ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 1 of 61 Marietta, Ohio, Source

- Receptor Study: Results and InterpretationATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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- Receptor Study: Results and Interpretation 

### CONTENTS

EXECUTIVE SUMMARY

................................ ................................ ................................ .............. 5

INTRODUCTION

................................ ................................ ................................ ................ 5 BACKGROUND

................................ ................................ ................................ .................. 5 SUMMARY OF FINDINGS

................................ ................................ ................................ 8

LABORATORY ACTIVITIE S

................................ ................................ ................................ ...... 10

SAMPLE RECEIPT AND D ESCRIPTION

................................ ................................ ...... 10 ANALYSIS OF SAMPLES/ ANALYTICAL BACKGROUN D

................................ ....... 11 GENERAL SAMPLE PREPA RATION

................................ ................................ ............ 13 ELEMENTAL ANALYSIS

................................ ................................ ............................... 14 Acid Digestion

................................ ................................ ................................ .............. 14 Inductively Coupled Plasma Optical Emission Spectroscopy

................................ ..... 14 Inductively Coupled Plasma Mass Spectrometry

................................ ......................... 14 LEAD ISOTOPE RATIO M EASUREMENTS

................................ ................................ . 14 Sample Preparation

................................ ................................ ................................ ....... 14 Column Separation

................................ ................................ ................................ ....... 15 Multi

- Collector Inductively Coupled Plasma Mass Spectrometry

............................... 15 SCANNING ELECTRON MI CROSCOPY

................................ ................................ ...... 16

LABORATORY RESULTS

................................ ................................ ................................ .......... 17

ELEMENTAL ANALYSES

................................ ................................ .............................. 17 LEAD ISOTOPE RATIO M EASUREMENTS

................................ ................................ . 21 SEM ANALYSIS

................................ ................................ ................................ ............... 24

DISCUSSION OF ANALYT ICAL RESULTS FOR TSP FILTERS AND FACILITY SAMPLES

................................ ................................ ................................ ... 31

LASER ABLATION RESPO NSES FOR MANGANESE I N RELATION TO WIND DIRECTION

................................ ................................ .............................. 31 TIME SERIES TRENDS O F MANGANESE LASER AB LATION RESPONSES

......... 37 COMPARISON OF ELEMEN TAL RESULTS FOR AIR FILTERS AND F ACILITY SAMPLES

................................ ................................ ................................ . 40 DISCUSSION OF LEAD I SOTOPE RATIOS

................................ ................................ .. 46 DISCUSSION OF SEM RE SULTS

................................ ................................ ................... 51

SUMMARY AND CONCLUSI ONS

................................ ................................ ............................. 55

REFERENCES

................................ ................................ ................................ ............................... 58ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### CONTENTS

— continued TABLES

1 The Seven N EIC Reports Comprising t he Airborne Manganese Source

- Receptor Study

... 6 2 Collection Date a n d Location o f 24 Facility Samples Collected b y N EIC Field Branch Personnel

................................ ................................ ................................ ............................ 10 3 Elemental Results for Facility Samples Extracted b y E PA Method I O

- 3.1 a nd Analyzed b y I CP

- O ES

................................ ................................ ................................ ........................ 17 4a Lea d Isotope Ratio Determinations f or T SP Filters

................................ ........................... 21 4 b Lea d Isotope Ratio Determinations f or Facility Sample s

................................ .................. 23 4 c Lea d Isotope Ratio Determinations f or Reference Material s

................................ ............. 24 5 Summary o f S EM data o f Manganese

- Bearing Particle s i n Facility Samples

................... 26 6 Results Summary

................................ ................................ ................................ ................ 55

FIGURES

1a SEI image of spherical Mn

- oxide particle with a 6.6

- μ m geometric diameter in sample of MOR heavies (ERM10) collected from Eramet in March 2009

................................ ........ 27 1b SEI image of spherical Mn

- oxide particle with a 4. 9

- μm geometric diameter in sample of MOR baghouse dust (ERM11) collected from Eramet in March 2009

............................. 27 2 a SEI image of angula r Mn

- oxide particle with an 8.3

- μm geometric diameter in s ample of beam dust above casting sands in furnace 1 building (ERM05) collected from Eramet in March 2009

................................ ................................ ................................ ......................... 28 2b SEI image of angular M n

- Si

- oxide particle with an 8.1

- μm geometric diameter in sample of C2P crusher baghouse dust (ERM02) collected from Eramet in March 2009

................................ ................................ ................ 28 2c SEI image of angul ar Mn

- oxide particle with a 6.5

- μm geometric diameter in sample of medium carbon FeMn ore (MIE02) collected from MIE in March 2009.

......................... 29 2d SEI image of angul ar Mn

- oxide particle with a 7.5

- μm geometric diameter in sample of electrolytic MnO 2 

### (EMD) product (EB02) collected from Energizer in March 2009

....... 29 2e SEI image of angular particle agglomeration of carbon with Mn

- oxide with a 5.8

- μm geometric diameter in sample of calcined ore (EB05) collected from Energizer in March 2009

................................ ................................ ................................ ................................ .... 30 2f SEI image of angular Mn

- bearing Al

- Fe

- sulfate particle with an 11

- μm geometric diameter in sample of jarosite skip (EB04) collected from Energizer in March 2009

....... 30 3 a Predominant wind direction from the west and west

- northwest

, with highest m anganese abundance observed (>100x) at the Boaz air monitoring site

, which was downwind from the former Union Carbide complex

................................ ................................ .................... 33 3b Predominant wind direction from the north

- northeast and northeast

, with highest manganese abundance observed (>25x) at the Neale Elementary School air monitoring site, which was downwind from the former Union Carbide complex and the MIE site

.... 3 4 3c Predominant wind direction from the east

- southeast

, with highest manganese abundance observed (7 x) at the Blue Knob Road air monitoring site, which was downwind from the former Union Carbide complex but not the MIE site

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### CONTENTS

— continued FIGURES

-- continued

3d Predominant wind direction f rom the south and south

- southwest

, with highest manganese abundance observed (>46x) at the Washington County Career Center air monitor ing site, which was do wnwind from the former Union Carbide complex and the MIE site

............ 3 6 4 a Time series trends of manganese abundance at two air monitoring sites northeast of the former Union Carbide complex. The Washington County Car eer Center sit e was fa rther from the Union Carbide complex than the Harmar Village site (designated sampler)

...... 38 4b Time series trends of manganese abundance at two air monitoring sites on opposing sides of the former Union Carbide complex. The Harmar Village (designated sampler) and Neale Elementary School air monitor ing sites were each approximately 4 miles from the former complex in the northeast and southwest directions, respectively

........................... 39 4c Time series trends of manganese abundance at two air monitoring sites on opposing sides of the former Union Carbide Complex complex. The Boaz and B lue Knob air monitor ing sites were approximately 1 mile from the former complex in the east and west

- northwest directions, respectively

................................ ................................ ................................ ....... 40 5 Elemental abundances shown as a relative fraction to manganese for TSP filters with the ten highest manganese concentrations

................................ ................................ ............... 41 6 a Elemental a bundances shown as a relative fraction to manganese fo r samples collected at Energizer and MIE.

................................ ................................ ................................ ............ 42 6b Elemental a bundances shown as a relative fraction to manganese fo r samples collected at Eramet

. ................................ ................................ ................................ ............................... 43 7 Eramet’s f urnace 12 during tapping releasing an abundance of evaporating metal fu me (gas) that is cooling and condensing as it rises

................................ ................................ .. 46 8 Lead isotope ratios for TSP filters and facility samples from Eramet, Energizer, and MIE

................................ ................................ ................................ ................................ ..... 50 9 a S EI image of spherical Mn

- oxide particle with a 2.1

- μm geometric diameter on filter G3009919 collected at Neale Elementary School on May 12, 2007

................................ .. 52 9 b SEI image of spherical Mn

- oxide particl e with a 4.9

- μ m geometric diameter in sample of MOR baghouse dust (ERM11) collected from Eramet in March 2009

............................. 52 9 c SEI image of spheric al Mn

- oxide particle with a 2.6

- μ m geometric diameter in sample of dust from furnace 1, 2 nd 

### level column (ERM04) collected from Eramet in March 2009

... 53 9d SEI image of spherical Mn

- oxide particle with a 4.5

- μm geometric diameter in sample of dust from furnace 18, 2 nd 

### level beam (ERM07) collected from Eramet in March 2009

.... 53 9e SEI image of spher ica l Mn

- oxide particle with a 14.0

- μm geometric diameter in sample of dust from furnace 12, west beam (ERM08) collected from Eramet in March 2009

.......... 5 4

This Contents page shows all of the sections contained in this report and provides a clear indication o f the end of this report.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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## EXECUTIVE SUMMARY

INTRODUCTION

On May 22, 2000, the Federal Agency for Toxic Substances and Disease Registry (ATSDR) 1



### BACKGROUND was petitioned by the director of the Ohio Environmental Protection Agency (Ohio EPA) to evaluate potential health impacts of air pollution on residents of Marietta, Ohio. Ohio EPA has historically collected total suspended particulate (TSP) data from tw o locations in the Marietta area and demonstrated that airborne particulate matter containing manganese (Mn) has routinely exceeded the current ATSDR health

- based comparison value (0.04 micrograms per cubic meter [μg/m 3 

### ] [U.S. Department of Health and Human Services [HHS], 2010]) as well as the U.S. Environmental Protection Agency (EPA) reference c oncentration (RfC) value (0.05 μg/m 3 

### [U.S. EPA, 2011]). EPA Region 5, Ohio EPA, and ATSDR determined that the potential emitters of manganese

- bearing airborn e particulate matter in the Marietta, Ohio, area were Eramet Marietta, Inc. (Eramet), Energizer Battery Manufacturing (Energizer), and Marietta Industrial Enterprises (MIE). EPA’s National Enforcement Investigations Center (NEIC) was requested by EPA Regi on 5 to conduct a source

- receptor study to determine the source or sources of the

manganese

- bearing airborne particulate matter.

NEIC involvement in this project began in 2003, when elevated ambient air levels of manganese and the distribution o f manganese

- bearing airborne particulate matter were not yet fully understood. NEIC was initially asked to determine if particulate matter from a Washington County Career Center (Career Center) welding shop could be responsible for the elevated levels
of manganese found on TSP air filters at the Career Center site. NEIC characterized particulate matter on TSP filters collected from March 2001 through July 2002. NEIC’s Field Branch collected welding dust from within the Career Center welding shop, ventila tion systems, and exhaust vents on the roof. The welding shop dust was characterized and compared to the TSP filter particulate matter. NEIC concluded that the Career Center welding shop dust was not a significant source of manganese on the TSP filters. Abundant spherical particles of nearly pure

manganese

- oxide (Mn

- oxide) on the TSP filters were consistent with a manufacturing origin involving the high

- temperature treatment of nearly pure manganese and were inconsistent with a welding shop origin. The relevant data and interpretations were presented in NEIC reports NEICVP0591E01, NEICVP0591E02, and NEICVP0591E03 in October 2004, December 2004, and September 2005, respectively (Table 1).

1 The Agency for Toxic Substances and Disease Registry (ATSDR) , based in Atlanta, Georgia, is a F ederal public health agency of the U.S. Department of Health and Human Services

. http://www.atsdr.cdc.gov/ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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. THE SEVEN NEIC REPORTS COMPRISING THE AIRBORNE MANGANESE SOURCE

RECEPTOR STUDY Marietta, Ohio, Source

- Receptor Study: Results and Interpretation

Report Number Date Title Contents Main Conclusion s

NEIC

VP0591E01 October 2004 Interim Results for Career Center TSP Filter Samples Initial c haracteriz ation of particulate matter on TSP filters collected at Career Center site (2001

- 2002) Mn

- rich particles on TSP filters mostly micrometer

- scale spheres of Mn

- oxide

NEIC

VP5091E02 December 2004 Interim Results for Career Center Welding Shop

Samples Collected September 18, 2003 S ampling and initial characterization of Career Center w elding s hop dust W elding s hop dust contained infrequent angular Mn

- rich particles and common spherical Ca

- Fe and Ca

- Ti

- rich particles

NEIC

VP0591E03 September 2005 Final Results and Interpretation Eramet Marietta, Inc. C haracterization of welding shop dust, ore, and facility filters / C omparisons with previously reported TSP filter data W elding shop dust not source of Mn on TSP filters

NEIC

VP0591E04 July 2008 Laser Ablation and Inductively Coupled Plasma Mass Spectrometry Analysis of Glass Fiber Filters collected at Multiple Locations in the Marietta, Ohio Area from April to October 2007 Relative e lemental characterization of particulate matter on TSP

filters collected from 5 sites in Marietta area for initial 6 months in 2007 At least one large source of Mn

- bearing

airborne particulate matter in the Marietta

area

NEIC

VP0591E05 June 2010 Eramet CAA/Mn Investigation. Marietta, Ohio Descri ption sampling and processes at th r e e Marietta area facilities None

NEIC

VP0591E06 July 2010 Results of Scanning Electron Microscopy (SEM), Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA

- ICP

- MS), and Digestion Analysis of Glass Fiber Filters Collected April 2007 to March 2008 around Marietta, Ohio Characterization of particulate matter on TSP

filters collected from 5 sites in Marietta area for

full year (2007

- 2008) Large emitter of Mn

- bearing airborne particulate matter in

the Marietta area/ M inimum risk level ( MRL ) for Mn exceed ed 95 percent of the time

NEIC

VP0591E07 April 2011 Marietta, Ohio, Source

Receptor Study: Results and Interpretation C haracterization of facility sample s , comparisons with previously reported

TSP filter data, and interpretations Eramet was the major source of Mn

- bearing

airborne particulate matter in the Marietta

area.



### In April 2007, to conduct more extensive particulate matter sampling, Ohio EPA and ATSDR put into operation five TSP air moni toring sites in the Marietta area, including the Career
Center site. Particulate matter was collected on TSP filters over 24

- hour periods every 6 days from all five TSP air monitoring sites from April 2007 through March 2008. In the fall of 2007,
NEIC wa s asked to conduct analyses of this new set of filters. By comparing laser ablation inductively coupled plasma mass spectrometry (LA

- ICP

- MS) responses for manganese from the five sites and considering prevailing wind direction, NEIC concluded that there w as at least oneATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### large source of airborne manganese particles in the Marietta area. LA

- ICP

- MS responses for other analytes indicated all TSP filters contained some common elements in similar proportions. Furthermore, analytical results for TSP filters col lected between March 2001 and July 2002 were consistent with results for filters collected between April 2007 and March 2008 (NEICVP0591E04).

