Field Investigation of 

Mine Waters in the 

Northern Anthracite Field 

Pennsylvania 

GEOLOGICAL SURVEY PROFESSIONAL PAPER 473-B 

Field Investigation of 

Mine Waters in the 

Northern Anthracite Field 

Pennsylvania 

By IVAN BARNES, W. T. STUART, and DONALD W. FISHER 

MINING HYDROLOGY 

GEOLOGICAL SURVEY PROFESSIONAL PAPER 473-B 

UNITED STATES GOVERNMENT PRINTING OFFICE, WASHINGTON : 1964 
UNITED STATES DEPARTMENT OF THE INTERIOR 

STEWART L. UDALL, Secretary 

GEOLOGICAL SURVEY 

Thomas B. Nolan, Director 

For sale by the Superintendent of Documents, U.s~·Government Printing Office 

Washington, D.C. 20402 
• 

CONTENTS 

Abstract __________________________________________ _ 

Introduction ______________________________________ _ 

Field methods _____________________________________ _ 

Page 

B1 

1 

2 

Results ___________________________________________ _ 

Summary and conclusions ___________________________ _ References ________________________________________ _ 

ILLUSTRATIONS 

Page 

B3 

6 

8 

FIGURE 1. Location of mine shafts from which mine waters were sampled_____________________________________________ B3 

2. Sections at shafts showing generalized stratigraphy_______________________________________________________ 4 

3. Eh and pH data plotted on diagram from earlier theoretical considerations _____________________________ ---_ 7 

TABLES 

TABLE 1. Analyses of water from Loree No.2 shaft---------------------------------------------------------------- B3 

2. Analyses of water from Storrs No.1 shaft________________________________________________________________ 6 

3. Analyses of water from South Wilkes-Barre No.5 shaft____________________________________________________ 6 

m 

717-952-64 

MINING HYDROLOGY 

FIELD INVESTIGATION OF MINE WATERS IN THE NORTHERN 

ANTHRACITE FIELD, PENNSYLVANIA 

By IvAN BARNEs, W. T. STUART, and DoNALD W. FISHER 

ABSTRACT 

Results of a chemical study of anthracite coal mine waters 

under field conditions show conclusively that the mine-water 

compositions are controlled by mineral-water reactions. 

Oxygen-free (strongly reduced) samples were obtained from as 

little as 60 feet below the water surface in open shafts. The 

results of the field study may be rigorously interpreted in 

terms of the postulated reactions and the information available 

on the mineralogy of the coal measures. Dissolved-iron concentrations and redox potentials observed at different levels in 

three mine shafts agreed with the principles in a published 

theoretical discussion. 

INTRODUCTION 

In an earlier report (Barnes and Clarke, 1964) the 

compositions of coal-mine waters were conside~ed using 

data from published sources. From the total Iron concentrations reported and the pH data cited, there was 

little likelihood of the occurrence of detectable dissolved 

oxygen in most coal-mine waters until such water discharged onto the land surface. 

The predicted absence of dissolve~ ox~gen c~st so~e 

doubt on the effectiveness of reactiOns Involving dissolved oxygen in producing the solutions found in 

mines. Reactions involving oxygen, however, are commonly accepted in the literature (Hanna a~d oth~rs, 

1963 is a recent example) as the cause of amd-beanng ' . . water. A frequently cited reactiOn IS 

2 FeS2+7 02+2 H20=2 FeS04+2 H2S04. 

Barnes and Clarke suggested that dissolved oxygen 

(or air) be discarded as a major reactant in mine waters and that reactions involving only water and minerals be considered as controls of subsurface mine-water 

quality. The effects of subsequent oxygenation were 

outlined, but, as was pointed out, the oxygenation effects 

are superposed on the initial water-mineral reactions. 

Mine waters are commonly observed to contain appreciable iron and sulfate in solution, and this observation 

717-952--64----2 

leads to the connnonly accepted and quite plausible conclusion that iron-sulfur compounds or minerals are responsible for the composition of mine waters. The most 

commonly observed iron -sulfur minerals in the coal 

measures are pyrite and marcasite, both having the 

composition FeS2 but differing in crystal structure. 

From the theoretical study based upon available chemical analyses, it was concluded that pyrite and water 

must be the reactants (oxygen being ruled out) and 

that iron and sulfate must be among the dissolved 

products. The theoretical study also showed that the 

iron in solution must be divalent (ferrous ion), leading 

to the partial reaction based on observation 

FeS.~~+s ao~Fe+ +2 so,-:. 

