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Results and Interpretation
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CONTENTS

EXECUTIVE SUMMARY.............................................................................................................. 5

INTRODUCTION................................................................................................................ 5

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

SUMMARY OF FINDINGS................................................................................................ 8

LABORATORY ACTIVITIES...................................................................................................... 10

SAMPLE RECEIPT AND DESCRIPTION ...................................................................... 10

ANALYSIS OF SAMPLES/ANALYTICAL BACKGROUND....................................... 11

GENERAL SAMPLE PREPARATION............................................................................ 13

ELEMENTAL ANALYSIS ............................................................................................... 14

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

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

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

LEAD ISOTOPE RATIO MEASUREMENTS................................................................. 14

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

Column Separation....................................................................................................... 15

Multi-Collector Inductively Coupled Plasma Mass Spectrometry............................... 15

SCANNING ELECTRON MICROSCOPY ...................................................................... 16

LABORATORY RESULTS .......................................................................................................... 17

ELEMENTAL ANALYSES .............................................................................................. 17

LEAD ISOTOPE RATIO MEASUREMENTS................................................................. 21

SEM ANALYSIS............................................................................................................... 24

DISCUSSION OF ANALYTICAL RESULTS FOR TSP FILTERS 

AND FACILITY SAMPLES ................................................................................................... 31

LASER ABLATION RESPONSES FOR MANGANESE IN RELATION 

TO WIND DIRECTION .............................................................................................. 31

TIME SERIES TRENDS OF MANGANESE LASER ABLATION RESPONSES......... 37

COMPARISON OF ELEMENTAL RESULTS FOR AIR FILTERS AND 

FACILITY SAMPLES................................................................................................. 40

DISCUSSION OF LEAD ISOTOPE RATIOS.................................................................. 46

DISCUSSION OF SEM RESULTS................................................................................... 51

SUMMARY AND CONCLUSIONS............................................................................................. 55

REFERENCES............................................................................................................................... 58
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CONTENTS—continued

TABLES

1 The Seven NEIC Reports Comprising the Airborne Manganese Source-Receptor Study... 6

2 Collection Date and Location of 24 Facility Samples Collected by NEIC Field Branch 

Personnel ............................................................................................................................ 10

3 Elemental Results for Facility Samples Extracted by EPA Method IO-3.1 and Analyzed 

by ICP-OES........................................................................................................................ 17

4a Lead Isotope Ratio Determinations for TSP Filters........................................................... 21

4b Lead Isotope Ratio Determinations for Facility Samples .................................................. 23

4c Lead Isotope Ratio Determinations for Reference Materials............................................. 24

5 Summary of SEM data of Manganese-Bearing Particles in Facility Samples................... 26

6 Results Summary................................................................................................................ 55

FIGURES

1a SEI image of spherical Mn-oxide particle with a 6.6-μm 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

2a SEI image of angular Mn-oxide particle with an 8.3-μm geometric diameter in sample of 

beam dust above casting sands in furnace 1 building (ERM05) collected from Eramet in 

March 2009......................................................................................................................... 28

2b SEI image of angular Mn-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 angular 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 angular Mn-oxide particle with a 7.5-μm geometric diameter in sample of 

electrolytic MnO2 (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

3a Predominant wind direction from the west and west-northwest, with highest manganese 

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 .... 34

3c Predominant wind direction from the east-southeast, 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......................................................... 35
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CONTENTS—continued

FIGURES--continued

3d Predominant wind direction from the south and south-southwest, with highest manganese 

abundance observed (>46x) at the Washington County Career Center air monitoring site,

which was downwind from the former Union Carbide complex and the MIE site............ 36

4a Time series trends of manganese abundance at two air monitoring sites northeast of the 

former Union Carbide complex. The Washington County Career Center site was farther 

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 monitoring 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 Blue Knob air monitoring 

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

6a Elemental abundances shown as a relative fraction to manganese for samples collected at 

Energizer and MIE. ............................................................................................................ 42

6b Elemental abundances shown as a relative fraction to manganese for samples collected at 

Eramet. ............................................................................................................................... 43

7 Eramet’s furnace 12 during tapping releasing an abundance of evaporating metal fume 

(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

9a SEI 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

9b 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 ............................. 52

9c SEI image of spherical Mn-oxide particle with a 2.6-μm geometric diameter in sample of 

dust from furnace 1, 2nd 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, 2nd level beam (ERM07) collected from Eramet in March 2009.... 53

9e SEI image of spherical 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.......... 54

This Contents page shows all of the sections contained in this report 

and provides a clear indication of the end of this report.
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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 two 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/m3] [U.S. Department of Health and Human Services [HHS], 2010]) as well as 

the U.S. Environmental Protection Agency (EPA) reference concentration (RfC) value (0.05

