# MEMORANDUM

TO: Portland Cement NSPS Docket

FROM: Keith Barnett, USEPA/OAQPS/SPPD/MMG

DATE: February 17, 2010

SUBJECT: February 16, 2010 meeting with Representatives of As h Grove Cement and

Lehigh Cement.

Meeting Participants

Keith Barnett, USEPA

Elineth Torres, USEPA

Sharon Nizich, USEPA

Curtis Lesslie, Ash Grove Cement

Yim Matz, Lehigh Hanson Cement

Information discusse d in the Meeting

This meeting was to discuss dust shuttling as a mercury control technique. Information

presented at the meeting is attached.

# Follow Up Information from February 16, 2010 Meeting

Curtis Lesslie

to:

Peter Tsirigotis

02/26/2010 10:56 PM

Cc:

"Matz, Tim", "Richard Wilson", "Fran Streitman", Keith Barnett

Show Details

Peter:

Thank you for taking the time to meet with us on 2/16/10 to discuss the

innovative mercury reduction efforts being developed and implemented at

Ash Grove’s Durkee plant and Lehigh’s Union Bridge plant.

Both Ash Grove and Lehigh are very interested in sharing more ideas with

EPA, however at this time I simply wanted to provide the presentation we

gave during the meeting and a couple of documents that were promised

during the meeting.

I have attached the EERC paper on the role of selenium versus mercury

that

I mentioned to Keith. I have also attached the PCA scrubber report and a

B&W paper showing re-emissions of mercury from wet scrubbers. Keeping in

mind that both Durkee and Tehachapi are located in arid regions, have a

high fraction of elemental mercury in the exhaust, and have insufficient

water rights to accommodate a wet scrubber, I wanted to reiterate that a

wet scrubber would not provide any significant added benefit for mercury

control at either of these plants. Activated carbon is the only viable

control option.

We look forward to sharing additional ideas in the near future. In the

meantime, please let us know if we can provide any additional information

that may be useful.

Sincerely,

Curtis

Curtis Lesslie, P.E.

Vice President of Environmental Affairs

Ash Grove Cement Company

11011 Cody Street

Overland Park, Kansas 66210

Desk (913) 319-6065

Cell (785) 550-6330

Fax (913) 451-1686Selenium’s Importance in RegulatoryIssues Regarding MercuryLaura RaymondEnergy & Environmental Research CenterGrand Forks, NDSeptember 24, 2007History•Minimata Bay, Japan, 1950s–From 1932 to 1968, ChissoCorporation dumped anestimated 27 tons of mercurycompounds into Minamata Bay.–Hundreds of people died.–Over 3000 victims have beenrecognized as having "MinamataDisease."–Fish Hg levels <50 ppm(typical ocean fish <1 ppm)•Iraq 1971–1972–Grain treated with mercurycontaining fungicide.–459 people died.–Hospitalization of over 6000.–Hair Hg levels up to 674 ppm(today <1.4 ppm)Two Major EpidemiologicalStudies•Faroe Island study–Neurological defectsin children neonatally exposed to Hgfrom fish and whale consumption.•Seychelles Island study–No adverse effectsin children born to mothers exposed toeating fish.–Fish consumption levels are 10–20X higher than common U.S.consumption.Reference Dose 0.1μg/kg bw/day•WHO - estimate a Benchmark Dose (BMD)–Increased prevalence to adverse response•Benchmark Lower Limit (BMDL)–No Adverse Effects Level (NOAEL)–At least 2 standarddeviations below BMD–1.2 -2.4 ug/Hg/kg/d•Add a 10 fold “safety factor”.–0.4 ug/Hg/kg/d•EPA calculated the RfD - Safe daily intake for lifetime exposure–Faroes data–Includes an additional 10 fold “safety factor”–results in 4 fold reduction from WHO NOAEL–0.1 ug/Hg/kg/d•Reference dose ––135-lb woman: 1.5 oz of swordfish or 7 oz of tuna/week.–50-lb child: 0.5 oz of swordfish or 2.6 oz of tuna/week.•Centers for Disease Control and Prevention indicate thatno onein the United States tests anywhere near the BMDL.Reference Dose 0.1μg/kg bw/daySafe daily intake for lifetime exposure•The 2000 National Research Council report statedthat 60,000 newborns annually are bornat riskbecause of methylmercury.–Assuming that women eating the most fish (the top5%) are risking their babies’ health.•2002 government hearing – this number wasassumed to be increased to 400,000 pregnanciesper year.•July 2006 national survey conducted by OpinionResearch Corporation found that 40% of Americansbelieve at least 10,000 childhood cases of mercurypoisoning are documented by scientists each year.•There are NO documented cases of mercurypoisoning from fish consumption.Third StudyUnited Kingdom Study•Increased risksfor neurodevelopmental defects withdecreasedfish consumption:–Maternal compliance with the EPA RfD increased risks of their children scoring inthe lowest quartile for verbal IQ and increased risks for pathological scores infine motor, communication, and social skills compared to mothers exceeding theRfD recommendation.–Children of mothers that avoided fish during pregnancy showed developmentalimpairments of a magnitude estimated tobe 60 times greater than the worstcase impairments associated with the highest pilot whale consumption in theFaroes.Huh?????•The Great DebateNeurological defects– Faroe Island studyNo adverse effects– Seychelles Island studyIncreased risks withdecreasedfish consumption– UK StudyHealth Benefits of Fish•Health effects–Neurodevelopment–Fetal development•Decreased preterm deliveries and longer gestation, increased birthweight, lower prevalence of pregnancy-induced hypertension–Cardiovascular health•Stroke, atrial fibrillation, arrhythmias, congestive heart failure, highblood pressure–Mood disorders and PMS–Memory loss, Alzheimer’s disease•Nutrients–Omega 3 fatty acids–Lean protein–Micronutrients–SELENIUMSelenium Physiology21st amino acid – Selenocysteine•Development•Thyroid homeostasis•HIV and other viruses•Cancer•Immune system•Cardiovascular disease•Reproduction•Mood•Disease links–Congenital muscular dystrophy–Autism–Alzheimer's, Downs syndrome–Brain tumors–Diabetes–Liver diseases–Any condition associated with increased oxidative stress or inflammation(rheumatoid arthritis, pancreatitis,asthma, obesity, septic diseases)Selenium Is a MercuryAntagonist•“Protective effect” of selenium.•Numerous reports indicating seleniumsupplementation counteracts the negativeimpacts of exposure to mercury.–Neurotoxicity–Fetotoxicity–Developmental toxicity•Protective effects of selenium against Hg toxicityhave been shown in all investigated species ofmammals, birds, and fish.Se-HgH2Se+MeHgProtective Effect of SeleniumBinding Affinity ~1045Extremely low solubility ~10-58to 10-65Se binds to mercury, so mercury is unavailable to cause harm.Hg-SeMeHg+H2SeOr Is It theThieving Effect of Mercury?Hg is binding to selenium, so selenium is unavailablefor its needed roles.During Se depletion, there is retention and redistribution of Se to the brain,endocrine organs, and reproductive organs.Mercury has the ability to cross the placental and blood–brain barriers anddiminish selenoenzyme activities!Effects of MeHg in rats fed low,normal, and selenium-rich dietsObjective: To investigate the effects of dietary methylmercuryexposure in rats fed varying concentrations of selenium.All of these rats were fed diets prepared with 10 ppmmethylmercury added. The rat on the left has been fed aselenium-deficient diet,the center rat was fed aselenium-adequate diet, and the rat on the right was feda selenium-rich diet.Effects of MeHg in Rats Fed Low,Adequate, and Selenium-Rich Diets1002003004005000 14 28 42 56 70 84 98 112 126Study Day

