001R80100
                             BLACK RIVER
                    WASTE LOAD ALLOCATION REPORT

                               Volume II
                      Water Quality and Effluent Data

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                                                   VOLUME !!


                                   WATER QUALITY AND EFFLUENT  DATA
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                        SURVEY 0? THE BLACK HIV3R IN THE SLYRiA, OHIO AREA.
           I n t ro clu ct i o n
                  This survey was  conducted at  the  request of  the  staff of the Division      e

        of Engineering.  Ohio Department  of Health,  in  September, 1970.  The purpose of       5.
                                                                                         X  |i
        the survey was to determine the  effect  of untreated municipal, industrial and        &
                                                                                            tf

•       storm sewer discharges on  the Black River.   The  survey.was conducted  from Rt. 20

        bridge on the west branch  and Coonville Road bridge on the east branch of the

•       Black River to the Ford Road bridge on  the  Main  Stem of the Black River which is

        one-half mile down stream  of the Elyria sewage treatment plant.  River samples were

        collected at ten locations as shown in  Table I.

•                 Three- individual surveys were conducted to collect Black River water

        samples (l) October 7, 1970, (2) October 13, 1970 and  (3)  November 11, 1970.  On

*       October 7, 197--> and October !>> 1970,  samples were also collected from the over-

•       flow of the 1'our.t Street, Pumping Station, Elyria Foundry,  a combined  sewer overflow

        west of Earshaw Chemical on October 19, 1970.  A  sample was also obtained of the

•       Harshaw discharge to the east branch.

_                 During the survey, the Fisc'nar Body  plant of General Motors was on strike.

*       This plant is a large plating operation involving the  use  of  chromium, copper and

I       zinc.

        Sample Analysis

•                 All stream samoles were analyzed  for field dissolved oxygen and temoera-
m                                                                                           \
_       ture, BOD, COD, color, conductivity, pH, total alkalinity, suspended  solids, volatile

*       suspended solids, dissolved solids, chlorides, fecal coli, and heavy  metals: cadmium

I       total chromium, total iron, nickle and zinc.  The results  are tabulated in Table II

        through Table V.  The most significant  data are  shown  graphically in  Figures 1
           through ^.

-------
Observations




          iiui'l:*., alx s-r.-j;, tl.ป v-e?^ Branch ,/f 'die Lla^k ?\iver w;,.j very black




in color.  The source of this black color was traced to the discharge of Elyria      *




Foundry.  An engineer from the Northeast District Office visited the foundry to




initiate procedures to place them under a Water Pollution Control Board discharge




permit and to begin corrective measures.




          Large brown oil slicks were also observed on the east branch of the




Black River for considerable distances upstream and downstream of Marshal Chemical.  ['




The exact source of the oil was not determined, but was traced to a storm sewer




discharge just downstream of the East Bridge Street bridge.




          Foam was observed along the banks of the east branch at Washington Avenue,




and was generally orange in color.  It is believed that this material is discharged




by Obetts Chemical Company.




Results




          The data are tabulated in Tables I through V and are shown graphically




in Figures 1 through k.




          The d.E.'ca show a substantial increase in BOD and NH-, at station 10,         I



                                                                                     I
Washington Aver.ua, on the east branch of the river.  This increase undoubtedly re-   ?




fleets the overflow of domestic sewage from the combined sewer west of Harshaw and   |




the overflow from the Mound Street pumping station.  It is also noted that the




fecal coli. count at all stations exceed the standard of 200 per 100 ml.  This




substantiantiates the fact that there is domestic wastes being discharged to the




river over the entire section under study.




          The data also show that in general there is a substantial increase in




heavy metal concentration on the east branch below East Bridge Street.  The data




in Table V indicate that there is heavy metals being discharged to the river from




the combined sewer overflow and the Mound Street oumoin^ station overflow.  While

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part of this Increase in heavy raetals  can be  contributed to Harshav; Chemical,


the data also indicate there are other sources  in  the  City of  Elyria v/hich  are


disehnr-riru; heavy netals to the sanitary sewer.
 1-25-71
                                       -~->-

-------
                                TABLE I
Sample Locations

A.  Black River

      1.  Beio>.' Elyria Sewage Plant at Ford Road bridge,
      2.  At entrance to Cascade Park.
      3-  In Cascade Park above dan.

B.  West Branch Black River

      h.  Lo-ii Street Bridge
      5.  V. Third Street Bridge
      6.  1'ussay Avenue Bridge
      7.  Ht. 20 Bridge

C.  East Branch Black River

      8.  Coonville P.sad Bridge
      9-  East Bridge Street Bridge
     10.  Washington Avenue Bridge

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                                                Attachment E



                                           EPA  Survey,  March i-3, 1972
Pi.

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D.   Fish Flesh Tainting Study

       From March 1, 1972 to March 3, 1972, a fish flesh tainting
    study using caged channel catfish (Ictalurus punctatus)  was
    conducted in the Black River in the area of the U.S. Steel  -
    Lorain V/orks.  The flow of the river at the USGS cage in
    Elyria was 585 cfs on March 1, 1972, 2720 cfs on March 2,  1972,
    and 2670 cfs on March 3, 1972, generally above the average
    March flow of 800 cfs.  The survey was conducted in March  to
    avoid low dissolved oxygen concentrations prevalent in the
    warmer months which would tend to cause fish mortality.
                                                               \
       At each location baskets containing three catfish (one
    pound average) were placed on both the right and left bank of
    the river.  The fish  remained in the river for two days (^8
    hours).  Mortality controls were maintained in wall water  for
    the same period.  Upon  recovery, all fish were cleaned and
    immediately frozen using dry ice, and then shipped to the
    Department of Food Science and Technology at Oregon State
    University for taste  evaluation.

       The fish were thawed  in the laboratory at 3-3ฐC and then
    wrapped  in aluminum foil.  After baking, the fish were removed
    from the oven and flesh  from each sample was flaked and sub-
    divided  for the test  panel.  Panelist were given a known
    reference along with  the test samples.  Each sample was pre-
    pared as two  replicates  and was rated by ten judges on a
    seven point scale.  "Blind" references were also included  in
    the study.  Fish scoring five to seven points were considered
    to have  acceptable flavor.  Analysis of variance techniques
    were used to  determine  least significant differences between
    test and  reference samples.

       The  results of the study are tabulated in Table  I I I -3.   Thes
    data indicate that fish  flavor was significantly affected  in
    the stream segment from  the coke plant discharge (Outfall  002)
    to below Outfalls 003 and 004 at the downstream end of the
    turning  basin.  The effect on flavor was most likely due to
    phenolics and possibly  oils.  Concentrations of phenolics  were
    highest  on March  1,  1972 when the stream flow was much lower
    than on  March 2 and 3,  1972.  The improvement in flavor below
    the turning  basin was probably the  result of the stream mix-
    ing with intruding lake  water.  These  results must be evalu-
    ated  in  terms of  the  stream flow encountered during the survey
    and the  time  of year.   Since the effects of the discharges
    from the Lorain V/orks were mitigated by the large amount of
    dilution afforded by  the stream, more  severe results at lower
    stream  flows  and  similar waste loadings would be expected.
    However, significant  reductions  in the coke plant phenolics
    discharges  since  1972 may have improved the situation at
    critcal  flows.
                    111-37

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-------
                                           Attachment  F



                              U.S. EPA Survey, September 12-1&,  1972
7

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         Attachment G


U.S. EPA Survey,  April 30, 197*

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April 30, 1974 Survey



     Table  G-l presents station  descriptions for  the 43 sampling points

employed during the spring survey.  The data obtained are presented at the

end of this attachment. Figure G-i illustrates the station locations. Beaver

Creek and the East and West Branches of the  Black River and one point on

the main stern (USGS gage - Cascade Park) were  sampled on April 30, 1974.

The lower Black River from Elyria  to its mouth and two stations in Lake

Erie were  sampled on May 2, 1974.  These data are reviewed in Attach-

ment H.



Beaver Creek (Stations 3C1 to BC5)



     On April 30, 1974 the flow  of Beaver Creek ranged from 2.7 cfs at

RM 10.7  (Russia Road), above  Amherst, to 20.6 cfs  at  Kolbe Road  about

1.7 miies above its mouth in Lake Erie. This is about 10 times the estimated

water quality design  flow of about  2 cfs which  would be expected during

extremely  dry weather.  The  pH of the  stream ranged from 6.5 to 7.0

standard units.    Dissolved  oxygen  concentrations  ranged  from 7.1 to

11.5 rrg/, at the six stations, with Stations BC3 and BC4 having concentra-

tions in excess of saturation values indicating  possible algae problems.  The

dissolved oxygen dropped from 11.5  mg/1 at Station BC3 to 8.5 mg/1 (100%

saturation) at Station BC2 due  to the effects  of the Amherst  STP, but  was

again abc'/e saturation at 9.8 mg/1 at Station BC1.  An ammonia concentra-

tion of 2.38 rng/'l was  recorded below the Amherst  STP, a violation of the

previous  1.5 mg/1  water  quality  standards.    The BOD,-  concentration

increased by a factor of 4 below the Amherst  STP and the total phosphorus

concentration more than doubled. Figure G-2 illustrates these trends.

      Aside  from  arsenic concentrations at the  detectable limit of  2 yg/1

found below the Amherst STP, Beaver Creek  was free of contamination by

heavy  metals on the sampling  date.  The bacteriological data indicate the

possibility of  continuing violations of fecal coliform criteria most probably

the result  of  discharges from the numerous  semi-public sewage treatment

plants and the Amherst STP.

-------
East Branch of Black River (Stations El to E9)

     On April 30,  1974, the  flow in the main stem of the Black River at the
USGS gaging station in Elyria was 132.5 cfs, or about 15 times the estimated
water quality  design  flow of about 9 cfs at that point.  This flow is  only
about one-fifth of the average April flow of 645 cfs.  Hence, the flow on the
East Branch was probably below normal for April,  but well  above critical
flows on the sampling date.  Aside  from bacterial contamination at all  nine
stations, the water quality  of the East Branch  was generally  within Ohio
Water Quality Standards on the sampling date.  There were increasing levels
of organic contamination and phosphorus with  travel downstream toward
Elyria.   Cadmium was  detected at concentrations of 10 and 12 yg/1 at
Stations E7 and E8, respectively, the new water quality standard  is 12 yg/l
and the standard in effect at the time of the survey was 5 pg/1.  Lead was
detected  above the  water quality standard of 30 yg/1 at  Station E3,  just
upstream of Elyria, and at 42 and a 48 ug/1 at Stations E4 and  E5, just below
Graf ton.  Sources  of cadmium and lead have not been positively identified.
However, tne  lead appears to originate in the Graf ton area, and cadmium
may be r.onpoint source  oriented, as was found in the Grand River, Ashtabla
River, and Conneaut Creek basins in Northeast Ohio.

West Branch (Wl to WS)

     The upper West  Branch was well within water quality standards on the
sampling  date  as evidenced by  data obtained at Station  \V6,  however,
Charlemont Creek (Station W8) exhibited severe bacterial contamination and
high concentrations of  BOD_,  phosphorus, ammonia, and total  Kjeldahl
nitrogen, suggesting contamination by the Wellington STP.  There  does not
appear  to be any metals contamination in the upper  West Branch.   The  poor
quality  of Plum Creek  is a result of the  Oberlin STP which was being
upgraded during the survey.  The  stream  BOD5 concentration was 18  mg/1
and the ammonia concentration  was 12.7 mg/1, greatly exceeding  the  1974
1.5 mg/1 standard.  The phosphorus concentration was  4.66 mg/1.   With the
flow of Plum Creek close  to 5 cfs, the loadings from the Oberlin  STP were

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exceptionally high on the sampling date. The effect of this discharge is also

seen at Stations W5 and W4, although mitigated somewhat by dilution.  Lead

appears at 48 yg/1 at Station W5, which is above the 30 yg/1 standard, and it

would appear that Plum Creek is the source, but data at Station \V7 on  Plum

Creek show no lead. Arsenic was also found at the detectable limit of 2 yg/1

at Stations W3, Wf, and NV5.  Dissolved oxygen concentrations in  excess of

saturation at Station W2,  W3, and NY4 indicate  algae problems,  no doubt

aggravated by the  Oberlin STP  discharge.  Bacterial contamination in the

lower West Branch probably results  from  the Oberlin  STP and  numerous

semi-public discharges in the area.

-------
















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                          FIGURE G-l
                 BLACK RIVER PLANNING AREA
                   STREAM SURVEY  STATIONS
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                 LE2
LAKE

-------
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-------
                                   UNITED  STATES  ENVIRONMENTAL  PROTECTION  AGENCY

                                                       REGION 3C
                                             MICHIGAN-OHIO  DISTRICT  OFFICE
STREAM:  BEAVER CREEK
STATION   IDENTIFICATION:  See  below
SURVEY  DATE: April 30, 1974
TABLE
STATION NUMBER
RIVER WILE
MODO SAMPLE NUMBER
Row (cfs)
pH (STD. units)
Ternpsr^ture (ฐF)
CorxJijcT'ฅ:*y (umhos/cm)
Diซ->v2d Oxygen (mg/l)
Dissolved Oxygen % Sat.
8C05 (mg /I)
BCD 20 fag/I)
COD (mg/'i)
TOC (ma/!)
Sal ds. Total (tig /I)
ScJ'as, 0;ssc!vsd (•ng/i)
?c] ds, Soscended (m/l)
i--'cniS5 (rg/l CaCO,)
Anc'.P.tty '>g/i CaCOj)
Chcncie C^g/l)
Fluoride (mg/l)
Su!f.3?3 (,T.g/l)
Phcspho'i-s, Tefal (-^'i.P)
Tote! Xje.dcol-N . (mg/l)
Ar-.mor'io-N fag/I)
Nifrc'e-::'Titi-rj (ma/!)
C,i cr-; GI-.-CSS (ff.s/0
Cyai :. 7o^a! (.T-g/i)
p-.snc: (•''IS/I )
MB AS (-rg/l)
F^;Q C-'.-jrtn (>Joa/ICOrri)
Feco! S:,- •;. (;\os./iOOml)
AI-iTtir-jm, Total (ug/l)
Arse^-c, TotaS (ug/l)
Bcrv.m, To'cl (ug/l)
Beryliium, Tolc! (ug/l)
Cad.-niu-n.Totcl (ug/i)
Cn'orriium, Total (ug/l)
Cnromium, Hexava'ant (ug/l)
Copper, Total (ug/l)
Iron, Tote! (ug/l)
Iron, -Dissolved (ug/l)
Lead, Total (ug/l)
N'ongan^s*, Total (ug/l)
Mangcnsse, Dissolved(ug/l)
Merc-jry, Total (ug/l)
Nic^l, Total (ug/l)
Sc-''.rium, Total (ug/l
Silver, Total (ug/l)
Tin, Total (ug/l)
-ป• T- , _ I / _ / 1 \
BC1
1-7
927**
20.6
7-0
-
2200
9.8
-
5.*ป
14.9
M
11
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^20
5
197
123
65
0.26
93
0.8'(7
0.9
0.70
0.83
1
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-
0.36
4i(00
650
<200
2
<50
<2
<10
<30
<5
<15
M>0
55
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70
85
<0.2
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<5
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2.9
9275
12.2
6.5
75
2000
8.5
100
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55
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192
127
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2
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760
40
46
80
90
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-------
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                                    UNITED  STATES  ENVIRONMENTAL  PROTECTION  AGENCY
                                                        REGION  3T
                                             MICHIGAN-OHIO  DISTRICT  OFFICE
STREAM:  EAST BRANCH BLACK RIVER
STATION  IDENTIFICATION: see below
SURVEY DATE: April 30, )974
TABLE
STATION NUMBER
RIVER MILE
MODO SAMPLE NUMBER
Flow (cfs)
pH (STD. units)
Temperature (ฐF)
Conductivity (umhos/cm)
Dissoivsd Oxygen (mg/l)
Dissolved Oxygen % Sat.
BOD5 (mg /!)
BCC20 (mg/1)
CC3 (mg/0
TCC (mg/0
ScxCs. Total {mg/O
Sdiis, Dissolved (mg/i)
Sc';0s. Suscended (rr.g/1)
Har.-.2S5 (mg/i CcCC-)
A.\;-.iP!ty (mQ/l CoC03)
Ch'cnce (mg/l)
Fborics {rrg/0
SuSt3-e (me/I)
Pr-.wor'js, Total (rrg/!,Pj
To'c! K]?!dah!-N (-nt;/:)
Amr-c-.ia-!'-; {mg/!}
rJ::r=r^-Nirrite — N (mg/l}
0:: end Grecss - - {^g/O
Cycr;de, Totai {mg/i)
Fi-.epci (mg/l )
MS AS (rr.g/l)
rs:ci Cci'orn (NcsAGO .7>')
Fe:=; Streo. (NJos./iCOml)
Aluminum, Totc! (u;/l)
Arsenic. Toial (ug/l)
ficr-rn. Total (ug/l)
Beryllium, Total (ug/l)
Cadmium, Total (ug/l)
Chromium, Total (ug/l)
Chromium, Heaavalent (ug/l)
Coppsr, Total (ug/l)
Iron, Total (ug/l)
Iron, Dissolved (ug/l)
Lead, Total (ug/l)
Mcmganesa, Total (ug/l)
Manganese, Dissolvstl(ug/l)
Mercury, Total (ug/l)
Nickel, Total (ug/l)
Selenium, Total (ug/l)
Silver, Total (ug/l)
Tin, Total (ug/l)
-7-. — T_..,I /..,,/n
El
0.1)
9287
„
8.1
63
630
7.2
77
6.2
H.5
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9
i.i*it
436
7
234
iMt
37
0.13
116
0.227
1.1
0.19
0.28
3
<0.005
<2
0.14
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-
<200
<2
55
<2
<10
<30
15
25
620
25

-------
                                   UNITED  STATES  ENVIRONMENTAL  PROTECTION AGENCY
                                                       REGION 3ZT
                                             MICHIGAN-OHIO  DISTRICT  OFFICE
STREAM:   see  below
STATION  IDENTIFICATION:  see  below
SURVEY  DATE:  April 30,  1975
TABLE
STATION NUMBER
RIVER MILE
MODO SAMPLE NUMBER
Flew (cfs)
pH (S TO. units)
Temperature (ฐF)
Conductivity (u mhos/cm)
Dissolved Oxygen (mg/1)
Dissolved Oxygen % Sat.
3 CD 5 (mg /I)
eoo2o (mg/D
, COD (mg/l)
TOC (mg/0
Scitds, Total (-g/l)
Soiids, Dissolved (mg/i)
ScMs, Suspended (rrg/l)
hcrcrssss (rrg/l CaCO^)
AXclipity (mg/i CcCOj)
Chloride (mg/l)
Fluoride (mg/l)
Suiiafe C^g/0
Phosphorus, Total (mg/!,P)
Totd Kjeidchi-N (mg/l)
Ammonia— N (mg/l}
Nitrcte-Nifrjte-N (me/i)
Gil end Gr3cs2 (rrg/l)
Cyanide, Total (mg/l)
Pr.enol (mg/l )
M3AS (rrg/l)
F2=d Conform (Ncs/.OOm!)
reco! Strep. (Nos/iOOml)
A'ljminum, Total (ug/1)
Arseric, Total (ug/1)
Bcrisjrn, Total (ug/ 1)
Beryllium, Total (ug/1)
Cadmium, Total (ug/1)
Chromium, Total (ug/1)
Chrcmium, Hexavalsnt (ug/l)
Copffr, Totni (ug/1)
Iron, Total (ug/1)
Iron, Dissolved (ug/1)
Lead, Total (ug/1)
Manganese, Total (ug/1)
Manganese, Dissolvsd(ug/l)
Mercury, Total (ug/1)
Nickel, Total (ug/1)
Selenium, Total (ug/l)
Silver, Total (ug/l)
Tin Total (ua/ll
E9
H.3
9292
-
7.3
63
630
6.6
71
2.k
5.2
16
7
533
489
20
316
182
31
0.15
H3
0.138
0.7
0.05
0.^9
<1
<0.005
<2
0.05
250 '
<*30
680
<2
<50
<2
<)0
<30
<5
<15
1040
25
<40
80
70

<30
<5
<10
400
B18
15.2
9296
-
7.7
63
760
9.5
101
5-2
1).6
17
8
475
456,
10
246
138
41
0.20
126
0.150
0.9
0.12
0.32
4
-
-
0.09
9900
950
240
<2
<50
<2
<10
<30
10
20
830
25
<40
90
60

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<10
<400












































































































































































































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                                   UNITED  STATES  ENVIRONMENTAL  PROTECTION AGENCY
                                                       REGION  3C
                                             MICHIGAN-OHIO  DISTRICT  OFFICE
STREAM:  WEST BRANCH BLACK RIVER
STATION  IDENTIFICATION: see below
SURVEY DATE:  April 30,
TABLE
STATION NUMBER
RIVER MILE
MODO SAMPLE NUV.3ER
Flow (cfs)
pH (STD. units)
Terrpercfure (ฐF)
Conductivity (umhos/crn)
D;sso!v2d Oxygen (mg/1)
Dissolved Ox>?sn % Sal
BOD5 (mg /I)
BOD 20 (mg/l)
COD (mg/l)
'" TOC (mg/1)
Soiids, Total (mg/1)
Sci'ds, Dissolved (mg/1)
ScSds, Suspended fag/ I)
Hardness (-rg/i CaCO^)
Alkc'mify (mg/! CaC03)
Chloride (mg/l)
Fluoride (mg/1)
Sulfate (mg/1)
Phosphorus, Total (mg/l,P)
Totci KJ3ldnh!-N (mo/1)
Amrr.onia-'-N (mg/1)
Nitrcie-h'itrtta — N (mg/i)
Oil end Grscsa (mg/1)
Cyanide, Total (mg/1)
Ffieno! (mg/! ]
M3AS '.n-g/0
Feed Cc..-form (NcsViOO rr.Q
re:cl Strep, (Nos/IOOml)
Aiurnir-um, Tote! (ug/i)
Arsenic, Total (ug/ 0
Barium, Total (ug/l)
Beryllium, Total (ug/l)
Cadmium, Total (ug/l)
Chromium, Total (ug/l)
Chromium, Hexavalerrt (ug/l)
Coffer, Total (ug/l)
Iron, Total (ug/i)
Iron, Qissolved (ug/l)
Lead, Total (ug/l)
Manganese, Total (ug/l)
Manganese, Disso!ved(ug/l)
Mercury, Total (ug/l)
Nickel, Total (ug/l)
Selenium, Total (ug/l )
Silver, Total (ug/l)
Tin, Total (ug/l)
•?:__ -r, A_| / _ / t \
Wl
0.3
3279
-
7.9
62 '
750
9-3
35
4.8
9-8
28
8
532
491
13
262
129
31
0.31
164
0.11
1.3
0.23
0.59
2
<0.0d
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0.09
14000
470
220
<2
<50
<2
<10
<30
<5
<15
1070
20
40
110
100
<0.2
<30
<5
50
46
15
528
505
15
._J>44
197
52
0.69
139
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14.2
12.7
0.17
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6700
4000
<200
<2
<50
<2
<10
<30
<5
<15
1090
75
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220
225
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<10
<400

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-------
STREAM!  Black River Basin

SURVEY DATE! See below
UNITED  STATES  ENVIRONMENTAL  PROTECTION  AGEN
                     REGION  3T
          MICHIGAN-OHIO  DISTRICT OFFICE'
                           ( Hg/l  Unless Otherwise Stated )
                                                                        TABLE
STATION NUMBER
April 30, 1375
BIS
E3
F9
W4
BC3

May 2, 197^
Bl
S6
B15
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STATION NUMBER
Asril 30, 13/i
813
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315
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>C.001
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PHTHALATE

0.63
0.35
0.56
'l,5
2.1


1.8
0.6?
2.1
0.17




















o-BHC

<0.001
.O-OOli
<0.001
<0.001
<0.001


<0.001
0.007
0.005
<0.001


PHT HAUTE

0.12
0.70
0.36
0.73
0.59


0.56
1.1
].k
0.36




















LINDANE

<0.00!
0.001
0.001
0.002
0.001


<0.001
0.003
0.002
<0.001


o,p-DDE

<0.001
<0.001
<0.001
<0.001
<0.001


<0.001
0,00^4
<0.001
0.001




















HEPTACHLOR

<0_JL01
<0.001
<0.001
0.004
0.001


<0.001
<0.001
<0.001
<0.001


P,P-DDE

<0.001
<0.001
<0.001
<0.001
<0.001


0.001
<0.001
<0.001
<0.001




















GAMHA-
v-CHLORDAN!

<0.001
<0' 001
<0.001
<0.001
<0.001


<0.001
0.002
<0.001
<0.001


o,p-DDD

<0.001
<0.001
<0.001
<0.001
<0.001


<0.001
<0.001
<0.001
<0.001




















HEPTACHLOR
EPOXIDE

<0.001
0.001
<0.001
0.001


>0.001
<0.001
<0.001
0.001


o,p~DDT

<0.001
<0.001
<0.001
<0.001
<0.00!


<0.001
0.002

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                                             Attachment  H

                                     U.S.  EPA Survey,  May 2,

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B.   Existing _ Water Quality


        Water quality data for the Black River from surveys con-
    ducted prior to 197^ Indicated violations of  water quality
    standards for temperatures, dissolved oxygen, ammonia,  cyanide,
    phenol ics, and various metals.  These violations were attributed
    to discharges from the Elyria sewage treatment plant and the
    U.S. Steel - Lorain Works.  These previous studies also
    indicated the possibility of a pronounced inflow of water frorn
    Lake Erie well up into the Black River in the vicinity of the
    Lorain Works.  Because of the complicated hydrology caused by
    lake Inflow, two/ add i tional stream and discharge surveys v/ere
    completed to adequately determine alloy/able waste loadings
    to the river.  The first completed in May 137^ by U.S.  EPA
    provided a preliminary evaluation of the stream.  Based upon
                        I I 1-2

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this survey, sampling locations and sampling frequencies were
established for a more comprehensive study conducted in July
197^.  The May }S~fk survey was unannounced by U.S.  EPA, while
the July 197^ survey was completed in cooperation with U.S.
Steel.  The results of both surveys are presented below:

   1.  May 2, 197^ U.S.  EPA Survey

        Tha river flow as recorded at the USGS gaging station
   at RM 15-2 was 168 cfs, slightly less than half of the
   mean flow for May of 3^6 cfs.  Grab samples were taken at
   eighteen stations in the Black River, two in Lake Erie,
   one in French Creek, and at U.S. Steel Intake Wl-2 and
   Outfall 002.  Sampling locations are shown in Figure III-1
   and described in Table I I 1-1.  Data obtained from the
   survey are presented in Appendix Ml, Attachment A.
   Figures  ii!-2 to 111-10 present graphs of temperature,
   dissolved oxygen, ammonia,  cyanide, phenol, lead, and zinc vs.
   river mile.  Profile analyses for temperature (Figure 1 I! -3) ,
   dissolved oxygen (Figure 111-5) and conductivity were con-
   ducted at 12 stations in the Black River from river mile
   5.0 to  its mouth and at the two Lake Erie stations.
   Samples could not be obtained from U.S. Steel Outfalls
   003 and 00^ because of the  positioning of two ore boats
   in front of the outfalls just prior to sampling.  This
   was done shortly after the  U.S. EPA sampling boat entered
   the turning basin.

        Figure  111-2 illustrates the significant increases \n
   stream  temperature resulting from U.S. Steel - Lorain Works
   discharges between mile point 5-0 and 2.^.  A violation of
   the 5ฐFAT temperature standard occured immediately below
   Lorain Works Outfall 001 at RM 5-0, where surface river temp-
   eratures were increased from 5&ฐF to nearly 70ฐF with a further
    increase to 7^ฐF below Outfall 002 at RM 3. if.  Although some
   cooling occured, surface conditions did not significantly
    improve  in the turning basin from RM 2.9 to 2.4 where dis-
   charges  from Outfall 003 and 00^ enter the river.  Figure
    111-3 demonstrates temperature stratification i n t he turning
   basin at RM 2.9 and continuing to the mouth of the river,
   strongly suggesting  intrusion of colder Lake Erie v/ater.
   This had the effect of  lowering the average temperature of
   the  river as  illustrated in Figure 111-2.  The lake water
    intrusion effect is confirmed by analysis of the conductivity
   profiles and chloride data found in Appendix 111, Attachment A.

