...-~---
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f.
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This paper not to be cited without prior references to the authors
C. M. 1971/E:32
International Council for
Fisheries Im.provement Committee
the Exploration of the Sea
.
.
EXPERIMENTAL DUMPING OF WASTE FERROSULFATE
INTO THE
SY~GERRAK
by
•
G. Berge. L. Fpyn. R. Ljpcn and K~ H. Palmork
Institute of Marine Research. Bergen, Norway
INTRODUCTION
Thc production of TiO
from ilmenite using H S0 in dissolving the
Z
Z 4
minerals. results in vast quantities of " c' iified FeS0 waste. The waste
4
is known as two somewhat different categories: The "Dünnsäure" which
roughly consists of 10-20
% H ZS04
and 15
% FeS04
in water and the
wet "Copperas" which mainly consists of ironsulphate in chrystaline form
(75
•
%).
Disposal of "Dünnsäure" into the sealna become a practice fromoevcral
factories. For instance quantities of 200.000 tons FeSO4/year ~:.:-.e diecharged this .way from tankerc into the New York bight and 10J.000 tons
FeS0 /year into the North Sea 25 km NV of Helgoland. Harmful effects
4
even in great dilutions have been shown experimentally using variouc
marine organisms Kinne and Rosenthai 1967. Kinne and Schumann 1968,
Halsband 1968. Kayser 1969) but little. is known about the ecological effectc
in general (Redfield and Walford 1951 , Hickel 1969). Weichard (1970)
reported that "Dünnsäure" released into the propeller water of the chip
was rapidly diluted, and caused only a short term effect on the oxygencontent and a reduction in pH of the water. Rachor (1970) investigated
the disposal area of Helgoland, and demonstrated changes in organisms
composition over aperiod of 4 years. He was unable, however, to draw
'any definite conclusion as to whether the changes were due to natural
fluctuations or to starting effects from the waste dicposals •.
- 2 -
The effects of dumping "Copperas" into the sea is to our knowledge not
investigated and there is reason to believe that this material will behave
somewhat differently from the "Dünnsäure" in the marine environment,
since it is in crystaline form and thus concentrated.
From the 1'J:>rwegian Ti0
2
producer the waste is released through pipe
lines into the lower part of the river Glomma which empties into the
Oslofjord. Some effects in the river estuary has been reported on the
fauna ao weIl as on thc flora and the bottom sediment.·
•
In cooperation with thc Norwegian producer of Ti0 , and The Norwegian
2
Institute for \Vater Research, which m.ade the studies of thc river outlet,
experimental dumpings were planned to collect inforraation on the behaviour
of dispooed "Copperas" in the open
Skagerral~
waters. The purpose of the
experiment was to study the general behaviour of the disposed material,
in particular the discolouration, changes in turbidity, the effect on both
primary production and oxygen content, as weIl as the scavenging effect
of the ironhydroxide formed.
Two different dumping -oites \vere used for the experiments, one in the
outer Oslofjord and one in the open Skagerrak at the eastern slcpe towards the Skagerrak deep. The watermasses at these localities nre known
to bc a top layer of Baltic origin covering North Sea watermasceo o Thc
•
Baltic waters are usually identified by salinitieo less than 30 o/~oo .
Especially i~ thc summer a pronounced stratification occurs b::.t-m.,all
these layers. The movement of the surface watero dependo
wind conditions as has clearly been ccmonstrated by one
1971) fig.
1.
mzj~"Üy .:l::l
0: Ci"
{:L;;6,m
Three situations' of approximately one weelc intc:'~t:~l.:~ de-
monstrates in the first sequence a piling up of the Baltic watero aguinot
the western coasts of Norway and Sweden. In the second situation different
wind conditions off western Norway and in Skagcrrak result in a piling up
of thc &lti c water s against the southern and coutheastern Norwegian coast.
and a latheral movement of t.."'le Baltic waters away from the coast.
The last situation demonstrates a transport of the
B~ltic
water mainly
southwards and a brake up of these waters into vorticcs. The sequence
of the demonstrated situationo result in a fortIl and back transport of the
surf'ace waters within the area, as weIl as a. pun'lping ef'f'ect of' thio wa.ter
in and out of Skagerrak.
, .
!
- 3 -
Prior to the experimental dumping some laboratory testo were carried
out by the Titan Co., Fredrikstad, Norway, to invcotigate thc aolubility
.
,
of the "Copperas" when rc1eased direct1y to sea.-water. Thc resulta, which
are given in table 1, demonstrates that pure "Copperas" as well as the
iron -oulphate solution both were dissolved main:ly in the upper 1 meter
of a column. The above reaults indicated that "Copper~s" \vhen discharged
.