Body Weight (g)0.1 μmol Se/kg1.0 μmol Se/kg10 μmol Se/kgEffects of MeHg on NeurobehaviorThis rat, fed a selenium-deficient diet with10 ppm methylmercury, showed significantsigns of neurotoxicity.(hind limb crossing, uneven gait, poor motor coordination,and loss of balance).This rat, fed a selenium-rich diet with10 ppm methylmercury, showed nosigns of neurotoxicity.SELENIUM’S THERAPEUTICEFFECTTo examine potential therapeutic effects of selenium, at week11 the toxicity group was further divided into three groups.•No change in diet•Same amount of Hg with added Se•No Hg with added SeResults Show...•Hair and blood Hg levels accurately reflectexposureBUT not risk.–Increased Hg in hair, blood, and brain was associated with decreasedtoxicity.–The lowest Hg concentrations in hair, blood, and brain were associatedwith the highest toxicity.–It was themolar ratiosof Hg to Se that determined toxicity.•MeHg toxicity was only apparent with Se-deficient diets.–The increasedmolar excessof Hg:Se indicated toxicity.•Se therapy effects were nearly identical in treatment groupsregardless of whether MeHg exposure was discontinued or not.Why Is This Important?05101520 Sole Flounder Salmon Tuna Pollock Halibut Cod Snapper Grouper Swordfish US average Pilot Whale

nmol/gMercurySelenium•Fish are among the richest sources of nutritional selenium in theAmerican diet.•Out of 1100 foods commonly consumed in the United States, 16of the top 25 sources of dietary selenium are from fish.Fish data depicted from Hall et al.(1978); pilot whale from Julshamn et al. (1987)and swordfish from Friedman et al. (1978).Can Selenium Explain“The Great Debate”?•Faroe Island study–Neurological defects in children neonatally exposed to Hg fromfish andwhale consumption.•Seychelles Island study–No adverse effectsin children born to mothers exposed toeating fish:–Fish consumptionlevels are 10–20X higher than common U.S.consumption.•United Kingdom Study–Increased risksfor neurodevelopmental defects withdecreasedfish consumption.Se Health Benefit Value•Seafood safety criterion•Considering fish health benefits•Levels of selenium–Antagonistic to mercury–Selenium health benefitsSe-HBV =(Se:Hg molar ratio × total Se)−(Hg:Se molar ratio × total Hg)Se Health Benefit Value•Freshwater fish0.1–0.4 ppm•Ocean fish0.6–0.8 ppm•Predator fish>1.0 ppm•Fish in “polluted” water>10 ppm•Fish from Minamata Bay ~50 ppm•Whale meat~4 ppm•Whale liver>1000 ppmSelenium Levels•Worldwide area with lowselenium–Northern Europe–Finland–Sweden–New Zealand–Parts of China–AfricaFDA and EPA Message•The reference dose and risk assessments are basedon mercury levels only.•“Avoidshark, swordfish, golden bass, and kingmackerel.Limit yourfishintaketo two meals perweekand choose low mercury containing fish.”•74% of women of childbearing age and 85% of pregnant womenconsume <6 oz/wk.•By focusing only on MeHg exposure without consideration andmeasurements of additional nutrients in fish, these warningstatements are inadequate, inaccurate, misleading, and potentiallydangerous.Time for New Message•It is essential that the beneficial effects are consideredand integrated into the evaluation of risk assessmentsregarding seafood consumption.–Avoidance of fish consumption may be detrimental to fetaldevelopment and cardiovascular health.•Se-HBV criterion provides an improved safety standard.–More comprehensive and meaningful.–Differentiates between seafood and freshwater fish that providea rich source of selenium from those that are potentially harmfulbecause they contain an excess of mercury.–May be used to establish a rank order of ocean fish based onnutritional benefits.–Promote healthy choicesrather than unnecessary avoidance ofnutrient-rich, low-mercury fish.

