Geochemical Techniques for Identifying Sources of Ground-Water Salinization 9781566700009, 9780203753668

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Geochemical

Techniques

for

Identifying

Sources of

Ground-Water Salinization

Bernd C. Richter Charles W. Kreitler

Bert E. Bledsoe EPA

Project Officer

CRC Press Taylor & Francis Croup Boca Raton London New York CRC Press is

Taylor

an

imprint of the Group, an informa business

& Francis

First

published

Published 2021

Taylor &

1993

by

by CRC Group

C. K. SMOLEY Press

Francis

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Parkway NW, Suite 300

Boca Raton, FL 33487-2742 © 1993

by Taylor & Francis Group, LLC an imprint of Taylor & Francis Group,

CRC Press is No claim to

original

an

Informa business

U.S. Government works

ISBN-13: 978-1-56670-000-9

(hbk)

DOI: 10.1201/9780203753668 This book contains information obtained from authentic and

highly regarded

sources.

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efforts have been made to

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ACKNOWLEDGMENTS

Funding

for this

project

provided by

was

Robert S. Kerr Environmental Research

Cooperative Agreement

the U. S. Environmental Protection

Laboratory,

Office of Research and

No. CR-815748 to the Bureau of Economic

Texas at Austin. Burt E. Bledsoe

was

EPA

project

reviews.

Geology,

Agency

the information in this document has been funded

Although

Environmental Protection

Agency,

it does not

Development, the

officer. His continued support is

We thank the reviewers from the U. S. Environmental Protection

necessarily

Agency,

University

of

appreciated.

for their

manuscript

wholly by

reflect the views of the

under

the U. S.

Agency

and

no

official endorsement should be inferred.

Manuscript preparation were

drafted

by

was are

edited

were

completed

at the Bureau of Economic

Geology. Figures

Maria Saenz, Tari Weaver, Kerza Prewitt, Jana Robinson, Michele

Margret Koening, typesetting

was

and Joel Lardon under the direction of Richard Dilon. Word

done

by Kitty

by Susan Llyod

Chalstromn and

processing

under the direction of Susann Doenges. The

designed by Margret

LaHaye, and

publication

Evans. The efforts of all these

people

greatly appreciated. Bernd Richter is

America. 78763.

presently traveling, driving

Any comments or questions can be directed to Charles Kreitler is

University of Arizona,

a

professor

where he teaches

in the

his VW bus

the

highways

of

Mr. Richter at P.O. Box 5543, Austin, TX

Department

hydrogeology.

across

of

Hydrology

and Water Resources,

EXECUTIVE SUMMARY

This report deals with salt-water sources that

commonly

water. It reviews characteristics of salt-water sources and

used to

identify these

sources

mix and deteriorate fresh

geochemical techniques

sources

of salt water

are

distinguished:

(2) Halite solution, (3) Sea-water intrusion, (4) Oil-and

and

can

be

together, illustrating

which ones are

United States. In separate sections, each

potential

a

step-by-step

(1) Natural saline ground water,

gas-field brines, (5) Agricultural effluents,

(6) Saline seep, and (7) Road salting. The geographic distribution of these

individually

that

after mixing has occurred.

The report is designed to assist investigators of salt-water problems in fashion. Seven major

ground

potential

sources was

sources at any

given

mapped

area in the

source is then discussed in detail

regarding

physical and chemical characteristics, examples of known techniques for identification of mixtures between fresh water and that source, and known occurrences

parameters that

by a

discussion

are used within these

concerning where study

are

presented

and how to obtain them. Also

graphical and statistical methods that references for further

techniques

are used

frequently in

concludes this report.

by state.

Individual geochemical

in a separate section, followed

provided is

a

description

of basic

salt-water studies. An extensive list of

TABLE OF CONTENTS

Executive

Summary

iii

AcknowledgmentsV 1.

1 Introduction

1.1.

Purpose

1.2.

2. 3.

Geographic

and

Use

of

this

Report

1

Background

Distribution of

Major

2

Major Salinization Sources6

Salinization

Sources

17

3.1. Natural Saline Ground Water17 3.1.1.

Mechanism

Different Sources of Naturally

Occurring Salinity22

3.1.2.

Hydrochemistry of

3.1.3.

Examples of Geochemical Studies of Natural Saline Ground Water28

3.1.4.

Significant

3.1.5.

State-by-State

17

Parameters

35

Summary

38

56 3.2. Halite Solution

3.2.5.

3.2.1.

56 Mechanism

3.2.2.

Composition of Halite and other Evaporites5

3.2.3.

Examples of

3.2.4.

Significant

62 Geochemical Studies of Halite Solution

75 Parameters

State-by-State

Summary

of

Halite

Occurrences

75

81 3.3. Sea-Water Intrusion

3.3.1. 3.3.2.

3.3.3.

Mechanism 81 Chemistry

Reaction

3.3.5.

State-by-State

Characteristics

Summary

of

Water

of

Sea-Water

Sea-Water

Oil-Field

3.4.1.

3.4.1a.

3.4.1b. 3.4.1c.

Sea

86

88 Examples of Geochemical Studies of Sea-Water Intrusion

3.3.4.

3.4.

of

Intrusion

Intrusion

Brine

Mechanism

Surface

disposal

109

115

115

117

Injection wells119

Plugged

3.4.2

Oil-Field Brine

3.4.3.

Examples of

and

abandoned

boreholes

Chemistry122

122 Geochemical Studies of Oil- and Gas-Field Brine Pollution

103

119

Parameters132

3.4.4.

Significant

3.4.5.

State-by-State Summary

134 of Oil- and Gas-Field Contamination

142 3.5. Agricultural Sources

3.5.1.

142 Mechanism

3.5.2.

Water Chemistry 147

3.5.3.

Examples of

3.5.4.

Significant

3.5.5.

State-by-State Summary

Geochemical Studies of

of

Agriculturally-Induced

Ground-Water Problems 156

Seep159

3.6. Saline

Mechanism

3.6.2.

Water Chemistry 162

3.6.3.

Examples of

3.6.4.

Significant

3.6.5.

State-by-State Summary

3.7.

Geochemical Studies of Saline

159

Seep163

170 Parameters

of Saline

Seep

Road

Occurrences 172

Salt

3.7.1.

175 Mechanism

3.7.2.

Road-Salt

Chemistry179

3.7.3.

Examples

of Geochemical Studies of Road

3.7.4.

Significant

181 Chemical Parameters

3.7.5.

State-by-State Summary of

175

Salting 180

181 Road-Salt Issues

188 Geochemical Parameters 188 Discussion of Individual Parameters

4.1. 4.2.

5.

149 Salinization

Parameters156

3.6.1.

4.

Agricultural

Summary

Data

Availability

of

Field

Techniques

201

204 and Selection

204 5.1. Sources of Data 209 5.2. Selection of Data Criteria 6.

Graphical

6.1.

6.2.

7.

and

Statistical

Graphical

Statistical

Techniques

211

Techniques

Techniques

211

221

230 References

FIGURES 1.

Map of tha United States showing areas of ground water containing more than 1,000 mg/L total dissolved solids at depths less than 500 ft below land surface 7

2.

Map of the United States showing the approximate extent of halite deposits 8

United States

showing

areas of

potential

9 sea-water intrusion

3.

Map of the

4.

Map of

5.

Major irrigation

6.

Saline-seep

7.

Map of the United States showing amount of road salt used in individual states during the winters of 1966-1967, 1981-1982, and 1982-1983 14

8.

Composite

9.

Relationship

the United States

areas of oil and

11 gas production

in the United States 12

areas

areas in

showing general

13 Montana, North and South Dakota, and Texas

map of potential salinization sources 15 between

ground-water quality

and

recharge-discharge

areas 19

10.

Discharge of regional,

saline

ground water and mixing with local, fresh ground water21

11.

Relationship

between

depth

of

12.

Geochemical composition of

13.

Separation of

14.

Use of bromide, iodide, boron, and chloride concentrations in bivariate plots for identification of salt-water sources 31

15.

Separation

screen

and chloride content in two

ground water in

a

of different

16. 17.

wells 23

gypsum playa, West Texas 27

local recharge water from nonlocal

ground water using

ground-water origins using the

water

adjacent

stable isotopes29

strontium-iodide

relationship

in

ground

32

Ground-water flow directions and salinities in parts of the

Murray Basin,

southwest Australia

33

Differentiation between fresh-water contamination caused by oil-field brines versus brine 34

evaporatively concentrated

ground water in parts

California 36

Natural salinization of

19.

Stable-isotope composition

20.

Solution of halite

21.

Discharge points of halite-solution brine at land surface in the Rolling Plains of north-central Texas and southwestern Oklahoma 59

22.

Bivariate plots of

23.

Classification of

24.

Modified Piper diagrams of chemical composition of brine springs and surface waters in southern Manitoba 64

25.

Comparison of Na/CI weight ratios for oil-field brines and

26.

of

of the San

Joaquin Valley of

18.

ground water affected by evaporation37

by circulating ground water,

major ions

58 Palo Ouro Basin, Texas

and Br/CI ratios versus chloride for natural halite-solution brines

61

oil-field/deep-basin waters according to TDS and bromide concentrations63

brines from salt springs in western Oklahoma and southwestern Kansas 65 Differentiation of oil-field/deep-basin brine from halite-solution brine using bivariate Br/CI weight ratios versus chloride concentrations 67

plots of 27.

Grouping of brine analyses according to molar Na/CI ratios and Br/CI weight ratios typical for halite solution and oil-field/deep-basin brine 69

28.

Bivariate plots of chemical constituents in brines collected from salt springs and shallow test holes in the Rolling Plains of Texas 70

29.

Molar ratios of (Ca+Mg)/So4 versus Na/CI in salt-spring and shallow subsurface brines, Rolling Plains of Texas 71

30.

Relationship between s 18o and CI with depth Texas

in shallow brines in

parts

of the

Rolling Plains, 72

31.

Differentiation between halite-solution waters and oil-field/deep-basin brines using differences in I/CI weight ratios 73

32.

Theoretical mixing curves for fresh water and potential salinization sources in Kansas using sulfate and chloride concentrations 74

33.

Typical ground-water flow patterns along

34.

Schematic cross section showing mixing mechanism of sea water with fresh water through sinkholes and solution openings in a carbonate aquifer 85

35.

coast lines 83

Bivariate

plots of major ions

samples

90

and of Br/CI ratios versus chloride for sea-water intrusion

36.

Increase in chloride concentration with time in coastal wells,

37.

Landward movement of sea water mapped by the position of the 500 mg/L chloride contour in two shallow aquifers, Monterey County, California 94

38.

Piper diagram of

39.

Piper diagram of chemical composition of selected saline waters from the Manhattan Beach area, California 97

40.

Iodide concentrations

41.

Bivariate plot of SO4/CI ratios and SO4 concentrations for coastal saline ground water of southwest Florida 101

42.

Dilution diagrams of major ions with theoretical mixing lines between sea water and local fresh water 104

43.

Relationship between flow regimes and hydrochemical facies in ground water in a big coastal plain105

44.

Geochemical processes and changes in ionic composition along the flow path in a coastal aquifer 106

45.

Map of shallow oil

46.

Schematic diagram illustrating possible communication scenarios between deep saline aquifers and shallow fresh-water units through boreholes 121

47.

Bivariate

48.

Monitoring of chloride concentrations in contamination

chemical

as

composition of coastal

Monterey County,

saline water,

California 93

Monterey County,

California

indicator of residence time 9

120 fields in the United States

plots of major ions

123 and Br/CI ratios versus chloride for oil-field brines

ground water as an

aid in

identifying salt-water

125

49.

50.

Relationship between soil chloride and depth inside and outside an abandoned brine-disposal pit 126 Bivariate plots of major ions versus chloride from water-supply wells and test holes in the of an abandoned brine-disposal pit127

vicinity

using bar graphs,

Stiff

diagrams,

and contouring 129

51.

Identification of salinization sources

52.

Mapping of point source of salinity and the resulting salt-water plume through contouring of chloride concentrations from water wells 130

53.

Determination of fresh

ground

geochemical constituent criteria that indicate

water in

54.

Transport of

salt to

55.

Classification of

parts

brine contamination of

of Oklahoma 133

discharge

areas as a

result of

144 irrigation-retum flow

irrigation water based on sodium-adsorption

ratios and

conductivity 148

95

56.

Increase in TDS concentration in the Arkansas River alluvial aquifer as a result of irrigation-return flow 151

57.

Use of Stiff diagrams for identification of water-quaity changes as a result of agricultural activities 152

58.

Salt content in irrigation water, irrigation runoff and in soil during and after three controlled irrigation experiments 154

59.

Relationship between TDS, Na, CI, Ca+Mg, SO4 and depth in soil under irrigated and

nonirrigated 60.

land 155

Diagrammatic cross

section of

ground-water flow with

saline seep in

topographically

low

areas and in intermediate areas 161

61.

Correlation between SO4 and TDS concentrations in seep waters from the Colorado Group, Montana 164

62.

Relationship between

63.

Summary of

64.

Modified

65.

Piper diagram of

66.

Variation in calcium, magnesium, and sulfate concentrations with chloride concentration in shallow ground water from a two-county area in parts of West Texas 171

67.

Rate of growth of saline seep

68.

Salt

69.

Correlation between increase in salt usage applied to highways and chloride concentrations in ground water, Massachusetts, 1955-1971 178

70.

Bivariate

71.

Location map of ground-water stations for which a chloride value is available at U.S. Environmental Protection Agency's data base STORET 206

72.

Location map of water wells in Texas for which a chloride value is stored at the Texas Natural Resources Information System data bank 207

73.

Graphical illustration of chemical analyses by contouring of individual parameters onto maps and cross sections 212

74.

Presentation of major ions in form of bar graphs, pie charts, Stiff diagrams, and Schoeller diagrams 213

75.

Presentation of chemical constituents on trilinear (Piper) diagram and classification scheme of hydrochemical facies 215

76.

Bivariate

77.

Use of bivariate plots for identification of mixing trends between fresh ground water and potential salinization sources in parts of West Texas 218

78.

Modified Schoeller and

79.

Calculation of mixing percentages between fresh water and salt water using mixing graphs of chloride and bromide 220

80.

saturation states and salinity in well waters affected by saline seep, north-central Montana 165 chemical and transport processes

Piper diagram of

production

plot of

chemical

in

a

saline-seep system 16

composition of ground water in

shallow ground water in two

near

operating

adjacent

saline seeps, Montana

counties of West Texas 169

173 Fort Benton, Montana

and usage of salt for deicing 177

Br/CI ratios versus CI for selected water

plots of

Na versus CI for halite-solution and

samples from northeastern Ohio182

deep-basin

Piper diagrams using concentration

brines 217

ratios as end

points219

Bivariate plots of ratios determined by application of Stepwise Discriminant Analysis as the ratios to distinguish sea-water intrusion from oil-field brines 226

statistically best

167

81. 82.

Bivariate plots of ratios determined by application of Stepwise Discriminant Analysis as the statistically best ratios to distinguish halite-solution brine from oil-field brines 227 Bivariate

plot of Na/CI ratios versus Ca/CI

ratios for Illinois

ground water,

llinois oil-field

brines, and ground water contaminated by oil-field brine 229

TABLES standards established for

inorganic

constituents 3

1.

Drinking-water

2.

Ground-water classification based

3.

60 Mineral composition of salt from domes in Louisiana and Texas

4.

Concentration of

5.

Landward

6.

Changes in chloride concentration between 1977 and 1981 in the Farrington aquifer of New Jersey as a result of sea-water intrusion 91

7.

changes

Changes in intruding

major

on

TDS ranges 4

and some minor chemical constituents in sea water 87

in chemical

composition of Gulf of

Mexico water as

ionic ratios due to ion exchange in relation to the

a

position of

89 result of dilution

the

water 108

8.

Methods of disposal of produced oil- and gas-field brine in the United States during 1963 116

9.

Percentage of

saline and sodic areas in seventeen western states and in Hawaii146

salinity classification in

150 the United States

10.

Soil

11.

Reported use of road salt and abrasives during the winters of 1966-1967, 1981-1982, and 1982-1983 176

12.

189 Geochemical parameters used for identification of salinity sources

13.

Approximate

14.

Description

15.

Listing of constituent

costs of chemical and

isotopic analyses192

208 of literature data bases

ratios that separate best brines from Texas, Louisiana, Oklahoma, California, Ohio, and Canada, as determined through Stepwise Discriminant 225 Analysis

1. INTRODUCTION

1.1.

Purpose

and Use of this

The purpose of this report is to summarize

Report

geochemical techniques

that

can

be used in studies of

salinization of fresh water. The report is designed to assist investigators through detailed discussion of

potentially useful chemical parameters and techniques, characteristics of potential salinization The

topic of

of references

compiled. sources

of

document

of physical and geographical

salt-water contamination has been extensively researched,

compiled for this report.

No

compendium of

a

researcher will have

a

the overall

develop

but to summarize known

ground-water salinity, that

as

sources.

The purpose of this document is not to

so

well

as

new

evidenced

as

has

topic, however,

approaches for all

different

be helpful to

depend

to

a

experienced reference to

geochemical

for

identifying

into

sources

list

been

previously

geochemical techniques

a

single

reference manual that reviews available work.

Salinization of fresh water is perhaps the most widespread threat to ground-water document deals with

by the long

characteristics of the

major known

sources

of

salinity,

resources.

and

as

This

such will

investigators

of salt-water problems. The extent to which this document will be of help will

large degree

on

the

background knowledge

researcher in the field of some

of the known

of the

problem

ground-water quality, this document

techniques

that are

being

and of the

investigator.

To

an

may serve as a summary of and

used. To investigators

new

in this field,

we

suggest the following possible methodology of investigation in combination with this report. Step

1:

The general geographic distribution of major potential salinization sources, that is

(1) natural saline ground water, (2) halite solution, (3) field brines,

Chapter

(5) agricultural effluents, (6)

2 of this

report. Through

source as well as the

idea which any given

potential area

overlap

sea-water

saline seep, and

(7)

intrusion, (4) oil-and gas-

road salt, is addressed in

a series of maps that show the distribution of each

between these sources, the

salinization source

of the country. There

or sources

are some

investigator

exist at her/his local

can

get

area

limitations to the maps,

as

a

general

of interest at discussed in

Chapter 2. Step

2:

After

potential

sources of salt water have been

for a discussion of the sources. This will

background

information about the

discussed in detail,

including

characteristics, geochemical

provide

source(s)

mechanisms of case

identified, Chapter 3 should be consulted the researcher with the necessary

of interest. Each of the seven sources is

mixing

with fresh

For each source,

a

water, chemical

studies, recommended chemical techniques for

identification of salinization caused by these sources, and occurrences.

ground

a

variety of techniques that can

state-by-state summary of be used is

presented.

DOI: 10.1201/9780203753668-1

Each section includes a

state-by-state summary

individual salinization sources. Before absent in the

area

of known

disregarding

problem cases

associated with

any source identified in

Step

2 as

of salinization and of interest, the investigator may want to review all

summaries pertinent to her/his state(s). With the help of references listed in Chapter 7, extensive background information of the problem

Step

3:

After selecting techniques that

geochemical parameters investigator Step

4:

a

techniques Depending

on

the

techniques

likely will on a

parameter

area

selected in

basis

sources, agency

Step

3 may be

existing data can be representative

files,

or

very of

give

the

sampling

helpful

potential

may not be available to the

or

computerized data banks. Some of

applicable using existing data,

samples for parameters

(for example, isotopes). Chapter 5

of data selection and for a discussion on

be

characteristics as well as

of interest, chemical data may

necessitate collection of water

regular

4. This will

Chapter

laboratory analyses.

investigator from published the

useful for the particular problem case, the

of interest should be reviewed in

overview of

general

and costs of

are

be obtained.

can

computerized

but may also be salinization

that

but others most determined

are not

should be consulted for

guidelines

data banks. This step is crucial, as

misleading.

sources can

Chemical

analyses that

may

be found in the referenced

literature.

Step

5:

Once data have been selected from can

be

existing

accomplished using techniques

statistical methods are discussed

briefly

sources or collected in the

selected

in

during Step

Chapter 6. Hopefully,

field, evaluation

2. Useful

graphical

the source of

and

salinity will

then be determined.

1.2. Background All natural waters contain gases,

mixing

some

dissolved minerals

through

with other solutions, and interaction with the

the interaction with

biosphere

and

these processes result in natural waters that contain total dissolved solids

atmospheric and

lithosphere. (TDS)

soil

In many cases,

concentrations above

those recommended for drinking water (Table 1 ). This deterioration of water quality is enhanced

by almost

all human activities through water consumption and contamination.