,
either direct1y or as a solution would be distributed within the homogenouD
top layer of the sea. Some further experiments revealed that the ironaulphate turned slowly into Fe(OH)3' a proceos which used oxygen and
further reduced the pR of the waters.
'.
Experiment 1. - Direct releaGe of 80 tons "Coppcrao". Date: 27 -' 28
October 1970.
The "Copperas" had bcen otored in sacks for Dome weeks and consequently
the cryotals had elogged. VTith a current crooo placed at 1 m, the contentc
were continously dumpcd while the ship circulated around this drifter •
. During the operations (4 hrs) the drHtcr mooved in a south-west direction
over a distance of 3~ n. miles. At the start the weather was calm but '
a southeasterly wind developed du ring the durnpirig and increased in force
to a gale
befor~
the end of the experiment.
Visual observations ac well ac chemical analyaeo of the contaminated
waters showed that some of the material bad bcen diotributcd within thc
upper \Vater masa. Echo recording during the dumping, however, revealed
that considerable amounta Gunk right to the bottom; fig. 2. These' findingo
•
ware further confirmed by the transparency recordings. Although the dumping was made continously the yellow brownish fe~rohydroxide formed waG
localizcd as patcheG. Caused by the weather coriditions a ceosation in the
sampling waG. found neceosary after 6 hrs. By that time the patches had
moved elose to the shore, and the next day when the \veather had calmed
11.0
sign of the waote waG observed. This was probably caused by the gale
which obviously had blown the dissolved iron waste ashore.
, Experiment 2. - Eighty tono "Copperas" (= 33 t FeGO4) dissolved in hot
3
wa.ter to 118 m • Da.te: 11 - 12 May 1971.
The liquidizcd waste \vas pumped into the sea while the sbip was circulating around a current crooo placed in 1 m depth. Observationo on
o
. 0
S /00 and t C revcaled a upper mixed lay~r of 5-7 m~ The patch wao
just after dumping about 500 m acroBs, giving a strong yellow brownish
. colcur distinct1y separating from the ourrounding waters.
- 4 -
Dui-ing the two previous days as well as during the \vhole experimen.t
thc wind was rather stable from south west, force 3-4 Bt.
The pn.tch
was observed from the reoearch vessel during 31 hrs. at thc positiono
showed in the map Hg. 3 starting at thc position B, 14
hrs~
after thc
release the size of thc patch was estimated to 2. 500 by 500 m.
The
current cross in 1 m more or less followed the patch, whereas two current
crosses placed in 10 and 15 m respectively showed a retarded movement
of the subsurface waters, Fig. 3.
The transparency measuremento
examples of which are shown in Fig. 4, ab, prooved to be a suitable
technique in identifying the vertical and horizontal distribution of the
•
material showing good agreement with iron measurcments done, Fig. -1c •
During the situations A~' Band C Fig. 3, samplings were made for iron
measurements, giving the surface values shown in Fig. 3~
Plotting the
measured surface values against time, the maximum values recorded in
each situation give an
appro~dma.tion
of the centervalucs of the patch Fig. 5,
and a probable time scalc for the disappearance of thc discoloration.
A
slight decrease in the m:ygen content of the contaminated water as compared with the outside pattern was observed in accordance with the findings
of Weichard (1970) during and immediately after the release of 'Dünns!!ure~'.
Chlorophyll and the primary production measured in simultanous sampie s
were used to calculate the turnover rates in the phytoplankton.
The results
after dillution indicatcd that the pollutant had primara,ly an inhibit?l'y effect
•
which later secmed to act stimulating on the primary production•
DISCUSSION
Toxicity of ironsulphatc waste to marine animals, both on pelagic and
bottom fauna are fairly well documentcd (Kinne and Rosenthai J.967,
Kinne and Schumann, 1968).
Like the findings by Ketchum ct. al.
(1958) our measurements of the rates of primary production at standarized
condition indicated. howevcr. that thc contaminated sea water acted only
negligably on the turnover rates in the phytoplankton, an initial decrease
soon being countcracted by a slight increasc.
Scveral ccological cffects might, however, be expected when great
quantitieo of ironsulphate are being introduced to the sea.
pronounced are probably:
3) rcduction in pH, 4)
Thc most
1) increased turbidity, 2) discolouration,
o,:ygcnconsuinption~
- 5 -
Thc former two would act on the light penetration.
Vlhen the material
is diooolved in the surface 1ayors thc availablc light cnergy \vould be
reduced with a nearly proportional effect on the rate of integratcd
primary production (Berge 1969).