        Figures  I I ! -^ and  111-5 illustrate the adverse effects of
   the  Elyria STP and U.S. Steel on the dissolved oxygen content
   of the  stream.  Above the Elyria STP, dissolved oxygen
    concentrations slightly above saturation values, about 11 mg/1 ,
   were measured.  The dissolved oxygen dropped to 9 mg/1 just
   below  the STP at RM  10.0 and to 8.3 mg/1 about four miles
   further  downstream at the East 31st Street bridge.  From
    this point, the velocity of the river becomes very low as
                              A,,,,-.,. !-,+-„,} K

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•LE.2
                                        FIGURE E-I
                    LOWER BLACK RIVER WATER QUALITY SAMPLING STATIONS
                                  MAY  2, 1974 STREAM  SURVEY
                                                      I! }~k

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STATION LOCATION
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temperatures from U.S. Steel discharges, which lower
saturation concentrations and increase oxidation rates,
the dissolved oxygen continued to drop to a range of
6.2 to 6.5 mg/1 near Outfall 001 at RM 5.0 and to 5-3
to 6.0 rng/1 at RM k.O near U.S.  Steel  intake V/l-3-
The dissolved oxygen concentration dropped to 2.5 to 3.^-
mg/1 below Outfall 002 at RM 3.k, well below the k.Q
daily ninimum water quality standard as well as the 5-0
mg/1 daily average standard.

     Figure  ill-5 further illustrates the lake water
intrusion effect occurring  in the lower stretches of the
river.  From the turning basin downstream, the lowest
dissolved oxygen concentrations were not found at the
bottom of the stream as expected but at mid-depth,  a trend
which continued to the mouth of the stream.  Violations
of water quality standards did not persist below the
turning basin owing to the significant inflow of cleaner
lake water.

     Significant violations of the 1.5 mg/1 ammonia stand-
ard are illustrated in Figure I I 1-6.  High concentrations
above the Elyria STP were most likely the result of dis-
charges from the Elyria sewerage system.  The Elyria STP
discharge  increased the concentration to over 3.2 mg/1.
Ammonia decreased to  1.1 mg/1 above the U.S. Steel  coke
plant, Outfall 002, but was increased to 2.1 mg/1 below
the o'jifall, and to over 3 mg/1  at the downstream end
of  the turning basin.  U.S. Steel was discharging about
1500  Ibs/day of ammonia from Outfall 002 on the sampling
date.  Slightly higher values observed just below the
turning basin  at RM 2.k may have been the result of flow
patterns from  the Lorain Works Outfalls 003 and 00^, which
may not have fully mixed with the receiving stream at  that
point.  However, higher concentrations reaching 3-6 mg/1
at  RM  1.0  appear to result  from discharges from the Lorain
sewerage system.

      Figure  1 I I-7 illustrates the effect of the Elyria STP
and the U.S. Steel coke plant discharge on cyanide concen-
trations  in  the  river.  The STP discharge raised the stream
concentration  from 6  to ^2  ug/1, which corresponds to  a
loading of  about 35 Ibs/day.  Cyanide concentrations dropped
to  26  ug/1  above U.S. Steel Outfall 002 but were increased
to  230 ug/1  by the coke plant discharge, a violation of the
200 ug/1 total cyanide water quality standard.  Cyanide
loadings from  the coke plant were about 580 Ibs/day on the
sampling date.  The cyanide concentration dropped below
the standard to  110 ug/1 at the head of the turning basin
and to 93  ug/1 at the downstream end of the turning basin.
Loadings  from  U.S. Steel's  blast furnace discharges, Outfall
003 and 004, could not ba determined because of the  inaccess-
 ibility of  the outfalls as  described above.
                  1! 1-10

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     Figure 111-8 indicates a violation of the water qual-
ity standard for phenol  (10 ug/l)  just below U.S. Steel's
coke plant discharge at  RM 3-^-  The measured phenol con-
centration was 19 ug/l and the loading from the outfall
was about 1^0 Ibs/day.  Phenol ics v/ere not detected above
Outfall 002.  Figure  111-9 shows the effect the discharge
of Outfall 001 on zinc concentrations in the river, which
caused an increase to the 100 ug/l water quality standard.
This  increase is particularly  significant considering that
the streamflow at the time of  sampling was about eight times
greater than the water, quality design flow.  Figure  111-10
shows  a violation of  the **0 ug/l  lead standard also caused
by U.S. Steel's discharge at Outfall 001.  Lead concentra-
tions  reached a peak  of 12 ug/l below the outfall and
persisted above the-standard  to RM 3.1*.  Outfall 001 also
caused an  increase from- 30 ug/l to 50 ug/l of the chromium
concentration  in the  river.  The  total chromium v/ater
quality  standard  is 300 ug/l.  Finally, data obtained also
suggested a continuing violation  of  the fecal coliform
standard  of 200 organisms/100  ml.  The standard was  exceed-
ed  at every station  in.the river.

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                                   UNITED  STATES   ENVIRONMENTAL  PROTECTION AGENCY
                                                       REGION  x
                                             MICHIGAN-OHIO DISTRICT  OFFICE
STREAM:   BLACK RIVE*
STATION  IDENTIFICATION: See Below.
SURVEY  DATE:  May 2,  1974
TABLE
STATION MJ.V.3ER
RIVFR MILE
MODO SAMPLE ?,"JV2SFt
Flow (cfs)
p'rl (surface) (STD units)
Ternperatara (ฐF)
Conductivity (urnhss/cm}
Dissolved Oxygen (mg/i)
Craved Oxซsr. % Sst
SOQ5 l-s /I)
8C.'D;>o (m5/0
COO (rig /i)
TOC (rttj/1)
Soil t*, Total ><-s/l)
Solids, Dissolved irr.g/0
SeJds, Suspenses (~9/0
Hardness (rrg/l C=CD-)
A3ic:iflify (mg/: CcC03)
Chio^cs f.-.g/l)
Fluoride (--;/!)
Sofa's (rrs/0
FhPSjterus, Trtcl '-;/!,?)
Total Kj2ld3h!-N f^s/i)
Ammonia— M ("5/0
Mirrets-Nitrre-N (-rg/i)
Oil rrd Gracse (T.;/|)
Cyanide, Tots! (tin/I)
Phsnoi (rr-s/l )
M3AS - (f.g/1)
Feed Coi;rcrn (rJcs/! 20 rnl)
Fecal Strep. (."•'os/'COmi)
Abminsn, TOTO'I (ug/l)
Arsenic, Totel (ug/l)
. .


Ber>Mium, Total (ug/l)
11
Co drnium, Total US/!)
.
Chromium, Total (ug/l)
-
Chromium, Haavclent (yg/l)
1
Copper, Total (ug/l)
Iron, Total (ug/l)
Iron, Dissolved (ug/l)
. . .
Lead, Total \ugfi)
Manganese, Total (ug/l)
Manganese, Dissolved(ug/l)
...

i /IA

Selenium, Total (ug/l)
Silver, Total (ug/l)
Tin, Total (ug/l)
7isc, Tatul ('JO/I)
LE 1
—
9301

8-3
p
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ฐf
'l

1.5
3.6
14
6
245
222
IS
125
93
15
0.16
26
0.075
C.8
0.23
1.43
--
—
—
0.03
—
—
1040
2

50





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1370
25

50
25




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310
210
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                                    UNITED  STATES  EJJV1HONMENTAL  PROTECTION  AGENCY
                                                         REGION 7C
                                              MICHIGAN-OHIO DISTRICT  OFFICE
STREAM:   BLACK RIVER
STATION  IDENTIFICATION:   see Below
SURVEY DATE:   nay  2,  is?1*
TABLE
STATION' NUMBER
RiVER MILE
MODO SAMPLE I.UV5ER
Flew (cfs)
pH (STO. units)
- T;-r;;ฃ:returs (ฐr)
CoriCuctivtty (-jmhos/cm)
D-cxiv^ Oxygen (ng/l)
Os;;ivปd Cxygan % Set.
BC05 (T.3 /I)
BGDHO (">3/U
COD '>•;/>)
TOC ' ' (mg/0
Si' is. Total (~g/i)
Si-is, Dissciyed (rr-g/O
Sc-:,is, S-jspendsd Crr^/!}
K-d-sss (ns/; CcCO,)
tXc-i-.V to /I CaCD^
Cr.^.-ci to/0
F'eXf'.C* (~"/i)
S^.fctT (rr.:/i)
Prc-sts-crus, Tstor (.-$/',. p)
T.i:ci K;e.richi— M (rng/l)
A-nrr; 51-.; o — M (n n/ I )
r;.:Tc'i-N.r;'t-N i.-s7;)
C-J =--4 3r=csa (~s/l)
C,-i^e. Totai (rrc/l)
rT.aซ:: ' (-r-.gr,}
MB AS . (.-3/1
Feco Cci'fcrm (f;cs/;DD mi)
=ecci STCM. {Xc^/iCOmi;
A'j-.rs,-, Tafol (yg/i)
Arsi-ic, T^toi (1^5/1)
Bzr^^n, T^'cl (uo/0
-^ . . ; t,\

Cid-u-i, Total (ug/l)
ChrsiTii^-n, Total (uQ/l)
0-rooii.m, Hacvclent (ug/l)
Ccppsr, total (us/I)
Iron, Tola) (-J3/I)
Iron, Dissolved (ug/l)
Leod, Total (ug/l)
Manganese, Total (UQ/ )
Maoqcnesa, D;550'vปd{'jrj/l)


tiicket, Total ('J?/))

Selewo, Total ('J9/I I
Silver, Total (ug/l)
Tin, Total (u-]/l)
Zirc, TyMl !ug/l)
B7
2.75
9303

8.4
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2.7
15-2
3^
7
36if
339
13
IS!
Hit
4!,
O.iO
55
0.256
3.5
2.66
1.Q3
~
—
—
0.11
—
._
SCO
2 '
<50



<10

50
B3
2.9
9310

B.II
P
ฐf.
'le

5.0
17-2
40
12'
453
422
18
224
12?
52
0.36
121
0.470
3.!
1.97
0.8S
2
0.110

-------
STATES  ENVIRONMENTAL PROTECTION  AGENCY
             REGION 3C
  MICHIGAN-OHIO  DISTRICT  OFFICE
STREAM: See Below
STATION IDENTIFICATION: See Below
SURVEY DATE: Ha, 2, 1974 BIac, PIver French Creek Un!ted State5 „„,
STATION rjlJV.BcR
RIVER N":LE
H030 SAMPLE NUVBc.R
Flow (:(:;)
pH (STD. un:ti)
Te.T.pefCture (3r)
Cor-.3jc!:virj (umhoi/crn)
D'U"'v^d CAjQsn (-n;/!)
D:=so!v?d Ox>c,in % Sot.
bC!5 (rr.Q /;}
EOD20 (ms/l)
CCD (mg/-)
TCZ to/.}
Sy -is, Total (TO/I;
Ss-5/! CsCD-; 255
&,-:'.-••:ฅ (7:3/1 CcCOr,)
O^r.de (rr.j/i)
Fwcria (rr.,;/i1
Sjifc's (~-=/l)
r>c-..:^r-5. Total (ni'i.P)
T-:d K;a'.dchl-N (^J/l)
Am.— CJ-ia— N (m1;'''}
t.;trrte-N'ftt;-M {.T;/|
C-.S ~d S.'ฃose (rr.^/i)
Cvoi-ce, Tote! (oryi)
f^sl (-3/1)
M2AS ffrr/;}
Fe:cl Co.TCr.-n C'.'o./;^^ -^.'}
Fs;ai Srrsp C\fss/.CO.-iO
A..-T.-J.-., Tot;: (ag/l
Ar^Sc.TDlal (u;/0
B^jm.Tcta! (-jg/l)
Eeryl'ij-n, To:al (jg/I)
Cad^i'.'m, Total (ug/l)
Cftror-'ijm, Tr'al (ug/l)
ChrcmUim, Hปavo;jnt (ug/l)
Copper, Torn! (ug/1)
Iron, T::al (ug/l)
Iron, Bissolyed (ug/0
Lead, Tolol (ug/l)
Manganese, Totol (ug/l)
Mcngonesf, Dio5olvsd('jg/l)
Mercury, Total (ug/l)
Nic'usl, Totoi (ug/l)
S'-lai'.um, Total (ug/l)
Silver, Tola! (ug/l)
Tin, Total (ug/l)
Zinc, Tote: (ug/l)
IS1*
3J
0.2J(
125
0.552
B18
15.2
93!o
163.2
7.^
57
700
10.8
1C!*
3.1
9.8
2<ป
8 '
^3
f(22
<5
246
H5
3s!
0.22
126
0.1 ฃ8
3.1 1.8
1.81
O.M
1


O.C3
3303
250
120

ฃ0
<2
<3
*30
Trace
<15
8^0
15
K
i/1. a

2.8?







































































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STIIKAM:   BLACK RIVER Planning Area

SURVEY DAT!::  **Y 2,  1974
                Stream Monitoring Tata
UNITED  STAFEC  Oi/liiOr.'Miri TAL  PHOTCCDOM  AGENCY

                      REGION  Ti:

           MICHIGAN-0!iIO  DISTRICT  OFFICE
STATION NUMBER
LAKE ERIE
(LE-I)












1



HA'r'jS. (OUTH
(LE-2)
.













RIVES MILE 0.0
(8-1)












DEPTH
(feet)
0
^
6
9
12
15
18
2;
24
27
30
33 |
35 I
33





3
5
J
"i I
15
',3

2-,
27
32
33
i 35



0
3
6
9
12
15
18
21
24
27
30
32


If IT'.
50
50
49.6
43.7
47.3
45.2











CC O

57
56-5
50.9
43-3
49.3
48.6
48.2
46.4
46.4
46.4
46.2
45.2



59.9
59-7
56.3
55.0
54.0
53.6
53.4
53.4
53.2
52.9
51.8
52.2


I3SOLVED
^•T"''n
11.5
11.5
II. 5
11.7
11.8
11.8
11.9
12.0
1



12.2
12.2

-



9-0
9-0
10.2
10.6
11.0
11.0
11.0
11.4
11.5
11.5
11.7
11.8



7.3
6.6
6.4
6.8
7.1
7-4
7.5
7-9
8.2
8.3
8.7
8.9


corn
3c
3ฃ
3?
3E
3'












1,

4
4
3
3
3
3
3
3
3
3
3
3



5
5
c
t,
<
i
i
i
;
/




.
0
0
0
0
tO














75
50
60
70
75
60
70
40
40
4o
45
50



20
20
00
60
25
25
ilO
125
25
125
580
400


DISSOLVES
SOLIDS
(na/11
222














^.-

•}tr.
















290













CHLOKIDE
("3/1 )
15





18






IS



•?A






21





19



25




25





22





































































































-------
STRh.AM:  BLACK RIVER Planning Area

SUHVEY DATE: Kay 2, 1974
              Stream Monitoring Data
UNITED  STATF.S   i:NVlRON\'tN1AL   PHOTflCriO:)  AGENCY
                     REGION  X
          MICHIGAN-OHIO  DISTRICT  OFFICE"
STATION NUMBER
RUฃR HILE 0.4
(B-2)












i
S!.':K r>!U 1-04
<3-3)





-







RIVER MILE 1.35
(3-4)















DEPTH
(feet)
0
3
6
9
12
15
13
21
Ik
**>
30




r>
•j
.J
6
i
12

•.s
2?
2n
27
30




0
3
6
9
12
15
18
2i
24
27
30
33





TE!1.".
(ฐ0
67.3
65.3
61,. 2
61.7
52-0
55. 4
53.6
53-2
. 52. S
52.5
52.2




70.3
70.0
66.it
61. 5
= 3. -5
57. <•
55.5
54.7
53. ^
52.2
51.8




70.0
7D.Q
70.3
68.5
67-5
55.0
57.6
57.2
55. a
55. i.
5". 3
53. '*





~* S 5 C _ V 1 D
G?i:)>;
6.1
5.6
5.6
5.3
6.3
7-1
S.I
3.5
_ 9-1
S..
U'liSo/cn)
650
550
575
525
450
440
400
400
400
400
330



-
700
650
550
500
450
475
440
420
390
380
380




700
675
675
640
600
475
475
490
490
475
450
450





DISSOLVED
SOLIDS
(HK,/!)
344














^L^.














360
















CHLORIDE
(mg/1)
41




26




24




49




&




25




42





35




3ป






































































































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STREAM!  BLACK RIVER Planning Area

SURREY DATE:  Kav 2- >9?4
               Strea.-n Monitoring Data
UMITEO  STATES   CIJVIUOMM-.mAL  PltOTCCCION  AGENCY

                     REGION  TT

          MICHIGAN-OHIO  DISTRICT  OFFICE'
                                                                               I
STATION NUMBER
RIVE". HILE 1.85
<3-5)










.

i
r.lVJ* rMLE 2.LC
:a-S)















RIVER ,MILฃ 2.73
(S-7)













DEPTH
(feet)
0
3
6
9
12
15
13
2!
2k
27
30
31



0
3
6
9
T>
0
IS
21
2'-,
2?
33
33 '
35




0
3
6
9
12
15
18
21
24
27
2J




TEMP.
(ฐr-)
69.8
68.9
67.6
6*1.9
62.1
6o.it
59. S
56.8
54.5
53. &
53.6




68.it
67.8
6S.2
63.9
62.6
ฃ3.0
61.5
60.8
53.3
56.8
55. t
53.3
52.3
50.3



68.3
67.3
6S.2
62.6
61.7
61.2
59. 't
59.0
57.2
56.8
56.3
55.1.
55-V


l5SOLVft)
DX.YOEIi
f-:./P,
5.ซt

-------
STREAM'  BLACK RIVER  Planning Area

SURVEY DATE'.  Kay 2,  1974
                Stream Monitoring Data
U.'JITFD  S'fAfCS  KNVIIIO.'iME.riTAL  PROTECTION  AGENCY
                      REGION  X
           MICHIGAN-OHIO  DISTRICT  OFFICE
STATION NUMBER
11. 5. STEEL
Water Intake - 2
RIVER MILJ 2.85


!
i

1
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RIVER Mi IF. 2-3
(5-3)





















___ 	 _: 	
DEPTH
(feet)
0
1
2
3
4
5
6
7
S
9
io
1)
n
13
iii
15
16
17
17.5



0
5
2
3
* 	 1
5 1
S
7
L E—
: 9
S1 S"












	
irtsp.
(ฐF)
71. &
71. &
71.4
69.8
68
kk.tt
60. Ji
60.0
59.0
58.8
58.8
58.6
58.1... .
57.2
56.3
55.3
55.9
55.7




71.6
71.5
71.6
71-6
71-6
69.8
63.1ป
6&.2
(^.k
62.6














ISSOLVLD
DvYcrti
fno/O
3.3
3.3
3-1
3-0
3-0
3-1!
3-9
it.it
A. 6
4.8
it. 9
4.9
5.0
5.0
5,0
5-0
5-0
5.0




3-3
3.0
3-0
2.9
2.9
2.6
2.5
2.6
.. 3.3
3.6













	
COIW.
jmho/C'"n)
790
760
7'fO
710
6!fO
575
525
5iiO
5^0
5itO
540
550
540
525
525- '
525
525 '
525




790
775
775
775
775
723
700
610
. 575
550













	
DISSOLVED
SOLItr,
(n-i/U
336





















422






















(___ .-_
CHLORIDE
(mg/ 1 )
34





















52




53




47












	














































	














































1

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STREAM!  BLACK RIVER Planning  Area

SURVEY DATE!  Hay 2, 1974
               Strean Monitoring  Data
tWITFD  STATES   CHVIHONMr.riTAL  PROTECTION  AGENCY

                     REGION  IT

          MICHIGAN-0(110  DISTRICT  OFFICE"
STATION NUMBER
RIVET MILE 3.35
(3-9)











?,!V'H?, MILE 4.0
(2-10)










RIVES *llฃ - A. 5
(3-11)



.





RIVER MILE 5.0
(3-12)








ป
DEPTH
(feet)
0
]
2
3
4
5
6
7
8
8.5



0
1
2
3
4
5
6
7
7-5



0
1
•7
'- 3
if
5
6
6.6



0
1
2
3
it
5
5.5




TEIW.
(ฐF)
JD-8
73
73
71.8
71.8
71.6
6it.it
63-0
62.2




68.0
68.0
68.0
67.6
67.5
67.5
67.3
67-3




68.5
68.it
63
68
66.2
66.2
66.2




69.8
69.8
69.8
68.0
66.2
6k. 3





3ISSCLVEB
w,s
3^
3.1
2.S
2.8
2.6
2.6
2.5
2.9
2.9




S.O
5-5
5-3
5.3
5-3
5-3
5-5
5.5




6.6
6.5
6.4
6.3
6.2
6.2
6.it




6.6
6.5
6. it
6.J
6.2
6.2





C05IO.
umho/cn)
750
725
725
725
725
725
530
560
660




790
750
750--'
750
750
750
750
750




790
790
750
750
750
750
750




790
790
775
750
7*tO
7^0





DISSOLVED
SOLIDS
(nq/l)
404












444











441










426










CHLORIDE
(n:3/l)
45












45











50










43































































\











































-------
STREAM".  BLftCK- RIVER Planning Area

SURVEY DATE:     H*y 2,  Wt
                  Stream  Monitoring Data
LIMITED  STAffCS  CNVIRONMENTAL  PROTECTION  AGENCY

                     REGION  7ST

          MICHIGAN-OHIO  DISTRICT  OFFICE"
STATION NUMBER
BLACK RIVER
(Between French
Creek E USS
C0E 001)
(5-13) •




BLACK RIVER 6
3CO' above raoutn
''-IM


I




1



























DEPTH
(feet)
0
1
2
3
i,
5



Q
1
2
3
4

































TEMP.
<ฐF)
69.1)
68.9
67.2
6(4
62.6
61.5



61.7
60.8
60.8
60.8
60.8

































1S50LVEC
0''YCE!(
fn~/n
6.5
6.1.
6.3
6.3
6.3
6.3



6.6
6.6
6.6
6.1*
6.5

































co:;-j.
ur^ho/cn}
800
790
800
750
750
750



800
790
790
790
790


-•'





























I
DISSOLVED
SCL1DS
__fjin ' I ]_















































HLOK1UE
(mg/1)
















































































































































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                                          Attachment I
                                U.S. EPA  Survey, July 23-26,
 I

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2.  July 23-26, 197^ Survey  U.S. EPA

     Tb.s July 197^ survey was conducted to obtain sufficient
data to validate dissolved oxygen and temperature water
quality simulation models.  These models were used to de-
termine acceptable waste loadings for the Elyria STP and
the U.S. Steel - Lorain Works consistent with Ohio Water
Quality Standards.  Data obtained during the Hay 197^
survey were used to establish stream and effluent sampling
stations and to determine the method and frequency of
sampling and other date needs.  A complete review of the
July survey is presented below.

     a.  Sampling Locations

          Figure  111-11 illustrated the location of the
     stream and effluent sampling points.  Table  111-2
     presents  the river mile  indices for each station and
     describes the  types of samples and measurements made.
     The main  stern  of  the Black River was sampled at 12
     locations from above the Elyria sewage treatment plant
     to Lake  Erie.  One station on French Creek and one
     5n Lake  Erie were also sampled.  Temperature monitors
     were set>at  six additional stations surrounding the
     Lorain Works.  Surface, mid-depth, and bottom samples
     were obtained  at  six stations for dissolved oxygen,
     temperature, chlorides and sodium.  River Station 7
     was  sampled  at  Intake WI-3 and served as the Intake
     sample as well.   Effluent samples were also obtained
     at  the Elyria  and Lorain sewage treatment plants.
                                                I 11-13

-------
L AK E   ERIE
                                                    IE  m-u
                                    STREAM SAMPLING  LOCATIONS
                                           BLACK RIVER SURVEY
                                             JULY 33-26, 1974
                                                  OUTFALL OOI
                                                 OUTFALL OO5
                                          OUTFALL O02
                              OUTFALL 003
O'J7FA.LL 001
                          RIVER  MILE
                              0.0 .
                               1.04
                               1.85
                              2.40
                              2.85
                              3.35
                              3.83
                              4.85
                              5.10  (FRENCH CREEK)
                              6.50
                              8.60
                              10.10
                              10.CO
                                                                        ELYRIA STI

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                               TABLE I I 1-2


                       U.S. EPA BLACK RIVER SURVEY


                            JULY 23-26,  1974


                        SAMPLE STATION LOCATIONS
STATION NUMBER
13
12
11
10
9
8
8a
8b
7
7 a
7b
6
63
6b
6c
5
5 a
ป
li
3
2
1
LAKE ERIE
RIVER MILE
10.8
10.1
8.6
6.5
(French Creek)
4.85
it. 76
4. 65
3.83
3-79
3.69
3.35
3-35
3.26
3.16
2.85
2.85
2.40
1.84
1.04
0.0
— —
SAMPLE TYPE (See below)
B
B,E
B
B
B,E
B
fa
D
B
D
D
A
C
0
D
A
C
A
A
A
A
F
SAMPLE TYPES
                                                                                          f
A.  2'i hour composite of surface sample for all  constituents  (see Appendix  III).
    2'f hour composite of nid-depth and bottom samples  for dissolved  solids,
    sodium, chloride, fluoride, sulfate.  12 measurements/^  hours  for tempera-
    ture, dissolved oxygen, pH, and conductivity.  .  .  at  surface, mid-depth  and

    bottom.                                                                              !
B.  Same as "A".  Except only surface sanples were taken.                      .           j
C.  Continuous temperature and dissolved oxygan monitor                                  j
D.  Continuous temperature monitor.                                    .                  '"
E.  Stream flow measurement at time of sample collection.                      *           ! .
F.  Grab sample for dissolved oxygon, dissolved solids, conductivity,  sodium,             i   ,
    chloride, fluoride, and sulfate.                      .                               J  (
                             111-18

-------
b.  Sample Types and Sampling Frequency

     Three consecutive 24-hour equal volume composite
samples were obtained at Stations 1  through 13 from
July 23-26, 197^.  The composites were made up of 12
grab samples obtained at tv/o hour intervals for
Stations 1-8 and 10 which were sampled by boat, while
eight to twelve grabs were combined  to form the com-
posites for Stations 9 and 11-13 which v/ere sampled
from land.  Fewer grabs were employed in the latter
composites because of the time requirements for stream
gaging at Stations 9 and 12.  Grab samples for dissolved
oxygen, pH, and conductivity were obtained at the time
of sampling for other constituents.

c.  Sarnpl ing Methods and Analytical  Procedures

     Samples were collected in polyethylene containers
for all constituents except polychlor i nated biphertyls
which were collected in glass containers with teflon-
lined, caps.  Dissolved oxygen grab samples were obtained
directly in BOD bottles by hand For  surface samples
and with APHA samplers for mid-depth and bottom samples.
Samples were composited in the field from the polye-
thylene sample containers on an equal volume basis.
Dissolved oxygen samples were fixed  at the time of
collection and titrated within a maximum of one .hour
of collection.  All samples collected at Stations 1-8
and 10 were Iced immediately upon collection and kept
Iced until analysis, although samples from Stations 9
and 11-13 v/ere not  iced as well as samples from other
stations.  Preservatives v/ere added  to the composite
sa^.ple containers berore the incremental grab samples
were added.  The metals sample for Station 13 on July
23-24,  1974 was contaminated prior to analysis and
was discarded.