# The Babcock & Wilcox Company 7 

# Role of Sulfides in the Sequestration of Mercury

by Wet Scrubbers

BR-1787 

# Technical Paper

Presented to:

EPRI-DOE-EPA-AWMA

Combined Power Plant Air Pollutant Control

Mega Symposium

August 28-31, 2006

Baltimore, Maryland, U.S.A. B. Ghorishi, B. Downs, and S. Renninger

The Babcock & Wilcox Company

Barberton, Ohio, U.S.A.

# Copyrighted page/s removed. Copyrighted ma terial is not available in

Regulations.gov since it may not be reproduced without consent of

the copyright holder.

Contact the EPA Docket Center’s P ublic Reading Room to view

or receive a copy of this document.

Requests for copies may be made as follows:

In person/writing:

Environmental Protection Agency, Docket Center

1301 Constitution Ave NW, 2822T, Room 3334

Washington, DC. 20004

Telephone:

202-566-1744

Fax:

202-566- 9744

Email:

docket-customerservice@epa.gov

# PORTLAND CEMENT ASSOCIATION

SCRUBBER TESTING PROGRAM

TO DETERMINE

MERCURY CONCENTRATION

AND REMOVAL

SUMMARY REPORT

October 2008

Emission Monitoring Inc.

8901 Glenwood Ave.

Raleigh NC

27617

919.781.3824

# ii 

# Key Words

Elemental Mercury, Flue Gas Adsorbent Merc ury (FAMS) Sampling, Limestone Scrubber,

Method 30B, National Emission Standards for H azardous Air Pollutants (NESHAP), Oxidized

Mercury, Percent Removal, Su lfur Dioxide, Total Mercury

Abstract

The Portland Cement Association (PCA) sponsored a test program of five scrubber controlled

kilns located at four Portland cement plants. The scrubbers were in stalled downstream of

particulate matter removal device (i.e., fabric fi lter baghouses and/or ESPs) to control sulfur

dioxide and other acid gases. These five scr ubber controlled kilns we re identified by EPA as

potential maximum controlled sources for mercur y in their review 2006 of the Portland cement

NESHAP.

Testing for mercury compounds in the flue gas was conducted simultaneously upstream and

downstream of the limestone scrubbers to de termine the effects on the mercury compounds.

Concentration testing using EPA Method 30B and the “FAMS” method were performed

concurrently along with diluen t oxygen measurements. Mercur y results are reported as μg/m 3



# normalized to 7% oxygen. A percent removal for the individual mercury compounds (as well as

total mercury) was calculated using the average inlet and outlet normalized concentrations.

The results were analyzed using a bias correctio n combined with the stan dard deviation of the

paired results to determine the signifi cance of the percent removal calculation.

# iii 

# TABLE OF CONTENTS

1.0 INTRODUCTION 1

2.0 EXECUTIVE SUMMARY 3

3.0 DISCUSSION OF FINDINGS 4

3.1 Method Comparisons 

# 4

3.2 Effect of Raw Mill Operation 

# 4

3.3 Effect of Limestone Scrubber 

# 5

4.0 METHOD 30B RESULTS AND RANGE OF Hg REMOVAL 5

Table 4-1 Method 30B Tabulated Results 

# 6

5.0 FAMS RESULTS 7

Table 5-1 FAMS Speciated Results 

# 7

6.0 PROJECT CONCLUSIONS 8

APPENDIX A Analyses of Mill On Results – Bias Correction and

Statistics

APPENDIX B EXAM PLE CHARTS

# 1 

# 1.0 INTRODUCTION

The U.S. EPA (EPA) published a Federal Regi ster Notice on December 20, 2006 (Vol. 71, No.

244, Pg.76553) that directly affected the Portland cement industry. In this Federal Register

Notice, the EPA requested speciat ed mercury (Hg) testing on sc rubber equipped cement kilns to

understand more fully Hg speciation and emissions at Portland cement plants. Data from this

testing program were expected to be used by EPA, in part, to determine what (if any) mercury

standard would apply to the Industr y during a subsequent rulemaking.

In response to EPA’s Notice of Reconsidera tion identified in the December 20, 2006 Federal

Register Notice, the Portland Ce ment Association (PCA) and its member companies sponsored a

test program to quantify mercury concentra tions upstream and downstream of limestone

scrubbers.

Many rounds of discussions were held between PCA, Emission Monitoring Inc. (EMI) and EPA

regarding which test method would be employed. Fi nal negotiations resulted in the selection of

two methods to be used simultaneously to prov ide the requisite information; Method 30B, and a

method referred to as “FAMS”. Both methods employ adsorbent media to collect mercury.

Method 30B produces a total mercury result and the FAMS method produces results for

particulate, oxidized and elemental mercury species. (PM bound Hg was quantified by FAMS,

but not really of concern to the overall project.)

Four individual plants having a total of five scrubber controlled kilns were tested from July

through December 2007. Air Sampling Associated Inc. (ASA - Lewisville, TX) performed the

testing under the direction of Dr. Laura Kinner of EMI.