μg/m3 [U.S. EPA, 2011]). EPA Region 5, Ohio EPA, and ATSDR determined that the potential 

emitters of manganese-bearing airborne 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 Region 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 of 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, ventilation 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 Federal public 

health agency of the U.S. Department of Health and Human Services. http://www.atsdr.cdc.gov/
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Table 1. THE SEVEN NEIC REPORTS COMPRISING THE AIRBORNE MANGANESE SOURCERECEPTOR STUDY

Marietta, Ohio, Source-Receptor Study: Results and Interpretation

Report

Number Date Title Contents Main Conclusions

NEICVP0591E01October

2004

Interim Results for Career 

Center TSP Filter Samples

Initial characterization 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 

NEICVP5091E02December

2004

Interim Results for Career 

Center Welding Shop 

Samples Collected 

September 18, 2003

Sampling and initial

characterization of Career 

Center welding shop dust

Welding shop dust

contained infrequent 

angular Mn-rich 

particles and common 

spherical Ca-Fe and 

Ca-Ti-rich particles

NEICVP0591E03September

2005

Final Results and 

Interpretation

Eramet Marietta, Inc.

Characterization of 

welding shop dust, 

ore, and facility filters /

Comparisons with 

previously reported TSP 

filter data

Welding shop dust 

not source of Mn on 

TSP filters

NEICVP0591E04 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 elemental 

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

NEICVP0591E05 June 2010

Eramet CAA/Mn 

Investigation.

Marietta, Ohio

Description sampling and 

processes at three 

Marietta area facilities

None

NEICVP0591E06 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/ 

Minimum risk level 

(MRL) for Mn

exceeded 95 percent 

of the time

NEICVP0591E07 April 2011

Marietta, Ohio, SourceReceptor Study:

Results and Interpretation

Characterization of facility 

samples, 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 monitoring 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 was 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 was at least one 
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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 collected 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 conducted Clean Air Act (CAA) inspections at 

Eramet, Energizer, and MIE near Marietta, Ohio. Eramet and Energizer were located at the 

former Union Carbide complex about 4 miles southwest of Marietta, and MIE was located about 

2 miles farther southwest. Operations 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 batteries. MIE conducted 

grinding, sizing, packaging, transportation, and storage for a wide variety of materials which 

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); limestone; gravel; 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 the 

five TSP air monitoring sites. Details of the field inspections and sample collection are 

documented in NEICVP0591E05. 

NEIC report NEICVP0591E06 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. The report contains 

the following conclusions: (1) LA-ICP-MS manganese concentration estimates for airborne 

particulate matter indicated the ATSDR minimum risk level (MRL) for manganese of 0.04 μg/m3

was exceeded 95 percent of the time in the Marietta area; (2) manganese-bearing particles 

occurred mainly as manganese-oxide spheres, consistent with a high-temperature process 

producing a metal fume; (3) the 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) correlations 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 relatively large emitter of airborne 

manganese particulate matter in the Marietta area.
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This report, NEICVP0591E07, presents results of facility sample characterization, 

comparisons with previously reported TSP filter data, and interpretations.

SUMMARY OF FINDINGS

• Eramet’s furnace areas were 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 Eramet 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 greatest abundance of 

manganese were mostly downwind of the former Union Carbide complex, where Eramet 

was located. Examination of the relative manganese abundance at the five TSP sampling 

locations air monitoring sites on multiple days showed that at least one major industrialscale 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. 

• Elemental analysis results indicated that chromium, lead, and zinc were co-contaminants 

of the manganese collected on the TSP filters. These results were consistent with 

chromium, lead, and zinc being common contaminants associated with the 

ferromanganese alloy industry and, according to Eramet personnel, the ore used at Eramet 

containing 48 percent manganese and trace amounts of chromium, lead, and zinc (Olsen et 

al., 2007; NEICVP0591E05). 

• Relative elemental 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 spheres. 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 spheres 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 collected 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 ratios, and 

SEM) comparing MIE samples with TSP filters consistently distinguished MIE particulate 

from that on the TSP filters. LA-ICP-MS Mn response and wind data frequently 

distinguished 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 highheat 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-bearing 

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 distinguished 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 plate 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. Furthermore, 

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, and such particles were not observed in any of the Energizer samples.
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LABORATORY ACTIVITIES

Laboratory activities included analysis 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-ICPMS), and scanning electron microscopy.

