Occurrence of Minor 

Elements in Water

GEOLOGICAL SURVEY 

CIRCULAR 445
Occurrence of Minor Elements

in Water

By W. H. Durum and Joseph Haffty

GEOLOGICAL SURVEY CIRCULAR 445

Washington 

7967
United States Department of the Interior

STEWART L. UDALL, SECRETARY

Geological Survey

THOMAS B. NOLAN, DIRECTOR

Free on application to the U. S. Geological Survey, Washington 2.5, D. C.
CONTENTS

Page Page

Abstract. _______ ____________________ 1 Radioelements. _________ _____________ 10

The problem ________________________ 1 A few details on methods _____________ 10

Three studies Three methods________ 1 Summary.________________-_________- 11

Principal rivers.__________________ 1 References cited.____________________ 11

Occurrence of strontium ___________ 8

Studies in California__-_____--_____ 8

ILLUSTRATIONS

Page 

Figure 1. Strontium and barium in water and water discharge __________ _ __________ 7

2. Calcium, strontium, barium, in water and water discharge... __ _____ _____ 7

3. Strontium, barium, and dissolved S'olids in water ________________ _ _ __ 8

4. Map of the United States showing concentration of strontium in surface water at

selected sites____________________________________________________________ 9

TABLES

Page 

Table 1. Spectrographic analyses for minor elements in waters from principal rivers of

United States and Canada. _______ _________________________________________ 2

2. Summation of radioelement data ________________________________________ 10

III
CONTENTS

Page Page

Abstract. ___________________________ 1 Radioelements. ______________________ 10

The problem ________________________ 1 A few details on methods _____________ 10

Three studies Three methods..______ 1 Summary..__________________________ 11

Principal rivers. __________________ 1 References cited. ____________________ 11

Occurrence of strontium ___________ 8

Studies in California_______________ 8

ILLUSTRATIONS

Page 

Figure 1. Strontium and barium in water and water discharge __ _______________________ 7

2. Calcium, strontium, barium, in water and water discharge...___________ _____ 7

3. Strontium, barium, and dissolved s'olids in water ____________________________ 8

4. Map of the United States showing concentration of strontium in surface water at

selected sites._.__.________..______.__...________. ___ _______________ 9

TABLES

Page 

Table 1. Spectrographic analyses for minor elements in waters from principal rivers of

United States and Canada__________________ ___________________________ 2

2. Summation of radioelement data ____________________________________________ 10

III
Occurrence of Minor Elements in Water

By W. H. Durum and Joseph Haffty

ABSTRACT

Presented at Conference on Physiological Aspects of Water 

Quality, September 8, 9, 1960, Washington, D. C.

Three basic studies, using spectrographic methods, have 

been used to establish the occurrence of minor elements in 

natural waters. One study, of oceanborne chemicals in principal rivers, has established a method for the quantitative 

analysis of many minor elements. Strontium, barium, lithium, 

rubidium, chromium, nickel, copper, lead, boron, titanium, 

molybdenum, manganese, and vanadium occur most frequently 

in measurable quantities.

Reconnaissance of the strontium in surface waters of the 

United States, shows that surface waters in parts of northern 

and western Texas and southern New Mexico and Arizona are 

comparatively high in strontium. A study of minor elements in 

selected waters of California is continuing.

Assessment of preliminary data on uranium and radium in 

waters is facilitated by grouping data for 10 geotectonic 

regions of the United States.

THE PROBLEM

In the past few years important advances 

have been made in the study of minor elements in natural waters. Once considered an 

area of chemical and geochemical curiosity, 

but having limited practical application, the 

study of minor elements is now an integral 

part of serious investigations of water chemistry. As used herein, minor elements are 

those dissolved elements that do not generally exceed 1 milligram per liter in natural 

water. Only a few minor elements are determined in routine water analysis, hence 

they are often not available in computing the 

ionic balance.

High on the list of accomplishments is 

improved methodology, which has provided 

means for quantitative measurement of elements that are currently of special interest. 

Of singular importance is the refinement of 

techniques for sensitive, practical, and reproducible spectrographic determination of 

minor elements in water.

The principal bulk of dissolved constituents in natural water consists of soluble

products of chemical weathering and soil 

formation. Thus, factors that control chemical weathering are among those that control 

the amounts of minor elements available for 

solution. Some chemical factors that affect 

release of minor elements from rocks and 

soils and their stability in solution are solubility of the constituent, pH of the environment, adsorption characteristics of the solid 

material, hydration, coprecipitation, cplloidal 

dispersion, and complexes.

An important but generally neglected 

source of minor elements in water is vegetation. Many plants selectively concentrate 

minor elements, as well as major elements, 

that become available during the decay and 

movement of the plant debris in the hydrologic cycle. Decay and solution of organic 

matter may form metal-organic complexes, 

an example of which is the stabilization of 

ferric iron in swamp waters.

