sodium isopropyl xanthate
TRANSCRIPT
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.
UTE TOXI ITY
OF
SODIUM ISOPROPYLX NTH TE TO THE
F THE D
MINNOW
Pimepha1es prome1as ND
Daphnia
pu1icaria
September
197
This document is made available electronically by the Minnesota Legislative Refas part of an ongoing digital archiving project. http://www.leg.state.mn.us/lrl/lrl.a
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UTE TOXI ITY OF
S O I ~
ISOPROPYLX NTll TE
TO
THE
F THE D
MINNOW Pimephales
promelas N
Daphnia pulicaria
Submitted in fulf i l lment
of
Contract 69 9 for
the Minnesota
Pollution
Control Agency
Kevin Alto
University of M
September, 1978
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STR CT
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INTRODUCTION TO mE REGION L COPPER NICKEL STUDY
The
Regional Copper-Nickel Environmental
Impact S tudy
is
a
compr
examination of
the potent ia l cumulative environmental socia l an
impacts
of copper-nickel
mineral development
in
northeastern Min
This
study
is
being
conducted
for
the Minnesota Legislature and s
Rxecutive Branch agencies under the direct ion of the Minnesota
mental
Quality Board ~ [ E Q B
and
with the funding review
and
co
of the
Legislative
Commission on Minnesota Resources.
A reg:i.on along th e
surface
contact
of
th e Duluth Complex in
St.
L
Lake
counties
i n nor thea st er n
Minnesota
contains
a
major domes ti c
of copper-nickel sulf ide
mineralization. This
region
has been
ex
several
mineral resource
development
companies
for
more
than twe
and recently two firms ~ ~
and
Internat ional
Nickel
Company, ha
considered
commercial
operations. These
exploration
and
mine
pla
act iv i t ies indicate the potent ial est ab li shmen t o f
a new
mining
a
cessing
industry in
Minnesota. In addit ion
these act iv i t ies ind
need for
a comprehensive
environmental
socia l and economic ana
the
s ta te
in
order
to consider the
cumulative regional imp li ca ti o
new industry and to provide adequate information fo r future sta te
review
and
development. In
January 1976
the MEQB organized and
the
Regional
Copper-Nickel Study.
The major
objectives
of
the
Regional Copper-Nickel Study are: 1
characterize
the region
in
i t s
pre-capper-nickel development sta t
ident i fy and
describe t he p robabl e t echnolog ie s which
may
be used
the
mineral
resource
and to
convert into
salable
commodities;
identify
and
assess
the
impacts
of
primary
copper-nickel
developm
secondary regional growth; 4
to
conceptual ize al ternat ive degree
regional copper-nickel development; and 5 to
assess
the cumulati
enVironnlental social and economic impacts of such hypothetical
ments. The Regional Study
i s
a sc ient i f ic
information
gathering
analysis
effor t and
wil l not
present subject ive socia l
judgements
whether \. here Hhen
or
hOH copper-nickel development should or
not
proceed. In
addit ion th e Study
\ . il l not
make or propose sta
pertaining
to copper-nickel
development.
The Minnesota Environmental Quality Board i s a sta te agency r es po
the
implementation of
the
ULnnesota
Environmental
Policy
Act
and
cooperation betHeen sta te
agencies
on environmental
matters.
The
Copper-Nickel Study
is an ad hoc
ef for t
of the MEQB and
future
re
and
s i te
specif ic environmental impact studies
wil l
most l ikely b
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T LE OF CONTENTS
R ~
STR CT I
INTRODUCTION TO THE REGION L
COPPER NICKEL
STUDY
T LE OF
CONTENTS
LIST OF
T LES iv
LIST
OF FIGURES
v
INTRODUCTION
} ~ T E R I L S ND
METHODS
3
RESULTS
8
DISCUSSION
LITER TURE CITED 6
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Page iv
LIST OF T BLES
Table 1.
