EPA-905/9-74-008
               GREAT UUCESINIT1AT1YE COHlRAa PROGRAM
                                              JANUARY 1975

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Copies of this document are available
   to the public through the
National  Technical  Information Service
     Springfield, Virginia 22151

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WATER POLLUTION  INVESTIGATION:   ASHTABULA AREA
                       by

           P. Michael  Terlecky,  Jr.
              John G.  Michalovic
                 Sharon L.  Pek
              CALSPAN  CORPORATION



                In  fulfillment of

          EPA Contract No.  63-01-1575

                     for the

        ENVIRONMENTAL  PROTECTION AGENCY

                    Region  V
    Great Lakes  Initiative  Contract Program

       Report Number:   EPA-905/9-74-008
       EPA Project Officer:   Howard
          U.S. Environmental Protectkw Agwqr
          Region 5, Ubrary (PL-12J)
          77 West Jackson Boulevard, 12th Floor
          Chicago, IL  60604-3590
                  uanusry iy/b

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This report has been developed under auspices of the Great Lakes
Initiative Contract Program.   The purpose of the Program is to
obtain additional  data regarding the. present nature and  trends  in
water quality, aquatic life,  and waste loadings in  areas of the
Great Lakes with the worst water pollution problems.   The data  thus
obtained is being  used to assist in the development of waste discharge
permits under provisions of the Federal  Water Pollution  Control Act
Amendments of 1972 and in meeting commitments under the  Great Lakes
Water Quality Agreement between the U.S.  and Canada for  accelerated
effort to abate and control  water pollution in the  Great Lakes.

This report has been reviewed by the Enforcement Division,  Region  Y,
Environmental  Protection Agency and approved for publication.   Approval
does not signify that the contents necessarily reflect the views of
the Environmental  Protection  Agency, nor  does mention  of trade  names or
commercial  products constitute endorsement or recommendation  for use.
                               n

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                                  ABSTRACT
          This investigation reports the results of a historical data collec-
tion of information concerning the lower Ashtabula River, Harbor and nearshore
area, a detailed water sampling and biota collection made during 1973 and
1974, and an evaluation of present and future discharges on the water quality
and biota of the area.

          The quality of water passing through the Ashtabula complex including
Fields Brook has been recognized for many years as a serious environmental
problem.  NPDES permits have been issued during 1973 and 1974 for an indus-
trial complex of nine major industries.  Total residual chlorine, mercury,
dissolved solids, and metals content appear to be the most serious water
quality parameters which affect this area.  Measurement of these parameters
from the harbor to Fields Brook demonstrate the source of the materials.
Commonly observed' values of mercury in Fields Brook were 1.3-1.4 yg/1, although
measurements as high as 4.3-4.8 ug/1 were observed.  Total residual chlorine
values measured at the Fields Brook mouth ranged from 1-12 mg/1 indicating
much higher values closer to the source of the discharge.  Dissolved solids
and conductivity values increased from both the upstream and downstream
direction toward Fields Brook.  Values of dissolved solids in Fields Brook
ranged from 1495 to 1612 mg/1 with corresponding conductivity values ranging
as high as 1850 pmho/cm.  Flushing time calculations for Ashtabula Harbor
during low flow conditions indicated near stagnation for late summer.  Diatoms
and phytoplankton recovered in the harbor and lower river indicated the pres-
ence of a eutrophic, pollution tolerant type of community.  Cell counts were
found to be low, an observation verified by other researchers.   Low biomass,
low diversity, and dominance of only a few species at each sample station
indicated a seriously degraded water quality situation.

          If the requirements of current NPDES permits are met for the 1976-
1977 period, improvements can be expected in the water quality of the area.

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Further improvement in the reduction of pollutants in the 1977-1983 period
is also expected.

          Continued monitoring of the total residual chlorine, mercury, con-
ductivity and dissolved solids during the next two years is recommended.
                                        VI

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                              ACKNOWLEDGEMENTS
          The authors wish to thank Mr. Howard Zar, Project Officer, of the
USEPA for his guidance and assistance during the course of this investigation.
His many suggestions and comments were useful in the definition of the problem
areas and methods of obtaining the data.  Mr. Gary Amende la (USEPA-Cleveland)
was particularly helpful as to the field aspects of this study and assistance
in obtaining previous data.  Thanks are due also to Mr. Stasys Rastonis, USEPA,
for suggestions made in the early phases of this work.  We wish also to thank
Mr. Jack Fisher of Calspan for his technical and analytical assistance during
the chemical analysis portion of this work.  We wish also to acknowledge the
cooperation of Mr. Edward Bento, City Manager of Ashtabula, and Mr. Allan
Buchler, City Sanitarian.  Mr. Donald Sutherland was most cooperative in
assistance with logistic arrangements.
                                      Vll

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                               TABLE OF CONTENTS


Section                                                                Page
   1        INTRODUCTION .......................    1
   2        SUMMARY .........................    3
   3        CONCLUSIONS .......................    5
   4        RECOMMENDATIONS .....................    7
   5        HISTORICAL DATA ANALYSIS ................      9
            Physical and Chemical Properties ............      9
            Flushing Time in Ashtabula Harbor ............  15
            The Aquatic Community at Ashtabula,  Ohio ........    20
            Water Chemistry .....................    36
   6        CURRENT WATER QUALITY AND BIOTA .............  48
            Sampling Program .....................  49
            Results .........................  55
                 Organic Chemical Constituents  ............  60
                 Metals  ........  .  ..............  61
                 Conductivity and Dissolved Solids ..........  68
                 Chlorine Residuals ..................  70
                 Sodium  .......................  71
                 Sediment Chemistry ..................  74
                 Variation of Water Quality with Depth ........  74
            Biota Sampling and Analysis ................  77
                 Biota   .......................  78
                 Diatom Analysis ...  ................  84
   7        DISCUSSION ......... '  ...............  93
            Water Quality Aspects  ..................  93
            Biota Aspects .......................  105
   8        PRESENT AND FUTURE IMPACT OF  DISCHARGES  ON WATER QUALITY
            AND BIOTA     .......................  m
            Current  Impact
            Predicted  Future  Impact
                                      IX

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                           TABLE OF CONTENTS (Cont . )

Section
Literature Cited
Appendix 1.     Methods of Analysis-Water Chemistry ..........   120

Appendix 2.     General Standards of Water Quality for Ohio Streams .  .  122

Appendix 3.     Development of a Theoretical Model to Predict Free
                Residual Chlorine Concentrations in Fields Brook ....  124
                                  LIST OF  FIGURES

 Figure
   1       Ashtabula Harbor  Area  	    10
    2       Median Coliforn Concentration  in  Lake Erie  (1963-1964)   ...    35
    3       Ashtabula and Fields  Brook  Sample Locations  	    50
    4       Conductivity Profile  of Ashtabula River  	    69
    5       Total Residual Chlorine Distribution Sept.  5-6,  1973  ....    72

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                               LIST OF TABLES

                                                                        Page
        Summary of Low Flow Discharge During September 1-16, 1973 ...  11
        Ashtabula Waste Discharges to Lake Erie 1966-67 (Short Tons/Yr)  13
        Tributary Waste Discharges, Flow and Concentrations Lake
        Erie, 1966-67	14
 4      Average Phytoplankton Populations of the Central Basin of Lake
        Erie	21
 5      Benthic Fauna in River and Harbor at Ashtabula, Ohio  	  27
 6      Benthic Fauna at Disposal Site, Ashtabula, Ohio 	  28
 7      Phytoplankton Standing Crop and Percent Dominant Group  ....  31
 8      Yearly Phytoplankton Averages 	  32
 9      STORET Coliform Data (1963-1964)  	  34
10      1967 U.S. Lake Survey Study	37
11      Water Quality  Nearshore and Harbor 	  33
12      Water Chemistry Comparisons 1963-64 - 1967-68 	  40
13      Comparison of Determinations made During Dredging with National
        Water Quality Standards at Ashtabula, Ohio  	  42
14      Representative Data from STORET Station 0412700 for 1971-73 .  .  44
15      Applicable STORET Stations Related to this Study  	  45
16      Recent Chemical Data for Ashtabula River and Fields Brook ...  47
17      Ashtabula River Flow Conditions During Primary Field Sampling
        Period	52
18      Sample Groupings	-	53
19      Ashtabula River AS-I	56
20      Ashtabula River AS-III  	  57
21      Ashtabula River AS-IV 	  58
22      Ashtabula River AS-V	59
23      Ashtabula River AS-III  	  62
24      Metals - Ashtabula River AS-III 	  63
25      Metals - Ashtabula River AS-IV $ AS-V	64
                           1                                            ^
26      Mercury Data (ug/1)    	66
27      Total Chlorine Residuals (mg/1)  8-10 May 1974	71
                                    XI

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                           LIST OF TABLES  (Cont.)
                                                                      Page
        Sodium Content of Ashtabula Water Samples 	   73
        Fields Brook Sediment		   75
        Ashtabula River AS-III  	   75
        Description of Various Water Quality Parameters at Station
        Location at the Time of Biota Sampling	   79
32      Stations from Which Planktonic Organisms were Obtained and the
        Abundance in Terms of Cells per Liter-Surface Samples ....   80
33      Stations from Which Planktonic Organisms were Obtained and the
        Abundance of Plankton Present in Terms of Cells per Liter-
        Mid-Depth 	   81
34      Stations from Which Planktonic Organisms were Obtained and the
        Abundance of Plankton Present in Terms of Cells per Liter
        Bottom-Depth  	   g2
35      Diatom Distribution of the Upper Ashtabula River (Station 1).   85
36      Diatom Distribution in Fields Brook (Station 2) 	   85
37      Diatom Distribution in the Ashtabula River (Station 3)  ...   87
38      Diatom Abundance in Ashtabula Harbor (Mid-Harbor Station 5)  .   88
39      Diatom Abundance in Lake Erie off Ashtabula Harbor (Station  6)  89
40      Total Chlorine Residual  (mg/1) Measured at Sample Sites on
        Different Dates 	

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                                   Section 1
                                 INTRODUCTION
         This investigation is a detailed examination of one of eleven "special
interest" areas designated by the USEPA as worthy of particular attention in
the Great Lakes area.  The study reported herein basically consists of three
parts:  first, a presentation in historical perspective the information cur-
rently available concerning the water quality and biota of the Ashtabula River,
Harbor and nearshore area including the mouth of Fields Brook; second, a report
of the results of field investigations conducted by Calspan Corporation during
1973 and 1974; and third, a comparison of these conditions to those expected to
exist with the implementation of EPA's NPDES permit requirements and a projec-
tion based on current data on whether any actual improvement or changes will occur.

         Two reports serve as precursors to this report and form integral
parts of this final product:  The draft Task I report submitted in final form
on 29 October 1973 which serves together with some later additions  as  Section
II of this report; and a report entitled "The Prediction of Free Residual
Chlorine Concentrations in a Flowing Stream" (Pereira,  Terlecky and Yaksich,
1974) submitted on 30 January 1974 which is included as an Appendix to this
report.

         The Ashtabula River, located in northeast Ohio, drains generally north-
ward and empties into Ashtabula Harbor on the south shore of Lake Erie.  The
harbor is located approximately 59 miles east of Cleveland, Ohio and 44 miles
west of Erie, Pennsylvania.   The general locality is shown on United States
Lake Survey Chart Numbers 3,  34,  and 342.

         The quality of water passing through the Ashtabula complex including
Fields Brook has been recognized for many years  as a serious  environmental
problem.   Inadequately treated and sometimes raw industrial discharges have
seriously degraded the river water quality and illustrate the need  for

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improved treatment methods in the area and the  imposition  and enforcement
of strict standards for effluent and water quality.   Fields  Brook,  a tributary
of the lower Ashtabula River exhibits strong medicinal  and chemical  odors  and,
at times, white and brown discoloration (Lake Erie Report, 1968).

          An industrial complex of nine major industries in the Ashtabula area
which discharge to Fields Brook includes the following:

          Reactive Metals, Inc.  - Sodium and Chlorine Plant
          Reactive Metals, Inc.  - Metals  Reduction Plant
          Reactive Metals, Inc.  - Extrusion Plant
          New Jersey Zinc Co.  (formerly Cabot Titania)
          Detrex Chemicals - Muriatic Acid Plant
          General Tire Co.
          Olin Corporation - Chemicals Group
          Diamond Shamrock Chemical Co.
          Sherwin Williams Chemical Division

          The purpose of this report, therefore, is  to  survey both historical
 and current data and to determine what measures,  if any,  might be necessary
 to improve the water quality and enhance the environmental  conditions  present
 for the indigenous biota.

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                                  Section 2
                                   SUMMARY
         This study has examined the water quality and biota of the lower
Ashtabula River and Harbor area both from a historic and current standpoint.
The development of an industrial complex discharging into Fields Brook since
1950 has seriously degraded water quality conditions in the study area.   Large
scale changes in the biota in Fields Brook to a point where the brook is
extremely toxic have resulted.  This study focused on the water chemistry aspects
of the area and included biota sampling to assess the effects of the seriously
degraded water conditions in the vicinity of the Fields Brook entrance to the
Ashtabula Harbor.

         Total residual chlorine, mercury, high temperatures, dissolved solids,
and metals content appear to be the most serious water quality parameters which
affect this area.  Measurements of total residual chlorine in Fields Brook
varied from approximately 1 mg/1 to 12 mg/1 near its mouth.  On one occasion
a measurement of 35 mg/1 total residual chlorine was recorded at an outfall
along Fields Brook.  Mercury  levels in Fields Brook were measured and nearly
always exceeded the State of Ohio standard of 0.5 yg/1.  In fact, a value of
21 ug/1 was recorded.  Commonly observed levels of mercury in Fields Brook dur-
ing this study were 1.3-1.4 pg/1 in September 1973.  During May 1974 values
from 1.4 to 5.8 ug/1 tig were measured near E. 15th St.  This occasionally
               /
resulted in values as high as 4.3-4.8 yg/1 being observed upstream and at off-
shore stations.

         Dissolved solids levels were measured in Fields Brook ranging from
1495 to 1612 mg/1 with corresponding conductivity values ranging as high as
 1850 ymho/cm.  A conductivity profile showed the extent of Fields Brook
influence of this parameter from the Coast Guard Station to the Penn Central
Bridge - a distance of approximately two miles.

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         Flushing time calculations for Ashtabula Harbor during low flow
conditions of the river at 1.5 cfs indicated near stagnation for late summer.
A sixty day flushing time was postulated for the harbor under the conditions
present at the time.

         The absence of an indigenous population suggested the presence of
toxicity conditions in the study area.  Diatoms and phytoplankton recovered
in the harbor and lower river indicated the presence of a eutrophic,pollution
tolerant type of community.  Cell counts for the entire area appeared to be
low, which indicates either dilution (by high lake level) or toxic conditions
present.  Low biomass, low diversity and dominance of only a few species at
each sample station indicated a seriously degraded water quality situation
and further supports the conclusion that toxic materials present are affectinc
the biota.

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                                  Section  3
                                 CONCLUSIONS
         The most serious water quality problems associated with Fields Brook
 and the  lower Ashtabula River and Harbor are total residual chlorine, mercury
 and other metals, dissolved solids, and chloride concentrations.  Elevated
 temperatures associated with Fields Brook further degrade the water quality
 situation.  Low cell counts and low biomass throughout the study area support
 the conclusions based on water chemistry that the levels of pollutants present
 are toxic to indigenous species.

         The effect of Fields Brook on the Ashtabula River and Harbor area
 decreases with increased distance.  Low nutrient loading with the exception
 of nitrates from Fields Brook and the presence of small amounts of organic
 material attest to the absence of significant amounts of sanitary wastes al-
 though fecal coliform values are occasionally elevated.

         Organic chemicals and pesticides were not detected in Fields Brook
 or the river, although an unknown organic component was traced from Fields
 Brook to Ashtabula Harbor.

         Mercury and total residual chlorine measurements made in May 1974
 indicate levels which are in excess of Ohio standards and contribute to con-
 ditions which are detrimental to the indigenous aquatic population.   If the
 effluent levels called for by April 1975 are met by local industries, a sig-
 nificant improvement in water quality can be expected in the near term.   Tem-
perature effects have not been considered in permits  granted to date, and this
 situation should be reexamined in light of cooling water discharges  to Fields
 Brook and Ohio State stream standards.   The final permit for the last remain-
 ing industry (which had not received a new permit in  1973)  was expected to be
issued on December 31,  1974.   Lowered levels with respect to chlorine residuals
might be expected to be delayed 1-2 years but should  be at  reduced levels  by
June 1,  1976.   By July  1,  1977,  chlorine residual levels  should be at levels

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which will protect aquatic biota,  if the requirements  of the NPDES permits are
met by industries on Fields Brook.

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                                   Section 4
                               RECOMMENDATIONS
         Based upon the information gathered in this study,  the following re-
commendations are made with respect to the Fields Brook-Ashtabula River area:

         1.    A detailed sampling program should be undertaken to define the
              levels of chlorine present in effluents,  Fields Brook,  Ashtabula
              River and Harbor.   This study should employ an amperometric
              titrator to determine free as well as combined residual chlorine.
              We recommend that the study should begin  in July 1975.   Results
              of a 1973 hearing on the conditions in Fields  Brook indicate a
              considerable amount of public interest in solution of the prob-
              lems associated with effluent discharges.  Compliance with issued
              permits should improve water quality in the area.  An area-wide
              assessment is recommended by State and Federal agencies to evalu-
              ate the environmental condition in the Ashtabula River Basin.
              Results of this assessment could be distributed to the public  and
              include the schedules, construction milestones, and remaining
              abatement actions  which are scheduled by  local industries.  It
              is proposed that this assessment be conducted  during late 1975.

         2.    A detailed, comprehensive study preferably with an on-site analysis
              capability is recommended to be conducted for  mercury to determine
              the source(s) levels and degree of compliance  with water quality
              standards in Fields Brook and the Ashtabula River.  This program
              could be carried on in conjunction with (1) above.

         3.    The theoretical model developed in Appendix 3  should be field
              tested and verified to provide a method for predicting chlorine
              residuals in a flowing stream.

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4.    Based upon data presented here,  the State and Federal Agencies
     should rigorously enforce effluent levels required in existing
     permits.   Because of the presence of potentially hazardous mate-
     rials such as mercury and chlorine, continued surveillance is
     recommended.

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                                 Section 5
                          HISTORICAL DATA ANALYSIS
      The primary purpose of this section is to present available historical
information on the Ashtabula River, Harbor and adjacent Lake Erie areas as
they relate to the present study.  No attempt has been made to draw conclu-
sions as to the historical changes in Lake Erie or to survey lake conditions
as a whole.  Recent papers presenting useful discussions of changes in fish
populations caused by overfishing (Regier et_ al, 1969) and changes in lake-
wide water quality (Beeton and Edmondson, 1972) have been presented, but
relatively little specific data concerning the Ashtabula Harbor area is
available.

Physical and Chemical Properties

      The Ashtabula River Basin encompasses some 137 square miles.  Based
on commerce and total tonnage of all commodities shipped through Ashtabula
Harbor, the harbor is an important deep draft, inland commercial port.  Net
tonnages of major commodities shipped were in excess of 11 million tons in
1971 with a substantial increase in shipping experienced between 1966 and
1971.

      Average flow for the Ashtabula River is approximately 169 cubic feet
per second into Lake Erie; dry weather flow is normally around 10 cfs and
decreases to zero occasionally  (Vol. 4, ACE 1968 Report).  During the period
1-16 September 1973 daily flow averaged approximately 1.5 cfs  (Refer to Table
1).

      The outer harbor of Ashtabula Ohio, encompasses 185 acres, while the
inner harbor extends approximately two miles up the Ashtabula River.  The
outer harbor is enclosed by two breakwaters:  the western (7,780 ft. long)
and the eastern (4,400 ft. long) breakwaters (See Figure 1).

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 *   *   K   f '-~
                                 *   I . t
                                  Source: Great Lakes Harbor Study --
                                  Second Interim Report on Ashtabula
                                  Harbor, Ohio, U.S Army Corp
                                  Engineers, 1965
Figure 1   ASTABULA  HARBOR AREA
                  10

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                                     Table 1
             SUMMARY OF LOW FLOW DISCHARGE DURING SEPTEMBER 1-16,  1973
Date

Sept. 1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Discharge (cfs)

1.5
1.1
0.9
0.7
0.6
4.0
3.5
2.8
1.8
1.3
1.1
1.0
0.81
0.81
0.81
0.73
       Of the 24 major tributaries flowing into Lake Erie, the Ashtabula River
 (Lake Erie Report,  1968) has the:

               1)  smallest  drainage  area (137  mi )
               2)  lowest average  flow (169  cfs)
               3)  lowest recorded 7  day low flow (0.0 cfs)
               4)  fifth  highest percent  runoff from precipitation  (45%)
*Coincides with sampling period - Task II,  this study.   Source:   U.S.
 Geological Survey Water Resources Division,  Columbus,  Ohio
                                       11

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      The small drainage area is reflected in the rather low average flow.
Based on dilution potential alone, the Ashtabula is the least able to
handle large volumes of oxygen demanding wastes.  Steep terrain and soil
characteristics convert a high percentage of the precipitation into runoff
water.

     Only 0.072% of the total water supply to Lake Erie is provided by
the Ashtabula.  The pollutant load based on 1967 figures is shown in
Table 2.

      In an attempt to place the Ashtabula River in perspective, Table  3
was constructed to compare six major tributaries of the Lake Erie  Central
Basin as to their BOD5,  total  solids,  and chloride  content.   This  com-
parison illustrates  that the Ashtabula River  contributes  the lowest pollu-
tant load of any of the  rivers  for which calculations  were  made.   This
indicates that, even though the Ashtabula has the lowest annual average
discharge; it also has the lowest pollutant load.  This observation,  however,
can be misleading unless additional data are examined.  A case in point is
the data for annual minimum flow and data for the Ashtabula River obtained
by the U. S. Geological Survey.   Minimum flow as provided by the Lake Erie
Report (1968)  is 0.0 cfs and the 7-day Low Flow (10 year recurrence)  is
0.0 cfs at the mouth.   Of all  significant U.  S.  tributaries to Lake Erie,
the Ashtabula has the lowest minimum flow and is the only one which has a
value of 0.0 cfs for the 7-day Low Flow (10 yr.).

      The annual minimum commonly occurs during  late August and  September,
a condition which creates conditions in which essentially  the  only flow
recorded, in the river is waste  effluent from  the Ashtabula  industrial
complex.

      Enlargement of harbor areas near the mouth of the river has significantly
reduced stream velocities and thus increased the need for expanded dredging
operations.  Dredgings,  totalling over 345,000 yd  were removed from the
                                       12

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                                                Table 2

                      ASHTABULA WASTE DISCHARGES TO LAKE ERIE 1966-67 (SHORT TONS/YR.)


                                                PARAMETER  (short tons/yr)


Ashtabula River
Lake Erie Totals
% Ashtabula
Contribution

BOD

200
159,480
0.13%
SOLIDS
Total Susp.

24,600 4,600
39,417,213 4,536,548
0.06% 0.10%
Total Nitrogen
(N)

100
167,835
0.06%
Total Phosphorous
(P)

14
27,342
0.05%
Chlorides

2800
4,449,646
0.06%
Source:  Pollution of Lake, Erie, Lake Ontario, and  the  International  Section of the
St. Lawrence River, Vol. 2, Report to the International  Joint  Commission,  1969.

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                               Table 3
TRIBUTARY WASTE DISCHARGES, FLOW AND CONCENTRATIONS LAKE ERIE 1966-67
                     (U.S.  Central Basin Rivers)
RIVER


Ashtabula
Conneaut
Ck.
Grand R.
Cuyahoga
Vermillion
Rocky R.
AVE FLOW
cf/sec

169
257
784
850
228
273
cf/yr

5.33xl09
8.10xl09
24.72xl09
26.8X109
7.19xl09
8.61xl09
WASTE LOADING
TOT. SOLIDS
short -
ton/yr

24,600
45,100
1,510,000
509,000
90,000
160,000
Ib/yr

O.OSxlO9
0.09xl09
3.02xl09
1.02X109
0.18xl09
0.32xl09
poll.
cone.
Ib/ft *

0.0092
0.011
0.122
0.038
0.025
0 . 037
WASTE LOADING
BODS
short -
ton/yr

200
400
1300
8900
200
1400
Ib/yr

4xl05
8xl05
26xl05
178xl05
4 x 105
28xlOS
poll.
cone . ,
Ib/ft

O.VSxlO"4
0.99xlO~4
l.OSxlO"4
6.64xlO~4
0.56xlO~4
3.25xlO"4
WASTE LOADING
CHLORIDES
short -
ton/yr

2800
5700
680,000
79,000
4,400
21,000
Ib/yr

0.056xl08
0.114xl08
13.6xl08
l.SSxlO8
O.OSSxlO8
0.42xl08
Poll.
cone. ,
Ib/ft

10.5 x 10~4
14.1 x 10"4
550 x 10"4
60 x 10"4
12.2 x 10~4
48.8 x 10"4

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harbor in 1968 (ACE Report, 1968).  Local reports indicate that in recent years
no dredging has been done up river from the 5th St.  Bridge, approximately 0.7
miles from the river mouth.

      As mentioned before, sluggish flows, particularly prevalent in
late summer and fall, greatly increase sedimentation near the mouth of
the river with a resultant lowering of water quality in the harbor.  The
time of travel in dredged channels has been estimated to be a week or
more (FWPCA, 1968).
 Flushing  Time  in Ashtabula Harbor
       Flushing  time  in Ashtabula Harbor  is  extremely  variable,  depending

                      1)  Volume of  flow  from  the river
                      2)  Volume of  water in the harbor
                      3)  Circulation patterns within  the harbor
                      4)  Effluent wastewater  volume
Results of  sampling in the ACE  (1968) study indicate that most of the
river  flow  is discharged  through  the northern breakwater opening while  small
amounts are discharged through  the shallow opening  in the east breakwater
near shore.

       Flushing time for the harbor was computed for the period 9-11 May 1967.
During this period, the average flow of the river was 586 cfs  (more  than three
times  the average annual flow).   The sodium ion was chosen as a tracer for the
river water distribution in the harbor because it is not readily removed by
chemical precipitation or biological uptake in this environment.
                                       15

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      Analysis of sodium in the open lake yielded an average value of 13.5


mg/1 selected as a background value.  Harbor samples analyzed enabled selection


of 21.0 mg/1 as a representative sodium concentration.  Samples taken 3/8


mile upstream from the mouth of the river had a mean concentration of 30.6


mg/1.




