Hot-Spring Drainages of 

Yellowstone National Park

GEOLOGICAL SURVEY PROFESSIONAL PAPER 1044-F
Chemical Studies of Selected 

Trace Elements in 

Hot-Spring Drainages of 

Yellowstone National Park

By R. E. STAUFFER, E. A. JENNE, and J. W. BALL 

GEOHYDROLOGY OF GEOTHERMAL SYSTEMS

GEOLOGICAL SURVEY PROFESSIONAL PAPER 1044-F

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1980
UNITED STATES DEPARTMENT OF THE INTERIOR 

CECIL D. ANDRUS, Secretary

GEOLOGICAL SURVEY 

H. William Menard, Director

Library of Congress Cataloging in Publication Data

Stauffer, R. E.

Chemical studies of selected trace elements in hot-spring drainages of

Yellowstone National Park.

(Geohydrology of geothermal systems) (Geological Survey

professional paper ; 1044-F)

Bibliography: p. F18-F20.

Supt.ofDocs.no.: I 19.16:1044-F

1. Trace elements. 2. Geochemistry-Yellowstone National Park. 

3. Hot springs-Yellowstone National Park. 4. Yellowstone 

National Park. I. Jenne, Everett A., 1930- joint author. 

II. Ball, J. W., joint author. III. Title. IV. Series. V. Series: 

United States. Geological Survey. Professional paper 1044-F.

QE516.T85S76 551.2'3'0978752 79-607187

For sale by the Superintendent of Documents, U.S. Government Printing Office

Washington, D.C. 20402

Stock Number 02^-001-0329^-5
CONTENTS

Page

Abstract ________________________________ Fl

Introduction-__________________________________ 1

Acknowledgments ____________________________ 2

Sample sources ____________________________________ 2

Lower Geyser Basin _____________________________ 2

Yellowstone Canyon ______________________ 2

Madison River system _______________________ 3

Sampling methods _________________________________ 4

Analytical methods ________________________________ 4

Results _____________________________________ 5

Data reliability _______________________ 5

Pure analytical error_______________________ 5

Sampling errors _________________________ 6

Results—Continued

Statistical definitions ___________________— F7

Octopus and Azure Springs________________—_ 7

Oxidation and diffusion processes ____—-____ ——— 7

Precipitation reaction __________________ 10

Unnamed sulfide-bearing springs in Yellowstone Canyon — 11 

Madison River system ___________________— 14

Sorption controls on arsenic in geothermal waters _ ___ 15 

Arsenic flux of the Madison River_ ———————— —— ——— 17 

Potential ecological significance of arsenic ____________ 17

Conclusions ______________________________ 18

References cited ________________________— 18

ILLUSTRATIONS

Page

FIGURE 1. Sketch map showing rivers and major hydrothermal areas sampled in Yellowstone National Park, Wyo _____ —— _______ F3

2. Schematic diagram of Madison River and Yellowstone Canyon sulfide-bearing mixed spring systems and

sampling sites ___________________________________________ —— ———— ___ —————— —— ——— — __ 4

3. Physical and chemical parameters of two hot springs and their drainages __ ——— _-__ —— __________ —— —— ___ — _____ 7

4. Concentration factors of several parameters for two hot springs and their drainages ——— __ —— ——— __ —— _ ——— _- — 8

TABLES

Page

TABLE 1. Analytical precision of solute data ______________________________———______————— ——— _ ——— _______ F5

2. Chemical and physical parameters of Octopus Spring and its drainage-________——___ —— ———— —— — --——— 6

3. Chemical and physical parameters of Azure Spring and its drainage ------- —— —— ______ ——————— ______ —— ——— 7

4. Selected physical and chemical properties of additional hot waters _--_______-_-- — ——— __ — __ ———— __ —— __ — -- 11

5. Chloride, aluminum, iron, and manganese in selected geysers and hot springs ———_ ————— __ —— —— —— —— ———— 11

6. Chemical and physical parameters of Calcite and two other unnamed sulfide-bearing springs in Yellowstone Canyon

with the drainage of the mixed spring system _________________ — — __ — — ——— ——— — — — --- 12

7. Estimated solute losses following mixing in Yellowstone Canyon mixed spring and Madison River systems _ — __ — ___ 13

8. Chemical and physical parameters of the Madison River drainage.--__ ——— _________ ————— ________ ——— _ ———— _ 15

III

GEOHYDROLOGY OF GEOTHERMAL SYSTEMS

CHEMICAL STUDIES OF SELECTED TRACE ELEMENTS IN HOT-SPRING 

DRAINAGES OF YELLOWSTONE NATIONAL PARK

By R. E. SrAUFFER, 1 E. A. JENNE, and J. W. BALL

ABSTRACT

Intensive chemical studies were made of S(-II), O2 , Al, Fe, Mn, P, 

As(III), As(V), and Li in waters from two high-Cl, low Ca-Mg hotspring drainages in the Lower Geyser Basin, a warm spring system 

rich in Ca and Mg in the Yellowstone Canyon area, and the Madison 

River system above Hebgen Lake. Analyses were also made of other 

representative thermal waters from the Park.

Soluble Al concentrations were generally low (< 100 fj-gfL and frequently <50 fJig/L) except in Azure Spring in the River Group of 

Lower Basin (—500 A/.g/L). Approximately 90 percent of the Al was 

found to precipitate in the upper drainage channel and nonflowing 

satellite pool of Azure Spring and was accompanied by an 8 percent 

(250 Atg/L) loss of the Li flux.

Solute Fe and Mn concentrations were typically very low (<10 

fjig/L) in the alkaline high-Cl thermal waters. Soluble reactive P and 

total P concentrations were low (<2 fj-gfL as P) in all of the high-Cl, 

HCOi-buffered hot springs. The Firehole, Gibbon, and Madison Rivers contained 4 to 6 fj-gfL.

Total solute As acted conservatively in the alkaline drainages 

studied, including the Firehole-Madison River. However, the 

As(III)/As(V) ratio was strongly bimodally distributed (~50 or <0.1) 

according to whether dissolved S(-II) or O2 was dominant in the 

thermal water. Oxidation of As(III) proceeded rapidly at the elevated 

temperatures (30° to 90°C) in the drainages, but only following the 

oxidation of dissolved S(-II). In contrast to the Firehole River, approximately 60 percent of the thermally related As flux in the Gibbon River drainage basin is precipitated prior to the Gibbon's confluence with the Firehole at Madison Junction. The As/P atomic ratio is 

typically -500 for the alkaline hot-spring waters, and —15 during 

base-flow conditions on the Madison River. The differential toxicities 

of the As species, the variable As(III)/As(V) ratios, and the very large 

As/P ratios all suggest that As may be ecologically important in the 

Park's thermal waters.

INTRODUCTION

The trace-element chemistry of hot springs and 

geothermal drill-hole waters has attracted interest in 

the past because of the hypothesized relationships between hydrothermal solutions and base metal ore 

genesis (Barnes, 1967). Trace-element chemistry is 

also valuable in assessing both subsurface physicalchemical conditions and potential environmental impacts of geothermal commercial exploitation.

The principal solutes present in hot-waterdominated geothermal fluids, SiO2 , Na, K, Li, Ca, Mg, 

Cl, HCO3 , SO4 , F, and B, have been investigated in 

diverse geothermal settings throughout the world (Ellis, 1970). The concentrations of the prominent nonconservative solute species (SiO2, Ca, Mg, F, K) have been 

rationalized using mineral equilibria models (Ellis, 

1967, 1970, 1973). The rare alkalis, Cs and Li, and the 

metalloid, As, are regarded by Ellis (1970) as weakly 

conservative because they are sometimes partially precipitated in the epithermal zone. The elements Cl, Br, 

and B are considered highly conservative, once dissolved in the hot circulating water.

Ellis (1969, 1973) interprets the low levels of Fe, Mn 

and Al in HCO3-buffered hot waters as convincing evidence that solubility controls are acting on these 

geochemically abundant elementSv Sulfides of Fe, Cu, 

Pb, and Zn are being deposited at depths of 250 to 800 

m at both Waiotapu and Broadlands, New Zealand 

(Browne, 1969), from hot water containing up to 1.7, 

10, and 2.2 ju-g/L (micrograms per liter) of the latter 

three elements, respectively (Ritchie, 1973). Heavymetal mineralization at depth is largely absent at 

Wairakei, although some pyrrhotite (FeS) is found. 

The abundant mineralization at Broadlands is attributed to the high concentration (120 mg/L) of solute 

sulfide species, S(-II), in the effluent. At Wairakei, 

S(-II) is 12 mg/L, or about one order of magnitude 

larger than most of the values reported for Yellowstone 

(Thompson and others, 1975) or Steamboat Springs, 

Nevada (White, 1967). Spectrographic analyses of 

evaporated residues of typical alkaline Yellowstone 

thermal waters (Rowe and others, 1973) indicate levels 

of transition series elements comparable to New Zealand thermal waters (Ellis, 1969).

Greater than milligram-per-liter concentrations of 

Fe, Mn and Al commonly occur in "acid-sulfate-type" 

geothermal waters as a result of attack on the country

'Present address: Water Chemistry Laboratory, University of Wisconsin, Madison, Wisconsin 53706.

Fl
F2 GEOHYDROLOGY OF GEOTHERMAL SYSTEMS

rock by sulfuric acid (White and others, 1971). The sulfuric acid is thought to be derived from oxidation of 

S(—II) in the near-suface zone.

White (1967) noted that the semimetallic elements 

As, Sb and Hg are especially mobile in geothermal systems and are present at relatively high concentrations. 

Sb and Hg sulfides are epithermally deposited along 

with sinter at Steamboat Springs (White, 1967) and at 

Broadlands (Weissberg, 1969). Neither of the two 

prominent arsenic sulfides (orpiment, As2S3 ; realgar, 

AsS) was observed as a discrete mineral, either in the 

sinter or at depth in drill cuttings. However, As coprecipitated with stibnite (Sb2S3 ) as —5 percent impurity (Weissberg, 1969). Weissberg noted that Tl, Ag, Au, 

and Hg, in addition to As, were highly enriched in 

stibnite in the near surface at the Broadlands. Arsenopyrite in minor amounts has been ejected from a 

Wairakei drillhole. Weissberg (1969) estimated that 

less than 10~4 percent of the As flux from a Broadlands 

drill-hole discharge was precipitated with the amorphous silica, in contrast to 0.5 to 5 percent of the Sb.

Research on the thermally related fluxes of Hg and 

As into the Waikato River (Axtmann, 1975) was 

motivated by geothermal power development in the 

Taupo Basin, New Zealand. Elevated levels of both As 

and Hg were found in the sediments of Lake Aratiatia 

below the discharge of the Wairakei effluents. The macrophytic dominant in Lake Aratiatia, Lagarocipon 

major, featured an As concentration factor (over the 

Waikato River concentration of 39 /^g/L) of 5,300 

(Reay, 1973). However, because of the very large As 

flux in the Waikato (estimated at 158 metric tons/yr, 

Axtmann, 1974), less than 4 percent of the As entering 

the river system is removed by vegetation before discharge into the sea.