Man's activity in mining and manufacturing 

is an important unmeasured source of minor 

elements in natural water.

This paper summarizes a few recent studies made by the U.S. Geological Survey on the 

occurrence of minor elements in water.

THREE STUDIES THREE METHODS

Three different spectrographic methods 

have been used in three widely different field 

programs with different objectives. The 3- 

prong approach shortened the time required 

to select adequate tools for each program and 

thus broadened experience in a relatively 

short period of investigation.

PRINCIPAL RIVERS

One program (Durum, Heidel, and Tison, 

1960) updates basic information in Clarke's
OCCURRENCE OF MINOR ELEMENTS IN WATER

Table 1. Spectrographic analyses for minor elements in 

[Spectrographic analysis in microDate of 

collection

Discharge 

(cfs)

Silver 

(Ag)

Aluminum 

(Al)

Boron 

(B)

Barium 

(Ba)

Beryllium 

(Be)

Cobalt 

(Co)

Chromium 

(Cr)

Copper 

(Cu)

Iron 

(Fe)

Lanthanum 

(La)

Lithium 

(Li)

Apalachicola River at State Highway

Dec. 17, 1958

Mar. 30, 1959

Aug. 24

Sept. 29

11,000

54,000

11,900

9,030

0,11

<*058

.098

<.071

73

2,550

173

135

5.0

11

5.5

5.6

42

21

29

26

0

<.058

0

0

0

0

<.75

0

2.2

2.2

6.9

7.8

2.1

7.0

51

6.2

96

1,220

150

85

0

0

0

0

0.096

.70

<.075

.12

Atchafalaya River from railroad bridge, 0.6 mile below

May 10, 1958

Oct. 14

Mar. 13, 1959

May 18

QOQ nnn

130,000

276,000

166,800

0

.33

0

0

725

1,640

462

14

17

19

14

4?

132

52

122

O.X

0

<.22

0

O.X

5.2

0

0

2.4

30

2.6

4.9

3.6

9.9

3.7

10

1,230

1,240

517

0

0

0

0

4.5

1.9

2.6

Colorado River on bridge on U.S.

Sept. 16, 1958 

Jan. 20, 1960

b l,020 1.0 

0

12 

153

52 

34

152 

128

0 

0

0 

0

24 

10

8.8 

8.5

160 

111

0 

0

35 

37

Columbia River below The Dalles Dam,

June 11, 1958

Dec. 1

Sept. 8, 1959

503,000

114,000

124,000

0.09

.15

< !!

238

82

11

3.9

5.0

33

48

44

0

0

0

0

0

<1.1

9.2

18

20

Q 0

3.8

27

280

131

0

0

0

3.9

.59

Hudson River at Ford Motor Co. powerOct. 29, 1958

Jan. 22, 1959

Aug. 17

Oct. 19

23,000

63,000

1,940

3,790

0.15

.18

.59

<,13

304

775

251

225

9.0

15

20

10

28

46

60

49

0

0

0

0

0

<1.3

<1.1

0

30

15

40

19

8.6

15

44

4.5

207

650

414

300

0

X.O

0

0

2.2

1.1

.28

.89

Mississippi River just above bridge on U.S.

May 10, 1958

Oct. 14

Mar. 13, 1959

May 18

865,000

262,000

655,000

415,000

0.13

<.22

0

0

1,050

1,010

281

29

22

15

6.1

78

127

72

84

0

0

0

0

0

5.8

0

0

2.6

8.5

4.6

84

10

6.9

9.0

74

1,670

828

663

0

0

0

0

4.9

1.8

2.4

Mobile River at Mount

Dec. 16, 1958

Apr. 1, 1959

Aug. 25

Sept. 30

b 24,000

b 92,000

b !2,000

b !5,500

0.13

.28

<.089

<.085

186

818

84

289

3.3

17

1.6

4.3

75

47

64

52

0

0

0

0

0

0

<.89

0

2.0

3.4

6.8

1.9

3.5

5.6

28

2.7

392

735

125

204

0

X.O

0

0

1.7

2.4

.14

.70

See footnotes at end of table.
THREE STUDIES THREE METHODS

waters from principal rivers of the United States and Canada 

grams per liter except as indicated] 3

Manganese 

(Mn)

Molybdenum 

(Mo)

Nickel 

(Ni)

Phosphorus 

(P)

Lead 

(Pb)

Rubidium 

(Rb)

Scandium 

(Sc)

Tin 

(Sn)

Strontium 

(Sr)

Titanium 

(Ti)

Vanadium 

(V)

Yttrium 

(Y)

Ytterbium 

(Yb)

Zinc 

(Zn)

Zirconium 

fZr)

20, near Blounstown, Fla., U.S.A.