In March 2009, NEIC field personnel co nducted Clean Air Act (CAA) inspections at Eramet, Energizer, and MIE n ear Marietta, Ohio. Eramet and Energizer we re located at the former Union Carbide complex about 4 miles southwest of Marietta, and MIE was located about
2 miles farther southwest. O perations at these facilities included high

- temperature, electrochemical, and grinding processes. Eramet produced manganese alloy

, and Energizer produced electrolytic manganese dioxide (EMD) for the manufacture of batteri es

. MIE conducted grinding, sizing, packaging, transportation, and storage for a wide variety of materials whi ch included, but were not limited to

, slag materials (such as manganese furnace slag and silicon (Si) dross from a silicon metal furnace); ore materials (such as iron ore); various types of carbon
materials ( such as carbon aggregate, coke, and coal ); limes tone; gra vel; sand; and deicing salt. Felman silicomanganese (SiMn) slag was crushed at MIE and stored on site for Green Global LLC (Green Global)

. During inspections of these facilities, a variety of materials were sampled, including process materials ( such as ore) and non

- airborne particulate matter (such as product material, baghouse dust, and deposits of dust within the facilities). The facility samples were collected for comparison to the manganese

- bearing airborne particulate matter collected at th e five TSP air monitoring sites. Details of the fi eld inspections and sample collection are
documented in NEIC VP0591E05.

NEIC r eport NEIC VP0591E06 documents further characterization of particulate matter on
TSP filters from all five sites , including relative elemental abundances; manganese concentrations; and manganese

- bearing particle composition, size, and shape. Th e report contains the following conclu sions : ( 1) LA

- ICP

- MS manganese concentration estimates for airborne particulate matter indicated the ATSDR minimum risk level ( MRL ) for manganese of 0.04 μg/m 3 

### was exceeded 95 percent of the time in the Marietta area; ( 2) m anganese

- bearing particles occurred mainly as manganese

- oxide spheres, consistent with a high

- temperature process producing a met al fume; ( 3) t he median aerodynamic diameter of manganese

- bearing particles
was between 3.85 and 4.06 micrometers ( μm ) , with 21 percent of the particles having an aerodynamic diameter of less than 2.5 μm; and ( 4) c orrelations of manganese with chromium (Cr ) , lead (Pb) , and zinc (Zn) on TSP filters indicated a consistent composition of manganese

- rich airborne particulate matter over a widespread area, which, along with an abundance of spherical manganese particles, was consistent with the presence of a relat ively large emitter of airborne manganese particulate matter in the Marietta area.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### This report, NEIC VP0591E07, presents results of facility sample characterization, comparisons with previously reported TSP filter data, and interpretations.

SUMMARY OF FINDINGS

**•** Eramet ’s furnace areas w ere the primary source of manganese

- bearing airborne particulate matter in the Marietta area based on the location of its facility and analytical results of samples from its facility. Analytical results of samples from Era met were considerably more consistent with TSP filter results than were sample results from Energizer or MIE.

**•** LA

- ICP

- MS results indicated that the TSP filters with the gr eatest abundance of manganese were mostly downwind of the former Union Carbide complex , where Eramet was located

. E xamin ation of the relative manganese abundance at the five TSP sampling locations air monitoring sites on multiple days showed that at least one major industrial

scale source of manganese

- bearing airborne particulate matter was located in an approximately central location between all five TSP sites, i.e., in close proximity to the former Union Carbide complex.

**•** E lemental analysis results indicated that chromium, lead, and zinc were co

- contamina nts of the mangan ese collected on the TSP filters. These results were consistent with

c hromium, lead

, and zinc being common contaminants associated with the ferromanganese alloy industry and, according to Eramet personnel, the or e used at Eramet containing 48 percent manganese and trace amounts of c hromium, lead

, and zinc (Olsen et al., 2007 ; NEIC VP0591E05).

**•** Relative e lemental composition profiles of dust samples from Eramet that were produced from metal vapor condensation were most similar to TSP filter elemental profiles.

**•** Lead isotope ratios in the downwind TSP filters were indistinguishable from the lead isotope ratios in six dust samples collected above Eramet’s furnaces 1, 12, and 18 . This

was consistent with particulate matter on the TSP filters originating in Eramet’s furnace
area processes that included smelting, tapping, and casting

.

**•** Scanning electron microscopy (SEM) showed manganese

- bearing airborne particles in the Marietta area occurred mainly as Mn

- oxide spher es. Approximately 77 percent of
manganese

- bearing particles found on TSP filters occurred as Mn

- oxide spheres, consistent with a high

- temperature process from which a metal fume forms, cools, and condenses into spheres. Similar particles of Mn

- oxide sphe res were only found in samples associated with the furnace areas at the Eramet facility

– in dusts above furnaces 1, 12, and 18; in the furnace 1 tapping baghouse; in the manganese oxygen refining (MOR) process baghouse; and in the particulate matter colle cted from the MOR emission control cooling tubes (referred to as MOR “heavies”).

**•** MIE was not the major contributor of airborne manganese particulate matter in the Marietta area. Results of three different tests (elemental profiles

, lead isotope ratio s , a nd SEM) comparing MIE samples with TSP filters consistently distinguish ed MIE particulate from that on the TSP filters. LA

- ICP

- MS Mn response and wind data frequently distinguishe d the location of MIE from the location of the primary source of airborne Mn particles. Furthermore, the MIE facility did not have the capability of conducting high

heat processes consistent with the production of abundant spherical, micrometer

- scale Mn

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### oxide particles , which accounted for approximately 77 percent of manganese

- be aring particles on the TSP filters

.

**•** Energizer also was not the major contributor of airborne manganese particulate matter in the Marietta area as represented by the five TSP air monitoring sites

. Although the Energizer and Eramet facilities could not be d istinguished as potential sources of airborne manganese by their relative locations, results of other tests were more discerning. Lead isotope data indicated that only one Energizer sample was indistinguishable from the downwind TSP filters

– product plat e from the plate shed (EB03). However, the product plate sample did not consist of particulate matter and, along with the other four samples from Energizer

, did not display elemental profiles similar to the TSP filters. F urthermore

, the Energizer facilit y also did not have the capability of conducting high

- heat processes consistent with the production of abundant spherical, micrometer

- scale Mn

- oxide particles, and such particles were not observed in any of the Energizer samples.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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## LABORATORY ACTIVITIE S

Labo ratory activities included analys i s of facility samples collected in March 2009 using elemental analysis by acid digestion followed by inductively coupled plasma optical emission spectroscopy (ICP

- OES) and inductively coupled plasma mass spectrometry (ICP

- MS), lead isotope ratio analysis by multi

- collector inductively coupled plasma mass spectrometry (MC

- ICP

MS), and scanning electron microscopy

.

SAMPLE RECEIPT AND D ESCRIPTION

On April 7, 2009, Steve Machemer of the NEIC Laboratory Branch received 24 facili ty samples from Rob Hoelscher of the NEIC Field Branch via FedEx shipment. There were five samples from Energizer, four samples from MIE, fifteen samples from Eramet, and two bag blanks (Table 2).

Table 2

. COLLECTION DATE AND LO CATION OF 24 FACILITY SAMPLES COLLECTED BY NEIC FIELD BRANCH PERSONNEL Marietta, Ohio, Source

- Receptor Study: Results and Interpretation 1

Date Sampled Facility Location/Material NEIC Sample

Site Number NEIC Sample

Tag Number March 17, 2009 Eramet Furnace 1, 3 rd level beam dust ERM01 NE25080 March 17, 2009 Eramet C2P crusher baghouse dust ERM02 NE25081 March 17, 2009 Eramet Furnace 1, NW bin for tapping baghouse dust ERM03 NE25083 March 17, 2009 Eramet Furnace 1, 2 nd level beam dust ERM04 NE25086 March 17, 2009 Eramet Furnace 1, beam dust above casting sand ERM05 NE25087 March 17, 2009 Eramet Furnace 18, 4 th level beam dust ERM06 NE25090 March 17, 2009 Eramet Furnace 18, 2 nd level beam dust ERM07 NE25092 March 18, 2009 Eramet Furnace 12, west beam dust ERM08 NE25094 March 18, 2009 Eramet Furnace 12; east beam dust ERM09 NE25096 March 18, 2009 Eramet MOR 2 heavies (particulate matter) ERM10 NE25097 March 18, 2009 Eramet MOR baghouse dust ERM11 NE25099 March 18, 2009 Eramet Assoman ore 3 ERM12 NE25102 March 18, 2009 Eramet Comilog f ine ore 3 ERM13 NE25104 March 18, 2009 Eramet Comilog r egular ore 3 ERM14 NE25106 March 18, 2009 Eramet Comilog s inter 3 ERM15 NE25107 March 18, 2009 Eramet Bag blank B01 NE25065 March 16, 2009 Energizer Electrolytic MnO 2 p roduct bag #14 (particulate matter) EB01 NE25069 March 16, 2009 Energizer Electrolytic MnO 2 p roduct bag #13 (particulate matter) EB02 NE25072 March 16, 2009 Energizer Stripped product plate in pile in plate shed 3 EB03 NE25073 March 16, 2009 Energizer Jarosite skip (particulate matter) EB04 NE25075 March 16, 2009 Energizer Calcined ore (particulate matter) EB05 NE25078 March 16, 2009 Energizer Bag blank B01 NE25063 March 19, 2009 MIE Highlander slag 3 MIE01 NE25109 March 19, 2009 MIE Finished medium

- carbon (MC) ferromanganese ( FeMn ) (particulate matter) MIE02 NE25111
March 19, 2009 MIE Beam dust, NW corner of building 3A MIE03 NE25113 March 19, 2009 MIE Felman slag @ Green Global 3 MIE04 NE25116

1 From NEICVP0591E05, June 2010
2 MOR = manganese oxygen refining process
3 S ample ground for analysisATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### Seventeen of the 24 facility samples consist ed of abundant fine particulate matter

. However, s even feedstock and product samples, representing ore, sinter, slag, and product plate

, consist ed primarily of material in the granule

- (2 to 4 millimeters [mm] ) to cobble

- size range, up
to 7 to 8 centimeters (cm) in diameter

. Samples varied in color from reddish

- brown to light

- grey, and the consistency of the samples included fine dr y powders and oily, consolidated particulate
material. Specific sample descriptions are presented in the NEIC report NEICVP0591E05.

ANALYSIS OF SAMPLES/ ANALYTICAL BACKGROUN D

Elemental abundance results for the facility samples were generated by acid dig estion and
ICP

- OES by Theresa Hosick from April to July 2010 and by James Stamey from May to October 2010. SEM for the facility samples was conducted by Steve Machemer from June to September 2010. Elemental abundance results for the TSP filters were gene rated by Theresa Hosick by LA

ICP

- MS from January 2008 to May 2009 and were reported in NEICVP0591E04 and NEICVP0591E06. This work was conducted by NEIC personnel at the NEIC laboratory in accordance with the NEIC quality system.

Lead isotope ratio anal ysis was performed by MC

- ICP

- MS on both TSP filters and facility samples by Mike Pribil of the U

. S

. Geological S urvey (USGS) from December 2008 t o July 2010. This work was contracted because NEIC lacked the required instrumentation to perform this type
of analysis . NEIC personnel determined that adequate quality control and data package reviews

were p erformed to obtain scientifically valid and legally defensible data from the USGS laboratory . Data analysis and interpretation were provided by Steve Machem er, Mike Pribil, and
Theresa Hosick.

LA

- ICP

- MS was conducted only on the TSP filters, and results were reported in
NEICVP0591E05 and NEICVP0591E06. LA

- ICP

- MS is a relatively novel technique that allows
for direct ICP

- MS analysis of solid samples without a n initial labor

- intensive digestion technique. Direct analysis made it possible to analyze many more TSP filters than would have been possible otherwise. It was important to obtain discrete results for each air monitoring site for every day that samples were collected in order to observe the maximum and minimum Mn levels relative to wind direction and speed. The major weakness of laser ablation analysis is the lack of certified standards in the various matrices. However, it has been demonstrated that th e LA

- ICP

- MS responses for a given analyte are directly proportional to the concentration of that analyte (Arroyo et al., 2009; Latkoczy et al., 2005; NEICVP0591E06). While quantitative concentrations (μg/m 3 

### ) were not obtained directly by this method, rela tive responses for Mn and other elements were measured, allowing determination of relative elemental abundances and minimum and maximum Mn responses.

Quantitative analyses of TSP filters by acid digestion and ICP

- OES and ICP

- MS were performed to establ ish quantitative concentrations (μg/m 3 

### ) of manganese in ambient airborneATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### particulate matter on the TSP filters and to demonstrate the linear relationship between the LA

ICP

- MS and ICP

- OES/ICP

- MS techniques. These results were reported in NEICVP0591E06. Q uantitative analyses of Mn and other elements in facility samples were performed by acid digestion and ICP

- OES and ICP

- MS and are reported in the “ Laboratory Results ” section of this
report.

Isotopic ratios of lead were used in this study to distinguish between potential sources of manganese in airborne dust collected on the TSP filters. Because a strong correlation between manganese and lead was found on the TSP filters (NEICVP0591E06), isotopic ratios of lead were identified as potential tracers of man ganese in the collected airborne dust. In addition to dust from the three facilities sampled, other potential sources of airborne lead included automobiles, municipal waste incineration, oil and gas refineries, fertilizer plants, ore processing facilities

, lead

- based paints, deteriorating steel structures, and the re

- suspension and remobilization of lead contaminated aerosols in dust and soil (U.S. HHS , 2007).