N i n e t y s i x
hour LCsO
v alu es f o r
sodium
i so p r o p y l x a n t h
Table
2.
Chemical charac te r i s t ics of
di lut ion
w ater
Table 3. T es t c on dit io ns fo r
fathead
minnow
b io as s ay s
Table
4. T es t c on dit io ns fo r p h n i ~ b i o a s s a y s
Table
5.
D e g r a d a t i o n
T es t
Table
6. Spearman Karber e st i m a t e s
o f
LCsO s
mg
sodium
i sopropyl /xantha te / l i t e r
Table
7. Spearman Karber e st i m a t e s
o f the
LCsO s
in b i o a s s a y s
u s in g aged
st o c k
s o l u t i o n s
Table 8 . A bs orb an ce o f Sodium
I so p r o p y l x a n t h a t e
solu t ions over
96 hours
Table
9. Xanthate c o n c e n t r a t i o n s o f
s o l u t i o n s
aged
under
d i f fe ren t
c o n d i t i o n s
Table
lO . C o p p er x an th ate
m i x t u r e b io as s ay
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ACUTE
TOXICITY
OF SODIUM ISOPROPYLXANTHATE
TO
THE
FATHEAD
MINNOW Pimephales promelas
AND Daphnia pulicaria
INTRODUCTION
Xanthates
are
dithiocarbonates which
are used
in
the f lo ta t ion
pr
for most
sulf ide
min era ls , th e metal l ic elements such
as
copper,
lead, zinc, s i lver
and
gold, and a number of oxidized m inerals of
and copper. Flotat ion i s a physiochemical
method
of
concentratin
ground
ores.
The
process involves
chemical
tre atmen t o f
an
ore
p
create conditions favorable for the
a tta chment o f certain mineral
to a ir bubbles. The a ir bubbles carry the selected minerals to t
face of the pulp and form a s tabil ized f roth
which i s
skimmed off
other
minerals
remain submerged in the pulp. Xanthates
f i t
into
by funct ioning a s collectors Collectors aid in
t he a tt achmen t
par t ic le
to
an a ir bubble. Sodium isopropylxanthate i s one of th
monly
used
xanthates Dow
Chemical Co., 1976 .
Since
xanthates
may be discharged from t a i l ing ponds into nearby
toxic i ty information is important. Acute toxic i ty values found
i
are summarized
in
Table 1.
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trout in
water of 348 ppm hardness found
that
the 96-hr LCSO of
xanthate was 18-20 mg/1.
TABLE Ninety-six
hour
LC5 values for sodium isopropy1x
96-hr LC5
Species
mg/1
Refe
Daphnia
magna
0.1-1.0
Hawl
Natrapis atherinaides 0.01-0.1
Hawl
Pimepha1es
prame1as
0.32-5.6
Hawl
Catfish
>10
Hard
Snails
10-100
Hard
Tadpoles 10-100
Hard
a ma gairdneri
100-180
Webb
Chemical degradation
i s
also of concern in xanthate toxici ty.
X
tions are not stable
in
acid medium Dyer and Phifer ,
1969 .
Ho
a tu re r epor ts indicate that alkal ine
solutions
of xanthate are so
Harris
1970 ,
quoting o th er p apers, re por te d that , in one study
si t ion of a xanthate
solution
took place
over
an e igh t-day period
but only 25 a t pH
10.8.
Other studies showed
that
decompositio
solutions
was
minimal a t pH
10-13.
Fuerstenau
1974 ,
working w
o
solutions
of
ethy1xanthate
and amy1xanthate a t 12 C and pH 8.6,
s ignif icant
decomposi tion . Tro fimovich , e t a1.
1976
reported
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Page
3
The
present
study was
undertaken
to dete rm in e the acute toxici ty
isopropy1xanthate
and
to determine whether
the toxicity
of
sodium
xanthate changes with time.
MATERIALS
N
~ i l l T H O S
Acute
Toxicity
- Fathead minnows
and Daphnia pul ica r ia .