Salinization, that is, the increase in TDS, is the most widespread form of effect of salinization is

an

water contamination. The

increase in concentrations of specific chemical constituents

as

well

as

in overall

chemical content. A variety of terms have been introduced in the literature to reflect the changing character of the water

as

salinity increases, such

brine (Table 2 ). For the purpose of this report,

(1958),

which is one of the most

widely

as

saline, moderately saline, very saline, brackish, and

we

followed the classification of Robinove and others

used. The term “salinization,"as it will be used in this report,

Table 1. Drinking-water standards established for inorganic consituents (data from Freeze and Cherry, 1989 ). 1979 and U.S. Environmental Protection Agency, 1989). 1979, ,

Recommended concentration limit

Constituent

(mg/L) Total Dissolved Solids

(TDS)

Chloride (Cl) Sulfate (SO4) Nitrate

(NO3)

500.000 250.000 250.000 45.000

Iron (Fe)

0.300

Manganese (Mn) Copper (Cu) Zinc (Zn) Boron (B) Hydrogen Sulfide (H2S)

0.050 1.000 5.000 1.000 0.050 Maximum

permissible

concentration

(mg/L) (As) (Ba) Cadmium (Cd) Chromium (Cr) Selenium (Se) Antimony (Sb)

0.050

Lead (Pb)

0.050

Mercury (Hg) (Ag) Fluoride (F)

0.002

Arsenic Barium

Silver

1.000 0.010 0.050 0.010 0.010

0.050 1.4-2.4

Table 2. Ground-water classification based ranges (in mg/L).

on

TDS

Roblnove and others. 1958: Fresh

Slightly saline Moderately saline Very saline Briny

0

1.000 3.000 10,000 >35,000

-

-

-

-

1,000 TDS 3,000 10,000 35,000

Freeze and Cherry, 1979: Fresh water Brackish water Saline water Brine

0 1,000 TDS 1.000 10,000 10,000 -100,000 >100,000 -

-

indicates an increase in TDS from

Of the variety of

potential

sources of

sulfuric acid, "acid rain”). can

by any

salinity,

Strong

areas

such, salinization may

or

may not

even

anthropogenic.

before it reaches the earth's surface,

winds carry mineral matter and solution droplets (for example,

ocean

be dissolved and incorporated into precipitation. Surface runoff dissolves mineral matter

body, where it

enters the soil is

to additional chemical,

evapotranspiration,

subject

mineral solution and

mixes with water of different chemical

precipitation,

Water-rock interaction and mixing

is often enhanced

by human

are

physical,

and

water

mixing

on

Water that such

as

with other solution.

along flow paths from recharge

the dominant processes.

activities. For example, improper

composition.

biological changes,

solution of gases, and

Changes in chemical composition continue in ground areas.

as

of high sulfur dioxide content in the atmosphere (formation of

its way toward a surface-water

discharge

source. As

some are natural and others are

atmospheric gases and particles

interacts with

reflected in often low pH values in

spray) that

levels

higher than drinking water standards.

cause concentrations

Precipitation

background

areas to

Mixing of different waters

drilling, completion,

and final construction

of wells may create artificial connections between fresh-water aquifers and saline-water aquifers. Pumping of fresh water may toward the

change

directions of

ground-water flow

pumped well; improper waste-disposal

that contaminate natural Some

areas

and may cause encroachment of saline water

activities or

techniques

may introduce artificial solutions

ground water.

of the country experience very little

problems regarding

resources, whereas in other areas most of the available

ground

water is

salinization of fresh-water

saline, reflecting natural and

human-induced degradation. Where such conditions for salinization of fresh water exist is discussed in the

following chapter.

2. GEOGRAPHIC DISTRIBUTION OF MAJOR SALINIZATION SOURCES

For the purposes of this report,

seven

major salinization

singled

sources were

They

out.

are,

(1) natural saline ground water, (2) halite solution, (3) sea-water intrusion, (4) oil-and gas-field brines, (5) agricultural effluents, (6) saline seep, and (7) road salt. The geographic distribution of these potential sources and areas of

overlap

between these sources are discussed in this

of each individual source will follow in the next Saline

ground

water

(TDS>1,000 parts

chapter.

A detailed discussion

chapter.

per million

[ppm])

of variable

origin

underlies approximately

two-thirds of the United States (Feth and others, 1965). It may be encountered in water wells that drilled too deep for local conditions and it is

a

threat to those wells that

rate to induce salt-water flow toward the well. Shown in are

figure

are

pumped

at a

at

1 are those areas where TDS concentrations

depths, the cut-off value of 500 ft

areas

was

wherever wells

are

pumped

at

high

rates and from great

from Feth and others (1965) because the search for

adopted

usable ground water (and with it drilling activities to greater depths) may be greatest in fresh water is available. Conditions may change in the future

ground

occur, but

depths greater than 500 ft below land surface (Feth and others, 1965). Although the potential

of salinization exists in these outside

or

may be different

locally,

where less

areas as

the demand for

water increases.

Many sedimentary basins salt domes that

sufficiently high

greater than 1,000 ppm within 500 ft of land surface. Outside these areas, saline water does

generally

were

are at

(Fig. 2). Some

are

of these

known to contain

large deposits of

deposits occur at great depths,

rock salt in the form of salt beds or

such as those in southernmost Florida

greater depths than 10,000 ft below land surface. Others

occur close to land

surface, such

as

those in parts of Utah ( Dunrud and Nevins, 1981 ). Shallow occurrences of salt in Texas, Louisiana,

Alabama, and Mississippi along the Gulf of Mexico millions of years old indicates

ground water comes especially

a

are

due to salt diapirism. The presence of salt deposits

relatively high stability,

into contact with salt

deposits, often

that is, little contact with ground water. Where enhanced

by heavy drilling

in salt-dome areas, solution of salt and salinization of local

shallower the salt are considered

deposit, the higher the potential of

potential

Where coastal

salinization sources,

aquifers

are

ground

as a

result of

high

mining activities,

waters will

regardless of the depth

or

where

pumping

deposits

of occurrence.

interconnected with the open ocean, sea-water intrusion

sea-water levels,

or

is

intruding

induces landward flow of

can occur.

into coastal

sea

water, the

potential of well-water salinization exists. For the purpose of this report, all coastlines of the country considered

scale,

potential

intrusion areas,

some coastal areas can

regardless

probably

be

of the nature of the coastal

disregarded

The

occur.

fresh-water salinization. In this report, all salt

Where formation water hasn't been flushed out, where sea-water has intruded

aquifers

and

as a source of

aquifer ( Fig. 3 ).

were

On a local

salinity, especially where ground-

water pumpage is low.

DOI: 10.1201/9780203753668-2

Figure 1. Map of the United States showing areas of ground water containing more than 1,000 mg/L total dissolved solids at depths less than 500 ft below land surface (data from Feth and others, 1965).

Figure 3. Map of

the United States

showing

areas

of

potential

sea-water intrusion.

Associated with the

of oil and gas is the creation of avenues for water

exploration

great depths into the shallow subsurface. Subsequent production brings huge land surface. These drilling activities and the disposal of these brines hazards in the country. Parts of 25 producing states

are

from

migration

amounts of brine to the

of the biggest salinization

are some

potentially affected by this hazard,

mapped by

as

the general distribution of oil and gas fields in the United States (Fig. 4 ). Salinization as pose a

result of

evapotranspiration

enhanced by

agricultural

activities is found all over the country.

threat in the western half of the United States

potential

and where

a

agriculture

( Fig. 5 ),

rates and salt contents in soil are

where

Irrigation-return

precipitation

rates are low

Another salinization

high.

waters

source

is dryland saline seep. Terracing of land and destruction of natural vegetation

caused this phenomenon in several states,

resulting

in the salinization of soil and

Weather conditions favor concentration of road

( Fig. 7 ). There, millions of tons of salt

are

applied to

salting

ground water ( Fig. 6 ).

in the northeastern part of the country

roads each winter,

imposing

a salinization threat to

soil, plants, and surface and ground water in the vicinity of highways.

Mapping sources of

of

potential

salinity

at any

salinization sources, as done in

particular

area in the

figures

1

through

country. By overlaying all

7 is ,

helpful

In

determining variety

seven sources, a

of

combinations between these sources becomes evident. This large variety complicates generic

approaches

depending sources

to salt-water on

the kind of combination of sources involved. In addition, not

change from

the same

studies, because salt-water characteristics change considerably from

everywhere, greatly increasing

or

sources

the number of

sources. In

be easier than in other parts, where three

Limitations that should be

does not

composite

combinations of

kept

necessarily

potential

applicability

in mind when

sources discussed in this

an

actual salinization

source

could

through 8 ) presented

here.

sources exist.

of the maps

( Figs.

1

selecting or eliminating potential

report were mapped; (2)

indicate that the source

these sources may be felt away from the

actively

point

of

the sole presence of a

contributes to any

origin; (4)

sources at any

changed since originally mapped. Not included sources, such as sewer

areas of occurrence were

or

more

effects of

generalized

with

sources may have

mining

areas, all of which

complicated and would have resulted in

small areas of overlap. Also, chemical characteristics of these sources vary to a ones

source

in some areas. These sources were not considered because

large-scale regional mapping would have been

the

potential

area

on these maps are some other known salinization

systems, thermal springs, waste-disposal facilities,

ground-water salinization

given

salinity problem; (3)

approximated boundaries; and (5) the known distribution of potential salinization

may contribute to

possible mixing

map ( Fig. 8 ) of the above-mentioned

these areas, identification of

or more

There are several limitations to the

(1) only the

potential

indicates, approximately three-quarters of the country could possibly be affected by two

less than two of the selected

are

the potential salinization

area to area, but also the chemical characteristics of individual sources may not be

between fresh-water and salt-water sources. As the

potential

only

area to area

even more

higher degree locally than

discussed here, which would have complicated the discussion even further. The

seven

Figure

4.

PennWell

Map of the United States showing general Publishing Co., 1982).

areas

of oil and gas production (modified from

Figure 5. Major irrigation

areas in the

United States (moditied from Geraghty and others, 1973).

Figure 6. Saline-seep areas in Montana, North and South Dakota, and Texas (data trom Bahls and Miller, 1975 and Neffendort, 1978). ,

Figure 7. Map of the United States showing amount of road salt (in thousands of tons) used in individual states during the winters of 1966-1967, 1981-1982, and 1982-1983 (data from Field and others, 1973; Salt Institute, undated).

Figure

8.

Composite map of potential salinization

sources as

mapped in figures

1

through

7

.

potential

conditions. For

may or may not be active at any area,

mapped

sources

oil-field activities

example,

imply that either cause salinity of ground states with a

long history

year in 1966)

was

area

of road-salt use

salinity,

or

value of

(cut-off

for reasons of simplicity, only those

greater than 30,000

tons of road salt use per

exists in

applied

an area

a

problem,

where

here, either transport of salt water from

a

no

every

potential

storage

area or

a

problem

now or

a

in

source in that area should be considered. If

potential salinization source

bordering

a

less than 30,000 tons per year at that time is not

that increased usage in some other states may not pose

ground-water salinity is

salinity problem

specific area. Also,

used in the overlap map of figure 8. This should not imply that, for example,

source of

the future. If

natural and human-induced

the presence of halite in the subsurface don't necessarily

water in a

of road salt in any of the states that

potential

a

or

depending on

from

is indicated

a source not

on

figures presented

covered in this report should

be considered. It also should be kept in mind that some of the base maps used in constructing these maps

are

up to 30 years old, and may be somewhat outdated

regarding the present

these sources on a local basis. In any case, these maps should idea of

potential

sources

involved, after which available maps with

The scale factor alone should make it should be in this

mapped

report. The

following chapter.

at the

probably

imperative

beginning of each

sources

mapped

that the

salinization

in this

chapter

only

to

get

of any of

a

general

more local detail should be consulted.

geographic

study using

be used

occurrence

distribution of salinization sources

local maps instead of maps

will be discussed

presented

individually and in detail in the

3. MAJOR SALINIZATION SOURCES As discussed in the introduction

country. Some of these

are more

judged

sources

of salinization sources exists

variety

a

dominant than others, and

place but not in another, depending salinization

chapter,

as most

on

individually

sources

may be active in

natural conditions and changes induced by

important

regional level

on a

are

throughout man.

the

some

Individual

(1) naturally occurring saline ground

water, (2) halite solution, (3) sea-water intrusion, (4) oil-field and gas-field brines, (5) agricultural byand

products

techniques, (6) saline

seep, and

(7)

road salt.

Each section on individual salinization sources is divided into

(1)

a discussion of the mechanism of

contamination, (2) the chemical composition of the salinity source, (3) examples of geochemical studies that

were

that

are

source.

conducted to

identify

commonly used This way,

various salinity

complexity

a

the

specific salinity

to trace the

respective

researcher is provided with

sources.

(4) the most significant chemical parameters

source, and

an

A cookbook approach for

of local contamination and

source,

(5)

salinity,

the

Although comprehensive,

identifying salinity

hydrogeology precludes

Local have

sources a

hydrogeologic setting, the

of reference for the

following

state-by-state summary of the salinity

in-depth review of geochemical methods for identifying

the information contained in a section, a researcher needs to based on the type of

a

a

sources is not followed because the

step-by-step approach.

develop

his/her own

and the type of data and

After

reviewing

hydrochemical

budget

criteria

available.

discussion of safinization sources cannot be complete.

of interest should be incorporated by the researcher, who should

area

general understanding of ground-water conditions in

the area.

3.1. Natural Saline Ground Water

3.1.1. Mechanism Natural saline

ground water,

as used for this

manual, is regionally occurring saline ground water that

underlies fresh-water aquifers. This chapter deals with natural

pumping-induced mixing between ground

water

saline

boreholes drilled

along

ground water and fresh water,

through

ground

and with oil-field brine

ground water, with

and the upward

migration of saline

(see chapter 3.2),

production (see chapter 3.4),

waters. Chemical characteristics of

saline

the fresh-water section into the salt-water section. Not

discussed is salinization associated with solution of halite

chapter 3.3),

discharge of such

deep-basinal

with sea-water intrusion

all of which also deal with natural saline

formation brines are similar or identical to most

brines produced from oil and gas reservoirs. The nature of occurrence in salt-water

however,

as

contamination

migration pathways, result of natural or

by oil-field brines

involves

whereas contamination

pumping-induced

(see

probX

pumping and disposal of brine or crc

by deep-basin

brines involves subsurface

jI

migration

as a

conditions. This difference in mechanisms of contamination but

DOI: 10.1201/9780203753668-3

similarity in chemical

characteristics creates some

in the discussion of natural saline

overlap

in this section and the discussion of oil-field brines in

chapter 3.4.

Saline ground water underlies the country at variable depths. Some

ground water, whereas in other

areas

ground water

don't contain any fresh

areas

thick fresh-water aquifers overly saline ground water. For example,

little or no saline water is known to occur within 1,000 ft of land surface in most of Nebraska and

whereas in

some

other states, such

less than 500 ft below land surface overlies shallow saline water, Iowa

almost the entire state

throughout

major problems of

no

salt-water

The occurrence of saline ground water is dependent

can be residual

(connate)

or

nature of

uses

on a

discharge

water from the time of

as

conductivities

low.

are

Typically,

below land surface as chemical reactions with increase. Ground water in

discharge

areas

because of water-rock interactions and In some

an

variety of factors, including distribution

origin of

natural saline

by evapotranspiration, by precipitation through

settings, especially in

natural

aquifer

typically is

salinity

in

ground

ground

water

intrusion of sea

time.

material, resident time, and of lower quality than

possible mixing with

and others,

(Geraghty

Evaporation

by transpiration

southwestern states. Woessner and others from 2,000

mg/L to 11,000 mg/L in

accumulates in the soil areas

during

the

low and

mixing

ground water in recharge

saline water along the flow

depth

of different waters areas

path ( Fig. 9 ).

the western half of the United States, salts may be concentrated in the

1973). Significant recharge pulses

is enhanced

Relatively

are

water increases with

shallow subsurface due to evaporation rates that exceed precipitation by up to

a

of water

by plants,

order of magnitude

which is a serious problem in several

(1984) reported that phreatophytes can

single growing

growing

one

may dissolve this salt and flush it into ground

season in

season, from 403

parts of Arizona and mg/kg

to 28,177

cause TDS increases

Nevada. The salt that

mg/kg,

is flushed toward

during major recharge periods.

Many ground-water basins in the western United States

are

closed. In those basins, natural recharge

along the surrounding highlands flows toward the basin centers. Along the flow path, ground dissolves mineral matter, areas.

in

any mixture of the above. Residual saline water is not found very often within the shallow

hydraulic

discharge

as

New Mexico, where

young coastal aquifers may still contain pockets of connate water where hydraulic gradients

water.

such

in a saline environment, solution of mineral

deposition

subsurface because of the normal flushing of formation water

where

fresh water

(Ong, 1988).

areas. The

matter in the unsaturated and saturated zones, concentration or

plenty of

and recharge rates, type of soil and aquifer material,

precipitation, evapotranspiration

residence time and flow velocities,

water,

Where

mixing with fresh water may occur,

estimated 75 percent of all ground water is too saline for most

and rates of

( Fig. 1 ).

and others, 1986). Other areas may not be so fortunate, such

(Atkinson

Missouri,

Indiana, Ohio, and North Dakota, saline water is encountered at

as

Evaporation in the

resulting in basins and

process in the

development

settings (Boyd

and Kreitler, 1986).

a

general increase in

recharge

areas to

discharge

in salt flats in the center of the basins is the most influential

especially

of the chemical

TDS content from

water

composition

Evaporation

of the shallow, saline

and mineral

ground

precipitation concentrate

the

water in these

ground

water to

9. Relationship between ground-water quality and recharge-discharge areas (from Kantrowitz, 1970 ). Solution of aquifer material and evapotranspiration in discharge areas commonly cause waterquality deterioration along the flow path.

Figure

the

composition

(Hunt

of a

and others,

Lake in

Na-Mg-SO4-CI-type brine,

1966),

Oregon (Jones

noted for

and Sierra Nevada Basin

Deep Springs

(Garrels

Lake

and MacKenzie,

(Jones, 1965), 1967)

Death

California,

in

Valley

for Abert

and others, 1969), for Teels Marsh in Nevada ( Drever, 1982 ), and for the northern

Salt Basin of West Texas ( Boyd and Kreitler, 1986 ). Surface water that accumulates at topographically low areas in

the center of the basins is often concentrated by evaporation. Infiltration of these concentrated

waters can reach the water table and cause severe

which

are now

which

high

of low

permeabilities, of

these salts may have been water

good-quality ground depleted

water sources are

can

Barton

(1971)

.

(1961)

settings

during

Because

under natural conditions.

lead to inflow of these saline ground waters,

or

ground

as

fresh-

water occurs where salt water from saline

(b) mixes with fresh

water in the subsurface,

at many localities in the United States, such as in New York

reported

Ward

by

in these

deposits.

lacustrine

areas

and waters are drained out oflow-permeable units.

aquifers (a) discharges at land surface have been

low-permeable,

preserved

Natural contamination of fresh water by saline

Oklahoma

In the western United States, many

drained by major river systems may have been under closed conditions in the past,

concentrations of residual salt were left behind in

Overpumpage

springs

pollution.

,

in Texas

by

Richter and Kreitler

(a)

by Crain (1969)

or in Arizona

(1986a,b),

Some of these natural springs contain TDS of up to 300,000 mg/L

Natural saline

by

,

in

Fuhriman and

result of solution of

as a

halite in the shallow subsurface (see also chapter 3.2.). Geothermal springs associated with fault

zones or

volcanic activity

nonpoint

are

contamination, such

often mineralized. In other areas, saline-water discharge

as

along the Colorado River, where more than 50 percent of the average annual 10.7

million tons of salt is contributed

by diffuse

seepage ( U.S.