     Stream flows were measured at the time of sample
collection at Stations 9 and 12  in accordance with
established USGS procedures.  Standard U.S. EPA, Region
V custody  procedures v/ere employed throughout the survey
Sample preservatives and analytical  methodology  in
conformance with Section 304 (g) of the 1972 Amendments
v/ere employed for all  laboratory analyses except for
fluoride and  sulfate which were determined v/i th  lab-
oratory  techniques  currently under consideration as
alternate  test  procedures  in accordance with  Section
304(g).   MBAS analyses v/ere not completed within the
recommended holding  period of 24 hours.
           ! ! 1-19

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d.  General  Conditions

     !•  Weather - Climatological  data were obtained
     for the survey period  from the  U.S. Coast Guard
     Station at Lorain  and  the  U.S.  Department of
     Commerce weather station  at Elyria.  Daily
     maximum air temperatures  at Elyria  ranged from
     73 to 8lฐF with daily  minima from 5^ to 6lฐF,
     whi1e daily maximum air temperatures at Lorain
     ranged from 70 to  77ฐF and daily minima from
     62 to 68ฐF.  Winds were from the northeast at
     0 to 10 knots as measured  at Elyria, while the
     Coast Guard recorded wind  velocities ranging  ^
     from 3 to 15 knots with highly  variable direction,
     (One knot is equal to  1.151 mph).   There was  no
     precipitation throughout  the survey and weather
     conditions ranged  from clear to partly cloudy and
     cloudy.  The Coast Guard  also reported haze at
     times.  Air pressure varied from 30.00 to 30.14
     inches of mercury as measured at Lorain.

     2.   Hydrology  - Figure 111-12  is a daily hydro-
     graph of  the  Black  River  for the month of July
     1971* at  the USGS  gaga  In  Elyria, RM 15.2.  As
     shown,  the  hydrograph v/as declining for the en-
     tire month  preceding  the  survey and was extremal)
     stable during  the sampling  period.  The 197^
     summer  period  preceding the  survey was abnormal-
     ly  dry,  resulting in  relatively low sustained
     flews  in  many  streams.  The  flow recorded at the
     USGS gage during  the  survey  approximated the com-
     bined discharger  flow above  the gage Indicating
     the Black River was at or near  critical flows.

          In  addition to  conventional stream gaging, t\
     amount of lake Intrusion  near  the Lorain Works
     was  determined four times during the survey by
     taking  velocity and cross-section measurements
     at  Stations k  and 5.  Velocity  data were obtainec
     boat with a  Bendix  Q.-15 current meter employing
     a two-point anchoring system for stability.
     Velocity  profiles were made at  three points on
     a line  perpendicular to the  direction of'flow at
     Station  5 and  at  four points at Station k.
      Instantaneous  flow  values were  determined at each
     station  by  applying the upstream and downstream
     velocities  to  the corresponding stream cross-
     sections.   These  data confirm  that lake water
     actually  flows upstream into and above the U.S.
     Steel  turning  basin.  Because of manpower and
     equipment limitations such measurements could
     not  be  completed  around the clock.  Twenty-four
     hour sodium and chloride  composite samples were
     obtained  at all stream stations and at multiple
     depths  for  Stations 1-6.   Using these data in
     conjunction with  measured  flow  rates above U.S.
     Steel and flow and  loading data from the Lorain
        ! I 1-20

-------
                                  FIGURE  m-!2

                   DAILY HYDROGRAPH  OF THE  BLACK  RIVER

                 U.S.G.S.  STREAMFLOW GAGE  AT  ELYR1A  (R M 15.2)
   60
   oo
   40
in
ซซ-ป
o


?
O
_J
u.
3O
   2O
    10
                              r
                                                      SURVEY
                          I   I  f   I  I
                      10
                                  15           20


                                    JULY  1974
                                                           25
                                                                        30
                                      111-21

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     Works,  estimates  of  24 hour average  lake  instru-
     sion flov;s were made consistent  v.'ith the  remain-
     der of  the sampling  survey.  A rnore  detailed  dis-
     cussion of these  data and  their  use  in  stream
     temperature simulation Is  presented  in  Appendix V.
     The sodium and chlori.de data were also  used to
     compute a dispersion coefficient for dissolved-
     oxygen  simulation as discussed  in Appendix VI.

e.  Discussion of Results

     Figures 111-13 to 111-23 summarize the  results^of
the three-day survey.   The complete  stream data and
effluent data for the  Elyria and Lorain sewage treat-
ment plants  can be found  in Attachernents  B,  C, and D,
respectively, of Appendix 111.

     Figure   !i!-13 contains plots of  sodium  and chlor-
ide concentrations vs. river mile for each day.  These
data ;511ustrate that the  daily average streamflow  and
discharge loadings of  sodium and chloride were approx-
imately constant throughout the survey.  Hence, steady
state conditions in terms of streamflows  and intrusion
flows were encountered.  Any significant  variations  of
st rearnf low v.ould produce  vastly differing plots for
each day.  Since the flow remained remarkably  stable,
the three plots for each  constituent  are  nearly  ident-
ical in terms of concentrations at each sampling  statior
and at  each  depth.  The drop in concentration  as  the
stream  flows to the lake  indicates longitudenal mixing
as a result  of  lake intrusion and U.S. Steel pumpage.
A  substantial amount of dilution is afforded by Lake Eri


     Surface temperatures  vs.  river  mfle are  illustrate
 in Figures  II I-14,  11 1-15,  and  IN-16.  The effect
or the  Loralr)  Works was  quite  evident downstream  of
Outfall 001,^RM 5-0.   Increases In stream temperatures
of about 15ฐF  were recorded each day on  a 24-hour
average basis,  a  substantial violation of the 5ฐF
 Increase in temperature  allowed by the water  quality
standards.   The, stream cooled  by about 4 to 5ฐF  by
the time It reached  Intake UI-3,  RH  3.88.  At this
point,  the  hsat loading  from Outfall  005 appeared to
have had a  neglfgible-effect.

     Downstream of Intake  UI-3  the combined effects
of Outfall  C32  at  RM  3-5 and Outfalls 003 and 004 at
RM 2.63 and 2.56,  respectively, elevated the  entire
stream  surface  from RM 3-8  to  2.4 to a range  of approx-
 imately 84  to 8oฐF on  an average basis.   Figure  111-17
presents temperature  profile data for various sampling
stations in the turning  basin  indicating stratifica-
tion of cooler  lake water  on the stream  bottom vs.
thfi heated  effluent at the  surface.   This also con-
firmed  the  results of  the  May  2,  1974 survey.
         I I 1-22

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                           I   i   r   Is—:_-.'   !   .1  t   i   I.   I   (  t  I   t   t   I ,  i   I. I   i   i   j   i   I   i   i   i   i   i   ;   [   i   i   I   i   i  t   i
   o:
   ui
   
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=*,  *~~  ^*-   v?
'—  til  O   >^



b!  i^  >   ซ

1ซฃ5
E  >  ซ   2
                                                                                                                                          I  I  1-27

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Figures 111-18 to 111-21  depict the dissolved
oxygen levels in the stream and levels of related
carbonaceous and nitrogenous oxygen demanding sub-
stances.  Figure 111-17 illustrates maximum,  minimum,
and average dissolved oxygen concentrations at each
sampling station for the  three 2k hour sampling
periods.  Data at mid-depth and at the bottom are
also presented from Stations 1-6.  These data demon-
strate that discharges from the Elyria sewage treat-
ment plant resulted in a  violation of the 5-0 mg/1
dissolved oxygen water quality standard uith 2^-hou'r
average values of 2 to 3  mg/1 recorded.  The stream
recovered to k to 5 mg/1  above the Lorain Works, but
because of the extended time-of-t ravel in the lower
portion of the stream, elevated stream temperatures
at the Lorain Works, and  discharge loadings from the
Lorain Works, the surface dissolved oxygen concentratic
was lowered to between 1.5 and 3.0 mg/1 from the Lorair
Works to the mouth of the. river.  Mid-depth and bottom
concentrations ware somewhat lower except near the
nouth of the river due to lake intrusion.

     The diurnal variation of dissolved oxygen at
Stations 7, 8, 10, 11, 12 and 13 is presented in
Figure  lli-19.  These data demonstrate considerable
photosynthetic activity at Station 13 above the
Elyria sewage treatment plant on July 2^- and July
25, 197^.  There was relatively little photosynthetic
activity on July 23, which was the cloudiest of the
three days.  Photosynthesis was evident at Station 12
just below the Elyria sewage treatment plant, but
only to a minor extent since the discharge from the
plant adversely affects the stream at this point.
Data at Station 11 show some photosynthetic activity
similar to that at Station 13.  However, data at
Stations 10, 8, and 7 do not evidence daytime photo-
synthetic activity.

     Plots of chemical oxygen demand, total organic
carbon, and 5 and 20-day biochemical oxygen demand
are presented in Figure llt-20.  Plots of total
kjeldahl nitrogen (TKN) ,  ammonia -nitrogen, and nitrite
nitrate-nitrogen are presented in Figure IM-21.  The
general trend of all plots are similar, demonstrating
the severe effect of the Elyria sewage treatment plant
discharge which is followed by an apparent recovery
at the  Lorain V/orks.  However, the flow regime of the
area must be considered,  i.e. an increase in stream-
flow of about k times by the discharge from Lorain
Works, Outfal 1 001 at RM 5.0.  The Lorain sewage
treatment plant discharge is hardly noticeable near
the mouth of the river.  The BOD,- and BOD^g concen-
trations at Stations 13, 12, 11 ,  and French Creek
(not shown)  may be somewhat  low due to inadequate
icing of the samples during  collection.
         111-28

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1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
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MI-29

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  to
   2 3
U  X
   >	I   1  II	l_
                                                              
-------

o
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  o <
  ^ a
                               111-31

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)/ฃ>'"

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   Nitrogen series data presented in Figure I N-21
are particularly significant in that gross violations
of the 1.5 mg/1 ammonia criterion are shown above and
below the Elyria sewage treatment plant and downstream
past the Lorain Works.  Violations above the Elyria
sewage treatment plant are attributed to discharges
from the Elyria sewerage system, while the Elyria
sewage treatment plant and U.S. Steel cause the
downstream violations.  Most of the TKN discharged
from the Elyria sewage treatment plant was in the form
of ammonia rather than organic nitrogen.  Although the
TKN and ammonia concentrations sharply decreased at ^
Lorain V/orks Outfall 001, the nitrite-nitrate con-
centrations renamed relatively constant.  Considering
the large volumes of water circulated in the stream
by Lorain V/orks pumpage and Lake intrusion, these
data indicate that conversion of ammonia to nitrate
was occurring.

   Figure  111-22 contains plots of total cyanide and
phenolics vs. river mile for the three-day survey.
The abnormally high cyanide discharges from the
Elyria  STP nearly resulted  in  violations of the
200 ug/1 stream standard on each day with a high value
of  180 ug/1 recorded on July 2k, 197**.  The sewage
treatment plant loadings result from discharges of
untreated and partially treated metal finishing wastes
to the Elyria sewerage system.  The STP discharge has
a much greater adverse impact at low flow periods as
evidenced by a comparison of these data with data
obtained during the May survey.  The effects of the
Lorain V/orks are evident below Outfall 002 and Out-
fall 003 and 00^, but water quality standards for
cyanides were not violated. The 10 ug/1 stream standard
for phenolics was exceeded below the Elyria STP each
day and  slightly on July 2k below Lorain Works Outfalls
003 and  QOk.  However, the phenol standard was achieved
in  the area of U.S. Steel for  the most part during the
entire  survey.  Due to the high reaction rate of
phenolics  and the dilution afforded by the stream, the
minor violations of standards were not persistent.
It  is  important to note that discharges of ammonia,
cyanide, and phenol from the Lorain V/orks Coke Plant
were  significantly  less than encountered on May 2,
when  unannounced samples were  obtained.  However,
during  the May to July 197^ period the company was  in
the process of repairing a substantial portion of the
flushing liquor piping in the  coke plant which may
account  for the substantial reduction in waste loadings,

    The  adverse effects of the  Elyria sewage treatment
plant  and  the  Lorain V/orks are also demonstrated  in
Figure  111-23 where metals data are presented.  Data
for Station  13, RM  10.8 upstream of the Elyria STP,
are not  available for  July 23,  197'.L as the sample was
contaminated  prior to  analysis.  However, data for the
         111-33

-------
remaining tvra days at Station 13 demonstrate  vtolatior
of the chromium, copper,  and zinc stream standards  oF
300 ug/1, 10 ug/1, and 100 ug/1  respectively.   The
stream standards for copper and  zinc are for  a hard-
ness range of 80~l60 mg/1.  These violations  can be
attributed to discharges  from the Elyria 'sewerage
system and metal finishing and chemical  plants in
the area.  The Elyria sewage treatment plant  also
contributed abnormally high metals loadings to the
stream as evidenced by a  comparison of data from
Stations 12 and 13.  The  effects of the Lorain Works
are evident at Station 8, RM ^.85, where the  zinc
standard was exceeded as  a result of the discharge^
from Outfall 001.  Effects of Outfalls 003 and OQk
are shown at Station k, RM 2.40, where zinc concen-
trations increased causing violation of standards
on July  25-26,  197^.  The violation of the copper
standard at RM 2.kQ apparently did not result from
Lorain Works discharges as copper was generally not
detected in Outfalls 003  and QQk.  The sharp increase
in zinc  and copper near the mouth of the river on
July 25-26, 1974 appeared to result from the Lorain
sewage treatment plant discharge.

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II1-31*

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111-35

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TAULE:
      M:  BLACK RIVER
SURVEY DATE:   July 23-2-'!, is?4
                  (mg/J  unless otherwis-
   UNITED  STATES  ENVIRONMENTAL  PROTECTION  AGKN<

                         REGION 31

             MICHIGAN-OHIO  DISTRICT  OrFICE
noted)
STATION t;U.V,3ER
RIVER MILE
Flow, cfs (average)
phi, ranQe
Cond. (-^-ihos/cn)
Tenperaturs F nax.
avg.
rain.
DO . max.
avg.
ntn.
Total So! Ida
- Dissolved to! ids
Sjspendei So! ids
COD
TCC
ECD
B0t>.o
60=zo
80ฐ30
Phosphorus, Total
TKfl
A^jrioila-!!
Hi trs:e-iJ; ;ritซ-K
ChlorWe
Fiuori-ie
Sulfa Je
T. Sodlu.-n
M3AS
T. Cyanide (ug/1)
PhenoHcs (u9/l)
T. CocHium (ug/1)
T. throii-j.ii (yg/l)
T. Copper (ug/l)
T^ Iron (lig/1)
T. LCD-J (ug/l)
T. H:rcury (pg/l)
r. Hicks I (Pg/l)
" Zinc (iVO
13
10.8

7-1-7-5
825
1 Cnn
71.6
69-7
65.4
7-7
7-3
7-1
635
530
9
3!
12
6
36
1|0
A2
0.219
6.2
5-53
A.rs
117
0.81
183

0.18
40
<2








12
10. 1
13-8
7-1-7-5
870
-1050
73- ^
72-9
71.8
4. 4
3.2
2.2
635
>55
15
65
22
17
25
93
S3
2.53
13-0
lt.0
1. 91
123
0.78
166
101
0.2*t
ISO
11
10
320
40
480
<50
<0.2
150
64
11
8.6

.0-7.6
20
-1020



3-0
2.0
I. A
635
590
15
62
20
16
26
75
87
2.71
12.6
11.3

126
0.72
166
100
0.21
ISO
5
10
250
30
600
<50
<0.2
120
67
10
6.5

0.3-7.5
10
-SCO
69.8
68.7
68. o
5.8
4.2
3.0
575
535
7
39
15"
8
19
97
97
2.60
12.9 '
12.02
1.15
102
0.76
153
85
0.21
30
3
<8
200
20
500
<50
<0.2
<30
26
8
'1.85

5.7-7-3
500
-oฐ.0
ฃ5.6
84.6
83-1
4.0
2.3
0.5
450
410
12
31
13
8
29
36
36
0.7S7
4.6
3-72
0.74
74
0.56
107
53
0.17 .
20
<2
<8
180
<15
2300
75 .
<0.2

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                                        UNITED  STATES  ENVIRONMENTAL  PROTECTION  AGENCV

STREAM:  Et-ACK R!VER                                         REGION -z
surivEY  DATE: July 23-24. 1374                     MICHIGAN-OHIO  DISTRICT  OFFICE
                  (mg/l  un!j!t olhscwis? noled)
STATIOM t;U.\OER
RIVER MILE
Flow, cfj
pH, ranje
Cori. (vohos 'en)
^ O-
lenpcracure " nox.
avg.
Mif>.
PO max.
. W. ,
otn.
Total Solids
Dissolved Sol ids
Suspend-d Sol iai
COD
TOC
E0t>5
E00,0
B0020
EOB30
Phospnorus, T"-:.-><
TKM
AT,7"Drna-ri
Hltratc-f-r.rtrfti^".'
Cfttorldc
Fluoride
SuTfate
7. Sodium
K3AS
T. Cyanide (ซD/ป)
Phenol ics C^3'":5
T. Cod.Tiiu.ii ('.g/'}
T. ChrcTilun (uj/l)
T. Copper ('JQ/I)
T. Iron (iiu/l)
T. L-.IC! (-.3/1)
T. Mercury (^a/1)
T. liiclcl (^tj/D
T. Zinc (xj/l)
7o
3.79



83.8
ฃ2.4
81.5

'











~
f
•
-
L
F












7b
3.63



83.8
82.3-
82.0

h
.








"





-














6T
3.35

6.3-7.7
330
-wo
82.4
61.4
80.6
2.2
1-7
0.8
3J5
300
"
20
8
7
22
25
25
0.302
2.6
2.13
0.2'.
5a
G.?3
63
31. 5
0.&3
30
&
t
l.'i
KO
0.8












- -
.















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TABLE:
STREAM:  BLACK RIVER
SURVEY DATE: July 23-211.  1374
                  {mg/l iK.l^st; otherwise nolecf)
UMITED  STATES  ENVIRONMENTAL  PROTECTION AGENCY

                     REGION  ~X

          MICHIGAN-OHIO  DISTRICT OFFICE
STATION KU.VatR
F.iVFK niu
Flow, cfs
pH, range
Coni. (y-.spO5/cn)
Temperature F rax.
avrj.
IT. i n ,
tO nax.
avg.
ntn.
Tota! Soiidi
ฃ issotveci Sol :cfs
SL'spendecJ Solids
CC3
TOC
S035
E03,0
E0020
-ฃM30
?hosphorus, Tota!
1Wป
A™on i <*— Jl
f;:trate*l!icrt:e->!
ChToride
FluoricJe-
S'j!f.ite
T. SodiuCT
H3=>S
T. Cyanide (ar;/!)
Phrnolici (u'g/l)
T. Ca-Jnlfa (u'J/l)
T. Chrootu.T) (vs/l)
T. Copper (vg/1)
T. Iron 05/l)
T. LซJ (i.g/1)
T. fcrwry (u'j/l)
•'. lllcVol (yj/t)
' Zinc (|.y/l)
5T
2.85

(>.i*-7.5
liOO,
-ligo
81-5
80.5
73.8
2.0
1.7
'U5
300
260
7
17
7
6
13
15
17
0.26!
2,i
.1.23
0.77
ซ5
O.^"
62 •
27.9
0.03
20
<2
<8
54
<15
seo
<50
<0.2
<30
3''
5M
2.65

6.5-7.8
37-V
80.6
77-2
75-2
3-5
1-9
1.2

200











36
o.'.o
55
2t.l|











58
2.85

6.2-7.6
35?.',oo
77.3
74.8
73.4
2.3
1.0
0.3

230











32
0.^3
45
17.8











4T
2.'iO

6.3-7.6
310,
-Uo
82.4
80.5
79-3
2.7
1.7
1.5
260
230
16
II
%
li
12
17
17
0.122
2.0
1.54
0.70
" 36
0.43
43
18.0
0.06
liO
3
<8
<20
<15
1500
<50
<0.2
<30
62
4M
2.i)0

6.4-7.6
2I)-V
76.6
75.7
74.3
2.0
1.0
0.4

ISO











30
0.30
44
15.7

- "•
-








4o
2.'lO

5.1-7.7
220 ,
-360
76.3
74.5
73-4
1.3
0.6
0.3

170











23
0.42
J.O
14.2


-








3T
1.S4

6.1-7.4
35^,o
79.3
78.8
77.9
2.7
1-9
1.1
260
200
12
13
4
3
10
15
15
0.116
1-9
1-37
0.72
36

!
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TADLE:
STREAM:  BUCK RIVER
SU.WEY DATE:  Ju'v 23~2!|
                  (mo/I  ur:!esป o'hsrwise noted)
UNITED  STATCS  ENVIRONMENTAL  PROTECTION  AGENCY
                     REOIOU ~y.
          MICHIGAN-OHIO DISTRICT  OFF1CC
STATION NUMBER
RIVEK HUE
Flow, cfs {c-,CI.i:;ej
pH, rang;
Cond. (i..V.os/c.-0
Tcnp;rdtl/reฐF risx.
ปV9.
c*.Tn.
DO MX.
s*'3.
BTln.
To:al Sot ids
Dissolved Solid*
Suspend-d So3:ds
COD
toe •
6005
B0310
BOD2Q
Eฐฐ30


TfX
fnaioni &~S
|Jitrate+HIcri?e-X
Chloride
Fluarfde
''Sutfate-
T. .ScxJiura
H8A3
T. Cyanide- (pg/1)
Phenol ics (yg/i)
.T. CadTiiu.Tt - (ป9/l)
T. ChrcKiiun (yg/1)
T. Copper (uo/1)
T. Iron (1:3/1)
1. l*.ad (us/I)
T. Kercury (rg/l)
-. Hicfcel (u-r,/l)
Zinc (uq/1)
2T
1.0
<8
<20
<15
6ca
<50
<0.2
<30
^^
2M
1.04

6.7-7.5
3fiO
-37^
76.li
75.5
y..?
i.e
i.^
0.8

570
.








•


SI
O.lo
41
15- S










.
2S
l.O'i

6.6-7.5
300
-jc.-i
73-8
72.5
71.2
t.4
1.0
0.6

ISO











~-~
- 27-
0.3}'
' sa
13-9











IT
0.0

e.it-s.o
310
~37n
76.1
7<..5
73.4
2.7
2.1
1.5
235
185
12
10
ซi
3
5
8
8
0 1S&

0.9S
0.85
0.73
30
.0.32
40
14.1
0.05
10
<2

-------

STREAM:  BLACK  RIVER
SURVEY  DATE: July 2^-25,
                  (m;/l  ur.
19711
STATES  ENV1SON.VENTAL  PROTECTION  AGE;

             REGION  7C

  MICHIGAN-OHIO  DISTRICT  OFFICE
STATION NUM3ฃR
P.IVER HUE
Flow, cfs (average
pH, ronge
Cc.-.d. ((.mhos/en?
Tenperoture F rax.
avg .
min.
CO 03X.
avg.
win.
Total Solids
Dissolved So! ids
Suspended Sol ids
CC3
70C
oo5
BซiO
K03,0
PA"*
E"-30
Prospr-orus, Total
TK.1:
•SfTor- "a-,1!
M i trace*M Ttr f te-'.'
CMorUe
Fluoride
S'jlfact
T. Sod tun
MS AS
T. Cyanid- fug/1)
Phenol tcs (vg/l)
T. Cadmiu-T (pg/.i )
T, ChrcnluT (^g/I )
T. Copper (un/1 )
' T. Iron kg/!}
T. Lead (..3/0
T. C.ercui"/ (ug/l)
T. IHc^!ll (to/!)
T. Zinc (WM
13
10.8

7.2-8.3
550
-loon
73. 8
71.2
67.1
11.5
7.3
*.8
605
575
6
20
IS
8
32
!.0
M
0.230
1.1

82.6
eo.s
4.4
3-1
1.9
390
350
9
11
9
8
13
33
35
0.426
3-6
2.83
O.So
64
0.52
ฃ4
41-3

30

<10
60
<15
1200
<50
<0.2
<30
~43_








































-------
                                         UNITED  STATES
STHF.AM:  BLACK RIVER
SU.WEY DAIE:  J-ily 21-25,  1971
                  (rntj/l i"i!?s> otherwise rofcd)
                      PROTECTION  AGFNCY
           I.TGIOM  TC
MICHIGAN- OHIO  DISTRICT OFFICE
STATION NUSBJK
RIVCR MILE _r
Flc-.--. cfs
pM, rjn^e
Co,-J. (-...-iSos/cn)
Tt^per^tore F cax.
avj .
nl.-i.
DO max.
a -,'3 .
ซ;?!.
Total Solids
Dissolved Solids
S'JS?ฑnicd So! Ids
COO
. foe
Kป5
ปOD10
"'Zft
B0!)3o
rhoSyhoru^, Tot'j :
TM
AifSonle-H
llitrvite-?-;;itr:t--:t
Cht^rldi
Fluorids
Sulfate
T. SoJiua
KB AS
T. Cyanide (us/1)
Phenol ics fe/1)
T. Cad^iuTi (up/I)
T. .Chrc/iiu/i (',3/1)
T. Cc??er (v.n/l)
T. Iron (113/1)
T. Lcjd (uo/0
T. H-rc-jry (liQ/l)
T. ll!'.^! (113/1)
T. Zinc (vo/1)
7J
3-73



85.3
C3.a
82.2





1
^






1

















71>
3.C9



85. C
8",. 3
82. A














'_
--
[
•













6T
3.35

i. 5-7.5
1.50
-520
S5.1
52. 5
6o.fi
2.3
1.8
1.3
355
315
17
17
7
6
..
IS
29
35
C.3!-0
3.1
2.1*
0.7?
. 5!
0.16
6?
32. 1
0.10
10
2-
<10
50
^15
1500
<50
<0.?
<30
32
CM
3.35

6. '.-7. 3
Uo
-510
81.5
80.6
79.7
1.6
1.0
0.3













19
0.50
72
32.2











ฃD
3-35

6.5-7.2
39-ฐ490
77.0
76.1
73- "i
0.7
0.3
0.0












-
. 37
0.1
53
21.1











(•3
3.35



86. 0
Sj. 6
81.5
2.1
1.3
1.6




























ft,
3.'/f.





































fc
3.16



81. 9
P3.?
82.8































5*
2.85



87.8
85-9
81.2
1.2
0.9
0.6





























-------
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STREAM;  "LACK RIVER
SURVEY DATE:  J"'v 2i--25.
                  (wq/l  un
              UNI

 1974
ejs o'h-irwise noled)
reo  SUTEIS  rNvmoNMFNTAL,  PKOTTXTION  AGCIICY

                  HEGIOIJ ~X
       MICHIOAN-OHIO  DISTRICT  C.rFICE
STATIOM NUY.a.-.R
RIVER MILE
Florf. cfs (average)
pM, range
Coni. d.n'-Oi/cri)
TcnpcrafjreฐF r.ax.
avg.
!>iin.
00 max.
av-j ,
nin.
Tow! Solids
Dissolved Solids
Suspended So* ids
COD
TCC
BCD.
ES310
BOD2C
Bฐฐ30
Phosphorus, Tc-taป
TX.f
A-;.-.onia-M
('i trete+Ni Jrtte-!!
Chloride
Fluor iu'ซ
Sulfate
T. SoJiu-Ti
K3AS
T. Cyanide (ug/i)
Phenol ics (iia/1)
T. CsdrrJuT (ug/U
T._Ch.'cniui (i.'j/l)
T. Copper (1:5/1)
T. Iron (iKj/l)
T. Ua-J d:a/l)
T. Kirrary (vy/\)
T. Illct-cl (i'ij/1)
' Zinc ('/I/I)
2T
t.Oli

6.6-7.3
310,
-liOO
79.2

77.0
3.0
2.1
1.5
255
225
11
8
5
it
1!)
,8
22
o.i 5:
1.6
1.26
'0.72
33
0.39
42
15-2
O.C6
30
<2
<10
<20
25
850
.7
1.5
1.2
0.9













3S
0.37
M
15-3











2B
I.O'i

6.S-7.2
320
-350
71.. 7

72.0
2.7
1.6
1.3













33
C.35
39
13-1











IT
0.0

-.6-7.3
320
-370
76.1

73.8
3.0
2.5
1.9
2*5
210
23
8
t>
\
8
8
' 9
0.427.
'1.2
0.82
0.73
35
0.28
39
13.5
0.05
20
<2
10
<20
25
070
<50
<0.2
'30
36"
1M
0.0

6.7-7.3
300 ,
-3^0
73.2

70,2
5-2
4.0
2.5













30
0.21
37
12.3











IP
0.0.