The attenuation of geothermally related trace elements in hot-spring drainages and receiving waters 

has apparently not been previously studied in the 

United States. Boylen and Brock (1973) and Zeikus 

and Brock (1972) reported chemical analyses of the 

Firehole River (Yellowstone Park, Wyo.) at stations 

selected to show qualitative influences of hot-spring 

influents on the river biota. Among the elements which 

can properly be thought of as geothermal trace elements, only PO4 data were reported and were seriously 

biased by an As interference (Stauffer, 1980a, b).

The present paper reports chemical studies of O2 , 

S(-II), Al, Fe, Mn, As, P, and Li in two hot-spring 

drainages in the Lower Geyser Basin, two warm-spring 

drainages in the Yellowstone Canyon, and the Madison 

River system above Hebgen Dam. The differential effects on the solutes of temperature, pH, and redox 

changes accompanying adiabatic cooling and source 

water mixing are examined using the conservation of

mass principle and employing statistical contrast with 

Cl as the prominent conservative geothermal tracer. 

Our use of ratio estimation involving Cl as a tracer 

follows the early initiatives of Ellis and Wilson (1960). 

The intensively studied thermal drainageways are also 

compared chemically with representative springs sampled in the Upper, Norris, and Mammoth thermal 

basins.

ACKNOWLEDGMENTS

The cooperation of the U.S. National Park Service in 

facilitating the sampling program for this study is 

gratefully acknowledged. The authors thank A. H. 

Truesdell for his help in collecting a set of samples in 

1973 and for many fruitful discussions with him; and J. 

M. Burchard and D.K. Nordstrom for assistance in 

sample collection and onsite analyses. Fluoride data 

were provided by D. K. Nordstrom. The authors acknowledge J. M. Thompson for analytical assistance 

and for his generous contribution of river samples for 

As comparisons, and John Hem and R.O. Fournier for 

helpful discussions.

SAMPLE SOURCES

LOWER GEYSER BASIN

The most intensive geochemical studies on hotspring drainages were on Octopus Spring (Marler, 

1973, p. 435), in the lower White Creek area, and 

Azure Spring (Marler, 1973, p. 574), in the River Group 

(Fig. 1).

Octopus Spring, with its long (—50 m) distinct drainage channel, relatively constant flow regime, easy accessibility, and luxuriant microbiological flora, is one 

of several sites in the lower White Creek area where 

the ecology of thermophilic blue-green algae and associated bacteria has been intensively studied by T. D. 

Brock and coworkers (Brock, 1967, 1969; Brock and 

Brock, 1966, 1967, 1968a, b, 1969a, b; Walter and 

others, 1972).

Azure Spring has a well-developed drainage channel 

—100 m in length discharging westward into the 

Firehole River. The hotter satellite pool on the southwest edge of Azure Spring's main pool was also sampled. Azure is one of a large number of springs in the 

River Group on which major chemical constituents 

have been determined (Thompson and others, 1975).

Sampling stations along the two drainageways were 

selected to correspond to — 10°C intervals in water 

temperature.

YELLOWSTONE CANYON

An unnamed sulfide-bearing spring was studied, 

which is 20 to '30 m vertically above the west bank of
TRACE ELEMENTS IN HOT-SPRING DRAINAGES, YELLOWSTONE NATIONAL PARK

111°00' 110°50'

F3

48°40'

48°30'

Cable Car

PARK COUNTY

TETON COUNTY

RIVERJ Gibbon Fa"s West Entrance

Yellowstone National Park I2 f

• 1

Firehole Falls

Azure Spring

Basin :±

River Group

Hot springs 

Geyser basin 

Sampling site Midway 

Geyser; 

Basin °o

Upper 

Geyser 

YELLOWSTONE Basin

NATIONAL PARK

SCALE 

4 6 8 KILOMETERS

024 MILES 

FIGURE 1.—Sketch map showing rivers and major hydrothermal areas sampled in Yellowstone National Park, Wyo.

the Yellowstone River, about 0.5 km south of Tower 

Falls. About 5 m below its source in a hillside fissure, 

the spring water (46°C) mixes with water from a cooler 

(14°C) spring (fig. 2). Below the confluence the mixed 

water runs steeply downslope until it encounters a relatively flat, poorly grained area, 5 to 10 m above the 

Yellowstone River. Samples were taken in both tributary spring drainages about 1 m above the confluence, 

immediately below the confluence, at the bottom of a

small riffle, at the base of the steeply dropping combined-drainage section, and at a point intermediate 

between the confluence and the base. Below station 5 

the drainage into the Yellowstone River was indistinct.

MADISON RIVER SYSTEM

Stations 1 and 2 are on the Firehole and Gibbon Rivers, respectively, each about 1 km above their confluence forming the Madison River. Station 2 is
F4 GEOHYDROLOGY OF GEOTHERMAL SYSTEMS

downstream from the entry of Terrace Spring drainage. Stations 3 and 4 are located on the Madison River, 

about 1.8 and 6.0 km, respectively, by road below the 

confluence (fig. 2). Station 5 is at the West Yellowstone 

Madison River Gaging Station. Station 6 is at the 

spillway of Hebgen Dam.

All of the spring and river samples used in the 

drainage studies were collected during daylight hours, 

September 18 to 27, 1974. The entire period was precipitation free on the Yellowstone plateau.

Sampling sites (numbers) Distances (horizontal)

Yellowstone Canyon

1. 40°C source water a. ~1 m

2. 14°C source water b. ~1 m

3. Station below confluence c. ~0.5 m

4. Down drainage station d. ~10 m

5. At base of steeply sloping drainage e. ~15 m

Madison River

1. Firehole River a. 1.0km

2. Gibbon River b. 1.0km

3. Madison below confluence c. 1.8km

4. Madison Canyon d. 6.0 km

5. Madison at West Yellowstone e. 12.0km 

gaging station (inactive)

6. Spillway of Hebgen Lake f. ~30 km

FIGURE 2.—Schematic diagram of Madison River and Yellowstone Canyon sulfide-bearing mixed spring systems and 

sampling sites.

SAMPLING METHODS

Water samples from hot springs and their drainages 

were obtained and processed as described by Ball, 

Jenne, and Burchard (1976). Briefly, the samples were 

obtained with a Masterflex2 portable electric pump 

equipped with silicone tubing. Filtered samples were 

obtained by attaching a barrel-less pressure filter assembly (142 mm diameter, 0.1 /am pore size) to the 

silicone outflow tube of the pump (Kennedy and others, 

1976). This arrangement allowed sample collection 

from boiling hot springs without air contacting the 

sample, and with a maximum temperature drop of 2°C.

"Mention of brand names is for the convenience of the reader and does not constitute 

endorsement by the U.S. Geological Survey.

A segmented aluminum pole was used to suspend the 

inlet tube over, and into, the large hot springs. Samples for S(-II) were fixed in the field by adding zinc 

acetate (50 mg/250 mL of sample) immediately after 

filling the polyethylene bottle. AIL trace-metal sample was collected and acidified to a pH of 1.0 to 1.3 

using concentrated redistilled HNO3 . Another subsample was acidified with concentrated HC1 (1 mL/250 

mL sample) for determination of As (III), As (V), P, and 

some major cations. Filtered-unacidified samples were 

also used for major ion analyses.

Most samples were acidified in the mobile laboratory 

within an hour of collection; samples from the Yellowstone Canyon area, Mammoth hot springs, and 

Hebgen Dam were acidifed within 10 hr of collection. 

No HCl-acidified samples were obtained from the latter 

areas; hence filtered HNO3-acidified samples were used 

for the As(III), As(V), and P analyses.

ANALYTICAL METHODS

Water temperature, pH, Eh, and dissolved O2 were 

determined onsite. Spring temperatures were measured with a calibrated mercury thermometer on samples rapidly withdrawn in a Thermos-type bottle 

clamped to the sampling pole. Temperatures in the discharge channels were measured by direct immersion of 

the thermometer. Eh and pH were measured onsite 

using a Sargent Model PBX specific ion meter and a 

flow-through cell (Ball and others, 1976). Dissolved 

oxygen was measured using the azide modification of 

the Winkler procedure (American Public Health Association, 1971); the fixed samples were titrated within 3 

hr of collection.

Total alkalinity and F were determined in a mobile 

field laboratory on the day of sample collection. Alkalinity was determined by titration with standard 

H2SO4 to a pH 4.5 end point. Both uncomplexed and 

total F activities were measured using an Orion 

specific ion electrode and procedures specified by the 

manufacturer.

Li, Na, K, Mg, and Ca were determined by flame 

atomic absorption using a Perkin Elmer Model 303 or 

306 spectrophotometer, following procedures issued by 

the manufacturer. SiO2 was analyzed by direct current 

plasma spectroscopy using a Spectrospan III operating 

in single element mode.

Cl and SO4 were determined by cation exchange 

using a refinement (Stauffer, 1980b) of the method of 

Mackereth (1963). The refinement was necessary to 

cope with the high F levels in Yellowstone Park thermal waters. P, As(III), and As(V) were determined following an adaptation (Stauffer, 1980b) of the 

molybdate procedure of Johnson and Pilson (1972a).
TRACE ELEMENTS IN HOT-SPRING DRAINAGES, YELLOWSTONE NATIONAL PARK F5

Fe, Mn, and Al were determined using flame atomic 

absorption spectrometry, following 8-quinolinol MIBK 

extractions. Al was also extracted from filtered, unacidified, cooled water samples on the day of sampling 

following the procedure of Kennedy, Zellweger, and 

Jones (1974). Field-extracted Al (back extracted from 

MIBK into 1.0 molar HNO3 ) was subsequently 

analyzed by flame atomic absorption.

Total dissolved Sb was analyzed using a modification 

(Stauffer, 1977) of the Yanagisawa, Takeuchi, and 

Suzuku (1973) atomic absorption procedure.

Total dissolved S(—II) was determined on fixed samples using the potentiometric procedure of Baumann 

(1974).

RESULTS

DATA RELIABILITY

PURE ANALYTICAL ERROR

Identification of chemical processes acting in the 

hot-spring drainages depends in part on the magnitude 

of the analytical errors. Estimates of the analytical 

coefficients of variation (c.v.) for pertinent solute levels 

and the most important solute species are contained in 

table 1. The errors (table 1) apply to individual variates; the variance of the mean X of n independent 

identically distributed (statistically) X values is given 

by equation 1 (Hogg and Craig, 1970):

= VarX/n. (1)

The mean square errors (squared bias plus variance) 

for K and Li are the smallest. The low levels of Ca and 

particularly Mg in the "typical" alkaline Upper or 

Lower Basin hot springs imply large analytical coefficients of variation.

In general, the low levels of SO4 and high concentrations of F in the Upper and Lower Basins result 

(table 2) in significant potential biases in SO4 estimates obtained using the cation-exhange method. The 

problem is ameliorated considerably in the river waters, and in hot-spring waters from north of Madison 

Junction, because of large associated increases in the 

SO4/F molar ratio (Rowe and others, 1973; Thompson 

and others, 1975). Because of the dominance of Cl in 

most of the waters being considered here, the Cl data 

has a c.v. of 1 percent, about equal to that for data 

published elsewhere on these waters (Rowe and others, 

1973; Thompson and others, 1975).

