(Usa) Form Confidential

REPORT

Site Assessment and Risk Evaluation Based on 2010 and 2011 Field Sampling Investigation of Soil and Sediment In Areas Potentially Impacted by The Cass Lake Biological Testing Site For Zinc Cadmium Sulfide Compound Cass Lake, MN Leech Lake Band of Ojibwe

DRAFT

Prepared By: IECIS Group Stillwater, MN

For: Brandy Toft, Project Officer Division of Resource Management Leech Lake Band of Ojibwe Cass Lake, MN

February 2012 Version 2

Executive Summary

Zinc Cadmium Sulfide Dispersion Tests were conducted in 1964 on the Leech Lake Indian Reservation, Minnesota, by the U.S. Army Chemical Corps as part of the United States Biological Warfare (BW) program established in 1942. This report provides the final confirmation sampling results aimed at measuring Zinc and Cadmium levels within areas of concern within the Leech Lake Indian Reservation, MN. Zinc and Cadmium in soils and wetland areas were investigated in several areas, including areas that are culturally sensitive. Samples were collected by Leech Lake Band of Ojibwe (LLBO) staff following the approved Quality Assurance Project Plan and chemical analyses were conducted by Test America, the LLBO contracting laboratory. Overall, a summary of the validation and audit of Test America analytical results is provided for all soil and sediment samples collected as part of Site Screening Investigation of Cass Lake Biological Testing Site, Cass Lake, MN in 2010 and 2011. The samples were collected from designated areas and shipped to Test of America Laboratories for testing. The chain of custody of each sample is documented and the samples were received in good conditions. The samples were prepared and analyzed in four different batches. Cadmium and Zinc were determined using ICPMS, moisture, percent solid and pH of each sample was also determined. A separate report was issued for each batch by Test America Laboratories.

The results of the analysis show: 1. No cadmium detected above the screening level 1 mg/kg for soil. The results ranged from 0.012 to 0.3 mg/kg. All samples analyzed were below the screening level for 1 mg/kg for soil. 2. The amount of Zinc detected varied from one sample to another and the results ranged between 12 and 86 mg/kg which were above the screening level of zinc in soil of 10 mg/kg, but within background conditions and findings by the Minnesota Geological Survey in a till geochemistry and indicator minerals study for the entire State of Minnesota. 3. The pH of the samples varied between acidic pH 2.3 for sample S13 to slightly basic pH 8.0 as for sample S07. The moisture content varied from one sample to another (73-86 %). 4. No correlation was found between the pH values and the metal content of the samples.

Based on the 2010 and 2011 field investigations, no further sampling is recommended.

Several Band/community Members have expressed their wish to avoid hunting and gathering in the area of the Site and intent to make sure their children are aware of the location. The technical study did not clear their minds given the fact that the U.S. Army’s Zinc Cadmium Sulfide Dispersion Tests could have also involved simultaneous exposures to other dispersants such as biologic stimulants, e.g. Serratia marcescens or Bacillus globigii. There are rumors of other biological stimulants being used, such as tularemia being released during this testing. Evaluation of other biological agents was not within the scope of this evaluation. Based on comments collected during the initial scoping for risk evaluation of Zinc Cadmium Sulfide there is reason to be concerned about public perception of this evaluation method. Several Band members reported their concern of the use of other biological compounds in addition while practicing traditional activities observed signs of tulerima in the project area.

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the government test objectives, it is impossible for the Band members and leadership to conclude there are no lingering risks to the Leech Lake community or their natural resources.

We will attempt to address the Band members’ concerns with community meetings and the Tribe will conduct extensive outreach as part of future mitigation efforts to address cultural impacts attribute to the Cass Lake Biological ZnCdS Testing Site.

Based on information we have today with the technical and best available science for zinc cadmium sulfide deposition, this report indicates there are no residual impacts to the natural resources from the Zinc Cadmium Sulfide compound. Without the completed reports from the project by the government and complete evaluation and potential risks outlined, the Band cannot state that health risk and environmental impacts associated with this project have been fully evaluated. As such, the Band reserves the right to revisit the Site if further information regarding the Site presents itself.