6.6-7.3
00
-320
72.7

6S.3
3.
-------
STREAM:   BUCK P.IVCR
SURVEY DATE:  July :s-:6.  1974
                  (rrg/i  unless o'Nerw1
UNITED  STATES  EMVIRCNVEflTAL  PROTECTION AGfNCV

                     IIEGION  XT

          MICHIGAN-OHIO  DISTRICT OFFICC
STATION .VJV3S3
RIVtR Ml IE
Flew, efs (average]
pM, ra.iji
Co,-.;?, (•-nbos/e.-i)
Ttx:?c;rjtcrecF nax.
av'3.
eiin.
CO . nax.
av3.
nln-
Totoi Solidj
Cissslvei Solids
Sirs-endsd Solidi
CC3
TSC '
8WS
8:3.o
3C32..,
MB33
Ptwsphorvs. Total
Tffii
A-.ror?s-:l
n?T'^ t a-7* ; r 1 1 c - 'I
Chloric-
rru-orTJe
Sutfa:e
T. Sodii^t
K3AS
T. Cyanide Cu5/'}
Phirotic- .(iiS/1)
T. Cadmiurrr (us/!)
T. Chroifu-3 (•jj/I)
T. Copperr (i,s/l)
T. Iron (U3/I)
T. Lead (,.g/l)
T. f.srcury (-^5/1)
T. Nickel ('-s/1)
T. Zinc (^3/1)
13
10.6

6.5-8.0
10:0
-liOD
77.0
70.7
66.2
13.5
7-3
3-2
c35
555
7
28
52
8
29
35
35
C.317
4.7
3-63
;.o2.
ras '
O.S5
182
93
O.IZ
JO-
3
10
220
70
330
<50
0.3
6*1
110
12
10.1
22.2
6.4-7.6
1075
-HOC
75-2
73-9
72.5
4.3
2.2
0.3
645
6)0
20
SO
26
21
25
100
100
3.32
hu.i
2-43
_ l-5V~
tJ3
o.sz
J60
105
0.21
170
18
10
ISO
45
530
"50
<0.2
160
83
1!
8.6

6.4-7-3
JCCO
-it:1
75.2
71.1
ฃ3.0
e.o
3-7
1.1
630
535
15
62
2*
17
22
55
55
2.63
10.5
S.43 .
I. IS
-
* T29
C.32
155
102
0.22
50
c
^
12
133
40
450
<50
<0.2
HO
C2
10
6-5

ฃ.3-7-4
SCO
-o'O
73.4
71.6
63.8
7.1
4.7
2.6
615
580
10
45
12
9
16
32
32
2.18

JI.O "
0.24
125
0.85
157
102
0.13
eo
6
<8
110
25
570
<50
<0.2
110
24
S
4.55

6.3-7.2
550
-;e!L
ฃ6.0
84.8
82.%
3.0
2.7
2.1
4nS
4iO
13
36
16
3
25
. 33
33
0.350
1.7
MO
0.32-
72
1.2
J22
54
0.25
20
4
<8
62
<15
2303
*50
<0.2
'.2
S3
Sa
1.7&



65.6
64.3
Si.O































Eb
4.56





































7
3.83

6.3-7.:
520
-61D
85.1
82.4
80.6
5.1
3-2
2.0
385
5iO
18
23
8
8
20
31
31
0.433
3.5
3-09
C,83
., 61
0.55
88
42,0

20

<&
30
<15
1100
<50
<0.2
^.2
33








































-------
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TABLE:
STfiEAM'  BLACK RIVER
SURVEY DATE:  Ju'v 2^26- W'
                  (trig/I unless otherwise noled)
UNITED  STATES  EtJVIHONMFiNTAU  PROTECTION AGENCY

                     REGION  1

          MICHIGAN-OHIO  DISTRICT OrFICE
STAflON NUMBER
RIVER MU
Flow, cfs
pH, i-a.-igs
Cord, {vahos/c-i)
o
Temperature r n^x.
avg.
tiJn.
DO nax.
Bvg.
nln.
Total Solids
Dissolved Soi;d5
Suspended Sol ids
COO
TOC
BOD,
E03!0
80t)20 j
BM30
Phosphorus, Tota!
T;CI
A~^O.T1 3-M
;!i trate+Vitri t-o-.'i
ChlorTdf
fiiiorlde
Sjifate
T. Sodju-a
K3AS
T. Cyanide C^s/i)
fhenollcs (pS/l)
T. CarffliL-n (l.s/1)
T. Chronlun (j.;/l)
T. Copper (ua/l)
T. Iron (p-j/D
T. lead d.3/1)
T. ftrcury (i-a/1)
T. Hiclcl (PQ/I)
T. Zinc (uVD
?J
3-79



85-5
e"i.o
82. ซ|















^ •















7b
3-6?



86.0
8I..7
83-3































6T
3.35

^.'.-7.2
60-510
85.1
83-0
82. k
2.1
1.8
0.8
3^0
290
12
13
3
7
19
27
27
0.33S
3.2
2.63
0.72
43
O.fiZ
' 63
31-6
.0.10
10
1.
<3
27
<15
1?00
<50
<0.2
32
37
6.H
3.35

6.1.-7.2
41C-5JO
f2.!|
fl.O
$0.6
1.1
1.1
o.s

275











48
0.45
73
31.fi










-
6B
3-35

6.1.-7.2
360-1150
77.0
76.2
75-2
0.3
0.2
0.0

360











36
0-36
58
20.7











6a
3-35



85.4
M.2
62. 8
2.4
1.3
1.6




























Cb
3.26




>85.0
86.0































6c
3.16



85-1
81.. 7
84. 4































5a
2.85



S3. z
86.3
86.0
1.2
1.0
0.8




























 I

-------
TAOLF.I
STKEAM: BLACR RIVE*
SURVEY DATE:  •>">* 25~26. '97
                  (og/l  un'tป3s
iss noted)
      UNITED STATES  FNVIRONMKHTAL  PHOTECTION  AGENCY

                          RCC10M  3:

                MICHIGAN-OHIO  DISTRICT  OFFICE
STATION NJM3ER
RIVER MILS
Flow, cfs
pH, range
Cord. (u-V-o S/CT)
Tenpsrature F r.3y._
avg.
nin.
DO nax.
a ,'5 .
Pi*.
ToraT Solids
Dissolved So) Ids
S-.ispsnded Solids
coa
TO'-
BODj
BOD.o
8o:.20
80 ->o
Ph-sphorus, Totaf
Tr.-i
Araxvila-*;
Hitrc!:e-;;i:r: t--.1*
Chloric! s-
F^uorUe
Suifate
T. Sodiua
KEAS
T. Cyanide (ซS/1)
Phenol tcs (w/i)
T. CAcfnlu.-n C'J3/i)
T. Chr •?
1.2
0..

-5


.








4t
o.;:
62
2-,. 3











53
2. ฃ5

6.I.-7.1
33o-;so
77:0
75.2
73-V
0.7
C.4
0.1

2'D










^~-
, 3ซ
0.3S
-55
20.7











4T
2.
-------
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TADLE:
STREAM:  BLACK RIVER
SU.WKY DATE:  Jul^ 25-26,
1974
.•ss olberwise  noted)
UNITED  STATES  ENVIRONMENTAL  PROTECTION AGENCY

                     REGION IT

          MICHIGAN-O'llO  DISTRICT  OFFICE
STATION NUMBER
RIVER NILE
Flow, cfs (avpr.igt-)
pH, range
Cond. (:l.^05/cn)
Temperature F rax.
flvrj .
nin.
CO r.ax.
avg.
nin.
Total Solids
Dissolved So! ids
Suspended So] ids
CC3
TOC
SODj
BMIO
B0320
E:'D33
Phosphorus,. Totnia-M
/iilrate+::rtr Jtft-Ii
Chloride
FitoriJs
Sulfats
T. Soditra
HSAS
T. Cyanide (ug/l)
Phenol ics (pg/l)
T. Cadmium (p^/O
T.. Chron ium (wy/l)
T. Copper (|ig/l)
T. Iron (ys/1)
T. Lead (j.,/1)
T. h^rcury (uu/l)
T. Illckel O's/l)
Zinc (uu/l)
2T
I. Oil

f.3-7.2
360-liOO
82.0
73.3
77.5
2.8
2.1
1.4
255

16
12
7
3
8
12
13
0.1 C3
2.0
1.57
-0.7*1
37
0.33
A7
19-1
0.07
20
3
<3
<20
50
930
<50
0.'.
<30
S-'ซ
2H
J.OI.

6.3-7.1
3^0-330
77-2
7&.3
75.7
1-5
1-5
0.8

250











33
0.39
<-?
15.1











26
l.Ci

6.3-7.:
320-350
74.S
73.7
72.0
3,5
2:5
1-7

255











25
0.35
"'id
1'!.2











IT
0.0

6.1-7.2
330-370
78.8
75-7
70.7
4-7
3.1
2.5
235
210
11
13
7
3
3
3
13
0.103
J.2
0.82
0.75
-27
0-31
36
15.2
0.05
10
2
<8
<20
195
820
<50
'0.2
43
" ~T30
1H
0.0

6.3-7.1
300-350
77.0
73.1
70.7
5.5
4.0
2.2

185 .











28
0.27
40
12.9











IB
0.0

6.3-7.2
:6o-330
7'..5
72.3
68.9
5-2
3.1
1.6

165











26
0.22
39
11.8











lake
Erin


6.6
300



-
8.8
-

180











24
0.16
35
10.5











freoch
Crci-V.
5.1
0.95
6.9-3.4
I000-117i
75.7
71.2
65.8
11. 1
8.3
5-3
750
6$0
35
25
14
4
7
5
3
2.34
1.2
O.OS
3.27
.107
0.65
224
121
0.14
10
<2
<8
<20

-------
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o
•Ciปซ
UJ
CO
ซC

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{—
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BN
Cฃ
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r^"* ^v—
^c^" ^••'i-
LU
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^y
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cz
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to
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LU|
CJ
d
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t_> ;
*— • .
CC 1
gl
Q!
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* — * i
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• i i
-*~ *

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tiJ
cc
UJ
o
52
CD
          .3-
          r-.
           >.

          *3
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 _

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UJ
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CO — •'^
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Attachment
 •

                             U.S. EPA Survey, July 9-11, 157^
 '•                           (Benthic  and  Sediment  Chemistry)




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                                   APPENDIX IV

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                           BIOLOGY OF THE BLACK RIVER
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                      U, S, ENVIRONMENTAL PROTECTION AGENCY
•                     OFFICE OF ENFORCEMENT & GENERAL COUNSEL
                 NATIONAL FIELD INVESTIGATION CENTER - CINCINNATI
                              WATER SCIENCES BRANCH
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p       "               The benthic data collected during the survey of July 1974, show


•     •             the Black River to be degraded downstream from the Elyria, Ohio,


                    sewage treatment plant.  The river is further contaminated through


•                  the reach, river miles 4.35 to 3.45, apparently by the U.S. Steel


                    outfalls 001  (from the plant hot forming operations) and 002 (from


•                  the coke plant).  Trie river recovers slightly at river mile 2.85, at


•                  the head of the navigation channel, but is again degraded, although


                    not as severely as upstream (river mile 4.85 to 3.45), at river mile


•                  2.6 in the turning basin.  The U. S. Steel discharges servicing the


                    blast furnaces, sinter plant, power house, steel plant and lime plant


•                '  discharge into the turning basin and could cause this degradation.
                       *
•                  Also the effect of these discharges could be moderated bv lake water


                    intrusion to  the head of tas navigation channel (personal coninuni-


I                  cation with Phil Gehring MODO-EPA).  From rivnr mile 2.36 to 0.83 the


_                  river generally shows signs of recovery from the upstream conditions.


                    At rivsr mile 0.0, and the harbor mouth, the river is again degraded


•                  probably as a result of the discharge of the Lorain, Ohio, sewage


                    treatment plant.


I
                        Sediment  chemistry data show the reach from river miles 4.85 to


•                  3.45 to have  the greatest concentrations of pollutants.  The most


                    affected station is station 8, river mile 3.45.  This coincides with
                     the biological  data which show station 8 to be the least nroductive.

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    Comparing data obtained by the Michigan-Ohio District Office of




Region V, U. S.  Environmental Protection Agency, in July of 1972




(Table III) with the present biological data, it appears the water




quality in the Black River has degraded in the past two years.  The




July 1972 data show that midges and leeches in significant numbers,




in addition to sludgeworms, were inhabiting the reach of the river




froa downstream of U. S. Steel outfall 002 to upstream from U. S.




Steal outfall 001.  The present data indicate that only sludgeworms




now are found in this area (with the exception of station 8-A x^here




pollution tolerant snails were found).  The navigable portion of the




river also shows signs of further degradation.  This is indicated by




a l.irge reduction in the gill breathing snails (Prosoborarichia) in




this teach, and the disappearance of midges from river miles 2.36 to




2.S5,

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rTTRnnuCTTON
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                        At the request of the Enforcement Branch, Region V, U. S.
•               .   Environmental Protection Agency, a biological and chemical water
                    quality investigation of the Black River of Ohio from upstream of
                                                 I*   *
                    Elyria, Ohio, to the Lorain, Ohio, Harbor  (Figure 1) was conducted
•                  from July 9 to 11, 1974, by the National Field Investigations Center-
                    Cincinnati of the U. S. Environmental Protection Agency.  The purpose
•       .           of the study was to delineate the effect,  if any, of the wastewater
                    discharges of the Lorain Works of the United States Steel Company,
. •    -'.              which is situated on the west side of the  river from approximately
•     •             river mile 2.4 to 5.0, on the biota and sediments of the river and
                    harbor.  The biological results of this study were also to be
•    .      f       compared with benthic data collected in July of 1972 by the Michigan-
_         '         Ohio District Office, Region V, U. S. Environmental Protection
   •                 Agency, to ascertain whether any change in water quality had
I    ":'             occurred.

•    .                  The purpose of macroinvertebrate studies is the measurement of
                    the density, diversity and generic composition of the benthic
•                  organisms living in the substrate of a river or lake.  These
                    organisms are totally dependent on the aquatic environment for their
™                  needs, thus changes in the water quality are reflected by
0    .              modifications in the benthic population.

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  N!
                        LAKE ERIE\
      Sfa.2
     Sfa.l
City! oH-orainj
 V/ater lntake\
       Sta.3_\
       (R.M. 0.0)|
                                                         (Frenchl Creek
                                                          ., R.M .~b. 2) |
              LORAINl       •  U.S.S.002I
               Sta.4 (R.M.I 0.83)
                     Sta.7\"
                   -M.l2.85)!
                                          Sta.9 (R.M. 4.0)1 .

                                                      Sta.10 (R.M.|4,85
        (R./A.]2_.36)|
U.S.S. 003 a 004F _sta."6l
                    (R.M.| 2.6)1
                                              U.S.S
                                               005
                                               Sta.121
                                             (R.M. 5..5)|.
      LEGEND
     R.M.=River Mile
                                       Sta.141
                                     (R.M. 15.2)L
                                                           BLACK I
                                                           RIVER I
                               Sta.l6|
                           (Greenfield Rd.)|
                                            ELYR1A
                                                   Sta.15:
                                                 (FulierlRd.)
                                            E. BR.\
               SCALE!
        0\
    FIGURE 1|
11        2! MILES!
SAMPLING LOCATIONS
            JULY - 19741
                                 - BLACKl RIVER, OHIO!

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I

                       For  the purpose of  this report  the  terms pollution intolerant,
•    •             facultati"2 and pollution  tolerant  will be used when referring to the
                   ability  of an  organism  to  withstand environmental  stress.   Intolerant
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                   organisms are those which are unable to withstand any major

                   deterioration in water quality.  Facultative organisms are able to

                   withstand a wider range of pcolr, ,-ical conditions.  Members of this

I                  group can be found in clean water as well as in dilute organic

                   wastes.  Tolerant forms are found in the widest range of situations

•                  frcn clean to grossly polluted water.  Under extreme conditions,

B    '              (e.g. toxic wastes), even this group can be eliminated.
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                        IILTIinnS AND MATERIALS




    Benthic Macroinvertebrates



    Samples in the study area were collected,  in most cases,  at sites


previously established by the Michigan-Ohio District office of Region


V.  Many of the stations were sampled at. three sections (A,B,C).


Across the river facing upstream, section A was located near the left


bank, section B at midstream, and section C near the right bank.  All


samples in pool  (lentic) areas were collected with a Petersen dredge


while those samples from riffle (lotic) areas were taken with a


Surber sampler or were qualitative samples from the various


substrates at the sampling point.  In most cases, three replicate
    f

sample? were collected at each station section.



    After collection the samples were washed in a standard No. 30
                                               ^
sieve to remove  the bulk of  the substrate material,  The sample


remaining in the sieve was placed in a labeled plastic jar and


preserved with a solution of  formalin, alcohol, water and Rose Bengal


dye.  The jar was  then  capped and sealed with an EPA seal.  All


samples were kept  in  the possession of the field team until their


return  to NFIC-Cincinnati, where  the samples were logged into  the


Biology Section  sample  log book and placed in  locked storage until


analysis.

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    In the laboratory each sample was washed again to remove the


preservative and excess sediment and placed in a white enamelled pan.


The benthic organisms, except for sludgeworms (oligochaeta), were


picked from the samples and placed in plastic petri dishes according


to general groupings.  Later all organisms were identified to genus


when possjible.
•                       Because of the large number of sludgeworms per sample only


                     approximately four hundred individuals from each sample were picked

     I' '
                     at random.   The sludgeworms remaining in the pan were counted and


•    -               returned with the other sample residue to the original sample jar.
Sediment Chemistry                                       '


   *•

    Sediment sairples were collected for chemical analysis with a


Peterson dredge at one section per sta.tion from river mile 5.5


downstream to the Loraia Harbor mouth and Lor-ain water intake.  The


three sediments were placed in plastic tubs and only the top layer of


sediment taken for the sample.  The sample was placed into a labeled


cne pint plastic jar sealed with an EPA seal, and iced.  The samples
_


                     were kept in the possession of the field crew until their return to
NFiC-Cincir.nati where  they were turned over to the laboratory samole


custodian, who logged  thc-in into the Chemistry Section sarmle log book


and placed them in locked storage until analysis could be made.



    Mercury was analyzed by the flarieless atomic absorption method


developed by  the National Field Investigations Center-Cincinnati.

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Samples for the remaining metals (see Table IV)  were acid digested




and also analyzed by atonic absorption.







    Cyanide, phenol, percent moisture, volatile solids and oil and




grease were analyzed as outlined in Standard ? let hods for the




Examination of 7,Tater and Wastewater, 13th Edition, 1971.  Acid




leachates of the sediments were analyzed for ammonia nitrogen using




the automated sodium phenolate method.







    Methods and results of the organic analyses of the sediments can




be obtained from a report titled "United.States Steel, Lorain, Ohio,




Works, Black River Survey: Analysis for Hexane Extractables and




Polyr.uclear Aroroacic Hydrocarbons," October 1974 by Herbert Brass, et




al.- •

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                   RESULTS AT JO DISCUSSION
Benthic Macro invertebrates
•    -                  Data on  the .taxonomy and  diversity of the benthic organisms at


ซ    "               each  sanpling  site  arc  displayed  in Table I.  The sedinent types


                     encountered  during  the  survey as  well as the type of area sampled


I                   (riffle or pool)  are  given  in Table II.



•-  ~i                  Control  stations  15 and 16  were located upstream fron Elyria,


                     Ohio, on  the east and. west  branches of the Black River,  respectively.


•    .               Samples 16-1 and  16-2 were  collected in a pool  area.  The substrate

      -                                                                       •
_     •              at this station consisted  of  gray sandy clay,  silt, and  detritus.


                     The*benthic  fauna was indicative  of a clean water situation,  composed


•                   of low nunbers of sludgeuorms,  a  few faculative fingernail clans, and


                     pollution intolerant  midges,  amphipods, burrowing mavflies,

      Ii
                     aldertlies,  an-d beetles.



 •                      Findings at station 15 were indicative  of  a clean water  riffle


 —                  situation.   The station was characterized by low numbers of


 *   -               individuals  but a large number  of taxa.  The benthic fauna was


 I                  composed  of  nayflies, caddisflies, beetles,  tolerant and intolerant


                     midges and sludgeworms.  Sample 15-1 was  collected  with  a Petersen


 I                  dredge in an eddy area where the  substrate  was composed  of detrital


 _   •              accumulations, while  sample 15-2  and  15-r3 were collected with a


                     Surber sampler from large flat  bedrock  areas.   As might  be expected,

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sample 15-1 contained a somewhat different midge nopulntion than 15-2



and 15-3 and was devoid of the caddisflies found in the other two



samples.





    Station 14 was located between Elyria, Ohio, and the Elyria



sewage treatment plant at river mile 15.2.  Sample 14-1, a



quantitative Surber sample, and sample 14-2, a qualitative sanple,



were both collected in a riffle area, while sample 14-3, a



qualitative sanple, was collected just upstrean in a pool area.  The



substrate cf the lentic environment was composed of large rocks and



r.e sediment.  The benthos indicated a slight decrease in water



quality from the upstream control stations.  This is exhibited by a
                                                         *


decrease in diversity of the riffle organisms when compared with

   f

these collected at station 15.  The fauna, however, was still



composed of rrainiy facultative and intolerant types and not pollution



tolerant organisms.                          _/





    Station 13, downstream from the Elyria sewage treatment plant,  at



river mile 10.0, was another riffle-pool situation.  Here a Surber



sample (sample 13-1) and two Petersen samples (samples 13-2 and 13-3)



were collected.  The substrate in the riffle was shale while in the



pool it was composed mainly of sand, gravel and detritus.  The



benthic fauna collected show an abrupt decline in water quality when



compared to the upstream station (station 14).  The increase in



organic load to the river, by the sewage treatment plant, is shown by

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M                  a large increase in sludgeworms, and a drastic decrease in the
                    diversity of the benthic fauna.
™    ,                  All samples at station 12 (river mile 5.5) were taken in a sludge
B    '              deposit located along the west bank of the river.  Here the soft gray
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sediment had an oily smell and gas bubbles were emerging at the

surface.- The remainder of the river width at this station was

composed of shale and gravel.  The slack current at this station
     '[              indicated the possibility of pollutants being carried upstream from

•    "              U. S. Steel during of flow reversals caused by varying lake levels

                    and wind direction.  However, the paucity of sediment deposited at

I    •              this location, indicates scouring during high flow conditions.  The
                                                                             •
I                    benthic fauna was indicative of an organically enriched environment.
                                                                          •\  -)
                    Kutr-bars of sludgewoms were extremely high (502.2 x 10J/m  in sample 2)

•    '              while the diversity of organisms was low with only facultative and

                    pollution tolerant ta::a being present.


                        At station 11, on French Creek, the bottom material was rubble

I
and organic sludge with a brown silt overlay.   Traces of oil were

present.  The benthic community indicated only slightly better

conditions than those found at station 12..  It is concluded that the

input from French Creel: has little or no effect on the water quality

of the Black R.iver.
I
                        At station 10, river mile 4.35, downstream from the U.S. Steel
•                  hot forming operation discharge, outfall 001, the diversity of the
                                 10

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benthic fauna was limited to large numbers of sludgetv-orms.   This



indicates poorer water quality than that found at station 12.   The

    j

difficulty in obtaining replicate samples at this station because of



the rock, shale and gravel indicated that the area is scoured.





   -At station 9, river mile 4.0, gray brown sludge with a silt



overlay was found at all sections, indicating that suspended solids   ^



readily settle in this area of the river.  The benthic fauna was



again limited to sludgeworms, showing no improvement over conditions



found at station 10.





    Sludgeworns were again the only benthic organisms found at.



station 3, river mile 3.45, downstream from the discharge'from  the U.



S. Steel coke plant discharge, outfall 002, except at section 8A,



samcle 1 where pollution tolerant snails were present.  The effluent



discharged from outfall 002 apparently inhibited the proliferation of

                                             */'

sludgevorns at sections SB and SC.  At these locations the .' -erage



number of sludgevorns for the three replicate samples was m'jch  less


                             32                         32
than ac section 3A  (14.6 x 10 /in  at section 8B, 41.4 x 10 fu~  at section


                               3  2
SC, as compared with 353.1 x 10 /m  at section 8A).  The substrate also



differed between the three sections (8A - gray brown sludge, SB -



black sludge with a brown silt overlay and SC - gray sludge).



However, oil was abundant at all locations.





    The appearance of a few genera of leeches and fingernail clams at



station 7, at the head of the navigation channel, river nile 2.85,
                                 11

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                  indicates a slight improvement over the conditions noted in the reach
|    •            from stations 8 through 10.  The sedinents at this station were
_                composed of black silt and sand, fly ash and detritus.  Oil was
                  abundant in the samples collected from all sections.

*
fl
mm.

•

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                      United States Steel discharges the wastes from its blast furnace

                  area, lime plant, and steel plant into the turning basin (outfalls

                  003 and 004) near the head of  the navigation channel.  Results from

                  statior. 6, river nile 2.6, located in the turning basin, indicate a

                  slight decrease in water quality by a reduction in the diversity of

                  the benches when compared to station 7.  The seidments in the turning

                  basin were composed of gray sludge with a light brown silt overlay

                  and oil was noted in the sediments at all sections.
     ;                 At  station 5, river nile 2.36, sections A and C, pollution

|   '              tolerant  leeches and facultative fingernail clams again begin to

_   •           .   proliferate, indicating improving water quality.  However, the

     '            "  benthos collected at section 5B show conditions to be similar co
   I*  -:
                   those at  station 6.  This could result from pollutants flo'-'ing

                   downstream in  the center dredged portion of the river, the dredging

|   i              operation upsetting  the benthic population or propeller wash from

M   '              commercial shipping.   Sedinents in this area were similar to those at

                   station 6.


™                    The diversity of the benthic population increases further at

I                 station 4,  river mile  0.83.  Here, in addition to the leeches and


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fingernail clans found upstream,  were pollution tolerant nidges and



snails, and facultative to intolerant snails and scuds.   Samples from



midstream, section B,  at this location show a less diverse benthic



coimunity, similar to  that at station 5B.   The sediments, differing



from those found upstream were composed of a gray brown  sludge with a



brown silt overlay.  Some detritus was noted in the samples from



section C and oil was  present in samples from all sections.






    The effect,of the  Lorain sewage treatment plant discharge near



the south of the river was not dramatically evident o'n the benthic



fauna at station. 3, river mile 0.0 and at the harbor mouth, station



2ป  There was a sone reduction in diversity of the population,
                                                         •


involving mainly the leeches and fingernail clams.  The  moderate of



the treatment plant effect could be due to proper wastewater



treatment or lake waf.er dilution.  Sediments at this locations were



sinilar to those at station 4.               ^





    The benthic fauna  collected at station 1, near the Lorain, Ohio,



water intake, were devoid of the scuds which one might exnect to



associate with the sand substrate at this location.  Only pollution



tolerant midges and sludgeworms were collected at this location.