The facilities, and geographic lo cations presented in the order of testing are as follows:

**** Lehigh North (1-kiln, SNCR, ESP, Sc rubber) Mason City, Iowa, July 2007

**** Holcim US (1-kiln, FF, Scrubber), Florence, Colorado, July 2007

**** Holcim Texas LP (2-kilns, SNCR, FF, Scr ubber) Midlothian, Texas, October 2007

**** Texas Industries (1-kiln, FF, Scrubber, RT O*) Midlothian, Texa s, December 2007

o Testing did not involve RTO

All of the plants were contem porary pre-heater/precalciner py roprocessing systems having inline raw mills. All facilities used a fabric filt er system for PM removal upstream of the scrubber

with the exception of Lehigh North which uses an ESP. The scrubbers were installed by the

facilities to control sulfur dioxi de and other acid gases. The Lehigh and the Holcim Midlothian

facilities also employed SNCR for NOx abatement during these tests.

Testing was conducted during two distinct proces s operating conditions; with the in-line raw mill

operating and while not operating. Testing using EPA Method 30B and the FAMS method for

# 2 

# speciated mercury compounds was conducted simu ltaneously upstream and downstream of the

scrubbers.

Complete reports including descri ptions of the sampling locations, results of all quality assurance

activities and supporting data for each plant were prepared by ASA and reviewed by EMI.

These reports were submitted to the PCA as th ey became finalized, and entire report package

was submitted in February 2008 to Keith Barnett of the US EPA.

This document presents an ove rall summary of the results an d provides conclusions from the

testing program that are not provided in the ASA reports.

# 3 

# 2.0 EXECUTIVE SUMMARY

Testing was performed to determine the total mercury and speciated mercury concentrations

upstream and downstream of the limestone scrubber s, and to determine th e scrubber’s affect on

the mercury speciation and removal. Two distin ct modes of process operation were tested; inline raw mill on and off.

During raw mill on operation, four of the five kilns tested had total Hg concentration levels of

less than 10ug/m 3 

# at the stack or scrubber outlet. Ra w mill off operation always produced higher

stack concentration levels which ranged from15 ug/m 3 

# to 50 ug/m 3 

# for the facilities tested.

The following presents the pertinent results a nd observations from th is testing program.

1. During raw mill on operation,

a. the Lehigh North facility and the Holcim Portland facility exhibited negative Hg T



# removal across the scrubber indicating oxid ized mercury conversion to elemental

mercury with subsequent re-emi ssion of elemental mercury,

b. the Holcim Midlothian Kiln #2 exhibited minimal Hg T 

# removal in the range of 4-

11%,

c. the Holcim Midlothian K iln #1 and the TXI kiln had Hg T 

# removal efficiencies of

from 22-38%,

d. The cement plants operate with raw mill on approximate ly 80-90% of the time,

and the scrubbers were observed to ha ve minimal effect on mercury control

during this process condition.

2. During raw mill off operation,

a. All kilns exhibit some amount of Hg removal which is directly proportional to the

inlet Hg +2 

# concentration levels.

b. The amount of removal ranged from 58% (TXI) to 93% (Holcim Portland)

reflective of corresponding inlet Hg +2 

# concentration levels.

c. The cement plants operate with raw mill off approxima tely 10-20% of the time,

and much of the oxidized mercury captur ed during this process condition is

gradually reconverted back to elemen tal mercury and released back to the

atmosphere during raw mill on operation.

# 4 

# 3.0 Discussion of Findings

3.1 Method Comparison

Comparisons between EPA Method 30B and the FAMS method based on total mercury catch

were comparable for inlet locations.

Because of the design of the FAMS probes, th e method was found to be better suited for dry

stack sampling.

Inlet sample results for the FAMS are not in que stion except for TXI (which was a “wet” sample

location due to its proximity to the scrubber itself), but some of the outlet FAMS results for the

kilns tested are in question eith er because of water droplets en tering the probe, or because the

probes had to be operated at elevated temperat ure to prevent water droplet entrainment which

caused problems with mercury capture on th e appropriate section of the trap.

3.2 Effect of Raw Mill Operation

Overall, oxidized mercury was observed to be captured by the scrubbe rs during raw mill off

operation (positive removal), and elemental mercury was observed to be released during raw mill

on operation (in many cases negative removal for total Hg was observed across the scrubber). In

most cases, elemental Hg was higher at the scru bber outlet than scrubbe r inlet during raw mill on

testing.

The in-line raw mill has a tremendous affect on both mercury speciation and concentration. The

in-line raw mill acts as a dry scrubber for oxidized mercury much as it does for sulfur dioxide

and certain other compounds. When the raw mill is operating, the kiln feed materials adsorb the

oxidized mercury and thus reduce mercury levels at the stack exit. When the raw mill is not

operating (i.e., periods of routine maintenance or malfunction), the natural scrubbing does not

occur. Additionally, previously s ilo’d material is used for kiln feed thus releasing previously

sequestered mercury.

Scrubber inlet concentrations for raw mill off versus raw mill on were observed to be 40-50

times greater in some circumstances. The in-line raw mill and silo system sequester the

oxidized mercury and subsequently release much of it back to the effluent during raw mill

off conditions.

# 5 

# 3.3 Effect of Scrubbers

The scrubbers were observed to reduce the am ount of oxidized mercury during raw mill off

operation since this compound is water soluble. In most cases, re-emission was observed across

the scrubbers during raw mill on operation as observed by higher elemental mercury at the outlet

than at the inlet to the scrubber. Re-emission is a phenomena encountered in the utility industry

as well 1 

# . It occurs when oxidized mercury captured by the scrubber is reduced back to elemental

mercury in the alkaline conditions encountered in the scrubber liquo r. The elemental mercury is

not water soluble and thus it is stripped out of the scrubber liquor and re leased back into the

effluent. The scrubber system sequesters the oxidiz ed mercury, with release of elemental

mercury back to the stack effluent. This is particularly evident during mill on conditions.

