Water-Supply and Irrigation Paper No. 186 Series L, Quality of Water, 16

DEPARTMENT OF THE INTERIOR

UNITED STATES GEOLOGICAL SURVEY

CHARLES D. WALCOTT, DlBECTOB

STREAM POLLUTION BY ACID-IRON WASTES

A REPORT BASED ON INVESTIGATIONS 

MADE AT SHELBY, OHIO

BY

HERMAN STABLER

WASHINGTON

GOVERNMENT PRINTING OFFICE 

1906
DEPARTMENT OF THE INTERIOR

IJNITE0 STATES GEOLOGICAL SURVEY

CHAKLES D. WALCOTT, DiBECTOK

 f'/ *8>

'a**.

EAM POLLUTION BY ACID-IRON WASTES

A REPORT BASED ON INVESTIGATIONS 

MADE AT SHELBY, OHIO

BY

HEUMAISr STABLER

WASHINGTON

GOVERNMENT PRINTING OFFICE

*®^
CONTENTS.

Page.

Introduction.............................................................. 5

History of pollution by acid-iron wastes at Shelby, Ohio, and resulting litigation .. 6

Effect of acid-iron liquors upon sewage-purification processes................... 11

General conditions..................................................... 11

Total solids........................................................... 19

Loss on ignition....................................................... 21

Oxygen required...................................................... 21

Albuminoid ammonia and organic nitrogen............................... 22

Free amonia........ ^................................................ 23

Nitrites and nitrates................................................... . 23

Alkalinity-........................................................... 23

Summary............................................................ 23

Present conditions along the stream......................................... 25

Recovery of copperas from acid-iron wastes.................................. 28

The pickling process................................................... 28

Character of liquors at Shelby...................................---.._. 30

Rinse water.......................................................... 32

Spent pickling liquor.................................................. 32

Copperas plant at Shelby.............................................. 33

Other processes for disposal of pickling liquor................................. 35

Summary................................................................ 35

Index.................................................................... 37

ILLUSTRATION.

PLATE I. Plan of sewage-disposal plant at Shelby, Ohio.
STREAM POLLUTION BY ACID-IRON WASTES.

By HERMAN STABLER.

INTRODUCTION.

Stream pollution by ironworks effluents has always been an important question in countries where the iron industries are prominent. 

The polluting liquors, commonly known as " acid-iron" liquors, are 

derived from the "pickling process" common to galvanizing, tin 

plating, tube and sheet iron treatment, and, in fact, all work in which 

a clean iron surface for coating or other purpose is required. The 

clean surface is obtained by immersing the material in a fairly strong 

solution of hydrochloric or sulphuric acid, which readily removes the 

surface impurities and at the same time attacks the material itself, 

dissolving it or uniting with it to form new compounds. As a result 

of the process the material treated comes from the bath with a surface 

as clean and bright as if newly polished. By continued use the acid 

solution becomes gradually weaker, iron chlorides or sulphates being 

formed, and the whole bath becomes more or less impregnated with 

impurities, chief among which are practically insoluble iron oxides. 

Finally the solution becomes too weak for further profitable use and 

is discarded as waste, technically known as "waste pickle." This 

waste pickle, it is said, has been bottled and sold as tonics for human 

consumption, though not with great success. Used in small quantities, however, it is beneficial to both animal and vegetable life. It 

is not a desirable addition to streams (1) because it produces a reddish 

discoloration and turbidity, making the stream waters, bed, and 

banks unsightly; (2) because, by reason of its avidity for oxygen, it 

robs the waters of their natural supply of ttiis essential gas and 

thereby, when it is present in comparatively large quantities, causes 

the death of fish, and (3) because it gives rise to a large quantity of 

iron in the stream, and thereby impairs the usefulness of the water 

for domestic and laundry purposes and for certain manufacturing 

processes.

In many cities waste pickle is discharged into the sewers. Where 

the quantity of pickle is relatively very small this method of disposal 

is not objectionable. Too frequently, however, there is enough free 

acid in the waste liquors to corrode the sewer joints and metal fittings,

5
6 STREAM POLLUTION BY ACID-IRON WASTES.

and, in case there are sewage purification plants, to interfere seriously 

with the working of the purification processes.

At Shelby, Ohio, acid-iron wastes have been discharged into a 

watercourse and also into the sewers of the town, causing conditions 

which have led to lawsuits and complaints directed to the Ohio State 

Board of Health. It was determined, therefore, to investigate at this 

city the factory processes which are accountable for the alleged 

nuisance and the conditions at the sewage-disposal farm and along 

the stream. The investigations were performed under a cooperative 

agreement between the United States Geological Survey and the State 

Board of Health of Ohio, each bureau participating equally in the 

expenses involved. All expenses for analytical work and for transportation of samples, together with the traveling expenses and subsistence of the investigators, were borne by the Ohio State Board of 

Health,"so* that joint credit should be given to the two bureaus 

participating in the work.

The pollution at Shelby having extended over a term of years under 

varying conditions, it was thought advisable to make the investigation cover (1) the history of the pollution and the attendant litigation;

(2) the effect of acid-iron liquors upon sewage purification processes;

(3) the^onditioiis along the stream, and (4) the disposal of acid-iron 

wastes without discharge into watercourse or sewerage system.

It is desired to make acknowledgment of assistance received in the 

investigation from Mr. William F. Sonnanstine, superintendent of the 

Shelby sewerage system; Messrs. Mansfield and Long, attorneys, and 

Mr. A. C. Morse, superintendent of the Shelby Steel Tube Company. 

Mr. M. O. Leighton, chief of division of hydro-economics, U. S. Geological Survey, personally supervised and directed the course of the 

investigation. In addition to sharing the expense of the investigation 

the Ohio State Board of Health accorded active cooperation by affording the use of its laboratory to the writer and by making sanitary 

determinations of the eight samples of' sewages listed in the table on 

page 18, which were made in the laboratory of the Ohio State Board 

of Health under the direction of Mr. E. G. Horton, bacteriologist 

and chemist.

HISTORY OF POLLUTION BY ACID-IRON WASTES AT 

SHELBY, OHIO, AND RESULTING LITIGATION.

The Shelby Steel Tube Company maintains a large plant on the 

bank of a brook within the city of Shelby. The tube mills were first 

operated in 1890, since which time the present company and its predecessors have, to a greater or less extent, discharged their liquid wastes 

into the adjacent brook, which, for convenience, we shall designate 

Red Brook, no generally recognized local name being applied to it. 

Tlie flow of Red Brook varies perefeptibly-with the flow,of waste water
HISTOBY OF POLLUTION AT SHELBY, OHIO. 7

from the tube works, but is generally about one-fifth or one-sixth 

as great as that of Black Fork, °. into which it discharges in the upper 

part of Shelby. Black Fork traverses the city from south to north, 

passing on through an agricultural district, and finally reachMg 

Muskingum River.

Until sometime in 1902 the entire waste of the tube works was 

discharged into a settling basin, from which it overflowed to R$l 

Brook, giving to it and to Black Fork a red discoloration for miles 

below. No very vigorous protest against this pollution seems to 

have been made until October 20, 1902, when petition was filed and 

suit for $2,500. damages was begun in the court of common pleas of 

Richland County, Ohio, against the Shelby Steel Tube Company by 

Isaac Noecker, a farmer having 50 acres of bottom land subject to 

overflow from Black Fork about 4 miles below the tube works. Previous to this time it was apparently the view of all parties concerned 

that the tube works, employing a large number of men, was an industry to be fostered; that the stream was the only available means foj 

the disposal of its waste, and that any inconvenience resulting from 

stream pollution by the works should be borne on account of its 

general benefit to the community. This is probably the view now 

taken by the city in allowing the effluent from the tube works to 

enter its sewerage system, permission for such use of the sewers being 

taken advantage of by the company in 1902 a direct result, no 

doubt, of the growing legal complications attending the discharge of 

the waste liquors into the stream. At the time sewer connection for 

the ttibe works was made the overflow from the settling reservoir was 

conducted to a filtering bed of crushed limestone, from which tile 

underdrains carried it to the sewer. This arrangement supposedly 

stopped all pollution of Red Brook, but actually served merely to 

divert a moiety of the polluting liquors, for infiltration, leakage, and 

probably overflow from clogged filters still carried to this stream a 

considerable flow of acid-iron waste. However, it transferred the 

principal point of pollution to the sewer farm outlet, 3 miles below 

Shelby, and bettered conditions all along the stream very materially.

In the petition above mentioned, it was claimed that 

Defendant [the Shelby Steel Tube Company] in operating its said factory pours into said 

stream great quantities of poisonous matter and offals from said factory, which poison the 

.water in said stream and render it destructive of animal and vegetable life. And said poisonous deposits in said stream, when the water is high, overflow plaintiff's said low lands, 

thereby poisoning the vegetation and pasture thereon, rendering it unfit for animal food 

and dangerous to animal life.

. Said poisonous matters poured into said stream render the water unfit for domestic use 

and sicken and poison plaintiff's animals that pasture on said ground when they drink 

thereof.

o Black Fork is a small stream having at this place (Shelby) a watershed of about 40 square miles, and 

a dry-weather flow of perhaps 1 to 3 cubic feet per second. Eighteenth. Ann. Kept. Ohio State Board 

ot Health, 1903.
8 STEEAM POLLUTION BY ACID-lBOtf WASTES.

In the answer of the defendant to the petition, it was claimed 

that if said stream is polluted to such an extent as to be a nuisance and of injury to this 

plaintiff, that the same is caused by causes other than those alleged in the petition.

The case came to trial in June, 1903. Nearly all witnesses for the 

plaintiff were farmers owning land along the Black Fork below Shelby. 

With few exceptions these men had instituted or were intending to 

institute similar suits against the company, concerted action having 

been determined upon. Each, as he testified,- realized that the successful outcome of his own suit would be largely dependent upon the 

winning of this first suit of the series.

The testimony of witnesses for the plaintiff, in brief, was about as 

follows:

1. Previous to the operation of the tube works the Black Fork was 

satisfactory as a water supply for stock; gave no appearance of pollution ; was the home of numerous healthy fish, and was used as ice 

and boiler supply and for domestic purposes.