SAMPLE RECEIPT AND DESCRIPTION

On April 7, 2009, Steve Machemer of the NEIC Laboratory Branch received 24 facility 

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 LOCATION OF 24 FACILITY SAMPLES COLLECTED BY NEIC 

FIELD BRANCH PERSONNEL

Marietta, Ohio, Source-Receptor Study: Results and Interpretation1

Date Sampled Facility Location/Material

NEIC 

Sample 

Site 

Number

NEIC 

Sample 

Tag 

Number

March 17, 2009 Eramet Furnace 1, 3rd 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, 2nd level beam dust ERM04 NE25086

March 17, 2009 Eramet Furnace 1, beam dust above casting sand ERM05 NE25087

March 17, 2009 Eramet Furnace 18, 4th level beam dust ERM06 NE25090

March 17, 2009 Eramet Furnace 18, 2nd 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 MOR2 heavies (particulate matter) ERM10 NE25097

March 18, 2009 Eramet MOR baghouse dust ERM11 NE25099

March 18, 2009 Eramet Assoman ore3 ERM12 NE25102

March 18, 2009 Eramet Comilog fine ore3 ERM13 NE25104

March 18, 2009 Eramet Comilog regular ore3 ERM14 NE25106

March 18, 2009 Eramet Comilog sinter3 ERM15 NE25107

March 18, 2009 Eramet Bag blank B01 NE25065

March 16, 2009 Energizer Electrolytic MnO2 product bag #14 (particulate matter) EB01 NE25069

March 16, 2009 Energizer Electrolytic MnO2 product bag #13 (particulate matter) EB02 NE25072

March 16, 2009 Energizer Stripped product plate in pile in plate shed3 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 slag3 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 Global3 MIE04 NE25116

1

 From NEICVP0591E05, June 2010 2 MOR = manganese oxygen refining process 3 Sample ground for analysis
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Seventeen of the 24 facility samples consisted of abundant fine particulate matter. 

However, seven feedstock and product samples, representing ore, sinter, slag, and product plate,

consisted 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 dry powders and oily, consolidated particulate 

material. Specific sample descriptions are presented in the NEIC report NEICVP0591E05. 

ANALYSIS OF SAMPLES/ANALYTICAL BACKGROUND

Elemental abundance results for the facility samples were generated by acid digestion 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 generated by Theresa Hosick by LAICP-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 analysis was performed by MC-ICP-MS on both TSP filters and facility 

samples by Mike Pribil of the U.S. Geological Survey (USGS) from December 2008 to 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 performed to obtain scientifically valid and legally defensible data from the USGS 

laboratory. Data analysis and interpretation were provided by Steve Machemer, 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 an 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 the 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/m3

) 

were not obtained directly by this method, relative 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 establish quantitative concentrations (μg/m3

) of manganese in ambient airborne 
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particulate matter on the TSP filters and to demonstrate the linear relationship between the LAICP-MS and ICP-OES/ICP-MS techniques. These results were reported in NEICVP0591E06. 

Quantitative 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 manganese 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 (204Pb, 206Pb, 207Pb, and 208Pb). Only 204Pb is non-radiogenic, whereas 206Pb, 207Pb, and 208Pb

are the radiogenic decay products of the parent isotopes of uranium with atomic mass 238 (238U), 

uranium 235 (235U), and thorium 232 (232Th), respectively. The proportion of 206Pb, 207Pb, and 

208Pb in various ore bodies may vary significantly because of differences in the initial amounts of 

238U, 235U, and 232Th in the ores; different decay constants for 238U, 235U, and 232Th; 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 206Pb/207Pb 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; Hopper 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 the 
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Results and Interpretation

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

source 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 by 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 particle data frequently reveal information about the origin of 

particles and the processes that formed them. For example, spherical morphology of micrometerscale, metal oxide particles is consistent with particle formation via condensation of metal fume 

produced in a high-temperature process.

GENERAL SAMPLE PREPARATION

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 seven feedstock 

and product samples, consisting primarily of granule- to cobble-size material, were reduced to 

pea-size 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 ground to 

evaluate possible contamination from the grinding 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 transported by the wind so that the particles could be 

analyzed and compared 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 extraction with methylene chloride in a Soxhlet extraction apparatus overnight,

followed by 24 hours of drying at 95 °C before sieving. 
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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 (HNO3) 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 and 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 Spectroscopy

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 Methods for the Determination of 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 Plasma 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 dilution.

LEAD ISOTOPE RATIO MEASUREMENTS

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 instructions 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 and 
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Results and Interpretation

plastic ruler were used instead of the specialized template and cutting 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 Elemental Analysis, NEICPROC/00-062R4. 

After digestion, both the facility sample and TSP filter digestates were analyzed for lead by ICPMS. 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 Class 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 precleaned Savillex® vials and evaporated to dryness. The dried lead samples were reconstituted in 

10 to 20-mL 2 percent HNO3 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 the USGS high resolution MCICP-MS laboratory in Denver, Colorado, using a Nu Instruments HR, double-focusing MC-ICPMS. Samples were spiked with the National Institute of Standards and Technology’s standard 

reference material, NIST SRM 997, isotopic standard of thallium 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 cycle 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 205Tl/203Tl

value of 2.3875. Greater detail on the USGS MC-ICP-MS instrument configuration and mass 

bias correction for Pb isotopes is described by Ridley (2005).
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SCANNING ELECTRON MICROSCOPY

SEM was conducted by Steve Machemer on the 24 facility samples (Table 2). The 

objective was to characterize the composition and morphology of manganese-bearing particles in 

the less-than-150-μm-size fraction of the 17 sieved samples of particulate matter. 

