Special Report on




WATER QUALITY OF LAKE SUPERIOR




      in the Vicinity of




     SILVER BAY,  MINNESOTA

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I          SECTIOi;  3   -   IWESTIGATI01IS BY CHICAGO PROGRAM OFFIG
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             SECTION 1  -  INTRODUCTION                   .                    1

             SECTION 2  -  SU121ARY ALT) COIICLUSIOriS                            5
             SECTION 4  -  INVESTIGATIONS BY NATIONAL WATER QUALITY        3^3
                           LABORATORY
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 SILCI10N   ].


IKTSODUCTJC
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             SECTIOil 1  -  3IITKGUUGTIC;!
       This  report  presentj  the findings of studies r.iadc in Lake
Superior by  the  Federal Water Pollution Control Administration
(Fb'l-CA) as one part of a  Dopart: .cut of the Interior inter-agency
study.  The  purpose of the siudy was to determine v;hat effect the
waste discharge  of  the Reserve Kin Jr. 13 Company has on the v;ater
quality of LM:e  Superior  and associated present or potential in-
p-iir.vent cf  water uses.

       The Reserve  Mining Ccrapany has operated a taconite pellet:.'/,-
ing plant at Silver Bay,  Minnesota since 1953.  The ore in mined
and crushed  at Babbitt, Minnesota, and shipped by rail to Silver Pay
on Lake Super:; or for reduction,  concentration and pallet, i'.ing.  An
average of 90,O'X) lonf/-tons  of ore is processed by the riill daily,
resultir;; in the production  of .30,000 long-tens of pellets and
60,000 lors=;-tor;s of waste tailings which are discharged to Lake
Superior,

       In 19<^3,  the U.S.  Amy Corps cf Engineers granted a permit
to Reserve Dining Company to discharge taconite tailings into Lake
Supericre  This  permission is subject to periodic review, and in
Nove;:!er 19<->7> the  Corps  issued a notice of intent to revalidate
the perrr.it for another five-year period.  Earlier in 196? the
Corps had asked  the Department of the Interior to .Take recormer.da-
tions in regard  to  the proposed revalidation.  Pursuant to a
Menora;idv.:n of Understanding  between the Secretary of the Ar:ny
and the Secretary of the  Interior, the Regional Coordinator,
Deportr.ent cf the Interior,  organised an investigative ccrmittee
made up of representatives from five Interior agencies (F.-'PCA,
Gco]ogic?l Survey,  Pureau of Sport Fisheries and Wildlife, Bureau
of Co;rr;iercial Fisheries,  and Bureau cf Mines) and the States of
V.'isccnsin and Kinnesota.

       Section 2 of this  report £UT_rr.a.rizes the findings of the
FJPCA tean.  Section0. 3 and  4,  which follow,  give detail? cf in-
vestigations conducted respective].;/ by the Ch:'cage Program Office
and the National Water Quality Laboratory, Duluth — each part of
the Great Lakes  regional  organization of the Federal Water Pollu-
tion Control Administration.
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                                       SECTION 2


                                SIM'ARY MD COKCIUSIOHS

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                                       AND CGIICLUSVOHS
1.  60,000 long tons pel* (levy of t aconite waste  solids in TOO million
    gallons per day of water era discharged frcra the E. W. Davis Works
    of Reserve 1 lining Company directly iuto I^ake Superior.

2.  5thQQ long tons per day of the waste solids discharged are less than
    k microns in diameter.  Part.ic3.es of this diameter stay suspended in
    water for a considerable tine after discharge.

3-  Current measurements in the vicinity of Silver Bay indicate that the
    prevailing current:':-:- to tr. •; southwc-^t and 01' sufficient v ^'o-rlty to
    transport particles of '4- anici'ona or less more than 9 mile? ^cr day.
k.  The figures which indicate the distribution of results, show that
    the study area selected (9 miles by 5 railes) was too small  bo define
    the full extent of the area adversely affected .  Several parameters
    were in excess of Federal-State Standards and other criteria at a
    series of stations leading to the edge of the area studied, indicating
    that the affected area extended beyond the farthest sarrpling point .

5.  Results of analyses of sar.rples collected from Lake Superior during the
    September 196? study in the vicinity of the waste disposal area in-
    dicated copper and sine in concentrations normally considered toxic to
    aquatic life.

6.  The investigations of June -July 1968 in the vicinity of Silver Bay
    revealed lead and copper levels in excess of Federal-State Water
    Quality Standards.  Aluninun, lead, copper, zinc, cadraiun and nickel
    were also found to be in concentrations in excess of ccrrnonly accepted
    levels for supporting aqaatic life.

7 .  Iron concentrations io. the area affected by Reserve Mining Company
    discharges exceed the Federal-State Standards.  The 5ron concentrations
    increased fro.ii sire face to bottom and were 10 to 12 tines higher than
    those observed in the open waters of the lake .

8.  Lover iron values were found in the area influenced by Reserve Mining
    Company discharge in July thc,n wore found in June .  The reason for bhe
    lower values is attributed to toraporarily curtailed operations by
    Reserve Mining.  It was ncted that Reserve Mining shut down at least
    one-half of their operation preceding and during this sealing period .

9-  In the June -July I960 Reserve Mining Ccupany area studies, total
    cbrc.id.ura values were found up to seven ti;:;es the Federal -State Standard
    for hexavaleut chrc::iiua.  ITo chrc.TLi.u:a was detected in the 1960 or
    lake survey sasiples or in the Silver Bay area in the 1967 study,
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indicate that they would appear green to the eye.
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10.  Turbidity rtsasvireiiients were observed to be relatively high in the
     vicinity of the Reserve Mining Company discharge.  Turbidity values
     were higher than adjacent waters, forning a pattern to the south
     and southwest of the discharge.  The values diminished somewhat
     with increased distance froni the discharge.  The bottom water tur-
     bidity values were frcra two to forty tirr.es higher than those found
     on the rest of the lake iu the 1567 lake-wide survey.

11.  Benshic organisms were scarce in samples taken frcci stations affected     •
     by the taconite waste outfall.  Pollution-sensitive scuds were absent     *
     from these samples which were collected at depths between 20 and 252
     raeters.                                                                   I

12.  Water transparency measured by Secchi disc readings was ^.5 meters
     in the green water and 12 raeters in the lake beyond that area, which      •
     indicates that the turbidity of the green vrater reduces the light         I
     penetration in the area iuf3.uenced.

13.  The green water area vas definitely visible on September 19 and 22        •
     ami October 25, 1967.  Aerial observations and color photographs          "
     obtained on September 22 fo3JLo»red the groin water frca. the waste dis-
     posal area westwe-rd to the Split Reck Lighthouse about 10 miles away.     •
     The green water wa^ nore pronounced on October 22, 1967.  It was ob-      I
     served frc.i the shore and extended westward to the Gooseberry River,
     about Ik miles away.

Ik.  SCUBA divers observed "green water" around Reserve Mining Ccstpany's
     effluent delta en each of their ]Jl- visits during the period of
     Septenber 15 to October 11, 1968.  On scaia days during this period        •
     the "green water''1 appeared as a continuous bend aloag the Lake Superior   •
     shore between Silver Bay and Gooseberry River and appeared to arise
     frca the effluent delta of Reserve Mining Ccin^any.                        •

15-  This "green water" has a, r.easurable increased turbidity sud contains
     at least 2 to 3 tines tacre suspended solids than doss water that          M
     appears clear to the eye.                                                 I

16.  Tae reflectance spectra of the solids, collected on OAp micron niters
                                                                               •
17-  Ills particles in this '''green water'1', collected en 0.!>-5 inUrr-j-n  ,"in t •,•-•.;,  are
     chiefly quartz and cur-ningtonite .                                         •

l8.  The fine l.-ike sedinents froii the w 2 stern end of Lalce Superior  contain
     proportionately rauch less eumsri.in-jtonite than taconito tailings .           •

19.  The five north shore strft.3i.is, northeast and southwest of  Silver Bay,
     contained much loss cur^ilngtonite than was found in Reserve Mining
     Company's t aconite tailings.                                              I
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20.  Tha small particles in the effluent of Reserve Mining, contain much
     larger quantities of c/ruiin^tonite tho,n the email particles in the
     streams of the area or lake sediments of the western end of Lake
     Guperior.  They are sufficient to distinguish taconite tailings from
     stream and lake sediments in that area.


21..  Pieces cf nylon net suspended in the lake as far as approximately 12.
     niles southwest of Silver B~.y collected larger concent rations of taccirlte
     tailings than those pieced northeast of Silver Bay.


22.  Tae "green water" stapled during this study was caused by taconite
     tailings and was found 1.8 miles scuthvc-Gt from the effluent delta of
     Reserve Mining Ccrapany.
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              SECTION  3


INVESTIGATIONS BY CHICAGO PROGRAM OFFICE

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                                        TABLE Ol'1  CONTOIS
             IteTi                                                        Page
             INTRODUCTION                                                   13
I                  Field and Laboratory Studies                              13
                  Definitions                                               ill-
                  Criteria                                                  15

g           LAKE CURRENT STUDIES                                           17
                  Purpose                                                   17
_                Current Meter and Temperature Recorder Studies      .      17

™           LAKE SURVEYS, 1966-1967                                        21

             11967 PRELIMINARY STUDIES                                       22
                  Company Discharge Survey, May 1967                        22
                  Company Discharge Survey, Septenber-October 1967          23
m                Observations                                              2.k

             1968 IK-PLANT SURVEY                                           27
                  Introduction                                              27
                  Pelletizing Process and Plant Sampling Points             27
                  Saripling                                                  28
                  Results                                                   28
•                Settling-Rate Characteristics of Taconite Wastes          29

             1963 FIELD AI\D LABORATORY STUDIES                              30
I                  Introduction                                              30
                  Liclogy                                                   30
                  Oil eras try                                                 32

I           REFERENCES                                                     39

             LIST 0? rTGURES                                                Ul

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             LIST OF TAJBJjES

             FIGURES

             TABLES
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             SECTION 3 - IKVESTIGAriCNS BY CHICAGO TOGR/iM OFFICE
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                                       lilTP.OD'JCTION
       Tliis report presents the findings of studies made in Lake
Superior by the Federal Water Pollution Control Administration (FV.'rCA)
in 1963.  The purpose of the studies was to determine what effect the
vaste discharge of the Reserve I'dning Company has on the water quality
of Lake Superior.  Included i3 information on che gonerpl vater quality
and movements of 'Western L-ike 3uvcrior from lake surveys made in 1°66
arid 1967 and a pi-el ird nary study of the Reserve 2'ining Go Tpany dis-
charge no.de in 196? •

Field and Laboratory Methods

       Field and laboratory chemical analyses were performed using
the F17PCA Interim Methods as developed by the Committee on Methods
Validation and Analytical Quality Control.  Biological sampling
and classification methods are described in ^atejr Pollution Biology,
Il^M S^l^ Laboratory l^anual, CPO, FWPCA.          "~ "   ~ ~  -

       Bottom sediment and benthos samples were obtained using a
Shipek* dredge which collects a 1/25 square meter sample.

       Water samples were collected from the 1 meter depth, mid-
depth and bottom layers.  Kycrrpprcouqts;* l6 liter P.V.C. water
collection bottles tripped by inessenger for the top and mid-depth
layer were used.  The bottom sampler was tripped by a bottom
activating foot which closed the bottle when the lower end was
about eight inches above the bottom.  Modifications of sampling
arid analytical methods are described in later parts of this report.

       Interferences from all preservatives used have been investi-
gated and none was detected.  Ho contamination of samples was
ir•'• o'-.cjuced from the use of filters.  Reagent blanks were routinely
processed with the samples to compensate for any contamination
from reagents.
* Disclaimer:  Mention of products and manufacturers is for identi-
  fication only and does not imply indorsement by the Federal Water
  Pollution Control Administration or U. S. Department of the Interior.
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       The results of  chemical  analyses  are functions of the
analytical methods used and must,  therefore,  be  interpreted in
light of those methods.   The analytical  methods  used in this
study are suramari'/.ed in the following  table:
 PARAMETERS
 Aluminum
 Cadmium
 Chromium
 Copper
 Lead
 Manganese
 Nickel
 Zinc
 Iron
Phosphorus
 rsenic and

  all others
SOLIDS
atomic absorption,
sodium carbonate
   fusion
Bureau of Mines
  Method
sodium carbonate
  fusion
Standard Methods
polarography
                       Standard Methods
 Standard Methods,
 soluble phosphorus
 was paper filtered
 Standard Methods
atomic absorp-
tion, acid
digestion
  except soluble
  metals which
  were paper
  filtered
       The following are definitions for terns used in this report:
       ^iSESI-^'lS'- 3 el ids are those materials retained on a glass
fiber filter THoeVo Angel, * grade. 934AH).

       Dissolved salida are comprised of the dried filtrate  passing
the above filter.
       SLota.! E?lL39J}oru.5. includes ortho--, hydroly/able, and  organic
phosphorus as measured using the persulfate digestion procedure.

       If^^Lk sJ5iull}-? phosphorus is the same as total phosphorus
except it is that which passes a Whatman Xo. 12*  filter.  (Total
soluble phosphorus determinations were discontinued after the
Cctober-flovember 1966 study period.)

  ---Disclaimer:  Menticn of products and manufacturers is for identifi-
   cation only and dees not imply indorsement by  the Federal Water
   Pollution Control Administration or U.S. Department of the  Interior.
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        Unless otherwise -specified, all metal values are  tctal_
rn.etal_s  as found after treating the ur.Ci Itered, nitric-acid-prcscrved
samples with aqua re pi. a.

        SoluMe metals are these found in that portion of a  sample
passing through a Whatnan Ho. 2V* filter.

        The chemical state of the metals mentioned in this report
is  difficult to assess, and it might be presunptious to  say that
all of  the elements in a given sample o.re biologically available.
The solubilities of the materials in suspension have not been
determined.
       The following is a list  of  parameters of major concern and
the Federal-State Standards ts^on  from ^^
for the Interstate Waters of Miwi
of the Interior;
                                      a as approved by the Secretary
Parameter

Arsenic
Cacun ium
Chror.ii.vm (Yl)
Copper
Iron
Lead
Manganese
MBAS
Zinc
                       Federal-State
                       	St_anda_r_ds

                       0.01 mg/1
                       0.01 m<:-/l
                       K^t  i;o exceed  a trace
                       Not to exceed  a trace
                       0.5 i:aA
                       0.05 rig/1
                       0.05 r.g/1
                       0.5 rig/1
                       5 n.7/1
Water U s e_Prpt. e ct ed

Domest Lc conounpt:i on
    11         11
Fisiieries and recreation
    »      it      ii
Domestic consumption
    U         it
  J<"Discla::mer:   I'tntion of croduots r-.:id manufacturers is for identi-
   fication  only and  dees r.ot imply indorsement by the Federal 'Jater
   Pollution Control  /idminist,ration or U,o. Deoartment of the Interior.
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       The Federal-State Standards also say:  "The aquatic habitat
which includes the interstate waters and stream beds shall not be
degraded in any material manner...  The normal fishery and lower
aquatic biota upon which it is depended and the use thereof shall          •
not be seriously impaired or endangered, the species composition           I
shall not be altered materially, and the propagation or migration
of the fish and other biota normally present shall not be prevented
or hindered by the discharge of any sewage, industrial waste or            •
                                              I
other waste effluents to the interstate waters.

       In addition to the above standards, other commonly accepted
levels necessa.ry to protect aquatic life have been recommended.
Other parameters and their concentrations suggested in the FV/PCA report on
Water Quality Criteria as necessary for the protection of aquatic          tm
TifeTIreTcadxaTun"(oTo02 mg/l), copper (0.008 mg/l), lead (0.03 aig/l),    I
K3AS (0.2 mg/l), nickel (0.1 mg/l), and zinc (0.003 mg/l).  The
California i^te_r__Quality Crite_rj.a publication lists an aluminum
concentration of 6.67 mg/'l as being a maximum for the protection
of stickleback fish.

       A value of 0.01 mg/l for phosphorus has been used, based on
the widely accepted observations by Sawyer (l95'0 •  He found that
this amount was required for the production of algal blooms at the
start of the growing season when all other necessary growth factors
are present in sufficient quantity.  Total phosphorus values are
now used for water quality evaluation instead of soluble phosphorus
cnly, since the persulfate method employed measures ortho-phosphate,
hyclrolyzable and organic phosphorus, all of which are part of the
total phosphorus pool biologically available in lakes.
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                                        LAKE CURI>Eir.D STUDIES
Puropse

       In order to assess the effects of lake water movements on
the distribution and dispersion of pollutants in the western end
of Lake Superior, studies ".'era conducted by FUPCA personnel in  1966
and .'-95T •  Figure 1 shows the study area with lake bottom contours
at intervals of 10 or 20 fathoms.  A previous study of surface
currents reported by Ruschrr.eyer and Olson (1958) is also surraiarized
in this section.

^J-rlr1:!? feter and Tcrrperature Eocorder Studies

                                Program

       Circulation studies of Lake Superior were begun in October,
3.966.  The purpose of this study was to determine the water circula-
tion of the lake, to establish the cause and effect relationships so
as to be able to predict the movement of pollutants occurring in,
and being discharged into the lake, and to develop a more accurate
description and understanding of the physical, biological and
chemical phenomena of the lake.

       To accomplish this, seven current-Entering stations were em-
placed in Leke Superior in October, 1966.  The number of stations
set in October was limited because of logistical problems, therefore,
i.'icst of the stations (three of which were located in the study  area)
were located along the southern shore.

       In J-Iay 1967, all of the original seven stations were re-
covered and replaced and the curreut-rretering network was expanded
to a total of 17 stations (11 of which ware located in the study-
area, Figure 2)»  These stations were recovered in October, 1967.

       The current-meters wore Richardson type, self-contained  recording
instruments, clock-activated periodically (every 30 minutes in  this case),
recording directional and speed data for one joinute on 16 r-.ji film then
shutting off until the start of the next cycle.  At each station current
ueters were suspended at depths of 30, 50, 75 ar.d 100 feet and  every  100
feet thereofter.  Touperature recorders were also intalled ot these depths,

                        Factors Governing Water Circulation

       The ipajor factors governing vater circulation in Lake Superior
are:  the over-lake winds, density differences arising from water tenpera-
ture differences, the gradient flow of inflowing stranns to the outlet at
Sault St. llarie, and be.i-or.otrie pres&m-e differences o\er the lake.   Of
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these, the winds ever the lake are the most lupoi-carvc factor.  The flow
itself is modified by various factors:  the rotation of the earth
(Coriolis force), the shape of the lake basin, local bottom and shore       _
topography and bottom and internal friction.  For Lake Superior, the        I
dimensions of the basin and hence the scales of flows are sufficiently
large that the Coriolis force is important; for smaller lakes this
force can be ignored.                                                      • I

                              Winds

       The wind data collected at the current metering stations shows       |
that the speed of the lake winds is higher than the land winds by nearly
a factor of 1.5 and that the average directions vary,  The average wind     _
velocities observed (l4vy - October 1967) were about 20 knots.  The data     I
shows that surface currents in Lake Superior flow approximately 30° to
the right of the mean wind direction and current velocities were about
2 percent of the mean wind velocity.  (O.k knots.)                          I

       In consideration of the above information it should be pointed
out that most of the stations were located fairly close to the shoreline    •
and thus the currents were affected to some degree by the shore.            |

       In cor._ ii'ing the nuluth wini dit';. . nd wjivl d-ita f'roT. st'.tion 1,
it was apparent that the height of land along the northern shore
affected the da.ta.  V.lien the wind at Dulutn was from the west the wind
at station 1 was from the east.  This was probably the result of a         —_
zone of low pressure being created as the west wir.d passes ever the         •
higher land, which pulls air in Crcm the lake,  ulsc, the higher land       ™
tends to channel the winds so that they tend  to parallel the shore at
station 1.  V'ir.d velocities ever the lake ranged from 0 knots to over       I
60 knots during the period of record.  V,rhi.le the data has not been          I
computerized as yet, the moan lake wind speed is about 15-20 knots.
The estimated speed of lake winds is about 50 percent of the land           •
wind up to about 25 knots after which the percentage appears to drop.       •

       Winds were also observed to have a marked effect upon the
thermal structure of lake, particularly in the Duluth emca^ient.            •
Upwellings along loth the north and south shoreline are related to          •
the wind regime.
                                                                            I
       Lake Superior is a lake having a  surface temperature above          •

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hypolimnion.  The layer separating the epilinnion and hypoli;r:nion,
a region where a rapid temperature change takes place, is called the
Ihennocline.  The thermocline begins to develop in mid-June.  The
epilinnion reaching its maximum temperature (heat content) in late
August.

       From July on, major drops in temperature occurred periodically
at stations 3 and 4 which ware due to upwelling caused by winds.
Winds iron the southwest to north caused upwelling along the northern
shore line (station L) ^nd winds from the south to west caused up-
welling along the south shore (station 3).  Wind speeds on the order
of 10 knots or above will cause upwelling.

       In the winter months the lake again becomes stratified.  At
this time the bottom layer will again be made up of water that is
denser than the surface water.  Its minimum temperature, however, will
be a few degrees above 0°C while the surface layer nay cool to 0°C.
Thus in winter there is a layer of warmer, but denser bottom water and
a colder, but lighter layer at the surface.

