A TANEERY ·WASTE DISPOSAL PROBLEM
BERNARD CANTER
and
ARTHUR
IfEIF:ETZ
Submitted In Partial Fulfillment of the Requirement
for the Degree of
BACHELOR OF SCIENCE
from the
M.A.SSACHUSETi'S INSTITUTE OF TE CHNOLOGY
1930
Course VII.
Signature of Authors:
Certification .of Departme:p.t:
Oambridge.Massachusetts.
I\!ay 28.1930.
Professor A. L. Merrill,,}
Secretary of the Faoul ty.,
Massachusetts Institute of Technology,·
Cambridge ,Massachnse tts~
Dear Sir:
Herewith is submitted a thesis entitled:" A
T~ery
of the
Waste Disposal Problem"J in
requ~rements
part1e~
fUllf111ment
for the degree of Bachelor of
Respectfully submitted,
Sc1ence~
Aclc'lO va edge me n t s.
The authors herewith express their thanks and appreciation
to Professor Samuel
advice and
C.~scott
encGura~ment
for his untiring co-operation.
in the prosecution of
~his
thesis.
The authors wish to express their thanks and appreciation
to the L·ord Tannery Company of WobuI'n,Mass8.chusetts t for their
co~oper8tion
in
ma~1ng
The autho rs also
this investigation possible.
~'ish
to express thei r thanks and
aPl1r~c-­
iation to Metca.lf and EddY,Eng1neers,of Boston,Mass. for use
of some of their data 11?- this report"
I
I
. . . .L~--- .
Introduction
I
Part I.
............... . ..... .... ......
1
Freliminary ·Study of the Tannery 'iVsate
Problem.
..
I. Character of Tannery Wastes and Methods of
Treatment
6"
.
II.· Co·ndi tions Ex·isting B.t Various Plants and
Metho·ds .of Treatment and. Disposal •••
Gloversville ,N.Y.
• .•••. ~a • • ~..........
Harrims,n TannerY,North Vifilmington,:Ms,ss ••
\~'h.i te-Son
Co., Walpole,Masa.
it. •• •• • ••• • •
Wi.nslow Bros. and 8mi th Co. ,Norwoodjl~~ass. •
National Calfskin Co.~ ,J:'eabodY,}1I1ass•.••
~
ltTer Meer t ' Treatment ,Ge nnany ••• ~ • ~ ...... '
II.
I
III.
19
The Gries-Pfleger Ten.ne ry Experiments
Iennsylve~1e Tannery Waste Disposal
Committee Investigation
•• ~......
20
b..
I. Froes ss of Ta,nn1ng Hide s and Was.tes rrodl1ced
27
s......
27
••••••••••••
33
•• ~ •••••••••••
t·.
r&
ii'
~ft
L·
23
Experimen'tal Investigation Conducted at
the Lord Tanne ry, Woburnt~Ias8.
Volume of Waste Discharged
~';.4!
17
U.S.Public Health Service ·Experiments •••
\llastes Produced •• ".a ••••••••••••••••••••
Character of Vu.a,stes a·s Discharged ,from
the tannery .
• i? • • • • .. • • • • .. • • • • • •
,I
10
11
13
19
'Tal1nlng the Hides
I
II
9
9
Review of Important Investigations.......
Part II.
I
9
?
29
32
IJ;:. Descrj.ptlon of Ext stin,g
Screens
•••••..••••••
hmp' -well and PUmp
Settling Tanks ,
•
Treatment Plant.
35
a •••••••••••••••••••••
36
\~a8tes
e ••
'.
B8~1ns
Earthen Settling
'• • • • • • • • • • • • • • • • •
II •
•
•
•
•
•
•
oj
e" •
•
•
•
••••••••••••.••••••••
"'0
d s .. • • • '. • ~ -. • • • •• • • • • • • • .. • • • • • ., • • • • •
8111 d' g e .De,'
Tri cklillg Filters •• • • • • • • • • •• • • • • .. • • • • • • • • •
III. Experimenta,l
\~ork
. ••• •••
36
36
37
38
38
•••
41
Chemi alai Analys1'-s ;-~.•••••••••••••••••••••••
of Results •••••••••••••.•••••••••
41
<I
It
••
Disc~ssion
Extent of Po ll-q. t1 on of Aberjona, River ••••••
Se ttl,ing and :Freei pi tati on Te st s •••• w • a _ • • "
42
45
47-
Plant .••••••••• , •••••••••••••••
51
E~per1mental
IV. Bacterial
Investigati~on
,. ••••••••••••••••
Bacterial ..;,;\nalysis
tl
.••
_
It
•
QI.
Effeot of StTeem
Dilution on Bacterial Action
" l
..~
V. Conclusions>]
55
55
57
•
59
..
63
I. Technique a.na Appare,tus Employed for Tests ••••
65
VI. -Recommendations
•
• • •
• • • • • • a • • • • • •
• • • • .,. • • • •
......................
b.
• • •
GIl
~
Part III. Appendices
IIi) Bi bJ~i ography
I
..L.,
•••••••••••••••••••••••••••••••
72
- ...._--.. . . . . .---- _
List OI Tables,
Measurements of Quantity of Wastes PUmped
at Lord Tannery under No~al Bus1ness
Con·di tiona. April 1-930.
•
.
34
Analysis of Vfastes" at Lord Tsnnery ••••••••••
40
Comparis"on of'Lo.rd Tannery,Effluent and
Ave'rage .P.Jnerican., Sewage ,.~ •••••••••••
1Il
,
•••
'
Results of Analyses by. R_ and ]jt. Industrial Lab.
of Smnples of Brook ~nd Riyer Water Below
~ffluent Outlet from ~ord T.;arnnery. in
:IIo rth
~\1'Oburn
• • • • • •••••
* • ~ • • • • ••• •
Com'parison of Settl·eabj-B Solids Vii th 'and
Without Ferrous
S~lfate
•.•••••••••••••••••
43
46
50
Introcluc. tion.
The p':ellution of streams by ·industrial \V&.stes has been
recognize i for many years as an impending problem to the use of
water supplies for "domestic and municipal pu.rposes. !lany industries
produce patresc1ble and deleterious wastes. Some "of the more important producers of such wastes are:- coal m1nes,gas works,
chemical works,coke ,'ere emeries .·tanneries, oil re fineries, distillar1es
and brewer1es,eanneries,'pulp end paper mills,steel works and mun-
icipal
~ewage.
Many of these industries lately have appreciated the
fact that the treatment of industrial" vastest"regardless of whether
marketable or useful pro due ts can be recovered from them.is a
just charge against their processes. This more reasonable att1tuie
has resulted both from economic conti tiona and from increasing
po'wer given the state and municipal authori ties regarding stream
pollution.
The importance of stream pollution is emphasized by the fact
that almost every State has such a problem and that legislative·
and eonstructive me a sure s for 1 ts preyent10n have been stea.dily
increasing. Practically every eta te and many munieipali ties have
scme law dealing vv1 th the pollut1.on of the waters within their
'jur1sdict1~n.
The importance of the tannery waste ,disposal
problem is brOUght out by the fact that the value of all leather
produce d in the Un! ted States is roughly $500,000,'000
Per
year
and probably 50 .~OOO men are employed in .the tanner! es as wage
earne ra.
Just what position,on the list of industrial w8ste,tannery
waste would occupy is a matter of conjecture.'although the
general public usually considers it the source of obnoxious
clore and unsightly,colored and poisonous liquids.and being
governed thereby would probably rate it among the worst. The
problem of tannery waste disposal has never been adequately
solved to the satisfaction of interested parties,although the
11teratu~e
contains many references to tannery waste disposal.
Most of them,however,are descriptions of specific treatments
and disposal plants and do not contain much data. No account
has been found of an investigation Which would presume to set
forth any-general prillc1ples governing the treatment of these
wastes. This is due "to the fact that there are so many different
methods of tanning leatherjsnd so
m~y
different types of
effluents produced,'as well as such grea.t variability in the
effluents produce d in th.e Bame method of tanning.that each
tSlllle ry repre sents an 111~T~dUal p~blem.
The disposal ef the liquid or semi-liquid waatesfrom
tanneries is a problem that in a great many cases causes as
much trouble and annoyance as any of the d,ifficul ties en-
c'ountered in the productive departments of the plant. Handling
-3--
or treatment of such wastes 1s not usually :taken up
voluntarily by the t,anneries
unle~s
there is some economic
purpose or commercially valueable product to be derived
from such measures. Ordinarily it is because of some out-
side
1nfluence~usually
1 ties,that they become
local or governmental health
intere~ted
author~
1nlearning of that system
of treatment. wh1 ch will ~ with the le ast 1n1 t1a.l expense, g1 ve
the results requ.ired.
~4"
Part I.
i'relim.inarystudy of the Tannery Waste lToblemp
-5-
I. Character of Tannerz Wastes and. Met.hods Employed for
!reatmen~,
The waste wate"rs from various branches of the leather
trade are mostly_of a very polluting character. They are
highly charged '14 th suspende d matters and dissolved solids,
both
0
rgani e and ine rgan1c. They nearly always swarm wi th
patrefaetive organ1sms.:and were it not for the quantity of
lime present would be un'\;)earably offensive. The process of
putrefaction is checked by the presence of the lime which
inhibits the growth of the bacter1a,but when the wastes are
cl11uted by 'being discharged into a stream the bactericidal
act'ion of the lime is weakened and putrefaction sets in
rapi dly. "
The complete purification of liquors so complex and so
highly charged with organic matter is not an easy matter. It
is fortunate that in most cases
san1ta~
authorities are
willing to receive the refuse into pUblic sewers for treatment
along wi th 1;he dome at! c sewage, and th1 s is gene rally the best .
. course to be adopted.
-Where s: manufacturer in the leather trade is obliged to
deal wi th his own tr.ade refuse,he must nearly
al~rays
treat 1 t
f1 rst for the settlement of the suspended solids.l ·and for this
purpose it ssould be ItQssed through effective. settling tanks.
In the case of tanyard refuse the lime liquors and the tan
liquors precipitate on.e another to some extent,·but it will
be found advantageous to use additional precipitants,such
as lime and copperas used together,81so alUDdno-ferr1c t slum.
In using such precipitants care must be taken to have sufficient
11me present or the i ron may combine wi th the tannin to form
an inky solution. The tan efflu.ent after preclpi tatio:t1 is still
a very impure 11qu~d.
t
more polluting than ordinary do~estic
sewage,but is 1n such a condition the.'t it can readily be further
pr1fled•.
It is. a recognized fact tha.t a great deal of the hair,
fleshings,and small leather scraps may be most economically and
satisfaotorily r,emoved by mechanical fine screening. This
feature has been adopted at some of the largest end leading
~anner1es
and the
in the United States. Removal of the coarser solids
hairtb~
mechs·;Iieal fine scre-ens,eliminates not only
several of the elements of unsightliness and trouble where
tannery wastes are conveyed in sewers or streams,but also lightens
.mate ris.lly t the load on subsequent units of treatment, 'Where re-
quired. Screenings are mechanically handled and placed in convenient receptacles for final removal. Mechanical. screening is
usually done by
&
revolving screen unit. This unit is unique in
that it is self-cleansing, that is 1 t does not require any brushes
scrape-rs ,or jets to remove the se reen1ngs from the' screen pl ates.
It consists of a perforated cylindrical
t~~,mounted
on a
horizontal shaft with the drum partially submerged in the
flow of raw waste. The screened waste,after passing through the
);)erforat1ons into the cylinder, nows out through a discharge
opening provided
i~
one end of the drum. An effective seal
around the disoharge opening prevents unscraened waste from bypassing the screening medium. The combinat'ion. of the design and
a·ct1on of the screened effluent causes a sprouting action
wh~eh
cleans the screenings into screening pits. Tests made at plants
where the screens are in operation show removals of 15-20% of
sus pende d
S
011 ds with 1/8" perfo ratione.
Tannery wastes contain large quantities of solids. These
are
mo~tly
organic and" therefore ,highly putreseible t and their
redu-ct1on is desired at the lea.st cost. If scr.eelng is accompanieS.
D~ sedimentation alone(3-~
hours detention period) 50-76% of
these solids will usually be removed. The addition of chemicals
will add to this percentage,so that if necessary,a clear effluent
may be pro cure .d.
Clarity,howe~r,eosts·
money and all phases of a problem
should be investigated before it is, declared necessary to remove
at least to a point of invisi b111 ty in the effluent. After all,·
why remove i t to that extent 1 f the dilution factor of
8
stream
is so high as to d.issipate calor when the effluent is mixed wi th
it?
Sedimentation basins have been
dev~loped,wh1ch
eliminate
the dif1eulties of the older types. Manual handling of sludge.
dewatering to remove it, duplicate basins ,and deterioration of
effluent by accumulating sludge,"all have been eliminated by
the use of the modern,mechanically cleansed,sedimentation basins.
which have been
~ecesfu.l1y
used at
a number of tennety waste
treatment plants.
Se dimentatlon alone wi II no t remove color and bacte ri 8e If
their removal 1s req,u1red,other methods of tl·eatment will be
necessary.
J;:-I. COX1d1tions 1Sx1st1ng at Various Ple.nts and Methods of
Treatment and . Dispos ale
At
Gloversv111e~N.Y
•• the
tannery wastes constitute such a
large. proportion. of the sewa.ge of the city,that for studying
the sewage disposal problem,s testing station was operated for
about
8'
7ear .in 1908 and 1909 to determine how the tannery
wastes YJOuld affect the differ,ant methods of sewage treatment.
It was found
t~at
these waates, more than doubled the strength
of the sewages bu.t d1 tmot .render the methods of sewage treat..
ment inapplicable. A very good effluent was produced b1' pre-liminary sedimentation,and intermittent sandfiltratioll."an.d
a treatment
p~snt
was built embodying these features. This
plant has functioned we'll but diff1culties have been experienced
in handling the slUdge becau.se of excessive quanti ties of li'me,
.nei,r and fleshings in the tannery wastes,whlQh were. expected
to 'b e removed by tanks at the tanne ries prior to d1 seharge into
" the sewers.