Characterization was also conducted for 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 onsite. Results 

were compared between samples and with manganese-bearing particles found previously on the 

TSP filters (NEICVP0591E06).

Particulate matter was dab-mounted on 12-mm diameter, aluminum SEM specimen stubs 

using carbon adhesive tabs. Specimens were 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 parameters 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 μm 

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. 
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LABORATORY RESULTS

ELEMENTAL ANALYSES

Results of elemental analysis of facility samples extracted 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 EXTRACTED 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 Uncertaintyb

Relative %

MDLc

(mg/kg)

NE25069 NE25072 NE25073 NE25075

NEIC Sample 

Site Number EB01d EB02 EB03d 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

Leada 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 1.0e <0.9 <0.9 68.1

Nickel 10 0.1 <0.1 <0.1 2.44 140

Phosphorus 12 3 3.9e 2.7e 12e 2,070

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

Titanium 6.0 0.4 1.0e 0.8e 9.75 1,890

Vanadium 5.2 0.6 <0.6 <0.6 <0.6 672

Zinca 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, resulting 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 limit.
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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 EB05d MIE01d MIE02 MIE03d 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

Leada 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

Zinca 366 1.3e 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 limit.
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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 NE25080 NE25081 NE25083 NE25086 NE25087

NEIC Sample

Site Number ERM01 ERM02 ERM03 ERM04d 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

Leada 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

Zinca 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 limit.
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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 NE25090 NE25092 NE25094 NE25096 NE25097

NEIC Sample

Site 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

Leada 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

Zinca 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 limit.
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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 NE25099 NE25102 NE25104 NE25106 NE25107

NEIC Sample

Site Number ERM11d ERM12d 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

Leada 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

Zinca 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 limit.

LEAD ISOTOPE RATIO MEASUREMENTS

Results of lead isotope ratio determinations are presented in Tables 4a and 4b for TSP 

filters and facility samples, respectively.

Table 4a. LEAD ISOTOPE RATIO DETERMINATIONS FOR TSP FILTERS

Marietta, Ohio, Source-Receptor Study: Results and Interpretation 

Filter ID

Wind a

Speed/Direction/Precipitation Sampler Location Date of Sampling 208Pb/207Pb 206Pb/207Pb

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 Career 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-located 6/5/2007 2.406 1.138

G3009906 3 MPH WSW None Wash Career Center 5/24/2007 2.433 1.169

G3009913 4 MPH NNE None Harmar 5/18/2007 2.440 1.179
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Table 4a. LEAD ISOTOPE RATIO DETERMINATIONS FOR TSP FILTERS

Marietta, Ohio, Source-Receptor Study: Results and Interpretation 

Filter ID

Wind a

Speed/Direction/Precipitation Sampler Location Date of Sampling 208Pb/207Pb 206Pb/207Pb

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-located 5/6/2007 2.444 1.180

G3009927 7 MPH West None Wash Career 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 4/12/2007 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 Career 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-located 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 Career 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-located 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 2/12/2008 2.431 1.161

G6017034 3 MPH W Rain Harmar 9/9/2007 2.420 1.160

G6017052 5 MPH SW Rain Wash Career 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 Career 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 Career 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 Career 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-located 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 Career 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 Virginia
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Table 4b. LEAD ISOTOPE RATIO DETERMINATIONS FOR FACILITY SAMPLES

Marietta, Ohio, Source-Receptor Study: Results and Interpretation

NEIC Sample

Site Number Sampler Location 208Pb/207Pb 206Pb/207Pb

ERM01 Eramet furnace 1 3rd level beam dust 2.486 1.156

ERM02 Eramet C2P baghouse dust 2.386 1.103

ERM03 Eramet furnace 1 tapping baghouse dust 2.418 1.153

ERM04 Eramet furnace 1 2nd level beam dust 2.478 1.157

ERM05 Eramet furnace 1 beam above casting sand 2.426 1.155

ERM06 Eramet furnace 18 4th floor beam dust 2.392 1.109

ERM07 Eramet furnace 18 2nd level beam dust 2.410 1.140

ERM08 Eramet furnace 12 west beam dust 2.397 1.122

ERM09 Eramet furnace 12 east beam dust 2.389 1.115

ERM10 Eramet MORa heavies 2.369 1.072

ERM11 Eramet MOR baghouse 2.365 1.066

ERM12 Eramet Assoman ore 2.337 1.089

ERM13 Eramet Comilog fine ore 2.368 1.055

ERM14 Eramet Comilog regular ore 2.354 1.043

ERM15 Eramet Comilog sinter 2.357 1.054

EB01 Eveready electrolytic MnO2 product bag 14 Insufficient lead Insufficient lead