                         Circulation

       The net circulation in western Lake Superior is iruch like that
found by Ruschmeyer and Olson in the summer of 1957 (see Figure 3). A
net flow towards the southwest occurs along the northern shore, with
some of it breaking away in the area of Grand :!arais and Isle Royal
and flowing southward until it joins a flow to the east.  The southwest
flew along the northern shore continues until it is deflected in the
vicinity of Duluth.  A strong flow develops along the southern shore of
the Duluth cmbayment.  Tn order to maintain fluid continuity, this is
caused by the southern shoreline having a much more gentle slope than
the northern shoreline.  V.T.cn this flew reaches the Apostle Islands,
part of it is deflected northward because of the t-hcal which extends
northeast of the Islands; as it flows across the shoal area, eddy3
appear to develop.  These eddys become incorporated in the drift along
the Michigan shore.

       Tho surface water of Lake Superior can respond rapidly to wind
stress.  A current change in less than six. hours is-cordon in mid-lake.
In inshore areas the response can be more rapid.  The net circulations,
while on a long-term basis may be considered to be the circulation of
the lake, exists for only short periods of time.  Cne week would be
considered a long psricd of time for the net circulation pattern to
be operating.

       In profile the current speeds decreased with increased depth
(Figure 4), however, near the ICO foot depth a velocity increased
occurred, which is related to the depth of the thenviocline.

       P.usclrieyer and Olson (195") determined the currents in Lake
Superior using drift bottles and the dynamic height method for the

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evaluation of bathythermograph records.  According to their findings,     ^m
currents travel down the north shore of the Lake in the vicinity of
dilver Bay, Minnesota.  The drift of the current is southwest and          •
sweeps around to the Wisconsin shore, past Port "ing, Wisconsin and        |
into the Apostle Islands.  A counter-clockwise current forms an eddy
between Port Wing and Beaver Bay, Minnesota.  Drift bottles near the       •
Minnesota shore were not caught in this current as often as those set      I
adrift nearer the center of the Lake.

       Figures 5, 6, and 7 show the surface current patterns for the       I
dates of July 29-30, August 15, and August 29, 1957.  The drifts of        •
the currents during this period were computed from bathythermograph
traces referenced to the 61 meter decibar.                                 •

       A logical assumption is that if the counter-clockwise current
is net a seasonal condition some concentration of nutrient and other       »
materials would build up nore in the bulk waters of the Lake.              •

                      Inertia Currents

       Inertia currents were a commonly observed feature in western        •
Lake Superior throughout the period of record.  These circular water
motions are usually imposed on a net flow circulation, have a 16.5
hour period and are the result of decaying wind stress.  This motion
is necessarily anticyclonic (clockwise).
*;
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                                 LAKE SURVEYS, 1966-196?
        The  analytical  results  obtained on two  deep water cru.iees in
 Lake  Superior show several  high values en some parameters.   The  first
 of  these  cruises  was made during October end Kovc-nber 1966.   Sump] ing
 stations  are  sho'.vn in  Figure 3, and results  are listed in Table  6.
 This  cruise showed two high value,3  for copper  - a value of .037  mg/l
 at  Station  2  and  a value of .036 r.ig/1 at Station 3 (See Figure 9).
 These stations are respectively on  the north shore of the lake in the
 vicinity  of the French River,  and on the South Shore  near Port Wing,
 Wisconsin.  Both  stations,  however,  are located in the same  current
 pattern as  described in the section on currents.

       Notable concentrations of total phosphorus were also found
during this cruise.  All samples contained at  least 0.010 ng/1
total phosphorus.   The highest  concentration (0.016 mg/l) was
found in bottom samples collected near the Apostle Islands.

       The second lake survey cruise took place during l-'ay and June,
1967.  Sampling stations are shown in Figure 10 and analytical re-
sults are listed in Table 7.  A high value for copper was again
recorded.  A copper concentration of 0.113 n\g/l was fourd northeast
of the .Apostle  Islands (Figure  9).

       Total phosphorus concentrations ranged  from 0.003 ng/1 to
0.104 mg/l.  The 0.104 ng/1 value was observed in the  surface
sample from Station 4.  Samples having a concentration of total
phosphorus greater than 0.01 mg/l were encountered in  an area from.
Pert Wing, Wisconsin to the reach of the Minnesota shore between
Beaver Bay to Grand Marais, Minnesota. Sora1? phosphorus i^esults in
excess of 0.01 mg/l were also encountered along the South Shore of
the east end of the lake aad in White fish Bay,  Mid-depth samples
showed high phosphorus values east of the Apostle  Islands, north of
the Kewcenaw Peninsula and along the Michigan  shore east of
l-'unising.  High bottom values were encountered in the  eastern por-
tion of the lake and Whitofish  Bay.

       High lead concentrations were found along the Minnesota
shore, east of the Apostle Islands, north of the KeweGnaw Peninsula,
and east of I-'unisir.K, Michigan.  The^e readings were from  .017 to
.306 mg/l.

       Zinc in concentrations greater than .03 rcg/1 were found off
the Knife River in Minnesota, off Port Wing, Wu.ycor.sin, oouth of the
Apostle Islands, off Orand Marais, Minnesota,  around  the Ksweer.aw
Peninsula, east of Munising, Michigan, and in  Wnitefish Bay.

       Results of all the cf.'ner parameters tested were found to be
below those criteria usually citod for protection of aquatic life.

                              21
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                  1967 PRELIMINARY STUDIES
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       The initial observations of the Reserve Mining Company's
taconite palletizing operation at Silver Bay, Minnesota were made         •
on Ray 12, 196?.  A routine recoravaissance flight was conducted en        |
that date along the north shore of Lake Superior.

       Color slides were taken of the taconite pelletizing operation      •
from various angles with emphasis on the material being discharged to
the lake.  Solid waste material is discarded as an aqueous suspension
after the magnetic separation of the taconite ore has been made.          I
This waste material is conveyed by a flume from the mill or plant to      I
the lake shore where it forms a delta.  Large (up to t") granular
materials deposit near the end of the flume and lighter solids and        •
suspended materials carry over the delta to the lake.  The flume has      |
to be extended or relocated as the solids build up on the lakeward
end.

       On this date "green water" was not observed in the lake at
any noticeable distance from the shore.  A green-colored interface       _
between the gray of the delta and waste discharge stream and the          I
blue of th-3 lake could be seen.  This green interface was not over        •
20 feet wide and was only in the area where the discharged material
entered the water.                                                        •

       The plane was in the vicinity of the plant for about 20
minutes during which period the whole complex was circled about five       _
times at different altitudes.  At no time was there any evidence of       •
a green color other than at the waste-lake interface.                     ™

       Ground reconnaissance on May 24 did not show any "green water"      •
in the vicinity of the taconite pelletizing operation at Silver Bay,       •
Minnesota.
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                       is charge Survey, Sejjjefflber-Cctobejr, _lj?6_7.
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       During the periods, September 14-22, 196? and October 23-2?,
1967, the water quality of Silver Bay was investigated by personnel
cf the Chicago Program Office,  On September 15 and 19, 1967, water
samples were collected at various sites in Lake Superior in the
Silver Bay area (See Figure 11).  Six, one-half gallon, polyethylene
containers of water were collected at each station.  Five of these
wore preserved with chloroform, nitric acid, sulfuric acid, formalin
and rr.erthiolate.  No preservative was added to the sixth portion.
Sanples were collected at the followirg stations:

   Station 1.  - Lat.  47° 17' 41"   lake Superior about 30 feet
                 Long. 91° 14' 46"   from the waste disposal area.

                 Date: 9/15/67
                 Depth of Sample:  20 feet
                 pH:   8,0

   Station la. - lake Superior at the sj.irfac_e_ at Station. 1 .

                 Date: 9/15/6?
                 Water temperature:  12 °G

   Station 2.  - Lat.  47° 18' 00"   Waste discharge, a short dis-
                 Long. 9-1° 14' 40"   tance north of Station 1.

                 Date: 9/15/6?

   Station 3.  - Lat.  kl ' ltf> 30"   Lake Superior at a site between
                 Long. 9.1° 14' 10"   the northern pai^t of the waste
                                     area and a nearby island.
                                     10 feet
                                     4.5 meters
Depth of Sample:
Secchi reading:
Water temperature:  14°C
cH:  6.8
   Station 4.  - lab.  47° 18' 00"   Clear effluent entering by
                 Long. 91s 14! 46"   pipe northern waste area
                                     west of Station 3•.

                 Date: 9/19/67
                 Water temperature:  17°C
                 pH:  7.0 "
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                                            23

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Station 5.
   Station 6.
   Station 7.
Lat.  47° 17'  05"
Long. 91° 11'  15"

Date: 9/19/6?
Depth of Sample:
Secchi reading:
Water temperature;
pH:  7.3

Lat.  47° 14!  48"
Long. 91° 15'  30"

Date: 9/19/6?
Depth of Sample:
Secchi reading:
Water temperature:
pH:  7.8

Lat.  47° 11'  52"
Long. 91° 17'  42"

Date: 9/19/6?
Depth of Sample:
Secchi reading:
Water temperature;
pH:  8.0
                                     Lake Superior east of the
                                     waste disposal area.
                                     36 feet
                                     12 meters
                                     13 "C
                                  Lake Superior,  south of
                                  Station 5«
                                     40 feet
                                     13 meters
                                     13 °C
                                  lake Superior,  south of
                                  Station 6.
                                     40 feet
                                     13 meters
                                     13 °C
Observations
       The "green water" area was definitely visible on September 19,
1967; September 22, 1967; and October 25, 1967.  Aerial observations
on September 22, 196? indicated that the "greenish" colored area ex-
tended from the vicinity of the waste disposal area of the Company
westward to at least the Split-Rock Lighthouse.  A similar observa-
tion was reported by Putnam and Olson (I96l) on September 13, I960.
On September 22, 1967, the green colored area appeared some distance
offshore to the east.  The "green water" was particularly apparent in
Silver Bay.  It began at the waste disposal area and extended west-
ward for son.e distance.  Some of the "green water" curved to the
right into Silver Bay and some continued westward discoloring a por-
tion of the Lake proper.

       On October 22, 1967, windy weather occurred in the Silver Bay
area.  Waves were beating the western snore and the waste disposal
area of the Company.  Although the weather was too rough for aerial
reconnaissance, observations were made along the north shore of Lake
                              24
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Superior at various sites scattered between Palisade Head, located
a few miles northeast of Silver Bay, and    Duluth.  The "green
water" was very much in evidence.  It was more pronounced than it
was on September 22, 196?.  The line of demarcation between the
"green water" and the natural blue water of Lake Superior was dis-
tinct.  This "green water" extended from the waste disposal area of
the Company westward to Gooseberry River.  In most places it ex-
tended two miles south-eastward, from shore.  It was not in evidence
north of the waste disposal area.  Looking south-west from Palisade
Head, note was made that the "green water" began at the waste dis-
posal area and extended south-westerly from that point.  Putnam and
Olson (1961) reported similar observations on August 29, I960.

                   Results and Discussion

       Biology - Phytoplankton samples collected on September 15
and 19, 19&7 were analyzed by the personnel of the Chicago Program
Office during the latter part of September 196?.  The samples taken
at Stations 1, la, and 2 were too turbid for plankton analysis.
Data or. phytoplankton analysis of samples collected at the other
stations are shown in Table 8.

       Few numbers of any one phytoplankton group were taken at
the stations.  Green coccoids were the most abundant at each sta-
tion.  Centric diatoms ranked second.  Scenedesrais ranked first in
numbers taken.  Other genera in order of abundance in the samples
included C\^cJU^eJQa_::Ste-pJiaj2cd4£c_u3, Sy_n_e_dra, unidentified green
coccoids, KMz£solenia:, PJ£°j^£yj2S.j "i.t'/jchia, Eu^lena, Tejtrastruin,
and Golenkini§_.
                 ~  Data on the chemical analysis of the samples
are found in Table 9.  Excepting the sample from Station 2, concen-
trations of copper in the samples ranged from 0.04 to 0.10 mg/1.
These concentrations exceeded the Federal-State standards.  Zinc
concentrations in all samples except that from Station 1 ranged from
0.03 to 0.10 rng/1, which exceed the value corrraonly accepted as
necessary for the protection of aquatic life.  The fact that both
copper and zinc occurred in the samples at or above criteria neces-
sary to protect aquatic life indicates that their synergistic effect
upon fish and aquatic life in the water should be considered.

       According to Dr. Donald I. Mount, Director, National Water
Quality Laboratory, Duluth, 1'innesota, who reviewed the chemical
analysis of the samples, there was sufficient copper in Samples 5,
6 and 7, taken several miles from the discharge, to cause toxicity
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                  Significance of Findings
ordered at the same time follows.
                              26
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to numerous animals and at least 3 and possibly 4 times the amount         •
necessary to totally inhibit reproduction of fish species.                 •

       Jjip'ht. Ferietration - Secchi disc readings obtained at                _,
Stations 3, 5, 6, and 7 were 4.5m, 12m, 13m, and 13m, respectively.        •
In the "green water" at Station 3 the light penetration was only           ™
4.5m, whereas, in the natural blue waters of the Lake at Station 5
further eastward, the light penetration was 12m,  This indicates           •
that the turbidity of the "green water" may be reducing the light          •
penetration in the water of Lake Superior.

                                                                           I

       Analysis of phytoplankton samples did not provide much in-          _
formation on the pollutional effects of the wastes.  Few numbers           •
of organisms were recorded at the stations sampled.                        ™

       Ch.eirj.cal analysis of the samples revealed concentrations of         H
copper in excess of Federal-State standards and copper and zinc in         |
excess of levels considered as necessary to protect aquatic life.

       Secchi disc readings at most of the stations indicated that
material in the "green water" reduced the light penetration into
the water of the affected part of the lake.                               —^

       In view of these findings, further study of this problem            •
was deemed necessary and another field survey was ordered which is
described in the next section.  The in~plant study that was also           •
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Introduction

        On May 7 and extending through tky 10; 1958. an in-plant  survey
of reserve Mining Comrc.ny ' s liruid ar.d solid process vas1.es was corducted
bir both the Bureau of Mines and F'.TCA.  The purpose of this survey we-.s to
determine the waste load ce::r.~ discharged to La^e  Superior by  the
Co'"oanv and to determine 'it \.'liich "ooirit in the pelletizing process the
f.-r^atest pollutioral load occurred.

       UiLg^Pr oce 3 sand PlsnSa-rplin- Po irrts
       The  Reserve Mini eg Company processes tacoriite ore into pellets
 containing  over  60%  iron.   To produce one ton of pellets approximately
 three tons  of  crude  taconite  must be  ir.ined and processed.   The soui^ce
 of raw taconite  for  the  Reserve  Mining Company's Silver Bay operation
 is the Peter Mitchell  mine in the Mesabi range near Babbitt,  Minnesota.

       The  ore is blasted loose  and ground to less than four inches
 (-'4-") in disaster by dry crushing before shipment by rail to Silver
 Bay.  Calcium  chloride is added  to the ore in the winter to prevent
 its  freezing in  the  railroad,  cars. At Silver Bay, the cars are
 unloaded and the ore is  reduced  to -3A" size by successive dry
 crushing and screening.   The  ore is then sent by conveyor to the rod
 mills.

       The  closed-circuit rod Kills reduce the ~3/V' ore to a -10
 me:;h size at the rate  of .1.00  long tons per hour.  The discharge
 fro;a the rod nills is  fed to  cobbing  T.agaetic separators.   These
 separators  furnish feed  for tvo  ball  mills.  The cobbing magnetic
 separators  produce tailings which comprise the first liquid waste
 that can be conveniently sampled.  The ball mills reduce the -10 mesh
 fc-cd to "325 rr.esh.   Feed fron these ball mills goes to a battery
 of belt -type niagnebic  separators.  The second source of liquid waste
 ir; at the tailing end  of these separators.  Magnetic material from
 the rougher magnetic separators  is fed to sumps where '?•.*. <;-U'V'S
 trc-nsfer the ore concentrate  to  cyclone classifiers.  The ore con-
 centrate is then classified,  the oversize being fed back to the
 lif-^d of the ball mill'.

       The  concentrate containing approximately 5o/o iron is fed. to
 two primary siphon sizers  or  de- si infers.   These "de-sliming type"
 separators  are each  equipped  with a magnetic coil.  Underfeed from
 these de-slir.ers is  pumped to finishing magnetic separators.   De-
 r;liming overflow is  the  third source  of liquid industrial waste
 that can be conveniently ssr.-pled within the plant.  The finishing
 r.'; gnetic separators  each tmve a  cop.? city of 28 long-tons per  hour.
                                            2?

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       Concentrate from the finishing magnetic  separator  goe.3  to        ^H
"thickener-type" separators.  Overflow fron these  thickeners  is
discharged as tailings and is the  fifth  conveniently located  liquid
industrial waste in the plant.  Concentrate from the thickeners            •
goes to a disc-type vacuum filter.  The  filter  cr,ke  produced  con-         B
tains approximately 65% iron and 10$ moisture ar.d  is discharged
to a conveyor for transportation to the  taconite pelletizing               tt
plant.  No liquid wastes are produced from the  remainder  of the            |
pelletizing operation.  The travelling-grate pelletizing  machine
has a capacity of 120 to 1^0 tons  per hour.  After the  pellets            M
have been ignited, they are cooled by air.  After  air cooling,            •
the pellets are fed to a vibrating-screen  classifier and  sent  by
a conveyor system to pellet storage-for  subsequent shipment by
lake ore boats to steel mills.  The liquid wastes  including that          •
from the five sources mentioned are combined and discharged to the        •
lake at the shore.  A large delta  has been formed  fron the larger
particles settling out as the waste discharge flows  over  the  delta
into Lake Superior.
        xne liquid samples  for the  industrial waste  survey were collected
in new. rectenguiar five-gallon  carboys.   These  carboys  were constructed
from linear polyethylene.   I Jo preservatives were added.   A pilot plant
operates for four days and  on the fifth day it is set  up for the next
week.  Hie main plant operates 2h hours a  day seven  days a week with only/
a couple of off-days ~oer year.   Samples were composited  over an eight-hour
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<_u ^w i i.^.j.'v.. W-L sj- i. -L ~* •- -C'vj' n i.-"^. -i. j t^T*.™ t  ot~-.-..j_.>a.cro  K I;;A. e: w w-'__._,' wo .L oc:u.  \j v ^ JL  '-'.a  r~.~ j. ^J i v — u.^ uL,^^^^
period (one ore sample every  two hours)  in the pilot plant and  over a      •
four-hour period in the main  concentrator buildir-fc.  Dnp] icate liquid sariplPb

                                                                            I
were obtained for the Bureau of Mines.
        Intake water1 samp3.es were collected on  sampling  days  and split.
Those split samples were preserved with sulfuric acid; nitric acid,
chloroform, formalin, and merthiolate depending upon  the  analysis to  be     m
performed.  A rior-presorved split sample was a3.so prepared  for each         •
composite,  F3.y ash samp3.es were collected on two days.   These were taken
from the discharge l.'.no from the power house at the point where the line
discharged into the .launder in the concentrator building.                   I

        Twenty gallons of r,~mple were collected from  the  Fast launder
(firme) for bioassay work at the "ational Uater Quality  Laboratory.   This
sample was not representative as it was collected at  the  surface using a
rope and bucket.  It may be assumed that the larger solids  were not co3.1~.

        See Tables 1, 2 and 3 for location of stations and  information     •
on samples collected.                                                       ^
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Results
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        Table k- presents the analytical results  of  composite  samples  of
           .1 from  tho 7 )i I"31 Feed C
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              cadr.iu'Ti.  nickel,  •sine,  lead,  rhror.-ii.un and tro.c
              Quantities  of the primary constituents of the ore entering "lie pL.irt and
              wastes  lea\in- the plant are  as follows:
                                        Percent Total Solids
        Cons t ituert

        Silica               .    1*5.3              67.1  (67.6)*
        Calcium                   0.7               1.1  ( 2A)
        Iron                     UO.T              26.8  (l6.8)
        Vanganese                 0.7               0.8  ( 0.5)
        Alumnura                 - 0.9               0.6  ( 0.2)
The values in parentheses  are  Bureau of L'ines results obtained by totaling
the results of analysis  of the several individual samples.   The other
   suits were obtained  fron a composited sample.
        Table 5 presents  the  analytical results of composite water samples.
Collected volunes were  proportional to the flow at each step in the con-
centration process.   Dissolved solids ranged fron 38 to 192 ng/l and
suspended solids ranged fron  530 to 27>510 ir^/1.  There was a wide range in
turbidity values which  varied fron 96 to 9;500.  Arsenic values ranged from
0.003 to .160 ra/l  in the process sarvples end the arsenic values for the
two flyash sarroles  were 0.620 and 0.660 rr£/l.   Phosphorus concentrations
rai-ged fror.i 0.15-1- to  19-7 "-S/1-   Iron,,  nickel, zinc, lead end aliyainum
results show the wioest spread of all the r.etals in the process samples.
The other parameters  tested showed only sr^all differences in concentration
throughout the plant.