2. After the installation of the tube works the stock would not 

readily drink the water; cows watered from the creek suffered decrease in milk; cattle pastured adjacent to the creek got sick and 

some died, removal to a field from the creek effecting the recovery of 

stock. The creek water was sometimes very red and sometimes blue, 

turbid, and had a black ashy sediment; overflow of the stream stunted 

crops, turned them red, and destroyed grass; stock refused to eat 

pasture which had been overflowed; dead fish were found along the 

stream, and few, if any, live fish could be caught, and the value of the 

stream as a source of ice and boiler supply was destroyed.

3. Injury to stock was believed to be due to use of creek water or 

pasture that had been overflowed by the creek. In some cases, however, death of stock was certainly due to other causes, as shown by 

autopsy.

4. Said damage occurs all along the stream from 3 to 12 miles below 

tube works.

Witnesses for the defense testified that:

1. No difference in pasturage was noticeable in last twenty-five 

years; that they had caught fish or seen others fishing all along the 

polluted stream^and that no damage to stock or pasture resulted on 

land immediately below entrance of tube works effluent. *

2. Damage on stream might have resulted from bursting of an oil 

tank.

3. Chemical analyses in January, 1903, of samples taken from Red 

Brook below the tube works and from Black Fork above, 3 miles 

below and 4 miles below the entrance of Red Brook, showed a little 

free acid in Red Brook, but none in Black Fork. The Stream 4 miles 

below showed: the presence of the following amounts of solid matter, 

in parts per million: Silica, 11.97; iron and alumina, 8.55; lime,
HISTOE1 OF POLLUTION AT 8HELBY, OHIO. 9

127.99; sulphuric anhydride, 102.60. The expert witness who*made 

these analyses, Prof. Albert W. Smith, of the Case School of Applied 

Science, Cleveland, Ohio, testified, in part, as follows:

In the process of pickling, an acid is used for the purpose of cleaning the surface of iron. 

The iron surface is covered with what is called rust, and the acid dissolves rust; it combines 

with it chemically, and both acid and the rust, as such, are destroyed they become a new 

substance. When two things combine chemically a new thing is formed; that is what is 

meant by chemical action. When acid and iron rust come together, both the acid and rust, 

as such, are destroyed, and they form a new substance, green vitriol or iron sulphate. That 

cleans the surface of the iron, and the iron sulphate forms a clear solution with the water that 

the acid is dissolved in, but the acid and the iron have been destroyed as such.

When this liquid flows into this little stream [Red Brook] it makes it acid, and the little 

stream contains this sulphate of iron. It is a clear liquor solution, just like sugar in tea. 

The large brook [Black Fork] contains lime hi solution, a clear, transparent liquid, but the 

lime is there, just the same, in solution. When the lime and the iron sulphate come together 

they combine chemically and form a new substance. They form sulphate of lime, or land 

plaster, which is soluble in water, and the same iron rust that was present in the iron; that is, 

the iron has gone back to the same condition it was in when it was rust on the iron, and 

as such is not soluble in water. It will not dissolve any more, so it spreads out, a yellowish 

and brownish rust. The iron rust settles to the bottom of the creek, and hence is separated 

from the water. There would be no iron in the water, as it selves to the bottom and stays 

there, just as so much clay or mud would. It settles in the water below, and there is neither 

acid nor iron.

The iron, after it separates and is precipitated to the bottom, is of a yellow or reddishyellow color, just like yellow clay, and is veiy much the same hi its chemical properties.

I think it would have the same effect upon plants or animals as so much clay would. 

This is inert matter, just like clay or mud.

The charge of the court (Robert M. Campbell, trial judge) is of particular interest, voicing as it does the rights of riparian owners and 

the views of such rights that obtain in Ohio. The prominent points 

in the charge are as follows:

1. All riparian owners have a right to the use of stream waters in a 

normal state.

2. Their right to the use of the water is limited to such use as shall 

not substantially decrease the value of the stream to riparian owners 

below them.

3. Their right to the water in a normal state is subordinate to a 

usual and ordinary use of the water by riparian owners above them.

4. Every party contributing to stream pollution is responsible for 

damage done thereby.

5. Riparian owners injured by stream pollution have a right to 

compensation for such injury in direct proportion to the loss sustained.

6. The injury sustained may be in the nature of a deprivation of 

the use of the water for any reasonable purpose or of damage done to 

property, but must be substantial and not mere inconvenience or occasional annoyances in order to warrant an award for damages.

Verdict for the plaintiff was returned, damages being fixed at $317. 

This is at the rate of $6.34 for each acre of plaintiff's bottom land for
10 , STREAM POLLUTION BY AOID-IBO3ST WASTES.

the four years to which the statute of limitations confined the consideration of pollution.

The case was appealed to the circuit court of Richland County and 

then to the supreme court of Ohio, the judgment of the lower court 

being affirmed in each case.

A careful review of the testimony given at the trial convinces one 

that the acid-iron pollution rendered the stream less suitable for 

domestic purposes as a boiler water, as an ice supply, and as a water 

supply for animals. The riparian rights of landowners below Shelby 

had been interfered with, and, in the judgment of the jury, interfered 

with in a substantial degree.

Injury to vegetation or stock was, to say th]e least, problematic. 

The only evidence offered indicating such injury was circumstantial 

and merely indicated the possibility of such injury. The claim for 

injury to vegetation was based on the flooding of lands. From the 

plaintiff's testimony it appears that the cross section of the stream 

at his farm is about 150 square feet, and the stream (at lowest flood 

must carry at least 30,000 pounds of water per second. Only 6,000 

pounds of 78 per dlht acid are used at the tube works in a day, and 

nearly all of this is converted into iron sulphate before it is discharged 

as waste. From a scientific standpoint, therefore, it seems incredible that by any means the pollution : arising frolii this acid, or ten 

times as much acid, could noticeably affect the. pasture land or crops. 

Were the waste liquor stored for days and discharged only at time 

of stream flood (a practice that was no(t followed to any great extent), 

it would not pollute the water sufficiently to kill vegetation by 

merely washing over it. It is of course physically impossible under 

the conditions existing that any free acid should be in the stream 

after the polluting liquors have been thoroughly mixed with the 

stream water. The alkalinity of the Black Fork at its lowest dryweather flow is sufficient to neutralize twice as much acid as is used 

at the tube works were the acid not already nearly neutralized in the 

pickling process before being discharged into the stream. It is to 

iron oxides and sulphates that we must look for injurious pollution; 

but with added information regarding the qualities of these substances the probability of ill effects upon vegetation grow still fainter. 

In Thorpe's Dictionary of Applied Chemistry, vol. 2 (1891), page 367, 

we find the statement that the coloring matter of clays is chiefly 

iron oxide, and clays, except so far as by their compactness and 

impermeability they prevent the percolation of water, certainly are 

not injurious to vegetable life. Furthermore, on page 368 of Thorpe's 

Dictionary we find the following statement concerning ferrous sulphate: "In weak solution it is said to promote the growth of certain 

plants, especially of roots."
U. S. GEOLOGICAL SURVEY 

SLUDGE BAS/N

PLAN OF SEWAGE-DISPOSAL PLANT AT SHE
EFFECT OF SUCH LIQUORS ON PURIFICATION ' PROCESSES. 11

Injury to stock depends upon a different set of conditions. The 

time of lowest stream flow in dry weather would be the time of 

greatest pollution. It is possible that large charges of waste pickle 

at such times might at certain hours of the day produce^ a pollution which would be injurious to animal life, for although iron 

sulphates and oxides are beneficial in small quantities and ar^s largely 

use.d in tonics for human consumption, great amounts of jthe sulphates might do harm. The testimony was more or less cojnflicting 

upon this point, but a careful review of all statements leads to the 

conclusion that probably no actual injury was suffered by stock 

because of the condition of the stream water.

The winning of this action by the farmers was followed by a succession of suits for damage to lands farther downstream. This sort 

of litigation has been kept up intermittently until the pres0nt time, 

when three or more suits, recently filed, are awaiting trial.

The discharge of pickling wastes into the city sewers, withj more or 

less direct pollution of the stream, was continued until August, 

1904, when a plant was installed for disposing of the strcjng ironsulphate liquors by converting them into crystal copperas] A full 

description of this plant is given later. At this point it wijl be sufficient to state that one-fifth of the acid used is thus recovered as a 

commercially marketable substance. Waste of valuable jmaterial 

and stream pollution are therefore obviated by this plant to a considerable extent. No further changes have been made in the disposal of the waste pickle, except that the copperas plant was enlarged 

somewhat in June, 1905.

At present, therefore, a part of the waste liquor from the^ pickling 

process is recovered as copperas; a part is discharged into! the city 

sewers, passes through the sewage-purification works, and ^hence to 

Black Fork, and the remainder flows into Red Brook and thence to 

Black Fork.

EFFECT OF ACID-IRON LIQUORS UPON SEWAGE PUtBIPICAT10K PROCESSES. !

GENERAL CONDITIONS.

I

To understand the discussion that follows, no detailed knowledge 

of the polluting liquors is necessary beyond a mere recognition of 

the fact that they consist chiefly of iron sulphate, with an admixture 

of iron oxides and free sulphuric acid in varying quantities.

A brief description of the sewage-disposal plant at Shelby (see PI. 

I) is, however, essential. The plant is located about 3 mifles north 

of Shelby on a 25-aere tract owned by the city and know^i as "the 

sewer farm." An 18-inch sewer from the city acts as a gravity conduit for the sewage, which amounts to 250,000 or 300;000j gallons a
12 8TEEAM POLLUTION BY ACID-IROH WASTES.

day, varying in quantity with the amount of ground water that finds 

entrance to the system. Rough measurement by the waiter in July, 

1905, indicated a flow of about 275,000 gallons. The sewage first 

enters a sludge basin for the removal of the larger suspended matter, 

a wire screen of J-inch mesh being placed over the exit. There ar.e 

two of these basins, which are used alternately. Each is of brick, 

10 by 24 feet and 6 feet deep, and contains about 8,000 gallons. It 

is customary to use one basin about three months and then to pump 

out the accumulation of sludge for use as manure on the farm. 

The sludge is said to be an excellent fertilizer and promotes the 

growth of unusual crops.