Harriman
Tanne.rl~·North .W1~ington,:Mass,
At the C.S.Harriman Tannery,in North W11mington,M.ass.,where
heavy leathers are manufactured, studies in 1913 indicated that
the combined wastes eould be satisfactorily treated 'by sedimentation
· "10 ..
and intermittent sand filtration.and a plant built for such
treatment has proven very
sat1sfacto~.
The effluent is
41 scherged into a small brook. The slu.dge found in the sedimentation tanks is removed periodically and dewatered on
small sand beds. The dewatered sludge is reported to be exc'ellant material for application to grass land. The slu.dge
when pumped to the sludge beds ,'created
~hich
was
ve~
S"-"'
objectionable for several
st.rang H2S odor
d~s.
This trouble
has been overcome by applying creolin or crude coll-tar dis..
1nfeetant to the sedimentation tank the night before cleaning,
after t·he tank has been pu t ou t of service.
Wh'1te,-Son Compav ,'Wal pole !'M~s.
The wastes from the tannery of the White-Son CompBnY,1n
Walpole,Mass. ,manufacturers of fahcy leathers are quite cl1f£erent
frOID· the wastes produced by the heavy leather tannery in North
Wilmington. Nevertheless,s1m11iar treatment by sedimentation
and interm1 ttent· sand fl1 tration,·has been satisfactory. The
effluent 1s discharged into a
~mall
mill
POJl~.
The slUdge is
drawn about once a month onto one of the sand filter beds and
the dewatere d mate rial or slUdge is
us~d
for filling low land
nearby_ This slUdge \\blah is largely spent ,graound sumac,has
no val·u:·e. but is not objectionable in character.
·Winslow Bro,thers . and 8m!th Companl,Nor1Nood,Ma.ss,
.A.t the tannery of .Winslow Brothers and Smi th Company in
Norwood.Mass. 11 where sheep,·goat. and calf sldns are tanned and
wool is scoured,1t was found adviseable to seperate the
ws.stes into three classe s; rinse waters from the wool department.
wool scouring wastes; and combine d wastes from the tannery and
wool 'scouring wastes,degreasing plant. The effluent one was discharged into a small brook emptying into the Neponset River,
which 1s· already polluted by paper mill wastes.
The combined wastes from the tannery and degreas1ng plant
are pumped to sedimentation tanks. The resulting slu.dge is
drawn to slUdge beds eve ry 2-4 weeks in warm .weather and every
3~6
weeks in cold weather. The dewatered slUdge is used in part
for fertilizer by farmers in the vicinity and the remainder 1s
haule d to was t'e land.
,During periods of cold weather and high stream flow,"the sedimentation tank effluent is discharged iDto the stream wi thout
further treatment. Sedimentat10n accomplishes the removal of
about 50% of the suspended solids,but the effluent is still
colored and extremely turbid.and contains much finely divided
suspended and colloidal organic matter.
During periods of warm. weather and low stream flow. the
settled wastes are trea.ted by chemical prec1pi tatio:B wi th sulfate
..12-
"of alumina,the pH value of the wastes being controlled by"
the addition of sulfuric acid to give the most eff10ient
and most economical treatment. The wastes .are usually strongly
alkaline. V\'heneTer there is a deficiency in alkalin1 ty,"ml1k of
lime is added to the wastes. The combined wastes vary greatly
in strength and composition during the
.-r
and it is
to equalize the quanti ty of the wastes, as b,.
passa~
necessa~
through
the sedimantat10n tanks,prior to chemical precipitation. The
chemically treated wastes are passed through tanks and the
sluige resulting is discharged periodically on to the slUdge
beds.
The chemical effleunt is well clarif1ed,but contains considerable dissolved organic matt er and is quite putreseible.
The effluent is further treated by intexm1ttent sand filtration
to the capac1 t~l of the available area of sand. filter beds., and
the' remainder is treated by dilution in the brook wi th water
drsW!1 from a reservoir O1Vl1e d by the company. Du.ring periods of
extremely low flow. practically all of the tank effluent is
filtered. The filter bed effluent is practically clear and
colorless and non-putresc1ble.
It has been pointe d out
t~a t
local condi tiona will govern
the extenlt of treatment required at diff·erent places. It is
also true that the extent of treatment refJuired at a given
"place will vary with varying cond1 tiona of temperature and
stream flow· at different seasons of the year. This fact is
well 111ust;rated by the regulation of the treatJIJlant of the
waste s from the Wlnslo w Brothe rs and 8mi th Company tannery
aec.ording to the requirements
of
the stream.
National Calfskin Companz,Peabodz.Mass,
Some years ago the National Calfskin Company installed
two concrete sedimentation basins,each 56 feet by 28 feet
by 7 feet deep. Various baffle arrangements were tried out
in the tanks to insure proper mixing and to endeavor to
settle out the flocculated precipitate.
The system did not differ greatly from the average se
imentat1o~
d~··
plant installed at various tanneries,exeept that
special provision was made to insure effectual mixing of
liquors of opposite character and ample area for the sed-
imentation of the resulting precipitate )y doubling the capaci ty specified by the c1 ty engineers.
It was faund possible to secure the neutralizing effect
. by regulation of the beam house liquors,that iS,by removing
the readily settleable"11me grounds" from the beam house
vats, and discharging only the supernatent liquor. This had
the de sired effect
0
f reacting wi th the Bei d liquors from the
tannery, resulting in an effluen t ?fni ch. was substantia11 y
neutral and chemically inactive.
However, the mechanical difficulties encountered in trying
to make the. prec1p1 tate settIt. and in removing the sluclge
which did accumula.te,proved a serious :problem, end the cost of
cleaning the basins was excessive. Frequent cleaning was
necessa,ry because men sludge accumulated in the tank sedimenta.tion ceased and the plant accomplished nothing. The
company was obliged to put up wi th this 81 tuat10n for a
number, of years as no better method of handling the problem
was presented,but finally after considerable experimental
work,they decided to install a Dorr Thickner,an apparatus
which has successfully operated on various other types of
industrial wastes,and which has been almost universB,lly adopted
in the metallurgical industrY,wherever sedimentation is
required.
The Dorr Thickener has for 1 ts object continuous sediment-
ation,with the production of a uniformly clarified
overfla~.
s,nd the removal of sludge a.t the highest poss1 ble density. It
consists of a slow moving mechanism set in a circular tank or
basin. This mechanism 1s made of four radial arms attached to the
lower end of a vertical shaft driven by a worm and worm gear.
The arms carry plow blades set at an angle
~vh1ch, through
slow
rota t10n of the mechanism, gradually mo've the settled slUdge to
the center of the tank,w1thout disturbing sedimentation. The
effect of the plOWing action is that the slUdge is slowl y
turned over and over as· it is moved to.
t~e
center.so that the
~15-
particles become, tightly packed together ,and the moisture
is aquae zed out t thus pro ducin:g a sludge, of maximum densi ty.
The bottoll of the concrete tank slopes gradually to ·the
center,'and the radiaJ. arms confo11!l to this slope. Supported
on the,se arms.and Sllfrou.nd1ng the eha-ft,'is a 6 foot diameter
cylinir1cal sheet iron well extending just above the su.:rtace
o:f l1qui.d in the tank. The th1ck~ned sludge,-as it reaches the
center.is forced up into this well by the hydrostatic pres,sure
of the liquor outside the wel1."atld the slUdge 1 teelf forms an
effective seal,'so that only thick slUdge can find 1 te way into
the central "velle
The thickened sludge 1s removed from the well by means of
a ".stuff pump" delivering to an elevated storage
tank~from
which it is drawn off into wagons and taken to the dumping
grounds. This' method of handling slUdge was n.ecessary at the
Bat10Ral Calfskin' plant,in as much as no space, was available
for slud@9 drying beds. It is not possible for any bUilding
up of' the sludge on the bottom to
t~e
place owing to the
'fact that the bot,t:omi s swept by the thickener arms. As the
slUdge 1s kept constantly in motion septic nuclei have no
chanoe of forming,'sethe surface of the tank is at all times
free from all-smelling bubbles or floating masses.
~he t~ is equipped with a peripheral wooden launder into
which the clear liquor ove'rflowB,spreading out in a thin film,
"16-
and consequently the veloel ty of flow through the tank is
re duced to a minimum. One section of >the launder,'ii vided off
fram the overflow port1on,"is reserved for the sewage feed. The
Sel'lsge flow enters the tank through this launder.and 1s uDiformly distributed throu,ghout the
tank by a baffle. The'
veloci ty of flow 1s cut down as each individual particle seeks
its exit at S0me point in the circular overflow. Reduction of
velo~1t7
gives the suspended material ample opportunity to
se ttl,,,. there being no su.pporting currents to carry it alo"ng.
The peripheral overflow trough collects the effluent liquor
an"d discharges it into a sump which leads to the city sewer.
The thl okene r un1 t is prec eda d by a Dorrco sewage screen
for the removal of coarse material such as ha.lr,"flesh1ngs.
It-s.ther scraps,etc. ,·which have
&
commercial valu.e as fertilizer
base. This is a self-cleaning revolving drum screen of naval
eenstraotion. The pe rfora tiona of the shea t metal shell are
C).I inch in diameter but.:due to the rapid rotation of the drum ,
p8rt~cles
of even smaller diameter are remove40_ At the National
Calfskin Company the screenings amounted to 3.000 pounds per
;
ds,. at 82 per cent moisture or 540 peDis of dry solids.
'~~~The
removal of this material made possible the handling of the
slUdge through pumps and pipes.
!he National Calfskin pl,ant wa.s treating 525,'000 gallons
of sewage in 10 hours. The teet data made in 1919- was:-
Powe,r Regulremen t,8
fl'·) Screen and aU transmission •••••••••••• 3.8 horsepower.
(2) Th1~kener mechanism••••••••••••••••••••• O.2
n
(3) ~p
,
~
~ •••••••• 1. 1
t
Total
I",
5.1"
The plant was removing 75 per cent of the suspended 8,11d8.
!fhe sludge was about 25,'000 pounds daily at 88.2 per cent
m01sture or 3,000 pounds of dry so11ds. ,The effluent produced
was clear and containe d but a sme,ll amount of red flooculent
prec1 p1~ate. It was practically, odorless when fresh.and in
eve 17 resp'ect suitable for discha.rge into the 01 ty sewer.
"'ITer Me!,r~, Treatm,e:nt,
Whe,~
the required ground area is not available for other
methods of treatment,the use of a recently perfected continuously
operating centrifugal machine, the so calle d 'fter meer J1 made 111
Germany,:1s suggested. This maohine occupying only a few square
fee't of floor space wiU"scrtlb-out" 96% of the suspen4e~ matter
in the form of 8016 moist~re slUdge- Cak~.d1scharged automatically
and ,delivering at thesame time a clear e,ffluent.
Another recent dlscover7 may change the recovery of
tann~r7
waste from the debit to the crecl1t side. By Using the 80calle i sulfide proce ss for de-ha1ring, whereby the
h~1r
is
completely diseolved,i t 1s now commerca111y profi table to re-
cover this waste sulfide liquor as fertilizer
~ime
~emOTe
from
tanne~
and
at the same
wBste a large. percentage of the most
" ;;obIl'OXOU,'S1' material. When ,spent su'lfide liquors are rendered
sligh,tly ac1d,the dissolved ha1r(proteid colloids) 1s immediately
-18-
prec1pi tate d ·in the form of a spongy,'porous mass from whieh.-
the water is readily expressed. This can be accomplished "by
means of
8,
continually operating process whic"h runs 1 tself
automaticallY,consisting of very simple equipment and reqU1re1ng 11 ttle labor. The resul t1ng fertilizer material is
un1fo"DJl in composition and averages 13% ammonia on a 10%
:;"
.. -
moisture basis,with 97% of the ammonia available. An interesting
slde,-light in thie c;onnection 1s that the proces,s provides
for t"he reooverr of a considerable portion of the original
sodium sulfide used,wh1ch,together with the fertilizer produced
makes the sulfide
de~ha1ring
process much cheaper per unit of
leather them the liming process.
I
-19--
III. Review of Previous Important Investigations.
tT. S.F.H.S.Expe.r1ments.
Probably the first most extensive experiments were those
carried on the the U.S.P.R.. S. 1914~16,; attheDeforci Tannery
at Luray,·V a •• 8 nd later verified ona different type of
J
t'a~ery wastes at the Haffner Brothers Tannery,·C1nc1:rmati,O.
These experiments covered a period of three years
~nd
all
results were c,arefully. de termined by laboratory analysis. In
this installation the wastes were
~ombined
in a ratio which
would. permit the lime ViJater wastesf·.to react mostfavorabl.y
wi th the tan liquors so the t preclp1 tation was accomplished
and the effluent VIas 81 ways alkaline.· Further' preeipi ta tiOl1
was accomplished by means of ferrous sulfate and a._ settling
tank provided for removing the settlab;le solids. A roughing
filter of c:).;ay ,cinders,or stone was next used. and further
treatment Was accomplished in a sand filter. The result
was an effluent well n1 tr1fled,'1n wh1chthe color was also
red.u.ced to such an extent tha t in di lu tion of
1{~1
or
1~2
the QDlor imparted to the stream was hardly noticeable and
:fish life was not affeoted.
The resul ts of the Pa.b11e Health Service experiment and
a very complete description of the methods for treatment of
the wastes can be found in the Public Health Bulletin No.lOO
_ _ _ _ - ~_ _ ,w
•• _~__•• ~,-~. -
-,_,,'~_"~_~_
.,"~ ~~.~~ "-~
--
,
--.- --,-
~.-
- ---.--- "
-' - -
~
----------
' . ,-
ea
be .,ita1lle·d bf
~i ~i~~ t·~
It mi.$ilt be
t:bese
iDeJ~}~~.()n'_4
the. t the tanners whG)
e~~~1~.ept~ ~a) e~1eve_
o~ t~~.at_~t \V.BS +,~~Qn.111~
:-,,:~<a." 8Oe~~~. ~~ta
t_e T.••~~ Depl\rtment,'
tl1at the,
11l eO,at alt.ough we have
as to .at the .eost
.lJ..et~~11y w~s.