      The percent volume of river water (V ) present in the harbor during


this period was determined using the relationship:




                   VS   +  VS=(V+V)S
                    rr      n  n     r    n'o
      where:  S   =  sodium concentration in harbor
               o


              S   =  sodium cone, in lake
               n


              S   =  sodium cone, in river
               r


              V   =  % lake water in harbor
               n


              V   =  % river water in harbor
               r
       since  V  =  (100-V  )
              n    v     r
       solving:   Vr  Sr +  (100-V )  Sn  =  (Vr  +  100-Vr)
                      V  S   +  100  S   -  V   S   =  100  S
                      r r       n    r  n        o
                      V   S   -  V  S   =  100  S   -  100  S
                      r r    r n       o        n
                      V  (S  -  S  )  =  100  (S   -  S  )
                       r ^  r   n'        ^ o    n'
                      V   =    100  (S -S  )
                       r             o n'
                                S  -  S
                                 r    n



                      v  = 100 (21.0  - 13.5)  =  100 (7.5)   =  43.86 = 44%


                            (30.6 - 13.5)          17.1
                                       16

-------
      Therefore, 44% of the water in the harbor was river water according to
this calculation.

      Total volume of water in the harbor was determined in the Army Corps
of Engineers study by dividing the harbor into zones of equal depth and
determining the area of each depth by planimeter.  The area times the average
depth equals the volume at L.W.D. or 294,270 X 10  cubic feet.  The total
volume of the harbor at L.W.D. + 2.3 ft. (the value at the time of the
measurements) is 327,321 X 10  cubic feet.   Average daily river inflow into
the harbor was 50,630 X 10  cubic feet.

      Flushing time was then computed from the relationship:

          Flushing time = V "      143,367 X 1Q3 cubic feet
                          Q~ =    50,630 X 103 cu.  ft./day

where Vr = 43.86%(from above) of 327,321 X 103 cu, ft,

           or 143,367 X 103 cu. ft.

      Q  = discharge (daily river inflow)

      Assuming a flow of river discharge along a path 1200 feet wide from
the river mouth to the harbor entrance, and further assuming that 80% of
the river flow followed this path, the Path Flushing Time was calculated
at 29.8 hours (ACE, 1968) under the flow conditions at that time (higher
than average flow).

       From the  analysis  performed  in Ashtabula Harbor,  it is  apparent  that
 flushing time calculations  cannot  be generalized in  these circumstances
 because of several  factors:

                     1)   lake levels
                     2)  wind direction and  set-up
                                      17

-------
                     3)   river discharge
                     4)   presence of "dead spots" on the bottom

      Further, this technique is difficult to evaluate because it is not
known where the discharge values were taken,  i.e., gaging station upstream
or at the river downstream of several additional outfalls, particularly
Fields Brook.

      Since the Ashtabula River discharge decreases to nearly zero during
low flow periods, the technique used in the Army Corps of Engineers report
would be difficult to apply unless simultaneously the following parameters
are known:

      1}  Concentration of sodium in the river,  harbor and lake,
      2)  Discharge including river (upstream)  Fields Brook and
          other contributors.

      Data examined  from  the STORE!  system was  inadequate to attempt to
construct a profile  of values  for different discharge conditions.   These
data, particularly low flow  flushing times, would be valuable as  indicators
of "worst case"  conditions existing  in the waterway,

 Dispersion of Pollutants  in  Lake

      Mixing  patterns  of  tributary  discharges with  lake  water  are
 extremely  important  if the net effect  of pollutants  released is  to  be
 determined  (FWPCA,  1968).  The following are important considerations  in
 determining mixing patterns:

                       1)  thermal  structure
                       2)  bottom and  shoreline topography
                       3)  prevailing  winds
                       4)  longshore currents
                                       18

-------
      Generally speaking, tributary discharges on the southern shore tend
to stay near shore and move eastward primarily as a result of the prevailing
south westerly winds during the spring and summer.  However, in the fall
and early winter, similar discharges may under-run the lake water and be
distributed over the entire basin Cp. 75, FWPCA, 1968).  Temperature
differences, however, may override density differences due to dissolved
solids in allowing river water to flow over lake water (p. 51, FWPCA, 1968),

      The fact that the Ashtabula River exerts an important influence on Lake
Erie was found in a study by the Department of Health,  Education,  and Welfare
(1965).   As evidenced by coliform counts in the HEW study, the river exerted
an influence on Lake Erie water quality 1.5 miles from the mouth during flow
of 5.1 cfs (low flow).  Higher flows should create a greater sphere of influ-
ence and thus seasonal variations in river water quality,  as well as Lake
Erie water quality in the vicinity of the harbor.  Distribution of several
measured parameters lakeward from the harbor area suggests that increased
river discharge combined with the predominant eastward current flow of the
lake produces a significant influence that may extend for 2-3 miles or more
from the harbor entrance, at least during peak flow (ACE,  1968).

      Former practices for discharging dredged materials  offshore in the
Ashtabula area could detract from water quality if they were to be continued.
The discharge of dredged materials on the Canadian side of Lake Erie takes
place in deeper waters and further offshore because Canadian regulations
require dredging contractors to dispose of dredging spoils in "water no less
than 15 meters (50 ft.) nor within three miles of dredging site" unless faced
with unusual conditions (IJC, 1969).  Most dredgings from Ashtabula have pre-
viously been discharged in an area two miles or less northeast of the harbor
entrance (ACE, 1968).  Therefore, aggravation of the existing situation may
take place during dredging and dredge disposal.  Current U.S. Army Corps of
                                                             **.
Engineer plans call for construction of a diked disposal  site on the outside
of the west breakwater.  At the time of preparation of this report, construc-
tion of the site had not begun.  Dredging has not been performed in Ashtabula
Harbor in the past two years.

                                      19

-------
The Aquatic Community at Ashtabula,  Ohio

Plankton - A search for literature pertaining to the phytoplankton of the
Ashtabula River yielded very little specific information.  A 1950-51
survey  (State of Ohio, 1953) inspected  the phytoplankton and benthos in
Ashtabula Harbor, as well as toxic effects of river water on Daphnia magna,
a  cladoceran zooplankton  (Class Crustacea, Phylum Arthropoda).  Poppin
(State  of Ohio, 1953) found only one of fourteen samples of river water,
which was obtained from the Ashtabula Harbor bridge (probably the 5th St,
bridge) to be toxic to Daphnia;  50 percent were immobilized in 96 hours,
Sullivan  (State of Ohio,  1953) identified phytoplankton collected from the
mouth of the Ashtabula River.  Samples  of water from the lake, river mouth,
and upstream (probably  =0.7 miles) had phytoplankton concentrations of
8.48, 4.27 and 3.02 X 108 p , respectively.

        Lake water in the  area contained the diatoms Melosira, Stephanodiscus,
Fragilaria, and Asterionella in order of dominance.  Water samples obtained
from the harbor yielded the same plankters in the same order of dominance,
a  phenomenon explained by Sullivan to be due to influx and mixing of lake
water and river water.

Phytoplankton  - Lake Erie phytoplankton exhibit classical vernal
and autumnal phytoplankton maxima, separated by winter and summer minimum.
Spring  maximum exceeds the fall maximum in abundance of phytoplankton, but
usually lasts for a shorter time.  Davis (1964) has shown that over  the
years at Cleveland there  is a consistent lengthening and intensification of
fall and  spring maxima, and a shortening of summer and winter minima.
Table 4 gives average phytoplankton populations for the Central Basin of
Lake Erie.

        Davis (1962) summarized literature concerning dominance in the three
major basins.  All investigators agree  on dominance of diatoms in winter
and spring except Verduin (1960) who listed green phytoflagellate Chlamydomonas
as an important item in addition to the diatoms.

-------
                               Table 4
AVERAGE PHYTOPLANKTQN POPULATIONS OF THE CENTRAL BASIN OF LAKE ERIE
  (ORGANISMS PER ml, CLEVELAND PROGRAM OFFICE DATA, FWPCA, 1968)
Type of Algae

Diatom
Blue-green
Green
Flagellate
Total
Diatom
Blue-green
Green
Flagellate
Total
Diatom
Blue-green
Green
Flagellate
Total
Diatom
Blue-Green
Green
Flagellate
Total
Season

Spring
H
H
it
it
Summer
"
"
"
it
Fall
"
"
11
"
Winter
11
it
"
it
Abundance (# of Org/ml)

238
91
81
51
461
45
101
137
32
315
284
12
180
28
504
391*
20*
177*
58*
646*
Data averaged from all stations.
                                21

-------
      Studies of plankton from the years 1928-1951 also showed a summer
dominance of diatoms, occasionally along with chrysophyte phytoflagelate
Dinobryon.  Davis (1962) and Verduin (1960) showed that Ceratium hirun-
dinella, phytoflagellates, and Pediastrum to be of great importance, some-
times along with diatoms, sometimes without them.   In many studies, fall
months have shown a tendency to have larger quantities of green and blue-
green algae, usually with admixture of diatoms.

      Davis (1964, 1965) has shown that the total  quantity of the phyto-
plankton in the central basin of Lake Erie has increased steadily over the
years, according to records taken by the Cleveland Division of Water and
Heat.  In daily records for 13 of the years between 1919-1934 counts exceeding
4 X 10  cells/liter occurred twice, whereas counts of in excess of this
number occurred in all but one of the 19 yrs for which records are available
between 1934-1964.  Average years for which data were available indicated
a regular increase from a low of 81,000 cells per liter in 1928 to 2,423,000
cells per liter in 1962 and 2,578,000 per liter in 1964.  Davis (1965) showed
that between 1927-1964 the annual average of the phytoplankton increased at
a mean rate>of 44.3 cells/ml/yr, but between 1956-1964 the mean rate had
increased to 122.0 cells/ml/yr.  These rates and totals were thought to be
an indication of rapid and increasing eutrophication of the lake, sped
undoubtedly by enrichment with domestic, industrial, and agricultural wastes.

Zooplankton.  The zooplankton in the Great Lakes have been studied quantita-
tively but much less than the phytoplankton.  As with the phytoplankton,
historically more studies have been undertaken in  Lake Erie than in the other
Great Lakes (Davis, 1966), although recent work indicates that this trend has
changed.

      Protozoans have  formed only a minor portion of the total zooplankton
as a rule.  Burkholder  (1960) found Vorticella attached mainly to  colonies
of Anabaena to be the  most abundant, with Difflugia common in the  eastern
                                       22

-------
and central basins  1928-30.  Chandler  (1940)  listed  in  addition Codonella
cratara as conunon in the warm months of  1939.  Davis  (1954b) described
Vorticella and Codonella as the most common and regular of  the protozoans
in the Cleveland Harbor area in 1950-51  with  Tintinnidium also common at
times; Codonella became very abundant  in the  summer  and fall of 1951, the
mid summer maximum  containing an average of 248 per  liter.  On September
30, 1951, Codonella dominated the  zooplankton with an average of 1,130
per liter, and in one sample there were  3,500 per liter.

       Rotifers tend to be abundant in the spring and the fall in central
Lake Erie studies.  The most abundant  rotifer species in all of the
studies included Polyarthra sp., Keratella cochlearis (Burkholder, 1929 a,
b, 1960; Ahlstrom,  1934; Chandler, 1940; Davis,  1954,  1962; Williams, 1962).

       In addition, Burkholder found Chromogaster ovalis to be abundant
at times, as did Ahlstrora (1934) for Synchaeta sp.,  Filinia longiseta and
Brachionus angularis; Chandler (1940)  for Synchaeta; Davis  (1954), for
Synchaeta sp; Davis (1962) for Conochilus unicornis.

       Three-seasonal quantitative studies of Lake Erie zooplankton have
shown both summer and autumnal maxima  of the  Cladocera, a judgment supported
by Wright (1955).   In studies by Davis   (1954, 1962), the summer cladoceran
maximum occurred in June and coincided with the extremes of the phytoplankton
minimum.  According to Davis (1966), the genus Daphnia has been the most
important, both because of size and abundance.  Several authors have listed
Daphnia retrocurva  as the most abundant  daphnid in Lake Erie (Davis,   1954,
1962;  Bradshaw, 1964;  Bigelow 1972).

       Of non-daphnid cladoceran genera, Diaphanosoma, Bosmina, and
Leptodora are most  frequently listed as  common or abundant  (Davis, 1966).

       The calanoid copepods that have been listed regularly for Lake Erie
consist of five or six species of Diaptomus,  one of Epischura,  and one of
Limnocalanus.   The most abundant calanoids have been the diaptomids
particularly Diaptomus ashlaudi,  D. oregonesis and D. siciloides (Davis,  1966)
                                       23

-------
Several studies have shown that Diaptomus siciloides was rare in 1928-30,
present but limited in 1939, but by 1946-47 in the western basin and
1956-57 in the central basin, common during the warm months in all three
basins.  This development is considered significant because it is an
indication of fundamental changes in the lake itself.  D. siciloides is
known primarily as an inhabitant of ponds and warm eutrophic waters
(Davis, 1966).

Macrofauna
        According  to Henson  (1966),  the  Great  Lakes have  the following
approximate  number of species  of major  animal  groups:
                                          No. of Species in
                 Taxon
                                            the Great Lakes
               Porifera                 '       2
               Oligochaeta                     10
               Turbellaria                     10
               Ostracoda                       11
               Isopoda                         3
               Amphipoda                       7
               Gastropoda                      60
               Pisidium (Pelecypoda)           17
               Sphaerium (Pelecypoda)          10

               Benthic fauna reported present for Lake Erie (Henson,  1966 ;
Carr and Hiltunen, 1965).

               Crustacea                   Pontoporeia
                                           Gammarus
                                           Hyalella
                                           Asellus
                                           Mysis  relicta
                                       24

-------
Insecta
Hexagenia
Ephemera
Ephoron
Oecetis
Procladius
Coclotanypus
Cryptochironomus
Tendipes
Pelecypoda
Sphaerium  (4 species: S. corneum
                      S. occidentale
                      S. striatinum
                      S. transversum )
                      S. lacustre
Pisidium (7 species:  P. amnicum
                      P. casertanum
                      P. compressum
                      P. henslowanum
                      P. nitidum
                      P. punctatum
                      P. subtruncatum

Lampsilis
Anodonta
                         Elliptic)
Gastropoda
Amnicola
Bithinia
Campeloma
Goniobasis
Heliosoma
Physa
                         Pleurocera
                         Somatogyrus
                         Stagnicola
                         Valvata
                         Bulimus
                         25

-------
      Tables 5 and 6 provide a breakdown of benthic fauna found in
the Ashtabula River (stations 18, 19), harbor (20, 21, 22, 23) and lake
dredging disposal site (station 9 encircled by stations 1-8).  It is
interesting to note that the pollution sensitive mayfly larvae CHexagenia
sp.) were found at a few stations in mid-lake of the central basin but
only at one station (northeast of Ashtabula off  the southern shore in a
1963-64 study (FWPCA,  1968).

     'Brown (State of Ohio, 1953) investigated the benthos of Ashtabula
Harbor in 1950-1951.  He described the bottom sediment as "organically
rich, dark colored muds".  Brown reported 210 tubificids for 36 in  of
sediment.  Of ten rivers studied, only the Maumee and Black River sediments
contained higher amounts of tubificids.  Genera isolated from the Ashtabula
Harbor sediments were:

                   Chironimidae  (midge larvae)
                   Elmis*  (beetle larvae)
                   Herpobdellidae (leeches)
                   Musculium transversum (Mollusca)
                   Pisidium sp.  (Mollusca)
                   Tubifex sp (Tubificidae, Oligochaeta)
                   Limnodrilus sp (Tubificidae,  Oligochaeta)

      During Spring 1967, two harbor stations were sampled for benthic
fauna at Ashtabula  (ACE, 1968).  In all samples from the lake, harbor
and river, Oligochaetes  (Family Tubificidae) were the dominant organisms.
The Tubificid species Peloscolex multisetosis (Smith) was reported in all
samples and averaged 0.7% of river Tubificids, 1% of harbor, and 4-6% of
spoil Jump-ground Tubificids.  Examination of the study data indicate that
the harbor samples had the lowest variety of organisms with mollusca and
Chironomus (midge larvae) as the only significant organisms present in
addition to Tubificids.
*
  Misclassified, Elmis is actually a European genus not found in the
  Great Lakes.
                                       26

-------
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CRUISE
AND INDIVIDUALS PER SQUARE METER OF BOTTOM
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EXCL. PELOSCOLEX
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-------
                                                           . Table 6
                                          BENTHIC FAUNA AT DISPOSAL  SITE,  ASHTABULA, OHIO
               w
               o
             Ss-. w
             W D,
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                                                            H
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                                                                  M := (V,
                                                                  Q U W
                                                                                                                REIARKS
K)
00
CRUISE
 AND
STATION
                              INDIVIDUALS
     PER    SQUARE
      11ETER
                                      OF
                                                           BOTTOM
         A6702-01
         A6709-01
         A6702-02
         A6702-03
         A6702-04
         A6702-05
         A6703-06
         A6709-06
         A6703-07
         A6709-07
         A6703-08
         A6709-08
         A6702-09
           1650
           2375
           2025
           5425
           7425
           8800
           1950
           2525
           3175
           1700
           3550
           6025
           1475
 75
225
175
350
275
 25
200
300

 50
550
25
25
25
25
  75
  50

  50   100
175
 25
150

100
 50

175
250
         A6709-09   800
 50
200
250
375
325
375

125
100

125
250
 50

 50
                           25

                           25
                           25
                                       25
                                       50
                                       50

                                       75
                                       50
                                       25
                               75
                                                          25

                                                         125
                                                          50

                                                          25
                                                          25
                                     25
                                                  50    100

                                                  50
                                                  25
                                                        50
                                                        25
                                                        75
                                                        25
                                              25
                                             175
                                             375
                                             225
                                             425
                                             100
                                             275
                                             225
                                             100
                                             575
                                             450
                                                                   +25 Amnicola Sp7
                                                                   +25  Amnicola?
                                                                   Slope  location
                                                                      sand bottom
                                                                   Slope  location
                                                                      sand bottom
             SOURCE:   Dredging  a"d Water Quality Problems in the Great Lakes, Vol.  4,  U.  S.  Army Corps Engineers  (1968).

-------
      There has been relatively little attention to macroinvertebrates
in Lake Erie and tributary streams.  Some attention, at least in terms
of noting the population characteristics of bivalves and crayfish,
should be given.  Other invertebrates, e.g.,  Eurytemora affinis,  a euryhaline
copepod, are now apparently established in Lake Erie and harbors  (Eugel, 1962),
but no quantitative information is available.

      The 1967  U. S, Lake Survey  (ACE, 1968) also included a study
of the macrofauna in the Ashtabula River and Harbor,

      Organisms were collected and identified  at two stations in the
river, five in  the harbor, and nine in the lake "dumping ground".

      Organisms which were found  in the river  and harbor stations
included:

                   Oligochaetes  (Family Tubificidae)
                 --  Molluscs
                   Chironomus (midge larvae)

      Organisms which were found  in the macrofauna of the lake include;

                     Oligochaetes
                     Sphaerids
                     Gastropods
                     Chironomus  (tendipes sp.)
                     Leeches (Helobdella stagnalis, H. fusca)
                     Nematodes

      It was concluded by the ACE (1968)  study that judging from the
number of variety of fauna present that the Ashtabula river samples
indicated a polluted environment.   For example, the only living organism
other than the pollution tolerant Tubificids  (sludge worms)  found in the
                                      29

-------
river sediment  consisted  of  one  sphaerid  clam  (genus  Pisidium).  Tubificids
found on the river bottom were much darker  in  color and  twice  as large  (1")
as those found  in the open lake,    In contrast to the river,  stations  in
                                                         2
the harbor  exhibited populations of 25,000  individuals/m and  also  exhibited
a greater variety of organisms.  All harbor stations  had sphaeriid  clams,
although a  station at the mouth of the river appeared to have much  fewer
individuals than all other harbor locations.
 Recent Data - The dominance of diatoms during cooler months and of green algae
 in  summer at Lake Erie water intakes located at Ashtabula, Ohio, was estab-
 lished during a five-year study  (Reitz, 1973).    Phytoplankton at Ashtabula,
 as  well as other Lake Erie intakes, have decreased in abundance during the
 1968-1972 investigations.  Tables 7 and 8, taken from the Ohio EPA report show
 the annual phytoplankton standing crop for 1968-1972.  Table 8 compares
 average yearly phytoplankton of  nine areas in Lake Erie.   Green algae  domi-
 nance began as early as June and persisted as late as November.  Dilution of
 plankton concentrations by rising Lake Erie waters could account for the
 reduction in cell numbers.  However, decreases in enrichment of the water
 may  also explain the reversal in eutrophic conditions.  Low cell numbers as
 reported by the Ohio EPA and as noted in this study may attest to the effect
 of  industrial discharges on nearshore and harbor areas like Ashtabula.

      Sediment within a 1000 ft radius  of the water intake was  grey-brown
 sand, silt,  and gravel.   Biota included tubificids, sphaerids,  amphipods,
 chironomids,  ephemeropterans,  prosobranchids, pulmonatans,  hydra,  and
 Bryozans.

 Pollution Indicators - A dependable index for the classification of
 the extent of pollution has not emerged yet.   Many have used the types
 of phytoplankton present to evaluate the eutrophication of a water body.
 (Davis,  1964;  Williams, 1972;  Meyer, 1971).  Others have considered a
 tubificid dominance to be indicative of organic pollution (Brinkhurst and
Jamieson,  1971; Aston, 1973),   The percentage of Limnodrilus hoffmeisteri
                                       30

-------
                                                       Table 7

                      Phytoplankton standing crops and percent dominant group.  (Values repre-
                      sent number of cells per 100 ml.) Code for % abundance is as follows: D = diatoms,
                      BG = Bluegreen, G = Green, Fl = Green flagellate, FLO = Flagellate (others).
StationAshtabula

Month      1968    % abund
1969    % abund
1970   % abund
1971    % abund
1972   % abund
Jan
Feb
Mar.
Apr
May
June
July
Aug
Sept
Oct
Nov
Dec


3784
5278
1 193
295
520
410
325
538
208
205


94D
84D
59D
43G
69G
31G
73G
64G
55G
68D
166
582
3015
1010
577
81
323
341
490
360
247
548
61D
82D
93D
74D
76D
50G
79D
61G
59G
47D
50D
71D
1080
1282



36
163
504
328
236

219
100D
92D



75G
39G
68BG
66G
35D

60D

45

1310
356
136
377
320
183
680
247
378

40D

100D
46D
60D
76G
46D
35D
68D
52D
60D
160
85
280
447
246
134
138
100
212
291
285
82
58D
84D
98D
99D
72D
60G
SOD
82G
70G
42D
47D
560
                                                      Source:   Distribution of Phytoplankton and Coliform Bacteria in Lake Erie,
                                                              Ohio Environmental Protection Agency, March 1973

-------
                                                                   Table 8
                  Station
                                                         Yearly phytoplankton averages. Values represent the #
                                                         phytoplankters/100 ml.
                                       1968'
1969
19702
197V
1972
KJ
Toledo
Port Clinton
Sandusky
Vermilion
Cleveland Crown
Loram
Cleveland Division
Cleveland Eastlake
Pamesville
Ashtabula
4,870
6,822
1,970
1,358
1,059
15,554
965

1,739
1,276
2,155
2,956
1,093
856
449
686
395
588
728
645
1,198
1.820
1,022
'755
666
788
558
570
902
481
2,070
1,474
1,891
609
476
673
333
1,070
703
403
513
1,079
1,142
582
364
565
404
312
320
205
                                                         1  January, February missing
                                                         2  March, April, May,  November missing
                                                         3  January, March, June missing
                                                                        Source:  Distribution of Phytoplankton and Coliform Bacteria in Lake Erie,
                                                                                Ohio Environmental Protection Agency, March 1973

-------
(common Oligochaete) in relation to the total number of oligochaetes may
be a very useful guide to the degree of organic pollution in a locality
(Brinkhurst, 1967; 1969),  In grossly polluted situations, the number of
oligochaetes stays hign with representatives of other groups absent or
scarce.  The central basin of Lake Erie is dominated by Peloscolex ferox,
a different  species but  same genus,  found  in river  sediment samples from
the Ashtabula  River.  Species of oligochaetes appear to be characteristic
of pollution levels as well as  temperature to some  extent.

       Heavy  sewage  and organic  pollution are often  associated with high
numbers  of Tubifex  tubifex and  Limnodrilus hoffmeisteri.  These organisms
are able to  adapt their  respiration  to withstand  low oxygen concentrations,
or even  anaerobic conditions for up  to four weeks  (Aston, 1973).  L. Hoff-
meisteri is  able to reproduce under  very low oxygen conditions as well.

       Diatom community structure has been  accepted  by Williams (1972) and
others as indicative of  water quality.  These less  obvious organisms show
high  diversity in cleaner waters,  and high numbers  of a few common, tolerant
species  under  conditions of pollution.  They are  easily identified by the
wall  structures and readily available in plankton samples.

       Prominent species  of the  clam, Pisidium, are  little known as to
their  depth, temperature or pollution dependence, although twice as many
species  are  found in Lake Erie  as  in Lake  Ontario.  According to Brinkhurst
(1969),  the  trend and tolerance of these fresh water clams might be very
useful indicators to environmental conditions.

Coliform - In addition to the coliform counts available in the  STORET system,
information in the ACE Dredging Report (1968)  indicates  that  the  normal
lake background of coliform bacteria varies but  usually  averages  about
100/100 ml.   About one and one-half miles from the Ashtabula  River,  values
were 150/100 mi in 1964  (HEW,  1965).    Total coliform counts  near the  city
water intakes averaged approximately 250  and 490 organisms per 100 ml  for
1971  and 1970 for the data examined here  (EPA,  1972, 1971).   East of the
City's sewage treatment  plant a count of 920/100 ml was  obtained  in 1968.

                                       33

-------
Dumping of dredged material from the river and harbor in the past has not
aided the situation and at least raised the count during the short term
the samples were taken.  Scarce e_t al_. (1964) showed that coliform can
persist in the vicinity of dumping areas for some time.

       Figure 2 illustrates median coliform  concentration in surface samples
 in Lake Erie  1963-64.  An interesting pattern emerges showing a vast area
 in the central basin where median values of total coliform are less than
 1 organism per 100 ml while it has been reported that median values of  total
 coliform  levels in the mouth of the Ashtabula River and harbor have
 exceeded  1000 organisms per 100 ml (FWPCA,  1968).

       To  illustrate coliform data available for the Ashtabula area, sample
 STORE! data for the period 1963-1964 is shown in Table 9.
                                     Table 9
                          STORET COLIFORM DATA (1963-1964)
STORET STATION

380142

380141
380137

380136

MILE PT.