Natural lead is a mixture of four stable isotopes with atomic masses of 204, 206, 207, and 208 ( 2 04 

### Pb, 206 

### Pb, 207 

### Pb, and 208 

### Pb). Only 204 

### Pb is non

- radiogenic, whereas 206 

### Pb, 207 

### Pb, and 208 

### Pb are the radiogenic decay products of the parent isotopes of uranium with atomic mass 238 ( 238 

### U), uranium 235 ( 235 

### U), and thorium 232 ( 232 

### Th), respectively. The proportion of 206 

### Pb, 207 

### Pb, and

208 

### Pb in various ore bodies may vary significantly because of differences in the initial amounts of

238 

### U, 235 

### U, and 232 

### Th in the ores ; different decay constants for 238 

### U, 235 

### U, and 232 

### Th ; and differences in ages and geologic histories of the ores (Faure, 1986). The isotopic composition of lead in an ore body can be indicative of the geographic area from which it was mined. For example, the ratio of 206 

### Pb/ 207 

### Pb is 1.03 in the Broken Hill Australian ore, an older lead deposit; in the younger U.S. deposits of the Mississippi Valley, the ratio is as high as 1.42 (Maddaloni et al., 1998). Thus, lead from different sources in soils and airborne dust may have distinct isotopic lead signatures

, depending on the isotopic composition of the original lithogenic or anthropogenic
source material from which lead

- bearing soil or dust particles were derived. Furthermore, because lead isotopes have heavy atomic masses, they do not fractionate appreciably during natural or anthropogenic processes, allowing their relative abundances to be used as geochemical tracers (Shiel et al., 2010; Bollhöfer and Rosman, 2001 and 2002). Therefore, lead

- bearing airborne particulate matter from industrial facilities may be traced through the smelting, transport, and deposition processes. Lead isotopes have been used for source discrimination in soils (Gulson et al., 1981; Rabinowitz, 1988; Erel et al., 1997) and in atmospheric aerosols and dust (Flegal et al., 1989; Hopp er et al., 1991; Mukai et al., 1993; Mukai et al., 1994; Hamelin et al., 1997; Veron and Church, 1997; Neymark et al., 2008; Ewing et al., 2010).

Determinations of two

- component mixtures with varying proportions of end

- member compositions plot as straight mixing lines in the 208Pb/207Pb

- 206Pb/207Pb coordinate system.
Positions of two

- component mixtures on mixing lines depend on the isotopic compositions of theATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 13 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation 

### end members and their respective lead concentrations. Mixing relationships between potential

sou rce materials in dust on the TSP filters may be evaluated by comparing the isotopic ratios of lead in the TSP filters and facility samples.

To differentiate between potential manganese sources and typical ambient background manganese on TSP filters, TSP filters were identified as upwind, downwind, or neither. Because
LA

- ICP

- MS data indicated that the primary source of manganese

- bearing particulate matter originated in the proximity of the former Union Carbide complex, downwind TSP filters were
selected b y consideration of wind direction relative to the former complex, wind speed (between 4
and 17 miles per hour [ mph ] ), and high laser ablation signal for manganese. TSP filters downwind of the former Union Carbide complex were considered to be impacted the most by plumes of airborne manganese particulate matter. Upwind TSP filters were similarly selected with respect to wind direction and speed ; however, they also exhibited little or no manganese laser ablation signal. Upwind TSP filters were selected to represent ambient background manganese. Facility samples represented possible sources of manganese

- bearing airborne particles.

The examination of individual particles for chemical composition, morphology, and size was conducted by SEM. Individual particl e data frequently reveal information about the origin of particles and the processes that formed them. For example, s pherical morphology of micrometer

scale, metal oxide particles i s consistent with particle formation via condensation of metal fume produc ed in a high

- temperature process.

GENERAL SAMPLE P REPARATION

All 24 facility samples were prepared for analysis by drying in a VWR Scientific convection oven (Model 1350 GM) at 95 degrees Celsius ( °C ) for 24 hours. The s even feedstock and product samples, consisting primarily of granule

- to cobble

- size material

, were reduc ed to

pea

- siz e by crushing in a BICO jaw crusher and then ground in a Spex Shatterbox (Model 8520) with a tungsten ring and puck at full speed for up to 45 minutes. Sand blanks were grou nd to evaluate possible contamination from the grindin g process. Seventeen samples of particulate
matter from the facilities were sieved to less

- than

- 150

- μm . This particle size limit was chosen to separate particles that were most likely to be transporte d by the wind so that the particles could be analyzed and compar ed to particles on TSP filters. The less

- than

- 150

- μm

- size fraction was a very fine powder. Two samples of particulate matter (NE

- 25086 and NE

- 25096) were saturated with oil, requiring extrac tion with methylene chloride in a Soxhlet extraction apparatus overnight

, followe d by 24 hours of drying at 95 °C before sieving.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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- Receptor Study: Results and Interpretation 

### ELEMENTAL ANALYSIS

Acid Digestion

Approximately 0.20

- gram aliquots of each sample were accurately weighed and extracted
in 25 milliliters (mL) of a solution containing 5.6 percent nitric acid (HNO 3 

### ) and 16.75 percent hydrochloric acid (HCl), as described in Compendium of Methods for the Determination of Inorganic Compounds in Ambient Air, EPA Compendium Method IO

- 3.1 (Mainey a nd Winberry, 1999) for the hot acid extraction. The extracts were diluted to 50 mL with polished reversed osmosis (PRO) water with 18.2 mega ohm (MΏ) resistivity and then filtered through 0.45

- micron
filters.

Inductively Coupled Plasma Optical Emission Sp ectroscopy

Sample extracts and all associated quality control (QC) samples were analyzed by Theresa Hosick using a PerkinElmer Optima 5300 dual view ICP

- OES with Winlab control software
version 4.0.0.0305. The Compendium of M ethods for the Determination o f Inorganic Compounds in Ambient Air, EPA Compendium Method IO

- 3.4

, was used as guidance (Winberry, 1999a). Baseline correction points and PerkinElmer’s inter

- element corrections (IEC) were employed for
interference correction.

Inductively Coupled Plasm a Mass Spectrometry

Sample extracts and all associated QC samples were analyzed by James Stamey using a
PerkinElmer Elan DRCII ICP

- MS with instrument control software version 3.4. The Compendium of Methods for the Determination of Inorganic Compounds in Ambient Air, EPA Compendium Method IO

- 3.5

, (Winberry, 1999b) was used as guidance. Samples were analyzed at various dilutions to ensure measurements were made within the calibration range. Analyte concentrations were reported from the most appropriate di lution.

LEAD ISOTOPE RATIO M EASUREMENTS

Sample Preparation

This preparation was performed by Theresa Hosick (NEIC) and Mike Pribil (USGS) for TSP filters and facility samples, respectively. All reagents were prepared using PRO 18.2 MΏ
water and certified clean acids (Fischer Optima grade). All materials used in the digestion, separation, and collection were washed in hot 10 percent HCl and rinsed in PRO water. For the TSP filter samples, a 1

- by 8

- inch strip was cut from each filter according to instruct ions in the Compendium of Methods for the Determination of Inorganic Compounds in Ambient Air, EPA Compendium Method IO

- 3.1 (Mainey and Winberry, 1999) except that a clean razor blade andATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 15 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation 

### plastic ruler were used instead of the specialized template and cutt ing tool. For the solid samples,
a 0.2

- gram aliquot of each ground or sieved sample was extracted according to the aqua

- regia digestion described in NEIC’s operating procedure E lemental A nalysis

, NEICPROC/00

- 062R4

. 

### After digestion, both the facility samp le and TSP filter digestates were analyzed for lead by ICP

MS. The lead concentrations were adjusted to yield 10 mL with an approximate concentration of 20 micrograms per liter (μg/L). The preparations were then evaporated to dryness at 85 °C

, cooled, capped, and transferred to the USGS for separation of lead from the sample matrix.

Column Separation

Columns for lead separation were prepared by Mike Pribil (USGS) using Samco pipets (Cat #242, 8/5cm x 2.5mm, National Packaging Services, Inc., Secaucus, NJ, USA) with the tips
cut off and fitted with Bel

- Art porous frits (0.70

- μm pore size, Bel

- Art Products, Paquannock, NJ, USA). The columns were loaded using 0.25 mL of pre

- cleaned Eichrom strontium (Sr) (Eichrom, Lisle, IL, USA) specific resin (Gale, 1996). The resin

- loaded columns were rinsed using five 1

- mL aliquots of PRO water and conditioned using three 1

- mL aliquots of 2

- molar (M) HCl. All chromatographic separation work was performed in C lass 100 laminar flow hoods within a Class
1000 clean room.

All samples received from NEIC were reconstituted in 0.5 mL of 2M HCl and loaded on the preconditioned Eichrom Sr specific resin. The loaded samples were allowed to absorb to the top of the resin bed before they were rinsed with two 0.5

- mL aliquots of 2M HCl, followed by
two additional 1

- mL 2M HCl aliquots to remove the matrices. Lead was removed from the column using eight 1

- mL aliquots of 6M HCl. The eluted lead fraction was collected in pre

cleaned Savillex® vials and evaporated to dryn ess. The dried lead samples were reconstituted in
10 to 20

- mL 2 percent HNO 3 

### and allowed to sit overnight before MC

- ICP

- MS analyses.

Multi

- Collector Inductively Coupled Plasma Mass Spectrometry

All lead isotope analyses were conducted by Mike Pribil at t he USGS high resolution MC

ICP

- MS laboratory in Denver, Colorad o, using a Nu Instruments HR, double

- focusing MC

- ICP

MS. Samples were spiked with the National Institute of Standards and Technology’s standard reference material, NIST SRM 997

, isotop ic stand ard of t hallium at the concentration equivalent to Pb (10 parts per billion [ppb]) and introduced in the MC

- ICP

- MS using a desolvating nebulizer (DSN 100). Samples were analyzed in a single block consisting of 30 cycles with 10 second integration per cycl e for a total duration of 5 minutes per lead isotope measurement . A typical analysis procedure involved a 4 to 5 sample set, bracketed by the NIST SRM 981 lead isotope standard. Mass bias was corrected using the exponential law (Ridley, 2005) using a 205 

### Tl/ 203 

### Tl
value of 2.3875. Greater detail on the USGS MC

- ICP

- MS instrument configuration and mass
bias correction for Pb isotopes is described by Ridl e y (2005)

.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 16 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation 

### SCANNING ELECTRON MI CROSCOPY

SEM was conducted by Steve Machemer on the 24 facility samples (Table 2 ). The objective was to characterize the composition a nd morphology of manganese

- bearing particles in
the less

- than

- 150

- μm

- size fraction of the 17 sieved samples of particulate mat t e r. C haracterization wa s also conducted f or compositional, and not morphological , comparison of

manganese

- bearing particles produced as a result of Shatterbox grinding of the seven feedstock and product samples that did not consist of fine particulate matter when collected onsit e

. Results

were compar ed between samples and with manganese

- bearing particles found previously on the TSP filters ( NEIC VP0591E06).

Particulate matter was dab

- mounted on 12

- mm diameter, aluminum SEM specimen stubs using carbon adhesive tabs. Specimens wer e carbon

- coated using a Denton Vacuum Bench Top carbon evaporator. Sample specimens were analyzed using a JEOL JSM 6400 SEM with a Thermo Scientific energy dispersive x

- ray spectrometer (EDS) and Noran System Six software. The following instrument parame ters were used: acceleration voltage was 20 kiloelectron volts ( keV ) , beam current was 1 to 2 nanoamperes ( nA ) , working distance was 11 mm, magnification was varied as needed, the count acquisition time for spectra was 60 seconds with approximately
20 to 40 percent dead time.

Filter mounts were systematically scanned in backscattered electron imaging (BEI) mode at 1000x magnification to search for manganese

- bearing particles less than approximately 20 **μ** m in geometric diameter. Manganese

- bearing particles and associated particles of interest were documented by collecting a secondary electron image (SEI) and spectrum of the particle.
Examination of each stub was concluded after documentation of 12 to 24 Mn

- bearing particles. Documented particles were manually classified by composition and particle shape, and the longest dimension for each particle in the 17 sieved samples was measured manually.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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- Receptor Study: Results and Interpretation 

## LABORATORY RESULTS

ELEMENTAL A NALYSES

Results of elemental analysis of facility samples e xtracted by EPA Compendium Method
IO

- 3.1 and analyzed by ICP

- OES (or by ICP

- MS as noted) are presented in milligrams per kilogram (mg/kg) in Table 3.