5.0

25

20

4.0

0

<.17

.46

.62

4.6

2.6

23

34

0

<58

0

0

6.2

2.1

3.6

2.7

1.0

2.1

<.75

2.1

0

.OX

0

0

0

0

0

1.3

34

7.5

28

25

<0.80

99

8.3

6.9

0

2.2

0

0

0

.X

0

0

0

.OX

0

0

0

0

0

0

0

X.O

X.O

X.O

bridge on U.S. Highway 190, at Krotz Springs, La., U.S.A.

100

68

12

0

<.93

0

<2.7

O.X

47

6.5

10

0

<186

0

0

1.1

11

2.6

11

2.2

2.4

<2.7

0

0

.X

0

n

0

0

0

n

154

22

139

10

20

107

14

0

0

<6.5

0

0

X.O

X.O

0

0

0

.X

0

0

9

0

0

0

X.O

X.O

0

Highway 80, at Yuma, Ariz., U.S.A.

21 

37

6.9 

6.5

30 

0

0 

0

<8.0 

16

<8.0 

0

0 

0

0 

0

802 

715

<8.0 

10

0 

0

0 

0

0 

0

0 

0

0 

0

about 3 miles above The Dalles, Oreg., U.S.A.

14

5.5

O.X

2.1

1.0

X.O

10

36

0

0

0

1.2

5.0

3.4

1.4

<1.1

0

0

0

n

0

0

30

112

60

2.9

5.2

2.1

X.O

0

4.0

0

0

0

0

0

0

0

0

0

0

0

0

plant, at Green Island, N.Y., U.S.A.

35

150

78

56

0

.65

1.7

.55

12

8.6

71

5.5

0

0

0

0

2.9

11

9.4

6.6

1.9

1.6

<1.1

2.1

0

.X

0

0

0

0

0

0

106

84

72

106

<1.4

55

10

18

0

5.6

4.3

3.8

0

X.O

0

0

0

.X

0

0

0

<125

0

0

0

X.O

X.O

X.O

Highway 190, near Baton Rouge, La., U.S.A.

185

46

12

0

<1.1

0

<2.6

O.X

19

13

33

XOO,

<223

<184

0

4.0

7.8

4.0

9.4

2.5

7.4

-«c2.6

0

0

0

0

0

0

0

0

34

105

61

97

62

6.7

72

12

X.O

0

<5.5

0

0

X.O

0

0

0

0

0

0

0

0

0

0

X.O

0

X.O

0

Vernon Landing, Ala., U.S.A.

41

20

7.4

6.7

0

.28

.35

.27

6.9

6.1

29

6.8

<98

<93

0

0

15

3.1

1.5

1.2

1.3

3.9

<.89

2.6

0

.X

0

0

0

0

0

1.4

68

39

59

51

3.6

38

2.7

12

0

4.0

0

0

0

X.O

0

0

0

.X

0

0

0

0

0

0

0

X.O

X.O

X.O
OCCURRENCE OF MINOR ELEMENTS IN WATER

Table 1. Spectrographic analyses for minor elements in waters

Date of 

collection

Discharge 

(cfs)

Silver 

(Ag)

Aluminum 

(Al)

Boron 

(B)

Barium 

(Ba)

Beryllium 

(Be)

Cobalt 

(Co)

Chromium 

(Cr)

Copper 

(Cu)

Iron 

(Fe)

Lanthanum 

(La)

Lithium 

(Li)