Acute
toxic i ty of sodium isopropy1xanthate
to
the
fathead
minnow
by
48-hr
and 96-hr b ioassays
in
s ta t ic solutions. Dilution water
tes ts came
from
a well a t the Department of Entomology, Fisheries
Universi ty of Minnesota, St.
Paul,
and
from
the South Kawishiwi
R
Minnesota.
Dilution
water
for
the 96-hr
tes ts
was
taken
from Lak
the U.S. EPA Environmental Research Laboratory, Dulu th , Minneso ta
character is t ics of
th e
waters are
given in Table
2.
The fish
used in
the 48-hr tes ts
were f o u r w e e k ~ o l d fathead minno
prome1as,
reared
at
th e
St.
Paul
laboratory.
The f ish
used
in
th
were
eight-week-01d
fathead minnows reared a t the
Duluth
laborato
were
placed in testing chambers 24 hours before
the addition of
Ten f ish were placed in
each
chamber. The
fish
were
not fed duri
ments.
Twen ty - li te r g la s s
t es t
chambers
50 cm
x 25 cm x 16
cm
high
we
St. Paul laboratory and
6 1i ter
cylindrical polyethylene chambe
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Item
TABLE
Chemical characterist ics of
dilution water
Conc en tra t ion mg / 1
Laboratory
South
Kawishiwi
Well River
Date sampled
L ?L@?
Total Hardn ess a s
CaC
3
Calcium
as
CaC
3
Magnesium
as
CaC
3
Iron
Chloride
Sulfate
Fluoride
Total
Phosphates
220
140
76
2
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age
Th e following
day,
f i v e young d aph nids , 1 2- 12 hours ol d,
were
each
tes t
chamber. The
temperature
in each chamber was recorde
The pH and t oxi cant l e v e l in each
chamber,
an d the lk l ini ty
conductance in
c o n t r o l s
w er e m ea su re d
t
th e
end
of each exper
c on ditio ns a re summarized in Table 4.
TABLE
4.
T es t c on d it io n s
for
Daphnia bioassays
Fa c tor Hean
Range
Temperature
18.1
17.5-18.5
pH
7.8
7. 6-8. 0
T ot al
A l k a l i n i t y
39
Hardness
46
S p e c i f i c
Conductance
9
The trimmed
Spearman-Karber
method
described by
Hamilton,
e t
used
to estimate LC50 s.
pegradat i on Tests
Two experiments were ru n with
s o l u t i o n s
of sodium i so p ro p y lx a n
determine
th e
degree
of
xa ntha te
breakdown over tim e. Two bioa
also ru n
to
determine whether t o x i c i t y
changes as
a
xanthate
s
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Page 7
of lO mg/l and
50 mg/l. Another se t of solut ions was
prepared
ionized water t a
xantha te concentra tion
of 5g/ l .
In the second ser ies of exper iment s, six test
chambers
were se
determine the
effects of pR
aeration and
xanthate concentrat i
breakdown r te of xanthates. Lake Superior water was
used
as
t
water. The
design
is summarized
in Table
5. Absorbance readin
t
the
beginning,
f te r 24
hr,
and
fter
96
hr.
TABLE
5.
Degradation
Test
Chamber
Xanthate Cone
Factor
mg/l)
1
Aerated
with
irs
tone
2
75
Rel added
,.
3 75
NaOR
added
4
5
150
6
0
Two series
of 48-hr
s t t i bioassays were
ru n
to
determine
whet
toxi,city
changes with time. These bioassays
were
conducted in
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Page 8
The third used 48 hr
old
stock
and
th e
fourth used
9 day old
Well
water
was used for
the dilut ion water .
Daphnia pulic r i
were
used
in the sec and series of 48 hr s t
assays.
Lake Superior
water was used as the
dilut ion
water .
solution of
xanthate
which had been allowed to stand uncovere
was used. The stock was
mixed
t a nominal concentration of
After
72 hours the stock
solution
was cloudy and the analyzed
256
mg
xanthate/I .