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1.0 INTRODUCTION

1.1 Background

Because of concern over the possible use of biological warfare (BW) by a foreign power against the United States and its allies, President Roosevelt in 1942 established the U.S. Biological Warfare Program. From January through August 1964, , the U.S. Army Biological Warfare Center in Fort Detrick, Maryland, contracted with Litton Industries to conduct an experimental monitoring station for airborne releases of zinc cadmium sulfide (ZnCdS) powder. The test was designed to determine the potential effects of a biological or nuclear attack on U.S. cities by measuring the movement of airborne particles released in urban and rural environments, and to determine the munitions requirement (the quantity of material required to achieve a particular military objective). In light of today’s homeland security preemptive measures, such an experiment may help identify the potential ecological and health impact associated with a terror act conducted using elements similar to those utilized by the experiment.

The ZnCdS compound used in the Cass Lake Biological Testing Site 1964 experiment was not considered to be a biological warfare agent. It was viewed as a desirable non-biologic stimulant of bacterial particles for the following reasons: it fluoresces under ultraviolet (UV) light and therefore can be easily detected; its particle diameter (2-3µm) and mass, and thus its behavior in air, are similar to those of BW agents; and it is economically feasible to use. At the time, ZnCdS was thought to be nontoxic to humans, animals and plants, and relatively stable in the atmosphere to conduct the tracer experiment (hours to days).

1.2 Site Location

The site is on LLBO Reservation and within Chippewa National Forest in North Central Minnesota, approximately 350 km north of Minneapolis-St. Paul, 5-6 km from main roads, 8-10 km southeast of nearest town of Cass Lake (population 1,500), 32 km southeast of Bemidji (population 10,000). It is situated along U.S. Forest Road 133, approximately 3 ¼ miles from the junction of Forest Road 133 and U.S. Highway 2 (Figures 1a and 1b). The legal description for this area is SE ¼ Section 33 and SW ¼ Section 34, Township 145 North, Range 30 West, and the NE ¼ Section 4, Township 144 North, Range 30 West. (Figure 1)

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Figure 1: Site Location

The Cass Lake Biological Testing Site was selected for many reasons. It was to provide: non- marshy terrain with uniform and dense coverage of hardwood or deciduous forest conditions; continuous site at least 3 miles upwind; a minimum of hills, streams, lakes, built-up areas for several miles; presence (but not excessive) of snow in winter; accessibility by road; access to manpower, supplies, and facilities; reasonable convenience of aircraft facilities; and access to meteorological data for previous years.

Two series of 12 tests were then conducted during the winter and summer of 1964. To simulate a line source, about 700 pounds of zinc cadmium sulfide were released by an Army Piper Apache aircraft flying at 150 mph ground speed along a line of 16 km within the boundaries of the Leech Lake Reservation. In addition, individual bomblets were exploded to simulate point sources (See Figure 2, a general historic data map located at the U.S. Forest Service).

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Figure 2: Historic Release Map - Tower System (NW-SE) and Release Lines (SW-NE)

Upon learning of the dispersion tests in the early 1990s, the Leech Lake Band of Ojibwe (LLBO) became very concerned about possible health effects of exposures to ZnCdS by people in its community, and expressed outrage about being exposed to chemicals by the government without being informed. After some information on the test became public, it was believed that the LLBO tribal lands may have been potentially at risk, which lead to a Cooperative Agreement between the Leech Lake Band of Ojibwe and the U.S. Department of Defense (DOD) to conduct a screening investigation of environmental impacts associated with secret testing conducted on the Reservation.

The Department of Defense, through the Native American Lands Environmental Mitigation Program (NALEMP), began funding the screening study of environmental impacts and preliminary environmental mitigation program management activities at the formerly used defense site known as the Cass Lake Biological Testing Site located near Cass Lake, MN, FUDS #E05MN1062. The U.S. Army Corps of Engineers (USACE) administers NALEMP for DoD.