EB02 Eveready electrolytic MnO2 product 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 1.110

EB05 Eveready calcined ore 2.400 1.108

MIE01 MIE Highlander slag 2.476 1.166

MIE02 MIE finished medium-carbon FeMn 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 NEICVP0591E03) 

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 208Pb/207Pb of 2.370 ± 0.002 (2 standard 

deviations [SD]) and a 206Pb/207Pb of 1.095 ± 0.002 (2 SD). NIST SRM 981 certified values for 

208Pb/207Pb and 206Pb/207Pb are 2.370 and 1.093, respectively. NIST 2709 soil standard resulted in 

208Pb/207Pb of 2.483 ± 0.003 (2 SD) and 206Pb/207Pb of 1.217 ± 0.003 (2 SD), similar to the values 

reported by Takaoka et al. (2006) for 208Pb/206Pb of 2.483 ± 0.002 (2 SD) and 206Pb/207Pb of 1.217 

± 0.002. Multiple samples were processed through the sample preparation method in triplicate 
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and resulted in an expanded uncertainty for both 208Pb/207Pb and 206Pb/207Pb of ± 0.002 (2 SD). 

These results demonstrated negligible bias and are summarized in Table 4c.

Table 4c. LEAD ISOTOPE RATIO DETERMINATIONS FOR REFERENCE MATERIALS

Marietta, Ohio, Source-Receptor Study: Results and Interpretation

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

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

BCRa 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 2.370 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 class because they were 

clearly not spheroidal. Because silicon was the most common major element to occur in the Mnbearing particles, most of these particles were classified as either “Mn-oxide” or “Mn-Si-oxide”

based on the relative EDS response for silicon. Similarly, the classification of carbon particles 

containing Mn-oxide was based on a relatively strong EDS response for carbon. Most highcarbon particles were large enough (i.e., considerably larger than the electron beam excitation 

volume) that contributions 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-Sioxide particles were only found in samples collected at Eramet and were particularly abundant in 

the size range of less than 10 μm 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. 
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In contrast, angular Mn-oxide 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 with frequent concomitance of aluminum, calcium, iron, silicon, and sodium (Figures 2a

and 2b). However, most furnace dust (ERM01, ERM03, ERM04, ERM06, ERM07, ERM08, and 

ERM09) 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, ERM14, and ERM15) 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 dust (MIE03) from 

MIE contained angular Mn-oxide particles with frequent concomitance of aluminum, iron, 

phosphorous, silicon, and sodium. Angular Mn-oxide particles in beam dust (MIE03) also 

exhibited frequent concomitance of magnesium and sulfur. In contrast, Highlander slag (MIE01) 

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 Highlander and Felman slags appeared most similar to each 

other. 

Electrolytic MnO2 (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 amounts 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 (EB03) appeared most similar to the EMD 

product (EB01 and EB02). Jarosite skip from Energizer (EB04) contained abundant angular Mnbearing 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 in 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. 
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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 Sample 

Site Number Common Mn-bearing particle types Common elemental concomitance 1

Eramet Furnace 1, 3rd 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 C2P 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, 2nd 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 sands NE25087 ERM05 Angular Mn-oxide & Mn-Si-oxide Al, Ca, Fe, K, Mg, Na, Si, S

Eramet Furnace 18, 4th 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, 2nd 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 MnO2 Product bag #14 NE25069 EB01 Angular Mn-oxide Al, Na, Si, S

Energizer Electrolytic MnO2 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 building 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 preparation
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Figure 1a. SEI image of spherical Mn-oxide particle with a 6.6-μm geometric diameter in sample of 

MOR heavies (ERM10) collected from Eramet in March 2009.

Figure 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.
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Figure 2a. SEI image of angular Mn-oxide particle with an 8.3-μm 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-μm geometric diameter in sample 

of C2P crusher baghouse dust (ERM02) collected from Eramet in March 2009.
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Figure 2c. SEI image of angular Mn-oxide particle with a 6.5-μm 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-μm geometric diameter in sample of 

electrolytic MnO2 (EMD) product (EB02) collected from Energizer in March 2009.
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Figure 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.

Figure 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.
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DISCUSSION OF ANALYTICAL RESULTS FOR TSP FILTERS AND 

FACILITY SAMPLES

The following discussion considers: (1) the analytical results for airborne particulate 

matter collected on TSP filters from April 2007 to 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 filters, 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 RESPONSES FOR MANGANESE IN 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 when 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 3a to 8d). This was true regardless of the location of the TSP air monitoring site as 

illustrated on the maps in Figures 3a to 3d. 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 

(NEICVP0591E06).