Department

of

Agriculture,

others, 1986). (b) Mixing of saline ground water and fresh recharge water

regional

and local

aquifer systems,

Mississippian formations in

and others, 1989). Fresh-water and salt-water facies are

nongeological time scale,

water. Drawdown of the water table or the

contamination of wells after some time of

through

discharge

is

depression

pumping. Mixing

central Missouri ( Fig. 10 ) a zone

may vary in response to

mostly

in response to

potentiometric surface in

this interface moves to within the cone of

occur

occurs in

generally separated by

position of this mixing or transition zone

flow component, which, on a

1975 ; Atkinson and areas of

such as in the outcrop areas of Permian formations in north-central

Texas ( Core Laboratories, Inc., 1972 ) and of

variable thickness. The

occurs as

some

heavy

(Banner

of mixing of

changes in

either

pumpage of fresh

aquifer systems

is

so severe

of individual wells or well fields,

that

resulting

in

between fresh water and saline water can also

any type of boreholes that penetrate and are open to both types of waters. If heads in the

fresh-water unit are water heads are

higher than

in the salt-water unit, fresh-water will drain into the saline formation. If salt-

higher than fresh-water heads, contamination of

an entire

aquifer in

the vicinity of the well

may occur. Intermittent

pumping of wells

within the cone of

subsequent

depression.

can lead to

Oxidation of

solution of iron and sulfate

changes

pyrite

during the

in water

quality associated with

within the cone

during pumping

chemical reactions

of the well and the

recovery of water levels to prepumping levels when the

Figure 10. Discharge of regional, saline ground water and mixing with local, fresh ground water. Meteoric recharge in the Front Range of Colorado acquires high salt contents from Permian evaporites under the High Plains aquifer along its flow path to recharge areas in central Missouri, where it mixes with local meteoric, fresh ground water (modified from Banner and others, 1989).

well is not

Changes in water

(Fig.

pumped,

often leads to

water quality

high

iron and sulfate concentrations in well waters

during pumping

may also

depend on the depth of

(Custodio, 1987).

the well. For example, in

a

salt-

study in Arkansas, Morris and Bush (1986) sampled two adjacent wells of different total well depths

11a ). Over

time, chloride

content increased in the shallow well and decreased in the

deep well ( Fig.

11b ). The increase in the shallow well suggested inflow of deep saline water, whereas the decrease in chloride in the deep well suggested inflow of fresh water (Morris and Bush, 1986 ). 3.1.2.

Hydrochemistry of

Nearly geochemical as

all

Different Sources of

environments may contain

geologic

some

as

very high in deep-basin brines,

as

often contain

other brines, such The

origin

sometimes

as

as

are

resulting

typically

waters associated with saline

major anion. Calcium concentrations

of NaCI and

entirely

unusually high

from

have chloride

are

sometimes

TDS concentrations approach several hundreds of thousands

These brines are comprised almost

deposits

saline waters

the dominant cation. Exceptions

salt flats, which often have sulfate

saline water

naturally-occurring

geologic setting. Natural, highly

processes within each

the dominant anion and sodium

seep and

Naturally Occurring Salinity

mg/L.

Natural brines associated with mineral

CaCI2.

concentrations of ions that are

normally

not concentrated in most

Cu, Zn, Ni, Co, Mb, Pb, or Ag.

of the chemical

disputed. Depending

composition on

the

composition of saline water may differ, Basin waters often

are

of brines in

hydrologic

as outlined

referred to

as

ground

water that

basins is

widely

discussed and

environment of each respective basin, the chemical

by Kreitler (1989) :

either connate, meteoric,

"connate" is defined for this paper as water that “meteoric” indicates

sedimentary

was

originated

trapped

or a

mixture of both. The term

at the time of sedimentation. The term

as continental

precipitation. By definition,

the age

of connate waters coincides with the age of the host sediments. Basinal waters of meteoric

origin

younger than the host sediments.

of marine

Though

sediments, formation waters generally do concentration.

greater than

Many

most basins are

composed predominantly

not resemble sea water in either chemical

composition

basins contain waters with total dissolved solid concentrations

sea water concentrations and as

section of the Gulf Coast Basin are

high

as

are

or

significantly

400,000 ppm. Maximum salinities in the Tertiary

approximately 130,000

ppm; in the East Texas Basin, 260,000

ppm; in the Palo Duro Basin, 250,000 ppm; in the Illinois Basin, 200,000 ppm; in the Alberta Basin,

300,000 ppm; and in the Michigan Basin, 400,000 ppm ( Bassett and Bentley, 1983 ; Hanor, 1983). Two different types of brines are generally found,

a

Na-CI brine and a Na-Ca-CI brine, neither

having

chemical composition ratios similar to sea water. In recent years, three mechanism have been used to

explain

the

chemical composition of the brines (Hanor, 1983) (1) the brines solutions left after the

precipitation

high

ionic concentrations and the

originated

as

residual bittern brine

of evaporites; (2) basinal waters have dissolved halite that was

Figure 11. Relationship between depth of screen and chloride content in two adjacent wells (from Morris and Bush, 1986). (a) Pumpage-induced changes in flow directions cause upward migration of saline water into fresh water in well No. 178 and downward migration of fresh water into saline water in well No. 177, resulting in (b) water-quality deterioration and improvement, respectively.

present

shales (reverse

permeability

At present, there is to the

salt; and (3) basinal waters have been forced through low-

as either bedded or domal

a brine on the

osmosis), leaving

no consensus

about the relative importance of each of these three mechanisms

origin of brine.

The theory of salt sieving (reverse osmosis)

the

on

clay-mineral

clay layers, maybe

first introduced by DeSitter (1947)

was

compaction, and in response to flow through tightly charges

side of the membrane.

high-pressured

packed

clays, anions

surfaces (membrane effect), whereas

in a

This way, chloride as well

large,

exchange

multivalent cations and

During

repelled from negative

are

positively charged

fashion moving from one cation

stepwise

.

ions may pass

through

site to the next (Atkinson

heavy isotopes

tend to be

and others,

1986).

enriched

the high-pressure side of the membrane. Schwartz (1974) proposed that this process may

on

as

also be active at relatively shallow depths in parts of Canada, across

residual effective stress conditions

till layers. According to Land (1987), opponents of the salt-sieving theory note that (a) sufficient

pressure

gradients

may not be

doesn't appear to conform to observed in similar source

involving

of salinity

settings.

are

in nature,

generated

and (c)

expected patterns,

Instead of the

(b) the chemistry of brines in shale-rich sections wide

a

salt-sieving theory,

of formation-water types

variety

Land (1987 ) suggested that the

evaporite deposits. Evaporites have always been deposited

Increasingly

MacKenzie

estimated that present evaporites have been dissolved and

(1971)

primary

through geologic

time

in progressively older rocks, suggesting dissolution. Garrels and

but have become

rarer

are

in

the last three billion years,

resulting

subsurface may be the best

explanation

an

cycle

average

for (a) this

precipitated

15 times in

of 200 million years. Dissolution of salt in the

relatively

short

the

cycle, (b)

missing

salt in older rock

formations, and (c) the abundance of sedimentary basin brines (Land, 1987). In addition to evaporite solution, mineral equilibria control the overall composition of brines. Sodium and calcium most dominant cations in almost all brines because and

K-feldspar

result in sodium dominance

and dolomite result in calcium dominance other constituents in brines, Land the

over over

equilibrium

conditions between

far the

Na-feldspar (albite)

potassium, and equilibrium conditions between calcite magnesium (Helgeson, 1972; Land, 1987). To explain

(1987) proposed

two types of rock-water interaction, one occurring in

and the other

occurring

in the basement

The massive destruction of detrital

feldspar

releases

sedimentary basin itself

by

are

underlying

significant

the

sedimentary

amounts of calcium,

basin.

potassium,

strontium, barium, lithium, etc., to solution. Feldspar equilibria prove that large amounts of potassium cannot remain in solution until temperatures reach very consumed in the formation of diagenetic illitic day from

1979). The strontium and barium contained in brines

a

high values,

and

potassium

is

commonly

smectitic precursor (Schmidt and McDonald,

are known to be

vastly

more abundant than

predicted simply by the evaporation of seawater, and the 87Sr/86Sr ratio of the brine is commonly elevated. 87Sr is produced by the decay of 87Rb, an element characteristic of silicate phases, especially K-feldspar. Thus, significant is proven. Other

isotope ratios,

involvement of silicate

such as

18O/16O (Clayton

phases

in

and others,

determining 1966)

brine

chemistry

and D/H (Yeh, 1980)

are shifted from the values

expected

for surficial seawater-derived brines,

additional

providing

evidence for extensive rock-water interaction in the subsurface. It is well known that fluid inclusions in minerals of

commonly

very saline ( Roedder, 1984 ).

which carbon dioxide and water

hydrothermal, metamorphic,

Metamorphism

is

or

igneous origin

are

accompanied by devolatilization, during

released, presumably to overlying sediments. The formation of

are

slaty cleavage during low-grade metamorphism apparently requires the loss of large volumes of the rocks themselves ( Buetner and Charles, 1982 ). The loss of appreciable volumes of insoluble

components, such addition to such

SiO2 and Al2O3

at the Earth’s surface are

the H/Na of a solution in

example,

of magnitude

means that

over

they must

reaction sequence is

increases with

inorganic

as

sources

nearly two

orders

one

possible

metamorphic reactions into the overlying Ca-enriched solutions and

generating

reason

why the

of natural gasses

CO2 content 13C/12C ratio

in natural gas also

more carbon is

apparently derived

and Land, 1986). The

13C with increasing CO2 content as

In

CO2.

opposed to organic sources.

Occurrences of brines in

possible

albite and kaolinite increases

water lost from

increasing depth (Lundegard

tends to become enriched in from

strata. In

the temperature interval 25 to 200°C (Helgeson, 1972). In solutions dominated by

sediments will be neutralized by minerals like calcite, a

overlying

progressively replaced by cations during metamorphism.

equilibrium with

chloride, weak HCI is thus produced. Acid

fact, such

be transported into

material transport, the protons which are bound in alumino-silicates

large-scale

during weathering For

as

suggested

igneous

rocks may be of multiple origin,

in the literature. Edmunds and others

as

(1987)

suggested by list the

a

long list of

following

modes of

possible origin: (1) marine transgression and subsequent concentration (for example, Frape and Fritz, 1982 ),

(2) migration fluids

hydrothermal

of

sedimentary

(for example,

basin brines

Alderton and

(for example, Grigsby and others, 1983), (5) (for example,

(for example,

Sheppard,

silicate mineral

Edmunds and others, 1984, 1985;

Frape

1977 ),

Fritz and

(4)

Frape,

dissolution of

hydrolysis and and others,

1982 ),

(3)

residual

grain-boundary

salts

related water-rock interactions

1984), (6)

breakdown of fluid

inclusions in quartz and other minerals (for example, Nordstrom, 1983 ), and (7) radiolytic decomposition of water

during

a-series decay (Vovk, 1981 ). Some of these processes

concentrations of up to 550,000

mg/L

TDS

( Vovk,

extensive list of chemical reactions to the above list to of Cornwall, United

are

believed to have caused brine

1981 ). Edmunds and others

(1987)

added

explain the origin of saline ground water in

Kingdom. Eliminating ancient sea water as a potential source

(δ18O andδD

a

an

granite

indicated

a

local, meteoric origin), chemical reactions along the flow paths down to approximately 4,000 ft and at temperatures reaching 131°F (55°C)

can

Some results of these chemical reactions

origin of ground-water salinity, (b) zoned

plagioclase, (c) high

explain are:

these saline waters

having

TDS of up to 19,300

(a) acid hydrolysis of plagioclase and biotite

enriched Ca/Na ratios

by selective

as

mg/L.

the prinicipal

reaction of the more calcic centers of

lithium concentrations related to biotite reaction, and

(d) high

Cl

concentrations as a result of

hydroxyl exchange

for Cl in the biotite

interlayer (Edmunds

and others,

1987). Evaporation from

a

shallow water table (within three

or

four feet of land

surface)

can

lead to

high

salt

concentrations in soils. This is known to have occurred in the San Joaquin Valley of California. There,

ground-water salinity

in Coast

molybdenum, vanadium, that accounts for

high

Range alluvium

and boron ( Deverel and Gallanthine, 1989 ).

Evaporation

is the major process

salinities in some closed basins in the western half of the United States.

processes and selective mineral further.

be correlated with high concentrations of selenium,

can

Major inorganic

precipitations modify

reactions in such

settings

the chemical are

silicate

composition

Weathering

of closed-basin waters

hydrolysis, uptake

of

CO2

from the

atmosphere and/or of sulfate from oxidation of sulfides, and precipitation of alkaline earth compounds (Jones, 1965). Concentration ratios of major chemical constituents brines than in most

deep-basin brines,

the latter

are much less uniform in closed-basin

being nearly exclusively

Na-Ca-CI dominated. Closed-

basin brines may be (1) chloride dominated, such as those in the Bonneville Basin,

dominated, such

as those in Alkali

Valley, Oregon,

or

(3)

(2)

sulfate dominated, such as those of the

Desert ( Jones, 1965 ). These differences are due to differences in inflow characteristics and reactions

although,

carbonate

in most instances, increased salinization

(evaporation)

Mojave

precipitation

is associated with

a

trend

toward Cl dominance until halite precipitation is reached. Closed-basin brines start out by simply dissolving

readily soluble mineral compounds, such fluids may be another process that

subsequent evaporative processes that

as

halite.

provides

Leaching

of absorbed ions

the

of trapped interstitial

dissolved minerals to the water. Silicate hydrolysis and

concentration is the source of some of the

subsequently change

or

composition

high

of the waters are:

carbonate contents. Other

mixing

with other water types,

CO2 addition by organic activity at lake bottoms or interstitially in lacustrine sediments, organic matter,

and loss of sulfate

(Jones, 1965).

anaerobic

decay of

As the waters increase in concentration due to

evaporation, precipitation reactions induce major changes to concentrations of individual ions. Calcium carbonate

precipitates first,

as described

simultaneously, carbonates

followed

precipitate

by

by

gypsum, and

finally by alkali

salts. These processes can

Hunt (1960) and Jones (1965) for the Death

Valley

happen

salt pan. There,

in the outermost areas, sulfates in the intermediate zones, and chlorides at the

center. Ground-water evolution in closed basins may be similar to any other evolution from a low-TDS,

Na-Ca-HCO3 recharge water to a high TDS,

calcite dissolution and near

induce radical evolution of

a

changes

in the water type.

Ca-SO4 recharge

evolution included

discharge

areas,

Boyd

mixing

path,

and

evaporation

in

as

discharge areas

between this recharge water and brine may

and Kreitler (1986) demonstrated the

water to a Na-CI brine in a gypsum

precipitation of calcite,

the flow

Na-CI water, as a result of reactions such

precipitation, cation exchange on clay minerals,

the center of the basins. In

along

gypsum, and dolomite.

playa

geochemical

in West Texas (Fig. 12 ). Brine

Figure 12. Geochemical composition of ground water in a gypsum playa, West Texas. Ground water evolves from a Ca-SO4 type in recharge areas to a Na-CI type in discharge areas (salt flat) (from Boyd and Kreitler, 1986 ).

In many areas of the United States, cases, these waters are

temperatures and

at

hydrothermal

in mineral content as a result of increased mineral reactions at elevated

high

large depths from which these

geothermal systems have been found physical

more

waters are found close to or at land surface. In some

waters

originate. Stable isotope compositions

recharge of local meteoric waters, modified by

to reflect

3.1.3.

for

Bradys

Hot

Springs,

a case

a

single potential

used chloride concentrations and temperature values to

open boreholes

or

County,

along

average

background

Florida.

Upward flow

source of salt water,

identify deep,

in that

natural fault and fracture systems.

inflow of saline water in the

Glynn County

levels of 23

fresh-water zones was the concentration (evaporation)

mg/L to

cause as

the

area of

area

Georgia by an

several hundreds of

of intrusion. source

Sowayan

In parts of West Texas, natural and sources are

anthropogenic

associated with oil- and

natural salinization is associated with shallow

as

the source of

is possible through either abandoned, Wait and

Gregg (1973)

identified

increase in chloride concentration from

mg/L. There, heavy pumpage from and

of saline water in

absence of other possible salt-water sources, such as brines,

and others (1972)

Sproul

artesian salt water

Similarly,

a

Allayla (1989)

shallow

identified progressive

part of Saudi Arabia by plotting sodium

concentrations versus chloride concentrations. This was indicated

anthropogenic

reported by Welch and Preissler

Studies of Natural Saline Ground Water

of salt-water intrusion from

intrusion in parts of Lee

as

Nevada.

Examples of Geochemical In

one or

chemical processes (Truesdell, 1976 ; in Welch and Preissler, 1986). One of these

or

processes may be evaporation at land surface prior to infiltration,

(1986)

in most

by

a

slope of

near

unity and the general

evaporite deposits, or geothermal springs.

salinization sources are common. Some of the

gas-field operations

or

agricultural techniques

evaporite deposits, discharge of

while

saline formation water, and

high evapotranspiration rates. Richter and Kreitler (1986a,b) and Richter and others (1990) used major cations and anions, the minor constituents Br and I, and the sulfur-34 to

distinguish

between these sources.

local recharge from nonlocal from

deep-basin discharge.

such as I/CI,

recharge (Fig.

isotopes oxygen-18, deuterium,

and deuterium concentrations separated

Oxygen-18

13 ) and Br/CI and Na/CI ratios

These two sources also were differentiated

Mg/CI, K/CI, Ca/CI,

and

(Ca+Mg)/SO4 (see

also

and

separated

natural halite solution

clearly by other constituent ratios,

chapter 3.2).

The same constituents have

been used in Oklahoma and Kansas to differentiate natural halite solution from oil-field brines

(for

example, Ward, 1961 Leonard, 1964 Whittemore and Pollock, 1979 Gogel, 1981 and Whittemore, ,

1984

,

,

1988 ). The concept of local and nonlocal

isotopes

was

also used

Missouri are much

According to

by Banner

and others

lighter than typical for Missouri recharge water picks up high

recharge

reflected in oxygen and

(1989). Isotopic

hydrogen

stable

concentrations in saline waters of central

rain water, which suggested

a source

further to the west.

Colorado is the most

likely area of recharge for

salt contents from Permian salts

(indicated by Br/CI ratios)

Banner and others (1989), the Front

these waters. This

,

,

Range of

water from nonlocal ground water using the stable isotope ratios the meteoric water line at the composition of local precipitation (open dots and open triangles), whereas nonlocally derived ground water typically is either enriched or depleted in isotopes compared to local precipitation (solid dots) (from Richter and Kreitler, 1986b).

Figure

13.

Separation

of local

recharge

δ8O and δD. Locally recharged ground water plots along

underlying water

or

finally

mixes with fresh water near

intensive interaction of

possible ground

Kansas and

sources

water were

plots of Br/CI

were

saline

water intrusion

sea water

and in local host rock. Bivariate

are

a

of salt-water contamination in parts of Arkansas (Fig. 14 ).

source

(1985)

demonstrated the use of strontium and iodine concentrations for

ground water in

plotted on

off this dilution line

aquifer

also used by Morris and Bush (1986) in combination with plots of l/CI and B/CI to

and Heathcote

differentiating

water with

significantly different from those in Paleozoic

identify deep formation water as the

Lloyd

material were

precluded by these authors as isotopic compositions of 87Sr/86Sr and 144Nd (Neodymium) in

ground

of salinity because

areas in central Missouri. Ancient sea

discharge

the Lima Basin alluvial

dilution line between

ocean

aquifer,

Peru. Saline water derived from sea-

water and alluvial water

associated with inflow from saline

Waters that

(Rg. 15).

One of these is characterized

aquifers.

plot Sr

by

enrichment and the other is associated with iodine enrichment. Saline

playas

and gypsum flats

natural

are

western United States (Boyd and Kreitler, 1986 ). of southeastern Australia. Saline

TDS, appears to be relict

discharge

They

also

occur

water in that area,

ground

sea water with

changes

of closed basins in many parts of the

areas

elsewhere, such

ranging

in concentrations

as

from 20,000

mg/L

local

reflecting

in the Murray Basin to 50,000

mg/L

recharge/discharge

conditions (Macumber, 1984). Concentrations increase due to evaporation at three major discharge

points ( Fig. 16a ). Under these lake basins, ground recharge from the lakes. The similarity to

sea

water

water is

salinity also increases

preserved

as

the heavy brines

in these waters with little

changes

in

concentration ratios. Brine under these lakes will continue to accumulate and spread beneath the less saline water in these basins until a massive inflow of fresh water lakes

(Macumber, 1984). Similarly,

Southern

High

rather than

changes

dissolved solids concentrations in saline

Plains of Texas and New Mexico are the result of

discharge

the concentrations of the brine

of saline water from

deep brine aquifers,

springs

evaporation

as indicated

and lakes on the

of shallow

by constituent

ground

water

ratios of Cl/Br,

Na/K, and CI/SO4 being consistently smaller in evaporated waters than in deep-basin brines (Wood and Jones, 1990). Salinities increase in lakes and springs

recycled Southern

from the lakes to the

High

springs ( Fig.

Plains is affected

Locally, ground

by these evaporated

these two sources can be differentiated waters are characterized

16b ).

as surface water

through

by Na-SO4 waters

evaporates, and percolation

water in the

waters, but also

by oil-field

high-TDS,

Na-CI facies

Formation of the

brines. Salinization

salinity diagrams (Fig.

the use of

in contrast to

Ogallala

water is

17 ), as

by

evaporative

typical for oil-field-brine

affected water ( Nativ, 1988 ). The distribution of natural

salinity in

shallow

ground water reflects the geomorphology and hydrology

of the system, such as in alluvial fans in the western San

Gallanthine, 1989 ). Lowest salinities

(greater 5,000 mg/L TDS) than

larger

of California ( Deverel and

were found in the upper and middle fan areas and

in the lower fan areas and at the

poorly drained. Historically,

Joaquin Valley

soils associated with

intermittent streams and, therefore,

highest

salinities

margins of the fans where fine-grained

ephemeral were more

streams received less water and less saline.