Recapitulating the reasoning, the iron in mine water 

must come from iron-sulfur minerals, which are also 

the major supply of the sulfate. Production of sulfate 

from sulfide or disulfide minerals requires oxygen, but 

there cannot be enough dissolved oxygen as a reactant, 

and the only other sources of oxygen are water and silicates. The silicates are not deoxygenated, so the major 

supply of oxygen must be the water itself. The reduction of water to supply the oxygen raises a further 

problem. The complete reaction suggested by Barnes 

and Clarke was 

FeS2+8 H20=Fe+2+2 804-2+2 H+1+7 H2, 

and the problem raised was the fate of the hydrogen. 

It was suggested that in addition to dissolved hydrogen 

some of the hydrogen could be used in hydrogenation 

of nonaromatic fractions of the coal. Some of the hydrogen might also dissolve in the coal. A less likely 

reaction between the coal and hydrogen might produce 

methane. Many other organic products containing and 

not containing sulfur may be postulated. In the absence of detailed analyses of gases dissolved in mine 

water, no test may be made of the postulates. 

Bl 
B2 MINING HY.DROLOGY 

A purely inorganic consumption of hydrogen was 

suggested by Henry G. Jacobson of the U.S. Bureau of 

Mines in a personal communication. The suggested 

reaction was the reduction of ferric minerals such as 

hematite by the hydrogen produced by the reaction of 

pyrite and water. The reduction of hematite may be 

written 

FIELD METHODS 

A field study of mine waters was undertaken to test 

the earlier theoretical conclusions. The techniques developed by Back and Barnes (1961) were adapted to 

the problem of sampling water from shafts of flooded 

mines. As was mentioned by Barnes and Clarke ( 1964), 

reliable dissolved oxygen and redox measurements are 

mutually exclusive. The theoretical study showed oxygen to be essentially absent; and hence the theory was 

cast in terms of redox potential (Eh), pH, and compositional variables. 

The problems found in the investigation of minewater cmnpositions were anticipated from the earlier 

work of Barnes and Back (1963). Essentially, the 

sampling was done by pumping from a predetermined 

level to the land surface, care being taken to avoid the 

ingress of air or any other contaminant into the san1ple. 

To accomplish this, a submersible plastic-coated pump 

was lowered into the water in the mine shafts. The 

water was pumped to the land surface through 1112-inch 

plastic pipe (high-pressure polethylene) which had nylon insert couplings. The only metals in contact with 

the water in the pumping system were bronze pump 

impellers, a brass gate valve for throttling the flow on 

the land surface, 6 inches of copper tubing, and the 

brass top of the sampling chamber. The metals in contact with the water are all nonferrous and, considering 

the brief contact time, could not produce an appreciable 

effect on the water composition. No check valve was 

used on the pump. The 1naximum residence time for 

water in the pumping system from the deepest sampling 

level was less than 6 minutes, and nearly all that time 

the water was in contact with the inert plastic pipe 

and fittings. 

In the South Wilkes-Barre mine, an operating 4,000-

gpm turbine pump was used for sampling. The residence time of the water in the turbine pump column 

was less than 1 minute, which was an insufficient time 

for appreciable water composition changes. 

Where the submersible pump was used, it was set in 

the shaft at elevations corresponding to the elevations 

of openings from the shaft into the 1nine workings 

where possible. The pump used was operated continuously until sampling was complete. Each level was 

sampled as the pump was lowered to minimize contamination. The water in the South Wilkes-Barre shaft 

was sampled at the fixed level of the pump intake. 

The water pumped from the mines was sampled for 

Eh using the techniques of Back and Barnes (1961) 

using a saturated calomel reference electrode ( SCE) 

and a platinum thimble electrode. The operation of 

the electrodes was tested frequently using the solution 

described by ZoBell, as reported in Garrels ( 1960, p. 

68). The observed Eh of the ZoBell solution deviated 

by no more than 0.012 volt from the known value; so the 

Eh data should be regarded as reliable within 0.012 volt. 

Sampling for Eh was assumed complete when there 

was no detectable change in the measured electromotive 

force (Eh+EscE) over a 10-minute period. The meter 

used for Eh measurement was a Beckman model G, 

which yields readings reproducible to ± 2 millivolt. 