-c: e 111 ing F.a t e Characteristics of Taconite 1,'astes

        Figure 12 presents typical settling-rate curves, by volume,, of
wastes from Carious points of the concentration process.  Figure 13 is a
settling rate curve,  by weight,  of siphon sizer tails.   At the end of one
day,. 700 r.2/1 of the  original 26,280 rag/1 regained in suspension.   After
four fjays, 250 nr/1 rer:.p,ir.ed  in surjp-ension and at the end of fourteen days
there was 50 !.%::/! still in suspension.   From this data one could e:;pect a
large anount of solids  to r^-r.ain in suspension and be carried OUT; into the
lake for considerable distances  before settling out.

        The U. S. Geological  Survey determined the particle-size distribu-
tion of the tailings  and  reported that 6l;' of the naterial was between h
and 62 raicrons in dianejoer and 9/'- ">"r~s less than l\- micron in diameter.  Since
60,000 long tons of this  waste is discharged daily, calculation indicates
that 9v or 5;^'-'0 3,ong tons of this discharge is less than four microns.
This material would not be hea^ enough to settle but r.ay stay suspended in
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              1963 FIELD /Cv'D LABORATORY STUDIES
                                                                      ^ ~*
Introduction

       The B-areau of Commercial Fisheries cooperated by providing
the research vessel, Siscowet, and crew for a week's study in June
(Cruise 5) and a week's study in July 1968 (Cruise 7).  F.fPCA pro-
vided the study personnel for the cruises who collected water samples
and a few bottom sediment samples for chemicaJL and biological
examinations.  Thirty-three sampling stations were established at the
intersections of latitude and longitude lines spaced one minute apart.
The latitude and longitude coordinates for these stations are included
in tables in the back of this repoi't.

       An additional cruise to collect bottom dredge seiaples and core
samples was made by personnel of the Minnesota Conservation Department
with the cooperation of personnel from the Wisconsin Department of
Katural Resources, the Minnesota Water Pollution Control Agency, Fi'.'PCA,
and the Reserve Mining Company.  The latter furnished a vessel, the
Alma, for this project.  The findings from the Alma cruise are presented
in a separate report by the Minnesota Conservation Department.
                             Benthos

       Since the Minnesota Conservation Department collected bottom
and core samples in the area in July of 1968, only a few bottom samples
were collected by CPO personnel on Cruises 5 and 7 of the Siscowet.         B

       Table 10 and Figures Ik and 15 show the benthic organisms
collected during Cruise 5 °f the Sj^scjDweJ;.  Samples from five of the        •
nine stations collected below the waste disposal are-?, contained no          B
benthic organisms.  The samples at the other four sto.tions contained
20, 50; 90, and 200 benthic organisms per square meter, respectively.       •
These samples contained, no scuds (pollution-sensitive organisms).           |
However, at one station (Lat. hj° 3.8', Long. 91° lV ) above the waste
area, 250 of the 1,290 benthic organisms per square meter recorded          «
were scuds.                                                                 B

       Table 11 and Figures l6 and 17 show the benthic organisms
collected during Cruise 7 of the Siscovet.  All these samples were          B
collected above the waste area.  Scuds ranging in numbers from 20 to        B
120 per square meter were found in each of these samples.
       Since few bottom samples were collected, from the Si-^cowet^ during
Cruises 5 and 7> observations of the bottom types were limited.  However,
note was made that fine grey material was found in some of the samples
collected below the waste area, whereas, samples collected above the
waste area contained mostly reddish colored sand (Table 12).
                               30
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       Briefly, benthic  organisms  vere oca,'c;5 }.:\ ^u::ji::> o.:1:r.">. ;Vo.:i
stations affected by  the toconLte  wp.c tc outfall.  Pollution-sensitive
scuds were absent from  these  ScV'iples which were taken at depths
between 20 and 252 meters.

                            Fhytoplaikton

       Tables 13 and  14  and figures 18 through 23 show the species
and numbers of phytoplankton  collected at each depth at each station
on Cruises 5 and 7 of the Sis_cowet.  Table 15 indicates that the mean
surface phytoplankton population collected on Cruise 5 w?-3 about 100
per milliliter and that  of  Cruise  7 was about ISO per nilliliter.
These figures compare quite well with  the mean population recorded at
widely scattered stations in  the main  part of Lake Superior in the fall
of 1966 and in the spring of  1967• These populations were about 50 and
about 250 per nilliliter, respectively.  Small populations of plankton
are frequently found  in  deep,  clear, cold,  oligotrophic lakes having
small amounts of nutrients.

       §2£;£l£:;lSJiiLl^ a Sreen coccoid, vss the most dominant genera
noted in the samples.  ^!J-tzs_chi_a,  a peonate diatom,  ranked second.
       Generally speaking,  the  population of phytoplankton decreased
somewhat with an increase  in  depth  (Table 16).   On Cruise 5>  the mean
population of the  surface  samples was  about 100 per mi111liter,  that
for the mid-depth  was  about 80  per  rnilliJ.iter and that of the bottom
was about 70 per milliliter.  The mean of populations recorded on
Cruise J, a month  Hater, indicated  a slight rise in populations.  The
mean of the surface sonples was about  .1.80 per milliliter,  that of the
mid-depth samples  \fas  about 100 por milliliter,  and that for  the bottom
samples was about  90 per milliliter.   So.-'e ir.cres-Te in water  tereera-
tures during Cruise 7  as compared to tho.se of Cruise 5 --ray account for
this increase in population.  Sc.3 Tables  12 and 17.

       The ohytoplanktcn popalatioiis above the wiste disposal area did
not differ greatly from the populations below the waste dia-posal area.
The mean of surface samples collected  at  seven stations above the waste
area on Cruise 5 was 103 per  milliliter,  and -the mean of surface samples
collected at 20 stations below  the  waste  arc-a was 98 par millilitor.
A similar condition was noted du~cing Cruise 7 wlv.re the mean  of  surface
samples collected  at nine  stations  above  the waste arc-a was 1'V)-  per
milliliter,  and the mean of surfe.ee samples collected ,?.t 19 stations
below the waste area was 203  pei* Milliliter.
                                31

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                        Surc.ary, Biology
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       Although the number of bottom samples collected on the two
cruises of the Si_scowet_ were limited, it should be noted that benthic       M
orgcaiisms were found in only four of the nine stations sampled below        •
the waste disposal area.  Pollution-sensitive scuds were not found
in the sample.s collected below the waste area.  Each sample collected
above the waste area contained a. number of benthic organisms, and           I
scuds were found in each of these samples.  There was little differ-        •
ence in the numbers of phytoplankton col-lee tod above and below the
waste disposal area.
                                                   I

cowet_ Cruise 5 Findings                            I
       The analytical results from Cruise 5; made in June 1968, are
presented in Table IS.  .Figures 2^, 25 and 26 show cross-hatched            •
areas where the iron concentrations approached or exceeded  the Federal-     •
State standards of 0.3 mg/1.  Iron concentrations increased from top
to bottom.  There was one high value at the surface in the sonth/estern     •
corner of the area sampled.  One high value was observed at mid-depth       |
cut about two miles from shore southeast of the Company.  Figure 26
shows very high iron concentrations over the ma.jor part of the sample
area near tha Lake bottom.  The highest values were in close p^::xlnity
to the Company's property.  How far these high concentrations may extend
out inb-j vie lake is not known because samples were not taken to the
south-east beyond the area shown by the cross-hatching.  These iron
valu.es were ten or twelve times higher then those observed in the lake-
wide survey made in May ar.d June 1967.  Concentrations observed in this
area in June 1953 were much lower than those found in the sano area in      •
September 1967.                                                             |

       Manganese concentrations were the highest in the near vicinity
of the Reserve Mining discharge, increasing toward the Lake as shown in     •
Figure 27.  All the values were veil belcw the Federal-State standards.     ™

       Distribution of aluminum values in the sampling area of Silver       •
Bay is shown in Figures 28, 29 and 30.  The shaded areas indicate those     I
areas where the aluminum concentrations exceeded 0.07 mis/J-.? khe value
for protection of aoj:.atic life eit-;:l In tho 'luufoviTia 21"->^"> £}V-V-JiL        •
J^jL!;^:' '--2.'  •'-"'"-£ -oaceritraticns incre^ed from top to bottom end wove the     •
highest near Reserve Mining.  Surface samples exceeding the value of
,07 mg/1 were scattered throughout the area, but the mid-depth samples
exceeding this value covered a large area north end east of the Company's   •
property.  Very high cone soorations were observed over most of the area     •
in the bottom water samples with the highest values found near Reserve
r-Lrnir.g and about a mile south near  the shore.  The ehe?,iical form of the     •
aluminum was not determined.                                                •
                               32
                                                4
                                                   I

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*
       Those areas where  l..".id  values  met  or exceeded the federal-
State standard of 0.05 mg/1 are  shown by  the shaded areas in Figures
31, 52 and 33-  Except Tor the fe..r  shaded areas  there was little
variation with depch.  The concentrations were about the sane as
•ohose Toimd in the some area in  September 19o7,  and differed little
from values recorded for  the open Lake in May and June 1957 •

       The shaded areas shown  in Figure 3^ contain those stations
where the levels of copper exceeded O.C03 mg/l,  the level commonly
accepted for the protection of c.quatic life.  Most of this area also
exceeds the Federal-State standards.   A large area starting about
o:ie~half mile south of the Comp;iny  and extending about three miles
s ;'ir(,hward and out toward  the lake exceeded this  value.  The values
observed in the Silver Bay area  were  auch greater than those observed
out in the bulk waters of the  lake  in 1967.  Concentrations observed
in this area in Septen.ber 1967 were three to twelve times higher than
those found in June 1968.

       It can be seen in  Figure  35  that there were two sampling
stations where the zinc values exceeded the 0.03 !^S/1  value commonly
accepted for the protection of aquatic life.  Some of the concentrations
observed out in the bulk  waters  of  the lake in May and June 1967 were
higher than those obsei^ved in  Silver  Bay  at this time, but much higher
levels were found in Silver Bay  in  September 1967 as previously dis-
cussed.

       Figure 36 indicates three stations where  values were observed
which cqup-led the cadmium level  of  0.002  mg/1.  This value has been
cited as the amount recmircu to  protect aquatic  life but is well below
the Federal-State standard for domestic use.  Cadmium was not detected
out in the lake in May and June  19&7  or i"n '^-s Silver Say area in
       Figure 37 docs not show any 'nickel  concentrations  above the
0.1 mg/1 criterion.  Concentrations  observed in  the Silver Day area
in 1963 were about the sans as those observed in the Silver Bay area
in 1967 and in the previous lake  sircveys.

       According to the Federal- State standards,  hcxavalont chromium
should not be present in tho lake in excess  of a trace.   ;\ ..r.?.jo is  any
thing above O.C03 mg/1 according  to  Standard ^thjods_.   Figure 38 shows
total chromium values up ~oo five  tines  this  amount in the study area.

       Standard i^ecliods_ also states  that chromium may exist in water
supplic-s in both the hexavslent and  t?.*ivalent forms although the tri-
valoat form rarely exists in potable water supplies.  In  view of this
state.-. ent the total chronv.rri values  found  i;ay be significant foi* both
the fisheries and domestic use p?,rticu.larly  if they shouJLd be cai-ried
far c-ncugh to influence a weter supply.  IJ";-:ava.l3iit f.hro;.iiiui was not
dotsr'vlned since poa] ysis :~v:r:t bo, "cco^plinhed during the <3uy of
coll :c lion c'.l thc-:e :;:-; .p1 cv: :r;v..i3 in trcnsit for 307Gr^l  dr-.-'s.
                                           33

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                                                                            I
       No chromium was detected in the Iy66  or  19t>7  lake  survey
samples or in the Silver Bay area in the 19^7 study.                         _

       Figures 39, ^0 and 4l show shaded areas  where the  phosphorus          •
concentrations exceeded 0,01 ng/1.  Ilearly the  entire sampling  area
exceeded this concentration in the bottom water.   The phosphorus             B
concentration increased from top to bottom,  Surface and  mid-depth          |
values closely matched concentrations foucd  throughout the  Lake but
the near bottom water values were abou.t five to ten  times higher             mm
than those observed in the lake in May and June 19o7«                       •

       Figures ^2, k-3 and hk illust?.'a'te those areas  where suspended
solids exceeded the values normal to tha major  portion of the lake.          •
Suspended, solids increased from top to bottom.  In near-bottom  water        •
tliere was an area extending from Company property  to the  south, which
had suspended solids ranging from 13 to 3.1 mg/1.   Samples collected          •
in this area in September 19^7 had about the came  amount  of suspended       |
solids as those collected in June 19o8.

       Figaro ^-5 shows the area at the surface  whei'o the  turbidity
was greater than one turbidity unit.  Figure h6 shows the area  at
mid-depth where the turbidity was greater*  than  one and Figure k-J
shows the area in the bottom water where the turbidity exceeded ona.
Turbidity values increased from top to bottom.  Tie  values  in the
bottom water were ton to sixuy times higher  than at  the suvface.
Surface and mid™depth values were about tha  some as  those observed
out in the lake in 1'ay and June 19^7, ~nd  the bottom water  values            •
were two to forty times higher,  Tne 1968 turbidity  levels  wore two
to six times higher than those of September  19o7-  Trie highest  values       mm
occurred in the vicinity of Reserve ILining ss.3.  extended southwai'd.           •

       Figure ':3 presents tho .average aj'cenic values  oboerve-1 in
June 1968.  Tli33a values are about one-third to one-fifth of the             I
Federal-State standards.                                                     I

                    S_is^jjv_et Cruise 7 Findings                               •

       Tiie analytical reoults from Cv'iiso 7, vhich WJLS made in  July
1968 are presented in Table 19.  Par-meters  which  .;kovod  lit..-.le vurintion    —
horizontally or vertically were not shown in figures.  Iron results  are      •
shown in Figures -$, ^0 and 51j and those areas whe^e the total-iron        ™
concentrations approac'ied or exceeded the Federal-State standard of
0.3 mg/1 ere defined.  The bottom water samples were the  only samples       •
which contained total-iron concentrations above this  level.  The area       I
which exceeded the standard WPS a band about a  mile wide  on the outer
edge of the area sampled end extended from Reserve Ui.aing south to           mm
Split Rock Point.  The highest values were at the  northern  end  of  this       •
band and wore three or four "hcu-'ani t"5r,c-o high'r  "*•;:•:-'! i-hr-  h1g?i,3t v'J.ui
observed in the lake' in k'ay ar.d June 1967 and in Silver Bay in
September 1967.  The concentrations increased from  top  to bottom.
*

  I

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'rlie June concentrations were up  fco four times higher than those for
July.  The reason for the lover  values in July are attributed to
tcr.porarily curtailed operations "by Reserve Mining.  It was noted
that Reserve shut down at .least  one-holf of their operation preceding
and during this sampling period.

       Stations vhcre soluble-iron determinations wore made are pre-
sented in Figures 52, 53 t'fid 5.';.  The values increased from top to
bottcn.  The highest values were opposite and south of the Company
proTK:rty.  The surface and mid-depth valiies were about the same as the
total-iron values, and the soluble-iron values in the water near the
bottom wore one-fourth the total-iron values in the bottom water.

       Total-manganese concentrations observed in the Silver Day area
ore shown in Figures 55, $6 nnd  57.  There was only a slight increase
from tot> to bottom, with the eurfe.ce and mid-depth values being equal.

       Trie soluble-manganese values shown in Figures 58, 59 and 60
were about half as high E.S the total manganese values.

       The shaded areas shown in Figures 6l, 6?- and 63 are those areas
where the total-aluminum, concentrations exceeded the 0.07 -rng/l limit
cited for protection of cq.ac.tic  life,  ITearly the entire area sampled
and all depths exceeded this value.  More of the mid-depth samples
exceeded 0.07 i~£/l than either the surface or near-bottom samples.

       Figures 6k} 65 and 66 show shaded areas where soluble-aluminum
concentrations exceeded 0.07 ng/1.  There was little variation from
top to bottom in the analytical  values.  The total-aluminum values were
approximately ten times greater than the soluble values.

       Figures 67, 63 and 69 show the lead concentrations in Cruise J.
There was little difference in lead concentrations from top to bottom.
Leal values in the Like in I'oy ?tid June 1967 were about equal to those
observed in Silver .Bay in 2,968.  '[he values from tho 1^67 Silver Bay
sampling wore tho sr-me as those from the uor.e area in 3.968.  However,
the July cT.clytieal results were slightly .less than those found in
the June study.

       The soluble-le'jd averrge values aro show^n. in Figure JO.  Tne
total-lead values were approximately five times higher than the soluble-
lead.

       Copper concentrations exceeded the Federal-State standards at
many sampling points and olso exce.-ded the aquatic life criteria of
O.OC-S rag/1 at nearly every sampling point at the surface, mid-depth
and bottom as shown by the shaded area in Figures 71 ,> 72 end 73•
There was very little difference in cooper levels from top to bottom.
The highest concentrations were couth of Silver Bay.
I

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                                                                            I
       The concentrations observed in September 19^7 were four tines
higher than those found in July 1968.  The July values were approxi-
mately one snd one -half times higher than the June values.                  I

       Soluble -copper average values are shown in Figure jh.  One
area near Split Rock Point was the only place where the 0.008 mg/1          •
value was :net or exceeded by the soluble-copper results.                    |

       A total copper concentration of 0.119 ng/1 vea found in a            m
sample of water collected by the ITational Water Quality Laboratory          I
at a point 100 feet deep and 100 feet off-shore from the Reserve Mining
Company's point of discharge.  The sariple, filtered through a O.k$          m
micron :?.e-ribrane filter, contained copper in sufficient concentration        •
to produce a toxic effect on sensitive organic- ;.i3.  Bioassays did not        ™
indicate such acute effects, however, and additional checks were made
to determine the- reason.  Filtration of a sample, originally contain-       •
ing 0.119 rag/1 of copper, through a 0.^5 r:det\,n filter left 0.051 ;;;g/l      8
of copper in the filtrate.  This sor.iple vas subsequently filtered
through a 0.1 micron filter and contained 0.036 ng/1 or 0.015 mg/1. Ics-3.    •
Following is a listing of particle size and corresponding copper con-       •
cen 'orations remaining in the filtrate.
       Total sample                      0.119
       Particles'" < 20.0 microns          0.111                              •
       Particles <. 5-0 microns           0.088                              |
       Particles < 2.0 microns           0.067
       Particles < 0.^5 microns          0.051                              _
       Far-tides < 0.10 microns          0.036                              I

       It is reasonable to assume additional particulate copper would
be removed by further filtration using a smaller pore size.  Apparently,    I
sor.e of the particulate copper is not biologically active in such short     •
tests.  The hazard, due to copper shifting from biologically inactive to
active copper should be doocr.rined ia crder to assc-oS long-term effects
'',hrxt :iight occur in the Lake.
                                                                            I

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       The criterion commonly accepted for zinc based on protection
of aquatic life is 0.03 "-£/!•  Areas '.-.-here this value was exceeded
are shown in Figures 75, 76 and 77.  In some areas the values were
higher at the top and in others at the mid-depth.  There were several
very high values at the surface and mid--depth located southeast of
the Company but no values exceeding 0.03 nig/1 were observed in the
bottom water samples,  1'any of the lake samples collected in J'ay and
June Iy67 were above 0.03 nig/1, and a few had fairly high values of
about one-third the zinc values found in the Silver Bay samples of
July 1968.  In general, the July values were higher than the June
values.

       The soluble-zinc observed in July is shown in Figure 78.
The soluble-zinc was about ore-third the total values at the points
tested.

       The shaded areas in Figure 79 represent those stations where
the total cadmium values equaled or exceeded the level of 0.002 mg/1
referred to for protection of aquatic life.  Cadmium was not de-
tected in the Lake or in Silver Ray sa.mp.les in 1967.  Cadmium was
observed in concentrations of 0.002 mg/1 at twice as many stations
in June as in July.

       Figure SO shows those stations having 0.002 mg/1 or soluble
cadmium or mere.  There were three stations just southeast of
Reserve Mining where 0.002 mg/1 of soluble cadmium was observed.
Soluble cadmium was detected less frequently than total cadmium.

       Stations where 0.1 mg/1 of nickel was exceeded can be seen
in Figures 81, 82 and 83.  This is a level of nickel commonly
accepted for the protection of aquatic life.  There were two sta-
tions northeast of the Company where 0.100 mg/1 of total nickel was
exceeded in the surface samples and one station east and one north-
east where this value was exceeded in the bottom samples.  None of
the stations at mid-depth exceeded this value.  There was neb much
difference between levels found in Silver Bay in July 1968 and those
found out in the lake and in previous Silver Pay studies.

