Environmental Levels of Radium in

Water of Central New York

Thomas F. KraemerU.S. Geological Survey, Reston, VA

December 4, 2010

Finger Lakes Research Conference

How Does Radium Get Into Groundwater?

• Decay of uranium and thorium, mostly in rocks and minerals, produces radium isotopes.

• Dissolution of host phase releases radium to solution.

• Alpha-particle recoil during decay of parent also releases radium directly to solution.

• High salinity keeps radium isotopes in solution.

Modified from Schmidt and Kirk, 2010

Uranium and Thorium Decay Chains

t1/2=1600 y

t1/2=5.8 y

Th/U Ratios:

Sandstone: ~4

Black Shale: ~0.2

Slide provided by Elizabeth Rowan, USGS

Compiled by W. Lasseter

Slide provided by Elizabeth Rowan, USGS

Why Should We Care About Radium?

• Isotopic variations of radium can be used as hydrologic tracers to identify sources and mixing of water bodies.

• Radium can be an environmental contaminant.

Approx. northern limit of Utica Shale

Approx. northern limit of Marcellus Shale

Detailed USGS surface water/ near-surface water

sampling areas

USGS Radium

Sampling Regions

in Central NY

Mean 226Ra Values, in dpm/L

Seneca

0.040

Keuka

0.020

Cayuga

0.046

Owasco

0.037

Skaneateles

0.036

Otisco

0.032Canandaigua

0.027Conesus

0.013

Hemlock

0.019

Canadice

0.006

Honeoye

0.012

Taughannock

Creek

Salmon

Creek

Fall

Creek

0.0310.067

0.034

Mean 228Ra/226Ra Activity Ratios

Seneca

0.69

Keuka

1.02

Cayuga

0.77

Owasco

080

Skaneateles

0.85

Otisco

0.89Canandaigua

0.80Conesus

0.97

Hemlock

0.98

Canadice

1.01

Honeoye

0.93

Taughannock

Creek

Salmon

Creek

Fall

Creek

0.900.83

0.83

Riv

er

8

6

5

4

3

2

1

G

F

D

E

C

A

H

B

7

I

J

Susquehanna/Unadilla River Basin Radium Values

Site # 226 Ra* 228/226

Rivers

1 0.04 1.0

2 0.03 0.8

3 0.07 0.8

4 0.05 0.8

5 0.08 0.9

6 0.11 0.8

7 0.09 0.8

8 0.03 0.8

Tributaries

A 0.02 1.0

B 0.02 1.1

C 0.02 1.1

D 0.02 1.0

E 0.04 1.0

F 0.03 0.9

G 0.02 0.7

H 0.14 0.6

I 0.11 0.6

J 0.15 0.7

(*in dpm/L)

23

4

1

Site # 226 Ra* 228/226

1 – Lake (mean, 15 sites) 0.040 0.78

2 -- Stream 0.035 0.78

3 -- Stream 0.081 0.67

4 -- Stream 0.043 0.76

Otsego Lake Radium Values

(*in dpm/L)

226Ra Activity

<10 dpm/L

10-100 dpm/L

100-250 dpm/L

> 250 dpm/L

Onondaga Lake Area Radium Values

Site Sample Type 226 Ra* 228/226

1 lake (mean, 18 sites) 0.17 1.58

2 bedrock well 1464 0.71

3a deep alluvium well 1.3 0.86

3b bedrock well 11.9 1.49

4a shallow alluvium well 10.5 3.31

4b deep alluvium well 34.4 2.25

5a deep alluvium well 17.3 3.02

5b bedrock well 81.8 2.09

6 bedrock well 249 1.19

7 creek 0.56 2.48

8 bedrock well 203 1.75

9 spring 8.0 4.39

10 deep alluvium well 13.3 2.90

11 city water 0.12 1.23

12 deep alluvium well 38.0 1.86

13 spring 5.2 8.28

14a shallow alluvium well 4.1 11.53

14b deep alluvium well 37.6 2.25

15a deep alluvium well 2.14 2.38

15b bedrock well 122 1.1

16 deep alluvium well 16.7 2.69

17 spring 0.51 1.27

3a

2

3b 4b4a

15b

5a 6 8

7

9

10

1112

15b

13

14b

17

16

14a

15a

(*in dpm/L)