From the sludge basin the sewage flows through two shallow reservoirs, together holding about five days' flow, which are arranged 

in series, and thence is distributed by half-tile carriers over filter 

beds of cinders and gravel. The filters are two in number and have 

a total area of 25,000 square feet. Six-inch underdrains are laid 20 

feet apart in depressions and covered with.a 6-inch layer of gravel 6 

or 8 feet wide, the sides of the depressions sloping to the drains. 

The whole is then covered by 18 inches of cinders averaging onefourth inch in diameter. The underdrains lead to an 18-inch outfall 

sewer, which discharges into Black Fork a few yards away. The 

filters are used only during the warm months and receive no attention except an occasional weeding. A by-pass provides for the discharge of raw sewage into the outfall sewer, and gates lead from each 

reservoir to the stream. The whole plant is subject to occasional 

overflow of high water from Black Fork.

As originally constructed the sludge basins discharged upon the 

filter beds. Because of rapid clogging the smaller, and later the 

larger, sedimentation reservoir was constructed, with beneficial effect.

When visited first by the writer in February, 1905, the filter beds 

were not in use, while on the second visit, in July of the same year, 

they were both being flooded. They showed every evidence of being 

badly clogged, the sewage standing over them to a depth of 18 inches. 

Only about half the sewage passes through the beds in any case, 

the remainder escaping to the stream by infiltration through the 

banks or by direct flow from the leaky waste gates of the reservoirs. 

Black Fork, which passes by the full length of both reservoirs, 

receives a large part of this waste flow, as is indicated in the stream 

by a strong discoloration pf iron oxide. Indeed, a superabundance 

of iron oxide is apparent about the whole plant. The filtering material of the filter beds and the banks of beds and reservoirs are heavily 

coated with it. The sewage flow also is frequently highly discolored, especially as it nears the filter beds. The effluent from the 

beds is clear and free from suspended matter, but upon standing 

becomes turbid and receives a reddish cast from precipitation of
THE SEWAGE-DISPOSAL PLANT AT SHELBY, OHIO. 13

iron. There is a lack of odor about the plant generally, which is no 

doubt due to the presence of a great quantity of ferrous sulphate" 

in the sewage. The odor is noticeably greater in summer, however, 

than in winter. During the warm months a considerable septic 

action or gasification is apparent in the shallow reservoirs, more 

especially in the first or smaller one. Much sedimentation takes 

place in these ponds, and a thin scum and at places a heavy crust is 

formed upon the surface over a considerable area.

Analyses of sewages at this plant are shown in the table on pages 

14 and 15, which is adapted from the Eighteenth Annual Report of 

the Ohio State Board of Health (1903), pp. 550-552.

o " When added to excremental matters, it [ferrous sulphate] absorbs ammonia and other volatile 

substances and renders the matter almost odorless." Thorpe's Dictionary of Applied Chemistry, 

vol. 2 (1891), p. 368.
Chemical examination of sewages and effluent from 

[Parts per million.] 

BEFORE ACID-IRON WASTES HAD BEEN ADMITTED TO SEW

No. of 

sample.

2042

2045

2168

2172

2043

2046

2169

2173

2170

2174

2044

2047

Description of sample.

Sludge-basin effluent.

moved.

ervoir.

ervoir.

moved.

Filter-bed effluent. . . .

Filter-bed effluent.. . .

Date and hour of 

collection.

December 28, 1901, 8

a. m.-7 p. m. 

December 28-29 1901,

8 p. m.-7 a. m. 

May 7, 1902, day......

May 7-8, 1902, night ..

December 28, 1901, 8

a. m.-7 p. m. 

December 28-29, 1901,

8 p. m.-7 a. m. 

May 7, 1902, day......

May 7-8, 1902, night...

May 7, 1902, day......

May 7, 1902, night....

a. m.-7 p. m. 

December 28-29, 1901,

8 p. m.-7 a. m.

h

0

8

15

16

37

20

22

18

17 '

22

20

19

14

20

22

21

4.5

6

5

Turbidity.

73

135

300

98

152

90

73

20

16

50

67

SI.

SI.

SI.

75

Tr.

Tr.

Sediment, o

Con.

Con.

Con.

Con.

Con.

Dec.

Dec.

SI.

SI.

SI.

Tr.

Tr.

a

(4

O

 « 

O

Oily....

1 oily.

oily.

Oxygen required.

11:73

28.51

26.11

11.38

19.43

13.09

9.62

5.73

8.53

9.24

52

5.41

6.22

5.82

70

2.42

3.01

Alb. ammonia.

1.404

1.608

2.780

1.350

.896

.632

2.260

.960

1.187

34

.750

.780

.765

57

.260

.268

BJ a

o

ft

2.740

2.560

3.800

3.930

3.258

3.520

2.508

3.450

3.370

3.212

1.4

2.830

3.090

2.960

9.1

2.580

3.100
2171

2175 Filter-bed effluent. . . ,

moved.

May 7-8, 1902, night ..

19

18

12

45

Tr.

Tr.

Tr.

90

Tr.

Tr.

Tr.

90 80

3.78

2.90

3.03

84

.360

.336

.308

83

2.80

3.28

2.94

9.8

AFTER ACID-IRON WASTES HAD BEEN DISCHARGED INTO SEWERS FOR S

3359

3360

3361

QOfiO

moved.

' moved.

moved.

TlAf«iTttVi*iT T f\ 1QOQ 9

p. m.

p. m.

p.m.

Tlo^fYm'Hor 1 ^ IQO^ O

p. m.

307

129

00

89

24.8

91

1.890

1.700

11

1.200

37

.300

84

3.56

3.61

1.4

2.15

40

3.15

12

a Abbreviations: SI., slight; tr., trace; con., considerable; dec., decided; sew., sewagic. The numbers 

0, no odor perceptible; 1, distinct; 2, considerable; 3, decided; 4, strong. 

6 Increase, 

c Removal of acidity.
16 STREAM POLLUTION BY ACID-IRON WASTES.

The samples of 1901 were taken before either reservoir had been 

constructed, the effluent of the sludge basin being then passed 

directly to the filters; the samples of 1902 were taken after the first 

or smaller settling reservoir had been built, and the samples, of 1903 

were taken after both reservoirs were in use.

The first part of the table shows a rather dilute sewage, ground 

water doubtless having access to the long outfall sewer in considerable 

quantity. The presence of nitrites and nitrates indicates that a 

supply of oxygen is available, though we have no corroboration of 

this. The nitrites, nitrates, and relatively high free ammonia indicate putrefaction in the sewers in about the stage one would expect 

from the somewhat wide separation of city and disposal plant, about 

three hours being required for the sewage to pass from the city to the 

plant.

It is of interest to note that the sludge basin, through which the 

sewage passes in from one-half to three-fourths of an hour, has more 

effect in reducing the organic matter than any other one feature of the 

purification plant. By oxygen required the reduction is 52 per cent 

and by albuminoid ammonia 34 per cent. A reduction of 12 per cent 

in total solids is accomplished. The larger reduction in oxygen 

required and the increase in nitrites and nitrates indicate rather vigorous oxidation, presumably accomplished by oxygen dissolved in the 

sewage.

In the small sedimentation reservoir, which affords one day for 

settling, anaerobic conditions seem to have been established to some 

extent. The free oxygen is doubtless used up, and then the nitrites 

and nitrates are robbed of their oxygen to assist in breaking up the 

carbonaceous matter. By oxygen required a reduction of 18 per cent 

and by albuminoid ammonia a reduction of 23 per cent is effected by 

the reservoir.

The filters accomplish 14 per cent purification by oxygen required 

and 26 per cent by albuminoid ammonia. The entire plant shows a 

very good percentage of reduction. The effluent, having a slight 

musty odor, would seem to be somewhat putrescible, but is not 

chemically a poor one. It can not be regarded as a source of serious 

pollution of the stream into which it is discharged, even at lowest flow.

It is worth while to note that, although, owing to the construction 

of the sedimentation reservoir, the sewage flowing to the filters was 

in much better condition in 1902 than in 1901, the effluent is decidedly 

worse. This indicates deterioration of the filters from overwork and 

neglect.

The latter part of the table, giving the tests of 1903; shows a sewage in which the "acid-iron" conditions are extreme. Iron is present 

in large quantity and the acidity is very high, probably sufficient to 

prevent bacterial action. Another characteristic feature is the high 

value for oxygen required, the figures being practically a measure of 

the ferrous salts present and affording no information regarding the
SEWAGES AND EFFLUENTS AT SHELBY, OHIO. 17

carbonaceous matter. The very high solids and loss on ignition are 

also worthy of special notice. The loss on ignition in this case bears 

scant relation to the organic matter present. ' The albuminoid and 

free ammonia tests show a rather small amount of organic matter and 

a somewhat advanced stage of putrefaction. The diminution in 

acidity is surprisingly rapid. No doubt some rather complicated reactions, including a circle of reduction and oxidation, take place, the 

results of which are largely the change from ferrous to ferric salts and 

the deposition or gaseous escape of sulphur compounds at the expense 

of the free acid. This determination is borne out by the similar 

diminution in total solids and oxygen required. The organic matter 

is reduced but little in the early processes of the disposal plant, but 

is removed chiefly by the niters.

The effluent is a very good one from a sanitary standpoint, so far 

as may be judged from the analyses under consideration. The little 

free acid it contains can not be considered as an objectionable addition 

to the highly alkaline waters of Black Fork. The high oxygenabsorbing power, however, would tend to produce conditions unsuitable 

for fish life and the extreme amount of iron would render the stream 

unsightly and its waters unfit for domestic use.

In the following table will be found analyses of sewage samples 

taken by the writer in 1905. This set of samples differs from those 

of 1903 chiefly in the fact that the acid-iron waste is less in the later 

samples by reason of the installation of a copperas plant at the tube 

works. Of the determinations in the table, dissolved oxygen, acidity, 

sulphates, and iron, and the plating of bacteriological samples and 

preparation of cultures for transplanting were the work of the writer. 