3.3

2.3
0.70

0.0

DATE
1/8/64-11/25/64
4/15/64-11/25/64
1/8/64
10/16/63-11/25/64
4/15/64-11/25/64
10/16/63-10/28/64
4/30/64-10/28/64
MEAN TOT.
COLIFORM/
100 ml
9998

9500
74,637

8073

FEC. COLIFORM
MFM-FCBR/100 ml


1537


32894


                                         34

-------
CO
CTI
                                                                                                                      < I ORGANISM /lOOml
                                                                                                                      1-10 ORGANISMS /lOOml
                                                                                                                      IO-IOO ORGANISMS/lOOml
                                                                                                                      IOO-50O ORGANISMS/lOOml
                                                                                                                      bOO-l,OOO ORGANISMS /lOOml
                                                                                                                      I.OOO-2.4OO ORGANISMS /lOOrnl
PENNSYL V A N I A
                                                                                    Suiuce l*ioteedinys Pollution o(
                                                                                        tut- aiul lu
                                                                                    F w IJ C A . Otpi Inieiior.
                                                                                                                     MEDIAN COLIFORM
                                                                                                                    CONCENTRATION   IN
                                                                                                                   SURFACE SAMPLES  OF
                                                                                                                       LAKE  ERIE
                                                                                                                          1963-64
                                Figure  2   Median Cohform  Concentration  in  Lake  Erie (1963-1964)

-------
Water Chemistry

      Extensive literature research concerning the water quality of the
study area turned up very little in the way of published articles with
the following exceptions:  STORE! data, the ACE report (1968), IJC Report,
V. 2 (1969) and the FWPCA Report (1968).  Most of the published data
concentrates on Ashtabula Harbor, the nearshore area, and the Central Basin
of Lake Erie.  The U.S.G.S. Water Resources Division headquartered in
Columbus has installed a continuous flow analytical device which samples
and provides analysis for temperature, conductivity, pH and dissolved oxygen.
This sampling station is located at Jack's Automarine at approximately the
0.8 milepoint of the Ashtabula River.

      Revised water quality standards for Ohio were adopted by order of the
Director of the Ohio Environmental Protection Agency on 27 July 1973,  On
9 August 1973, these standards were submitted to Francis T, Mayo, EPA
Regional Administrator for approval.   Standards were being revised again
in late 1974.  This is discussed under the heading, "Sampling Program",  in
Section 6 of this report.

      The U. S. Lake Survey (ACE, 1968) surveyed water quality at several
points in the Ashtabula area in 1967 during average discharge of 385 cfs.
Although station depths were not given, it is probably safe to assume surface
samples were taken. These data tend  to be somewhat in agreement with other
data except for conductivity.   Table 10 lists parameters measured and their
concentrations.  All river sample stations (2) were located between mile point
0,8 and the mouth of the harbor.  Other sample stations were located in the
harbor and in Lake Erie  (nearshore).

      The Army Corps of Engineers Dredging Report also lists several harbors
along Lake Erie and a table comparing Ashtabula Harbor to Erie, Fairport,
Cleveland, Lorain, Sandusky and Maumee Harbors is included here (Table 11).
The concentrations of most parameters are in agreement with previous work
with the exception of conductivity and pH.
                                       36

-------
                                                            Table  10
                                                   1967 U. S. LAKE SURVEY.STUDY
                                                        ASHTABULA RIVER
                                          SAMPLING DATES:  9,  10,  11, 15, 16, 17 MAY 1967
                                RIVER DISCHARGE:  low  120 cfs  (5/15); Hi 780 cfs (5/11); AV. 385 cfs
mg/1 (UNLESS OTHERWISE SPECIFIED)
Station

18
19
20
21
22
23
24
25
26
38
Location

River
River
Harbor
ii
it
ii
M
Lake
M
n
pHa'

RIVER/HARBOR 6.83-7.31
LAKE 8.06-8.11
D.O.

RIVER/HARBOR 99-103% SAT.
LAKE 99-100% SAT.
Tot.Alkb<

28
27
66
50
59
64
94
92
Sp. Cond.
(Micromhos)

330
362
355
345
347
355
--
Eh. (volts)

0.075
0.088
0.085
0.083
0.108
0.076
0.126
0.086
P4

0.2
0.2
0.2
0.2
0.2
0.1
0.2
0.0
0.0
N03

2.0
1.6
2.7
2.0
2.5
1.9
1.7
2.4
2.0
so4

33.8
35.5
34.5
35.8
33.7
36.5
34.0
29.5
32.5
C1C"

58,3
64.6
43.1
49.6
44.4
43.6
--
--
Si02

3.2
3.3
1.0
2.1
1.7
1.5
1.0

--
Ca

39.2
40.1
41.4
40.4
41.2
42.1
40.4
41.8
40.6
Mg

5.3
5.6
7.2
6.4
6.9
7.0
6.7
8.8
8.6
Na

26.3
30.6
20.2
22.5
21.8
21.8
20.5
IS. 6
13.5
K

2.3
2.5
2.2
2.S
2.4
2.0
1.2
1.4
1.0
a.   Acidic water flowing from Fields  Brook  during  this  same  time  averaged  2.9.
b.   Low alkalinity in river related to  acidic  discharges  from Fields  Brook.
c.   -Cl range of 85-539 mg/1 found in river between Fields Brook  and  station  19.
     -Fields Brook ran 681-1854 mg/1.
     -Upstream "background" levels ran 28-50 mg/1.
REFERENCE:  Dredging and Water Quality Problems
In The Great Lakes, Vol. 4 U. S. Army Corp
Engineers, (1968).

-------
                                                Table  11
                                 WATER QUALITY-NEARShORE
iLITY-NEARShORE AND
 (mg/1 or ^mhos/en)
ID HARBORS
Parameter
Cond (E5C)
DS
TS
Chlor.
Sol PO,
sou
SiOp
K
Mg
Ca
Na
ABS
Alk
pH
Temp
DO*S
BOD
COD
Phenol
Total N
Org N
Aram N
Nit N
Michigan
waters of
Lake Erie
Min Max



27 82
.05 .20






<.025
78 157
8.U 9.2




o.o 0.058

0.20 0.30
0.20 0.30
0.11 0.91
Jteumee
Bay
Min Max
28o U6o
200 290
200 350
20 32
.02 ,19

0.6 1.7
l.U 2.6
12 18
35 1*2
12 20
.05 .15
86 120
7.14 9-7
21 25
60 95
1.5 fc.O
12 53

.82 3.145
.07 1.33
.30 1.80
.00 .80
/
Sandusky Lorain Cleveland Fairport Ashtabula Erie
Bay Harbor Harbor Harbor Harbor Harbor
Min Max Min Max Min Max Min Max Min Max Min Max
256 800 300 31*0  330 5920  330 360
190 680 160 230 180 370 l80 6000 170 230 180 290
210 760 170 270 180 680 190 6lOO 180 250 200 290
16 32 19 25 1U 88  2k k2 26 38
.02 .17 .02 .11   .02 .06 .01 .03
25 256 27 37 --   26 liU
0.3 5.9 .1<0 1.10    .3 .5
1.2 J.0 1.3 2.2   -_ i.U 1.9
10 38 9 11   9 9
38 llU 3U 38  ~ -_ 1,2 U7
10 16 10 13 --   17 21
.05, .20 .05 -15    .07 .lfc
87 '120 83 99 81 130 90 110 9U 100 90 96
7.5. 9-1 7.5 8.7 6.7 9-5 7.1 8.7 8.2 8.5 7.3 8.1
23 26 2U 25 16 21 23 29 15 17 l6 19
65 115 80 95 70 95 80 130 95 110 Avg. 60*
2.1 6.3 1.0 2.3   2.0 5.6 Avg. 3.3
13 'i2 10 28 8 22 8 12 7 11 Avg. 2U
  .*. .. *._
.82 3.50 .50 U.20  .66 .80
.53 2.30 .01 1.10  .29 .1*9 .30 .59
12 .90  .03 1.55 .12 .23

 *->j. JL . ou uu  . yu  .07 !**
SOURCE:    Dredging and Water  Quality Problems of the Great Lakes, Vol. 4, U. S. Army Corp Engineers  (1968)

-------
       Water Chemistry data compiled from the Cleveland Program Office of
 the then FWPCA (1968)  in 1963-64 and 1967-68 are reprinted here for comparison
 (Table  12a,  12b).  These tables  give data for the Western, Central and
 Eastern Basins of Lake Erie.   For purposes  of this  study,  the  values in
 the Central Basin are  emphasized because the Ashtabula is  a  tributary
 of the  Central Basin.   With respect to  every parameter except  nitrate
 nitrogen (% change -44.4%),  chlorides  (-4,2%) and silica  (-45,6%), the
 values  of measured substances  increased by  3-100 percent.  Soluble phos-
 phorous  (ortho phosphate)  increased the  greatest (100  percent)  over  the
 four year period.  The  data  are  particularly important with  respect  to
 phosphorous  which  is usally  listed  as a  limiting factor in algal growth.

      The ACE  study also compared several parameters measured  during dredging
 to  National  Water  Quality  Standards  (Table  13).   These data, for the parameters
 measured  (pH,  DO,  DS)  indicate   that surface waters were within applicable
 limits.   Determinations of metals  content,  suspended solids, organic  chemicals,
 etc. were not  made however.  Samples taken  during dredging  (new work) in
 Ashtabula Harbor were  analyzed as part of this study.  New work dredging
 effects  are  expected to be minor  because of  the nature of the material
 dredged.


      The use of data contained in Tables 10,11,12   13 will  serve  as a  bench-
mark for  "background levels" to be compared with data obtained'in this effort.
 It is important to note that almost all samples  collected for the Lake Erie
 1967-68 study were taken along an east-west survey route while the  1963-64
Lake Erie study incorporated nearshore as well as mid-lake samples  in north-
south traverses of the lake.
                                      39

-------
                  Table 12
WATER CHEMISTRY  COMPARISONS  1963-64  -  1967-68
       (Cleveland  Program Office  Data)/

                                    L
Western Basin %

Conductivity
Dissolved Sol Ids
Total Solids
Chlorides
Silica
Soluble Phosphorus
Total Phosphorus
Total Nitrogen
Organic Nitrogen

1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
max.
364
,370
2-20
247
250
356
34
26
5.0
1.87
0.33
0.10
0.19
2.66
1.98
0.71
mi n .
196
2,38
1 10
135
140
143
10
10
0.3
0.43
0.00
0.01
0.02
0.17
0.27
0.07
avg. Change
272
285 +4.8
162
170 +4.9
181
188 +3.9
21
19 -9.5
1.20
1.06 -1 1.7
0.03
0.04 +33.3*
0.06
0.71
0.74 +4.2
0.36
0.37 +2.3
r .
Central Basin %
max.
353
330
239
283
2/8
307
46
29
9.6
0.98
0.07
0.03
0.05
1.30
0.95
0.78

mi n .
260
283
137
147
159
153
19
19
0.2
0.15
0.00
0.00
0.01
0.07
0.28
0.12

avg. Change
300
312 +3.7
178
196 +10.1
185
202 +9.2
24
23 -4.2
0.68
0.37 -45.6
0.01
0.02+100.0*
0.02
0.43
0.47 +9.3
0.25
0.32 +28.0*

Eastern Basin %
max.
328
333
233
297
240
308
31
28
3.5
0.72
0.04
0.02
0.08
1 . 18
0.75
0.55
mln.
284
310
150
138
167
175
21
24
0.2
0.18
0.00
0.01
0.01
0.10
0.30
0.21
avg. Change
301
318 +5.6
179
204 +14.0
188
220 +17.0
24
25 +4.2
0.47
0.37 -21.2
0.01
0.01 0.0
0.02
0.42
0.47 +11.9.
0.24
0.34 +41.6"
Total
Lake Avg.
298.9
312.6
177.6
197.3
185.8
207.1
23.9
23.4
0.64
0.40
0.011
0.018
0.022
0.44
0.48
0.25
0.33

-------
                                       Table 12  (Cont'd)
                         WATER CHEMISTRY COMPARISONS  1963-64 -  1967-68
                                 (Cleveland Program Office Data)


Western Basin %

Ammonia Nitrogen
Nitrate Nitrogen
Chemical Oxygen
Demand
5-Day Biochemical
Oxygen Demand
Alkalinity
Eh
PH
" Eliminated from

1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
1963-64
1967-68
average to
max.
0.77
0.56
1.50
0.96
29.0
18.9
4.1
240
105
560
8.8
Insure
mi n.
0.01
0.04
0.02
0.01
I.I
5.5
0.4
57
75
474
7.6
statl
avg. Change
0. 16
0.17 +6.3
0.12
0.20 66.7*
'0.4
9.8 -5.8
1.7
99
90 -9.9
511
8.3
stlcal valldlt


f
Central Basin %
max.
0.39
0.21
0.84
0.43
16.0
11.9
2.7
130
102
612
8.9
y.
ml n.
0.00
0.02
0.00
0.00
3. 1
5.2
0.0
71
92
354
7.7

avg. Change
0.09
0.10 9.0
0.09
0.05 -44.4
7. 1
8.6 +21. 1*
1 .0
97
96 -1.0
470
8.4




Eastern Basin
max.
0.32
0.17
0.85
0.16
27.0
1 1 .0
2.5
134
109
444
8.7
mln.
0.00
0.04
0.01
0.00
4.7
6.1
0.2
59
92
324
7.5
avg.
0.09
0.07
0.09
0.06
7.4
8.2
1.2
99
98
385
8.3
% Total
Change Lake Avg.
0.09
-22.2 0.09
0.09
-33.3 0.06
7.36
-HO. 8 8.53
1.10
-1.0 96.3
445
8.36
SOURCE:
Proceedings,  Pollution of Lake Erie and Its Tributaries,  F.W.P.C.A.,  Dept'.  Interior, Cleveland, Ohio,

-------
                                                      Table  13
                           COMPARISON OF DETERMINATIONS MADE  DURING DREDGING' WITH NATIONAL
                                WATER QUALITY STANDARDS AT ASHTABULA,  OHIO
PARAMETER
ph
DISSOLVE!-
OXYGEN
(mg/1)
DISSOLVED
SOLIDS
(mg/1)
TEMPERATURE
TOXIC
SUBSTANCES

all uses:
industrial:
aquatic life:
industrial :
Industrial :
aquatic life:
aquatic life:
USE & STANDARD
- 5.0-9.0 any time
(6.5-8.5 preferable)
2.0 rain, dally average
1.0 min. any time
.* .0 mir.. for 16 out of 24 hrs.
J.O min. any time
750 max. monthly average
1000 max. any time
95 F max. any time
93F max. May through December
78CF max. December through April
not to exceed 1/10 of the 48-hour
median tolerance except when
justified and approved
DISPOSAL AREA-LAKE
Low High
8.06 8.13
10.9V 11.23
212 223
NOT
NO DATA
RIVER-HARBOR
Low High
6.83 7.31
11.18 11.64
173 253
APPLICABLE
AT PRESENT
SOURCE:   Dredging and Water  Quality Problems in the Great Lakes, Vol. 4, U.  S.  Army Corp Engineers,  (1968)

-------
      One STORE! station, operated by the USGS at Jacks Automarine  (0.80
mile point,  station #04212700) has the most complete data available  for the
river over the longest period of time.  Continuous monitoring of temperature,
pH, conductivity and dissolved oxygen is performed at that station.  It appears
that the station is serviced approximately every two weeks.  At that time
water samples are taken because additional information appears sporadically
in STORE! for alkalinity, bicarbonate, nitrate, hardness, chloride,  sulfate,
fluoride, arsenic, mercury.  Occasionally, other parameters are run such as
copper, lead, nickel, silver, strontium, zinc, selium are entered into the
system.

     !able 14 lists recent available STORET data for the 1971-72-73 period
which are most useful for comparison to present day values,  Except  for early
data (1963-64), this is the most complete data set available in the system for
the Ashtabula River.  STORE! station #502760 contains data for radioactivity
parameters and several chlorinated hydrocarbons and pesticides.   All parameters
measured at this station yielded no trace amounts of the parameters tested
with the exception of beta emissions (measured as 5.5 picocuries per liter).
Parameters tested included the following:
                 Aldrin                          Dieldrin
                 Lindane                         Endrin
                 Heptachlor                      Methoxychlor
                 Heptachlor Epoxide              Malathion
                 ODD                             Parathion
                 DDE                             M-Parathion
                 DDT

      A recent  STORE! print-out  (Aug.  24,  1973)  yielded summary  data for
several  /ears arranged in a much more  convenient  format  than  obtained July 16,
1375.   S10RET stations of interest  in  the Task II  portion of  this  study are
listed in  Table 15.
                                      43

-------
                              Table 14
REPRESENTATIVE DATA FROM STORET STATION 04212700 (2* 0.8 MILE POINT)
         FOR 1971-73 (VALUES mg/1 UNLESS OTHERWISE NOTED).
Date
71/11/01
71/12/Oi
72/01/10
72/02/08
72/03/01
72/04/06
72/06/0"
72/07/08
72/09/06
72/10/26
73/01/04
73/02/02
73/03/02
T(CJ
18.5
2.1.
T '
i . C
2.0
- r
18. f
20. 0
23.0
10. C
2.0
3.0
1.5
Jondpmho
;:oc
539
646
30S
479
524
--
580
737
--
303
664
572
DO
3.6
--
--
13.2
--
--
--
--
--
--
--
--
--
pH
7.2
--
--
--
--
--
--
--
--
--
--
--
--
T AIK
94
25
44
33
52
41

54
89
--
34
45
70
HC03
114
*5 j.
54
40
63
SO
--
6C
108
--
42
3
85
NO-
1.40
2.1
0.5
0.80
1.0
--
--
--
--
--
2.8
2.9
3.0
TOG
--
--
--
--
--
--
2o . C
--
--
1.0
--
--
--
Hard.
240
98
16C
45
140
130
--
170
180
--
93
180
150
Cl"
290
42
130
' 41
77
89
--
110
140
--
48
130
99
S4
80
60
76
51
62
69
--
49
50
--
47
69
64
F"
0.2
0.1
0.2
0.2
0.1
0.1
--
0.4
0.5
--
0.1
--
0.3

-------
                                  Table  15
             APPLICABLE  STORE! STATIONS RELATED TO THIS STUDY
                 (F.B.-FIELDS BROOK,  A.R.-ASHTABULA RIVER)
STORE! #
MILEPOIN!
          LA!-LONG
                                                        DESCRIP!ION
390024

380142

380141

390027


0421270

380137

380136

393303
   6.3

   3.3

   2.3

   A.R.I.5
   FB-0.30

   0.80

   0.70

   0.00

   Lake

   Lake

   Lake
41  51   20.0  080  45   44.0

41  52   23.0  080  46   55.0

41  52   30.0  080  47   42.0

41  53   36.0  080  47   35.0


41  54   00.0  080  47   44.0

41  54   07.0  080  47   55.0

41  54   38.0  080  47   55.0

41  54   30.0  080  48   38

41  54   38.0  080  47   54

41  56   20.0  080  46   04.0
USGS Gaging Station

0.1 mi No of Rt 20

E 24th St.  Bridge

F. B. - E.  15th St.


Jack's Automarine

5th St. Bridge

A. R. Mouth

Lake Erie 23'  deep

Sludge Station 27' deep

Dredge Dump Station
                                      45

-------
Recent Ashtabula River-Fields Brook Data

      Data obtained by the Cleveland Office of the USEPA and stored in their
files in raw form were examined.   The samples were collected between the
period April 19 and May 5, 1973 and the values for each parameter averaged.
Tables 16 (a) and (b) are a complete compilation of the available data.  These
data were entered into the STORET system in July 1974 (Zar, 1974; personal
Communication).
                                     46

-------
                                    Table 16-a

       RECENT CHEMICAL DATA FOR ASHTABULA RIVER (A.R.)  AND FIELDS BROOK (F.B.)
   MILEPOINTS ARE GIVEN IN PARENTHESIS.   VALUES IN mg/1 UNLESS OTHERWISE SPECIFIED.
SAMPLE DATES APRIL 19 - MAY 5,  1971,  VALUES AVERAGED (DATA FROM CLEVELAND OFFICE EPA).
STORET
STATION
380142(2.3)
AR-1.57
421270(0.76)
390027
(FB0.38)
TS
199
431
465
1100
SS
10
14
27
58
Turb
JTU
4
8
15
25
pH
7.6
7.8
7.7
8.0
COD
16.3
24.8
21.1
26.8
Cl"
31
129
138
405
S4
51
72
75
137
Oil $
Grease
0.9
1.1
1.0
1.7
Phenol
Mg/1
0.7
5.0
2.0
10.0
Cyanide
0.0
0.0
0.0
0.0
                                    Table 16-b

       RECENT CHEMICAL DATA FOR ASHTABULA RIVER  (A.R.) AND FIELDS BROOK  (F.B.)
   MILEPOINTS ARE GIVEN IN PARENTHESIS.  VALUES  IN mg/1 UNLESS OTHERWISE SPECIFIED.
SAMPLE DATES APRIL 19 - MAY 5, 1971, VALUES AVERAGED  (DATA FROM CLEVELAND OFFICE EPA).
STORET
STATION
380142(2.3)
AR 1.57
421270(0.76)
390027(FB0.38)
Ba
Mg/1
<333
<400
<465
867
Sr
Mg/1
<1400
<1400
<1400
<1400
Cr
j^g/1
<20
<30
<23
<296
Cd
Kg/1
<40
<31
<20
<20
Pb
HS/1
<200
^200
<200
<200
Cu
Mg/1
<42
<45
<42
--52
Fe
/xg/1
950
922
1100
3164
Zn
A
-------
                                Section 6
                     CURRENT WATER QUALITY AND BIOTA
         This part of the study addressed the current water quality and biota
present in the Ashtabula area.  This program was begun as part of the Great
Lakes Initiative Program and primarily addressed the current water quality
picture of the Fields Brook-Ashtabula River and Harbor area.  The sampling
took place during three periods in 1973 and 1974.  The delineation of current
water quality over the reaches of Fields Brook was not a part of this effort
with the exception of a sampling station located approximately one-half mile
from its mouth and sampling for conductivity, chlorine residual and other
parameters at the Fields Brook confluence with the Ashtabula River.

         As previously discussed, nine major industrial discharges presently
dispose of their effluent into Fields Brook and thence to the Ashtabula River
although there are minor contributions to the river also from storm drainage
and at least one small tributary in the study area near the Penn-Central bridge.

         The United States-Canada Water Quality Agreement of 1972, the 1972
Amendments to the Federal Water Pollution Control Act (PL92-500),  the special
needs of the USEPA for allocation of waste loadings in this area,  as well as
a need to make projections of water quality based upon current data were the
primary factors which led to the sampling study of the Ashtabula River and
Harbor area.

         The objectives  of this water quality assessment program were to
produce a comprehensive  picture of the water borne impurities,  standards
violations, impact of major discharges and the aquatic biology in  the Ashtabula
River and Harbor area.   Emphasis was  placed upon the  water quality which
existed during a period  of low river flow, although a limited special purpose
sampling was  performed during the spring also.  Due to limitations of the scope
of this study, major emphasis was placed upon the water quality rather than
biota aspects.

                                     48

-------
Sampling Program

         Field sampling for this project took place  during three  periods:
5 July 1973 (preliminary sampling at four stations;  4-11  September 1973
(primary sampling period); and 8-10 May 1974 (limited sampling for total
residual chlorine, temperature, conductivity, Hg,  Cr, Cu, Fe,  and Na).
These periods  gave ample opportunities  to sample,  begin on-site analysis,  and
identify, for later investigation, potential problem areas.

         During the September 1973 sampling period,  Calspan's  large mobile
laboratory was located at Sutherland's  Marina on the Ashtabula River near  the
5th Street Bridge.  This location enabled ready access to the  harbor as well
as the river and the mouth of Fields Brook by boat,  and to return samples  for
immediate analysis.  Many measurements  were performed in  situ.  Samples were
transported back to our mobile laboratory for further testing, refrigeration
and transportation back to Calspan's water quality laboratory  in  refrigerated
containers for further detailed analysis.

         The purpose of the preliminary sampling of July 5,  1973  was to obtain
information on the concentrations of parameters which might  be expected and to
assist in design of a sampling plan which would delineate problem areas.   The
sampling period from 8-10 May 1974, was a special, limited sampling which
focused on specific objectives: (1) obtaining additional  information on
mercury, conductivity, and total residual chlorine at specific sites;  and
(2) to obtain samples for subsequent analysis for sodium, iron, chromium  and
copper.

         Seven permanent sampling stations were selected for the  purpose  of
this study with an eighth station added for completion during the first
sampling series.  Their locations were  as follows (also Figure 3):
                                      49

-------
                                      "
                                       , ~
                             *vw?.;iM   i
                           f'
                           xf --.5l*lH^
Figure 3 ASHTABULA AND FIELDS BROOK SAMPLE LOCATIONS
                   50

-------
           it ion                        Location
            1              Above the 24th St.  Bridge -- Ashtabula River
            2              Fields Brook -- 15th St.  Bridge
            3              Ashtabula River --  5th St.  Bridge
            4              Ashtabula River Mouth
            5              Mid Harbor
            6              1/4 mile outside breakwater light on Lake Erie
            7              1/8 mile N.  of Pinney Dock  (Harbor)
            8              Harbor Entrance

         Each sampling station was carefully chosen  so that an  as-complete-as-
possible water quality picture could be developed, with a minimum number of
sampling sites .

         The primary sampling of 4-11 September 1973 was conducted during a
period of excellent weather and low river flow  (Table 17) .  Days were sunny
to partly cloudy, temperatures in the 70-80F  range, and precipitation  was
zero except for the morning of 6 September (0.1 inch rain recorded).  Con-
ductivity, pH, DO, and temperature were measured in  situ, after which samples
were removed, refrigerated, and then shipped to Buffalo for immediate analysis
of the parameters listed in the Task II Field  Plan.  Specially  collected
samples were obtained of the biota (phytoplankton, zooplankton  and benthos),
organic chemical constituents of Fields Brook  water, and a sample of Fields
Brook sediment near its mouth.  Total residual chlorine was measured
colorimetrically using the orthotolidine method.

         As part of the development of a field plan, a sampling program was
designed using the sample locations listed above.  The types of analyses
performed were broken into three separate groups.  The following listing
summarizes which analysis groups were performed in_ situ or on samples
collected at each sample site (also Table 18).
                                     51

-------
                                Table 17
ASHTABULA RIVER FLOW CG.^ITIONS DURING PRIMARY FIELD SAMPLING PERIOD
                         (4-11 September 1973)
                Period
             (September)                 Flow (c.f.s.)