Errors associated with the As and P species are discussed in detail elsewhere (Stauffer, 1980a, b). The P 

levels in the typical alkaline hot-spring waters are

TABLE 1.—Analytical precision of solute data

Solute

LiLi————

Na —— _

Na __—

K ————

Mg _____

Mg _____

Ca _____

Ca _____

Cl—— —

Analytical 

method*

Flame AA ._ __ _

__— do— —— — ——

330 nm line 

_— _do——— — — — -

———do—— __— ___ —

—— _do———— ——— .

———— do—— ——— ———— ——

—..do—————

cation exchange.

Level

(mg/L)

._ 0.50

_ 5.00

100

_500

.. 10.0

._ .1

.. 1.0

.. 1.0

_ 5.0

50

Coefficient 

of variation** 

(c.v.) (percent)

0.3-0.5

.3- .5

.5

.2- .3

.2- .3

3.6

2.0

2.5

1.0

1.0

Remarks

sively worse for levels

tive method.

mately as the term

[1 + (SO4 + FVC1J 

when F, SO4 , and Cl are 

expressed in milliequivvalents.

SO4 — __.

F ________

Alkalinity.

As ______

As

Al ______

Al ______

Al

Sb ______

Sb ______

Mn ______

Mn

Fe

Fe — —

O2 (aq)__ _

S- 2 ______

s-2

.———dO———————_ ———

electrode.

Titration _ _-

. Spectrqphotometric

Mo-blue.

———dO—— —— - —— ——

Flame AA, solvent

extracted in field

——do— — — .— -

extracted in lab

._ Flame AA, lab

solvent extracted

———dO———— —— —— ,——

—Flame AA, lab

solvent extracted

——do———————

. Flame AA, lab

solvent extracted

—— _dO———— —— —— ——

-Winkler——— ——

Specific ion

electrode.

——do——————

30

-..200

.20

__ 2.00

.10

__ .025

- .200

.25

._ .5

.001

__ .010

.003

__ .020

__ 1.0

8.0

3.0

.-1.0

2.0

1.0

2.0

.3

8.3

12.0

7.0

4.0

2.0

5

2

1.5

2.5

5.0

1.0

3.0

C.v. increases with nonzero F, SiOj levels.

Noncarbonate alkalinity

may be _*25 percent of

total.

C.v. increases with decreasing level, sensitive to PO4 at low level.

Recovery dependent upon

volume solvent extracted.

*AA = Atomic absorption.

"""Coefficient of variation (c.v.) = 100 sxV_cwhen sx is the estimated standard pure 

analytical error for an individual replicate.

near the detection limit of ~2 /u-g/L. At these low levels 

the P estimates are also positively biased by the very 

large concentrations of SiO2 invariably present in 

geothermal waters. The relative root-mean-square 

errors and c.v. for total As are among the smallest for 

any of the solutes analyzed in these hot-spring waters. 

Both the accuracy and precision of the total As components, As(III) and As(V), suffer, however, from uncertainties in the preservation of As(III) at the time of 

sampling of the boiling hot-spring waters, as well as 

methodological constraints associated with 

molybdenum-blue (Stauffer, 1980a, b).

The precision of the total F data decreases at the low 

concentrations found in high-Ca waters in Yellowstone 

Canyon.

The c.v. for S(—II) is likely to be small compared with 

ZnS oxidation biases which may have resulted from 3 

months of storage of the samples prior to analysis. Possible oxidation effects (resulting in negative biases) 

were not evaluated. However, Brock, Brock, Bott, and 

Edwards (1971), citing thesis work of Pachmayr, state 

that the ZnS precipitates are stable against oxidation 

for weeks. The sulfide data reported here are likely to 

be minimum values.
F6 GEOHYDROLOGY OF GEOTHERMAL SYSTEMS 

TABLE 2.—Chemical and physicial parameters of Octopus Spring and its drainage

[Temperature, Eh, pH, and O2 are field determinations; other analyses performed after return to Menlo Park Laboratory, except as noted]

Concentration

Parameters'

Sample 74WA _______ ____________________

Eh(mV)_____ — .__________________________

O2 (aq) (mg/L) ____________ _ ______________

Alkalinity (mg/L)

Na (mg/L) „ __ _ __ _

K (mg/L) _______________ _ _______________

Mg (mg/L) _______________________________

SO4 (mg/L) _ __ „ _

Cl (mg/L) _________________________________

F(mg/L)—________.. _______________________

S= (/tg/L) ________________________________

Al (Fl) (/ig/L) _____________________________

Al (Ff) (/ig/L) ____________________________

Al (Ul) (ftg/L) _____________________________

Fe (Fl) (/ig/L) ____________________________

Fe (Ul) (ftg/L) _____________________________

Mn (Fl) (fig/L) _____________________________

Mn (Ul) (ftg/L) _____ __ ___ _____ _

As (V) (|ug/L) _____________________________

As (V) + As (III) (,ug/L)_____________________

Sb 0*g/L> _________________________________

P6 (/ig/L) ____-__:____.____________________

1*

____________________ 112

_____________________ 82-85

_____________________ 7.78

_____________________ +18

_____________________ .92

__ _____ __ _ 340

_____________________ 307

_____________________ 15.2

_____________________ 3.42

_____________________ 21

_____________________ 262

_____________________ 22.0

_____________________ 41

_____________________ 47

____________________ 51

_____________________ 2.8

_____________________ 1.4

___________________ 3.0

____________________ 3.4

________________ ____1,455

_____________________ 58

_____________________ 2

2

114 

63-75

+242 

2.68

"317 

15.4 

3.53 

.018 

1.27

269

256

54

3.7

1,525

Station No

3

115 

53-61 

8.3 

+288 

3.93

~~3 22 

15.5 

3.57 

.007 

.64

269

257

64 

~~~~3.4

1,510

. of spring and its drainage

4

116 

50 

8.6 

+305 

5.38

"3 26 

16.1 

3.64 

.008 

.64

"262

258

26 

""3.1

1,545

5

117 

40 

8.8 

+289 

5.90

"336 

16.5 

3.72 

.010 

.79

275 

261

9 

"""S.O

1,575

6

118 

30 

9.0

""6.65

"335 

16.4 

3.75 

.009 

.59

"286

216

"~33

1.1 

1,630

7*

113 

23-26 

8.65 

+332 

6.78 

367 

332 

16.4 

3.72 

.010 

.73 

23.0 

284 

25.0 

219 

<15 

47 

16 

47 

3

"" .7 

.8 

1,610 

1,620

.9

Difference2 Ratio3

(7-1)

-59 

+ .87 

+314 

+5.9 

+27 

+25 

+ 1.25 

+.30

+ .19 

+2 

+22 

+3.0 -51

+6 

-31 

-4 

+ .2

""-2.3 

-2.6

+ 230 

+ 160 

n.a. -1.1

(7/1)

sn.a. 

n.a. 

n.a. 

n.a. 

1.08 

1.08 

1.08 

1.09

L35 

1.14 

1.08 

1.14 

.815 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

1.11 

n.a. 

n.a.

* Filtered samples, except as noted. Stations 2-6 were unfiltered.

'Ff = filtered and field extracted; Fl = filtered and lab extracted; Ul = unfiltered and lab extracted.

Concentration at station 7 minus that at station 1.

'Concentration ratio of station 7 to station 1.

"Temperature variations in response to discharge periodicity was measured at selected stations only.

5Not applicable.

6Soluble reactive phosphorus as P (Strickland and Parsons, 1968;.

The alkalinity data were adjusted for partial protonation of F (Ellis, 1963) and incomplete protonation of 

HCO3 at the pH = 4.5 alkalinity end point. Corrections 

for the protonation of dissolved borates and silicates 

were not made. However, the protonation of dissolved 

silicates may introduce an error in some instances (D. 

V. Vivit and others, unpub. data, 1978).

Among the solvent-extracted elements quantified by 

atomic absorption (Al, Mn, Fe, and Sb), Al and Sb suffer from the largest analytical variances. Low levels of 

Al tax the sensitivity constraints on Al analysis by 

flame; flameless atomic absorption for Al is inherently 

imprecise. Furthermore, the field extractions of Al 

have error components resulting fom the following factors: (1) Field constraints prevented extracting the 

samples immediately after sampling; in fact, the time 

lag varied from 1 to 24 hr; (2) the solution temperature 

during the extraction procedure varied from about 6° to 

50°C, with possible effects on solvent-extraction efficiency. The Sb procedure is influenced by SiO2 levels; 

the high and variable levels of SiO2 in the hot-spring 

waters and the very complex polymerization chemistry 

of SiO2 contribute the major analytical component of 

variance to the Sb analyses (Stauffer, 1977).

SAMPLING ERRORS

Although physical-chemical conditions in the 

springs are relatively invariant, the estimated concentrations of solutes at fixed points along the down 

drainages vary (time scale = minutes) with spring discharge. The channel-water temperatures are positively 

correlated with discharge, and evaporative cooling results in a concentration of solutes in the remaining 

liquid phase. From the Bowen equation (Bowen, 1926) 

it can be shown that 95 percent of the heat dissipation 

of 85°C (spring orifice temperatures) and 88 percent of 

the heat dissipation at 50°C is evaporative (latent heat 

transfer). A latent heat transfer model implies a 0.18 to 

0.19 percent increase in conservative solute concentration for each 1°C of evaporative cooling. The sun's 

radiant heat input may approximate 15 cal/g water. A 

purely latent heat transfer model approximates total 

water losses through evaporation in the channel. Thus, 

the small amount of sensible heat exchange is approximately balanced by dissipation of the added radiant 

energy.

Drainage stations could not be synoptically sampled; 

thus variable spring discharge introduces a withinstation and a between-station component of sampling 

variance to the estimated solute concentrations. Based 

on the coefficient 0.19, and the observed short-term 

temperature variations in the Lower Basin drainages 

studied (tables 2, 3), the "sampling" component (c.v.) of 

solute concentration errors is —1.0 percent, a value 

larger than the analytical "pure error" for the major 

alkali ions but =£ analytical c.v.'s for the major anions 

(table 1). The analytical and sampling errors should be
TRACE ELEMENTS IN HOT-SPRING DRAINAGES, YELLOWSTONE NATIONAL PARK F7

TABLE 3.—Chemical and physical parameters of Azure Spring and its drainage

[Temperature, Eh, pH, and O2 are field determinations; other analyses performed after return to Menlo Park laboratory, except as noted.]

Concentration

Station No. of spring and its drainage

Parameter1

Sample 74WA _________________ ___ __________

Temperature (°C)4 ___ _ _ __ __ - _ ____

pH

Eh (mvl _ __ _ ____ ___ ___ _ __ __ ____

O2(aa) (mg/L) _ _ __ __ _ ____ _ _ _ __

Na (mg/L) __________________________________

K (mg/L) _ _ . __ _ __ _ _ __ --.

Li (mg/L) ___________________ ________________

Mg (mg/L)________________________________ ____

Ca(mb/L) _________________ ___________________

Cl (mg/L) _____________________________________

S- (/ig/Ll ____________________ ______________

Al (Fl) (/j.g/L) _ _

Al (Ff) (/j.g/L) _______

Al (Ul) (/j.g/L) ___ _ __________ _______

Fe (Fl) (/xg/L) ____________ ___________ __ ____

Fe (Ul) (jug/L) _________________________________

Mn (Fl) (/Ag/L) __ _ _ __ _ Mn (Ul) (/Ag/L) _____________ _____________ __ __

As (V) (/Ag/L) __ _ _ _ __

As (V) + As (III) (/Ag/L) ___ ___ _

Sb (jiig/L) _________________________________

P6 (/Ag/L) ____________________ ________

1'*

_________________ 136

_________________ 89

_________________ 7.49

________________ -76

_________________ .0

_________________ 311

_________________ 13.4

2.93

_________________ .079

_________________ 2.10

______________ 50

_________________ 310

_________________ 28.6

_____________ 69

_________________ 7.7

— — -________. 30

________ ____1,420

70

_________________ 2

1*

132 

86 

8.62 

-185 

.0 

198 

322 

13.8 

3.23 

.028 

1.20 

52 

316 

29.8 

240 

1,500 

465 

90 

595 

6.3 

60 

.61 

4.3 

30 

1,480 

81 

3

2

135 

64-70 

9.18 -36 

.38

328 

14.5 

3.10 

.054 

1.14

"230 