The remaining work is all that of officials of the laboratory of the Ohio 

State Board of Health. The following methods of analyses were used: 

Organic nitrogen, Kjeldahl; free ammonia, distillation; residue in 

platinum, drying at 100°; chlorine, silver nitrate with potassium 

chromate; oxygen required, boiling five minutes; acidity, sodium 

carbonate tablets with methyl orange indicator; sulphates, candle 

turbidimeter; iron, colorimetric; putrescibility, incubation five days 

at 37°. Regarding the methods referred to in brief that are not in 

general use, it may be mentioned that those used for acidity, sulphates, and iron are the field methods of the United States Geological 

Survey.

This table shows a strong acid-iron sewage with a moderate content 

of organic matter. The acid-iron element is greater in the night than 

in the day sewage. Owing to the iron sulphate the sewage is only 

moderately putrescible by odor upon incubation. The bacterial content is very low, probably one-fourth that of a purely domestic sewage of similar concentration. The effect of the acid is shown in 

reduction of bacteria from day to night, and more strikingly in 

reduction of acid-forming bacteria, to which the acidity appears to be 

specially unfavorable.

DRR186 06 2
Analyses of sewage from the sewage-purification plant at Shel

[Parts per million.]

Source.

General average ............................................

Per cent removed ....... ....... ... .....................

Filler-bed effluent ...............................................

Filter-bed effluent ...............................................

>, "3

t-s 

oJ 

"§

ft

13

12-13

12-13 

13-14

12-14 

12-14

12-13 

13-14

12-13 

13-14

12-14

Organic nitrogen.

2.94 

2. til

.278

2.34

2.59

2. 4G 

2. 02

1.10 

1.07

59.00

.74 

1.30

1.02

61.00

Free ammonia.

3.50 

3.25

3.38

3.00 

2. C6

2.83 

3.10

4.00 

3.75

 1 00

( 25

4.00 

4.00

4.00

o29

Residue on eva

ration.

"3

4J 

O

EH

3,492 

3,142

3,317

4,062 

3,710

3, 886 

3, 002

2,116 

2, 5fi9

2,342 

35

2,062 

2,312

2,187

39

Dissolved.

3,233

3,128

3,180

3,942 

3, 657

3,800 

3,490

2,012 

2, 4(14

2,238

] , 79S 

2,109

1,954

a Lost, overgrown, or slipped. 6 In 0.05 cubic centimeter 
SEWAGES AND EFFLUENTS AT SHELBY, OHIO. 19

The effluent is, organically, a fair one from a chemical standpoint 

and is nonputrescible. Bacteriologically it is very good, containing 

but a small number of bacteria, and these not of the colon family. 

Its content of iron sulphates, however, makes it unsuitable for addition to any but a very large stream.

It will be observed that the filters take but little part in the purification. From their physical aspect this was to be expected, although 

the extent of their deterioration is surprising. Their chief value at 

present seems to be in accomplishing a reduction in acidity and 

oxygen-absorbing power. The plant accomplishes an organic purification of about 60 per cent and a reduction in mineral matter between 

35 and 40 per cent.

The values obtained for suspended solids are subject to variation, 

owing to a gradual precipitation of iron, especially from the effluent. 

The absence of dissolved oxygen serves to show more decidedly the 

avidity for oxygen possessed by ferrous sulphate. The large reduction in sulphates is not unlocked for, but the permanence of the iron 

is surprising. One would naturally expect the sulphates to be the 

more persistent.

A comparison of the three sets of analyses and their relative conditions will assist in answering the following questions, which are 

of general interest in their relation to sewage disposal in those cities 

where acid-iron liquors are encountered:

1. How does a disposal plant consisting of sludge basin, large, 

shallow sedimentation reservoirs, and cinder and gravel filters 

affect acicl-iron sewage as compared with domestic sewage?

2. How is such a plant affected by these two classes of sewage ?

3. Should large quantities of acid-iron liquors be admitted to a 

sewerage system?

'4. Is a copperas-recovery plant of value as a means of preventing 

the overcharge of sewage with such liquors ?

TOTAL SOLIDS.

Reduction in total solids occurs chiefly in the sludge basin and reservoirs, the filters having little or no effect on any of the sewages 

considered. Such effect of filters as is shown by analyses is less 

than the sampling error. In sludge basin.and reservoirs the per cent 

of solids removed increases with the increase of solids in the sewage. 

By far the greater part is removed in the sludge basin, and the 

ratio of per cent removed by sludge basin to per cent removed by 

reservoir increases with the increase in solids in the sewage.
Effect of acid-iron wastes, and of such wastes modified by a copperas-recovery plant, upon the 

[Parts per million and percentage remov

Sludge basin:

Difference (a-b)... ..................

Sedimentation reservoir:

Difference (a 6) .....................

Basin and reservoir combined:

Filter beds:

Entire plant:

Difference (6-c) .....................

Oxygen 

required.

Parts 

j>er 

million.

10.19 

178.00

-167.81

3.42 

96.00

- 92.58

13.61 

274.00 

50.10

-260. 39 

- 36.49 

223.90

2.79 

8.20 

22.30

- 5.41 

- 19.51

- 14.10

16.40 

282.20 

72.40

-265.80

- 56.00 

209.80

Per 

cent.

52 

58

- 6

18 

31

-13

70 

89 

40

-19 

30 

49

14 

3 

18

11 

- 4

-15

84 

92

58

- 8

26 

34

Organic 

nitrogen.

Parts 

per 

million.

1.54

.06

1.60

Per 

cent.

 

59

2

ei

Albuminoid 

ammonia.

Parts 

per 

million.

0.599 

.190

.409

.422 

.500

- .078

1.021 

.690

.331

.457 

.900

- .443

1.478 

1.590

- .112

Per 

cent.

34 

11

23

23 

26

- 3

- 57 

37

20

26 

48

99

83

84

- 1

Free 

ammonia.

Parts 

per 

million.

0.046 

- .050

.96

.252 

1.460

-1.218

.298~ 

1.410 

- .780

-1.112 

1.078 

2.190

.020 

-1.000 

- .120

1.020 

.140 

- .880

.318 

.410 

- .900

- .092 

1.218 

1.310

Per 

cent.

1.4 

-1.4

2.8

8 

41

-33

3 

40 

-25

-31 

34 

65

1

-28 

- 4

29 

5 

-24

10 

12 

-29

- 2 

39 

41

P

p

mi

-0.

T

- 

- 

- 

- 

- 

- 

- 

- 
LOSS ON IGNITION OXYGEN BlQtllBlB. 21

The removal of solids in the acid-iron sewage occurs probably in 

greatest measure as sedimentation of certain compounds after chemical change by reduction, oxidation, and substitution. Next comes 

the influence of water of crystallization. Total residue, as determined upon the water bath, includes water of crystallization for both 

ferrous and ferric sulphates. Oxidation from the ferrous to ferric 

sulphate is accompanied by a loss of 36 per cent of such water, which 

is, of course, thus lost to the total residue determination. It seems 

probable that about three-fourths of the reduction in solids can be 

attributed to sedimentation, nearly all the remainder to change from 

ferrous to ferric compounds, and a little residue to the escape of volatile compounds.

The effect upon the plant of the increased deposition of solid 

matter after the acid-iron waste has been introduced will be rapid 

loss of efficiency of sludge basin, which can be prevented only by 

frequent cleaning. The same effect will appear in the sedimentation reservoirs to a lesser extent, particularly with "modified" 

sewage. Furthermore, the fact that reduction by filters is so much 

greater for "modified" sewage indicates a less complete purification 

in the preceding processes, and consequent crowding of filters, to 

their detriment.

The copperas plant appears to effect about 60 per cent reduction 

in the solids in the raw sewage, due to the acid-iron liquors.

LOSS ON IGNITION.

For this determination we have comparison only on normal and 

acid-iron sewages. The ratio of loss on ignition to total residue is 

nearly the same in both cases, being slightly less for the acid-iron 

sewage. Loss on ignition for the acid-iron sewage would appear to 

be due largely to breaking up of water of crystallization. The 

variation of the ratio of loss on ignition to solids and its decrease by 

oxidation of ferrous salts therefore affords a means of rough comparison of oxidation and sedimentation in the purification processes. 

Sedimentation seems to be the greater force in the sludge basin, but 

is unable to keep pace with oxidation in reservoirs and filters. In 

other words, the combined forces tending to a reduction of solids act 

more vigorously in the sludge basin and less vigorously in the reservoirs and filters than does the single force of oxidation. The variation is not, however, extensive.

OXYGEN REQUIRED.

This determination means two different things with the different 

classes of sewage. With normal sewage it may be taken as an 

approximate proportional measure of the carbonaceous material. 

With acid-iron and modified sewages it ^measures the ferrous salts
22 STREAM POLLUTION BY ACID-IRON WASTES.

also, and these are so abundant, the carbonaceous matter being 

comparatively insignificant, that its value as a measure of organic 

matter is nil. For the latter classes of sewage therefore the oxygen 

required may be assumed with but little error to be a measure of 

ferrous salts present in the sewage. Loss in oxygen required will 

therefore be proportional to decrease of ferrous salts. Decrease of 

ferrous salts probably occurs in this case in two ways (1) by reduction of ferrous sulphate to iron sulphide and sedimentation of the 

iron sulphide, and (2) by oxidation of ferrous to ferric sulphate. 

Just what changes take place we have not sufficient data to determine, but it seems probable that at Shelby the former is the more 

prominent reaction in the sludge basin and the latter predominates 

in reservoirs and filters. This conclusion is borne out by the fact 

that the ratio of loss on ignition and of oxygen required to total 

solids increases from raw sewage to sludge basin effluent and decreases 

thereafter.

The ratio of loss on ignition to oxygen required for aeid-iron sewage 

is practically constant in sludge basin and filters, but undergoes a 

slight increase in the reservoirs. This is in marked contrast to the 

variation in the similar ratio for normal sewage, which undergoes 

rapid increase as the sewage passes through the works. This ratio 

offers the most distinctive difference in the action of the purification 

processes upon the two sewages.

ALBUMINOID AMMONIA AND ORGANIC NITROGEN.