The meter used for pH was a Beck1nan model N, 

which has been shown accurate to ± 0.02 pH under field 

conditions (Barnes, 1964). The pH was measured by 

the two-buffer technique described by Barnes to correct 

for departures from ideal behavior of the pH measurement system. Analyses in the field for ferrous iron concentrations were made by the permanganate method 

(Furman, 1962, p. 544-546), not using the Jones 

reductor. The permanganate method results are preferred for the high concentrations observed. Laboratory sulfate analyses were by the spectrophotometric 

titration method (Rainwater and Thatcher, 1960, p. 

281-282). The manganese determinations were the 

same as described by Rainwater and Thatcher (p. 205-

207) except that the excess hydrochloric acid was removed by evaporating the samples almost dry after 

adding nitric acid. Aluminum detern1inations were 

made by the method described by Rainwater and 

Thatcher ( p. 97-99) after a preliminary separation as 

given by Furman (p. 78). The separation of magnesium and calcium was effected by the precipitation of 

iron, aluminum, and manganese by ammonimn hydroxide at a pH of 7 .5-8.0. Total hardness and calcium were 

determined in the filtrates by the methods of Rainwater 

and Thatcher (p. 174-176, 127-129), except that the pH 

adjustment in each sa1nple was measured by a pH 

meter rather than by adding a standard volmne of base 

to all samples. Magnesium was calculated as the difference between total hardness and the calcium concentration. Silica was determined following the procedure of 

Rainwater and Thatcher (p. 259-261). For sodium and 

potassium, samples were evaporated and the soluble 

material was dissolved in hot water, filtered and then 

analyzed on a flame photometer. For chloride determi-
MINE WATERS, NORTHERN ANTHRACITE FIELD, PENNSYLVANIA B3 

nations, the samples were neutralized by adding sodium 

hydroxide and boiled to remove iron and aluminum. 

The chloride concentration in the filtrate was determined following the method described by Rainwater 

and Thatcher (1960, p. 141-143). 

The location of the mine shafts sampled is given on 

the index map, figure 1. The approximate stratigraphic 

sections are given in figure 2, which has been compiled 

from mine company records and by projection from 

other sections. Althorl,gh the location of the coal is well 

known, the relative proportion of clastic materials is 

approximate. Descriptions of the detailed mineralogy 

I 

0 10 20 

LORE£ 2 rJ l'l Pittston 

;?"Wi I kes- Borre 

SOUTH WILKES-BARR£ 5 

FIGURE 1.-Map showing location of mine shafts from which mine 

waters were sampled. 

of the coal beds would not materially improve the interpretation of the water composition obtained because 

the detailed flow path to any sampling point is not 

known, even though the regional hydrology is known 

in general. Interconnections exist between beds as a 

result of mining practices. There has been collapse or 

failure of the rock strata by subsidence since active 

mining began in most of the basin, but the channels and 

pathways for water movement opened by such failure 

are not known. The lack of detailed knowledge about 

flow paths in no way invalidates the theoretical geochemical considerations. Iron disulfides (FeS2 ) are 

known to be ubiquitous in the northern anthracite field, 

as are coal and water; hence the chief reactants are 

present. Subsequent side reactions which would further 

modify mine-water compositions are probable but speculative. The nature of some of the inorganic side reactions has been discussed briefly by Barnes and Clarke 

(1964). 

RESULTS 

The results of the field investigation and analyses of 

the water from Loree No. 2 shaft are smnmarized 

briefly in table 1, which gives the Eh, pH, cmnpositions, 

and field description of the water as it emerged from 

the plastic pipe in the field. 

The water in the shaft is not homogeneous; there are 

three chemically distinct layers of water in the mine. 

Stuart and Simpson's data (1961) also indicate compositional variation of coal-mine waters according to 

depth. The solution constituting the upper layer of 

water having Eh values in the range +0.31 volt to +0.32 

volt is more reduced (less oxidized) than the intermediatelayer (Eh +0.53voltto +0.56volt). The water body 

which is intermediate in depth is the most oxidized soluTABLE 1.-Analyses of water from Loree No.2 shaft 

[Concentrations in parts per million; water level 162 feet below land surface] 

Depth 

below 

land T (°C) surface 

Eh(v) pH Color Gas Odor Fe+2 S0c2 Mn+a AJ+3 Ca+a Mg+2 Si02 Na+l K+l CI-1 

(feet) 

-- --------------_....._ 

224 14 +O. 322 3.41 Clear _______ Slightly ef- None _______ 34 1, 260 12 7 180 148 14 ----- ----- ---- fervescent. 