)!lle .j-ri8g'1( !fle gr f.'annerJ:~xpe:r:~m~~~s.,
f8lU1 e17 wastes havecreat ed very- ebj eetlonable conti tions
.$n Ithe NQrvh ~~tl-nQh of the C~~g·E1.gQ li1v,_" for ·marq 7ea1'8. I:;n
:1920
,.8
testing stat:ion was bullt at the 'largest of these plants
j,_e G,~e8.-F·tl~·ge···r Tp.ne~7. ~q1i.~c8117 all of the thirty
tamler1es in
eAtcQ~O
·use the chrome process.
Attbe time o£ the tests the Gr:1_s,EJ,.Pf~eger T&mlery empl·€)7ed
about 5·$€> meD,:.and operated about 25 da_s per menth.'lO hours per
day. ~he mGnt~ly t8lU1age was '90 ~00() p'oUDds .0'.£ calf skin.s an~
li30$~()_e pounds of:l~w hides. ~.~e J,.osses PE'-r 1,'000 pounds of
hides were 6'1.5 POlUlds sus"t>eilded s011ds,':'4., poUDds organic
n1trogem and 36.1 pOunds of oxygen demand,'equlvalent to the
sewage of 164 people.
W'.aetes were of three typeB: (l)e()~ 11quo~s in whieh ci:ried
er salted kides were soaked or ~a~hed,(2) li~e liquors fr~.
liming pits and druiDs; an.d (3) t~ liq11Ors,from the chro.e
tanning proces s.
~he
average volumes of these
waste~
per d a7 were:
~1+'.~!~'~ ~l~Q_ •
J..'~:J,;,,~~'
... , ... '.~ -~ ~ , ~. .,-·ljla~,SJlMJ.
'~Q1;~
·:<·41-"·':;7;~l{":: "
• • • t •
~,
, , •
"
• • • • 0; • • , • • • • .
m,he p:rocesses studied. a,t the t$Dnery testing station
~:;;:··\:-.::tJlltll',~~·~
-f1·De s creen1ng,:s.e dime~lta"t1 o:J1J'activa te d sludge t·reatment.
·t:rat1on th-"·,ta~h a crushed stone trickllng -filter,s 8Qreened
.·::L-·na.,e·r fi'lter and a-and f11t_rs-,-- a.nd
-~11t~r
pressin.g .ani
of sludge.
s :rine screen of ck'uJJl type was tlsedw1~h 3/16"
h·ole·s. ~p.e~e wasa
re d.uetion of 1~.21' Qf t)le 814_·-
. ,ian de4 s~lids. !l1e screenings contained 82.4~ mo.1stl'lre,8)Ow.1;
$.~$£ "',~latilematter aRd 9.i% ~ trogEum.
,·~~::~~e.~~~,~C!~!
.?I.~:,s
s at·tIed ·in e
~;_ the
the mixtureo:f screened lime and tan wastes
D~rr Qlarif1ext.
The chrcullium 8l1d Bu1f1 tee
tan l1ql1o:rs were -preei-p:ltated by the 1·1me , l1-q110rs. thus
~.ereas1ng the amOU!lt of sludge. Tile lJ1crease being abO>l1t a~.
Af·te r ae ttllng there was a reduet10n
0
f 80%:0 f -~ru.spe:nded
_s.o11~~
-!he DQr" Ql~1f1er was very- sat~~fector7 fo·r elarif·ication
.Clf the wastes ,but the .reduotion in oxygen de·m·and was q1l1 te
~ow.aTerag1ng only 10-16%.
~~e;~,'Qe,~~:,~!~a~".J~~t~. the effluent from tl1e DQX':r CIeri fier was
.
;
iirea_! by tje activated sludge prooess '&l1d also
Oil
filters of
stolle. cinders, 8Ddsand. The caustic et'£luent from the Do~:r tank.
__.u1 d nest be
ap:pl1e~
directly to any' of these process,es until
or f1:L ter f1lJGs
'~.d b:~;n b_1-~t
up fJrG,pa the' eoa}[
Ii "t~8 f.o~n~ t~-.t "tJ1e ~e~lv,~1itfta
sl~dge
,....
.
teo.
-prOC'S$
care full' _~c~,'t,o ;prevent 0&118t-'c1t7 ani p.r1;1&1
,~te~111zat1on. "~!9 till tel-.·~ile4 van.8.t1o~s and overloads
~:t caustic liqaors mere satisfact.orily thaD acti.vated sludge•
Ter~
. TA_ tr1ck11J1g :til ter was not
_.legge·a. Dadly
~.iQ.1 t1011
ew~g
sa t'sfactO:r7 as! t
to deposi ts of ealeiua carbonate anel in
did not pro duce a. elarifie d t celorless effluent.
·-!_.ei:n~er f·11 ter was bull t of 6
inches.of 2" stone
'1;'he ,'bett€ID cove:red D:F $ inches of cinders ratainel ~n
.E?·~.,J!~D and th.e~· 5
'$"':_ftt'~:_tl
feet of cinders pas..s ing
th~Qu.gb.
wastes we're &Jpl;led
a.lstr1b~tlq
troughs
a~ r$t~s
p~~dq. TAla f11 ter gave the
b·t.~:L.o.~eal
a,:-n
.8
.OJl
I"
'e·OJ'een. ~he
perforated r'adial
llP to -lOO .-OCt.O gal1tns 'pe, aore
".oat
sat~:~faelory results of 8J17
preee sa stud1e a. and was the only- device that
re..
.JA~·'Y:ei the color f,r,,.,,, tl1e wastes,as well as 'producing the _oat
_'1ghl!, nitrified effluent.
~ere \V8S
some j'emienc7 toward
poo11ng _d surface clogging, but the £11 ter was still ingeGi.
~oD.di ti,OD
a1; the end of the tests" after 21 months ef can.tin.ous
lpa .ration.
As a
~es~:J.t
of the tests .on the G:J;.l,ss-Pfleger
lt was eo:nel_ded that
~~.·re
screen~ng
and settling in a
fll1:1*e satisfactory f<>:r pre11mimarr treatment.
the aiffieul t7
0
!~e"r,
DQ~'~
wastes,.
e'lar1f1er
U W1ng
l Jll.$._t~in1Dg biologieal treatmen t of the
to
d,-c-ia.,a
tlled ~-.stes.,1t was
at tAe
tap~--r1~"-u't:
V4t:b l.rge Yolq_-,. of
lHm.J1$rl es al orig the
-~t'.efore
per da 7
:~-'(J:~t<t %'eQGJnDteJld a117 fllrt-her
\_0 '__:reo$t ~~ s~ttle4 wa_te~
4Ql1.l,-,,-t~o sewage.~e W$st-ss
troll
'branch o:f the C~:s. e ago 114..er
lUI) rib.
be treated along -with 1'15 millio. gallons of
1i,~t~
N:~rth
the
A"l~Yated Sl~dge P~~Jllt"or
8148
~ih the 4013 m111:l,o:l'.l ga110ns per
as,.
tr1bu:liar7 of the 'West
-~-,',de !~eatment Works 1J1h~ bu-11 t. FQl: isolated tanneries
_r,qll1_r1ng complete trea1ment Qf wastes,it is probable th-s't
ltt:,:st s,_1;-;~.-s-fe;Letory reS111 ts can. be obtail1ed 'by the eperatloD
J~;f
settl-;1-ng tanks followed
oy
eln·der f11 tel's.
le_s71v8l:l1a TannertWyte,l)1sJ?9sal eQmm1ttei".Inves1iigat1<ult
.
'.'
.'
.'. '.
~~ ..
--~
...
.
"~"..
.
'.
-",
~- . . "
.....:-
...
". . ;
=
-,~~;.-_.-~. . ', .:.-.. :......
-
_
..
-
.. ',- '.-
~.
c--"'" _.-,-
.-~,~ .._' ... :
.
,.....
..... __ -,~:.o,
•
• --
.-~. • • . -
'.
-
'''_j,~_'_;-.'''''<
A two year investigation was conduetel b,. the Tannery
Wllate l>4.spesal Committee of Pe:rmsylva:hia, wh1eh waspres1ied
OTer'b,. tae O1Iltef hgineer of the Pe:Qns71vania Health
_nt.a_ was cemposed of representati.ve emgineers
from. .the tanning
1n~eres ts
and
Dep.rt~
chemists
of that state. -
The wastes 'Used throughout the investigation were produced.
b-;r 8 meeJiUID sized sole leather tannery at which the vegetable
tam11ng process was emploY'e d. Tile stuq as present-ed 1n
,pa-lSr Gu"Studies -en !fe.nnery Waste
Dlsposal'~~~Jby -W~.:walt
~ s,. eavett( Froe.Am. S~e. Clv.Eng. -1927. pp1675-1712) was in
:f.~'~:r:~7m8in
p,pta Be folloW8:-
8
and
-P.. ]:''t l.... ~~~Q;t'~tC!)r,. &$~~ qf the I~ti'Yi 411611 Wastes
- iil¢lu.l1gQj,.c~l ~.. $l7s 1s of :Each.
.
resu-l;"t·. ,ob·tal11ed a nUJIbe r of treatments
we%'edeveloped~and selected for fail-seale
e xpe r1me nt$t 1 on.
p~,.t ~:tJ.-E~pe:E'1Il8ntal ~J._t: 'fhe experiment$l plant
_
·lecate4. 'It I~.,tan~er,'Pa.,'w~ equipped to
opera te at full seale. The seleetei treatments were e~r1mented·with in this plant.
st11e11.8s being made by analysis ()f the various
effluents and sludges. A11 eperatif)l1 iata,
voll1!Des of sludge prodllced,:chemica.l
consumption,etc. were collected.
such
88
Pa.:rt IV. - The manner in which the various fall';'seale
treatments af~ected the rec·elv1ng 'body of
water was de term111:~d by analyzing th~. r1v.er
water at certain places for a distance of
12 miles below the tannery.
A report of the final results o:f 1IMs im.Testlgation have
not been pu.b1ishei yet. The general Summar,. of th.e last report
011
the inves t·1gat1on was as fOU0~:-
1. ellamical ana l 7S,ls of the individual resul'tarevealei .
th.e fact that the inte1'lli ttent waste'jc-'iJdri.bllted aboll:t
~~ :;l;h;B~O;fv~::~:~nt:ea;:~~~~l~~;~a~~;:e
2. The la\o:rat017 experiments indioated that ehemioal
t1'".ent was necessary for dependable results.
3. Several d1fferent types o:f treatment were developed
in the laboratory.
,4. Two full-sca.le tests aco olilpli she Ii satisfaeto%'7 removal
of suspend.,d 1Il8tter in the wastes treatei,one treating
th!t im.te:rm11rtemt wastes Qnly, and. the other treating. .
aJ,.J. the wastes, exee pt the green stock.
,.
~~ ~1v~:r ~~q,_e.s prQved1.Dl",ttant. T)l.e
~,alyse.s 'of t~. ~~v~r wate.r 's)l<)wed tn·at about
50~ o:f ~~e 1~p-rOVeJ.BeDt 1 s ace ()JIlpli she i.1m the
first 3 J.Ule$ of the 12 m~le at'retch lmmedi·ately
below
~aJmer7.
'Q"
Tb. t.v.~~;ft!,~~~:t'1 ~~endueted;~~ !he LQ;ra.i!~6)2rf,
.!p~u.~~j::las~,
'he . .lPr,o.ee:ss. G)f,./.'$Q·~ng,B·lies, . .~ntl-Jlas1i-:es.,,,,I'~·_C)illCed ~t the
I
~ .'.-~.
•
•
~: ••
~ .,• • • ; ..
,-~~ ~:. ' . ~ ' • • ~ : " : ..
'.- _.' • '.~ '.
••
••
••
•••
~ ~,
•
~
.0
. -'
.:
• • ':
.~
~
~e~roeess~s C)~ 1$~1.ng .~tdes are cQD.1plex 8.Ilcl vary in
t.~.e.r·le·SJand the ·wastes proti~ced are l&rgel.y in:",.::,\'.',.:.::,.. :·.:.L..:....i,;;\iLII:"::.
.J.J.L:;ed by the particular met~od ueed. A descripti~n of ~ne
Qes.~ e·f t~~.ng hides at the Lo.~d Tann.~ry anti of the
;l~..~:tu.re
of
t~e
was te s
pr()du~e
a.
is, therefo.ret·~l1lpertan.t 1m
.Q:rder that tbe 'best method of treatment can be obtained.
T.·ann! ng the. Hi des.
~his
company uses the chrome method of tanning. The
_ermal rated capacity in"1500 sides per day,but the output
duri:n.g the tests exceeded this figure slightly, and facts
s'eem to indicate that a greater output is due in the near
·~·f1J. tll
r e.
The hide~ are receive d heavily salted to prevent de-
composition and are first thoroughly soaked in a solution
~fsedium sufide~
4% of weight of hides and then washed
wi th fre sh rUllTJ.ing water. This removes the blood,'lIl:anure
dirt. an.d salt and brings the hides to i ts natural soft
. condition. After sQaking, the hitle s are fleshed tEl remove the
exeess fat and flesh and passed into the liming te.nks. These
are a series of tanks containing lime wate~. ~n SQ'lutiorl ef
'
· .
:.
..~:"
,
~
..·2e~·
paiu,.lly ine.reas·:1ng
":'
streJ1g·t~s, :t1;l~ollgh
pas$ .frQm the we skeat to the
._'b"e e-t $£ liJ1t1ng is to
't~e·reb·y
t~
whie:' the
.st.r~n.gest solut~on.
so3:~13il~1ze
b·~a..~
!AfJ
the ep1derBlis layer,.'
.:l.cosen1ng the hairs:b.eath and rendering it easy-
remove the h$ir by m'ecl1SJlical means, and to swell the
hide fibers to· tbe degree requisite f'or the production of
~e ather
po,ssessing the desired properties.