~~~45

2.7 

1~505 

""""5

3*

133 

45-63 

9.25 

+ 75 

1.78 

204 

332 

15.0 

3.16 

.018 

1.21 

49 

342 

31.0 

226 

60 

36 

29 

39 

12.9

2.01 

2.6 

27 

1,520

4

137 

49-50 

9.20 

+351 

2.62

"337 

14.6 

3.16 

.027 

1.49

321 

230 

52

"2.5 

1,540

5*

134 

33-41 

9.42 

-342 

.4.78 

209 

353 

14.6 

3.30 

.075 

1.25 

55 

352 

32.5 

210 

20 

36

~~~39 

8.4

2.02 

2.6 

810 

1,615

""""3

Difference2 Ratio3

(5-1)

""-49

+.80 

+527 

+ 4.78 

+ 11 

+31 

+.80 

+.07 

+.05 

+.05 

+3 

+36 

+2.7 -50 

-1,480 

-429

"-556

+ 2.1

+ 1.4 

-1.7 

+ 780 

+ 135

5/1

1.09 

n.a. 

n.a. 

n.a. 

1.06 

1.10 

1.06 

1.02 

2.68 

1.04 

1.06 

1.114 

1.091 

.875 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

1.09 

n.a. 

n.a.

1/1'

*n.~a~. 

n.a. 

n.a. 

n.a.

1.04 

1.03 

1.10 

.354 

.571 

1.0 

1.02 

1.04

69.4

17.2 

"7.69

*Filtered samples, except as noted. Stations 2 and 4 were unfiltered.

'Ff = Filtered and field extracted; Fl = filtered and lab extracted; Ul = unfiltered and lab extracted.

Concentration at station 5 minus that at station 1.

Concentration ratio of station 5 to station 1, 1 to 1'.

Temperature variation in response to discharge periodicity was measured at selected stations only.

5Not applicable.

"Soluble reactive phosphorus as P (Strickland and Parsons, 1968.)

independent (hence additive) in reckoning the total 

uncertainty in solute concentration at any point along 

the drainage channel.

STATISTICAL DEFINITIONS

LetR(S)j,j be the ratio/? of concentration for solute S 

at stations i andj, respectively, along a drainage channel. Let.R,(S) be the ratio where the base station^ = 1. 

For mixed water systems, letP,(S) denote the fraction 

of water at station i which is contributed by source 1 

calculated (equation 2) using the conservation of mass 

principle for solute S (equation 3):

= (C,--C2 )/(C,-C2 ) 

, + (1-/?)*C2 =C,,

(2)

(3)

where C denotes the concentration of solute S, and/? is 

the mixing fraction.

OCTOPUS AND AZURE SPRINGS

OXIDATION AND DIFFUSION PROCESSES

Several oxidative and diffusion-controlled processes 

have been identified in these two Lower Geyser Basin 

hot-spring drainages (figs. 3 and 4). Oxygen concentration and Eh increase with station number because of 

oxygen diffusion from the atmosphere into the cooling 

turbulent flow; pH increases 1 to 2 units, presumably

A. OCTOPUS SPRING

DRAINAGE STATION NUMBER

- 400 - 100

- 200 >

— 2O 1— 0

I- X

£§ "-&

DRAINAGE STATION NUMBER

FIGURE 3.—Physical and chemical parameters of two hot springs 

and their drainages. (Vertical bars on curves represent the 

range in observed values. Sulfide was below detection in Octopus Spring.)
F8 GEOHYDROLOGY OF GEOTHERMAL SYSTEMS

DC

e

z 

o

Ul

O

O 

O

1.110 r1.100 h

1.090 \-

1.080 h1.070 h

1.060 h1.050 r1.040 h1.030 r1.020 h

1.010 \-

1.000-

O ALKALINITY 

D ARSENIC TOTAL

1 23456 

STATION NUMBER ALONG DISCHARGE CHANNEL

FIGURE 4.—Concentration factors of several parameters for two hot springs and their drainages. (The vertical bars on the T curves 

represent limits on the concentration factors which are attributed to the observed temperature range. The concentration 

factors for the satellite pool in figure 4B are inverted to economize on graphical representation).

because of CO2 losses accompanying evaporative cooling. Analytical dissolved O2 concentrations in the 

upper channels are particularly sensitive to discharge

fluctuations because gaseous diffusion is sensitively related to water temperatures, turbulence, and residence 

time in the channel.
TRACE ELEMENTS IN HOT-SPRING DRAINAGES, YELLOWSTONE NATIONAL PARK F9

1.110 -

1.100

0.970 -

0.960 -

0.950

234 

STATION NUMBER ALONG DISCHARGE CHANNEL

FIGURE 4.—Continued.

If dissolved O2 is detectable by Winkler titration, 

S(-II) is below detection, Eh is positive, and the 

As(III)/As(V) ratio is much less than 1 (figs. 3, 4). Conversely, the presence of analytically detectable S(—II)

implies near-zero dissolved O2 levels, negative Eh values, and large As(III)/As(V) ratios (in some cases >50). 

Arsenite (As(III) ) is not oxidized in significant quantities until after the S(-II) has been either volatilized
F10 GEOHYDROLOGY OF GEOTHERMAL SYSTEMS

or oxidized. The S(-II)-dissolved O2 relationship (fig. 3) 

suggests that at 90°C the rate of diffusion of molecular 

O2 into the hot pools is the rate-controlling step in the 

oxidation of S(-II). Traces of dissolved S(-II) sometimes accompany nonzero oxygen levels in cooler 

down-drainage water (tables 2, 3); this thermodynamic 

disequilibrium probably reflects delayed oxidation at 

the lower temperature. The abiotic oxidation of S(-II) 

is known to be approximately first order with respect to 

both S(—II) and O2 , to be relatively insensitive to pH, 

and to be relatively slow compared to the expected hydraulic residence times (minutes) in the lower drainage channels (O'Brien and Birkner, 1977). Brock, 

Brock, Bott, and Edwards (1971) noted that sulfur 

bacteria are active in oxidizing S(-II) (using molecular 

O2 ) even at boiling temperatures (approximately 92°C 

on the Yellowstone plateau) in the alkaline hot 

springs. Some H2S volatilizes from the channels, yielding the characteristic odor. The first dissociation constant of H2S is near 7.0. Thus, H2S volatilization is 

decreased at the pH values near 8 observed in the 

lower channel reaches.

PRECIPITATION REACTION

The hypothesized evaporation-solute concentration 

model (T curves in fig. 4) adequately describes changes 

in F, Cl, As, and Na in the two drainage channels (fig. 

4). Statistical inferences based on iheR(S) ratios lead 

to acceptance of the null hypothesis (conservative behavior) for Na, K, Li, F, alkalinity, and total As in the 

downdrainage of Octopus Spring. Because of the very 

high concentrations of Na in Azure Spring (13.5 millimolar) relative to other constituents, the anticipated 

low reactivity of Na in this situation, and the superior 

analytical precision for Na as compared to Cl in the 

high-SO4 , high-F water, Na is the element of choice for 

evaluating the conservatism of other solutes in the 

Azure Spring system. There is no convincing statistical 

evidence of As precipitation in either the satellite pool 

or along the down drainage of Azure Spring. Applying 

the statistical properties of the solute ratio statistics, 

with probability —95 percent, the losses of As along the 

drainageway are less than 1.8 percent of the spring 

flux.

The Azure Spring K ratios increase prior to station 4, 

as expected of a conservative solute, and then decrease 

significantly in the latter part of the channel. Approximately 95-percent confidence limits on the K losses prior 

to station 5 are 3.5±0.9 percent, or 0.48 mg/L of K.

Li is nonconservative in the Azure Spring system. A 

7.5 percent loss of Li is indicated prior to station 2 of 

the downdrainage and an 8 percent loss in the satellite 

as compared to the main upwelling pool (fig. 4). After 

station 2, the Li ratios increase at a rate which is not

statistically distinguishable from the T, Cl, Na, As, 

and F curves, indicating conservative behavior after 

initial Li deposition in the immediate vicinity of the 

upwelling. The filtered and unfiltered HNO3-acidified 

sample sets yielded similar results (8 percent loss of Li 

in the downdrainage, all of it prior to station 3; 9*/2 

percent low concentration anomaly in the satellite). 

The Li losses occurred in two sharply contrasting regimes of temperature and pH.

The Li losses in the Azure Spring system are likely 

to be the result of coprecipitation with Al, because 430 

/xg/L, or 92 percent of the original soluble Al, was lost 

from solution prior to station 3 and >395 /xg/L, or 85 

percent, was lost in the satellite pool as compared to 

the main pool. Total (solute -I- suspended) Al losses 

were 525 and 555 /xg/L in the satellite pool and prior to 

station 3, respectively. The field-extracted Al data for 

the main pool and channel show the same trend as the 

laboratory-extracted Al data (table 3); however, the 

field-extracted Al estimate is only 19 percent of the 

laboratory-extracted estimate for the main pool. One 

explanation for this contrast is that the field-extracted 

Al (filtered through a 0.1 /mi membrane) includes a 

colloidal fraction which* is not extractable with 

8-quinolinol-MIBK but which becomes soluble during 

sample storage at pH — 1. The difference between the 

field- and laboratory-extracted soluble Al estimate is 

greatest for the main pool, where the soluble Al is presumably in the process of being precipitated.

In Octopus Spring the field-extracted Al decreases 

from 47 to 16 /xg/L, concomitant with a pH increase of 

about 1, between stations 1 and 7; no significant 

change occurs in the laboratory-extracted Al along the 

drainage way. Although the main pool Al level is an 

order of magnitude higher for Azure as compared to 

Octopus Spring, at the ends of the two drainage channels the Al levels have converged to similar values.

The Li losses in the Azure Spring system may be due 

to precipitation of a Li-bearing aluminosilicate mineral. The Li mica, lepidolite, was identified as a deposition mineral at a depth depth of 25-40 m (below surface) in the Y-3 drill core (Barger and others, 1973), 

about 75 m northwest of Ojo Caliente Spring. Like 

Azure Spring, Ojo Caliente has an elevated Al concentration (1.0 mg/L, Barger and others, 1973). Both the 

scientific drilling experience (White and others, 1975) 

and the typically high Cl/Li ratios for the River Group 

hot springs (R. E. Stauffer and J. M. Thompson, unpub. 

data, 1975) suggest that Azure Spring and Ojo Caliente 

are derived from a common hot-water upflow regime 

where Li is being precipitated in the epithermal zone.

If lepidolite is, in fact, forming in Azure Spring, the 

Li losses are probably not confined to the formation of 

this mineral. The Al/Li molar loss ratio for Azure
TRACE ELEMENTS IN HOT-SPRING DRAINAGES, YELLOWSTONE NATIONAL PARK Fll

Spring is estimated to be 0.42, in contrast to the ratio 

1.27 for lepidolite found by Barger, Beeson, Fournier, 

and Muffler (1973). Furthermore, the stoichiometry of 

lepidolite (K2Li3Al3(AlSi3O10 )2(OH F)4 ) calls for K 

losses in the Azure Spring system twice as large as 

those inferred from figure 4.

The concentrations of Mn and Fe in Azure and Octopus Spring waters are representative of the very low 

levels of these two elements in typical alkaline high-Cl 