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1.3 Leech Lake Band of Ojibwe Site Investigation Program

From 2004 through 2007, the Leech Lake Band collected several soil samples throughout areas determined to have been potentially affected by US Army releases of ZnCdS in the air. Sample locations with high likelihood for ZnCdS to be found were guided by multimedia chemical transport modeling tools. This initial sampling was designed to help delineate the areas of concern within the vast Chippewa National Forest boundary, and hence to produce a more focused and targeted areas where refined sampling effort with cultural factors included is needed for risk characterization and assessment purposes.

Below is a preliminary evaluation of the data generated and validation of the data as a prerequisite task to any risk assessment work. The analyses of the samples collected under an agreed upon QAPP were conducted by the US Army COE laboratory and the Minnesota Chippewa Tribe (MCT) Research laboratory. The analysis conducted by MCT Research Laboratory did not result in any significant finding and cannot be used to draw any conclusion. The data as recorded in the notebook does not comply with Good Laboratory Practice (GLP). There is no notebook page, no signature of who recorded the data and no review of the data. In addition, there is no definition of the columns and no calculation formulae on how the values were obtained. For these reasons, the values generated for the sample analysis are questionable which renders any evaluation of this data unacceptable.

Soil and water samples were analyzed by the Department of the Army Corps of Engineers. Most of the samples showed a higher amount of Zinc due to higher natural abundance of Zinc in the soil and water. However, few samples showed higher level of cadmium above the average background level as determined by control samples. The finding of higher level of cadmium is of interest because it might be due to higher amount of residual level of Cadmium Zinc Sulfide.

A Memorandum summarizing the LLBO Site Investigation Program up to September 2009 is attached in Appendix 1, and recommendations made on how to proceed next. Basically, it is an established fact that Cadmium Zinc Sulfide is a dense and stable compound; it is insoluble in water, slightly soluble in strong acid and should not be affected by a small change of the pH or temperature. It is composed of about 80 percent zinc sulfide and 20 percent cadmium sulfide. The question that arises is why cadmium was not detected at higher level in the various selected sampling locations where the Army Chemical Corps conducted dispersion tests. Did cadmium zinc sulfide decompose over time and the resulting cadmium and zinc ions migrated away from the target site and consequently depleted from the areas? Or did the complex seeped in the ground to greater soil depths? Or did it get transported via surface runoff and wind and finally deposited at the bottom of the lakes and other surface water bodies due to its density? For this reason it was recommended that the following confirmation sampling activities be completed:

• Soil sampling at various depths (up to five feet) to gain insight about the fate and transport of the insoluble complex cadmium zinc sulfide in soils. • Sediment sampling from the bottom of surrounding water bodies such as wetlands and lakes.

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• Focus of the sampling effort to areas that are culturally sensitive, and to high deposition zones as shown by the preliminary modeling work.

A first round comprehensive sampling was completed in 2010 following updates and concurrence of the LLBO Quality Assurance Plan with the U.S. Army Corps of Engineers. The 2010 sampling gathered:

• 60 stratified soil samples from 66 locations which include 3 QA field duplicate samples • 240 non stratified sediment samples which include 12 QA field duplicate samples (Total of 15 Field Duplicate for QA -1 per 20 samples) • 1 per day for equipment rinsate • 1 per day field blank

Confirmation sampling to include culturally sensitive areas was completed in the spring of 2011. A total of eighteen samples were collected in soils and sediments within areas of concern to the LLBO.

2.0 Objective of the 2010 and 2011 LLBO Field Investigation

The objective of the 2010 soil sampling was to establish the presence or absence of chemicals of concern above screening values (SV) thresholds in various soil and sediment samples within the study area using an updated Quality Assurance Project Plan with concurrence of the U.S. Army Corps of Engineers. Appendix 2 summarizes the findings of the 2010 sampling round. It was concluded that the data did not show any measurable residue of cadmium above the screening values. The higher zinc values obtained were consistent with background level of zinc described in the Minnesota Geological Survey Report “Till Geochemical and Indicator Mineral Reconnaissance of Minnesota” (L. Harvey Thorleifson, Kenneth L. Harris, Howard C. Hobbs, Carrie E. Jennings, Alan R. Knaeble, Richard S. Lively, Barbara A. Lusardi, and Gary N. Meyer; Open File Report OFR-07-01, St Paul, MN 2007). The pH varied between acidic pH 4.2 to slightly basic pH 7.9 with no correlation obtained with the amount of either cadmium or zinc values.