Wind roses shown in the upper left of each map in Figures 3a to 3d are visual 

representations of how wind speed and direction were distributed around Marietta, Ohio, over a 

given 24-hour time period. Wind direction is 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 indicates the frequency of 

the wind speed in a given range for that wind direction. The point of the longest spoke of the 

wind rose points in the direction the wind was blowing most frequently (National Resources 

Conservation Service [NRCS], 2011). If the center of the wind rose were placed at the site of the 

former Union Carbide complex (EB and ERM triangles in Figures 3a to 8d), 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. 
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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 airborne 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 immediately downwind from the former Union Carbide complex (Figure 3a). 

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, 2007, 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 3b). Similarly, 

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 approximately 7x observed at the Blue Knob Road air monitor,

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

With the wind from the east-southeast, most of the manganese impact observed at the Blue Knob 

Road monitor was not likely the result of MIE emissions. 

The predominant wind direction on January 7, 2008, was from the south (S) and southsouthwest (SSW), with the highest manganese abundance by about 46x observed at the Career 

Center air monitor, which was downwind from the former Union Carbide complex and the MIE 

site (Figure 3d). 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, emissions 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) indicated the source of the 

airborne manganese particulate matter in the vicinity of the former Union Carbide complex was 

industrial in scale.
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Figure 3a. Predominant wind direction from the west and west-northwest, with highest manganese abundance observed (>100x) at the Boaz air monitoring 

site, which was downwind from the former Union Carbide complex.
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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 downwind from the former Union Carbide complex and the MIE site.
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Figure 3c. Predominant wind direction from the east-southeast, 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.
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Figure 3d. Predominant wind direction from the south and south-southwest, with highest manganese abundance observed (>46x) at the Washington County Career Center 

air monitoring site, which was downwind from the former Union Carbide complex and the MIE site. However, impacts at the Blue Knob and Boaz air monitors were low. 
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TIME SERIES TRENDS OF MANGANESE LASER ABLATION RESPONSES

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 particulate 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 the 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 

Village 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 onehalf mile closer to the former Union Carbide complex than the Career Center 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, 2008, 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. 
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Figure 4a. Time series trends of manganese abundance at two air monitoring sites northeast of 

the former Union Carbide complex. The Washington County Career Center site was farther from 

the Union Carbide complex than the Harmar Village site (designated sampler).

Figure 4b exhibits the time series trends 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 School 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 

Village 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

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Sampling Date

Manganese Response (counts per 

second)

Harmar Washington
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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 former 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 4c 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 Union 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 approximately 1 mile east (see Figures 3a to 

3d). However, because the MIE facility was not located in between these two air monitors, it 

was not likely that emissions from MIE could have contributed the inverse patterns observed in 

this case.

Manganese Time Series

0

200000

400000

600000

800000

1000000

1200000

1400000

1600000

1800000

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Sampling Data

Manganese Response (counts per 

second)

Harmar Neale
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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 directions, 

respectively. Note: On October 15, 2007, winds were about 1 mph, and on January 13, 2008, the 

wind direction was variable.

COMPARISON OF ELEMENTAL RESULTS FOR AIR FILTERS AND FACILITY 

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 correlations 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., 2007). 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 

components 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

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Sampling Date

Manganese Response (counts per second)

Boaz Blue Knob
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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-10/9/2007

Element / Mn

1e-6

1e-5

1e-4

1e-3

1e-2

1e-1

1e+0

1e+1

Chromium 

Lead 

Zinc 

Manganese 

Figure 5. Elemental abundances shown as a relative fraction to manganese for TSP filters with 

the ten highest manganese concentrations.

For comparison to the TSP filters, chromium, lead, and zinc concentrations as a fraction 

relative to the manganese 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 consistency 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. Only 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 Ore

Element / 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 Slag 

Element / Mn

1e-6

1e-5

1e-4

1e-3

1e-2

1e-1

1e+0

1e+1

Figure 6a. Elemental abundances shown as a relative fraction to manganese for samples 

collected at Energizer and MIE.
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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 Beam

Element / Mn

1e-6

1e-5

1e-4

1e-3

1e-2

1e-1

1e+0

1e+1

Chromium 

Lead 

Zinc 

Eramet Manganese 

ERM09-F12 E Beam

ERM10-MOR Heavies

ERM11-MOR BH

ERM12-Assoman Ore

ERM13-Com. Fine Ore

ERM14-Com. Reg. Ore

ERM15-Com. Sinter

Element / 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.
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Energizer obtained calcined manganese ore that consisted of Comilog ore (80 percent) 

and Australian Groote ore (20 percent) from Prince Minerals in Quincy, Illinois 

(NEICVP0591E05). Both ores were composed of the manganese ore minerals, pyrolusite 

(Mn+4O2) and cryptomelane (K[Mn+2Mn+4]8O16) (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 calcination. Calcination 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 from 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 from 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 these 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 comparison to calcined ore. Furthermore, 

because lead and zinc were absent from the EMD profiles and chromium 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 elements 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 well 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 

abundant than lead.