(>250 mg/L) hot springs in the Upper, Lower and Morris Geyser Basins (tables 4 and 5). Significantly, water 

collected from the base of Porcelain Terrace at Norris 

has the lowest levels of both Fe and Mn of all the waters tested; this spring also has the highest Cl level, 

hence the minimum dilution of hot-spring water, in 

Yellowstone Park. Ear Spring, representative of the 

high-Cl, low-HCO3 waters of Geyser Hill, Upper Basin, 

also features low levels of both Fe and Mn. An unnamed spring north of the Old Faithful interchange is 

a warm spring formed by near-surface dilution of hot 

high-Cl water with meteoric water. By contrast, this 

diluted spring has relatively high levels of both Fe and 

Mn. Steady Geyser is a dilute (low-CD hot spring in the 

Lower Basin characterized by low Fe levels and a large 

Mn/Fe ratio (table 5). The elevated Mn/Fe ratio indicates preferential oxidation of Fe(II) and losses from 

solution following dilution near surface waters. Little 

Whirligig water is a mixture of high-Cl, low-HCO3 

Norris deep water with acid-sulfate water (low-CD of 

surficial origin. The acidic pH of the mixture preserves 

the relatively high levels of both Fe and Mn and the 

small Mn/Fe ratio to be expected from leaching of country rock by the acid-sulfate water component. Brock,

TABLE 5.—Chloride, aluminum, iron, and manganese in selected 

geysers and hot springs

Sample Source

Upper Basin: 

YT- 73-71 ___ Ear Spring, Geyser Hill ____________ 

YT- 73-62 Sannhire. Biscuit Basin

74WA122U1 

74WA123U 

74WA124U

74WA125U 

74WA126U

74WA127U 

74WA128U

74WA129U 

74WA13OU

Lower Basin: 

YT 73-68 _.

YT 73-69-

Norris: 

YT-73-61-.

YT-73-74 .

Mammoth: 

YT-73-65- 

74WA146U 

74WA147U

Seep near Old Faithful

_ Tortoise Shell

_ _ Unnamed, largest geyser

_ _ Unnamed, east of 

Old Faithful, across

_ _ Unnamed, new, below Old

____Unnamed, Black Sand Basin ___ _ __ 

_ _ Unnamed, north of

. __ Little Whirligig _ ___ _______

.____New Highland _- _ _ ___ ___ _ _____

_ .Unnamed, new, blue colored

Cl Al Fe 

(mg/L) (Mg/L) (Mg/L)

*403 

*297 

*266 

365 

389

382 

377

272 

317

242 

314

353

*300 *46

*587 *704

*166 

171

166

<5

7 

23 

45 

26

56

27

<6 

29

16 

23

36

11 

11

10 

<5

6

18

53

1.1 

7.9 

1.5 

24 

2.4

6.7 

1.6

5.2 

3.5

154 

64

20

2.7 

5.1

160

7.9 

7.1

14.3

Mn

1.0 

.9 

18.3 

1.3 

.5

.5 

1.2

1.5

.7

14.3

7.4

1.4

.7 

54.7

20.8 

.4

15.0 

15.8

12.7

"Chloride analyses by J. M. Thompson on HNO3 acidified samples.

'The letter U following the sample number indicates these samples are unfiltered; the other

samples were filtered.

Cook, Peterson, and Mosser (1976) have found pure 

"acid sulfate type" (White, 1957; White and others 

1971) thermal waters in Gibbon Meadows and Norris 

Basin with total soluble Fe levels (Fe(II) and Fe(III)) 

exceeding 50 mg/L.

UNNAMED SULFIDE-BEARING SPRINGS IN YELLOWSTONE 

CANYON

Generically, both the 46°C source waters in the unnamed sulfide-bearing spring system in Yellowstone 

Canyon would be classified as "warm" springs of

TABLE 4.—Selected physical and chemical properties of additional hot waters

[Temperature, Eh and O2 are field determinations; other analyses performed after return to Menlo Park Laboratory]

SBimple

Temperature 

Source (°C)

Lower Geyser Basin: 

74WA119 White Creek 1 ___________ 51

Upper Geyser Bi 

74WA122U

74WA123U 

74WA124U

74WA125 

74WA126U

74WA127U 

74WA128U 

74WA129U 

74WA130U

Mammoth: 

74WA146U 

74WA147U

asin: 

Seep near Old 

Faithful ________________ 89.5

Tortoise Shell _ ____ ____ 93.5

Unnamed, largest 

geyser near Sawmill ________89.5 

Witches Cauldron 91.0

Unnamed, east of 

Old Faithful across 

Firehold River __________ ___87

Spouter, Black 

Sand Meadow 85

Unnamed, new, below 

Old Faithful Interchange _ _ 73.5 

Unnamed, Black 

Sand Meadow _ _____ _ _88.5

Unnamed, north of 

Old Faithful 

Interchange _ 82

Unnamed, new blue-colored, 

near New Highland2

Eh

(mV)

274

-170 -156

- 37 

-108

-116 

+ 185 

-109

O2 (aq) 

(mg/L)

.0 

.0

.22 

.0

.0 

.0 

.60 

.0

.0

S(-II)

630 

550

150

390 

190

90 

130

As(V)

As (III) 

(ug/L)

345

1,280 

1,620

1,590 

1,500

850 

1,495 

895 

1,455

1,255 

690 

680

As(V)

315

=£30

-1,260 

=£40

=£20 

=£70 

860 

=£280

=£15

As (III)

-30

-1,245 

-1,590

-330 

1,460

-830 

-1,425 

-35

> 1,055 

3=675 

3=610

As (III)/As (V)

0.10

3=35 

3=53

.25 

3=36.

3=41.

3=20 

.04 

>4.2

>5.3 

>45 

>9

'Filtered sample; the other samples are unfiltered. 

2On HNO-i-acidified samples.
F12 GEOHYDROLOGY OF GEOTHERMAL SYSTEMS

"mixed" origin (see Fournier and others, 1974; Fournier and Truesdell, 1974; Fournier and others, 1976). 

The intermediate Cl levels and high HCO3 , Mg, and Ca 

concentrations (table 6) identify the two source waters 

as high-Cl, high-enthalpy deep water which has been 

extensively diluted by meteoric water and has reacted 

with underlying carbonate rock strata. The high S(-II) 

and SO4 concentrations of the springs, and the extensive solfataric activity in the surrounding region of the 

Yellowstone Canyon, may have their explanation in 

hot water leaching underlying sulfur-rich sedimentary 

rock. Similar conditions also exist in the Mammoth 

area, where some warm springs have reduced Cl levels 

and concentrations of major constituents which resemble the 46°C source water studied here (Rowe and 

others, 1973).

The low F levels and high Cl/F ratios in the Yellowstone Canyon Springs (derived from data in table 6) 

probably result from fluorite equilibria acting on these 

high-Ca waters (Mahon, 1964; Nordstrom and Jenne, 

1977).

The sharp increases in pH, Eh, and dissolved O2 concentration below the confluence and the decreases in 

S(-II) reflect gas exchange (CO2 , H2S ) with the atmosphere and S(-II) oxidation, respectively. The highcarbonate alkalinity of these waters dominates the pH 

despite the release of protons accompanying S(-II) 

oxidation.

Inferences based on the solute mixing fraction statistics P(S) (equation 3) must account for the solutespecific variances. The Li and K statistics are the most 

precise because of the large concentration differences 

between the two source waters for these two elements, 

and the high analytical precision at the concentration 

levels analyzed. The high SO4 concentrations increase 

the analytical c.v. for Cl to —2.5 percent. The large 

SO4/F equivalence ratio insures adequate analytical 

precision for the SO4 statistics. However, the high concentrations of S(—II) species in the source 1 water, and 

their potential for oxidation to SO4 , add uncertainty to 

the SO4 statistics. The P(F) statistics are imprecise because of the low F concentrations and small concentration difference between the two source waters. The precision and accuracy of the P (As) statistics in this sytem 

suffer from the relatively high P concentrations, and 

the high and variable levels of S(-II) species among 

the samples (Stauffer, 1980b).

TheP3 (S) (subscript identifies station) for S(-II), Cl, 

Na, K, and Li are statistically equivalent. The P4(S) 

statistics for these four solutes are all significantly 

smaller than the P3 (S) values, indicating that the 

water sample obtained from immediately below the 

confluence was biased in favor of source 1 water. The 

sampling bias reflects incomplete mixing of the two 

source waters. The steep gradient and adequate mixing 

length between stations 3 and 4 insure that P4 (S) values are unbiased (best estimate P4 = 0.375 ± 0.007). 

The equivalence of the Cl, Na, K and Li mixingfraction statistics indicates conservative behavior for 

the three alkalis in this system. Because of the high

TABLE 6.—Chemical and physical parameters of Calcite and two other unnamed sulfide-bearing springs in Yellowstone Canyon with the

drainage of the mixed spring system

[Temperature, Eh, pH, and O2 are field determinations; other analyses performed after return to Menlo Park Laboratory, except as noted]

Stations along common discharge drainage 

of two unnamed springs*

Parameter1

Sample 74WA ______ _________________

Time (hr) _____________ ___ __________

pH __________________________

Eh(mV) ___________ _________________

O?(aq) (mg/L) __ _ _

Na (mg/L)

K (mg/L) _ _______ __ _ .

Li (mg/L) _ _ _ ___ __

Ca (mg/L) _ _ __ ___ _ _.

SO4 (mg/L) _______________ _ _____

F (mg/L)___.__ ____ _______________

SiO2 (mg/L) __ ______ _______________

S= (/ng/L) __________ __ _ _ ________

Al (Fl) (/u,g/L) __ ___ __ ___ _ _ ____.

Al (Ff) (/itg/L) _________________________

Fe (Fl) (/itg/L) ________________________

Mn (Fl) (ug/L) ____ _ ___________

As(Vl +As(III) (/u.g/L)___ ______________

P6 (/ug/L) ________________ __ _ _ _ .

Calcite 

spring

90

__________7.72

____-166

_ ________.o

._______261

._______196

.________95.8

__________2.24

____12.6

.___ 203

_______242

_ _ ______4.3

———— 169

_-_.__2,800

-_______113

3 5

__________7.4

______1,450

54

__________2

Spring

142 

-1,400 

46 

5.98 

-94 

.0 

798

~28.5~ 

227 

251 

112 

2.2 

72 

3,210 

239 

328 

190 

283 

742

~61~"

1

141 

-1,300 

40 

6.90 -66 

.0 5 -600 

116 

56.4 

1.09 

29.1 

232 

279 

127 

2.5 

78 

4,800 

243 

415 

215 

98 

710

"57""

2 

Spring

143 

-1,500 

14 

7.45 

+ 14 

4.60 

207 

36.6 

14.1 

.22 

16.4 

62.0 

86 

25 

1.6 

68 

55 

11 

<4 

35 

89 

150

~57"~

3

140 

-1,215 

23-26 

7.22 

-30 

.80

75.3 

34.8 

.65 

21.4 

141 

187 

78 

2.0 

68 

2,250 

128 

69 

113 

88 

395

~53~"

4

139 

-1,130 

19 

8.05 

+ 185 

5.10 

399 

63.0 

29.9 

.54 

19.4 

120 

159 

64 

2.0 

69 

<15 

94

108 

88 

280

56"

C

Mixing fraction2 1

5 P3(S) P4(S)

138 

-1,030 

14.5 

8.35 

+ 139 

5.80

64.8 

29.5 

.56 

20.3 

123 

171 

63 

2.0 

66 

<15 

12 

<4 

6 

37 

270

60

4n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

.487 

.489 

.495 

.394 

.465 

.523 

.487 

.550

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a.

n.a.

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

.333 

.374 

.368 

.236 

.341 

.378 

.382 

.470

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a.

n.a.

.oncen- 

: ration 

ratio3

(5/4)

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

1.03 

.987 

1.03 

1.05 

1.02 

1.08 

.987 

1.00

______

*Filtered sample, the other samples are unfiltered.

'Ff = filtered and field extracted; Fl = filtered and lab extracted; Ul = unfiltered and lab extracted.