       Values for soluble-nickel are shown in Figure ?A.  The total--
nickel values were two to five times higher than the soluble-nickel.
                              37

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                                                                            I
                                                                            I
       The total-chromium average results are shewn in Figure 85.
Soluble-chromium was not detected in ay of the samples analyzed.
Tne total-chromium values reached about the same levels in July but
were detected in fewer stations than in June.  These values are up
to five times the trace amount which is the Federal-State standard
for hexavalent chromium.  Referring to the previous discussion              M
regarding chromium in the June study, there is cause for concern in         •
these results inasmuch as most of the value could be a result of
hexavalent chromium.  Since hexavalent chromium requires analysis
the same day it is collected, it was not feasible to obtain hexavalent      I
results during this study.                                                  •

       Areas where phosphorus equaled or exceeded 0.0.1 cg/1 are shown       •
by the shaded areas in Figures 86, 87 and 88.  Both surface and mid-        |
•depth samples opposite Reserve Mining and in the vicinity of Baptism
River contained phosphorus equal to or greater than the limit.  The         •
bottom water samples equaled this value in the vicinity of Baptism          •
River.  Also, extending out two miles east of Reserve Mining and
south to Split Rock Point the values in the bottom layer were far
above the critical level of 0.01 mg/1.  Tne July levels were con-           I
siaerably lower than both the June levels and those in Silver Bay in        •
September 19^7 •  This reduced effect in July may also be associated
with the fact that Reserve !lining had shut down at least half of its
operation during the July study period.

       Trie suspended solids values are shown in FLguros 89, 9C- s^ 91-      •
In general the suspended solids were higher in Jnr.e than, in July.  Tne      I
July data did not show any definite pattern.                                ™

       Turbidity valuos ave shewn in Figures 92, 93 and 9?!-.  Some of        •
the highest values "ore in the irn^riiate vicinity of Reserve Mining.
Turbidity increased from top to bottom.  The turbidity values in the
Lake were about the same as those in Silver Bay in July at the surface      •
and mid-depth, but the bottom valuos in Silver Lay were many times          •
greater iu the vicinity of Company property.  Trie surface said mid-depth
values for the June study ware about the same £•.; in July but the bottom     _
layer values Tor June were nany times higher then those Tor the July         •
study.                                              .                        ™

       The lower suspended solids results and turbidity values found         •
in July are undoubtedly directly related to the reduced operation of         |
the Reserve Mining Co. palletising plant during this period.

       Figure 95 shows the arsenic volues observed in Cruise 7 samples.     I
One sample contained arsenic in a concentration three times the Federal-
State standard of 0.01 mg/1.  All other values were below this limit.
                                                                            I

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DOUDOROSF, P. AND M. KATZ.   1953-  Critical Review of Literature
      on the Toxicity of Industrial Wastes and Their Components
      to Fish. II.  The Metals, As Salts.  Sewage and Industrial
      Wastes, 25 (7): 802-839-

FEDERAL WATER POLLUTION C017IROL ADMINISTRATION 1963 Water Quality
      Criteria. Report of the National Technical Advisory Committee
      to the Secretary of the Interior, U. S. Government Printing
      Office, Washington, D. C.  20;r02.

McKEE AKD WOLF. 1963. Water Quality Criteria.  Pub. No. 3-A,
      Resources Agency of California, 2d ed.

PUTNAM, H.D, AND T.A. OLSON. 1961.  Studies on the Productivity
      and Plankton of Lake Superior.  University of Minnesota
      School of Public Health, 2k p. d- 1^ tables and 13 plates
      (inulti graphed).

RUSCHMEYER, O.R. AND OLSON, T.A. 1958.  Water Movements and
      Temperatures of Western Lake Superior.  University of Minnesota
      School of Public Health.

SAWYER, C.IT. 195^'  Factors Involved in Disposal of Sevage Effluents
      to Lakes.  Sewage and Industrial Wastes, 26 (3): 317-325.

STANDARD METHODS FOR THE EXAMINATION OF WATER AND WASTSWATER 1967.
      12Uth ed. A.r.erican Public Health Association, N.Y.

U. S. DEPARTMENT OF HEALTH, EDUCATION AKD WELFARE. 1962. Public Health
      Service Drinking Water Standards.  Public Health Service Publication 956.
      U. S. Government Printing Office, Washington, D0 C«  20^1-02.

WATER QUALITY STAIHDARDS FOR THE ItiTZP.STATE WATERS OF MTJINESOTA. 1967.
      Minnesota, Vfater Pollution Control Commission.

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I
                                     LIST  0? FIGURES
            Figure No.                            Title                   Page

•                1        Lake  Current Study Area                          51

•                2        Location  of Current Metering Stations            52

                 3        Direction of Net Flow                            53

I                k        Horizontal Speeds at Various Depths,
                          May-October 1967                                 5*4-

•                5        Surface Currents, July 29-30,  1957               55

                 6        Surface Currents, August  15, 1957                56

|                7        Surface Cut-rents, August  29, 1957                57

_                8        Sampling  Stations, Lake Superior Cruise,
I                         October-November 1966                            58

                 9        Lake  Superior Sampling Results - Copper,
                          October-November 1966 and May-June 1967          59

                 10        Sampling  Stations, Lake Superior Cruise,
•                         May-June  1967                                    60

                 11        Lake  Superior Sampling Stations,
_                         Silver Bay, Minn., Sept.  15-19, 1967             6l

*                12        Settling  Rate, Reserve Mining  Company,
                          Wastes                                           62

I                13        Settling  Rat 3, Reserve Mining  Company,
                          Siphon Sizer Tails                               63

J                               Lake Superior Sar.rpling Results

                 1^        Benthos,  June 17-22, 1968                       6k

'                15        Scuds, June 17-22, 1968                          65

•                16        Benthos,  July 15-20, 1968                       66



I

                                            Ul

   V-
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                                                                               I
                          LIST CF FIGURES
                            (continued)
FjLgureJKo .                              Title                  P_age_
17
18

19


20

21

22

23

2k

25

26

27

28


29


30


Scuds, July 15-20, 1968
Phytoplankton, Surface Values,
June 17-22, 1968
Phytoplankton, Mid -depth Values,
June 17-22, 1968

Phytoplankton, Bottom Values,
June 17-22, 1968
Phytoplankton, Surface Values,
July 15-20, 1968
Phytoplankton, Mid-depth Values,
July 15-20, 1968
Phytoplankton, Bottom Values,
July 15-20, 1968
Iron, Surface Water Samples,
June 17-22, 1953
Iron, Mid -depth Water Samples,
June 17-22, 1968
Iron, Bottom Water Semp3.es,
June 1.7-22, 1968
Manganese, Composite Depth Samples,
June 17-22, 1968
Aluminum, Surface Water Samples,
June 17-22, 1968

Aluminum, Mid-depth Water Samples,
June 17-22, 1958

Aluminum, Bottom Water Samples,
June 17-22, 1968

67

68

69


70

71

72

73

7k

75

76

77

78


79


80

1







|

I
•


-
1



1

1





I
•

1
                                                                               I

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I
                                       LIST OF FIGURES
                                         (continued)

        £i£&£lJ<2i                          Zil^                             £Srf£
           31                    Lead,  Surface Water Canplos,                  Ol
                                 June'l7-22, 1968
I


           112                    Lead,  Mid-depth Water Samples,                82
                                 T-    1 "~7 ^ O  1 '"/"'O

           133                    Lead,  Bottom Water Samples,                   83
                                 J-uno 1Y-22. 1968
                                 " ^     1    y  ^

           13^                    Copper,  Cornoosite Depth Samples,              8-1-
                                 June 17-22/JQ68

           135                    Zinc,  Composite Depth Samples,                85
                                 June 17-22, .1.968

           36                    Cadmiun, Composite Depth Samples,             86
•                               June 17-22, 1968

           37                    "Nickel,  Composite Depth Samples,              87
                                 June 17-22/1968

           38                    Chronluri, Composite Depth Samples             88
_                               June 17-22, 1958

           39                    Phosphorus, Surface W-.tcr Samples,            89
                                 June 17-22, 1968

•         40                    Phosphorus, Mid-depth Water Samples,          90
                                 Jur.e 17-22, 1968

|         lj-1                    Phosphorus, Bottom W-ator Samples,             91
                                 J-r.6^17-22, 1968

I         hS.                    Suspended Solids, Surface Water Samples,      92
"                               June lf-22, 1963

           1^3                    Suscv^dei Soiiclo, Lid-depth Uater Sa;;ip3.eG,    93
                                 Ji;:;o 17 -22, 19'od

           I'W                    Suspended. Solids, Bottoui I'fatei' Samples,       9^
                                 Jur.2 17 -22, • 19 6 8

           1^5                    Turbiditv, Helli^e, Surface Water San-pie,     95
                                 June 17-22, 1968
I

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Figure Kg.
                             LIST OF FIGUE3S
                              (continued)
                                                                                 I
  '46                Turbidity, Hellige,  Mid-depth Water Samples,       96       •
                    June 17-22, 1963

  47                Turbidity, Hellige,  Bottom Water Samples,          97       |
                    June 17-22, 19-58

  k3                Arsenic Average Values  for all Depths,             98       I
                    June 17-22, 1968

  lj-9                Total Iron, Surface  Water Samples,                  99       I
                    July 15-20, 3-963                                             •

  50                Total Iron, Mid-depth Water Samples,              100       •
                    July 15-20, 3.968                                             I

  5.1                Total Iron, Bottom Water Samples,                 3.01       •
                    July 15-20, 3.968                                             g

  52                Soluble Iron,  Surface Water Samples,              102
                    July 15-20, 3.968

  53                Soluble Iron,  Mid-depth Water Sorties,            103
                    July 15-20, 1968                                             •
  5^                Soluble Iron, Bottom Water Scrip las ,
                    July 15-20, 1968                                             .

  55                l-i.n5ar.Qse, Surface  Water Se,mp].es,                  105
                    July 3-5-20, 1968

  56                Manganese, Mid-depth Water Samples,               106       •
                    July 15-20, 1968

  57                Manganese, Bottom Water 3ainp3.es,                  107       I
                    July 15-20, 1968

  58                Soluble Manganese,  Surface Water Sa: voles,         108       I
                    July 15-20, 1968                     "

  59                Soluble Manganese,  Mid-depth Water Sainples        109       I
                    July 15-20, 1968                                             •

  60                Soluble Manganese,  Bottom Water Sanples,          110       •
                    July 15-20, 1968                    "                         I


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™
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            63
                                      LIST 0? FIGURES
                                         (continued)
         |Fi;,ure_o.
           '
            6l                AluTiir.un,  Surface v-ater Samples,                    111
_                            July  15-20,  1963

™          6?.                Aluninun,  nid-depth Water Samples,                  112
                              July  15-20,  1968
            63                Alu_-5inuv.,  Botton Water Samples,               .      113
                              July  15-20,  1963

|          6J-;-                Soluble  Alu^.inua, Surface Water Seoples,            llA
                              July  15-20,  1968

•          65                Soluble  Aluminum, 1 lid-depth Water Samples,          115
•                            Jaly  15-20,  1968

            166                Soluble  Alumnun, 3otta,i Water Sanples,             116
                              July  15-20,  1968

            6j                Lead,  Surface '.feter Ssir.ples,  July  15-20, 1968      117
                              Lead, Mid-depth Water Samples,                      118
                              July  15-20,  1968
            69                Load, Bottori Vfcoor Samples, July 15-20, 1968        119

            170                SolubD.e  lead,  Avarase Values for all Depths,        120
                              July  15-20,  1968

•          71                Copper,  Sui-face .,'ator Samples, J-ily 15-20,  1,968     121

            72                Copper,  Kid-iapth Water Pornples, July 1.5 -20,  1^63   122

I          73                Copper,  J;cttora >"?.ter S-tiiples, Juny 1>:-PO, 1968
                                                                                   323


            7k                 Soluble Copper, A-^raje Values for all  Dsp^hs,      124
                                              '
                               -  -I   -, -~. ' •,
                               ouly  1>--2
            75                 Zine,  Surface W-cer Sa-voles, July  15-20,  1968      125
            76                Sine, Mid-depth Water Sacioles, July 15-20,  1968     126

                                            Water Ss-ples, July 15-20, 1968        127
            78                Holiible  Zirxc,  Avsra£:e Values for all Depths,        128
                              July 15-20,  19'"8_

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                                                                                 I
                               LIST CF FIGURES
                                 (continued)

Fi-;ure ifo.                         Title                                Pa;;e
                                                                                 I
   79                 Cadr.u.ir.1, Average Values  for all Depths,          129
                      July 15-20, 1968                                           •

   60                 Soluble Cadnii;;n, Average Values for all Depths,  130
                      July 15-20, 1968

   81                 Nickel, Surface Water Scuptes,  July 15-20, 1968  131      •

   82                 Nickel, Mid-depth Water  Samples,                 132      •
                      July 15-P.Q, 1.968                                           |

   83                 Nickel, Bottoi.i 'Water Samples,  July 15-20, 1968   133      •

   Qk                 Soluble Nickel, Average  Values for all Depths,   13>4
                      July 15-20, 1968

   85                 ChrorrJ.uin, Averaje Values for a 1.1 Depths,         135      ™
                      July 15-20, 1968

   86                 Phosphorus, Surface  Water Samples,
                      July 15-20, 1968
                                                                               •^

   67                 Fhosphovus, Kid-depth Water Samples,             137      I
                      July 15-20, 1968

   88                 Phosphorus, Bottom Water Sanples,                138      I
                      July 15-20, 1968                                           •

   89                 Suspended Solids, Surface Water Samples,         139      •
                      7,.-I,. 1C- O,0  lO^'^L                                           I
                      o aJy i-5-c-'-', J->'oo                                           B

   90                 Suspended Solids, I lid-depth Water Eanpl.es,       l'i-0      •
                      July 15-20, 1968         "                                  |

   91                 SuGponded Solids, Dot ton >feter Ss.;ap].es,          !"•!
                      July L5-20, 19w3                                           I

   92                 Turbidity, Helli^e,  Surface Water Samples,       1^2
                      July 15-20, 19C8                                           |

   93                 Turbidity, Helli^e,  Mid-depth vfeter Samples
                      July 15-20^ 1968                                           .
                                                                                 I

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 I
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                                       LIST 0? FIGURKS
                                         ( c out inue d )
Page
 •         E

              94                 Turbidity,  Hellige,  Bottom Water Samples,
                                 Julj^ 15-20, 1968

 •            95                 Arsenic,  AvGi-aje Values for all Depths,           l!:-5
                                 July 15-20, 1968

 I


 I


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 I

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         Table No.
                                        LI31T OF TABLES
I

I
            2
I
            3
I

I          ,
                              Company, Water, May 7-10, 1968
|          6                 Chemical Determinations, lake Superior,           172
                             . Water, October 17 - IToveriber 6, 1966
                              In-Plant Survey (Pilot Plant),                    lUj
                              May 7, 1968

                              In-Plant Survey (Pilot Plant),                    150
                              May 8, 1968

                              In-Plant Survey (Concentrator Building),          153
                              May 10, 1968

                              Chenical Determinations, Po serve Mining           157
                              Company, Solids, May 7-10, 1968

                              Chemical Determinations, Reserve Mining           Io2
            7                 Chemical Determinations, Lake Superior,           182
                              Water, May - June, 1967

            8                 Phytoplankton, Lake Superior,                     203
                              September, 1967

            9                 Chemical Determinations, Silver Bay,              205
                              Lake Superior, Water, September 15-19, 19°7
I

I
_        10                  Benthic Fauna, Lake Superior,                     210
•                            June 17-22, 1968
           11                 Benthic Fauna, Lake Superior,                     213
                              July 15-20, 1968
           12                  Physical Observations, Lake Superior,             215
•                            Jxme l'f-22,  1968

           13                  Phytoplankton,  Lake Superior,                     223
                              June 17-22,  1968
           1*4-                  Phytoplankton,  Lake Superior,                     239
                              July 15-20,  1968

           15                  Phytoplankton,  Lake Superior, Averages,           257
                              June 17-22,  and July J-5-20, 1968

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                              T T'^fil fYu1 rnArj-i ^^
                              JJ.'.OJ. Ur .U-i_D.U.'j
                               (continued)
Table Ho.                        Title                                   Pa^e
   19                 Chemical Determinations,  Lake Superior,
                      Water, July 15-19, i.968

                                                                                   I
I
   16                 Phytoplankton, Lake  Superior,  Averages,           258
                      June 17-22 and July  15 -20,  1968
   17                 Physical Observations,  Lake Superior,             259      •
                      July 15-20, 1968
   18                 Chemical Determinations,  Lake  Superior,           268      |
                      Water, June 17-20, 1968
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                         May-Ocfobsr,  1987

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                                    18
                   SILVER  BAY
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                             LAKE SUPERIOR SAMPLING STATIONS
                                  SILVER  BAY, MINN.
                                  SEPT.  15 - 19,  1967
                                                                         FIGURE  II

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                      LAKE SUPERIOR SAMPLING RESULTS
SISCOV/ET CRUISE 5, JUNE 17-22,1968
             65
FIGURE

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              67
                                  FIGURE 17

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                                68
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               73
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                                                   FIGURE ?i

-------
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                                  K.'
                                                     -47° 20
                                                           IG'
                                         12'
         Boundory Of Sompling ^roa^^


                         -12'
9I°20'
         18'
                                                      0
                                                      SCALE   IH  KILES
                                                   *  not founi
    16'
                 ALU]:i!ILv! -  u^/i

                BOIT3M WAlKR SAi'-PLF.S

        LAKE SUPERIOR SAMPLING  RESULTS


         SISCOV/ET CRUISE  5,  JUNE 17-22,1968
                       80
                                                          FIC
I

I
I
I
I
I
I


I
I
I
I
I
I
                                                                            I

-------
     18        16
           LEAD ~ -az/1
         U^'AC;] ;.ATSR SAi-.PLZS
LAKE SUFDER!OR SAMPLING RESULTS
  S1SCOY/ET CRUISE 5, JUNE 17-22, 1968

                 81

-------

-------
•«• noi  found
          IEAD - ug/1
        BOTTOM ;-rATEK  SAl-.PL^S
LAKE SUPERIOR SAMPLING RESULTS

 SiSCOY/ET CRUISE 5, JUNE 17-22,1968

                 83
FIGURE
                 ?3

-------
                                                            I
        COMPOST1!7; r!iJ?TH SAXFLI'3

LAKE SUPERIOR SAMPLING RESULTS


  SiSCOV/ET CRUISE 5, JUNE 17-22,1968
                81:-
                                                            I
                                                            I
                                                            I
                                                            I
                                                            I
                                                            I
                                                            i
            i
            i
            i
            i
            i
            i
FIGURE
I

-------
             TNG  - ug/i
      CO>.?0£I'iU DEPTH JV.i-.t'LSS
LAKE SUPERIOR  SAMPLING RESULTS

  SISCOV/ET CRUISE 5, JUNE 17-22,1968

               85
FIGURE y

-------
                        47° 20'-	\y--~
22'
             91°20'
18'
16'—I
                          Sitver
           xll_ L  ^"x_--J
            j  E.Beaver toy/

                 j      V7  Becv-Jr Boy

             Bcover B oy' f._^'._-=\-._
                                                                       «7°20'
                                                                               N
                                                                    9ldiO'
              -_-l-™Jill£?IL2L?a'ILE!i!!9 ^Lcci
                                           R\
                                                                       Q

       ^/.
   22'
          9IP20'
 18*
                                                   V*
                                                         V'
                                                            0       I       2

                                                             i ________ '._ ______ !

                                                                SCALE . IN   WILLS
                                                                    * not found
IG1
                           CCi-.l'051'i?; D'^VTi-I S^-^PLiS


                     LAKE SUPERIOR  SAMPLING RESULTS



                      SiSCOV/ET CRUiSL" 5, JUNE 17-22,1908
                                      86
                                                                            FISUKE
                                                                  I

                                                               hi
                                                                  i
                                                                  i
                                                      i
                                                      i
{

 i
 i
 i
 i
 i
 i
                                                                                            i

-------
Split
47°itf	
   22'
       Rock
Pi.
               91°20
                    jour dory Of S o_r n p 1 i n g Area




                               '-1—-12'
                                                V
                                                     ^^
                                                                  - 1
                          -  47° 10*



              18'        16'



                     MJ.CKKL - U.-/1




                 COITC31Tlii DriiTi! SAMPLES



          LAKE SUPERIOR SAMPLING RESULTS





           S1SCOV/ET CRUISE  5, JUNE 17-22,1968






                           87
                                                               SCALE  IN  WILES
                                                                   Jound
                                                                       FIGURE 37

-------
                                                     N
 BoundcryOfSonp!ino Area
                                                               I
                                                               I
                                                               I
                                                               I
                                                               I
                                                               I
                                                               I
                                                             •
      COiiPOSriii DErTH SAMPLES
LAKE SUPERIOR SAMPLING RESULTS

  SISCOWET CRUISE 5, JUNE 17-22 ,IS68
                83
             I
             I

             I
             I

             I

             I

             I
FIGURE 35
                                                              I

-------
I
I
I
I
I
I
                                                                              N
                                                                            -O-
^>5,o//7 \Kock
47° 10-—
      22'
Pi.
           Boundary Of Sompring Area
                                       -12
  9I°20
18'
                                       -  47°10
\B'
                                    PHOSPHORUS - ug/1


                               SURFACE WATK.-t SAKPLiiS

                       LAKE SUPERIOR SAMPLING RESULTS


                        SISCOY/ET CRUISE  5, JUNE 17-22,1968



                                        89
                                                                             J
                                                                   91° 10'
                                                                      0
                                                                  SCALE  IN  MILES
                                                                             FIGURE

-------
14'
                                                                 f"
IG- t 14' ; 12' f, ^;iu
47°
o r\'
v
y



\

P
22* 9i°2O' IB*

,1


^/
r







pe



\




a^--^





_/"

(Silver

E . B c c v e r P
W/"
Beaver B Q)']^?