Sacramento River at tower bridge on

May 1, 1958

Nov. 25

May 1, 1959

Sept. 16

b 49,900

b !3,300

b ll,800

b 9,900

0

<.086

0

<.16

60

286

1,110

22

10

9.8

25

9

31

25

56

0

0

0

0

0

0

<3.3

<1.6

<0.72

4.4

2.4

7.0

1.4

2.9

7.0

14

112

1,210

764

0

0

0

0

2.1

.77

.66

Snsquehanna River at hydroelectric

May 7, 1958

June 10

Sept. 11

June 5, 1959

126,000

19,600

10,000

17,300

0.29

0

.25

<.15

27

102

10

12

16

4.3

24

38

25

37

0

0

0

0

0,X

0

0

0

1.9

4.5

3.7

1.3

5.1

4.0

5.3

105

31

154

0

0

0

X.O

3.5

3.4

Yukon River at Mountain

May 28, 1958

Jan. 7, 1959

^450,000

d 30,000

0.31

<.20 82

11

13

26

109

0

0

O.X

0

2.3

7.0

6.3

2.5 1,130

0

0 2.0

Churchill River east of island off Drachm Point,

June 24, 1958

Sept. 25

Feb. 20, 1959

June 27

e40,700

e42,500

e27,000

e61,000

<o;o?8

.37

.21

<.084

148

103

183

134

3.7

13

16

4.5

19

38

49

33

0

0

0

0

0

0

0

0

5.5

3.6

2.8

12

2.0

9.5

8.5

2.9

172

79

157

185

0

0

0

0

1.0

.95

2.6

.51

Fraser River at Mission City,

July 1, 1958

Oct. 1

Feb. 12, 1959

June 12

255,000

166,000

37,100

275,000

0

<.073

0

0

327

526

261

51

2.6

11

2.6

1.4

17

18

20

14

0

0

0

0

<1.9

1.9

0

0

2.9

6.0

23

2.8

1.6

2.5

3.0

.83

1,180

635

 363

52

0

0

0

0

0.50

.18

.40

1.3

MacKenzie River about 3 miles upstream from separaJuly 24, 1958

Oct. 2

June 9, 1959

470,000

270,000

360,000

0

<.16

0

1,410

440

869

13

8.6

4.7

65

70

85

0

0

0

5.0

0

0

12

5.7

11

11

3.9

4.2

1,390

1,030

706

0

0

0

1.1

1.0

2.5

Nelson River near Amery, Manitoba, Canada (observations

Oct. 5, 1958

Jan. 29, 1959

Mar. 9

Apr. 9

May 1

June 3

e 85,000

e49,000

e38,000

e36,000

e75,000

e84,000

0

0

0

0

0

<.18

226

664

105

89

81

2.5

7.6

21

3.6

7.8

58

45

50

58

56

57

53

0

0

0

0

0

0

0

0

0

0

0

5.1

5.7

2.5

1.9

4.7

3.4

21

2.3

1.0

2.5

4.2

6.0

11

287

389

38

81

198

0

0

0

0

0

0

2.9

4.8

7.5

8.1

3.9

1.7

See footnotes at end of table.
THREE STUDIES THREE METHODS

from principal rivers of the United States and Canada Continued

Manganese 

(Mn)

Molybdenum 

(Mo)

Nickel 

(Ni)

Phosphorus 

(P)

Lead 

(Pb)

Rubidium 

(Rb)

Scandium 

(Sc)

Tin 

(Sn)

Strontium 

(Sr)

Titanium 

(Ti)

Vanadium 

(V)

Yttrium 

(Y)

Ytterbium 

(Yb)

Zinc 

(Zn)

Zirconium 

(Zr)

Capital Street, at Sacramento, Calif., U:S.A.

6.3

50

34

0

<.43

0

<.47

O.X

7.1

6.6

20

0

0

<110

0

0

4.5

4.2

4.4

1.0

1.1

<1.6

0

0

0

0

0

0

0

0

6.3

46

15

61

3.1

<.86

14

106

0

0

0

6.7

0

0

0

0

0

0

0

0

0

<86

<110

0

0

0

0

X.O

plant spillway at Conowingo, Md., U.S.A.

<2.1

79

0

.X

0

.54

X.O

.X

11

3.9

0

0

0

0

3.6

1.1

<2.1

7.2

<2.1

<1.5

0

0

0

0

0

0

0

0

12

40

25

74

3.2

0

<2.1

5.7

0

0

0

0

0

0

0

0

0

0

0

0

XOO.

0

0

0

0

0

0

0

Village, Alaska, U.S.A.

181

0

1.2

X.O

17

XOO,

<195

1.5

8.6 0

0

0

0

0

1 R

129

16

<2.0

0

0

0

0

0

0

0

0

0

0

8 miles south of Churchill, Manitoba, Canada

17

2.6

4.4

8.4

0

0

.49

<.25

4.1

5.6

11

14

0

0

0

0

2.5

4.0

4.3

2.4

<0.78

1.1

1.2

0

0

0

0

0

0

0

0

0

22

37

33

23

8.6

3.1

7.1

5.8

0

0

0

0

0

0

0

0

0

0

0

0

0

0

<122

0

0

0

0

X.O

British Columbia, Canada

26

32

23

3.0

0

0

.79

<.21

5.0

12

13

2.6

<62

73

-<79

0

<0.62

1.8

3.9

1.3

2.6

.95

.79

.90

0

0

0

0

0

0

0

0

16

18

40

23

17

16

18

2.6

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

0

tion, at Arctic Red River, Northwest Territory, Canada

60

20

36

0

0

.80

36

8.2

22

259

0

0

2.9

6.4

7.6

1.6

<1.6

2.4

0

0

0

0

0

0

96

228

125

8.4

6.0

24

0

0

0

0

0

0

0

0

0

0

0

0

0

0

X.O

on Jan. 20, Apr. 9, and June 3, upstream at Kelsey powersite)

9.6

8.7

0

<2.8

3.4

177

0

.87

1.3

0

0

<.53

5.9

4.1

5.5

7.8

8.8 55"

