furan) test data for evaluation in the setting of numeric

MACT floor standards versus establishing work practice standard s for the Clay Ceramics ( CC )

P roposed Rule.

1 Sierra Club v. EPA , 479 F.3d 875 (D.C. Cir. 2007)

.

### 2 II. Sources and Pollutants Evaluated

For CC kilns

, the run flags for each HAP metal

, including Hg

, and each D/F toxic equivalen t (TEQ) 2 

### test run w ere evaluated to determine the “non

- detect” status of the run

. For CC glazing operations

, the run flag for each HAP metal

, including Hg

, test run was evaluated to
determine the “non

- detect” status of the run

. In addition, f or CC dryers

, each D /F TEQ run flag

was evaluated to determine the “ non

- detect” status of the run

. The guidelines from EPA’s

memo randum Determination of “non

- detect” from EPA Method 29 (multi

- metals) and EPA Method 23 (dioxin/furan) test data when evaluating the setting of MACT floors versus establishing work practice standards (Johnson 2014) were followed for each evaluation

.

I II. Definitions from Guidance Memo randum (Johnson

, 2014)

The following definitions appear in the Johnson guidance memorandum (2014) and also apply to this memorandum:

ADL (Above Detection Limit) : R esults from the lab show measured values above the MDL. (B e sure to distinguish reported values as being above the MDL versus above the RL or other lab ‘confidence’ level).

BDL (Below Detection Limit) : A laboratory result where detectable amounts of an individual pollutant or congener are not found. Again, eval uate the data to ensure BDL means

“below MDL” and not “below RL” or some other ‘confidence’ level.

DLL (Detection Limit Limited) : A test result where some fractions of the analysis return detectable amounts of a pollutant or congener (above MDL), while ot her fractions are

BDL.

EDL (Estimated Detection Limit) : For Dioxin/Furan tests, a commonly reported estimate of the concentration where a given analyte would have to be present to produce a signal with a peak height of at least 2.5x the background noise s ignal level. The EDL determination is done for each sample set at the time of analysis. This is specific to the analytical technique and is affected by factors such as sample size, dilution, etc., commonly reported for non

- detected analytes instead of oth er values such as PQL, RL, QL, etc. It is important to note that EDL and MDL are not the same, but EDL is a standard benchmark for determining detection from an isotope dilution analysis, common to dioxin/furan emission testing.

MDL (Method Detection Limi t) : Syn onymous with the term LOD (Level of Detection) the MDL is defined as the lowest quantity of a substance that can be distinguished from the absence of that substance (i.e. a blank value) with a stated level of confidence. For the purposes

of this document, the process of identifying the MDL of a given substance is defined in EPA Method 301, Section 15.

2 For these runs, d ioxin/furan emissions are expressed in terms of 2,3,7,8

- tetrachlorodibenzo

- p

- dioxin ( TCDD ) toxic equivalents ( TEQ )

.

### 3 RDL (Representative Detection Limit) : S ometimes referred to as the Representative Method Detection Limit (RMDL) this is the mean MDL value of a specific analyte determined by an MTG review of l lab analyses represented by labs who provided data for best performing sources, thereby creating a representative value by which to assess detection such that the best performing lab handing any particular analytical sample does not drive all detection limit discussion and decision making. By establishing this value as the mean of several labs we allow for the selection of local and cost effective analysis of environmental samples while maintaining

a balanc e of quality analyses. The Westlin/Merrill memo randum defines RDL for dioxin/furans

as EDL x 2 (Westlin and Merrill, 2011)

.

IV. Run Flags

Run flags are determined by the facility/analytical laboratory for each run. They compare each analytical fraction m ass to the MDL or other detection limit values ( e.g

. , Reporting Limit) as available. Mercury runs have five analytical fractions and the other HAP metals have two analytical fractions. The run flag is BDL if all of the fraction masses are below the MDL

, DLL

if one or more of fraction masses are below the MDL

, and ADL if all of the fraction masses are above the MDL. Similarly

, for dioxin/furan testing

, there are multiple congeners for each TEQ run. The run flag is BDL if all of the congener masses are be low the MDL; DLL if one or more congeners are below the MDL; and ADL if all the congeners are above the MDL. For each fraction/congener mass that is below the MDL, the MDL mass is used for the fraction/congener mass and subsequent emissions calculations.

V. Mercury

For each kiln and glazing operation with Hg test data, each run flag was evaluated to
determine the “non

- detect” status of the run, according to Johnson (2014). I f the run flag was ADL or DLL, the run was considered ADL. If the run flag was BD L, the run mass (sum of five fraction masses, as available) was evaluated and compared to the RDL value provided in the guidance document Data and procedure for handling below detection level data in analyzing various pollutant emissions databases for MACT and RTR emissions limits (Westlin and Merrill

, 2011) for Hg analyzed by Cold Vapor AA, 0.56 μg . If the run mass was less than the RDL, the

run was considered BDL. If the run mass was greater than the RDL and was based on MDL values, the run was consider ed BDL. If the run mass was greater than the RDL and was based on other detection limit values ( e.g. , Reporting Limit), the data was set aside and not used for the analysis. ( Note that data set aside for this analysis were not set aside for actual MACT f loor rankings and floor calculations. ) The following figure displays the steps in determining the

“non

- detect” status of a run for this analysis based on the guidance provided by Johnson (2014)

.