Hixture Bioassay Daphnia
The t e s t solutions
were
prepared
with
an
attem pt to keep
the
r tio
constant . The
low
treatment
level contained about
37
value of each toxicant . The
high
treatment level
contained a
the LC5
value of
each treatment. f the toxic interact ion
o
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Results
of the
degradation
experiments
are
given in
Tables
8 an
Results
of the
copper-xanthate mixture bioassay are given in T
LC5 was
calculated
by exp re ss in g t he
level
of toxicant in
each
the
sum of
the f ract ions of xanthate and copper LC50 s present
Thus an LC5 of l:toxic uni t would indicate a st r ic t ly
addit i
would indicate more than
addit ive
effects and >1, less
than
effects
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Page
10
TABLE 6. Spearman-Karber estimates of LCSO s
mg sodium
isopropyl/xanthate/l i ter
Fathead JIlinnow Tests
Water Duration LC50 95
confid
Well
water
48
hr
31.11 26.24, 36
River water 48 hr
32.52
27.32, 38
River
water
48 hr 35.65
29.63,
42
River water
48
hr
46.45
41. 77
50
L.Superior
96
hr
47.079 41. 24, 53
L.
Superior
96
hr
39.33
25.52,
60
L.
Superior
96
hr
31.34 24.43, 40
L.
Superior
96
hr
37.98 31. 67, 45
L.
Superior
96
hr
28.35
26.55,
30
L.
Superior
96
hr 39.177
33.95,
45
Weighted mean
of
96 hr
LC50 37.72
Daphnia
Tests
L.
Superior
48
hr
21.
74
20,00,
23
L.
Superior 48
hr
21. 72 19.49,
24
L.
Superior
48
hr
22;
76
19.46,
26
Weighted mean
of
96 hr
LC50
21.
97
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TABLE 7. Spearman-Karber estimates of
the
LC50 s
in bioassays
using aged
stock solutions
Fathead minnow t t
Age
of Stock
Solution
Fresh
1-day-01d
2--day-01d
9-day-01d
Daphnia Test
48 hr
LC5
mg/1
95
Con
24.86
2 1. 7 4
39.81
35.25
25.14
20.00
30.49
27.33
72-hour-01d
13.42
10.62-1
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Page
T LE
bsorbance of Sodium
sopropyl-
xanthate
solutions
over
96
hours
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TABLE 9. Xanthate concentrations of solutions
aged
under
different conditions
Xanthate Concentration (m
Chamber
Factor
a
hrs
f
hrs
96
aerat ed 81. 6 82.5
85
2
acidic 0.0
0.0
0
3
basic
80.4 80.0 79
80.0
79.9
79
5
doubled concentration
157.1
155.7
158
6
0.0
0.0 0
TABLE
10 .
Copper-xanthate mixture bioassay.
[eu]
(jlg l)
Xanthate
(jlg l)
Chamber
fraction
of LC5
fraction
of
3.40
.37
5.82
.26
2 3.85
.41
8.05
.37
3
5.25
.57
10.87
.49
4
5.95
.64
19.82
.90
5 7.55
.81
19.01 .87
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DISCUSSION
ACuLe Tests
The LC5 v l ~ s reported
in the l i te ra ture a re gener all y
low
LC values found in the present study.
The
course of
toxic
action
of
sodium
isopropylxanthate
appea
inconsistent. Mortali ty of
fathead minnows
would
occur eith
f i r s t
24-hr period or
af ter
the
second
day.