The considerab1e reduction in red light penetration observed here
indicate that serious decreaoe in the integrated primary production this
way has to be considered in a permanent dumping process of this
n"laterial.
Although not observed, changes in the r.nentioned parameters
over longer periods must be considered harmful to the marine lHe.
•
The first experiment with crystalline "Copperao", ohowed that the
m.aterial part1y penetrated the pycnocline and Gunk to the bottom.
Deposited on the bottom the high1y concentrated material wou1d act
both on the pH and the
o~~gen
content of the water near thc bottoln
and consequently on the organisIr s
living there.
In the actual region
where important trawling for ohrimps takes p1ace, regular dumping
of this kind wou1d probably cause serious harm to these and other
resourc ~o.
In the second experiment where disso1ved "Copperas" was re1eased
the material dispersed in the water 1ayer above the pycnocline and
formed
•
0.
otrong1y yellow- brownish coloured patch.
The colour
persisted and the patch increasing in size with time, was still distinct1y
observable after 2 days.
The floccu1ation of ferric-hydo:dde progressed slowly.
By vigorous
otirring floccu1ation took place immediate1y, indicating that rough sea
might speed up the process.
The chemistry of the ironsul!ate behaviour
in sea water is not fully underotood, but it io stated by Cooper (1948)
that part of it will be comp1cx bounded and remain in oolution for a
pro10nged periode.
The oboerved varied wind conditions and the rapid and great changes in
the movement of baltic waters roust be considered ordinar.
It is thus
not predictab1e where patches of contaminated water wou1d be transported.
Serial introductions of waste cou1d this way be transported forth and
back any place whithin the area as well as in and out of the Skagcrrack
- 6 -
and along the south-western Norwegianbanks.
in.1.portant nursery groundo for Hsh
stocks~
These areas are
and harm to the fish
recruitr...1.ent cannot be eJ:.c1uded.
References
_.- .. _......-
'-----_. -,-~.~_._------------.'
•
Berge, G., 1969.
Predicted effects of fertilizers upon the algae
production in Feln Lake.
FiskDir. Skr. Sero HavUnders.,
15: 339-355.
Cooper, L. H. N., 1948.
The distribution of iron in the waters of the
weotern English Ch;mneL
Jo_ur~Ia.!:.. .13iol.~s-~.,
27:
279-313.
Halsband, E..
1968.
Physiologische Untersuchungsmethoden zur
Bestimmung deo Schälichkeitsgrades von Abwassergiften
in Süss-, Brack- und Salzwasser.
Helgoländer '\"::1no.
Meeresunters. , 17: 224-246 •
•
Hickel,
vr.,
1969.
Sedimentbeschaffenheit und Baktericngcha!.t im
Sediment eines zukünftigen Verklappungsgebiet:-s von
Industrieabv.rässeren nortwestlich Helgol,mds.
He1goländer
wias. l.ieereounters., 19 (1): 1-20.
Kayser, H., 1969.
Züchtungacxpcrimentc an zwei marinen Flagellaten
(Dinophyta) und ihre Andwendung im toxikologischen
Abwasserteat.
Helgoländer wisse Meereaunters., 19 (1):
21-44.
Ketchum, B. H., Yentsch, C. S. and Corwin, N., 1958.
of the disposal of iron wastes at sea.
Some studies
1. The distribution
of plankton in relation to the circulation and chemistry of
the water.
Vloods Hole Oceanographic Institution, Reference
No. 58-55: 1-35.'
(Unpublished Manuscript.)
- 7 -
_ Kinne, -0. and Rosenthai, H., 1967.
Effects of sulfuric water
pollutanto on fertilization, embryonie development and .
larvae of the herring, Clupea harengus.
Mar. Bioi.,
1 (1): 65-83.
Kinnp.. O. :\nn Schumann. K. H ••. 1968.
Biologische Konsequenzen
schwefelsäure- und eisensulfathaltiger Industrieabwässer.
Mortalität junger Gobius pictus and Solea solea (Pisces).
Helgo1änder wisse Meereounters., 17 (1-4): 141-155.
Lj~en,
•
R., 1971.
On ahort-term variations of the hydrographica1
conditions in the Skagerrak and adjacent sea.
The first
international conference on port and occan engineering
under arctic conditions.
The Technica1 University of
Norway, Trondheim, Norway, August 23-30, 1971.
Rachor, E., 1970.
On the influence of industrial waste containing
H SO 4 and FeSO4 on the bottom fauna off Helgoland
2
(German Bight) F AO Technica1 Conference on Marine
Pollution and its Effecto on Living Resources and Fishing.