Table 3

. ELEMENTAL RESULTS FOR FACILITY SAMPLES EXT RACTED BY EPA METHOD IO

- 3.1 AND ANALYZED BY ICP

- OES (mg/kg) Marietta, Ohio, Source

- Receptor Study: Results and Interpretation

NEIC Sample Tag Number Uncertainty b
Relative % MDL c (mg/kg) NE25069 NE25072 NE25073 NE25075 NEIC Sample Site Number EB01 d EB02 EB03 d EB04

Aluminum 9.2 9 204 154 466 44,400
Antimony 5.8 0.8 <0.8 <0.8 <0.8 <0.8

Arsenic 11.0 0.8 14.2 10.7 10.9 124

Barium 6.5 0.2 3.03 2.46 17.7 1,660

Cadmium 7.5 0.05 <0.05 <0.05 1.174 16.1

Calcium 4.0 10 239.8 208.6 619 900

Chromium 9.5 0.1 5.22 5.95 45.4 151

Cobalt 7.6 0.1 <0.1 <0.1 6.74 241
Copper 9.2 1 <1 <1 10.00 1,041

Iron 8.1 60 <60 <60 3,800 137,000

Lead a 10 0.03 <0.03 <0.03 17.4 91.2
Magnesium 8.8 7 304 252 355 444
Manganese 7.2 50 292,000 237,000 247,000 83,000
Molybdenum 9.5 0.9 1.0 e <0.9 <0.9 68.1

Nickel 10 0.1 <0.1 <0.1 2.44 140
Phosphorus 12 3 3.9 e 2.7 e 12 e 2,070

Sulfur 15 0.1 2,900 2,370 3,340 29,400

Titanium 6.0 0.4 1.0 e 0.8 e 9.75 1,890

Vanadium 5.2 0.6 <0.6 <0.6 <0.6 672

Zinc a 8.7 0.5 <0.5 <0.5 192 525

a Lead and zinc results were from ICP

- MS analysis.
b A type B evaluation of the uncertainty was performed assuming a uniform distribution based on the quality control data, resul ting in standard uncertainty expressed as a relative percent (Taylor and Kuyatt, 1994).

c Method detection limit (includes preparation process)
d n=3

e Analytes are present, but results are considered less precise because they are less than five times the method detection limi t.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 18 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Table 3. ELEMENTAL RESULTS FOR FACILITY SAMPLES EXTRACTED BY EPA METHOD IO

- 3.1 AND ANALYZED BY ICP

- OES (mg/kg) (continued) Marietta, Ohio, Source

- Receptor Study: Results and Interpretation NEIC Sample Tag Number NE25078 NE25109 NE25111 NE25113 NE25116 NEIC Sample Site Number EB05 d MIE01 d MIE02 MIE03 d MIE04

Aluminum 18,900 23,700 1,870 16,000 29,100
Antimony <0.8 <0.8 <0.8 320 5.56

Arsenic 75.9 19.8 839 165 2,060

Barium <0.2 1,750 14.01 873 4,570

Cadmium 8.55 2.36 22.7 13.29 3.13

Calcium 879 97,100 583 14,300 60,600

Chromium 47.5 25.9 348 575 106

Cobalt 738 28.1 442 152 33.7
Copper 382 28.2 633 466 645

Iron 34,000 24,400 181,000 38,500 32,300

Lead a 52.7 4.31 128 154 74.4
Magnesium 1,030 16,500 897 10,480 18,600
Manganese 520,000 162,000 636,000 93,800 247,000
Molybdenum 42.1 5.19 67.6 42.6 89.0

Nickel 340 21.1 320 253 82.1
Phosphorus 1,080 59.5 1,310 467 364

Sulfur 2,590 2,200 790 4,460 4,840

Titanium 814 200 32.0 585 1,396

Vanadium 192 <0.6 377 99.0 39.4

Zinc a 366 1.3 e 69.8 1,270 14.7

a Lead and zinc results were from ICP

- MS analysis.
d n=3

e Analytes are present, but results are considered less precise because they are less than five times the method detection limi t.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 19 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Table 3 . ELEMENTAL RESULTS F OR FACILITY SAMPLES EXTRACTED BY EPA METHOD IO

- 3.1 AND ANALYZED BY ICP

- OES (mg/kg) (continued) Marietta, Ohio, Source

- Receptor Study: Results and Interpretation NEIC Sample Tag Number NE25080 NE25081 NE25083 NE25086 NE25087 NEIC Sample S ite Number ERM01 ERM02 ERM03 ERM04 d ERM05

Aluminum 16,900 4,050 8,630 13,400 10,530
Antimony 10.26 <0.8 5.56 5.87 <0.8

Arsenic 319 89.4 67.0 282 97

Barium 2,780 956 420 2,030 931

Cadmium 18.6 11.76 93.4 15.4 16.6

Calcium 15,600 9,370 2,442 17,210 12,470

Chromium 1,300 504 126 1,360 412

Cobalt 179 1,128 73.3 310 368
Copper 344 714 471 321 322

Iron 65,200 96,600 164,000 66,000 57,700

Lead a 11,100 14.4 2,810 2,170 146
Magnesium 10,730 11,500 2,940 10,630 16,500
Manganese 265,000 546,000 153,000 303,000 269,000
Molybdenum 82.0 48.8 29.9 63.9 29.5

Nickel 229 588 87.9 287 307
Phosphorus 606 1,200 369 1,050 910

Sulfur 15,400 1,100 12,800 9,900 4,600

Titanium 1,319 706 413 1,600 1,106

Vanadium 115.7 81.6 <0.6 138.3 71.0

Zinc a 4,150 54.4 23,400 1,370 611

a Lead and zinc results were from ICP

- MS analysis.
d n=3

e Analytes are present, but results are considered less precise because they are less than five times the method detection limi t.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 20 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Table 3 . ELEMENTAL RESULTS F OR FACILITY SAMPLES EXTRACTED BY EPA METHOD IO

- 3.1 AND ANALYZED BY ICP

- OES (mg/kg) (continued) Marietta, Ohio, Source

- Receptor Study: Results and Interpretation NEIC Sample Tag Number NE25090 NE25092 NE25094 NE25096 NE25097 NEIC Sample S ite Number ERM06 ERM07 ERM08 ERM09 ERM10

Aluminum 37,900 8,390 18,400 23,300 1,240
Antimony <0.8 <0.8 <0.8 <0.8 <0.8

Arsenic 100 126 143 161 39.7

Barium 2,360 994 2,070 1,850 26.7

Cadmium 42.3 15.0 12.79 40.3 12.47

Calcium 11,720 11,250 14,930 14,760 360

Chromium 82.5 476 251 242 431

Cobalt 730 472 360 407 1,053
Copper 593 487 280 397 205

Iron 46,400 76,000 43,700 55,400 104,900

Lead a 514 246 184 330 62.1
Magnesium 4,750 19,900 9,200 8,380 1,980
Manganese 313,000 390,000 259,000 280,000 540,000
Molybdenum 17.6 31.0 37.9 57.8 27.4

Nickel 274 355 224 258 418
Phosphorus 970 890 782 1,070 1,110

Sulfur 7,100 19,900 7,300 5,350 633

Titanium 680 461 896 925 673

Vanadium 43.5 63.6 67.8 82.9 199

Zinc a 3,400 971 1,540 2,700 546

a Lead and zinc results were from ICP

- MS analysis.
d n=3

e Analytes are present, but results are considered less precise because they are less than five times the method detection limi t.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 21 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Table 3 . ELEMENTAL RESULTS F OR FACILITY SAMPLES EXTRACTED BY EPA METHOD IO

- 3.1 AND ANALYZED BY ICP

- OES (mg/kg) (continued) Marietta, Ohio, Source

- Receptor Study: Results and Interpretation NEIC Sample Tag Number NE25099 NE25102 NE25104 NE25106 NE25107 NEIC Sample S ite Number ERM11 d ERM12 d ERM13 ERM14 ERM15

Aluminum 555 1,760 22,100 25,200 39,300
Antimony <0.8 <0.8 <0.8 <0.8 <0.8

Arsenic 40.5 30.7 14.8 10.0 65.1

Barium 4.40 4,900 1,620 1,375 3,000

Cadmium 1.77 9.82 6.57 5.31 8.54

Calcium 191.1 48,300 709 266 1,728

Chromium 77.5 7.60 21.1 13.1 63.3

Cobalt 215 84.8 1,073 734 1,183
Copper 203 55.6 390 346 565

Iron 14,800 83,700 22,700 22,300 35,100

Lead a 457 135 27.3 17.5 47.0
Magnesium 3,240 4,820 509 441 1,190
Manganese 594,000 402,000 183,000 131,800 529,000
Molybdenum 4.15 <0.9 <0.9 <0.9 12.9

Nickel 99.6 14.1 307 335 499
Phosphorus 314 265 533 437 1,190

Sulfur 940 1,670 303 212 618

Titanium 42.4 65.9 102.1 94.5 1,173

Vanadium <0.6 <0.6 9.06 10.35 63.0

Zinc a 1,310 54.7 317 275 554

a Lead and zinc results were from ICP

- MS analysis.
d n=3

e Analytes are present, but results are considered less precise because they are less than five times the method detection limi t.



### LEAD ISOTOPE RATIO M EASUREMENTS

Results of lead isotope ratio determinations are presented in Tables 4 a and 4 b for TSP filters and facility samples, respectively.

Table 4 a. LEAD ISOTOPE RATIO DETERMINATIONS FOR TSP FILTERS Marietta, Ohio, Source

- Receptor Study: Results and Interpretation

Filter ID Wind a

S peed/ Direction/Precipitation Sampler L ocation Date of S ampling 208 Pb/ 207 Pb 206 Pb/ 207 Pb

G3002862 9 MPH WNW Rain Boaz 4/6/2007 2.394 1.127
G3009889 4 MPH N None Neale 6/11/2007 2.406 1.136
G3009894 9 MPH NW Rain Neale 6/5/2007 2.447 1.178
G3009895 9 MPH NW Rain Boaz 6/5/2007 2.401 1.131
G3009896 9 MPH NW Rain Wash C areer Center 6/5/2007 2.447 1.190
G3009898 9 MPH NW Rain Harmar 6/5/2007 2.406 1.139
G3009902 9 MPH NW Rain Harmar co

- lo cated 6/5/2007 2.406 1.138
G3009906 3 MPH WS W None Wash C areer Center 5/24/2007 2.433 1.169
G3009913 4 MPH NNE None Harmar 5/18/2007 2.440 1.179ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 22 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Table 4 a. LEAD ISOTOPE RATIO DETERMINATIONS FOR TSP FILTERS Marietta, Ohio, Source

- Receptor Study: Results and Interpretation

Filter ID Wind a

S peed/ Direction/Precipitation Sampler L ocation Date of S ampling 208 Pb/ 207 Pb 206 Pb/ 207 Pb

G3009919 6 MPH NNE None Neale 5/12/2007 2.434 1.174
G3009920 9 MPH ENE Fog Harmar 5/6/2007 2.497 1.208
G3009925 7 MPH West None Boaz 4/30/2007 2.438 1.175
G3009926 9 MPH ENE Fog Harmar co

- lo cated 5/6/2007 2.444 1.180
G3009927 7 MPH West None Wash C areer Center 4/30/2007 2.448 1.184
G3009928 7 MPH West None Harmar 4/30/2007 2.407 1.138
G3009934 6 MPH NE None Neale 4/18/2007 2.405 1.136
G3009939 13 MPH WSW Rain Neale 4/1 2 /2007 2.439 1.191
G3010213 8 MPH SSW None Neale 11/20/2007 2.467 1.202
G3010227 2 MPH ENE None Neale 11/2/2007 2.432 1.169
G3010241 3 MPH S None Wash C areer Center 10/21/2007 2.360 1.093
G3010242 3 MPH S None Boaz 10/21/2007 2.417 1.154
G3010247 1MPH E None Boaz 10/15/2007 2.400 1.141
G3010248 1MPH E None Harmar Co

- lo cated 10/15/2007 2.441 1.177
G3010250 1 MPH E None Harmar 10/15/2007 2.453 1.187
G3010256 5 MPH SSW Wash C areer Center 10/3/2007 2.421 1.156
G3010257 5 MPH SSW None Boaz 10/3/2007 2.420 1.157
G3010258 5 MPH SSW None Harmar 10/3/2007 2.433 1.167
G3010260 5 MPH SSW None Harmar Co

- lo cated 10/3/2007 2.438 1.174
G6010506 1 MPH SE Fog Blue Knob 5/30/2007 2.412 1.148
G6010507 9 MPH NW Rain Blue Knob 6/5/2007 2.430 1.162
G6010515 1MPH ENE Fog Blue Knob 7/23/2007 2.409 1.146
G6010525 4MPH SSE Fog Blue Knob 9/21/2007 2.385 1.125
G6010530 3 MPH S None Blue Knob 10/21/2007 2.361 1.092
G6014302 8 MPH SSW None Blue Knob 11/20/2007 2.456 1.193
G6014316 5 MPH E Rain, Snow Blue Knob 2/12 /200 8 2.431 1.161
G6017034 3 MPH W Rain Harmar 9/9/2007 2.420 1.160
G6017052 5 MPH SW Rain Wash C areer Center 8/16/2007 2.444 1.182
G6017080 6 MPH SW Rain Boaz 7/11/2007 2.409 1.142
G6017081 6 MPH SW Rain Wash C areer Center 7/11/2007 2.412 1.147
G6017088 6 MPH SW Rain Harmar 7/5/2007 2.412 1.146
G6017094 2 MPH North Fog Neale 6/23/2007 2.446 1.198
G6017161 12 MPH WSW Rain/Snow Wash C areer Center 2/18/2008 2.454 1.201
G6017164 5MPH E Rain/Snow Neale 2/12/2008 2.445 1.179
G6017166 5MPH E Rain/Snow Wash C areer Center 2/12/2008 2.468 1.209
G6017167 5 MPH E Rain/Snow Boaz 2/12/2008 2.459 1.192
G6017168 5 MPH E Rain/Snow Harmar Co

- lo cated 2/12/2008 2.473 1.215
G6017169 15 MPH SW Rain Neale 2/6/2008 2.434 1.170
G6017170 5MPH E Rain/Snow Harmar 2/12/2008 2.473 1.216
G6017196 9 MPH SSW Wash C areer Center 1/7/2008 2.390 1.121
G6017214 5 MPH NNW None Neale 12/14/2007 2.438 1.178

a http://www.wunderground.com/history/airport , for Parkersburg, West VirginiaATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 23 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Table 4b. LEAD ISOTOPE RATIO DETERMINATIONS FOR FACILITY SAMPLES Marietta, Ohio, Source

- Receptor Study: Results and Interpretation NEIC Sample S ite Number Sampler L ocation 208 Pb/ 207 Pb 206 Pb/ 207 Pb

ERM01 Eramet f urnace 1 3 rd level beam dust 2.486 1.156

ERM02 Eramet C2P baghouse dust 2.386 1.103

ERM03 Eramet f urnace 1 tapping baghouse dust 2.418 1.153

ERM04 Eramet f urnace 1 2 nd level beam dust 2.478 1.157

ERM05 Eramet f urnace 1 beam above casting sand 2.426 1.155

ERM06 Eramet f urnace 18 4 th floor beam dust 2.392 1.109

ERM07 Eramet f urnace 18 2 nd level beam dust 2.410 1.14 0

ERM08 Eramet f urnace 12 west beam dust 2.397 1.122

ERM09 Eramet f urnace 12 east beam dust 2.389 1.115

ERM10 Eramet MOR a heavies 2.369 1.072

ERM11 Eramet MOR baghouse 2.365 1.066

ERM12 Eramet Assoman ore 2.337 1.089

ERM13 Eramet C omilog fine ore 2.368 1.055

ERM14 Eramet C omilog regular ore 2.354 1.043

ERM15 Eramet C omilog sinter 2.357 1.054

EB01 Eveready electrolytic MnO 2 p roduct bag 14 Insufficient lead Insufficient lead