2P3(S) is defined as the apparent fraction of water at station 3 which is source 1 water; similarly, P4

Concentration ratio of station 5 to station 4.

4Not applicable.

5Best estimate; sample poorly mixed.

"Soluble reactive phosphorus as P (Strickland and Parsons, 1968).

(S).
TRACE ELEMENTS IN HOT-SPRING DRAINAGES, YELLOWSTONE NATIONAL PARK F13

K/A1 atomic ratio (93 for source 1, higher for source 2) 

and the very short hydraulic residence time in the system, the conservation of K is to be expected. The mean 

mixing fractions (P3 , P4 ) for the conservative elemental 

suite (Na, K, Li, CD are used to quantitatively evaluate 

the behavior of Ca, Mg, Al, Fe, Mn, As and P in the 

mixed-water system.

The concentrations of Mg and Ca recovered at stations 4 and 5 indicate minor losses of both elements 

below the confluence (1.3 mg/L Mg, or 6 percent; 6 

mg/L Ca, or 5 percent). Temperature-dependent mineral equilibria calculations performed using WATEQF 

(Plummer and others, 1976) revealed supersaturation 

with respect to carbonate and silicate minerals at station 4. The saturation indices (Is = Iog10 (IAP/KT) * at 

station 4 were: calcite (Is = 1.07); magnesite (Is = 0.25); 

and well-ordered sepiolite (Is = 0.35). The pH increase 

and temperature decrease below station 4 (table 6) result in increased supersaturation with respect to 

sepiolite at the lower station. Neighboring boiling 

"Calcite" spring is also strongly supersaturated with 

respect to both well-ordered and poorly ordered sepiolites (7S = 4.22; Is = 2.63). The "Calcite" spring was near 

saturation with respect to calcite (Is = -0.14) and 

magnesite (7S = 0.37).

The Yellowstone Canyon thermal springs are also 

supersaturated with respect to a broad class of aluminosilicates, especially the montmorillonites. 

Clearly, the potential exists for Ca and Mg solute 

losses via a variety of mineral reactions. However, because of the great stoichiometric excesses of Mg and Ca 

over Al in these springs, carbonates and pure silicates 

are likely to be the more important solubility controls. 

Wollast, MacKenzie, and Bricker (1968) noted that the

*IAP/KT is the ratio of ion-activity product to thermodynamic solubility constant.)

precipitation of sepiolite is not kinetically hindered at 

low temperatures (25°C).

Field-extractable soluble Al decreased rapidly below 

the confluence (table 7), whereas laboratoryextractable Al did not show a decrease until at least 

station 4, continuing the lag pattern noted earlier for 

the Azure Spring drainage channel.

Iron precipitation in the drainage (table 7) likely results from at least two mechanisms: amorphic FeS deposition from the high S(-II) waters accompanying the 

rapid pH rise, and Fe precipitation as amorphic hydrous oxide from the oxygenated waters as they attain 

positive Eh values (Hem, 1977). Large quantities of 

black precipitate (presumed to be FeS) were observed 

above station 3 in the mixed water, and especially 

above the confluence in the source 1 tributary. 

Reddish-brown hydrous oxide coatings were abundant 

in the drainage channel of the oxygenated 14°C source. 

The oxidation of both Fe(II) and S(-II) is probably 

mediated by the luxuriant growths of white filamentous bacteria observed in the drainage channel above 

station 4 (Castenholz, 1973). Calculations using 

WATEQF confirmed supersaturation with respect to 

amorphic FeS at station 1 (Is = 0.90) and with respect 

to amorphic Fe(OH)3 at station 4 (7S = 2.12).

Soluble Mn and Fe concentrations were characterized by minor losses prior to station 4 and losses of 

60 and 95 percent, respectively, by station 5 (table 7). 

The increases in the Mn/Fe ratio with distance below 

the confluence indicate a less rapid oxidation rate of 

Mn(II) than of Fe(II) in the aerated water. Singer and 

Stumm (1970) discussed the enormous kinetic enhancement of Fe(II) oxidation associated with bacterial 

oxidation. The rate of oxidation of Mn(II) increases 

with increasing pH and increasing MnO2 surface area, 

a catalytic effect (Morgan, 1967; Delfino and Lee, 

1968). The observed delay in oxidation of Mn(II) and

TABLE 7.—Estimated solute losses following mixing in Yellowstone Canyon mixed spring and Madison River systems

Projected 

concentration 

at 

Constituent confluence 1

Yellowstone Canyon mixed springs: 

S(-II) ________

AHFf)3 ____________

Fe(Fl) _____________

Mn(Fl) _____________

As+5 + As" ____ _

Madison River system:

AHFf) ___________ _

Fe(Fl) _________ ___

Mn (Fl) _____ _____•__

As(V) + As (III) ____

P

_ 151

_ 95

101

92

___ 354

___ 57

-_ 102

__ 18

8.5

-__ 206

5.4

Concentration 

found

....

____

67 

111 

16 

7.6 

212 

6

Station 32

Loss from 

confluence

(i"g/L)

- —

39 -9 

2 

.9 -6 

-.6

(percent)

— -

37 -9 

11 

11 -3 

-11

Concentration 

found

0

94 

108 

88 

280 

56

56 

97 

13 

5.8 

200 

8

Station 4

Loss from 

confluence

(«/L>

1,782

1

-7 

4 

74

1

50 

5 

5 

2.7 

6 -2.6

(percent)

100

1 -7 

4 

21 

2

74 

5 

28 

32 

3 

-37

Concentration 

found

0 

<4

12 

6 

37 

270 

60

62 

90 

14 

1.6 

204 

2

Station 5

Loss from 

confluence

(jixg/L)

151 " 

83 

95 

55 

84

_ O

44 

12 

4 

6.9 

2 

3.4

(percent)

100 

87 

95 

60 

24 

-5

42 

12 

22 

81 

1 

63

'Computed from source waters using mean mixing fractions for Na, K, Li and Cl from tables 6 and 8. 

2Station in Yellowstone Canyon Mixed Spring System omitted due to nonrepresentativeness of collected sample. 

3Ff = filtered and field extracted; Fl = filtered and lab extracted. 

4Soluble reactive phosphorus as P (Strickland and Parsons, 1968).
F14 GEOHYDROLOGY OF GEOTHERMAL SYSTEMS

hence the increase in the Mn/Fe ratio down drainage 

fits the Mn oxidation model.

The relatively low concentrations of S(-II), Fe, and 

Al found at station 2 (14°C source) are probably residuals of higher concentrations prevailing before interaction with the atmosphere. The high Mn/Fe ratio for 

source 2 is also evidence of the delayed oxidation of 

Mn(II) relative to Fe(II).

Soluble reactive P shows no statistical evidence of 

precipitation losses below the confluence. Whereas 

Fe(II) and S(—II) are potential energy substrates for 

the filamentous bacteria in the channel, P is used only 

for steady-state maintenance of the bacterial population. The precipitation of ^102 /ug of Fe/L between stations 4 and 5 did not result in a significant reduction in 

P or As concentration. The high pH (>8.0) is unfavorable for P and As(V) sorption on hydrous ferric oxides 

(see later discussion). An estimated 2 percent of the 

total solute As was lost between stations 4 and 5, the 

region where the principal losses of Fe and Mn through 

oxidation occurred. The As loss is not statistically 

significant.

MADISON RIVER SYSTEM

The date/time group is different for each of the sampling sites in the Madison River system. Time of day 

can be expected to affect temperature, pH, and dissolved O2 at a site because of diurnal effects of the solar 

cycle on heating and photosynthesis. The estimated 

fraction of Madison River water at station 3, which is 

derived from the Firehole River and calculated using 

solute concentrations (equation 2), is biased unless the 

solute concentrations were independent of time during 

September 18-21. Because the period September 

18-21 was precipitation free for the water, and was a 

low-flow period for the Madison River, the assumption 

of time independence in solute concentrations is equivalent to assuming that the cold-spring and hot-spring 

fluxes in the Gibbon and Firehole River drainages were 

invariant during the 3-day span. One indication of the 

near correctness of that assumption is provided by the 

close comparisons (mean difference <2 percent) in two 

sets of total As data for stations 1 and 2, collected 11 to 

14 days apart during late September-early October 

1974. The steadiness of the geothermal solute flux over 

short timespans has been noted by others (Fournier 

and others, 1976).

The best estimate of the Firehole River mixing fraction P3 (fraction of Madison River discharge at station 

3 derived from the Firehole Tributary) lies in the 

interval 0.70 to 0.75 (table 8). The geothermal indicator element, Li, defines the fraction most precisely because of the high analytical precision and the large 

concentration difference between the two tributaries.

The P3 (As) value, 0.76, indicates that As being 

transported in the Gibbon and Firehole Rivers remains 

in solution below the confluence and above station 3.

Using solute concentration ratios defined analogously to those for the Lower Basin, the geochemical behavior of Li and As can be contrasted with that of Cl in the 

Madison Canyon region. ~LetRi/3(S) where i = 4,5, 6, be 

the ratio of solute S concentration at station i to the 

concentration at station 3, immediately below the confluence. The R4/3(8) and R^3 (S) ratios apply to the 

Madison River between West Yellowstone and Madison Junction. The R 6/3(>S) ratios reflect the extensive 

dilution of Madison River water by stored water and 

other tributary water flowing into Hebgen Lake. Additions of geothermal water between Madison Junction 

and West Yellowstone are considered here to be negligible. This assumption is only approximately correct; 

however, inferences based on the solute ratio statistics 

are rather insensitive to minor unaccounted geothermal fluxes within Madison Canyon.

Elements which are well represented in nonthermal 

waters (particularly K, Ca, and Mg) can be expected to 

have -R 4 , -R 5 and R6 ratios higher than for Cl. This was, 

in fact, observed (table 8). The #4/3 and R^ ratios for K, 

Ca, and Mg are only slightly higher than for Cl because 

of the very slight tributary development of the Madison River within the Madison Canyon. The -R y3(Cl) 

statistic shows that the water at Madison Junction has 

been diluted by approximately 5 percent when it 

arrives at West Yellowstone gaging station.

Elements of geothermal origin which behave conservatively in the river will have concentration ratios 

which are not statistically distinguishable from the Cl 

ratios. Nonconservative behavior is identifiable by 

concentration ratios significantly lower than for Cl. 

Thus, the concentration ratios indicate that both Li 

and total As are conservative in the Madison Canyon 

(table 8). The mean percent difference between the 

As/Cl and Li/Cl ratios for stations 4 and 5 is only -0.3 

percent. A -2.0 percent mean difference between the 

As/Cl ratios, or between the Li/Cl ratios, is necessary to 