Rome, Italy 9-1B December 1970, FIR: MP/70/E - 101,
25 November 1970.
•
Redfield, A. C. and Walford, L. A.
waste at Dca.
A study of the dioposal of chemica1
Publs. natn. Reo. Coun., Wash., (201):
1-49.
Weichan4, G., 1970.
Chcmical and physica1 invcstigations in the
German Bight on marine pollution caused by wastes of
a Ti O
factory.
FAO Technical Conference on Marine
2
Pollution and its Effects on Living Resources and Fishing.
Rome, Italy 9-18 December 1970, FIR: MP/70/E-44,
28 September 1970.
--
---------------------------------------------------------------
0
27 ~0 sol. FeS0 ,. 40 C, sp.v.• 1,34
4
SampIe
Gramme FeS0
3,7
4
Time interval
1 mine
Mo'15 t "Cop
7H 2
.
pe r as " - 76 1 5FeSO
.
.4'.
0
37
5 mine
37'
°
370
1 mine
5 mine
1 mine
5 mine
1 mine
5 mine
~ <l.J
22
3,3
2,3
24,0
14,2
18,3
14,8
139
122
r-lrcl
<l.JlI-l
.Ql-l
48
2,1
2,0
16,6
15,0
16,1
13,6
139
122
<l.J Ul
90
0,7
1,1
8,1
12,2
11,6
12,1
113
118
0,02
0,44
0,5
84
111
o ()
::1
()
s.::::
rcl
+J
127
Ul
7,9'
4,9
9,6
-.-I
Cl
Homogenous solution
equals g/l FeS0
4
1,17
11,7
11,7
117
Table I. Vertica1 distribution of ironsulfate added in various concentrations to seawater
at the top of a co1umn, 1,4 m
h~gh
and with a diameter of 4,6 centimeters.
~
....
".;.
,5S'
.~
'5]'
,, .
-.
5')'.
"
•
I
.
!,.S'
.
,
1
i !>7'
,,
!>9'
•
1\
:
i
:
!lS'
l, .
,
,
,,
!>B'
ht
,,
,I
....\
57'
.':.
I.
57~'. , . - - , , - - . . - - . - - - . -
S'
8'
4'
'.
Depths of 30
Average Wind conditions
Figure
0/00
isosurface
I
"
•
,
,
:1
.
,
.\
\
.~
t
,'. <_,; .'''';. "'.-J,~~
f, .. ·.:1'1·~~.".r"
....1
, ',.':
..
',;.
"
~
"
:~
..
.
, ....
Fig 2. Echo
record~ng
showing the dumped "Copperas" penetrating to the
bottom ( Simrad EH, sca1e 0
125 m, force 5 )
,
.
..
,
•
I
I
10
-.r......
I_
-.-
5
Skagerrak
/s
-------
Fig. 3. Experiment 11, the patch and drifter movements with
the surface concentrations of iron in fg/l plotted
on a Decca chart (Decca chain lOB/MP, Skagerrak).
"
\
Area
map~
,
~
;
--------------
_.. ',
._..,._...
_.,;~_
.. ..-.. ..._._ ..._.. ....
,;
% Transmission
80
100
I
_ --:-- ...... _----_
...
-._-_ ..•
.
.-
... _. ' ......
._-_..
-_
_--------------------:-------,.
_.
__
, . __..
_--
% Transmission
60
100
80
60
40
...
'- .-
Iran, Fe in 100 g/l
30
20
1
,
2
3
4
--....
+'
10
~/
S
'--'
20
\
~
~
.'" 30
10
........
........
s
.........
.s::
S
'--'
.s::
I
+'
(
P..
-
... ....
"
----.
6
5
~-
101)
20
,
/
...
. _______ -c;--
...u
##
J
20
+"
0..
0..
(!)
Q)
A
A
30
I
30
( a ')
..
1
( b )
( e )
Station no .159, 11.5.,
6.15 p. In.
Station no 160, 11.5.,
Ou tside the "Pateh".
M.iddle of the "Pateh"
6.30.p~m.
0
Fig. 4. (a) and (b) Vertieal t~ansparency measurements, % transmission of read light.
~
(e) Vertical distribution of iran.
..
7
.......
8
10000
5000
1000
500
--
C J)
::1.
100 .
50 -
10
5
~
...
1 "'~•.- ----.....-----~;----.....-,.;:------'--;Jr-----_,;.----.._..o:.o
5
10
15
20
25
30
TI,ME IN HOURS
Fig. 5 .. Experiment 2, rnax~murn surfaee values of iron in the middle of the pateh
plotted'against time interval from the release of the ironsulphate.
'
.. """.'