EB02 Eveready electrolytic MnO 2 p roduct bag 13 Insufficient lead Insufficient lead

EB03 Eveready stripped product plate in pile in plate shed 2.418 1.151

EB04 Eveready jarasite skip 2.403 1.11 0

EB05 Eveready calcined ore 2.400 1.108

MIE01 MIE H ighlander slag 2.476 1.166

MIE02 MIE finished medium

- carbon F e M n 2.447 1.161

MIE03 MIE beam dust NW corner of building 3A 2.457 1.181

MIE04 MIE Felman slag 2.495 1.165

S11444 (2005) b Eramet Comilog sinter 2.366 1.061

S11445 (2005) b Eramet Comilog regular ore 2.374 1.037

a MOR = manganese oxygen refining process
b Sample received from facility (see NEIC VP0591E03 )



### Instrument performance and analytical procedure reproducibility were measured by running the USGS BCR 1 standard (Basalt Columbia River), the NIST SRM 2709 soil standard, and the NIST SRM 981 standard through the sample preparation process. NIST SRM 981 (n=61) was analyzed throughout the analysis period, both processed through the sample preparation
method and unprocessed, and resulted with an average 208 

### Pb/ 207 

### Pb of 2.370 ± 0.002 (2 standard deviations [SD]) and a 206 

### Pb/ 207 

### Pb of 1.095 ± 0.002 (2 SD). NIST SRM 981 certified values for

208 

### Pb/ 207 

### Pb and 206 

### Pb/ 207 

### Pb are 2.370 and 1.093, respectively. NIST 2709 soil standard resulted in

208 

### Pb/ 207 

### Pb of 2.483 ± 0.003 (2 SD) and 206 

### Pb/ 207 

### Pb of 1.217 ± 0.003 (2 SD), similar to the values reported by Takaoka et al. (2006) for 208 

### Pb/ 206 

### Pb of 2.483 ± 0.002 (2 SD) and 206 

### Pb/ 207 

### Pb of 1.217 ± 0.002. Multiple samples were processed through the sample preparation method in triplicateATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 24 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation 

### and resulted in an expanded uncertainty for both 208 

### Pb/ 207 

### Pb and 206 

### Pb/ 207 

### Pb of ± 0.002 (2 SD). These results demonstrated negligible bias and are summarized in Table 4c.

Table 4c. LEAD ISOTOP E RATIO DETERMINATION S F OR RE FERENCE MATERIALS Marietta, Ohio, Source

- Receptor Study: Results and Interpretation

USGS this study Woodhead, 2002 Georem database Takaoka et al., 2006

Standard 206 Pb/ 207 Pb 208 Pb/ 207 Pb 206 Pb/ 207 Pb 208 Pb/ 207 Pb 206 Pb/ 207 Pb 208 Pb/ 207 Pb 206 Pb/ 207 Pb 208 Pb/ 207 Pb

BCR a 1 1.204 2.476 1.204 2.476 1.204 2.477 NA NA

NIST SRM 2709 1.217 2.483 NA NA 1.218 2.488 1.217 2.482

NIST SRM 981 1.095 2.37 0 1.093 2.369 1.093

- 1 .100 2.360

- 2.374 NA NA

a USGS Basalt Columbia River , BCR 1 standard



### SEM ANALYSIS

Documented Mn

- bearing particles were classified on the basis of the dominant morphologies and elemental compositions. The dominant morphologies exhibited were

“ spherical ” (spherical and spheroidal particles and aggregates thereof) and “ angular ” (very angular to sub

- angular particles and aggregates thereof). Infrequent particles exhibiting indistinct
sub

- angular to sub

- rounded morphologies were included in the angular clas s because they were clearly not spheroidal. Because silicon was the most common major element to occur in the Mn

bearing particles, most of these particles were classified as either “ Mn

- oxide ” or “ Mn

- Si

- oxide ” based on the relative EDS response for silico n . Similarly, the classification of carbon particles containing Mn

- oxide was based on a relatively strong EDS response for carbon. Most high

carbon particles we re large enough (i.e., considerably larger than the electron beam excitation volume) that cont ributions to the EDS spectra from carbon in the carbon tape adhesive were negligible . In addition, carbon particles may be expected because of the large amount of carbon found in the products used in the sampled facilities and in the form of coke used in the processes
at Eramet.

A summary of SEM results for detected Mn

- bearing particles in facility samples is presented in Table 5 . The majority of Mn

- bearing particles in most samples from the three
facilities occurred as Mn

- oxide

, commonly with silicon. Angular Mn

- oxide and Mn

- Si

- oxide particles occurred in samples from all three facilities. However, spherical Mn

- oxide and Mn

- Si

oxide particles were only found in samples collected at Eramet and were particularly abundant in the size range of less than 1 0 **μ** m geometric diameter. MOR heavies ( ERM10 ) and MOR baghouse dust ( ERM11 ) from Eramet were nearly entirely composed of spherical Mn

- oxide particles (Figures 1a and 1b). Concomitance of aluminum, copper, magnesium, silicon, sodium,
and sulfur was common in the spherical Mn

- oxide particles in the MOR samples. In Table 5

, elements detected in approximately half of the particles of the indicated set of particle types in a sample are noted as common concomitance elements.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 25 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation 

### In contrast, angular Mn

- oxid e particles from Eramet also exhibited frequent concomitance
of iron ( Fe ) . For example, beam dust above casting sands at furnace 1 ( ERM05 ) and C2P crusher baghouse dust ( ERM02 ) from Eramet contained primarily angular Mn

- oxide and Mn

- Si

- oxide particles wit h frequent concomitance of aluminum, calcium, iron, silicon, and sodium (Figures 2 a and 2b ). However, most furnace dust ( ERM01

, ERM03

, ERM04

, ERM06

, ERM07

, ERM08

, and

ERM 09) from Eramet contained both spherical and angular Mn

- and Mn

- Si

- oxide particles. Furnace dust and baghouse dust also contained infrequent spherical and angular carbon particles
with minor Mn

- oxide.

Various ore materials ( ERM12

, ERM13 , E RM14

, and ERM 1 5 ) from Eramet, ground for examination, contained primarily angular Mn

- oxide particles with frequent concomitance of aluminum, calcium, iron, phosphorous, potassium, silicon, sodium, and sulfur. The sinter material ( ERM15 ) also contained abundant angular Mn

- Si

- oxide particles.

Finished medium carbon FeMn ore ( MIE02 ) (Figure 2c ) and beam dus t ( MIE0 3) from MIE contained angular Mn

- oxide particles with frequent concomitance of aluminum, iron, phosphorous, silicon, and sodium. Angular Mn

- oxide particles in beam dust ( MIE0 3) also exhibited frequent concomitance of magnesium and sulfur. In contr ast, Highlander slag ( MIE0 1) and Felman slag ( MIE04 ), both ground for examination, contained angular Mn

- Si

- oxide particles with frequent concomitance of aluminum, calcium, and iron. Except for the concomitance of strontium ( Sr ) in the Felman slag, the Hig hlander and Felman slags appeared most similar to each
other.

Electrolytic MnO 2 

### (EMD) product ( EB01 and EB02 [ Figure 2d] ) and stripped product plate (ground for examination) ( EB03 ) from Energizer contained angular Mn

- oxide particles with
minor to trace a mounts of aluminum, silicon, sodium, and sulfur. Calcined ore ( EB05 ) from Energizer contained angular particles of Mn

- oxide and angular particles of carbon with Mn

- oxide exhibiting frequent concomitance of aluminum, iron, phosphorous, potassium, silicon, sodium, and sulfur (Figure 2e ). The ground plate shed product ( EB0 3) appeared most similar to the EMD product ( EB01 and EB0 2). Jarosite skip from Energizer ( EB 0 4 ) contained abundant angular Mn

bearing particles of aluminum and iron sulfate with frequent concomitance of barium, copper, iron, phosphorous, potassium, silicon, sodium, and titanium (Figure 2f ).

In addition to the unique occurrence of spherical Mn

- bearing particles in Eramet materials, the following similarities and contrasts may be noted i n the SEM data. Although angular particles
of Mn

- oxide and Mn

- Si

- oxide from MIE and Eramet commonly contain iron, similar particles from Energizer typically do not. In addition, whereas many spherical Mn

- oxide and Mn

- Si

- oxide particles in Eramet furnace dust contain iron, spherical Mn

- oxide particles in Eramet’s MOR dust typically do not contain iron

.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 26 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Table 5

. SUMMARY OF SEM DATA OF MANGANESE

- BEARING PARTICLES IN FACILITY SAMPLES Marietta, Ohio, Source

- Receptor Study: Results and Interpretation

Facility Station Description NEIC Sample Tag Number NEIC S ample Site Number Common Mn

- bearing particle types Common elemental concomitance 1

Eramet Furnace 1, 3 rd level beam dust NE25080 ERM01 Angular Mn

- Si

- oxide Spherical Mn

- Si

- oxide Al, Ca, Cl, Fe, K, Mg, Na, P, Pb, Si, S, Ti Al, Ba, Ca, Fe, K, Mg, Na, Pb, Si, S

Eramet C 2 P crusher baghouse dust NE25081 ERM02 Angular Mn

- oxide & Mn

- Si

- oxide Al, Ca, Cu, Fe, Mg, Na, P, Si

Eramet Furnace 1, NW bin for tapping baghouse dust NE25083 ERM03 Spherical Mn

- Si

- oxide Angular Carbon w/ Mn

- Si

- oxide Al, Cl, Fe, K, Mg, Na, P, Si, S, Zn Al, Cl, Fe, K, Mg, Na, P, Si, S, Zn

Eramet Furnace 1, 2 nd level beam dust NE25086 ERM04 Angular Mn

- oxide & Mn

- Si

- oxide Spherical Mn

- oxide & Mn

- Si

- oxide Al, Ca, Cu, Cl, Fe, K, Mg, Na, Si, S, Ti Al, Ca, Fe, K, Mg, Na, Pb, Si, S, Ti

Eramet Furnace 1, beam dust above casting sand s NE25087 ERM05 Angular Mn

- oxide & Mn

- Si

- oxide Al, Ca, Fe, K, Mg, Na, Si, S

Eramet Furnace 18, 4 th level beam dust NE25090 ERM06 Angular Mn

- oxide & Mn

- Si

- oxide Spherical Mn

- oxide & Mn

- Si

- oxide Angular Carbon w/ Mn

- oxide Al, Ca, Fe, K, Mg, Na, Si, S, Zn Al, Ca, K, Mg, Na, Si, S Al, Ca, K, Mg, Na, P, Si, S, Zn

Eramet Furnace 18, 2 nd level beam dust NE25092 ERM07 Angular Mn

- oxide Spherical Mn

- oxide Al, Ca, Cl, Fe, K, Mg, Na, P, Si, S Al, Mg, Si, S

Eramet Furnace 12, west beam dust NE25094 ERM08 Angular Mn

- oxide Spherical Mn

- oxide Al, Ca, Cl, Fe, K, Mg, Na, P, Si, S Al, Ca, K, Mg, Si, S

Eramet Furnace 12, east beam dust NE25096 ERM09 Angular Mn

- oxide Spherical Mn

- oxide Spherical & Angular Carbon w/ Mn

- oxide Al, Ca, Cl, Fe, K, Mg, Na, P, Si, S, Zn Al, Ca, K, Na, Si, Zn Al, Ca, Cl, K, Mg, Na, P, Si, S
Eramet MOR heavies NE25097 ERM10 Spherical Mn

- oxide Al, Mg, Na, Si, S

Eramet MOR baghouse dust NE25099 ERM11 Spherical Mn

- oxide Al, Cu, Mg, Si, S

Eramet Assoman ore pile 2 NE25102 ERM12 ( Angular ) 2 Mn

- oxide Al, Ca, Cu, Fe, Mg, Na, P, Si, S

Eramet Comilog fine ore 2 NE25104 ERM13 ( Angular ) 2 Mn

- oxide Al, Ba, Fe, K, Na, P, Si, S

Eramet Comilog regular ore 2 NE25106 ERM14 ( Angular ) 2 Mn

- oxide Al, Ca, Cu, Fe, Mg, Na, P, Si, S

Eramet Comilog sinter 2 NE25107 ERM15 ( Angular ) 2 Mn

- oxide & Mn

- Si

- oxide Al, Ca, Cu, Fe, K, Mg, Na, P, Si, S
Energizer Electrolytic MnO 2 Product bag #14 NE25069 EB01 Angular Mn

- oxide Al, Na, Si, S Energizer Electrolytic MnO 2 Product bag #13 NE25072 EB02 Angular Mn

- oxide Al, Na, P, Si, S Energizer Stripped product plate in pile in plate shed 2 NE25073 EB03 ( Angular ) 2 Mn

- oxide Al, Na, Si, S

Energizer Jarosite skip NE25075 EB04 Angular Mn

- oxide, Angular Mn

- Fe

- Al

- sulfate, Angular Carbon w/ Mn

- Al

- oxide/hydroxide/sulfate Al, K, Na, Si, S Al, Ba, Fe, K, Na, P, Si, S, Ti Al, Ba, Fe, K, Na, P, Si, S, Ti Energizer Calcined ore NE25078 EB05 Angular Mn

- oxide Al, K, Na, P, Si, S

MIE Highlander slag 2 NE25109 MIE01 ( Angular ) 2 Mn

- Si

- oxide Al, Ca, Fe, Si

MIE Finished medium

- carbon FeMn ore NE25111 MIE02 Angular Mn

- oxide Al, Fe, Si

MIE Beam dust NW corner of b uilding 3A NE25113 MIE03 Angular Mn

- oxide & Mn

- Si

- oxide Al, Fe, Mg, Na, Si, S

MIE Felman slag @ Green Global 2 NE25116 MIE04 ( Angular ) 2 Mn

- oxide & Mn

- Si

- oxide Al, Ca, Fe, Mg, Si, Sr

1 Elements detected in approximately half of the particles of the indicated set of particle types in a sample

2 Sample ground to produce particulate for examination and compositional comparison only; angular morphology was the result of sample preparationATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E07 Page 27 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 1 a. SEI image of spherical Mn

- oxide particle with a 6.6

- **μ** m geometric diameter i n sample of MOR heavies ( ERM10 ) collected from Eramet i n Ma rch 200 9

.