                  4                          0.7
                  5                          0.6
                  6                          4.0 (.1" rain)
                  7                          3.5
                  8                          2.8
                  9                          1.8
                 10                          1.3
                 11                          1.1

      *Source: USGS Water Resources Division, Columbus, Ohio.
                                    52

-------
                          Table 18
                     SAMPLE GROUPINGS
                    Parameter
          Dissolved Oxygen
          Total Dissolved Solids
          Total Organic Carbon
          Chloride
          Chlorine(Total Residual)
          pH
II        Coliform (total)
          Coliform (fecal)
          Settleable Solids
          Suspended Solids
          Oil and Grease (extractibles with Trichlorotrifluoroethane)

III       PCB's
          Pesticides (Chlorinated hydrocarbons)
          Selected.Organics (GC Analysis)

          Hardness                 Metals  (12)
          Alkalinity                  As
          BOD5, BOD2Q                 Ba
          COD                         Cd
          Kjeldahl Nitrogen           Cr
          Nitrate                     Cu
          Chloride                    Fe
          Phenols                     Hg
          Ammonia                     Pb
          Cyanide                     Ni
          Phosphorus (total)           Se
          Fluoride                    Ti
                                      Zn
                            53

-------
         Station
             1
             2
             3
             4
             5
             6
             7
         Group  I parameters were run at all stations and at three depths  (1
meter depth, intermediate depth, 1 meter above the bottom).  Group  II para-
meters were run on at least one sample depth  (1 meter depth).  Group  III
parameters were run at surface  (1 meter depth) only.  In addition,  dissolved
oxygen, conductivity and temperature data were obtained at 1 and 2  foot
intervals at most stations.  Table 18 lists the parameters analyzed for each
Group.

         Methods employed for the water quality analysis follow the procedures
outlined in Appendix 1 and which are presented in "Methods of Chemical Analysis
of Water and Wastes" (EPA, 1971) and "Standard Methods for the Examination of
Water and Wastewater", 13th edition, 1971.

         The Ashtabula River is classified as a warm water fishery by the State
of Ohio.   Standards applicable to the river have been revised recently (1973)
and proposed 1974 revisions subjected to public hearings during August 1974.
Revisions were to be finalized and issued for public notice in December 1974
during which time the final draft of this report was prepared.   Appendix 2
lists the most relevant general water quality standards applicable to the
Ashtabula River.
 All depths  for T, DO, Conductivity;  three depths for TDS, Cl", Cl  , pH.

                                      54

-------
Results

         As part of a reconnaissance investigation to determine final choices
of stations and ranges of water quality parameters which might be present in
the study area, a preliminary sampling was performed on 5 July 1974.  The
lesults of analysis for twenty-eight parameters are presented in Table 19 as
the AS I series.  Evaluation of this data indicated that some of the most
important water quality parameters for the examination of the study area were
total dissolved solids, chlorides, and conductivity.  Since this was a limited
purpose sampling, water sampling equipment was not employed other than glass
gallon containers, and no in situ measurements were made, although the strong
chlorine odor associated with Fields Brook was noted.  The particularly high
values of dissolved solids noted at the Fields Brook mouth and downstream
showed the influence of the discharges even though river flow was higher than
the subsequent sampling in September.  Based upon this sampling series, subse-
quent sample station locations and choice of parameters were made.

          The AS II sampling series was a sampling series for biota, and data
on the biota is presented later in this section.

         The primary sampling period resulted in a series of detailed sampling
and analysis at stations selected according to the sampling program previously
discussed.  In addition to specialty analyses [such as metals, organics,  etc.
which are described later)', twenty-eight water quality parameters were obtained
at each station.  Tables 20, 21, and 22 list the results of the analyses  for
three dates during the September 1973 sampling period.  The AS III series has
an additional sampling station (8) located at the harbor entrance.  Examination
of the data on the three sampling dates indicates that the significant water
quality parameters in the study area are conductivity, dissolved solids,  nitrates,
total residual chlorine, and chlorides.  It is clear that the source of most
anomalous concentrations of parameters is Fields Brook, and this indicates
the importance of the brook's contribution to- water quality during low flow
conditions.  The flow of Fields Brook .nearly accounts for the discharge of the
Ashtabula during these periods.  Concentrations of the above parameters in the
Fields Brook samples (upstream of any possible lake effect or water back-up)
indicate the source of most significant water quality parameters.

                                       55

-------
       Table 19
ASHTABULA RIVER AS-I
PARAMETER
DATE 5 JULY 1973
HARDNESS (as ppm CaCOq)
PH
ALKALINITY (as ppm CaCO3)
TOC mg/ mg/ i
SUSPENDED SOLIDS mg/ 1
DISSOLVED SOLIDS mg/ i
TOT ALSO LIDS mg/i
CHLORIDES mg/i
OIL & GREASE mg/i
NITRATE NITROGEN (as N) mg/i
KJELDAHL NITROGEN (as N) mg/i
SULFATE mg/i
TOTAL PHOSPHORUS (as P) mg/i
SURFACTANTS mg/i
PHENOLS mg/i
CALCIUM mg/
MAGNESIUM mg/i
COBALT mg/i
IRON mg/i
CHROMIUM mg/i
CADMIUM mg/i
MANGANESE mg/i
LEAD mg/i
NICKEL mg/i
COPPER mg/i
ZINC mg/i
SODIUM mg/i
MERCURY mg/i
1
(UPSTREAM
(GAGING STA.))

115
7.10
73.8
10
22
214
236
15
< 1.0
3.10
< 050
60
<0.1
<0.05
0.030
24
75
< 0.03
0.120
< 0.02
< 0.005
0.025
<0.02
<0.02
0.025
0.014
12
< 0.001
2
(FIELDS BK.
MOUTH)

325
350
88.4
24
27
1514
1541
280
3.6
1.80
0.75
72
< 0.1
<0.05
0.050
93
72
<0.03
0570
<0.02
< 0.005
0.050
<0.02
<0.02
0.030
0.010
750
< 0.001
3
(5th ST.)

200
8.35
86.8
9
39
658
697
220
< 1.0
150
0.75
63
<0.1
<0.05
0.010
48
7.4
<0.03
0.310
<0.02
< 0.005
0.100
<0.02
<0.02
0.020
0.020
78
< 0.001
4
(HARBOR)

137
8.85
92.6
10
19
272
291
35
< 1.0
0.90
0.56
45
< 0.1
<0.05
0.030
29
7.0
< 0.03
0.160
<0.02
< 0.005
0.025
<0.02
< 0.02
0.030
0.014
15
< 0.001
         56

-------
       Table 20
ASHTABULA RIVER  AS-III
PARAMETER
DATE 5 SEPT 73
PH
TEMPERATURE C
HARDNESS (as mg/l CaCO3)
ALKALINITY (as mg/|CaCO3)
CONDUCTIVITY ^mho's/cm
DISSOLVED OXYGEN mg/l
BOD (5 days) mg/|
BOD (20 days) mg/|
COO mg/|
TOC mg/|
SOLIDS (SETTLEABLE) mt/J
SOLIDS (SUSPENDED) mg/|
SOLIDS (DISSOLVED) mg/l
SOLIDS (TOTAL) mg/l
COLIFORM (TOTAL) #/100 ml
COLIFORM (FECAL) #/100 ml
PHOSPHORUS (TOTAL) mg/tP
PHOSPHORUS (ORTHO) mg/JP
AMMONIA mg/t
KJELDAHL NITROGEN mg/l
NITRATE mg/t
PHENOLS mg/l
CYANIDE mg/|
CHLORIDE mg/l
FLUORIDE mg/l
SULFATE mg/|
CHLORINE (TOTAL) mg/t
OILS AND GREASE mg/l
1

7.60
24.5
214
98.5
600
7.7
1.05
-
12.9
33
<0.1
35
372
407
1600
180
0.85
< 0.02
0.175
0.23
0.07
< 0.01
< 0.005
52
0.20
120
< 0.010
4.5
2

7.35
31.0
415
108
2650
7.5
9.90
11.0
4.3
30
0.2
50
1612
1662
<2
<2
1.08
0.07
0.50
0.43
6.0
0.01
< 0.005
570
<0.05
140
12.0
2.0
3

7.08
27,0
234
91.5
1400
4.3
2.20
-
8.6
29
<0.1
32
887
919
>6000
300
1.25
<0.02
0.13
0.65
1.20
<0.01
< 0.005
285
<0.05
83
0.050
2.0
/
4

7.35
25.1
159
93.5
590
6.0
1.60
-
8.6
28
<0.1
30
387
417
1200
150
0.74
< 0.02
< 0.10
0.23
1.60
<0.01
< 0.005
101
C 0.05
43
0,040
2.0
5

8.70
25.9
131
94.5
329
8.6
1.10

4.3
29
< 0.1
13
201
219
720
80
0.60
< 0.02
< 0.10
0.42
0.05
< 0.01
< 0.005
33
< 0.05
29
0.010
1.5
6

8.30
25.0
130
92.5
295
8.4
0.95
1.33
25.8
23
<0.1
15
206
221
10
<2
0.94
0.02
< 0.10
0.23
< 0.02
<0.01
< 0.005
35
< 0.05
28
< 0.005
2.5
7

8.60
25.0
132
94.0
335
8.2
0.83
_
12.9
25
< 0.1
15
210
225
80
10
0.85
< 0.02
0.10
0.33
0.06
< 0,01
< 0.005
33
<0.05
27
0.010
2.0
8

7.90
25.8
133
93.0
315
8.1
0.90
1.84

24
<0.1
20
231
251
6
<2
1.40
< 0.02
<0.10
0.23
0.07
<0.01
< 0.005
35
<0.05
31
0.005
<1.0
        57

-------
        Table 21
ASHTABULA RIVER  AS-IV
PARAMETER
DATE 8 SEPT 73
pH
TEMPERATURE C
HARDNESS (as mg/J CaCOg)
ALKALINITY (as mgjt CaCO-j)
CONDUCTIVITY ^mho's/cm
DISSOLVED OXYGEN mg/i
BOD (5 days) mg/i
BOD (20 days) mg/i
COD mg/i
TOC mg/i
SOLIDS (SETTLEABLE) mill
SOLIDS (SUSPENDED) mg/i
SOLIDS (DISSOLVED) mg/i
SOLIDS (TOTAL) mg/i
COLIFORM (TOTAL) #/100 mi
COLIFORM (FECAL) #/100 mi
PHOSPHORUS (TOTAL) mg/t?
PHOSPHORUS (ORTHO) mg/lP
AMMONIA mg/i
KJELDAHL NITROGEN mg/i
NITRATE mg/i
PHENOLS mg/i
CYANIDE mg/i
CHLORIDE mg/i
FLUORIDE mg/i
SULFATE mg/i
CHLORINE (TOTAL) mg/i
OILS AND GREASE mg/i
1

8.70
19.0
192
95.5
445
7.3
0.30
2.05
16.3
24
< 0.1
8
360
368
7000
4000
0.48
< 0.02
0.20
0.46
0.07
< 0.010
-
44
0.20
116
< 0.005
3.5
2

6.55
27.0
420
86.5
2200
6.5
8.60
9.35
30.2
21
0.2
37
1504
1541
< 2
< 2
0.40
< 0.02
0.10
0.75
4.40
< 0.010
-
554
0.20
100
1.10
3.5
3

7.30
24.9
198
93.0
880
5.7
0.70
1.20
18.5
21
<0.1
22
534
556
5600
1000
0.14
< 0.02
0.20
0.75
4.70
< 0.010
-
174
< 0.05
68
0.01
2.0
4 '

8.60
24.0
138
92.5
332
6.9
0.80
2.50
18.5
18
< 0.1
15
238
253
110
40
0.24
< 0.02
< 0.05
0.46
0.10
< 0.010
-
44
< 0.05
30
< 0.01
3.0
5

8.10
24.5
137
93.5
310
6.7
1.50
2.35
4.7
20
< 0.1
13
209
222
20
< 10
0.28
< 0.02
< 0.05
0.28
0.08
< 0.010
-
38
< 0.05
29
0.01
1.0
6

8.70
24.8
130
92.0
280
7.2
1.30
2.70
4.70
19
< 0.1
< 5
216
216
6
< 2
0.32
< 0.02
< 0.05
0.19
0.05
< 0.010
-
26
< 0.05
28
0.01
< 1.0
7

8.65
24.9
128
92.0
290
7.1
1.40
1.80
14.0
18
< 0.1
< 5
178
178
< 2
< 2
0.63
< 0.02
0.30
0.28
0.05
< 0.010
-
29
< 0.05
29
0.05
1.5
          58

-------
       Table 22



ASHTABULA RIVER  AS-V
PARAMETER
DATE 10 SEPT 73
pH
TEMPERATURE C
HARDNESS (as mg/JCaCOg)
ALKALINITY (as mg/i CaCOg)
CONDUCTIVITY u mho's/cm
DISSOLVED OXYGEN mg/i
BOD (5 days) mg/i
BOD (20 days) mg/i
COD mg/i
TOC mgJt
SOLIDS (SETTLEABLE) mUl
SOLIDS (SUSPENDED) mg/i
SOLIDS (DISSOLVED) mg/i
SOLIDS (TOTAL) mg/i
COLIFORM (TOTAL) #/100 mi
COLIFORM (FECAL) #/100 ml
PHOSPHORUS (TOTAL) mg/tf
PHOSPHORUS (ORTHO) mg/*P
AMMONIA mg/i
KJELDAHL NITROGEN mg/i
NITRATE mg/i
PHENOLS mg/i
CYANIDE mg/i
CHLORIDE mg/i
FLUORIDE mg/i
SULFATE mg/i
CHLORINE (TOTAL) mg/I
OILS AND GREASE mg/i
1

8.80
17.9
201
94.0
420
8.5
1.90
2.30
22.2
21
< 0.1
6.5
302
309
400-
55
0.12
< 0.02
0.05
0.28
< 0.02
< 0.010
-
41
0.20
115
0.02
2.0
2

8.65
24.0
439
91.0
2210
6.6
2.55
3.00
6.6
20
0.15
28
1495
1523
< 2
< 2
0.06
0.03
<0.05
0.36
5.0
< 0.010
-
598
0.20
110
6.5
2.0
3

8.10
23.3
200
93.0
825
8.0
3.30
4.90
13.4
18
<0.1
21
503
524
6600
1400
0.16
< 0.02
<0.05
0.56
2.0
< 0.010
-
166
0.10
55
0.02
3.5
4

8.75
23.2
132
92.0
318
7.8
1.75
2.10
8.9
19
< 0.1
8
205
213
320
30
0.14
< 0.02
0.05
1.49
0.06
< 0.010
-
35
<0.05
33
. 0.01
< 1.0
5

8.75
23.2
133
93.5
308
7.8
2.30
2.40
15.6
17
< 0.1
7
443
450
300
40
<0.02
< 0.02
< 0.05
0.42
0.06
< 0.010
-
36
 0.05
29
0.01
1.5
6

8.90
23.7
129
94.0
288
8.2
1.90
2.00
11.1
17
< 0.1
1
180
181
< 2
< 2
0.04
< 0.02
< 0.05
0.47
0.04
< 0.010
-
26
< 0.05
30
< 0.01
< 1.0
7

7.85
23.5
131
93.0
300
7.7
2.20
2.20
15.6
18
< 0.1
5
184
189
10
2
<0.02
<0.02
0.05
0.42
< 0.02
< 0.010
-
29
<0.05
29
0.01
1.5
         59

-------
          Organic Chemical Constituents.  According to the Field Plan prepared
for this program, a single water sample from Fields Brook was to be analyzed
for its organic chemical constituents.   The results reported here,  however,
include analysis of samples from Fields Brook (2),  Mid-harbor (5) ,  and the
Offshore (6) sampling stations.   The method used for extraction was similar to
extractive procedure for pesticides (EPA,  1971).  One liter samples were
extracted three times with a hexane-diethyl ether (85-15) mixture.   The hexane-
ether extracts were then concentrated to a volume of five milliliters using a
Kuderna Danish evaporator.  Aliquots of this sample with no additional clean-up
were injected directly into a gas chromatograph.  A gas chromatograph (Hewlett-
Packard 5700) with an electron capture detector was used.  This detector was
selected since most of the materials to be surveyed were chlorinated species
and excellent detection limits would-be obtained.  The separation column was a
6' x 1/4" OD glass, packed with 1.5% OV17 and 1.95% QF-1 on Gas Chrom Q,
80-100 mesh.

         Most of the components eluted very early in the chromatogram.  A major
component was detected in all three of the samples.  The component could not be
identified  in view of the limited program restrictions, however, the relative
response of this component in each sample is listed below:

                    Fields Brook  (2)    290,000
                    Mid-Harbor  (5)        9,300
                    Outside  (6)           1,200
                                                         *
         Some  idea of the boiling point of the  material  can be postulated
since  the unknown material elutes  after hexachloroethane and before
hexachlorobenzene.   It  may be assumed  that the  material  is halogenated  due
to  the detection of  the  component  in lake water.   Due  to the sensitivity  of
our detector for halogenated compounds, it still could be  detected even
though it was  present in extremely dilute  concentrations.  A non-halogenated
compound probably would not  have been  detected.  The  source of the material
is  clearly  Fields  Brook.
                                       60

-------
         Other components were also detected in the samples, but none of the
components could be identified as being those listed in the table below.
Some of the eluted components observed could be lower chlorinated ethanes
and/or ethylenes that elute near the tail of the solvent peak.

                               Materials Surveyed
      (Results from gas chromatographic scans of extract concentrates)

               Tetrachloroethane           Hexachlorobenzene
               Hexachloroethane            Toluene Diisocyanate
               Monochlorobenzene           Dimethyl phthalate
               1,2,4 Trichlorohenzene      Dibutyl phthalate

         None of these components were detected as present in the samples.

         In addition to the above, a survey was made for the presence of
seventeen chlorinated pesticides and PCB's to determine if they were present
or absent in samples from Fields Brook (2), mid-harbor (5), and offshore (6).
Table 23 lists the results of the analyses.  None of the listed parameters
was found to be present above the limits of detectability (<.01  pg/1  for
chlorinated pesticides and < .1  pg/1  for PCB's).

         Metals.   Analyses for heavy metals concentrations were performed
for all sampling stations for the following metals:  As, Ba, Cd, Cr, Cu, Fe,
Hg, Ni, Pb, Se, Ti, Zn.  Tables 24, 25 a,b list the results of the analyses.
Most parameters are present in the  ug/1  range with the exception of barium
and titanium.  The analysis for titanium proved to be difficult, and it was
not possible to refine our measurement below 1 mg/1 .  Specific values worth
highlighting here include the presence of mercury concentrations averaging
1.3-1.4  ug/1  in Fields Brook at Station 2.  Nickel concentrations in Fields
Brook on 5 September were slightly higher than other sample locations and this
was true also on 8 September.  Nickel concentrations on 10 September were the
same at all locations.  Iron concentrations at Fields Brook and the upstream
station were higher than the lake and harbor areas probably reflecting the

                                      61

-------
                      Table 23
              ASHTABULA RIVER  AS-ll!
CHLORINATED PESTICIDES AND POLYCHLORINATED BIPHENYLS
PARAMETER
DATE 5 SEPT 73
Oi-BHC
LINOANE
HEPTACHLOR
ALDRIN
KELTHANE
HEPTACHLOR EPOXIDE
tf-CHLORDANE
ENDOSULFAN 1
p,p'-ODE
DIELDRIN
ENDRIN
o,p'-DDT
ENDOSULFAN II
p,p'-DDD
,p,'-DDT
METHOXYCHLOR
PCB's


fig/i
H41
M9/i
M9/J
yg/l
W9/1
yg/1
Ata/l
JU8/1
MS/i
JJ9/I
M9/J
M9/I
pg/1
Hg/1
H9/1
ua/I
2

< 0.01
< O.Q1
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
<0.1
5

< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
<; 0.01
< 0.01
< 0.01
< 0.01
< 0.1
6

< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0,01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
<0.1
                         62

-------
       Table 24
       METALS
ASTABULA RIVER  AS-I
PARAMETER
DATE 5 SEPT 73
ARSENIC [is/I
BARIUM mg/jt
CADMIUM jug/1
CHROMIUM jg/|
COPPER Jig/I
IRON ptg/i
MERCURY jzg/i
NICKEL ptg/1
LEAD /ig/l
SELENIUM ig/t
TITANIUM mg/
ZINC ^(g/|
1

<10
1.4
1.0
< 5
6
260
0.6
5
5
<5
0.0
16
2

<10
2.9
2.5
<5
10
250
1.4
15
5
<5
<1.0
13
3

<10
2.1
1.0
<5
S
60
0.6
<5
5
<5
<1.0
17
4

<10
1.1
0.3
<5
9
60
0.6
<5
3
<5
<1.0
15
5

<10
1.5
0.3
<5
7
80
1.2
<5
<3
<5
<1.0
12
6

<10
1.1
0.3
<5
7
30
4.8
<5
<3
<5
<1.0
22
7

<10
1.0
0.3
<5
3
- 120
0.9
<5
<3
< 5
< 1.0
12
8

<10
1.1
0.3
<5
8
40
1.4
<5
5
< 5
< 1.0 .
22
       63

-------
            Table 25
            METALS
(a)  ASHTABULA RIVER  AS-IV
PARAMETER
DATE 8 SEPT 73
ARSENIC pg/i
BARIUM mg/i
CADMIUM ^g/|
CHROMIUM jjg/i
COPPER Mg/|
IRON jig/
MERCURY ^g/I
NICKEL ^g/|
LEAD ^g/J
SELENIUM ngJl
TITANIUM mg/1
ZINC jjg/J
1

< 10
1.5
1.0
< 5
6
360
4. 0.3
< 5
4
< 5
< 1
12
2

< 10
2.5
1.0
< 5
10
140
1.3
5
< 3
< 5
< 1
22
3

<10
2.0
0.6
< 5
8
260
< 0.3
: 5
4
< 5
< 1
10
4

<:iO
1.5
0.6
< 5
8
240
<0.3
< 5
4
< 5
<1
10
5

<10
1.5
< 0.3
< 5
8
280
<0.3
< 5
< 3
<5
<1
8
6

< 10
1.0
<0.3
< 5
8
20
<0.5
< 5
< 3
<5
< 1
22
7

< 10
1.0
< 0.3
< 5
8
70
<0.5
< 5
< 3
< 5
< 1
16
 (b)   ASHTABULA RIVER  AS-V
PARAMETER
DATE 10 SEPT 73
ARSENIC pg/J
BARIUM mg/|
CADMIUM pjg/1
CHROMIUM ngH
COPPER pg/l
IRON jig/i
MERCURY (tg/l
NICKEL ^g/1
LEAD jjg/
SELENIUM n&t
TITANIUM mg/|
ZINC pta/i
1


-------
leaching of iron from soils and its presence as a component of process water
in plant effluents.

         Mercury, due to recent interest in its toxicity,  has been
examined in greater detail in this report because of seemingly anomalous
concentrations upstream at Station 1 on 10 September 1973 (4.3 Mg/1 ) and
offshore at Station 6 on 5 September (4.8 yg/1 ).  In addition to Calspan's
sampling, the Ohio District office has  conducted sampling and mercury analysis
on three separate occasions during 1973.

         As discussed above, sampling of the Ashtabula River and Harbor, near-
shore Lake Erie  and  Fields Brook, was performed  during the period 4-11 September
1973.  During this period, anomalous concentrations of mercury were discovered
at selected stations, and the information has been assembled here together
with subsequent  data in an attempt to identify the possible source.  The
results  compiled, therefore, represent  Calspan's efforts on 4-11 September 1973,
USEPA sampling on April 11, June  25, and July 31, 1973, and Calspan sampling
on 8-10  May 1974.

         Previously  it had been thought that Fields Brook industries supply a
relatively constant  source of mercury,  but the presence of concentrations of
mercury  of up to three times greater than samples obtained from Fields Brook
suggests either  another source  (especially if dilution is taken into considera-
tion), or the possibility that sporadic, high concentrations are discharged
from time to time and are not mixed well with river water.  The latter could
be favored because of the high temperatures measured in Fields Brook
compared to river water producing a layering effect with little mixing with
cooler,  denser waters below and thus less-dilution than expected.

         Data compiled on mercury from  the above sources is presented in
Table 26.  Several important points are worth noting here concerning the data
gathered by the  USEPA and Calspan.  Further sampling of upstream sources
including a small tributary near the Penn Central Bridge and of the river
water upstream of the first small falls and at the USGS gazing station indicates

                                       65

-------
                                                       Table 26

                                                MERCURY DATA (ug/i)1
STATION
UPSTREAM - PC BRIDGE
ASHTABULA RIVER - E. 24th ST.
FIELDS BROOK - STATE RD.<2)
FIELDS BROOK - STATE RD.(3)
FIELDS BROOK - RT. 20
FIELDS BROOK - E. 15th ST.
FIELDS BROOK MOUTH
ASHTABULA RIVER - E. 6th ST.
ASHTABULA RIVER (MILEPOINT 0.0)
ASHTABULA MID HARBOR
HARBOR ENTRANCE
OFFSHORE
PINNEY DOCK
4/11/73
-
0.4*

-
0.2*
0.8*
-
0.2*
-
-
-
-
-
6/25
-
0.3*
-
-
0.8*
0.5*
-
0.6*
-
-
-
-
-
7/31
-
0.2*
-
-
0.3*
0.4*
-
0.2*
-
-
-
-
-
9/5
0.6
-
-
-
-
1.4
-
0.6
0.6
1.2
1.4
4.8
0.9
9/8
< 0.3
-
-
-
-
1.3
-
< 0.3
^0.3
^0.3
-
^0.5
^0.5
9/10
4.3
-
-
-
-
1.3
-
^0.3
0.4
^0.3
-
t 0.3

-------
value- of <0.5 yg/1 Hg on all sampling occasions during May  8  and  9,  1974.
This  appeal-  to rule out upstream or tributary sources of mercury,  above  the
Penn  Central  Bridge  (our Station 1).  USEPA sampling in Fields  Brook  and  the
Ashtabula River were performed during a period of flow of 160  cfs  (4/11),
13.3  cfs  (6/25), and 2.75 cfs  (7/31).  Considerable dilution might  be expected
during the  early sampling period but with such an interval separating the
dates, it is  doubtful if the subsequent samplings which were taken  in such a
limited area  might reveal  (other than by chance) anomalous concentrations of
mercury.  The intensive sampling both in frequency and locations conducted as
part  of the September and May sampling serves' as a baseline  for examination
of  the mercury problem, at  least in a preliminary way.  The  USEPA  sup-
plementary  sampling at an outfall located at  E 24st St (which  was  described
as  containing discharges from the Ashtabula General Hospital and a  sanitary
bypass) was found to contain 2.2 pig/1 mercury on 12/10/73.   This points out a
need  to monitor this discharge and determine  the mercury concentration, flow,
and duration  of discharges.  Certain disinfecting agents are known  to contain
mercury, although they are  not so commonly used today as in  the past.