Elemental profiles of the following Eramet samples most resembled profiles of the TSP 

filters (Figures 5 and 6b): furnace 1, tapping baghouse dust (ERM03); furnace 18, 4th level 
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building beam dust (ERM06); furnace 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 relative to chromium, lead, and zinc were generally higher, 

by about one to two orders of magnitude, compared to the TSP filters. 

It should be noted that the elemental profile of dust from the 4th level beam of Eramet’s 

furnace 18 (ERM06) more closely resembled the profile of the TSP filters than the profile of dust 

from the 2nd level beam of furnace 18 (ERM07). Consideration of the boiling points of 

chromium, lead, zinc, and manganese at 2,671; 1,749; 907; and, 2,061 °C, respectively (CRC,

1996), may explain this 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 shows 

an abundance of evaporating metal fume cooling and condensing during tapping of Eramet’s 

furnace 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 (2nd level beam dust) relative to ERM06 (4th

level beam dust). Eramet samples with elemental profiles similar to ERM07 included furnace 1 

beam dust above casting sand (ERM05); furnace 12 west beam dust (ERM08); and MOR heavies 

(ERM10). All of these samples were 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 lead 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 temperature for ferromanganese alloy 

production at around 1,500 oC (Matricardi and Downing, 2005). The large temperature 

difference may explain why the elemental ratios of chromium, lead, and zinc to manganese were 

conserved during calcination, but not during the production of ferromanganese alloys. The 

elemental profiles of 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 processes at 

MIE were not high-temperature processes 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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Figure 7. Eramet’s furnace 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 ISOTOPE RATIOS

In this section, isotopic ratios of lead for facility samples were compared to each other 

and to the TSP filters. Lead isotope ratios were identified as potential tracers of manganese in 

the airborne dust collected on the TSP filters because a strong correlation between manganese 

and lead was found on the TSP filters (NEICVP0591E06). Furthermore, because 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 materials 

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 understand 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 ratios (Matricardi and 

Downing, 2005; Olsen et al., 2007). Before they are introduced to the furnace, ore fines are 
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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 ore 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 components 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 ores 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 collected on beams above the Eramet furnaces or in associated baghouses 

were deposited largely from gaseous metal fume which evaporated from the furnaces during 

production and condensed into metal oxide particles (see Figure 7). Beam dust likely 

represented significant historical composites of airborne particulate matter produced primarily 

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 for lead (Figure 8), six of these Eramet furnace area dust samples 

had an approximately linear relationship (spearman’s correlation coefficient, rs

2 = 0.89) 

consistent with a mixing line for materials with two different lead isotope compositions. These 

samples included: furnace 1 tapping baghouse dust (ERM03), furnace 1 beam dust above 

casting sand (ERM05), furnace 18 4th level beam dust (ERM06), furnace 18 2nd level beam dust 

(ERM07), furnace 12 west beam dust (ERM08), and furnace 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 Assoman and Comilog ores, suggesting consistent mixing 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 Earl, 1972). The 

main source of atmospheric lead in rural areas or isolated industrial sites is coal combustion or 
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ore reduction (Hutchinson et al., 1996). Coal from nearby Appalachian coal fields also powers 

the Eramet furnaces (Hughes, 2011a; 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 an approximately linear relationship (rs

2

= 

0.97) and coincided very well with the lead isotope ratios of the six Eramet furnace area dust 

samples described above (Figure 8). This relationship was consistent with some of the 

particulate matter on the TSP filters forming in the furnace area processes at Eramet. TSP filters 

collected downwind of the former Union Carbide complex are shown as inverted green triangles,

TSP filters collected upwind are shown as upright blue triangles, and TSP filters that were 

neither upwind nor downwind are shown as crosses. Downwind TSP filters plotted with the six 

Eramet dust samples, upwind 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 were significantly less radiogenic than those of the other TSP filters because they were 

enriched in 207Pb, 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 collected downwind of the former 

Union Carbide 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 uncertainty estimates (2SD = ±0.003) for 

both 208Pb/207Pb and 206Pb/207Pb. Samples of EMD products (EB01 and EB02) contained 

insufficient lead to make isotope ratio measurements. 

As may be expected, the lead isotope ratios of many of the dust samples collected at 

Eramet resembled the lead isotope ratios of samples collected at Energizer, because feedstock 

materials for the respective processes were similar (NEICVP0591E05). Lead isotope ratios 

observed in Energizer samples were consistent with the blending of Comilog ore and 

Appalachian 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 was processed at elevated temperatures offsite in Quincy, Illinois. Calcined ore is typically 

processed at just over 850 oC (Todd, 2010), whereas Eramet’s materials experienced a much 
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higher temperature of approximately 1,500 oC for ferromanganese alloy production (Matricardi 

and Downing, 2005). Lead isotope ratios were 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 samples from MIE were not 

consistent with the lead isotope ratios in the TSP filters. 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 

furnace 1 3rd level beam dust (ERM01), and Eramet’s furnace 1 2nd level beam dust (ERM04). 