0

0

0

0

0

425

5.3

0

0

22

4.9

5.0

2.3

0

0

<2.8

<2.6

5.1

0

.0

0

0

0

.X

0

0

0

0

0

2.1

121

73

105

86

107

55

9.2

32

5.3

5.9

14

67

0

0

0

0

0

5.7

0

0

0

0

0

X.O

0

0

0

0

0

.X

0

0

0

0

0

0

0

0

X;0

0

0

X.O
OCCURRENCE OF MINOR ELEMENTS IN WATER

Table 1. Spectrographic analyses for minor elements in waters

Date of 

collection

Discharge 

(cfs)

Silver 

(Ag)

Aluminum 

(Al)

Boron 

(B)

Barium 

(Ba)

Beryllium 

(Be)

Cobalt 

(Co)

Chromium 

(Cr)

Copper 

(Cu)

Iron 

(Fe)

Lanthanum 

(La)

Lithium 

(Li)

St. Lawrence River at water

Aug. 25, 1958

Sept. 3

Sept. 24C

Dec. 3

Apr. 20, 1959F

Apr. 23°

June 16e

342,000

340,000

342,000

348,000

551,000

550,000

404,000

0.94

0

<.14

<.14

<.ll

<.ll

0

276

186

1,050

828

206

13

6.3

11

11

7.8

5.8

4.1

30

26

46

36

39

40

29

0

0

0

0

0

0

0

0

0

4.0

0

<1.1

<1.1

0

12

9.6

23

5.8

6.8

9.7

7.0

4.3

4.7

59

4.7

8.1

580

257

1,190

718

288

0

0

0

0

0

0

0

0.41

.40

.60

1.1

97

.36

.55

a Looked for but not detected: As, Au, Bi, Cd, Ce, Cs, Dy, Er, Eu, Ga, Gd, Ge, Hf, Hg, Ho, In, Ir, 

Lu, Nb, Nd, Os, Pd, Pr, Pt, Re, Rh, Ru, Sb, Sm, Ta, Tb, Te, Th, Tl, Tm, U, W. 

bDaily mean discharge. 

cAt Quebec. 

dEstimated discharge at Kaltag.

"Data of Geochemistry," and provides current data on rates of continental chemical 

losses to the oceans. A product of the study 

of oceanborne chemicals in principal rivers 

is new and meaningful quantitative data for 

dissolved minor elements. Samples were 

obtained in the lower reaches of selected 

rivers just above tide and were prepared in 

the field by a unique and simple filter system. 

Minor elements were retained in solution by 

addition of concentrated nitric acid. Duplicate residue analyses were made on the 

spectrograph using1 regions of the spectrum 

(2250-4750A and 6250-8750A) in which most 

of the metals have sensitive analytical lines.

Emission spectrography (Haffty,l960) using 

direct-current arc excitation of the water 

residue is rapid and reliable for quantitative 

determination of many minor elements commonly found in natural waters. It has been 

used successfully for samples from principal 

rivers of the world. Major elements are determined chemically and are not reported in 

this paper.

Let us look briefly at a few data for the 

United States and Canada (table 1). Of the 

alkaline earth metals, barium occurs in all 

waters examined in concentrations - ranging 

up to about 150 micrograms per liter, and 

strontium up to about 800 micrograms per 

liter. Undoubtedly these values are exceeded 

at very low flows, although barium concentrations seem to be independent of the rate of 

water discharge.

Generally, there is no well-defined relation 

between strontium content and streamflow. 

However, samples from the Mississippi and 

Atchafalaya Rivers do show an increase in the 

strontium content and in the ratio of strontium to barium as discharge decreased 

(fig. 1). Also-, the ratios of calcium to strontium and calcium to barium tended to increase with increase in flow of the two river 

waters (fig. 2). The alkaline earths also increased with an increase in dissolved solids 

for the Mississippi River (fig. 3), as indicated 

from observations shown in figure 1.

The occurrence of the metals, cesium, rubidium, and lithium in or below the lower 

levels of detection suggests that the alkali 

metals in principal rivers are strongly 

sorbed by soils and rocks upstream. Zinc 

and cobalt rarely occur in measurable quantities. Chromium, nickel, copper, lead, and 

boron were found in most waters, but no relation to streamflow is evident. Titanium 

occurs in most waters, and at times exceeds 

70 micrograms per liter. Molybdenum and 

vanadium were detected in many samples in 

low concentrations. The content of copper, 

manganese, and boron was of the same order 

as that reported by Konovalov (1959) for 

major rivers of the U.S.S.R.