The :next s tap ill the process is the 'washing and delim·1ng, whic'h consists in. wash'ing the hides and neutra.liz·1ng
t·he lime wi th a solution of ammonium chloride to which
creatic Enz1J11•.,is .added. These hides are
sO'~u1i&QIL, Af'~er
this step
th~
padd~ed
P·::g.
1.n th·1s
hides are' piekled. This con-
sists in soaking and paddling the hides in a drum containing
a dilute sclu1;ien of sulphuric acid to which common salt
118-S
be en. addeci.
The ab·ov·e proce as 1s carrie a~ out in t)le be am house.
,Theh1des are now ready for tanning. In th,is p·roeess the
h~·des
are put throu.gh drums containing solutions of in-
creasing strengths of nQ:hrome ale" liquor,which is a solution.
sf chrome alum and chr.omium sulfat e. This imparts a bluish
violet co'lor to the hides and a greenish colQred effluent.
The hides ',are then reduced with a. dilute a.cidified solu.tion
(0'£
sodiWll thiosulfate. The hide's are new ready for further
"
.'
~~'. ~
.:
.~. : ~ •
t~.e~t.eDt .$~e.h
'. .~. '.
'1,' .
sba,v~-~~,W~$~_~n~ ~a. ~eu.tr~l~za.~g wi tl1
as
'" 'weak sGlu~lo.n of w~.Bh1ng soda ~n.d _on~·\Ull ei11o~1tie and
then d1 ein g,T)1$ cl~ng does noti»f].uence the W9.ste$
produced..-materlallY,'Bn_d therefo:r'e 1s not lmportant from
thi-s s t~ndpo4.~t •
.F':l'·OJ11 ·the precess outlined above different and dist!net
wastes
s~re
produce ~ which present vari ed probleJlls for traet-
men't s·t·uci1es. The cons'tructionor arrangement of the factory
1tself,whereb-·y di·'fferent wastes are m:1xeci,is also an :1mp·ortant factor. At LQ-rd Tannery Coo. the wastes ma.y be
s'WIIln.ariz.ed as follows:
·Wasn'water from the green hides.
·W~stes f,rom
the
11mi~g
Wasn water from the
vats and unha1r1n.g machine.
f1es~1ng
and graining
'floors~
Exhausted or spent tan liquors and rinse water from
vats in th e lay-away yard..
Exeess tsn11quors dur·ing removal from tarm:ll1g vats.
Le ~age from the leaching vats and was.A \vater.
S-~nt
alkali and acids from blea.ching vats.
Wash Wa'te,r fro,m Gx-een -:Elides:
Th.e ._hides are rece i ved bundle~ and heavily salted. At 'the
tannery they are unfolded and thoroughly washed with clean
._-_.~
,
,
'.
'
w~t,:r tO~JQ.ev~ t:tJ,e ~l..\l t .~~ d,$.r~~" ~~;,_,., W~~ ~ters.
th~re:f:o+e,arelt.eav~ly Qha"gecl "p'tl1 El0dl~ ehlQ~itle ,'b11t
~E)~t~'l~ :r~~",.t;1vel':y sm,~~:l 81Q9P~;3 o~ sv.s'pend~,d sQlitls
'. &lllQ.d~ss,ol va d organlc m~tter. ~eJ" do
d1t~1eult~es in t:r~a~~~nt"and
not present
arlY
f;lerve to "'11ute tlle stronger
wasteSf:n')ID oth~:r s~ctions qf the be~ house with which they
"are
~,1 x~ ti.
Yla8tes.. from~i.mine:: . . Va~e . and Unh~rin&...a~:t2:1ne:
The unhairing waste may be divided into three distinct
classes. Tw"ar,oesul tfrom the liming process, the liqllor
Which is emptied from the vats wh~n the liquors beeome
exhausted,8!ld the solid residue which settles to the
bottom. The l,atter is shoveled awa,y for fert11·1zer. I~ does
not.therefore,of itself enter into the problem of treatment.
The liquid JP9rtion,however,mJist be treated.
sus-pension small particles of
It
~ontains in
insolllble l,me wi th some hair,
and in solution, the solul)le portion of the lime not absorbed.
by-the hides, together with some organic m,atter dissolved.
from the hides~ The solids in this waste,which constitute
the bulk of the wa.ste from 'the beam house, settle qu.ickly,
leaving a clear supernatent that is not difiicult to treat.
-The third. waste. from theuDhairing process is that from
the l1nhairing mach.ine. This effluent contains finely divided
lime and d.irt washed. from the hair with a ve~y small amount
'of hair 1. teal!.
..... l"
,
.
.
I
.
.~ ' ...
_I
~
·r·'
;.,"
~~~l\W8ter frena ~~",~~:e,~~~l':1-~,a.~~!t.2."~~:l1.~~t~~~~·""'!'~
!be w.sete fr()~ t.h~ gra1~1,p.g a-l1d fle.shinJ flOQr co~s·1st
.~.~ t~e wza.s~ ~at~r U~~f~:;eq~r C\Jle~1'ng.
.
·'o~f·
Al ~()ugh the total
yo·lqe ts EI_mall,! t lE1/~~ly pol1~ti#g character owing to
,the heavy Sl1spended Jllatter which are composed largely of
p1,ee~s
.s·JBall
. Spe.nt
.
'
,\::..•...• ~:.:.:
-.:
!..:..
'"
tr1~med
of fleshingS
~an. ,Li.q'llQ_rs._' and.R:1:.Daing
,"
. . . • • • . " \ ..
_.-.'.'~->'''.''
''._
'--,;
·.·L' •• -_-·. · ••. : .. _.~l_..·._.:-·
~:_.:.::.::!./
:,•.. ;:._~.. ;'.,
r• •~
from
tJ1e h.ides •
Water:
•
_
~- •• ~ ••
~, •• -
;.:.
The most important ()'f these wastes is the exhausted liquors
·from the rocker pi ts. Several of these tanks are emptied ea.eh
daY,llsual1y in the morning. The second source of waste tan.
'liquors is the sQak tanks :in lay-away or main yards. To t,hese
spent tan ,liquors, are added sma.ll quant-i ties of leakage from
t~e
tal1.ks
0
r bllcck 11 quor ..
!£:eess ,'~an:L1,guors dUring Re,ll1oval from TanningVsts:
The excess water
'~d
some tan liquors earr·ied over from t·he
rin·.se water from the ble a.chin-g vats result in a wastage of a
.small amount of 'fairly strong waste •.A.
ch~rge'd
from the revolving wash drum in
simili.~r
whl~h
waste is dis-
the excess spent
tan and dirt ·1s lr.emoved.
~e akBB'!!. 11.':0JD
the
.~.~8eh1,~g _Vat~ and Wa._sh
.Water:
The waste frCDm the leach house is small in value and con...
~1sts
prino:1pally of the leakage from the' vats in which the tan
1.iql1ors are leached. To this there .is added
.
~I
-
_ _ m."
".-,
8
small amount of
. '.'~: wash. water *1~h .~y eon~a~~ stJ:ong tall solu.tlol1s.
. Sent. Alkali aEd .lei iu f·rolD .B·,l.eaching Vats :.
.. ',
~
~
'-""\',
0".
•
•••••.
',
•••
"• •
:.
{o
~'" . •
-,'
.".
'._
~:~
•
. . '. .
";
".',.'
,-
.,",
_~'.'.<".'_'.".'~"._."_
~_~':'~"
-••• ~;- •• ~ •••-._
.'"
•.•. -•• ....:.~.~'
.",
.••••••
From the bl:escbing proce ss there ·is discharged waste
ecrntE4n1mg spent!4.kali
an'~
spent sO'ids t together with the
liquors reSl11·ting from bleach1ng the hides. ~<m)ae fina,l
reactions c·f the mixture is strongly
a~1dt!bl1,t t
as it is d1s-
c·harged into the di tch carrying the beam house w~s,~,,:which
!s strongly
aJ.~a11ne.1t
is neutrali.z'ed and. its treatment must
be considered with the latter waste.
,Oharacter of Wastes as
~.<s,cha~mrd. from ..~_~e.~emne:rY.
The waste or mixture of waste
UpOB
which studies were made
weredischarge;d through two separate outlets.
B.eaml.ie~se
Waste:
.....
~,.,,,,
.This cons,lata of the wash water from the green hidea,tha
water discharged from the liming vats,thefloor wash.ings from
the graining and fleshing
bleaching tanks
~nd
~locrs. the 80' d
waste from the
a small amount crf black liquor
froIa the
rocker sets. This effluent also contains the discharges from a
new tan house,also. discharges from the hair machine.
was~e
is
gr8,y1~h
in color du.e to the
Th~is
lim~.
Tan .. Ro.use Wastel
Spent tan rinse water and black liquor comprise the
entire waste. The
~etteB.ble
suspended matt.er can be removed
in about two hours se·t'tl1ng,but the greenish color is very
,
di:f~~ ~ul t
to rem0Ve.
rece~1vi.ng
stream
~d
.sou·rs amd putrefies
~us·t
Tll:~s Jises .~,y ~v$1~~1;)le
in. tp,e
r~p1dJ-y
oxygen in a
~p'~e110e o~ o~~n.
so
~h~t
the liquor
the' dilution factor
be extremely high to prevent nuisance and support
fisll life.
VolUlDf),s .: ~.:f .. W~ste. Diseharg~ d.
'The rate of :pUmp11'1gie ql1i-te variable;aeperldin:g on. the
flow of wastes. During
&,20
minute period when there was a
surplus of vV6st'es the quantity pumped into the settling tanks
was 9 ,.36,0 . gallon~
0
r a bou t 4'0 gallons :per minute.
The tanks, were operat ed a1 ternately on fill and 'draw p1an
f01" one day under nonnal bus1nesscondi tiona and the times
.~reeorded
when each tank was fi).led to a depth of 6 ·:feet above
the draw-off level,cQrrespond·ing to a volume of ll,500gallons.
The results o·f the measurements which were made by MErtealf and
Eddy· are recorded
in the following tah:;te.
I~·
."
T·able.. . l.
M•.• sJ1~.ements
<J:t
Q\1..antit·Y.of. l$s.tee .. ,~p_d .at" ~J~,.r.d
TaJm~rr~der,~:"rmeJ.., BU~ l.nea~ tlo:mai,tions.
Aprl1193Q.
~i!.l.$ 'wifeJ1 tanks'
;)"\:?';':'·.~:'--':;~;.~:e·.e.·f111.el•. ,
,i:--'"
,~" start
7:·32
8:1'@
8:45
9 :25 .
lV1=-lmutes to
:t'snk B
',11,11
Ra1ie of' flew
,.' g.~./m1n.
32
3i9
3$
308
329
36
40
10,: ~5
al8
U:25
60
60
1.2:·f)5
'40
288
12 :~'3'
'1:18
32
41
359
2:18
60
192
192
- 281
192
2,:46
28
411
3:30
5G
'250"
268 .
Total
-516
average
Tet:al' flow '1 :00 a. m. to 3 :36 p.,m. ;: 138,'eeo gallons.
Allowing one hour longer operation for inerease in business •
the flow. of waste to be treat'ed will be approximately 154,000
gal.lons per day.
~~~~~(~,~~;l;l~'~'~"~~~i~;~~.!~~i~I'~';,!,~!~,!~.!;~,~!-!.!!!~~~,;;.;~.~.
!h·:ecemb:1n~·a. w$s·te·.s fr()aili• .a·idtan ·htras'e· "sRd f~~_ the
•
I
.
0."•. '.
beam_o:tlse
·t" ..
·t·.
'.'
B.l1Q.
"
• -
'.. '.
~
,-' : '
'",
'.'1"
~ -
"_~"'~:'--:'~'~'~'.
-.
.;.~
.... ~'~d':
.•'
• '•. ,~
..'..
....
._,
new t~b"1l4;~'. ~.Q'w tlur"ugl1 f;1n~pen ~)!),~el
~._, we·~ .~~d .~~ ~p.El~ t"9 $e1itl~l~ t~.'_.e,
effllt·ent f~o"_ tll~$e ~anks .p~.~se_ thr<o.~g:n e~rt~en b~si.ns and
~h~els
.leatl'~llg
"be a diteh
t.o
~er.~T.',:r- near
'~·~m:'1cal ~l~·~. TAeslu~ge aec~+ating i~1
d1s.chargei everyothe r da3' t;osludge
f)a~~he:D bas~ns ne~r
waste land. for
t.he
'~ill in.
t~,alld.
A
i~ds
the :me~~Jn~f)
the tanke .1s
1nthe
fo~m
of
afteX' drn~g is removed to
bJ·~p~ae a~ound
the tan.ks is pro-
.Ttde..El for use when thE;t pump is n·ot in operation.
T~,layout
"is shown. in ·the enclosed plan,
A sore·en in the form e:f parallel i.ron bars
ab~ut
one
ineb apart ·is located in the channel just befer.e the pllltlp
we.i·l.· ~)lls1s cleaned 1?Y re~oT1ng~he screen and shaking gf·f
the eieelUlulated
ma~ter
to one side of ·the channel. 'fat.,
screeD 4. B frequent'ly clogge d.c811s1ng- the was tea to back up
and , flew through the :by-pass u.ntreated.
.A Q·e.ge
sc~een
in
:~_)1
is also provided at the outlet
,.,
end of tJ;le channel leading to theP\Ul1p
wel,~ T~·~~
·ls also
frequently clogged and the w8steJi' overflow to P\UDP well
c au.,s1ng t--rouble.
.
,
:\\,:';,;',:':",',":',",,:,K'f]la
Q$'_f;t7ef
~~lJ a
-:A-_tI ':1
,·,,~~,tJ. "t~e
$\l()at$f$~O ~3.1.!1l!l Up tQ
~be pu.Dll:»110uS-~,'~l+,e
,,,;E;tlltrifupU. llntl, ::~-e" ;):~Ji])1
~.t'~_a,t·~o
, w',ltlt :.an
I)
ene fee"
PUUlP~S ~ 4 1~~h
.ot.o:r.~~'s ~s
J1,ot ellppliej.
inechani~"
s,t-e,-rt 8Jlld st'op
·:'ie,t'~it.'g:':,T:83tkS~':
..;.