Together the two competing phenomena create a dynamic equilibrium between capture and

release of mercury compounds.



# 4.0 SUMMARY OF TOTAL MERCURY RESULTS – METHOD 30B

Table 4-1 presents the results for each facility in terms of total mercury, and range of calculated

mercury removal. These results are derived fr om Method 30B results only, FAMS speciated

results are presented in Section 5.

For raw mill on operation the results have been: 1) corrected for spike recovery and, 2) the

precision of the paired results were used to pres ent the range of possible percent Hg removal.

The apparent removal during mill on operation was either a negative number of a very low

percentage removal.

The correction of raw mill on results for bias ba sed on spike recovery is possible and plausible

since the spike levels were very close to the actual effluent concentrations. Appendix A

presents the application of spik e correction, and the statistical an alyses employed. Note that in

some cases the precision was excellent and theref ore contributed little in the error analyses

presentation.

Raw mill off operation did not employ a spike correction or statistical analyses of the data for

two reasons. First the spike correction for bi as could not be determined at the stack

concentrations encountered during mill off (spike le vels were simply too low to employ for this

purpose), and secondly, there appears to be actu al Hg removal during raw mill off operation due

to the elevated Hg +2 

# observed during this process condition.

1 

# Ghorishi, B., Downs, B., & Renninger, S., “Role of Sulfides in Sequestration of Mercury by Wet Scrubbers,”

EPRI/DOE/EPA/AWMA Combined Symposium on Power Plant Air Pollution Control, Baltimore, MD. August 28

‐ 31,

2006.

# 6 

# TABLE 4-1 PCA-Hg Scrubber Project Results Summary

MILL ON



# Method 30 B Results Inlet

Hg T 

# Outlet

Hg T 

# % Removal % Removal Range

Facility ug/m 3 

# ug/m 3 

# ug/m 3 

# 2-SIGMA

Lehigh North 16.7 18.8 -13%

Spike Corrected 17.5 21.1 -20% - 56% to 9%

Holcim Portland 1.2 2.8 -133%

Spike Corrected 1.2 2.7 -120% - 188% to -72%

Holcim Midlothian - K#1 4.2 2.9 31%

Spike Corrected 4.1 2.6 38% 31% to 38%

Holcim Midlothian - K#2 7.3 6.5 11%

Spike Corrected 6.6 6.4 4% 4% to 11%

TXI 4.9 3.6 27%

Spike Corrected 4.8 3.6 26% 23% to 29%

MILL OFF



# Method 30 B Results Inlet

Hg T 

# Outlet

Hg T 

# % Removal

Facility ug/m 3 

# ug/m 3 

# ug/m 3



# Holcim Portland 193.0 14.0 93%

Holcim Midlothian - K#1 182.0 22.0 88%

Holcim Midlothian - K#2 180.0 50.0 72%

TXI 96.0 40.0 58%

Note that all concentration resul ts are normalized to 7% oxygen

# 7 

# 5.0 FAMS Results

Table 5-1 presents the FAMS testing results fo r speciated mercury on a plant-by-plant basis.

Suspect data are high lighted in yellow.

Some of the FAMS outlet data were questiona ble for two reasons; 1) liquid water droplets

solublized oxidized mercury from the potassium chloride (KCl) media and transported it through

the trap as was noted in the Lehigh North scr ubber outlet data, and 2) elevated temperatures

employed to eliminate water droplet collection resulted in oxidized merc ury being transported

through the trap. This phenomenon was noted in the Holcim Midlothian and TXI scrubber outlet

data where there is an apparent reduction of elemental mercury as indicated by the FAMS data.

This occurs when the mercury originally capt ured on the KCl section (designed to capture

oxidized mercury) of the FAMS trap is desorb ed at elevated temperature and then carried

through to the carbon (section of the trap for elem ental Hg) and thus counted as inappropriately

counted elemental mercury.

Questionable FAMS data are flagged in yellow.



# Table 5-1 Results Summary

Mill On

ug/m 3 

# at 7% O 2 

# Inlet Results Outlet Results Removal



# Facility Hg p 

# Hg +2 

# Hg 0 

# Hg p 

# Hg +2 

# Hg 0 

# Hg p 

# Hg +2 

# Hg 0



# Lehigh North 0.06 0.61 11.60 0.50 5.51 20.17 -804% -

800% -74%

Holcim Portland 0.03 0.48 0.48 0.05 0.13 1.74 -61% 74% -258%

Holcim Midlothian - K#1 0.04 1.31 2.94 0.05 0.02 3.06 -20% 99% -4%

Holcim Midlothian - K#2 0.05 4.06 1.85 0.01 0.04 3.90 83% 99% -111%

TXI 0.05 0.42 3.49 0.02 0.05 2.25 67% 88% 36%

Mill Off

ug/m 3 

# at 7% O 2 

# Inlet Results Outlet Results Removal



# Facility Hg p 

# Hg +2 

# Hg 0 

# Hg p 

# Hg +2 

# Hg 0 

# Hg p 

# Hg +2 

# Hg 0



# Holcim Portland 2.74 165.52 0.67 0.50 2.20 6.51 82% 99% -865%

Holcim Midlothian - K#1 0.29 59.22 93.27 0.02 0.01 17.80 94% 100% 81%

Holcim Midlothian - K#2 0.78 73.16 33.26 0.05 0.08 38.81 93% 100% -17%

TXI 0.03 0.33 84.68 0.11 0.18 27.24 -229% 46% 68%

Yellow at inlet indicates a suspect error in speciated results. Likely that it is mostly oxidized

based on the percent removal indicated.