         Examination of Table 26 indicates that over the dates  sampled  
Fields Brook  concentrations of mercury are quite variable and in one instance
(5/10/74) quite high (21 yg/1) compared to the Ohio standard for mercury
(0.5  yg/1).   The concentration of mercury upstream of the State Rd bridge
points to a source as does  the value for the  outfall in the west side of the
bridge (1.9 yg/1).  The area to the east is a lowland, swampy area with
normally sluggish flow.   Therefore,  high runoff caused by precipitation may
directly influence the mercury concentration  in Fields Brook.  The influence
of Fields Brook may be even more important when examination of the data for
9/5/73 is made.   A concentration increasing from the river mouth to the off-
shore station indicated the probability that movement of mercury in solution
over the upper layers of water took place probably during the last 24 hours,
perhaps less.   Sampling in Fields Brook and in the river on 8 September
indicated no anomalous  values but two days later a high concentration of
mercury (4.3 yg/1)  was  found at the  Penn-Central  Bridge.   Apparent upstream
                                      67

-------
movement of water (lake effect) extends to this station and the wind was
blowing generally onshore that day.   It is, therefore,  postulated that a high
concentration of mercury was discharged within the previous 24 hours and the
warm, Fields Brook waters were pushed, relatively undiluted upstream.
Confirmation of this effect and of the levels and source(s) of mercury by
detailed field measurement is believed necessary and is recommended by this
report.  The most effective manner to perform this study will be by on-site
analysis and a detailed sampling program.

         Conductivity and Dissolved Solids.   Extensive and detailed in situ
measurement of conductivity was made as part of this effort and partially repor-
ted previously in Tables 20-22.  In addition, conductivity data as a function of
depth will be reported later in this section as part of the data obtained during
the September 5 sampling.  As part of the field sampling portion of this work, a
conductivity profile was made by use of a technique of towing the probe at a
known depth  (1 meter) and velocity.  A profile of the results of this data col-
lection is presented in Figure 4.  Comparison of the data gathered using this
technique with measurements made on station indicates complete agreement and has
proven the method to be a rapid, accurate method of assessing the dissolved solids
content of thev water.  Dissolved solids concentrations  in Fields Brook ranging
from 1495 to 1612 mg/1  were measured during the period of the conductivity
investigation.  Dissolved solids concentrations and, in particular, chloride
concentrations vary in the same order downstream from the Fields Brook mouth
and also in the upstream direction.   Conductivity is a  rapid, relatively
inexpensive measurements of dissolved solids, and it is recommended for use
in areas such as Ashtabula where wide variations of dissolved solids can be
expected.  The profile illustrates graphically what the tabular data also shows;
that Fields Brook is the primary source of dissolved solids in the lower Ashtabula
River.   Measurement of the dissolved solids and conductivity in Ashtabula
Harbor and offshore, however, indicates little variation from what can be
considered to be ambient, although in general harbor values are higher than
offshore values.
                                      68

-------
                                                       CONDUCTIVITYjzmhos/cm @ 25C
ON
<>
I
CD
*k

O
o

o
c
o

<

H
                               -o
                               30

                               O
                               m

                               O
                               -n



                               I

                               >
                               CO
                               c
                               m
                                            . o
                                            CD
                                                     2
                                                     O
                               oo  o
                               o  o
                               a  o
  u
  o
  O
                                                                              O)
CO
o
o
8   K
g   8
                                         c
                                         33
           33
           O
           2 a.
           on
           C

           m r
           33 e
                                                                       RIVER MOUTH
COAST GUARD STATION


 -.	5th STREET
                                                                                        RIVER BEND
                                                               -FIELDS

                                                                BROOK
                                                                          31st ST

-------
         Chlorine Residuals

         Industries located in the Fields Brook area are known to discharge
concentrations of chlorine (present in the form of calcium hypochlorite) in
concentration levels which frequently vary from 40 to 120 mg/1 .   These levels,
as will be discussed later, represent an extremely toxic condition to biota
in Fields Brook and in the vicinity of its mouth.   Brungs (1973)  recommended
certain "safe" levels of chlorine residual which are far exceeded in most of
the lower Ashtabula as measured in this study.   Data have become  available
recently on the levels of toxicity of chlorine to several fish species,
phytoplankton and zooplankton (Brungs, 1973; Brook and Baker, 1972; Hamilton,
et al., 1970).  In general, recommended disinfection levels are between 0.5
and 1.0 mg/1 which is well below known toxicity levels to mammals; however,
concentrations not to exceed 0.002 mg/1  (continuously) have been recommended
for the protection of most aquatic organisms.   Accurate determination of
residual chlorine  (free and combined) is best  obtained by use of the amperometric
method  (see Standard Methods, 1971).  The orthotolidine method with pre-mixed
visual standards was used in the field during  this study.  As part of Calspan's
investigation of determining what levels of chlorine might be expected in the
Ashtabula River and Fields Brook, a theoretical study of the prediction of
chlorine residuals in a flowing stream was undertaken (Pereira, Terlecky, and
Yaksich, 1974).  A copy of the report of that  investigation is included here as
Appendix 3.  The fundamental assumptions are to determine what the safe levels
are for biota in the river and then calculate  by use of a model what levels
can be tolerated at the discharge point(s).  Based upon an examination of the
data requirements  (chlorine demand, free and residual chlorine measurements all
along the course of the brook, other parameters),  it was determined that the
costs associated with obtaining the data and testing the model were too large
for the current effort.  Therefore, after detailed examination of a method of
approach, and determination of a method of testing the model, no  further work
on the model was done.  It was hoped that with the detailed chlorine data
obtained here, a projection of chlorine concentrations could be made in an
empirical way.
                                      70

-------
         Tables on water quality presented in a previous section list data
obtained on total chlorine residual.  In addition to that data, additional
measurements were made at selected points on September 5-6, 1973 and are
presented in Figure 5.   Measurements of total chlorine residual were also
made on 8-10 May 1974 for selected stations and are presented in Table  27.
High concentrations of chlorine residual can be observed in Fields Brook.. The
outfall sampled at the west side of the bridge at State Road on Fields  Brook
had a value of 35.0 mg/1 total residual chlorine when sampled on May 10,  1974.
Depending upon conditions of flow, time, etc., values measured in the
Ashtabula River at the mouth of Fields Brook are clearly quite high.  Values
measured within an hour or two on each sampling day illustrate the dilution
effect of the river with values of 0.03 and 0.05 mg/1 recorded.  The detection
limit for the orthotolidine method as used in this study was 0.01 mg/1.
            Table 27  Total  Chlorine  Residual  (mg/1)   8-10  May  1974
Station (#)
Upstream (1)
Fields Brook - 15th St (2)
Fields Brook - State Rd (W)
Fields Brook - State Rd (Outfall)
Mouth of Fields Brook
Ashtabula River (3)
5/8
^0.010
6.5
-
-
9.5
0.03
5/8
4 0.010
4.5
-
-
4.0
0.05
5/9
^0.010
4.5
-
-
3.0
0.05
5/9
^0.010
3.0
-
-
3.0
0.05
5/10
-
2.4
0.2
35.0
-
-
          Sodium.    Although measurement  of sodium concentrations  was  not  a
 part of this  effort originally,  it was decided to obtain analyses for sodium
 for possible  use  in flushing time calculations such  as  performed  previously
 by the Army Corps of Engineers  as presented in Section  2.  As a result,  75
 samples were  analyzed for sodium and the results  are presented here as Table
 28.   It was  determined that the prime source of  sodium was Fields Brook  with
 sporadic additional contributions from upstream sources.   Highway runoff  may
 be the source of  this upstream  sodium which was originally derived from deicing
 salt (V, 1-3).
                                      71

-------
      01


      z
      o


      g
      cc
      (-
      z
      tu
      u


      I
      III
      z

      E
      o
      Q

      w
      LU

      CC
         1.0
.1
         .01
        .005
-------
       Table 28  Sodium Content of Ashtabula Water Samples

                 (Concentrations in mg/1; ppm)
                            AS III
 AS IV
                 AS V
Sample No., Station

     1-1
     2-1
     3-1
     3-2
     3-3
     4-1
     4-2
     4-3
     5-1
     5-2
     5-3
     6-1
     6-2
     6-3
     7-1
     7-2
     7-3
     8-1
     8-2
     8-3
Additional Samples Analyzed and the Sodium Concentrations
41
340
210
86
64
60
20.0
16.5
21.0
37.0
18.5
15.0
15.0
14.0
20.0
23.5
20.5
21.0
16.0
15.5
32
310
100
95
78
24.0
23.5
23.0
20.5
22.0
24.0
14.0
14.0
14.5
16.0
16.0
16.5
-
-
_
37
350
88
86
170
21.0
22.5
27.0
21.0
21.0
19.5
15.5
16.0
19.5
16.0
15.0
15.0
-
_
_
                                    Na  (mg/1)
    Fields Brook at the River
    III 6-5
    III 6-9
    III 3-7
    III 3-11
    III 5-7
    III 6-7
    III 2-3
    III 3-9
    III 5-9
    III 5-5
    III 1-3
    IV  1-2
    III 1-la
    V   1-3
,5
.5
.5
330
 16.
 14.
 23.
220
 19.0
 15.5
340
115
 19.
 20.
 42
 32
 35
500
.5
,5
                             73

-------
         Sediment Chemistry.   A brief examination of the sediment chemistry
of Fields Brook was made in an effort to determine what contributions are made
by the brook to the sediments of the river.  A single sample was obtained from
near the mouth of Fields Brook and analyses for several metals were performed.
The results are presented in Table 29.   Significant contributions of barium,
chromium, copper, iron, nickel, lead, and zinc were found.  Mercury concentra-
tion in the sediment was 2.6 pg per gram of sediment dry weight.

Variation of Water Quality with Dep_th_

         Data obtained for eight parameters at surface (1 meter), intermediate
depth, and one meter above the bottom was assembled for each of the sample
stations examined in this study.  The upstream and Fields Brook samples were
taken at an intermediate depth because of the shallowness of the water at each
site.  Temperature, pH, conductivity, dissolved oxygen, total dissolved solids,
total organic carbon, total residual chlorine, and chloride concentration were
measured on September 5.  Table 30 lists the results of the analysis.  Changes
in concentrations of most parameters with depth were not pronounced with the
exception of temperature, conductivity, dissolved solids  and chloride concen-
trations at the 5th St. Bridge.  Dissolved oxygen concentrations  are expected
to be reduced near the bottom especially if the organic nature  of these sedi-
ments is considered.  Chlorine concentrations at Fields Brook  (12.0 mg/1),
5th St. Bridge and the mouth of the river were higher than expected.
                                      74

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         Table 29

FIELDS BROOK SEDIMENT
PARAMETER
DATE 6 SEPT 73
Ug/g DRY WEIGHT
ARSENIC
BARIUM
CADMIUM
CHROMIUM
COPPER
IRON
MERCURY
NICKEL
LEAD
SELENIUM
TITANIUM
ZINC
FIELDS
BROOK
SEDIMENT


< 1.0
860
17
158
80
33,000
2.6
59
61
<. 2
_ *
210
TOO MUCH FLAME EMISSION TO GIVE
 AN ACCURATE ANALYSIS.
            75

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         Table 30
ASHTABULA RIVER  AS-III
SAMPLE
DATE 5 SEPT 73
UPSTREAM (1)
FIELDS BROOK-15th STREET (2)
5th STREET BRIDGE (3)
MOUTH OF RIVER (4)
MID HARBOR (5)
OUTSIDE HARBOR (6)
OFF PINNEY DOCK (7)
HARBOR ENTRANCE (8)
DEPTH
(meters)

0.2
0.5
1.0
3.4
5.5
1.0
4.6
8.2
1.0
4.9
8.8
1.0
6.7
12.8
1.0
4.9
9.2
1.0
5.5
10.0
TEMP
C

24.5
31.0
27.0
26.1
25.2
25.1
24.2
24.0
25.9
24.9
23.5
25.0
24.5
17.0
25.0
24.9
24.0
25.8
24.9
23.8
pH

7.6
7.35
7.08
7.48
7.40
7.35
7.85
8.05
8.70
8.45
8.60
8.30
7.75
7.55
8.60
8.35
7.60
7.90
8.30
8.25
COND
(y-mho/cm)

600
2650
1400
1000
700
590
320
310
329
430
310
295
300
275
335
350
338
315
302
302
DO
(mg/i)

7.7
7.5
4.3
3.9
3.3
6.0
5.9
6.4
8.6
7.1
5.4
8.4
7.8
2.0
8.2
7.6
4.9
8.1
7.5
5.0
DISSOLVED
SOLIDS
(mg/W

372
1612
887
479
441
387
230
221
201
287
202
206
217
216
210
243
225
231
201
212
TOC
(mg/|l

33
30
29
26
29
28
26
26
29
25
27
23
25
34
25
25
27
24
25
29
CHLORINE
RESIDUAL
(mg/i)

< 0.010
12.0
0.050
0.100
< 0.010
0.040
0.020
0.020
0.010
0.025
0.010
< 0.005
< 0.005
0.100
0.010
0.010
0.040
0.005
< 0.005
0.020
CHLORIDE
(mg/D

52
570
285
148
124
101
35
29
35
64
27
35
29
26
33
36
34
35
29
27

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Biota Sampling and Analysis

          Locations were chosen (Stations 1,  2,  3,  5,  6)  for plankton sampling
(surface, intermediate,  near bottom)  and sediment sampling for benthic inverte-
brates (sludge worms).   A great deal  of literature has evolved in recent years
relating organisms to water quality,  and therefore, as a minimum, these groups
should be characterized in any study of water quality.  Limited benthic sampling
was performed in this study.

          Phytoplankton were identified from collections made in the following
manner:  A three liter sample from the desired depth was collected and poured
through  a plankton net.  The sample of plankton thus obtained was to be
transfered to a small sample container and 70% alcohol fixative solution was
used for preservation.  An  additional one liter sample of water from each depth
was collected, preserved and also transfered to the laboratory for analysis
of the phytoplankton.  A double sample technique was preferred because of the
concern  that fine  sized forms  (diatoms) might escape  the plankton net  used.
Water was collected in specific amounts because of a  need for absolute  knowledge
of the volume sampled.  We  have been dissatisfied  with techniques of towing in
the past and feel  that with this method, the sample volume which has passed
through  the net can be determined precisely.

          An Eckman dredge was used for the bottom biota sampling of sludge
contents. Limnodrilus sp. appeared to be the dominant form in the study area.
The sample was dredged up,  a known volume of sediment was placed on a specially
designed sieve and the worms were sieved out and preserved for later iden-
                                                                2
tification.   The Eckman dredge used had a sampling area of 36 in .  Results of
benthos  collections at each station were obtained by at least two casts, and
the analyzed samples reflect the combined results.  The presence or absence of
other benthic invertebrates such as Musculium transversum and Pisidium sp.
(molluscs)  was noted, and specimens collected if present.  Sediment samples were
removed and transported for later analysis, if necessary.
                                      77

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          Biota
          Samples were obtained from Stations 1, 2, 3, S and 6 during the
period 4-11 September 1973.  The "as is" sample was digested and centrifuged
with a goal of looking at the diatom population at each site only, while the
filtered sample was taken to assess the population characteristics of the
entire plankton population.  It should be noted that the nets used were #12
mesh.  Organisms less than 100 p could pass through this net.  In general,
the results of the study indicate that communities can be identified which
are common to the lower Ashtabula River, the Harbor, and the Lake.  In situ
chemical measurements made during sampling are presented in Table 31.

          Samples from Station 1 (upstream, a lotic environment) contained
little diversity of plankton in comparison to the lower river and harbor
(Table 32).  A maximum of 12 inches of water during the sampling period
(except for pools) was observed, and black bass (Micropterus), suckers  (uni--
dentified), and crayfish (unidentified) were also observed.  No fish samples
were captured for later identification.  No benthic organisms were obtained
from the gravel and rock river bottom at this time.  The dominant diatom was
Cyclotella at this station.  This observation per se does not provide defini-
tive information because, within this genus, species found occupy a great
diversity of environments ranging from oligotrophic to eutrophic.

          Station 2, Fields Brook, also a shallow environment, yielded high
residual chlorine values (see Table 31).  Vegetation at the brook's edge was
damaged.  Plankton samples contained low organism counts.  Three Pediastrum
species were present, as well as Keratella, a rotifier.  (Table  32)  Diatoms
were present in significant amounts.  No benthic organisms were recovered
from the sediments.

          In the Ashtabula River, at the 5th St. Bridge  (approximately one mile
below the mouth of Fields  Brook), plankton samples were obtained at 1 meter,
3.6 meters, and 6.7 meters.  Organisms recovered were common to Lake Erie.
Benthic samples from Station 3 revealed a rich population of small tubificid
Oligochaeta
33, and 34.
Oligochaeta (115/36 in2; 5QQO/m2).      The plankton are listed in Tables 32,
                                       78

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Table 31   DESCRIPTION OF VARIOUS WATER QUALITY PARAMETERS
           AT STATION LOCATION AT THE TIME OF BIOTA SAMPLING


Date (Sept. 73)
Depth of Sample
(plankton)
Temperature
of H20
Dissolved
oxygen
Chlorine
residual
PH
Conductivity
(umhos)
Station Station
1 2
4 4
surface surface
29.5C 31C

7 . 8ppm 7 . 5ppm

< 0 . Ippm 8 . Oppm
7.3 7.35
620 2650
Station
3
5
1 meter
27C

4 . 3ppm

0 . OSppm
7.08
1400
Station Station Station Station Station
33666
55555
3.6 m 6.7 m 1m 6.7m 12.8m
1
' |
26.1C 25.2C 25C 24.5C 17C
1
3 . 9ppm 3 . 3ppm 8 . 4ppm 7 . Sppra 2 . Oppm
1
O.lppm O.Olppm 
-------
                                 Table 32   STATIONS  FROM WHICH PLANKTONIC ORGANISMS WERE
                                            OBTAINED  AND  THE  ABUNDANCE  IN TERMS OP CELLS
                                            PER LITER - SURFACE SAMPLES.
Station 1
(6 in. depth)
Upper Ashtabula River

Cyclotella
Cymbella
Cladoceran
Idamaged)
Pediastrum sp.
simplex


68
4
1
2
Station 2
(6 in. depth)
Fields Brook

Pediastrum
simplex
Pediastrum sp.
2
Pediastrum sp.
Keratella
cochlearis
Navicula
Cyclotella


12
6
6
12
*
*
Station 3
(1 m)
Ashtabula River

Closteriopsis
longissima .
Ceratium
hirundinella
Keratella
cochlearis
Staurastrum sp.
Fragilaria sp.


83
33
25
8
8
Station 6
(1 m)
Lake Erie

Staurastrum sp.
Ceratium
hirundinella
Keratella
cochlearis
Fragilaria sp.
Closteriopsis
longissima
Pediastrum
simplex


183
67
67
50
25
17
Station 5
(1 m)
Harbor

Keratella cochlearis
Fragilaria sp.
Ceratium hirundinella
Staurastrum sp.
Anacystis
Pediastrum simplex
Tabellaria
Closteriopsis
longissima
Stephanodiscus
Difflugia
Cosmarium
Botryococcus


92
75
67
50
50
33
25
25
25
25
8
8
00
o
     * will  be quantitatively reported  in  specific diatom studies

-------
                                 Table  33   STATIONS FROM WHICH PLANKTONIC ORGANISMS WERE OBTAINED
                                           AND THE ABUNDANCE OF PLANKTON PRESENT IN TERMS OF CELLS
                                           PER LITER   MID-DEPTH
Station No. 3
(3.6 meters)
Ashtabula River
Pediastrum simplex
Keratella cochlearis
Ceratium hirundinella
Codonella cratera
Copepods (damaged)

Various diatoms

Staurastrum sp.



250
100
75
17
17

--

17


Station 6
(6.7 meters)
Lake Erie
Ceratium hirundinella
Keratella cochlearis
Anacystis sp.
Closteriopsis
longissima
Staurastrum sp.

Diaptomus sp.

Fragilaria sp.


100
58
58

58
33

25

25

Station 5
. (4,9 meters)
Harbor
Closteriopsis longissima
Fragilaria sp.
Pediastrum simplex
Ceratium hirundinella
Keratella cochlearis

Anacystis sp.

Staurastrum sp.

Difflugia sp.

317
200
167
150
83

75

50

25
CO

-------
                             Table 34  STATIONS FROM WHICH PLANKTONIC ORGANISMS WERE OBTAINED
                                       AND THE ABUNDANCE OF PLANKTON PRESENT IN TERMS OF CELLS
                                       PER LITER - BOTTOM DEPTH
Station No. 3
(6.7 meters)
Ashtabula River

Ceratium hirundinella
Pediastrum simplex

Staurastrum sp.

Fragilaria sp.

Closteriopsis
longissima
Keratella cochlearis
Diaptoraus sp.
Tabellaria sp.
Anacystis sp.
Difflugia Sp.
Cladoceran



100
75

58

58

42
25
17
17
17
8
8

Station No. 6
(12.8 meters)
Lake Erie

Staurastrum sp.
Closteriopsis
longissima

Pediastrum simplex

Ceratium hirundinella
Fragilaria sp.
Keratella cochlearis
Anacystis sp
Codonella crate.ra
Asterionella Sp.





92

92

83

33
25
17
17
8
8



Station No. 5
(8.8 meters)
Harbor

Fragilaria sp.
Pediastrum simplex

Ceratium hirundinella

Closteriopsis
longissima
Staurastrum sp.
Anacystis
Keratella cochlearis
Tabellaria sp.






75
75

58


50
42
33
8
8




OO
KJ

-------
          Plankton samples from the harbor (Station 5) were obtained at
depths of 1 meter, 4.9 meters, and 8.8 meters (Tables 32, 33, 34). The
harbor water contained a more numerous and diverse plankton community than
the lake or river (Table 33).  Benthic organisms from mid-harbor sediments
contained approximately 50 "unhealthy"* tubificids, one leech, 5 Pisidium
(clam) and 2 tiny Sphaerids (Sphaerium) per 36 sq in.  This was similar to
the 1950 collection of benthic organisms  (Brown, State of Ohio, 1953).

          Plankton samples from Station 6  (Lake Erie) were obtained at 1
meter, -6.7 meters, and 12.8 meters.  The  dominant plankters at this station
were  no more diverse than that found at Station 3, but some species were
more  abundant  (Tables  32, 33,  34).  Most  of the organisms common in the
lake  were also present in the  river at Station 3.  Lake sediments  contained
few tubificids  (3/36 sq in) and tiny Sphaerium  (clam).

          Cell counts observed in these measurements are lower than might
normally be expected in the Great Lakes.  However, several reasons may be
cited for these low counts:

          (1)  The use of a #12 mesh allows organisms finer than 100 p to
escape the net and thus be inadequately represented.

          (2)  The presence of potentially toxic conditions in harbors like
Ashtabula with low natural flow during the time of sampling and relatively
high discharges of industrial waste.  A comparison of this habor with open
lake conditions is thus difficult to make.

          (3)  Forms such as Closteriopsis longissima (a large form caught
on the net) are present in low numbers also.

          (4)  Diatom cell numbers were also low at Station 6, the most open
water station in the study.  Another study, Ohio EPA  (1973),  also observed
low cell counts.
 Tubificids examined were present in very poor condition for  identification  at
 Station 5  (sluggish, flaccid) in contrast to those recovered from  Stations  3
 and 6 (active, solid).
                                       83

-------
          (5)  The "as is" samples did not indicate large number of organisms
which would refute the above observation of low cell numbers.

Diatom Analysis

          Diatom communities have been summarized on samples obtained from
the upper Ashtabula River (Station 1, above Penn Central RR Bridge), Fields
Brook (Station 2),  the Ashtabula River below the entrance of Fields Brook
(5th St.  Bridge,  Station 3), mid-harbor (Station 5), and outside the harbor
(Station 6).

          Diatoms were concentrated from 300 ml of sample by gentle filtration
through a 0.45umembrane filter.  The filter, debris, and organic materials
were digested by concentrated sulfuric acid at room temperature for 23 hours.
The resulting diatom sediment was washed in distilled water until the pH of
the solution was approximately 7.  Microscope slides were made using Caedax
and were examined at 430X and 1000X  (with oil) magnification.

          The abundance of each diatom genus or species was expressed as
the percent of the total number of cells counted.  In nearly all cases at
least 100 individual diatoms were examined if 100 could be counted within
45 minutes.  Tables 35-39 list the diatoms identified and their abundance at
each locality.

