EPA-440/5-77-015A
       EVALUATION OF
   THE PROBLEM POSED BY
    IN-PLACE POLLUTANTS
    IN BALTIMORE HARBOR
    AND RECOMMENDATION
    OF CORRECTIVE ACTION
               .
            United States
     Environmental Protection Agency
   Office of Water Planning and Standards
        Washington, D.C. 20460

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                EPA Review Notice
This report has been reviewed by the Environmental
Protection Agency and approved for publication.
Approval does not signify that the contents neces-
sarily reflect the view and policies of the
Environmental Protection Agency, nor does mention
of trade names or commercial products constitute
endorsement or recommendation for use.

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EPA 440/5-77-015A
       Evaluation of the Problem Posed by
     In-Place Pollutants in Baltimore Harbor
    and Recommendation of Corrective Action

                     United States
             Environmental Protection Agency
           Office of Water Planning and Standards
                                 APPENDICES

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                   LISTING OF APPENDICES



APPENDIX A  -  The Baltimore Harbor Environment


APPENDIX B  -  Field Data


APPENDDC C  -  Geochemical Analyses


APPENDIX D  -  Polychlorinated Biphenyls


APPENDDC E  -  Bioassay of Baltimore Harbor Sediments
APPENDIX F  -  Supplementary Data on Dredging,  Disposal,
                 and Blanketing Techniques
APPENDIX G  -  Bibliography


APPENDIX H  -  Acknowledgements and Participants
                                   - 11-

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              APPENDIX A





THE BALTIMORE HARBOR  ENVIRONMENT

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A. 1      STREAMFLOW INTO BALTIMORE HARBOR







Baltimore Harbor is located on the Patapsco River upstream from




where it joins the Chesapeake Bay.   Fresh water enters the Harbor by





way  of land runoff into storm sewers and by stream drainage to the Harbor.










The  U.  S.  Geological Survey measures (1975) continuously various stream





flows which enter Baltimore Harbor.  The major points of gauging stream-





flow are listed below:
Station No.
15860

15875

15890
15893
Station Name
North Branch
Patapsco River at
Cedarhurst, Md.
South Branch
Patapsco River
at Henryton, Md.
Patapsco River at
Hollofield, Md.
Gwynns Falls at
Villa Nova, Md.
Drainage
Area
(sq. mi. )
56.6

64.6

285
32. 5
Discharge (ft3/sec. )
Average
63.4

71.6

*
36.2
Maximum
27,800

26,900

80,600
16,200
Minimum
3. 1

0.4

9.6
1.7
* Flow regulated by Liberty Reservoir 11 miles upstream
beginning July 22, 1954.
                                    A-2

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As can be seen from the table above,  the average fresh water flow into





the Harbor is relatively low compared with the volume of the Harbor of




15 billion cubic feet.
                                    A-3

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A. 2     METEOROLOGY







A. 2.1   Winds







The winds in the Baltimore Harbor area blow predominantly from a





westerly direction.  Table A-1 is a chart of the frequency of occurrence





of surface winds at Baltimore- Washington International Airport,  about





10 miles from the Harbor.  The  chart shows that the wind will have a




velocity of four  miles per hour or more about 93 percent of the time.





Of this percent, winds will  be from a westerly direction 48 percent of





the time,  and from an easterly direction about 30 percent of the time.





Three percent of the time the wind will have  a velocity of 25 miles per





hour or greater, and be from a westerly direction.










A. 2.2   Hurricanes







Most  hurricanes that have affected the eastern coast of the United States





have formed either near the Cape Verde Islands or in the western





Caribbean Sea.  The tracks of tropical hurricanes are extremely irregular





Hurricanes that affect the Baltimore metropolitan area most severely





usually  arrive from the south-southwest after recurving east of Florida





and skirting the  coastline.  The hurricane season is from July through





October.
                                 A-4

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Table A-1       Percent of Occurrence of Designated Velocities and Directions of Surface Winds
                at Friendship Airport
s
Direction
N
NNE
NE
ENE
E
ESE
SE
SSE
S
SSW
sw
wsw
w
WNW
NW
NNW
Totals
Calm
















2. 3
1 - 3
MPH
. 3
. 3
.4
.2
.4
.2
. 3
. 2
. 5
. 3
.4
. 2
.4
.2
. 3
. 2
4.8
4-12
MPH
4.4
3. 1
4. 1
3. 3
4.7
2. 3
2.8
2.6
6. 5
3. 3
5.2
3. 3
5.9
3. 3
4.4
3.4
62.6
peed
13-24
MPH
1. 3
.9
1. 0
1. 0
. 9
.4
.7
1.4
2.8
1. 3
1.6
1. 1
2. 9
3. 5
4. 1
2.2
27. 1
25 - 31
MPH
. 1






. 1
. 1
. 1
. 1
. 1
. 3
.8
.7
. 2
2.6
32 - 46
MPH












. 1
. 3
.2

.6
47 & over
MPH

















Total 4
& over
MPH
5. 8
4. 0
5. 1
4. 3
5. 6
2. 7
3. 5
4. 1
9.4
4.7
6.9
4. 5
9.2
7.9
9.4
5.8
92. 9

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The frictional effects of the land surfaces between the Baltimore Harbor





area and the Atlantic Ocean decrease the intensity of hurricanes which





move into the  area.  The greatest damage is produced along waterfronts




and shores by the high tides and waves and the flooding due to heavy rain-





fall.   Records indicate that the most violent hurricane ever to have struck





the North Atlantic  Coast of the United States was the  one which  occurred





during September 1944.  This hurricane is referred to as the "Great





Atlantic Hurricane", the "1944 Cape Hatteras Hurricane",  or the




"14 September 1944 Hurricane".  The storm center passed about 40





miles seaward of the coast of Maryland and did not inflict  severe damage





in the Baltimore area.










Records for the Baltimore area for the period 1667-1958 show  that twenty





damaging storms that narrowly missed the Baltimore area have occurred.





These storms include both hurricanes and tropical disturbances of large





proportions.   Dates of the more  severe of these storms are as  follows:











           June 12,  1858                 August 23, 1933




           July 24,  1868                 October 15,  1954 ("Hazel")




           October 1877                 August 12-13,  1955 ("Connie")




           August 20, 1879              August 16-18,  1955 ("Diane")




                                        June  21-23,  1972 ("Agnes")
                                   A-6

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The most severe storm on record in the Baltimore area was the storm





of August 23,  1933.  This hurricane moved from a sea path to the coast





at a latitude higher than most tropical storms and entered Chesapeake





Bay directly from the ocean.  Accordingly, there was no attenuation by





passing overland.  Wind velocities reached 60 miles per hour,  and water





levels rose to a record height of 8. 33  feet above mean low water at Fort





McHenry.  Damage from tidal flooding in the Baltimore area was estimated





to be  about $5 million (in 1933 dollars).










Other hurricanes of note include "Hazel",  "Connie", and "Agnes"-





Hurricane "Hazel" struck Baltimore in October 1954, with wind velocities





of 45  miles per hour, and river and bay levels reached a stage of six feet





above mean low.water.   This  storm was tracked some 60 miles west of





Chesapeake Bay.  Damage would have been more severe had the storm





been farther eastward.   The storm of  August 12,  1955 ("Connie") caused





river and bay  levels to  rise about seven feet above mean low water.





Hurricane "Agnes", June 5,  1972,  caused river  and bay levels to rise to




3. 8 feet above mean low water.
                                   A-7

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A. 3      OCEANOGRAPHY OF BALTIMORE HARBOR







A. 3. 1    Water Movement







A study of Baltimore Harbor was made in the period 1958 through I960




by the  Johns Hopkins University for the State of Maryland (Stroup,




Pritchard, and Carpenter, 1961).  The principal objective of this study





was to determine the mechanisms which bring about flushing of the Harbor





and the rate at which this flushing occurs.










Based  upon  this intensive three-year study,  the following conclusions





were reached:











   "1.    The   physical circulation pattern in the Harbor and the




        chemical properties of the Harbor waters are primarily





        related to phenomena occurring in the  adjacent Chesapeake





        Bay; they are not in any measurable manner affected by





        the relatively small inflow of the Patapsco River.
   '2.   The primary factor contributing to the renewal of





        water in Baltimore Harbor is a density-induced,  three-





        layered flow pattern.  This type of circulation has not




        previously been described for estuarine embayments.







                                 A-8

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    "The vertically averaged salinity (and density) is essen-





     tially constant from the mouth to the head of the Harbor.





     However there is less vertical variation in  salinity





     (and hence, density) within the Harbor than there  is in





     the adjacent Chesapeake Bay. Therefore,  the surface





     waters of the Harbor are more saline (and hence,  denser)





     than the surface waters in the Bay just outside the Harbor.





     Likewise,  the deep waters  in the Harbor are less  saline





     (and hence, less dense) than water at the corresponding





     depth in the adjacent Bay.  As a consequence,  both





     surface and bottom layers exhibit a net inflow to the





     Harbor, while the water at middepth flows out of the





     Harbor into the open Bay.










"3.  The evidence for this type of circulation pattern is





     strongest after  a period of  high discharge from the





     Susquehanna River, when the vertical salinity gradients





     are large,  and weakest after a period of low flow  when





     the vertical salinity gradients are small.  There is  some





     indication that the strength of this circulation is greatest





     in the winter and early spring months, and least in the





     summer and fall months.
                               A-9

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   "4.   The average fractional-renewal rate for the main Harbor





         during the study period was 12% per day, with individual





         values ranging between 6% and 20%.   These values are





         remarkably high in comparison with previous estimates,





         which had not taken the three-layered circulation into





         account.  The renewal rate does not appear to depend





         to any significant degree upon tidal flushing or upon wind-





         induced motion.










   "5.   Comparison of acid-waste concentration, determined





         from the  observed-alkalinity anomaly, with the observed





         pH indicates that there is little or  no exchange with the




         atmosphere of the excess CC>2 produced  during acidification





         of the Harbor waters.  Therefore, the full potential buffer





         capacity of the Harbor waters is not realized, and lowered





         pH values are accompanied by increased CCX tension. "








Sediments, both suspended  and bottom,  maybe moved by  tidal currents.





Tidal current observations  in  Chesapeake Bay. as recorded in the files of





the Coast and Geodetic Survey began in the  year 1845.  The Coast and





Geodetic Survey published the only comprehensive study of the  tides and





currents in the Bay available  (Haight,  1930).   This study was based





upon all records accumulated  to that date.







                                 A-10

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A survey of tidal currents conducted between I960 and 1965 by the Coast





and Geodetic Survey gives some  values for the near bottom currents.  The





maximum observed velocities and their true directions near the bottom





and surface in the proximity of the five recommended soil disposal sites





are shown  in Table 2-2 (State of Maryland, 1970).
                                  A-ll

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                                   TABLE A-2
                      Maximum Observed Bottom and Surface
                  Currents in Vicinity of Five Recommended Sites

Site
Hart-Miller
Hart-Miller
Black Marsh
6-7-9 Foot Knolls
6-7-9 Foot Knolls
Belvidere Shoal
Patapsco River
Patapsc.o River

C&GS
Station
No.
63
82
60
52
59
51
54
55
Maximum Observed
Bottom Current
Depth
(feet)
16
18
7
30
14
32
29
24
Velocity
(knots)
0. 7
0. 65
0. 5
1. 3
0. 5
1.5
0.7
0.4
True
Direction
017
032
036*
337
009*
352
297
182*
Maximum Observed
Surface Current
Depth
(feet)
8.0
5.0
7.0
6.0
7.0
6.0
6.0
5.0
Velocity
(knots)
1. 1
0.77
0.5
1. 1
0.7
1. 1
0.4
0.4
True
Direction
227
230
036*
347*
322*
182
290*
347
* Approximate direction only as variations occur frequently.  All directions in
  degrees azimuth with respect to geographical North.
                                           A-12

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A. 3.2   Bathymetry







Baltimore Harbor is a relatively shallow draft harbor with a mean depth




of slightly less than 16 feet (Quirk, et al,  1973).   Exclusive of the shipping




channels, which have been dredged to 42 feet deep after dredging,  the




deepest part of the Harbor is a 40-foot area lying north of Hawkins Point.




This is of only limited extent and may be due to dredging  af a ship's




turning basin north of Hawkins Point.










Only a relatively small area of the Harbor has depths in the range of 30 to




40 feet.  The major part of the Harbor in  the vicinity of the shipping  chan-




nels is between 15 feet to 25 feet in depth.  Along the shores of the Harbor,




and in the Middle Branch, the depth is less than 15 feet.  Considerable




shoaling exists in these  areas.  A sizeable portion of these areas have




depths that are less than five feet.  Where the Patapsco River  broadens




into the Harbor, and where Gwynn Falls enters the Harbor, shoaling has




resulted from the  deposition of river-borne  sediments. In the past,  spoil




dredged from the shipping channels was disposed of within the  Harbor




itself.  These areas are indicated on Coast and Geodetic Survey nautical




charts.  While  this practice has been all but discontinued, the  shoal areas




remain and are labeled "Discontinued Spoil Areas" on Harbor charts.
                                  A-13

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APPENDIX B




FIELD DATA

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B. 1      LOCATION OF CORE SITES








Baltimore Harbor is depicted in Figure B-l relative to the adjoining land





areas, the City of Baltimore, the Chesapeake Bay, and shipping channels.





Figure B-2  depicts the locations of sampling sites where  core borings and





grab samples were obtained.  Baltimore Harbor proper is divided into





several segments,  each named  as follows:  Inner Harbor, Northwest





Harbor,  and Middle Branch, which are all directly south  of Baltimore





City proper.











The main section of the Harbor  is named the Patapsco River with the





Outer Harbor extending from the southern end of the Patapsco River area





out into the Chesapeake Bay.  As different maps and charts from various





sources define these Harbor areas in slightly different locations, we have





followed the map and Harbor section names  as outlined in EPA's Region III





Technical Report #59,  dated January 1974 and titled, "Distribution  of





Metals in Baltimore Harbor Sediments. "











In order  to measure the amounts of heavy metals and other pollutants





present in Baltimore Harbor sediments,  twenty  sites were chosen for





sampling and chemical analyses.  The sampling sites were chosen so as





to correlate to the  main channels and to locations  where previous work
                                  B-2

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              BALTIMORE   HARBOR

                       AND

                     VICINITY
                 /
STUDY AREA
                 /
                 I
                        \    HAVRE DE
                        \    GRACE

                /        ^>»
                .  BALTIMORE    N
                t  COUMTV     [
                                         ^==. SALISBURY
                                        T/GU&E: B -/
                          B-3

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                        M ARBOR.
                                                ij
   _, ---	- v.
== ==- ^-	.x N
                       \^ ,^$\*.r*
                           m^'^
75AMPLE



'BIOAS5AY SAMPLE. S1TE.5
                           B-4
                                       FIGURE: B-2

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had been performed.  The sites sampled in this study cover the same





areas as those used in the January 1974 EPA study. The same heavy





metals analyzed in the 1974  EPA  study were analyzed in this study.