To confirm the 2010 results and provide additional reassurance that culturally sensitive areas have likely not been impacted by ZnCdS, soil and sediment sampling was repeated in 2011 in those areas. The following preliminary benchmark screening values for ecological effects and the analytical achievable values used in this study are summarized in the table below:

Chemical Media SV RL MDL Soil 1 mg/kg 0.1 mg/kg 0.007 mg/kg Cadmium Sediment 0.990 mg/kg 0.1 mg/kg 0.007 mg/kg Soil 10 mg/kg 0.5 mg/kg 0.0648 mg/kg Zinc Sediment 1 mg/kg 0.5 mg/kg 0.0648 mg/kg

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3.0 Applicable Documents

Document Name Document Number

Quality Assurance Project Plan Addendum method SW846 6020 ICP-MS for analysis of Cadmium and Zin SM20 2540G Percent Moisture SW846 9045D Determination of pH Reports number Location of Raw Data

180-2007-1, 180-1851-1, 180-298-1, 180-1919-1 Test America Laboratories (Appendix 3)

4.0 Sample List Analysis The following table provides a brief summary of the acceptance criteria for the analysis of the samples as shown from the determination of limit of quantification, blank analysis and percent recovery of spiked matrix samples.

The samples were analyzed for cadmium, zinc, percent solid and pH. The samples were analyzed in three different batches and a report was issued for each batch. A summary of the results is shown below.

1-Job number 180-2007-1 (cadmium and Zing are expressed in mg/Kg) Lab Sample ID Sample ID Matrix Cd Zn % solid pH

180-2007-1 S09 Sediment 0.079 18 81 5.5 180-2007-2 S08 Sediment 0.041 13 82 6.2 180-2007-3 S04 Sediment 0.087 16 82 6.3 180-2007-4 S06 Sediment 0.070 12 80 5.5

2-Job number 180-1851-1 Lab Sample ID Sample ID Matrix Cd Zn % solid pH

180-1851-1 S13 Sediment 0.13 27 84 2.3 180-1851-1 S14 Sediment 0.012 30 83 5.9 180-1851-1 S16 Sediment 0.10 18 86 6.0 180-1851-1 S15 Sediment 0.12 31 78 7.2 180-1851-1 S03 Sediment 0.30 59 79 7.0 180-1851-1 S02 Sediment 0.12 31 78 7.8

3-Job number 180-1919-1 Lab Sample ID Sample ID Matrix Cd Zn % solid pH

180-1919-1 S12 Sediment 0.31 45 80 6.7 180-1919-1 S01 Sediment 0.28 37 84 6.4 180-1919-1 S07 Sediment 0.25 49 73 8.0

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4-Job number 180-2098-3 Lab Sample ID Sample ID Matrix Cd Zn % solid pH

180-2098-1 S11 Sediment 0.10 23 80 6.0 180-2098-1 S17 Sediment 0.10 23 82 6.0 180-2098-1 S10 Sediment 0.13 32 83 5.2 180-2098-1 S05 Sediment 0.099 35 76 6.3 180-2098-1 S18 Sediment 00.081 25 78 6.2

5.0 Sample Preparation The sample were prepared and analyzed per the methods as described. The percent moisture was determined and the final weight for determination of Cadmium and Zinc was based on the percent moisture content of each sample. The reagents used for sample digestion for each batch of samples prepared such as nitric acid, hydrogen peroxide, and hydrochloric acid are described as well as the digestion temperature.

6.0 Sample Analysis All samples were prepared and analyzed following a typical Sample List bracketed by blanks, Quant Standards, initial calibration verification, continuing verification control samples, spike control sample, etc.

7.0 Discussion Overall, the limit of detection, blanks and percent recovery were acceptable in addition to the control samples used for continuing calibration bracketing the samples.