           In the upper Ashtabula  River,  the  diatom,  Cyclotella, dominated
 the plankton community  (Table 35).   This  station, when  compared to  others  of
 this  study,  was not significantly different  in  diversity,  though  Field's
 Brook  and  Lake Erie appeared to  have the fewest  number  of  genera.   The
 primary  organisms  found  in  the water were  diatoms.
                                       84

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Table 35   Diatom Distribution  of the  Upper Ashtabula River  (Station  1)
DIATOM

Cyclotella sp
Navicula sp
Tetracyclus lacrustis *
Cymbella sp
Rhoicosphenia curvata
Svnedra sp
Frustulia sp
Surirella sp
Nitzschia sp
Fragilaria crotonensis
Cocconeis sp
Melosira sp
Amphora sp
Gyros igma sp
Hantzschia sp

ABUNDANCE (%)

64.0
13.2
4.6
3.2
3.2
1.9
1.9
1.2
1.2
1.2
1.2
0.6
0.6
0.6
0.6
* Identification is not consistent with the fact that T. lacrustis
    has not previously been reported  in Ohio
                                   85

-------
 Table 36  Diatom Distribution in Fields  Brook  (Station 2)
      DIATOM
ABUNDANCE  (%)
Fragilaria crotonensis




Stephanodiscus sp




Coscinodiscus "~sp ~~




Tabellaria  sp




Melosira  sp



Nitzschia  sp




Navicula  sp




Surirella  sp



Cyclotella  sp



Fragilaria




Cocconeis  sp



Rhoicosphenia curvata
   32.0



   17.8




   10.2




    9.3




    6.8



    5.9




    5.9




    4.2




    2.5



    2.5



    1.7




    1.7
                                 86

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Table 37   Diatom Distribution in the Ashtabula River (Station 3 - Mile
           Point 0.7,  5th St.  Bridge)
DIATOM (1 Meter)

Cyclotella sp
Nitzschia sp
Navicula sp
Coscinodiscus sp
Synedra sp
Cymbella sp
Cocconeis sp
Surirella sp
Rhoicosphenia
curvata
Melosira sp
Diatoma vulgare
Fragilaria sp




%

54.5
22.0
11.0
3.0
2.5
2.0
1.5
1.5


1
1





DIATOM (3.35 m)

Cyclotella sp
Navicula sp
Nitzschia sp
Cymbella sp
Coscinodiscus sp
Melosira sp
Fragilaria sp
Caloneis sp
Tabellaria sp

Gomphonema sp
Stephanodiscus sp
Surirella sp
Synedra sp
Diatoma vulgare
Tetracyclus sp

%

35.0
23.0
15.5
6.5
5.0
3.0
2.5
2.5
2.0

1.5
1.5
1.0
1.0
0.5
0.5

DIATOM (6.70 m)

Cyclotella sp
Navicula sp
Nitzschia sp
Cymbella sp
Fragilaria crotonensis
Coscinodiscus sp
Melosira sp
Surirella sp
Stephanodiscus sp

Amphora sp
Cocconeis sp
Rhoicosphenia curvata
Diatoma vulgare
Tetracyclus sp
Tabellaria sp

%

22.3
16.5
14.0
9.1
9.1
8.3
3.3
3.3
2.5

1.7
1.7
1.7
0.8
v
0.8
0.8

                                87

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Table 38   Diatom Abundance  in Ashtabula Harbor  (Mid-Harbor,  Station 5)
DIATOM (1 meter)

Stephanodiscus sp
Fragilaria
crotonensis
Cyclotella sp
Coscinodiscus sp
Fragilaria
virescens
Nitzschia sp
Tabellaria fenestrata
, Melosira sp
Rhoicosphenia
curvata
Navicula sp
Cocconeis sp

Surirella sp




%

19.5
16,9

14,5
13.0
8.5

8.0
7.3
3.6
3.0

3.0
1.5

1.5




DIATOM (4.88 m)

*
Cyclotella sp
Fragilaria
crotonensis
Stephanodiscus sp
Melosira sp
Tabellaria
fenestrata
Navicula sp
Nitzschia sp
Coscinodiscus
Rhoicosphenia
curvata
Diatoma vulgare
Cocconeis sp

Gyrosigma sp
Amphora sp
Fragilaria
virescens

%

23,3
20,0

19.5
7,3
6.0

5.3
4.6
4.6
2.6

2.0
2.0

1.3
0.7
0.7


DIATOM (8.84 m)

Fragilaria virescens
Cyclotella sp

Stephanodiscus sp
Melosira
Diatoma vulgare

Tabellaria fenestrata
Nitzschia sp
Coscinodiscus sp
Fragilaria
crotonensis
Navicula sp
Rhoicosphenia
curvata
Achnanthes sp
Surirella sp.
Cocconeis sp

Gyro sigma sp
%

18.2
18.0

12.0
7.8
7.8

6.6
6.0
6.0
4.6

3.6
3.0

3.0
1.8
1.2

0.6
                                88

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         Table 39   Diatom Abundance in Lake Erie off Ashtabula Harbor (Station 6).
                    Diatoms encountered in surface sample were rare.   Only ten
                    individuals were encountered during a 45 minute counting period.
DIATOM (1 meter)

Fragilaria sp

Nitzschia sp

Navicula sp

Stephanodiscus









%

60

20

10

10









DIATOM (6.7 m)

Fragilaria
crotonensis
Fragilaria
 virescens
Tabellaria
fenestrata
Stephanodiscus sp
Nitzschia sp
Cyclotella sp
Navicula sp
Coscinodiscus sp
Melosira
Cocconeis



-%

45,0

20.0

15.0

5.3
5.3
4.0
2.5
1.3
1.3
1.3



DIATOM (12.8m)

Cyclotella sp

Tabellaria
fenestrata
Melosira sp

Stephanodiscus sp
Fragilaria sp
Coscinodiscus sp
Nitzschia
Navicula sp
Diatoma vulgare
Gyrosigma sp
Surirella sp
Cocconeis sp
***
%

15.0

14.0

12.5

12.5
11.5
9.2
9.2
5.8
4.6
2.3
1.2
1.2

***  In addition to the diatoms counted in this  sample,  a significant amount of
     fragments belonging to the Genera Cymbella  and Fragilaria  were observed as
     being present at this depth.
                                        89

-------
          Fields Brook, containing 8 ppm residual chlorine, also yielded live
green algae and rotifers, as well as many species of diatoms.  In view of the
high residual chlorine values, these organisms are thought to have been carried
downstream to the sampling area from areas of Fields Brook above industrial
discharges.  Fragilaria crotonensis dominated the diatom community of Fields
Brook.  Table 36 lists the diatoms recovered from water samples.  Stephanodiscus,
Coscinodiscus, and Tabellaria were found in highest concentrations with Fragi-
laria.  Only two significant diatom species ( 5%) were recovered in the upper
Ashtabula River, but seven species of significance were recovered from Fields
Brook and represented 88% of the total diatom community.  It was not within
the scope of this study to sample and assess attached (sessile) algal forms.
Planktonic diatom forms were of major concern.  A "control" sample of attached
forms in the areas of sampling would have had to be obtained by a diver.  In
addition, back-up of lake waters to the Penn Central Bridge affected any samples
which would have been gathered below the first small falls at Station 1.  Sta-
tion 1 biota samples were taken at a point just above the small falls in a
shallow, lotic environment.

           Greatest diversity  and abundance of diatoms occurred at Station 3,
the  lower  Ashtabula  River.  The influence of  Field's Brook could be seen
by the  presence  of Stephanodiscus and Coscinodiscus in  significant concen-
trations.   Cyclotella  and  Navicula dominated, as  in the upper River.
Table 37 summarizes  the results of studies at three depths.

           In the mid-harbor waters, the  diatom  community represented contri-
butions from lake, river and  Field's Brook communities  (Table  38).
Dominance  was  shared by  Stephanodiscus  (Field's  Brook), Cyclotella  (River),
Fragilaria crotonensis (Field's Brook),  Fragilaria virescens  (Lake Erie)
and  Coscinodiscus (Field's Brook).  These  species represented  85-72.5 percent
of  the  diatom community  at Station  5.  Melosira was recovered  here in
significant concentrations at 4.9 meters and  8.8 meters.

           Surface water  samples from Lake  Erie,  outside the  harbor, were
nearly  devoid of diatoms.   Concentrations  increased with depth,  but were

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 low even in bottom samples  (Table  39).   Dominance varied more with depth
 than it did at other stations.  Fragilaria, Tabellaria,  Stephanodiscus,
 Melosira (6.7 meters) and Cyclotella  (at 6.7 meters) were the dominant diatoms.
 In 1950 (State of Ohio, 1953) the lake water at Ashtabula was dominated
 by Melosira, Stephanodiscus, Fragilaria and Asterionella.  In the present
 study, no Asterionella was recovered in any amount.  Melosira was present
 but not dominant, except at 6.7 meters where it represented 12.5% of the
 diatom community.  Asterionella has been the dominant organism in Lake Erie
 for many years but began to disappear from samples after 1950.  It is known
 to peak in spring and winter, which may explain the absence of Asterionella
 from these  late summer samples.  Therefore, no significance should be attached
to a seasonal form which might not have been sampled in the present study.
Fragilaria  occurred frequently in samples observed for the present study and
often dominated.   This diatom has dominated many samples from Lake Erie since
 1950 and has a late summer or early autumn peak.

         The low biomass, low diversity (in relation to studies of unaffected
areas  of Lake Erie),  and dominance of only a few species at Station 6 may
indicate toxic conditions at the harbor mouth.   (See also discussion of low
cell counts under Biota).

         Many of the algae genera represented in samples from the Ashtabula
 River, Field's Brook, Harbor and Lake Erie have been classified as organic
 pollution tolerant organisms  (Palmer, 1969).  Nitzschia and Navicula appear
 high on the tolerance list.  Synedra, Melosira, Cyclotella, Pediastrum,
 Fragilaria, Surirella, and  Stephanodiscus appear on the first half of the
 pollution tolerant genera list.

          As association was noted in samples in which Fragilaria  crotonensis
 dominated.   Tabellaria  fenestrata, Stephanodiscus and Coscinodiscus were
 also found in high concentrations.
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          Species,  such as Rhoicosphenia curvata,  Navicula sp,  Cymbella sp,
and Synedra were recovered only in the River.   These were also  recovered in
the Harbor, where River influence was felt.

          Diversity and biomass of diatoms increased with depth at nearly
all stations.  This could be due to an increase of available nutrients with
depth,  photo inhibition of diatoms,  and sinking of diatoms.
                                       92

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                                  Section 7
                                  DISCUSSION
Water Quality Aspects
         An overall view of the data presented in Section 6 indicates that the
prime water quality problems associated with the Fields Brook-Ashtabula River
area involve discharges of chlorine, dissolved solids, chlorides, and mercury.
Fecal coliform bacteria have been found present to a degree which indicates
discharge of sanitary sewage at selected points in the river.  The  lift bridge
at 5th Street is a case in point where fecal coliform values have revealed the
presence of a sanitary discharge not connected to the municipal sewage treat-
ment facility.  Occasional upstream samples contain high concentrations of
fecal coliform, but the sampling program here was not designed in such detail
as to determine their location.  For the periods sampled, the harbor or lake
area sites did not contain values of coliform which were high.  In view of the
residual chlorine values present over much of the river and harbor areas, coli-
form values could be expected to be low.  Over the next 2-3 years, however,
lowering of residual chlorine in discharges will necessitate increased atten-
tion to this parameter.

         The general water quality picture appears to have improved somewhat
over the past several years in Ashtabula.  Floating algal masses, high fecal
coliform values, and noticeably pigmented discharges have all decreased during
the period 1968-present.  With the exception of near bottom values, dissolved
oxygen concentrations at most stations are in the 6.5-8 mg/1 range.  BOD and
COD values for Fields Brook usually (AS III, IV)  are above those for the river
in the near vicinity of Fields Brook.   The AS V sampling series was a notable
exception (the BOD on that date was lower than the previous sampling days).
Settleable solids measurements, were,  in general,  negligible at all stations
with the exception of Station 2, Fields Brook,  measuring a relatively constant
0.15-0.2 mg/1.   Suspended solids measurements were relatively low at all sta-
tions including the Pinney Dock area where new work dredging was being done.
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         With the exception of Fields Brook, nutrient elements present as
total phosphorous at most stations yielded values which were relatively
similar within each sampling series but varied greatly from date to date.
Phosphates (ortho) remained at low levels for most of the stations on each
date sampled.   Nitrate levels at Fields Brook and Station 3 were elevated
and remained at higher levels throughout the study.   Nitrate levels measured
at Fields Brook 4.4-6.0 mgA   for the three dates in the primary sampling
series.   Downstream values generally decreased with  increasing distance
from Fields Brook.  Values of nutrient parameters measured in the harbor can
be considered as conducive for the stimulation of phytoplankton and algal
growth in the harbor.   This does not take into account the presence of poten-
tially toxic components.  Phosphate contributions from Fields Brook to the
river and harbor are relatively minor, but it does appear clear that the
nitrate source is Fields Brook.

         Sulfate concentrations are high upstream and decrease in the down-
stream direction.  Fields Brook sulfate levels are close to upstream values.
This decrease demonstrates the dilution of Fields Brook and upstream water
by lake water.

Organic Constituents

         The presence of a major unknown organic component in Fields Brook
waters was detected in the limited sampling and analysis program for organic
chemicals.  The results of this preliminary survey indicate that the unknown
material is halogenated and that it elutes after hexachloroethane and before
hexachlorobenzene.  None of the other materials surveyed by gas chromatography
were above the limits of detectability for several organic components.  A
survey of chlorinated pesticides and PCB's indicated none to be present above
the limits of detectability  (Table 23).
                                      94

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Metals

         Most metals surveyed in this study appear to be at sufficiently low
levels at all stations as to present no major problems.  With the exception
of iron, metal ions present in Fields Brook are normally at levels higher
than the other sampling sites.  Mercury, however, demonstrates the complexity
of circulation patterns in the river and harbor, and the need for closely
controlled sampling patterns and frequency.  The Ohio standard for mercury
is Q.S/ug/l .   This standard is exceeded in nearly every measurement made
in Fields Brook during the course of this program and by previous USEPA
sampling.  Examination of Table 26 points out the need for closely spaced
and frequent sampling.  USEPA samplings were done during periods of higher
flow than sampling done in the primary period of this study.  A return
visit to Ashtabula during May 1974 indicated the presence of mercury concen-
trations at Fields Brook (Station 2) and the Fields Brook mouth to be from
3 to nearly 12 times the maximum allowable concentrations.  From time to
time high concentrations of mercury are discharged and appear at other
locations at fairly high levels (e.g., 4.8  /ig/1 , Station 6 on 9/5/73;
4.3  Mg/1  Station 1 on 9/10/73).  An elevated concentration of mercury
was measured by the USEPA at an outfall at E. 24th St of 2.2  Mg/1 on
12/10/73.  However, follow-up sampling by Calspan in May 1974 indicated no
significant presence of mercury in the river at that location on four
separate occasions.  A measurement on Fields Brook made on 5/10/74 at
the east side of the State Road Bridge yielded 21  y.g/1   mercury, while
measurement of an outfall on the west side of the bridge yielded 1.9  Mg/1 
Both measurements are clearly in excess of the Ohio standard of 0.5 yg/1.
It appears that the presence of mercury in these two samples is very real
because a measurement at Station 2 downstream on Fields Brook on the same
day indicated the presence of a concentration of 5.8  yg/1 Hg.  The fact
that warm, less dense water was discharged from Fields Brook at all sampling
times may account for the presence of high concentrations of mercury appear-
ing at selected sampling locations during this study.  Warm Fields Brook waters
are, postulated to override colder, more dense river and harbor waters and thus
be prevented from full mixing and dilution.  This is true even though high
dissolved solids concentrations are discharged and contribute to density increases

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          We recommend a detailed,  comprehensive  survey preferably with an on-
 site analysis  capability (Atomic Absorption)  be  conducted during the late
 Spring,  Summer and early Fall  of the  year to  determine the levels and degree
 of compliance  with water quality standards for discharges into Fields Brook.
 Further,  we recommend that  the outfall  near the  E.  24th St area be monitored
 in addition.

Chlorine Discharges
         Brungs'  (1973) recommendation of chlorine residuals of 0.002 mg/1
or less for the protection of most aquatic organisms causes a dilemma in
relation to the use of chlorine as a disinfection agent in municipal sewage
treatment.   One one hand,  disinfection is necessary to remove potentially
hazardous micro-organisms; conversely, the presence of chlorine at disinfection
levels can be toxic to some species present in the receiving waters.  The
problems specifically involved with Fields Brook are the accurate determination
of free versus combined chlorine residuals and the determination of chlorine
demand and degassing parameters.  A theoretical model has been developed as
part of this effort and is presented here (Pereira, Terlecky and Yaksich, 1974)
as Appendix 3.  The method used in this investigation was the orthotolidine
method for determination of total residual chlorine concentration.  Because
of the absence of any appreciable amount of ammonia present in Fields Brook
waters and because of large quantities of chlorine added to the water, all  of
the ammonia should be oxidized at the pH values encountered.  Normally 8 to 10
parts of chlorine per part of ammonia nitrogen are required to remove all of
the ammonia at what is called the breakpoint.   Excess chlorine remains as
free chlorine.  Fields Brook, with low ammonia values and high total residual
chlorine values,  thus should have high values  of free residual chlorine in
relation to combined residual chlorine.  The model developed in Appendix 3
thus would be directly applicable to the Fields Brook situation.  Based on the
average amount of ammonia present in Fields Brook and total residual chlorine
values measured,  it is estimated that as much  as 80 to 90% or possibly more of
                                       96

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the total residual chlorine is actually free chlorine.  Residual chlorine
values present in Fields Brook clearly have an important effect upon biota
associated with it.  Vegetation which is near the brook is brown and mottled
in appearance.  At many places, most of the vegetation is dead.  Station 2,
Fields Brook had very low planktonic cell counts and had a relatively low
diversity of organisms present during plankton collection.

         Most of the organisms  (plankton) found in the Fields  Brook samples
were alive when collected which suggests being washed in  from  upstream Fields
Brook areas above the major chlorine discharge  (and thus  above Station 2)
since tolerance of chlorine levels measured here would not be  expected.  Flow
velocities in Fields Brook exceed 2 feet per second which reduces exposure
time.  Throughout this study,  cell counts of planktonic organisms were low
in Fields Brook confirming the presence of postulated toxicity conditions.
Because of the levels of chlorine discharged from Fields  Brook, and the presence
of residual chlorine concentrations above the recommended levels, it is relatively
safe to conclude that continued discharge of chlorine from Fields Brook at the
levels measured in this study  causes the deterioration of water quality from
the Penn Central Bridge to the entire harbor area.

          Several  options  are  available  for control of the chlorine discharges.
Sulfur dioxide or  sulfite  treatment is well known and has been proven  to be
effective in  reducing the  chlorine toxicity of  wastewaters.(See,  for example,
Baker, 1964;  White,  1968;  White,  1972, p. 456;  Dean,  1974).  Lagooning, pH
control between 7  and 8, and  retention for a very few minutes  should be suffi-
cient to control  chlorine  levels  to tolerable levels.  Injection  of SO- or
sulfite in the wastewater  in  sufficient  quantities to reduce residual  chlorine
levels to tolerable  limits in  the range  of 1-.5 mg/1  at  the State Road outfall
on  Fields Brook should  be  sufficient  to  preclude harmful  effects  to resistant
aquatic biota in  the Ashtabula River.  Other dechlorination methods available
include  activated carbon  (White,  1972;  Bauer and Snoeyink,  1973)  and ammonia
 (White,  1972).  Each method  has its own  limitations which must be explored
fully for application to a specific case.
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         A second option which should be examined is the piping of all or part
of the chlorine-containing effluent to the municipal sewage treatment plant,
a distance of approximately one mile.  The possible utilization of this waste-
water might therefore eliminate two problems.   The purchase of chlorine by
the treatment plant and the elimination of a harmful effluent from Fields
Brook.  Undoubtedly, there are many serious facets to this solution which must
be explored to determine feasibility, but consideration of this appealing
option should be made.

          The presence of many chlorinated organic compounds previously sus-
pected as possibly being present in Fields Brook waters was not confirmed in
this study.  Phenol levels also were quite low.   Therefore, the reactions which
might be suspected to take place in Fields Brook between chlorine and other
organic compounds were not detected.
          Examination of the  empirical data for  Fields  Brook,  and the Ashtabula
 River and Harbor area for total chlorine residuals enables an estimate to be
 made of what levels of control might be necessary to reduce chlorine concentrat-
 ions to acceptable levels.   It should be borne  in mind that these estimates
 are empirical estimates and  should be used only as indicators rather than
 absolute guidelines.  Table  40 was constructed  to-assemble available chlorine
 data for key stations and facilitate this empirical estimate.  A sample of the
 outfall on the west side of  the State Rd. bridge over  Fields  Brook indicated
 the presence of 35.0 mg/1 total residual chlorine concentrations (5/10/74).
 The maximum amount of discharge allowed for this period by NPDES permits issued
 by the USEPA was 25 mg/1 for one company in the Fields Brook area.
          Levels of residual chlorine concentration of 3-12 mg/1 at the E.  15th
 St. sampling location and Fields Brook may represent values of from appoximately
 30 to greater than 100 mg/1 at the upstream outfall in the absence of diluting
 waters.  A reduction of total residual chlorine concentrations at the State Rd.
 outfall at least to 0.5-1 mg/1 thus appears necessary to reduce concentrations
                                       98

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                                  Table 40
TOTAL CHLORINE RESIDUAL (mg/i) MEASURED AT SAMPLE SITES ON DIFFERENT DATES
Date
Station
Outfall on
Fields Brook
2
Mouth of F.B.
3
4
5
8
6
9/5/73

12.0
-
0.05
0.04
0.01
0.005
< 0.005
9/8/73

1.10
-
0.01
*0.01
0.01
-
0.01
9/10/73

6.5
-
0.02
0.01
0.01
-
<0.01
5/8/74

6.5
9.5
-
-
-
-
-
5/8/74

4.5
4.0
-
-
-
-
-
5/9/74

4.5
3.0
-
-
-
-
-
5/9/74

3.0
3.0
-
-
-
-
-
5/10/74
35.0
2.4
-
-
-
-
-
-
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at the Fields Brook mouth to 0.1 mg/1,  a value which should protect resistant
species in the Ashtabula River.  Such reduction would also reduce levels in the
lower river and harbor to values of 0.01 and less during low flow periods.
Present measurements vary from 1-5 mg/1 commonly at the mouth of the brook.
This value is highly variable depending upon runoff, sunlight, and initial
concentration in the outfall.  Clearly if the use of empirical measurements  is
valid in this case, it will be necessary to drastically reduce Fields Brook
chlorine residuals from present levels to protect river and harbor biota.  During
periods of relatively high flow of the river  (discharge in excess of 150-200
cfs), the permissable limits of discharge can be set higher-  No reduction of
Fields Brook chlorine residuals was seen during the May 1974 sampling period,
a period during which the new NPDES permits have been in effect.  One discharge
source is known to contribute wastewater of a total residual chlorine value
as high as -200 mg/1 at various times.  This source is expected to be under
permit at the end of 1974.
         A detailed monitoring program for chlorine concentrations appears
warranted, therefore, to quantitatively determine empirically what relation
outfall values have to values in Fields Brook, the Ashtabula River, and Ashta-
bula Harbor.  Based on the above data, it is necessary to reduce values at the
Fields Brook mouth to .1 mg/1 total residual chlorine to insure protection of
resistant species in the Ashtabula River.  For protection of less resistant
species, further reduction of values measured in the Fields Brook mouth to
<.05 mg/1 will be necessary.  The only definite way to insure that these  values
are attained is to significantly reduce discharge limits of total residual
chlorine to at or below those recommended for attainment at the State Road
outfall.  In this way, variations in flow rates and other conditions can  be
accommodated.

Dissolved Solids and Conductivity
          Examination of  conductivity data as an index to dissolved solids
 concentrations, plus the data obtained by direct measurement in the primary
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sampling series of this study leads to the conclusion that one of the prime
deterents to improved water quality is the presence of large amounts of
dissolved .solids.   Because of the nature of the industries located on Fields
Brook, this observation could be expected.

         Total dissolved solids content of Fields Brook ranged from 1495 to
1612 mg/1 at Station 2 during the primary sampling.  Examination of the con-
ductivity profile presented in Figure 4 clearly shows the source of dissolved
solids in the study area.  Because of the large amount of dilution in the lower
river and harbor area, lake levels are exceeded only slightly.  Therefore, the
major effect of large dissolved solids concentrations entering the river from
Fields Brook are seen approximately one-half mile upstream and one mile down-
 stream.   Biota differences  in  the  study  area will  be  discussed  later, but  the
 presence of dissolved solids at  these levels  (with approximately  one-third
 represented by chlorides) must affect the character of the  biota  inhabiting
 this  portion of the  river.   Data in the  literature do not appear  definitive
 as  to the effect  of dissolved  solids  on  biota.   Forms tolerant  of high  dis-
 solved solids  concentrations might be present because the concentrations  at
 these levels will  affect the osmoregulatory organs of the organisms.  The
 chief effect upon fish and  other higher  forms may  be  to  prevent them from
 inhabiting the area because of avoidance.  Planktonic forms not adaptable
 to  dissolved solids  at these levels simply-will  not survive during periods
 of  low river flow.
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Flushing Time
         Flushing time has been reported on the basis  of data presented in
Section 5 of this report for Ashtabula Harbor during the period 9-11 May 1967.
There are many factors which complicate the rather simplified method and might
cause the results to be viewed as estimates rather than precise figures.  In
the absence of a superior method, The Army Corps of Engineers method was applied
to this case.   The concentration of the sodium ion was measured at many stations
and depths in the river and harbor in order to enable  a calculation of the
volume of river water present in the harbor at any one time.

         The values used for the calculation were as follows  (average values
for 5, 8, 10 September 1973):

              S  = sodium concentration in harbor =< 21.2 mg/1
               o
              S  = sodium concentration in lake   = 15.3 mg/1
              S  = sodium concentration in river  =108.6 mg/1

              V  = % of river water in harbor
               r

         Using the method presented in Section 1,

              v  .
               r     S  -S
                      r n
              V  = 100 (21.2-15.3)  _
               r    108.6-15.3	
         Therefore, 6.32% of the water in the harbor was river water according
to this calculation (low flow conditions).  Discharge of the Ashtabula River
during the sampling days average 1.57 cubic feet per second or 135,648 cubic
feet per day.  The total volume of the harbor at L.W.D.*is 294,270 x 10
cubic feet.
*
 Low Water Datum was used because the volume of the harbor was previously deter-
 mined by the Army Corps of Engineers (1968).

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         Flushing time was then computed from the relationship:

              Flushing Time = ~ = .0632 (294,270 x 105) ft3
                                       135,648 ft3/day
                                   18597.86 X 103 ft3
                                     135,648 ft3/day
                                   .1371 X 103 = 137.1 days
          Assuming a flow of river discharge along a path 1,200 feet wide (the
dredged channel) from the river mouth to the harbor entrance, and further assum-
ing that 80% of the river flow followed this path*, the Path Flushing Time was
computed at 60 days.

         To view this in perspective, the following table was constructed to
illustrate the conditions which the flushing time calculations represent:

                                     9-11 May 1967         5, 8, 10 Sept. 1973

Discharge of River                   586 ft3/sec              1.57 ft3/sec
                                  50,630 X 103 ft3/day   135.6 X 103 ft3/day
Volume of River Water in Harbor           44%                    6.32%
Harbor Flushing Time                   2.83 days               137.1 days
Path Flushing Time                1.24 days (29.8 hr)           60 days

         Examination of this data illustrates the problem facing the Ashtabula
Harbor area with receipt of concentrated discharge during periods of low flow
 Following  ACE  methods  (ACE,  1968),  the  remainder would  leave  the  harbor by
 flowing to the East  around  the  East breakwater.
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which are typical for the Ashtabula River during late Summer and early Fall.
With very little inflow of water,  there is very little water available for
dilution of wastes.   Therefore, dilution must occur with harbor or lake water.
These calculations can be viewed as conservative,  i.e., that they do not take
into account wind and current effects, circulation patterns in the harbor and
the effluent wastewater volume.  Discharge as expressed here is Ashtabula River
discharge.  Therefore, during the  annual minimum flow of the river, essentially
the vast majority of the river flow to the harbor is waste effluent from the
Ashtabula industrial complex through Fields Brook.  The water present in the
harbor, however, is  lake water for the most part during low flow periods.
Chemical data which illustrate Fields Brook influence extending upstream to
the Penn Central Bridge (Station 1) substantiate this conclusion.  High con-
centrations of conductivity, chloride, and on one occasion mercury have been
measured at this upstream station  indicating the basically stagnant nature of
the river and harbor areas during  low river flow.
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Biota Aspects

Historical vs.  Present Biota

         A variety of methods commonly used to express the abundance of zoo -
and phytoplankton makes comparison of present data with historic data
difficult.  Phytoplankton data, for instance, have been presented as volume
per unit volume of water (State of Ohio, 1953), dominant category in percent-
of-total phytoplankton population (FWPCA, 1968; Reitz, 1973), total cells per
unit volume of water without reference to species present (Reitz, 1973;
Davis, 1964,11965), or simply the genera, and sometimes the species, of
organisms present  (Davis, 1962; Verduin, 1960; Metcalf, 1942).

         Species of phytoplankton recovered from Station 6 (Lake Erie outside
the harbor) were not the typical dominant lake species normally expected
based on available literature, although none were foreign to Lake Erie water
samples.  Diatoms have always dominated Lake Erie phytoplankton populations;
however, important chlorophytes reported have included Pediastrum simplex,
Closteriopsis longissima and Staurastrum.  Dinophytes commonly recorded in
high concentrations were Certium hirundinella.  Cyanophytes common to Lake
Erie included Anacystis.