Arsenic and hexane extract were  also analyzed.
B. 2     FIELD DATA







Table B-l provides the latitudes and longitudes of the  sampling sites used





in this study, along with the water de'pth information recorded by the





motor vessel AQUARIUS.










Table B-2 provides salinity and temperature data obtained during sampling





operations.  These data are recorded in a format to show the salinities





in parts per thousand and the temperatures,  in degrees Celsius, at the





surface  and at the  bottom at each site.










Table B-3 provides a general verbal description  of the appearance and





color of the materials obtained while sampling at the indicated sites.
                                  B-5

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                            TABLE B-l
                 GEOGRAPHICAL POSITIONS AND
                 RECORDED DEPTHS OF WATER
                       AT SAMPLING SITES
9 June 1976
    Site 1
    Site 2
    Site 4
    Site 5
    Site 6
    Site 7
    Site 8
    Site 9
  Position

39° 16'  31"
76° 35'  51"

39° 16'  43"
76° 34'  59"

39° 15'  21"
76° 32'  10"

39° 14'  21"
76° 29'  43"

39° 11'  41"
76° 27'  37"

39° 10'  36"
76° 29'  21"

39° 12'  39"
76° 31'  40"

39° 13'  06"
76° 36'  04"
Water Depth

    20'


    15'


    22'


    15'


    17'


    20'


    20'


    20'
10 June 1976
   Site 6
   Site 11
   Site 12
39° 11' 41"
76° 27' 37"

39° 11' 22"
76° 27' 00"

39° 10' 14"
76° 27' 14"
                                          Hard Sand
                                                        17'
    15'
    17'
                                     B-6
                                                       Continued

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                            TABLE B-l (Continued)
    Site 11
    Site 13
  Position

39° 11' 22"  Hard sand
76° 27' 00"  and shell

39° 12' 56"
76° 27' 01"
                                                     Water Depth
17'
 11 June 1976
    Site 7
    Site 14
39° 10' 37"
76° 29' 30"

39° 11' 25"
76° 29' 05"
19'
19'
    Site 15
    Site 16
39° 13'  15"
76° 30'  09"

39° H1  39"
76° 30'  48"
16'
15'
    Site 1
39° 16'  31"
76° 35'  51"
19'
12 June 1976
   Site 2
   Site 3
39° jfci  3311
76° 34'  58"

39° 15'  56.5"
76° 34'  21"
14'
33'
14 June 1976
   Site 4
39° 15' 22"
76° 32' 10"
24'
   Site 5
39° 14' 21"
76° 29' 43"
15'
                                     B-7
                                                       Continued .

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                           TABLE B-l (Continued)
                               Position               Water Depth

   Site 8                     39° 12' 38"                  19'
                             76° 31' 40"

   Site 17                    39° 13' 57.5"                17'
                             76° 31' 33"

   Site 9                     39° 13' 06"                  18'
                             76° 34' 02. 5"
15 June 1976
   Site 10                    39° 14' 51"                  15'
                             76° 36' 03"

   Site 18                    39° 13' 27"                  21'
                             76° 32' 41"

   Site 19                    39° 14' 26"                  36'
                             76° 32' 54.5"

   Site 20                    39° 14' 55"                  22'
                             76° 34' 08"
                                     B-8

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                TABLE B-2



      Salinity (S) -  Temperature (T) Data


Site


                                            T  °c

surface -
bottom -
CD
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(10)
(ID
(12)
(13)
(14)
S ppt

5.44
5.22
5.33(5.36)
6.21(5.42)
5.30
8.05
5.65(4.60)
5.87(7.78)
4.68(3.22)
5.90(4.20)
2.92
5.37
4.16(3.63)
5.26(5.85)
4.22(5.90)
5.03(5.91)
5.02(5.62)
5.72(5.63)
3.83(5.28)
5.12(5.72)
2.83
5.63
3.02
7.70
3.50
3.62
3.70
7.78
                                          25.00
                                          24.66

                                          25.05(23.95)
                                          24.17(22.63)

                                          24.72
                                          19.92

                                          23.68(25.80)
                                          23.67(20.78)

                                          23.93(28.22)
                                          23.30(26.71)

                                          24.50
                                          21.83

                                          26.07(24.61)
                                          23.18(23.67)

                                          26.58(24.02)
                                          26.07(23.52)

                                          25.15(24.50)
                                          22.06(25.70)

                                          27.39(23.77)
                                          21.87(23.72)

                                          25.53
                                          24.65

                                          25.66
                                          21.00

                                          28.20
                                          28.70

                                          25.05
                                          21.78

                                          Continued . . .

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                       TABLE B-2 (Continued)
(15)
(16)
(17)
(18)
(19)
(20)
Notes on S-T Data
3.60
5.68
4.54
5.84
5.54
5.64
5.88
5.88
5.57
6.92
5.54
5.76

                                               26.59
                                               27.50

                                               26.88
                                               28.33

                                               24.00
                                               23.64

                                               23.82
                                               23.44

                                               24.17
                                               23.56

                                               26.10
                                               26.38
1.   Numbers in (  ) are data taken at or near the same site 1-3 days later.

2.   Data taken at  the same site before coring and then after coring
    (about 1 hour) agree within t . 02 S units.
                                B-10

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                       TABLE B-3

        FIELD DESCRIPTION OF CORE SAMPLES (ss)



                  (2  cores per station)

(1)       8-9 ft  of core  oil-grease appearance  (black) -
         bottom  4 feet is tan sand (lower interstitial
         ^0 sample was black)

(2)       9.5-10  ft  Black mud-similar to #1 - some sand
         (interstitial mud smells strongly asphaltic)

(3)       11.5-12 ft Black oily-asphaltic to about 10 ft -
         last 1.5 ft is tan sandy clay

(4)       7-9 ft  Black asphaltic clay to about 6 ft grading
         into sandy clay containing shell debris

(5)       11-11.5 ft   1.5 ft of black asphaltic mud - rest
         of core is sandy clay with shell fragments

(6)       10.75 ft     top 3 ft is black asphaltic mud. The
         rest is grey mud

(7)       6 ft    gray-tan silty m.ud with high water content-
         the top two ft. contains shell fragments.

(8)       11 ft of  Black asphaltic clay - bottom ft is
         sandy day core cutting head is covered with red
         pigment (Fe203?)

(9)       11-13 ft  top ft. contains a yellow-green greasy
         substance-rest is black mud grading into sandy
         clay near the bottom 2 ft

(10)     6.5-8 ft  Black asphaltic mud  - lower  1/3 of core
         is sandy, black mud

(11)     1.5 ft    gray mud with shell fragments  (initial
         cores were hard packed sand that broke the core  liners)

(12)     10-13 ft of black clay

(13)     6-10 ft of black mud-last ft is grey sand  (shallow
         water 5-8 ft so core could not penetrate)

(14)     10 ft -of gray sandy clay grading to It.'brown

(15)     10 ft black asphaltic mud   last 3  ft  is sandy mud

(16)     10 ft top two ft is black clay   the rest  is  tan
         sandy clay

                                                  Continued . . .
                                B-ll

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                    TABLE B-3 (Continued)
(17)      9-11  ft  top  5  ft  is  asphaltic black mud   next
         4-6 ft is  sandy  clay -  pebbles at 9 ft

(18)      9-11  ft  top  3  ft  is  black mud - the  rest is grey clay

(19)      8  ft  top 4 ft  is  black  and'oily-bottom 4 ft is gray  clay

(20)      8-11  ft  black  mud grading to gray mud in the last  4  ft
                           B-12

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      APPENDIX C




GEOCHEMICAL ANALYSES

-------
 C. 1      SAMPLE PREPARATION









 Filtered Water Samples




 A composite water sample of the water  column at each site was collected





 with polyethylene tubing and buckets.  The water was pumped up in three





 fractions (lower 1/3, middle 1/3, and upper 1/3) by a completely  plastic





 submersible pump.  The water was mixed and this composite used directly




 for the elutriate test.  A portion of this  water was filtered through a





 0.45pm filter  (Millipore),  acidified with Ultrex HNO^ and refrigerated





 at or near 4°C for analyses as the filtered water sample.










 Interstitial Water Samples





 The interstitial water sample was collected by removing,  with  plastic





 spoons,  two portions of each core (5-10 and 40-45 cm depth), quickly





 placing each sample  in a Reeburgh-type sediment  squeezer (Bricker,





 1975).  The entire operation is done under a nitrogen gas atmosphere.





 Fifty to 60 rnls of water is  extracted and then acidified with Ultrex HNOo,





 and refrigerated at 4°C.  Detailed operation of this equipment can be





found in Bricker (1975).  The interstitial water passes through  a 0. 22




ym filter  and so  represents dissolved metals.
                                   C-2

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Sediment Analysis





The  sediments were  collected with a  15-ft. piston corer with a poly-





carbonate core liner.  The samples for the bioassay were collected with





a Ponar type grab sampler.  Sediment samples were removed and kept





from contact with metals.  Metal and hexane samples were immediately





placed in polyethylene bags and refrigerated above freezing (near 4°C).





Samples for PCB analyses were placed in clean glass bottles topped with





acetone washed aluminum foil and then capped. Separate  samples were





also prepared for sediment size and B.E.T. analyses.










Elutriate Test
Unfiltered water from the composite batch was mixed with fresh sediment





in a 4:1  ratio by volume,  sealed and shaken for 30 minutes by a mechanical





shaker.   The mixture was then centrifuged at 10, 000 rpm for 5  minutes,





and the entire sample filtered through a 0.45ym filter.   The water was





then acidified with Ultrex HNOo and refrigerated at 4°C..  The entire pro-





cess normally took from  1-3 hours per sample.
                                    C-3

-------
C.2   ANALYTICAL METHODS





Oil and Grease




Samples of waters were extracted in a  separatory funnel with hexane.





Sediment samples were extracted in a soxhlet extractor.  Quality control





was maintained by spiking selected samples with a high boiling point lab





oil.  Completed details of these methods  is in Standard Methods (APHA





1976).










Arsenic




Samples of waters containing nitric acid were boiled down with sulfuric





acid to remove nitrates.  Sediments were digested with a mixture of





sulfuric  and nitric acids followed by boiling off the nitric  acid.  Arsenic





was determined by UV-Vis Spectrophotometer using Standard Methods





(APHA 1976; US-EPA 1974).  Quality control was  maintained by spiking





selected samples with sodium arsenate.  The UV-Vis Spectrophotometer




used was the Spectronic 20.










Metals (other than arsenic)





Water  samples were obtained with nitric  acid present and were analyzed





as nitrates.  The sediment samples were digested with reagent quality





HNO3 - water mixture  1:1 ratio.  Two grams of dried sediments to 20 mis.
                                   C-4

-------
of solution was heated to near dryness.  This procedure was repeated





three times.  The decanted liquid was then analyzed for the metals.










AA Flame Methods





All sediments and most water samples were analyzed using a Perkin-





Elmer Model #117 Atomic Absorption Spectrophotometer.  Where suf-





ficient volume  of water samples was  available,  water samples were





boiled down to concentrate metals.   Quality control was maintained by





spiking selected sampled with the metal to be analyzed.










AA Flameless  Methods
Water analyzed by flameless methods were all eluted waters or inter-





stitial waters.  The instruments used were the Perkin-Elmer Model





#503  AA Spectrophotometer, the HGA-2100 Graphite Furnace,  and the





Perkin-Elmer Background Corrector.  Quality control was maintained





by analyses of spiked samples and by analyses of standards  containing





0.0%, 0.1%,  0.3%, 0.5%,  0.7%,  andl.O%NaCl.  There proved to be  no





salt background which could not be  removed by normal operation of the





charring cycle up to about 0. 7% to  1. 0% NaCl (salinity of 7 to 10).  All





NaCl used was either reagent grade or Baker "ULTREX" purity depend-





ing on the  content of the metal in the reagent salt.
                                   C-5

-------
Even "ULTREX" NaCl contained sufficient nickel to interfere and a




minimum detectable limit of 5 ppb was the best that could be obtained





for nickel.   All standards used to calibrate the instrument and water





used to zero it contained  0. 5% NaCl and 1% HNC>3.  The best analytical





line for chromium is outside usable spectrum of the deuterium back-





ground lamp and, therefore, no background  correction was  used for





chromium.  The high charring temperature  proved sufficient to avoid





any background problems as evidenced by the lack of any smoke peaks





during the atomization cycle of the instrument (a  chart recorder was





employed).  Zinc was analyzed by flameless methods in the 56 samples





submitted to the Devon lab only where zinc was less than 25 ppb.  Normal





flame AA methods were used for higher concentrations of zinc.










Mercury





The standard cold vapor technique was used  for mercury using the





Perkin-Elmer Model 117  AA and the Perkin-Elmer mercury system.





Quality control was maintained by spiking selected samples  with mercury




standard.
                                  C-6

-------
C.3    ANALYTICAL PROCEDURES, DISCUSSION,  AND RESULTS
Elutriate Test
The elutriate test (Lee and Plumb, 1974) developed by the Army Corps





of Engineers, is probably the single most pertinent test available to test





for metal release as a result of dredging operations.  This test attempts





to determine the amount of toxic metals released into the water column





from (or removed from the water column by) the sediment.  The procedure





is to  shake  a fixed volume of sediment with four times the volume of har-





bor water and then filter and analyze the elutrient.   Modifications were





required in order to process the samples during the ship time available





to us.  Rather than  shake for 30 minutes and then filter, the sample ^as





centrifuged for  five minutes  after being shaken.  This  modification  was





required because of the inordinate length of time involved  in filtering a





thick suspension through a 0.45 ym filter.  As  this procedure decreases





the sediment water  exchange period slightly (straight filtering,  without





centrifugation,  would be longer because of filter clogging), it might lead





to less  exchange of  metals.   Bricker (1975)  suggests that times related





to the settling time  of dredged  materials be  used (4-6 hours in this area,





Ibid.) for the elutriate test.
                                   C-7

-------
As the most accessible  (to the water column) metal-rich portion of the





sediment is the interstitial water,  one might expect the  elutriate test to





reflect the interstitial water composition.  In fact, the elutriate test in





most cases shows less of the metal than is found in the interstitial water.





This very important result puts a serious restraint on the use of the





elutriate test  in anoxic bottom sediments such as much of Baltimore





Harbor.










Tables C-2 -  C-21 show the metal concentrations  in the elutriate





samples taken from each available core interval (0. 16,  0.5,  1.0,  2.0,





3.0, 5.0,  7.0, 10.0, 15.0ft.  The Army Corps of Engineers suggests





that concentration of each dissolved metal not exceed  1. 5 times its





original  concentration in the filtered water column (Bricker, 1975).





Where the  metal concentration is higher in the elutriate as compared to





the reference water, metals are  presumed to be released from the





sediment.   Where the metal level is  lower in the reference water,  the





metal is presumed to have been removed by the  sediment.