Leaching

soils

are

flushing

of soil salinity by irrigation

Figure 14. Use of bromide, iodide, boron, and chloride concentrations in bivariate plots for identification of salt-water sources. Mixing between fresh water and salt water is suggested by linear trends between potential endmembers of mixing (from Morris and Bush, 1986).

Figure 15. Separation of different ground-water origins using the strontium-iodide relationship in ground water. Data shown are from the Lima Basin alluvial aquifer, Peru: Group I water is associated with alluvium; Group II water enters the alluvium from Jurassic sediments; Group III water enters the alluvium from granodiorites; Group IV water results from sea-water intrusion (from Lloyd and Heathcote, 1985 ).

Figure 16. Ground-water flow directions (arrows) and salinities (in percent) in parts of (a) the Murray Basin, southwest Australia, (from Macumber, 1984) and (b) at saline lakes, Southern High Plains of Texas (from Wood and Jones, 1990). Evaporation at major discharge sites and mixing causes TDS increases along the flow path.

Figure 17. Salinity diagrams of brines (from Nativ, 1988 ).

Ogallala

water contaminated

by (a)

saline lake water and (b) by oil-field

water

the

was

process that

primary

initially

formed shallow, saline

ground

water.

Subsequently,

evaporative concentration caused further increases in salt content. This evaporative trend is illustrated in plot of δ18O

and δD, which shows that samples collected at the lower fan

( Fig. 18a ). Waters with the highest salinities in the

ones

concentrations controlled Geothermal

by gypsum precipitation,

spring water in

Churchill

area are

of the

suggested by

as

County, Nevada, is

a

the most enriched

areas are

Na-SO4 type ( Fig.

18c ), with sulfate

saturation indices ( Fig. 18b ).

of local, meteoric origin

as

indicated by δ 18O

and δD values ( Fig. 19 ) (Welch and Preissler, 1986). Salinization caused by evaporation is suggested by

a

shift toward oxygen and

a

hydrogen isotope

enrichment. This evaporation trend

also indicated by

was

uniform Br/CI ratio. Of the minor constituents Ba, B, Br, F, Pb, Li, Mn, and Sr tested, bromide is largely controlled mineral

by evaporative concentration, such

phases

as

whereas barium, fluoride, lead, and manganese

ground water trapped

waters, as concentrations

in

of aquifers since

portions

deposition

does not contain any tritium because of the tritium

generally

12.4 years.

Anthropogenic

amounts of

tritium,

relationship

hydrothermal

sources

of salt, such

Snow and others

by

higher

in the

(1990)

since subsequent salt-water

or

isotope’s

short half-life of only

road salt, in contrast, may contain measurable

as

as these salts are dissolved and flushed into

was used

are

and Preissler, 1986).

higher temperature samples (Welch intrusion

controlled by

barite, fluorite, cerussite, and rhodochrosite, respectively. Boron, lithium, and

strontium may be indicators of the presence of

Saline

are

to

aquifers by modern precipitation. This sea water from road-salt

distinguish trapped

contamination in the coastal wells of Maine.

3.1.4.

Significant

Most of the

they or

Parameters

salinity

mix with fresh

facilitated

sources described in this

ground water.

by anthropogenic activities,

water and salt-water

bearing

characteristics will not differ of the

same

salinization

In other cases,

significantly

heavy

disposal

the same

Salinization is

indicated

suddenly

if the

naturally

at some

change

by

an

place

pumpage of fresh water,

produced

or

another, where initiated

drilling through

fresh-

water. In most instances, chemical

mixing of fresh

and salt water and artificial mixing

significant parameters

those for any individual source discussed in the

generally

substantial and occurs

suspected. However,

as

of

between natural

salt water with fresh water. Therefore,

are

occur

mixing of naturally saline water with fresh water is

such as

zones, or

report

for identification of natural

following

sections.

increase in chloride concentration. If this increase is

and is localized, a nonnatural mechanism and source should be is subtle and of

regional scale,

a natural mechanism or source may be

responsible. The stable

precipitation

isotopes Oxygen-18

and deuterium are

generally

useful to

water and water that is derived from a nonlocal source and

recharge water.

Molar ratios of

major chemical constituents,

distinguish

between local

identify evaporation

such as Na/CI, Ca/CI, and

Mg/CI,

of local

can be used

Figure 18. Natural salinization of ground water in parts of the San Joaquin Valley of California, controlled by (a) evaporation and (b) gypsum saturation, resulting in (c) a shift from low-TDS mixed-cation mixed-aniontype water to high-TDS, Na-SO4 water (from Deverel and Gallanthine, 1989 ).

Figure 19. Stable-isotope composition of ground water affected by evaporation, causing enrichment in oxygen-18 and deuterium as salinity increases. Chloride ranges: A 1,000 ppm)

1957).

has been

and

Segall, 1973).

reported along

the western

border, from the northeastern part (along the shore of Lake Superior), and the southwestern and southeastern parts of the state

(Feth

and others, 1965; Albin and Breummer,

1988).

In northwestern

Minnesota, mineralized ground water discharges from Ordovician and Cretaceous bedrock. Pumping from

area has caused

glacial aquifers in this

(Newport, 1977 ). Natural discharge in

overlying

alluvial

upward

intrusion of saline water from these

occurs from the Red

deep

bedrock aquifers

River-Winnipeg aquifer, degrading water quality

and in the Red River of the North. Chloride concentrations of up to

deposits

46,000 mg/L have been reported from wells along the shore of Lake Superior (Albin and Breummer, 1988).

Mississippi: below land surface of the state

Saline ground-water

(Feth

generally

and others, 1965).

underlies the state at depths of

Geohydrologic data indicate that

more

than 1,000 ft

most of the principal aquifers

previously contained salt water. This salt water was later partially replaced by fresh water but still

occupies downdip portions Missouri: Saline third of the state at

of these

ground

depths

aquifers (Bednar, 1988).

water

containing

more than

1,000 ppm TDS underlies the northern

less than 500 ft below land surface. This includes an area of very saline water

(TDS from 10,000 to 35,000 ppm)

that stretches from

Clay County in

the west to Marion

County in

the east

(Feth and others, 1965). The intrusion of natural salt-water from saline formations into shallow fresh is

spreading

Vernon Counties

(1)

history

meteoric

( Carpenter and Darr, and flow

recharge

path

migration

to shallow

ground-water withdrawal

has occurred in Bates, Barton, and

1978 ).

of saline

in the Front

of Kansas, (3) interaction with and

water

from the northwestern part of the state toward the south (Atkinson and others, 1986).

Intrusion of brackish water in response to

The

one-

Range

ground

water in central Missouri has been

suggested

to be

of Colorado, (2) dissolution of Permian halite in the subsurface

predominantly

silicate mineral

assemblages in

Paleozoic strata, (4) dilution

aquifer levels in central Missouri, and (5) mixing with local meteoric recharge

through Mississippian carbonates (Banner and others, 1989). Montana: Most of the eastern half of the state is underlain

depths

less than 500 ft below land surface.

Locally, TDS

by saline

water

(TDS> 1,000 ppm)

concentrations exceed 10,000 ppm

others, 1965). Maximum TDS concentrations in the glacial-deposits aquifer

are

(Feth

at

and

30,000 mg/L and in the

Virgelle aquifer 5,100 mg/L (Taylor, 1983). Nebraska: Saline

ground water (TDS>1,000 ppm)

underlies the state at 500 to 1,000 ft below land

surface in the southeast and at greater than 1,000 ft below land surface in the remainder of the state. TDS increase to values greater than 3,000 ppm in the southwest Salt water appears to be no serious threat to

ground

(Feth

and others,

1965).

water in the state except for the easternmost

part where TDS up to 3,500 mg/L are reported from the Dakota Aquifer and Paleozoic rocks (Engberg and Druliner, 1988). Taylor (1983) reported maximum TDS concentrations in the Dakota aquifer of 30,000 mg/L. According reported

to Atkinson and others

(1986), local

occurrences of salt-water intrusion have been

in Saunders, Lancaster, and Saline Counties. Saline surface water occurs in some of the

sandhills lakes in western Nebraska and in

some

localities in eastern Nebraska

(Krieger and others, 1957).

Approximately

24 percent (290,000 acres) of Nebraska’s total irrigable acreage

considered saline

were

and alkaline in 1960 ( Fuhriman and Barton, 1971 ). Nevada: Saline surface water and shallow saline

throughout

water has been

reported locally

central and western Nevada. TDS concentrations vary between 1,000 ppm and 35,000 ppm

(Feth and others, 1965). As much alkaline

ground

as

42 percent (475,000 acres) of the state’s

irrigable

acreage is saline

or

(in 1960).

Evaporation

of ground water in the many closed basins is the principal salinization mechanism in

Nevada. There

are

in the

Basin in Soda

Tonopah

Seepage

two places where TDS in ground water exceeds 10,000 mg/L; these

flows from two

Spring Valley and Clayton Valley a few miles south

springs

contain TDS of 15,000 and 30,000

mg/L.

are

point

sources

and east of Walker Lake.

Water from most aquifers is

saline in the Smoke Creek Basin, the Desert Creek Basin, and the Black Rock Deserts in the lower Quinn River Basin, as well

ground water in

as

in the Lovelock area in the lower Humboldt River basin.

sediments

containing large

amounts of salts is the

greater than 1,000 mg/L, and whereby mineral

mineralized

underlain by saline water most

likely

source of the

ranging

high

Closed-basin lakes of

in TDS from 1,000 to 3,000

which

some

of

a

few thousand acres that is

soluble salts in the aquifers

mg/L;

high salinity include Big Soda Lake, Pyramid Lake, a closed-basin sump northeast of

Ground water in

geothermal

areas

1988). Evaporative concentration of composition

area of Churchill

County.

are

the

Walker Lake, Winnemucca

Fermly.

The

of these lakes probably are unconsolidated sediments in the Lahontan

highly concentrated ground water discharges into

the chemical

an area

salt content (Fuhriman and Barton, 1971 ).

Lake, Carson Sink, Rhodes marsh, and salt in

for TDS concentrations

Lake contain about 50 to 60 percent of all the

Pyramid

water in the state. North of Lake Mead is

ground

reason

residence time of

content increases toward the center of the basins. The

of Carson Sink, Walker Lake, and east of

areas

primary

Long

frequently

The hottest water

exceeds 1,000

concentrations of greater than 6,000

mg/L

springs

sampled

sources of

from

Valley Group,

rivers and lakes (Whitehead and Feth, 1961 ).

meteoric water before

of thermal waters from

primary

at

recharge

mg/L

(Thomas

and Hoffman,

and mineral-rock interactions govern

and wells in the

Bradys

TDS

Hot

Bradys

Springs

Hot

Springs geothermal

contained 2,600

have been reported from the Desert Peak

area

mg/L

but

(Welch and

Preissler, 1986). New New

Hampshire: Jersey:

southeastern

parts

Tidal waters have intruded

Saline

ground

of the state at

water

depths

aquifers

(TDS>1,000 ppm)

Jersey coastline (Feth

and others,

present along the New Jersey Atlantic Coast:

generally

below the 800-ft sand. The

bodies depends

on

underlies most of the southern and

at or greater than 1,000 ft below land surface.

water decreases toward the coast in the south and is the entire New

in the Portsmouth area (Newport, 1977 ).

position

a

generally

Depth

to saline

less than 500 ft below land surface

along

1965). Two major water bodies of salty ground water are shallow one in Pleistocene

deposits

and

a

deep

one,

of the salt-water/fresh-water boundaries in those water

the head distribution of fresh water in the respective units (Upson, 1966). Salt water

from tidal estuaries and in the areas of

dredging Rahway,

Camden

has intruded into water table and artesian

bays

aquifers

Sayreville (Raritan River), Gibbstown-Paulsborough,

due to

Newark

and

pumping

(Passaic River),

and Salem.

(Delaware River),

New Mexico: With the exception of isolated areas in the north-central and southwestern parts of the state, saline

ground

water

(TDS>1,000 ppm) underlies New Mexico

at shallow

depth (1,000 ppm)

reaching from the coast approximately

underlies the eastern part of the state

100 miles inland in the south and 30 miles inland in the

north. Depths to saline water generally exceeds 500 ft with the exception of coastal and the northeast, where

salt water, which extends associated with salt

saline water

depths to

has caused

less than 500 ft (Feth and others, 1965). The

upward

lowered water levels in the Black Creek

Survey,

sources

of

and downward intrusion from

layered

aquifer to

(Miller

more than 100 ft below land

saline

aquifers

and others,

and lateral

1977).

It has

surface, threatening fresh

with the potential of lateral and upward intrusion of saline water (U.S. Geological

1984). concentrations of sodium and chloride in the Black Creek

Background Georgetown greater than

Counties are less than 280 those may indicate

intrusion caused

mixing

mg/L

and less than 40

aquifer

mg/L, respectively.

of

Horry

and

Concentrations

of sea water and fresh water. There is no indication of sea-water

by pumping, suggesting

migration of salt water. Residual in a

zone

and others, 1988).

intrusion from the Atlantic Ocean in the Beauford and Charleston areas

ground-water

in the southeast

the center of the state from the southwest to the northeast, is

through

deposits (Speiran

Heavy pumpage

are

areas

that deterioration of water

sea water may not be flushed from

quality

is associated with vertical

downdip portions of aquifers, resulting

fairly wide zone of dispersion and diffusion (Zack and Roberts, 1988 ). South Dakota: Ground water of

TDS underlies the state at

(Feth

and others,

Upconing

which exist

variable quality

containing

between 1,000 and 10,000 ppm

between less than 500 ft and greater than 1,000 ft below land surface

1965). reported

at various

in the Black Hills area of southwestern South Dakota

(Newport,

of saline water due to pumpage of fresh water

places throughout 1977 ). But the

depths

highly

the state,

major

including

salt-water

throughout

problem

aquifers

has been

in the state is associated with the occurrence of saline seeps,

most of the northern, central, and northeastern parts of the state (Atkinson and

others, 1986). In 1950 it was estimated that water into

aquifers

above them.

permit upward migration

approximately 12,000

Inadequately plugged

to 15,000 artesian wells within the state leak

test holes drilled for oil, gas, and uranium may

of saline water even in areas where no

concentrations in the state’s

aquifers

are:

production

is

occurring.

Maximum TDS

glacial deposits, 10,000 mg/L; Dakota, 8,000 mg/L; Inyan Kara,

10,000

mg/L; Sundance, 7,600 mg/L; Minnelusa, 4,300 mg/L; Madison, 120,000 mg/L;

130,000

mg/L;

and Deadwood, 40,000 mg/L

More than 70 percent

Red River,

(Taylor, 1983). of the state’s

(1,196,000 acres)

land surface was considered saline

irrigable

or

alkaline in 1960 ( Fuhriman and Barton, 1971 ). Tennessee: The western two-thirds of the state are underlain than 1,000 ppm TDS. The

depths

by ground

water

containing

to the interface between saline and fresh water is 1,000 ppm)

water

in the southern

along

part

at

depths

1 found in most fresh waters and

compared

brines. Ion

possible

as

aquifer matrix

results in an increase in

ratio of sea water. This increase may be more

pronounced

in older

waters than in modern waters, which led Sidenvall (1981) to propose that saline water in the Uppsala,

Sweden,

area

is fossil ground water representing the last

by Snow and others (1990) on

to

distinguish

sea

transgression.The ratio of CI/SO4 was used

sea-water intrusion from road-salt contamination in Maine, based

the fact that sulfate concentrations and

CI/SO4

ratios

are

substantially

lower in road-salt affected well

waters than in sea-water affected well waters. This ratio can also be used to intrusion from

previous

by Pomper (1981) characterized

intrusion in waters

by CI/SO4

undergone

Ba/CI

ratios that

Floridan of

use

SO4/CI

aquifer of

SO4/CI

anhydrite the

source

exchange

are

of saline water in the Santa Barbara, California

and sulfate reduction. In addition to the the source of the

ratio also seems to indicate

southwest Florida, as shown

ratios versus

SO4

mixing

mg/L,

as done

SO4/CI

ratio

as a

tracer of

sea

water and

( Fig.

mixing.

41 )

downgradient in

Because of the

that

ratios of B/CI and

recharge

the theoretical

( Steinkampf,

are

similar fashion,

area as ocean water

CI/SO4 ratio, the

by samples that plot close to

concentrations

a

deep saline ground-water in that

between

solution causes sulfate concentration to increase

of the

500

higher than those found in modernseawater. In

appeared to indicate that sea water is

1982 ). The

plot

ion

having chloride concentrations greater than

in the Netherlands. As a result of sulfate reduction, older saline waters

Martin (1982) explained the had

modern sea-water

distinguish

area

(Martin,

water in the

mixing

line in

a

1982 ). However, gypsum-

some

of the samples, limiting

generally high degree

of water-rock

interaction in this carbonate-dominated aquifer which governs concentrations of calcium, magnesium, and bicarbonate and masks the source of was used

by Steinkampf (1982)

salinity,

the conservative nature of the chloride and bromide ions

to demonstrate that dilution of marine-like

mechanism in the evolution of saline

ground

water in this

aquifer.

interstitial waters had been flushed from the sediments, are the

ground

water is a

significant

Past marine inundations, after saline

probable

source of

salinity (Steinkampf,

1982 ).

The Br/CI weight ratio in waters.

Therefore, mixing of

sea water

sea

is approximately 3.3 ×

10-3,

water and fresh water may cause

which is comparable to most fresh

only a slight change

in Br/CI ratio in the

Figure 41. Bivariate plot of SO4/CI ratios and SO4 concentrations for coastal saline ground water of southwest Florida. Sea-water intrusion is indicated in those samples that plot close to the theoretical mixing line between sea water and fresh water (modified from Steinkampf, 1982 ).

mixing

water when

compared to

of 3.4 ×

10-3

samples

in the Manhattan Beach area, California.

Cl, this ratio

for Pacific Ocean water and

can

example, Brennan (1956) reported Br/CI ratios 3.2 × 10-3 to 3.7 × 10-3 for sea-water intrusion

the fresh-water value. For a

range of

However, because of the conservative

often be used to differentiate between salt-water

brine is typically characterized by Br/CI ratios smaller than 5 × smaller than the value in

significantly higher

sea

sources.

10-4,

nature of Br and

For example, halite-dissolution

which is

one

order of

magnitude

water. On the other hand, oil-field brines often have ratios of Br/CI that

are

than sea-water and halite-dissolution brine values ( Whittemore and Pollock, 1979 ;

Richter and Kreitler, 1986a ,b; Whittemore, 1988 ). Therefore, the Br/CI ratio may be useful to differentiate between sea-water intrusion and oil-field contamination in coastal settings that include oil fields. In settings that include storage and application of salt for road deicing, such

part of the United States, the Br/CI ratio contamination. Saline

ground

water

can

also be used to

as

along the

distinguish

typically contains Ion

intruding

exchange

little bromide with Br/CI

carbonates,

as

weight

and carbonate dissolution are

sea water.

This is the

shown in

a

case even

sea-water intrusion from road-salt

from past or current intrusion of

originating

detectable bromide with Br/CI ratios similar to sea water, whereas saline salt

coast in the northeastern

ratios less than 1 ×

major chemical

contains

sea water

ground water originating from

10-3 (Snow and others, 1990).

reactions that alter the

composition

study of rock-water interactions and seawater-freshwater mixing in coastal dune

to act

conservatively although

of silt,

clay,

K-feldspar,

organic

and Ca-Na base

considerably from the

the

aquifer consisted of

matter. Sulfate reduction, oxidation of

exchange on clay

theoretical

composition

sea

was

water,

(b) Ca-Mg exchange, (c)

minerals cause the

Oahu, Hawaii. Even at

deposits

on

a very small

in the intruded water as

compared

zone

Na-Ca or Na-Mg base

shown by Mink (1960) who studied concentration

calcareous and alluvial

decreasing by

the coastal zone of

the ocean bottom before

degree of dilution,

in

indicated

(3)

by a

more

solution-precipitation

lower Na, K, and

water

entering

as

of

authigenic

saline water to differ

zone. Nadler and others as

being (a) dilution

reduction. The

the water

the basaltic

moves

aquifer

changes

Similarly,

in

major cations

sea-water intrusion

mixing composition

reactions cause (1)

are very

potassium samples

in

of sea water and

higher

Ca content,

HCO3 content than expected from simple mixing

assumption that old water had

to occur and, therefore, would be characterized

through

chloride concentration of 17,600 ppm

(Ikeda, 1967 ). The increase in Ca content with time was used by Jacks (1973) to distinguish old from young sea water, based on the

same

of southern

than 100 percent and the

do not reflect the theoretical

fresh water. Instead, ion exchange and and

sea

to 19,000 ppm in open sea water,

Fuji City, Japan,

mixing

exchange, and (d) sulfate

more than 50 percent (Mink, 1960 ).