         Typically, Asterionella formosa dominated Lake Erie water until 1950,
when Melosira became the most frequently recovered diatom.  Cyclotella rose
to prominence during the 1960's, included at least four important species.
Fragilaria has been a dominant component of all lake samples and all seasons.
F. capucina and F. crotonensis were most prevalent in samples prior to this
study.

         The data reported here for 1973 however isolated high concentrations
in Lake Erie in F. virescens and F. crotonensis (60-65%) of total.  Seasonal
variations in diatom populations may explain the absence of Asterionella from
lake and harbor samples obtained in late summer, as Asterionella might be
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expected to reach its peak in the spring.   Melosira, however, would be
expected in samples from all seasons, but  was, in fact, absent or in low con-
centrations (0-12%) in September, 1973.   Cyclotella, which had been isolated
as a dominant diatom frequently in previous Lake studies (Huntz, 1954, 75-79%;
McQuote, 1954; Wujek, 1967, Detroit River; Verduin, 1962; Davis, 1954),  was
found to comprise only 4% of mid-depth samples, but 15% of bottom samples,
sharing the dominant position at 12.8 meters with Tabellaria fenestrata (14%),
Melosira (12.5%), Stephanodiscus (12.5%) and Fragilaria (11.5%).

         Zooplankton historically have been a minor component of lake plankton
samples and have included cladocerans (Daphnia), copepods (Diaptomus) and
rotifers (Keratella).  Only Keratella cochliaris was recovered in significant
proportions in lake samples during this  study, although Codonella and
Diaptomus were in evidence in mid-depth  and bottom samples only.

         Benthic organisms from Lake Erie near the Ashtabula River have
traditionally included tubificids, molluscs (pelec'ypods and gastropods),
dipterans  (Chironomus), leeches and nematodes (ACE, 1968; Brown, 1953).
Samples dredged during the present study contained very few tubificids
                  2                                                   2
(approx. 150 per m ) and approximately 50 tiny Sphaerium (clams) per m .
Toxic silts deposited by the river flow may cause loss of diversity and lack
of abundance in benthic populations.  Previous work has indicated that quan-
tities of potentially toxic metals deposited in the sediments of the river
and harbor area annually reach 112 pounds  of mercury, 2,534 tons of iron,
14 tons of chromium, =28 pounds of cadmium, -56 pounds of arsenic, 22 tons
of zinc, =11 tons of lead, 3 tons of copper and 1 ton of nickel (Leonard,
1972).  In 1967, Peloscolex comprised 4-6% of benthic populations located
in or near the dredgings dump ground (ACE, 1968).  The concentration of
populations of Peloscolex and Pisidium (clam) increased in the lake, as dis-
tance from possible toxic situations increased.  In 1973 samples from this
survey, however, neither organism could be found in Lake Erie samples outside
Ashtabula Harbor.
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          The Ashtabula River  and Harbor have historically contained similar
 biological communities though the harbor  has a nutrient  rich  environment.-
 Plankton concentrations  (State of Ohio, 1953) in  lake  and harbor water were
          83              83
 8.48  x  10  V  and 4.27 x  10   ]i respectively, but populations  consisted  of
 similar organisms and in  the  same order of dominance:  Melosira,
 Stephanodiscus, Fragjllaria, and Asterionella.

         1973 studies indicated a fairly diverse environment in harbor and
lower  river waters, but cell concentrations had followed  a trend of declining	
abundance.   Surface samples from the harbor were more diverse in species than
surface water from the river at Station 3, though the communities were similar
in dominant species.   Closteriopsis longissima dominated  in the river, but
dropped to a much lower position in harbor communities, where Anacystis, a blue
green  Algae, appeared, though  not in significant concentrations.

         Diatom communities were not similar between harbor and lower river
samples.  Harbor communities were similar to those reported for 1950, except
that Cyclotella has emerged as  a prominent species and Asterionella was not
recovered.   Melosira has declined in abundance also, so that Cyclotella,
Stephanodiscus, Fragilaria virescens, F. crontonensis, and Coccinodiccus
comprise 58.8 (bottom) to 72.4% (surface) of the community.

         Benthic organisms from mid-harbor r'esembled 1950 and 1967 collections:
tubificids,  leeches,  and clams, except that studies in 1967 (ACE,1968)  had
recovered a more diverse community including Peloscolex, Amnicola and Chironomus,
As in previous studies,  the harbor benthos was more diverse than river benthos.
                                                                   2
River benthos included approximately 5750 immature tubificids per m .   No other
                                                                      2
organisms were recovered.   Harbor tubificids numbered 2500 worms per m .   The
greater number of species  recovered indicates  the  harbor is  a healthier
benthic environment than the Ashtabula River below Fields Brook.
                                                             
         Prominent lower river diatom species  also support this conclusion.
Cyclotella,  Nitzschia,  Navicula and Synedra are  highly rated as pollution tol-
erant  (Palmer,1969).

                                      107

-------
         No previous  historic  data  on  the  biota of  Fields  Brook and the upper
Ashtabula River could be located, therefore,  comparisons of biota upstream of
Station 1 in this study to  previous  studies cannot  be made.
                                       108

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Relationship of Water Chemistry to Biological Communities
         In estimating the level of pollution, biological communities are
frequently used to evaluate the quality of the environment.  Diatoms and other
phytoplankton may indicate the level of organic pollution, pH differences,  or the
eutrophic state of the water.  Benthic organisms, such as the abundance of
various tubificid species or the diversity of communities, may indicate the
extent of organic pollution or the toxic metal content of sediments.  In general,
the phytoplankton in the Ashtabula River area did not include blooms of indivi-
dual species or an abundance of blue green algae, which might be expected in late
summer.  This did not indicate favorable water quality, but instead, pollution-
tolerant organism groups present, relatively low diversity and low concentra-
tions of plankton cells in the River-Harbor-Lake area indicate a toxic situa-
tion in which the biota are severely inhibited.  In view of the previous dis-
cussions of low cell counts encountered in this study, it could be concluded
that smaller forms escaped the plankton net.  However, larger forms present
(>100y) and diatoms (sampled without the use of a net) were also found to be
present in unusually low numbers confirming the importance of toxic substances
in inhibiting suitable environmental conditions for high diversity and high
cell numbers.

         Station 3 was chosen to show the influence that Fields Brook contaminants
may have on biological communities downstream.  Plankton analyses showed few
species present.  Cell numbers were also extremely low, with only a few species
dominating.  Water conditions, chemically, were poor due to influence of Fields
Brook water which carried high concentrations of chlorine, dissolved solids,
mercury, other metals, and chlorides into the river above Station 3.  The
results of the unfavorable addition of contaminants have been to reduce dissolved
oxygen concentrations, produce high dissolved solids concentrations, to elevate
chloride and chlorine concentrations.   The water has been further degraded  by
sanitary sewage input directly to the river at certain points by private sources. -
                                      109

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This has resulted in elevated fecal  coliform concentrations.   The  turbidity  of
river and harbor waters may have had serious effect  on  phytoplankton  growth.

         The result of dilution of these  contaminants by  river flow and in
harbor waters can be seen by an improvement  in  diversity  and  abundance  of biota
in the mid-harbor samples.  Benthic  conditions  were  improved,  as well as  the
planktonic biota of harbor water, over that  observed in the river, where  dnly
tubificids could be found.

         Lake Erie water samples also contained inhibited populations of
plankton and benthos, especially diatoms  in  surface  waters, which  were  extremely
scarce.  This finding does not agree with previous reports of Lake Erie plankton
concentrations in this area and would, therefore,  indicate a  toxic influence of
water from the Ashtabula River and Harbor on Lake  Erie  water  outside  the harbor
breakwalls.  This conclusion should be confirmed by a more detailed biological
study.
                                      110

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                                   Section  8
       PRESENT AND  FUTURE  IMPACT OF DISCHARGES ON WATER QUALITY AND  BIOTA
 Current  Impact

         Examination of the previous two sections of this report indicates the
 major problem areas for Fields  Brook and therefore Ashtabula River water quality:

              1.   Control of chlorine discharges
              2.   Control of mercury discharges
              3.   Control of dissolved solids discharges

 Solution of these three problems should eliminate the vast majority of water
 quality-related adverse effects.  Although with the exception of one sampling
 instance, the purpose of this study was not to sample effluent from individual
 plants, measurement of water quality at selected positions along Fields Brook
 and the Ashtabula River enable  conclusions to be drawn concerning upstream, and
 thus effluent water quality..

         The impact of present  discharges on the water quality and biota of the
 Fields Brook and Ashtabula River area has been discussed in Section 3 and 4 of
 this report.   Significant changes in water quality and the biota of the area
 have occurred since 1950,  and as this study shows, continued through 1973 and
 early 1974.   To date (Summer 1974),  permits issued by the USEPA after public
 hearings in Ashtabula have made no significant impact in improvement of water
 quality in Fields Brook and the lower river as far as the critical  parameters
 enumerated by this study are concerned.   Slight improvement in the  river and
harbor areas  has been detected but it is not known whether this is  caused by
reduction of effluent  or the high water levels (and thus dilution)  of the past
two years.   The organic loading of Fields  Brook is low.   Relatively low values
of COD,  BOD and TOC attest to the capability of current  permit levels to control
discharges  which would influence those  parameters.   Nitrate values  for Fields

                                       111

-------
Brook, at least during late 1973,  remained at levels  which act as a nutrient
source for phytoplankton and algae.   No limitation has been placed on nitrates.
Temperature limitations at this writing have not been imposed on the Fields
Brook industries.   We conclude from examination of Fields Brook temperature
conditions that thermal limitations  should be imposed, particularly with
reference to cooling water discharges.   During the May sampling period,  the
discharge entering the turning basin from the west side was red in color after
a short rainfall.   A scrap yard further up the drainage ditch appeared as the
possible source of the rust-colored particulates or suspended matter.

         Fields Brook water quality as  far as chlorine residuals, mercury
concentrations and dissolved solids  content are concerned has not improved.
In fact, during the low flow period of the primary sampling period, conditions
appeared to worsen.  On one sampling day, reports of people being overcome by
chlorine fumes the previous night  were  relayed by local people.  Hearings held
on October 30,1973 confirmed this.

         In summary, water quality conditions in Fields Brook for the period
October 1973 to April 1975 could be expected to improve if the issued permits
were complied with, but the data show that the level of chlorine and mercury
residuals in Fields Brook, even after dilution by natural water, exceed the
maximum levels allowed in any of the NPDES permits.  There is no doubt there-
fore that current compliance with  the existing permits is not complete as far
as Fields Brook as a whole is concerned.  Other less crucial parameters such
as temperature, metals, and minor organic contxioutions are expected  to  improve
slightly.
Predicted Future Impact

         If the terms of the permits for the period 1975 to 1978 were complied
with, the data gathered here indicate that significant improvement of water
quality can be expected in a short period of time in Fields Brook.  The maximum
total, residual chlorine allowed after April 1975 would be 0.3 mgA at each outfall
for  existing NPDES permits.  One permit  for a  chlorine discharging facility
has  not been granted  at this writing.  The draft permit, however, currently
has  a 0.3 mg/1 limitation  for  total residual chlorine  to be met by July  1,

                                       112

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1977.  Reduction of chlorine concentrations to this maximum level above (and
0.1 mg/1 average) should result in the lowering of Fields Brook total residual
chlorine levels to the range 0.05-0.005 mg/1 at the Fields Brook mouth.
Chlorine demand parameters present in Fields Brook such as the presence of
ammonia (forming chloramines) and metals would further reduce the toxicity
of this discharge and complex the available chlorine.

         The control of mercury discharges in the parts per billion range is
an extremely difficult procedure by standard methods.  Because of the State
of Ohio standard of 0.5 pg/1 (.5 ppb), it appears that either total recycle,
routing to another receiving water body, or the segregation and treatment or
extraction of mercury and source discharges must be considered.  Recent advances
in mercury discovery from wastewater and sludges may provide methods useful for
removal of the mercury at its source (Perry, 1974).  An additional possibility  .
would be use of a different method or type of electrode for sodium and chlorine
manufacture.

         There appears to be no demonstrated technology for the  large scale
removal of dissolved solids.  The permits  granted to the  Fields  Brook industries
indicate that no relief is in sight  for the dissolved solids concentrations in
Fields Brook and thus the Ashtabula  River.  Levels as high as  5000-6800 mg/1
as an  average are allowed by current permits.
         Suspended solids  concentrations as measured in this study do not
reveal a major problem.  Other data that exist suggest that a problem does
indeed exist.  A more extensive sampling program seems required to define its
extent.  Suspended solids concentration in cooling water obtained from Lake
Erie may at times reach levels as high as 200 mg/i  or more as a result of
natural phenomena.  The discharge of this cooling water into Fields Brook
certainly increases suspended solids concentration in that stream.  Compliance
with permits therefore, would cover suspended solids concentrations in Fields
Brook.  Perhaps the greatest source of water exchange during periods of low
flow in the Lower Ashtabula River and Harbor is lake setup and wave action.

                                       113

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During periods of high natural suspended solids  in the lake (maximum setup and
wave action), the natural suspended solids concentration of lake water would
control suspended solids in the harbor and lower river.   Compliance with
permits therefore would have little effect in these reaches.

         The technology to remove suspended solids by settling and floculation
is available and can be applied to attain the final limitations mandated by the
permits.  If the permit levels are attained, a definite  improvement in suspended
solids content can be expected in Fields Brook.   No control is available for
Lake Erie, however, and it is well known that lake effect extends upstream to
the Penn Central Bridge.

         If reduced to permit levels, the lowered metals concentrations of Fields
Brook discharges should serve to improve water quality with respect to these
parameters.  Lower concentrations of cadmium, copper, nickel  and lead required
by the new permits, will contribute to improved conditions for biota in the
lower river.  The chief effect of the permits in this area should be to lower
the levels of metals deposited as part of the sediments  in the study area.  This
will improve bottom conditions and be more conducive to more  desirable benthic
populations.

         Recycling process water  should be considered by the industries as a
possible  solution  to  metals  discharge, particularly  mercury.   The  piping  of
chlorine containing wastewater to the Ashtabula municipal  sewage treatment
plant  for  mixing with  the STP effluent may provide a solution  for  removal
of  at  least part of the  chlorine  residual problem.  Temperature  limitations
have been  ignored  on present permits and  should be reexamined  in light  of
elevated  temperatures  present throughout  the year in Fields Brook.

          In summary, permit  limitation  levels with respect to  chlorine  and
mercury levels  do  not  appear  to be met  at present.   If  the discharges are
reduced to permit  levels  in  1975,  significant improvements in  water  quality
can be expected to occur.  The  important  factor appears  to be  compliance  with
the permits,  and,  in  cases of non-compliance, prompt enforcement action.
                                      114

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                               LITERATURE CITED
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Aston, R.J., 1973, Tubificids and water quality:  A Review:   Env. Poll.,
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Bauer,  R.C. and  Snoeyink, V.L., 1973, Reactions of Chloramines with  Active
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Bradshaw, A.S.,  1964  The crustacean zooplankton picture:  Lake Erie  1939-
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Brinkhurst, R.O., 1967, The distribution of aquatic oligochaetes in Sagninaw
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	, 1969, Changes  in the benthos of Lakes Erie  and Ontario:
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 Brinkhurst, R.O.,  and Jamieson,  B.G.M.,  1971, Aquatic Oligochaetes of  the
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 Brooks, A.J.  and  Baker, A.L., 1972, Chlorination at  Power Plants:  Impacts
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 Brungs, W.A., 1973, Effects of Residual  Chlorine on  Aquatic  Life:  Jour.
      Water Poll.  Cont. Fed., vol. 45, No.  10.

 Burkholder, P.R.,  1929a, Microplankton studies in  Lake Erie:  Bull.  Buffalo
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           , 1929b, Microplankton studies in Lake Erie:  N.Y. Cons. Dept.,
       Suppl. Ann. Rept., vol.  18, p. 60-66.

      	,  1960, A  survey of  the Microplankton of  Lake Erie:  U.S.  Fish
       Wild.  Serv., Sp. Sci Rept., Fish., vol.  334,  p.  123-144.

                                      115

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Carr, J.F.  and Hiltunen, J.K., 1965,  Changes in the Bottom Fauna of Western
      Lake  Erie from 1930-1961:   Limnology and Oceanography,  vol.  10, p.  551-
      569.

Chandler, D.C., 1940,  Limnological studies of western Lake Erie, I.  Plankton
      and certain physical-chemical data of the Bass Island region,  from
      Sept. 1938 to Nov. 1939:  Ohio Jour. Sci., vol. 40,  p.  291-336.

Davis, C.C., 1954, A preliminary study of the plankton of  the Cleveland
      Harbor area, Ohio, III.   The zooplankton, and general ecological
      considerations of phytoplankton and zooplankton production:   Ohio Jour.
      Sci., vol. 54, p.  388-408.

	, 1962, The plankton of the Cleveland Harbor area of Lake Erie in
      1956-57:  Ecol. Mono., vol. 32, p. 209-247.

      	, 1964, Evidence for the eutrophication of Lake Erie from phyto-
      plankton records:  Limnol. and Ocean., vol. 9, p. 275-283.

      	, 1965, The standing stock of phytoplankton in Lake Erie at
      Cleveland Ohio, 1964:  Info. Bull. Planktol. Japan, vol. 12, p. 51-53.

Dean, R.B., 1974, Toxicity of Wastewater Disinfectants:  Advanced Waste Treat-
      ment Resh. Lab. News, U.S. Environmental Protection Agency  (NERC-Cincin-
      nati), July 5, 1974.

          , 1966, Plankton studies in the largest great lakes of the
      world:  Publ. Great Lakes Res. Div., Univ. Mich., vol. 14, p. 1-36.

Eugel, R.,  1962, Eurytemora affinis, a calanoid copepod new to Lake Erie:
      Ohio  J. of Science, vol. 62, p. 252.

Environmental Protection Agency,  1971, "Lake Erie Ohio, Pennsylvania,
      New York Intake Water Quality Summary 1970," 311 pp., August.

           ,  1972, "Lake Erie Ohio, Pennsylvania, New York Intake Water
      Quality Summary, 1971," 501 pp., April.

 Federal Water Pollution Control Administration, 1968, ProceedingsPollution
      of  Lake Erie and Tributaries, Dept. Interior, Cleveland, Ohio  (June
      4,  1968).

 Great Lakes Harbor Study, 1965, Second Interim Report on Ashtabula Harbor,
      Ohio, U.S. Army Corps Eng.

 Hamilton,  D.H., Jr., et.al., 1970, Power Plants:  Effects of Chlorination and
      Estuarine Primary Production:  Science, vol. 169.

 Health, Education and Welfare,  1965, Report on Pollution of Lake Erie and
      its  Tributaries, Pt 2, July.
                                      116

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Henson, E.B., 1966, A. review of Great Lakes benthos research:  Publ. #14,
      Gt. Lakes Resh. Div., Univ. of Mich., p. 37-54.

Hintz, W.J., 1955, Variation in populations and cell dimensions of Phyto-
      plankton in the island region of Western Lake Erie:  Ohio Journal
      of Science 55:271-278.

International Joint Commission, 1969, Pollution of Lake Erie, Lake Ontario
      and the International Section of the St. Lawrence River, vol. 2.

Lake Erie Report, 1968, A Plan for Water Pollution Control:  U.S. Dept.
      Int., FWPCA, August.

Leonard, R.P., 1972, Assessment of the Environmental Effects Accompanying
      Upland Disposal of Polluted Harbor Dredgings, Ashtabula Harbor, Ohio,
      Calspan Report No. NC-5191-M-2 prepared for the U.S. Army Corps of
      Engineers, Buffalo District, 4 October 1972.

McQuate, A.G., 1956, Photocynthesis and Respiration of the Phytoplankton
      in Sandusky Bay:  Ecology  37:834-839.

Metcalf, I.S.N.,  1942, The  attraction of fishes by disposal plant effluent
      in a  fresh water  lake:  Ohio Jour. Sci., vol. 42, p. 191-1971.

Meyer,  R.L.,  1971, A study  of phytoplankton dynamics in Lake Fayetteville
      as a  means  of assessing water quality:  Arkansas Univ. Fayetteville,
      Pub.  10, Aug., 67 p.

Palmer,  C.  Mervin, A Composite Rating of Algae Tolerating Organic Pollution,
      J. Phy. Col. 5:   78-82, 1969.

Perry,  R.,  1974,  Mercury  Recovery from Contaminated, Waste Water and  Sludges:
      United  States Environmental Protection  Agency Report EPA-660/2-74-086
       (December), 119 p.

Regier,  H.A., Applegate,  V.C., Ryder, R.A., Manz, J.V., Ferguson, R.G.,  Van
      Meter,  H.D. and Wolfert, D.R., 1969, The Ecology and Management  of the
      Walleye in  Western  Lake Erie:  Great Lakes  Fish. Comm. Ann Arbor,  Mich.
      Tech.  Report., vol. IS, 101 p.

Reitz,  R.D.,  1973, Distribution  of Phytoplankton  and Coliforra Bacteria in
      Lake  Erie,  Ohio Environmental Protection Agency, Division of
      Surveillance.

Scarce,  L.E., Rubenstein, Megregian, 1964, Survival of indicator bacteria
      in receiving waters under various conditions:  Proc. 7th Conf. on
      Great  Lakes Research, Univ. Mich., publ. no. 11.

State of Ohio, 1953, Lake Erie Pollution Survey:  Dept. of Nat. Res., Div.
      of Water.
                                      117

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Verduin, E.J.,'1960, Phytoplankton communities of Western Lake Erie and
      The C02 and 02 changes associated with them:  Limno.  Ocean., vol. 5,
      p. 372-380.

Verduin, J., 1964, Changes in Western Lake Erie during the  period 1948-1962:
      Vert. Inter. Verein. Limnol. 15:639-644.

White, G.C., 1968, Chlorination and Dechlorination:  A Scientific and Practi-
      cal Approach:  Jour. Amer. Water Works Assn., vol. 60, p. 540-561.

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      New York, 744 pp.

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      Serv., Nat. Water Qual. Netwk. Suppl. 2, 90 pp.

         ,  1972, Plankton diatom species biomasses and the quality of
      American rivers and the Great Lakes:  Ecology, vol. 53, p. 1038-1050.

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      Erie, U.S. Dept. H.E.W. (July 1965).

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      Indiana, and Michigan Sources, U.S. Dept. H.E.W. (July, 1965).

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      Conference on Great Lakes  Research, (1967) .

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      Ohio Dept. Natural Resources,  (Dec. 1968).

Proceedings, Conference in  the Matter of  Pollution of  Lake Erie  and Its
      Tributaries, F.W.Q.A.,  F.W.P.C.A..  U.S.  Dept.  Interior,  (1966,  1969,
       1970).

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      Ohio Dept. Nat'l  Resources, Div. Water,  (1960).

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       Report  12a, State of  Ohio, Dept. Nat'l  Resources,  Div.  Water (1967).
                                      118

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Water Inventory of the Mahoning and Grand River Basins and Adjacent Areas
      in Ohio, Report No. 16, Ohio Water Plan Inventory, State of Ohio,
      Dept. Nat'l Resources, Division of Water.

Great Lakes Harbors Study -- Interim Report on Ashtabula Harbor, Ohio,
      U.S. Corps Engineers, (1959).

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Standard Methods for the Examination of Water and Waste-water, 13th ed.,
      1971, American Public Health Association.
                                      119

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                                  APPENDIX 1.
 Methods of Analysis for the Ashtabula Ohio Water Quality Analysis
 (A = "Methods for Chemical Analysis  of Water  and Wastes,"  B = Standard
 Methods for the Examination of Water and Wastewater," 13th ed.,  1971)
  Parameter

Temperature
Hardness
Alkalinity
Conductivity
Dissolved Oxygen
BOD5
BOD20
COD
TOC
Solids (Settleable)
Solids (Suspended)
Solids (Dissolved)
Solids (Total)
Coliform (Total)
Coliform (Fecal)
Phosphorus (Total)
Phosphorus (Ortho)
Ammonia
Kjeldahl Nitrogen
Nitrate
Phenols
Cyanide
Chloride
Fluoride
Sulfate
Chlorine (Total Residual)
Oils and Grease
Reference
Method
B
B
A
A
A
B
B
B
A
B
B
B
B
B
B
A
A
A
B
B
A
A
A
A
A,
B
A
559
179
6
284
53,60
489
489
495
221
539
537
539
535
679
684
242
235
134
458
469
232-233
41
29
64
286
117
217
162
122A



219
219 (20 days)
220

224F
224C
224E
224A
408A
408B



213B
216





114C

                                      120

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                           APPENDIX 1    (Cont'd)
 Methods  of Analysis  for the Ashtabula Ohio Water Quality Analysis
 (A = "Methods  for Chemical Analysis  of  Water  and Wastes,"   B =  Standard
 Methods  for the Examination  of Water and Wastewater,"  13th ed.,  1971)
  Parameter
Organochlorine
  Pesticides
Reference
                   Method
Methods for Organic Pesticides in Water and
Wastewater, EPA 1971 (also Federal Register
V. 38, #125, 29 June 1973 App. II)
Organics
Extraction with suitable solvent and gas
chromatographic techniques employing flame
ionization detection and electron capture
detection
Arsenic
Barium
Cadmium
Chromium
Copper
Iron
Mercury
Nickel
Lead
Selenium
Titanium
Zinc
    B
    B
    A
    A
    A
    A
    A

    A
    A
    62          ,    104A
   210              129A
    83
    83
    83
    83
   121
Atomic Absorption
    83
   296              150A
Atomic Absorption
    83
                                     121

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                                 APPENDIX  2
            GENERAL STANDARDS OF WATER QUALITY FOR OHIO  STREAMS
Ammonia
Arsenic
Barium
Cadmium
Chloride
Chromium
Chromium (hexavalent)
Cyanide (Free)
Cyanide (Total)
Fluoride
Surfactants (MBAS)
Iron (Dissolved)
Lead
Manganese
Mercury
Oil and Grease  (hexane ext.)
Phenols
Selenium
Silver
Copper
Zinc
Phosphorous (Total)

Total Dissolved Solids

Dissolved Oxygen
Fecal Coliform
 mg/1
  1.5
250
            ug/1

              50
             800
               5

             300
              50
   .005
  0.2
  1.3
  0.5   '
            1000
           '   40
            1000
              .5
  5
              10
               5
               1
              75-500 (varies with hardness)
               5-75  (varies with hardness)
(limited to prevent nuisance growths
 always <_1 mg/1 daily ave. in nuisance
 growth areas)
may exceed one but not both:  1500 mg/1,
150 mg/1
>5.0 mg/1 (daily ave.); >4.0 at all times
<200/100 ml - 30 day geom. mean
<400/100 ml   in 20% or less of samples
                                      122

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Temperature
Radioactivity:
              Gross Beta
              Strontium 90
              Alpha emitters
5 F (2.8 C) over ambient with max. limits
set forth in a table in para. G, EP-1-02
^100 picocuries/liter
<_ 10 picocuries/liter
<_  3 picocuries/liter
                                      123

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                                          APPENDIX 3
On November 17, 1972 Cornell Aeronautical Laboratory (CAD changed its name to Calspan Corporation and converted to
for-profit operations. Calspan is dedicated to carrying on CAL's long-standing tradition of advanced research and development
from an independent viewpoint.  All of CAL's diverse scientific and engineering programs for government and industry are being
continued in the aerosciences, electronics and avionics, computer sciences, transportation and vehicle research, and the environ-
mental sciences. Calspan is composed of the same staff, management, and facilities as CAL, which  operated since 1946 under
federal income tax exemption.
                            THE PREDICTION OF FREE RESIDUAL
                  CHLORINE CONCENTRATIONS IN A FLOWING STREAM
                   Norman C. Pereira, P. Michael Terlecky, Jr. and Stephen M. Yaksich

                                Calspan Report No. ND-5358-M-1
                           Prepared For:

                           U.S. ENVIRONMENTAL PROTECTION AGENCY
                           REGION V, ENFORCEMENT DIVISION
                           30 JANUARY  1974
                           CONTRACT NO. EPA 68-01-1575
 Calspan Corporation
 Buffalo, New York 14221                    124

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                               ABSTRACT

       Chlorine use for disinfection and as an antifouling agent,
as well as its presence as a product of industrial processes has
resulted in possible toxic effects to aquatic biota.  A model
which predicts free residual chlorine concentrations is developed
here which considers hydrodynamic transport, chlorine demanding
reactions, and gaseous exchange with the atmosphere in a flowing
stream.  The mathematical expression of the model is written as:


            3CF            d\          3CF
         	  =   E  	L.  - u	  +  r    +   r
            at              axz          dx        L        L

This expression thus expresses the rate of change of free residual
chlorine concentration as a function of turbulent diffusion,
convective motion, chlorine demand and gaseous escape.  A method
is also suggested by which parameter values may be obtained from
laboratory and field experiments for use in the model.
                               125

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                           ACKNOWLEDGMENT

       The authors wish to thank Mr, Howard Zar (Region V
Enforcement, USEPA) and Mr. Gary Amendola CUSEPA, Cleveland] for
suggestions on the possibility of modeling chlorine and discussions
leading to the initiation of this paper*  Thanks are also due to
Mr. John Michalovic also of Calspan for technical suggestions and
discussions on various parts of this report.
                                  126

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                          TABLE OF CONTENTS


Section


  1      INTRODUCTION                                          1

  2      DEVELOPMENT OF THE MODEL                              5


         The Chemical System                                   6


  3      DEVELOPMENT OF PARAMETER VALUES FROM
         LABORATORY AND FIELD DATA                            U

  4      SUMMARY                                              16

         Literature Cited                                     17
                                  127

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                            Section 1.
                           INTRODUCTION

     The widespread use of chlorine for disinfection, and the
high chlorine concentrations in the effluents of various manufacturing
processes, leads to a concern for the potential adverse effects of
residual chlorine on aquatic organisms.