Because of the limited nature of this study,  many elements could not be





analyzed by the most sensitive  available technique, i.e., flameless





atomic absorption spectrometry.  The result is  that some elements will
                                    C-i

-------
show concentrations below detection limits.  This will not always allow





for direct comparison between elutriate and filtered overlying water.










Interstitial Water





Analyses of interstitial water was deemed vital because it may be the





major source of the releasable metals  during dredging  and because no





data exists of metals for these fluids in Baltimore Harbor.  Interstitial





water data is very dependent on the manner in which the sample  is col-





lected (Bricker, 1975; Sommer and Diachenko, 1974); great  care must





be demonstrated in preventing oxidation of anoxic sediments, as iron





may precipitate and scavenge or adsorb trace metals out of  solution.










The samples are collected and quickly  (in a matter of a few  minutes at





most) placed in a nitrogen gas squeezer apparatus which is completely





enclosed within a nitrogen atmosphere.  The collected liquid is audified,





refrigerated, and stored for analysis.  Interstitial water was squeezed





from two portions of each core, at 5  -  10 cm and at 40  - 45  cm.  Bricker





found maximum concentrations of metals at 5 - 10 cm depth, and rela-





tively constant concentrations below 50 cm depth.
                                    C-9

-------
The data in Tables C-2 - C-21 indicate that maximum concentrations are





very often found at the lowest core interval, probably indicating a gradient





increasing with depth.  Pb appears to be at high levels  at sites 6,  12,  2,





and 7; Cd at sites 9,  16, 19, and 20; Cu at sites 6 and 7; Cr at sites 2, 5,





and 12; Ni at site 9; Zn at sites 2,  6,  7,  10, 14, and  16; Mn at sites 3, 7,





and 12; Hg at sites 2, 6, 16; and As at sites 3, 18, 19, and 20.  The sites





with the highest levels appear to lie on the western side of  the Harbor with





Pb and Cu highest near the Bay mouth; Ni, Cd, and As  highest in the cen-





ter; Cr high at the 'head and mouth of the Harbor,  and Mn,  Zn, and Hg





dispersed throughout the area.  An important  point to note  is that inter-





stitial water samples often have higher concentrations of metals than





elutriate samples from the same site.  The high levels are much higher





than can'be accounted for by dilution during the elutriate test (4:1).  If one





further takes into account the fact that many of these  metals are thought





to be released from the sediment during the elutriate procedure, the high





interstitial (or low elutriate) values may be indicative of oxidation and





precipitation during the elutriate analysis, with subsequent loss of dis-





solved metals for analyses.  This interpretation would indicate the elu-





triate test,  for anoxic sediments, would tend to underestimate the con-





centrations of those elements that tend to be scavenged or precipitated





with hydrous iron oxides.
                                    C-10

-------
Sediment Analyses





Sediment samples were collected by coring with a 15-foot piston corer.





Sediment samples were retained in a polycarbonate core liner.   All





samples for metal analyses were protected from metal contamination by





preventative handling or by removing, by hand,  any portion of the sample





that came into contact with metal portions of gear.  Samples used for





he"xane  extraction and especially for PCB analysis were treated so as not





to incur any organic contamination.   The samples were refrigerated at





approximately 4°C until analysis.   Eight sediment  intervals were delin-





eated for sampling from 0. 16 to 10.0+ 2 ft (corrected core depths utili-





zing Piggot's (1941)  correction  factors,  due to compaction).   All sample





collection,  processing,  and refrigeration took place within 30 minutes of





collection -- usually in  less time.










The data for the nine metals,  As,  Hg, Cd,  Cr- Cu, Mn, Ni, Pb, Zn,





hexane  extractable hydrocartons,  and moisture content are illustrated in





Tables  C-22 through C-41.










There is  no doubt that metal levels at most sites and  at most depths  are





polluted by  EPA (1973)  standards.  The  only element  for which  standards





exist (Cd, Pb, Hg, and  Zn) that is not routinely  above polluted levels ia
                                    C-ll

-------
Hg.  The technique used to extract metals is slightly more vigorous than





that used by Villa and Johnson (1974)  so that higher metal values for the





same site may be expected.










Grain Size and Surface Area Analyses




Dried sediment samples were  processed for grain  size by an automated





grain size  apparatus  called a Sedigraph.   This device measures the sedi-





mentation rates of particles in suspension and presents these data as a





cumulative percent distribution in terms of  Stokes  or equivalent spherical





diameter.  The range of size determined was from 100 ym to 0. 1 ym..





Accuracy is believed to be better than 1% with reproducibility of about





0. 5%.   It should be noted that size and surface area data for these sedi-





ments  do not represent those characteristics as found in the natural state





as they have been dried prior to  measurement.  However,  the data should





be internally consistent and thus comparable -within this set of data.  The




top and bottom of all  cores were analyzed.










The grain size distribution,  Table C-l, as indicated by average particle





size varies from a high of 22. 5 ym (7-6) to  a low of 1. 8 ym (9-8).   The





general size range is in the clay range with a few in the silt class.   The





specific surface area (meters 2/grain) varies from a high 62. 6  (9-1) to





a very low 0. 7 (10-7) with most values falling in the 20 range.






                                   C-12

-------
C-4    SUMMARY







Reference to Tables C-2 to C-41 indicates that Cd is highest in Colgate





Creek and Bear Creek (Sites 4 and 5) with moderate levels in the Inner





Harbor area (Site 2).  Cr is  particularly high at the Inner Harbor (Sites





1, 2, and 3),  Colgate Creek (Site 4),  Bear Creek  (Site  5), Sparrows Point





(Site  15), at scattered sites, e.g.,  6,  17,  18, and 20.  Cu is very high in





the Inner Harbor  (Sites 1,  2,  and 3)  and at Colgate Creek (Site 4).  Pb





shows high values in the Inner Harbor (Sites 2 and 3), Colgate Creek





(Site  4), Bear  Creek (Site  5), Curtis Bay  (Site 9),  and near Old Road





Bay (Site 13).  Mn is high  throughout the Harbor;  except  for the inner





portion, it is particularly  high at surface  or depth at the  following sites;





5, 6, 1, 8, 12, '13,   14, 16, 17,  18,  and 19.










Hg shows elevated levels in the Inner Harbor (Sites  1,  2,  3), Colgate





Creek (Site 4), and  Curtis  Bay (Site  9). Mi is high in the Inner Harbor





(Site  2 and 3),  Curtis Bay  (Site 4), and Site 19.  Ni is relatively constant





at 75 -  100 ppm through much of the Harbor.  Zn  is high  everywhere,





but highest of all  in the Inner Harbor,  Colgate and Bear Creeks,  Old





Road Bay, Curtis Bay,  and Sparrows Point area.  The  metals discussed





above were selected because they are the  metals determined by Villa and





Johnson (1974).  In  almost every case (the only exceptions are Hg levels
                                   C-13

-------
at a few sites),  the high and low sediment levels  agree within the limits





of coverage.  This is remarkable considering that three years passed




between sampling,  during which dredging,  storms and traffic have left





their imprint.  It probably indicates that the degree  of industrial output




is sufficient to replace  quickly, any removed or transferred metal con-





centrations.  In addition to the metals listed above,  As was found to be




very highly concentrated  in the Inner Harbor (Sites 2 and 3), Colgate





Creek  (Site 4), the Curtis Bay-Hawkins Point area  (Sites 8 and  9),  as





well as the Middle Harbor area.










It is worth noting that many of the metals show marked decreases in con-





centration at particular core intervals or sediment depths.  At Site  1,





most elements remain  constant until level 6-7, and then decrease rap-





idly.  This corresponds to about 5-7 feet.  Moisture and hexane levels





also decrease at level 7.  Sites  2,  8, 14, 16,  17, and 19 show a  marked





decrease in metals and hydrocarbons at or near layer 6 (5+ft).  Site  15





and 18  show the marked decrease between layers 6 and 7 (3 - 5 ft).  Sites





9 and 20 show the decrease  at or near layer 7-8 (7 -  10 ft).   Sites 3, 10,





11, and 12 show no change or have very low concentrations.  Sites 5, 6,





and 13  show decreases  near layers 3-5 with 13 showing a very strong





change at  layer 4.  In general, there appears to be a major decrease in
                                   C-14

-------
most metals,  hydrocarbons, and moisture content at about 5 ft 1 2 ft,





everywhere in the Harbor.
                                   C-15

-------
The majority of chemical analyses for metals were conducted by flame





atomic absorption analyses, a standard technique for these  substances.





The relatively low  cost and high sensitivity of this technique allowed for




the analyses of a large number of both sediment and water samples.





A selected number of water  samples were analyzed by a more  sensitive





analytical technique, that of flameless atomic absorption analysis.  The





higher cost of this  technique dictated that only a limited number of samples





could be analyzed by this method.  This approach results in the analyses





of a maximum of samples, while still allowing for a small number of





samples to be analyzed at very low concentration  levels.  Direct com-





parison between the water samples analyzed at  low detection levels (flame -





less)  and sediment/water samples  analyzed by the conventional flame





technique, is  not possible  as  one set of data is below the detection limits





of the other for those samples containing  concentrations at or near the





detection limits of the conventional technique.   While this  presents data




that are  difficult to compare on an individual basis, a total analysis is





possible when viewing all samples  together as contained in the  tables




for the sediment and water-metal concentrations.
                                  C-16

-------
                           TABLE C-l
         Particle Size Analysis and Surface Area Analysis
    Sample
 Identification
Site # - Depth*
     1-1
     2-1
     3-1
     4-1
     5-1
     6-1
     7-1
     8-1
     9-1
    10-1
    11-1
    12-1
    13-1
    14-1
    15-1
    16-1
    17-1
    18-1
    19-1
    20-1
     1-7
     2-7
     4-7
     5-7
     7-6
    10-7
    19-7
     3-8
     6-8
     8-8
     9-8
    12-8
    13-8
    14-8
    15-8
    16-8
    17-8
    17-8-2
    18-8
    20-8

  * 1 =  0.16 feet
    7 =  7.0  feet
    8 =  10. 0  feet
Average Particle Size
  (E. S. D. ,  microns)

          9.2
         14.0
          8.0
         12. 5
          9.0
          2.4
          2. 5
          7.8
          4.6
          8.0
          3.3
          2.5
          8.0
          2.3
          7-6
          6.8
          2. 8
          2.7
          2.8
          3.7
          6.0
          4.8
          5.0
          2.4
        22. 5
          3.6
          2.0
          3.2
          2.0
          3.2
          1.8
          2. 1
          8.0
                     Specific Surface Area
                           (m2/g)	
  95
 ,6
 ,0
2. 1
2. 1
2.8
11.7
15. 7
18. 1
13.5
24.3
28.1
47.3
60.0
62.6
 9.5
11.4
28.3'
20. 6
28.0
21.2
43.4
28.3
53.4
33.4
18. 5
10.4
16.9
15.2
19.2
 0.7
19.2
22.5
16.0
25.6
17.4
27.7
25.0
11.0
25.7
17-9
17.6
22.9
25.0
26.1
18.8
     C-17

-------
                                                 TABLE  C-2
Trident
No.
1
l(5-10 cm.)
l(40-45 cm.)
Sample
Type
filtered
H2O
interstitial
H20
interstitial
H20
1-1 elutriate
1-2
1-3
1-4
1-5
1-6
'
1-7





elutriate
elutriate
elutriate
elutriate
elutriate
elutriate





Metals yg/1 |
As
< 8
34
< 100
< 25
<25
<25
< 25
<25
< 25
< 25





Hg
<0.2
1
2
< 1
< 1
< 1
< 1
<1
<1
< 1





Cd
8
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2





Cr
19
~1
99
273
14
16
16
18
15
15
13





Cu
14
< 2
16
10
14
16
12
23
10
6





Mn
380
1, 840
1, 670
420
740
340
480
660
340
240





Ni
43
< 5
< 5
< 5
< 5
< 5
< 5
< 5
< 5
< 5





Pb
< 50
68
107
8
3
5
5
4
5
36





Zn
20
610
1, 500
24
20
10
21
35
3
4





<  Less than detection limits

-------
                                                        TABLE C-3
T T i H f*rtf
No.
2
2 (5-10 cm.)
2 (40-45 cm.)
2-1
2-2
2-3
2-4
2-5
2-6
2-7






Type
filtered
HzO
interstitial
H2O
interstitial
H20
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate






As
< 8
< 50
< 50
< 25
<25
55
33
< 25
< 25
< 25






Hg
< 0. 2
3
6
< 1
< 1
< 1
< 1
< 1
< 1
< 1






Cd
8
< 25
< 25
< 25
< 25
< 25
< 25
< 25
< 25
< 25






Cr
17
100
88
< 38
< 38
< 38
< 38
< 38
< 38
< 38





Metals y
Cu
13
50
<50
<50
< 50
<50
< 50
< 50
<50
< 50





g/1
Mn
320
1, 900
1, 500
330
210
170
190
320
330
310






Ni
36
<75
< 75
< 75
125
< 75
< 75
< 75
< 75
< 75'






Pb
<50
570
< 290
< 290
< 290
< 290
< 290
< 290
< 290
< 290






Zn
19
1, 100
2,500
31
38
44
31
19
31
25





o
I
     <   Less than detection limits

-------
                                                       TABLE C-4

No.
3
3 (5-10 cm.)
3 (40-45 cm.)
3-1
3-2
3-2
3-3
3-4
3-5
3-6
3-7





Type
filtered
H?O
interstitial
H20
interstitial
H2O
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate





As
< 8
74
67
< 25
< 25
44
< 25
38
< 25
< 25
< 25





Hg
<0.2
2
2
< 1
< 1
< 1
< 1
<1
< 1
<1
< 1





Cd
10
< 25
< 25
< 25
< 25
<25
25
31
<25
<25
<25





(
Cr
< 5
50
38
< 38
< 38
< 38
< 38
< 38
< 38
< 38
< 38




Metals p
Cu
17
< 50
< 50
< 50
< 50
<50
<50
<50
< 50
< 50
< 50




R/l
Mn
450
2,700
2, 700
310
190
470
330
200
280
330
530





Ni
50
< 75
100
< 75
< 75
< 75
<75
<75
<75
< 75
75





Pb
< 50
< 290
< 290
< 290
< ?90
< 290
< 290
< 290
< 290
< ?90
< 290





Zn
24
350
390
25
25
19
19
19
25
25
31




o
     <  less than detection limits

-------
                                                       TABLE C-5
Trident
No.
4
4 (5-10 cm. )
'
4 (40-45 cm.)
4-1
4-2
4-3
4-4
4-5
4-6
4-7





Sample
Type
filtered
H2O
interstitial
H2O
interstitial
tio O
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate





Metals yg/1
As
< 8
41
140
< 25
<25
<25
31
45
< 25
28





Hg
<0.2
<1
<1
<1
< 1
< 1
<1
<1
< 1
< 1





Cd
8
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2





Cr
<5
103
90
14
14
17
17
14
15
18





Cu
14
12
< 2
10
22
26
12
11
8
5





Mn
410
750
1,490
460
690
580
400
130
< 50
220





Ni
36
5
< 5
< 5
< 5
< S
< 5
< 5
<5
< 5





Pb
< 50
55
26
8
5
6
7
9
4
6





Zn
39
180
150
30
35
29
35
35
47
47





O
I
IV
      <   less than detection limits

-------
                                                        TABLE  C-6
Tri H f*nt-
No.
5
5 (5-10 cm. )
5 (40-45 cm.)
5-1
5-2
5-3
5-4
5-5
5-6
5-7






Type
filtered
H2O
i nte r stitial
H20
interstitial
H2O
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate






As
< 8
< 25
< 25
< 25
< 25
< 25
< 25
< 25
< 25
< 25






Hg
<0. 2
<1
<1
<1
<1
<1
<1
<1
<1
<1






Cd
7
<2
<2
<2
<2
<2
<2
<2
<2
<2






Cr
<5
466
46
15
12
10
18
18
16
16





Metals y
Cu
12
< 2
10
14
12
7
5
30
13
18





3/1
Mn
420
310
<50
80
320
220
740
820
< 50
900






Ni
47
< 5
< 5
10
< 5
< 5
< 5
< 5
< 5
<5






Pb
< 50
73
240
8
4
4
16
27
< 5
11






Zn
73
120
53
35
82
35
25
76
22
25





o
I
ro
INI
      <   less than detection limits

-------
                                                  TABLE C-7
•~n • J _ — j.
No.
6
6 (5-10 cm. )
6 (40-45 cm. )
6-1
6-2
6-3
6-4
6-5
6-6
6-7
6-8
6-1 (A)




Type
filtered
H2O
interstitial
H20
interstitial
2
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate




As
<8
<100
<100
<25
<25
32
<25
<25
<25
<25
<25
<25




Hg
<0.2
11
6
<1
<1
<1
<1

-------
                                                  TABLE C-i
Trident
No.
7
7(5-10cm. )
7 (40-45 cm.)
7-2
7-3
7-4
7-5
7-6







Sample
Type
filtered
H20
interstitial
H2O
interstitial
H2O
elutriate
elutriate
elutriate
elutriate
elutriate







Metals yg/1
As
< 8
<100
<100
< 25
< 25
37
28
< 25







Hg
<0.2
6
6
1
1
< 1
< 1
<1







Cd
9
<25

<25
<25
<25
<25
<25







Cr
< 5
38
< 38
< 38
< 38
< 38
<38
< 38







Cu
15
50
-,<*
<50
<50
<50
<50
<50







Mn
410
980
3, 700
450
1, 200
1, 100
1,200
1,200







Ni
36
<75
<75
<75
<75
<75
<75
<75







Pb
< 50
360
< 290
< 290
< 290
< 290
<290
< 290







Zn
32
1, 000
'!c
44
31
56
44
100







<   less than detection limits
*  ran out of sample

-------
                                                        TABLE C-9
Trident
No.
8
8 (5-10 cm. )
8 (40-45 cm.)
8-1
8-2
8-3
8-4
8-5
8-6
8-7
8-8




Sample
Type
filtered
H20
interstitial
H20
interstitial
HZO
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate




Metals yg/1
As
< 8
64
240
< 25
< 25
< ?5
< 25
< 25
< 25
< 25
< 25




Hg
< 0.2
<1
<1
<1
<1
<1
<1
<1
<1
<1
<1




Cd
9
<2
< 2
< 2
< 2
< 2
< 2
< 2
<2
< 2
<2




Cr
< 5
29
43
16
14
15
17
13
15
14
14




Cu
12
7
< 2
2
< 2
< 2
< 2
< 2
3
6
7




Mn
450
970
1, 580
260
740
640
<50
820
560
530
80




Ni
36
< 5
< 5
< 5
< 5
< 5
< 5
< 5
< 5
< 5
< 5




Pb
< 50
508
399
5
5
9
5
< 5
8
5
13




Zn
31
250
170
24
20
47
24
41
35
65
53




o
I
K)
     <   less than detection limits

-------
                                              TABLE C-10
Trident
No.
9
9 (5-10 cm. )
9 (40-45 cm.)
9-1
9-2
9-3
9-4
9-5
9-6
9-7
9-8




Sample
Type
filtered
H20
interstitial
H2O
interstitial
H20
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate




Metals yg/1
As
<8
55
57
<50
<50
<25
<25
<25
<25
50
<50




Hg
< 0. 2
< 1
1
1
2
<1
<1
<1
<1
<1
1




Cd
9
22
21
15
13
25
< 25
< 25
< 25
< 25
12




Cr
17
57
61
< 20
< 20
< 38
< 38
< 38
< 38
< 38
34




Cu
11
<17
<17
13
13
<50
<50
<50
<50
<50
<10




Mn
390
190
250
63
63
36
64
64
71
28
330




Ni
85
910
920
260
190
< 75
< 75
< 75
125
< 75
130




Pb
< 50
< 170
< 170
< 100
< 100
< 290
< 290
< ?90
< ?90
< 290
< 100




Zn
31
160
70
23
26
25
56
50
77
19
15




less than detection limits

-------
                                                  TABLE C-ll
Trident
No.
10
10(5-10cm.)
10 (40-45 cm.;
10-1
10-2
10-3
10-4
10-5
10-6
10-7





Sample
Type
filtered
H2O
interstitial
H2O
interstitial
H26
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate





Metals y g/1
As
<8
53
64
< 25
< 25
< 25
< 25
44
< 25
< 25





Hg
<0.2
<1
<1
<1
< 1
<1
<1
<1
< 1
< 1





Cd
9
<2
<2
<2
<2
<2
<2
<2
<2
<2





Cr
<5
47
42
14
14
15
16
17
15
15





Cu
14
4
10
<2
<2
4
<2
12
2
<2





Mn
360
1,670
2, 000
110
270
<50
< 50
160
500
< 50





Ni
36
< 5
< 5
< 5
<.5
< 5
< 5
< 5
< 5
< 5





Pb
<50
284
102
<5
18
5
6
16
5
4





Zn
24
950
210
29
82
35
76
47
59
47





<   less than detection limits

-------
                                                  TABLE C-12
Trident
No.
11
il (5-10crn.)
11 (40-45 cm.)
11-1
11-2
11-3









Sample
Type
filtered
H?O
interstitial
I-I?O
interstitial
H2O
elutriate
elutriate
elutriate









Metals p g/1
As
< 8
<50
<50
<50
39
58









Hg
<0. 2
3
2
< 1
< 1
1









Cd
6
<25
<25
10
<25
10









Cr
38
<100
<100
57
<38
41









Cu
19
84
<50
17
<50
17









Mn
330
4,400
1, 600
790
500
400









Ni
94
1,450
1, 550
240
< 75
230









Pb
<50
< 500
< 500
<100
<290
<100









Zn
84
370
150
70
83
81









<   less than detection limits

-------
                                                       TABLE C-13
Trident
No.
12
12 (5-10 cm.)
12 (40-45 cm.)
12-1
12-2
12-3
12-4
12-5
12-6
12-7
12-8




Sample
Type
filtered
H20
interstitial
H20
interstitial
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate




Metals yg/1
As
<8
< 100
<100
< 25
< 25
< 25
< 25
< 25
< 25
< 25
< 25




Hg
<0. 2
2
2
< 1
< 1
< 1
< 1
< 1
< 1
< 1
<1




Cd
7
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2
< 2




Cr
< 5
80
39
14
14
14
14
16
14
15
14




Cu
12
35
19
18
7
35
31
23
5
11
18




Mn
300
1,860
2, 370
570
460
600
280
1,460
830
310
850




Ni
29
<5
70
<5
< 5
< 5
<5
<5
<5
<5
<5




Pb
< 50
1,400
1,900
10
5
5
11
13
8
5
5




Zn
32
550
320
5
24
24
29
82
29
53
47



L^.^-.™,— _____ 	 ___;
o
I
     <  less than detection limits

-------
                                                      TABLE C-14
Trident
No.
13
13 (5-10cm.)
13 (40-45 cm.)
13-1
13-2
13-3
13-4
13-5
13-6
13-7
13-8




Sample
Type
filtered
H20
interstitial
H2O
interstitial
H2O
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate




Metals yg/1
As
<8
<50
<50
30
<25
<25
<25
<25
<25
<25
<25




Hg
<0.2
2
4
< 1
< 1
< 1
1
< 1
< 1
< 1
< 1




Cd
6
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25




Cr
< 5
<38
<38
<38
<38
<38
<38
<38
<38
<38
<38




Cu
12
<50
<50
<50
<50
<50
50
<50
<50
<50
<50




Mn
90
510
1, 200
210
250
240
36
420
100
160
230




Ni
32
<75
<75
<75
<75
100
<75
100
<75
<75
<75




Pb
<50
<290
<290
<290
<290
<290
<290
<290
<290
<290
<290




Zn
15
260
350
44
63
100
31
83
71
77
77




o
I
w
o
     <   less than detection limits

-------
                                                       TABLE C-15
Trident
No.
14
14 (5- 10 cm.)
14 (40-45 cm/
14-1
14-2
14-3
14-4
14-5
14-6
14-7
14-8




Sample
Type
filtered
H2O
interstitial
H20
interstitial
H2O
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate




Metals yg/1
As
< 8
<50
< 50
< 25
< 25
< 25
< 25
< 25
< 25
<25
32




Hg
<0.2
3
3
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1




Cd
8
<25
<25
<25
<25
<25
<25
<25
<25
<25
<25'




Cr
< 5
< 38
< 3G
< 38
< 38
< 38
< 38
< 38
< 38
< 38
< 38




Cu
15
<50
<50
<50
<50
<50
<50
<50
<50
<50
50




Mn
380
480
290
260
190
260
200
71
820
1, 300
1, 300




Ni
36
<75
<75
<75
<75
<75
<75
100
<75
75
<75




Pb
< 50
1, 100
<290
<290
<290
<290
<290
<290
<290
<290
<290




Zn
22
530
1,200
25
19
25
25
31
38
25
25




o
I
OJ
     <   less than detection limits

-------
                                                         TABLE C-16
Trident
No.
15
15 (5-10cm.)
15 (40-45 cm.)
15-1
15-2
15-3
.15-4
15-5
15-6
15-7





Sample
Type
filtered
H20
interstitial
H2O
interstitial
H2O
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate





Metals yg/1
As
< 8
< 50
< 50
<25
< 25
< 25
< 25
< 25
< 25
<25





Hg
<0.2
3
3
< 1
< 1
< 1
< 1
< 1
< 1
< 1





Cd
8
< 25
< 25
< 25
< 25
< 25
< 25
< 25
< 25
25





Cr
< 5
38
<38
<38
<38
< 38
< 38
< 38
< 38
< 38





Cu
15
<50
<50
<50
50
83
<50
<50
<50
66





Mn
380
390
450
50
36
57
570
390
250
1, 100





Ni
36
175
<75
< 75
75
75
<75
< 75
< 75
<75





Pb
<50
360
< 290
< 290
<290
<290
<290
<290
<290
<290





Zn
48
270
240
31
136
19
19
19
44
89





o
I
LO
IN)
      <   less than detection limits

-------
                                                TABLE C-17
Trident
No.
16
16 (5-10 cm.)
16 (40-45 cm.)
16-1
16-2
16-3
16-4
16-5
16-6
16-7
16-8




Sample
Type
filtered
H20
interstitial
H20
interstitial
LJ
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate




Metals y g/1
As
<8
< 10i
<10(
<25
<25
<25
<25
<25
<25
<25
<25




Hg
<0. 2
) 5
) 16
< 1
< 1
< 1
< 1
< 1
< 1
< 1
<1




Cd
8
< 25
31
< 25
< 25
< 25
< 25
25
< 25
25
<25




Cr
<5
< 38
<38
<38
<38
<38
<38
<38
<38
<38
<38




Cu
18
<50
<50
<50
<50
<50
<50
<50
<50
<50
<60




Mn
450
460
1, 600
240
110
310
270
200
490
760
1, 600




Ni
43
150
<75
75
<75
<75
100
<75
125
100
"M600




Pb
<50
800
360
< 290
< 290
< 290
< 290
<290
<290
<290
< 75




Zn
23
1,200
1, 000
56
<19
<19
19
44
44
25
25




<   less than detection limits

-------
                                                  TABLE C-18
Trident
No.
17
17 (5-10 cm.)
17 (40-45 cm.)
17-1
17-2
17-3
17-4
17-5
17-6
17-7
17-8




Sample
Type
filtered
H20
interstitial
H20
interstitial
2
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate




Metals y.g/1
As
<8
50
<10C
<25
<25
<25
<25

-------
                                                       TABLE C-19
Trident
No.
18
18 (5- 10 cm.)
18 (40-45 cm.]
18-1
18-2
18-3
18-4
18-5
18-6
18-7
18-8




Sample
Type
filtered
H2O
interstitial
H20
interstitial
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate




Metals yg/1
As
<8
< 50
200
<25
< 25
<25
< 25
25
< 25
<25
<25




Hg
<0.2
2
1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1




Cd
9
< 25
< 25
< 25
< 25
< 25
< 25
< 25
< 25
< 25
< 25




Cr
< 5
< 38
< 38
< 38
< 38
< 38
< 38
< 38
< 38
< 38
< 38




Cu
17
<50
<$0
<50
83
<50

-------
                                             TABLE C-20
Trident
No.
19
19 (5-10 cm.)
19(40-45 cm.)
19-1
19-2
19-3
19-4
19-5
19-6
19-7





Sample
Type
filtered
H2O
interstitial
H2O
interstitial
2
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate





Metals u g /I
As
<8
71
84
<25
<25
<25
<25
<25
<25
<25





Hg
<0.2
2
3
< 1
< 1
< 1
< 1
<1
<1
< 1





Cd
10
25
<25-
< 25
< 25
< 25
< 25
31
< 25
50





Cr
<5
<38
38
< 38
< 38
< 38
< 38
< 38
< 38
< 38





Cu
17
<50
<50
<50
<50
<50
<50
<50
<50
<50





Mn
540
310
820
120
130
140
110
64
750
810





Ni
50
<75
<75
<75
<75
75
<75
75
<75
<75





Pb
<50
290
<290
<290
<290
<290
<290
<290
<290
<290





Zn
30
180
180
19
25
19
25
130
31
19





less than detection limits

-------
                                                 TABLE C-21
Trident
No.
20
20 (5-10 cm.)
20 (40-45 cm.;
20-1
20-2
20-3
20-4
20-5
20-6
20-7
20-8




Sample
Type
filtered
H20
interstitial
H2O
interstitial
H2O
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate
elutriate