reject the null hypothesis (equivalent) at the 5 percent 

level. The statistical test is thus capable of discerning 

an ~2.0-percent loss of either Li or As in the Madison 

River above West Yellowstone.

The RK ratios for Cl, As, and Li also show quite close 

agreement (table 8). Because the Cl concentration at 

station 6 was determined by a different analytical 

method and different analyst, the Cl ratio has an additional error component. Furthermore, the analytical 

coefficients of variation for As and Li increase at the 

low concentration levels characteristic of station 6. 

Hence, the small negative differences between -R 6 /3(Li) 

and RR/3(C\) and between #6/3 (As) and RR/3 (C\) are
TRACE ELEMENTS IN HOT-SPRING DRAINAGES, YELLOWSTONE NATIONAL PARK F15

TABLE 8.—Chemical and physical parameters of the Madison River drainage

[Temperature, Eh, pH, and O2 are field determinations; other analyses performed after return to Menlo Park Laboratory, except as noted]

Stations along Madison River drainage*

Parameter1

Sample 74WA _________________

Time ----- _ __ _ ___ ..

Date (1974) __________ ______

Temperature (°C) __ _ _ _.

pH _____________________

Eh(mV) _____________________

O2 (aq) (mg/L) _ _______________

K (mg/L) _____________________

Li (mg/L) _ _ _ _ ____

SO, (mg/L) ___________ _______

Cl (mg/L) ____ __ ________ ___.

F (mg/L) ________ _ ______ _.

SiO2 (mg/L) __

Al (Fl) (ftg/L) —-_ — - — ___.

Fe(Fl) (jig/Li ________________

Mn (Fl) (,.ig/L)__ — ___________

As (V) + As (III) (ftg/L) __ _ .

Firehole 

1

_______ 107

________ 9/18

.- — ___ 15.0

______ 8.40

________ 452

________ 7.60

__ _____ 106

________ 73.6

________ 6.75

________ .528

______ _ .483

e 94

________ 10

________ 54

________ 7.2

________ 100

________ 52

________ 57

________ 14

2.6

.__-_ _ 245

----____ 252

6

Gibbon 

2

108 

1,230 

9/18 

14.0 

7.04 

402 

9.10 

115 

55.4 

8.40 

.323 

1.23 

8.29 

18 

33 

4.1 

75 

235 

235 

30 

24 

-92 

83 

4

Madison

3

109 

1,600 

9/18 

18.5 

7.50 

358 

8.40 

115 

68.1 

7.25 

.477 

.704 

6.37 

13 

47 

6.4 

92 

111 

67 

16 

7.6

212" 

6

4

110 

1,730 

9/18 

18.5 

7.68 

394 

8.15 

108 

67.5 

7.15 

.457 

.691 

6.04 

12 

45 

6.4 

86 

97 

56 

13 

5.8 

-185 

200 

8

5

111 

1,400 

9/19 

16.5 

8.25 

448 

8.20 

109 

66.4 

7.15 

.450 

.762 

6.12 

12 

44 

6.3 

87 

90 

62 

14 

1.6

~2~04 

2

6

120 

1,600 

9/21 

14.0

4.30 

.186 

1.83 

11.9

20" ~~~

1 

15

24 

24

"88

7

Mixing 

fraction 

P3 (S)2

n.a.4

n.a. 

n.a. 

n.a. 

n.a. 

.18 

.70 

.70 

.75 

.70 

.63 

.60 

.66 

.74 

n.a. 

.68 

.94 

.87 

.78

".76

Concentration 

ratio3

5/3

n.a.

n.a. 

n.a. 

n.a. 

n.a. 

.948 

.976 

.986 

.947 

1.08 

.961 

.954 

.949 

.984 

n.a. 

.811 

.910 

.875 

.205

"962

6/1

n.a.

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

.601 

.412 

2.40 

1.94

~4~49 

n.a. 

n.a. 

n.a. 

n.a. 

n.a. 

n.a.

~4~3l

*Filtered sample, the others samples are unfiltered.

'Ff = filtered and field extracted; Fl = filtered and lab extracted; Ul = unfiltered and lab extracted.

2P3 (S) is defined as the apparent fraction of water at station 3 which is source 1 water.

'Concentration ratio station 5 to station 3, station 6 to station 3.

4Not applicable.

'Soluble reactive phosphorus as P (Strickland and Parsons, 1968).

inconclusive evidence of Li and As losses in Hebgen 

Lake. The ratio comparisons suggest that only a minor 

fraction of the soluble Li and As fluxes in the Madison 

River are lost in Hebgen Lake during fall base-flow 

conditions. The near conservatism is not surprising 

since the elevated river water temperature and low 

suspended-solids load of the Madison should lead to 

short circuiting through the surface waters of Hebgen 

Lake. Similarly, Axtmann (1974) noted the near conservatism of total As in the Waikato River and Lake 

Taupo below Wairakei in New Zealand.

The mean P concentration for the Firehole and 

Madison Rivers (5.5 /xg/L) is typical of low levels found 

in unpolluted rivers derived from forested drainage 

basins; the present estimates are smaller by a factor of 

20 than the As(V)-biased P data previously reported by 

Boylen and Brock (1973) and Zeikus and Brock (1972) 

for the Madison River system.

The field-extracted Al estimates reveal a significant 

loss of Al immediately following the mixing of the Gibbon and Firehole Rivers (table 7). However, following 

the pattern described for the other drainages studies, 

the laboratory-extracted Al data reveal smaller decreases, occurring more slowly as a function of distance 

below the confluence. The methodological difference 

may the result of the formation of nonextractable Al 

polymers (Smith, 1971), which are depolymerized during storage in 0.1 molar HNO3 . The loss of Al is not 

accompanied by a detectable loss of Li.

The Gibbon River contains higher Al, Fe, and Mn 

concentrations than the Firehole River. The concentration of soluble Mn decreases gradually below the confluence to ~1.6 /Ag/L near West Yellowstone; however, 

no significant change was detected in soluble iron (table 7). The large increases in Mn, Ca, and Mg concentration (1,400, 94, 140 percent, respectively) between 

stations 5 and 6 are a result of nonthermal waters entering Hebgen Lake from other drainage areas.

SORPTION CONTROLS ON ARSENIC IN GEOTHERMAL 

WATERS

Amorphic hydrous Fe oxides are the most efficient 

As scavengers in the class of amorphic precipitates 

formed by Al, Fe, and Mn in natural waters (Gulledge 

and O'Connor, 1973; O'Connor, 1974; Singer, 1974). 

The almost quantitative removal (>99 percent) of 

As(V) from neutral to acidic solutions using ferric hydroxide coprecipitation has been the chemical basis of 

many concentration schemes for analyzing As at low 

levels in the environment (Portmann and Riley, 1964). 

Furthermore, it is well known that the sorption affinity 

of ferric hydroxide for As(V) is greatly reduced under 

alkaline conditions (Portmann and Riley, 1964; 

O'Connor, 1974). Trivalent As is inefficiently sorbed at 

all pH values. For example, Logsdon, Sorg, and 

Symons (1974) found only about 50-percent removal of 

As(III) (initially at the 0.3 mg/L level) using a 30 mg/L 

ferric sulfate dose; the percentage removed was independent of acidity in the pH range 6 to 9. For As(V) 

(initially at 0.05 mg/L) O'Connor (1974) reported 88 

percent removal at pH 8.0 in the presence of 10 mg/L 

Fe(III).

Al is less effective than Fe at scavenging both As(III)
F16 GEOHYDROLOGY OF GEOTHERMAL SYSTEMS

and As(V), the differences increasing above pH 7.0. 

Logsdon, Sorg, and Symons (1974) found that 30 mg/L 

alkali aluminium sulfate (alum) treatments removed 

about 90 percent of As(V) and 10 percent of As(III) in 

the pH range 5 to 7. The initial As levels tested were 

0.30 mg/L, very similar to the total As concentration in 

the lower Firehole River. Above pH 7.0, the percent 

removal of As(V) by 30 mg/L alum declined almost 

linearly to 15 percent at pH 8.5.

The authors are not aware of quantitative studies on 

As sorption by MnO2 . However, in light of the chemical 

similarity between H3AsO4 and H3PO4 (the two acids 

have nearly identical pK values for all three dissociations, Sillen and Martell, 1964), and the inefficiency of 

phosphate sorption on MnO2 , Mn may play a relatively 

minor role in the sorption chemistry of As. As sorption 

on MnO2 is likely to be insignificant for two additional 

reasons: (1) The acid leaching of typical igneous rock 

solubilizes great stoichiometric excesses of both Fe and 

Al as compared to Mn; (2) the oxidation and precipitation of Mn is often delayed in geothermal waters until 

the pH is far too high to effect efficient removal of 

As(V).

The conservative behavior of total As in Octopus 

Spring is an expected consequence of the high pH and 

very high As/Fe atomic ratio of 570. Furthermore, very 

large As/Fe ratios are typical of alkaline hot springs 

throughout the major hot-spring basins. In Azure 

Spring, the initial soluble As/Al atomic ratio is only 

1.20, in contrast to the As/Fe atomic ratio of 183. However, Al precipitation occurs prior to station 3 in the 

drainage channel, and prior to the oxidation of a 

significant amount of As(III). This oxidation lag can be 

expected to greatly reduce the effectiveness of As removal by oxidic Al precipitates. Coprecipitation of Al 

with SiO2 to form montmorillonite (R. O. Fournier, oral 

communication, 1975) may also reduce As losses onto 

oxidic Al in the high-Al springs of the River Group. 

Thermodynamic calculations indicate Azure Spring is 

supersaturated with respect to several montmorillonites.

The levels of both P and As in the Yellowstone Canyon warm spring indicate that, even in the presence of 

anomalously high Fe levels (—200 /ug/L), the removal 

of As by sorption is relatively insignificant in this alkaline spring water. The low Fe/As molar ratios, the 

very large As(III)/As(V) initial ratios, and the rapidly 

rising pH after the emergence of the spring water at 

the ground surface all combine to reduce sorption by 

hydrous Fe oxides as an important mechanism affecting As in the drainages of alkaline hot springs.

As behaves nearly conservatively during the long 

base flow period (losses <2 percent of flux) in the 

Madison-Firehole River system. In addition to evidence previously discussed, samples obtained from the 

Firehole River at Madison Junction and just below 

Lower Basin (early October 1974) had Cl/As atomic 

ratios of 466, and 456, respectively. Given the probable 

analytical errors in the Cl and As determinations and 

the lag time in sampling, the ratio difference is not 

statistically significant. The Cl/As atomic ratio in the 

Firehole River is close to the median ratio for hotspring groups in the Firehole River drainage (R. E. 

Stauffer and J. M. Thompson, unpublished data,

1975). Because of inadequate spring flow data, a flowweighted mean Cl/As ratio for the hot springs in the 

Firehole River drainage cannot be precisely calculated. 

Based on Fournier, White, and Truesdell (1976) and 

the difference between the Upper, Midway, and Lower 

Basin Cl/As ratios, the Firehole River Cl/As ratio is 

close to a weighted mean for the springs of the drainage basin.

Near conservatism of As during low flow occurs because of the following factors: (1) The soluble Fe/As 

ratio is too low to significantly affect As by sorption or 