/
! J
V
/
Ss /
1 i-""™
\/




,

5
/?ocA-




.

5
pt.





6
/r
/
\s

li

c "Tfe""""
^ I

«=_^^


1:
i a -
cnt Dis
Arc
\


^
^x-

/ \
l '\

A^'--':-3


charge
-i ^v^-
f~\j__
Bey/
,^Z_ j
/
Silver

x:^
?
4/

u 7.
Z^ffy ffcrbcr

954
^'"•i'sjF.*
1^
(||
f , ->\ -~ •-"•,, i L

172




5


0 '"* 8


^-; ^V

5
5™


T" ""

5

]-t
'










//«
-------
              18
            Plant Di£.;hars
  . DseverEoy /

Beaver Boy! "^
             BOTTOi-, V.'ATEi! S.U-.PLiS
   LAKE SUPERIOR SAMPLING RESULTS
     SISCOY/ET CRUISE 5, JUNE 17-22,1968
                     91
FIG'JRf.

-------
                               16
                        4 7° 20'— V	
                                                                — 18
22
                                                                       --47° 20'
                                                                          N

                                                                          Ii
                                                                 --I61
 v
47°IO'	


      2.2'
f- 	


7
Pt.


I*""


2



-«=-^-c-.
Bound





                                                                --I41
                                                               9!°iO'
                         Boundary Of SompIlng_Ar_ea


                                        -12'
         9I°20'
                                                   '
                                                           i	
                                                           C~T""~". ~~~
                                                              SCALE  IN  MILES
                                 -  47°IO'
16          16'


    SUSPy.i'.'DED COLITj£
                 LAKE SUPERIOR SAMPLING RESULTS
                  SISCOY/ET CRUISE  5, JUNE 17-22,1968
                                    2
                                                                             FIGURE  -V.1
                                                                                    I
                                                               I
                                                               I
                                                                                           I
                                                                                           I
                                                                                           I
                                                                                           I
1
I
I
I
I
I
                                                                                     I

-------
LAKE SUPERIOR SAMPLING RESULTS
 S!SCO\VET CRUISE 5, JUNE 17-22,1968
                                             FIGURE !:?

-------
         Plont Dischors
          Sompling Area




                —12
        SUSPENDED SOLID? - ng




          BOTTOiI ;;ATK:; S,-J.PL5
LAKE SUPERIOR SAMPLING  RESULTS
  S1SCOV/ET CRUISE 5, JUNE 17-??. ,1968

-------
I
4
1

1

1

1

1
1

II
Io
47°
^ T]1
s
J
t_ L.' j^
(


10*
2


x16"
I/
"~x_/
,
ft!

1

I

l
1

l

1

1
1 1^'

\

\ ^^
i



22
2' 9ic
1
!


&

^
s

N
^



\ X

l>

V
fc.*!!S*---«JB3O
0.60




1
0. 21C
0.35




91°








H_j -- - -
Plant DiscV.aroc
18' Areo^^


Silvet
	 / "^V..^
E . E3 D o v c r L c y^/
Beov
/
/

'

»<»-«»
0.23
3.35




zo1
c r F o y


>





-»==.-«.
0.35
-----



i£
0,?f;

"
X \>
Dry /•
/

1 0>_20

0.39


0.3'!


0,20


0,26
Y i S^
\ i f
-~^
! \
7**~
.
r*
j



%ffi

0.20

0,36


0. 20


0,09
arbor

0.16

0.20


n "* ^
/
7
j p
0.16-


o.os

0.20

0.23

0.23



T !i so at
0. 'j:'


0.36


0.27







•


Head
0.26


0.23











47°20'
N
j !
/;
i •(' •
T

^
--!&'



14'

!4' 12' 91° iO'
	 ^v^ Boundary Of Scrpplin-g^rea
0.20
	






— 	




1
fO *
&
r* ^
,c"°
1 ?
	 : 	 - z. it. 	 	 	 Ki . 	 r .— 	
V^ SCALE IN MILES

/• v o ; o1
.1
TuKUiblTY, HclLIIGB
SURFACE ;^T;iH S'UiPLiS
                      LAKE SUPERIOR SAMPLING RESULTS
                       SiSCOY/HT CRUIS:-: 5, JUNE 7-22,1968
                                     95
                                                                  FIGURE

-------
•\2
" V"-
)~^
V
f
• • v c'1 o •
ie' , 14' ; \z' (, S1 10
A 7 O 0 ')'
/ \
r -.. T-

\

18* -
PlantDis
22.' S!°20' 18' Are<


1


K -
\

1

T?

\
\

\







E.B
Beav
/
/


^




5^///

°IOl-
X
0.20
Rock





•0-T6-
Pi.




OTI5"

Silver
caver Be y >•'
erBayj>
X7

0.^0


0.20 10.39"

oTecf


o.:..-

Y
fS

chorge / J-'k°
- f^':-"^'
/%\~
Bay y^
...,.
0.20

"0.20"



/ 0.31 jc.3i>
5Y/K^/^'//W.r,-
_r 	 r>_L 	
J.<-;:r-'2/f D.20


3.09
V
/i
/ Po/isco'c
0.23


O.CJ

6 . Pf
'0^3




0.20

^oTIS

o.icT







Hood
O.lt


0.26







(




-18'


-16'


-14'
14' 12' ' 91° iO*

•_ " Bcunrfcry Of Scmpliri? Area • iO
-0^3










""•

-



-— 	
•



^

^
• ^ tJ* 0
p> fc


1


fl


N
J
!\

J'
1
J


|

1

1
1

1
1
1
wT
•
•



I 2 3
SCALE IN WILES
- 47°!0'
2.2' 9I°20' 18' ' 16'
TUilRlLilTT. H7.L],1G£
LAKE SUPERIOR SAMPLING RESULTS
SiSCOV/ET CRUISE 5, JUNE 17-22,1968
of, FICU





;;F i;-.

1

1
1
1
1
1
*
1

-------
                      Boundary Of SompHna Area
               j-. '..'ATr^ SA:-PLLS
LAKE SUPERIOR SAMPLING RESULTS
  SiSCOV/ET CRUISE 5,  JUNE 17-?.?. ,1968
                 97
FIGURE

-------
                      4 7° 20'—V	^
                                                                      N
22
    Mont D<5cl,ar c,5
13'      Area
                 Boundary Of Sarnpting Area

                                — 12
                                                    not detected at
                                                    sensivity of test
                              ARSEXIC  - ug/1

                     AVERAGE VALUES FOH ALL DEPTHS

                LAKE SUPERIOR SAMPLING  RESULTS'

                 SISCOY/ET CRUISE  5, JUNE 17-22,1968
                                                                  FIGURE

-------
             Boy /silver Day Harbor
L . £ D o v c r L, o y
             Bearer Boy
             TOTAL THOfl - uf/1
             Urll-'ACZ  ,,ATcR l'AJ-.Fl,L
   LAKE SUPERIOF^ SAMPLING  RESULTS
    S1SCOV/ET CRUISE 7, JULY 15-20,1968

-------
   Sounciary Of Somp'lr.g Area
                — 12"
                                           *Not found.
               16
            TOTAL IKON - iu;/l
       l-jLD-LY;iPrH VJA'i'rl.i SAMPLES
LAKE SUPERIOR SAMPLING RESULTS
  SISCOV/ET CRUISE 7, JULY 15-20,1968

                100  -
            I
            I
            I
            I
            I
            I
FIGURE  ::••'
                                                                 I

-------
               IB---	
            Plant Dischcrc
                              "117 j12200 300
         Silver Boy Ssi,YC )-n0 Yhf?^ \
E. E o c v c r D o v
     Bcundcry Of Sc.TipIing Area

                   -12'
              TOTAL IRON - up/1
          BOTTOI. ;.ATKi SAM'LK

  LAKE SUPERIOR SAMPLING  RESULTS
    S1SCOV/ET CRUISE-: 7, JULY 15-20,1968


                   101  •

-------
                                                                 Sl°lO'
                                                                            N
      22
47°!0l
               Sr20'
     18"         16
        SOLUBLE I.-iON - uc/1
        SUK:ACE ..ATrLi SAI^I^S
LAKE SUPERIOR SAMPLING  RESULTS

  S1SCOY/ET CRUISE  7, JULY 15-20,1968
                                     302
                                                                        FIGURE
  I
  I
  I
  I
  I
  I

*
  I

-------
                                              -~<'r7020'
     dory Of So moling Arts
                                            SCALE  IN  MILES
          SOLiUSL^ IRON - ug/1




       UD-LL',P1 tl .-.'AiER S,\. ?I^3



LAKE SUPEF^IOR SAMPLING RESULTS





  S1SCOV.T,T CRUiSF 7, JULY 15-20,1968
                  10 V
                                                    FIGLTxcI W

-------
                                 IG
                          47° 20'	\/	
                                                                9I°10"
            	47° 20*
16	
                E. B t c v o r £ o y.-


                   I      V
               Beaver Boy! ,- •
                                                                91° 10"
                     Bouno'cry Of Sarr,p!in5 Area
                    	  "^	I _ |o"
       .0^
                                                              :t
                0
                                                                     t
e
                                                  ^
^
    i
   —!_
   ---(._
                                                               SCALE  IK  MILES
                                   - 47°iO'
                                  IG'


                             SOLUBLi TuOJ « vg/1




                            BOTTOM WATER SA, PLZ3



                   LAKE SUPERIOR SAMPLING RESULTS




                     SISCOV/ET  CRUISE 7,  JULY 15-20,1968






                                    loU •
                                                                                  I
                    FIGURE -.'
                    i

                    I


                  9

                    i

-------
                            Bountfcry Of Sompilng Areo
                                         I
                                                                     SCALE  IN  MILES

                                                                   #Not found
1
         MANGANESE - us/1
        SUHFAC2 ' .A'fER SAI-.PLiS
LAKE SUPERIOR SAMPLING  RESULTS

  S1SCOV/ET CRUISE  7, JULY 15-20,1968

               105   '
F1GURC  ^3
I

-------
             Plan! Discharge
        IB*       Area .._ *
                       or. Boy rfaric.
 E. E D a v c r D o v
              Deoyer Bay \
Be-over Boy
      Boundary Of Sor;ip!inj Arco
                    - 12
                                                ->- Not' i our.a
                   :;GA,::-S^ - ug/i
   LAKE SUPERIOR SAMPLING RESULTS
     S1SCOV/HT CRUISE 7, JULY 15-20,1968

-------
                                                          B
c ^
Y
J'
h - •
1
702"
2

i:
5"
•}/isa'.
•
3
Head
1 ' '
5


9!c
iu
- ^7°20'
) fj1
ir*

-K'
iO'
                                                                                 N
                                                                                I
                                                      V
                                                        ^
e
                                                               S^>
       pf-
                                                                      flt
             0
                                                                           p
I
             ;>
            —J
          SCALE  IN  MILES


      -x- Not  found
                                    OTTO"' '<•' '''"'R ^-' I' "-'T.7^
                                    ^_' J J Wi jl i ,^*1 d.	fit ' / . • ' -J J Ji>Ji_J


                          LAKE SUPERIOR SAMPLING RESULTS



                           S1SCOV/ET CRUISE  7, JULY 15-20,1958




                                         107  '
                 FIGURE;/,
I

-------
       47°20-—
         OLUBLE :-.A;:GJ;:r,5F, - ur
        SURFACE V;;TER SAr.
LAKE SUPERIOR SAMPLING  RESULTS
  S1SCOV/ET CRUISE 7, JULY 15-20,1968
                                                               I

-------

                            Boundary Of ^omplirig Area
  • •^.•J^>-Jfc-^,tyJ.
                                    SOLUBLE IV\NGA:\TESE - ug/i
                                     KID-DEPTH V:ATER SAMPLES
                          LAKE SUPERIOR SAMPLING  RESULTS

                            SISCOV/ET CRUISE 7, JULY 15-20,1968

                                            109-
FIGURE  39
I

-------
          47°20	\-—
             Plant Discharge
 E.Be-over D.oy/ |      |5
              Be over Bay
Bcover B oyf
     Boundary Of Sampling Area
        18         16

          SOLUBLE MANGANESE - ug/1

          BOTTOM WATER SAMPLES

   LAKE SUPERIOR SAMPLING  RESULTS
     S1SCOV/HT CRUISE 7, JULY 15-20,1968

-------
                           |BL	
            E.. E o o v c r Lo; ^vj^Y;:"
            Beaver D
                        Of SQm?Iing_Area .•
                               — 12
y,_i>^^-t»iibn»---i>  -;
I  536 \ *
                                                             --- Sob  found
                           ALUK1XUM - ug/1
                        Uf{F^CZ i.'AT?R SAl-.PISS
               LAKE SUPERIOR "SAMPLING RESULTS
                 SISCOV/ET CRUISE 7, JULY 15-20,1968

-------
                                       SCALE  IN  WILES




                                            found
LAKE SUPERIOR SAMPLING RESULTS





 SISCOV-'ET CRUISE 7,  JULY 15-20, !968






                112-
FIGURE
                                                          I

-------
         Plant Discharge
  Boundary Of Sampling Area
                                           SCALE  IN WILES




                                          -x-'Not found
            AI.UwlNUH - ug/1




         BOTIOX T.\TATER SAMPLES



LAKE  SUPERIOR SAMPLING RESULTS
  SISCOV/ET CRUISE 7, JULY 15-20,1963

-------
22

\-^
x^
..^ -a*^-
3o
Rock





Pt.







9I°20'
                    18*
                                                         SCALE  IN  WILES



                                                          * Not found
    16*


SOLUBLE
                              uM - u
                                            /1
                         SURFACE V:ATER SAMPLES

               LAKE SUPERIOR SAMPLING RESULTS


                 S1SCOV/ET CRUISE 7, JULY  15-20,1968
                               111;
  I
  I
  I
  I
  I
  I
*
  I

-------
                                                                  SCALE  IN  WILES
                                                                  ' --• Not fornd
        SOLUBLE; ALW-IIKUH - ug/i
        KID-DEPTH WATER SALTLLS
LAKE SUPERIOR SAMPLING RESULTS
  SISCOV/ET CRUISE 7, JULY 15-20,1968

                115 '
                                                                          FIGURE
I

-------
                                    16
      ?.2
47°iC£
                             SOLUBLE ALUI-.INTJM - ug/1
                             BOITOM V.'ATER SAMPLES
                      LAKE SUPERIOR SAMPLING RESULTS
                        SISCOV/ET CRUISE 7,  JULY 15-20,1968

                                       116-
                                                                                      l
                        Boundory Of Scrhpllr-j Area
            I
            I
            I
            I
FIGURE
*
                                                                                      I

-------
                               ndory Of SompllnpArea
                                   SURFACE WATirt SAIvPl.aS
                          LAKE SUPERIOR SAMPLING RESULTS

                           S1SCOV/ET CRUISE 7,  JULY  15-20,1968
                                                                            FIGURE:  6V
i

-------
            Plon? Dischcrc,
 t.B D o v o rBoy

Bcover B o
     Boundary Of Scmpling Area

                   — 12
                                              SCALE  IN  WILES


                                             * Not found
                 LEAD - uc/1
                           SAIPLES
   LAKE" SUPERIOR SAMPLING RESULTS
     SISCOV/ET CRLMSE  7, JULY 15-20,1968
                                                                  i

-------
                                      Pclisacfc Head
            Plonf Discharge
 E.B&over Coy
         \7   Be ever Boy
Beaver Coy! „-'
               15   !  37  !
     Boundary Of
                                               SCALE  IN  MILES


                                               Mot found
                 LEAD  - ug/1
             BOTTOM WATER SABLES

   LAKE SUPERIOR  SAMPLING RESULTS
     S1SCOY/ET CRUISE 7, JULY 15-20,1968


                    119-

-------
                   Boundary _0f S
                                                         Ci~ — "~~  ; I __ , _ ?~~,~'~~ ""-' '-j
                                                            Not found
22
           SOLUBLE LiAL) - ug/1
      AVERAGE 7ALlj_,S FOR ALL DEPTHS
LAKE SUPERIOR SAMPLING  RESULTS

  SISCOV.'ET CRUISE 7,  JULY  15-20,1968

                 320 -
                                                                    FIGURE  70
I
I
I
I
I
I
                                                                                 I

-------
                                  16'
                                     C
              47o2o	L^-
             9I°20'
                 Plant Disc

            18*       Area-
                                                                   ,~47° 20

                                                                    -18
                         .Silver
14
                 E. B c o v c


                Beaver
                   	I  ^^iW!^?:^. _
                        /§§i%"K->%^ - ; <"->^:-i Q    o




           ^_            l_       ^
           rcoy^lliliir:^ i5
                                             K'
                                           12'
                                                                   -16'
                                        91° !0'
                                                                    0
it


10
Reck


0
F't


0





   22'
9I°20'
\6'
                                     -12
                                      47°IO'
\B'
                                 COPPER - ug/1


                             SURFACE V:AT£R S.iLPLE5


                    LAKE  SUPERIOR SAMPLING  RESULTS



                     SiSCOV/ET CRUISE 7, JULY 15-20,1968
                                      121-
                                                            FIGURE  71

-------
 Boundary Of Sampling Area
                                                               I
     16'
16
           COPPER - ug/1
       hlD-D^PTI! WATrR SAMPLES
LAKE SUPERIOR SAMPLING RESULTS

  SISCOWET CRUISE 7, JULY 15-20,1963
                                                               I
                                                               I
                                                               I
                                                               I
                                                               I
                                                               I

                                                             J
                 122-
                                   FIGURE
                                                 I

-------
      4 7° 20—V-	
  Boundary Of Sampling,Area
               — 12
             COPPER - ug/1
         BOTTON '.'ATiR SAMPLES
LAKE SUPEF^iOR SAMPLING RESULTS
  SISCOV/ET CRUISE 7, JULY  15-20,1968

                123 '

-------
                                                                   	47° 20'
      22
^2 Spin ^>;k
ft.
47010"
      22'
                                                                  9!°iO'
                         Boundary Of Sampling Area
   9r20'
18'
                                        12
                                               cVlP
                                                                 '.?•
                                                         0
                                                                       p
                                      I
                                                     ^
                                                  0       I

                                                  b^E=EEfclZ
                                                       5

                                                      Ed
                                                                  SCALE  IN  MILES
                         - -  47° !0'
                                     16
                                 SOLUBLE COPPER - ug/1


                           AVERAGE VALUES FOP. ALL DEPTHS

                      LAKE SUPERIOR SAMPLING RESULTS


                        SISCOWET CRUISE 7,  JULY  15-20,1968
                                                                         FIGURE 7a
                                                                                      I
I
I
I
I
I
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                                                                                       I

-------
                           ,8!	1
                         Plant Di2chore;c

                     IB1       Area
I
I
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22
J
-«-j;



*~ «S*-«T,-1
D
Pt.



