DOMESTIC PETS AS BIOSAMPLERS OF MINING-RELATED CONTAMINANTS Stacie

DOMESTIC PETS AS BIOSAMPLERS OF MINING-RELATED CONTAMINANTS Stacie Barry

Presentation Overview Introduction Background Results and Discussion General Statistics Risk Analysis Identification of Pets of Concern and Elements of Concern Probability Distribution Analysis Spatial Analysis Remediation Investigation Summary Questions

Introduction Overall goal Improve the understanding of chronic exposure to mining-related contaminants in the environment Overall objectives Sample additional dogs in Butte and Anaconda Analyze the data and investigate probability and spatial distributions; Apply the biomonitoring method to document efficacy of localized remediation efforts.

Practical Questions Are levels of toxic elements in Butte dogs higher than reference levels? Are the levels of toxic elements in dogs living inside the Butte Priority Soils Operable Unit (BPSOU) higher than elsewhere in the community? Are there areas, or hotspots, where exposures are highest? If yards or homes are remediated, what is the effect on the biosamplers?

Background Mining Activity 1870 s – Start of mining activity 1890 s- 113 million concentrated pounds copper year s Heap roasting employed in the initial stages of smelting. s Mines, mills, smelters, and concentrators created metalbearing tailings and waste piles 1900 – Washoe Smelter 1880 -1980 – Over 500 mines 1955 -1982 – Berkeley Pit

Environmental Impact Silver Bow Creek Superfund Site Designation in 1983 and 1987 Operable units: • • • Butte Priority Soils Operable Unit (BPSOU) West Side Soils Active Mining Area Streamside Tailings Rocker Timber Framing and Treating Warm Springs Ponds Contaminants of concern: Arsenic, cadmium, copper, iron, lead, manganese, mercury, sulfate, and zinc. BPSOU database Concentrations of arsenic, cadmium, copper, lead, and zinc Approximately 2, 700 soil samples collected in the Butte area.

Sentinel Species Animal testing is often the basis for toxicity information in humans. Sentinel species: Animals tested to assess the extent of contamination in the environment and provide information regarding human health effects as a result of exposure to the same environment. Use of dogs Exposure to the same soil, sediments, water, air, and house dust as their human counterparts.

Hair Sampling and Risk Analysis Hair samples with subsequent analysis using Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) Simple Non-invasive Indicate chronic environmental exposure Madden risk analysis method of hazard quotients and hazard indices for: s Pets of Concern s Elements of Concern s Based on Reference Concentrations

Reference Concentration and Range Element concentration: Reported in units of milligram percent (milligrams of the element per 100 grams of hair), one milligram percent (mg %) = ten parts per million (ppm). Reference concentrations and ranges: Represent the level of the element seen in healthy dogs, based on a major study of all common breeds. Toxic elements, such as arsenic, are examined with respect to a specific reference concentration, while nutritional elements, such as calcium, are compared to a reference range. This range, comprised of a lower reference limit and an upper reference limit, represents the zone of element concentrations seen in a healthy dog. The Rf. C for arsenic, for example, is 0. 02 mg % Acceptable Rf. C range for calcium is 41 -129 mg %.

Hazard Index To determine if the metals concentration is a hazard to the health of the animal, the method used in Risk Assessment to determine a Hazard Quotient (HQ)was used: Ci represents the concentration of pollutant i. Rf. Ci represents the reference concentration for pollutant i. Concentrations below the Rf. C threshold should result in no adverse health effects, so the target HQ is less than 1. 0 for a single pollutant. The Hazard Index is equal to the sum of the Hazard Quotients: Where where N is the total number of pollutants. This approach assumes that health effects are additive from exposure to multiple pollutants at once.

Hazard Index (cont’) To arrive at indices that were not dependent on the same number of elements in the lab report nor the same number of pets in the study, Madden normalized hazard values by the number of elements and pets as follows: and where the target value was 1. 0 for both HIj and HIi. Pets with HIj values greater than or equal to 1. 0 were defined as pets of concern (POCs), and elements with HIi values greater than or equal to 1. 0 were defined as elements of concern (EOCs).

Methods 200 samples in Butte and Anaconda Variety of ages, breeds, and socio-economic areas. Sampling Procedure: 150 mg of hair between shoulder and neck Questionnaire Specimens sent to Trace Elements Laboratory GIS mapping Rfc concentrations statistics HQ and HI for pets and elements Kolmogorov-Smirnov test (KS test) for pets inside and outside BPSOU Remediation investigation Four dogs at houses undergoing remediation followed for five months One control dog at a house not undergoing remediation followed for same time period.

Results and Discussion Reference Concentration Statistics: Wide variation in concentration range for many elements Great variation in % samples over Rfc Arsenic over Rfc in 72. 6% of samples Mercury, tungsten, and platinum are not observed over Rfc.