Albuminoid ammonia for normal and acid-iron sewages and organic 

nitrogen for modified sewage are the only determinations from which 

may be gathered the comparison of effect of plant upon the organic 

matter of the sewages considered. The sludge,basin appears to cause 

three times as much reduction in organic matter for normal as for 

acid-iron sewage; the reservoirs seem to have about the same effect 

upon the two, while the filters offset the effect of the sludge basin, 

making the effluents of about equal purity. Although the organic 

nitrogen of modified sewage should not be directly compared with the 

albuminoid ammonia of normal and acid-iron sewage, a general consideration of these determinations would seen! to indicate equally 

as good reduction for modified as for normal sewage in sludge basin 

and reservoirs, but practically no reduction is secured by the filters 

on modified sewage. From the condition of the filters this last result 

was to be expected.

It may safely be said that the introduction of acid-iron wastes 

interferes with the reduction of organic matter in sludge basin and 

reservoirs, and thus tends to crowd work upon the filters. The effect 

upon the plant will be a more rapid decrease of efficiency than would 

otherwise be the case. The copperas plant is beneficial in alleviating 

these conditions, apparently to a very great ex'tent.
FREE AMMONIA -NITRITES AND NITRATES ALKALINITY. 23 

FREE AMMONIA.

This determination shows wide variation under the different conditions. With normal sewage there is a slight but persistent decrease 

'in free ammonia in all the purification processes, the greatest decrease 

being found in the reservoirs. With the strong acid-iron sewage 

there is a slight increase in the sludge basin, a very great decrease in 

the sedimentation reservoirs, and, finally, a great increase in the 

filters. It appears as though the saline nitrogen in sludge basin and 

filters is held in the sewage, while the reservoirs allow a very considerable, escape of nitrogen gases. With the modified sewage there 

is a steady increase in free ammonia throughout^ the plant. Evidently the absorbing power of iron sulphate and the combining 

power of the free acid in acid-irpn sewages tend to hold in the sewage 

the nitrogen or nitrogenous- compounds, but under favorable conditions these volatile substances may escape to a greater or less 

extent.

NITRITES AND NITRATES.

The addition of acid-iron waste to the sewage very largely diminishes the nitrites and causes the nitrates to disappear entirely in all 

the sewages examined. This action is doubtless due to the reducing 

qualities of the iron sulphate and bears no relation to organic purification.

ALKALINITY.

The alkalinity of normal sewage is affected but little by the purification .processes. The acid-iron sewage, on the other hand, with its 

high acidity, undergoes great change and is practically neutralized 

by the action of the disposal plant. Most interesting is the reduction 

of acidity by the filters. Apparently they provide conditions specially favorable for change from ferrous to ferric sulphate, and the 

free acid is thus used up. The effect of the acid upon the plant is to 

interfere seriously with bacterial action and in so doing to destroy in 

great measure the pathogenic quality of the sewage.

SUMMARY.

1. Introduction of acid-iron waste into domestic sewage (a) largely 

increases its total solids, loss on ignition, iron, sulphates, and oxygen 

required, causes the disappearance of nitrites and nitrates, and 

changes it to a highly acid liquid; (6) reduces the effect of the 

sludge basin upon organic matter, and tends toward a rapid deterioration of every part of the sewage-disposal plant; (c) interferes with 

bacterial action, but in so doing lessens the harmful quality of sewage; 

(d) reduces obnoxious odors from the sewage and reduces its putrescibility by absorption of gases;" (e) renders the effluent of the sewage-
24 STREAM POLLUTION B? ACID-IRON WASTES. -

purification works unfit to enter any but a very large stream because 

of its content of iron sulphates.

2. A sewage-disposal plant consisting of sludge basin, five-day 

sedimentation reservoirs, and cinder and gravel filter beds (a) 

removes organic matter from highly acid-iron sewage as completely 

as from domestic sewage; (6) affords less freedom from free or saline 

ammonia when treating acid-iron sewage; (c) accomplishes greater 

reduction but affords a worse effluent as regards oxygen required 

when treating acid-iron sewage; (d) renders extremely acid sewage 

nearly neutral but affects the alkalinity of domestic sewage very 

little; (e) affords an effluent with one-fourth the quantity of nitrites 

in acid-iron as in domestic sewage, but with no nitrates or dissolved 

oxygen in acid-iron sewage; (/") may reduce total solids as much as 

79 per cent in acid-iron sewage, while domestic sewage is reduced 

not more than 20 per cent; (g) reduces sulphates in same proportion 

as total solids but affords only slight decrease in iron content of acidiron sewage; (h) lessens the number of bacteria in acid-iron sewage 

by 99.5 per cent and frees it from B. coli communis and other acidproducing bacteria.

3. The installation of a copperas plant recovering 20 to 25 per cent 

of the acid used in pickling, such plant treating the wastes before 

they enter the sewers, reduces the harmful effects of acid-iron sewage 

upon such a disposal plant by about 60 per cent, and in consequence 

reduces in like proportion the attention requisite for proper maintenance of the plant. The copperas plant, however, will not take 

the place of attention to the sewage processes; a better effluent may 

be obtained with an extremely concentrated acid-iron sewage and 

careful attention than with a 60 per cent better sewage without the 

attention.

In connection with these conclusions, based upon meager and fragmentary data, it will be of especial interest to review the conclusions 

of Kinnicutt and Eddy, based upon two years' constant work upon 

Worcester sewage. This sewage is about 4| times as strong, organically, as the sewage here considered, but contains only 10 per cent as 

much solid matter and 4 per cent as much free acid as what is here 

designated ' 'acid-iron" sewage, and 22 per cent as much solid matter, 

24 per cent as much iron, and 50 per cent as much free acid as what 

is here termed "modified" sewage. The results of Kinnicutt and 

Eddy's work, quoted below, from pages 44 and 45 of the Fourth Report 

of the Connecticut Sewerage Commission, 1902, are based upon 

observations of- the slow passage of such sewage through a closed 

septic tank. From this summary of results it appears 

That about one-fourth' of the total solid matter contained in the sewage will be removed.

That the effluent from the tank will contain about 20 per cent less soluble matter than 

the crude sewage, owing to the soluble matter in the sewage being decomposed or changed 

into insoluble substances.
BISULTS Otf EXAMINATION OF WoBCCBSTfiB SEWAGE. 25

That the amount of suspended matter removed from the sewage will not greatly exceed 

30 per cent unless special precautions are taken to retain in the tank the finely divided 

iron sulphide formed by the reduction of the soluble iron sulphate in the sewage.

That the amount of organic matter removed from the sewage as determined from the 

albuminoid ammonia will average from 20 to 25 per cent.

That of the suspended orgar ic matter the amount removed will average a little under 50 

per cent, and that the amount of soluble organic matter removed will not average much 

more than 10 per cent of the soluble organic matter in the sewage.

That of the suspended matl er taken out of the sewage in its passage through the tank, 

from 60 to 70 per cent will remain in the tank and have to be removed; only from 30 to 40 

per cent of the arrested suspended matter being changed by the action of the bacteria into 

soluble or gaseous substances

That the amount of sludge that will have to be handled when it is necessary to clean out 

the tank will not, however, equal 60 or 70 per cent of the weight of the sludge that would be 

formed from *he removal of the same amount of suspended matter in a sedimentation tank, 

but will not be more than 50 per cent of this amount, owing to the fact that the sludge in a 

septic tank contains less water than the sludge in a sedimentation tank.

That with an acid-iron sewage containing street washings the amount of mineral matter 

in the sludge will be about 50 per cent of the total solid matter in the sludge, and of this 

mineral matter over one-third will be found to be iron sulphide

That decomposition of the sludge, as shown by the evolution of gas, will take place in 

winter as well as in summer if the temperature of the sewage in the tank does not fall below 

45° Fahrenheit, but the rate of decomposition will be much slower, one-half of what it is in 

summer.

That the amount of gas evolved from the septic tank with a sewage similar to Worcester 

sewage and having about the ~ame range temperature as Worcester sewage, will average a 

little over one-half a cubic foot for every 100 gallons of sewage passed through the tank, 

the rate of flow of the sewage through the tank being eighteen hours. In the warmest 

months the amount evolved will, however, be about 1 cubic foot; in the coldest months 

about one-fourth of a cubic foot.

That the gas given off from a septic tank with acid-iron sewage does not contain hydrogen or sulphide of hydrogen, but a mixture of marsh gas, carbon dioxide, and nitrogen, in 

about the following proportions: Marsh gas, 75 per cent; carbon dioxide, 6 per cent; 

nitrogen, 19 per cent.

PRESENT CONDITIONS ALONG THE STREAM.

In July, 1905, an investigation was made of conditions along 

Black Fork for 7 miles below Shelby. Pollution by acid-iron wastes 

was easily apparent at two points. The first is at the mouth of the 

small stream (Red Brook) which passes by the tube works. This 

stream obviously receives acid-iron liquors, presumably the wastes 

from the pickling tubs and the copperas plant hereinafter described. 

The waters are highly colored with iron, and numbers of small dead 

minnows were found below the tube works. Lack of oxygen in the 

water was the apparent cause of their death, the fish coming to the 

surface gasping for breath and finally giving up the struggle, floating 

downstream belly upward. A short distance below the tube works 

this stream empties into Black Fork and gives its waters a high iron 

discoloration. For a few hundred yards.below this point Black Fork 

is shallow and its current rapid. Then follow a succession of deep
26* STREAM POLLUTION BY ACID-IRON WASTES.

pools of slowly moving water. These conditions are ideal for the 

oxidation and sedimentation of the iron. Consequently, more than 

three-quarters of a mile below the tube works no discoloration is 

noticeable.

The extent of the pollution is shown roughly by the following table:

Effect of tube ivorks effluent upon Red Brook. 

[Observations made July 13, 190.3; in parts per million.]

Location.

One-half mile above tube works. 

One-fourth mile below tube 

works, one-fourth hourly

Do........................

Do........................

Do........................

Do........................

Average below tube

Iron as 

Fe.

3.0

QO £

40 0

90 0

10.0

2.5.0

51 "

Sulphuric 

acid as 

SO3 .

120

°85

9S5

640

35.5

355

355

380

Alkalinity as 

CaC03.

180 

190

190

74

47

78

89

111

Dissolved 

oxygen.

5.6

0.0

0.0

0.0

0.0

0.0

Period.

8.45 a. m. to 10.30 a. m.

10.45 a. m. to 12.30 p. m.

2.45 p. m. to 4.30 p. m.

6.45 a. m. to 6.30 p. m.