-:.': ..: . ' .,":,.,
~ ;'.:.;~ .~.:,,' ~'-\
<:"~
~.:j":-'
;-,
:~:.:::
• :-;,..:.... ":~~"
Tl1.re
-'
I ; ~ .:-~ ."~: ,:'.' •• :'.\ ••,,...."".:.....~;.;~.
B-re
'; '.:~
2 re-1,nfore::'i cQncrete settliq tanks.':lD feet
sq\1ar, amdapp~.ma1;elY10~5 t:ee t dee, ha~ng an &is'rega:te
t_t.. i capac,! t7 of ab eu 1; 3,9.;700
,fflu~t
draw~off p1pe~n
There 1s a 3 :1noA
,the mi44:ae o'f ea,ch tank about $
f,e'etbelow 1;'11e top of the wal-:J..
ti1.rou.gJa.. woolen trough.s to
ga11Qns~
!~ese
eart~en
p1..pes discharge
basins. )i.s'·iot about
,It
':. '9" la"a be'D 0U:t ;In the wall between the two tanks feJr an
Qverflow ~,r.1I one taa to the o the r. The ~apae1 ty of e aek
"':':'!8-nk frQIBthe e:f:flaent d-raw-o.f1 to ~e "verflew is approX1-
tas,te1:,,.
l_f.,.
gall ens.
A.t the bettORl of each tank about 2.5 feet below the
38
e.f~f·l11e,llt
draw-off pipe,is a 6" slUdge p;lpe discharging
'
...
. ,nte t,roughs 'leadill6 to t'he slUdge
beds~
'fhetotal capac·1t7
of each tank from the overflow to slUdge draw-off pipe 1s
approximately lB.,-40Q gall-one.
." ... ,.r" ..
.,,:
_.u, te B
~e pliUIlP.' t,~ O'l1.Ch ~ ~J'J'~~c' .~ r~lJ,lt)l •
....
w~Q·49.n t,~o~.8~ .,l~ce.A ~.~;n.g1~~~~,~~.U'7
~ve.·r
1ib:~ .~citl:Le qf th~ 1;QJpl ,~~~~xt~lI,cii~ ~G)utt j~e 1'I$V
'Ailt~O e~
e.n
~P.~~~!' t:~ov.ghi.'Jre"y~c1ea. with stop
t,
,ate s so a.
il,s~l1~X'ge t)l.e w~ te
1.nto
1'+s.Dt
el~per t~
.137 the pre ae.t meth,.,"q.
. ef,per~;t;i-Q:n.tl11 waat~e'~flow 1nt"
.
ene t."k: 8.11d eV~:t!now j,n~ the atlle r , wlli e1:l 11,1l.S th~ val~,;e
1nU1e gn 1I.:J:$w"!"o:;ff pipe open. T~~s p:S,pe 1s not of s\1f~eient
size to carQ" the enl~re f19 W
ot
w~stes which .graduall·y f~1i
th.e second tal'.llt, Be.~or. tl1tis tank is fi1.1ecl the v,"lve in the
.fir.at iraw~o:ff pipe is opened, thus gradlla.lly d~awing-off
t'hts tank al$~. Wh,e~ tnt.s tank has bee~ drawn ,down, the valve
en the draw-off pipe is olosed and the eperat'ion is repeate4,
.
'\
'_is preliminsn aettl1ng removes some of tl!le au-spaniel
8011 i~ ~rom t~e waste s ,'bu t . the tanka a~e not l$rrge enough
and the detentlop period is ~eb too sh,or~t to accomplish
satisfactory results. KC?st, of the suspended matter floats en
t!1e su.rface
Eaar .t hen
; .:..- ...... :,. . . ,....
formi~ga
grayish
SC~
,.S·~e,. t.t11n.g. Basins·:.
. . " ".' .. '.--' ""."
... _'" '.'.
'. . . ,.-,-,,·.cr
At tb.e bepnning of th.e investigation the fl... thr,ough
the e~th~!l settliBg 'basins andehamlels was quj. te rapli.ie.~i.
was. not distributed over tlle entire width of tb~ basin bu.t
'-:p
••q
a :rt~"Jl'." fl1eltltll ':r:J;~s;i~.~. !t!~, 'Pasins ha.i ~1ge
·e.c • •1 a1;.4_As),..\~ <£l;.~ .~iil1$" 'li'·$..;Jt';;"l1t4"~aJ.
~d SllS']l8:rttl•• $011(18 1)e~eri !tt1:o.-.:n"r ~J)j,~g t)\e w.s.s
basl.sbl')w~d tllat instead ofsettlin,. we
'tAts.
tlt,:tcrug;
obtail1e4sn:l.erease :lmtotal and 8tlspenled sOliis,;showin,
, 'hew fi,11eit)le bas,ins
we~.-
·····'~~ter 1. the 111lves tigatt on these be.s a~10wed to iI'a:1. ani
dry
Guta:niQ ~rnow in the prooes s of
beillg eleane4,
.5",1,.1.... B~,~:
~e 3 smaJ.l earth basins excavatel for the slll,4ge bed_.
are new being used fer settllng basins. !hes1.udgefr.
the tanks are being dumped to the right of tne tanks amd
carte d aW&7 wh en dried,
!~1
c:kllDI ,-F~1·1t,er·8,.:;_.,
"...i
,,0;
' ; " , ':
• "
.:",
" "'.
., _
....
<,., ".'
,-
,
'
': ~'., .' c: '
'fliese !ilters ha.ve en area of about 1/8 acre and a
depth of 6 feet of f1e14 stones and gravel varying from 2
tt
~
t,o aft most17 of the larger die, !his material. is much
large for efficient purification. Ifh.
•
tOQ
4esf,.~able size is
> t '
" 21""(0
...
tv
The £il ter hea a t114.1'1 l&Jer of cinders on tep,not
~
dee·'!, enou.gh to be e ffect1 ve,
The betto. ef e$ch filter was lUlderdrained with
i
rout
10" vitriflei clay plp8 draw:l1'lg towards the center to a
main 8" pipe leading to an effluent d:ltcn. ~hese filters
~~;
have not been used for about 17 year s and were found to
be in poor conti tion. The cone'rete side wall be ems have
, disintegrated badly and had given way in several places
allowing the f11 ter1ng material to fall
'out~
It would be
quite expensive to put these f11 ters in operation.
Tab·le 2,
Ane.l;l.s! ~ of Wastes at Lord Tannerl~ *
(Feba -lWiay 1930)
Avera e
2 28
1,170.
1,022.
1. 864~
2. 5
hr~
2. hr.
2.
24.
3.5
\',;: (1) ::: Composite
S
8II1ple •
hr.
2. 5 hr.
-
..
1,170.
1,022.•
IJ 864.
20 hr.
20
4.
2.5 hr
22.
4.
III. Experimental' 111orli.
Ch~mical
malus 180
Chemiosjl and settling tests were made on sa,mples collected
at various :Pe rio ds. The teohnique and a'pparatus employed for
t,his is des'cribed in the t:ll'pendix of the report. Precipi tation
te ate 1N1 th va.ry1ng das as of fe rrous sulfate were made in Imhoff
Cones to determine the most economical dosage. This was aJ.so
carried out on a large scale in a wooden te.nk hav1nga capacity
of over 2.000 gallons.
In, most cases"snap" samples were taken,8,lthough a
samp~e
com~Qaite
was taken March 17,'1930. This composite sample was
posed of small sa,mples taken every
t
com~
hour from 7:00 A.1L. to
6 :30 F.'Iv[. and pooled. Results of the chemical analysis are
sho'wn in Table 2. Results of settling and prec1pi tat,ion tests
are shown. in Ta,ble 6.
Results of chemical test's on
'JI~ay
sam:pl~s
obtained April 17 to
6 t 1930 are high due to the fact that the wastes were being
discharged directly from the settling tanks at ,the beginning
o~
that period,and the pump was out of order during the later
,.part 'so that the wastes received very 11 ttle preliminary treatment.
-42-
Discussion 0'£ Resu.lts Sho"vvn .in Table 2.
The nitrogen content in the form of albuminoid
aT~onia
and organic nitrogen is extremely high. The avera,ge albl.lminoid
ammonia content in t·he final effluent being
',P.P.M.
~hich
app,roxlma.tel:~1·
13.5
1s even hi[;h.er tha-11 any of the results obtained in
tl1e fl'\rerage sevvage ene.lysis of .A.merioan oi ties as
8hov~
In
Table 3. The orgd.nia nitrogen content in thefina,l effluent
from the tannery,as vlsl1 as the oxygen consumedjis muoh higher
than that found in combined sewers of J_IDecrican 01 ties. The
ni trogen I fo·r the most part, in all trie waste s a,nd in the final
effluent after treatment is very highly putrescible as indicated
by its high degree of insta.bili tYt as
stability
sho~m
by meth Jt lane blue
tests~
The tot,gl soJ_ids found. in the final effluent are almost
ten times that found in the sevv8.ge of modern }..me·rics,n oi tie'8~
( Se eTab 1 e :3) .•
r.rhe· above results indicate that the present treatmen,t
employed at the Lord Te.nnery is very inefficient. In many
ca~ses
'
the tot'al solids found in the final ef:fluent\rvere greater than that
found in the raw wastes'$ This is probably due to the fa,at
tha,t the earthen
b8,siJ1S
are badly clogged and. tp.e fast, mov+ng
effluent from the settling t8.nk is picking
1.19
solids instead of
as:
~r.
Cities
129.
153.6
261.
450.
303.
1052,.
Dis. Solids
488.
608"
Resul ts are expres sed in Parts Per JVril11·on.
Solids
1058.•
1355.
342.
SUSP.i
Tota.l Soli ds.
21~2.
4'.
71.0
~
.
603.
83.
10'7.
-
-
23.8
7.8
18.0
27.2·
Communities
01 tie S B,nd Rtll"'al
38.9
11.3
l\~frg.
Small Amer. Amer. Res.
730.
Alkali!li ty
109.
48.
Chlorine
133.
1.12
o. 26
26.5
11.9
24.1
01 ti as
59.0
10.6
7.0
8.0
0 •. 11
0.44
Combined Sewers
Amer.Mfrg~
Ox. con.8umed
Nitrates
r~i tri tea
Orga.nic
Free Arom.
Alb. Amm.
l~i troge.n
Constituents
Large Amer.
American Sewage,
.9.~rison of Lord Tannery Effluent an.d .Avers,ge
Table~•
-Tanner~f
~
. 58·50.
'.
5730.
lO840jU
1170~
.-
25.0
13.5
39.5
Effluent
. Avera,ge
Lor-a.
I
•
~
()1
~44-
.deposi ting them;also to the fact tha.t the distribution in
the earthen basins is very
~oor.
A little over 50% of the solids are in the dissolved
form. This indicates that efficient settling without the
addition of a coagulant can not remove much more than 50%
of th"e solids.In most cases the Beam hQuse ws,ste is worse than the
Tan hOllse waste. Ordina.rily, \~je should expeot that the
T~n
house waste would be much more poll11tive in character. The
seemingly contrary resul ts here obtained. s,re due to the fact
that the new Tan house discharges its waste into the same
channel
~s
the Beam house waste, as sho'Nn in the a,ccompanyirig
b]_11e print. Thi s means tha.t no t only nIl the tan. ,waste
cause an increase in the nitrogenous content.but also that
the precipitating effeot of the acid and alkaline wastes will'
. greatly increase the content of solid ms,tter"
To. determine what qua,nti ty of dies 01 ve d solids were
ni"trogenous in character,samples taken May 6,1930 were treated
for nitrogen
a~
free and 2,lbur.oinoid a.mmonia on filtered and
unfiltered sareples. The results are
8ho~n
below:
Filtere if Sampl:s Until tered sfhP~es
Free Amm. Alb.am. Free Am.
Final Effluent as discharged.
i way to 1V!err1mac Chem. Co.
At Merrimac Chem.Co.(l mile)
12.0
12.0
13.6
7.5
6.0
7.5
Results are expre.ssed in Parts Per lviill1on.
25.0
36.8
29.5
A
b.J.~m.
15.0
20.0
18.0
This indicates that more than
t of the ammonia nitrogen
is in the dissolvefl form. Removs.·l of suspended solids alone
not give a
~~ll
non~putresclb~e
ef£luent. There must be a
high stream dilution factor to take care of such a putrescible
effluent. This
C,9J1
only be obtained by ha,ving s.dequEtte storage
of the fina'l effluent so as to dischs:rge it uniformly over a
.period of 12-24 h9urs per daYtinstead of discharging the entire
efflu.ent at one time as. is now the practice.
Exte·nt of Pollution of Aberjona River.
The
result~
of analyses by the R, and M. Indus_trial Labs.
of the water of the river at sampling
~oints
the effluent outl,et of t11e Lord Tanner3'
nos. 1 and 2 below
Co. are
Sh01\T1 in
Table 4.
,.-
The results a,ra &xpressed in parts per million"
seen
about
th.~t
t
thesampl.es col1eatd a.t Boutwell'
B
I~
will be
Bridge,which 1s
mile south of The Merrimac C~emic~l Qo. plant. co:nt~ins
large amounts of suspended matter, the remaining results being
'for f11tere·d samples. The high suspended matter is probably
due toa la.rge extent to chemical prec1pi tation resulting from
the action of the a.aid wastes of th-e
1!~rrimac
Chemical Co. upon
the alkaline tannery wastea( The pH of th.e wastes
j~s t
bafo re
the Merrimac Chemical Co. was found to be 8.2 on's filtered
4~
Table
Results of Analyses bl R.and M.lndustrial. L~b.of SamtJles of Brook
and River 'Water Below Effluent ,Outlet from Lord. Tannery
in
.....
,
No rth \Afoburn•
"
'
July 13 and 26, 1929.
Mi shaw9~un B.r1.dge
"July 13
July 26
11 ~ 55 AM
;2.: 55 Evr
4 .