Percent of samples where the concentration exceeded the reference level. Ratio of the maximum concentration to the reference concentration.

Arsenic Statistics N Range (mg %) AVERAGE & MEDIAN (MG %) Standard Deviation (MG %) ≥ Rf. C (%) Pets residing in Butte 180 0. 0060. 272 0. 043 & 0. 030 0. 042 71. 7 Pets residing in Anaconda and Opportunity 15 0. 0170. 217 0. 077 & 0. 048 0. 062 93. 3 Pets residing in Deer Lodge and Whitehall 2 0. 0120. 015 0. 0135 & 0. 0135 0. 002 0. 0 Male pets 116 0. 0060. 272 0. 044 & 0. 032 0. 045 72. 1 Female pets 81 0. 0070. 270 0. 046 & 0. 034 0. 044 72. 8 Pets residing within the BPSOU 94 0. 006 – 0. 272 0. 049 & 0. 032 0. 051 78. 7 Pets residing outside of the BPSOU 84 0. 008 – 0. 210 0. 038 & 0. 030 0. 035 64. 3 Group

Identification of Pets of Concern Pet of Concern = Pet with a Hazard Index greater than 1 Thirty-six Pets of Concern 30 reside in Butte 26 reside inside the BPSOU

Hazard Index Charts

Identification of Elements of Concern Eight elements are identified as elements of concern (EOCs), based on element hazard indices (HIi) of 1. 0 or greater: Aluminum = 1. 15 Arsenic = 2. 24 Boron =2. 16 Lead =1. 38 Lithium =1. 04 Manganese =2. 24 Molybdenum =1. 03 Selenium =1. 29

Probability Distribution Analysis The Kolmolgorov – Smirnov (KS) Test Goodness of Fit Test Determines if two datasets belong to the same population Non-parametric Does not assume a specific distribution of data Null hypothesis is that there is “no difference” between the probability distributions of the datasets Two statistics are considered: • D-value, representing the maximum difference between the cumulative distributions; • p-value, used to reject or accept the null hypothesis. s Null hypothesis is rejected if the p-value is small, approaching 0. 000, and accepted if the p-value is large, approaching 1. 000

D value p value

KS Test Results Highest D statistics and the lowest p-values, indicating a difference inside and outside the BPSOU : Manganese and lead Lowest D statistics and highest pvalues, indicating no difference inside and outside the BPSOU : Copper, zinc, and phosphorous Of the eight elements of concern Manganese and lead greatest difference between inside and outside the BPSOU Selenium and molybdenum show the least difference.

Spatial Distribution Analysis Geographical Information System (GIS) program Developed from State of Montana, DNRC, Montana Bureau of Mines and Geology, Butte Silver Bow GIS Department and Butte Archives sources. Maps of residence locations for pets with HQ values greater than 1. 0 for the eight EOCs: Arsenic Aluminum Boron Lead Lithium Manganese Molybdenum Selenium

Aluminum

Boron

Lead

Lithium

Manganese

Molybdenum

Selenium

Remediation Investigation Five dogs for five months 1 control dog, Luna 4 dogs at houses undergoing remediation • Attic Dust Remediation : Trip • Yard Remediation: s Sweetie s Max s Teddy Investigated elements identified by KS test as significantly different inside and outside the BPSOU: Aluminum Arsenic Lead Lithium Manganese

Summary Thirty-six pets (POCs) 30 resided in Butte 26 lived inside the BPSOU Eight elements were identified as elements of concern (EOCs): aluminum, arsenic, boron, lead, lithium, manganese, molybdenum, and selenium. Arsenic was above the Rfc concentration in 72. 6 % of samples Inside BPSOU: 78. 7% Butte Outside BPSOU 64. 3% Anaconda: 93. 3% KS Test showed differences in: aluminum, arsenic, lead, lithium, and manganese inside and outside BPSOU Remediation study Control dog remained constant Dog with attic dust remediation showed large reduction Dogs with yard remediation had variations in reductions and increases

Recommendations Expansion of the biosampling project Follow areas, houses, and particular pets over time Follow more remediation houses for several years to account for seasonal variations Environmental sampling at houses with POCs and arsenic over Rfc Epidemiological study of houses with POCs and arsenic over Rfc Large scale epidemiological study of Butte and Anaconda Cancer Neurological Respiratory Cardiovascular Developmental Secondary causes of death Correlation to environmental history and reclamation efforts.

Thank You Dr. Holly Peterson Mine Waste Technology Program Tina (and Lucy) Donovan Mark Peterson EPA Diana Bless MSE-TA Jay Cornish Michelle Lee Helen Joyce Environmental Engineering Department Jeanne Larson Dr. Kumar Ganesan Melody Madden Trisha Robertson Peretti Veterinary Clinic Anaconda Veterinary Clinic Butte Spay and Neuter Task Force Butte GIS Department Friends and Family

Questions?