The data in table 1 suggest a pattern of 

occurrence or absence of a particular minor 

element in waters from a large drainage network. Hydrologic and geologic implications 

are evident by the relatively wide range in
THREE STUDIES THREE METHODS

from principal rivers of the United States and Canada Continued

Manganese 

(Mn)

Molybdenum 

(Mo)

Nickel 

(Ni)

Phosphorus 

(P)

Lead 

(Pb)

Rubidium 

(Rb)

Scandium 

(Sc)

Tin 

(Sn)

Strontium 

(Sr)

Titanium 

(Ti)

Vanadium 

(V)

Yttrium 

(Y)

Ytterbium 

(Yb)

Zinc 

(Zn)

Zirconium 

(Zr)

works plant at Levis, Quebec, Canada

21

6.7

30

18

RQ

en

16

1.7

2.4

2.6

1.1

< 34

37

.60

13

11

22

13

1 3

1 9

16

0

0

173

0

^119

xl 1 9

0

3.7

4.9

55

3.2

7 3

3.6

3.6

1.4

1.4

2.9

1.4

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<1.1

1.5

0

0

0

0

0

0

0

0

0

0

0

n

n

0

66

92

78

86

45

58

69

21

6.6

50

51

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X.O

X.O

0

0

0

0

0

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.X

0

0

0

<144

0

<112

0

0

0

0

0

X.O

X.O

XO

0

Approximate.

< Detected, but less than figure indicated. 

..Not determined.

0 Below limit of detection for the specific element in designated sample. 

X Refers to semiquantitative determination in the digit order shown.

uj 6.0 

5.0 -

-©

4.0

3.0 

2.0 

1.0

1°

100 200 300 400 500 600 700 800 900 1000

DISCHARGE, IN THOUSANDS OF CUBIC FEET PER SECOND 

A

100 200 300 400 500 600 700 800 900 1000

DISCHARGE, IN THOUSANDS OF CUBIC FEET PER SECOND 

A

tcJj h- 

_l

r

i.

OT

K

Z

i

I

L>

Z

5

J

CD

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4.0

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_ _

 _

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_ * _

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1 1 1 l°l 1 1 1 1 1 1 1 1 1 1 1 1 1 l~ 0 

100 200 300 400 500 600 700 800 900 1000

DISCHARGE, IN THOUSANDS OF CUBIC FEET PER SECOND 

B

5.0

II

ptui !§

zz

S.S

_ 0

o

100 200 300 400 500 600 700 800 900 1000 

DISCHARGE, IN THOUSANDS OF CUBIC FEET PER SECOND

B

Figure 1. Strontium and barium in water and water discharge. A, 

Relation of strontium content to water discharge; B, Ratio of 

strontium and barium content to water discharge. Open circle, 

Atchafalaya River at KrotzSprings, La. Closedcircle, Mississippi 

River near Baton Rouge, La.

Figure 2. Calcium, strontium, and barium in water and water 

discharge. A, Ratio of calcium and strontium content to water 

discharge; B, Ratio of calcium and barium content to water 

discharge. Open circle, Atchafalaya River at Krotz Springs, 

La. Closed circle, Mississippi River near Baton Rouge, La.
OCCURRENCE OF MINOR ELEMENTS IN WATER

200

100

1.0 3'.0 

Sr, IN MICIROEQUIVALENTS PER LITER 

A

5.0

LJ omj.

o 

en

a

UJ

<n

a

200

100(

1 1 1 1

0

0 

 

 0

~0

1 1 1 1

) 1.0 3.0 5.

Sr, IN .IWaROjEQUIVALENTS PER LITER 

Ba, IN MICROEQUIVALENtTS PER LITER

B

Figure 3. Strontium, barium, and dissolved solids in water. A, 

Relation of strontium content to dissolved solids; B, Ratio of 

strontium and barium content to dissolved solids. Open circle, 

Atchafalaya River at Krotz Springs, La. Closed circle, Mississippi River near Baton Rouge, La.

content of some elements and the uniform 

content of others. Waters in the lower reaches 

of these principal rivers are a meld of many 

upstream tributaries. Probably much greater 

divergence in the kinds and amounts of minor 

elements will be found within the drainage 

networks than is evident from data for the 

main stem. This must be kept in mind in 

assessing current results.

water to their radioactive counterpart in fallout, such as strontium-90.

Skcmgstad used a Beckman Model DU spectrophotometer with flame attachment for 

strontium concentrations more than about 

0.2 ppm. For greater sensitivity, a spectrographic procedure based on the copper-spark 

technique of Fred, Nachtrieb, and Tomkins 

(1947) and Nachtrieb (1950) was used for 

samples containing less than about 0.2 ppm 

of strontium.

In the strontium study, surface-water samples were obtained from about 65 places in 

the United States to represent, insofar as 

possible, the major streams and drainage 

areas of the country. At each site, three 

samples were obtained at intervals of several 

months to a year, to obtain water during 

high-, low-, or median-flow conditions for 

the stream.