44
Bou tvtJell i s
july 26
July 13 "
De te nnina ti on
11:40 AM
.Sus pe.n de d Ms tta r
164
2:43 PM
."280
Filtered Sample
clear
slight
Turbid.ity
clear
clear
brown
brov,~n
bro\VZ1
decidedly
disagreeable
distinctly
very strong
dis.a.gree s:ble
slight
Color
brown
very strong
Odor
Nt trogen as:
Free Amm.
l\.lb.Amm..
pu·trid
4.7
-3 0 7
.6.1
0.3
Ni tri te s
Nitrates
O~OOI
Alkalinity(as NaOH)
0.07
r\ira5~esiu1D
716.1
513~ 3 .
~,
,
~ .. ,
~
,
. .. __.,,:.:.
,
-:._~
_ _
\,._."
..• ~--,
~, ,--, -.-.-
__ -
16,.8
24.
61~8
965~
1612.
302. ]~
741. 5'
197.
18.
Re suIts are expresse d in ra.rts Fer
.'.~
15~6
1123.
1488.
303.6
774.
2258.
197.1
44.3
Oxide
4a 5
0.02
1•
2.4
29.4
66.7
38.1
8.'7
13.8
Aci d.1 ty( e~s H2 S04) 585.
Residue . on E.van., 2012.
Chlorides491.
Sulphu.r. Trioxide
627.3
Iron + Alu.min-u~m
Oxide
7,,6
OniOO2
5:_
. Oxygen Consume d
Total Orga.nic N.
pu.trid
. _-_.-.-.
~-_.--...--....--..-----..--~.""~.-.~,..,--_
_--.,.._
_~.
-_.
Millior~
_
~ ~ .~ "~'
-~~.~---------:....-~~.
---
--_._..
~_
_
..
,
_
.
s~l'le
collecte,d Me,y 6,1930. ,. The filtered samples show
j
-
!
"j
co,ns1de rable -mnolln,ts of orge-nic matter ,but undoubte dly much
less then would have been ShovVll by the unf11 tared samples.
On samples collected just before the Merrimao Chemical Co.
results showed that about 50% of the organic ma,tter was in
the dissolved state. This indicates that probably results on
unf11tere d
Bam~les
at .stations 1 and 2 would
as high as the un-filtered sa.mples
he~ve
been twice
ShO'NEtc4
The re,sults for samples at the
~!ishawa:lln
Brldge,as the
river leaves the pond,show that most of the Eus:pended matter
had settled in the pond,leaving the water clear but still
offensive in odor. The results for oxygen consumed and organic
and albuminoid ni trogen show a large content of orge.nic matter.
These results indicate excessive pollution of the brook and
Settlin.g and Preclpi tation Tests,
Imhoff Cone Tests.
These tescts vvere carried
01'- t
in the following manner:
Samples of the various wastes were taken. The samples were
shaken thoroughly in collecting bottl'es and immediately poured
into Imhoff Cones up to 'the 1,000 c. Co mark. The samples were
not disturbed and readings of the quantity of so11ds which
·...49-
.sa ttled out at ·defini te inte rvals were takena Thi s wa,s done
for Beam House., Tan House snd Final Effluents also for equal
emounts of Beam end Tan House .wastes mixed. In this way we
were able to determine the rate of settling,the amount of
rea,dily settleJile Bolids ,and the precipi tat10n effect of the
Ian on the Beam wastes.
In addition to the above· tests precip1tBItion tests with
. addi tion of varying qua.nti ties o:f ferrous sulfate were made.
The proceoure for these tests was similiar to that employed
above.. The same samples as·· above were shaken up again. and
·pored into the Imhoff Cone 4r Then va.rying quantities of a freshly
prepared 1% soluti on of ferrous sulfate were a.ddedto gi vethe
re~uired
doesJge. The readings ,/Vera made as
above~
Results of
these tests are shown in Table Sa
In addition to tests on suspended matter,tests.were made
for total solid content of supernatent with a settling period
with
B~d
lvithout
were made
l~ay
order and.. t.he
treatment.
treatmen~
with ferrous sulfa.te. These tests
6,1930• .A. t this time the pump had b·een aut of
~,a,8tes
were being discharged directly 'Vvithout
*
O.
5.
Final
10~:
10.
o.
_
0.6
-
.60. _ _
125.
160.
85.
90.
11.
Ii ij •...
80.
90.
-
..
O.
80.
40.
19 9
19.5
-
18.
. 380 •.
~.
3~
0'.
20.
12.
10.5
27ijj
15
.
-
~
~9_~_
~
140.
70 •
110.
'70 1ll.
3 4i •
19.
. .
250.
0.5
..
~
lIoIi,I
O.
34.
~
]-4.
. __P_Q ~_.__
60.
140.
95 s
65.
31.
20.
32.
49:
34.
0 ..
14. 8
20.
floatedtQ_~QP
o.
~o
minutes
33.5
26
i.n
all solids
o.
32.•
~tJ
Settl'1ng . time
lB.
o.
10
10.
O.
10.
10.
O.
O.
o.
o.
o.
10.
o.
Final
Tan' Beam
. Tan.... Beam
i
Beam
TBni"'Beam
. Bes.m
*Tan
Tan
Tan
Beam
Ta·n
Final
-Beam
Tan
Final
Tan
* Filtered Sample.
5/6/30
4/4/30
3,/17/30
2/28/30
~
- ---- -- -------- - Fe-rrous slilfate
Date
Sample
grf3i.nsjgal,
eParts Fe r Thousand)
Comparison of Settleable SoJ.lds 'Wi th and!!i thout Ferrous Sulfa.te-
T.able 6.
15. 5
210 •
~ .._
60
-
1
01
•
o
~xper1mental
Plant.
In order to see the efIect of ferrous sulfate as .,ooagulant
i~
olarifying the wastes, a small plant was set up at the Lord
Tannery,. This consisted of a wooden ta.nk ,having the following
measurements: 9 faat-- x 5 feet x 6. 5 feet deeP.t g1 ving a· capaoi ty
'of approximately EEOO gallons. The outlet. pipe was 2.5 feet from
the top and was situated near one corner of the
tank~
trough led from the concrete settling basins to this
-A wooden
tank~thus
giving a gray! ty f'low from the top of the concrete basin. Some
of the wastes
''V~1ch
were. pumped. up ·to the ooncrete basin were
by-passel into the trough by means of a wooden plank\thus
gi v1ng a regular flow into the woo den tank. A wooden bucket
~ri
th a
flo8~t",valve
arrangement, by which a regular dosage of a
ferrous 8ulfa,te solution could be obtained,'-t'VBS arranged on top
of this tank. A dosage of approximately 10 grains per gallon
was 'used. The incoming wastes were so regulated as to stir up
the chemical.
ResultsThe ferrous sulfate precipitated a large
percentag~
of the
suspended and dissolved solids and elso produced a thick brownish
green s cum on the surface·. The di.scharge opening wa.S so 81 tuat ad
a,s to discharge the li(].uid bet¥reen these two laye.rs of solid
matter. The effluent was very clear in character,bnt had a bluish
green colo r.
Settling tests on this effluent showed little or no
suspended matter end 11 ttle or no se'ttleable solids. The
color can
ea~ily
be taken care of by proper
The de tention 3l9riod was short. being
i ..
stre~
dilution.
1 hour.
Methylene blue stability tests on the effluent from the
coagul~.tion
tank shovved little imJ,ro,rement. This is probably
due to fs,ct tha.t the iron had no time to 'be oxi.dized,but vve
believe. tha,t 'vvi~h the dilutions obtained in a stree,m the
improvement in stability would be much greater than that expe r1enced by
settling .s"lpne.
In attempting to 'improve the stab111 ty end general
character of the effluent !311bsequent tests were m·ade on the
fill ana. drallJ plSl1. The ts,nk was allov{ed to fill s,nd then the
ferrous sulfate was added and stirred up with long paddles.
This \vas then allo 1JVed to settle 1.5 hours. The resulting
ef:fluen t vv8.S clear t light green in color and, gave. n'o settleable
solids after 15 minutes
sett~1ng.
The same waste without the addition of chemioals gave the
fo+lowing results on settling:
15 minutes" 120 Parts Per Thousand.
30
This clearly
11 .
lndic~1rtes
10 grains per gallon even
140
'-
n
'l
"
tha,t ferrous sulfate in doses of
tlV!
th s. short sa ttling period of 1-.1.5
hours, will remove elmo.at all of the suspended. ma.tter and
:Perhaps some of the dissolved matter. thus giving at
le~tst
a
50% xaeduction in total solid-s. Longer settlin"g bV-Quld increa;se
the percentage ,of solids removed.
Filtering the effluent from the coagulation tank through
3 feet o~ b·roken rocl(
of
i ..liinch
t-2t
inches in diameter covered by 1 foot
coke did not irnprove the color nor the effluent to
any etppreciablB extent. 'The measurements of this roughing filter.
were 6\~'feet x 4 feet x 4 feet deep.
A cOylOerin.g of s8.nd or cinders would have improve'd the
effluent but we' had
no more
time available"for testing.
Re"sul ts of Settling and Ferrous SuI,fate on the
Total Sollds,
1930.
*
]'linal Ef:fluent
wi 't'hou t t re a tment
Superns,ten t
4 hI'S. settling
Supernatent
10 grains/ gal.
FeS04 with
~~~.~~~~~~~~~~~~__~~~4~h_r_s~._settling
Total
Solids
10,840
S'l"Oe rna tent
i/} grains/ ga.l.
,F p S0 4 with
hrs~settling
I
1?~F.M.
3,'304
%Reduction
* Result
3,978
69.6
63.3
taken from Table 2.
Results seem to indicate the. t the addition of ferrous
sulfate at a rate of 5.. 10 grains IJer gallon follovved by sedi-
mentation 1Nill remove over 60% of -the total solids.
If we had a preliminary settling followed by treatment of the
superna tent from this
the~e
Vili
th the above (los age of fe rrous sulfate"
1s- little reason to doubt that as much as 75% of the total
solids \A/QuId be removed--.
'
IV o Bacterial
Investigatio~
b9 t~i a1
Analysi s-
In ord.er to determine the ba.. otericidal effect of J(jb_€ vs,rioue
VV'8.stes,samples for bacteria,l examina.tioTI,S Viera taken from the
Beam House,Tan Hcuse,and Final Effluents B,t the
ta,nnery;.~lso
jus t before passing the rvIerr,1mac Chemical Co. ,a.nd just after' the
lv!errima,a Chemical Co.
Dilutio~ns
on the first set of sEJm:p1~ecttaken ~larch 17,'1930,of
1:100,000;1:1 million and 1:10 million. These were plated on agar
r;iates in dllpliaate and incubated 24 rlours B.t ~'7°C~ t).nd then 48
'.
o.
hours at 20,0. The fcllovrlng
Averag~ ,BacteTi~l
'
result~
were obtained:
Analysis of Wastes at Lord Tanner:
lvIarch 17 &1930.
. '
Dilutions
Sample
l:HT
Beam ~B:ouse"
0.5
3.
].~
1.5
1.5
4.5
Tan House
Final
Be fo re 1v!e rrlm a.c
0.5
Afte r lilerrima,c
OlJo
O.
,... ....,-- 01.
''..,
2~6,··
6.
4.
5.5
8.
9.
Thes'e results seemed to indica te that as the dilution was
inCTOElsed the nu.mber of c·olonies per plate increa,sed. The total
counts for the greatest
pe r
C'.
c.
0
f 1Naste.
~iilu ticn
being over 60 million bacteria
"#
·.T his seems to indicate that triese taIll1ery wastes have a.
definite bacterioid·al effect up to dilutions of 1:1 million.
This experiment was duplicated on April 4.1930. This time
higher dilutions were employed and' also the pH of the waste
was determined•
.R .esu.l tEl.
P!i
C)..f E.fflu.e,nt at Lord Tannery.
C·omb in·en Infl nen t
Effluent as Discharged
t Way to }"ierrimao Chem. CO.
At Merrimac Chem. Co.
.
Average Bacte.rial
l:lM
Sample
7• 8
8.4
6.4
80 2
A~a~ysist.
Dilutions
. :1:8.
l:lB
o.
Tan
B"s·.
0.5
0.5
Final
Colonies per plate increase in the Tan and Final Effluent
.up to dilution 1.:10:0 million a:nd -then decrease. This vvould
'seem to indicate that ,in dilutions up to 1:100 million there is
a definite baotericidal action. The Beam H·ouse ef,fluent has a
defil1i te bactericidal effect in dilutions up to 1: 1 million a·s
shown bef.ore,"beyond
t~is
there is no ba.cterlc1dal action.
The. average
bacterie~l
counts on the above wastes would be
be tween 200 million and 1 billion bs,cteria. per c. c.
Effect of
St~e~.
D11u.tion
~n
Be,eterial Aeti()n.
Ba,.cter1al ana.lyses indicate that the waste ·:dlscharged
the tannery
fro~
has a distinct bactericidal effect up to dilutions
as high as 1:100 million. This means that when the wastes are
discharged from the tannerYtlittle putrifaotlon of the nitrogenous rna tt er in the e ;fluent can ta.ke plac eo But "as the wastes go
dpwn stream and the alkalini ty of the
effiu~_nt
is partly neutral,,,
1zed by the acid wastes of the Ilerr1mac Chemical
Co.'~ tbe
1n-
hib1 ting action on the growth of the bacteria. is diminished and
putrefaction starts to set in. The further doVJn stream the
. wg,stes go the higher is the dilution
f~,ctor
and the less is the
baa teric1dal ftoti onj:so. that all the way from the I!/Ierrimac pla,nt
to the Aberjona River ,putrefaction is taking
~lace
with the
liberation of highly disagreeaole odore. This is distinctly
noticeable during the hot summer weatheri.
Note:Abou-t 35 'pure cultures of organisms from tannery wa.stes wer·e
1 solated and are being kept on hand in case of fu.rther invest! ..
gation along this line. In, many of these cases the organisms
produced pigments of various kinds after a few weeks of
cultivation at 20 o C·•• although only few developed pigments
on agar sIan ts Sifter 48-72 hours.
v.
.Q.gnclus ions-.