The results obtained for Zinc showed a large difference from one sample to another as previously obtained. All sample results were below 86/mg/kg which is above the 10mg/kg screening level. As for Cadmium, the highest value was 0.79 mg/kg for sample S18 which is still below the screening of 1 mg/kg. The moisture content varied from one sample to another (73-86 %) and the pH varied between acidic pH 2.3 for sample S13 to slightly basic pH 8.0 for sample S07.

The results of samples analysis obtained for cadmium, zinc, moisture and pH are plotted below.

Results and Graphs

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Sample ID Cd (mg/kg) S09 0.079 S08 0.041 S04 0.087

S06 0.07

S13 0.13 S14 0.012 S16 0.1 S15 0.12 S03 0.3 S02 0.12

S12 0.31 S01 0.28 S07 0.25

S11 0.1 S17 0.1 S10 0.13 S05 0.099 S18 0.081

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Sample ID Zn (mg/kg) S09 18 S08 13 S04 16

S06 12

S13 27 S14 30 S16 18 S15 31 S03 59 S02 31

S12 45 S01 37 S07 49

S11 23 S17 23 S10 32 S05 35

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Sample

ID pH S09 5.5

S08 6.2

S04 6.3

S06 5.5

S13 2.3

S14 5.9

S16 6.0

S15 7.2

S03 7.0

S02 7.8

S12 6.7

S01 6.4

S07 8.0

S11 6

S17 6

S10 5.2

S05 6.3 S18 6.2

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Sample % ID Moisture S09 81 S08 82 S04 82

S06 80

S13 84 S14 83 S16 86 S15 78 S03 79 S02 78

S12 80 S01 84 S07 73

S11 80 S17 82 S10 83 S05 76 S18 78

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8.0 Conclusion

In conclusion, the 2011 field data confirmed that no measurable residue of cadmium above the screening values is found in selected culturally sensitive areas. No correlation was found between the pH values and the metal content of the samples. Further comparison of the Cadmium and Zinc ranges with findings by the Minnesota Geological Survey in a till geochemistry and indicator minerals study for the entire State of Minnesota supports the conclusion that Cadmium and Zinc levels on the Cass Lake Biological Testing Site are within background levels . Based on the 2010 and 2011 field investigations, no further sampling is recommended. No ecological and health risk assessment work is warranted based on the field sampling results including culturally sensitive areas as 1) Cadmium in soils and sediments are found in the field at below screening levels, and 2) Zinc in soils and sediments are found within background levels in soils.

Through consultation with Band Members regarding traditional harvest practices there is a sincere concern and/or fear that the Site has been contaminated in the past. Several Band/community Members have expressed their wish to avoid hunting and gathering in the area of the Site and intent to make sure their children are aware of the location. The technical study did not clear their minds given the fact that the U.S. Army’s Zinc Cadmium Sulfide Dispersion Tests could have also involved simultaneous exposures to other dispersants such as biologic stimulants, e.g. Serratia marcescens or Bacillus globigii. Several Band/community Members have expressed their wish to avoid hunting and gathering in the area of the Site and intent to make sure their children are aware of the location. The technical study did not clear their minds given the fact that the U.S. Army’s Zinc Cadmium Sulfide Dispersion Tests could have also involved simultaneous exposures to other dispersants such as biologic stimulants, e.g. Serratia marcescens or Bacillus globigii. There are rumors of other biological stimulants being used, such as tularemia being released during this testing. Evaluation of other biological agents was not within the scope of this evaluation. Based on comments collected during the initial scoping for risk evaluation of Zinc Cadmium Sulfide there is reason to be concerned about public perception of this evaluation method. Several Band members reported their concern of the use of other biological compounds in addition while practicing traditional activities observed signs of tulerima in the project area.

For the purposes of the Zinc Cadmium Sulfide releases this report indicates there are no elevated residual levels of Zinc or cadmium in the project area. However, without access to the completed reports and deliverables from the entire project by the government, which includes comprehensive evaluation of its test results, follow up testing, and final conclusions on the potential risks as outlined in the government test objectives, it is impossible for the Band members and leadership to conclude there are no lingering risks to the Leech Lake community or their natural resources.