(2) slightly higher SO4 content,

composition of the

within sandy sediments

changes

noticeable, with the calcium concentration increasing by concentration

plant material, formation

of diluted sea water in the

,

one

rather uniform quartz sand with only minor amounts

(1981) summarized processes occurring in the transition of

of

in aquifers that contain only small amounts of clay and

aquifers of Oregon. Magaritz and Luzier (1985) found that of all the major ions, chloride was the only

and some

road

by higher Ca

more time for ion

exchange

sea

water

reactions

contents than younger sea water. Under

certain

circumstances,

sea-water intrusion water

are

manganese concentrations may be indicative of ion

samples

This is the case in

from Manhattan Beach, California, in which sodium ions of the

intruding

sea

exchanged for manganese in the sand and gravel aquifer. Largest manganese concentrations

appear to be associated with Mg/Ca ratios close to Dilution diagrams

were

theoretical

mixing

away from and

exchange,

or

slightly greater than

one

( Brennan, 1956 ).

used by Howard and Lloyd (1983) who investigated the relationship of three ,

groups of saline ground water in east-central

points

exchange.

line between

sea

42 ). On these plots, data points close to the

England ( Fig.

water and local

water indicate

ground

simple mixing, whereas data

lines indicate chemical reactions, such as mineral dissolution and

mixing

reduction. It is

sulphate

attempt differentiating saline waters by the

use of

and the l/CI ratio to distinguish three groups.

explanation

of the

resulted in a

big cluster of

hydrochemical data

to note that Howard and

interesting

ion

precipitation,

Lloyd (1983)

did not at first

major chemical constituents but instead used isotopes

Only because of this grouping did dilution diagrams

allow

an

evolution of the individual groups that otherwise would have only

points.

3.3.4. Reaction Characteristics of Sea-Water Intrusion The chemical in response to

changes

composition

of sea water

changes

mixing and chemical reactions

are most

intrusion deviates little from sea-water

just

water

can

data points. On bivariate

above

background

concentration values to

theoretical Ion

mixing line between

of

major cations

on trilinear

cations in direct

and anions versus chloride, data

as discussed below.

points plot

close to the

local fresh water and sea wetter.

proportion

calcium ions, whereas in a

have free

negative

surface

charges that

to the abundance of cations in the water and to the

characteristics of the cations and the minerals. In a

mainly with

by ion exchange

less than sea-water

plots in the straight-line relationship between

Exchange: Clay minerals, especially montmorillonite,

occupied by

just

typical

typical

salt-water

fresh-water

aquifer,

aquifer,

water intrusion into a fresh-water

aquifer, ion exchange will

these sites are saturated

the sites are occupied

solution and calcium will be released from mineral for calcium but the Na-Ca

Lloyd (1983) attributed

more

exchange

exchange

occur

sites.

is the most

whereby

are

sorption

mainly by sodium

ions. Whenever the relation of calcium to sodium in the water changes, for example in response to

exchanged

by

dilution characterizes deviation of the brackish water from sea-

easily be identified

plots

Subsequent

sea water occurs within a transition zone, which is characterized

ion-exchange front, simple

composition. This

occur

43 and 44 and below. These

sea-water front that mixes with fresh water.

concentration. The front of this transition zone is characterized Behind the

Figures

aquifer. Changes

composition.

Mixing: Mixing of fresh water and chloride concentrations from

summarized in

as

pronounced within the initial

as it intrudes a fresh-water

sea-

sodium will be taken out of

Magnesium and potassium may also be

significant

one. For

example,

Howard and

than 96 percent of the base exchange in the Chalk aquifer of east-central

Figure 42. Dilution diagrams of major ions with theoretical mixing lines between sea water and local fresh water. Simple mixing is indicated for samples plotting close to theoretical mixing lines. Deviations from these lines suggest additional chemical reactions (from Howard and Lloyd, 1983 ).

Figure 43. Relationship between flow regimes plain (from Back, 1966 and Custodio, 1987). ,

and

hydrochemical facies

in

ground

water in a big coastal

Figure 44. Geochemical processes and changes aquifer (from Custodio, 1987).

in ionic

composition along the flow path

in a coastal

England

to Na-Ca

Intrusion of fresh water into

major changes not affected

intrudes

a

on

This

exchange.

salt-water

a

ionic ratios

as a

aquifer will cause the opposite ion exchange.

result of these

potential

a

water. In contrast, if fresh water replaces marine water

sea

in the

early part

of the

can

result

intruding

(Custodio, 1987). Figure

sea-water front as

plotted

the lowest chloride

representing

values),

as chloride content increases. The

the matching decrease in Na+K, and the

changes

because all the of sea water

ratio)

whereas

diamond-shaped

high

increase in

ratios often

washes out marine

Piper diagram.

triangle (samples

characterizes the

mixing

or

one to

39 illustrates this process of ion

on a

between calcium and sodium characterizes the cluster in the cation

No

tracer of intrusion. If sea water

fresh-water aquifer, Na/CI ratios will decrease from ratios often greater than

sediments, very high Na/CI ratios

triangle

Table 7 summarizes

in water facies. The chloride concentration is

changes

by ion exchange, which makes the Na/CI ratio

less than the value in

exchange

is assumed to be instantaneous ( Kafri and Arad, 1979 ).

exchange

field reflects the

CI+SO4 percentages ( Fig.

1

exchange

through 12,

line in the anion

straight slight

Ion

increase in

Ca+Mg,

39 ).

in the Na/CI ratio will occur in water that intrudes behind the front of ion exchange sites are

exchange

(0.85

molar

ratio),

already occupied. Therefore,

which differs from the

and from the small ratio characteristic for many

typical

the Na/CI ratio should

ratio of halite-dissolution brines

oil-field/deep-basin

degree of change that occurred because of ion exchange may

not

brines

the ratio

approach

(

decrease in sulfate concentration relative to the

composition.

Bromide: Sea-water intrusion may lead to bromide concentrations greater than liter in coastal

aquifers.

This has a

big potential impact

on future

drinking-water

a

few

milligrams

per

resources because

elevated bromide concentrations make water treatment more difficult. Traditional chloride treatment

or

Table 7.

Changes in

ionic ratios due to ion exchange relative to the of the intruding water.

position

Fresh-water Recent

Salt-water

Intrusion

(a)

Intrusion

(b) Behind

Advancing

advancing

front Ca/Na

A|Ca+Mg|/A|Na| Na/CI

increase constant decrease

front no

change change

no

change

no

decrease constant increase

ozonation of

high-bromine

water causes the formation of bromoform and other brominated

trihalomethanes, which may, at bromide concentrations greater than 2 mg/L in the water, exceed allowable concentration in future (1992) standards (McGuire and others, 1989, U.S. Water News, 1990a ).

through muds

Minor Constituents: As sea water passes

enriched in those minor constituents that

are

on

estuary

or ocean

bottoms, it may become

typically concentrated in those muds, such

as

iodide,

strontium, and fluoride (Lloyd and Heathcote, 1985 ). 3.3.5

State-by-State Summary of Sea-Water Intrusion Sea-water intrusion is not

phenomenon and

a new

of the United States. For example, the

early

as

city of Galveston

has been

reported to occur in

had to abandon

one

every coastal state

of their water-supply wells

as

in 1896 (Turner and Foster, 1934 ) and in Florida, intrusion has been experienced along most of

the Gulf and Atlantic Coast (Atkinson and others, 1986). The following section lists the published occurrences

for sea-water intrusion for all the states with marine shorelines. This discussion includes

water intrusion due to coastal times of

aquifers

anthropogenic

activities but also mentions the occurrence of saline

related to natural processes, such as inclusion since

higher sea-water levels.

deposition

or

sea-

ground water in

past intrusions during

This compilation is a result of Iterature review.

Alabama: Sea-water intruded fresh-water aquifers from Fort Morgan to Gulf Shores (Atkinson and

others, 1986), and overdevelopment of

a

well field in the Mobile-Gulf Coast

of saline water from the Mobile River into Pleistocene water contamination of wells in Baldwin

County has

sea-water flooding and natural sea spray, and California: In southern California, the level at the turn of the century but

sand-gravel aquifers (Miller

been caused

(Poland

and others,

1959).

potentiometric

(A) Mission, County,

San Luis

Rey,

Santa

(B),

a fresh-water zone,

surfaces of coastal

decreased in the

following

aquifers

were above sea

decades. Because of

heavy

water levels have declined in some areas to as much as 70 ft

salinity

Banks and Richter

threatened sea-water intrusion areas

and others, 1977). Sea-

by overproduction of

below sea level (Brennan, 1956). In the Manhattan Beach area of Los wells were abandoned after 1940 when

lateral intrusion

leakage from salt-water ponds (Chandler and others, 1985).

gradually

developments in the 1920’s and 1940’s

region caused

and

Margarita,

Malibu Creek, Trancas Creek, Morre

of

ground

(1953)

potential

Angeles,

most of the

original water

water increased due to sea-water intrusion

summarized: known sea-water intrusion areas sea-water intrusion areas

Coastal Plain

Bay, Salinas,

Orange County,

Coastal

(C)

in California as

Coastal Plain Los

(A),

being:

Angeles

strip Salinas Valley and Pajaro Valley,

Pajaro, Santa Clara, and Sacramento-San Joaquin Valley between Pittsburgh, and Antioch; (B) Tia Juana,

Otay,

Santa Clara River,

Carpenteria, Goleta, Arroyo Grande;

and

(C) Sweetwater,

San

Dieguito,

San

Onotre, San Mateo, San Juan, Ventura River, Santa Ynez River, Santa Maria River, Carmel, Ygnacio

Clayton, Napa-Sonoma, Petaluma,

Eel River, Mad River, and Smith River. Of those, the most serious sea-

water intrusions have occurred in the West Coast Basin of Los

Angeles County,

East Coastal Plain

Pressure Area of

Orange County,

Valley in the San Francisco Bay

Petaluma

Valley in

Sonoma

County, Napa-Sonoma Valley,

Pajaro Valley in Monterey and

area,

Santa Clara

Santa Cruz Counties, Salinas Valley in

Monterey County, Oxnard Plain Basin in Ventura County, and Mission Basin in San Diego County ( Fuhriman and Barton, 1971 ). intrusion were

Valley,

Elkhorn

(A)

Eel River

slough

In

1975, the

Valley,

Petaluma

area, Salinas

Valley

Oxnard Plain Basin, West Coast Basin

(B)

14 known

(A) and

14

suspected (B)

Valley, Napa-Sonoma Valley,

areas

Santa Clara

of sea-water

Valley, Pajaro

pressure area, Monro Basin, Chorro Basin, Los Osos Basin,

(Los Angeles County),

Russian River Basin, Drakes Estero Basin, Bolinas

San Luis

Lagoon Basin,

Rey Valley,

and Mission Basin, and

San Rafael Basin, Suisum-Fairfield

Valley, Sacramento-San Joaquin Delta, Tonitas Creek Basin, and San Diego River-Mission Valley Basin (Smith, 1989 ). Farrar and Bertoldi (1988) identified and the delta area, around

Valleys,

Monterey Bay,

Morro

areas of salt-water intrusion around San Francisco

Bay

Bay

and at the mouths of Petaluma, Sonoma, and Napa

where the salt water infiltrated from tidal channels. Diversion of stream flow from the Sacramento

and San

Joaquin

whereas fresh-water

Pittsburgh, Alameda

Rivers has caused inland

County. Pumping

of salt water in the areas around Fairfield and

has caused sea-water intrusion and land subsidence in

pumping

of water for

migration

irrigation purposes

has led to sea-water intrusion

near

the mouths

of the Pajaro and Salinas Rivers (Farrar and Bertoldi, 1988). Connecticut: Lateral sea-water intrusion from harbors and tidal river estuaries due to heavy pumpage has contaminated many industrial and

including the cities of

New Haven and

municipal

for the abandonment of one to two

(Atkinson and others, 1986). During dry periods, far

as

Philadelphia (U.S. heavy

1974). High

pumpage from shallow

1953)

aquifers, specific

a

all

problem

the Delaware coastline and is

has migrated up the Delaware River nearly

dredging mg/L

impermeable

and 17,000

as

mg/L

soils

many well fields

(Miller

and others,

were measured in core

depths of wells from

to 60 ft below land surface (Woodruff, 1969 ). a

combination of permeable

and heavy pumpage in coastal areas. Intrusion was

municipal water supplies

1924. Interior drainage canals which lowered the water table and tidal action contributes to the

of

of sea-water intrusion stems from

locations and some 18

a

along

Atlantic Coast of southeastern Delaware. The

lengthy coastline,

Sea-water intrusion is

area

wells and 20 to 30 domestic wells each year

sea water

and the

samples were obtained ranged from 5

at 28

public

chloride concentrations between 6,000

Florida: The Florida limestone

reported

Bay and from the Atlantic has contaminated

aquifers

samples obtained from wells along the which core

Island Sound coastal

Environmental Protection Agency, 1973 ). Lateral and vertical intrusion of salt

water from the Delaware River and Delaware

due to

Long

Bridgeport (Miller and others, 1974).

Delaware: Salt-water intrusion has been

responsible

wells in the

problem ( Bruington,

reported (in

have been adversely affected since

permitted sea water to advance

1972 ; U.S. Environmental Protection

inland by

Agency,

1973 ).

permanent threat to the Biscayne Aquifer because the aquifer is unconfined, is

hydraulically connected to the sea,

is

heavily pumped,

and is

pumpage has resulted in water levels below sea level

extensively cut by a

near some

network of canals.

Heavy

well fields (Johnston and Miller, 1988).

Large

cones of

depression

and sea-water intrusion due to

areas, such as Jacksonville,

Tampa,

including

pumpage have been reported in many

and Miami. Intrusion on a smaller scale has been experienced

most of the Atlantic and Gulf Coasts the affected counties,

heavy

(Atkinson

Escambia

and others,

1986).

Miller and others

County (heavy pumping

near

Bayou

(1977)

along

listed some of

Chico caused intrusion

into sand and gravel aquifer and reversed flow gradient and induced salt-water migration from the Escambia River), Bay County (saline surface water leaked downward from bays contaminating two wells), Martin

County (encroachment

city wells),

Pasco

of water into shallow

County (sea-water

aquifer

from St. Lucie River due to overpumpage of

intrusion due to overpumpage of coastal

wells),

Charlotte

County

(sea-water intrusion from Gulf and estuaries and intrusion due to poor well construction and improper Palm Beach

abandonment),

during dry period

County (inland flow of

caused contamination of

Biscayne aquifer in coastal

areas due to

saline water through canals and intracoastal

Biscayne aquifer),

waterways

County (salt-water migration

Broward

into

heavy pumpage and construction of canals), Dade County (dry

period caused inland flow of salt water up the Miami canal and contaminated four water wells), and Miami

(contamination of due to

wells due to inland flow of salt water during

dry periods

and inflow of saline

ground water

heavy pumpage).

In 1943 in the Miami area, sea-water intrusion was restricted to wells within two miles of the coast

except

for some areas

1944 ). In Citrus

along

County

threefold, respectively,

tidal canals where intrusion was observed somewhat farther inland ( Love,

sodium and chloride concentrations exceed

as a

acceptable

levels twofold and

result of high pumpage of fresh water and seepage of salt water from the Gulf

(U.S. Water News, 1990b). In the Floridan aquifer of west-central Florida, the transition fresh water and saline water may be

as

zone

between

far as 50 miles inland from the coast. Future ground-water

withdrawal could lead to further landward movement of the salt-water front in that area at an average rate of 1982 ). In Pascola

approximately

0.35 ft per

ground water,

at 100 ft below sea level, is located

day (Wilson,

1972). Three encroachment mechanisms permeable limestone where the aquifer is in

are

heads caused

the interface between fresh and saline

approximately one to two

responsible

contact with sea

and canals in which sea-water intruded, and (3)

hydraulic

County,

upward

for that

miles inland

position:

(Reichenbaugh,

(1) lateral inflow

through

water offshore, (2) leakage from tidal streams

movement of salt water in response to lowered

by pumpage of fresh water (Reichenbaugh, 1972).

Sea-water intrusion into fresh-water reaches of the Caloosahatchee River occurs between La Belle and

Olga during

In 1968, the dam in the

low-flow

upstream

periods

as

repeated injections through

limits of water

deeper parts

containing

of the river and

less than 250

approximately five

the lock chamber at W. P. Franklin Dam.

mg/L of

chloride were 11.4 miles from the

miles from the dam at shallow

depth (Boggess,

1970 ).

Georgia:

Sea-water intrusion has been

County (Atkinson

and others, 1986).

reported

for Chatham

County (Savannah)

and

Glynn

Louisiana: Sea-water intrusion has occurred all along the coastal shores of Louisiana. In addition, the cities of Lake Charles and New Orleans have

high pumpage of ground

water

experienced

severe cases of salt-water intrusion due to

the Gulf of Mexico invades coastal streams and fresh-water aquifers, such River

area

Overpumping

in Kennebec and

salt-water intrusion, the

deep

well

as

the

one

in the Vermillion

( Newport, 1977).

Maine:

Augusta,

water from

(Atkinson and others, 1986). During periods of low flow, tidal

producing

has resulted in intrusion of tidal estuary waters into local aquifers south of Counties. Several domestic water wells have been affected

Sagadahoc

at times over the year

problem fluctuating

from the bedrock

aquifer

near

(Atkinson

and others,

the town of Bowdoinham,

1986).

by

A 300-ft-

Sagadahoc County,

was

contaminated by salt water from the tidal reach of the Kennebec River, resulting in abandonment of the well (Miller and others,

1974).

Maryland: Sea-water intrusion has been reported in St. Mary's, Anne Arundal, Harfork, Dorchester, and Somerset Counties activities appear to be

as

well

as on

responsible

for

Kent Island.

Overpumping, leaky

well

and dredging

casings,

ground-water contamination. Salty water from

the

Patapsco

River

estuary has intruded shallow fresh-water aquifers in the harbor district of Baltimore. Heavy pumpage and

leaky casings

also induced the inflow of salt water from

Chesapeake Bay into wells at Joppatowne,

County, and Westover, Somerset County. Lateral and vertical intrusion of salt

water from tidal river

estuaries, enhanced by casing leaks in abandoned wells, has been reported in the Dorchester

County.

Anne Arundal

The inland limit of saline

Cretaceous the

County, Annapolis, aquifer, along

Tertiary aquifer,

and

ground

County,

areas

of

Cambridge,

and the Solomons-Patuxent River, St.

water in coastal

plain aquifers

are

Harford

along

Mary’s

the coast for the

a line from Dorchester to the southwestern state-line comer with Delaware in

along

a line

half way between the shore and the

parallel

to the

Chesapeake

Maryland-Delaware

shoreline in the south and

state line in the north,

approximately

crossing the

state line just

north of 39 degrees latitude (Miller and others, 1974). Massachusetts: Sea-water intrusion has been

reported

in several areas in Massachusetts,

including Bristol, Plymouth, and Barnstable Counties (Atkinson and others, 1986)

as well as

Provincetown, Scituate, and Somerset Counties (Newport, 1977).

Mississippi: Heavy pumpage saline water from the Gulf and the Formations (Miller and others,

and the

resulting

Pascagoula

decline in water levels induced lateral intrusion of

River estuary at Moss Point into Miocene and the Citronelle

1977). Sea-water intrusion

has also been reported in Hancock and Jackson

Counties (Atkinson and others, 1986). New

Hampshire:

Tidal waters have intruded aquifers in the Portsmouth

pumpage has induced intrusion in Rockingham

County (Atkinson

area

(Newport, 1977) and

and others, 1986).

New Jersey: Intrusion of sea-water is a major problem that has been monitored since 1923 (Ayers and

Pustay, 1988).

1983 ).