Metals y g/1
As
< 8
71
63
<25
<25
<25
< 25
< 25
25
<25
<25




Hg
<0.2
2
2
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1




Cd
12
25
25
<25
<25
<25
< 25
< 25
< 25
< 25
25




Cr
< 5
< 38
<38
< 38
<38
<38
38
<38
<38
<38
<38




Cu
14
<50
<50
<50
<50
<50
<50
<50
<50
<50
<50




Mn
450
820
980
140
71
130
130
140
570
310
280




Ni
50
<75
<75
<75
<75
75
< 75
<75
75
<75
<75




Pb
<50
290
<290
<290
<290
<290
<290
<290
<290
<290
"^290




Zn
68
150
180
25
19
<19
< 19
56
< 19
< 19
< 19




<   less than detection limits

-------
                                                           TABLE C-22

Trident
No.
1-1
1-2
1-3
1-4
1-5
1-6
1-7




i



Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment








Moisture
%
62.48
63.49
63.23
57.45
59.69
54. 91
43. 70







Total
Hydro-
Carbons
Hexane
Extract
mg/kg
11, 600
17, 300
12, 500
7, 500
8, 500
8, 200
750








As
53
101
58
51
. 46
81
5








Hg
2.88
5.67
4. 55
7. 55
4. 70
2. 78
0.23








Cd
7
11
6
7
5
3
<1







I
Cr
1,870
3, 230
1,430
1, 500
1, 050
560
130







vtetals
Cu
570
1, 120
580
440
390
660
23







mg/kg
Mn
360
290
310
330
360
340
220








Ni
67
78
56
61
56
50
39








Pb
190
280
45
170
110
15
26








Zn
1, 140
1, 650
930
1
1, 040
580
350
56







o
I
LO
00

-------
o
I
OJ


Trident
No.
2-1
2-2
2-3
2-4
2-5
2-6
2-7









Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment









Moisture
%
80. 50
72. 18
62.45
62.68
64.25
56.23
60. 92








Total
Hydro-
Carbons
Hexane
Extract
mg/kg
48, 500
28, 600
52,900
59, 000
40, 800
5, 900
320







TABL

As
110
106
130
185
95
21
10




"


E C-23

Hg
4. 13
2. 61
5. 73
3. 82
4.56
3. 35
0. 11









Cd
23
14
23
22
11
2
< 1








1
Cr
4, 100
2, 500
3,600
3, 700
1,900
470
120








Vletals
Cu
2, 800
1, 900
2, 200
2,400
1,400
320
31








mg/kg
Mn
800
450
240
190
230
200
290









Ni
160
110
170
120
75
42
37









Pb
1, 300
930
1,200
1,800
1,500
430
13









Zn
2, 100
1,400
1,900
1, 700
1, 100
330
71








-------
                                                TABLE C-24
Trident
No.
3-1
3-2
3-3
3-4
3-5
3-6
3-7
3-8






Sample
Type
sediment
s ediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
54. 83
59. 52
60. 50
62. 65
63.46
65. 34
60.20
56. 23






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
58, 400
13, 600
17, 900
20, 200
29, 000
35, 700
31, 700
24, 700






Metals mg/kg
As
104
107
116
116
142
180
152
84






Hg
1. 77
1. 34
1. 09
2. 60
2.79
2. 85
2. 98
4. 35






Cd
5
5
7
7
11
10
11
5






Cr
750
920
1, 100
1,200
1,400
1,800
740
700






Cu
2, 900
1, 700
1, 800
1, 500
1, 400
1, 600
1, 500
1,200






Mn
430
550
480
380
310
340
310
360






Ni
170
100
93
74
69
66
71
71






Pb
640
630
690
660
1, 100
970
920
1,600






Zn
610
740
990
980
1, 400
1, 300
780
730






o

-------
                                                  TABLE C-25
Trident
No.
4-1
4-2
4-3
4-4
4-5
4-6
4-7







Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment







Moisture
%
81.73
62. 01
68. 06
69. 15
66.65
59.25
46. 34







Total
Hydro-
Carbons
Hexane
Extract
mg/kg
15, 500
15, 300
18, 000
22, 100
21, 300
7, 300
2, 500







Metals mg/kg
As
77
96
160
290
850
117
30







Hg
0. 73
1. 01
1. 60
2. 39
3.86
1.96
0. 28







Cd
30
92
130
270
340
77
20







Cr
440
900
1, 100
1, 300
1,000
430
140







Cu
340
710
690
910
750
260
61







Mn
270
380
350
230
180
740
540







Ni
42
74
75
80
56
50
32







Pb
430
630
800
1, 300
1,200
390
460







Zn
830
1, 700
2, 000
4, 000
3, 300
1, 200
380







o

-------
                                                  TABLE C-26
Trident
No.
5-1
5-2
5-3
5-4
5-5
5-6
5-7







Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment







Moisture
%
76.64
85.63
71. 96
61. 71
59.29
59.76
56. 91







Total
Hydro-
Carbons
Hexane
Extract
mg/kg
35, 200
46, 000
18, 000
8,400
1, 300
530
400







Metals mg/kg
As
103
117
112
83
20
18
21







Hg
0. 11
0. 95
0. 62
0. 33
0. 18
<0. 02
<0. 02







Cd
59
21
8
5
1
< 1
<1







Cr
4, 500
1, 700
1,200
350
170
130
95







Cu
540
370
300
180
43
11
12







Mn
490
370
280
370
820
610
1, 100







Ni
82
79
84
58
44
42
37







Pb
770
850
1,700
620
68
27
19







Zn
6, 200
3, 700
3, 100
1, 900
160
89
86







o

-------
                                                  TABLE C-27
Trident
No.
6-1
6-2
6-3
6-4
6-5
6-6
6-7
6-8






Sample
Type
sediment
sediment
sediment
sediment
s e d im e nt
sediment
sediment
sediment






Moisture
%
62. 64
55. 11
54. 51
59.49
61. 01
54.25
49.02
49.95






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
4, 700
3, 500
540
< 100
400
280
350
340






Metals mg/kg
As
22
38
21
7
11
8
8
12






Hg
0. 57
0. 71
0. 12
0. 05
0. 07
0. 06
0. 07
0. 06






Cd
3
2
1
1
1
<1
<1
<1






Ci
220
130
39
42
65
55
43
42






Cu
160
120
31
13
15
13
14
14






Mn
700
720
1, 100
950
1, 100
960
960
790






Ni
82
88
39
29
34
30
32
28






Pb
220
510
24
15
15
12
<10
15






Zn
1, 300
1, 100
140
80
89
83
88
85






o
I

-------
                                                   TABLE C-28
Trident
No.
7-1
7-2
7-3
7-4
7-5
7-6








Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment








Moisture
%
73. 09
55. 15
57. 32
57. 18
54.28
16.28








Total
Hydro-
Carbons
Hexane
Extract
mg/kg
2, 900
1,900
600
< 100
< 100
280








Metals mg/kg
As
18
76
27
18
14
1








Hg
0. 29
0. 45
0. 29
0. 05
0. 06
0. 02








Cd
1
2
2
1
1
<1








Cr
550
320
69
78
65
12








Cu
140
140
45
17
21
2








Mn
720
880
1, 100
1, 100
960
100








Ni
69
100
52
35
33
3








Pb
220
360
64
<10
13
<10








Zn
830
1, 300
230
100
88
15








o

-------
                                                TABLE C-29
Trident
No.
8-1
8-2
8-3
8-4
8-5
8-6
8-7
8-8






Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
68. 54
68. 90
66.55
70. 55
66.82
58. 54
52.76
55.69






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
13, 700
9, 000
12, 100
9,400
6, 000
3, 100
2, 200
1, 700






Metals mg/kg
As
82
122
159
256
177
42
18
21






Hg
0. 62
0. 74
0. 78
1. 30
1.40
1.42
0. 30
0. 19






Cd
4
3
4
3
2
1
1
1






Cr
670
390
900
310
200
110
41
36






Cu
320
250
330
310
330
85
62
40






Mn
740
750
550
530
550
860
1,790
1,250






Ni
56
53
55
52
64
50
39
31






Pb
260
250
480
210
18
15
53
<10






Zn
1, 430
1, 120
890
1, 140
840
300
100
140






o

-------
                                                   TABLE C-30
Trident
No.
9-1
9-2
9-3
9-4
9-5
9-6
9-7
9-8






Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
80.89
84.26
67. 33
67. 12
76. 15
64. 54
67. 04
63. 33






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
4, 200
2,600
9, 600
6, 500
16, 000
15, 000
17,400
3,700






Metals mg/kg
As
56
72
76
74
131
125
1, 117
14






Hg
0. 46
0. 36
1. 37
1. 33
4. 69
1.61
13. 08
0. 19






Cd
3
4
3
2
4
2
2
1






Cr
300
260
510
390
290
320
590
82






Cu
300
220
330
280
260
270
580
61






Mn
1, 710
2,290
720
540
210
220
300
510






Ni
115
73
52
46
53
32
38
66






Pb
176
< 100
300
320
350
510
1,600
<30






Zn
630
710
750
500
440
420
830
140






o
I

-------
                                                   TABLE C-31
Trident
No.
10-1
10-2
10-3
10-4
10-5
10-6
10-7







Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment







Moisture
%
53.43
55. 32
61.74
52. 34
54. 30
45. 87
46. 36







Total
Hydro-
Carbons
Hexane
Extract
mg/kg
4,600
7, 100
5, 100
6, 700
3, 500
1,800
3, 100







Metals mg/kg
As
31
49
45
37
77
37
93







Hg
0.42
0.46
0. 83
1. 26
0. 64
0. 34
0.66







Cd
3
4
5
4
3
1
1







Cr
680
320
400
260
260
160
200







Cu
160
230
230
280
230
150
160







Mn
380
280
290
280
230
350
370







Ni
76
73
71
58
50
46
48







Pb
170
180
170
160
160
97
130







Zn
390
650
710
480
350
180
220







o
I

-------
                                                            TABLE  C-32
Trident
No.
11-1
11-2
11-3











Sample
Type
sediment
sediment
sediment











Moisture
%
54.88
48. 36
45. 37











Total
Hydro-
Carbons
Hexane
Extract
mg/kg
400
260
<100











Metals mg/kg
As
11
10
5











Hg
0. 06
0. 04
0. 02











Cd
2
2
1











Cr
23
21
26











Cu
23
10
9











Mn
1, 360
690
680











Ni
50
29
48











Pb
<20
<10
<20











Zn
160
60
54











o
I
4^
00

-------
                                                 TABLE C-33
Trident
No.
12-1
12-2
12-3
12-4
12-5
12-6
12-7
12-8






Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
62.05
61.28
51. 05
56.40
58. 98
60. 79
58. 75
59.26






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
1, 200
<50
1, 000
560
260
<50
<50
<50






Metals mg/kg
As
19
19
17
25
12
14
11
12






Hg
0.20
0. 12
0. 15
0. 27
0. 06
<0. 05
0. 05
<0. 05






Cd
1
1
1
1
2
1
1
1






Cr
73
30
29
30
29
28
20
23






Cu
57
29
32
47
16
11
8
9






Mn
1,440
1,670
1, 720
1, 360
1, 100
1,230
1,400
1,260






Ni
49
41
42
62
35
35
30
33






Pb
37
<10

-------
                                                       TABLE C-34
Trident
No.
13-1
13-2
13-3
13-4
13-5
13-6
13-7
13-8






Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
64.41
53. 98
58.88
36. 35
48. 96
45. 39
44.84
36.75






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
6, 100
7, 800
7 , 500
<100
180
< 100
<100
< 100






Metals mg/kg
As
33
33
39
9
5
7
7
6






Hg
1. 34
2. 26
3. 37
0. 07
0. 05
0. 04
0. 03
0. 05






Cd
8
9
10
<1
1
<1
<1
<1






Cr
370
360
270
32
47
53
47
20






Cu
220
220
160
12
12
11
11
9






Mn
1, 100
1, 200
1,200
150
240
190
180
170






Ni
54
52
55
16
18
17
18
13






Pb
1, 300
1, 300
990
17
<10
<10
<10
<10






Zn
3, 400
5, 500
3, 900
51
64
59
51
44






o
I
Ul
o

-------
                                               TABLE C-35
Trident
No.
14-1
14-2
14-3
14-4
14-5
14-6
14-7
14-8






Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
65. 11
58.29
52. 67
66.73
61. 02
49. 13
58. 34
50. 36






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
2,400
3, 300
2, 600
6, 000
4, 300
< 100
280
180






Metals mg/kg
As
35
22
25
41
65
13
10
12






Hg
0. 50
0.97
0.47
0. 75
0. 89
0. 06
0. 61
0. 05






Cd
2
2
2
3
4
1
1
<1






Cr
300
120
150
340
200
69
51
45






Cu
150
57
89
190
170
16
16
16






Mn
620
1, 500
1, 900
860
790
1,200
1, 300
1,200






Ni
50
47
63
64
58
35
31
32






Pb
160
120
130
290
400
20
22
17






Zn
590
320
490
1, 300
1, 100
98
94
100






o

-------
                                                        TABLE C-36
Trident
No.
15-1
15-2
15-3
15-4
15-5
15-6
15-7
15-8






Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
67.72
65. 36
58. 34
55. 56
51. 52
53. 53
51. 30
56.45






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
21, 000
26, 000
17, 000
8, 800
1, 800
250
210
670






Metals mg/kg
As
48
65
75
51
9
8
6
7






Hg
1.63
1. 08
1. 11
0. 70
0.43
0.24
0. 06
0.40






Cd
15
13
11
8
1
2
1
1






Cr
1,700
1, 400
1, 100
760
130
100
48
68






Cu
500
480
360
250
38
23
16
26






Mn
660
630
540
640
640
550
800
920






Ni
75
68
54
47
33
29
30
35






Pb
500
470
690
300
52
18
13
30






Zn
2, 600
2, 200
2, 100
1, 200
140
110
77
120






o
I
in

-------
                                                 TABLE C-37
Trident
No.
16-1
16-2
16-3
16-4
16-5
16-6
16-7
16-8






Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
66.59
59.43
58.39
56. 58
62.46
62.70
58. 62
57.75






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
3, 900
5, 600
2,200
1,900
4, 100
<100
<100
<100






Metals mg/kg
As
48
27
38
34
93
12
10
8






Hg
0.40
0. 62
0. 52
0.47
0. 94
0. 51
0. 53
0. 06






Cd
3
1
2
2
4
1
1
2






Cr
435
240
150
210
360
57
47
55






Cu
160
140
130
110
330
17
17
16






Mn
870
1, 500
1,900
1,800
590
1, 500
1,400
1,700






Ni
56
55
68
53
88
36
36
38






Pb
160
190
160
170
700
52

-------
                                                    TABLE C-38
Trident
No.
17-1
17-2
17-3
17-4
17-5
17-6
17-7
17-8






Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
61.48
57.71
58.79
60. 14
74.43
48. 54
54. 18
54. 92