Carfeul consi'dera-tion of all the methods available in
tannery V\!aste purification leads us the conclusion that th-e
be-at mesns' of treatment of the wastes is by ehemicalpreci]?8t
1tation. iTot .only is the initial cost of such a treatment
pl ant relet! vely lovv,:bu t also the u]'keep 1s low and expert
eupervis10n s-,ndool1stant attention is no.t necessary.
For the best results chem1calprecipi tation shoula be
prece dad bye .p.reli'minary settling period of the combined
w!lstes in order te utilize the natura,l preci.pi tatlon of the
alkaline lime wastes by the acid. tan h9use wastestand also to
equalize the wastes for further chemical treatment. The detention
period in the prellmdnary settling should be of at least 4 hours
duration for most efficient
result~
.The effluent from. the preliminary settling should be
followed by chendca.l precipi ta.tio~ This .basin should be of
sv-ffioient size to pennit 24
and
provid€~
h011.. r~
operation of the filter beds
for a m.1nimum time cfp',assage of 4 hours. This tank
should be provided wit11
BClUn
boards and
baf~les
to ,prevent the
Calcu.lating on a total~' aischarge of 160 j~'OOO gallOll"S 'per day
these basins should each have a capacity of at
total quanti ty of waste per o.ay or -about
l~ast
80~;O:OO
t
the
gallons.
Tanks 100 feet x 25 fe-e t x 4 feet dee p wotlld g:(-ve s-pprOximately
that ,ea paci ty.
The 'pH bij.lue o·f the effluent from the prelimina.ry
settl~ng
tank should .bec.ontrolled. by the adi1 tion of suJ~.turic acid to
give the most efficient ;and most economicB,l tre'atment. Ou.r
experimerlts ,indioa·ted ths,t excellant results coul.d be obtained
with ferrous sul:fate(oopperas) as the co~gu.lant. ~e.~e the
,"
,chrome-alum method of tanning is employed ferrous sulfate
shou'ld give excellant results. 1Ihere the vegetable 1'.r:oceas is
employed., the use of alum' maybe prefe.rrable because of the inky
effluent and incre ase in diesol va d iron whi ch 'Vvould be obtained
by using ferrous sulfa te: 4
Doses of 5 ..10 grains per gal'lon or 0;; 75
~
1.5 pounds of
fe7Tous sultate per 1.000 gallons of waste gave good results
'without the addition of g,cid.,where the. pH of the waste trea.ted
'N.as about 8.0. The add! tl on of Slllfuri-c acid so that the pH is
between 6.8 and 7. 2 will probably: g1va better re sul ts flnd. 1'"ill
require less ferrous sulfate.
In general,the use of feIrous sulfate where possible is
preferrable to the use ·of aluminum sulfate because it 1s much
chea.per and less aci d will be necassary to .obtain an opti·mum pH
.. -,. ,..,.. ,', . ....
~
for.
GO ppe res
...~~::t':.":1
.;
as would be necessary for sulfate of a.lumina•
. Ai thoUf;h ·the effluent from the second sedime nt~ltion tank
should be free of most of the suspended matter it will b·a
putrescible in character. For this reason further treatment
should be employe d V'Jhere necessary. Intenni ttent sand £11 tration
has been shown to give as good results as any other final
treatment:- This n'eed only be employed during the summer months t
when the putrescibili ty .is
m08
t noticeable o Du.ring vvinter th·e
wa,stes could probably be discha.rged·wi th little treatment over
a 24 hours period so as to be best taken
CB,re
of
b~r
stream
dilution.
The £11 ters employed should have a c.;.' depth
·of abou,t 6 feet
and sufficient a·rea t'o allow for a rate of not more
th~
200:.'000
ga.llons per ·acre per day. These filters may b·e constrttcted of
4 feet of coke or broken rock-t -
2t
nco.ve~ed by 2 feet of
rough,.shar.p medium-size sand f~e of olay or dirt.
~
The function of the filters is to .strain out the bu.lk of
the susl1ended solids carried over from t·he sedimentation. tanks
a.'1d mainly to oxidize the effl.:tlent o The effluent from these
f·iiters should contain very Ii tt.le suspandec. matter and should
be sufficiently oxidized to maintain stability with low stream'
dilution.
.
-62-
Provision should also be made for taking care of the
slUdge" Sludge be ds of suffioient size and consistency of
a,'bout 1 foot of f1necindere ,coke or sand., properly underdraine·d would prove satisfactory.
The process of trea·tment recommended
1s,~n
general outline.,:;
as follows:
Pre lim1nary settling tank 100 feet x 25 feet x 4 feet deep,
proViding fo r a minimum s'ett.11ng period of, 4 hours•.
•
p' •
~
Trea tm:ent of effluent from this tank with a precip:l. tant such
as ferrous sulfate in doses of 0.75 - 1.0 POli11d
per 1.000 galle'ns
m·th l'roper a.djustment of' pH by use of sulfuric acid.
Secondary settling and coagulation in another tank simil1ar
. to above. B.oth tanks should be provided wi th scum boards a.nd
'baffles.
For a tempor.ary measur:e earthen ba.sins can be employed ,and
effluent from secondary settling tank disch'arged directly over
a
~riod
I·f a
of 24 hours.
mo~e
satisfae to ry J non-pu tresc1 ble effluent, is re qui red.,
.further tree tmen t by f11 tra tion at a rate of about 200."000
gallons pe.r ac re 'per day.,
Utilization of the dried slUdge as fertilizer and fill ...·1n.
~art.
III,
~65·~
Tec.... h n1gue _ployed..
FQJ!
Making
Chemical Tes.t.s•
..
...
.' ." ..
.
,.
;
-",
.
"
.
-
-'
_
~
'.
-',
"
-~."
. -.--
-"'~.':"-'"
.
'."
...
-~;~'.'
".:
-
'-
.'"
Alp~~n~1 d ~1.~;r,~.n~
Albuminoi d nl tr0.gen is the n1 troge1'1 equivalent of
ammonia formed or l1beratedfrom nl trogenous matter by the
act1~n
of alkaline permanganate in water after expulsion of
ammonia nitrogen by distillation.
:Ap]~a.ra-tu.~.:
Distillation
carried on in a glass flask with a
~~S
condenser
.. attachment.
.
standard 50 .~~ c. l~esBler Tubes were used for the color
comparisons.
:tl.e.ap;ents:
( 1 ) Amtnonla fr,ee.. wate r.
(2) Nessl.er ".X'.e,8S!,nt.
'Dissolved 50 gm. of potassium 10dideln about 35 c. C. of
cold ammonia free
water~
Added a saturated solution of mercuric·
ch.loride until a. slight precipi tate persistet. Added 400 c. c~
of eN sodium boyd-ronde which had been clarified by sedimentation.
Diluted to 1 liter.allowed the solution to clarify,and decantea..
This reagent gave the characteristic color wi'th ammonia within
5 minutes after addition,snd did not produce a precipitate
with small Emounts .0£ ammonia within two hours.
(3) Aika,11ne pt)~af3s1umpe1'!Bart~a.~.t~~
Boiled 1.2 liters of distilled
wate~
in a 2.5 liter
porcelain dish for 10 minutes to drive off the
mnmonia"~'
Stirred 16 gr. of potass1p permanganate into the SQlu t1on.
Adtiei eOQ c. e, of clarified 9Ii sodium hydroxide ,'sRd mnmonia
free water to make up to 2. 5 11 tars. Conc·entrated to 2 11 ters.,
Determined the amount o£ ammonia on 50 c. e, of reagent and
used the result as
~
basis of
oorrectio~
(4) Stsndar.4 .ammonium ohloride ...so.lution,
Dissolved ;;.819 gr. of ammonium chloride in ammonia free
water Slld diluted to 1 liter; from
thi~
the standard solution by diluting 10
stock solution prepared
e.c~
to 1 liter with
arcmonia free water. One e·. c. then contains 0.01 mg. of n1 trogen
which is equivalent to ().012Se mg. of Im •
4
Pro.ce··du·:re-:
Freed the
ap~aratus
from ammonia by boiling distilled
water'in it until the distillate showed' no traces -of ammonia.
Then took 50c.e. of 'sample and d11u ted it to 300 c. c. wi th
ammonia fr·ee water. Distilled at the rate of about 8 e.e. 'per
minute urrb11 200 c. c. had been dist1"11ed offo This procec1_ure
distilled off all of the free ammonia.
Then added 50c. c~ of alkaline permangans.te solution to the
oontents of the distilling flask. and continued distillation'
unti150 c.o, of distillate had been collectea,
bep&.red a series of Nessler standards b7 dissolving
ti·xed volumes of standard ammonium chloriQ.e s·olu t10D in
ammonia free water and making thevolllme up to SO c. c. in the
Nessler tubes, The standards contained 10 p.p... (pa.rtsper
million) af nitrogen fO! each 1 e.c, of standard solution.
The.n dissolved a fixed volume of .distlllate in ammonia.
free water and made the volume up to 50
0.0,
in a Nessler
Tube.
Then a"dded 1 c. c. of Nessler reagent to each tube~: atad
"by a comparison of colors determined the m;nount of alblUllineid
ammon1 a in the: s ampl e,
O~el3.~'c-N1t"r~.gen:
OrganiC 1'11 trag-en comprises the. ni trogel1 eql1ivalent of
n~ trogenoue
c;ompounds in various stages of hydrelys1s,"from. the
complicated proteins to amino acids.
Beage~ts:
(1) Copper su,lfate
Dissolved 100 gr. of copper snlfate in ammonia free distilled
water,diluted to one 11 tar.
e2 ) ·S\1.1 f\t.:r1 CJ a c·l d
Cone,ntrate a., low in n1 troge~
( 3) Po,taesium -sulfate
P.()wie re d.
Jl1r-o,c"e;dll'nt:- ,
Placed 100 c. e. of the sample in a 500 c.o. Kjelie.hl
flask and boiled. off the free smmonis;8dded 100. c"
,sulfuric
acid~l
p~tass1um
c.c,
of the
of copper sulfate soluti'on and ,p gr.
sulfate. Digested in a hood
Q~_r
a low flame for
30 minutes 6fter the liquid had become colorless, Cooled
somewha'tj r1'nsed colled di gee t into a 20() c. e. flask. and
diluted. to mark with ammonia free water. Shook and pipetted
50 e. c" 1n~o a 100 c. c. flas~ Added sodium hydroxide u.ntil
alkaline to phenolphthalein _lIe cooling in cold water.
Dil11tei to mark' with ammo!11a free water. Mixed and allowed
to, at SJ3.d 24 hou.rs. Nesslerized ,an ad.equate portion 8lld compared
With steniards.
Relatl va •Stab-1Ittlo! Ef:f1uents(Meth:zlene ,Test) •
The time required to 'exhaust the oxygen available in a
sample unde r defin1 tely controlled tempera ture condi tl0.ns.as
indicated by deoolorization of methylene blue as the incidence
of pu trescence,"1 s a measare of the relative at ab111 ty,
'Reage,nt:
Me th'llene ~lu~.
'Dissolved G.I gr.of the double zinc salt in water,and
diluted to 1 liter.
Pro,ce du.re ~
Collected the sample in a clear,glasB.stoppered bottle of
Jieagell"ts·,:
, (1) S1iandari EIJ1~men11UD oxalate a.olution:
Dissolved 0.888 gr. of pure ammonium oxalate in 1 liter
sf distilled water. One o.c. 1s equivalent to c).GeOl gr.
eX:'gfJIl consumed.
(2) Pot.aBet.lUIl. p!rmang~.at-e s-olution.•.
Dissolved
e.4
gr.af potassium permanganate in 1 l·iter, of
distilled water and standardized against the ammonium oxalate
80111 tlen.
Pro c e.4u.re :
St.~dard1zed
in the
fol~ow1ng
the potass1WD. permanganate against the oxalate
way:,
Measured 100 c. c. of sulfuric acicl(1--3) and then added.
frem a burette
solution.
8
~8ced
me asured quanti ty of the potassium perinanganate
the flask on a wire gauze and heated qU1ek17
to boiling. Boiled the solution gently fer exactly five
minutes·,removed 1 t from the
flame,'coo~led
for one minute,and
added from a, burette. sufficient. ammonium oxalate to decolor1ze
the~
solut1o:rJe Ti trated back wi th the permanganate to a faint
permanent plnk colo r. Calculated the vehe of the permanganate
in terms of standard gnm.0n1um oxalate and of oxygen. For the
analysis proceeded just as in the stsndartUzatioll,replacing
the 'distilled water by the sample to be teste d.. The oxygen
-'71'~
oon.s..~mei. value for the water under examination is obtained
fr~m ···the
number of e.. c. of permanganate
used in excess of
-
that required to react with the oxalate added in the
dete Imination.
Settleable . Selids:
.Shake u_pthe' sample thoroughly and pour into an Imhoff
cone up to the 1,000 c. c. mark., Make rea,dings of settlecl
solids at various intervals. Readings are directly in parts
per 1.'0<)0.
Ooagulation
~est,s.:
Sh.ake up vaming amounts of the coagulamttd.wi th the
sample to give the desired concentra.tion .of the coe.gulant end
pour into the Imhoff cone,'proceeding as above.
These tests were run on fll te red as well as on unfil tere d
samples to determine the e ff'ect on dissolved solids.
These tests we.re also carrie d ou.t on a large sca·le in a
woo den tank o£ over 2,cOOa gallons capaei ty.
Hzdrogen Ion COBcentration(pH):
Colorimetric standards were used for comparison.
ProcedUre:
Colorim.e·tric standards were used for. comparison. ~'Q 2 e. c.
o~ .f11tered semple -inv.,1J, standard. test tube!t added B c. c.. of
distilled water. Repeat above also adding to sec9 n d tu.be indicator
solu t1 on up to m.~k. Used e~lor1metrio b1Stii for comparison.
'1i1l~r;~
~.
,
R~7&1 eo_is~Oll 011 1l~ver8 Fo11ution.
.lst. Jepcart,'p.22; Ird. Report','P. 36.
•••
.T
~eyal C~~8el,n Ga'R1ve~s Pollution.