In 1977, the salt-water

Overpumping, leaky casings,

and

monitoring

dredging

network included more than 400 wells ( Schaefer,

have led to intrusion in Salem, Gloucester,

Cape May,

Middlesex, Monmouth, Ocean, and Atlantic Counties (Miller and others, 1974; Newport, 1977 ; Schaefer, 1983 ). The most

significant

intrusions have occurred in the areas of

has been observed for more than 40 years, in the had to be abandoned in 1976, and in

inland, such

Keyport-Union

Sayreville,

where salt-water intrusion

Beach area, where the

Cape May City ( Schaefer,

original

1983 ). Even areas 20 miles or more

in Gloucester and Atlantic Counties, have experienced sea-water intrusion due to

as

pumping and corroded well casings. At Somers Point, Atlantic County,

a

wedge

of salt water has moved

3,000 ft inland into the Cohansey aquifer. At Artificial Island, Salem County, high pumpage

generating plant

well field

has induced salt water (Miller and others, 1974; Newport, 1977). Since the

well waters in the Old

Bridge

aquifer in the

have shown

high

background

levels of less than 5

chloride concentrations,

Walker, 1981 ). In the Sayreville

mg/L

Boroughs

indicating

to

greater

of

presented

early 1970’s,

and Union Beach, Monmouth

Keyport

than 600

mg/L

in some coastal wells ( Schaefer and

area, the transition zone between fresh water and salt water has

by Schaefer (1983)

County,

sea-water intrusion. Concentrations increased from

0.2 to 0.4 miles inland between 1977 and 1981 (Schaefer, 1983 ). A in New Jersey was

at a nuclear

listing

migrated

of previous salt-water studies

.

New York: Sea-water intrusion has been documented

Long

on

Island ( Lusczynski and

Swarzenski, 1966), in the Town of Southampton, the Eastport-Remsenburg-Spoenk-Westhampton and the North

Haven-Sag

Harbor area ( Anderson and Berkebile, 1976 ). Coastal

contaminated with salt water in the Port

Long-term

use

Washington

plain aquifers

area, where sea water was used in

area,

have been

settling ponds.

of the salt water in sand and gravel pits has raised chloride levels in nearby shallow and

deep wells from

a

normal level of less than 20 mg/L to greater than 1,000

mg/L in

an area

of

more

than two

square miles (Swarzenski, 1963 ; Miller and others, 1974).

Heavy pumping producing aquifers

on

southeastern Queens and two more

and reduced natural

Long

Island

have caused lateral intrusion of ocean water into

recharge

(Newport,

1977). Sea-water intrusion in southern Nassau and

Counties, Long Island, occurs as one wedge of salt water in

wedges in

the upper and lower portions of the

underlying

artesian

shallow

glacial deposits

aquifer (Miller and others,

1974). Salt-water intrusion may be occurring in two

Remsenburg-Spoenk-Westhampton

area

and the North

lense of fresh water in the area,

underlies

a

vertically.

The

depth

areas in

the Town of

Haven-Sag

possibly allowing

Southampton,

the Eastport-

Harbor area, Long Island. Salt water

salt-water intrusion both

laterally

and

to salt water in three testholes was found to be at 350, 620, and 1,060 ft below sea

level, respectively. Chloride concentrations in affected wells range from 200 to 13,890 mg/L (Anderson and Berkebile, 1976 ). North Carollna: Sea-water intrusion has been documented in Carteret, Pamlico, Beaufort, Hyde,

Dare, and Tyrell Counties (Atkinson and others, 1986). Tidal action resulted in intrusion of saline water into

ground-water sources through drainage canals on former marsh Carolina. This forced abandonment of large

areas of

cropland

land in the Coastal Plains of eastern North in parts of

Tyrell, Dare, Hyde, Beaufort,

Pamlico, and Carteret Counties ( U.S. Geological Survey, 1984 ). Heavy pumpage could also induce

recharge

of salt water from streams affected

sea water

by

resulting

from tidal action and/or decreased

fresh-water flow.

Oregon: Sea-water intrusion has been documented in Eugene (Lane County), North Bend (Coos County),

in the Willamette

Valley in the West Cascades, and in Clatsop and Tillamook Counties (Atkinson

and others, 1986). Sea-water overrides fresh-water storms

( Magaritz

aquifers in

the Horsfall Beach

area as a

result of winter

and Luzier, 1985 ).

Pennslyvania: Dredging of sea-water intrusion near

tidal rivers and

Philadelphia in

heavy

pumpage from wells near tidal rivers have caused

the eastern part of the state

Rhode Island: Heavy pumpage from wells Warwick in Bristol and Kent Counties and

near

near

and others,

(Atkinson

1986).

tidal rivers has caused sea-water intrusion

Providence in Providence

County (Atkinson

near

and others,

1986). South Carolina: Sea-water intrusion has occurred at several locations

including

areas in

along

the state's coast,

Charleston, Beauford, and Horry Counties (Miller and others, 1977; Atkinson and

others, 1986). Background concentrations of sodium and chloride in fresh ground water within the Black Creek

aquifer

of

Horry

and

Counties are less than 280

Georgetown

Concentrations above that may indicate mixing of fresh water with

mg/L

and 40

sea water

mg/L, respectively.

(Zack and Roberts, 1988 ).

The most extensive encroachment at present occurs in an area that extends from the Beaufort Basin to the Cape Fear Arch (Siple, 1969 ). The upper Eocene and

Oligocene deposits

are

subject

chloride concentrations of up to 8,500 ppm Texas: Sea-water intrusion is Arthur areas and around

Corpus

of Eocene limestones and the sub-sea contact of

to considerable salt-water encroachment, with maximum

( Siple,

occurring

Christi

zones

1969 )

in the Galveston, Texas

(Atkinson

and others,

City, Houston,

1986). Along

and Beaumont-Port

the Gulf Coast, sea water

mixes with surface water in the tidal reaches of the rivers, such as in the Calcasieu River channel, Calcasieu

Lake, Sabine Lake, and lower Sabine River (Krieger and others, 1957). Sea-water intrusion

occurs also

along the lower 36 miles of the Neches River and 3 miles of Pine Island Bayou (Port of Beaumont) during 6 months of the year. Salt-water barriers, which divert fresh water into a canal system upstream, cause this unhindered inflow of salt water; tidal action flushes the salt water back and forth below the barriers it to become

increasingly concentrated.

Deterioration of water quality is

the water way (Harrel, 1975 ). Sea-water intrusion from the Houston

causing

aggravated by waste disposal

Ship Channel

into

has been reported from

shallow wells between Baytown and Houston. Large withdrawals of ground water (525 million gal/d),

resulting

in a decline of artesian pressure

equivalent

intrusion over an area up to four miles wide at

to a 400 ft

Baytown

drop

of

hydraulic head,

has caused this

at a rate of several hundred feet per year

(Jorgensen, 1981 ).

Virginia: saline

ground

Sea-water intrusion due to the water has occurred in

overpumping

Northhampton

of fresh

and Isles of

ground

Wight

water in areas of shallow

Counties

(Atkinson

and others,

and in the areas of

1986)

Newport

Cape Charles ( Newport,

News and

historic

changes

wedge

of salt water coincident with the mouth of

1977). According to Larson

in chloride content of water wells are a local rather than

Chesapeake Bay

areas

cases

appears to be

a more

a

was

measured.

of sea-water intrusion have been documented in the Puget Sound

and along the Pacific Coast. Affected

Olympia, Kitsap County,

general,

,

extends into the York-James and

southern Middle Neck Peninsula, where the greatest chloride increase (175 mg/L)

Washington: Several

In

regional phenomena.

(1981)

include Island County, the

areas

and northern Jefferson

widespread problem

County (Kimmel,

areas

around Tacoma and

1963 ). While sea-water intrusion

in Island and San Juan Counties, it is of only local

significance in

Clallam, Jefferson, Renee, Thurston, and Whatcom Counties ( Dion and Sumioka, 1984 ). 3.4 Oil-Field Brine 3.4.1 Mechanism

This chapter deals with salt water that is

deep-basin

produced with

oil and gas. This water is naturally-occurring,

formation water that differs from the type discussed in

mechanism of

mixing with fresh water than through

its water chemistry. The

mechanism is that formation brines unassociated with oil and gas are water

by a

transition zone of

slightly to very

chapter

saline water, which

3.1 more

major difference

its

through in the

mixing

normally separated from fresh ground

normally

lessens the

degree of

natural

or

induced salinization. Anthropogenic contamination of fresh water by oil-or gas-field brine, in contrast, is not associated with a transition zone but instead water.

brings

concentrated brine into direct contact with fresh

Therefore, salinization of fresh ground water by oil-and gas-field brine is often very abrupt,

characterized

by large

There are

increases in dissolved solids within

currently

25

major

oil-and

relatively short time periods

gas-producing

drilling

country (Fig. 4 ).

states in the

more than one million holes have been drilled in search for oil and gas.

and short distances. In those states,

According to Newport (1977)

for oil and all other contamination hazards associated with the oil and gas

industry

are

,

this

major

contributors to salt-water intrusion in the inland part of the United States. Contamination hazards associated with the oil and gas salt water that is

produced with oil and gas.

with every barrel of oil in 1961

produced

( McMillion,

In Texas, 1965 ).

industry stem largely from the huge amount of

approximately 2.5 barrels of

Miller

(1980)

salt water were

produced

estimated that 4 barrels of salt water are

with every barrel of oil. Others estimate ratios of salt water to brine of up to 20:1, with ratios

generally increasing

as the

production of oil from

a

field decreases. In 1956, salt

the United States totaled 125 million tons, which is equivalent to

approximately

discharge in the United States (Thorne and Peterson, 1967). The total increases with time, as documented and more recent data

by early data reported by

reported by Michie

& Associates

Collins

(1988) (22

production

at oil fields in

one-half of the stream

amount of salt-water

(1974) (7.7 billion

billion barrels in

production

barrels per

1986).

year)

Production data

for 1963, listed state-by-state in Table 8 (Miller, 1980 ), identify Texas, Kansas, and Oklahoma

as

the three

Table 8. Methods of disposal of produced oil- and gas-field brine in the United States during 1963 (data from Miller, 1980 1980).). Current volumes State

produced

Alabama

Injection Injection water flooding disposal only

2,493

Arizona

_

Lined

pits

pits

Disposal Streams

_

Other

methods

603

539,132

89,082

340,734

California

2,740,850 202,194

445,768 131,500

208,665 5,000

Indiana Kansas

3,127 70

7,444

101,871

399,933 65,624

501

1,682,855

876,712 50,960

14,724

800,000

Montana

340,079 50.000

40.000 10.000

Nebraska

121,907

17,329

7,567

97,011

356,624

55,176

165,423

136,025

31.000

23,500 3,160,577

Pennsylvania

3,751,911 191,780

South Dakota

68

Kentucky Louisiana

Michigan Mississippi

Nevada

73,973 184,000

1,800 2,740

8,219

9.600 5,480 698,000

5,480 141,000

982

756

74,329 8.600

13,699

(A)

New Mexico New York

(A)

North Dakota Oho

2,785,000 149,587

982

15,132

4.200.000 35,616 1.762.000 147,849 203,836 31,400

5,011,400 123,287

7,500

(A)

Oklahoma

Texas Utah

West Virginia

583,280

5,370

2,685 191,780 68

6,127,671 81,634 115,068

2,736,755 2,981

23,682,022

7,821,601

1,472,954

1,262,719 4,862

615,566

39,677 73,790

115,068

Wyoming (A) Totals

(A) Brine

data not available;

pollution (B) (C)

Georgia (A) 876,712 81,797

brine

(B) (C) (B) (B) (C)

600

600

Illinois

Documented

100

Arkansas

Florida

Unlined

493

1,397

100

Colorado

Surface

(B) from Miller, 1980; (C)

9,182,173

see section 3.4.5

21,326

2,796,587

1,030,869

2,829,471

(B) (C) (B) (C) (C) (B) (C) (B) (C) (C) (B) (C) (B) (C) (C) (C) (B) (C) (B) (C) (C) (B) (C) (B) (C) (B) (C) (C) (B) (C) (C) (B) (C) (C)

largest producers

in the country,

making up more than

volume of brine

disposal

barrels per

Of this, 42 million were

injected

day.

50 percent of the total production. In 1986 the total

at oil and gas fields in the United States amounted to

injected

into

oil and gas formations, 17 million were

producing

an

underground

source

of

drinking

water is not present (primarily in the

San Joaquin Basin of California) (Michie & Associates, 1988 ). Assuming concentration of 50,000

mg/L in those waters, the disposal equals

Contamination of

ground

on the

disposal

percolated

method. Surface

disposal

and brine

ponding

high potentials

Texas, Louisiana, and California, where the largest amounts of brine to Miller

The

following

potential

ground. of this

produced

hazard is

in unlined surface

pits

highly have

of fresh-water contamination in

were

disposed of by this method

(1980) at least 17 oil-and gas-producing states (Table 8 ) have experienced ,

water pollution from disposal of oil-field brine, with time or another in all

into the

disposal

between brine and fresh water. This

mixing

been used widely in the past, which may have caused

(Table 8 ). According

conservative average TDS

water and surface water can occur where the

water is done in a way that allows

dependent

a

a total salt load of 8.6 million metric tons

into surface waters and of 5.8 million tons per year

deposited

per year

ground

60 million

into salt-water formations, three million were released into surface waters, and two million

percolated into the ground where

one

approximately

oil-producing

a

high

likelihood that contamination has taken place at

states.

sections will describe mechanisms that allow

mixing of oil-and gas-field brine with fresh

water.

3.4.1a. Surface disposal

Discharge of oil-field waters into coastal waterways, bayous, estuaries, and lakes

directly pollutes

will also occur.

to contaminate surface waters and

contaminating the

vadose zone and

At earlier times with little

Spillage

leakage through

from

disposal

( Krieger

post-oil-development

industry,

of the oil and gas

Kentucky,

increased from

potential

of

disposal

example,

pre-oil-development equal

chloride content in

levels of 10,600 tons in

to a 3,000 percent increase

of brines onto the land surface has caused

kill" areas in many old oil and gas fields in the past, and may still be a cause of serious

degradation of surface and ground water evaporation pits

were

could be reduced the Texas

has the

has the

the often indiscriminant disposal of

levels of 305,000 tons in 1959, which is

and Hendrickson, 1960 ). Indiscriminant

"vegetative

pit

drilling pits

ground water underlying the pit.

regulation

the Green River at Mundfordville,

and

the bottom of a

brines into surface waters caused severe contamination in many areas. For

1957 to

streams, creeks,

surface waters. Where these surface-water bodies are interconnected with

ground water, ground-water pollution potential

or into inland

introduced

by evaporation.

High Plains,

as a

As

as a result of

way of brine a

leaching. In

disposal

an effort to reduce water

pollution,

under the premise that the volume of brine

consequence, during 1961 alone, within the

more than 66 million barrels of brine were

disposed of

on the

Ogallala outcrop

of

surface, primarily in

unlined surface pits (Burnitt and others, 1963). This represented approximately 55 percent of that year's total brine production in the 500,000 acre-ft of brine communal

were

area. From a

single

oil field in Winkler

into

a

multitude of

point-contamination

mi2

an area of 13

were

disposed of in unlined pits

years of pit use, it was eventually realized that most of the disposed of

some

brine did not evaporate but infiltrated instead into the

Ohio,

or

disposal lake (Garza and Wesselman, 1959 ), adding millions of tons of salt to soils and causing

in 1969 ( Rold, 1971 ). After

a

more than

disposed of between 1937 and 1957 into unlined surface pits

contamination of local water wells. In Colorado, 27 million barrels of brine

creating

County, Texas,

was affected

the often porous

ground through

sources of brine. For

by brine pollution only

in the

example,

vicinity

of

pit bottom, Cardington,

three years after the first successful oil well

had been drilled. Disposal of brine into surface pits and indiscriminant surface dumping of salt water by contract truckers was the

pollution,

an

major

cause

of this contamination (Lehr, 1969 ). As

entire well field had to be abandoned. Similar uncontrolled surface

a

consequence of this

discharges were reported

by Baker and Brendecke (1983) in Utah, where water haulers may dispose of brine into unlined trenches, surface

depressions

on

undeveloped land,

Release of salt from soil

or into roadside ditches.

underlying former disposal pits can

affect

ground water for long times

and in

repeated plumes. Cyclicity of salt release from the soil is caused with every precipitation period that flushes salt from the vadose under

some

others under Texas

(Cl

pits a

even

pit

zone

into the saturated

(Cl

of 36,000

of 20,750 mg/L after 20

disposal pit in

This

many years after their abandonment,

in Ohio

concentrations return to

zone.

background

mg/L after 8 years) years).

Even

levels. Contamination of

southwest Arkansas covers an area of

as

and

longer

causes

extremely high salt concentrations

measured by Pettyjohn (1982) among

by Richter and others (1990)

time

ground water caused by an

area, Oklahoma.

Disposal pits

soil and ground water,

that have been used for only

especially

if

large

area

pit in

unlined surface-

mile and is estimated to last

for another 250 years ( Fryberger, 1972 ). The Oklahoma Water Resources Board

mi2

a

will be needed to see salt

periods

approximately one square

will take more than 100 years to flush all the salt from a 9

under

(1975 )

estimated that it

contaminated by pits in the Crescent

relatively

short

amounts of brine have been

periods

disposed

also

can

contaminate

of. For example, Lehr

(1969) reported contamination of ground water from two pits at Delaware, Ohio, which had been used for

only

15 months,

disposal,

during

which

chloride concentrations in

to more than

had received more than 225,000 barrels of brine. As a result of this

ground water increased from background

35,000 mg/L. A single pit

estimated that

one

pit caused

northeast Colorado. This 7 ft of

they

a

can cause

ground-water deterioration

on a

pit had

received

only

200 barrels of brine per

local fresh-water

aquifer ( Rold,

day

1972 ).

wide scale. Rold (1971)

but had been excavated into

1971 ). The amount of fresh water lost

to this kind of salinization can be substantial, such as in the case of Miller

disposal

mg/L

27 ppm per year salinity increase in the Severance ground-water basin of

gravel that directly overlay the

seepage from three

levels of less than 10

areas contaminated

approximately

60 million

County,

Arkansas, where

gallons of fresh water (Ludwig,

Often, highly These fluids are after

properly

360 million

saline fluids are also used in the oil and gas

temporarily

has been

drilling

ft3

stored in

pits

industry during

the

of boreholes.

drilling

and can cause fresh-water contamination if not

completed. Murphy

and Kehew

of brine have been buried in shallow

pits

(1984)

estimated that

in North Dakota

disposed

of

approximately

during pit closure, causing

variable degrees of soil-water and ground-water contaminations locally. 3.4.1b. Injection wells

Injection occurs in the

potentially

of salt water is done either for enhanced recovery or for brine

producing formation,

usable

however,

a

( Fig. 45 )

are

ground

hydraulic

water

which

typically

is not a fresh-water

(TDS 6,500

Classification

8-15 >15

Figure 56. Increase in TDS concentration in the Arkansas River alluvial flow (from Hearne and others, 1988).

aquifer as a result of irrigation-return

Figure 57. Use of Stiff diagrams for identification of water-quality changes as a result of agricultural activities: (a) (b) background water quality; (c) water affected by agriculture (from Denver, 1988).

whereas other trace elements, such as arsenic, cadmium, chromium, copper, lead, mercury, nickel, and zinc occurred below detection limits ( Waller and Howie, 1988 ). The

impact

experimentally by

of

flow on surface-and

irrigation-return

Law and others

(1970).

increases in TDS of between 8.5 and 32.2 the degree of change

being

ground-water quality

Surface-return flow after three

change between the June 28 and the July 18 irrigations ( Fig. 58a )

irrigation periods

irrigation applications.

was caused

which salt accumulated in the soil. The salt was dissolved and carried away with the

causing only water as

quality

slight

a

July

the irrigation

18 and the

season

Increases in soil

18

August

TDS increase in runoff after the third

is not reflected in water

percolating through

irrigation ( Fig.

the simple

and

by the relationship

between the

higher, up

18

July

a

to

irrigation.

A rain

alternating change

in

gradual TDS increase

twentyfold at

nonirrigated

and the

seen for sodium and

occurrences

are

a

depth of 18

to 24

associated with downward

of sodium and chloride with

depth ( Fig.

59b ). The

irrigated profiles was caused by salts brought in

by evapotranspiration. Sulfate, calcium,

depth relationship

( Fig. 59c ). Natural

by a dry period during

58a). This

the soil, as indicated by

at this site are many times

of salts, as shown

by the irrigation

The large

progresses ( Fig. 58b).

salinity

magnitude of difference

showed

in contrast, removed soil salts,

irrigations,

inches, than increases under nonirrigated land (Fig. 59a ). These increases

displacement

investigated

percent above irrigation-water concentrations ( Fig. 58a ), with

related to weather conditions between

event of 1.6 inches between the

were

and

magnesium

concentrations don't follow

chloride, but instead exhibit three significant peaks

and the solution of gypsum in the soil may control this distribution with

depth. The chemical of

an area.