### 4 Figure 1

. Steps in determining the “non

- detect” status of test run data for setting MACT

floors.



### Table 1 displays the percent age of ADL and BDL runs for Hg from CC kilns and glazing operations

. The run

- by

- run data used to calculate the percent ADL and BDL for Hg from CC

kilns and glazing operations can be found in Appendix A.

### 5 Table 1. Percent ADL and BDL for Hg from CC Kilns and Glazing Operations

Hg Floor tile
roller kilns Wall tile
roller kilns Tile glaze
lines First

- fire sanitaryware

tunnel kilns

Total Runs 15 6 9 18

No. Set Aside 0 0 0 0

No. Use d 15 6 9 100

No. BDL 0 0 0 0

No. ADL 15 6 9 18

% BDL 0 0 0 0

% ADL 100 100 100 100



### The percent BDL for CC k ilns and glazing operations was 0 percent; as such , the EPA is proposing MACT floor standard s for Hg for CC floor tile roller kilns, wall tile roller kilns, tile glaze lines and first

- fire sanitaryware tunnel kilns

.

VI. Non

- Hg H AP Metals

For each kiln and glazing operation with non

- Hg HAP metals test data, each run flag was evaluated to determine the “ non

- detect” status o f the run, according to Johnson (2014). If the run flag was ADL or DLL, the run was considered ADL. If the run flag was BDL, the run mass (sum of each fraction mass) was evaluated and compared to the RDL value provided in the guidance document ( Westlin a nd Merrill , 2011) for each individual non

- Hg HAP metal analyzed by either Inductively Coupled Plasma/Mass Spectrometry or Graphite Furnace Atomic Absorption Analysis [ICP/MS or GFAAA] or Inductively Coupled Atomic Emission Spectroscopy or Atomic Absorption Analysis [ICP/AES or AA]. Table 2 presents the RDL

values for each non

- Hg HAP met al for each analytical method.

Table 2

. RDL values for each Non

- Hg HAP Metal per Analytical Method ( Westlin and
Merrill , 2011)

Method 29 Non

- Hg

HAP Metals ICP/AES or AA RDL ( μg ) ICP/MS or GFAA RDL ( μg )

Antimony 1.2E+01 1.1E+00

Arsenic 1.9E+01 4.0E

- 01

Beryllium 1.1E

- 01 8.0E

- 02

Cadmium 1.5E+00 3.0E

- 02

Chromium 2.5E+00 3.0E

- 01

Cobalt 2.5E+00 3.0E

- 01

Lead 1.5E+01 3.0E

- 01

Manganese 7.0E

- 01 3.0E

- 01

Nickel 5.4E+00 5.4E+00

Selenium 2.7E+01 8.0E

- 01

### 6 If the run mass was less than the RDL, the run was considered BDL. If the run mass was greater than the RDL and was based on MDL values, the run was considered BDL. If the run

mass was greater than the RDL and was base d on other detection limit values ( e.g

. , Reporting Limit), the data was set aside and not used for the analysis. ( Note that data set aside for this analysis were not set aside for actual MACT floor rankings and floor calculations. ) Table 3 displays the p ercent age of ADL and BDL runs for each non

- Hg HAP metal from CC kilns and glazing operations

. The run

- by

- run data used to calculate the percent ADL and BDL for each

non

- Hg HAP m etal from CC kilns and glazing operations can be found in Appendix B.