The results of the study are summarized 

by Skougstad and Horr in figure 4. The regions where the natural stable strontium content of surface waters is relatively low (less 

than 0.50 ppm) include the Pacific Northwest, 

Northeastern United States, and the Central 

lowlands, including the lower Mississippi basin and the Western Gulf Coast area. Moderate amounts of strontium (0.50 to 1.5 ppm) 

are found in streams of Southeastern United 

States, most of the Great Plains Region, the 

Western Mountain and Plateau Regions, and 

California. Surface waters in parts of northern arid western Texas and southern New 

Mexico and Arizona are comparatively high 

in strontium.

Localized geologic environment such- as 

the extensive celestite deposits in northern 

Ohio give values for strontium that are uncommonly high for a particular zone shown 

in figure 4.

OCCURRENCE OF STRONTIUM

The second approach was used by Skougstad 

and Horr (1960) in establishing the general 

occurrence of strontium in natural water of 

the United States. National interest has been 

focused on stable strontium and its occurrence and distribution in natural waters. 

Today, one task confronting the scientist is to 

assess the relationship of stable elements in

STUDIES IN CALIFORNIA

The Geological Survey is studying the distribution and abundance of minor elements in 

various waters in California in cooperation 

with the California Department of Water Resources. The spectrographic method (Silvey, 

W. D., 1960, written communication) used in 

this study utilizes a chemical enrichment of 

the minor elements prior to spectrographic 

analysis of sea water, surface water, ground
EXPLANATION

O 

Less than 0.50 ppm

9 

0.5 to 1.5 ppm

 

More than 1.5 ppm

Strontium zone boundary

22

Sampling site number

Figure 4. Map of the United States showing concentration of strontium in surface water at selected sites. (From Skougstad an
10 OCCURRENCE OF MINOR ELEMENTS, IN WATER

waters, including springs, and connate brines. 

These results will be published in the regular report series of the U.S. Geological 

Survey.

RADIOELEMENTS

The natural radioelement content of water 

is a subject receiving wide attention and discussion. For our purpose, however, we may 

consider natural uranium and radium as important minor elements, and thus emphasize 

the generalized studies of uranium and radium in the United States, such as the study 

made by Scott and Barker (1958). In a paper 

prepared for the United Nations Conference 

on PeacefulUses of Atomic Energy (1958) at 

Geneva, the authors give statistic interpretation of uranium and radium data for 10 geotectonic regions of the United States, which 

boundaries were established from tectonics, 

geology, physiography, and ground-water 

provinces. Table 2 taken from their report, 

summarizes the then available radioelement 

data for ground water in the United States. 

Additional reports are in progress.

Scott and Barker report that neither radium 

nor uranium concentrations correlate well 

with concentrations of the more common 

chemical constituents of ground water, although "uranium concentrations do tend to be 

somewhat higher in water containing large 

amounts of bicarbonate ion." Table 2 shows 

the range, median, and "anomaly threshold" 

for uranium and radium concentrations, expressed as micrograms per liter (/^g/ 1) .and 

micromicrocuries per liter (yu/zc/1) respectively, for the 10 geotectonic regions. The 

anomaly threshold represents the lower limit 

of values which can be considered likely to 

have come from a population different from 

the bulk of samples that make up the frequency distribution.

The range and median values for uranium 

are largest in water samples from Region VI, 

in West-Central United States, and the largest 

median value for radium occurs in samples 

from Region VII, the Ozark-Ouachita Mountains.

A FEW DETAILS ON METHODS

Principal river studies. Evaporate sample to 

dryness on a steam bath in fused quartz or

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CN'-l'-lrHinCOO'-

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T

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CO

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CO

1

in ^ oo 

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rH ^f C

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t.

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EXPLANATION

Less than 0.50 ppm

0.5 to 1.5 ppm

More then 1.5 ppm

Strontium zone boundary

22 

Sampling site number

Figure 4. Map of the United States showing concentration of strontium in surface water at selected sites, (from Skougstad an
10 OCCURRENCE OF MINOR ELEMENTS.IN .WATER

waters, including springs, and connate brines. 

These results will be published in the regular report series of the U.S. Geological 

Survey.

RADIOELEMENTS

The natural radioelement content of water 

is a subject receiving wide attention and discussion. For our purpose, however, we may 

consider natural uranium and radium as important minor elements, and thus emphasize 

the generalized studies of uranium and radium in the United States, such as the study 

made by Scott and Barker (1958). In a paper 

prepared for the United Nations Conference 

on Peaceful Uses of Atomic Energy (1958) at 

Geneva, the authors give statistic interpretation of uranium and radium data for 10 geotectonic regions of the United States, which 

boundaries were established from tectonics, 

geology, physiography, and ground-water 

provinces. Table 2 taken from their report, 

summarizes the then available radioelement 

data for ground water in the United States. 

Additional reports are in progress.