The samples analyzed we* e made up of equal quantities taken from 

the stream every fifteen minutes during the two-hour periods shown 

by the table. The absence of dissolved oxygen in the stream is a 

point worthy of special notice and indicates the cause of the death of 

fish. The other determinations show that the polluting liquor contains large quantities of iron sulphates, but little, if any, free acid. 

At no time during the day was any free acid found in the stream 

waters, though their alkalinity was considerably decreased. This 

decrease could be accounted for by the reaction of the iron sulphates 

with the alkaline carbonates of the stream waters, though it is probable that a little free acid in the waste discharged is the chief contributing factor. A discharge of an increased amount of waste liquor 

evidently took place just before noon. Barring accidental cause, this 

circumstance would indicate that the pollution is to a considerable 

extent under control and not wholly due to uncontrolled leakage. 

It is estimated that the stream has a flow of about 40,000 gallons per 

hour. During the working day, therefore, apparently about 1,000 

pounds of SO3 are discharged into the stream at the tube works. 

Assuming a normal condition at the plant, this amount could come 

only from liquors wasted at the pickling tubs.

 The second point of pollution by iron liquors is at the city sewage 

farm, 3 miles below Shelby. Beginning on the morning of July 12, a 

forty-eight-hour test of the efficiency of the sewage-disposal plant was 

made, samples being taken every hour during that time. The average content of *the effluent, in parts per million, for this period is as 

follows:
CONDITIONS ALONG, STREAMS NEAR SHELBY, OHIO.

Content of effluent of sewage-disposal plant 3 miles 'below Shelby, Ohio.

Iron as Fe................................................................. 485

Sulphuric acid as S03 ...........-........................-.---.--.-..---.--- 1,310

Acidity as CaCO3 ........................................................... 25

Dissolved oxygen...............-........................-.-----..--.-----.- 0

Rough measurements of the sewage flow show that it was approximately 275,000 gallons a day. Apparently about half of this amount 

passes out through the effluent pipe, the remainder leaking to the 

stream from the sedimentation basins. Both effluent and leakage 

turn the stream waters red, from precipitated iron.

To determine the persistency of the effects of the polluting effluents 

samples from Black Fork were analyzed at suitable distances below 

Shelby. The results of these analyses and also of analyses of the polluting liquors are shown in the accompanying table:

Analyses of water of Black Fork and Bed Brook near Shelby, Ohio. 

[Parts per million.]

Red Brook J mile below tube

works.

Black Fork above mouth of

Red Brook.

Black Fork J mile below Red

Brook; Smiley street.

Black Fork ij miles below

mouth of Red Brook; State

street.

Effluent of sewage farm. .......

Black Fork opposite sewage 

farm, 3 miles below mouth ot

Red Brook.

Black Fork 4 miles below

mouth of Red Brook; J mile

northwest of London.

Black Fork 5f miles below

mouth of Red Brook; Isaac

Adams farm.

Black Fork 7 miles below

mouth of Red Brook.

Iron

as Fe.

51.2

3.0

3.5

3.0

485.0

4.0

14.0

O U

2.0

Sulphuric

acid as 

SO,.

380

70

140

120

1,310

120

320

185

145

Alkalinity as 

CaCO,.

Ill

190

190

170

a 25

1GO

100

130

150

Dissolved 

oxygen.

0.0

6.4

6.4

6.4

0.0

6.2

2.6

6.3

6.6

Date 

(July, 

1905).

13"

13

13

13

12-13

12

14

14

14

Remarks.

Average of samples

taken every 15 minutes from 6.30 a. m.

to 6.30 p. m.

100 yards above entrance of effluent.

1 mile below sewage

farm.

2| miles below sewage

farm.

4 miles below sewage

farm.

a Acidity as CaCO3 .

It will be noticed that the iron precipitates out very rapidly. One-' 

half mile below the entrance of the small stream it has decreased to 

within one-half part per million of the iron content of the Black 

Fork above the point of pollution. At the next sampling point, 

three-fourths of a mile farther down, it is normal, or, in other words, 

no pollution by iron can be detected. Opposite the sewage farm 

the leakage from the sedimentation basins causes a slight increase 

in iron content, while a mile below the farm an abnormal amount of 

iron was found. At this point the stream was highly colored by 

iron sesquioxide. Again, however, the iron quickly precipitates and 

becomes less 2f miles below the sewage farm than it is above Shelby.
28 STREAM POLLUTION BT ACID-IKON WASTES.

This decrease in iron content continues, so that 4 miles below the 

farm the stream contains one-third less iron than above Shelby.

The influence upon the dissolved oxygen, as would be expiated, is 

in inverse ratio to the influence upon iron content, and the result of 

this determination corroborates the results previously discussed. 

In a word, the polluting iron liquor rapidly takes up the oxygen in 

the stream and is itself precipitated thereby. Judging from the low 

content of oxygen a mile below the sewage farm, it is evident that the 

conditions for this distance are adverse to fish life and may cause the 

death of small fish.

Another effect we would expect would be decreased alkalinity and 

an increased sulphate content. Eeaction of the iron sulphates with 

the carbonates of the alkaline earths would eventually result in the 

production of iron oxide, carbonic acid gas, calcium sulphate, and 

magnesium sulphate. The iron oxide and excess of alkaline earth 

sulphates would precipitate and the gas would escape. The effect 

upon the stream, therefore, would be to give it, compared with other 

streams of this locality, an abnormally high content of incrusting 

sulphates, or permanent hardness, and a comparatively low alkalinity, 

or temporary hardness. That such reaction actually occurs is shown 

by the analyses made.

The effects of pollution by acid-iron wastes at Shelby may therefore be summed up as follows:

1. From the points of pollution to a point varying from one-half 

mile to 1J miles below, the natural condition of the stream waters is 

seriously impaired for general use and detrimental to fish life.

2. Beyond this point no effect can be noticed aside from an increase 

in permanent hardness and a decrease in temporary hardness of the 

waters. Such effect is not prejudicial to animal or vegetable life, 

but damages the value of the water for use in boilers and to a less 

extent for domestic purposes.

RECOVERY OF COPPERAS FROM ACID-IRON WASTES.

Before entering upon a discussion of the merits of a copperasrecovery plant as a means of disposing of acid-iron wastes, it will be 

advisable to describe the process which produces such liquors and to 

show in some detail their characteristic mineral content.

THE PICKLING PROCESS.

To clean iron and steel from rust and scale it is immersed in a 

solution of acid in tubs or vats of shape and dimensions suitable to 

accommodate the material to be pickled. In tube works the pickling 

tubs are naturally long and narrow to accommodate the sections of 

tubing. In such works the material is pickled before annealing, in
RECOVERY OF COPPERAS FROM ACID-IRON WASTES. 2&

order th.at this process may have most uniform and perfect results. 

Moreover, one of the last steps in manufacture is the passage of 

finished twbing through the pickling baths, after which it is rinsed 

and oiled,, so that it may be shipped in perfect condition. Much of 

such material is used in boilers and in other places where it is of the 

utmost importance that rust should be prevented; hence the special 

precautions. In tin-plate, galvanizing, and other work where iron 

is coated with another substance, it is necessary that the iron should 

be clean and free from rust in order that the coating may properly 

adhere. It is therefore pickled and rinsed before coating. In such 

works it is frequently customary to pass the material through more 

than one bath to produce the desired perfection of surface.

The acids used for pickling are commercial grades of hydrochloric 

and sulphuric acid. Until sulphuric acid was cheaply produced 

hydrochloric was used almost exclusively, but, except for special 

classes of work in which hydrochloric acid gives better results, it has 

now largely been superseded by sulphuric acid, a 60° grade (about 

78 per cent pure) being in most general use. The strength of solution varies somewhat with the work to be done. The best solvent 

for the sesquioxide of iron is a solution consisting of 8 parts of sulphuric acid and 3 parts of water. A much weaker liquor is used in 

pickling, however, a 10 per cent solution of the 60° acid being a 

common strength for making up the fresh pickling bath.

Circulation is a primary requisite of good pickling. Were the 

material allowed to lie in a heap in the acid, some parts would be 

more thoroughly cleaned than others, the surface would become 

pitted, and the material would be seriously damaged in value. To 

avoid such results a rapid circulation of the liquid or a movement 

of the material pickled is necessary. This is customarily accomplished by machinery which automatically alternately thrusts the, 

material into and draws it from the bath or which forces the liquid 

around the material by a plunger. The pickling solution is kept at 

a temperature ranging from 140° F. to a little more than 212° F. in 

order to increase the activity of the acid. This is usually done by 

forcing steam into the bath from open pipes.

At the Shelby Steel Tube Works circulation and heating are accomplished by closed steam pipes of acid-proof material laid in the bottom 

of each tub. The liquor is thus heated to a state of violent ebullition 

and an eminently satisfactory circulation obtained and very rapid and 

thorough pickling made possible.

As previously stated, the fresh pickling bath contains about 10 

per cent of acid. As the process of pickling continues, the per cent 

of acid becomes less and less because of the combination of acid with 

iron to form iron sulphates. More acid is therefore added in a continuous stream or by charges in order to keep the bath working
30 STBEAM POLLUTION BY ACID-IRON WASTES.

actively. Finally, when the liquor contains about 15 per cent of 

iron sulphates and 2 per cent of acid it is discarded as useless and is 

generally discharged into the most convenient stream.

This forms waste 1, the first waste from the process. It is to be 

noted that the waste liquor or "spent pickle" from any one plant 

will be of fairly uniform consistency and is disposed of in charges, 

usually once- or twice a day.

After pickling, the iron or steel material is passed through a rinse 

tub in order to free it from an excess of acid. Were it not rinsed the 

acid would continue to eat the material and would soon coat it with 

rust. The rinse tubs are usually similar to the pickling tubs in size 

and shape. A continuous stream of water passes through them, the 

discharge pipe leading to sewer or stream. This rinse water, of 

course, takes up a considerable quantity of iron and acid from the 

material pickled. It forms waste 2, the second waste from the process.