Sediment Chemistry






    The results of the chemical analyses of sediment samples from the



Black River are displayed in Table IV.
                                 13

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•                       In general the sediment chemistry data shou increases  in  all
                     parameters  except percent  moisture  downstream fron the  U.  S.  Steel
•                   discharges  001 and 002,  river miles 4.85  to 3.45 reslectively.  In
•                   most cases  the concentrations near  outfall f'002  were the highest found
                     in the studv area.
                         Downstrean from river mile 3.45  (station 8)  the  levels  of
•     :              pollutants in the sediments decline  until  station 6  (river  nile  2.6)
       ;       .       adjacent to U. S. Steel where most of the  parameter  values  increase
•                   although not as much as upstream.  Many of the narameter values
•     '              increase still mora at station 5 (river mile 2.36).   This increase
                     nay be because the sample for the  sediment chemistry was'taken from
•     :              an undredged area of the river. The pollutants in the sediment,
 _                   therefore, were not subject to periodic removal.   Fron station 5 to
*     .              the Lorain Harbor mouth and the water intake the levels of  all
 •     '              pollutants in sediments generally  decrease.  -^

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BLACK RIVER, OHIO,  BF.NTfJIC MACROINVERTEBRATES PER SQUARE METER
                              JULY 1974
Station Number 1
Location Water Intake
Section 1 2 3
Oligocheata X 103
Hirudmea
Hellobdslla sp.
H. Stagnalis
H . Etongata
Erpohdalla sp.
Sphaeriidae
Sphaerium sp.
S. Tranversurn
S. (MuscuJiu-n)
Pisidium so.
Chironornidae
Chironorninae
Chironomus sp.
CrvDtochiro.-iornus SP
FoiypechluTi sp.
Tna-Mos S3,
Stictochironomus sp.
Endochiro-.onus SD.
Tariytarsjs ; ' ,
Psectrcciadi'js so.
Chirofiom.ip.ae p'jpae
Orthoclachir.a'2
CrlcotopiiS sg.
Oithocladiina.; pupae
Tanypodiria?
Prociadiub :o. T
AblaXiesmvia sm
Simulidae
Sirnuliurn ss.
Physa sp.
ProsoVanchia
Pleurocera :o.
Velnata smosra
Bit'nTUฑ tc".'.ic-j!a*a
ArnnicLiia SD.
Pid-iorDUja sp.
Amphipocla
Hv^leUd asteca
Garnrnarus liJciatjs
Eplierneroptera
Hexigenia l-.rnbata
Cacnis so.
Baetis sp.
Trichoptera
Agrayjea sp.
Chimarra o'jscura
Hydropsyche sp.
Cheumatopsyclio sp.
Trichoptera pupae
Coicoptera
Helodidae
Dubiraphia sp.
Stenchnis sp.
Megaloptera
Sialis sp_._
Turbeilaria
Hydractirina
Total Number X 103
Total Taxa
10.3 4.3 9.3
T
T
F
F
T 1278 623 998
F-I
1
I
F-I
F-I
I
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-F 468 172 218
I
T
F
F-I
I
I
F
F
F
I
F-I
I
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I
F-I
F
I
I
F-I
F
1
2
Harbor Mouth
1 2 3
16.2 21.0 19.0
16 125
16
109 47 62
16
16
3A
River Mile 0.0
1 2 3
47
31
t
12.85.0 10.6 16.4 21.0 19.959.1 186.5128.1
33 45 2 42 1 3
3B
River Mile (
1 2
7.0 47.8 ,
468 '
47 I
47 l
62
31
16
16
156
7.1 47. S
2 9

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BLACK RIVER, OHIO, BENTUIC MACROINVhRTEIiRATES PER SQUARE METER

                             JULY 1974
Station Number 3C |
Location River Mile 0.0
Section 1 2 3
Oligocheata X 103
Hirudinea
Hellobdolla sp.
H. St.-iฃM.-th$
H. Elo-.g-ta
Erpobdsil'i sp.
Sphaeriidse
Sph.Teriu'n sp.
S. Tranvers'^m
PJsidiu.ii sp.
Chironornidae
Chironominae
ChircriOiTius so.
Cryptccln-onorrius sp
Poly pea :ium 3 p.
Tribeios so.
StictcC'h::roicmus sp.
Endochirooo'-ius sp.
Tanytcrs^s 32.
Psectrocl^o: J3 30.
Chironorrunae pupae
OrthoclaciKnae
Cricotopus 57.
26.6 20.2
4-ซ
to
o
T -1
T ^ f
rt
F 47
F
T
. T
F-I
I
I
F-I
F-I
I
I
Ofthociad.irvri pupae 1
Proclacvjs so. T-F
Ablnbcs TV- j ii sp.
Sirnulidae
Pulrnonata
Phvsa 53.
Prosobrar.cMa
Pieurocera SD.
Vaiuatu s^-ce-ra
BiThy-ila i;r taculata
Amr-.icu'i sp.
Pjancrbo;2 sr>.
Amphipoda
Hv-alelia azteca
Gapnma(-js fa-iciatus
Ephemeropt^ra
Hexisenla lirnbata
Caenis sp.
Baetis sp.
Trichoptera
Agrayiea sp.
Chimarra obscura
Hydropsy die sp.
Cheumr.tops/che sp.
Tricliopt-.-rj pupae
Coleoptcra
Helodidae
Stenelmis sp.
Megaloptcra
Siahs sp.
Turbellaria
Hydracanna
Total Nu.nber X 103
Total Taxa
I
T 62
F
F-I
I 47
1
F
F
F
I
F-I
I
I
I
F-I
F
I
I
F-I
F
I
20.8 29.1
6 1
4A
River Mile 0.35
1 2 3
6.0 4.1 7.2
16
561 108
3664 2822
795 187 218
47 94
125 218
16 31
16
312 405
6.9 9.0 11.1
3 8 3
River Mile 0.35
1 2 3
53.1 67.4 69.0
173
187 561
16
109 125 135
16
i
54.2 68.1 69.5
443
4C
River Mile
1 2
34.1 38.3
94 :
16
1828 :
234 ;
47 i
136 78 J
16
16
34.2 100.7 1
298

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BLACK RIVER, OHIO, BENTH1C MACROINVERTEBRATES PER SQUARE METER
                            3ULY 1974
Station Number 5A
Location River Mile 2.36
Section 1 2 3
Oiigocheata X 103
Hirudinca
Heilobdella sp.
H. Ma^nahs
H. i.Ton^ata"
Erpobdella sp.
Sphaeriidae
Sphaerium sp.
S. Tranversum
STTV^sculTum)
Pisidium so.
Chironomidae
Chironominae
Chiroriomus sฃ.
Cryptochirooomus sp
Polypediiurn sp.
Tribelos SP.
Stictochironornus sp.
Endoch;:onor~,us sp.
Tap1, t^rs'j* -D.
Psectrocldcius so.
Chironornir.ac- pupae
CrthGcladnnae
Cri'.otopi^s ;p.
42.3 63.7 43.8
T
^7 31
T
F 62 16
94
16
F 16
T
. T
F-l
I
1
F-I
F-I
I
I
I
Oft!:ociaa:.,~ae pupae I
Tanypod'nae
Prociadius sp. T-F
Abhsbesrnvia SD.
3iinu!1d;-.e
Puirnon,,;.^
Physa so.
Prosobranchia
Pleurocera so.
Valuata s'ncDra
Bithyri'a tentaculata
Atinicuia s;>.
PJanorb'jia sp.
Amphlpoda
Hyalell-i azteca
Gamrnarus tasciatus
Ephemeroptera
Hexi^enia limbata
Caenis sp.
Baetis sp.
Trichoptera
Agrayjea sp.
Chimarra obscura
Hydroj)sy_che sp.
CheuTiiitopsyclie sp.
Trichoptera pupae
Coleoptera
Holodidae
Dubirapliia sp.
Stenelmis sp.
Megaloptcra
Siahs sp.
TurbeMaria
Hydracarina
Total Number X I03
Total Taxa
I
T
F
F-!
I
I
F
F
F
I
F-l
I
I
1
F-I
F
I
I
F-I
F
1
12.4 63.9 43.2
3 6 1
5B
River Mile 2.36
1 2 3
11.3 16.2 21.3
16
16
11.3 16.2 21.3
2 2 1
5C
River Mile 2.36
1 2 3
68.5 40.6 37
16
16 7S 16
16
78 31 62
16
16 16 16
<
63.7 40.7 37.2
5 5 5
6A
River Mile
1 2
49.4 28.0 1
109
16
49.4 2S.1
1 3

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BLACK  RIVER, OHIO, BENTHIC  MACKOINVERTEBRATES PER SQUARE METER

                             JULY 197*
Station NUT
Location
Section
Oligocheata X 10
Hirudinea
Hcliobdelia sp.
H. Suv'.naUs
H. Elonnita
Erpobdeila sp.
Sphaeriidae
S. Tranv'jrsu'n
S. (MuscuKum)
PisicUuTi so.
Chironomidae
C-hirono'Tiinae
Chi.-oromus so.
Cr\ :>icohironomi!s s
-~>oiicฃa ' * u rn S2--
Tr:De.'cb so.
Stictochironomjs so
Enc'ocr);ror-onr"j.s so.
Tany tarsus sp.
Psectrociadius so.
CruronoiThnae p'jpae
Grihoda-Jinae
C'lCotOOUj SO.
Oit'nocia;'::aae pupa
Tanypodinae
Proclac'i'js so.
Ab!ab"5rf!V;a SD.
Pu'rnona'a
Frosooranchia
P!euroa-:a -~, .
V:Ij-;ta sinc^ra
Sit-vri.j teitc-c^lat
A'rni'-.j'a :--.
P^noriiuia to.
Arnpnipoca
H>alel!a azteca
Gar.-m--us fasciaic
Epberp.eraotera
Hexigerua ll'nbata
Caot'.is so.
Baetis sp.
Tricdoptera
Chiinarra obscura
Hydropsyche sp^
Chcu.ii.ii.ipjycl'ie sp
Triciior>iara pupae
Coleoptcra
Helodidac
Dubiraphia sp-
StenoJinis sp.
Megaloptera
Siaiis sp.
Turb'jliaria
Hydracarina
Total Number X 1C7
Total Taxa
her 6B
River Mile 2.6
1 2 3
16.1 9.1 22.5
T

T
F

r
T
3. T
F-I
I
.1
F-I
F-I
I
I
1
e I
T-F
1
T
F
F-l
> i
1
F
P
, F
j
F-I
I
I
I
F-I
^_F
I
1
F-I
F
I
16.1 9.1 22.5
11 1
6C
River Mile 2.6
1 2 3
16.6 5.3 8.0


16














16













17.7 5.3 S.9
4 I 1
7A
River Mile 2.85
I 2 3
24.0 25.5 41.5

125























1





24.0 25.5 41.5
1 2 1
River Mile 2.85
1 2 3
177.1 161.4
o
J
•i' 47
E 16
rt
m
16
16
16


























177.1 161.4
2 5

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BLACK  RIVER, OHIO, BLNTHIC MACROIN VERTEBRATES PER SQUARE METER
                            JULY 1974
Station Number 7C j SA
Location River Mile 2.S5 i River Mile 3.45
Section 123123
Ohgocheata X 10
Hirudmea
HeHubdella sp.
H. Stagnahs
H. Elongata
Erpobd'.'ua sp.
Sphaer iidae
SpYieriu-n so.
S. Tranversum
S. (Musculium)
Pisidiu.Ti so.
Chironornidae
Chironominae
ChKonomus sp.
CryatochlronoTius sp
Polyped.lum so.
Tri'jeJcs sp.
5tiCTOch:rorornus i.D.
Endochironoiri'js so.
Tcnytars'jS 3p.
Psec:roc;i-Jius sp-
Chironominae pupae
Ortroclaciinae
CrtcctODOS sp.
lfl.2 136. S 60.8
T
T
F
F
T
. T
F-!
I
I
F-I
F-I
I
I
I
Oithocladiinae pupae 1
Tariypoclinae
Proclac'ius sp. T-F
AbUbesmvsa 3D.
SimuJidae
S;ms.!!ium so.
PulMnmta
P^.ysa so.
ProsoorancMa
Pieuroc^r :, so.
Vaidata s:'ico"a
t;:"."yn a tc.'"t3C'j!=ta
Armjcijii s~.
Fliriorbjia sp.
A-.p>;poda
rivaie!'-i azteca
Ga-^'nar-js las'iatus
Ep^9.T,eroptc-ra
K-xi™eni.i linnbata
Caeris sp_._
Baetis '..j.
Trichoptera
Acraylea sp.
Cniu arra obscura
Hydrop_s>c'ie sp.
CheuiTiatopsyche sp.
Trichoptera pupae
Coleoptera
Helodidae
Dubiraphia sp.
Stencini's sp.
Megaloptera
Sialis s;j.
Turbeiiarra
Hydracarina
Total Ni;mbซ.T X 103
Total Tax 3
I
T
F
F-l
I
I
F
F
F
r
F-I
i
i
i
F-I
F
I
I
F-I
F
I
322. S 316.4 420.1
16
l'tl.2 136. S fO.S 322. S 31f,.0 420.1
1 1 1 2 1 1
SB
River Mile 3.45
1 2 3
26.2 7.9 15. S '
SC
River Mile 3.45
1 2 3
47.8 48.1 2S.2
\
26.2 7.9 15. S 147.8 '(S.I 2S.2
1 1 1 1 1 1

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          BLACK RIVER, OHIO, BENTHIC MACROINVERTEBRATES PER SQUARE  METER

                                             3ULY  1974
         Station Number
         Location
         Section
                                 9A
                          River Mile 4.0
                           1      2     3
      9Q
River Mile 4.0
1     2      3
               irr
Oiigocbeata X
Hirudinea
  HeiL'bdelia sp.
  H.  Stagnalis
  H.  Eiongata
  Erpobdella sp.
                         167.6  151.4 282.21321.8 139.5  59.3
                      T

                      T
Sphaeriidae
  Sphaerium  sp.
  S. Tranversum
  S. jMusculiurn)
  PislQiurn sp.

Cruronomidae
 Cniropominae
  Chironomus sp.
  Cryptocruronom'js sp.  T
  FoJvpedilu.Ti so.
                      F-I
                      I
  Tri'a&ios  sp.
  Stictocnironorr.'j.s sp. I
  EndochironoiTius so. F-I
                      F-l
                      I
     r.ytarsus sp.
  Psectroclac
              us  so.
 Chironominae pupae
 OrthoclaCiinae       I
  Crlcotoous sp.      I
  Oflhociadur.ae pupae I
 Taiiypcdinae
  ProcSadius sp.     T_F
  Ab.'abesmyia sp.     I

Sirnjlidae
  Simuliurn sr>.

Pulrnonata
  Physa sp.           T
 -Tosoo-ancnia
  Pl-iuroce^a so.
  VaUita
                      r
                      F-l
   ijit'vvnia tentnc'jlata 1
                      I
 Ep*i&;neroptera
   Hexigenia limbata
   ฃ^ฃill_5ฃjL
   SaOtiS Sp.

 Trichoptera
   Agrayiea sp.
   Cn.fpa.Ta obscura
   Hydrppsyche sp.
   Cneumatopsvche sp
   Trichoptera pupae

 Coleoptera
  Helodidae
   Dubiraphia sp.
            _sp.

 Megaloptera
   Sialis  sp.
 Turbellana
 Hydracarina
                      I
                      F-l
                      1


                      I
                      I
                      F-l
                      F
                       I
                       I


                       F-I
                       F
                       I
     9C
River Mile 4.0
1     2      3
                 107.4 153.8  209.9
    10A
River Mile 4.85
1     2      3
                                                                                      365.2
 Total  Number  X 10'
 Total  Taxa
                         167.6  151.4  282.2!321.8 139.5  59.3'107.4 155.8 209.9       365.2
                         1      1      1      jl     1      1    jl      1     1           1
                        	.	I	J	J	.	.

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BLACK  RIVER, OHIO, BENTHIC  MACROINVERTEBRATES PER SQUARE MUTER
                             DULY 1974
Station Number 10B
Location River Mile 4.85
Section
Oiigocheata X I03
Hirudinea
Hollobdslla sp.
H. Stasr.al'.s
II. Eiorvata
ErpoDdeKa sg.
Sphaeriidae
Sp'iaerijTi sp.
S. Tranversum
S'. (Wusojhum)
PlSiJlUrt S3.
C.Hronomidae
Cnironornlr.ee
Ch'roROTius S3.
Cr)piocr..rono!n'js sp
Poivoec'iium sp.
Tnoeio? sp.
Siictocruronorr.us SD.
I',"doch; ror.o.'TTjs 3.0 .
Trnvt^rscs so-
Ps^ctrociaci-js S3.
Chiranorninae pupae
OrihocSdc'unje
Cricotcp'js sp.
491.9
T
T
F
F
T
. T
F-I
I
!
F-I
F-I
I
I
1
Oiinccicdiinae pupae I
Tarwpodinae
Procladi'js so. T-F
Ablabes^i\:; so.
Slmiilidee
Sim'jii-jm bp.
i-'ulrr.onata
Pnysa sp.
Proscbranchla

Vol'ja-.} ^n-er^
r.ii'i.p.a tsr.tbc :!ata
Amiojia so.
^>'r^iOrPj;a Sp.
Amp^'ipoCa
HV2:e!!a azteca
Gsmrii'-s lasciatus
Ep'ne-neroptsra
Haxigpnia limbita
Caenis ^p.
Qactis S3.
Trichcotera
Apraylea sp.
Cr>;rnar-a obscura
Hydroo;^ 7he so.
CheuinatoDsyche sp.
Tricooptera pupae
Coleoptera
Hclodidae
Dubirapuii s_p.
St^nc-lTn. •• "sp^
MepaiopT'-ra
Siaiis TJ.
Turbcllaria
Hydracarina
Total N-.i-r.bcr X 103
Total Tcx-a
I
T
F
F-!
I
I
F
p
F
I
F-I
I
I
I
F-I
F
I
I
F-I
F
I
WJ.9
1
IOC
Ri\er Mile 4.85
1 2 3
342.5 529.2 249.7
\
342.5 523.2 249. /
1 1 1
1 	 . .
11 12
French Creek
River Mile 0.2 . River Mile 5.5
123123
41.8 143.9 40.8 >
47 31
16
i2 31
16
16
188.8 502.8 291.4
16
•\
16
16
41.9 143.9 40. S \ 1SS.8 502.8 291.
343222
i

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BLACK RIVER, OHIO, BENTHIC \1ACROI\\ ERTEBRATES  PER. SQUARE METER

                             DULY 1974
Station Number 13- A 13-B 13-C 14
Location River Mile 10.0 River Mile 15.2
Section i 1 2 3
Oilgocheata X 103
Hirudinea
Ko!!^bc!c-!)a sp.
h. Stagnalis
H . Elon^ata
E.-pJTdefi'a'sp.
Sp^aerlidae
Sphacriu:n sp_.
S. Tranversum
5. i .\iusculium)
PisidiLm sp.
Chironomidae
Ch:rcncrninae
C-iiranomus sp.
Crvr>tochironornus sp
ij"!vpeuii',jm sp.
Tribeios sp.
Stictochironorrius sa.
Lnc!och:ronornu5 s?.
T=-,>tarsu<, bp.
Fsectrociadius S3.
Chi'onominae pupae
C.'-.hocladiinae
Cricotopus sp.
30.6 3'-f.2 30.1
T
T
F
F
T 16
. T
F-i
I
I 16
F-I'
F-I
I
I
I 31
Oithociadiinae pupae 1 J2697 31
Tarv-podtnae 529^
Prociadius sp. T-F
Aolabt-siT.ysa sp.
S;,r,u!idae
SlnrwliuTi sp.
Puir-or.ata
IPhysa sp.
FT os j*Jr anchia
P.c-urocera sp.
'ป i. iota sincera
a't'-./rna tentaculata
-.rr;.ci-!i- so.
F:ar.crbaia sp.
Ampniooda
hvaieila azteca
Garnrnarus fasciatus
Ephemeroptera
Hexi::enia limbata
Cacnis sp.
Baetis sp.
Tric'noptera
Agravlea sp^
Cn;rr.ana obscura
H\c!ropsyche Sj3_._
Chi-ufnatopsyche sp.
Trichoptcra pupae
CoSeoptera
Helodidae
Diibiraphia sp.
Stfm'imis sp.
Megaloptcra
Sialis sp_._
Turbcllaria
Hydracanna
Total Number X 103
Total Taxa
!
344
T
F
F-I
!
I
F
F
F
I
F-I
I
I
1
F-I
F
I
I
F-I
F
1
.
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                                       Attachment K
                             U.S.  EPA Survey, July  9-11,
                                       (PAH Survey)
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        UNITED STATES STEEL, LORAIN, OHIO, WORKS, BLACK RIVER SURVEY":


ANALYSIS FOR HE:
-------
                          TABLE OF CONTENTS



                                                         Page Number


SUI-3'IARY                                                      1


INTRODUCTION                                                3


EXPERIMENTAL '                             '                  5


    A.  KEXAN3  K-CTHACTABEES (OIL AMD  GREASE)                5


    B.  LIQUID  CH?.0:-L\TOG5APHIC FRACTIOMTION              " 6


    C,  -GAS CHHCMA.TCC-2APHY                                 10


    B,  GAS CHRCy_\TOGRAPHY/MA5S SPEGTROMHTRY (GC/MS)      12


RESULTS                                                     15


    A." ฅ^r3 SAMPLES                                      15


    B.  HEJIA:^  EXTPACTABLES (OIL AKD  GREASE)               17


    C.  POLYZrCCLEAR ASO^TIC HYDROCARBON ANALYSIS IN
        CCTiTfC??^"! C''1''D~TrC                                   OA
        fcr^J-Ll-jjU^. o.-^-^rjjrjt)                                   c.\j


        1*   LIq_-aid Carosatographlc  Separations
             of PAH                                         20   .


        2ซ   Gas Chroaatographic Analysis                  25


        3.   Gas Chronatographic/Mass  Spectrornetric
             (GC/l-S) Analysis              •         "        33


DISCUSSION                                '           _      6^


    A.  SURVEY FIKDINGS                                    6^


    B.  OTHER COM'EIITS                                     66


REFERENCES                                                 67

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        ,/                   C               .                ซ,
I

I
                                            SUMMARY
•        '      '     Three water and twelve sediment samples, collected at the U. S.
             I.  Steel,  Lorain,  Ohio, works, were analyzed as part of an extensive
                                                                                      -x
               biological ar.d  chemical  survey  of the Black River in the vicinity of
|          -    the U,  S.  Steel site. Two water samples, taken from "blast furnace
_          .  '  effluents, were free of  contamination,.  The coke sewer (002) sample
               did show the presence of small  amounts of organic compounds, possibly
I              paraffins, eyeloparaffins, and/or olefins,- The concentration of any
              . individual component vas less than 20 ppm (wt/v).  Small amounts
*             (<1 ppm) of  polyiraclear  aromatic hydrocarbons (PAH) may have been
•              present in the  coke sewer sample.  Water sampleswere analyzed by gas
               ehrcmatography/r.ass spectrometry (GO/MS}.
|                   The sediment  samples were  extracted with ri-hexane to determine
M              organic solvent extractables  -  "Oil and Grease".  Values ranged from
               810 to 26^00 r.g/>g based on  dried sample weight.  Highest values were
•     .         at sampling  sites  in close proximity to the plant.
                    PAH were determined in sediment samples by gas chromatography (GC)
•              and GG/MS,  Liquid chromatography  (LC) vas used to separate PAH from other
I              classes of  organic  compounds in hexane extracted residues.  Quantitation of
               ten PAH in  eight samples was then made by GO,   These PAH represented an en-
|              velope of polynuclears  of increasing ring complexity ranging  from phenan-
•          '    threne and  anthracene (molecular weight 1?8)  through two dibenzanthracenes

i

I

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                                              ฃf
                                              V
 (Mv7 278), Several of the PAH guantitated are known carcinogens*  Values of


benz[a]- plus benz[e]pyrene ranged from 0.91 r.g/kg (sample 19U66) to


19 rag/kg (sample 19*472).  Values for dibenzanthracenes ranged fron 0.37


 (19467) to 12 mg/kg (191472).  Sample 19^72, collected just downstream

                                                                        ^\
 from plant outfall 002, contained the largest concentrations of PAH;


 this sample was exaniaed in 'detail by GO/MS.  A broad spectrum of PAH


vas seea to be present; these included unsubstituted as -well as methyl


 substituted pol^Tiuelears.  Specialized GC/MS data system techniques


were use-I to cLeterrdne the presence of PAH.  Isotope abundances were


 •used to confim noleoilar forraulas.

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                                          INTRODUCTION
                     At the request  of EPA Region V, KFIC-Cincinnatl's Organic Chemistry
                Laboratories were asked  to analyze twelve sediment and three water samples,
                collected by HFIC-Cincinnati personnel, at the U. S. Steel, Lorain, Ohio,
I              works:  this  plant discharges into the Black River.  This request is part
™                                                                                    s- \
                of an erctensive biological and  chemical survey of the Black River in the
• .             vicinity of the U. S.  Steel site in conjunction with EPA's pending court
•        •      case against U. S. 5-Deel.   The  sediment samples were to be analyzed for
                compounds extractable  into an organic solvent; this procedure is better
I       _      known as an Oil and Grease Determination.  In addition the sediments
• •-           were ta ~ฐ~  scanned for Polynuclear Aromatic Hydrocarbons (PAH).  Certain
                PAH, fcr example  ben-:[ajpyrene, are known to be powerful carcinogens.  The
                three vater samples vere to be  analyzed for the presence of organic com-
                pounds —_d in particular PAH.   Chain of custody procedures were followed
                in handling the samples.
                     The request for  PAH analysis  arose out of the survey, conducted by
                Mr. All~ri Lucas of these laboratories,  in which substantial concentrations
 |              of benz[a]pyrene (BaP)  were found  to be present in sediment samples collect*
 •              at a U. S. Steel - Calumet site.   Dr. Paul Clifford, who analyzed these
                samples,, reported concentrations of BaP ranging frora 1 to 380 rag/kg (dry
 •              sample weight) using  gas chromatography/mass spectronietry (GC/MSl and
                flxiorescence spectroscopy as analytical tools.
 '                   The approach taken in our  laboratory to analyze for PAH in the Lorain
                sediment survey was different than in the Calumet case.  In the latter

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instance PAH were found as part of a general  scan for organic compounds;




phenanthrene, anthracene., and EaP were then selected as measures of PAH




and carcinogenic content.  In the Loraln case it  was decided to analyse




the samples for a "broad spectrum of PAH from  phenanthrene  and anthracene, v




(Mtf=173) to the dibensaathracenes (MW= 2?8).   It  was felt  that it would




"be of greater value scientifically to examine selected  sediments  for  nany




indivii^al PAH than all samples for, say, BaP. In fact a  detailed PAH




scan was obtained for eight of the twelve Lorain  sediment  samples.

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I



I



I



I



|


•
                                (
                                         EXPERIMENTAL



              A.  HEXANE EXTRACTABLES (OIL AND GREASE)



                   The method used for hexane organic extractables  is essentially the


                                                                 2
              same as outlined in the Standard Methods  procedure,




                   Samples were weighed Into Individual wide mouth  porcelain crucibles^ ]



              removal each sample was_agitated In its original container to assure adegual



              mixing,  A control was prepared.  It contained 25 g of silica gel and 25 ml



              of water*  Samples and the control, ^a 50 g wet  weight, were air dried at




              30ฐC overnight In the Individual crucibles.  They were then crushed



              to fine particles ana allowed to dry an additional two hours.  Each residue



              was placed In a scxhlet thimble and extracted in individual soxhlet apparat-



              uses into ndistllled-ln-glass" n.-hexane for 10 hours. Hexane was evaporated




              to lp ml by allowing a stream of nitrogen to flow over the solvent in the



              extraction flasks .vhich were heated by a steam bath held at 80ฐC,  The re-



              raalnicg sample and solvent from each flask were  transferred to appropriate



|             Else vials.  The extraction flasks were washed with small portions of n-hexa



.   .          which were transferred to the vials.  Ko apparent residue remained in the ex



              traction flasks,  A stream of nitrogen was allowed to flow over 'each sample



I             vial, at room temperature, until the hexane solvent had evaporated.  Checks



              were made to be certain that samples had reached a constant weight indi-



•             eating complete hexane loss.  Oil and grease is  reported as mg, organic



•  •           residue per kg, dry sample.  It should be noted, that in all procedures,



              attempts were made to keep sample exposure to light In the laboratory to  a




•             minimum to prevent decomposition of compounds to be analyzed for in the resit
_



*



•








I



•
 I


 I

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B.  LIQUID CIIROMATO GRAPHIC FRACTIONATION


     Polymiclear aromatic hydrocarbons were separated 'frora other classes


of organic compounds In the hexane extractable residues "by a liquid

                 .                                           oc;
chrorcatographlc  (LC) procedure given "by Hoffmann and Vynder.     In orders


to determine recovery of PAH from the LC column an experiment was


performed.