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
8, 300
4, 300
1, 800
3, 300
18, 600
1, 500
< 100
<100






Metals mg/kg
As
50
32
34
45
184
13
13
12






Hg
0. 75
0. 44
0. 37
0. 36
1. 36
0. 52
0. 04
0. 09






Cd
2
3
2
2
8
<1
<1
<1






Cr
640
250
170
210
950
100
41
33






Cu
270
130
71
72
400
44
17
25






Mn
720
1, 300
1, 200
1, 100
390
660
720
1, 200






Ni
61
54
47
44
57
44
32
54






Pb
240
150
170
140
610
81
22
33






Zn
870
400
350
450
1, 800
120
100
100






o

-------
                                                                                         TABLE C-39
Trident
No.
18-1
18-2
18-3
18-4
18-5
18-6
18-7
18-8






Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
65. 11
67.88
64. 91
66. 00
59.42
55. 22
58. 59
50.43






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
16, 100
13, 100
10, 500
7, 400
2, 800
390
<100
1, 900






Metals mg/kg
As
108
116
103
150
77
10
6
10






Hg
0. 84
1. 15
1. 25
1.66
1. 30
0. 09
0. 05
0. 13






Cd
5
5
4
4
1
<1
<1
1






Cr
760
720
640
540
220
38
40
130






Cu
410
460
420
450
190
22
19
32






Mn
490
500
490
570
470
1, 900
2, 800
2, 300






Ni
65
61
53
56
61
41
43
53






Pb
300
320
350
400
280
29
30
28






Zn
1, 530
1, 740
1, 430
1, 060
400
83
92
100






o
I

-------
                                                       TABLE C-40
Trident
No.
19-1
19-2
19-3
19-4
19-5
19-6
19-7







Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment







Moisture
%
61.62
58.23
59.79
57. 50
62. 19
54.73
53.32







Total
Hydr^-
Carbons
Hexane
Extract
mg/kg
4, 500
8, 000
7, 300
6, 200
6,400
820
3, 300







Metals mg/kg
As
63
73
74
101
63
9
14







Hg
0. 73
0. 81
0. 96
1. 08
0. 96
0. 36
0. 58







Cd
4
5
4
4
5
2
1







Cr
330
480
370
390
440
100
160







Cu
260
390
400
320
350
48
96







Mn
830
930
690
790
730
1, 000
730







Ni
78
63
76
95
95
42
45







Pb
220
280
200
180
300
48
84







Zn
660
1, 100
1, 050
1, 190
1, 290
150
170







n
Ul

-------
                                                 TABLE C-41
Trident
No.
20-1
20-2
20-3
20-4
20-5
20-6
20-7
20-8






Sample
Type
sediment
sediment
sediment
sediment
sediment
sediment
sediment
sediment






Moisture
%
62.81
61.25
66.70
58. 50
55.66
53.42
56.28
50.64






Total
Hydro-
Carbons
Hexane
Extract
mg/kg
8, 900
9, 700
13,400
17, 100
12, 700
10, 100
1,900
13, 800






Metals mg/kg
As
58
50
68
75
96
116
8
87






Hg
1. 21
1. 04
1. 34
1. 81
2. 85
1. 64
0. 09
2. 16






Cd
4
3
4
4
3
2
<1
3






Cr
450
410
650
610
340
250
73
290






Cu
390
290
460
470
550
300
55
750






Mn
510
390
390
390
350
510
610
200






Ni
62
81
68
71
70
63
62
47






Pb
290
210
230
530
420
230
48
310






Zn
210
620
1, 050
920
700
460
110
120






o
I

-------
         APPENDIX D





POLYCHLORINATED BIPHENYLS

-------
D.I      INTRODUCTION




     Poly chlorinated biphenyls (PCB's) are aromatic organochlorine compounds




obviously named for their chemical structure, consisting of a biphenyl group




with ten available sites for chlorination.
                                                        PCB







                                                   X-CI






     In normal manufacturing, PCB's are not isolated for marketing as single




compounds, but rather as a mixture of chlorinated biphenyls.  Jensen (1970)




states that in theory, 189 different arrangements containing 1 to 8 chlorine




atoms are possible, but that in normal manufacturing, 4 to 8 chlorine atoms




attach to the parent biphenyl molecule (even with only 4 to 8 chlorine atoms,




there are 102 different molecular arrangements).   Walker (1976)  states that




there are 209 isomers in PCB mixtures and formulations.




     Since single polychlorinated biphenyls are not isolated for marketing,




the degree of chlorination (as percentage by weight of chlorine) identifies




the commercial product.  In the United States, PCB's are manufactured by




Monsanto Chemical Co., St. Louis, Missouri, with production somewhere between




15,900 to 38,600 metric tons per year (Walker, 1976) of Aroclor - the trade




name.  Eight Aroclor formulations  - 1221, 1232,  1242, 1248, 1254, 1260, 1262




and 1268 are marketed.  The "12" designation defines the product as a PCB




while the last two digits (42, 48,-retc.)  indicate the percentage by weight of




chlorine.
                                     D-2

-------
     Widespread use of PCB's started before 1930 (Penning, 1930).  The




primary use of PCB's is in manufacturing electrical transformers and capaciters




although they are also used in marine anti-fouling paints, in cardboard




cartons, as dust-allayers, in insecticides, as plasticizers, as hydraulic




fluids, in protective coatings, as sealers, in inks, waxes and adhesives, in




thermostats, as lubricants, as grinding fluids and as sealers in electrical




applications.




     The use of PCB's in the variety of applications previously mentioned




stems partially from their physical and chemical properties.  Generally, low




vapor pressures, low water solubility, high dielectric constants, inertness,




stability at high temperatures, resistance to acids, bases and microbial




activity, and fat solubility characterize PCB's.  Many of these characteristics,




especially fat solubility, inertness, and resistance to microbial activity-.




make PCB's persistent contaminants in the environment.




     Although PCB's are widely used (their early development is documented




in Schmidt and Schultz, 1881), concern over their toxicity first appeared in




the 1930's when workers making PCB's developed certain pathologies (Jones and




Alden,  1936; Good and Pensky, 1943; Drinker et al., 1937; Flinn and




Jarvik, 1939; Greenberg et al., 1939; Schwartz, 1943; Schwartz and Barlow, 1942;




and Schwartz and Peck, 1943).  However, PCB presence in the environment became




noticed when many investigators observed a series of unidentified peaks on




gas chromatograms (reviewed in Reynolds, 1971).  Most of the samples were




pesticide residues especially from fish and raptors containing fairly large




concentrations of organochlorine pesticides (many pesticides such as DDT,




methoxychlor, etc. are quite similar to PCB's in molecular structure).  Jensen




(1966) was the first to relate the unidentified peaks to PCB's.  The problem
                                      D-3

-------
of PCB interference with pesticide analyses is discussed in Reynolds (1971)>




Zitko (1972), Stalling and Huckins (1973), and Stalling et al. (1972).




     After Jensen's (1966) initial confirmation of PCB's in wildlife, more




reports of PCB contamination followed as reviewed in Walsh (1972) , Reynolds




(1971), Dustman et al. (1971), and Walker (1976).  Generally, these reports




continued to cover fish and raptors although some attention was beginning




to center on other species.




     After observing high levels of PCB's in many animals, concern was




expressed over the possible toxicity of PCB's especially after Mclaughlin




et al. (1963) reported that Aroclor 1242 was toxic and teratogenic.  Some




of these early studies are reviewed in Walsh (1972) , Reynolds (1971), and




Walker (1976) concerning toxicity and mode of action for PCB's.




     Walker (1976) points out that high concentrations of PCB's occur con-




comitently with heavy industrial activity.  In this  study, an analysis is made




of sediments from Baltimore Harbor for the presence  of two PCB's - Aroclor




1248 and Aroclor 1260.










 D.2        PROCEDURES






     A total of 20 stations  (Fig. D-l ) within Baltimore Harbor were sampled




by a piston corer equipped with a 4.6 m polycarbonate liner.   Two cores were




taken per station.  Completion of coring took 6 days during 9 June to 15 June




1976.




     Samples for PCB analyses were taken from the cores at four depths -




5 cm, 15 cm, 30 cm and 61 cm.  Core material was removed with wooden applicator




sticks and immediately transferred to clean glass vials.  Vials were sealed




by first capping with aluminum foil (acetone-washed) and then capping with







                                     D-4

-------
plastic lids.




     All samples were shipped to Analytical Bio Chemistry Laboratories, Inc.,




Columbia, Mo. for PCB analyses.  A weighed portion of the air dried sample




was adjusted to approximately 20% moisture.  Each sample was extracted with




methanol/chloroform (1:1) by blending in a Sorval Omni mixer.  Following




filtration, the extract was diluted with water and the PCB's partitioned




into the chloroform.  A series of repeated extractions and backwashings




removed the methanol from the chloroform phase.  The chloroform was evaporated




and the residue subjected to Florisil column chromatography (20 g, 22 mm i.d.)




in which the PCB's were eluted with 200 ml of hexane.  The eluant was




evaporated and transferred to a final volume of 5 ml.  Microliter injections




into a gas-liquid chromatograph equipped with Ni,., electron capture detectors




were used for identification and quantification.




     The GLC-EC parameters were:  injector temperature - 225 C; column -




1.83 cm x 4 mm, 2% OV-210, 1.5% OV-17 on Chrom W 100/120, temperature 205 C;




and detector temperature - 300 C.  Calculations were based on the middle




five peaks of Aroclor 1248 and the last nine peaks of Aroclor 1260 and




reported as ppm (w/w) air dried basis.  A peak ratio judgement was made to




determine the species or peaks to be considered for identification and




quan ti fi cation.




     A total of 80 samples were analyzed for Aroclor 1260 and  76 for Aroclor




1248.  A 5 cm sample was not run for station 7 (Fig.  D-l) .    Duplicates were




run on station 8 - 5 cm depth.




     Statistical procedures were from Sokal and Rohlf (1969).  Calculations




were performed on a Canon F-20P statistical calculator.
                                      D-5

-------
Figure D-l - Sampling (coring) stations for PCB analyses
             within Baltimore Harbor

-------
BALTIMORE  HARBOR

-------
D.3        RESULTS




     PCB concentrations by depth for the 20 stations  (Figure D-l)  samples




are presented in Table  D-l.  High concentrations, greater than 1.0 ppm total




PCB's, are present at stations 1, 2, 3, 4,  5, 10, 15, and 18.  Gross contamination




of the upper sediments occurs at station 1 where PCB concentrations approach




84.2 ppm and remain high throughout the sediment column.   Generally, stations




1, 2, 3, 4, 5, and 15 contain.extremely high PCB levels, especially in the top




30 cm of the core.




     Stations 6, 8, 9, 12, 13, 14, 16, 17, 19, and 20 are classified as being




intermediately contaminated since their PCB concentrations  are less than




1.0 ppm and greater than 0.05 ppm total PCB's.   Station 6 has intermediate




levels of PCB's in the upper 5 cm of the sediment, but concentrations  drop




with increasing depth.




     Station 20 did not have detectable PCB's in the upper  5 cm of the sediment




column, but intermediate concentrations of PCB's are present below 15  cm.




There is a possibility that recent scouring and dredging or a discontinuation




of PCB input may have occurred at this station.




     At stations 7 and 11, PCB concentrations are less than 0.05 ppm.   Both




of these stations are located in the outer harbor area near the reference




station 12.




     Generally, there is a decrease in PCB  concentration with -sediment depth.




Besides station 20, stations 9,  14 and 19 did not follow the pattern of lower




PCB concentrations with depth.  For three stations (4, 7S -11, and  12) no  apparent




pattern (within statistical limits) of PCB's  exist.  Eleven of the remaining




stations, within statistical range, show decreasing PCB levels with sediment




depth.





                                     D-8

-------
                       TABLE D-l
PCB concentrations (ppm w/w basis)  for Baltimore Harbor stations
(Figure D-l)  by depth.
Station Depth (ft) Depth (on)
I1 0.16
0.5
1.0
2.0
2 0.16
0.5
1.0
2.0
3 0.16
0.5
1.0
2.0
4 0.16
0.5
1.0
2.0
5 0.16
0.5
1.0
2.0
6 0.16
0.5
1.0
2.0

5
15
30
61
5
15
30
61
5
15
30
61
5
15
30
61
5
15
30
61
5
15
30
61

Aroclor 12,60
84.19
2.41
0.59
3.11
1.26
0.91
0.60
0.32
1.70
0.97
0.89
0.71
0.84
0.94
0.80
0.71
2.10
1.20
0.24
0.05
-0.10
<0.05
<0.05
<0.05
D-9
Aroclor 1248
	
	
	
	
0.87
0.54
0.39
0.13
0.57
0.76
0.76
0.64
0.51
0.71
0.39
0.55
3.50
1.50
0.14
< -0.05
0.11
<0.05
<0.05
<0.05

Total
>84.19
> 2.41
> 0.59
> 3.11
2.13
1.45
0.99
0.45
2.27
1.73
1.65
1.35
1.35
1.65
1.19
1.26
5.60
2.70
0.38
> 0.05
0.21
<0.05
<0.05
<0.05


-------
                       TABLE D-l





PCB concentrations (ppm w/w basis) for Baltimore Harbor stations




     (Figure D-l)  by depth,  (continued)
Station Depth (ft)
7 0.5
1.0
2.0
8 0.16
0.16
0.5
1.0
2.0
9 0.16
0.5
1.0
2.0
10. 0.16
0.5
1.0
2.0
11 0.16
0.5
1.0
2.0
12 0.16
0.5
1.0
2.0

Depth (cm)
15
30
61
5
5
15
30
61
5
15
30
61
5
15
30
61
5
15
30
61
5
15
30
61

Aroclor 1260
<0.05
<0.05
<0.05
0.16
0.15
0.06
<0.05
<0.05
0.41
0.12
0.64
0.14
0.29
0.17
0.19
0.17
<0.05
<0.05
<0.05
<0.05
<0.07
0.06
<0.05
0.07
D-10
Aroclor 1248
<0.05
<0.05
<0.05
0.11
0.22
0.07
<0.05
<0.05
0.23
<0.05
0.32
0.06
0.83
0.29
0.24
0.16
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
<0.05
0.11

Total
<0.05
<0.05
<0.05
0.27
0.37
0.13
<0.05
<0.05
0.64
0.12
0.96
0.20
1.12
0.46
0.43
0.33
<0.05
<0.05
<0.05
<0.05
>0.07
>0.06
<0.05
0.18


-------
                      TABLE D-l



PCB concentrations (ppm w/w basis) for Baltimore Harbor stations





      (Figure D-l) by depth,  (continued)
Station Depth (ft) Depth (cm)
13 0.16
0.5
1.0
2.0
14 0.16
0.5
1.0
2.0
15 0.16
0.5
1.0
2.0
16 0.16
0.5
1.0
2.0
17 0.16
0.5
1.0
2.0
5
15
30
61
5
15
30
61
5
15
30
61
5
15
30
61
5
15
30
61
Aroclor 1260
0.32
0.33
0.30
<0.05
0.06
<0.05
<0.05
0.10
1.48
0.55
0.25
<0.05
0.10
0.07
0.05
<0.05
0.47
0.57
0.06
0.08
Aroclor 1248
0.28
0.14
0.11
<0.05
0.06
<0.05
<0.05
0.07
0.84
1.32
0.14
0.05
0.09
0.06
<0.05
<0.05
0.31
0.19
<0.05
0.10
Total
0.60
0.47
0.41
<0.05
0.12
<0.05
<0.05
0.17
2.32
1.87
0.39
0.05
0.19
0.13
0.05
<0.05
0.78
0.76
0.06
0.18
                               D-ll

-------
                               TABLE D-l
         PCB concentrations (ppm w/w basis) for Baltimore Harbor stations
             (Figure D-l)  by depth.   (continued)
Station
18



19



20



Depth (ft)
0.16
0.5
1.0
2.0
0.16
0.5
1.0
2.0
0.16
0.5
1.0
2.0
Dep th ( cm)
5
15
30
61
5
15
30
61
5
15
30
61
Aroclor 1260
0.61
0.22
0,14
0.08
0.06
0.22
0.17
0.25
<0.05
0.28
0.23
0.12
Aroclor 1248
0.64
0.23
0.15
<0.05
0.05
0.25
0.21
0.28
<0.05
0.43
0.12
0.10
Total
1.25
0.45
0.29
0.08
0.11
0.47
0.38
0.53
<0.05
0.71
0.35
0.22
Aroclor 1260 was masking 1248 values  so that  total values may be

substantially higher for this one sample set.
                                       D-12

-------
      In Figure  D-2,   PCB  concentrations  for  the  Baltimore  Harbor stations are




plotted as a function of depth and channel length (in kilometers).  It




is obvious, except for the PCB concentrations at station 20, that from station




1 to 18, high PCB loading is present in the sediments.   A  localized high con-




centration of PCB's is observed at stations  5 and 15.