233 14 +. 312 3.40 ___ do _______ ___ do _______ _____ do ______ 34 1,260 13 9 172 152 15 ----- ----- ---- 292 17 +. 533 3.55 Yellow tur- Very effer- _____ do ______ 478 3,320 37 79 342 292 30 <25 <IO ---- bidity. vescent. 

438 17 +. 533 3. 51 ___ do _______ ___ do _______ _____ do ______ 488 3,400 39 83 343 299 31 <25 <IO ---- 467 17 +. 568 3. 36 Slight yel- No gas _____ do ______ 488 3,650 44 86 363 326 33 <25 <IO ---- low tur- evolved. 

579 17.5 +. 562 3. 40 

bidity. ___ do _______ Efferves- _ ____ do ______ 546 3,960 44 99 378 354 37 ----- ----- ---- cent. 

751 17 -. 025 4. 00 Clear _______ No gas Pronounced 1,073 5,800 90 135 439 452 60 ----- ----- ---- evolved. "rotten 

egg" smell. 

808 17 -.103 3.92 ___ do _______ Efferves- _____ do ______ 1, 463 6,720 92 143 456 462 85 35 <IO 11 

cent. 
B4 MINING HYDROLOGY 

STORRS SHAFT 1 SOUTH WILKES-BARRE SHAFT 5 LOREE SHAFT 2 

I~ (f) 

>-

(f) 

z 

~ 

z 

<( 

> ...J 

>-

(/) 

z 

z 

w 

a_ 

w 

....J 

....J 

> 

U) 

1-

1-

0 

a_ 

I 

1-

(f) 

0 

a_ 

a: z W C) 

CD i= :::?: u w w 

:::?: Ul 

Q) 

0 

3: 

Clear,~gs 

z :::?: 0 a: w i= w 1- <( CD 

Ul :::?: :::?: >- a: w Ul 0 :::?: lL 

Quat 

w z ....J 

~ ....J 

<( 

z > 

Ul > 1- ....J 

>- 1- Ul 0 z a.. z I 

w 1- a.. Ul 

0 

a.. 

z -c -g f/) 0 ~ 0 g i= 

u 0 cv ·c w E ., 0 a. Ul u g 0 

Land surface 

No.3 

Auble 

New 

Snake Island 

Abbott 

Kidney 

Upper Diamond 

Lower Diamond 

Upper Checker 

Lower Checker 

Upper Pittston 

Lower Pittston 

Q) 

~ 0 

Ul 

Water level 

Pump 

intake 

Q) 

0 

3: 

:::?: a: z "'0 "'0 "' c: Q) w w 0 Q) 0 g 1- CD i= .0 "i l Q) 

(f) :::?: u g E 0 

>- w w g Ul 3: (/) :::?: Ul u 

Land surface 

1-auo-,+--+--+~~.:~:~·~:r~~~ 

w 

....J 

....J 

> 

(/) 

II0 z a_ 

<( I 

1- z Ul 

<( 0 > a_ ....J 

>-

(/) 

z 

z 

w 

a.. 

Water level 

} Clear, 

gassy 

ll!!l!"!!~I!III!!-!~~~~ TuJ~~~y 

1!!!11!!!~~~~=.!...-.j-Siightly 

cloudy, no 

gas 

":.·~·.·~·; Bottom of 

w 2 • • • • shaft 

j ~ 

> 5 (/) 0 1- :!: 1- 0 a_ a.. a:: 

<( 

:c 

(/) 

EXPLANATION 

D No ovo i I oble dolo 

Glacial till and alluvium 

Conglomerate 

Sandstone 

Shale and siltstone 

~ Coal 

Boney 

~ 

~ 

cool 

FEET 

0 

100 

200 

300 

400 

Vertical scale 

FIGURE 2.-Sections at shafts showing generalized stratigraphy. 

tion found in the mine. The deepest part of the pool 

sampled is also the most reduced. The properties of 

the water observed in the field may be interpreted in 

terms of the theoretical study by Barnes and Clarke 

( 1964) . The uppermost layer of water should not be 

saturated with Fe(OH) 3 and should be perfectly clear 

as it emerges from the plastic pipe. If any Fe(OH)3 

is in contact with the water in the upper part of the 

shaft, it should be dissolving. The water is also unsaturated with pyrite, which if present should also be 

dissolving. The water at intermediate depths is in the 

range predicted by Barnes and Clarke for saturation 

with Fe( OH) 3 in terms of pH, Eh, and Fe+2 and indeed 

is actually precipitating Fe( OH) 3 (locally known as 

"yellow boy") as is indicated by the turbidity of the 

samples observed. The electrochemical model has the 

virtue of being consistent with the observations. The 

reactions 

and 

Fe+8+3Ita0=Fe(OH)a+3H+1 

apparently do poise the Eh as was suggested by the calculation of maximum Eh values based on the reactions. 