After it is rinsed the material to be coated is passed directly 

through the galvanizing, tinning, or other coating process, or it 

may first be subjected to a bath in very dilute hydrochloric acid to 

give a still better surface for coating. The waste from this last bath 

is usually inconsiderable in comparison with the others and passes 

out with the rinse water, waste 2. In the tube works, after pickling, 

the tubing is oiled in '' dope'' tubs similar to the pickling tubs. This 

process gives a little waste oil, which passes out with waste 2, but is 

not sufficient in quantity to merit special notice.

CHARACTER OF LIQUORS AT SHELBY.

In March, 1905, the writer visited the pickling plant at the Shelby 

Steel Tube Company and had samples of the various liquors collected. 

These samples were taken, and quantities of liquors, etc., were estimated or taken from the records of the company, by its employees. 

They can not, therefore, be vouched for by the writer. This is 

especially to be regretted, since later investigations upon stream and 

sewage show the presence of very much more acid-iron waste than 

the figures on wastes obtained from the company would lead one. to 

expect. The officials of the company, however, appeared to be acting iir good faith. Because of a disagreement between figures given 

for acid used and compounds of acid in wastes 1 and 2, corroborated 

by the writer's personal investigations in another pickling plant, it 

is believed that there is a large amount of drainage from pickled 

material and leakage from tubs, vats, etc., which passes out with 

these wastes, but is not taken into account in the measurements and 

does not influence the character of the samples taken. The writer 

therefore accepts without question all the figures furnished by the 

company. It is obvious, however, that in any plan to prevent
CHARACTER OF LIQUORS AT SHELBY, OHIO. 31

stream pollution, such drainage and leakage should be carefully collected and treated with waste 1 instead of being allowed to combine 

with waste 2, as it undoubtedly does in most plants. Being an 

unknown quantity, except from inference, it is not further considered' 

in this report.

The following table shows the results of analyses made of samples 

collected March 29, 1905:

Results of analyses of pickling-process liquors. 

[Parts per million.]

Acidity ( H2SO4 ) ............................... ......

Shelby 

rity water 

influent to 

rinse tubs.

28 

a 226 

302 

03fi 

9,550

Effluent 

of rinse 

tubs.

29 

260 

2,184 

1,388 

9,550

Pickling 

liquor at 

end of 

first day.

30 

110,600 

158,700 

50,400 

1,230

Pickling 

liquor at 

end of second day.

31

26,700 

100,400 

57,300 

1,230

a Alkalinity in terms of 112864.

Samples 28 and 29, being from continuous flows, are hourly composite samples, showing average composition for the working day. 

It is the custom to begin each day with three tubs of fresh pickling 

solution. At the end of the day these still contain active acid. They 

are retained, therefore, and used the following day for pickling the 

rougher material. At the end of the second day they are emptied. 

Each day, therefore, three tubs are filled ami three emptied, six tubs 

being used in all.

Sample 30 is composed of equal parts from tubs filled on the morning of March 29, and sample-31 of equal parts from tubs filled the 

previous day. Both samples were taken after the pickling for March 

29 had been completed. Sample 31, therefore, is "spent pickle," to 

be emptied from the tubs, and may be taken as the residual liquor 

from one clay's pickling, really representing the heavy work of March 

28 and the light work of March 29 combined.

Sample 30 is "the residual liquor from the heavy work of March 29 

and was used for the light work on March 30 for further neutralization of the acid.

On March 28, 6,300 pounds of 60° sulphuric acid were used in 

pickling, and on March 29 the amount required was 6,400 pounds. 

We may take, therefore, 6,350 pounds of acid as the quantity affecting the analyses shown in the table. This amount of 60° acid contains an equivalent of 4,030 pounds of SO3 .

From the report of the sulphuric acid industry appearing in the 

Twelfth United States Census, the average value of 60° acid is $14.47 

per ton, or $22.75 per ton of SO3 content.
32 STEEAM POLLUTION BY ACID-IBON WASTES.

RINSE WATEK.

At Shelby the rinse water is now discharged into the sewers. A 

comparison of results on samples 28 and 29 shows that the 9,550 

gallons of rinse water received from the material rinsed 150 pounds SO3 .

Of the SO3 thus lost little is in the free state, that which has not 

already combined with the iron or has not been neutralized by the 

alkaline water being only a small portion of the whole. This loss 

represents 5.7 per cent of the acid used, or $1.34 a day. The solution 

is made too dilute to admit of economical recovery of any compound 

it contains. Its effect upon the sewage is of interest. Let us assume 

that the sewage would have, normally, the same iron content and 

alkalinity as the city water (sample No. 28 in table). The flow of 

sewage during the working day is about 150,000 gallons, say 15 times 

the amount of rinse water. The alkalinity would therefore be 

decreased by about one-sixteenth the acidity of the rinse water, or 

16 parts per million, leaving it with an alkalinity of 210 parts per 

million, approximately. This effect is inconsiderable. The iron 

content would be increased by one-sixteenth the iron content of the 

rinse water, or 87 parts per million. There is no reason to suppose 

that this amount would affect injuriously the operation of the sewagedisposal works.

; It appears, therefore, that the rinse water might safely be added 

to the city sewage without fear of nuisance. While it is far too dilute 

for the economical recovery of iron or acid in any form, the iron might 

readily be reduced to an insignificant amount by precipitation before 

it is allowed to enter the city sewers. This could best be done, theoretically, by the use, daily, of 100 pounds of NH3 in the form of 

ammonia water, a small basin being provided for sedimentation. 

Satisfactory results could also be obtained by the use of 165 pounds 

CaO in the"form of lime water. The cost would approximate 65 cents 

a day for precipitant. The precipitated lime and iron would be of 

some value to paint manufacturers.

SPENT PICKLING LIQUOK.

In the 1,230 gallons of pickling liquor discarded at the close of the 

day, 1,230 pounds of SO3 are found, representing a value of $14 in 

,acid used. This exists chiefly as ferrous sulphate, some ferric 

.sulphate and about 2.5 per cent of free sulphuric acid being also 

present.

About 2,650 pounds of SO3 , or nearly two-thirds (more exactly, 

'65.8 per cent) of the active principle in the acid used, is lost in the 

pickling tubs. Although a part of this passes off as fumes, it is pre- 

-sumed that nearly all this loss is due to splashing and leakage from 

the tubs and drainage from the pickled material, and that most of the 

lost pickling liquor passes to the sewer together with the effluent of
RECOVERY OF COPPERAS FROM ACID-IRON WASTES. 33

the rinse tubs. The spent pickling liquor discarded at the close of 

each working day is at the present time passed through a copperasrecovery plant.

COPPERAS PLANT AT SHELBY.

With the twofold idea of preventing the discharge of the liquor 

into the stream and, if possible, of adding to the economy of pickling 

operations, a plant for the recovery of copperas from spent pickle 

was installed during August, 1904, at the works of the Shelby Steel 

Tube Company.

This plant is exceedingly simple in construction and operation. 

The spent pickle is drained by gravity into a lead-lined wooden 

receiving or storage tank of rectangular cross section, having a 

capacity of about 6,000 gallons sufficient to accommodate the spent 

pickle from four days' work. From the storage tank the liquor is 

drawn by charges into an evaporator for concentration. The evaporator is a wooden tub of rectangular plan and trapezoidal elevation 

having a capacity of a little more than 2,000 gallons. The tub is 

lined with one-eighth inch lead and heated by a steam coil. It is 

provided with a wooden hood and a draft for carrying off the vapor. 

A much more economical evaporator, though more expensive in first 

cost, could be used.

Iron or steel turnings are introduced into the evaporator to neutralize the free acid and to reduce ferric to ferrous sulphate. The 

liquor is concentrated to about 45° Baunie (sp. gr. 1.453; Twaddell, 

90.6°) and then drawn off into wooden crystallization tubs. These 

tubs are rectangular in cross section and have a capacity of about 

675 gallons each. To assist in the crystallization and to provide a 

support for the crystals, wooden strips are hung in the tubs. The 

dependent crystals are gathered, drained, and barreled for shipping. 

The mother liquor, together with the more impure crystalline copperas from the sides and bottom of the tubs, is pumped back by hand 

to the storage tank or the evaporator. Occasionally such matter 

is discharged into the stream with wash water from the tubs to dispose 

of accumulated impurities.

In the original plant three crystallization tubs were used, but three 

more were added in the summer of 1905, making six in all.

Analysis of the crystals produced gave the following results in per 

cent: Acidity as H3SO4 , 0.2; sulphuric acid as SO3 , 27.5; iron as Fe, 

18.9. This approximates the formula FeSO4 .7H3O for ferrous 

sulphate crystals, but indicates the presence of small amounts of ferric 

sulphate and free acid.

Average figures for several months show that the copperas produced is, by weight, 50 per cent of the acid used in pickling. For the 

6,350 pounds of acid used (average of March 28 and 29), therefore, a,

IRR 186 06 3
34 STEEAM POLLUTION BY ACID-IRON WASTES.

product of 3,175 pounds of copperas would be obtained, having a content of 875 pounds SO3 . This is 21.7 per cent of the SO3 in the acid 

used for pickling, or 71.1 per cent of the SO3 in the spent pickle.

There is therefore a loss presumably taking place by leakage in 

the evaporator, storage tank, and crystallization tubs of 8.8 per 

cent of the active principle of the acid used for pickling, or 28.9 per 

cent of the amount of such principle present in the spent pickle.

The estimated disposal of the SO3 , assuming an average daily use of 

5,000 pounds of acid, may be summed up as follows:

Losses and recovery of sulphuric acid at Shelby Steel Tube Company.

Total ...................................................

Per cent.

3.7 

65.8 

8.8 

21.7

100.0

Pounds per day.

Acid.

185 

3,290 

440 

1,085

5,000

80s.

144 

2,566 

343 

847

3,900

Value as 

60° acid.

$1.34 

23.80 

3.18

7.85

36.17

Original estimates on cost of recovery per ton of product were as 

follows:

Coal, at $2.25 per ton....................................................... $1.08

Iron turnings, at $13 per ton................................................. .89

Barrels, etc., for shipping.................................................... 1. 90

Total............................................................... 3.87

It is thought that $2 will more nearly approximate the actual cost 

of fuel for evaporation with the evaporator used, although, owing to 

the complication of heating arrangements, no exact figures are obtainable.