      From  station 9 to 6  (Figure D-2) and except for stations  18 & 16,




total sediment PCB concentrations are greater than 0.05 ppm but less than




1.00 ppm.   At stations 7 and 11, PCB's have essentially disappeared from the




sediment (no values are available for station 7 at the 5 cm level).  PCB's




are also starting to  disappear at the lower depths from stations  8  to 11.





      In Figure  D-3,   the  relationship of Aroclor 1248  to 1260 concentrations  is



plotted.  There is a  significant (at p<0.001, r=0.91)  correlation between




1248  and 1260 values  in the sediments.  Three significant outliers  occur.




At station 3, the level of 1260 is over three times greater than  the 1248 value.




At station 15 for the 15  cm depth, the 1248  concentration is almost 2.5




times greater than the 1260 concentration.  At station 10, the 1248 value is




also  2.5 times  greater than the 1260 value at the 5 cm depth.  These factors




may be a result of industrial usage patterns.









D.4       DISCUSSION







     Sediment concentrations of PCB's except for special cases at station




20 (low level) and stations 5, 15, ajid 18  (high  levels)  tend to  be  elevated from




station 19 to station'1 - the inner seven kilometers from approximately Colgate




Creek through the Northwest Branch.   From station 9 (Curtis Bay)  to station 12




(Old Road Bay),  PCB concentrations are greater than 0.05 ppm, but less than




1.00 ppm of total PCB's.   Outside of the entrance to the harbor, PCB







                                     D-13

-------
Figure D-2  - PCB  concentrations as a function of depth  and  channel




       length in Baltimore Harbor.  Dark shading indicates PCB




       concentrations  greater  than 1 ppm, lateral markings indicate




       PCB  concentrations less  than 1 ppm but greater  than 0.05 ppm,




       and  clear areas indicate PCB concentrations less  than 0.05 ppm,

-------
1       2   10 3       20
           STATION
4 19  9  18    17   58  15   16
                              14 7  13   6    11  12
       10
KILOMETERS
                                                                  15

-------
Figure D-3 - The  relationship  of Aroclor  1248  to Aroclor  1260




      concentrations  (in ppm)  in sediments  from Baltimore




      Harbor.   Paired values or single  values  less  than 0.05




      ppm PCB's were  not used  in the  analysis.

-------
TJ
H-
C
ro
a
10
a.
 I
oo

CN
    U
    O
    CtL
                                          O
                                 .4
                                                    .8
                                              AROCLOR
     1.0
1260 - PPM
1.2
1.6
1.8

-------
concentrations drop to levels below 0.05 ppm (station 12 has low PCB levels,




but primarily 1260 appears in the samples).   Two factors may account for the





accumulation of increased levels of PCB's in Baltimore Harbor.  Obviously,




PCB's have been released into the water in the past.  First there is the




possibility of present releases still being made into the harbor with PCB's




being entrapped into the sediment column.  Second, current patterns in




Baltimore Harbor may tend to contain pollutants within the harbor confines.




A unique three-layered circulation system (Pritchard, 1968) in Baltimore




Harbor may minimize transport of material out of the area.




     The predominance of Aroclor 1260 over 1248 is also of interest.  Either




more 1260 is in use in Baltimore Harbor or some of the 1248 is being slowly




lost since the lower Aroclors are more readily biodegradable  (Walker, 1976):.




Walker (1976) points out that for systems where a variety of Aroclors are




present, it is more important to measure PCB's as a sum of the chloro-homo-




logs (mono, di, etc.) rather than as 1242, 1248, 1260, etc.




     PCB contamination tends to be associated with industrialization or




with accidents.  Walker (1976) points out that PCB residues in fish are high




in heavily industrialized riverine systems.   Koo (1975) points out that over




170 potential sources of industrial wastewaters are present in Baltimore




Harbor with two major sewage treatment plants (a possible source of PCB's since




chlorination is a standard operating procedure) discharging 76,000 m-Vday  of




treated sewage into Baltimore Harbor.  In a summary section, Koo (1975)




also points out that environmental stress is present, with semi-healthy




conditions at the mouth and polluted conditions in the inner harbor area.




Pfitzenmeyer (1975) summarizes the available literature on the pollution of




Baltimore Harbor.  Heinle and Morgan (1972)  and Morgan et al. (1973) discuss




the sublethal effects of Baltimore Harbor water on a variety of organisms.






                                     D-18

-------
The input of PCB's into estuarine waters is the result of a variety of



processes  (Walsh,  1972) -  (1)  agricultural  runoff,  (2) industrial/




municipal  discharge,  (3) drift and  rainfall and  (4)  accidental/careless




discharge.  Although  PCB's  are relatively insoluble  in water,  they may be




made soluble by humic acids  as occurs with  pesticides (Wershaw et al., 1969).




PCB transport may  come not  only from water  movement, but also  from the involved




process  of sediment flocculation  and resuspension -  a phenomena in the




estuarine  system.  In addition,  differential solubilities of PCB's may result




in precipitation  (Walsh, 1972).   No matter  what  the  level of PCB input may




be to  a  system, the possibility exists  that biomagnification and bio-




accumulation  could occur to an extent which could be damaging  to a population




or to  the  entire  aquatic community.




     Any analysis  of  PCB accumulation'in sediments is complicated by  the




relative insolubility of the different  formulations.  Most of  the crystalline




PCB's  are  insoluble,  however,  resinous  and  liquid PCB's solubilize in




organic  solvents,'  thinners  and oils (Reynolds, 1971).  For oceanic waters,




90% of the PCB's  are  dissolved (Harvey, unpublished  data in Duce et al.,




1974).




     Sediments appear to be a  pool  for  PCB's in  estuarine and  marine systems




(Duce  et al., 1974) with concentrations of  sediment PCB's inversely pro-




portionate to water depth.   Harvey  (unpublished  data, Duce et  al., 1974)




found  PCB  concentrations ranging  from 500 ng/g sediment (ppb)  in inshore




Massachusetts to 0.3  ng/g sediment  in uie Hatteras Plain.  For San Francisco




Harbor,  PCB's range from 0.026 to 0.833 ppm (Pacific Northwest Laboratories,




1974).   Duke et al. (1970),  investigating an industrial spill  of Aroclor




1254,  found sediment  containing up  to 486 ppm of PCB's.




     Horn et al. (1974) observed PCB deposition rates of 1.2 x  10~^ 5/m2/year
                                     D-19

-------
in the Southern California Bight.




     Given either a value for sediment or water PCB content,  what are the




possible concentrations of PCB's  in estuarine populations or  communities.




Although some detailed analyses of ocean water have been made,  very few




studies have been concerned with  transfer mechanisms of PCB's in estuarine




and coastal systems where major ecological effects  could occur (Duce et al.,




1974).  An organic may become present in very low quantities  within an




aquatic community.  Based on a variety of factors such as salinity, sediment/




solution ratio, and concentrations, PCB's may accumulate in populations




and communities.  It appears that  chemical and some physical  factors such




as temperature, pH, Eh, and dissolved oxygen are not important when dealing




with PCB desorption from sediments.  Initially, a primary producer or hetero-




troph will take up the toxic material from either the water column or from




deitrus and suspended sediments.   Primary consumers will further concentrate




toxic materials.  Eventually, upper components (fish, mammals,  birds, etc.)




of an aquatic ecosystem will concentrate the material 10  to  10  - fold.




Within a population, the problem  is bioaccumulation, within a community




the problem is biomagnification.   Bioaccumulation or biomagnification of




toxic materials may reveal itself  in two ways - acute effects and sublethal




effects.  Acute effects, such as  mortality and increased vulnerability to




predation, could occur.  Sublethal effects, by definition, are the typical




consequence of biomagnification and bioaccumulation in aquatic communities.




     Bioaccumulation in a population is directly related to the lipophylicity




of PCB's and the overall bioenergetics of the population (Norstrom et al.,




1976).  Strongly lipophylic agents will probably be assimilated at maximal




or near-maximal efficiency.  Thus, the uptake rate of these residues will




fall within limits set by populational characteristics such as metabolic





                                    D-20

-------
rate and growth, which in turn are a function of the environmental variables




acting on that population (Norstrom et al.,  1976).




     The level of a residue within a single organism of a population is a




function of exposure, dose and absorption of the residue into the organism.




Within the organism, the concentration becomes a function of residue dis-




tribution, deposition, remobilization and excretion.  For lipophylic




compounds, prime areas of deposition are organisms such as fish, mammals




and birds.




     Wildish and Zitko (1971) propose that PCB uptake may be accomplished




by either absorption in the gut from food or water or through the body surface.




Harvey et al. (1974) find PCB concentrations in Atlantic plankton ranging




from 200 pg/kg to 100 yg/kg wet weight - samples with high PCB concentrations




contained large numbers of phytoplankton.  Duce et al. (1974) report that




unicellular algae can concentrate ng/g quantities of PCB's as much as ten-




thousandfold.  However, herbivores feeding on the same algae could only




accumulate PCB's two- to fivefold; larval fish also could only accumulate PCB's




two- to fivefold from feeding on the herbivores (Duce et al., 1974).  However,




sediment-feeding invertebrates living in an area of high PCB's could easily




ingest large quancities of PCB's.  This may shorten the link between the




higher trophic levels.




     Wildish and Zitko (1971) find that PCB uptake in amphipods increases




with increasing PCB concentration although the rate of uptake decreases




after 4 to 6 hours exposure.  Sanders and Chandler (1972) note that bio-




accumulation in invertebrates for short term exposures range from 160 to




6,300 times the water concentration, but bioaccumulation in  longer exposures




results in PCB accumulation from 27,000 to 48,000 times the water con-




centration.  In fish (Hansen et al., 1971) accumulation rates occur at
                                      D-21

-------
10,000 to 50,000 times the environmental levels.   Vreeland (1974)




points out, in a series of experiments with oysters, that PCB's containing




more chlorine atoms (such as 1260)  accumulate in greater amounts.   Based




on Vreeland's data, it was calculated  the correlation of degree of chlorination




versus the log of the equilibrium isomer concentration and found a highly




significant (r=0.97) relationship between the numbers  of chlorines on the




parent biphenyl and isomer concentration in oysters.  For any increase of




1 pptr in the water, oysters accumulate 1-2 ppb for the dichloro isomer




to 48 ppb for the hexachloro isomer (Vreeland, 1974).   Generally,  Vreeland




(1974) reports equilibrium of PCB content in oysters with environmental




conditions approximately one month after exposure.   In Florida, Duke et al.




(1970) found that many estuarine species accumulated 1254 in amounts from




1.0 to 184 ppm with a sediment concentration of 486 ppm (maximum).




     Although high concentrations of PCB's do accumulate in mammals, fish




and birds, many factors such as lipid content, degree  of chlorination,




physical and chemical factors, etc. may determine actual PCB concentrations




in aquatic food webs.  Norstrom et al. (1976) have developed a model for




pollutant accumulation based on pollutant biokinetics  linked to fish




energetics.  The uptake rate  of pollutants is dependent on both species-




specific factors (metabolism, growth,  lipid content, etc.) and environmental




factors (salinity; temperature, food,  etc.).




     As described before, bioaccumulation is a populational characteristic




(really an individualistic phenomena).  Once a pollutant is part of a living




organism, concern then shifts to the problem and process of biomagnification




through food webs and trophic assemblages,  Biomagnification is obviously




important, in relation to human health, if the upper components of the food
                                     D-22

-------
chain are accumulating PCB's in large enough amounts to cause damage upon




human consumption.




     Of equa."". importance to the problem of human health, is the effect of




PCB's on community structure and function.  Moore and Harriss (1972) found




that radiocarbon uptake by the phytoplankton is strongly inhibited at 5 ppb




of Aroclor 1242 and 1254 affecting lower trophic dynamics.  In a related paper,




Mosser et al. (1972) noted that competitive interactions between two species




of algae are altered at PCS concentrations as low as 1 ppb.  Nebeker et al. (1974)




studied the effect of PCB's on fish reproduction and survival; found growth




and reproduction still occurring at and below 1.8 ppb of 1254 and at or below




5.4 ppb 1242.  In their study, the newly hatched larvae were extremely




sensitive to 1254 and 1242.  Growth of the larvae was affected at PCS levels




greater than 2.2 ppb.  In a related study, Schimmel et al. (1974) studied




effects of 1254 on sheepshead minnows and found poor survival of fry at PCB




concentrations at or above 0.1 ppb, although embryos developed at 10.0 ppb.




The above studies point out that PCB's may affect community structure by




affecting growth and reproduction.




     Obviously, PCB's are toxic, but are usually less toxic than compounds




such as DDT and dieldrin (Walsh, 1972).  Generally in aquatic systems, toxicity




due to a substance is rarely observed.  However, sublethal effects of that




toxicant are more important especially if the compound is an accumulator with




a long biological half-life.




