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
1870s – Start of mining activity
1890s- 113 million concentrated
pounds copper per year
 Heap roasting employed in
the initial stages of smelting.
 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:
 Pets of Concern
 Elements of Concern
 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 RfC for arsenic, for example, is 0.02 mg %
Acceptable RfC 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
C
Quotient (HQ)was used:
HQi  i
RfCi
Ci represents the concentration of pollutant i.
RfCi represents the reference concentration for pollutant i.
Concentrations below the RfC 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:
iN
HI   HQi
i 1
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:
i N
HI j 
and
 HQ
ij
i 1
N
j M
HI i 
 HQ
ij
j 1
M
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.
100
GREATER THAN RfC (%)
80
60
40
20
Ca
Mg
Na
K
Cu
Zn
P
Fe
Mn
Cr
Se
B
Co
Mo
S
U
As
Be
Hg
Cd
Pb
Al
Ge
Ba
Li
Ni
Pt
V
Sr
Sn
W
Zr
0
ELEMENT
Percent of samples where the concentration exceeded the reference level.
MAXIMUM CONCENTRATION-TO- RFC RATIO
50
40
30
20
10
Ca
Mg
Na
K
Cu
Zn
P
Fe
Mn
Cr
Se
B
Co
Mo
S
U
As
Be
Hg
Cd
Pb
Al
Ge
Ba
Li
Ni
Pt
V
Sr
Sn
W
Zr
0
ELEMENT
Ratio of the maximum concentration to the reference concentration.
Arsenic Statistics
N
Range
(mg %)
AVERAGE &
MEDIAN
(MG %)
Standard
Deviation
(MG %)
≥
RfC
(%)
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
DOG 195 - CROCKETT
36
5
30
HAZARD QUOTIENT
6
4
3
2
24
18
12
6
0
0
Ca
Mg
Na
K
Cu
Zn
P
Fe
Mn
Cr
Se
B
Co
Mo
S
U
As
Be
Hg
Cd
Pb
Al
Ge
Ba
Li
Ni
Pt
V
Sr
Sn
W
Zr
1
Ca
Mg
Na
K
Cu
Zn
P
Fe
Mn
Cr
Se
B
Co
Mo
S
U
As
Be
Hg
Cd
Pb
Al
Ge
Ba
Li
Ni
Pt
V
Sr
Sn
W
Zr
HAZARD QUOTIENT
DOG 184 - MANDY
ELEMENT
ELEMENT
Pet Number
Pet 193
Pet 177
Pet 192
Pet 194
Pet 187
Pet 172
Pet 168
Pet 163
Pet 155
Pet 157
Pet 153
Pet 195
4
197
193
189
185
181
177
173
169
165
161
157
153
Pet 152
Pet 148
Pet 149
2.5
149
97
93
89
85
81
77
73
69
65
61
57
53
49
45
41
37
33
29
25
21
Pet 30
Pet 14
Pet 33
Pet 93
Pet 95
Pet 97
Pet 99
Pet 100
Pet 74
Pet 56
Pet 57
Pet 46
Pet 47
Pet 48
Pet 43
1
145
141
137
Pet 126
Pet 121
17
1.5
133
129
125
121
Pet 115
3
117
Pet 113
Pet 114
2
13
9
5
1
NORMALIZED HAZARD INDEX
2
113
109
1
Pet 106
1.5
105
101
NORMALIZED HAZARD INDEX
Hazard Index Charts
PETS OF CONCERN (POC) - 2005 CAMPAIGN
5
4.5
4
3.5
3
2.5
0.5
0
Pet Number
PETS OF CONCERN (POC) - 2005 CAMPAIGN
5
4.5
3.5
0.5
0
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:
As
B
2.5
Mn
3
Li
Mo
Al
Se
1.5
Pb
2
1
0.5
0
Ca
Mg
Na
K
Cu
Zn
P
Fe
Mn
Cr
Se
B
Co
Mo
S
U
As
Be
Hg
Cd
Pb
Al
Ge
Ba
Li
Ni
Pt
V
Sr
Sn
W
Zr
NORMALIZED HAZARD INDEX
Aluminum = 1.15
Arsenic = 2.24
Boron =2.16
Lead =1.38
Lithium =1.04
Manganese =2.24
Molybdenum =1.03
Selenium =1.29
ELEMENTS OF CONCERN (EOC) - 2005 CAMPAIGN
ELEMENT
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.
 Null hypothesis is rejected if the p-value is small,
approaching 0.000, and accepted if the p-value is
large, approaching 1.000
ELEMENT
p value
V
Sr
Sn
W
Zr
ELEMENT
Cd
Pb
Al
Ge
Ba
Li
Ni
V
Sr
Sn
W
Zr
0
Ca
Mg
Na
K
Cu
Zn
P
Fe
Mn
Cr
Se
B
Co
Mo
S
U
As
KS P-VALUE
D value
Cd
Pb
Al
Ge
Ba
Li
Ni
Ca
Mg
Na
K
Cu
Zn
P
Fe
Mn
Cr
Se
B
Co
Mo
S
U
As
KS STATISTIC D
1
0.8
0.6
0.4
0.2
1
0.8
0.6
0.4
0.2
0
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:
 Sweetie
 Max
 Teddy
Investigated elements identified by KS test
as significantly different inside and outside
the BPSOU:
Aluminum
Arsenic
Lead
Lithium
Manganese
REMEDIATION CONTROL DOG: LUNA
8
6
5
4
3
2
1
0
5/3/2005
6/17/2005
8/1/2005
9/15/2005
10/30/2005 12/14/2005
1/28/2006
3/14/2006
SAMPLING DATE
Al
As
Pb
Mn
Li
REMEDIATION DOG: TRIP
8
7
HAZARD QUOTIENT
HAZARD QUOTIENT
7
6
5
4
3
2
1
0
5/3/2005
6/17/2005
8/1/2005
9/15/2005
10/30/2005
12/14/2005
SAMPLING DATE
Al
As
Pb
Mn
Li
1/28/2006
REMEDIATION DOG: SWEETIE
8
HAZARD QUOTIENT
7
6
5
4
3
2
1
0
5/3/2005
6/17/2005
8/1/2005
9/15/2005
10/30/2005 12/14/2005
1/28/2006
3/14/2006
SAMPLING DATE
Al
As
Pb
Mn
Li
REMEDIATION DOG: MAX
8
HAZARD QUOTIENT
7
REMEDIATION DOG: TEDDY
HAZARD QUOTIENT
8
6
5
4
3
7
2
6
1
0
5/3/2005
5
4
6/17/2005
8/1/2005
9/15/2005
10/30/2005 12/14/2005
1/28/2006
SAMPLING DATE
3
2
Al
1
0
5/3/2005
6/17/2005
8/1/2005
9/15/2005
10/30/2005 12/14/2005
1/28/2006
SAMPLING DATE
Al
As
Pb
Mn
Li
3/14/2006
As
Pb
Mn
Li
3/14/2006
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?