Accepting the other items as correct and adding $1 per ton for labor 

and $0.50-per ton as a 10 per cent annual depreciation upon a plant 

valued at $2,000, we have, for the production of one ton of copperas, 

the following figures:

Average value of copperas (Twelfth U. S. Census).............................. $9. 64

Fuel, at $2.25 per ton................................................. S2.00

Iron turnings, at $13 per ton. ....................................-....' -89

Miscelfaneous supplies.............................-.-....--.-.----.-. 1. 90

Depreciation......................................................... .50

Labor.............................................................. 1.00

 6.29

Profit.---............................-.-....-.-......-------.------- 3.35

This is a very liberal estimate of costs, and will, without doubt, be 

sufficient to more than cover the actual conditions at Shelby. Were 

the plant arranged to save the liquor now lost and a better evaporator 

used, a much better showing could be made. It must be considered 

that the advantageous arrangement of the plant for gravity flow contributes in some measure to the low cost of the product. Were pumping required, the cost would not in any case be more than $6.64 per
PROCESSES FOE DISPOSAL OF PICKLING LIQUOE. 35

ton, leaving $3 per ton as a low estimate of profit under extremely 

adverse conditions.

With a capital of $2,500 and a yearly product of 400 tons of copperas, the foregoing figures would sh^w an annual profit of $1,340, or 

53.6 per cent upon the capital invested. The margin of profit, with 

the present price of copperas, is large enough to permit the application 

of the method to any plant of size sufficient to create a nuisance by 

stream pollution.

OTHER PROCESSES FOR DISPOSAL OF PICKLING LIQUOR.

Several other processes for the disposal of sulphuric-acid pickle have 

been tried experimentally and a few have been applied on a commer-' 

cial scale. The most prominent of these and their results are tabulated below:

Process. Result. 

Electrolytic regeneration of acid.........................................Expensive.

Recovery of basic ferric sulphate and acid by aeration......................Expensive.

Recovery of "sugar copperas"...........................................Practicable.

Chemical precipitation.................................................. Expensive.

So far as known, recovery of copperas in large crystals and as'' sugar 

copperas" are the only processes that will pay for the cost of disposal 

of the spent pickle from sulphuric acid.

For spent pickle from hydrochloric acid containing iron chlorides a 

cycle of regeneration has been perfected in England by Thomas Turner. The method is described at some length by Naylor in Trades 

Waste, pages 262-263. In brief, the pickle is fed into a reverberating 

furnace; iron oxide is retained and hydrochloric acid passes over with 

the fire products and is condensed in ordinary muriatic towers. The 

cost of 75 per cent acid recovered is stated at about $2. In this country it would doubtless be somewhat higher.

SUMMARY.

The investigations at Shelby, Ohio, have brought out the following 

points:

1. Stream pollution by acid-iron wastes has been taking place at 

Shelby for about fifteen years, to the annoyance of riparian residents 

below the city for a distance of 12 miles. Complaints against this 

pollution (wliich may be defined as the entire waste of pickling liquors 

in which one pound of 60° sulphuric acid is used to each 175 gallons 

per second of dry-weather flow in the stream) culminated in 1901 in a 

series of suits against the corporation responsible for the pollution, 

resulting in awards of damages in favor of residents along the stream 

living from 3 to 7 miles below the point of pollution.

2. Conditions along the stream were greatly bettered by the passage of the waste through the city sewage-purification works (consisting of a sludge basin, shallow five-day sedimentation reservoirs, 

and shallow cinder and gravel filters), diluted by from 10 to 20 times 

its volume of a weak domestic sewage.
36 STREAM POLLUTION" BY ACID-IRON WASTES.

3. The effect of the acid-iron sewage upon the sewage purification 

plant was to fill basin and reservoirs rapidly and thus decrease their 

efficiency, to destroy the working value of the filter beds in a comparatively short time, and to increase great y the care requisite for the 

proper maintenance of the plant. Bacterial action was seriously 

interfered with, the action of the early processes of the plant upon 

organic matter was diminished, and the effluent was rendered obnoxious by reason of a high content of iron sulphate. Odors about the 

plant and danger, from pathogenic bacteria in the effluent were 

decreased by the acid-iron character of the sewage.

4. The treatment of pickling waste in a plant for the production of 

crystal copperas, one-fifth of the acid used being so recovered, reduces 

the objectionable features of the sewage by about 60 per cent, and is 

therefore of great value as a means of preventing stream pollution by 

such wastes.

The copperas-recovery process is the best method known for treatment of sulphuric-acid pickling liquors, is attended with a large per 

cent of profit, and is applicable to pickling plants of all sizes. Such 

a plant, properly arranged, will entirely obviate stream pollution by 

"waste pickle."

5. Rinse water from the pickling process, not including leakage and 

splashage from the pickling tubs, can, in general, be discharged into 

the sewerage system of a town or into a stream without detrimental 

consequences, but it will produce a discoloration of the water unless 

the dilution is very great. Although such waste does not seriously 

affect the uses of a stream, it may be rendered entirely unobjectionable at a trifling cost by precipitation with lime or ammonia, and such 

treatment is advised.

6. Of the acid used in pickling at Shelby, only 21.7 per cent is recovered in the copperas product. Of the remaining 78.3 per cent, 8.8 per 

cent is lost in the copperas plant, 65.8 per cent is lost in the pickling 

process, and 3.7 per cent passes into the city sewerage system as rinse 

water. Of the 74.6 per cent not definitely accounted for by the officials of the company, a part passes off as fumes from the pickling tubs; 

some is known to be discharged directly into the streams as washings 

from tubs, and the remainder apparently enters the stream direct or 

by way of the sewers, presumably as leakage.

This "lost" acid is the cause of the present pollution at Shelby. By 

designing the plant so that this waste may be recovered as copperas, 

stream pollution can be practically obviated and the economic value 

of the plant greatly enhanced.

7. The present pollution at Shelby makes the stream waters red and 

turbid, seriously damages them for general use, and renders them 

deleterious to fish life for a total of not more than 2 miles. No other 

damaging effects were found except an increase in the permanent 

hardness of the water, by which it becomes less suitable for boiler and 

for domestic use.
CLASSIFICATION OF THE PUBLICATIONS OF THE UNITED STATES GEOLOGICAL

SURVEY.

[Water-Supply Paper No. 186.]

The serial publications of the United States Geological Survey consist of (1) 

Annual Reports, (2) Monographs, (3) Professional Papers, (4) Bulletins, (5) 

Mineral Resources, (6) Water-Supply and Irrigation Papers, (7) Topographic Atlas 

of United States folios and separate sheets thereof, (8) Geologic Atlas of United 

States folios thereof. The classes numbered 2, 7, and 8 are sold at cost of publication; the others are distributed free. A circular giving complete lists can be had on 

application.

Most of the above publications can be obtained or consulted in the following ways:

1. A limited number are delivered to the Director of the Survey, from whom they 

can be obtained, free of charge (except classes 2, 7, and 8), on application.

2. A certain number are delivered to Senators and Representatives in Congress, 

for distribution.

3. Other copies are deposited with the Superintendent of Documents, Washington, 

D. C., from whom they can be had at practically cost.

4. Copies of all Government publications are furnished to the principal public 

libraries in the large cities thruout the United States, where they can be consulted 

by those interested.

The Professional Papers, Bulletins, and Water-Supply Papers treat of a variety of 

subjects, and the total number issued is large. They have therefore been classified 

into the following series: A, Economic geology; B, Descriptive geology; C, Systematic geology and paleontology; D, Petrography and mineralogy; E, Chemistry and 

physics; F, Geography; G, Miscellaneous; H, Forestry; I, Irrigation; J, Water 

storage; K, Pumping water; L, Quality of water; M, General hydrographic investigations; N, Water power; O, Underground waters; P, Hydrographic progress reports. 

This paper is the fourteenth in Series L, the complete list of which follows (WS= 

Water-Supply Paper):

SERIES L, QUALITY OF WATER.

WS 3. Sewage irrigation, by G. W. Rafter. 1897. 100 pp., 4 pis. (Out of stock.)

WS 22. Sewage irrigation, Pt. II, by G. W. Rafter. 1899. 100pp., 7 pis. (Out of stock.)

WS 72. Sewage pollution near New York City, by M. O. Leighton. 1902. 75 pp., 8 pis.

WS 76. Flow of rivers near New York,City, by H. A. Pressey. 1903. 108 pp., 13 pis.

WS 79. Normal and polluted waters in northeastern United States, by M. O. Leighton. 1903. 192 pp.,

15 pis. 

WS 103. Review of the laws forbidding pollution of inland waters in the United States, by E. B.

Goodell. 1904. 120 pp. 

WS 108. Quality of water in the Susquehanna River drainage basin, by M. O. Leighton, with an

introductory chapter on physiographic features, by G. B. Hollister. 1904. 76 pp., 4 pis. 

WS 113. Strawboard and oil wastes, by R..L. Sackett and Isaiah Bowman. 1905. 52 pp., 4 pis. 

WS 121. Preliminary report on the pollution of Lake Champlain, by M. O. Leighton. 1905. 119 pp.,

13 pis. 

WS 144. The normal distribution of chlorine in the natural waters of New York and New England, by

D. D. Jackson. 1905. 31 pp., 5 pis.

WS 151. Field assay of water, by M. O. Leighton. 1905. 77 pp., 4 pis. 

WS 152. A review of the laws forbidding pollution of inland waters in the United States, second

edition, by E. B. Goodell. 1905. 149 pp. 

WS 161. Quality of water in upper Ohio River basin and at Erie, Pa., by S. J. Lewis. 1906. 114 pp.,

6 pis. 

WS 179. Prevention of stream pollution by distillery refuse, based on investigations at Lynchburg,

Ohio, by Herman Stabler. 1906. 34 pp., 1 pi. 

WS 185. Investigations on the purification of Boston sewage, by C.-E. A. Winslow and Earle B. Phelps,

1906. pp. 

WS 186. Stream pollution by acid-iron wastes, a report based on investigations made at Shelby, Ohio,

by Herman Stabler. 1906. 36 pp., 1 pi.

Correspondence should be addrest to

THE DIEECTOE,

UNITED STATES GEOLOGICAL SURVEY,

WASHINGTON, D. C. 

OCTOBER, 1906.

O