-^~ — —
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^
Bound
— _ 	


                   9I°20'
                     18
                                                           SCALE  IN WILES
  - 47°!0'


16'

ZINC  - ug/3
if
• L—
                        SUill-'ACE '.•;.\TF.R SAMPLES

                LAKE SUPERIOR SAMPLING RESULTS


                  SISCOV/ET CRUISE 7, JULY 15-20,1968


                                125  -                              FIGUR

-------




•

'

2

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16 	
v
2* 91°
• i
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20'
/•
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X


I41

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47°
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132






1







	
47°20'
I

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^^»
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6

V-
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^ i
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SCALE IN IHLE
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G1
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KID-DEPTH WATE? SIMPLES
SUPERIOR SAMPLING RESULTS
f



r






1

1

1


1
1
1

•
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s





SISCOY/ET CRUISE 7, JULY 15-20,1968

nog FIGUR
E 76
•

•

1

1
1
-
1

1
*
m

I

-------
         Plant Discharge
     c'-.'ry Of Sampling Area
             ZING - ug/
        BOiIC;-; VJAT^rl SAMPLES
LAKE SUPERIOR SAMPLING RESULTS
  S1SCOV/ET CRU1SM 7, JULY 15-20,1963

                127  '

-------
                                                    N
  Boundary Of Sampling Area
                                                     	J
                                         SCALE  IN  WILES
          SOLUBLE zi::c  - ug/i


      AY2H.u53 YALU33 FOR ALL DLPTH5

LAKE SUPERIOR SAMPLING  RESULTS


  SISCOWET CRUISE 7, JULY 15-20,1968


                128 •
             I
           fl
             I
             I
             I
             I
             I
             I
           J
             I
             I
             I
             I
             I
             I
             I
FIGURE
I

-------
I


I


I


I


I


I
                                          16
                        47°20'
                             18^-
22
9I°20
                                       £"0^ /'/arbor
                               	   	—^	 L^aj^-.-ias;!^
                                                                          9I°10'
     P1 Q n t Di s c h a r g e / ^fMs^ff < -'v

,8'      Areo^/^   ^^
Are_o-^v
                                                                12'-
                                                        -47°20
                                                                           N
                                                         -18'
r
                                                                           --K'
                                                                91° 10'
                                                                              0
                                                                    .0^
                                                          V
                                                            ^
                                                            I	I
                                                            CTT-1^—  .-..-—-—-.+
                                                            t_	1	
                                    	  47°IO'
                                                               SCALE  IN  MILES
                                                                            * Not found
                                 AVERAGE YALLBS  i-'O?. ALL DEPTHS


                           LAKE SUPERIOR SAMPLING RESULTS



                             SiSCOV/ET  CRUISr 7, JULY  15-20,1968
                                                                                  FIGURE  7

-------
                               16
                       4 7° 20'—-i-
                                                                         N
2.2
9I°20'
                 _.	,~,^-      -.
              E.Beaver Doy/    ^ :-. ;^^:       ^
                 I          £*o/^.;:      j
                            18'	
                          Plant Discharge
                      Silver
                                          14'        12-
                              Boundcry Of Scrnpling^Arec
                                                               T--I6'
                                                                -14
                                  •12'
                                                                 0
                                      ^
                                                   e5.
                                                              	i
                                 - 47°IO'
                           SOLIMLL;  CADMIUM - -ag/i
                     AVERAGE VALU7.3 FOR ALL DEPTHS
                LAKE SUPERIOR SAMPLING  RESULTS
                  S1SCOWET CRUISE  7,  JULY 15-20,1960
                                                             SCALE  IN  WILES
                                                              * Not found
                                                                                  i
I
I
I
I
I
                                                                     FIGURE
                                                                          I

-------
                                    is-	
                                  Plant Discharge
                          "Boundary Of ScmpHncj Area
f
I
I
                                     NICKEL  - ug/1

                              SURFACE '.JATIIR  SAMPLES

                       LAKE SUPERIOR SAMPLING RESULTS


                        SiSCOWET CRUISE 7,  JULY  15-20,1968
FIGURE  8l

-------
  Boundary Of Scrupling Area
        .'Tn_^^O'| ;j  .-,-, •"•LV} o-• > OT - o
        ij-.u~j.j. 
-------
 1    20
  Boundary Of SampIing'Aros
                --12
                                             # Not found
          EGTIQ;-; v;ATi-i SAI-PL^S
LAKE SUPERIOR SAMPLING  RESULTS
  SISCOV/ET CRUISE  7, JULY 15-20,1968

                 133
FIGURE  &3

-------
                                     IG'
                                                                      ~47°20
      22
                                                                               N
^ 7° icy	


      22'
                         Boundary Of Sampling"Area
9I°20'
                                                                I-...-.--.-4.-.-
                        -  47°!0'
                                                                   SCALE  IN WILES
                                                                       No I
     18'        16'


            SOLUBLE NICKEL - ug/1

       AVERAGE VALLiS  FOJi  ALL LliFTHS

LAKE SUPERIOR SAMPLING RESULTS


  SiSCOWET CRUISE 7, JULY 15-20,1968
                                                                           FIGURE
                                                                          I
                                                                          I
                                                                          I
                                                                          I
                                                                          I
I
I
I
I
I
I
                                                                                         I

-------
       47° 20'	-/	
PIcni Discharge
  Soundory Of Sorn'pling Ares
    AVSRAGb VALULS FOR ALL DEPTHS
v^

w - .


21


^

•x-
18 .
"5


•

j<~
Head
• •
3












                                             S!°IO'
                                    	47° 20'
                                                        N
                                                        J
                                    12 -
                                 ^
                                        tf
                                         fen
                                            SCALE  IN
                                                Not,  found
LAKE SUPERIOR SAMPLING  RESULTS
  SISCOV/ET CR'UiSE 7, JULY 15-20, I9GS
                                                    F1GUK5
                                                       v

-------
                 Plant Discharge
            18*       Area''
e"x.	i.   —s	
     L.Eoover Boy
                  Becver Bay
    Bea\'er Boy!
          Bpundcry Of Sampling Aroo
                        — 12
                    PHOSPHO.IUS -
                    UR?ACi ','ATES SAKPLi
        LAKE SUPERIOR SAMPLING RESULTS
         S1SCOV/ET CRUISE 7,  JULY  15-20,1968

-------
                      Boundory Of Sampling Area
          PHOSPHORUS - ug/1
        M'j~D>JrTH ";ATr/{ s;.>.PLH;3
LAKE SUPERIOR SAMPLING  RESULTS
  S1SCOV/£T CRUISE  7, JULY 15-20,1968

                 137-
FIGURE  br'

-------
             riant Discharge
 E.Beaver E: o v /
Beo v'er 0 oy'
     Boundary Of Sampling Aroc
                 	 47° 10'
              pHcsi -::«-Js - ug/i
              OI: VAT^R SALPLXS
   LAKE SUPERIOR  SAMPLING  RESULTS
     S1SCOV/ET CRUISE 7,  JULY 15-20,1968

-------
                                            Not found
         SUSPE^D.JD SOLIDS - r.g/1
        UitACK WATiCR SAKPLii'
LAKE SUPERIOR SAMPLING RESULTS
 SISCOV/ET CRUISE 7, JULY 15-20,1968

-------
                      la	
                    Plcnt Discharge
                                Boy tfarbor
•> ^ *-• f^    F-" R r> n v ft r F; i"i v >
 E. Boavor Doy '/ j      j"'-"

Beover B
            Boundary Of S3rnpiingArea
                                                         Not found
           LAKE SUPERIOR  SAMPLING RESULTS
             SISCOV/ET CF^UISE 7.  JULY  15-20,1968

-------
 Boundary Of SampIing_Area

               — 12
        B01 TOM V/ATI'H SAMPLES
LAKE SUPERIOR SAMPLING RESULTS
 SISCOWET CRUISF:  7, JULY 15-20,1968

-------
                                                                   .
                                                               9I°'°
                                                                         N
                                                                                  I
L_
                                    16
          TUR'JIDITY, HELLDE

        SURFACE ;-:AT>U SAMPLES

LAKE SUPERIOR SAMPLING RESULTS


 S1SCOWET CRUISE  7, JULY 15-20,1968


                1'42-
                                                                                  I
                                                                                  I
                                                                                  I
                                                                                  I
                                                                               ^
                                                                                  I
                                                                                  I
                                                                                  I
                                                                      FIGURE '-,
  I
  I
f
  I

-------
I
p
I
       i.iD-izPTH V;A

LAKE SUPERIOR SAMPLING RESULTS


 SISCOV.'ET CRUISE 7, JULY 15-20,1968



                Ui3-
FIGURE  :

-------
                                     is1
                              47°20'-
                                                               	47° 20'
    22
* Split
       Rock
47° |tf	

      22
0.12
ft.
                        B'oundary_0^f Sampling Aroa
             9I°20'

3.51










-^
f


It,1

A. V O i

                                                      ^
               IE1
                                      16
                                TURBIDITY, HELLIGL
                                BOTTOil V'ATEil SA1-.FLES
                       LAKE  SUPERIOR SAMPLING  RESULTS

                        SISCOV/ET CRUISE 7, JULY 15-20, 1968

                                        Ihh •
                                                                    91° 10'
                                                                     0
                                                                   SCftLE  IN
                                                               FIGURE  '^\\
                                                                                        I
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-------
            Boundary Of Sampling Arc-G .
                                             1      Z     5
                                             t	I	I

                                          SCALE  IN  MILES
                                   *  not  detected, at
                                      sensitivity of tost
LAKE SUPERIOR SAMPLING RESULTS


  SISCOV/ET CRUISE: 7, JULY  15-20,1953
                3.1,5
                                                 FIGURE

-------
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Chicago Fi-ogre-M Office,  F.ffCA                       Her?:   ?-Iinn, UL23
1319 W. Pershing Road                                Date:  8-1U-68
Chicago, Illinois 60609                              Pogc 1 of 3  Pages
Biology Unit
                     Table   10
                     BIOLOGICAL DKl-ERI-DGiATIONS, BEIITHIC FAUNA
                     Sample  Source:  Siscovst Cruise 5
                     Study Period:   JVT^ 17-22, 1968

                       Results  Expressed in Kuinbers of_ Organisms
                                   per Square Meter
 CPO fr
                                                                                  I
 Dep_tji_ _of Stjiti_on
 Date of Collection
 TlT'-n ^-P '' n - "1 i - - -T c
 i^ d i^ t, O i /-. 1 c. _L V o J. o
 Oligochaeta
              .
 s'phaeriidae
 __{ fir g ern_a i 1 _c2-a:n_s_
 Tendipedidae
 Hirudinea

 Pulr.onata (lung
 '°21Sr-* ^liP cl sn!!i~J
 Isopoda

 Ifenatoda

 Aaron i pod a
 ls.cvds)	
 Mysidacea
         __     _	
 Prosobrar.chia (gill-
 br_e-?.thing snai]_s )	
 Tcrbellaria
 (jf l_at vor^s }	
njnionidae
 Sphere-ropier a
 (va t er__j?lea3 ) ___
 Total
                                  T-13^8
                          20
                          20
                                              2 "52
                                                  o
                                                                                 I

                                                                                 I

                                                                                 I

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                                                                                I
                                                                                1
Methods Reference:

Remarks:

CPO Porn  8/8/68
                                             Preservative
                                                                             II

                                                                             11
                                                                              41
                                                                                I

-------
  I
i
Chicago Program Of/ice,  F^'PCA
lGi9 W. Pershins Read
Chicago, Illinois 6oSO?
Biology Unit
                                                     Ref:
                                                                     l-'irm,  -
                                                              Date:   8-li><-53
                                                              Page ? of 3 IY
•Table 1J
BIOLOGICAL DE-ISRMIJIATIONS, RKUTHIC FAUi;'-.
Sasiple .Source: S-j&crrLt i/j^i^e 5>
_ Study Period: Jur,:. 17-?25 IS/68
• Results Impressed, in Numbers of Organisms
per Souare Meter
1

1


1

1
|
•
1

1
I


1

1
|
1
^

CPO -.--
—~~i-f—~*-~-~ •— — - -- —————.
Stati on

i]7:'li.i'CO!:
S'T'l^'OO1'
])et)th of Statj^n_(rO_j_J?3jL___ 	
Bate of CoDlectJon
__ — 	 . ^ -~-; - -j . -_
Oligochaeta
S'ohaeriidae
_^f inr^erriail cla.'cs)__
Tendipedidae
Hirudinea
(leeches )
Pulmonata (lung
breathing H-nails/
Isopoda
I\rernatoda
(roundvorns }_
Aiiphipoda
Mysidacea
(jDiDossum shriri'oj)
Prosobrenchia (gill-
1"\>"*P n "i"}l "i T"i r* c7*t •" •? "1 c* J
LJ. CT (^ C • i J. I 1 -j O • 1 v-*._i. J^ (j ^
Turbellaria
Unioniclc'e
^unionid clans )
L'phei'.iero'otera
* ~ \
( niavj. Iv l^'^'vae )
Cladocera


Total
6-"20---/:.n

1,?' IbHj')"
??.'" 16 'CCi'!
*—"•-.— 	 -
VM^'OO"
91' "11 'CO/'
^__ 	 r 	 _. —
U?'l6'00:i
91" 3 3 'CO"
_1?C 	 J_3 li^ 	 „ 	 ! _UP______
6-2C-- f>i 1 6---20---o8 j 6--20- oo
""?, > ;' /^ C ~ j~ y ^ r,^^ ^ ^


	 —







20










20


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91'"j».i !OC''
._21;j 	
o~l/''-66
•/ „','/- ,.'- ,;;


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0
Me th o d s R e f e r e:i vc e:

Remarks:
                                                     Preservative
         CPO Form  8/3/6J
                                              01

-------
Chicogo Program Office, FWPCA                       Ref:  l'.inn. UL23
3.819 W. Pershing Road                                Date: 8 -Hi-68
Chicago, Illinois 6o609   •                           Page 3  of 3  Pages
Biology Unit
                     Table   lO
                     BIOLOGICAL DSTRRMLHAIICKS, B5JJTHIC VAUI5
0
0
0
0
0


160
                                                                               I

                                                                               I

                                                                               I
                                                                               I
                                                                               I
                                                                               I
                                                                               I
Methods Reference:

Herruu-ks:	

CPO Fora  8/3/68
                                            Preservative   Fornalin  IC'I

-------
  I
 I
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5
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        Chicago Program Office,  PW/CA                       Ref:  Jinn. VJL23
        1819 V. Porshiiig Road                               Date: 8-1^,60
        Chicago, Illinois 60609                              Page 1 of 2 Pages
        Biology Unit
                              Table  I; 1
                              BIOLOGICAL DrrTPr^flKATIONS,  BSNTHIC FAUifA
                              Sample  Source:  Sinccvrct Cruise 7
                              Study Period:   July 35-20, 1968

                               Results  Expressed in Numbers of_Organisms
                                           per Square Meter
CPO jf 	
Station
JDepth of 3^t«tipn__(ri)__
Date of Collection
Date of Ar. civs is
Oligocheeta
(_s_luda;evorris )
Sphaeriidae
_Jjfinp,ern8il clams)
Tendipedidae
^ *
Hirudinea
(leech e s )_ 	
Pulmonata ( lung
breath^n^ sn=n"ls/
Isopoda.
( ao u at i c s o vbu g s )
Nernatoda
(roundvorns )
Amphipoda
j(jLCuds)
Mysidacea
(opossum shrirro )
IVosobranchia (gill-
breathinn; snails)
Turbellaria
(flatvorms)
Unionidae
(unionid cla.ms )
Ephemeroptera
Jjiiayfly larvae)
Cladocera
(vater fleas)


Total
^rj"^r"T'^*;*"™'""" *" ~" "
91° 11 'CO"
-r~^T~£V 	
7-29,66
170
50

	

20
20



-




260
23h6
"k'l lo''CO!:
9:f 12 'CO"
J?,19_^, 	
| 7-29-68
120
20

	 -;—

50
120








310
'f23b9
1;Y' ld!CO':
JL9SI 	
7-29-68
50


— 	 • — ' 	

-
50








300
2350
IJ?"i9'cor'
91° 11 'CO"
_205 	 	
7-29-68
150


	 	


20








170
233'1
47° 19 '00"
TiiB^r—
7-29-68
920


— 	

20
50








990
I
         Methods Reference:

         Remarks:

         CPO Form  8/8/63
                                                    Preservative  Fo.ri'7-i.l:] n
                                              213

-------
         Ref:   l-'.inn. WL23
         Date:  8-1U-68
         Page 2  of 2  Pages
Chicago Program. Office, FcfPCA
lSl9 W. Perching Road
Chicago, Illinois 606G9
Biologv Unit                ,,
                     Table  1J-
                     BIOLOGICAL DSTSFLMINATIONS,  BKHI-HIC FAUNA
                     Scouple Source:   Siscowot Cruise 7
                     Study Period:    July 1$-20, 1?63

                       Results Expressed  in  JIumbers of^ Organisms
                                   per Square Meter
                                                                               I
                                                                               I
                                                                               I
}J22_iL____-__
Station
Benth of Station (n)
Date of Col].ection
Date 01" ir. a lysis
Oligochaeta
fslud:-.;ev:or.-s)
3ph?-?riidae
f f -i n .~ e r n p •)"1 c 1 a.^. s )l_
Tendipeaidae
(_bloodvorns )
Hirudinea
(leeches )
Pulr.ionata (lung
breath^ n-; sp.ai Is )
Isopoda
(aouatic sovbusjs)
!.:ematoda
j[_rour. d'^o iv:s_)
A'iphipoda
(scuds)_
My si dace a
(op_ossun shrino^
Frosobraiichia ( gill-
breath in nc snails)
T'urbellaria
(flatvor.r.3J__
Unionldae
(unionid cla^s )
Kpheneroptera
f ~ a v-r TV ~! - r '/-•"• a )
Cladocera
JVat_er__fleas)


Total
[_2^2____
U7C20ICO"
91°11'0011
97
7-1S-65
. 7-30-68
150
20




50
120



• -




	 3)10

































-



•










Total
1560
90




lUO
380








2170

|

I-I~an No.
1 Or £. /Scum
2UO
10


|
•
20
60








360
Methods Reference:

Remarks:

CPO Torn  8/8/63
Preservative   Forrralin
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                             TABU? --5
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                             IN LAK? <3l:r'\-tTCR I!"AR  TfLV1^ 1HY, FINN.,
                             CRUISES 5 A:;D 7 OF TH^ ^ISCO^T

I                                                            Ci'ulse 5      Cruise 7
             Total"" Nc.  !.n Gurftco Samples Analyzed           3030(30)      £890(32)
—           •''t-sn    '*   "      "       "       !t                1C1           181;
•           Total   »   "  '-'id Depth  "'       "               2L?0(29)      3080(31)
™           yoan    "   "      ;t       n       "                 8h            99
             Total   '•   1! CottoM Depth "      "               l6?0(26)      26^0(31)
                               "       "       "                 6U            3>
             """imo^r in p?rfnthf.ois —Ka:-:bcr of .1a:r.plos  Analyzed

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TA13LS 16
FHYTOPLANKTON F?R riLIIIH^ IN LAKE
p.r^v-'Rvn n:ii>;G co., STLVJTI BAY, "TUN.,
CRUISJlS 5 AID 7 OF 1HE SISCC*,-,'"T
Cruipe 5
Tobp.1 Uo.* in Surface Sanioles Collected Above Wsste Area 720(7)
i'ean " " " " " " !I !1 102.8
Total " " -.'id Depth " " " » » 6So(?)
Vfpn it il i! * n il il :t il 97.1
Total " " Bottom Depth " " » " " 700(6)
T ,-,,", II !1 I! !l !l it It It -i 1 < 7
1 c ail ±.1.0 t (
Total !-,To. in Surf see Samples Collected Alonjj !;7 17' 3kO(3)
!-'r-an '' !l " !t " " " 113.3
Total » » J'id Depth " " " " l'iO(3)
''n-T-i !l 11 'I 11 II II II ),< 7
/ con ijo . (
Total » !1 Bottom Depth " " '» " 110(3)
yean " » " » » » » 36.7

Total "o. in Surface S':rnples Collected Pclou ve.sto Area 1970(20)
Totol " " I 'id Depth !! " ;| !l » ] £30(19)
i''~rti " " " " '' '* " " '^ 8
Total » " Bottom Depth !i » !t " . '' 860(17)
'\N:U!r.ber in Fa'conthcsiG--''^^.^ of °-r.;"olec Anp.ly7.ed









Cruise 7
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370(3)
108.7
720(9)
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_                       "            SECTION ''4
•                        IIWESTIGi\TIOi;S BY KATIOIIAL HATER Qli-YLIEf
                                     LABORATORY
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  INVESTIGATION OF THE DISTRIBUTION

OF TACONITE TAILINGS IK LAKE SUPERIOR


      September - October 1968
  National Water Quality Laboratory

       6201 Congdon Boulevard

      Duluth, Minnesota  55SOH

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                                          3*7
                                COXTS1O3

                                                                  PAGE
LIST OF TABL33 AND FIGURES                                       3^9
OBSERVATIONS BY SCUBA DlV£v3                                     351
METHODS                                                           353
RESULTS AID) DISCUSSION                                           355
OBSERVATIONS                                                      371
SUMi-IAKY OF 3)IVU,'0 OB3.ERVATIOIJ3                                   375
HH'IER ^LOGICAL AUALYSIS OF V7ATER SA1-5PLE3                          377
     Mc«s^ds and Materials                                       377
     Results and. Discussion                                      3?8
   ER' LOGIC/0, ANALYSIS OP SEDU'IElfTS                              391
     Methods end Materials                                       391
     Results and Discussion                                      391
                                                                  397
•
              Experimental                                                397
•            Experimental Data and Results                               397
              Discussion  and Conclusions                                  399
I       BIBLIOGRAPHY                                                      404

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                    LIST OF 'jPAyiu-S AS) fr'V.GURLS
la      Diving Stations and Oboervvtiozts                     359
lb      Diving Stations end Observation'.;                     360
Ic      Divi"-?; f-tiitions and Observations
Id      Diving Stations and Observations
le      Diving Stations cp.d Obaorvatio^a                     363
2       Night BlvDUg Ol.?<:X'v£tionB
3       VJater Srnpling »S tat ions
1*       location and Depth of li'itex Cloth SuT)strateu
5       Su-oplinf.-ntal Swriplj ng Stations                        373
6a      Suspended Solids .Analyses of Reserve
              Min ins Co. Effluent and IForth Shore Stroacis     379
6b      Suspended Solids Analyser? of V/ater
              Sari'ples from Lake Superior-                      388
7       Mineralogical Analysis of Sediiaents
              Collected from Susponded /lets                   393
8       Mineralogical Analysis of < 2 l-Sicro;ahoc.
              Fraction of Bottom Sediments                    39^
1       Scuba Division Stations                              356
2       Water Stapling stations                              357
3       Secchi Disc  Readings by Dates                        358
4       X-Ray Diffraction Patterns of Solids
              Filtered Trow Tailings Effluent and
              "Green  Water"   -                                381
5       X-Ray Diffraction Patterns of Solids From
              Big Msisitou River Water arid "Clear"
              Lake  Superior Water                             383
6       Diffuse Reflectance Spactra ;"ron Equal
              Volumes of Clear and Green Water                Jt-00
7       Diffuse TiefleeUce Spectra "von Equal
              Weights of Solids from Clear and
              Green Water                                     401
8       Diffuse Eeflectence Spectra of Solids
              Froa  "Clear" and" "Gray" Water
 I

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     The SCUBA diving team of the National Water Quality Laboratory,


FWPCA, at Duluth, Minnesota observed and sampled the area under study.