# 8 

# 6.0 CONCLUSIONS

**** The in-line raw mill acts as a dry scrubber for oxidized mercury,

**** During raw mill off operation, oxidized mercury is not captured in the raw mill, but is

removed by the limestone scrubber,

**** During raw mill on operation, mercury (cap tured by the scrubber during mill off

operation) is released back to the atmo sphere because of mercury reduction (Hg +2 

#  Hg 0 

# )

and re-emission,

**** Together, the in-line raw mill, raw feed storage system, and limestone scrubbers

sequester and release mercury from th e process in a complex equilibrium.

**** Method 30B and the FAMS test methods provided comparable results where good FAMS

data were available for comparison,

**** Some simple modifications to the FAMS me thod could improve its function in wet stack

applications. For example, a probe that heat s uniformly and that is designed to reject

water droplets could be designed.

# A 

# APPENDIX A

Analyses of Mill On Results – Bias Correction and Statistics

# PCA Scrubber Test Program - Accuracy and Precision Results

**MILL ON**

Facility Lehigh North Holcim PD Holcim TX #1 Holcim TX #2 TXI

**Avg. Stack Concentration** ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3



# Inlet 16.7 1.2 4.2 7.3 4.9

Outlet 18.8 2.8 2.9 6.5 3.6

Apparent % Removal -13% -133% 31% 11% 27%

**Spike Accuracy** Percentage Percentage Percentage Percentage Percentage

Inlet % Recovery 95 97 102 109 102

Outlet % Recovery 88 103 112 102 101

**Spike Levels (conc. Eq.)** ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3



# Inlet 32 5 13 13 6.7

Outlet 13 5 13 13 6.7

Precision

**Average of Paired Differences** ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3



# Inlet 1.6 0.0 0.0 0.0 0.1

Outlet 2.0 0.0 0.2 0.0 0.1

**Stdev of Pair Differences** ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3



# Inlet 1.0 0.1 0.0 0.0 0.0

Outlet 1.6 0.1 0.0 0.0 0.1

**Standard Error of Pair Differences** ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3



# Inlet 0.45 0.05 0.00 0.00 0.01

Outlet 0.72 0.05 0.00 0.00 0.02

2 Sigma (95% coverage)

Inlet 2.00 0.22 0.00 0.00 0.04

Outlet 3.20 0.22 0.00 0.00 0.11

**Analyses done with duplicates analyses ("Pairs") from five trains (10 samples)**

**Pair difference is absolute amount each results differs from pair average = abs(X-Y)/Avg.**

Note - all concentration results are normalized to 7% oxygen

# LEHIGH NORTH - MILL ON - Error Analyses of Results Error Bars Error Bars Worst Case Best Case

Lehigh North Corrected for Spike SE 2 Sigma Range of Possible Results

Avg. Stack Concentration ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3



# Inlet 16.7 17.5 0.45 2.00 15.5 19.5

Outlet 18.8 21.1 0.72 3.20 24.3 17.9

Apparent % Removal -13% -20% -56% 9%

Spike Accuracy Percentage

Inlet % Recovery 95

Outlet % Recovery 88

Spike Levels (conc. Eq.) ug/m 3



# Inlet 32

Outlet 13

Precision

**Average of Paired Differences** ug/m 3



# Inlet 1.6

Outlet 2.0

**Stdev of Pair Differences** ug/m 3



# Inlet 1.0

Outlet 1.6

Error Bars

**Standard Error of Pair Differences** ug/m 3



# Inlet 0.45

Outlet 0.72

2 Sigma (95% coverage)

Inlet 2.00

Outlet 3.20

# Holcim Portland - MILL ON - Error Analyses of Results

Error Bars Error Bars Worst Case Best Case

Holcim PD Corrected for Spike SE 2 Sigma Range of Possible Results

**Avg. Stack Concentration** ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3



# Inlet 1.2 1.2 0.04 0.22 1.0 1.5

Outlet 2.8 2.7 0.04 0.22 2.9 2.5

Apparent % Removal -133% -120% -188% -72%

**Spike Accuracy** Percentage

Inlet % Recovery 97

Outlet % Recovery 103

**Spike Levels (conc. Eq.)** ug/m 3



# Inlet 5

Outlet 5

Precision

**Paired Results Difference from Avg.** ug/m 3



# Inlet 0.0

Outlet 0.1

**Stdev of Pair Differences** ug/m 3



# Inlet 0.1

Outlet 0.1

**Standard Error of Pair Differences** ug/m 3



# Inlet 0.04

Outlet 0.04

2 Sigma (95% coverage)

Inlet 0.22

Outlet 0.22

**Analyses done with paired run results from six trains (12 samples)**

**Difference from average is the difference between results of each pair (n = 6 pairs)**

**Variance is the square of the standard deviation and is a value that can be added and subtracted**

**Subtracting the variance of the paired sample results from the variance of the paired differences allows**

# Holcim Midlothian #1 - MILL ON - Error Analyses of Results

Error Bars Error Bars Worst Case Best Case

Facility Holcim TX #1 Corrected for Spike SE 2 Sigma Range of Possible Results

**Avg. Stack Concentration** ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3



# Inlet 4.2 4.1 0.00 0.00 4.1 4.1

Outlet 2.9 2.6 0.00 0.00 2.6 2.6