The very low Eh values for the deep waters in Loree 

No. 2 shaft indicate that the model of Barnes and 

Clarke ( 1964) was quite conservative. Eh data from 

below the Fe(OH)a-pyrite boundary (and also below 

the pyrite-Fe20a boundary) indicate that there ·are 
MINE WATERS, NORTHERN ANTHRACITE FIELD, PENNSYLVANIA B5 

species present which are even more reduced than 

pyrite. The nature of the more reduced species is problematical in the absence of more detailed geochemical 

studies of the coal, but possibly the coal itself is the 

more reduced reactant. 

The samples from the Loree No.2 shaft have a narrow range of pH values in spite of the wide range in 

values for Eh and composition. The probability of 

side reactions between mine water and silicates and 

carbonates has been mentioned earlier (Barnes and 

Clark, 1964), and the pH buffering effect of such reactions has been noted. It would be unlikely that the 

pH data from Loree No. 2 shaft would fall between 

3.4 and 3.9 if no buffer reactions took place considering 

the high yield of hydrogen ions from the solution of 

pyrite. The aluminum in solution is probably from 

the seat clays (underlying shale) dissolving in the acid 

solution. 

Samples of the gas which evolved from the water 

pumped from a depth of 292 feet from the Loree No. 2 

shaft were obtained. The gas neither burned nor supported combustion in a simple field test, but more detailed information on the composition of the gas is 

lacking. The gas may be nitrogen, especially if entrapped air is dissolved as the water level rises. Entrapped air might ·also be invoked to explain the 

turbidity of the water from the intermediate levels in 

the mine, and if so, then the pertinent reactions considered by Barnes and Clarke (1964) may be summarized as 

4Fe+9+0l!+lOH20=4Fe(OH)a+SH+1

• 

The low pH values in water near the mine-water 

surface and in the gas-charged wa;ter at intermediate 

depths relative to the higher pH values in the deepest 

two samples are not in conflict with a possible depletion 

of iron content by oxidation to Fe(OH) 3• The precipitation of iron from the water 3!t the shallowest 

depths, if precipitat1on ever took place by oxidation, 

has now ceased. Possibly any oxygen present in this 

water was exhausted as the mine first flooded, and ultimately reducing conditions were established from 

water-mineral reactions. The existence of pH buffering 

reactions is indicated, because the oxidation and precipitation of the iron should produce large amounts of 

hydrogen ions. The low concentrations observed probably result from the hydrolysis of the silicates and seat 

clays present. 

The noxious odor of the gases evolved from the water 

pumped from the deepest sampling levels presumably 

indicates the presence of sulfur compounds. More 

elaborate analyses than were possible in the field would 

be necessary to determine the exact nature of the volatile 

components. The occurrence of H2S is possible, but in 

part the sulfur may also be found to be organically 

combined. Further work on the detailed composition 

of the gases dissolved in mine water may well elucidate 

what reactions might be of significance in addition to 

those studied. The entirely inorganic reactions which 

were quantitatively studied would not produce such low 

Eh solutions as were found deep in Loree No. 2. .A 

semiquantitative analysis for reduced nitrogen compounds in the water gave negative results. Certainly 

either H2S or organic gas components should show that 

the dissolved or gaseous oxygen postulated by earlier 

workers cannot be a factor in producing compositions 

such as those obtained from the deep waters sampled. 

Although the samples of water from the greatest depths 

in Loree No.2 also have the lowest Eh and the highest 

iron and sulfate concentrations, to assume any depth 

control on water compositions might lead to error. Before any definite conclusion could be reached, it would 

have to be shown that the compositional differences 

could not be explained on the basis of different mineral 

assemblages or ooal compositions. Perhaps much more 

fieldwork could show empirically tlrat a depth-composition relation exists, but no firm theoretical basis for 

such a prediction has been obtained. 