The SCUBA project, as originally conceived, was to make qualitative and


quantitative studies of two itacro invertebrates, ^V_sl_s_ reli_cta, a free


swimming opossum shrimp, and Pontoppreia affinis. a "bottom duelling


amphipod crustacean.  Observations of sedimentation were to be made


both on the natural substrate of the lake and by the placement at


various stations of net substrates at different depths.  It was likewise


hoped that underwater as well as surface photography might be of value.


     As the investigation progressed it became apparent that redirection


of effort would be necessary since Mysis relicta and Pontoporeia affinis


could not be found in the initial survey because of the higher water


temperatures in the inshore areas.  The unit, therefore, redirected


its activity to:


          1.   The placement and collection of artificial substrates as


sedimentation indicators.


          2.   Turbidity studies in relation to the water having a green


color ("green water").


     3.   Visual, direct, underwater observations of the nature of
           "green water" and of natural substrate,  above and below the potential
influence of taconite wastes.


     U.   Photography, where possible, of the effect of taconite waste


at the water surface and below.
I
                                           351

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to allow precise saripHing, "by the  divers,  of "gray",  "green" and "clear"        •
vater for chair.ical and physical  analyses.
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                                  352
                                                                                 I

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                                METHODS







     Conventional SCUBA gear was used throughout this study.  Water




samples were taken either by immersing containers in surface waters




or by pumping water.  The pump hose was properly positioned at desired




depths by divers and water was pumped for a minimum of ten minutes before




the water sample- was collected.  Some samples were taken simultaneously




by hand and by pumping to check if the Dump itself contaminated the




sample.  All samples were collected in one-half and five gallon, screw




cap, polyethylene containers.




     Bottom samples were collected by scooping sediment into quart glass




jars, and formalin or ethyl alcohol was added for preservation.




     Turbidity determinations were read with a standard Secchi disc




(8" disc with black and white alternating quandrants);  attached to a




line marked off in fathoms.




     Artificial substrates were placed in Lake Superior for k weeks to




collect alga,e and particulate matter.  They were constructed of cloth




screen (#9^7 Nitex screening, 20 mesh) attached to wire coat hangers.




Each substrate was triangular in shape, measuring 13 inches at the base




and 6 inches in height.   These cloth screens were attached to a rope




and positioned near the  surface and bottom and midway between.  The rope




was suspended by a float.




     Surface mileages from the shore of Lake Superior were computed from




rate of speed and time.   Bottom depths at all stations were determined by




a Raytheon Fathometer, Holiday Mark II Model DE-716.  The Fathometer and




the divers depth gauge agreed within two feet.
                                353

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                        RESULTS AND DISCUSSION



     Diving station locations and observations are presented in Table 1.

All dives, except two, were performed between 9:00 a.m. to 4:00 p.m. CDT

from September 10 to October 11, 3968.  Tvo dives, on September 25 and

September 26, 1968 vere at night (after 5:00 p.m.) in "clear" and "green"

water areas.  Observations from the night dives are shown in Table 2.

Water samples were taken at most of the diving stations during the period

from September l6, 1968 to October 11, 1968.  Location and recorded field

data from these dives are found in Table 3.  Map location of the diving

and water sampling stations are depicted in Figures 1 and 2, respectively.

Figure 3 represents Secchi disc readings by map location.

     Throughout this diving period "green water" was not observed at

stations northeast (N.E.) of the Reserve Mining Company effluent delta

regardless of prevailing wind direction (See Table l).  On each visit,

areas of green water were always present beginning at the Reserve Mining

Company effluent delta and extending down the lake in a southwesterly

(S.W.) direction (Table l).  Continuous masses of "green" water have

been traced with diving operations and photography to just N.E. from the

mouth of the Gooseberry River (Sta. P).  Further, this mass of "green"

water has been observed by the divers from the beat and from an automobile

as far south as Crow River.

     As Reserve's tailings meet Lake Superior water, "billowy gray clouds"

of waste are visible both at and under the water surface near the shore

line (Sta. G).  Extending off shore as far as 300 ft. (Sta. J), gray

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                                       I
 £ake  Superior
     SCUBA DIVING STATIONS
                                       I
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                      Figure 1
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356
                                       I

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                 O|4
     J2ake  Superior
WATER SAMPLE STATIONS BY I D. No.
                           Figure 2
                                          35T
I

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                            9-10,24'
                      	9 10,18'
                      O 9-19,14'i 9 26,18
           	     i—920,18'
           nt c!e!'°"^	9 11,24^9  12,28'

                                   . 920,24'
                     •12,7'G         920,24'

            4C^-.9|2,6'     e   - .9-26,18'
            (Q)  ,.9 I2,7';9 19,7', 9 27,6'
SPUT    /     i;9-l2,7'-,9-l9,6'-,9-27,6'

 ROCKJ     ©0925,15'

       ©      '••-.. 9-25,6'
                                    ••-...9-27,9
                                                LEGEND

                                                 ® Less than 10 feet

                                                 ® More than 10 feet
                                                  Superior
   O 9 27,13'
Bl/rlingtcn Bay
                                     SECCHI DISC READINGS BY DATE
                                                                             lST
                                                                         Figure  3
                                                                                                     I
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                                   353
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                                                                                  I
Station



Date


Surface Water Clarity


Total Water Depth


Nature of Bottom



Water Clarity at 20 ft.


Apparent Color of Water
Maximum Vertical Depth
Diving Light Remains Visible
(when viewed at surface)


Maximum Penetration of
Light Beam
Horizontally (at 10 ft.
depth).
                                  TABLE 2
                         Night Diving Observations
Beaver Bay
(Sta. N)


9/25/68


Turbid


30 ft.


Rocks and Sand
with Silt Overlay


Turbid


Gray


18 ft.
21 ft.
Palisades
(Sta. C)


9/26/68


Clear


TO ft.


Clean Sand



Clear


None


106 ft.
(measured in
 deeper water)


120 ft.
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                                                                                  I

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  I
  b

I»te
9-16-68
9-*6-68
9*6-68
9^6-68
9-B6-68
•
9-16-68
9-»9-68

9-^9-68
9«9-68
•Hr
9^9-68
9-WO-68

9»0~68
J}>
opT-68
9*^-68
9*5-68
9»6-68
9^7-68
1
I.D.
Ko.
1
2
3
U
5

6
7

8
9

10
11

12
17
18
16
13
14
15

St at i on Location
Description
Palisades - 1/2 mi. out
Reserve's Effluent delta
50 ft. off shore
Reserve's Is. -50 ft. off shore
1 mi. So. Beaver Pt .
Reserve's Pilot PI a at--
raw mill eff.
Pr. Homo © Sil. Bay, Tap ?.?0
Reserve's Effluent delta-
100 ft. off shore
3 lA mi. So. eff. delta
50 ft. off Reserve's S.W.
breakwater
Palisades - 1/2 mi. out
1.5 mi- off shore from Reserve'
Effluent delta
3 mi. out from Reserve's
Effluent delta
Split Rock lighthouse bay
Split Rock lighthouse bay
Beaver River © Highway 6l Br.
3 1/2 mi. So. W. from Reserve's
Effluent delta
5 mi. off shore from Reserve's
Eff. delta from eff. delta
Midway from Split Rock and
Gooseberry River
Sar.ule
Yolu-.e
3 ga2.
2.5 6*1-
1 gal.
3 gel.
~J £! EL_L- .

0.5 gal.
3 gsl.

3 gal.
3 gal.

3 gal.
s
3 gal.
3 gal.
1 gal.
•2 r-^ ~\
J e>°-~ •
3 gal.
10 gal.
3 gal.
5 gal .

Sampling
Depth
50 ft.
50 ft.
50 ft.
12 ft.
-

-
35 ft.

60 ft.
60 ft.

60 ft.

60 ft.
60 ft.
surface
30 ft.
surface
surface
surface
surface

Ssr.rling
Method
TMT -- -*,
^J _t *-.-
~D"JT"T
bucket

faucet
pump

pur.o
pump

pump

pump
pump
hard
-r\i ~r •>-*-,
1^ d 	 s.'
hand
hand
hand
hand

Water
Color
c">e^
gray
r"rav
green
gray-bro:

clear
gray

green
green

clear

clear
clear
green
green
brown
green
clear
green

10-1-68   19
lB-l-68   20
1?
   §.. .3   21
   1-68   22
lf^-1-68   23
31-1-68   24

1C-1-68   25
—• -  xr'   26
Big Manitou River (Mouth)      1.5 gal.
1 mi. N.E. from mouth of Manitou
 R. & below Caribou R.-Lake
 Superior shoreline            1.5 gal.
Baptism River (Mouth)          1.5 gal.
Immediately So.  of Baptism R.  1.5 gal.
 & in Bay. l.ahe Superior shoreline
Beaver River (Mouth)           1.5 gal.
Above Beaver River and in Bay. 1.5 gal.
 Lk.  Superior shoreline
Split Rock River (Mouth)       1.5 gal.
1/2 mi. S.W. Split Rock River  1.5 gal.
 & @ S.R. resort-Lk Sup. shoreline
Gooseberry River (Mouth)       1.5 gal.
Just N.E. from Gooseberry River
 mouth and along Lk. Superior  i
 shoreline.              -,.--:-
                                                            surface
surface
surface
                                                            surface
                                                            surface
                                                                       hand.
                                                                       hand
                                                                       hand
                                                                       hand

                                                                       hanl
                                                                       hand
                                                                       hand
                                                             uace
                                                                       hard
                                                            surface    hand
                     brown
clear
brown
                     brcwn
                     green
                                                                                 Slightly
                                                                                 green.

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I.D.
Date No.
10-8-68 29

10-8-68 30

10-8-68 31

10-8-68 32

10-11-68 33
10-11-68 3 ^







1
TABLE 3 VB
(continued)
1
Water Sampling Stations
Station Location Sample Sampling Sampling Water ™
Description Volume Depth Method Color
	 u 	 __.„., 	 	 	 „ 	 	 	 j. 	 r 	
1/2 mi. off shore
Burlington Bay, N.E. Poin'c 1.5 gal. surface hand clear •
1/2 mi. off shore |
Crow River, 1/2 mi. off 1.5 gal. 60 ft. pump green
shore M
Crow River, 1/2 mi. off C.5 gal. surface hand green •
shore
Shovel Point, 1/k rni . 1.5 gal. 60 ft. pump clear V
off shore •
Shovel Point, 1/U mi. 1.5 gal. surface hand clear
off shore •
B
B
B
B
B
B
366

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 I
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fc
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clouds were observed at a depth of 35 feet.  Stations E and F (1/2 and


3 rni.  off shore) did not reveal gray clouds at 80 and ICO ft. respectively.


At least part of the tailings upon entering the lake, travel in a South-


westerly (S.W.) direction because gray clouds were observed at Station K


and water sample Station 3 (Table 3).  Gray clouds were never seen past


Reserve's southwest breakwall.  Gray clouds always appeared gray to divers


regardless of viewing direction.


     At the effluent delta and under the water's surface, it appeared that


"green" water was formed as gray tailings clouds diffused (become less


concentrated) and more daylight penetrated, among the particles.   "Green"


water looked green to divers regardless of visual direction (up, down,


or horizontally).


     Depth stratification of green water was observed at only one location,


Station K—near Reserve's southwest breakwall.  This stratified layer was


not influenced by temperature, because readings of 11-12° C were recorded


at all depths to 80 ft..  ITone of the remaining "green" vater stations


had color stratification ana "green" water extended from the water surface


to the lake bottom (range of 15 to 60 feet).


     The confluence of the Beaver River with Lake Superior water on


September 12 produced a sharply defined zonation, at arid below the water


surface, of brown river water against green, foggy lake water (Station L).


     Measurement of light penetration by the Secchi disc revealed water


clarity at Stations fj.E. from Reserve fining to be 3 to h times greater


than in "green" water at the effluent delta and S.W. from it (see Figure 3)


At Beaver Bay, Station N, "green" water was followed during the daylight
                                           3SY

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I
hours visually and with the Seech:  disc, and found to extend about 2




miles off shore.   From these Secchi disc readings and direct observations,      •




it appeared that the point source  of "green" wster during this period was




the Reserve Mining effluent delta.   From this point source, green water         •




fanned out in a broad band S.V,T.  as  far as the mouth of the Gooseberry




River (Station ?).  Both Secchi  disc readings and diver observations            •




showed that "green" water was consistently much more turbid than water          •




at "clear" water stations.  Underwa.ter visibility in "green" water was




limited to as little as four feet,  while at a comparable depth off Shovel       •




Point (Station A) or the Palisades  (Station C) it was consistently over




ten times as great.                                                             I




     The two night dives, one on September 25, 19^8 in "green" water and        •




the other on September 26, 1968  in  "clear" water, were made by positioning    ^^




the boat prior to darkness."  Night  dives in the "green" and "clear" water       •




areas showed clarity, by light penetration, to be 5 firr.es higher at the




Palisades (Station C) than at Beaver Bay (Station N).  "Green" water was        |




gray in color at night, and to the  divers the turbidity appeared due to         ,•




fine, suspended, gray-white particles appearing as dust in the diving




light beam (Table 2).                                                           •




     The station locations and recovery data from the Nitex cloth




substrates are presented in Table h.  Based on observation, screens             |




located near the surface at all stations had the greatest solids entrap-




ment and the bottom substrates the least.  The sediments were brown in




color and no station had a significantly greater amount of solids.              •
I
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1
1
• Location
TABLE 1*
Location and Depth of Nit ex
Date
Suspended

Cloth Substrates
Recovery Recovery Depth
Date of Screens
3—|T. point of Gooseberry
fiBer Mouth (l/l* mi.
off* shore)

NBjj'. point of Split Rock
R»er Mouth
    .mi.  off shore)

      r between Split Rock
and Beaver River Mouth
                                   9/13/68
                                                      10/8/68
I.
Rive
I'
SW. point from Beaver
River Mouth
     mi. off shore)
      mi.  N.E.  of
   erve's Effluent Delta

 !"/. roint of Baptism
R^ver Mouth
(Mh mi. off shore)
9/13/68
9/13/68
9/13/68 •
9/13/68
10/11/68
Not
Recovered
10/11/68
10/11/68
                                   9/10/68
                                                      10/11/68
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  , 1*0, and 60 ft,
                                                                     10,  30,  and 1*8 ft
10, 30, and 65 ft,


10, 30, and 65 ft,



10, 30, and 60 ft.

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                                                                                I
     Bottom deposits in Lake Superior ranged from clean sand to solid




bedrock with an overlay of silt.  It did ai^rear that many of the bottom         •




deposits from "green" water stations had a heavier than noriral "silt"




overlay present as compared to "clear" water stations.  Y,c attempt was          I




made to qualitate or quantatate lake benthos.  Scuds, oligcchaetes,




midges and snails were seen in some sediments from both "green" and             •




"clear" water stations.                                                         •




     On October 19 and 20, 1968 the National Water Quality Laboratory-




diving team collaborated with personnel from Reserve Mining Company in          •




an effort to find and obtain samples of "green" water in the vicinity of




Duluth and along the south shore.  Sightings of "green" water were              I




initially made by aerial reconnaissance.  Then the KWQL divers and Reserve      •




Mining Company personnel proceeded by boat to these areas.   As in previous




sampling, the divers directed the placement of the water sampler by under-    ^^




water observation to insure collection of representative water.  At both




stations, observations were made on the character of the water from the         |




surface to lake bottom.  Sediment samples were collected from the bottom        M




at each station utilizing a PVC Kemmerer water sampler.
                                                                                I



                                                                                I



                                                                                I



                                                                                I
                                 370
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•





I





•
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     On October 19 the Big Sucker River area was sampled.  Tne river


discharge into the lake was turbid and dark brown in color, causing


an area, of turbid brown discoloration in the lake.  Southwesterly from
an area of water that was muddy and green-brown in color at the surface.


This was designated as water sample station Tic. 60.   From divers'


observations under water, the color was light green and of uniform


appearance at all depths to the bottom (5^ feet).  Unlike "green" water


observed and reported previously, very little particu.late iratter was


seen in the water. "Visibility underwater was 10 feet from surface to


bottom and the water temperature was 8° C at all depths.  Water samples


for both the National Water Quality Laboratory and Reserve Mining Company


were taken at a depth of 30 feet (Table 5).


     On October 20, the report from aerial reconnaisance indicated "green"


water occurring along the south shore just beyond a zone of reddish brown


discoloration along the shoreline.   From Duluth to 2.5 miles K.E. of


Port Wing, Wisconsin, no "green" water comparable to that occurring below


the Reserve Mining Company delta was found.  From the boat, the water in


this area had a yellow-green appearance.   Divers' observed that to a


depth of ^5 feet, the water color was yellow-brown with a green cast.


Daylight penetration was zero at ^5 feet  and again,  very little partic-


ulate matter was seen in the water.  Visibility underwater was limited
I

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                                                                                I
to six feet at a depth of 30 feet.   The water temperature was 10° C           ^P*
at the surface and the bottom (65 feet).  Water samples were taken              •
at a depth of 30 feet and bottom sediments were collected.  This
station was designated as water sample station No.  6l (Table 5).                I
                                                                                I
                                                                                I
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                                                                                I
                                                                                I
                                                                                I
                                                                                I
                                                                              4
                                   372

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1
t





1
1




1

1
f
1





1















Date
Diving Station
Identification No.

Wind Direction
Weather
Secchi Reading
Surface Water Temp.
Depth of Dive
Total Water Depth
Temp . at Lake
Bottom
Nature of Lake
Bottom
Samples Taken
Sediment
Photographs
Water Sample I.D. No.
Observations








TABLE 5

Supplemental Sampling Stations

Big Sucker River Mouth
lA mi. off
shore
10/19/68

S

West
Cloudy
8 ft.
8° C
5^ ft.
51* ft.
8° C
-
Clay, sand and silt.

X
—
60
Water at surface muddy
green-brown in color,
underwater light green
cast to water.









2.5 mi. N.E. of
Port Wing, 3 A
mi . off shore
10/20/68

T

West
Partly Cloudy
8 ft.
10° C
65 ft.
65 ft.
-

Clay - sand.

X
-
61
Water at surface
yellow-green in
color. Under surf ace
yellow-brown in color
Visibility limited to
^5 feet. Temp, at U5
feet 10° C.
I
373

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I



I



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I       1.   "Green" water occurred along the shore from the plant southwesterly



_       as far as 18 miles.



™       2.   "Green" water causes a significant decrease in lake water clarity,'



•       and appeared to be caused by the presence of finely dispersed particles



         in the lake water.



•       3.   The distribution of "green" water in the Silver Bay area was as



         would be expected if the source was from the tailings and they were



•       moved by lake currents.






I






I


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I
             MINERALCGICAL AITALZSIE, OF WATi:? SAMPLES F?OM
                  LAKE SUPERIOR A?;D TEIBtnAP.Y STREAMS
     As a result of the observation made cv the divers that the green-

vater phenomenon appears to be due to turbidity or suspended natter in

the water, an investigation was rade to determine the nature and possible

sources of the suspended materials.  Since the suspended matter did not

contain large quantities of algae or diatoms, investigations were continued

on the premise that the materials vere finely divided inorganic particles

in suspension.  Mineralcgical methods including particle size separation

and X-ray diffraction analysis thus were selected as the means cf analys-

ing the samples.


Methods and Materials

     The location and data for vater and suspended sediment samples

collected from Lake Superior are shown in Figure 2 and Table 3.  All

water samples were filtered directly without pretreatitent (except for

storage at 10° C) to remove the suspended solids.   A total volume of

lake or stream water, estimated to contain approximately 1 to 15 mg.

of suspended matter, was filtered through a pre-weighed 0.^5 P (pore

size) membrane filter.  The filters (plus solids)  were dried overnight

at 70° C, reweighed, and the concentration of solids was calculated.