0

20

40

60

80

100

1 2 3 4 5 6

Nu

mb

er

226Ra, dpm/L Activity Interval

Distribution of 226Ra Activities

0 0.5 1 10 100 1000 2000

0

10

20

30

40

50

60

70

1 2 3 4 5 6 7 8 9 10

Nu

mb

er

228Ra/226Ra Activity Ratio Interval

Distribution of Radium Isotope Ratios

0 0.5 1 1.5 2 2.5 3 3.5 4 10 15

NY

TN

KYWV

OH

PA

AL

S

D

S

M

O

O

P

Pm

D

M

P

O

Geology from King & Biekman (1974)

Slide provided by Elizabeth Rowan, USGS

Geologic Map of Central Eastern U.S.

Approximate Outline

of Appalachian

Basin

Stratigraphy

(SW New York)

Gas reservoir

Oil reservoir Huntersville Chert /

(after Van Tyne+Copely,

1983)

Slide provided by

Elizabeth Rowan, USGS

Existing Oil and Gas Production Wells

Marcellus data

PA DEP (Prof. C. Kirby, 2010)

NY DEC (2009)

Non-Marcellus data

NY DEC (1999)

PA DEP (1992)

Dresel + Rose (2010)

Public domain

y = 1.68x - 5.92

R2 = 0.59y = 1.65x - 5.32

R2 = 0.65

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.0 4.5 5.0 5.5

TDS

Cl

Linear(TDS)Linear(Cl)

Log R

a (

tota

l, p

Ci/L)

Source: PA DEP NORM Survey1992

Log TDS or Log Cl (mg/L)

(Cambrian – Mississippian reservoirs)10,000

1,000

100

10

Slide provided by Elizabeth Rowan, USGS

Ra vs. Cl and TDS, Oil and Gas Well Brines, PA

100,000

10,000

1,000

100

10

1

0

Ac

tivit

y (

pC

i/L

)

L. Silurian–

DevonianDresel+Rose (2010)

Cambrian–

DevonianNY DEC (1999)

Marcellus

ShalePA DEP (2009-10)

Cambrian-

MississippianPA DEP (1992)

Marcellus

ShaleNYSDEC (2009)

Radium Activity Ranges in Produced Water, NY and PA

Industrial Effluent Limit

Median

Marcellus Shale Data

Non-Marcellus Shale Data

Slide provided by Elizabeth Rowan, USGS

Ra228/Ra226 vs. Ra (total)

0 4,000 8,000 12,000 16,000

Ra

228/R

a226

0

1.0

4.0

0.5

2.0

3.0

1.5

2.5

3.5

4.5

Total Radium (pCi/L)

Camb.-Ord. Ss+Sh (NYSDEC, 1999; PA DEP, 1992)

Marcellus Shale (NY DEC, 2009)

Marcellus Shale (PA DEP, 2009-10; Prof.

C. Kirby & students)

L. Devonian Oriskany, Huntersville (NYSDEC, 1999; PA DEP, 1992)

L. Silurian, Medina Ss (NYSDEC, 1999)

U. Silurian Dol (NYSDEC,1999)

U. Dev. Ss (PA DEP, 1992)

Slide provided by Elizabeth Rowan, USGS

0.001

0.01

0.1

1

10

100

1000

10000

100000

0.001 0.01 0.1 1 10 100 1000 10000 100000

22

8R

a, d

pm

/L

226Ra, dpm/L

Radium Isotopic Data from USGS Sites

non-Syracuse Area Syracuse Area Hypothetical Marcellus

Conclusions• Radium levels are low in most surface waters and

near-surface waters of Central New York State.

• Syracuse/Onondaga area has high radium in bedrock wells that penetrate shale, but that water is very saline and non-potable.

• The vast majority of the 228Ra/226Ra Activity Ratios in the sampled waters is > 0.5.

• If water from Marcellus and other U-rich black shales is highly saline and radium rich, with a 228Ra/226Ra ratio < 0.5, then any contamination of a water body by this brine should be recognized by its isotopic signature.

Thank You