.. 1e t. R~port ~ p. 3'1 sndp. lC>!.
Mass. State Be"srd of Health.
"
Experimellts- on Sewage of SaeepSk:1n Tanner,..
Tear1 7 Report.~-p."4:'11-3.
~.
.
I:ass. "State Board of Health•
. Further EQ8tillentson Sewage of Sheejski,n !annerf.
Ye ar1 7,Re PQ rt,'pp. 396-402.
-
If&yler.W•
Trea1ment of 'frade Waste'.·
.
Proc.1nst"o£ Civil Eng. ,'1896(123) p.402.
.lUi-
...
~
-.
~
·lH.'iill~W.J. and Th.llcUQnum,G. .,J ou.r. of Soc. Cnem. Ind. V,01.1'7 ,"p. 316 •
."-
...
M88S. St$te Board of Health.
Fu.~ther Work onSews.g8· of Sheepsldn Tsnneq.
Ye~r17 Report,'pp. 463.. 65. '
Snow'F.H.
,
-
1ie1.t1C!)D.of lIanufacFuring Wastes on Sewage Problem.
Eng• •ew8;1(:)99. Vo1.41;p.334.
Mass. State Board of Real the
E~per1mat,s on Sewage of !annel7 where Sewage IJlc1udes
Tana1ng;'Co1oring 8l!ld Wool Scouring Wastes. .
Year1 l Relto rt ,·pp.413-14.
114eal,!S.
"
Sewage . and th.e Bacterial hr1flca'tien of Sewage.
fp.2e5t291~'293-4. John W;l.le7 and Sons••l'ew York e1t7·
~
-...
~..
.
Be ale ,"Kind.
.
. Experiments on :Pu.rif1cati~n of Waste Water from Factories.
f;::;r~:~r: i;~~ie:~1;~~~5"I;~o;40.'P. ZOe
...,(
~, ...
. .,
".1'\
'
C·+_~~ ·_~~'ik."f~' ~ ~
~ 'P.rJ;~.~~~. 9£ a~r.~ b111~llfae1;u.rlJ1gWas1;e8
a_a: _Efta.ods fO'r fteveDtloL
1':~:;~;'~~f:'=~li::~~i9~~~;i:t:,V()1.1$ ,'pp.509-13.
.
,.-
B~ atd .of '1__1 the
~d.lr'1ee ·.'~~)1~ej$k:1:y!1 'f$.1inei7 Regartillg S,..age D:laposal.
Mae s. 'st'a' e'
YearqReHrt.t'pp·81-Z.
.
-
-
1,,19 r·;''-'•
.J~ac-.·r1al ~reataeDt of !rate' Waste.
j~i~~ 'Iil$t.e4-vl~ ~g.~·lge1-'2.".1.14,$.'p.1,Q.
( abstract) .. ling. Rec~ 1982.'V81. 46 ;'p. 2'8.
t~'bstract)-:rr()c. Amer. Cllem.Soc. ~'19tU~.:W5G3.
J~
1902------
I<:~l~ ,~:.,:.,!."
,tr·t111sat1eD o·fWaste Precll1cts.
!anne17 Wa..ste,'pp.91-B4~ .
Ba11 o r .W_
.
!rade Waste-Its !reatmel1t alld lJ~~liza1;ioJl.'pp.125-4S.
Charles Grift1n ~nd SODS•• -~.()BclOl1.
.-
__ba·r sndThl1Dl.· .
'
:Beitrag z~ a.erseitgen stai1d~.deX" AbwasserreiJJipllgs,
frage".140.1i.01denbour~~1lIUn1eh and :Berlin•
-----
. 1913-
·~r_etor.~R. R.
. "Principles t,):f ~ather.~u.fa.ctu1'iJlg ,Waste ~Qcluets
and !Ael:rJij.spos al.'pp. 460-74. Spow ancl {:)1$IB'e1'l8111 ,
:New York.'
-
,-
-,
.
-:_~·::''.4~:+
~t=~~~il:il'.~!,'~lfie:.~~.~.~'eO.J."b.S.'e_~.,
t~.,,-
.~i:=i~e:~,~IJ:~~Y'~lr~t~e
WE1Stes
(a)stract}.-~~ng: ••~ws~'190:'';p.197.
~
1908-
,as••
of Reaa1ng,'P~.
~
.q
-~~ ~,-, ~
.. SeieJit1fle Amer~c_ ~p:pleIr1ent 65~'p.19,Jal1.11te8.
T~__
11M 8. 'st -.te -~Q a rei
0
f ll~ 81 the
.
t~WreJ1ee.D. S~.. Amntallle,.rt~Vol.40.'p. 261.
'.
.
••.8-. Sta1;. B,Q_r4")--~'of" Health. ,
. ' ~l1eX"e.l 1l••1 ew ,~f the 1r Exp. Wo rk.
1'8a".1,7 ~ep(jrt,'PJ.~4~-'.
_ a1b Oll,r .:P. A•
.J~ltr~~g.S9c.ef
of
Pe• • ,'pp.~i-4'1.
~_~fJ pO,.~_&1
J4anllfactu~~ng ~aste8.
(~~,tr8et)~
Eng.
1,_
,'Vol. 62 ~ p. 99.,
labstarct) -J.Am.Chem. Soc. ,'p. 2'124•
•-:<"".
CIa.,]I. W.
».spos81 and h,riflcllt1on of Facto17 Wa,stelJ.
4'lst.Armlla1 Report lIass. state :Beard .of Health.
So_iele.
nt-lel1unP.:.11 allIS der !romp F. ruftin
. .gsanstalt,Ber11:m..
,Vol. 11; p. 4'1l,August I:I1rschwald,Ber111l. . .
'E447 and ,Vrooman. . .
. f~Ci:a:~~£~~:~:i;~:~~:~~t'2::;:~~:~ille
-i91€)..
Schiele.,'
Tanue,ries and' The
S~wage
Problem•
.S hoe and Leather ReportB'~:1lq 26;·p.53.
,·N. Y.
......
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....
~lii:!~t;~iJ.;~~<~·;·te8
.
':!::~;lll!:t~:'J~ .~~sal n.~t
.
.
.'. :": . - ( .
. "~:.' .
'..
.. i
:-
for
.
~~$r4.es ~~d ~'1f~·ge~,,\l~m.
.
$.~e liBel ~".1\lPiJl~i'ter~14:"726,p,.i3-5.
n.·l·cu"t~:-·.:rWiXl_slo"w
. ~ii~p
~l1ci
·Pratt•
jll~~$-~~ w~iQ1-~ci ~ons ~ Be w York.
e~~I.ia !e:~Q~_~
"
S.w~ J~_~sal ~d !#..t~e~t{~1~11Qgrapb.7Waste.s
··In<J:tl1ti:n~bj.st:Jl"1al W""atee).
:NMS.·S·tat.' lS~o,ar_d' of lle$lth.
f~;:~.;:;,~t.b'1:flea't1on of!$J:l1'lery Wa~tes.
19.. 11-
~
.:al;~:I:,~i8,B. R.
"
~''.$etratl4J107 S"JJ1tat1 t D ,A1r _4 W~te:r Sapp1 t:.
))l.,-;POB.:L of WgS~. W11e7 ani. Sons;Ne.w York.-·
s.
Jl~,~~s on,J -4!
T·~e.,,_nt_-c·f 'E~ery
Efflflenta.
J .. 4'l.:•. ~·". OJl,~m.A~,_. ~fp. 326; pp. 464-66.
Stl1Q'Qf . ~~'+3.l1.i,onO,f Rl v erfJ b7 Discharge of
"¥~",,~~J.ar,'W~~e rs from !-.ne~:les.
llePQ.~t b'~JDtUe8;te Gen.ra:l des Culrset p~"ux de
.
Fri."e.-- '.- ,
'.
Le:~". 'f+,ade's ··Rev~;e:w~VQ·l. 44~·p. 8'4.
i91"Z",
;.1.-...."',,
As·:J.._:p, E.~·e·~
_r:1:flc$t.s.OD of Llq\p.i T$I1Jle:ry Wal;rtes 07 Foree"
O·X!lation. ','
,
J ...... Le~.<C~_e•• AES' •• Pp. "/2-'" ;8•• e aDd
~ "Fell·. '223", p. 5 '1.
.
.
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.
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J~f':ur.~~. ~a. ell~m.As:lI. ;~191~ .~1.PJt.l€) .. 22.
".,:~::':.O:~ ~'J.• ;~~
i::~f~_lCi'~;f.:mi~f ~;~~!l~~·
J~u.r.
Soc'. O~_JD. ~.a.".;Vol,3.~.153.
J_:l_m~~·:J.
.
. ~~~fJ17 ~'i;11u~n~s . ~~...T__~~J'
(·4ll,"·)~c;·t·) ~J ~ ~~.Qb'D1. A_,~
~
~
~
-
!re-_tmen~.
~:r()m ~·o-~le.gi _, pp.5~9.
J~·l'·~_,~~., ~nd a~v.".:tt;H.:J,
. 'Tr_~, W,~~rt$
. ft~t~~~"~J1 ~d
_f,~:.J«
.
,T__er;
"fi£.,"~.$; T~e1r
.¢'l~·~.~.~.(J~tl()m.
~~,
and ~i s.po$e~•
Ef~·l\le!lts.
C.A1}.~tract)-. J~~.
:Ft~JIl
Natltre
14,. Oh'r4.AI1IJ.,"1,12
p.liS·.
9 1913.
L_ H.•:J.le ,aux
~-lr$,:Feb.
~
t
"
. ~~l.• ;J.'J ~ W~ ~~d 9Q:Aen t 'J .R.
V.~'''l1$,t·l:~!l and ,~. ~~~,_. of T• •ery Effluents.
J .~. Le~.·A$:_'. ,
,
Pl1. 426 -3e.
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.
. !.-.__ ,.q ·-.Il~.bs·e asa
F-~rt~11z~:r.
(R.p~_~.~l-g••r.~~~a.fJk~~A~s. ,·p.43,8.
- fr_,.. RU·~_·1· rew:Yo·rker;lI,. 19;J-2.
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ft~lflc_. tl,Qn~t .~_#t1-t7 Zf~:l-lJ.en's •
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L. )!a~ohe i.e, ~~.Fe'.26 ~';L9:J..4,'pp. 104-86.
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S~.o t '~1 e~
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Sc!r.~g~ l,)lSiposaJ. fl,nd. .Us,I~"f T• •e17 W.te.
~~~.~~:,.eJ1~~.A$._~ ~pp.'Q<~~.. 6.
V':~l.t_a,il:.; Q~
P\lJi'1f1e.~on ef'l~.er7:Ef~+uellts and Ref3o ver 7 of
..
Bt~'+·Qtl~~·ts
tleJ:e:frQm.
J .'.A:m.~'a. ~~'.~~·~BS·. PJ.l26·~:I'.
..'
•.•_t·o'f .r~41le;t;r.lal W~stes.,.
_._~;e~~,~·po
~:_,a
(lle'p~lnt )-J ~ADl~·~·a.:CA~m•.As~. ,·D. 293-.10".
SA.<.l8 aDd:.,Le~.lteportert'April 22,'1915,:pp.49-53.
R.el·1'n eh.·~JJ .•
_'a.covery. gt ~:llllges from Slllficle P~.ces8 of De"'latin,
~k"'..
J .Am.L$a. eh._fA•.A~·JI. ~:pp.36' ..9.
.
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'.
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,Bi~~·l!~fJ·¢·t:~:q_ ~;f ~I~·~n W~s'es.
J. ADl.··~$.Q]~lJ~_.A_:I:. ~Jpp. 229-53.
~$:.lfe.
~!V".i1.79;p.5S9.
ltec..
Ii.l1t~~\!'il
"J '!' Am. ~••
of !~e" ~,ste8.
e:p;em. AS~h .. pp. 30'~3 ale
111.sh_ell aDd (1)1ers.
, J)~EJel1E!sl.n-])~$~Dfeot19D of Tanne!7 Sewage 07 JleliL1ts of
Cklorine.
J
J~~.L~:-.. QAe~~~~$. ~-'pp.3e'-9i.
Le._.Jla~f. ~·'28t··2.·".45~4'.
:Peok,·:~~.;J4e ,.
'n".e·n.'t ef T$imery Se.wale.
J ~A_. Lea. Q_:e~.As,.~·'pp.422-..24.
•
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(4b,s"~t~·_'1i)·~
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A•.• Vol. 12 ,'p. 52'7.
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fA"'~i,aot)";fJfl;,~~~ .VQ1.~2~'p.~~il.
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-
1919-
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. •.
!f... a~llt8f
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(4b_l~:$Ct
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!une~7 Sewae;e•
,
e_~:JIl.A$'. 'Vol. 14;,p.I>7'-81.
).+ Cl\~,~A. ,·-Vo~ •.13 ,71'. 3263.
K~als11~·v.lt:and. Xaclisll'~H.L •
.t11:.\tt:tf~j~t:.!;:·':t:i;~'l~~~i:~te.
·li.'·$~~_t.' :l.~"~:9·B~::9'O ~Aprl1 1,1919.
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98-100.
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8~~D1 V·~·8.,:X.~ •
• ".factlireof Gl:u.e in Tropics from
~Pt.
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.
'Indl1st :rl e s'·~lIaclraB.
<.
CAlfstract)- Chem.A. ·,·Ve~1.14;:p.1460.
T~er7 Refuse.
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.
_D!@pO•.~3. of J:~~u.etr.:1.al W~$tee ~d ~t~eam Pollution.
d. i'jf~klln Ii1Ert. ~·VG;l.191~-,p. 81'1-18•
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Waters.
33·3~"703'~'1919.
Be'$.~1eT$r.~E.B •
. 'freatment of Ts;:rmE)rJ' Waste to Prevent Polll1tion of
.
st.re 8118.
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J • Am. Le~. Chem.Ass. ~-Vol.l'l~.'pp.685-11.
.
19
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Rop:t_'~·A..
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P1"~et:1cel Ta~ln•••K. 0.1$.1. rcl and
L_1)·;lL O.
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