     Flcrisil, 60/100 mesh, was heated for an hour at 110ฐC and cooled


In a cessicator.  Fcrty grains of the activated Florisll was weighed and


placed in a column chronatography tube whose dimensions were UO X 2 era


(id).  The volume occupied "by the Florisll vas 20.5 X 2 cm (id).  Aluminum,


foil vas placed  around the column to prevent any possible photochemical


reactions,  With the stopcock In an open position,, hexane was poured Into


the cclxna,  (it Is imperative that the solid packing be uniform and with-


out air bubbles) .  The initial hexane elutant was discarded.  The volxnae


of eluding solvent passing through the colurcn was determined to be 37 ftil-


Five ITU. of a 1 ir.g/nl standard of BaP In cyclohexane was applied and ad-


sorbed onto the  column.


     The  first eluting solvent was n>hexane - 200 ml.  Tlie flow rate was


375 ml/hour.  T^/enty-five ml fractions were collected and viewed under


•ultraviolet  (w) light (long wavelength - 365 rua) and observed for fluor-


esence.   Ho fluorescence was observed for all eight fractions.


     The  second  eluting solvent was an 8:1 hexane/ben^ene (V/V) solution.


The volume of this  solution to be applied was determined experimentally.


A critical), variable which affects the total volume of the solvent used

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                  is  the  flow rate  (i.e., slower flow rates require less eluting volume).

                  A flow  rate of 3^0 ml/hour vas established. ' Fifty ml' fractions were

                  collected  in  100  nl reagent "bottles.  Each fraction collected was covered

                  with aluminum foil and viewed under UV (3^5 nm) light.  The total volume

                  after vhich no further fluorescence was observed was 700 nl.  The frac-
 I
      I  •     *
 I

 I

 I

 I

 *               tions vere pooled and the total volune (700 ml) was concentrated in a
 I               1 liter round "botton flask "by use of a Buchi ROTAVAPOR-R.  After the sol-
                 vent vas evaporated to approximately 30 ml, the concentrate was trans-
 •               f erred to a 250 ml wide-iaouth. flask.  The original container was washed
 •               with. 8:1 hexaae/benzerte and the washings transferred to the 250 ml flask.
                 •Under a stean "bath (at ca 70ฐC) and a gentle stream of nitrogen, the volun
 ||               was further reduced to 2-5 ml.  This solution was transferred to a 15 wl
 .               centrifuge tube and the 250 ml flask washed with 8:1 hexane/benzene;
                 vashirgs vere added to the centrifuge tube and this volume was reduced to
 •               ca 2 ~1 and stored in a refrigerator until ready for analysis by GC.
                      Samples  were cnrcmato graphed in a fashion similar to that in the BaP
 *               recovery  experiment.  The Scheme (Page 8) outlines the procedures used.  '
 •               samples (i.e., hexane extractable organic residues) were dissolved in. 6 la
                 n-hexane  and  applied to Florisil columns.  n-Hexane was the first solvent
 |               it was employed to elute non-polar paraffinic type material.  Depending o
 _               the sample, 250 to 1000 ml of n-hexane were used. The n-hexane fraction
                 is defined as fraction A.  For one sample, number 19^70, where a duplicat
I               oil and grease determination was made, ten 100 ml fractions were collecte
I
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 I   ..-'   ,
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 I           in  125 ir.l ErlerL-neyer flasks.   No fluorescence was observed  indicating no
 —           "breakthrough  of PAH.  Fractions  2,  U,  6,  and 10 were  concentrated to ฃa
 ™           5 ral on  a stea^i "bath under a  streara of nitrogen. The concentrates of
I             these fractions were examined "by gas chromatography.
            •
                   After n-hexane, an 8:1 n-hexane/benzene (V/V)  solution was used to
                                                                                      I.
             eiute fraction B which contains  the PAH.   As fractions were collected
 •           they were checked for fluorescence.  Certain of the samples less concen-
             trated in ?AH, particularly in higher molecular weight PAH, displayed no
 I           fluorescence- after ca one liter  of solvent had teen eluted  from the column,!
 _           For these- sarrples elation was terminated when fluorescence  was no longer
             observed.  Other samples, for example 19^-72, displayed fluorescence after
 I           elution  "cj 3-5 liters of solvent.  For this sample  eluate from 0-2500 ml
             and 250-0-3500 nl vere separated.
 I                 Fraction. B vas concentrated to 10 ml by previously described methods.
 •           It vras thsr: extracted four times with 10 ral portions  of nitrornethane (KM). '
             The ir.-l e:-rt-rฃcts (fraction BTT in Schene)  were pooled  and evaporated to
 •           dryness  and redissolved in n_-hexane—1 to 5 ml depending on the sample.

I

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C.  GAS CHROMATOGRAFHY




     A gas chroraatographic (GC) method was employed, to analyze for specific




PAH, based oh the system of Lao et al.   A 10 ft X 1/8 in stainless steel




column was employed which was packed with 6% Dexsil 300 on 80/100 rn.esh Sxipel-




coport,  A similar column packed with 3% Dexsil 300 was equally efficient




and elated, compounds in a shorter time.  A Varian l^lOO GG equipped with a




flame ic-ication detector (FID) and a Hewlett Packard Model 7100B., 1 1-IV




recorder, were xised,  Injector temperature was 225ฐC and detector tempera-




ture 325ฐ^-  After injection the column was held at 165ฐC for two minutes




then programmed at UฐC per minute to 295ฐC and held until the




dibenzaa^hr-acenes "had eluted.  Total analysis time for the 6%'and 3/ฃ Dsx-




sil col'jnns were ca 120 and 80 ninutes, respectively.  The carrier gas




was h&lrun and its flov rate 30 rnl/min.  The cylinder pressure regulator




was set  tc deliver 80 psig to'i-iininize pressure drop accross the  coluron




during the temperature program.  Extreme care had to be taken to prevent




heliun leal
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 IT''  • ::   '.                C                               ?






 I


 —          anthracene., fluoranthene,  pyrene,  benz[a]anthracene, benz[a3pyrene,



             benz[e]pyrene, perylene, dibenz[a,h]anthracene,  and. dlbenzfajc'Janthracene.



 I          The concentration of each  PAH in the  standard was  50 ppm  (wt/v) except  for



             dibenz[a,h]anthracene which was 25 ppn.  Concentrations of PAH in the



 •          samples were calculated by comparison with the standard mixture.  Peak      v
                                                                                       ^


 •          heights were used to compare the earlier eluting PAH  (through benz[a'Janthra-



             cene) ; pealc areas were used for quantisations of BaP  and  EeP and later  elating



 |          compounds.  In calculating concentrations  of PAH components,  corrections



 m          vere applied for volumes of samples and  standards  s,nalyzed and for total



             sample vclizzes.  For comparison, the standard mixture was analyzed prior



 •          to sample analysis,  '^en more than one  sample was to "be  analyzed, the



             standard was run after every 2-3 samples,



 I               In analysing the paraffinic fraction  A, a Perlcin-Elmer Model 900 gas



 •          chromatograph equipped with a dual FID system and  a Honeywell potentiometric



             recorder was employed.  The GC was operated in. the dual differential mode.



 |           Two 6 ft r 2 rm (id) glass columns packed  with 3$  OV-1 on 60/80 mesb.



 .      '     Supelcopcr~ vere employed.  Injector and detector  temperatures were  220ฐ



                 320CC, respectively.  The column was held at 80ฐC for five- minutes  after
I


I


I
             then held for ca 10 minutes.
•           injection and then programmed at 10ฐC/minute to 220ฐC.  The temperature was




I



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                                               11

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              f
              \
D.  GAS CHROMATOGRAPIiY/l-'iASS SPECTROMETRY (GC/MS}



     Analysis of standards and samples "by GC/M3 employed a FInnlgan Model



1015 quadrupole GC/MS equipped with a System Industries Model 250 data'



system.  Inasmuch as the GG on the Finnigan unit is a modified Varian lUpp



instrument., columns could be interchanged with the GG possessing the FID.



     Tha mass spectrometer (MS) was scanned "by applying mass seb voltages



to the cuadrupole reds from a 15-bit digital-to-analog converter.  At a



given nass set voltage, only ions of a specific mass-to-charge ratio pass

                                                                 •7
through the quadrupole field to the electron multiplier detector.   The high

                                                              _rj
mass rar.ge of the MS vas used; the preamplifier setting was 10   amp/volt an



2600-2SOG volts were applied to the electron multiplier.



     Direct aqueous injection of water samples by GC/MS was accomplished


                                P
•using- t>e r.ethod of ludde et al,   A 6 ft X 2 mm. id, glass column was packed



vith Chrc3osorb 101 and conditioned at 270ฐC for ti-ro days.  Five ul of



sample -.ras injected ar.d the column oven held at 80ฐC-for two minutes and



then programed, at ^ or 8ฐC/ninute to 220ฐC.  The final temperature was


held so th=t the total analysis time was 35-^0 minutes.  The MS ionizer and


data systera were turned on after water had eluted from the GC column and bee



pumped froa the ion source.  It was allowed to scan, from 33-200 amu.



     Water samples were also extracted and the extracts examined by GC/MS.



One liter of sample was extracted twice with distilled-in-glass methylene ch'



ide.  The extracts were combined and dried by passage through two inches of
                                 12

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                                                             \
  *•     ป   >
I       ,                    I

I
ซ           prewashed  (with methylene chloride) anhydrous sodium siilfate-in a glass col-
             umn.  After the combined extracts had been dried, 100^ml of dlstllled-in-
I           glass acetone was poured through the column. The extract plus acetone was eva]
             orated to  5 ral employing a Kuderna-Danlsh apparatus.  In this way the
•          * methylene  chloride  (B? 39-8ฐC) was removed, leaving the sample dissolved id
•           acetone  (3? 56.1ฐC),
                  A 6 ft X 2 irm  (id) glass column packed with 1.5$ OV-17 + 1.95$ QF-1
|           on Supelcoport, 100/120 nesh, was used to analyze extracted water samples*
•    -       It was conditioned,  at  250ฐC for two days prior to analysis.  Two to four ul
             of sample-  -.-.-as injected onto the column and the MS was "turned oa" after the
•           solvent, acetone, had been pumped from the Ion source, ca 1 to 2 minutes,
            ' and all^vsc: to scan from 33-^-50 amu.
•                For cecLinsnt samples the 3$'Dexsil column described in the section on
•     '     gas chrcr.atcgrap'by  was used.  At the high temperatures needed for these
             analyses (-23. 30OฐC) G3/MS separator and transfer lines had to be adjusted
I           to 280CC and 230ฐC, respectively.  -
I                  The System  2pO data system has certain special features which were
                                          q
             applicable to these analyses.^  These include choosing mass set voltages
•           so that  one can  acquire data for selected ions.of interest.  This technique
             has the  advantage of allowing the detection of compounds at 10-100 times
•           lower concentrations than by normal scanning techniques. .Another feature
I           is being able to search the reconstructed gas chromatogram (EC-C) for a
             limited  number of ions.  The RGC is a plot of ion current, normalised to 100$
|           for the  spectrum yielding the highest ion current against spectrum number.

I
                                            13
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The limited mass search allows the operator to ignore "background and




search for contributions to the ion current "by selected ions of interest




as a i"unction of spectrum number.

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I

                                            RESULTS



I         .A.   WATER SAMPLES



•                  Three vater samples were received.  The  first was taken at the 1, 2,



               5 blast furnace (east clarifier),  the  second  at the 3, h "blast furnace " (west



ฃ             clarifier) , and the third  at the 002 discharge coke plant sewer.  The sample



_             -were scanned for organic compounds, using the laboratory's gas chromatograph



™             mass spectrometer ( GO/MS ^  unit.  Two approaches were taken.  First, a direct



I             aqueous injection of sample was made into the GO/MS,  This allows the



               detemina-tion of low molecular weight, -volatile, organic compounds of



I             varying types.  The second procedure involved extraction of the sample into



•             methyiene- chloride, addition of acetone, evaporation, and concentration  (see



               Experimental Section).



I                  Tiie —ater scrples were found  to "be essentially free of contamination.



.             The direct aatieo"s injection technique showed that the two blast furnace



               effiizents were free of lo;-rer molecular weight compounds though one of them



•             probably contained a. s~.all amount  of acetone. The coke plant sewer sample



               did show ฃ~=Lll quantities  of organic compounds; the concentration of any



•             individual component was likely less than 20  ppm (wt/v) ,  While individual



•             corriponents were not identified, two or three  classes of compounds were



               found possibly to be present; these are paraffins,  cyclop araf fins,  and, olefi



|             These classes were searched for by allowing the computer to scan the GC/MS



•             reconstructed gas chromatograph for the presence of particular ions -



               m/e k-3 and 57 for paraffins and m/e 55 and 69 for cycloparaffins and
                .,  ^,    10
               olef xns .
I


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     Few organic compounds were present, in samples extracted with nethylene

                                                    •
chloride, even though the extraction procedures concentrated the samples


some 200 fold.  Blast furnace effluents showed no detectable compounds,


while the coke plant sewer again showed small GC/MS peaks.  For this

              .            •                                             \\
sanrple the GC/MS was set to acquire data solely for ions corresponding to


base peaks, which are also the molecular ions, of certain PAH.  The ions


were ic/e 128 (naphthalene), 166 (fluorene), 178 (phenanthrene and anthracene


202 (fl-ooranther.e and pyrene), 228 (benz[a] anthracene  and chrysene), and


2p2 (benrCajpyrene arid benz[e]pyrene).


     GC/MS peaks were obtained, for the coke sewer extracted sample cor-


responding to n/e 165, 178, and 202 with 178 being the largest.  These data


indicate the presence of lor concentrations (<1-J? ppzn  wt/v)  of certain PAH,


Phenanthrene and anthracene have a molecular weight of 178 and their


presence vould not be surprising, particularly since substantial amounts


of these two PAH vere found in sedinent samples.
                                 16

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•               B.   1IEXAHE EXTRACTABLES (OIL AND GREASE)
                      Table I presents  data for the  n-hexane extraction of organic compound
I               from the twelve sediment samples collected at the Lorain site.  Table II
•        .       gives a description of the  sampling sites.  Values ranged from 8lO to 26,71
                 ing/kg based on the  weight of samples dried overnight at 30ฐC.  A blank •
I               containing 25 g of  silica gel and 25 ml of water yielded no significant
                 oil  and grease.  Five  duplicate  determinations were wade and yielded excel-
•               lent reproducabilitjr.
I
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Sample Sample
Kurriber Station
19^65 1
1&46& 2
19U67 33
19lf68 te
19U69 5C

1911-70 63

19V/0- 73

•19^72 83
19^73 - 93
19^ 10
19^75 11
19^76 12

aAll samples taken






c - -
TABLE II
r\
ISCRIPTIOiJ OF BLACK RIVER SAMPLING STATIONS
Mile Site Description
Point
Lake Water Treatment Intake
Mouth of Harbor: Lake Erie-Black River
0.0 Center of Black River (River Mouth)
1.0 Center of River
2.5 Right Hand Side of River, Looking Upstream

2.75 Middle of Turning Basin Opposite Outfalls
f 003 and 004
l
2*9 Head of River Turning Basin - End of
Commercial navigation
3. if _ca 500 ft. Downstream from Outfall 002
Jf.O Near Plant ttater Intake
5.0 ca 0,2 ni. Downstream frora Outfall 00.1
0.2 0,2 cii Upstream on French Creek
5-3 ฃS ฐ'2 ^-i- Upstream from Outfall 001

frcrn. the surface of the sediment layer.




19
•

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                                             c
C,  POLYIPJCLFAR AROMATIC HYDROCARBON ANALYSIS IN SEDIMENT SAMPLES


     The organic residues obtained in the Oil and Grease determinations


vere used to analyze for PAH.  These residues are complex mixtures of


organic compounds of varying classes and a method of separating the PAH

*                           -              •                   '              ป\
(fraction) was necessary.  The largest body of information on the separa-


tion and analysis of PAH, other than in the air pollution field, lies in


the tobacco smoke chemistry area.  PAH determinations in organic residues


obtained from sedinents should "be similar to determinations of PAH in


to"bacco tars.  Separation of PAH vas affected "by the method of Wynder and

         "^ *Z                                  T1 T &
Hoffmann."' ""  Several gas chromatographic (GC) "    and gas chromatographic/

                    ,   .   19
mass spectrcmetric  (GC/M3;   methods of measuring PAH are available.  Tech-


niques for GC and GC/I-3 analysis advanced "by Lao et al.  appeared to "be


xaost applicable and vere employed.


     1.  Liquid Chromatographic Separations of PAH


         PAH were separated by the liquid chromatographic (LC) procedures


outlined in the Scheme and detailed in the Experimental Section.  Paraffinic


type compounds are  eluted from an LC Florisil Column by jn-hexane (fraction A)


The next solvent is an 8:1 hexane/benzene solution which elutes the PAH


 (fraction B) .  B is concentrated and PAH extracted into nitromethane


 (fraction B-,,.) to separate the PAH from other organic compounds that are


eluted in fraction  B.


     Prior to analysis of the sediment organic residues an. experiment vas


devised to measure  PAH recovery from the LC column.  Five nl of a 1 ing/ml


 (1000 ppm) benz[a]pyrene (BaP) solution vas applied to a column and eluted
                                 20

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as In the Scheme except that the nitromethane (KM)  extraction was omitted.


The recovery of BaP was 97-/j.


     It was determined that 1 liter of n-hexane was likely  a sufficient


amount of solvent to elute fraction A.  For sample  19470  1  liter of

                                                                       •"V
n-hexane was elated from the LC column with ten 100 ml  fractions being -


collected.  Fractions 2, k, 6 and 10 were concentrated  and  examined "by


gas chromatography-using OV-1 as the liquid phase;  OV-1 is  efficient  for


non-polar materials.  Fractions 2 and 4 contained a broad envelope of


paraffirlc type material which eluted from the OV-1 column  as temperature


was programmed.  Fraction 6 was free of GC peaks  until  a  high column


temperature was reached, ca 2COฐC.  Reasonably, this  indicates high jnol-


eeular veight compounds which were late eluters from  the  LC column.


Fraction. 10 contained no GC peaks, thus signifying  a  complete separation


of total fraction A.


     Table III lists the volumes of n-hexane used  to elute fraction A  in


each sample.  Prior to GC analysis of the ri-hexane  cuts of  sample 19^70,


it was felt that 200-400 ml of n-hexane would be  sufficient to elute  a


total fraction A.  Clearly this is not the case.  Fortunately, however,  any


carryover of paraffinic material into Fraction B  did  not  appear to adversely


affect the final analysis; the nitromethane extraction  apparently Is  almost


exclusive for PAH, leaving behind other organic compounds in the hexane


layer.  For example GC/MS analysis of sample 19*472  (see below) revealed


only PAH; few other types of compounds were present.  Aa  exception vas
                                                21

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                              TABLE III

            VOLUMES OF n-HEXAlffi USED TO ELUTE FRACTION A



, Sample 11Xgber      .       _             Y^^Jii^ane^^

      19-65                                     1000
      19^3                                      to

      19^70                                     - 1|00

      15-71     '--                               1000

                                                 200

                                                 200

                                                1000

            (IniDli cate) a                        1000
a
 LA seccni I?0il and Grease" determination was made on this sample
 see T.a~-le 1.
                                 22

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sample 19-I-7U where an exceedingly high paraffin content (see explanation


below) did interfere somewhat with PAH analysis.  Elation of fraction A


with greater than 200 ml of n_-hexane was obviously necessary for this


sample.
                                                                        •A
     No fluorescence was observed in the 1 liter of n-hexane eluted for


sample 19^7^.  However, a low level of fluorescence vras detected for


samples 19^66 and 19^76-  The possibility does exist that small amounts


of low nolecular weight PAH were lost.


     One to three liters of 8:1 hexane/benzene was used to elute Fraction B.


Table T~ gives the volts.es of solvent used.  Elution. of samples 19^66 and


194-76 was terminated at 1600 and 1250 ral respectively since fluorescence


was no longer- observed in solvent passing through the column.  For sample


19^72 ฃ-5 liters of solvent were eluted; this was followed by elution with


an additional liter which was separated from the initial 2.5 liters.  Each


was concentrated and extracted with nitromethane (KM); the KM extracts.


(fraction 3 • ) were evaporated to dryness, redissolved in n-hexane
           j-J-                                             —~

and analysed by GC.  All  PAH through the dibenzanthracenes (MW 278) were


found to be in the initial 2.5 liters fraction.  Since fluorescence was


observed in the 2.5 to 3.5 liter fraction, including the last 100 ml of


this fraction, higher molecular weight strongly fluorescing PAH are no


doubt responsible for fluorescence at high elution volumes.  Saraple 19^-72


contained the highest amounts of PAIL  Thus, it was acceptable to term-


 inate elution  after 2  liters of solvent on all other samples (see Table IVV

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              (                              C
                              TABLE IV



        VOLUME OF 8:1 HEXANE/BEITZSNE USED TO ELUTE FMCTION B






.Sample la^ber             _              Volume 8:1 Hexane/Benzeae, ml



      19^66                                        I6ooa



                                                   2000



                                                   2200



      15-70                                        2100



      19-71     '-                                  2000



      19-72                                        3500   •



      19-7^                                    •    2050

        *-   -*                  '                          f\
                                                   1250

 n

   Ko ฃIw3rescence O"Dserved, vhen these volumes had eluted,

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     2.  Gas Chromatographic Analysis


         Excellent separations of PAH were achieved employing Dexsil 3$


and B'fj columns.  Figure 1 shows a gas chromatographic trace representing


a typical analysis of a ten component PAH standard mixture.  Table V


gives the structures and properties of these compounds.   Figure 2 shows v\


a gas chromatographic trace representing the analysis of sample 19^72;


the sarrole represents the first 2.5 liters of 8:1 hexane/benzene from


the LC coluna  (see page 9)•


     in Figure.1 it can be seen that phenanthrene and anthracene (peaks 1


and 2) are partially separated, benz[a]pyrene (EaP) and  benzfejpyrene


(BeP) (Peaks 6 and ?") are not separated and dibenz[a,h]- and dibenz-fa,cj-


anthracene (peaks 9 and 10)  are not separated.  These observations repro-


duce the data of Lao et al.                                     .   •


     Components in the standard mixture were chosen to represent a PAH


envelc-r-e that might be observed in sediment samples.  Phenanthrene and


anthracene are three ring PAH with molecular weights (l-.W) of 178. The


diben™ar.thracenes are five ring PAH with Mtf's of 278. In between there


can be PAH vith varying number of rings, ring structures, and substitu-


tions'en the rings.  Over 100 PAH are known between Kvf 178 and 278.


Effective  separations  are both  critical and difficult; with caution they


can be accomplished  and compound assignments be made.


     Figure  2  shows  assignment  of PAH to components of the standard mix-


ture.  In  addition to  comparing gas  chromatograms of standards and samples,


a comparison with the  data  of Lao  was useful in chromatogram interpretation.

  I

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•           a Ratings of carcinogenic behavior obtained from reference 20;  (-)
"             indicates not carcinogenic; (+0 uncertain or veakly carcinogenic,
               (+) carcinogenic;  (+-*-, +++, ++++} strongly carcinogenic.

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     The first major peak (labeled 1 and 2)  In Figure 2 represents phenan-



threne and anthracene.  The assignment _of these compounds is clear.  Howeve



since only one GC peak appeared it is probable that either phenanthrene or



anthracene predominates.  One cannot distinguish -unequivocally between the



and quantisation roist be made as the sum of phenanthrene and anthracene^-v th



situation, obtains for all other samples.  For sample 19-1-72 CC/riS experiment



suggest that the najor peak (l and 2) is predominantly phenanthrene -with a



minor contribution fron anthracene (see Figure 5, page H2) .



     The peaks labeled 3 and h can be assigned to  fluoranthene and pyrene.



Further support for these (and other) assignmenbs  v/ill be given in the



GO/MS data to be presented below.  Peak 5 certainly represents at least



two overlapping peaks.  This is consistent with the observation of Lao



et al  vhich notes that benz [a] anthracene is not separated froni chrysene



ana triphenylene using the Dexsil GG system.  Peak 5, then, should be



    g-ed to these three compounds; no other PAK of KV7 228 elutes near these
pounds  c-nd GC/M3 data show that the peak is due to PAH having molecular-


                                                               ?O
veights of 223.  Eenz[a] anthracene and chrysene are carcinogens   while



tripher.ylens  is not.



     Peaks labeled 6 and 7 are assigned to BaP and BeP; peak 8 is assigned



to perylene.  GO/MS data show these peaks to have molecular weights of



252.  The doublet consisting of a large and a small peak eluting before



Bap and BeP also have molecular weights of 252 (see below) .  Based on the



data of Lao   the compounds represented by these peaks may be the benzofluor-



anthene isoraers.
                                30

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I

                   Peaks 9 and 10 are assigned, to the dibenzanthracenes.  Other PAH


I            vhich elute in the dibenzanthracene region  and. which may be present in


•            certain samples are the benzochrysenes, picene, the benzoperylene s,


              o-pher.ylenepyrene, and the benzotetraphenes.



I           -      Table VI reports the -concentrations of PAH determined in sediment   0-


              samples (from fractions E  ).  Matching of individual components in the



™            samples was not always as simple as in 19^72 described above and in Fig-


•            lire  2.  ?or samples where certain components could not be compared T/ith the


              standard mixture a value is not reported in Table VI.



I                 Samples 19'{-66 and 19^76 display the lowest levels of PAH.  This is


• •           consistent -with thsir low oil and grease values and the fact that fluor-


              escence terminated after 1-1.5 liters of solvent in collecting fraction. B.


 •            It is al^D consistent with the locations of these two sampling sites.


 _            Sample 1^472 "being just downstream from outfall 002 shows by far the high-



              est  concentrations of PAH,  No explanation can be offered for the absence


 I            of lower molecular veight- PAH in sample 19^71.


                   Sample 19^7^- was different than all other sediments collected.  Frac-


 •            tion A shoved an apparently high paraffinic content.  This was observed by


 •            analysis of fraction A employing the Dexsil column.  Fractions A of several


              samples were scanned for qualitative information as to paraffinic content.
 I


 I
Sample 19^7^ contained at least a ten fold higher paraffinic level than any


other sample examined.  In addition examination of Fraction BTT for PAH



showed a different shaped GC elution pattern.   The GC trace in Figure 2
 I
                                               31

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                        ^             -,A~ 6,21,22
               •with spectra for known PAtt. '  '
               for 19'-l72 is typical of samples analyzed except 19^7^.   Consistent with



•              our observations concerning sample lyh'fh is the fact that U.S.  Steel



m              apparently discharges waste oils from outfall 001;  sample 19^7^ was taken




               0.2 rr.iles downstream from this outfall.



•                   3.  Gas Chromatographic/iMass Spectrometric (GC/MS)  Analysis




                        Sanple 19^72 was examined in detail by GC/MS,   In addition the ten




•              carnponeivt PAH solution was analyzed.  Both analyses employed the 3/ป Dexsil



•              column.  The "real-tine" and reconstructed gas chromatogram (RGC) for



               the standard mixture showed separations to be identical  to these shown



|              in Figure 1.  Mass spectra for the standard compounds were consistent








                    Figure 3 shows the "real-time" gas chromatogram for the analysis



•              of ssrrple 19^72.  (All further mass spectral data reported are  for this




               ssr.p'L^''1.  The GO is essentially the same as the trace shown in  Figure 2.



™              In C-C/-3 analysis the total ion current is plotted, as in Figure 3> after



•              each spectrum scan during the run.  Over sixty peaks can be counted.



               Figure - shows the reconstructed gas chromatogram (RGC)  of the  same



|              run shown in Figure 3-  The data system has normalized the largest peak



_              in the ?.~C to an amplitude of 100.  Because of the  way the data system



               acquires and processes information relative peak heights between the



•              "real-time" and reconstructed chromatograms are not always the  same.



               Further explanation cannot be given in this section, owing to space liitii-




'              tations.
                                               33

-------
FIGURE 3-  "Real-time" gas chromatogram of GC'/MS analysis of sample 19^72.




           Times in minutes and seconds v/ritten above each peak represent




           retention times of the eluting components.






FIGURE h:  Reconstructed gas chromatogram for GC/MS analysis of sample




           19^72.            _                                           A






FIGURE 5:  Reconstructed gas chromatograia for GC/MS analysis of sample




           19^72 e^ploj-ing a limited mass search for ions m/e 178, 202,




           223, 252, and 278.