For

composition of irrigation-return water reflects

example,

in the Yakima

Valley

of

local conditions and the

sodium and chloride concentrations show

Washington,

= 4.4;

higher net increases between applied irrigation water and outflow drainage (Nain/Naout 6.5)

than

magnesium

and sulfate concentrations

(MginMgout

Seabloom, 1963). The overall increase reflects drainage of because of

previous irrigation practices (Utah

irrigation history

=

2.0;

Clin/Clout

=

SO4in/SO4tout = 3.6) ( Sylvester and

an area

formerly waterlogged

and saline

State University Foundation, 1969 ). In the Grand Valley of

Colorado, in contrast, net changes between inflow and outflow show large increases in magnesium

(Mgin/Mgout = 11.4) Naout

=

2.5),

replacement minerals

(SO4in/SO4out = 10.8), a relatively small increase in sodium (Nain/ decrease in chloride loads (CIin/CIout = 0-6). This net change is due to

and sulfate

and even

a

of formation water in salt-rich shales and to reactions between

( Skogerboe and Walker,

Irrigation

and

water and soil

1973 ).

petroleum production

of south-central Kansas.

irrigation

account for ground-water deterioration in the

Irrigation-affected ground water is

characterized

High

by increased

Plains

Aquifer

concentrations of

calcium, magnesium, potassium, fluoride, and nitrate, whereas ground water affected by oil-field brine is characterized

by increased concentrations of TDS, sodium,

and chloride

( Helgeson,

1990 ).

Figure 58. Salt content in (a) irrigation water and irrigation runoff and in controlled irrigation experiments (from Law and others, 1970).

(b)

soil

during

and after three

Figure 59. Relationship between (a) TDS, (b) Na, Cl, and (c) Ca+Mg. SO4 and depth in soil under irrigated nonirrigated land. Downward displacement of salts occurs under both profiles, with differences in magnitude caused by salts brought in by irrigation, by evapotranspiration, and by the natural occurrence of gypsum in the soil (from Law and others, 1970).

and

3.5.4.

Parameters

Significant

Degradation

of ground-water

transport of chemicals, such waste water from animal return flow is the most

quality by agricultural

time,

important

reflecting

source

of

local conditions.

soil minerals

original

waste and

farms, and (c) irrigation-return flow. With respect to ground-water salinity, irrigation-

degradation. Evapotranspiration

are

and

leaching

components in drainage waters from irrigated

chloride and sodium concentrations show the

as

solution and

by (a)

herbicides, pesticides, and fertilizers, (b) disposal of animal

as

accounts for increases in most chemical

in some areas,

activities can be caused

highest increases, although parameters in

Significant

Typically,

areas.

other constituents may be

high

flow may change

over

irrigation-return

dissolved in the initial irrigation stage of

of soil minerals

an area

and minerals brought in by

irrigation water are dissolved in subsequent irrigation phases. A

significant parameter that differentiates agriculturally induced contamination from other salinization discussed in this report is nitrate. In agricultural areas, nitrate concentrations are often above

sources

background

values. Salinization associated with other sources, such as sea-water intrusion

or

oil-field

pollution, in contrast, is typically associated with increases in chloride, sodium, calcium, and magnesium concentrations and with small

3.5.5.

NO3/CI ratios.

State-by-State Summary of Agriculturally

The

following

associated with

magnitude

section

provides

summary of some of the

complete

but should serve as an overview of the

supplies

quality

has been

in

deep

and shallow

deleteriously

90 percent of all water

aquifers

affected by

consumption

that are

recharge

case where

of

in the state

(Sabol

and others,

Colorado River at Hoover Dam

caused

aquifer

irrigation-return water containing high contents of dissolved

depth to ground water is

contributed by

hydraulically

irrigated agriculture,

Basin of southeast Arizona, dissolved-solids concentrations in the alluvial result of

water-quality problems

problem.

Arizona: Ground-water

approximately

state-by-state This list is not

agricultural practices.

of the

surface water

a

Induced Ground-Water Problems

less than 100 ft

connected with

which accounts for

have increased

salt. This is

(Kister and others, 1966). Of the total

(9 million tons annually),

it is estimated that

In the Willcox

1987).

deterioration in the Wellton-Mohawk

Irrigation

and

especially the

salt load in the

approximately 37 percent

irrigation-return water (Jonez, 1984). Recycling of ground water for irrigation

water-quality

as a

Drainage

are

purposes has

District

(Effertz

and

others, 1984). Arkansas: As a

irrigation

general rule, approximately

is consumed and 25 percent returns to

75 percent of the

ground

aquifer systems (Holland

water removed for rice

and

Ludwig,

1981

).

Water-

quality deterioration from irrigation-return water has occurred along the Arkansas River (Scalf and others,

1973).

California:

Riverside,

is extensive

Agriculture

throughout

most of the Central

Valley, parts

of Imperial,

and San Bernardino Counties, and many coastal and Southern California counties

(Lamb

and

Woodard, 1988). Ground-water contamination by pesticides is widespread throughout these areas, indicated by a

(31 percent)

monitoring

were

survey of water wells from 1979

through

as

1984. Of 8,190 wells tested, 2,522

contaminated by pesticides (Lamb and Woodard, 1988). In the San Joaquin Valley,

selenium concentrations in agricultural drainage waters

are

high, exceeding 1 mg/L in

places

some

( Deverel and Gallanthine, 1989 ).

Approximately 32

million

gallons of

fresh water are used

(Miller, 1980 ). Irrigation water contributes

an average of

and Peterson,

the San

Joaquin Valley (Fuhriman and Barton,

and the Salinas Basin Colorado:

aquifer,

irrigation-return

(TDS

as

much

Irrigation-return

the San Luis

aquifer (Hearne

of the southern basins, such

1,000 mg/L)

as

as

water than

1988). Generally,

of excess

irrigation in

irrigation water and seepage

into the river

(Skogerboe

much as seven

times)

year)

increase in mineralization of surface and and others,

per year

reported from

ground

much

as

million

causes

2,500 mg/L)

1984 ).

ground

water in the

High

Plains

and the Arkansas River alluvial

aquifer,

water appears to be more affected

Valley,

insufficient

by

drainage

of

1900’s (Siebenthal, 1910 ). Approximately

early

Valley of western

Colorado. This contribution is

irrigation canals dissolving

irrigation purposes

(TDS as

Geological Survey,

and Law, 1971 ; van der Leeden,

for

has been

acre

of the total salt load in the Upper Colorado River Basin is

the Grand

from

saltjper

1984 ). Irrigation-return water also

Platte alluvial

shallow

saline soils had led to land abandonment in the 37 percent (700,000 to 800,000 tons per

irrigation

water. In parts of the San Luis

deep ground

attributed to saline flow from

result of

waters have caused TDS increases in

Valley aquifer system, the South

and others,

1.18 tons of

in the Ventura Basin

(U.S.

and livestock in California

imported irrigation water adds nearly 2

1971 ), where

Geological Survey,

tons of salt to soil and water each year (U.S. some

approximately

1967). Degradation of ground water as a

(Thorne

TDS increases in

daily for irrigation

1975).

The

salts and

repeated

a

result

subsequently discharging use of surface water

(as

within a 65-mi stretch from Denver to Kuner caused an

ground

water in the South Platte River

Valley (van

der Leeden

1975).

Irrigation

and feedlots contribute to

ground-water contamination

nitrate concentrations from animal waste

or

in Weld

fertilizer leachate have been

County ( Rold,

reported along

1971 ).

Black

High

Squirrel

Creek, the High Plains aquifer (Hearne and others, 1988), and in the San Luis Valley aquifer ( Edelmann and Buckles, 1984). Delaware: Coastal Plain nitrite,

aquifers

have been affected

from

farms

especially downgradient

problem

poultry

(Ritter

areas are located in Sussex and Kent Counties

background

levels as a result of

(Denver, 1988).

agricultural

by agricultural nutrients, and Chirnside,

(Denver, 1988).

1982).

such as nitrate and Most of the known

Other constituents above

activities include chloride, calcium, sodium, and

potassium

Florida: Of all the eastern states, Florida uses state’s rainfall is concentrated within crops

more or

heavy

use

a

by far the

most water for irrigation. This is because the

few months of the year, whereas the climate permits the

less year-round (Geraghty and others, 1973). Associated with long growing

of pesticides, which has affected

more

growing of is the

seasons

than 1,000 public and private water-supply wells (Inwin

and Bonds, 1988). In Dade

and

County, storage

concentrations of ammonia,

dumping

potassium,

and

of

agricultural

chemicals contributes more

organic nitrogen

in

severely

to high

ground water than does the application

of

these chemicals onto fields ( Waller and Howie, 1988 ). Illinois: It is estimated that 97 percent of all rural-domestic water systems

aquifers (Voelker and Clarke, 1988). These shallow aquifers

are

are

supplied from shallow

especially vulnerable

to contamination

by

irrigation-return waters. Kansas:

Irrigation-return

flows have caused increased concentrations of calcium, sodium, sulfate,

and chloride in

ground water of

north-central Kansas

Montana:

throughout

Agricultural practices

most of the state

contribute to the also

(see

ground water (Spruill, widespread

1985 ).

occurrence of

chapter 3.6). Irrigation-return

concentrations of nitrate have contaminated water wells in Rosebud

dryland

saline seep

flow with sometimes

County (van

high

der Leeden and others,

1975). Nebraska: Increased usage of

irrigation water may

Blue River Basins, the western parts of the Counties ( Exner and

Spalding,

Nevada: Contamination

irrigation-return water,

lead to future

in the

problems

Blue and Little

Big

Republican

River basin, and most of Box Butte and Holt

agricultural

sources in Nevada are caused

1979 ).

potentials

feedlot and

from

dairy-farm effluents,

and

agricultural

chemicals

by mineralized

(Thomas

and Hoffman,

1988). Large arsenic concentrations in ground water in parts of Churchill County have been traced to

irrigation-induced leaching of soils (Thomas and Hoffman, 1988). New Mexico: Ground-water connected with surface-water accounts for

problems

supplies

approximately 90 percent

have been

progressively in

(1,770 ppm), Texas, being nearly

(180 ppm), just below the Colorado-New Mexico deterioration from Oklahoma:

deleteriously

affected

a downstream

of

state line

irrigation-return

1970;

by about

van der

20 percent and in

percolating

are

hydraulically

by irrigated agriculture,

which

1987).

In the

(Sabol

and others,

direction, with the concentration

Bridge

( Fireman and Hayward, 1955). Water-quality Pecos River (Scalf and others,

1973).

waters identified several instances of surface and

ground-water deterioration. Compared with the quality of water applied, TDS increased

that

10 times the concentration at the Otowi

irrigation-return water has also occurred along the Investigations

aquifers

of all water consumed in the state

Rio Grande Basin, TDS content increases at Fort Quitman

in deep and shallow

soil water

by more

in

irrigation-water return flow

than 500 percent

(Law

and others

Leeden, 1975). Water-quality deterioration from irrigation-return water has occurred along

the Arkansas River

(Scalf and others, 1973).

Texas: In the Rio Grande Basin, TDS content increases a result of

TDS concentration at Fort Quitman, Texas,

irrigation-return flows.

the concentration at the Otowi

progressively

Bridge (180 ppm) just

in a downstream direction as

(1,770 ppm)

is

nearly

below the Colorado-New Mexico state line (Fireman

and Hayward, 1955 ). Water-quality deterioration from irrigation-return water has also occurred Pecos River

(Scalf

and others, 1973) where

some

10 times

wells in the

principal irrigation

along

areas of Reeves

the

County

have experienced significant increases in TDS (Ashworth, 1990 ).

Approximately considered saline in

parenthesis):

one million acres have been affected

(EC>4 milllimhos/cm).

Cameron

(275,000),

that

degree

Counties with more than 10,000 acres of saline soil are

Chambers

Jefferson

(350,000), Hudspeth (68,000),

to the

by irrigation

(20,000),

(10,250),

Culberson

Maverick

(44,000),

(10,000),

El Paso

Reeves

they

are

(acreage

(57,000), Hidalgo

(10,000),

San Patricio

(10,000), Ward (30,000), Willacy (10,000), and Zavala (50,000) (Texas State Soil and Water Conservation Board, 1984 ). Utah:

Irrigation-return water has caused

increased

salinity

of surface water in the Uinta River Basin

(Brown, 1984). In the Price and San Rafael River Basins of east-central Utah, irrigation-return flow led TDS increases from

(Johnson

and

River within

background

Riley,

stretch

area

irrigation wells

(Waddell

resulted in

and Maxell,

upward

and Peterson,

(Thorne

deterioration has occurred in response to

Enterprise

mg/L to contamination

levels of 2,000 to 4,000

mg/L

1984). The same process caused a TDS increase of 2,000 percent in the Sevier

200-mile-long

a

levels of 400 to 700

to

irrigation

1988),

1967).

Other areas where

ground-water

pumpage include the Pahvant Valley and the Beryl-

as well as the Curlew

movement of saline

Valley, where high

pumpage rates from

ground water from deep aquifers (Bolke

and Price,

1969 ).

Washington: Irrigation-return

flows with sometimes

high

contaminated water wells in the Odessa area and in Snohomish

concentrations of nitrate have

County (van

der Leeden and others,

1975). water in alluvial

aquifers

Rivers (Wyoming Department of Environmental

Quality,

Wyoming: Mineralized irrigation-return flows have contaminated ground

along

the Shoshone,

Bighorn,

and

Big Sandy

1986 ). 3.6 Saline

Seep

Salinization associated with saline seep is considered

agricultural sources because

of its

significance

in the Plains

separately

Region of the

from the

previous

section on

United States and Canada.

3.6.1. Mechanism

Saline seep nonirrigated

areas

was defined

that

by

Bahls and Miller

are wet some or

(1975)

as

"recently developed

saline soils in

all of the time, often with white salt crusts, and where crop

or

grass

production

is reduced or eliminated." It differs from salinization as a result of

the dominant salinization mechanism, that is, evaporation from

a

irrigation-return flow through

shallow water table accounts for high

salinities in saline-seep systems, whereas leaching of soil salts is the major mechanism that accounts for

high salinities in irrigation-return flows. Intensive studies of the saline-seep phenomenon in the United States have been restricted to the state of Montana,

even

the

though

problem

Northern Great Plains, saline seep causes loss of

more or

less

exists elsewhere. In many localities in the

productive farmland, impassable roads,

flooded

basements, stock deaths, and salinization of surface and ground water ( Custer, 1979 ). Conditions that favor

saline-seep development are widespread across the Northern Great Plains ( Fig. 6 ), covering an area exceeding 200,000 mi2 throughout most of North Dakota, approximately half the area of Montana and of South Dakota, and several Canadian

provinces (Bahls and Miller,

1975 ).

Several conditions have to be met for saline seep to develop, such as excess percolation of

recharge

water, soluble soil or

internally

drained flow system, and

creating

or

intensifying

natural vegetation and

drainage

as fallow

characterized

by optimal

environmental

changes,

cover

mostly

provides

low-permeable

a

ways (for example, by terracing of land),

adaptation

environmental

a certain

lost in monoculture

of

dry and wet periods

degree

of

systems.

protection

With

plant

characteristic of undisturbed systems is the efficient

significant

an

role in

by excessive irrigation,

periods.

plants.

This

A great

or

by

of water through the

spectrum of

diversity

adaptation

saline-seep development,

uptake

a

depths,

little water. Undisturbed ecosystems are

or hot and cold

to

play

covers that withstand a wide

to individual

regard

shallow

relatively

is often caused by destruction of

percolation

cropping or by planting of crops that use such as

unit at

activities often

evaporation. Agricultural

of these conditions. Excess

some

practices such

plant

aquifer minerals,

and

protection

the most

variety of

of natural is

important

natural

plants,

which prevents large increases in water-table elevation. Disturbed systems

are

uptake and allow

recharge the local ground-

a

greater portion of water to percolate through the soil and

to

often less efficient in

water flow system ( Bahls and Miller, 1975 ). Initial stages of saline seep are often indicated soil-surface wetness

following heavy

years of above average used up

steady

the

during

rains. Fallow areas can

undergo

spring precipitation (Miller and others, 1980). Although

growing

season, low stands of

increases in water levels over the

glacial till has been rising

an

previous

previous

years are

or

water will

move

occur

( Fig.

normally

Depending

on

not reached,

causing

years. In eastern Montana, the water table within the

average of four to ten inches per year (Bahls and Miller, 1975 ). Where the

60 ). A water table within three feet of land surface

up from this

during

some of this water will be

water table intersects or is close to land surface in response to these water-level

seepage will

by prolonged

a water-table rise of 1 to 15 ft

depth to the

surface

sodium-rich

as

1983 ).

along the flow path, water-logged or seepage

areas will be more or less saline. Minerals that are critical in salinization

pyrite,

signals potential problems,

by capillarity (U.S. Department of Agriculture,

the mineralogy of material encountered

the increased water table include

increases, water-logging

by excess percolating water and by

clays, carbonates,

gypsum, sodium and

magnesium

Figure 60. Diagrammatic cross section of ground-water flow with saline seep in topographically low topographic position (from Thompson and Custer, 1976).

and in intermediate

areas

sulfate,

and nitrate

( Thompson

the soil but are dissolved and increases the An

transported

salinity of discharge

percolation and by creating during drilling when

a

a

this shale

layer is generally

the shale

layer occurs within overlying glacial

zone

by

excess

water table. The presence of a

recharge. Evapotranspiration

perched

water table is indicated

encountered within 70 ft of land surface (Thompson and Custer, 1976 ). Where 30 ft of land surface, the

potential

for

saline-seep development

is very

high.

till is thicker than 30 ft, water-table elevation has not yet reached land surface correlation exists between soil texture and seep

a

80 percent of all saline seeps in that state

Approximately

are

controlled

occurrence.

by low permeabilities

of fine and

soils (Neffendorf, 1978 ).

Seep water may be locally, not regionally, derived, response to

(recharge)

areas

is penetrated before passing through powder-dry shale, in Montana,

( Bahls and Miller, 1975 ). In Texas,

fine-loamy

discharge

bound to

depths increases the potential of saline seep by preventing deep

perched

saturated

to

normally

water in seepage areas.

at shallow

impermeable layer

Where the

and Custer, 1976 ; Kreitler, 1979 ). These minerals are

precipitation.

The size of the seep

area ( Bahls and

as

(discharge)

indicated by the rapid rise in static water level in area is

directly

Miller, 1975 ). Recharge and discharge

areas

other and small in size or encompass thousands of acres. Runoff from surface-water quality. For example,

some

related to the size of the

upland

may be relatively close to each

discharge

of the largest rivers of Australia have

areas can

seen a

greatly impair

threefold increase in

TDS concentrations within the 50-year period from the 1910's through the 1960’s because of saline seep

( Peck,

1978 ). In southern Australia,

affected

saline seep as a result of

by

ha of

approximately 430,000 clearing

the

previously productive

indigenous vegetation

for

farming

farmland

are

purposes ( Peck,

1978 ). In some instances, saline seep is mistaken for oil-field

pollution

or for saline water

emerging

from

great depths along geologic structures. Characteristics that positively identify saline seep include during drilling,

wet material is encountered above a

rapidly

to

precipitation,

the water table reflects

local ground water rather than deep

recharge

areas

dry substrate, the static water level in saline seeps responds

ground

is typical for shallow,

topography, ground-water chemistry water, and changes in drainage

or

cropping practices

in

affect the size of seepage areas (Custer, 1979 ).

3.6.2. Water Chemistry

During

a field check of seep

conductivities

were

salinities, Custer (1979) noticed that seeps with low specific

most often associated with sandstone units

sandstones, whereas seeps with high specific conductance The increased salt content in the shale units

weathering

of

pyrite,

(up

or

were associated most often with shale units.

to 60,000 micromhos at

solution of carbonates and sulfates, and cation

1976 ). Oxidation and dissolution of

pyrite

creates

colluvium derived from nearby

acidity that

25°C)

is derived from the

exchange (Thompson

becomes available for

and Custer,

hydrolysis

reactions

and solution of carbonates

(Donovan

and others. 1981) and often leads to

in ground water. Breakdown of chlorite, illite, and

contributes

feldspars

high

selenium concentrations

Mg, K, Na,

and

SiO2

to seep

waters, which makes for a strong correlation between these constituents and TDS. Sodium is also derived from adsorbed

in smectites

positions

through exchange

(Donovan and others, 1981). Gypsum dissolution may be water with

(Miller

one

involving hydrogen

of the most dominant

and calcium ions

leaching

processes in

good correlation between SO4 and TDS ( Fig. 61 ). These chemical reactions produce

remarkably uniform water waters in

reactions

recharge

areas

and others,

chemistry

to

1980).

in Montana, from low-TDS (1,500 to 3,000 mg/L),

high-TDS (4,000 to 60,000 mg/L), Na-Mg-SO4 type

Sulfate concentrations of up to 33,000

mg/L

water in

Ca-HCO3 type discharge

salinization leads to

supersaturation

with

respect

many seep-water systems ( Fig. 62 ). Chloride concentrations are

constituents, such

as

most other

Saline-seep waters a dominance in

exception

normally relatively and Ag,

low but minor and trace

are

relatively high,

which

naturally saline ground waters (Bahls and Miller, 1975 ).

in parts of northeastern North Dakota differ from most seep waters in Montana

Mg-CI type

as

of

to calcite, dolomite, and gypsum in

NO3, Al, Fe, Mn, Sr, Pb, Co, Zn, Ni, Cr, Cd, Li,

distinguishes them from

areas

have been reported from test

holes in seep areas in the Fort Benton area, Montana ( Bahls and Miller, 1975 ). With the

recharge waters,

a

opposed to Na-SO4 type ( Sandoval and Benz,

1966 ). A

by

absence of

general

gypsum accounts for the low sulfate concentrations in those waters, which reach TDS concentrations of up to 34,000 ppm. Water-table elevations in salt-affected areas range from 1.5 to 5 ft ( Sandoval and Benz, 1966). Waters associated with saline seep in Australia are

Na-CI type, in contrast to

generally of the

saline seep in North America ( Peck, 1978 ). Oceanic salts found in rainfall may be these solutes

frequently

identified the minerals Loeweite

Major

chemical processes

figure

63.

occur on the

ground

operating

and Custer

at seep areas.

in saline seep

(1976)

used

Thompson

systems

Ca-HCO3

chemical below

waters

changes,

(Fig.

such as ion

dryland-farm

triangular diagrams (modified Piper diagrams)

exchange, involving Ca in Rapelje,

(Na2SO4).