Figure 1 b. SEI image of spherical Mn

- oxide particle with a 4.9

- μ m geometric diameter in sample of MOR baghouse dust (ERM11) collected from Eramet in March 2009.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E07 Page 28 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 2 a. SEI image of angular Mn

- oxide particle with an 8.3

- μ m geometric diameter in sample of beam dust above casting sands in furnace 1 building (ERM05) collected from Eramet in March 2009.

Figure 2b. SEI image of angular Mn

- Si

- oxide particle with an 8.1

- μ m geometric diameter in sample of C2P crusher baghouse dust (ERM02) collected from Eramet in March 2009.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E07 Page 29 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 2c. SEI image of angular Mn

- oxide particle with a 6.5

- μ m geometric diameter in sample of medium carbon FeMn ore (MIE02) collected from MIE in March 2009.

Figure 2d. SEI image of angular Mn

- oxide particle with a 7.5

- μ m geometric diameter in sample of electrolytic MnO 2 (EMD) product (EB02) collected from Energizer in March 2009.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E07 Page 30 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 2e. SEI image of angular particle agglomeration of carbon with Mn

- oxide with a 5.8

- μ m geometric diameter in sample of calcined ore (EB05) collected from Energizer in March 2009.

Figure 2f. SEI image of angular Mn

- bearing Al

- Fe

- sulfate particle with an 11

- μ m geometr ic diameter in sample of jarosite skip (EB04) collected from Energizer in March 2009.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E07 Page 31 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation 

## DISCUSSION OF ANALYT ICAL RESULTS F OR TSP FILTERS AND FACILITY SAMPLES

Th e following discussion considers : (1) the analytical results for airborne particulate
matter coll ected on TSP filters from April 2007 t o March 2008 (NEICVP0591E06), (2) location of the TSP air monitoring sites, (3) wind data for the TSP filter 24

- hour collection periods, (4) collection timing sequence (dates) of the TSP filter s, and (5) the analytical results for samples of particulate matter and feedstock and product materials collected in March 2009 from the three
Marietta facilities (Table 1)

.

LASER ABLATION RESPO NSES FOR MANGANESE I N RELATION TO WIND DIRECTION

Although NEIC did not collect wind speed or wind direction data, ATSDR showed in its Marietta Area Air Investigation Health Consultation that the wind speed and wind direction data available from the airport in Parkersburg, West Virginia

, represented wind data for the Marietta,
Ohio

, area (U.S. HHS

, 2009). The correspondence between wind direction and downwind manganese abundance was poor on days when wind speeds were very low ( less than 1 mph),
when wind speeds were very high ( greater than 22 mph), or whe n wind speeds and wind directions were highly variable. When wind speeds were between 4 and 17 mph and the wind direction and speed were consistent, the highest manganese LA

- ICP

- MS response (in counts per second) was mostly downwind from the former Union Carbide complex (EB and ERM triangles in Figures 3 a to 8 d). This was true regardless of the location of the TSP air monitoring site as illustrated on the maps in Figures 3 a to 3 d. The LA

- ICP

- MS responses for filters from each TSP air monitoring site from April 2007 through March 2008 are presented in a previous report ( NEIC VP0591E06).

Wind roses shown in the upper left of each map in Figures 3 a to 3 d are visual representations of how wind speed and direction were distributed around Marietta, Ohio, over a given 24

- hour time period. Wind direction i s plotted relative to compass direction

, with the size of the spoke (rose petal) proportional to the frequency of the wind in the indicated direction over
the 24

- hour time period. The size of the color bands on each spoke indicate s the frequency of the wind speed in a given range for that wind direction. The point of the longest spoke of the wind rose point s in the direction the wind was blowing most frequently ( National Resources Conservation Service [ NRCS ] , 20 11). If the center of the wind rose were placed at the site of the former Union Carbide complex (EB and ERM triangles in Figures 3 a to 8 d), the longest wind rose spoke typically would point at the location of the TSP air monitoring site with the maximum
LA

- ICP

- MS manganese response.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E07 Page 32 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation 

### Each of the following examples combining TSP air monitoring site locations, wind direction data, and relative manganese abundance indicated some constraints on the size and
location of the source of the ai rborne manganese

- bearing particulate matter. On April 6, 2007, the predominant wind direction was from the west (W) and west

- northwest (WNW)

, with the highest manganese abundance by more than 100x observed at the Boaz TSP air monitoring site

, which was im mediately downwind from the former Union Carbide complex (Figure 3 a). However, when the wind was blowing predominantly from the west, emissions from MIE impacting the Boaz monitor could not be easily ruled out. The predominant wind direction on May 12, 2 007, was from the northeast (NE) and north

- northeast (NNE)

, with the highest manganese abundance by about 25x observed at the Neale Elementary School air monitor

, which was downwind from the former Union Carbide complex and the MIE site (Figure 3 b). Simil arly, when the wind was blowing predominantly from the northeast, emissions from MIE impacting
the Neale monitor could not be ruled out.

On February 12, 2008, the predominant wind was from the east

- southeast (ESE)

, with the highest manganese abundance by a pproximate ly 7x observed at the Blue Knob Road air monitor

, which was downwind from the former Union Carbide complex but not the MIE site (Figure 3 c).
With the wind from the east

- southeast, most of the manganese impact observed at the Blue Knob
Road monit or was not likely the result of MIE emissions.

The predominant wind direction on January 7, 2008, was from the south (S) and south

southwest (SSW)

, with the highest manganese abundance by about 46x observed at the Career
Center air monitor

, which was do wnwind from the former Union Carbide complex and the MIE
site (Figure 3 d). The relatively low manganese impact of the Blue Knob Road and Boaz air monitors, only about 1 to 2 percent of that of the Career Center air monitor, indicated that few, if any, emi ssions had been released by MIE that day relative to some source(s) in the vicinity of the former Union Carbide complex. Finally, the combination of these examples with the large distances between all of the TSP air monitoring sites (2 to 8 miles) indicat ed the source of the airborne manganese particulate matter in the vicinity of the former Union Carbide complex was industrial in scale.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 33 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 3a. Predominant wind direction from the west and west

- northwest , with highest manganese abundance observed (>100x) at the Boaz air monitor ing site, which was downwind from the former Union Carbide complex.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 34 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 3b. Predominant wind direction from the **north**

**- northeast**  and **northeast ,**  with highest manganese abundance observed (>25x) at the Neale Elementary School air monitoring site, which was down wind from the former Union Carbide complex and the MIE site.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 35 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 3c. Predominant wind direction from the **east**

**- s**  **out heast,**  with highest manganese abundance observed (7x) at the Blue Knob Road air monitoring site, which was downwind from the former Union Carbide complex but not the MIE site.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEICVP0591E0 7 Page 36 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 3 d. Predominant wind direction from the **south** and **south**

**- southwest**  **,** with highest manganese abundance observed (>46x) at the Washington County Career Center air monitor ing site, which was downwind from the former Union Carbide complex and the MIE site. However, impacts at the Blue Knob and Boaz air mo nitors were low.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEIC VP0591E0 7 Page 37 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation 

### TIME SERIES TRENDS O F MANGANESE LASER ABLATION RESPO NSES

The following time series trends of manganese laser ablation responses from April 2007 to March 2008 indicated a regular occurrence over a one

- year time period of the patterns shown in Figures 3a to 3d. Time series trends indicated similar constraints on the scale and location of the source of airborne manganese particulate matter.

Figure 4a shows the time series trends of LA

- ICP

- MS manganese responses for both the Harmar Village and the Washington County Career Center TSP air monitors. The time series trends for manganese response at these two TSP air monitors corresponded well, suggesting that they were both downwind of a major source of airborne manganese partic ulate matter. The pattern of peak LA

- ICP

- MS manganese responses and wind direction indicated the existence of a large source of airborne manganese particulate matter located southwest of the air monitors.
Both t he former Union Carbide complex and the MIE facility were located southwest of the air monitors (see Figures 3a to3d).

The generally lower manganese response at the Washington County Career Center TSP air monitor compared to the response at the Harmar Village air monitor suggested the Harmar
Vill age air monitor was closer to a major source of manganese particulate matter than the air monitor at the Career Center. In fact, the Harmar Village air monitor was approximately one

half mile closer to the former Union Carbide complex than the Career Cent er air monitor. The MIE facility was located 2 miles farther southwest of the former Union Carbide complex. TSP filters from the Harmar Village TSP air monitoring site were not available for the October 21, 2007, collection date. However, on March 19, 2 008, the wind was blowing from the south and southeast, wind directions that from the former Union Carbide complex were much more in line with the Career Center site than with the Harmar Village site.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEIC VP0591E0 7 Page 38 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 4a. Time series trends of manganese abund ance at two air monitoring sites northeast of the former Union Carbide complex . The Washington County Career Center site was f a rther from the Union Carbide complex than the Harmar Village site (designated sampler).



### Figure 4b exhibits the time series tr ends of airborne manganese abundance at two air monitors on opposing sides of the former Union Carbide complex. In contrast to the previous corresponding patterns, trends of ambient air manganese detected at the Harmar Village and the Neale Elementary Sch ool air monitors exhibited a roughly inverse relationship, suggesting a major source of airborne manganese existed in between them. The former Union Carbide complex was located in between these monitors, approximately 4 miles southwest of the Harmar
Villa ge site and 4 miles northeast of the Neale Elementary School site. The MIE facility was
also located in between these monitors , but much closer to the Neale Elementary School site, approximately 1.5 miles north (see Figures 3a to 3d). Manganese Time Series

0 200000 400000 600000 800000 1000000 1200000 1400000 1600000

4/6/07 5/6/07 6/5/07 7/5/07 8/4/07 9/3/07 10/3/07 11/2/07 12/2/07 1/1/08 1/31/08 3/1/08 3/31/08 Sampling DateManganese Response (counts persecond)

Harmar WashingtonATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEIC VP0591E0 7 Page 39 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 4b. Time series trends of manganese abundance at two air monitoring sites on opposing sides of the former Union Carbide complex. The Harmar Village (designated sampler) and Neale Elementary School air monitoring sites were each approximately 4 miles from the forme r complex in the northeast and southwest directions, respectively. Note: on October 3, 2007, wind speed was a relatively low 5 mph and the wind direction was variable.


### Figure 4 c also exhibits a roughly inverse relationship between the time series trends of airborne manganese abundance at the Blue Knob Road and Boaz TSP air monitors. This inverse relationship also suggested a major source of airborne manganese was located in between these monitors, which were also located on opposing sides of the former U nion Carbide complex . In this case, the Blue Knob Road monitor was approximately 1 mile west

- northwest of the former
Union Carbide complex and the Boaz monitor was approxim ately 1 mile east (see Figures 3 a to
3 d). However, because the MIE facility was no t located in between these two air monitors, it was not likely that emissions from MIE could have c ontributed the inverse patterns observed in
this case. Manganese Time Series

0 200000 400000 600000 800000 1000000 1200000 1400000 1600000 1800000

4/6/07 5/6/07 6/5/07 7/5/07 8/4/07 9/3/07 10/3/07 11/2/07 12/2/07 1/1/08 1/31/08 3/1/08 3/31/08 Sampling DataManganese Response (counts persecond)

Harmar NealeATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

NEIC VP0591E0 7 Page 40 of 61 Marietta, Ohio, Source

- Receptor Study: Results and Interpretation Figure 4c. Time series trends of manganese abundance at two air monitoring sites on opposing sides of the former Union Carbide complex. The Boaz and Blue Knob air monitoring sites were approximately 1 mile from the former complex in the east and west

- northwest dir ections, respectively. Note: On October 15, 2007, winds were about 1 mph, and on January 13, 2008, the wind direction was variable.



### COMPARISON OF ELEMEN TAL RESULTS F OR AIR FILTERS AND FACI LITY SAMPLES

Relative elemental abundances by LA

- ICP

- MS on TSP filters at all locations were reported in two previous NEIC reports (NEICVP0591E04, NEICVP0591E06), where correlations of manganese with chromium, lead, and zinc were observed. These correlations were also observed by digestion of the filters and analysis by ICP

- OES or ICP

- MS for a 2

- month period of filter collection (NEICVP0591E06). These correlations suggested that chromium, lead,
and zinc were co

- contaminants associated with the airborne manganese particulate collected on
the TSP filters. These correl ations were also consistent with chromium, lead, and zinc being common contaminants associated with the ferromanganese alloy industry and, along with manganese, common components of air emissions from manganese alloy production facilities (Olsen et al., 20 07). According to Eramet personnel, ores from Namibia and Gabon contained 48 percent manganese and trace amounts of chromium, lead, and zinc, which are detrimental to the production of manganese alloy (NEICVP0591E05). A summary of possible emission

compo nents from production of electrolytic manganese dioxide included arsenic, cadmium, chromium, lead, and nickel (Pacific Air and Environment Pty Ltd, 1999). Emissions from a grinding, sizing, packaging, and transporting facility such as MIE could be highly variable, depending on the materials handled.

The relative abundances of manganese, chromium, lead, and zinc on TSP filters with the ten highest manganese content (as determined by acid digestion) are shown in Figure 5. Manganese Time Series

0 200000 400000 600000 800000 1000000 1200000 1400000 1600000 1800000

4/6/07 5/6/07 6/5/07 7/5/07 8/4/07 9/3/07 10/3/07 11/2/07 12/2/07 1/1/08 1/31/08 3/1/08 3/31/08 Sampling DateManganese Response (counts per second)

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### Chromium, lead, and zinc content as a fraction relative to the manganese content were of particular interest because of their correlations with manganese in particulate matter on TSP filters. Filters with the highest manganese content were selected to demonstrate the relationships
of these elements to manganese. The consistency of elemental profiles from all of the TSP air monitoring sites was consistent with airborne manganese

- bearing particulate matter originating from a single large industrial source.