coprecipitation; (2) although the suspended solids may 

be assumed to have surface-active coatings of Fe oxides 

(Jenne, 1968, 1977), the concentration of suspended inorganic solids in the rivers is low during the low-flow 

period; (3) the alkaline pH of the river during daylight 

hours is suboptimal for As(V) sorption on Fe oxides.

During high runoff periods (principally the MayJune snowmelt period, Fournier and others, 1976) the 

pH of the Madison River drops and the riverborne flux 

of sorption-active elastics increases dramatically. During such periods the increased contact opportunity between As (V) and the amorphic Fe oxide coatings on 

the particulates might be expected to result in 

significant losses of soluble As in the Madison River. 

The most likely sink for sorbed As(V) during spring 

runoff is the sediments of Hebgen Lake.

The Cl/As atomic ratio for the Gibbon River at Madison Junction is 760, a value significantly higher than 

the ratios for key indicator springs in both the Gibbon 

(Cl/As=400 ± 25) and Norris (Cl/As=543 ± 11) hotspring basins (R. E. Stauffer and J. M. Thompson, unpublished data, 1975). The Gibbon and Norris thermal 

basins constitute most of the geothermal activity in the 

Gibbon River drainage basin (Fournier and others,

1976). The Cl/Li atomic ratio for the Gibbon River at 

Madison Junction is 20.1, intermediate among the 

mean ratios for the Norris (23.8 ± 0.5) and Gibbon 

(Gibbon Meadows area: Cl/Li = 19.2 ± 1.4; Artist Paint 

Pots: Cl/Li = 16.4 ± 0.4) geyser basins (R. E. Stauffer 

and J. M. Thompson, unpublished data, 1975). On the 

basis of the Cl/Li ratios, it is possible to infer that in 

excess of 50 percent of the Gibbon River Cl flux originates in the Gibbon Geyser Basin. An immediate im-
TRACE ELEMENTS IN HOT-SPRING DRAINAGES, YELLOWSTONE NATIONAL PARK F17

plication of this inequality is that 60 percent or more of 

the geothermal As flux in the Gibbon River drainage 

basin during base-flow conditions is removed by precipitation and sorption processes. The high Gibbon 

River Cl/As ratio probably results from As(V) sorption 

on hydrous Fe oxides and oxidic Al above Gibbon Canyon as the river's Cl/As ratio is also elevated in the 

canyon. Some As may also be precipitated as FeAsO4 

and realgar (AsS) in the acidic spring environments 

(depending on redox potential). Acid-sulfate waters 

containing high levels of Fe and Al mix with poorly 

buffered high-Cl, high-As waters in both the Norris 

and Gibbon thermal basin (Alien and Day, 1935; 

White, 1957); the pH of the weakly acidic water rises, 

and large amounts of Fe and Al precipitate. The mixing of two geochemically distinct water types in the 

Norris-Gibbon region thus produces conditions which 

are optimal for the sorption of As(V) on both Fe and Al 

precipitates. The time delay required for mixing and 

Fe(II) oxidation (Brock and others, 1976) helps insure 

that As initially in the form of As (III) has been 

oxidized to the more readily sorbing As(V).

ARSENIC FLUX OF THE MADISON RIVER

Using the September concentration estimate of 202 

/u,g/L of As and available earlier discharge measurements during September low flow at the West Yellowstone gaging station (12.7 m3/s, U.S. Geological 

Survey, 1974; flow measurement was discontinued 

after 1973), the estimated base flow total soluble As 

flux for the Madison River is 220 kg/day, 90 percent of 

which is contributed by the Firehole River. An additional 25 to 30 kg/day of As is precipitated in the 

Gibbon River drainage basin. Because the September 

geothermal As flux can be assumed to be representative of the daily flux on an annual basis (Fournier and 

others, 1976; R. E. Stauffer and J. M. Thompson, unpublished data, 1975), the annual total (soluble+particulate) As flux of the Madison River at West 

Yellowstone is ^90,000 kg. It is likely that particulate 

As deposited in the Gibbon drainage basin is flushed 

out during peak discharge in May and June and deposited in the sediments of Hebgen Lake.

The annual As flux for the Madison River is less than 

the flux estimate by Axtmann (1974) for Wairakei (158 

metric tons) and the atmospheric As flux estimated for 

the ASARCO Copper smelter in Tacoma, Wash. 

(150,000 kg/year, Crecelius, 1975). The Tacoma smelter acquired notoriety as a result of its high As flux 

(Lawson, 1975). Swain (1949) reported an atmospheric 

As flux of 22.5 metric tons/day for the Anaconda Smelter at Anaconda, Mont., a value which is nearly 100 

times the Madison River flux. The reason for the large 

discrepancy between the present ASARCO and historical Anaconda fluxes is unclear; however, the high 

Anaconda figure applies to a period prior to any pollution abatement, and As is currently recovered as a byproduct at the Tacoma plant. Because the smelter As 

flux is almost exclusively the highly toxic particulate 

As2O3 (Crecelius, 1975), and the Madison River flux is 

dominantly soluble As(V) at the 200 /u,g/L level, an important distinction exists between the environmental 

impacts of the two As sources. At levels above 1 mg/L 

in drinking water, As is associated with long-term toxicity effects in humans, As(III) being notably more 

toxic than As(V) (Penrose, 1974).

During low-flow conditions the total As concentration at the Hebgen Dam spillway is about 85 to 90 

/u,g/L, or about 75 percent, above the U.S. Public Health 

rejection limit for municipal water supplies (50 /u,g/L, 

Environmental Protection Agency, 1972). With increasing distance downriver, this level is presumed to 

be progressively reduced by dilution and sorption on 

elastics.

POTENTIAL ECOLOGICAL SIGNIFICANCE OF ARSENIC

The ecological role of As in the microbiological communities of the hot-spring drainages, and in the receiving rivers, is mainly a subject of conjecture. As is 

known to be oxidized and reduced (between As(III) and 

As(V)) by microorganisms under a variety of natural 

conditions (Johnson, 1972; Myers and others, 1973; 

Pilson, 1974). As is also concentrated by a factor of 

5,300 by the dominant macrophyte in the Waikato 

River (Axtmann, 1974, 1975). However, as Penrose 

(1974) noted, the concentration factors are likely to be 

highly dependent on aquatic species, as well as redox 

state of the As. Nothing is known at present about the 

As concentration factors for algae and macrophytes inhabiting geothermally derived waters in Yellowstone 

Park. Because of the chemical similarity between 

AsO4~3 and PO4~3 , and the importance of P as a critical 

nutrient for all plant forms, both the low levels of P and 

the very high As(V)/P ratios for many of the hot 

springs and receiving waters may be of enormous 

ecological significance in Yellowstone Park. Limnetic 

environments enriched in As have become dominated 

by the relatively tolerant blue-green algae (J. Shapiro, 

oral communication, 1978), suggesting that the As/P 

gradients in Yellowstone thermal waters may also act 

to select blue green. Oceanographers have noted that 

the As/P atomic ratio approaches 1.0 in the oligotrophic waters of the ocean (Portmann and Riley, 1964; 

Johnson and Pilson, 1972b). Penrose (1974) has noted 

that marine fish have relatively high As contents, 

probably as a result of concentration within the food 

chain and the effects of the As/P ratio on the phytoplankton. As concentration in phytoplankton is also
F18 GEOHYDROLOGY OF GEOTHERMAL SYSTEMS

the probable cause of the high As concentration in organically rich marine shales (Onishi and Sandell, 

1955). In Octopus Spring the As(V)/P molar ratio 

reaches 350, two orders of magnitude higher than the 

upper bound ratios likely to occur in the ocean. Even in 

the Madison River the As(V)/P ratio is about 15.

CONCLUSIONS

1. Soluble Al, Fe, and Mn approach low limiting values of <5.0, 1.0, and 1.0 ^g/L, respectively, in the 

least diluted high-Cl waters of the Norris and 

Upper Geyser Basins. The springs so characterized represent zones of highest enthalpy flux in 

the park. The levels of Al, Fe, and Mn do not 

appear to correlate with the presence or absence 

of dissolved S(-II).

2. The soluble-Mn levels are strikingly elevated (approximately two orders of magnitude) in alkaline 

springs of "mixed water" origin. These springs include the Mammoth hot springs, Steady Geyser, 

the unnamed spring north of the Old Faithful 

highway interchange, and the warm springs in 

the Yellowstone Canyon. The Mn/Fe atomic ratio 

is >1 in almost all of the alkaline springs of 

mixed origin, the ratio tending to increase with 

temperature.

3. The Mn/Fe ratio increases along the drainage channels of S(—ID-containing springs of mixed origin. 

The increase in the ratio probably reflects the 

slower rate of Mn(II) vs Fe(II) oxidation and the 

less effective solubility controls on Mn(II) at low 

temperatures.

4. Al precipitates rapidly in the relatively rare boiling 

springs containing elevated levels of the element. 

Al precipitation apparently occurs in Azure 

Spring prior to emergence of the water at the surface; the reaction proceeds virtually to completion 

at 89°C and pH <7.5.

5. Li, and to a lesser extent K, behave nonconservatively if Al is being precipitated from hot-spring 

waters. The most likely mechanism of Li removal 

is through the formation of Li-bearing 

aluminosilicate minerals.

6. P is present in very low concentrations (~2 ^tg/L) in 

undiluted hot-spring waters of the Upper, Lower, 

and Norris Basins. Higher concentrations of P are 

associated with warm springs of mixed-water 

origin.

7. The As(III)/As(V) ratio in these thermal waters varies over three orders of magnitude and is strongly 

bimodally distributed according to whether or not 

S(-II) is present in detectable quantities.

8. Arsenite is rapidly oxidized to As(V) in the hotspring drainages, but only after the volatilization 

and oxidation of S(—II).

9. Total As is essentially conservative (losses under 2 

percent) in all of the surface-water systems 

studied, with the prominent exception of the Gibbon River. The major losses of total dissolved As 

in the Gibbon River occur above Gibbon Canyon 

and are hypothesized to result from As(V) sorption on oxidic Fe and Al formed as a result of the 

mixing of acid-sulfate and alkaline high-Cl waters in the upper Gibbon drainage basin.

10. The high levels of As, the variable As(III)/As(V) 

ratios, and the extraordinarily high As/P ratios 

in Yellowstone geothermal waters are potential 

adverse ecological factors in the park.

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GPO689-143