Apparent % Removal 31% 38% 38% 38%

**Spike Accuracy** Percentage

Inlet % Recovery 102

Outlet % Recovery 112

**Spike Levels (conc. Eq.)** ug/m 3



# Inlet 13

Outlet 13

Precision

**Paired Results Difference from Avg.** ug/m 3



# Inlet 0.0

Outlet 0.2

**Stdev of Pair Differences** ug/m 3



# Inlet 0.0

Outlet 0.0

**Standard Error of Pair Differences** ug/m 3



# Inlet 0.00

Outlet 0.00

2 Sigma (95% coverage)

Inlet 0.00

Outlet 0.00

**Analyses done with paired run results from five trains (10 samples)**

**Difference from average is the difference between results of each pair (n = 5 pairs)**

**Variance is the square of the standard deviation and is a value that can be added and subtracted**

**Subtracting the variance of the paired sample results from the variance of the paired differences allows**

# Holcim Midlothian #2 - MILL ON - Error Analyses of Results

Error Bars Error Bars Worst Case Best Case

Facility Holcim TX #2 Corrected for Spike SE 2 Sigma Range of Possible Results

**Avg. Stack Concentration** ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3



# Inlet 7.3 6.6 0.00 0.00 6.6 6.6

Outlet 6.5 6.4 0.00 0.00 6.4 6.4

Apparent % Removal 11% 4% 4% 4%

**Spike Accuracy** Percentage

Inlet % Recovery 109

Outlet % Recovery 102

**Spike Levels (conc. Eq.)** ug/m 3



# Inlet 13

Outlet 13

Precision

**Paired Results Difference from Avg.** ug/m 3



# Inlet 0.0

Outlet 0.0

**Stdev of Pair Differences** ug/m 3



# Inlet 0.0

Outlet 0.0

**Standard Error of Pair Differences** ug/m 3



# Inlet 0.00

Outlet 0.00

2 Sigma (95% coverage)

Inlet 0.00

Outlet 0.00

**Analyses done with paired run results from five trains (10 samples)**

**Difference from average is the difference between results of each pair (n = 5 pairs)**

**Variance is the square of the standard deviation and is a value that can be added and subtracted**

**Subtracting the variance of the paired sample results from the variance of the paired differences allows**

# TXI - MILL ON - Error Analyses of Results

Error Bars Error Bars Worst Case Best Case

Facility TXI Corrected for Spike SE 2 Sigma Range of Possible Results

**Avg. Stack Concentration** ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3 

# ug/m 3



# Inlet 4.9 4.8 0.01 0.04 4.8 4.8

Outlet 3.6 3.6 0.02 0.11 3.7 3.5

Apparent % Removal 27% 26% 23% 29%

**Spike Accuracy** Percentage

Inlet % Recovery 102

Outlet % Recovery 101

**Spike Levels (conc. Eq.)** ug/m 3



# Inlet 6.7

Outlet 6.7

Precision

**Paired Results Difference from Avg.** ug/m 3



# Inlet 0.1

Outlet 0.1

**Stdev of Pair Differences** ug/m 3



# Inlet 0.0

Outlet 0.1

**Standard Error of Pair Differences** ug/m 3



# Inlet 0.01

Outlet 0.02

2 Sigma (95% coverage)

Inlet 0.04

Outlet 0.11

**Analyses done with paired run results from five trains (10 samples)**

**Difference from average is the difference between results of each pair (n = 5 pairs)**

**Variance is the square of the standard deviation and is a value that can be added and subtracted**

**Subtracting the variance of the paired sample results from the variance of the paired differences allows**

# B 

# APPENDIX B

S elect Charts

# 0 5 10 15 20 25 30

Lehigh North Holcim Portland Holcim Midlothian

- K#1 Holcim Midlothian

- K#2 TXIug/m3@7% O2



# Facility 

# Mill On Comparisons

Total Hg Concentrations

30B INLET

FAMS INLET

30B OUTLET

FAMS OUTLET

# 0 20 40 60 80 100 120 140 160 180 200

Holcim Portland Holcim Midlothian

- K#1 Holcim Midlothian

- K#2 TXIug/m3 @ 7% O2



# Facility 

# Mill Off Comparisons

Total Hg Concentrations

30B INLET

30B OUTLET

FAMS INLET

FAMS OUTLET

# 0.00 2.00 4.00 6.00 8.00 10.00 12.00

Lehigh North Holcim Portland Holcim Midlothian

- K#1 Holcim Midlothian

- K#2 TXIug/m3 @ 7% O2



# Facility 

# Inlet Speciated FAMS Results

Hg p

Hg 0

Hg +2

# 0.00 2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00

Lehigh North Holcim Portland Holcim Midlothian

- K#1 Holcim Midlothian

- K#2 TXIug/m3 @ 7% O2



# Facility 

# Speciated Outlet Mill On

Hg p

Hg 0

Hg +2



# Suspect due to water droplets

# 0.00 20.00 40.00 60.00 80.00 100.00 120.00 140.00 160.00

Holcim Portland Holcim Midlothian

- K#1 Holcim Midlothian

- K#2 TXIug/m3 @ 7% O2



# Facility 

# Speciated Inlet Mill Off

Hg p

Hg 0

Hg +2

# 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00

Holcim Portland Holcim Midlothian

- K#1 Holcim Midlothian

- K#2 TXIug/m3 @ 7% O2



# Facility 

# Speciated Outlet Mill Off

Hg p

Hg 0