There is a concomitant rise in manganese concentrations with the rise in iron concentrations. The source 

of the manganese is not known. The ratio of Fe: Mn 

varies from 3 : 1 to about 10: 1 in Loree No. 2. If the 

manganese could he recovered, it might augment the 

meager domestic reserves of manganese. 

A series of samples was withdrawn from the Storrs 

No. 1 shaft, and the results of analyses of these samples 

obtained are given in table 2. 

The results of the field investigation show that there 

are two different water m'asses in the Storrs No. 1 shaft. 

The excellent agreement of Eh, pH, Fe+2, and S04- 2 in 

the upper body indicate the reproducibility of the analytical methods. The pH values obtained from the 

shallow water body in the Storrs No. 1 shaft were the 

highest observed from pumped samples. The nature of 

the mineral buffers in the pH at such high levels is not 

known. Carbonate minerals cannot be ruled out without further study, 'again emphasizing the need for more 

detailed work than has been reported in the past. 

Much of the discussion of the gases in Loree No. 2 

shaft applies to the gases evolved from the shallow 

samples obtained from Storrs N-o. 1. If carbonate minerals do participate in buffering high pH mine water as 

compared to the pH values obtained in the other two 

shafts, appreciable quantities of C02 may be evolved; 

there may b~ a subsequent escape of the co:! as a component in a gas phase as the confining pressure on the 

water decreases. 
B6 MINING HYDROLOGY 

The lower water body, as represented by the sample 

from a depth of 550 feet, was strikingly different froni 

the upper water body, the lower having about twice as 

high a dissolved-solids concentration and having a lower 

pH and a higher Eh. Probably the differences could be 

explained in terms of different prior histories of the two 

water masses; however, as has been noted earlier, a 

detailed discussion of differences in flow paths and environmental histories of the water bodies would be 

entirely speculative. 

In spite of the compositional differences, all samples 

drawn from Storrs No. 1 shaft are saturated with both 

pyrite and Fe ( OH) 3 or a less hydrous ferric oxide. 

The 1nineral pair Fe(OH) 3 -pyrite should poise the Eh 

of a coexisting aqueous solution, and hence it would not 

be surprising to find a preponderance of observational 

data along the pyrite-Fe(OH) 3 boundary. The ironn1anganese ratio is again about 10: 1. 

The properties of the water pumped from the South 

Wilkes-Barre No. 5 shaft are summarized in table 3. 

The water sa1npled from the South Wilkes-Barre 

mine is an1ong the three 1nost reduced solutions and yet 

it was withdrawn only 64 feet below the water surface. 

The Eh is well below the Fe(OH) 3 -pyrite boundary, 

again showing that more reduced materials than pyrite 

are reacting. 

SUMMARY AND CONCLUSIONS 

The electrochemical data are summarized in figure 3. 

Points 2 and 3 on the diagram represent samples that 

were turbid, and they lie in the area predicted for waters saturated with Fe( OH)s, which apparently is actually precipitating. The samples are the most oxidized 

found, and they show that the predicted upper limit 

of Eh is reliable. The reaction producing the turbidity 

from air trapped during mine flooding may be regarded 

as 

4 Fe+2+02+10 H20=4 Fe(OH)s+8 H+\ 

From the field data the reaction poises the Eh along 

the band predicted until the Fe+2 or the 0 2 is exhausted. 

The fact that the pH remains in the range 3.4 to 4.0 in 

the Loree shaft in spite of the wide variation in iron 

concentrations and in spite of the large production of 

H+1 frmn the oxidation and precipitation of iron bears 

out the earlier suggestion that side reactions with clay 

minerals should buffer the pH. Indeed, the source of 

the Al+3 reported in the analyses could only be the clays 

present. Carbonates, if present, would be expected to 

buffer the pl-I at higher levels (pH 5-8). 

Points 6 and 7 on figure 3 are data from Storrs No. 1 

shaft. All four samples represented are in simultaneous equilibrimn with iron oxyhydroxides and pyrite, 

and their properties are as predicted from the theoretical work. These samples have Eh values near the minilnun1 to be expected in systems poised by pyrite and 

ferric hydroxide. A less stable sulfide (marcasite) or 

a more stable oxide (hematite) would have only a slight 

effect on the oxide (or hydroxide) -sulfide boundary and 

would have only a slight effect on predicted Eh values 

even if large changes in the composition of the mine 

water are considered. The high pH (5.5) of the shallower water at Storrs probably indicates at least a 

partly effective buffering of pH by carbonate minerals. 