Stillwater

recharge

areas to

County,

is of the

oxidation of

pyrite,

processes like

solution of carbonate minerals,

leaking

displaying

Na-Mg-SO4 type, with

discharge

the water and Na on soil

for

particles.

areas induces

Ground-water

Na-Mg-Ca-SO4 type,

concentrations of about 9,000 ppm (Thompson and Custer, 1976). Rock weathering is the

including

(1976)

Seep

64). Ground-water flow from

sites near

dissolved constituents,

of

and discussed above are summarized in

chemical characteristics of seep waters in Montana. These waters are typically of the some

and Custer

at several locations, Thenardite

(Na12M97(SO4)13) and,

3.6.3. Examples of Geochemical Studies of Saline

Thompson

important

dryland

source

and Gailitis, 1976 ; Peck, 1978 ).

(Hingston

White salt crusts

an

with TDS source

of

of formation water rich in sodium chloride,

exchange of calcium for sodium on exchange sites,

and

Figure

61. Correlation between

SO4

and TDS concentrations in seep waters from the Colorado Group, as the major contributor to salinity (from Donovan and others,

Montana, suggesting gypsum solution 1981).

Figure 62. Relationship between saturation states and salinity in well waters affected by saline seep, north-central Montana. Seep salinization typically leads to saturation with respect to calcite, dolomite, and gypsum (from Donovan and others, 1981).

63. Summary of chemical and transport processes Donovan and others, 1981).

Figure

operating

in a

saline-seep system (from

Figure 64. Modified Piper diagram of chemical composition of ground water in saline seeps, Montana. Seep water typically is of a Na-Mg-SO4 type as a result of sulfate-salt solution and ion exchange (from Thompson and Custer, 1976).

precipitation

of

calcium, sodium,

concentrations have been measured.

and

magnesium

Deep percolation

sulfate. Below cultivated of

recharge

water

land, high

during fallow

nitrate

years leaches the

nitrate into ground water. Below uncultivated land, in contrast, nitrate is absent in ground water and Custer, 1976 ).

( Thompson

Experimental leachates of cored material from seepage areas

areas

bear little similarity to actual saline-seep

(Donovan and others, 1981). Apparently, the chemistry of ground water is affected by underlying

bedrock

aquifer geology,

or

Ca/Mg

changes

the

dissolution and ion

laboratory. Gypsum constituents

which

to a

degree

that cannot be duplicated in the

are dominant processes

exchange

in some waters.

(Na, Mg, SO4)

composition

governing

bicarbonate concentrations and

High

ratios indicate that carbonate dissolution is additionally

an

the

major

roughly equimolar

important process in other

waters

(Donovan and others, 1981). High water tables and poor drainage conditions contribute of North Dakota. Ground-water

salinity of

type in moderately saline of a

areas. In contrast to

regional flow system

water from the Dakota

seep

areas in

sandstone, is the

weathering,

vegetation

but vertical

and others,

(Benz

and covered with white crusts, chemical characteristics are

quite

total salt content as well as sodium and chloride concentrations are contaminated areas than in

dryland

and

flow of saline

1961). pollution. Although

Rolling

Red Plains of Texas

being

the

void of any

different. In most instances,

appreciably higher

seeps. The difference in chemical

affected and unaffected soils in the Central

(Benz

Mg-Ca-SO4-CI

upward

soils are very similar, both often

seep-affected

Red River

salinity. This is indicated by the chemical similarity

source of

saline seep in Texas is often blamed on oil-field

visual appearances of brine- and

along the

Montana, this occurrence of saline water is part

instead of a local flow system; not

dryland

soils

in the most saline areas and of the

between Dakota Sandstone Formation water and seep waters The condition of

high salinity in

up to 40,000 ppm has been measured in some areas

Mg-Ca-CI-SO4 type

others, 1961). The water is of the

to

composition was

in brine-

between seep-

investigated by the U.S.

Department of Agriculture (1983 ). All major ions increase significantly in the soil within the upper few feet below seeps, A

reflecting evaporation.

variety

of salinization sources,

is known to occur in

and oil-field

pollution,

and others

(1990) developed

sources,

including

parts of

West Texas. In a

ground water (Cl

1,000

mg/L to

CIm =

»

1,500mg/L; Clp

50mg/L; CIs

■

(35,000-1,500)/(35,000-50)

The fresh-water

source

35,000mg/L

=

.96

=

is represented by 96 percent and the salt-water

is represented by 4 percent.

source

Step 2: Na^ with 0.96 ==»>

mixing water,

Y

«

=

-

600mg/L; Nap

*

155mg/L; Nas

-

22,000mg/L

(22,000-Y)/(22,000-155) 22,000

-

0.96*(22,000-155)

1,029

=

The theoretical sodium concentration in the mixing water is 1,029 mg/L; the actual concentration is

only 600 mg/L, however. Ion exchange may account for the loss of sodium, shows a

comparable gain to

application

of statistics

base and the nature of the

salinity

depends

required

of readily available statistical

as

another cation

to a

Techniques

high degree

on the number of observations in the data

information. For the purpose of this report,

techniques was attempted.

which is presented

Analysis,

long

its theoretical value.

6.2. Statistical

The

as

as one

The

exception

only

is made with

a

general

Stepwise

discussion

Discriminant

possible technique to identify useful parameters for identification of

sources.

Hem

(1985) pointed

procedures. chemistry

The

major

is needed to

out that the literature abounds with

reason for this

may be that

successfully apply

a

statistics

as a means

strong background

some of the more

water-quality studies. Generally, for investigation of

questionable applications

water

of statistical

in statistics as well as in water

sophisticated

statistical

techniques during

chemistry, Hem (1985) suggested the

use

of

of testing and verifying theories instead of simply creating theories from statistical

data. Statistical available.

techniques

are the most useful and

Simple averaging

or determination of

appropriate when

frequency

a

large data base of observations

distributions are

widely

used in

is

water-analysis

interpretation.

Both are

for identification of

a

good techniques

salinization process.

often given, which is then used to salinization

source.

in

establishing

Together with

the

an

background water-quality

average value, a maximum background value is

identify anomalously high

Frequency distributions

are used on

data often needed

concentrations caused by mixing with data bases to

large

identify

any outliers

or

a

to

determine the number of data populations that make up the total data set. Outliers may indicate

contamination, faulty analyses, from wells that

produce

result in more than one

or

data

from different

grouping

points

not

representative

of the rest of the data.

or from wells located in different

aquifers

of the data. This is

Analyses

geographic

derived

areas may

when sources of chemical changes are

important

investigated, because these data groups may be unrelated to each other. During mixing between

a

fresh water and

a

salt water, absolute concentrations vary to

whereas constituent ratios may vary relatively little. With only absolute concentrations will most often

provide enough

process, as concentrations exceed normal source is

present

and a

background

absolute concentrations may still suffice to

identify the

levels. If more than one

actual

identification of the

because of overlapping concentrations,

source

one

of

separation

depend on the composition of the

examining scattergrams

endmembers of salinization (for

of

highly

from sea-water intrusion (Fig. 35 ) show

chemistry.

When

plotting

scatter can be observed,

oil-field brines

as the concentration of a

or more

diluted

potential

mixing

sea

sources

waters. In such

of endmembers. Na/CI and Br/CI are two

(see also chapters 3.2

and

3.4),

but

individual endmembers involved.

potential

water, halite-dissolution brines, and oil-field brines), it

becomes apparent that some sources are more variable than others. or

salinization

ionic constituents versus chloride for various

major

example,

mixing,

true source of two

ratios that are known to work well in a number of salinization scenarios

nhen

potential

out. More often, however, absolute

in the case of

especially

cases, concentration ratios may have to be used for

which ratio works best will

present,

information for identification of the salinization

particular parameter may increase significantly and stand

positive

high degree,

source

difference in constituent concentrations exists between them,

significant

concentrations will not allow

potential salinization

one

a

relatively

tttle scatter,

together from

reflecting the different origins

Samples from

indicating

different areas

halite solution (Fig. 22 )

little variation in end-member

( Fig.

47), in contrast, much

more

and mechanisms of concentration of these brines.

From this it is apparent that differentiation between sea water and oil-field brines or halite dissolution and oil-field brines cannot be done constituents to be used for the

same manner as

the

using

chemistry

may be

ratios

distinguish

This technique

was

universal chemical constituent

or

constituent ratio. Instead,

between these brines will vary from one location to another in

of the oil-field brine endmembers

distinguishing

by trial and

provided by Stepwise

variables that

single,

differentiating

which constituents work best for

plotting or calculating

a

good separation

Analysis (SDA),

between two or more

One way to determine

between salinization sources in any

error until a

Discriminant

changes.

given

case would be

has been found. A more efficient way

which is a statistical technique that identifies

predetermined groups

of cases

(Dixon

and others, 1981).

used successfully by Hitchon (1984) to group formation waters in the Western Canada

Sedimentary Basin, by Hawkins

and

Copper

by Novak and

River Basin, Alaska, and

salt from brine

Motyka (1984)

identify the origin

to

Eckstein

(1988)

of mineral

determine those chemical constituents

or

between given groups of waters, such

oil-field waters and

as

in parts of the

to differentiate salt water derived from road

derived from oil fields in Ohio. In terms of water

samples

springs

constituent ratios that

chemistry,

can

be used to

useful for distinguishing

are most

sea water.

SDA

When dealing with contamination

of fresh water by salt water, the main mechanism changing the chemistry of the fresh water is mixing, which can a

also be considered as dilution of the salt water. In the case of dilution, absolute concentrations vary to whereas concentration ratios

high degree,

doesn’t

get

used in the In

using

a

little. Therefore,

generally

long

as

the solution

following

better tracers of salt-water sources than absolute concentrations and

discussion of SDA.

SDA, each predetermined group of samples consists of

a

number of chemical analyses made

variety of parameters, for example, major ions. Any parameter or, in this case, parameter ratio (for

example, Ca/CI, Ca/SO4, Mg/CI, etc.) that is specified will be used during values

as

too diluted and doesn't take on the ratio characteristics of the uncontaminated water,

concentration ratios are were

change relatively

representative

a linear function

example, Ca/CI)

of each group. The difference between the groups of interest is then expressed in

using

the differences between the group means of each

incorporated

analyses in

into this equation first.

each group will be

cases, some of the

analyses

difference between the to their

given

will be

groups

determined variable into the

equation.

until a maximum number of

analyses

improvement Depending

in

assigned

groups. In the next

preassigned

groups that are

similarity

relatively

members into the

to the

step,

mean

The ratio

(for

most distinct between

this step a certain percentage of the that is, parameter

of the opposing group. However, in most

opposite

depending

group,

SDA will attempt to

by incorporating

on the

degree

of

the

remaining

another ratio in combination with the

previously

correctly assign

The addition of ratios (variables) will continue in successive steps was

sample assignment can

on the

During

are

assigned correctly to their preassigned groups,

ratios are closer to the respective group mean than to the

analyses

parameter.

that best separates the groups, that is, for which mean values

the two groups, is individual

a SDA run to calculate mean

assigned correctly

be achieved

to its preassigned group and

by incorporating

additional ratios into the

no

further

equation.

between the groups, any amount of ratios will be determined, that is, two

similar may necessitate inclusion of many ratios for

assigned groups, whereas two very different groups

or two ratios. The variables determined

by SDA can then

may be

be used for further

To illustrate the usefulness of SOA for identification of ratios that

separation

of their group

distinguishable by just one

study.

distinguish

between

given

groups,

several data sets of water chemistry were compiled from the published literature. Data sets include oil-field

brines, halite-solution brines, sea-water intrusion samples, and ground water. Chemical analyses

grouped according ratios that best

(Table

to brine type and location and then used in a

separated these groups.

variety

were

of combinations to determine

Ratios used were those identified as useful in salinization studies

12 ) and for which dataware available

(Ca, Mg, Na, K,

HCO3, SO4, CI, Br, and I): scenarios tested

(a)

were

oil-field brine versus oil-field brine,

versus halite-solution

(b)

oil-field brine versus sea-water intrusion,

a known case of

brine, and (d)

(c)

oil-field brine

ground-water contamination by oil-field brine. The

SDA software used in the following example is part of the BMDP software package, which is commercially available from the license holder to be SOA was

representing

performed

mainframe computers

run on

all 15 possible combinations between any two of six oil-field brine groups,

on

brines from Texas, Louisiana, California, Oklahoma, Ohio, and Canada.

ratios selected

each run, Ca/CI,

during

identified (Table 15 ). It is

probably

Mg/CI, Na/CI, Br/CI,

that the other ratios may be useful Solution of halite water of

local can

samples

same

and I/CI were the ones most

type (oil-field

only on a site-specific

frequently

and sea-water intrusion

(chapter 3.2)

or

in other areas and

deep-basin brines)

basis.

(chapter 3.3)

each produce brine and saline

relatively uniform chemical character ( Figs. 22 and 35 respectively). Therefore, where ,

from sea-water intrusion or halite solution are not

be used as

Among the first three

reasonable to assume that combinations of these ratios will also provide

good separation power between brines of the

ground

PC’s.

or

hypothetical

readily available, samples from other areas

endmembers with reasonable accuracy. This was done for identification of

ratios that separate oil-field brine from sea-water intrusion brine in California, Texas, and Louisiana, and from halite-solution brine in Texas, versus

Pennsylvania,

oil-field brine, combinations of 7 (out of

a

and West

Virginia.

In the

possible 12) different ratios

of sea-water intrusion

cases were

determined

the best

as

four ratios in the three test runs ( Fig. 80), whereas in the case of halite solution versus oil-field brine, 10 ratios were identified

( Fig.

81 ). Some ratios appear again

as more

ratio in the case of halite solution versus oil-field brine, or the intrusion versus oil-field brine. It should be statistical point of view and not from is not

here that SDA determines ratios from

as

identifying

the source of

salinity

given to any

in water contaminated

variable determined

by any

through

Plotting of step ratios 3 and SDA logic,

as

these ratios

are

4 in bivariate

as

done in

Nevertheless, combining these ratios in bivariate plots

be used to

identify which

be done

graphically

endmember compositions group for their

potential

chapter 4 bicarbonate ,

more

by interactions ratio allows

the ratio may be of little

of these two sources. The same

as discussed in

figures

chapters 3.4,

and 4

.

80 and 81 does not follow the ,

can

support group separations. Once the

endmembers of salinization, these ratios can

endmember is the true source of

or

strictly

determined after and in combination with ratios determined in step 1 and in

ratios are known that best separate

can

plots,

samples,

a

statistical methods. In the case of Br/CI

ratios, geochemical considerations support the statistical evaluation,

2.

out in

its concentration is affected

between some oil-field brines and sea-water intrusion

consideration should be

step

ratio in the case of sea-water

aquifer material and CO2 with water than by mixing. Therefore, although the HCO3/CI

good separation in

HCO3/CI

geochemical point of view. As pointed

conservative constituent in ground water,

a

between

help

a

emphasized

useful than others, such as the Br/CI

salinity

in a contaminated

possibly then

ground

water. This

through the SDA feature of checking individual analyses for their similarity

(group means). First,

representativeness

SDA checks individual

samples within

to

each endmember

of that group, thus enabling the researcher to check the initial

Table 15. Listing of constituent ratios that separate best brines from Texas, Louisiana, Oklahoma, California, Ohio, and Canada, as determined through Stepwise Discriminant Analysis. Ratios were determined by individual runs of any combination between two brine groups, totaling 15 combinations between the six areas.

Sequence Sequence of Selection

Ratio

1,1.1.1.1,2. 2 1,1. 1.3.3 1,1,2

Ca/CI

Mg/CI Na/CI Br/CI l/CI

1.1.2 2. 3, 3, 3. 3, 3

HCO3/CI Ca/Mg

1.2.2

K/Br

1.3

Na/K

2. 3.3 2. 2 2,3 2,3

1.2

S04/(Na+K) Ca/Br

(Br/CI)/(Ca/Mg) SO4/CI

Na/Mg Ca/K C a/304

(Ca+Mg)/S04

2 2 3 3 3

Explanation: 1

2 3 *

Selected as the best ratio during any one run (step ratio #1), providing the single-most separation between two groups. Selected as the second ratio after step ratio #1 during any run, providing improved separation between two groups in combination with step ratio #1. Selected as the third ratio after step ratios #1 and #2 during any run, providing further improvement of separation in combination with step ratios #1 and #2, Of the 15 combinations between the six data sets, Ca/CI was selected five times as the first

step ratio and two times

as the second

step ratio.

Figure 80. Bivariate plots of ratios determined by applcation ot Stepwise Discriminant Analysis as the statistically best ratios to distinguish sea-water intrusion (sofid dots) from oil-field brines (open triangles). Ratios change according to the composition of oil-field brines, derived from (a) California (data from Gullikson and others, 1961), (b) Texas (data from Kreitler and others, 1988), and (c) Louisiana (data from Dickey and others, 1972).

Figure 81. Bivariate plots of ratios determined by application of Stepwise Discriminant Analysis as the statistically best ratios to distinguish halite-solution brine (solid dots) from oil-field brines (open triangles). Ratios change according to the composition of oil-field brines, derived from (a) Texas (data from Kreitler and others, 1988), (b) Pennsylvania (data from Poth, 1962), and (c) West Virginia (data from Hoskins, 1947).

If initial

grouping.

was done well and/or if the two groups are

grouping

member will be identified by SDA

as

distinct, each individual group

being representative of that group. If, however,

groups exists because of poor grouping and/or of chemical similarity, endmember may actually turn out to be the

mean

similar to the

more

some

an

overlap of

the two

samples within any

composition of the other group than

mean

to

composition of the originally assigned group.

This feature of SDA

apparently

contaminated

contamination a test case

(the

can

also be used to test individual group members of a third group (for

ground water) regarding

two groups for which

separating

their chemical

similarity

to

potential

example,

endmembers of

variables had been determined). This is illustrated with

of known oil-field pollution in Illinois, where salt-water disposal into pits and indiscriminant

dumping of brine has caused local ground-water contamination (Lehr, 1969 ). Considering oii-field brines from Illinois as one endmember of

(retrieved from STORET) Ca/CI

only

provide

mixing

and Illinois’

as the other endmember of

ground water with mixing,

chloride greater than 250

SDA determined that the ratios Na/CI and

the most separation power between the two groups, with Ca,

available parameters.

82a illustrates this

Figure

Mg, Na, SO4,

with oil-field brines

separation,

,

to the oil-field brine endmember than to the

were

identified by SDA

and Cl as the

generally plotting

lower ratios than most of the ground-water samples. Water samples from the contaminated >200 mg/L (data from Van Biersel, 1985 and Stafford, 1987)

as

area

being

area

were identified as

approximately 20 percent

water

samples

ground-water

similar to

ground water.

were classified as

endmember

( Fig.

being

At the same time,

having Cl 250 mg/L), Illinois oil-field brines (open squares; data from Meents and others, 1952), and ground water contaminated by oil-field brine (open triangles; data from Stafford, 1987 and Van Biersel, 1985 ). Ratios determined through the use of Stepwise Discriminant Analysis (SDA) effectively separate ground water from brines (a). Statistical evaluation of individual analysis using SDA identified all contaminated water samples and 20 percent of the ground-water samples (open dots) as more similar to brines than to ground water (b). ,

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