In some of th
t re atment s, t he solution
would turn
cloudy overnight. No f i
in a cloudy solution. This cloudiness appeared with no app
Fo r
example, in
one case
the
second
highest
treatment level
in
24 hours
and
the highest treatment level
turned
cloudy
af
f
the
high treatment did not turn cloudy the
fish
would s t i
although at a slower ra te
Toxicity
was indicated by
er ra t i
loss
of
orientat ion,
followed
by
lethargy
and
gaspingll
on
t
the
tank,
and
f inally death. The type of dilut ion
water
did
to be a
factor in the toxic i ty of
xanthates :
Daphnids
would
occasionally
get caught
in the
surface
film o
solut ion,
but
th is
was
never observed
in
a
control
chamber,
became caught i t usually would
survive even i f the
other
dap
Degradation Tests
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Page 15
which led
to
rapid xanthate breakdown. Cloudiness was obse
the stream
from
the
pipet te
which
was
used
to in tro du ce the
solution. This cloudiness disappeared af te r a few seconds.
solutions turned cloudy
during
the
experiment.
In the bioassays conducted
with
fathead minnows
using
an ag
t ion,
toxici ty appeared
to
be lower af te r the
f i r s t
day, bu
no differences from
the
i n i t i a l toxici ty af te r 2 and 9 days
cloudy solutions were
observed.
The 48-hour LC5 value for the
Daphnia
bioassay using 72-ho
solution was
6
of the weighted mean LC5
value found
usin
The stock solution used in this
t es t
was cloudy. The lower
that
toxici ty i nc re as ed with
degradation.
Copper-Xanthate Ivlixture Bioassay
The survival of daphnids in higher
treatments
in
the
mixtur
Table
10) was the resul t
of
these daphnids becoming
trappe
surface f i lm. One organism
in
chamber 4 was trapped in
the
as were a l l
the
survivors observed in chamber 5. f these
counted as
mortal i t ies
the
Spearman-Karber estimate
of
the
is 1. 22 t ox ic u ni ts with
95
confidence l imits of
1.13-1.
Page
16
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Literature
Cited
American Water
Works Association and
Water
Pollution Control Federation.
Dmv Chemical
Co
1976. Flotation Fundamentals and Mining Chemicals.
78 pp .
Dyer
J.
a nd L.H. Phifer. 1969. Cellulose Xanthic Acid. T Studies of
Hodel Systems. Macromolecules 2;111=117.
Fuerstenau
M.C. 1974. The Toxicity
of
Se lec ted Su lfhydra l
Collectors
to
Rainbow
Trout.
Bureau
of Mines
Open
Fi le
Report
11-75.
28 pp.
Hamilton
M.A. R.C.
Russo
and R.V.
Thurston.
1977. Trimmed Spearman
Karber Method fo r Es timating ~ l e i n Lethal Concentrations
in
Toxicity
Bioas sa ys . Env ir on .
Sci.
Technol.
11:714-719.
Harris G.H. 1970. Xanthates. Pages 419-429 in Encyclopedia of Chemical
Technology Vol.
22 2nd ed . John Wiley and Sons Inc.
Hawley J.R. 1972. The Use
Characterist ics
and Tox ic it y o f Mine-mill
Reagents in th e Provi nc e o f Onte ri o. M in is tr y
of
th e Environment
Ontario 244 pp.
Joedodibroto R 1963.
of model
compounds.
The mechanism
of th e decomposition of Xanthates
PhD. Thesis Syracuse University New York.
Trofimovich E.M.
skaya. 1976.
Kaliya
C
2
-C v
lated
by Raiph
S.H. Rykova M.A. Molchanova and L.B. Aleksandrov
Materialy
po Gigienicheskomv Normalirovahiyv
Ksantogenator
Vode Vodoemor. Gigienina i Sanitariya 6:95-97.
Trans
McElroy Co. Custom
Division
Texas.
Webb }1. H Ruber and G Leduc. 1976. The Tox ic it y o f
Various
Mining
Flotation Reagents to Rainbow Trout Sa1mo
gairdner i .
Water Res.
10:303-306.
Wixson B.
and
N
Gale.
Related to Mining.
1974.
Pages
109-122
in
Water
Resources
Problems
Proc. No. 18 .
American
Water Resources Association.