FIGURE 5:  Reconstructed, gas chrorcatogran for GC/I4S analysis of sample




           19^72 employing a limited mass search for ions m/e 192, 2l6,




           2^2, 266, and 292.

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     Figure 5 gives an RGC limited mass search for  the parent  ions  cor-


responding to the compounds in the PA!I  standard mixture.   The  ions


causing the RGC-peaks are indicated above each individual peak.  A  peak


corresponding to m/e 2jQ is not observed since it is  small compared to
                                                                       \\

the 202 peak on which the RGG is normalized.   The mass spectra of PAH


almost always display intense parent ions. The parent is visually the


base peak.  Thus performing a limited mass search for the parent is an


effective way of defining particular PAH.  A  cluster  is often  present


about the parent representing the P-l,  P-2, P-3,  P+l, and P+2  masses; -  tha


is the parent less one, two, and three  and plus one and two amu.


     Figure 6 gives an RGG limited mass search for  the methyl-substituted


derivatives of cc-pounds in the PAH standard mixture. Thus the  iinsubsti-


tutei parents -ป-l4 erru vere searched. Again,  the  molecular ions  causing the


EGO peaks have teen indicated.


     .'. limited -ass search for dimethyl derivatives,  the  unsubstituted


parents 4-23 err.u.vas made but the data were not conclusive and  are not being


presented.


     Sear ailing for unsubstituted ions in the  standard and their-methyl


derivatives produced thirty-three separate GC/MS  peaks indicating at least


that many compounds.  In certain cases  two or more  PAH vere present for


a specific PvGC peak indicating more than one  PAH  was  eluting front the


Dexsil column into the ion source at the same time; this  observation


is quite reasonable.  Searching for the dimethyl  derivatives produced, an


additional eight distinct GC/MS peaks.

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     Mass spectral data show that the sample extract  contained almost exclu-


sively PAH.  The largest peak In the RGC (Figure U) vas  not  a PAH but a


phthalate derivative with a strong base peak of m/e 1^9. The presence of


this co.T.pcund cannot be explained.


     Presentation of all mass spectra Is precluded by space  limitations.   ""


In Figure 5, however, it can be seen that peaks for phenanthrene  4-


anthracene (m/e 173), fluoranther.e (first ra/e 202), pyrene (second large


la/e 202}, renzLa]anthracene and probably chrysene and tetraphene  (large


broad n/e 223), benz[al- and benz[e]pyrene (large peak of second  m/e  252


doublet; sr-d perylene (last m/e 2p2 peak) are present.   Comparison should


be made vritb Figure 2.


     Presentation, of selected spectra is useful.  Figures 7  through 11


show the nass spectra of major EGG peaks (Figure 5) having ra/e 252 as


the base pesk - the bsnsfluoranthene, benzpyrene, perylene area.


Figures 12 through 15 shew the mass spectra of major  RGC peaks (Figure 6)


having m/e 2^2 as the base peak.  These likely represent nethyl-PAH which


are not identified.  Other unsubstituted PAH having molecular weights of


2te are possible but unlikely.  It should be noted the computer was


allowed to subtract background from spectra of Interest. Thus in Figure  7


spectrum 525-520 signifies that spectrum 520 has been subtracted  from 526.


     Another method  In identifying and confirming molecular  formulas  by


mass spectroscopy employs isotope abundances of the common elements.   For-


PAII one need consider only carbon and hydrogen.  For  every carbon atom,

-------
FIGURES 7, 8, 9, 10, 11:  Mass spectra of PAH having rn/e  2p2 as  the base




                          peak in  sair.ple 19*1-72.
                                                       •









FIGURES 12, 13, lU, 15:   Mass spectra of PAH having m/e  2^2 as  the base




                          peak in  sample 195472.         "  .

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                                                      TO
ca 1.08/3 of the molecules containing carbon possess a   C atom and produce a
P + 1 (parent +l) peak. Each atom in an ion contributes an siaoxmt to the
intensity of the isotope peak that is equal to the relative abundance
                            2k
of the isotope of that atom.    Thus if a. strong molecular ion is present^
as in the case of PAH, the P+l abundance is useful in identifying a par-
                          2k
ticular nolecular formula.    The P+2 is also considered, for there exists
a probability that two "" C atoms exist in a single ion.  Values of P+l
and P+2 ha—e been calculated, for the various molecular formulas and are
presentee in tables.  '
     Table VII list F-fl and P+2 isotope abundances for selected PAH of
interest.  The values are theoretical except for tT.ro molecular formulas
which represent experimentally determined literature data.  Table VIII gives
P+l and "P-2 values for the PAH in the ten component standard mixture „
Excelled -.greener, t is observed.
     Table IX gives the values found for certain major PAH present in
sample 19^-72ป  The values were obtained from spectra defined by the
reconstructed gas chroisatograms shown in Figure 5 for unsubstituted and
Figure 6 for methyl substituted PAR.  Agreement for the unsubstituted PAH
is good.  In a sample containing often overlapping GO peaks one would not
expect agreement to be ideal.  This is especially true for the P+2 isotope
abundances vhich is a  second-order effect.  In addition, spectra were defined
by limited mass reconstructed gas chrornatographic searches.  Overlapping
compounds present vhich are not seen in the limited mass search can easily

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           interfere vlth  isotope abundance calculations.  The total amounts of
           methyl substituted PAH present are considerably smaller than un.substi-
           tuted polyrv-iclaars .  Thus, one would not expect isotope abundance calcu-
           lations to be nearly as satisfactory for these cases; this is exactly
           the situation.
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                                            c
                             TABLE VII


             ISOTOPE ABIMDANCE3 FOR MOLECULAR FORMULAS

                                             npp po per
             CORBESPOIJDIWG TO PAH OP INTEREST   ป   > ?
•Formula
ci4Hio
C15H12
ci6Hio
C17H12
C18H12
C19H14
C20H12
v^
Molecular
Weight
178
192
202
216
228
242
252
278
P+l
15.29
16. ho
' 17.45
18.56
. 19.64
20.76
21.9
23.5
Ph2
1.09
1.26
1.43
1.62
1.82
2.04
2.4
3-2
a Values s.re theoretical  (reference 23) except  for K-l 2^2  and 2785
  these values are experimental findings  (reference 2p^.
                                                                          \
                                  60

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                            TABLE' VIII
            ISOTOPE ABUEDANCE  FOR PAH  STANDARD MIXTUR
Corr.pc
Phenant
Anthrac
Fluora-r

BenzFaj
Bensfaj
Benz[ej
DibenzL
r

ucd Assigned Formula
hreae ) C^H^
^^•s C i If
~Viinck rj --^[
ci6Hio
anthracene Cl8H12
—-•rene )
'I ฐ20H12
""^rene j
:x,e] anthracene }
, .^ani>rfl^r._ ? ฐ22H1^

Molecular
V/eight P-f-1
l?8 15. 5a
202 17.6
202 17.7
223 19.7

252 21. lb

278 23. 5b

P4-2
i.V
l 6
-i- #• w
2:2.
V

•L
o -.t

  ฑ-ner.=r.tbrene and  anthracene vere slightly separated, as  in Figure Jf.
  Values -'or each side  of the peak were  calculated.
"b ,.
  Valuer, riven are  averages'for several  sections  of each peak;  each
  peak represents two  compoundsj see Figure 2,
                                  6l

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                         TABLE IX




ISOTOPE AEUKDAirCSS FOR CERTAIN PAH FOUI'.T)  IK SAMPLE




                             PAH
Spec bnra
A. Uasubstituted
211-206
215-2C6
337-333
3te-333 .
353-3~>
te-430
*36-iฃ0
526-520
5*fC-520
563-557
566-557
532-5-5
73^-775
821-835
B. Methyl ฃ-a"bsti tuted
268-262
278-252
372-369
375-369
378-369
386-383
393-390
1A6-M2
^57-^53
^60-^53
}(62-lj53
Parent Peak

178
178
202
202
202
223
228
252
252
252
252
252
278
278

192
b
216
216
216
216
216
2^2
2te
Sk2
2h2
P-H

15. If
15.6
18.3
16.8
17.9
20.1
20.0
20.3
21.9
19.6
20. k
21.5
26.7
19-3

18.2
b
16.0
I6o6
16.0
b
b
19.6
20.7
. 22. ^
23.2
P4-2

1.1
1.2
Ut-
0,9
2.0
iJf
1.2
2:1'
1.9
1-9
1.9
2.0
e
e

1.2
b
c
h.5
c
b
b
c
c
c
re
                               62

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I   •
_•;'.,                     v                               ^
™                                      TABU; ix (CO:;T)
•            a.  Refer to Figure 5 for unsubstituted PAH and Figure 6 for methyl
                  substituted PAH.
              "b.  Overlapping of two or more  compounds prevented analysis by this method.
              c.  P+2 value small or not present.
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             i                              *                     •-<;••;





                            Discussion




A.  SUKVBr FINDINGS




     Water sanples were found not to be contaminated to any significant




degree.  The coke sewer (002) did show small quantities of organic com-




pounds and likely contained lower rr.olecular weight polynuclear aromatic



hydrocarbons (PAH).




     The data of Table I shows the presence of substantial amounts of '




hexaaa- extractable organic residues in sediment samples.  All Lorain




sedinents were surface samples.  n~Hexane was xtsed as the extracting



solvent for two reasons.  First it was felt that use of a halogenated




solvent svieih as'-.Freen would later interfere with gas chrornatcgraphic/




xaass spsctronatric analysis of the residues for PAII.  In addition,




n-herc2—e was the e;ctraating solvent used in the U. S. Steel Calumet survey




and it. vas felt tn?.t comparisons between the two surveys would need to be




dravn.



     Calur.et data~ฐ show "oil and grease" values as high as 120,000 ppra



for one sar.ple and over 60,000 ppra for many others; some of these were .




core sarrples.  Lorain data show, overall, slightly lower oil and grease



values.  This could be consistent with the fact that the Black River has




recently been dredged.



     Reasonably, the highest "oil and grease" values in the Lorain survey




were found in the vicinity of the plant discharge points.  The lowest




values determined were at the harbor nouth and 2-3 miles downstrean from.




the outfalls.  The low value for sample 19468 cannot be explained.

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     It is tempting to try to draw analogies "between amounts of organic


residue and particular classes of org?.nic compounds .present in sedir.ent


samples.  In certain cases this can no doubt be done; however, caution.


must be exercised.  For example while samples 19^72 and 19^7*4 yielded
                                                                        \

similar amounts of organic residue, their chemical compositions are


quite different.


     Table VI and other data presented in the Results section shows


that a broad spectrum of PAH is  present in the sediment samples.  The


highest concentrations are in the vicinity of the plant outfalls with


the levels in 1QV/2 being 2-10 fold greater, depending on specific PAH,


than fcr any other sample analyzed.  Lowest values are found for sartrple


19^65 (harbor- ir.oirth), 19^67 (center of the river mouth), and 19*476


(0.2 r-iles irpstrear: from outfall 001).  It is reasonable that PAH were


found in all samples since the sampling sites were in close proxinity


to the plant.  A lahe effect is known to occur carrying water upstream

                                         27
at leas~ five niles from the river mouth.     Because this survey rep-


resented the first attenrpt in this laboratory to quantitatively analyze


for many PAH, one probably should place wide tolerance lirtits on the


accuracy of the data in Table VI.  The data certainly reflect  the levels


of PAH in the analyzed samples; however, errors of Hr 15$ would not be


•unexpected.

-------
     Many of the PAH found In the seditr.ent camples are without question


carcinogenic.  These include not only compounds reported in Table VI


(see also Table V),  Since a broad envelope of PAH "was- shoxm qualita-


tively to be present, many unidentified compounds containing four or


more rings,, are no doubt carcinogenic.  In particular are the methyl sub-
                                                                        \

stituted PAH •uhich have been shown to possess a high degree of carcino-


genicit".5'20


B,   OTHSR COMM2S-I3


     The general philosophy taken at the outset of the survey i-ras to


analyze for a broad envelope of PAH rather than for one or two compounds..


This approach, prcved to be successful and we believe that future surveys


should be handled  in a similar fashion.


     The analysis  for cciaplex inixtures of PAH constitutes one of the most


difficult detemi rations in organic chemistry; the data presented in this


report are clear evidence of this fact.  Optimum conditions for separating


PAH  fron other classes of organic compounds had to be determined.  GC and


GC/I-2 analyses techniques had to be perfected.  The PAH fraction (B,--,.) is


complex and requires careful and detailed analysis and interpretation.


These  criteria were net  and meaningful data vere obtained.


     In subsequent surveys,  in other geographical  locations, our capa-


bilities vill be extended.  For example, \re Intend on obtaining a stock of


PAH prircary standards  available from  the Canadian Air Pollution Control

                                                   2$
Directorate,  Department  of the Environment, Ottawa,    These vill allow


•us to  quantitate upwards of  50 PAH.
                                66

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                              REFERENCES


  1.  P. R.  Clifford, "Organic Analysis of the Grand Calumet Oil and
      Grease Samples," NFIC-Cincinnati Report, January,  1973.


  2.  "Standard Methods for the Examination of Water and Wastewater,"
     . Thirteenth Edition, M.J. Taras, A. E. Greenberg, R. D. Hook,  and
      M, C.  Rand, Eds., American Public Health Association,  Washington,
      75. C., 1971, P?- t09-l


  3.  D. Koffteaca.aad E. L. Wynder, Cancer,  27,  8^8 (1971).


  k.  r. Eoffnann and E. L. Wynder, Anal. Chem., 32,  295 (1960).


  5.  E. "ynder end D. Hoffmann, "Tobacco and Tobacco Smoke," Academic
      Press, ITew Ycr>, 1967 pp. 330-3UU.


  6.  ?.ป C, Laoj" Pi. S. Thomas, H. Oja, and L. Dubois, Anal,  Che:n.,  ji5>

      903 (1973)-


  7.  J. W. Sichelberger, L. E. Karris, and W. L. &adde, ibid, U6,  227
      .'•T-.y^N                               '                     "
      \-yl-rJ~


  8.  W. L, Eudde et si ibid. , in press


  9.  r System. 150 GC/I-'S Data Processor:  System Specifications,"  System
      Industries, Inc., Sunnyvale, California,
 10.  J. 3, Knight, "Computerized GC/MS For Quick Qualitative Identifi-
      cation of Hydrocarbon Types Included in Chromatographic Peaks,"
      Fir.nigan Corporation Application Tip lib. h3, Finnigan Corporation,
      S-onnyvale, California, 1972.


11.   K. Shatia, Anal. Chem., k3, 609 (1971).


12,   W. Lijinsky, I. I. Domsky, and J. Ward, J. Gas Chronu, 3_, 152 (I9o5)


13.   V. Cantuti, G. P. Cartoni, A. A. Leherti, and A. G. Tori, J.
      Chromatography, 17, 60 (1965^.


1^.   K. Carugno and S. Rossi, J. Gas Chrom., j>> 103 (1967).


15.   II. J. Dawson, Anal. Chem., 9, 1852 (196^).       .  •


16.   H. J. Davis, Talanta, 1ง, 621 (1969).
                                 67

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17.  H. J. Davis, Anal. Chen., Uo, 1583 (1

18.  J). A. Lane, H. K. Mc-e, and M. Kfifcz, Ibid., hj, 1776  (1973)

19.  P.. F. Skinner, J. B. Knight, D. M. Taylor, and E.  J.  Bonelli,  "The
     Determination. of Polycylic Aromatic Hydrocarbons in Air Follutioa
     Samples," Finnigan Corporation Application Tip No. 52,  Finnigan.
     Corporation, Sunnyvale, California, 1973.

20.  "Particulare Polycyclic Organic Matter," National  Academy of Sci-
     ences, Washington, D. C., (1972), Chapter 2.                   '

21.  Lป Dubois, R. Cป Lao, and R. S. Thomas, "Mass, Ultraviolet,  and
     Fluorescence Speetroraetric Data of Polycyclic Hydrocarbons Found
     in Urban Air and. Cigarette Smoke," l6th Spectx-oscopy Symposiuji,
     Montreal, Canada, 1969.

22.  "Adas of Mass Spectral Data," E. Stenhagen, S. Abrahams son, and
     ?> Tr-J. McLafferty Eds., Wiley-lnterscience, New York,  1969.

23.  ?-. r-I. Silvers tein and G. C. Bassler, "Spectror^etric  Identification
     of Crgaaic Ccnpour.ds," Second Edition., John Uiley, New  York, 19^7 >
     '-%-,—,— ^-r- T
     \^__C- ^ w v _ _Z- *

2^4.  S, H. Snre-cer, ''Ir.trocluctory Mass Spectroiuetry," Allyn  and Bacon,
     Ir.c., Boston., 1971, Cliapter 1.
.
                    ni A. E. V7illians,  "Mass  and Abundance Tables for Use
     in Mass Specrtrcrr.etry," Elsevier,  Amsterdam,  1963.

2o.  "Grand Calmet River Sediizent Measurements - Collection and Analysis,1
     17FIC-Cir.cinr-a.tI Report,  1972.

27.  T. Braidech, private conraunication.

28.  J. L. Monlonan, "Annual Report,  International Bank  of Polycyclic
    .Aro.-c.atic Hydrocarbons,"  World Health Organization, Lyon, France,
     December 3 1973-
                                 68

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ft,.
                                    Attachment L
                        U.S.  EPA Survey,  September 16,  1975

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 I
 II
  •; IH-I
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1
                                         Attachment  M
                               U.S. EPA Survey,  3uiy 16-19.  1979
 I
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                                              Table  M-l

                           United States Environmental Protection  Agency
                                              Region  V
                                       Eastern District Office
Stream:  Black River
Survey Date:  Duly 16-17,  1979
                                   (mg/1 unless otherwise stated)
Station Number
River Mile
Flow, cfs (avg.)
pH (range)
Cond. (pmhcs'crn)
Temp.ฐC max.
avg.
min.
DO max.
avg.
min.
Dissolved Solids
Suspended Solids
BOD5
BOD3Q
COD
TOC
TKN
Ammonia-N
Nitrate+Nitrite-N
Chloride
Sulfate
Cyanide (yg/1)
Phenolics (pg/1)
LE


6.9
180-290
25.1
23.5
20 = 5
10.5
9.0
ft.O
146
17
3.25
5.6
10
ft
0.16
0.05
0.64
19
27
<5
5
rf
-.6

6.9
1SO-320
27.5
23.8
21.0
12.4 .
8. ft
ft.2
202
16
3.1
6.0
13
ft
0.65
0.18
0.89
21
29
<5
ft
1
0.0

6.3-7.2
210-380
28.5
2ft. 1
21.0
12. ft
7.0
1.9
200
11
3.25
6.6
12
ft
0.7ft
0.34
1.03
2ft
35
<5
<2
2
1.04

6.2-7.1
210-ft35
28.5
2ft. 8
22.0
11.2
ft. 8
2.8
199
22
ft.O
8.8
15
ft
1.47
0.64
1.01
28
ft3
<5
5
3
1.85

7.1-7.9
220-580
30.0
25. ft
21.2
10.2
ft. 5
2.8
315
25
4.5
9.8
17
ft
1.36
0.93
1.08
30
47
7
3
ft
2.ftO

7.4-7.9
230-550
31.0
25.7
21.5
11.5
ft.O
1.8
245
15
ft. 6
10. ft
11
2
1.0ft
0.71
0.66
31
ftS
14
<2
5
2.85

7.4-7.8
300-650
30.5
28.9
26.5
6.3
4.1
3.0
312
14
5.7
13.8
18
5
2.19
1.62
1.53
41
70
18
3

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                                              Table  M-l

                           United States  Environmental  Protection Agency
                                             Region V
                                      Eastern District  Office
Stream:  Black River
Survey Date:  July 16-17, 3979
                                   (mg/1 unless  otherwise stated)
French Creek
Station Number
River Mile
Flow, cfs (avg)
pH (range)
Cond. (pmhos/crr.)
Temp.ฐC max.
avg.
min.
DO max.
avg.
m!n.
Dissolved Solids
Suspended Solids
BOD5
BOD3Q
COD
TOC
TKN
Ammonia-N
Nitrate-f-Nitrite-N
Chloride
Sulfate
Cyanide (pg/1)
Phenolics (),'g/l)
6
3.35

7.3-7.8
34C-7QO
32.0
29.7
27.0
4,5
3.0
1.*
294
3
6.25
14.5
24
6
2.36
1.75
1.95
45
78
18
5
7
3.88

7.0-7.6
600-700
31.0
29.7
28.0
6.5
3.8
1.2
468
14
8.1
17.4
30
12
2.03
1.09
1.66
65
123
28
6
8
4.85

7.3-7.8
650-820
32.0
29.2
24.0
5.4
4.2
2.9
473
6
9.25
21.1
45
16
2.66
1.51
2.92
62
117
27
7
9
5.10

7.5-8.0
670-920
27.5
24.1
21.0
9.6
7.7
5.8
662
5
3.4
6.3
18
5
0.58
0.08
8.46
92
174
<5
2
K)
6.50

7.3-7.7
660-740
29.0
26.2
24.0
7.9
4.9
2.1
523
18
8.7
22.1
34
12
3.95
2.86
3.20
58
108
31
5
JU
8.60

7.1-7.9
640-750
28.0
25.3
23.0
6.2
4.4
2.7
521
<5
13.25
30.8
44
15
4.98
3.59
3.12
60
106
25
3
12
10.10

7.0-7.8
680-770
28.5
25.7
22.2
9.2
7.0
4.7
522
8
14.0
35.6
50
20
5.50
3.90
3.11
60
110
16
3

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1
1
1
1
1
1
1

1

1

1

1

1

1

•
*
1
1
1
1
1


.

Stream: Black R.
Survey Date: 3u!
Station Number
River Mile
Flow, cfs (avg)
pH (range)
Cond. (ymhcs/cm
Temp.ฐC max.
avg .
O
mi FI-
DO max.
avg,
min.
Dissolved Sc'.l-ls
Suspended Solids
BOD3Q
COD
TOC
TKN
Amrnonia-N
Nitrate+Nitrhe-N
Chloride
Sulfate
Cyanide (ug/1)
Phenolics (pg/1)







Unit
iver
y 16-17, 1979
13
10. SO
6.8-8.4
) 510-600
29.5
26.2
24.0
11.6
7.9
5.S
396
6.1
12.3
33
14
1.05
0.10
3.94
46
112
<5
3




                   Table  M-l

United States Environmental Protection Agency
                   Region V
            Eastern District Office
        (mg/1 unless otherwise stated)

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                                              Table M-2

                           United States  Environmental Protection Agency
                                             Region V
                                       Eastern  District Office
Stream:  Black River
Survey Date:  July 17-IS, 1979
                                   (mg/1 unless otherwise stated)
Station Number
River Mile
Flow, cfs (avg)
pH (range)
Cond . ( ymhcs/ cm)
Temp. C max.
avg .
mi P..
DO max.
avg.
min.
Dissolved Solids
Suspended SoJcs
BOD5
BOD3Q
COD
TOC
TKN
Ammonia-N
Nitrate+Nitrite- N
Chloride
Sulfate
Cyanide (ng/1)
Phenolics (yg/l)
LE


7.3-3.7
220-325
25.0
24.0
22.0
9.7
8.6
5.3
179
9
2.1
4.3
9
4
0.63
0.09
0.57
19
25
<5
<2
H
-.6

7.4-8.6.
2*0-330
25.0
23.8
22.0
9.2
7.7
4.3
192
<5
1.8
4.2
11
3
0.44
0.10
0.71
21
26
<5
2
I
0.0

7.2-8.4
250-410
26.5
24.2
21.5
9.7
6.8
3.9
226
12
2.6
6.8
13
5
0.69
0.32
1.08
20
29
<5
2
2
1.04

7.3-8.3
260-450
27.0
25.2
22.5
12.0
5.5
3.0
247
12
3.2
9.6
14
5
1.38
0.80
1.20
27
41
6
<2
3
1.85

7.2-7.8
295-720
29.0
26.2
23.0
6.3
2.9
1.9
275
24
3.4
10.2
15
8
1.65
1.23
1.04
33
54
12
4
4
2.40

7.4-7.8
300-570
29.0
26.6
23.6
4.4
2.3
1.8
274
15
3.2
10.2
13
7
1.84
1.37
1.12
32
52
13
4
5
2.85

7.4-7.8
380-660
29.7
28. 2
24.5
4.1
2.3
1.7
296
19
3.9
12.0
14
9
2.38
1.78
1.41
39
67
13
4

-------
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
                                              Table  M-2



                           United States Environmental  Protection Agency

                                             Region  V

                                      Eastern District  Office
Stream:  Black River

Survey Date:  July 17-18, 1979
                                   (mg/1 unless  otherwise stated)
                                                      French Creek
Station Number
River Mile
Flwo, cfs (avg)
pH (range)
Cond. *)jmhos/crn3
Temp.ฐC max.
avg.
mi P..
DO max.
avg,
min.
Dissolved Sollcs
Suspended Solids
BOD5
BOD3Q
COD
TOC
TKN
Ammonia-N
Nitrate+Nitrite-N
Chloride
Sulfate
Cyanide (pg/1)
Phenolics (pg/1)
6
3.35

7.4-7.S
375-70Q
31.0
23.6
25.0
2,4
i.S
.6
325
1C
3.6
12.7
18
8
2.64
1.S5
1.51
42
73
25
6
7
3.88

7.0-7.8
600-700
32.0
29.8
28.0
6.2
3.5
1.4
465
11
7.9
3.3
36
31
2.73
1.50
2; 48
62
117
31
2
8
4.85

7.2-7.8
500-850
31.0
28.6
25.0
3.2
2.6
1.0
443
18
6.3
18.9
39
7
2.96
1.69
2.32
61
115
33
4
9
5.10

7.9
850-940
24.5
21.6
18.7
10.6
S.2
6.3
624
11
1.7
4.6
18
8
0.67
0.03
9.39
93
180
<5
4
10
6.50

7.5-7.8
670-790
26.8
24.3
22.5
5.4
3.9
2.2
462
30
9.2
24.0
38
16
4.38
3.12
2.93
64
118
29
4
_n
8.60

7.5-7.7
625-830
25.5
23.4
21.0
4.6
3.5
2.5
503
13
11.1
31.6
40
16
5.08
3.71
2.55
71
130
24
8
12
10.10

7.8-8.0
650-830
26.0
23.4
•?0.5
9.7
6.9
4.8
506
24
11.0
38.5
24
51
5.73
3.93
2.50
71
133
18
8

-------
                                              Table M-2

                           United States Environmental Protection  Agency
                                             Region V
                                       Eastern  District Office
Strearnr  Black River
Survey Date.:  3uly 17-18, 1979
  Station Number
13
River Mile
Flow, cfs (avg)
pH (range)
Cond. (jjmros/cm)
Temp. C max.
avg.
irdn.
DO max.
avg.
min.
Dissolved Solids
Suspended Solids
BOD5
BOD3Q
COD
TOC
TKN
Ammonia- N
Nitrate+Nitrite-N
Chloride
Sulfate
Cyanide (pg/1)
Phenolics (yg/i)
10.80

S.4-S.S
620-700
26.5
24.4
22.0
13.7
9.6
6.0
4-42
26
6.2
13,2
30
14
1.49
0.07
3.36
47
133
5
—
                                   (mg/1 unless otherwise  stated)

-------
1
1
1
1
1
1
•
1

1
•J



1

1

1




1

1
1
1
1
1
Table M-3
United States Environmental Protection Agency
Region V
Eastern District Office
Stream: Black River
Survey Date: July 18-19, 1979
(mg/1 unless otherwise stated)
Station Number
River Mile
Flow,cfs (average)
pH (range)
Cond. (umhcs/cm)
Temp.ฐC max.
avg.
min.
DO max.
svg.
min.
Dissolved Solids
Suspended Scilds
BOD5
BOD3Q
COD
TOC
TKN
Ammonia-N
Nitrate+Nitrite-N"
Chloride
Sulfate
Cyanide (ug/1)
Phenolics (pg/1)