     Data have become available on the levels of toxicity of chlorine
to several fish species, phytoplankton and zooplankton (Brungs, 1973;
Brook and Baker, 1972; Hamilton et_ al_., 1970).  In general, recommended
disinfection concentrations are between 0.5 and 1.0 mg/1 which is
well below known toxicity levels to mammals (Muegge, 1956; Brungs,
1973); however, concentrations not to  exceed 0.002 mg/1 (applied
continuously) have been recommended for the protection of most aquatic
organisms (Brungs, 1973).  Chlorine has been used for swimming pool
disinfection, municipal water supplies, sewage disinfection, industrial
waste treatment, and many other uses.  Chlorine is commonly used for
prevention of algal and slime growth in cooling towers (Nelson, 1973;
Brook and Baker, 1972; Hamilton et^ ad., 1970; Beauchamp, 1969; Sladekova,
1969), as well as an antifouling agent for water conduits and intakes
(Turner et_ al^., 1948; Hamilton et_ al^., 1970).

      The presence of high concentrations of residual chlorine in effluent
produced as a result of several industrial processes is well known.
The following processes are among those which may contribute to high
residual chlorine values in wastewater:

      (1)   Electrolytic decomposition of molten sodium chloride.
      (2)   Electrolysis of HC1 acid to yield H  and C12 as a
            recovery operation.
      (3)   Electrolysis of brine.
                                 128

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       C4)    Production of chlorates for bleaching paper,
       (5)    Production of sodium hypochlorite for laundry
             bleaching.
       (6)    Paper and pulp manufacture.
       Thus, the widespread use of chlorine and the presence of
chlorine discharges in the nation's water bodies require close
scrutiny.  In order to prevent and control potentially toxic
discharges, it is important first to understand the relation
between a specific discharge into a water body and its ultimate
effect upon the quality of that water.  If the cause-effect
relationships are known, then the effectiveness of prospective
control programs can be better evaluated.  This cause-effect
relationship can be expressed in the form of a mathematical model
where each known step or process is represented by a corresponding
mathematical analog.  The better each step is understood, and the
more accurate its consequent translation into a mathematical analog
is made, the more reliable the mathematical model will become.  A
rigorous comparison must also be made between the model and actual
data before the model can be used in a predictive capacity.

       The objectives of this study are to:

       (1)  Develop a mathematical model which predicts free residual
chlorine in a flowing stream.  The model will incorporate time and
position variables, concentrations, and will be based upon actual
process mechanisms.

       (2)   Design an experimental procedure to verify the model.

       As in any quantitative work under field and laboratory
conditions, it is necessary to make some assumptions about the
problem or impose some limitations on the generality of the results
before analysis can begin.  Implicit in the development of the model
are the following assumptions and limitations:
                              129

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       1)  The analysis is restricted to a one dimensional
           macro-scale system.
       2)  Specific functional forms are assumed to describe
           the dynamic behavior of the chemical components and
           physical conditions of the model.   An effort is
           made to accurately reflect the actual process
           mechanisms while not overcomplicating the model.

       In regard to the chemical considerations, it must be remembered
that chlorine is a powerful oxidizing agent which will react
chemically with inorganic reductants as ferrous, manganous, nitrite,
and sulfide as well as organic materials.  Since a large number
of water borne materials can consume chlorine, any attempt to
model individual chemical reactions would soon become overwhelming.
As in the case of oxygen, the behavior of chlorine in a given water
body can be more easily described if the materials which consume
chlorine are thought to exert a chlorine demand just as materials
which consume oxygen are thought to exert an oxygen demand.  There-
fore, when attempting to verify a chlorine model based on chlorine
demand, one of the parameters that is needed is the chlorine demand
of the water.  Measurement of parameters which consume chlorine
such as BOD, COD, phenol, organic and ammonia nitrogen, iron, and
manganese as are available from the data on Fields Brook will not
be suitable to verify this model.

       Chlorine in water may be present as free available chlorine
in the form of hypochlorous acid or hypochlorite ion or both.
Chlorine may also be present as combined available chlorine in the
form of ehloramines and other chloroderivatives.  However, free
available chlorine is more toxic and its effect is more rapid than
that of combined available chlorine.  Therefore, this paper emphasizes
the behavior of free available  (residual) chlorine.

* Ashtabula, Ohio.
                               130

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       If this approach to model the movement and consumption of
chlorine in a stream later proves to be too simplistic,  other
process mechanisms may be incorporated into the model  as needed.
                               131

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                             Section 2.
                     DEVELOPMENT OF THE MODEL

       The movement and reactions of chlorine through a stream
is a resultant of hydrodynamic transport within the stream,
gaseous exchange with the atmosphere, and biological and chemical
reactions.  These relationships can be expressed by a mathematical
model which reflects the various inputs and outputs in the aquatic
system.  Considering the free residual chlorine balance in a one
dimensional flowing stream, the following second order partial
differential equation which was used in the development of a dissolved
oxygen model is applicable (O'Connor, 1967):
                             F% ^r1            ^ /-
                             o *-T-           d Li-
          	  =  E  	E_-u        F        s      (i)
              d t             ax2            ax

where:
Cp  -  Concentration of free residual chlorine (mg/1)

t   =  Time at a stationary point in the stream (sec)
U   =  Flow velocity in the x direction (m/sec)
E   =  Stream diffusion coefficient in the longitudinal direction
       (m2/sec)
x   =  Distance downstream (m)
S   =  Sources and sinks of free residual chlorine (mg/l/sec;
       chlorine demand, gaseous exchange, etc.)

The one-dimensional assumption of equation (1) implies that the
concentration is uniform over the stream cross-section.  The concen-
tration of free residual chlorine in the incoming or tributary flow
is considered the initial condition Cpn in equation  (1).
                             132

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The Chemical System

       The chemical behavior in a given water body is very complex
and physical factors affect any given constituent.  This is
especially true in the case of chlorine, a powerful oxidizing agent
with a high solubility in water.  The following equilibrium equations
are obtained when elemental chlorine is dissolved in water (Fair
et_al_. , 1968; Connick and Chia, 1959):

       Hydrolysis:  C12 + H2
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       The free residual chlorine, normally referred to , is that
portion of the total residual chlorine which will react chemically
and biologically as hypochlorous acid or hypochlorite ion (Standard
Methods, 1971).  Consequently
                       CF = (HOC1) + (OC1")
                          = (HOC1)
            i.e.
                       CF = (HOC1)
     CH+)

OO   H-  :
                         (4)
In the above equation (4), it is assumed that the HOC1 and OC1  are
in equilibrium and the equilibrium relationship from equation (3)
is used to relate the free residual chlorine concentration Cp to the
pH, K. and the hypochlorous acid concentration.

       The consumption of the free residual chlorine is referred to
as the chlorine demand.  The chlorine demand of a particular water
body  is caused by such inorganic reductants as ferrous, manganous,
nitrite, sulfide and sulfite ions.  Ammonia and cyanide also consume
considerable residual chlorine, while chlorine substitutes on phenols
and other similar aromatic compounds to form chloro derivatives.
These materials have varying reaction rates with residual chlorine
and these reaction rates are temperature and pH dependent.  Rather
than  consider the free residual chlorine consumed by each of the
chlorine demanding substances, we shall assume that all these
substances can be lumped together under a single term--chlorine
demand.  The rate of free residual chlorine consumption can be
explained as:
                              134

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       The free residual chlorine, normally referred to  ,  is  that
portion of the total residual chlorine which will react  chemically
and biologically as hypochlorous acid or hypochlorite ion  (Standard
Methods, 1971).  Consequently

                       C- = (HOCl) + (OC1~)
            i.e.
                                     ,-K
                       CF = (HOCl)
                                   (H )
(4)
In the above equation (4), it is assumed that the HOC1 and OCl" are
in equilibrium and the equilibrium relationship from equation (3).
is used to relate the free residual chlorine concentration C_ to the
pH, K^ and the hypochlorous acid concentration.

       The consumption of the free residual chlorine is referred to
as the chlorine demand.  The chlorine demand of a particular water
body is caused by such inorganic reductants as ferrous, manganous,
nitrite, sulfide and sulfite ions.  Ammonia and cyanide also consume
considerable residual chlorine, while chlorine substitutes on phenols
and other similar aromatic compounds to form chloro derivatives.
These materials have varying reaction rates with residual chlorine
and these reaction rates are temperature and pH dependent.  Rather
than consider the free residual chlorine consumed by each of the
chlorine demanding substances, we shall assume that all these
substances can be lumped together under a single termchlorine
demand.  The rate of free residual chlorine consumption can be
explained as:
                              135

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    rc=    	   -   	1  =  -K  ILD)   (LF)  l?Hr    (5)
               dt  /     \  dt

where:

       r   =  rate of free residual chlorine consumption
              due to chlorine demand
       Cn  =  concentration of chlorine demand

       k   =  rate constant (temperature dependent)

 m, n, p   =  empirical constants


       The above rate expression indicates that the rate at which
free residual chlorine is consumed by reaction with chlorine demanding
substances is proportional to the free residual chlorine concentration,
chlorine demand concentration and pH.  A simplification of equation
(5) would result if a stream is well buffered and the pH remains
constant.  The rate expression in equation (5) can then be rewritten
as:
                  dt
where:
=  k (H)   a new rate constant.
        K

       In addition to the above chlorine utilization, there may be
a depletion of free residual chlorine through chlorine gas escaping
to the atmosphere at the air-water interface.  This rate of escape
can be expressed as
                     dC
                                -c  (Cc
                               136

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 where
        r  =  rate of free residual chlorine depletion as
               a. result of chlorine gas escape
        GC  =  chlorine concentration in water

        Cr.  =  chlorine concentration in air
        KG  =  gas escape rate constant

 The rate expression in equation (7) states that free residual
 chlorine depletion due to chlorine gas escape is directly
 proportional to the chlorine concentration difference at the
 air-water interface.  However, for all practical purposes C
                                                            LA
 may be taken as being negligible so that equation (7) reduces to

                             /  dCF\
                       rE=   	L   =  -KGCC           (8)
                             V  dt  /
 If we assume the chlorine concentration in water as being in
 equilibrium with HOC1 then by using equation (2) we obtain

                              (HOC1)  (CO   (H+)
 which can be further expressed in terms of free residual chlorine by
 using equation (4)  as
i.e.
                       CC  '  CF
         (H )   (Cl )        r
r   -   	  - ,	  .  LF
Lc      -p           =        h
                                                              CH+]
                               [(H+)  -  K.J
                               137

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   using  this result  in  equation  (8) yields
                          dCT
                          dt
             +) + K.] K
                                                                  (9)
   We have  therefore  expressed the gas escape depletion rate  in

   equation (9) in terms of the free residual chlorine concentration Cp.


          The  expressions developed above may now be brought  together

   to give  an  overall mathematical model describing the temporal and

   spatial  (one-dimensional) distribution of free residual chlorine in

   a flowing stream.  Equation (1) may now be expressed as
                         =  E
                  at
                                                   ac
         - U
                 ax
                         + r
                                                                        (103
   which  expressed  in words is
The  rate of change
of free residual
chlorine concentration
at a given point  in
the  stream
The rate of change
of free residual
chlorine concentration
due to turbulent
diffusion at that
point
                                 The rate of change
                                 of free residual
                                 chlorine concentration
                                 due to depletion by
                                 chlorine demand
The rate of
change of free
residual chlorine
concentration
due to convective
motion of the
fluid  at  that
point


The rate of
change of free
residual chlorine
concentration due
to depletion by
gas escape
Note that the rates r_ and r  developed in equations (6)  and (9), respectively,

are included in the model as free residual chlorine sinks.
                                  138

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                                Section 3.
        DEVELOPMENT OF PARAMETER VALUES FROM LABORATORY AND FIELD
                                  DATA
          In any realistic model, accurate information is not always
available for a great many parameters.  In order to overcome this  lack
of information, an experimental program has to be tailored to provide
data through which reliable parameter values can be extracted.  The
model expressed in equation (10) contains seven pertinent constants
namely, K. , K., E, 1C, K  , m and n.  Of these constants, 1C  and K. are
available in the literature; the remaining constants then must be
determined experimentally.

          Several simplifications can be made to the model in equation
(10) in order to facilitate the computational effort.  For instance,
when considering streams, the turbulent diffusion, i.e., longitudinal
mixing, is generally assumed to be insignificant.  This eliminates the
first term on the right hand side of equation (10) and the parameter E
with it.  Another assumption usually made is the steady-state condition
which implies no change in free residual chlorine loading with time at
a point source.  This assumption eliminates the time derivative on the
left hand side of equation (10).  With these two assumptions, equation
(10) is reduced to

                        dCp
                    U 	L_  =  rc  +  rE                    (ID
                        dx

with KQ, K , m and n unknown constants.  Equation (11)  is a simplified
version of the original model in equation (10),  and it is the starting
point for the purposes of estimating model parameters.

          Sometimes it is necessary to design small controlled experiments
to develop values of specific parameters.   These experiments must be
controlled to the extent that effects of only a single parameter are
                                 139

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studied and all other parameter effects are minimized.  For example,
in order to evaluate FL, m and n, the experiment must be designed
to minimize the effects of Kf.  This means that the experiment should
highlight the chlorine demand aspects (Kn dependent) and should
minimize the gas escape aspects (1C dependent).

Determination of K_, m and n
          The rate constant K.. and the constants m and n can be
determined by the method of Pseudo Order Reactions, whereby the
experimental conditions are varied such that the chlorine concentration
is much larger than the chlorine demand or vice versa.  In the case of
Fields Brook, a situation exists where the chlorine concentration is
much larger than the chlorine demand.  Equation (6) then reduces to
the form
To determine K'   and m experimentally, a batch of the stream water can
              \j
be dosed with known concentrations of chlorine.  The depletion of
free residual chlorine then should be measured as a function of time.

          Taking logarithms on both sides of equation (11) yields

                           dCn
                             2 -  =  In K  + n In CD
                           dt
                                             /  dCD  \
This expression indicates that a plot of -In (  - - ) V/S  In CD will
yield a straight line whose slope is n and intercept is In KQ ; thus
both parameters KQ  and n can be evaluated.  The  dCD   term is obtaine
                                                  dt
by plotting C   * VS ' t and computing the slope of the resulting curve
at various values of C .  Care must be taken in carrying out the above
experiment to make sure that the gas escape from the surface of the
 **
    where  K    =  KD  (CF)

                                  140

-------
water is prevented so that the effect of Kfi is eliminated to the
maximum extent possible and the depletion in free residual chlorine
is solely due to the chlorine demand of the water.

Estimation of K,,
          The parameter Kf may be estimated by repeating the previous
experiment and this time permitting the surface escape of chlorine
gas.  The water used in this experiment should be free of chlorine
demand so that the depletion in free residual chlorine is solely due
to surface escape of chlorine gas.  Now from equation (9)
                   dCt
                   dt
                                          (Cl")
Therefore a plot of -
                        dC.
                              v/
                        dt
            .]
S  Cp should yield a straight line
through the origin with the slope being equal to
                       v-  r (H*)2 (cr:)
                       *   _- 
                        G [_[(H+) H- K.]
If values of (H ), (Cl~) are measured and K. and K,  are obtained from
the literature, Kr can be determined from the slope.
          The K_ measured in the lab can then be related to a Kr
               G                                               u
which would be expected in the stream by the following equation
(O'Connor, 1958).
                      Kr   =  3.78
                       b
                                    (A/v)
               H
                5/4
                                     141

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for deep streams
where:
        A
         '/V  =  interfacial area between the gas and liquid
                per unit -volume of liquid in the lab

          S  =  slope of the stream
          H  =  average stream depth
          U  =  stream velocity
          The above experiments are sketched out primarily to indicate
the manner in which parameters can be evaluated through controlled
experiments.  Several variations and degrees of sophistication are
possible both in the experimental stage and the mathematical manipulation.
The extent to which this sophistication is carried out would be dictated
by the available time, money and manpower resources.

          The final test of the model of course is through actual field
tests where the laboratory evaluated values of Kn and K  and n are fine-
tuned so that observed data (free chlorine residual,  chlorine demand,
chloride concentration, pH, temperature and stream depth and velocity
or slope) and computed results are very close.  Repeated curve fitting
runs should be made by varying the parameter values in question to
reduce systematic bias.  Simply put, the free residual chlorine concen-
tration computed from equation (10) should be compared with observed
field measurements of free residual chlorine.  If the agreement is poor,
the parameter values should be systematically readjusted to close the
difference between the observed and the computed results.

                                     142

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      In the above context, one can recognize the process of
model building as an iterative one in which a proposed model and
experimentation lead to data analysis, which in turn leads to
further experimentation.  This combined approach continues in a
presumably converging cycle between analysis and experimentation
toward a choice of the most adequate model.  Since the investigation
cannot be exhaustive in examining all possibilities, no proof exists
that the correct model has been found.  The investigator must be
satisfied that he has determined only the most adequate representation
of the experimental data.
                                143

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                             SUMMARY

      The widespread use of chlorine for disinfection and in
industry raises questions as to its toxicity in the nation's
waters.  At present, little or no predictive capabilities have
been developed or utilized to mitigate toxic effects upon aquatic
biota.  In an attempt to provide a means by which free chlorine
residuals may be predicted, the mathematical model expressed in
equation (10) was derived.  In this expression, the concentration
of free residual chlorine at any point in a moving stream has been
related to turbulent diffusion, convective motion in the stream at
that point, chlorine demand, and gas escape to the atmosphere.

      A method by which the necessary parameters can be obtained
from laboratory and field experimentation has been suggested whereby
the assumptions of a one dimensional, steady state source are
employed.  Small controlled experiments can then be run in which the
gas exchange rate and chlorine demand can be measured under different
conditions.

      Finally, it is proposed that actual field data can be used to
adjust the model empirically.   In this way, the predictive capacity
of the proposed free residual chlorine model can be tested and
verified.
                              144

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                             LITERATURE CITED
Beauchamp, R.  S.  A., 1969, The Use of Chlorine in the Cooling Water
          Systems of Coastal Power Stations:  Chesapeake Science,
          vol. 10, p. 280.

Brungs, W. A., 1973, Effects of Residual Chlorine on Aquatic Life:
          Jour. Water Poll.  Cont. Fed., vol. 45, No. 10, p.  2180-2193.

Brook, A. J. and Baker, A. L., 1972, Chlorination at Power Plants:
          Impacts on Phytoplankton Productivity:  Science, vol.  176,
          p. 1414-5.

Connick, R. E., and Chia, Y. T., The Hydrolysis of Chlorine and its
          Variation with Temperature:  Jour. Am. Chem.  Soc., vol. 81,
          p. 1280.

Fair, G. M., Geyer, J. C., and Okun, D. A., 1968, Water and Wastewater
          Engineering, vol.  2, John Wiley, New York.

Hamilton, D. H.,  Jr., Flemer, D. A., Keefe, C. W., and Mihursky, J, A.,
          1970, Power Plants:  Effects of Chlorination and Estuarine
          Primary Production:  Science, vol. 169, p. 197-8.

Muegge, 0. J., 1956, Physiological Effects of Heavily Chlorinated
          Drinking Water:  Jour. Amer. Water Works Assn., vol.  48,
          p. 1507.

Nelson, G. R., 1973, Predicting and Controlling Residual Chlorine in
          Cooling Tower Slowdown:  U. S. Environmental  Protection Agency,
          PNERL Working Paper No. 9 (April 1973).

O'Connor, D. J. and Dobbins, W. E., 1958, Mechanism of Reaeration in
          Natural Streams:  Trans. Am. Soc. Civil Eng., vol. 123, p. 641-
          665.

O'Connor, D. J.,  1967, The Temporal and Spatial Distribution of Dissolved
          Oxygen in Streams:  Water Res. Research, vol. 3, No.  1.

Sladekova, A., 1969, Control of Slimes and Algae in Cooling Systems:
          Verh. Intl. Ver. Limnol., vol. 17, p. 532.

Turner, H. J., Jr., et_ al_. ,  1948, Chlorine and Sodium Pentachlorophenate
          as Fouling Preventatives in Sea Water Conduits:  Ind.  and Eng.
          Chem.,  vol. 40, p. 450.

White, G. C.,  1972, Handbook of Chlorination:  Van Nostrand. Reinhold
          Co., 744 pp.
                                 145

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HHL,O..APH,CDA '' R- ^_906/9_74_008
4. Title and Subtitle
Water Pollution Investigation: Asfitabula Area
7. Auchor(s)
P. Michael Terlecky, Jr., John G. Michalovic, Sharon L. Pek
9. Performing Organization Name and Address
Calspan Corporation
Buffalo, New York 14221
1Z Sponsoring Organization Name and Address
U.S. Environmental Protection Agency, Region V
Enforcement Division
3.S^ecipienc's Accession No.
"5. Report Date
January 1975
6.
8. Performing Organization Rept
No- ND-5358-M2
10. Pcojecc/Taslc/Wocfc Unit
No.
1 ). Concracr/Granr No.
EPA-68-01-1575
13. Type of Repoct & Period
Covered
Final
u.
15. Supplementary Nones
EPA Project Officer: Howard Zar
 16. Abstracts
   This  investigation reports the  results  of a historical data  collection of informa-
   tion  concerning the lower Ashtabula  River, Harbor and nearshore area, a detailed
   water sampling and biota collection  made during 1973 and  1974-,  and an evaluation
   of  present and future discharges  on  the water quality and  biota of the area.

   The quality of water passing  through the Ashtabula complex  including Fields Brook
   has been  recognized for many  years as a serious environmental  problem.  NPDES
   permits  have been issued during 1973 and 1974 for an industrial  complex of nine
   major industries.  Total residual chlorine, mercury, dissolved  solids, and metals
   content  appear to be the most serious water quality parameters  which affect this
   area.  Measurement of these parameters  from the harbor to  Fields Brook demonstrate
   the source of the materials.  Commonly  observed values of mercury in Fields Brook
                                                                   .(continued next page)
 17. Key Words and Document Analysis.  17a. Descriptors


   Water  Quality, Aquatic Biology, Water Pollution
 17b. Identif iers/Open-Eaded Terms


   Fields  Brook,  Ashtabula River, Lake  Erie,  Chemical Parameters,  Biological  Parameters
17c. COSAT! Field/Group
18. Availability Statement

   Limited number of copies without charge from EPA;
   at  cost of publication from NTIS.
19. Security Class (This
   Report)
20. Security Class (This
   Page
     UNCLASSIFIED
21- No. OE Pages
     148
22. Petes
FORM NTIS-3S ISEV. 3-72)
                                 THCS FORM MAY BE REPRODUCED
                                                                             'J5COMM-OC 1

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ABSTRACT (.continued)

were 1.3-1.4 ug/1, although, measurements  as  high, as  4.3-4.8  ug/1  were
observed.  Total  residual  chlorine values measured at the Fields  Brook
mouth ranged from 1-12 mg/1  indicating much higher values closer  to  the   '
source of the discharge.   Dissolved solids and  conductivity  values  in-
creased from both the upstream and downstream direction  toward  Fields
Brook.  Values of dissolved solids in  Fields Brook, ranged from  1495  to
1612 mg/1 with corresponding conductivity values ranging as  high  as  1850
umho/cm.  Flushing time calculations for Ashtafaula Harbor during  low
flow conditions indicated  near stagnation for late summer.   Diatoms  and
phytoplankton recovered in the harbor  and lower river indicated the  pres-
ence of a eutrophic, pollution tolerant type of community.   Cell  counts
were found to be low, and  observation  verified  by other  researchers.  Low
biomass, low diversity, and dominance  of  only a few  species  at  each  sample
station indicated a seriously degraded water quality situation.

If the requirements of current NPDES permits are met for the 1976-1977
period, improvements can be expected in the water quality of the  area.
Further improvement in the reduction of pollutants in the 1977-1983
period is also expected.

Continued monitoring of the total  residual  chlorine, mercury, conductiv-
ity and dissolved solids during the next  two years is recommended.

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