Hg +2GoalsofMeeting•Thefactsofdustshuttlingasweknowittoday–Whatweknow–Whatwedon’tknow•ActualDustShuttlingExperience–DataonshuttlingformercuryfromGermany–LehighUnionBridge–LehighTehachapi–AshGroveDurkee•ImplicationsforthefinalPCMACTmercurystandardTherearemanyvariablesthatmayinfluencemercurycontrol•Oxidizedvs.Elemental•RawMillTemperature•Baghouse DusttoRawMaterialRatio•DustShuttlingLimitationstoCement•Others?LehighExperience•UnionBridge–Shuttling(<3%)resultsin~40%mercuryremoval–ACIintothemainbaghouse,plusshuttling,notyetdemonstrated•Ifcarbonaddedwhenrawmillon,expecttoincreasemercuryconcentrationinthebaghouse dust•Tehachapi–Shuttlingexpectedtoresultin<10%mercuryremoval–ACInotyettriedDurkee RawMaterialtoDustRatio•Durkee BHdustRawMill(RM)onis50ppm•Durkee RawFeed(RF)isabout1.2ppm•Durkee Dust/RFratiois42whichindicates90%mercuryenrichmentfactor•EnrichmentFactor=Hgconc.RawMillAPCDDustHgconc.InRawFeedGossman Datavs.PCAStudy•SchreiberPCAstudy(1)indicated30‐70%systemremovalefficiency(SRE)‐11kilnsofvarioustypes•Gossman paperindicatesonekilnwithashighas99%butstudydonewithmostlyspikeddataathazardouswastecombustors(1)InherentMercuryControlswithinthePortlandCementKilnSystem,2005Dr.ClarkMercurySeminar•ModelbasedonChlorineAlkalibuildupintower•If99%SREinRawMillthenupto75‐83%removalbywasting3%dust•If90%SREinRawmillthen30%removalbywasting3%dust•SchreibermodelofDurkee indicatesapproximately30%removalata3%dustshuttling•BothmodelstendtoagreewhenpercentSREisdefinedCriticalFactorinDr.Clark’sFormula•99%SREwouldmeanaratioof100Dust/RFmercuryenrichmentfactor•EPA114datashowsthisisrarePHKilnswithEnrichmentFactor<3500501001502002503003500 10 20 30 40PH KilnsAllPHKilns‐EnrichmentFactor01002003004005006007000 10 20 30 40 50PH KilnsUnion Bridge =625Durkee = 42Tehachapi = 7.5AllKilnsEnrichmentFactor<3500501001502002503003500 20 40 60 80 100All KilnsAllPHKilnsStatistics•Averageratiois85•Medianratiois12•Stdeviationis168•Mostratiosbelow40Durkee ShuttlingModeled•2.14%or2.7tph•25%reductionfromshuttling•Adjustedfor66%groundonsite•Yields16.5%reduction•Uncertaintyremainsonbestshuttlingperiod:–RawMillOnaverage50ppm (range21to84)–RawMillOffaverage23ppm (range12to58)Durkee EffectiveMercurySRE•1000poundsmercuryperyear•Less16.5%controlfromshuttling•835poundsbalance•85%controlbyactivatedcarbon•Balance125.25poundsmercuryperyear•87.5%effectivecontrolAmountofDustThatCanBeShuttledisSiteSpecificThe range of dust shuttling at Ash Grove’s plants is 0.4% to3.0% based on meeting quality specifications. Four plantsare limited by IR, two plants are limited by LOI ,a two plantsare limited by Alkali limitations.CurrentSituation•WeareconcernedthatEPAmaybemovingtowardssettingastandardwithoutthecontroltechnologydemonstrationneededtosupportaspecificlevelofcontrol•Optimizationstudyneededtodemonstrateactualcontrolthatcanbeachievedbydustshuttling•Weagreethatshuttlingwillcontrolmercury,butextentofcontroliscurrentlyunknownDustShuttlingSummary•ShuttlingwillprovideadditionalcontroloverACIalone•Howmuchwillvarysignificantlybyplant•Technologyisstillunderdevelopment•Industrycanagreetomaximizeitscontrolefficiencyateachplant•IndustrycannotsupportaspecificpercentcontrolatthistimeControlOptionsConsidered•SelectiveQuarrying•LimestoneScrubbing•OxidizingTechniques(SCR,HalogenatedCarbon)•ImportingLimestone•Scrubbers•CKDTreatment/FLSmidth LimestoneRoaster•ACI•DustShuttlingBestBeyondtheFloorPackage(1of4)•>225ppbsubcategorymustinstallACI–75%minimumSRE–ImplementControlEnhancementActionPlantomaximizebenefitsofACI•Requireallreasonablemeasurestomaximizeperformance•RecurringassessmentofwhetherSREexceeds85%–Dutytoreassessinjectionratesandotherreasonablemeasures•Ensurescontinuousimprovementeffortstoreach85%BestBeyondtheFloorPackage(2of4)•ReduceHgenteringcyclefromoffsitematerials–RequireMercuryMinimizationPlan•Prohibituseofflyashinrawfeed•EvaluateandminimizeHginotherimportedmaterials•Requiredustshuttlinguptomaximumlevelachievablewithoutimpactingproductquality–Requiresitespecificevaluation:•Documentmaximizationofshuttling•DocumentoptimaltimingofdustbleedBestBeyondtheFloorPackage(3of4)•Couldresultin90%+SRE–Untiloptimizedatindividualplant,notclearwhatcombinationcanachieve–ThisapproachputsemphasisonoptimumpossibleHgreductionateachplantBestBeyondtheFloorPackage(4of4)•ThisapproachenablesAshGrove&Lehighto:–Employ“thebestcontroltechnologycurrentlyavailablesofarasisknown”–EmploytheonlycontroltechnologyknowntobeeffectiveonallformsofHg–KeepjobsintheU.S.–AvoidemissionsassociatedwithimportedcementConclusions•Proposedresolutionensures:–Protectionofenvironment–CompliancewithCleanAirAct–Protectionofjobsandcommunity•Avoidsoffshoring jobstocountry’swithpoorercontrols•IfplantssuchasDurkee &Tehachapiclose,theWesternU.S.willmeetcementdemandthroughimports•WhatisEPAthinkingaboutthisapproach?•WhatadditionalinformationdoesEPAneed?•NextstepsQuestions?