For mineralogical investigations, the dried filters were mounted on

glass slides and subjected to X-ray diffraction analysis.  The samples

were scanned at 2° (2-theta) per minute using a Picker horizontal arc

diffractometer, copper X-ray tube, and nickel filter.  DiffractJon
I

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intensities were measured using a NaT scintillation detector, single


channel pulse height discriminator, and a ratemeter recorder.  All
were nade by sedimentation (2) and the percentage of the fractions obtain-


ed were calculated (dry weight basis).
Results and Discussion
                                                                                I
                                                                                I
samp2.es were rur. using a ratemeter range of 0-1,000 cpn. and a 3 second


time constant.  For the resolution and accurate determination of spacings,      •


some samples were scanned at 1/2° per minute.   Size fraction separations
                                                                                I


                                                                                I
     Results of the mineralogical analysis of the suspended solids frac-


tion (O.U5 y) of Reserve Mining Company effluent and the north shore            I


streams are shown in Table 6a.  Examples of X-ray diffraction patterns


obtained, are shown in Figures k and 5-                                         I


     The X-ray diffraction analysis of the tailings indicate that cumming-


tonite and quartz are the major constituents of all fractions examined,


with minor amounts of chlorite and mica present.  The magnetite known           •


to be present is apparently not sufficiently crystalline to be shown by


X-ray diffraction.  Cummingtonite is proportionally higher than quartz          •


in the less than 2. u fraction; quartz is the dominant mineral in the


coarse fractions.  Some separation due to sedimentation of these fractions      •


can be observed in the tailings at the delta as evidenced by the two            •


water samples (Table 3 - Samples 3 and 7) that were collected by the


divers at 50 and 100 ft..  The sample at 100 ft. contained large silt           •


and sand particles (mostly quartz) that were easily visible following


filtration and were riot present in the samples collected at 50 ft..             •
                                   373

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CQ
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                                                                                                                    K

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                                  O

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               45
                S3

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                6
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                    C\

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                              ON
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                                                     H

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                                                            3T

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                                                                  I
                                                                  I
                                                                  I
                                                                  I
                  FIGURE k                                        I
                                                                  I
                                                                  I
a.)  Effluent Cloud out  50 ft.  from  Island.                        _
     (No.  3), 9/16/68.   250ml.,  59.U mg/1.                        |
X-RAY DIFFRACTION PATTERNS OF SOLIDS  FILTERED

  FROM TAILINGS EFFLUENT AND "GREEN WATER".
b.)  "Green Water" - Split Rock Lighthouse  Bay.
     (No. 18), 9/2V68,  2,000 ml.,  3.3 mg/1.
                    330
                                                                  I
                                                                  I
                                                                  I
                                                                  I
                                                                  I
                                                                  I
                                                                ft
                                                                  I

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I
30
26
22          18

     ANGLE 20, DEGREES
                                                                       i
                                                                       6

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                                                                           I
                          FIGURE 5






        X-RAY DIFFRACTION PATTERNS OF SOLIDS FILTERED



FROM BIG MANITCU RIVER WATER AND "CLEAR" LAKE SUPERIOR WATER
                                                                      I


                                                                      I


                                                                      I



                                                                •


                                                                      •

                                                                      •



a.)  Big Manitou River at Mouth (No. 19), 10/1/68.                    ••
     500 ml. ,  92-3 mg/1.                                            ^|

                                                                      ||
                                                                      •


                                                                      I


                                                                      I


                                                                      I


                                                                      I


                                                                      I


                                                                      I



                                                                    tf
     b.)  "Clear" VJater 5 Miles out from Effluent Delta.

          (No. Ik), 9/26/68, 3,000 ml., 0.7 mg/1.
                             332

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ANGLE 20, DEGREES

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                                                                              I
     In contrast, the samples from the north shore streams, that, were


collected by resusnending bottom sediment In river water, are marked bv       •

                                                                              I
an entirely different suite of minerals.   The normal group of soil clay


minerals prevail including kaolinit-e, mica, vermiculite, chlorite, the        •


feldspars, and quartz.   In two samples (1Q &r.d 21) minor traces of an







                                                                              I
     In cooperation with personnel from Reserve Mining Company additional


water samples were collected by the divers along the Wisconsin shore of       •


Lake Superior in early November.  On the basis of aerial observations


an area of "yellow-green" water was identified approximately 2-1/2 miles      |


northea,st of Port Wing, Wisconsin, and extended roughly one mile into         •


the lake.  This area of highly turbid water was produced by heavy local     ^^


runoff following rainfall.                                                    I


     Observations by the divers indicated that near the edges of the


turbid area the water color was a dull brown to greenish-yellow and           |


that becaiise of the turbidity light penetration was less than 6 feet.         •


     Analysis of a single water sample collected by the divers contained


a suspended solids content (> 0.^5 p) of 2.7 mg/1.  X-ray diffraction         •


analysis of these solids indicated that mcntmorillonite, mica, chlorite,


and quartz were the dominant minerals present.                                |


     Traces of feldspar and an unidentified amphibole, possibly cumming-      «


tonite, were present.  The X-ray diffraction pattern recorded fcr the
                                                                              I
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solids from this s&mple was similar to those obtained with the finer


fractions of "bottoir. sed.inen.ts collected in this area of the lake, by


the State of Wisconsin, described below.


     The distinguishing characteristics of the effluent tailings are:


1.) large quantities of cummingtonite especially in the 2 - .^5 V


fraction and 2.) absence of feldspars and kaolinite.  As early as 19^9


the conclusion was reached (3) that "identification of minerals in the


sediment will not likely enable an investigator to determine the source,


since many minerals are common to both the shore rocks and the iron ore


deposits."  Trathewey's identification of grunerite (by microscopic


examination) in a single fraction of a single bottorn sample appears to


be the basis for the general conclusion that "grunerite" is unreliable


as an "identifier" of taconite tailings (h).  This is a rather broad


generalization fror such limited data and ignores completely the marked


differences in mineralogy and particle size differences that do exist


between "tailings" and. natural sediments.   Grunerite (and similar


amphiboles) may occur in the stream and lake sediments, but as a minor


constituent of the silt and sand fractions only.  Only trace amounts


were found in two of the six streams sampled.  A complete absence of


grunerite or any of the amphiboles was noted in the <2y fractions of


the bottom sediment samples studied (See Table 6d).  Whereas, grunerite


(or most probably cummingtonite) is a major constituent of the taconite


tailings jn all size fractions, including those less than 2 y (clay


size).  This size fraction was not considered or analyzed in earlier


reports (3, 5).
                                            385

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                                                                              I
     The present study indicated that "grunerite" in the tailings is




a physical mixture of two amphiboles, cummirigtonite and grunerite.            M




Based on comparisons with X-ray diffraction studies of reference cumming-




tonite and grunerite specimens, and on published work (6) (7), cumrning-       •




tonite is the major amphibole mineral present in the taconite tailings




with an admixture of a small amount of grunerite.  A total of 7 X-ray         ||




diffraction spacings have been resolved for the major amphibole found         _




in the tailings and the spacings agree closely with those for reference       *




cummingtonite rather than those for grunerite.  The mixture of cumming-       II




tonite and grunerite thus found serves as a unique means of identifying




the taconite tailings.  The relative quantities of the two that are           •




present in a tailings sample may be dependent on the particular source(s)




in the mine, although this should be verified.                                ™




     Results of the analysis of the water samples are shown in Table 6b.




These results have been grouped on the basis of visual observation into




"clear" and "green" waters.  Within groups, the samples are listed in         •




order from Northeast to Southwest.




     The more obvious analytical differences shown in Table 6b, are in        W




the suspended solids and cummingtonite-grunerite content of these solids.     •




A suspended solids content of approximately 1 mg/liter or more occurred




in water having a characteristic "green water" appearance.  The water         •




samples collected in "green water" areas on October 1 and 8, 1968 (Nos.




26, 28, 31 and 32) were collected at the edges or near limits of the          •




"green water" areas and show solids contents near, or slightly less,          •




than the 1 mg/1 limit.
                                   336

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     The suspended solids frcr: Pegerve's discharge as identified by


their cummingtonite contents and shown in Table 6b, vary inversely in


proportion to the distance parallel to shoreline fro:r: the tailings


effluent delta, evidence that the effluent delta is the source of the


suspended solids and of the "green water1'.  As a further test of the


source of the "green water" solids, selected solids were subjected to


more detailed X-ray analysis.  Sample 8 (collected 3-lA rr:ile south-


west of the delta), sample 15 (collected midway between Split Rock and


Gooseberry Rivers), and sample 32 (collected 1/2 mile out from Crow


River) each showed the presence of the mixture of cummingtcnite and


grunerite which characterizes the taconite tailings, as noted earlier.


     As a further test of the validity of the cummingtonite-grunerite


mixture in the suspended solids as a unique tracer, the X-ray diffraction


peak heights for both the curnmingtonite and quartz in the samples were


subjected to statistical analysis.  Regression analysis of peak height


vs. the weight of suspended solids showed correlations of 0.90 for


cummingtonite and 0.79 for quartz with standard errors of estimate of


the mineral contents (X) of ± 0.133X and ± 0.201X respectively, for


10 mg samples.  The implications of these statistical analyses are:


     1.   The cummingtonite and quartz contents of the suspended
          sediments are essentially the same within a very
          narrow range, and


     2.   These suspended sediments arise from a common source

          which is relatively uniform in its composition of
          cummingtonite and quartz.


This is strong evidence that bottom sediments or stream sediments are


not the source of the cummingtonite or quartz in. the "green water".
I

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     With equal sample weights, kaolinite and other clay minerals are




below Units of detection ("by the X-ray techniques used) in the vicinity       •




of the plant, because of the predominance of cuimningtonite and quartz




in the suspended solids in this area.  Further "down-lake" the suspended       •




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portion.
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     Since mineralcgical analyses can "be used to characterize the


source of suspended material in vater samples, this technique could


be used for identifying the source of the sediment that accumulated


on the net substrate suspended in Lake Sirperior along the North Shore.



Methods an d Plater I als


     Material accumulated on the Nitex nets was rinsed with distilled


water, from the nets into a 250 ml beaker.  This suspended matter was


then dispersed thoroughly in approximately 200 ml. water, and a portion,


equivalent to 10 - 50 mg solids of the suspension, was filtered using a


0.1|5 V filter as described for water sairxles.  This material was retained


as a representative sample of the material collected and the remainder


was treated with 10 ml. of hydrogen peroxide to oxidize the organic


matter (mostly diatoms).  The inorganic solids were then resuspended


and a subsample of the less than 5 y size fraction was separated by


sedimentation techniques.  The <5 y subsample and the coarse fractions


remaining were then filtered and mounted as previously noted, for


X-ray diffraction analysis.



Results and Discussion


     A gross examination of the original material on the nets indicated


that most of the accumulated material consisted of organic matter.  There


appeared to be little, if any, difference in the total quantity of material
I
                                            391

-------
                                                                               I
at the different stations.  There was, however, a. distinct difference        '




with depth at f.ny location; the surface nets showing a more luxuriant          .




growth of the ci at or::-algae coating.  Since the bulk of the sample in




each case was organic in origin, and the inorganic residue contained           B




a variable number of diatom frustules (or shells), no attempt was




made to measure the rnineralogical content of the original sample.  Thus,       •




the results of the r.ineralogical analysis, as shown in Table 7, are            _




qualitative only and should be interpreted in this light.                      ™




     All the net samples analyzed, with the exception of that collected        B




at the mouth of the Baptism River, showed the presence of cumningtonite.




Detailed examination of the two fractions from the surface net at Beaver       B




River mouth (Ul and 50) showed them to contain the sar-e cummingtonite-




grunerite mixture as found in the tailings effluent and green water            •




samples.




     Nearly all the net sediments contained some material that originated




in the nearby north shore streams as evidenced by the presence of measur-      B




able feldspar and kaolinte in some fractions.  Additional microscopic
I
examination of the coarse inorganic residues indicated a large proportion




of diatom frustules.  The crystalline mineralogical particles made up a




minor fraction of the total sample.




     In summary, the crystalline inorganic portion of the material accumu-     •




lated on the nets located close to, or southwest of the tailings effluent




delta, contained cummingtonite but northeast of the delta at the mouth of      B




the Baptism River, none was found.  The inorganic portion, however, makes      •




up a minor part of the material on the nets.
                                                                               I

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                             MINERALOC-TCAL ANALYSIS OF BOTTOM

                      SEDTMEIITS COLLECTED BY WISCONSIN DEPARTMENT OF

                                     NATURAL RESOURCES
     A number of bottom sediment samples were provided by the Wisconsin


Department of Natural Resources.  These samples were collected with a


Peterson Dredge from the locations shown on the accompanying map (Figure


6).  For the present study, only the <2 u fraction of these samples has


been analyzed.


     The results of the X-ray diffraction analysis of these sediments


are shown in Table 8.  I!o attempt was made to measure the percentage of


fine material present, although from a visual examination samples 19


arid 20 were largely fine materials, while 23, 3^, and 5^ were mostly


sand or coarse sand with less than 10$ clay present.  The mineralogical


analysis show the fine fraction to contain a variety of clay minerals,


with kaolini'oe, vermiculite, mica, and montmorillonite making up the


bulk of the materials.  No trace of cummingtonite or any of the amphi-


boles was noted in these samples.


     Specie! note was made by the collectors, that sample 20 was of a


"hard thin b]ack strata".   Closer examination of the hard black material


showed it to be composed mostly of clay-sized material cemented with iron


and/or manganese oxides.  X-ray examination of the black material revealed


only peaks of quartz and a poorly crystalline oxide material—probably
I
                                              395

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             SPECTROSCOPIC STUDIES ON LAKE SUPERIOR WATER




     In order to differentiate quantitatively between the "clear",


"green", and "gray" water samples, the visible spectra of liquids


and suspended solids were examined.




Exp e r imen t a 1


     A Gary Model lU ratio recording spectrophotometer equipped


with a High Intensity Visible Source Accessory NO. 1U71200 was used


to record the optical density and wavelength measurements.  Reflec-


tance measurements were made on solids using the Cell Space Total-


Diffuse Reflectance Accessory, Model No. 1^11750.  Liquid samples


were viewed through 10 cm. cells with quartz windows.  The reflec-


tance spectra of solid samples were recorded directly from the O.U5y


Millipore filter membranes upon which they had been collected.


     The wavelength, X, calibration of the spectrophotometer was


effected by using a NBS holmium oxide glass, No. H-122.   The optical


density or absorbance calibration was made using neutral density

                                                         * ,
filters of known value.




Experimental Data and Results


     The spectra of "clear", "green", and "gray" water samples show


a small absorbance versus distilled water over the wavelength range

          0         °  , °                          ft   ^
from 7500 A to 3000 A, (A H Angstrom unit, 1 x 10  °cm.).  This


absorbance is characteristic of particles suspended in the liquid


sample and is due to scattered light.  The magnitude of this absorb-


ance is approximately proportional to the quantity of suspended
                                             397

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shape, showing an increase in absorbance at shorter wavelengths.  All
                                                                             I
particles present.  The concentration of the particles increased in


the order "cles.r", '"green", ''gray" for liquid samples.  The concen-          •


tration of any dissolved substance which could give rise to an absorb-


ance was not great enough to be detected using a 10 en. cell path            •


length .


     The scattered or reflected light due to the suspended particles         B


was studied by recording the total diffuse reflectance of the suspend-       im


ed solids after they were collected on a 0.^5 M Milliuore filter.


Typical spectra for the solids obtained by filtering the same yolume_         •


of "clear water" and "green water" sariples are shown in Figure 7-


The number of the spectral traces correspond to sariple numbers listed        |


in Table (3).  The lower two traces are from the solids in 3 liters


each of "clear water".  The upper two traces are from the solids in


3 liters each of "green water".  The absorbance bands at 1*200, 6lOO,

         o
and 6700 A have the sair.e approximate ratio as those for chlorophyll


A (8).  In Figure 8 typical spectra for the same weight of solids


obtained by filtering "clear1' and "green" water samples of different
                                                                             M
                                                                             I
volumes are shown.  The most striking feature is the increase in

                            o
absorbance of light at HOOO A can give rise to a visually (to the eye)       •


observed yellow-green color (9)^  Figure 9 gives a comparison of the


typical spectral traces for solids obtained from "clear", "green",           •


and "gray" water samples.                                                    —


     The reflectance spectra of all solid samples have the same general      ™
                                                                             I

-------
"the "green water" solids spectra are similar in shape.  The increase

in absoroance at shorter wavelengths r.ay be attributed to either an

absorption band vhich is characteristic cf the composition of the

solid o_r to a light scattering effect due only to the size distribution

of the particles or a combination of both.  For effective light scatter-

ing by small particles, the particle size must be in the order of 0.05x

(wavelength of the light being scattered or absorbed), (10).  The

theoretical absorbance due to light scattering by small particles

varies with the wavelength of the scattered light.  The equation (10) is:

     Absorbance (scattering) = (constant) x (wavelength) ~y, where

y = lj. (l).  In practice this equation is obeyed to the extent that y
                                                             o
ranges from 3 to U for particles whose size is less than 150 A (ll).

For particles greater than ^150° A, y is less than 3.  The mathematical

analysis of the average "green water" solids spectra obey equation 1,

where y ranges between 2.h to 3-7-   The analysis of the "clear water"

solids spectra give y in the range  of 2 to 3-

     The mathematical analysis of the "green water" solids reflectance

spectrum using a chromaticity diagram (12) gives the dominant wave-
                                           o
length of the reflected light of £§_.  5750 A.  Light of this wave-

length is visually observed as a yellow-green color.

Discussion and Conclusions

     The "clear", "green", and "gray" water samples can be differen-

,iated by the quantity of suspended particles "present in each and by

 he reflectance spectra of the filtered solids.   For the same volume
                                  399

-------
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                                          "Green"  Water
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the "green water" solids spectre, are similar in shape.  Ihe increase


in absorbance a.t shorter wavelengths r.ay be attributed to either an


absorption band which is characteristic cf the composition of the


solid o_r to a light scattering effect due only to the size distribution


of the particles or_ a combination of both.  For effective light scatter-


ing by snail particles, the particle size must be in the order of 0.05x


(wavelength of the light being scattered or absorbed), (10) .   The


theoretical absorbance due to light scattering by snail particles


varies with the wavelength of the scattered light.  The equation (10) is:


     Absorbance (scattering) = (constant) x (wavelength) ~^,  where


y = H.  (l).  In practice this equation is obeyed to the extent that y

                                                             o
ranges from 3 to k for particles whose size is less than 150  A (ll).


For particles greater than ^150° A, y is less than 3.  The mathematical


analysis of the average "green water" solids spectra obey equation 1,


where y ranges between 2.k to 3.7-   The analysis of the "clear water"


solids spectra give y in the range of 2 to 3.


     The mathematical analysis of the "green water" solids reflectance


spectrum using a chromaticity diagram (12) gives the dominant wave-

                                           o
length of the reflected light of ca.  5750 A.  Light of this  wave-


length is visually observed as a yellow-green color.



Discussion _and Conclusions


     The "clear", "green", and "gray" water samples can be differen-


tiated by the quantity of suspended particles present in each and by


the reflectance spectra of the filtered solids.   For the same volume
I

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          '*',— "Gray'' Water
                                   "'..     Solids
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                                             Solids
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                                             Solids
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                                   O    =«=

                                   H  fn ^i
                                   
                                   (L) -
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                                                                   to
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-------
 I
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 I

 I
 I
 I
 I
 I
 I
of each type of water sample the absorbance increases in the order


'"clear", "green", "gray" for the solids which have been filtered from


the samples.


     The chlorophyll absorption "bands which are superimposed on all


the "clear" and "green" water solids spectra ara approximately constant


indicating that about the same amount of plant life is present in each


type of sample.


     Since the spectra of the "green" water solids obey the scatter-


ing equation for small particles, the a.bsorbance of light can be


attributed to light scattering effects cf particle size (and geometry)


and not necessarily to the composition of the particle.  The dominant

                                                            o
wavelength of light reflected from these solids is ca. 5750 A.  This


gives a visually observable yellow-green color.


     The scattering efficiency of particles increases as the particle


size increases (10).  The "gray" water samples contain an appreciable


fraction of larger sized particles as is indicated by stronger


absorbance at longer wavelengths than that for the other sample types.


This absorbance would mask the absorbance of the smaller fraction of


small particles and therefore would not give the same visual appearance.
I

-------
                                                                              I
 1.    H.  D.  Pat n art and T.  A.  Olson;   Studies on the__Productivity and          I
      Plankton of Lake Superior,  196l, p.  16.

 2-    So i 1 Clie m i c ^ l__A.na ly sis, Advanced Course, M.  L. Jackson, Univ. of
      Wise., 1956.

 3.    Trathevey, W.  D., Lake  Superior Sediment.  A Condensation from          •
      the Monthly Reports  of  W.  D.  Trathevey,  19H8-19-9.                      I

 h.    Letter dated September  21,  1967 from Edvard Schmid, Director of         •
      Public Relations, Reserve  Mining Co., to Lyle E. Smith, Minnesota       I
      Pollution Control Agency,  Minneapolis, Minnesota.  Report attached
      on "Lake Superior Sediment".

 5.    Schwartz, G. M., 1958;   Report on Bottom Samples in and near            •
      Silver Bay, Lake Superior.   Minnesota Geological Survey.

 6.    Ghose, S. , 196l;  'The Crystal Structure of Cumr.ingtonite.               |
      Act a.  Cry st.  ill:  622-627-

 7.    Ghose, S. end Hellner,  E. ,  I960;  The Crystal Structure of              I
      Grunerite and Observations  on the Mg-Fe Distribution.  Jour.
      Geol.  67:  691.•
      J.  S.  Fruton and S.  Simmonds,  General Biocheitistry, 2nd ed. ,
      John Wiley, N.Y., 1958, p.  5^8.

      F.  W.  Sears and M.  W.  Zemansky,  University Phy s i c s, 2nd ed.,
      Addison-Wesley, Reading, M 285,  p. 8l6.
I
10.    H. C.  van de Hulst,  Light Scattering by Small. Particles,                I
      J. Wiley, N. Y.,  1957-    "

11.    Arlin Gyberg, Light  Scattering, Ph.D. Thesis, 1968, University          •
      of Minnesota, private communication.                                    •

12.    W. W.  Wendlandt and H. G. Hecht, Reflectance Spectroscopy,
      Intel-science Publishers, N.  Y. , 1966, pp 228-251.
I

I

I
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