Elemental Abundances - TSP Filters

TSP Location & Sampling Date Neale-5/12/2007 Boaz-10/15/2007 Harmar-Co 10/9/2007 Washington-10/21/2007 Blue Knob-5/30/2007 Harmar Des-10/9/2007 Boaz-10/9/2007 Blue Knob-5/24/2007 Washington-10/9/2007 Blue knob-10/9/2007Element / Mn

1e-6 1e-5 1e-4 1e-3 1e-2 1e-1 1e+0 1e+1

Chromium Lead Zinc Manganese

Figure 5. Elemental a bundances shown as a relative fraction to manganese for TSP filters with the ten highest manganese concentrations.



### For co mparison to the TSP filters, chromium, lead, and zinc concentrations as a fraction
relative to the man ganese concentration of the samples collected at the Eramet, Energizer, and MIE facilities are presented in Figures 6a and 6b. Although facility samples were not collected during TSP filter collection, comparisons were justified because of the relative co nsistency of the processes and materials used at the facilities over time. Furthermore, samples of beam dust likely represented significant historical accumulations of airborne particulate matter produced during production at the respective facilities . O nly the smaller size fraction of the beam dust samples most likely to be transported by the wind were analyzed

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### Elemental Abundances - Facility Samples

Energizer EB01-EMD EB02-EMD EB03-Plate Shed EB04-Jarosite Skip EB05-Calcined OreElement / Mn

1e-6 1e-5 1e-4 1e-3 1e-2 1e-1 1e+0 1e+1

Chromium Lead Zinc Manganese 

### Marietta Industrial Enterprises MIE01-Highlander Slag MIE02-MC FeMn MIE03-Bldg 3A Dust MIE04-Fellman SlagElement / Mn

1e-6 1e-5 1e-4 1e-3 1e-2 1e-1 1e+0 1e+1

Figure 6a. Elemental a bundances shown as a relative fraction to manganese for samples collected at Energizer and MIE.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### Elemental Abundances - Facility Samples

Eramet ERM01-F1 Beam ERM02-C2P BH ERM03-F1 BH Dust ERM04-F1 2nd Level ERM05-F1 Casting ERM06-F18 4th Level ERM07-F18 2nd Level ERM08-F12 W BeamElement / Mn

1e-6 1e-5 1e-4 1e-3 1e-2 1e-1 1e+0 1e+1

Chromium Lead Zinc Manganese 

### Eramet ERM09-F12 E Beam ERM10-MOR Heavies ERM11-MOR BH ERM12-Assoman Ore ERM13-Com. Fine Ore ERM14-Com. Reg. Ore ERM15-Com. SinterElement / Mn

1e-6 1e-5 1e-4 1e-3 1e-2 1e-1 1e+0 1e+1

Figure 6b. Elemental abundances shown as a relative fraction to manganese for samples collected at Eramet.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### Energizer o btained calcined manganese ore that consisted of Comilog ore (80 percent) and Australian Groote ore (20 percent) from Prince Minerals in Quincy, Illinois ( NEIC VP0591E05) . Both ores were composed of the manganese ore minerals, pyrolusite (Mn +4 

### O 2 

### ) and crypt omelane (K[Mn +2 

### Mn +4 

### ] 8 

### O 16 

### ) (Tangstad et al., 2004). Manganese ores such as these, containing manganese in the higher oxidation states (+3 and +4), are not soluble in sulfuric acid without first being reduced through a process such as c alcination. Calcinat ion of manganese oxide ore consists of crushing ore to a proper degree of fineness, adding bituminous coal as a reductant, and raising the temperature to just over 850 oC (Todd

, 2010). Energizer produced an electrolytic manganese dioxide (EMD) product fro m the reduced calcined ore, which was leached in a solution of sulfuric acid, ferric sulfate, and peroxide (NEICVP0591E05). The elemental profile of the Energizer calcined ore (EB05) most resembled the elemental profiles of the three Comilog ore samples f rom Eramet (ERM13, ERM14, and ERM15). Solids from the calcined ore leach process were sampled as jarosite skip material (EB04), in which chromium, lead, and zinc were more abundant relative to manganese compared to that in
calcined ore. An increase of th ese metals relative to manganese would be expected for the solids of a leach process to extract manganese. After additional processing steps, manganese was recovered from the leach solution in an electrolytic plating process. The resultant product plate (EB03) was stripped from titanium anodes and subjected to a series of washing steps to produce finished EMD product (EB01 and EB02). Elemental profiles of finished EMD product were consistent with considerable separation of chromium, lead, and zinc during the production process because the profiles lacked lead and zinc, and because chromium was much less abundant (about 5 times) relative to manganese in compar ison to calcined ore. Furthermore, because lead and zinc were absent from the EMD profiles and ch romium was nearly three orders of magnitude lower relative to manganese, the EMD profiles were not comparable to those of the TSP filters. Although profiles for the other three Energizer samples did include chromium, lead, zinc, and manganese, those eleme nts were not present in similar relative proportions as observed on the TSP filters. In particular, chromium was more abundant relative to lead and zinc. Thus, elemental profiles for the other three samples from the Energizer facility did not compare wel l to elemental profiles of the TSP filters (Figures 5 and 6a)

.

In the samples from MIE, relative proportions of chromium, lead, zinc, and manganese also did not compare well to those of the TSP filters (Figures 5 and 6a) . For Highlander slag (MIE01), finished medium carbon iron

- manganese ore (MC FeMn) (MIE02), and unwashed raw Felman slag (MIE04), chromium was more abundant relative to lead and zinc, and lead was more abundant than zinc. For beam dust near the baghouse (MIE03), chromium was more
abund ant than lead.

Elemental profiles of the following Eramet samples most resembled profiles of the TSP
filters (Figures 5 and 6b) : f urnace 1, tapping baghouse dust (ERM03); f urnace 18, 4 th 

### levelATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### building beam dust (ERM06); f urnace 12 east beam dust (ERM09); and MOR baghouse dust (ERM11). These samples contained chromium, lead, and zinc in similar relative abundances to each other and in increasing relative abundance to manganese, respectively, as in the TSP filters. However, abundances of manganese relativ e to chromium, lead, and zinc were generally higher, by about one to two orders of magnitude, compared to the TSP filters.

It should be note d that the elemental profile of dust from the 4 th 

### level beam of Eramet’s
f urnace 18 (ERM06) more closely resembled the profile of the TSP filters than the profile of dust
from the 2 nd 

### level beam of f urnace 18 (ERM07). C onsider ation of the boiling points of chromium, lead, zinc, and manganese at 2

, 67 1; 1

, 74 9; 907 ; and , 2,061 °C, respectively (CRC

, 1996), may explain t his difference. Because the boiling point of chromium is so much higher
than that of the other metals, as evaporating metal fume (gas) rose from the furnace melt and cooled, chromium would have tended to condense earlier than the other metals . Figure 7 s hows an abundance of evaporating metal fume cooling and condensing during tapping of Eramet’s
f urnace 12. The result would have been a greater abundance of chromium relative to lead and zinc in dust closer to the furnace as seen in ERM07 (2 nd 

### level beam dust) relative to ERM06 (4 th 

### level beam dust). Eramet samples with ele mental profiles similar to ERM07 included f urnace 1
beam dust above casting sand (ERM05); f urnace 12 west beam dust (ERM08); and MOR heavies (ERM10). All of these samples w ere composed of dust found in areas of the Eramet facility where metal fume was regularly formed. Furthermore, because of the much greater abundance of manganese present in the furnace melts

, along with the higher boiling point of manganese
relative to le ad and zinc, higher relative abundances of manganese might also be expected closer
to the furnaces.

The temperature for calcination for the production of Energizer’s calcined ore

, just over
850 oC (Todd

, 2010)

, was much lower than the furnace temper ature for ferromanganese alloy production at around 1

, 500 oC (Matricardi and Downing, 2005). Th e large temperature difference may explain why the elemental ratios of chromium, lead, and zinc to manganese were conserved during calcination, but not during the pro duction of ferromanganese alloys. The elemental profiles o f Energizer materials did not compare well to profiles of Eramet samples ERM03, ERM06, ERM09, and ERM11 or to the profiles of the TSP filters. Because proc esses at MIE were not high

- temperature pr ocesses like those in the furnaces at Eramet, conservation of elemental profiles for material from MIE would be likely on TSP filters . However, the elemental profiles observed in samples from MIE did not resemble the profiles observed for the TSP filters

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- Receptor Study: Results and Interpretation Figure 7. E ramet’s f urnace 12 during tapping releasing an abundance of evaporating metal fume (gas) that is cooling and condensing as it rises (courtesy M. Colledge, ATSDR).



### DISCUSSION OF LEAD I SOTOPE RATIOS

In this section, i sotopic ratios of lead for facility samples were compared to each other
and to the TSP filters. L ead isotope ratios were identified as potential tracers of manganese in
the airborne dust collected on the TSP filters b ecause a strong correlation between manganese
and lead was fo und on the TSP filters (NEICVP0591E06) . Furthermore, b ecause lead isotopes do not appreciably fractionate, the isotopic ratios of lead can be used as geochemical tracers. The only means by which lead isotope ratios may change is through mixing with mater ials containing different lead isotope ratios. Because many different materials are mixed during the furnace processes at the Eramet facility, an understanding of those materials and processes is important. The following description is provided to help u nderstand and compare the lead isotope ratios for the TSP filters and facility samples.

In the production of high

- carbon ferromanganese alloy (HC FeMn), ores from different sources are typically mixed to obtain the appropriate iron

- to

- manganese ratio s (Matricardi and Downing, 2005; Olsen et al., 2007). Before they are introduced to the furnace, ore fines areATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### fused together to produce sintered ore with a larger grain size. The sintering of fines is necessary
to ensure uniform distribution of reaction gases throughout the materials in the furnace. Raw material fines cause poor charge porosity, greater power consumption per ton of alloy, excessive fume and dust losses, and lower productivity. Coke made from coal is a typical source of carbon
for the o re reduction in an arc furnace. Coke is typically formed from coal in a high

- temperature oven to drive off volatiles and form a porous carbonaceous material. Limestone and dolomite are typical fluxes added to form slag, which aid in removing unwanted com ponents from the melt. The chemistry of the furnace charge is typically optimized by the controlled blending of input materials, ensuring prescribed properties for the alloy product and minimizing energy consumption. At Eramet, the Assoman and Comilog or es were blended, and coke made from nearby Appalachian coal and limestone/dolomite flux were added to furnace 12 and furnace 18 to produce HC FeMn (NEICVP0591E05 ; Hughes, 2011a ; Eramet, 2011).

In the production of silicomanganese alloy (SiMn), feedstock materials include manganese ore, HC FeMn slag, a source of silica, coke, and limestone/dolomite fluxes (Olsen et al., 2007). At Eramet, HC FeMn slag from furnaces 12 and 18 were mixed with manganese ore, silica dross, silica ladle dig

- out, coke made from nearby Appalachian coal, and limestone/dolomite flux to produce SiMn in furnace 1 (NEICVP0591E05; Matricardi and Downing, 2005; Hughes, 2011a and b; Eramet 2011).

Dust samples colle cted on beams above the Eramet furnaces or in associated baghouses

were de posited largely from gaseous metal fume which evaporated from the furnaces during production and condensed into metal oxide particles (see F igure 7 ). Beam dust likely represented significant historical composites of airborne particulate matter produced pr imarily during production processes that included smelting, tapping, and casting

. Only the smaller size fraction of the beam dust samples most likely to be transported by the wind were analyzed

. This, along with the relative consistency of the processes and feedstock materials, justified comparisons of facility samples with TSP filter particulate matter.

In a three

- isotope plot f or lead ( F igure 8 ), six of these Eramet furnace area dust samples
had a n approximately linear relationship (spearman’s correlat ion coefficient, r s 2 

### = 0.89) consistent with a mixing line for materials with two different lead isotope compositions . These samples included: f urnace 1 tapping baghouse dust (ERM03)

, f urnace 1 beam dust above casting sand (ERM05)

, f urnace 18 4th level beam dust (ERM06)

, f urnace 18 2nd level beam dust (ERM07), f urnace 12 west beam dust (ERM08), and f urnace 12 east beam dust (ERM09). If this line were continued to the lower left of the plot, the line would fall between the lead isotope
ratios of the Asso man and Comilog ores, suggesting consistent mixin g of those materials during furnace production . If this line were continued to the upper right of the plot, the line would fall on or near the lead isotope ratios of regional Appalachian coals (Chow and Ear l

, 1972). The main source of atmospheric lead in rural areas or isolated industrial sites is coal combustion orATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### ore reduction (Hutchinson et al., 1996). Coal from nearby Appalachian coal fields also powers the Eramet furnaces (Hughes, 2011 a; Eramet

, 2011 ). The linear variation of lead isotope ratios for these furnace dust samples was consistent with lead in the coke being released as the coke is consumed and deposited in the dusts in various amounts around the facility.