Scott and Barker report that neither radium 

nor uranium concentrations correlate well 

with concentrations of the more common 

chemical constituents of ground water, although "uranium concentrations do tend to be 

somewhat higher in water containing large 

amounts of bicarbonate ion." Table 2 shows 

the range, median, and "anomaly threshold" 

for uranium and radium concentrations, expressed as micrograms per liter (ngj 1) and 

micromicrocuries per liter (/z/zc/1) respectively, for the 10 geotectonic regions. The 

anomaly threshold represents the lower limit 

of values which can be considered likely to 

have come from a population different from 

the bulk of samples that make up the frequency distribution.

The range and median values for uranium 

are largest in water samples from Region VI, 

in West-Central United States, and the largest 

median value for radium occurs in samples 

from Region VII, the Ozark-Ouachita Mountains.

A FEW DETAILS ON METHODS

Principal river studies. Evaporate sample to 

dryness. on a steam bath in fused quartz or

<H -^

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REFERENCES CITED 11

vycor evaporating dishes. A weighed amount 

of the residue (12 mg) and synthetic standards mixed with a weighed amount of spectroscopically pure graphite powder (6 mg) is 

volatilized using a direct-current arc of 16 

amperes. The resulting radiant energy is 

recorded on photographic plates after passing through a dispersing medium (grating), 

and the intensity of the spectral lines formed 

is measured by means of a projection 

comparator-microphotometer. Concentrations of elements in the unknown samples 

are read from working curves established 

by the standards arced on the same plate. 

Concentrations as low as 1 microgram per 

liter (0.001 ppm for waters considered herein), or less, have been determined by this 

method.

Strontium studies. Use Beckman Model DU 

spectrophotometer with flame attachment, an 

oxygen-acetylene flame, a photomultiplier 

tube attachment, and a spectroscopic buffer 

solution.

The spectrographic copper-spark method 

requires about 30 ml of water sample and 

rapidly detects concentrations of strontium 

to about 5 parts per billion. Probable error 

of an analysis is about 10 percent of the 

amount present.

The usual chemical methods for the determination of strontium are not satisfactory 

when applied to water analysis because of 

small amounts of strontium present and difficulty in separating a small amount of 

strontium from much larger amounts of calcium and magnesium normally found in natural water.

California studies. .The chemical procedure 

uses chelating reagents (8-hydroxyquinoline, 

thionalide, and tannic acid) to selectively 

precipitate buffer metals. Indium is used as 

a radiation buffer, and palladium, the internal standard. The precipitate is ignited in a 

muffle furnace at a temperature of about 

450°C. The ignited precipitate is mixed with 

"specpure" graphite powder. This mixture 

is placed in craters of graphite electrodes 

and subjected to a direct-current arc of 6 

amperes. The resulting spectrum formed is 

recorded on film or photographic plates. Intensities of the spectral lines of the element 

and indium internal standard are measured

and the concentrations calculated from standard curves. Concentrations of 1 milligram 

to 1 microgram or less can be determined by 

use of this method.

SUMMARY

Knowledge of the occurrence of minor elements* in water is one additional step in 

man's continuous probe into the unknown. 

Only a few of many significant studies are 

described in this paper. However, the results make clear that a vast frontier in technical studies looms ahead for a better understanding of minor elements the end products of many earth processes.

REFERENCES CITED

Braidech, M. M. and Emery, F. H., 1935, The 

spectrographic determination of minor 

chemical constituents in various water 

supplies in the United States: Am. Water 

Works Assoc. Jour., v. 27, p. 557-580.

Durum, W.H., Heidel, S.G., and Tison, L.J., 

1960, World-wide runoff of dissolved solids: Internat. Assoc. Sci. Hydrology, Pub. 

no. 15, General Assembly of Helsinki, 

p. 618-628.

Fred, M.,Nachtrieb,N.H., and Tomkins,F.S., 

1947, Spectrochemical analysis by the copper spark method: Optical Soc. America 

Jour., v. 37, no. 4, p. 279-288.

Haffty, Joseph, 1960, Residue method for 

common minor elements. Spectrographic 

analysis of natural water: U.S. Geol. Survey 

Water-Supply Paper 1540-A, 9 p.

Heggen and Strock, 1953, Determinations of 

trace elements: Anal. Chem. v. 25, p. 859.

Konovalov, G. S., 1959, The transport of microelements by the most important rivers 

of the U.S.S.R. Doklady Akad Nauk SSSR, 

v. 129, no. 4, p. 912-915.

Nachtrieb, N. H., 1950, Principles and practice of Spectrochemical analysis: New 

York, McGraw-Hill Book Co.

Scott, R. C. and Barker, F. B., 1958, Radium 

and uranium in ground water of the United 

States: United Nations Peaceful Uses of 

Atomic Energy. Internat. Conf., 2d, Proc., 

Geneva, v. 2, p. 153-157.

Skougstad,M. W., and Horr, C. A., 1960, Occurrence of strontium in natural water: 

U.S. Geol. Survey Circ. 420, 6 p.

INT.DUP..D.C.61-93501