### 7 Table 3

. Percent ADL and BDL for Each Non

- Hg HAP Metal from CC Kilns and Glazing Operations a

Source Sb As Be Cd Cr Co Pb Mn Ni Se Total Non

Hg HAP

Metals

Total Runs Floor tile

roller kilns 15 15 15 15 15 15 15 7 15 15 142

No. Set Aside 0 0 9 0 0 0 0 0 0 0 9

No. Use d 15 15 6 15 15 15 15 7 15 15 133

No. BDL 0 0 0 0 0 0 0 0 0 0 0

No. ADL 15 15 6 15 15 15 15 7 15 15 133

% BDL 0 0 0 0 0 0 0 0 0 0 0

% ADL 100 100 100 100 100 100 100 100 100 100 100

Total Runs Wall tile

roller kilns 6 6 6 6 6 6 6 4 6 6 58

No. Set Aside 0 0 6 0 0 0 0 0 0 0 6

No. Use d 6 6 0 6 6 6 6 4 6 6 52

No. BDL 0 0 0 0 0 0 0 0 0 0

No. ADL 6 6 6 6 6 6 4 6 6 52

% BDL 0 0 0 0 0 0 0 0 0 0

% ADL 100 100 100 100 100 100 100 100 100 100

Total Runs Tile glaze

lines 9 9 9 9 9 9 9 6 9 9 87

No. Set Aside 0 7 9 4 0 0 0 0 0 4 24

No. Use d 9 2 0 5 9 9 9 6 9 5 63

No. BDL 4 0 0 0 4 0 0 0 0 8

No. ADL 5 2 5 9 5 9 6 9 5 55

% BDL 44 0 0 0 44 0 0 0 0 13

% ADL 56 100 100 100 56 100 100 100 100 87

Total Runs First

- fire sanitaryware

tunnel kilns 18 18 18 18 18 18 18 16 18 18 178

No. Set Aside 0 2 18 0 0 0 0 0 0 1 21

No. Use d 18 16 0 18 18 18 18 16 18 17 157

No. BDL 0 0 0 0 0 0 0 0 0 0

No. ADL 18 16 18 18 18 18 16 18 17 157

% BDL 0 0 0 0 0 0 0 0 0 0

% ADL 100 100 100 100 100 100 100 100 100 100

a Sb = antimony; As = arsenic; Be = beryllium; Cd = cadmium; Cr = chromium; Co = cobalt; Pb = lead; Mn =

manganese; Ni = nickel; Se = selenium.



### The majority of the individual non

- Hg HAP metals had a high percentage of runs above detection level, thus not meeting the criteria for a work practice standard. As a result , the EPA is proposing MACT floor standards for PM as a surrogate for non

- Hg HAP metals for CC floor tile roller kilns, wall tile roller kilns, tile glaze lines and first

- fire sanitaryware tunnel kilns.

### 8 VII. Dioxin/Furan ( TEQ )

Seventeen specific dioxin/furan congeners are considered in the calculation of TEQ

values. For the 17 specific dioxin/furan congeners

, the mass reported in the laboratory analysis

of the test report was multiplied by the 2005 World Health Organization (WHO) toxic equivalent factors (TEF) to calculate the TEQ value for each run

. If the mass for the congener was flagged

as BDL , then a value of zero was used as the mass. The mass of each of the 17 calculated TEQ values were summed together to get a total TEQ mass for each run

.

The total TEQ mass for each run was c ompared to the Utilities TEQ EDL

, 0.018 ng (Westlin and Merrill , 2011)

. I f the to tal TEQ mass was greater than the EDL

, the run was considered ADL. If the total TEQ mass was less than the EDL

, the run was considered BDL.

Table 4 summarize s the overall percent age of ADL and BDL runs for TEQ from CC kilns and dryers. The run

- by

- run data used to calculate the overall percent ADL and BDL for TEQ from CC kilns and dryers can be found in Appendix C.

Table 4

. Percent ADL and BDL for TEQ from CC Kilns and Dryers

Source No. Runs % ADL % BDL

Floor tile roller kilns 15 100 0

Floor tile press dryers 12 58 42

Floor tile spray dryers 15 73 27

Wall tile roller kilns 6 50 50

Wall tile press dryers 3 0 100

Wall tile spray dryers 3 100 0

First

- fire sanitaryware tunnel kilns
[ 8 stacks, 5 kilns ] 24 75 25

Sanitaryware ware dryers
[5 stacks, 3 dryers] 15 0 100



### T he percent BDL for floor tile roller kilns, floor tile press dryers, floor tile spray dryers, wall tile roller kilns, wall tile spray dryers, and first

- fir e sanitaryware tunnel kilns was not significant ; thus

, the EPA is proposing MACT floor standards for dioxin s/ furans (TEQ) for these

sources.

The percent BDL for wall tile press dryers and sanitaryware ware dryers was 100 percent ; thus , the EPA is proposing no limit for dioxin s/ furans (TEQ) for these two sources

.

### 9 VIII. Referenc es

Johnson, S. 2014. Determination of “non

- detect” from EPA Method 29 (multi

- metals) and EPA Method 23 (dioxin/furan) test data when evaluating the setting of MACT floors versus establishing work practice standards

. Memorandum from Stef fan Johnson, SPPD, MPG

, to SPPD management and MACT rule writers

. June 5, 2014.

Westlin, P., and R. Merrill. 2011. Data and procedure for handling below detection level data in analyzing various pollutant emissions databases for MACT and RTR emissions limits

. Memorandum from Peter Westlin, SPPD, MPG and Raymond Merrill, AQAD, MTG

, to SPPD management and MACT rule writers . December 13, 2011.

### Appendix A

C C Hg Data

### A

- 1 The run

- by

- run data used to calculate the percent ADL and BDL for Hg from CC kilns and glazing operations are provided in the corresponding Appendix A Microsoft Excel® file

### Appendix B

CC Non

- Hg HAP Metal Data

### B

- 1 The run

- by

- run data used to calculate the percent ADL and BDL for non

- Hg HAP metals from CC kilns and glazing operations are provided in the corresponding Appendix B Microsoft

Excel® file

.

### Appendix C

CC TEQ Data

### C

- 1 The run

- b y

- r un data used to calculate the percent ADL and BDL for TEQ from CC kilns and dryers are provided in the corresponding Appendix C Microsoft Excel® file

.