Lead isotope ratios of the TSP filters also had a n approximately linear relationship (r s 2 

### = 0.97) and coincided very well with th e lead isotope ratios of the six Eramet furnace area dust samples described above ( Figure 8 ) . This relationship was consistent with some of the particulate m atter on the TSP filters forming in the furnace area processes at Eramet . TSP filters
collected downwind of the former U nion C arbide complex a re shown as inverted green triangles, TSP filters collected upwind a re shown as upright blue triangles, and TSP filters that were neither upwind nor downwind are shown as crosses

. D ownwind TSP filters plot ted with the six Eramet dust samples, u pwind TSP filters plotted along the line between the six Eramet dust samples and the Appalachian coals , and the crosses representing the neither upwind nor downwind filters overlapped most of the upwind filters and the upper portion of the downwind
filters

.
The lead isotope ratios observed for the Blue Knob Road and Career Center TSP air monitoring sites sampled on October 21, 2007 (the two inverted green triangles at lower left of Figure 8), suggested much less blending of coke feedstock relative to ore . These lead isotope
ratios we re significantl y less radiogenic than th ose of th e other TSP filters because they were
enri ched in 207 

### Pb , as indicated by their position much further towards the lower left of the plot

.
Figure 8 shows that the isotope ratios of product plate (EB03) from the plate shed at the Energizer facility were consistent with those of the TSP filters collec ted downwind of the former
U nion C arbide complex. However, the product plate sample was not comprised of particulate

matter and did not display elemental profiles similar to the TSP filters. Isotope ratios of jarosite skip (EB04) and calcined ore (EB05) were similar to downwind TSP filters but distinguishable
from them when comparing even the largest expanded uncertaint y estimates (2SD = ±0.00 3 ) for
both 208 

### Pb/ 207 

### Pb and 206 

### Pb/ 207 

### Pb. Samples of EMD products (EB01 and EB02) contained
insufficient lead to m ake isotope ratio measurements.

As may be expected, the lead isotope ratios of many of the dust samples collected at
Eramet resemble d the lead isotope ratios of samples collected at Energizer, because feedstock materials for the respective processes were similar (NEIC VP0591E05 )

. L ead isotope ratios observed in Energizer samples were consistent with the blending of Comilog ore and Appal achian coal /coke

. Comilog ore , along with coal and coke most likely from Appalachian
coal fields

, were similar feedstock materials in the production of Energizer’s calcined ore (EB05)
that w as processed at elevated temperatures offsite in Quincy, Illinois

. C alcined ore i s typically processed at just over 850 oC (Todd

, 2010)

, whereas Eramet’s materials experienced a muchATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### higher temperature of approximately 1

, 500 oC for ferromanganese alloy production (Matricardi and Downing, 2005). L ead isotope ratios wer e not determined for the Australian Groote ore, which makes up approximately 20 percent of Energizer’s calcined ore and was not available for sampling , because the calcined ore was produced offsite

.
Figure 8 also shows that lead isotope ratios in most sam ples from MIE were not consistent with the lead isotope ratios in the TSP filter s

. Although beam dust from MIE (MIE03) exhibited similar lead isotope ratios compared to TSP filters, it did not exhibit a similar elemental profile or reveal any spherical Mn

- oxide particles. However, some similarity in isotope ratios was indicated between Highlander slag (MIE01), Felman slag (MIE04), Erament’s
f urnace 1 3rd level beam dust (ERM01), and Eramet’s f urnace 1 2nd level beam dust (ERM04).
To make a SiMn product i n Eramet’s f urnace 1, additional materials were used that were not
used in f urnaces 12 and 18 to make the ferromanganese product. These materials included silicon dross from Globe Metallurgical, Inc. (Globe) facilities in Bridgeport, Alabama, and silica
l adle dig

- out from Globe facilities in Beverly, Ohio, and Alloy, West Virginia (Hughes, 2011 b ). Highlander (MIE01) and Felman (MIE04) slags were SiMn slags produced at the Felman Production, Inc. facility in New Haven, West Virginia ( NEIC VP0591E05).ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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## Three-Isotope Plot for Pb TSP Filters and Facility Samples

208 

### Pb / 207 

### Pb 2.32 2.34 2.36 2.38 2.40 2.42 2.44 2.46 2.48 2.50 2.52206Pb /207Pb

1.00 1.05 1.10 1.15 1.20 1.25

F1 F1 F1 F1

F18 F18

F12

F12

C2P

MOR
MOR A

CR

CR
CR

CS CS MIE01 MIE02 MIE03

MIE04

ERM01 ERM05 ERM04 ERM03 EB03

EB04 EB05 Filters Downwind of Union Carbide Complex Filters Upwind of Union Carbide Complex Filters neither up nor downwind of Union Carbid Energizer Marietta Industrial Enterprises Eramet Furnace 1 F1 Eramet Furnace 18 (ERM06, ERM07) F18 Eramet Furnace 12 (ERM08, ERM09) F12 Eramet C2P Crusher (ERM02) C2P Eramet MOR MOR Eramet Assoman Ore

A Eramet Comilog Ore CR Eramet Comilog Sinter CS Appalachian Coal from West Virginia

Figure 8. Lead isotope ratios for TSP filters and facility samples from Eramet, Energizer, and MIE . Gray error bars indicate the largest estimate of expanded uncertainty ( 2SD = ±0.00 3). Literature values with uncertainty are shown for Appalachian coals from West Virginia ( Chow and Earl , 1972 )

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### DISCUSSION OF SEM RESULTS

As indicated in NEIC VP0591E06 , all of the Mn

- rich particles found on TSP filters
occurred as Mn

- oxide, 77 percent of wh ich exhibited a spherical morphology. The Mn

- oxide particles on the TSP filters were typically 1 to 2 μm in size , 21 percent of which were respirable in the size range of less than 2 .5 μm aerodynamic diameter

. Spherical morphology of metal oxide particle s was consistent with high

- temperature processes in which a metal fume forms, cools, and condenses.

Comparison of those earlier results to SEM results of the facility samples characterized above indicated similar particles of Mn

- oxide spheres were only found in samples from the Eramet facility and were particularly abundant in the size range of less than 10 **μ** m geometric
diameter . Spherical Mn

- oxide particles occurred in dusts a bove f urnaces 1, 12, and 18; in the
f urnace 1 tapping bagh ouse; in t he MOR baghouse; and in the MOR heavies. Spherical morphology of manganese

- bearing particles was not observed in samples of particulate matter from either Energizer or MIE. Examples of micrometer

- scale, spherical, Mn

- oxide particles from one TSP filter, three dust samples from above Eramet’s furnaces, and one dust sample from Eramet’s MOR baghouse showed numerous similarities (Figures 9 a to 9 e) , consistent with an origin in Eramet’s furnace area processes that included smelting, tapping, and casting.
Com parison of concomitant elements in Mn

- bearing particles in both TSP filters and facility samples did not prove useful because of the composition of the glass fiber matrix of the TSP
filters in which the airborne particles wer e embedded.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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- Receptor Study: Results and Interpretation Figure 9a. S EI image of spherical Mn

- oxide particle with a 2.1

- μm geometric diameter on filter G3009919 collected at Neale Elementary School on May 12, 2007.

Figure 9 b. SEI image of spherical Mn

- oxide particle with a 4.9

- 

### μ m geometric diameter in sample of MOR baghouse dust (ERM11) collected from Eramet in March 2009.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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- Receptor Study: Results and Interpretation Figure 9 c. SEI image of spherical Mn

- oxide particle with a 2.6

- 

### μ m geometric diameter in sample of dust from f urnace 1, 2 nd level column (ERM04) collect ed from Eramet in March 2009.

Figure 9 d. SEI image of spherical Mn

- oxide particle with a 4.5

- 

### μ m geometric d iameter in sample of dust from f urnace 18, 2 nd level beam (ERM07) collected from Eramet in March 2009.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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- Receptor Study: Results and Interpretation Figure 9 e. SEI image of sph erical Mn

- oxide particle with a 14.0

- 

### μ m geometric diameter in sample of dust from furnace 12, west beam (ERM08) collected from Eramet in March 2009.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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## SUMMARY AND CONCLUSI ONS

Table 6 summarizes the interpretations of the analytical data and other information in the previous sections b y indicating whether (1) elemental and lead isotope results f or samples from Eramet, Energizer, and MIE resembled analytical results f or the TSP filters; (2) spherical manganese oxide particles were observed; or (3) the facility in question was located at or near the former Union Carbide complex. Profiles of the relative abundances of chromium, lead, zinc, and manganese in airborne particulate matter indicated a consistent manganese composition over a widespr ead area, which, along with an abundance of spherical manganese particles, was consistent with the presence of a n industrial

- scale emitter of airborne manganese particulate matter in the Marietta area. Manganese responses by LA

- ICP

- MS on TSP filters relat ive to air
monitor ing sites and 24

- hour wind data indicated a large source of airborne manganese particulate matter was located at or near the former Union Carbide complex wher e Eramet and Energizer are now located. In addition, spherical Mn

- oxide particl es were a typical by

- product of the high

- temperature processes unique to Eramet’s production.

Table 6

. RESULTS SUMMARY Marietta, Ohio, Source

- Receptor Study: Results and Interpretation

Facility 1 Sample Location / Material NEIC Sample

Site Number NEIC Sample

Tag Number N ear former Union Carbide complex Elemental abundances

resemble TSP filters Lead isotope ratios resemble TSP filters Spherical Mn oxide particles observered

Eramet Furnace 1

- 3 rd level beam ERM01 NE25080 Yes No No Yes

Eramet C2P baghouse dust ERM02 NE25081 Yes No No No

Eramet Furnace 1 tapping baghouse dust ERM03 NE25083 Yes Yes Yes Yes

Eramet Furnace 1 2 nd level column ERM04 NE25086 Yes No No Yes

Eramet Furnace 1 beam above casting sand ERM05 NE25087 Yes Maybe Yes No

Eramet Furnace 18

- 4 th level beam ERM06 NE25090 Yes Yes Yes Yes

Eramet Furnace 18

- 2 nd level beam ERM07 NE25092 Yes Maybe Yes Yes

Eramet Furnace 12

- west beam ERM08 NE25094 Yes Maybe Yes Yes

Eramet Furnace 12

- east beam ERM09 NE25096 Yes Yes Yes Yes

Eramet MOR 2 heavies ERM10 NE25097 Yes Maybe No Yes

Eramet MOR baghouse dust ERM11 NE25099 Yes Yes No Yes

Eramet Assoman ore ERM12 NE25102 Yes No No N.A.

Eramet Comilog f ine ore ERM13 NE25104 Yes No No N.A.

Eramet Comilog r egular ore ERM14 NE25106 Yes No No N.A.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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. RESULTS SUMMARY Marietta, Ohio, Source

- Receptor Study: Results and Interpretation

Facility 1 Sample Location / Material NEIC Sample

Site Number NEIC Sample

Tag Number N ear former Union Carbide complex Elemental abundances

resemble TSP filters Lead isotope ratios resemble TSP filters Spherical Mn oxide particles observered

Eramet Comilog s inter ERM15 NE25107 Yes No No N.A. Energizer Product bag # 14 EB01 NE25069 Yes No N.A. No Energizer Product bag #13 EB02 NE25072 Yes No N.A. No
Energizer Product plate from plate s hed EB03 NE25073 Yes No Yes N.A.
Energizer Jarosite s kip EB04 NE25075 Yes No No No Energizer Calcined ore EB05 NE25078 Yes No No No

MIE Highlander slag MIE01 NE25109 No No No No

MIE Finished medium carbon FeMn MIE02 NE25111 No No No No

MIE Beam d ust NW corner MIE03 NE25113 No No Maybe No

MIE Felman slag @ Green Global MIE04 NE25116 No No No N.A.

1 Bolded

- blue text in Facility column = three or more of four tests consistent (Yes) with TSP filter particulate matter
2 MOR = manganese oxygen refining process



### (1) MIE was not the major contributor of airborne manganese particulate matter in the
Marietta area as represented by the five TSP air monitoring sites . Results of three different tests (elemental profiles

, lead isotope ratio s , and SEM) comparing MIE samples with TS P filters consistently indicated manganese

- bearing particulate matter in MIE samples w as distinguishable
from that on the TSP filters. Furthermore, an additional test ( LA

- ICP

- MS Mn and wind data as an indicator of Mn source location) frequently distinguis he d the former Union Carbide complex as the location of the primary source of airborne Mn particles collected on the TSP filters. Finally, the MIE facility did not have the capability of conducting high heat processes consistent with the production of abu ndant spherical, micrometer

- scale Mn

- oxide particles , which accounted for approximately 77 percent of manganese

- bearing particles on the TSP filters

.
( 2) Energizer also was not the major contributor of airborne manganese particulate matter
in the Marietta area as represented by the five TSP air monitoring sites

. Although the Energizer and Eramet facilities at the former Union Carbide complex could not be distinguished as

po tential sources of airborne manganese b ased on their relative locations, results of the other tests were more discerning. Lead isotope data indicated that only one Energizer sample was indistinguishable from the downwind TSP filters

– product plate from t he plate shed (EB03). However, the product plate sample was not comprised of particulate matter and, along with the
other four samples from Energizer

, did not display elemental profiles similar to the TSP filters. Finally, the Energizer facility also did not have the capability of conducting high heat processes consistent with the production of abundant spherical, micrometer

- scale Mn

- oxide particles.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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### Furthermore, spherical Mn

- oxide particles were not observed in any samples collected from Energizer.

(3 ) Eramet ’s furnace processes, that included smelting, tapping, and casting, w ere the primary source of manganese

- bearing airborne particulate matter in the Marietta area as represented by the five TSP air monitoring sites. This was based on the location of its facility and analytical results o f samples from its facility . Eramet sample results were considerably more
consistent with the TSP filter results , as follows:

**•** The LA

- ICP

- MS Mn and wind data frequently distinguished the former Union Carbide compl ex , where Eramet was located, as the location of an industrial

- scale and primary source of airborne Mn particles in the Marietta area as represented by the five TSP air monitoring sites

.

**•** Four Eramet dust samples exhibited elemental profiles similar to t hose of the TSP filters. Elemental profiles of an additional four dust samples tracked profiles of the TSP filters except for chromium’s greater relative abundance likely due to more rapid cooling of chromium as a result of its relatively high boiling poi nt.

**•** Six Eramet furnace area dust samples displayed lead isotope ratios that were indistinguishable from the lead isotope ratios found in the downwind TSP filters. This was consistent with particulate matter on the TSP filters originating from Eramet ’ s furnace area processes.

**•** Spherical Mn

- oxide particles were a unique particle type found on TSP filters from all five air monitoring sites. Approximately 77 percent of manganese

- bearing particles found on TSP filters occurred as Mn

- oxide spheres, consistent with a high

temperature process from which a metal fume forms, cools, and condenses into spheres. Eramet was the only facility conducting high

- temperature processes (at approximately 1

, 500 oC) consistent with metal fume formation and condensati on , and the only facility with samples in which spherical Mn

- oxide particles were observed. Eight Eramet dust samples and the MOR heavies and baghouse contained spherical Mn

- oxide particles , consistent with formation in Eramet’s furnace area processes

.

E valuation of all of the independent evidence presented in this and previous reports and
outlined above indicated that the furnace areas at Eramet w ere the primary source of airborne manganese particulate matter in the area covered by the five TSP air monit oring sites near Marietta, Ohio

.ATTORNEY WORK PRODUCT/ENFORCEMENT CONFIDENTIAL/FOIA EXEMPT

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