LE

8.3
220-2S5
24.5
23.5
22,0
9.0
8.7
8.1
195
11
1.3
3.0
7
<3
0.71
0.06
0.5S
18
27
<5




H-
-.6
8.0-8.2
270-345
26.0
24.2
22.0
8.S
8.0
7.2
208
14
1.9
4.3
11
3
0.40
0.05
0.68
20
29
<5
4




1
0.0
8.0-8.1
220-435
26.5
24.6
22.0
8.9
7.4
6.0
230
23
2.4
5.6
12
1.3
0.72
0.18
0.91
24
36
<5
12




2
1.04
7.7-7.9
320-500
27.0
24.8
22.0
9.8
5.8
3.2
269
17
3.3
8.8
18
4
1.45
0.81
1.22
31
50
<5
4




3
1.85
6.8-7.9
300-525
28.5
26.5
23.0
4.7
3.5
2.1
268
25
3.9
11.0
13
5
2.08
1.15
1.21
33
56
2




4
2.40
7.0-7.7
300-525
29.7
26.9
23.2
6.2
2.9
2.0
283
15
4.1
12.0
16
5
1.82
1.31
1.23
33
55
<5
<2




5
2.85
7.0-7.7
380-700
30.0
28.0
25.0
4.6
2.7
2.2
341
17
3.9
12.0
17
5
2.33
1.69
1,48
40
70
7
<2





-------
                                              Table  M-3

                           United States Environmental  Protection Agency
                                             Region V
                                      Eastern District  Office
Stream:  Black River
Survey Date:  July 18-19, 1979
                                   (mg/1 unless otherwise stated)
French Creek
Station Number
River Mile
Flow, cfs (average)
pH (range)
Cond. (pmhos/cm)
Temp.ฐC max.
avg.
min.
DO max.
avg.
min.
Dissolved Scuds
Suspended Solids
BOD5
BOD3Q
COD
TOC
TKN
Ammonia- N
Nitrate+Nitrite-N
Chloride
Sulfate
Cyanide (pg/1)
Phenolics (yg/1)
6
3.35

7.0-7.6
360-710
31.0
28.9
26.0
2.8
2.0
.7
354
7
3.9
13.4
21
9
2.56
1.77
1.60
44
78
7
6
7
3.88

6.8-7.5
5SO-650
30.0
28.9
28.0
4.9
3.7
2.4
433
34
11.0
2.4
38
14
2.96
1.67
2.25
59
115
<5
4
8
4.85

7.0-7.6
600-850
29.5
28.1
26.5
3.7
3.0
2.0
476
22
7.8
20.9
40
14
3.15
1.76
2.28
63
120
9
<2
9
5.10

6.9-8.1
890-960
23.5
20.9
18.0
10'.4
8.6
6.8
645
6
2.0
5.2
16
7
0.68
0.06
8.68
97
182
<5
4
10
6.50

6.3-7.7
710-810
25.5
23.9
22.0
5.5
3.8
2.3
537
17
6.6
27.4
34
18
4.65
3.25
2.27
74
137
17
4
11
8.60

6.4-7.7
700-850
25.0
23.0
21.0
4.0
3.3
2.1
555
16
10.8
33.0
43
15
5.36
3.84
2.00
79
140
10
6
12
10.10

6.6-8.0
700-860
25.5
22.9
20.0
10.6
7.3
4.6
539
14
12.7
>41.2
55
19
6.51
4.49
1.96
84
140
19
8

-------
1
1
1
1
1
w

1

1
^^B
1

1

1

1

|
^B

1

1

1
1
1
1
1








4
Unit

Stream: Black River
Survey Date: 3uly

Station Number
River Mile
Flow, cfs (average)
pH (range)
Cond. (ymhcs/cm)
Temp.ฐC max.
avg.
min.
DO max.
avg .
min.
Dissolved Solids
Suspended Sclids
BOD^
BOD30
COD
TOC
TKN
Ammonia- N
Nitrate+Nitrite-N
Chloride
Sulfate
Cyanide (pg/1)
Phenolics (ug/1)




18-19, 1979

11
10.80

6.6-S.*
615-700
26.5
23.8
20.5
15.0
10.8
5.7
10
6.5
15.0
3'-*
15
1.96
0.12
2.69
50
13S
<5
it




                   Table  M-3

United States  Environmental Protection  Agency
                  Region  V
            Eastern District Office
        (mg/1 unless  otherwise  stated)

-------
                                             Table M-*
                           United States Environmental  Protection Agency
                                             Region V
                                      Eastern District Office
Stream:  Black River
Survey Date:  Duly 16-17, 1979
                                   (mg/1 unless otherwise stated)
  Station Number        LE
River Mile
Calcium
Magnesium
Sodium
Silver       (pg/1)
Aluminum   (yg/1)
Boron       (ug/0
Barium      (pg/l)
Beryllium   (pg/i)
Cadmium   fug/1)
Cobalt      (vg/1)
Chromium   fyg/i)
Copper      (vg/13
Iron        (pg'l)
Manganese  (vg/J)
Molybdenum (pg/1)
Nickel      (pg/l)
Lead       (pg/l)
Tin         (pg/l)
Titanium    (yg/1)
Vanadium   (pg/0
Yttrium     (pg/l)
Zinc        (pg/l)
H _! 2
-.6 0.0 1.0*
4*. 5
9.5
12.9
296
<80
20
<2
<2
<5
<9
1010
88
<6
0
116
12
<2
<2
<50
3
1.85
*5.5
10.1
15.7
3^1
100
25
<2
<2
9
10
15*0
180
<6
12
<8
1*
3
3
<50
*
2.*
57.5
11
19.7
161
106
2*
<2
<2
<5
<9
1200
211
<6
<5
<8
11
<2
<2
88
5
2.85
58.7
11.2
2*
<90
163
19
<2
<2
8
<9
7*1
201
<6
6
<8
9
3
<2
115

-------
1
1
1
1
1
1
M



1

I
^v
1

1

1

1

•
•


1
1
1
1
Table M-4
United States Environmental Protection Agency
Region V
Eastern District Office
Stream: Black River
Survey Date: July 16-17, 1979
(mg/1 unless otherwise stated)
Station Number
River Mile
Calcium
Magnesium
Sodium
Silver
Aluminum
Boron
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Manganese
Molybdenum
Nickel
Lead
Tin
Titanium
Vanadium
Yttrium
Zinc







(vg/i)
teg/i)
teg/i)
teg/i)
teg/i)
teg/:)
teg/i >
teg/i >
teg/0
teg'D
teg'i)
teg/D
(yg.'i)
teg/i)
(ug/1)
teg/i)
(ug/l)
*yg/l)




6 7
3.35 3.88
59.5
12.7
30.2
<90
193
22
<2
<2
6
<9
745
202
<6
<5
<8
9
<2
<2
52




8
4.85
72.7
15.8
46.7
<90
355
26
<2
<2
10
10
1750
147
<6
<5
116
12
<2
<2
98




9
5.1
85.2
17.7
72
<90
411
24
<2
<2
<5
<9
251
36
<6
<5
<8
7
4
4
<50




10
6.5
72.1
17.2
41.0
<90
239
182
<2
<2
11
12
721
86
<6
38
<8
15
8
<2
<50




ซ
11
8.6
70.3
17.4
44.8
<90
296
190
<2
<2
16
18
479
72
7
22
<8
14
3
<2
<50




•<
12
10.1
69.6
17.5
43.5
<90
370
165
<2
<2
21
20
507
73
16
34
<8
9
4
<2
<50





-------
                                              Table  M-'f

                           United States Environmental Protection Agency
                                             Region V
                                      Eastern District Office
Stream:  Black River
Survey Date:  3uiy 16-17. 1979
Station Number
River Mile
Calcium
Magnesium
Sodium
Silver
Aluminum
Boron
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Manganese
Molybdenum
Nickel
Lead
Tin
Titanium
Vanadium
Yttrium
Zinc




(yg/D
(yg/D
(Pg/i)
(yg/O
(yg/i)
(ug/i)
(yg/i)
(ug/1)
(yg/l)
(^g;')
(yg/i'
(yg/l)
(yg/0
(yg/i)
(yg/D
(yg/l)
(yg/D
(yg/D
(yg/l)
13
iO.S
65.9
15.9
30. 6
<1

-------
1
1
1
1
1
1

1

1

1
•



1

1
M
1

1


1
1
1
1
Table M-5
United States Environmental Protection Agency
Region V
Eastern District Office
Stream: Black River
Survey Date: July 17-18, 1979
Station Number
River Mile
Calcium
Magnesium
Sodium
Silver (yg/i)
Aluminum (ng/J,*
Boron (pg/l-
Barium (^g/0
Beryllium (wj/1)
Cadmium (ug/i)
Cobalt (Kg/1)
Chromium (l-g/i":
Copper (ng/1)
Iron (pg/1'
Manganese (^g'i)
Molybdenum (ug<")
Nickel (yg/15
Lead (pg/0
Tin (yg/1)
Titanium (pg/1)
Vanadium (vg/i)
Yttrium (pg/1)
Zinc (pg/D




(mg/1 unless
LE H '
-.6
42.5 41.5
9.1 8.5
11 10.7
326 127
107 < 80
19 18
< 1 <1
<2 <2
<2 <2
<5 23
10 10
684 429
27 34
< 6 <6
<5 <5
<15 26
<8 <8
11 9
<8 <2
<2 <2
119 161




otherwise
0.0
41.1
9.4
14.8
483
157
22
<1
<2
<2
906
19
4660
139
63
<15
<8
13
4
<2
63




stated)
2
1.04
53
11
19.6
387
130
24
< 1
<2
<2
<5
<9
1140
176
<6
<5
<8
9
<2
<2
106




3
1.85
50.2
11.2
21.3
476
158
25
<1
<2
<2
<5
<9
1250
208
<6
<5
<8
11
<2
<2
73




4
2.4
48.6
11.2
22.1
498
170
28
<1
<2
<2
7
<9
1310
230
<6
<5
<8
11
<2
<2
67




5
2.85
54.5
11.9
27
342
178
25
<1
<2
<2
10
<9
1190
236
<6
<5
<8
65
<2
<2
72





-------
                                              Table M-5

                           United States Environmental Protection Agency
                                             Region  V
                                       Eastern  District Office
Stream:  Black River
Survey Date:  july 17-18, 1979
French Creek
Station Number
River Mile
Calcium
Magnesium
Sodium
Silver
Aluminum
Boron
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Manganese
Molybdenum
Nickel
Lead
Tin
Titanium
Vanadium
Yttrium
Zinc




(Mg/n
(yg/i)
(yg/l>
(yg/D

(yg/i)
(yg/0
(ug/i;
(yg/i)
(yg/i>
(yg/D
(yg/l)
(yg/D
(yg/D
(yg/i)
(yg/D
6 7
3.35 3.88
55
12.6
33
< 1
235
217
25
<1
<2
<2
<5
<9
1010
227
<6
<5
<15
<8
7
<2
<2
73
8
4.85
70.7
16.9
55.1
<1
229
331
29
<1
<2
<2
<5
<9
2480
168
<6
<5
<15
<8
8
<2
<2
102
9
5.1
82.8
18
87.8
<1
<90
449
18
<1
<2
<2
<5
<9
321
32
<6
<5
<15
<8
<6
<2
<2
<50
12
6.5
70.4
17.7
49.2
<1
258
467
70
<1
<2
<2
15
13
1080
96
11
<5
<15
<8
11
<2
<2
76
U_
8.6
70.5
17.5
57
<1
<90
558
71
<1
<2
<2
13
18
682
80
<6
<5
<15
<8
<6
<2
<2
68
.12
10.1
66.8
17.4
56.1
<1
<90
599
47

-------
1
1
1
1
1


Unit
Stream: Black River
1
1

1

1

1

1



1

1
1

1
1
1
1
Survey Date
: July
Station Number
River Mile
Calcium
Magnesium
Sodium
Silver
Aluminum
Boron
Barium
Beryllium
Cadmium
Coba't
Chromium
Copper
Iron
Manganese
Molybdenum
Nickel
Lead
Tin
Titanium
Vanadium
Yttrium
Zinc







(yg/l>
(Ug/l)
{{jg/0
I":/;!
fug/i)
(pg/1)
\ .- o; * ;
(•_T/i)
l-g/i)
(1:3/0
U-g/l>
(iig/D
(Pg/i)
(jig/1)
(Pg/i)
(Pg/l)
(ug/i)




17-18, 1979
13
10.8
69.2
17.3
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54




                   Table M-5

United States Environmental Protection Agency
                   Region V
            Eastern District Office
        (mg/1 unless otherwise stated)

-------
                                              Table  M-6

                           United States  Environmental Protection Agency
                                             Region V
                                      Eastern District Office
Stream:  Black River
Survey Date:  July 18-19, 1979
                                   (mg/1 unless  otherwise stated)
Station Number
River Mile
Calcium .
Magnesium
Sodium
Silver
Aluminum
Boron
Barium
Beryllium
Cadmium
Cobalt
Chromium
Copper
Iron
Manganese
Molybdenum
Nickel
Lead
Tin
Titanium
Vanadium
Yttrium
Zinc




(Pg/l)
(yg/i)
(yg/i)
(u'g/1)
(Vg/!)
fug/1)
d'g/1)
(,,?:'!}
••r-5< *'
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(us/1)
(ug/l)
(ug/1)
C^g/i)
(Pg/l)
(Vg/l)
(Pg/l)
(yg/l)
(ug/1)
(ug/1)
LE

38.7
8.7
9-1
< 1
217

-------
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Table M-6
United States Environmental Protection Agency
Region V
Eastern District Office
Stream: Black River
Survey Date: duly 18-19, 1979
(mg/1 unless otherwise stated)
Station Number
River Mile
Calcium
Magnesium
Sodium
Silver (yg/i)
Aluminum (vg/i)
Boron (pg/i)
Barium (ug/!)
Beryllium (vg/l)
Cadmium (vg/U
Cobalt (vg/i)
Chromium ivgfi>
Copper (ug.'I;
Iron (pg/J)
Manganese (pg/i1
Molybdenum (pg/1'
Nickel (pg/i)
Leaa (yg/1 /
Tin (pg/i)
Titanium (pg/i)
Vanadium (ug/1)
Yttrium (pg/i)
Zinc (pg/D




6 7
3.35 3.88
56.9
11.9
23.8
5
<90
1S8
22
< 1
<2
<2
32
11
860
236
S
46
21

-------
                                             Table  M-6

                           United  States Environmental Protection Agency
                                             Region V
                                      Eastern District Office
Stream:  Black River
Survey Date:  3uiy 18-19, 1979
  Station Number
River Mile
Calcium
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Sodium
Silver (pg/i)
Aluminum rug/! 3
Boron (pg/U
Barium (pg/1)
Beryllium (ug/1)
Cadmium (pg/l;
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Chromium (ug/i)
Copper Og, D
Iron (pg/I }
Manganese (pg/l?
Molybdenum (pg-'l)
Nickel (pg/l)
Lead (pg/I)
Tin (ug/I)
Titanium (pg/l)
Vanadium (pg/l)
Yttrium (pg/i)
Zinc (pg/J)
10. S
77.4
17.3
33. S
3
<-50
275
35
<1
<2
<2
22
21
409
62
<6
26
<15
<8
25
6
5
67
                                   (mg/1 unless otherwise stated)

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U.S. Environmental Protection Agency
Region V
Eastern District Office
Discharger: United States Steel Corporation
Lorain Works
Sample Date: 3uly 16, 1979
Sample Number Location
79EA13S36 Intake WI-3
79EA13540 Outfall 001
79EA13532 Outfall 005
79EAI35^7 Intake WI-2
79EAI3525 Outfall 002
79EAI3551 Outfall 003
79EA13S55 Outfall 00*
79EA13S52 Waste Oil at
Outfall 001
Sample Types - Grab














Total PCS (ng/1)
< 5.6
< 4.9
< 0.3
< 0.3
< 0.6
< 0.3
<60










-------
                U.S.  Environmental Protection Agency
                              Region V
                       Eastern District Office
 Discharger:  United States Steel Corporation
             Lorain Works
 Sample
Date:
3uly  16-17,  1979
Sample No^
              Oil and Grease Samples

      Time Oil (mg/i)            Sample No.     Time Oil (mg/0
         Intake Wl-2
  EA13S47
  EA 135 48
  EA13549
  Average
      1628
      1816
      0425
        < i
EA13S32
EA13S33
EA13S34
Average
                                 Outfall  005

                                        1255
                                        0445
2
3
                                                        1.7
         Intake WI-3
EA 13535
EA13S3?
EA1353S
Average
1247
2050
0431

3
1
*>
JL.
2
                                        Outfall 002
EA13S25
EA13S26
EA13S27
EA13S28
EA13S29
EA13S30
Average
1216
1629
2028
0013
0425
0906

5
2
2
2
3
< 1
I
         Outfall 001
  EA 13540
  EA13S41
  EA13S42
  EA13S44
  EA13S45
  Average
      1319
      1705
      2135
      0507
      1142
          3
          5
          7
          9
          6
         6.0

-------
1
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1

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1






Discharger:
Sample Date:

Sample No .


U.S



United
Lorain.
3uly

Time
Intake WI-2
EA14S47
EA14S48
EA14S49
EA14589
Average
O
1300
2020
0420
1000


Intake Wl-3



1

1



1



1
1
1
1
EA14S36
EA14S37
EA14533
Average


Cutfa
EA14S40
EA14S41
EA 145^2
EA14S43
EA14S44
EA14S45
Average




1343
2050
0424



11 001
1413
1845
2115
0046
0447
0848







. Environmental Protection Agency
Region V
Eastern District Office

States Steel Corporation
Works
17-18, 1979
Oil and Grease Samples
Oil (mg/1) Sample No. Time Oil (mt?/l)
Outfall 005
2 EA14S32 1355 <1
1 EA14S33 1830 <1
<1 EA14S34 0440 <1
< 1 Average < 1
<1

Outfall 002
<1 EA14S25 1323 5
<1 EA14S26 1812 2
< 1 EA14S27 2035 2
<1 EA14S28 0100 <1
EA14S29 0410 8
EA14S30 0807 < 1
Average 2.8

3
3
5
6
13
6
6.0





-------
               U.S. Environmental  Protection Agency
                            Region V
                      Eastern  District Office
Discharger:  United States Stee!  Corporation
            Lorain Works
Sample Date:  3uly 18-19,  1979
Sample No.
         Intake V/I-2

  EA15S47      1448
  EA155-S      2104
  EA15549      0413 .
  Average
                      Oil and Grease Samples

             Time  Oil (rng/1)             Sample No.     Time Oil (mg/1).
                                               Outfall 005
                                         EA15S32
                                         EA15S33
                                         EA15S34
                                         Average
                                         1225
                                         2133
                                         0435
                                         3
                                         2
                                         1
                                         1.7
       Intake \V!-3
                                   Outfall 002
EA15S36
EA15S37
EA15S3S
Average
EA155-J
EA15S-I
EA15S42
EA15S43
EA15S44
EA15S45
Average
 1212
 2122
 0425
1  001
 1240
 1643
 2150
 0053
 0450
 0838
 7
 4
 4
10
 5
10
6.7
EA15S25
EA15S26
EA15S27
EA15S28
EA15S29
EA15S30
• 1158
1619
2109
0020
0410
0804
2
3
2
1
3
< 1
                                         Average

-------
Attachment N
I
I
I
I
I
I
I
I
•                                     Discharger Monitoring Data
I
I
I
I
I
I
 I
 I
 I
 I

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1
1
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1

1

1

1
1

1


1

1


1

1

1

1

1

1


1
1
Flow Temp. BOD,.
Month MGD ฐC mg/P
January
Avg.
Max.
Min.
Februarv
Avg.
Max.
Min.
March
Avg.
Max. i
Mm.
April
Avg.
Max.
Min.
May
Avg.
Max.
Mir..
3une
Avg".
Max.
Min.
Avg.
Max.
Min.
Av^
Max.
Mm.
Seoternber
Avg.
Max.
Min.
October
Avg.
Max..
Min.
November
Avg.
Max.
Min.
December
Avg.
Max.
Min.



,38
.38
.27

.31
.36
.26

.62
.5
.3
.54
.33
s
.74
.38
.43
.56
.38
.4
,5
•2
.1
.5

.38

.39
.56
.3t
.34
.42
.27






10
17
5

5
9
3

11
14
7
13
13
8
9
12
6
7
14
3
6.5
12
i
5
10
i

7.1
16
2

10
14
5
9
17
5





Lodi Wastewater Treatment Plant
Effluent Quality
1978
TSS NH,-N TKN
pH mg/i mR/1 mg/i
- 7
16
0

- 3
16
0

8
0
8
12
0
12
64
0
	 3
8
0
2.6
8
0
4
16
0

- 0
0
0

- 6.7
16
0
- 13.4
32
0





   Total       Fecal     T.Res.
Phosphorus  Coliform     Cl?
   mg/1     #/100 ml    mgfl


                          .3
                          .8
                          .3
                          .6
                          .05
                          .2
                          .5
                          .2
                          .25
                          .1
                          .2
                          .3
                           .2
                           .3
                           .2
                           .4
                           .2
                           .3
                           .3
                          1.3
                          0
                           .29
                           .40
                           .2
                           .4

-------
Lodi Wastewater  Treatment Plant
        Effluent Quality
              1979
Flow Temp. BOD-
Month MCD ฐC mg/f
January
Avg.
Max.
Min.
February
Avg.
Max.
Min.
March
Avg.
Max. !
Min.
Agrii
Avg.
Max.
MIR.
May
Avg.
Max.
Min.
Ju-.e
Avg.
Max.
Mm.
OuJv
Avg.
Wax.
Min.
August
Avg.
Max. !
Min.
Seoternber
Avg.
Max. 1
Min.
October
Avg.
Max.
Min.
November
Avg.
Max.
Min,
December
Avg.
Max. 1
Min.

.3
.45
.22
.33
.97
.20
.46
.C4
.31

.38
.89
.39




.43
.43
.37
.42
c <;
.32

.45
.0!
.39
.
-------
I
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I
Lorain Wastewater  Treatment Plant
         Effluent Quality
               1978
Flow
Month MGD
Danuarv
Avg. " lt.9
Max. 25.5
Min. i2.4
February
Avg. 12,8
Max. 14.5
Min. 12.2
March
Avg. IS."
Max. 29.3
Min. 12.5
April
Avg. IS. 6
Max. 26.5
Min. 13.5
May
Avg. 16.'-
Max. 21.5
Min. 12.5
June
Avg. 15.4
Max. 3C.3
Min. 12,6
July
Avg. !".9
Max. 2t.?
Min. 12. S
August
Avg. 16.7
Max. 2^.5
Min. 12.6
September
Avg. 17.6
Max. 22
Min. 1". 6
October
Avg. 19.2
Max. 29.0
Min. 14.8
November
Avg. 15.4
Max. 16.7
Min. 12.4
December
Avg. 16.2
Max. 20.5
Min. 13.3
Temp.
ฐC

11
12
9

10
11
10

9
11
8

11
1^
9

15
17
13

20
21
18

22
24
19

24
24
23

24
25
24

21
24
19

18
20
14

14
15
11
BOD,
mg/F

30.2
90
6.6

16.7
33.3
6.6

17.4
43.5
6.0

19.!*
45
9.8

15.2
65.6
2.6

9.2
42.2
1.7

12.3
113
2.5

8.1
23.5
2.1

6.8
18.4
3.6

9.8
19.7
5.4

14.7
24.9
8.6

9.8
17.5
5.7
EH

—
7.2
7.0

—
7.2
7.0

—
7.2
7.0

—
7.2
7.0

—
7.3
7.0

—
7.3
7.0

—
7.5
6.8

—
7.4
7.0

—
7.3
6.9

—
7.2
6.9

—
7.1
7.0

—
7.2
6.9
T5S

33.4
118
8.8

30.4
56
12

41
142
10.0

36.8
76.7
13

35.8
150
11

23.3
98
1.2

26.7
202
2.0

13.7
41
1.8

14.9
31.3
5.6

22.8
43
8.5

44.7
84
17

24.4
59
12
NH,-N
mill

9.5
14.7
4.8

8-4
14.9
3.6

7.9
15.3
1.1

6.2
11.2
1.4

6.4
9.4
3.2

7.5
14.3
3.2

12.4
16.9
5.3

7.5
13.3
1.8

10.2
13.9
3.4

9.9
14.1
3.0

8.5
15.1
1.7

6.02
8.8
1.7
TKN
mg/1

11.8
19.4
2.3

12.5
20.4
7.3

10.8
21.9
4.9

9.7
16.5
3.97

9.8
19.5
5.6

9.4
14.9
5.6

15.5
20.5
6.8

8.9
17.1
3.8

12.7
16.3
9.1

13.9
17.5
6.2

14.5
20.9
7.9

9.3
12.6
7.1
6.0
9.5
2.6
6.3
8.1
3.8
4.8
8.5
1.3
5.2
7.5
2.9
6.3
8.8
4.2
6.1
9.0
2.7
7.7
12.2
4.8
8.43
10.2
4.9
7.1
10.1
2.2
7.6
10.5
5.11
9.4
12.9
5.9
7.2
10.4
4.8
31
260
4
18
38
3
21
170
4
98
1100
4
28
72
4
44
400
<1
38
80
6
39
180
1
40
330
2
85
640
15
80
550
4
19
110
3
                                                               .7
                                                               .8
                                                               .6
                                                              1.0
                                                               .7

-------
Lorain Wastewater Treatment Plant
         Effluent Quality
               1979
Flow
Month MGD
January
Avg. 16.5
Max. 24.0
Win. 13.5
February
Avg. 15.8
Max. 23,. 5
Mm. 12.3
March
Avg.
Max.
Min.
April
Avg. 19.0
Max. 2S.O
Min. 15. 1
May
Avg.
Max.
Min.
3une
Avg. 16. 3
Max. 27.2
Min. IC.7
3u!v
Avg. 17.2
Max. 2ฃ,r
Min. i'~.2
August
Avg. 15. Q
Max. 19. i
Min. 13. S
September
Avg. 14.1
Max. 30.3
Min. 11.5
October
Avg. 13.2
Max. 22.4
Min. 10.6
November
Avg. 16.2
Max. 24.4
Min. 12.7
December
Avg. 15.7
Max. 25.9
Min. 12.2
Temp.
ฐC

11
12
10

10
1!
8





11
14
10





19
21
16

2!
23
19

23
24
22

23
27
21

20
22
17

16
18
14

13
14
10
BOD,
mg/r

16.7
36
6.4

9.9
25.2
6.5





6,t
5.2
4.S





2.5
".5
i.3

1.9
4.0
,5

2.7
6.3
.8

3.4
S.9
1.7

3.9
6.7
2.7

4.9
15.6
2.7

3.4
4.4
2.7
ฃH

—
7.2
6.9

-,
7.3
7.0





_
7.2
6.9





—
7.3
6.7

—
7.1
6.4

—
7.1
6.6

—
7.1
6.7

—
7.2
6.7

—
7.1
6.7

—
7.6
6.6
TSS
mg/1

27.3
75
9

17.4
43
8.5





12.8
24
6.0





4.7
9.8
2.2

6.1
11.4
3.2

4.8
IS. 8
1.8

9.6
28
4.2

7.2
9.7
4.4

11.2
40
6.6

7.9
15.2
4.4
NH,-N
mgVl

4.5
10
.32

10.97
17.1
5.2













2.6
6.1
.32

3.4
6.4
1.3

3.5
.5.9
1.8

5.4
15.0
3.2

4.8
9.0
.9

4.5
8.6
1.45

5.4
9.3
.58
TKN
mg/1

8.1
13
4.5

14.4
21.8
12.0





5.7
11.5
2.1





4.1
7.8
1.8

4.6
7.0
1.8

5.0
7.5
2.1

7.8
34.4
4.2

6.5
11.5
2.4

6.0
11.3
2.9

6.5
8.6
1.9
Total
Phosphorus
mg/1

6.2
9.4
2.6

6.5
8.3
3.7













1.6
3.2
.7

.9
1.3
7

.8
1.1
.5

.9
1.7
.3

.82
1.85
.32

.97
2.01
.63

.66
.97
.31
Fecal
Coliform
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