To make a SiMn product in Eramet’s furnace 1, additional materials were used that were not 

used in furnaces 12 and 18 to make the ferromanganese product. These materials included 

silicon dross from Globe Metallurgical, Inc. (Globe) facilities in Bridgeport, Alabama, and silica 

ladle dig-out from Globe facilities in Beverly, Ohio, and Alloy, West Virginia (Hughes, 2011b). 

Highlander (MIE01) and Felman (MIE04) slags were SiMn slags produced at the Felman 

Production, Inc. facility in New Haven, West Virginia (NEICVP0591E05). 
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Three-Isotope Plot for Pb

TSP Filters and Facility Samples

208Pb / 207Pb

2.32 2.34 2.36 2.38 2.40 2.42 2.44 2.46 2.48 2.50 2.52

206Pb / 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

ERM05 ERM04 ERM01 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

F1 Eramet Furnace 1

F18 Eramet Furnace 18 (ERM06, ERM07)

F12 Eramet Furnace 12 (ERM08, ERM09)

C2P Eramet C2P Crusher (ERM02)

MOR Eramet MOR

A Eramet Assoman Ore

CR Eramet Comilog Ore

CS Eramet Comilog Sinter

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 = ±0.003). 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 NEICVP0591E06, all of the Mn-rich particles found on TSP filters 

occurred as Mn-oxide, 77 percent of which 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 particles 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 μm geometric 

diameter. Spherical Mn-oxide particles occurred in dusts above furnaces 1, 12, and 18; in the 

furnace 1 tapping baghouse; in the 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 9a to 9e), consistent with an 

origin in Eramet’s furnace area processes that included smelting, tapping, and casting. 

Comparison 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 were embedded. 

 
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Figure 9a. SEI 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 9b. 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. 
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Figure 9c. SEI image of spherical Mn-oxide particle with a 2.6-μm geometric diameter in sample of 

dust from furnace 1, 2nd level column (ERM04) collected from Eramet in March 2009. 

Figure 9d. SEI image of spherical Mn-oxide particle with a 4.5-μm geometric diameter in sample 

of dust from furnace 18, 2nd level beam (ERM07) collected from Eramet in March 2009. 
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Figure 9e. SEI image of spherical 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.
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SUMMARY AND CONCLUSIONS

Table 6 summarizes the interpretations of the analytical data and other information in the 

previous sections by indicating whether (1) elemental and lead isotope results for samples from 

Eramet, Energizer, and MIE resembled analytical results for 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 widespread area, which, along with an abundance of spherical manganese particles, was 

consistent with the presence of an industrial-scale emitter of airborne manganese particulate 

matter in the Marietta area. Manganese responses by LA-ICP-MS on TSP filters relative to air 

monitoring 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 where Eramet and 

Energizer are now located. In addition, spherical Mn-oxide particles 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

Facility1 Sample 

Location / Material

NEIC 

Sample 

Site 

Number

NEIC

Sample

Tag 

Number

Near 

former 

Union 

Carbide

complex

Elemental

abundances 

resemble 

TSP filters

Lead 

isotope 

ratios 

resemble 

TSP filters

Spherical 

Mn oxide 

particles 

observered

Eramet Furnace 1-3rd 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 2nd level 

column ERM04 NE25086 Yes No No Yes

Eramet Furnace 1 beam above 

casting sand ERM05 NE25087 Yes Maybe Yes No

Eramet Furnace 18-4th level 

beam ERM06 NE25090 Yes Yes Yes Yes

Eramet Furnace 18-2nd 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 MOR2 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 fine ore ERM13 NE25104 Yes No No N.A.

Eramet Comilog regular ore ERM14 NE25106 Yes No No N.A.
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Table 6. RESULTS SUMMARY

Marietta, Ohio, Source-Receptor Study: Results and Interpretation

Facility1 Sample 

Location / Material

NEIC 

Sample 

Site 

Number

NEIC

Sample

Tag 

Number

Near 

former 

Union 

Carbide

complex

Elemental

abundances 

resemble 

TSP filters

Lead 

isotope 

ratios 

resemble 

TSP filters

Spherical 

Mn oxide 

particles 

observered

Eramet Comilog sinter 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 shed EB03 NE25073 Yes No Yes N.A.

Energizer Jarosite skip 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 dust 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 ratios, and SEM) comparing MIE samples with TSP filters

consistently indicated manganese-bearing particulate matter in MIE samples was 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 distinguished 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 abundant 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 

potential sources of airborne manganese based 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 the 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. 
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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, were 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 of 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 complex, 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 those 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 point. 

• 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 hightemperature 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 condensation, 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.

Evaluation of all of the independent evidence presented in this and previous reports and 

outlined above indicated that the furnace areas at Eramet were the primary source of airborne 

manganese particulate matter in the area covered by the five TSP air monitoring sites near 

Marietta, Ohio.
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