TABLE 2.-Analyses of water from Storrs No. 1 shaft 

[Concentrations in parts per million; water level, 227 feet below land surface] 

Depth 

below 

land 

surface 

T (° C) Eh(v) pH Color Gas Odor Fe+2 S0c2 Mn+2 Al+3 Ca+2 Mg+2 SiOs Na+t K+t CI-1 

(feet) 

------------------

300 16 -0.030 5. 41 Clear Very efferves- Noxious ______ 107 1,340 11 0 247 145 16 ----- ----- ---- cent. 

363 16 -. 028 5. 41 ___ do ___ Not efferves- Slight!y 107 1,330 12 0 250 142 16 ----- ----- ---- cent. nOXIOUS. 

423 15. 5 -. 038 5.38 ___ do ___ _____ do _________ _____ do _______ 107 1,350 12 0 237 151 16 ----- ----- ---- 550 16 +. 078 3. 95 ___ do ___ _____ do _________ None ________ 249 2, 090 20 24 301 193 25 <25 <10 ----

TABLE 3.-Analyses of water from South Wilkes-Barre No.5 shaft 

[Concentration in parts per million; water level, 398 feet below land surface] 

Depth 

below 

land T°C Eb(v) pH Color Gas Odor Fe+2 socs Mn+2 AJ+3 Ca+2 Mg+2 Si02 Na+1 K+t CI-1 

surface 

(feet) 

-- -- ------ -- ---- ------

452 19 -0.012 4. 20 Clear No gas evolved ______ None ____ 839 4, 530 38 20 386 278 49 305 ---- 10 
MINE WATERS, NORTHERN ANTHRACITE FIELD, PENNSYLVANIA B7 

The possibility of such buffering was anticipated in the 

earlier examination of the controls on mine-water compositions (Barnes and Clarke, 1964). 

The low Eh values represented by points 4, 5, and 8 

in figure 3 would seem to require equilibria different 

from those so far mentioned. The mineral species that 

could be involved might include components of the coal, 

or other material left in the mine. 

1.1 

1.0 

0.9 

0.8 

0.7 

0.6 

0.5 

V> = 0.4 0 

> 

-~ 0.3 

L 

w 

0.2 

0.1 

0.0 

-0.1 

-0.2 

-03 

-0.4 

Successful predictions were made of the properties of 

the water in the mines studied based on the reactions of 

the natural materials present. There is little doubt 

about the validity of 1 he earlier proposed theoretical 

model. Because equilibrium conditions are frequently 

obtained, the compositions of mine waters will follow 

the model until deletion of the reactants considered, and 

hence n1ine drainage pollution will continue for an extended period of time. 

SAMPLE MINE DEPTH, IN 

FT BELOW LSD 

2 { 224 LOREE 

233 

LOREE 2 { 292 *2 

438 

{ 467 *3 LOREE 2 

579 

4 LOREE 2 751 

5 LOREE 2 808 

6 STORRS I ro 363 

423 

7 STORRS I 550 

8 S WILKES-BARRE 5 452 

*ALL SAMPLES TURBID 

FIGURE 3.-Eh and pH data plotted on diagram from earlier theoretical considerations. 
B8 MINING HYDROLOGY 

REFERENCES 

Back, 'Villi.am, and Bar.nes, Ivan, 1961, Equipment for field 

measurement of eleetrochemical potentials: U.S. Geol. 

Survey Prof. Paper 424-C, p. C366-C368. 

Barnes, Ivan, 1964, Field determinations of pH and alkalinity: 

U.S. Geol. Survey Water-Supply Paper 1535-H (in press). 

Barnes, Ivan, and Back, William, 1963, Geochemistry of the 

iron rich ground waters of southern Maryland: Jour. 

Geology, v. 71, no. 6 (in press). 

Barnes, Iva.n, and Clarke, F. E., 1964, Geochemistry of ground 

water in mine drainage problems: U.S. Geol. Survey Prof. 

Paper 473-A, p. A1-A6. 

Furman, N. Howell, ed., 1962, Standard methods of chemical 

analysis, 6th ed.: New York, D. van Nostrand Co., 1401 p. 

Garrels, Robert M., 1960, Mineral equilibria: New York, Harper 

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