     Toxicity of PCB's is reviewed by Dustman et al. (1971), Fishbein (1974),




Walsh (1972), Walker (1976) and Reynolds (1971).  At present, the majority




of PCB toxicology still deals with mammals and birds, although more emphasis




is being placed on aquatic organisms.




     On a sublethal basis, PCB's tend to produce a variety of pathological con-





                                     D-23

-------
ditions in man and rats including a variety of changes in hepatic function




(Allen and Abrahamson,  1973).   PCB's are embryolethal, teratogenic and




carcinogenic plus also  being immunosuppressive (Fishbein, 1974).   Other




sublethal effects are associated with community and populational processes




such as growth, reproduction and competition (Moore and Harriss,  1972;




Mosser et al., 1972;  Nebeker et al., 1974; Schimmel et al., 1974; Nebeker




and Puglisi, 1974).   Risebrough et al.  (1968)  observed that only a few molecules




of chlorinated hydrocarbons are needed  for steroid breakdown - an important




point when dealing with testicular and  ovarian function or normal endocrine




pathways in aquatic animals.




     Given the above  information and the data from this study, what are the




possible relationships  of PCB  levels in Baltimore Harbor sediments to plants




and animals on a local  basis.   First, there are some assumptions  before




the analysis.  One,  the water  concentration of PCB's is in some equilibrium




with the sediment concentration.  Second, the organism is neither hyper- nor




hyporich in lipid concentration.  Third, each organism has an equal probability




of accumulating PCB's based on populational and physiological attributes




inherent for that species.   Fourth, the organisms are exposed long enough




to take up PCB's to equilibrium.




     For this analysis, information from three studies is required (Duke et




al. , 1970; Forns, 1972; and Munson, 1972).  Duke et al. (1970) found 486 ppm




of 1254 in sediment and from 1.0 to 184 ppm in a variety of fish and in-




vertebrates.  In this case, the animal  to sediment  ratio varies  from 0.0021




to 0.379.  Munson (1972)  observed 1242  concentrations in Chester River sed-




iments ranging from 0 to 300 ppb with average values from 53 to 110 ppb.




(Munson also observed that PCB's bind to the sediment with an inverse relation-
                                    D-24

-------
 ship of concentration to particle size.)   In the biota,  Munson (1972)



 observed (averages)  for oysters - 55 ppb,  clams - 58 ppb,  fish - 185 ppb



 and crabs - 20 ppb.   Using a mean value of 87 ppb for Chester River sediment



 PCB concentrations,  the animal to sediment ratio varies  from 0.22 for crabs,



 0.63 for oysters,  0.66 for clams and 7.2  for fish.   Forns  (1972)  found PCB



 levels of 286 ppb  of 1242 and 79 ppb of 1254 in plankton (primarily zooplankton



 and values are maximum possible values).   For zooplankton,  the animal to


 sediment ratio is  4.2.



      Consider two  areas of Baltimore Harbor, the inner heavily contaminated


 area with sediment PCB concentrations greater than 1000  ppb and the other



 areas with PCB's greater than 50 ppb.  For zooplankton in  the inner harbor,



 PCB's may accumulate up to 4200 ppb.  Fish may accumulate  2200 ppb, clams -



 660 ppb, oysters - 630 ppb and crabs 200  ppb.  Using the data from Duke,



 accumulation would range from 2.1 to 379  ppm.  In areas  with sediment PCB levels
                       m


 of 50 ppb, zooplankton would accumulate 210 ppb, fish -  110 ppb,  clams -


 33 ppb, oysters -  32 ppb and crabs - 11 ppb.



      Based on the"sublethal information now known,  it appears that PCB levels



 in inner Baltimore Harbor are high enough to cause serious  problems in both



 population dynamics  and community structure.  Emphasis should now be placed



 on monitoring actual PCB levels in organisms from Baltimore Harbor.





 D.5        SUMMARY




Polychlorinated biphenyls were assayed in  sediment cores (at  four  depths)



from 20  stations in Baltimore Harbor.  Assay  techniques  included PCB extration



and detection through  electron capture gas-liquid chromatography.   Eighty



Aroclor  1260 and 76 aroclor 1248  samples were run.  PCB  concentrations were



high  (greater than 1.0 ppm total  PCB's) at  stations 1, 2, 3,  4, 5,  10, 15,  and  18.



                                      D-25

-------
   The highest level was 84.2 ppm of aroclor 1260 at station 1 in the Inner




Harbor area.   Heavy concentrations of PCB's (5.6 ppm)  were also observed at




station 5 in Bear Creek.  Non-existant or low quantities of PCB's were




observed at stations 7 and 11 with low levels at stations 6,  8, 12,  14,  and 16.




Generally,  high levels of PCB's correlated to large amounts of hexane extractable




total hydrocarbons.




      Levels of PCB's within the Inner Harbor area as  well as Colgate and




Bear Creeks are high enough to cause significant biological effect if exposure




to the PCB-laden sediments is of a long enough duration.




      PCB soluability is low in water and higher in oils and  fats.   The  coincidental




occurrence  of PCB's and hexane extractable materials at  some  stations strongly




suggests that exceptional care must be taken in handling materials from  such




sites to preclude significant PCB pollution at areas of  sediment placement.
                                    D-26

-------
          APPENDIX E

         BIOASSAY OF
BALTIMORE HARBOR SEDIMENTS

-------
E. 1      LITERATURE REVIEW







Literature pertaining to the  biology of Baltimore Harbor prior to 1971




was reviewed briefly by H.  T. Pfitzenmeyer (Center for Environmental





and Estuarine Studies,  1975).  He stated that natural resources  of the





Harbor rapidly declined before the turn of the century.   There were





3,800, 000 square yards of oyster bars within the Harbor,  northwest





of a line from Old Road River to Sellers Point, in 1884.  In 1907 the





northern limit of all oyster grounds was Rock Point at the  entrance to





the Harbor, and bottoms above Bodkin Point were not recommended for





oyster culture.  Yates (1913) made a  survey of oyster bars in Chesapeake





Bay in 1906-1912, and no oyster bars were shown for Baltimore Harbor.










Olson, et al,  (1941) studied the effects of industrial pollution  of copperas,





Fe (OH)^, on the biological productivity of Curtis Bay and  nearby water




in Baltimore Harbor.  This red-brown precipitate appeared to decrease





dissolved oxygen concentration of water during the  summer,  affecting





plankton by  asphyxiation and then indirectly  affecting higher organisms.




In a laboratory study, the floe of copperas caused a heavy  coagulum on





gills of killfish (Fundulus),  silversides (Menidia), and white perch





(Morone americana). They believed that this red-brown precipitate accu-





mulated on the bottom and contributed to a marked  ecological disturbance
                                  E-2

-------
of the area.  Later; Davis (1948) also studied this copperas-polluted





area of Curtis Bay and confirmed the Olson, et al, (1941) findings; but





he found more diatoms present per liter in the polluted area than in the





relatively unpolluted area.










Weiss  (1950) investigated the possibility of an outbreak of marine wood





borers caused by a reduction in pollution of Baltimore Harbor.  No





molluscan or crustacean borers were found in the Harbor.  Of the three





species of wood borers occurring in this latitude, sporadic sets  by





Bankia gouldi might occur.   Salinities were too low for Teredo navalis





and Limnoria lignorum.  There was no evidence  supporting the belief





that a reduction in pollution  of the Harbor will increase shipworm





infestation.










Garland  (1952)  made the first extensive water quality survey of Baltimore





Harbor and the Patapsco estuary.  He stated that in some seasons of the





year fishing was good  at the entrance to the Harbor, but within the Harbor





fishing and crabbing diminished during the previous quarter of a century





and had virtually stopped.   This,  he concluded,  resulted  from waste





discharges.
                                  E-3

-------
Stroupe, et al, (1961) investigated the physical hydrography of Baltimore





Harbor to determine  the flushing rate and hydrographic mechanisms of





the Harbor.  They suspected that  fish and other animals were probably





not affected by the range of pH which occurred in the Harbor, and that





any deleterious effects might have resulted from increase in carbon




dioxide. However, high carbon dioxide concentration was favorable for





the growth of phytoplankton and marine plants.










Hohn and Hellerman (1966)  studied diatoms in Lewes-Rehoboth Canal,





Delaware,  and Baltimore area of  Chesapeake Bay.   They described four





new species from Curtis Bay,  a major tributary of the Harbor,  in  the





vicinity of  Sledds Point.  These were Diploneis hormopunctata,  Navicula





agmastriata, N.  cumvibia  and  N.  taraxa.










Chesapeake Biological Laboratory (Center for Environmental and





Estuarine Studies,  1975) conducted a comprehensive biological study of





Baltimore  Harbor in  1970-1971.   Four major biological groups were




studied: fish eggs and larvae by W. L. Dovel; invertebrate benthos





by H. T. Pfitzenmeyer,  adult fish by M. L. Wiley,  and blue crabs by





R. L.  Lippson and R. E. Miller.  The results were summarized and




edited  by T.  S. Y. Koo.  It was found  that the water column in Baltimore





Harbor still supported many species of fish,  but the bottoms were unfit





for ground  fish and for many species of benthic macro-invertebrates.





                                 E-4

-------
Dyer  (1971) of the Maryland Fish and Wildlife Administration investi-





gated fish kills of Bear Creek on September 16,  1971;  and Riggin (1972)





of the Maryland Water Resources Administration investigated -water quality





of effluents and offshore waters at Bethlehem Steel Corporation Sparrows





Point Plant.   Heavy metals were found in toxic concentrations in water





off Sparrows Point and cited as a major  contributing factor for fish





kills in Bear Creek.   Acids,  caustics, cyanides,  ammonia, and phenol





v/ere  also detected in acutely toxic levels in the Harbor water.










Villa  and Johnson (1974) of the Environmental Protection Agency's





Annapolis Field Office, Region III,  studied the heavy metal contamination





of Baltimore Harbor sediments.  They indicated that heavy metal contam-





ination might be a major  contributing factor to the biological deterioration




of benthic communities of the  Harbor.










Maryland Environmental  Service (1974) studied the water quality of the





Harbor from  1968 to 1971 and produced a Draft Report. In this project,





the phytoplankton were studied by G.  A.  Bowman,  St. Mary's College





of Maryland; and chronic bioassay of the Harbor water on clams,  cope-





pods and fish was  conducted by D. R. Heinle and R. P.  Morgan,  Chesa-





peake Biological Laboratory.  Chlorophyl ji concentration and biomass





suggested that the Harbor was not highly eutrophic but  that the phyto-
                                 E-5

-------
plankton community was less diverse than that in the Chesapeake Bay.





The results of chronic bioassay showed that there were some effects





of the Harbor water on the  survival of clams (Macoma balthica) and





inhibitory effects  on brain acetylcholinesterase activity in two species,





the hogchoker (Trinectes maculatus) and the white perch.  Otherwise,





there was no clear indication of damaging  effects.  The same report





indicated that fishermen were observed in the Inner and Outer Harbor





and on the Patapsco River bridge.  In  1972, a 28-pound bluefish was





taken at Ft. Smallwood in the Outer Harbor and won the Sun Paper's





Annual  Sport Fishing Contest.











Morgan, et  al, (1976)  studied antibiotic resistant bacteria in the Upper





Chesapeake Bay.  Of nine water sampling  stations, three stations were





located  in Baltimore Harbor.  The results showed a three-fold or greater





increase in  the number of antibiotic resistant coliforms, extending up





the Bay from the Chesapeake Bay bridge north to Baltimore Harbor. The





increase in  number of antibiotic resistant bacteria in the Harbor and its





vicinity suggested that sewage effluents had a detectable  influence on





water quality.
                                  E-6

-------
E. 2      INTRODUCTION







Baltimore Harbor receives great amounts of domestic and industrial





wastes from the City of Baltimore (Maryland Environmental Service,





1974).  The Harbor sediments have been known to contain high concentra-





tions  of organic silts (Center for Environmental and Estuarine Studies,





1975), volatile solids,  mainly oil and grease (Garland, 1952),  ferric





hydroxides (Olson, et al,  1941; Davis,  1948), and iron and heavy metals





(Villa and Johnson,  1974).  Iron sulfate contributes a  large portion of the





total  industrial discharge to the Harbor (Garland,  1952).   Chemical





constituents and toxic contaminants of the polluted sediments of Baltimore





Harbor are extremely  complex, and their total  chemical  load  and pollu-





tion load  are not known.  It is impossible to select a small number of





chemical parameters for a conventional chemical test, such as a bulk




test or the recently developed elutriate test, for determining the toxic





level  of such sediments.  In order to determine the toxic level of the





Harbor sediments, Lee and Plumb (1974) suggested that a sediment bio-





assay be  made.










For this study, a bioassay was designed for determining  the total bio-





logical impact of sediments from a set of stations widely distributed over





the Harbor system and including  stations  of known high pollution load and
                                  E-7

-------
of relatively low load.  Since only a partial chemical analysis could be





conducted at each  site, it is impossible to  assign with certainty the cause





or causes of biological damage,  although some coincidences could be





considered.  Such a bioassay series  determines the range of toxicities





likely to be found, provides a ranking of the biological threat in various





locations,  and suggests the more extensive research which would be




required for full quantification of effects and determination of their pre-





cise chemical or physical causes. The objectives of this study were:





(1) to determine gross toxicity of representative Harbor sediments  for





several appropriate organisms; (2) to supplement the chemical data of





the Harbor sediments to further  define and describe the problem areas





of the Harbor; and (3) to suggest the possible environmental effects of





dredging or other  corrective actions.










E. 3      PROCEDURES







Nine sediment sampling stations were designed, representing the various





polluted parts of Baltimore Harbor noted in earlier studies (Figure E-l).





At each station,  about thirty gallons of sediment was collected on




June 9,  1976 from the top one foot of bottom material.  Salinity and





water temperature at the time of  sampling  are shown in Table E-l.  Of the





total sample,  about a half-gallon  was  removed for bulk chemical analyses
                                 E-8

-------
  .. MIDDLE: '£>'££A/Ctf.
  '
O 'SAMPLE-,  sir EX.

Q)'BIOA55AY &L& S1TLS
 Figure E-l
                                    E-9

-------
                TABLE E-l
SALINITY AND TEMPERATURE OF WATER
 AT THE SEDIMENT SAMPLING STATIONS
IN BALTIMORE HARBOR ON JUNE 9, 1976
Station
1
2
4
5
6
7
8
9
10
Site
—
B ott om
Surface
Bottom
Surface
Bottom
Surface
Bottom
Surface
Bottom
Surface
Bottom
Surface
B ott om
Surface
B ott om
Surface
Time
—
1305
—
1530
—
—
1730
1800
—
Temperature
°C
—
22.63
23.94
20.78
25.80
26.71
28.22
21.83
24.50
23. 18
26. 07
26. 07
26. 58
22.06
25. 15
21.87
27.39
Salinity
ppt
—
5. 42
5. 36
7. 78
4. 60
4. 20
3. 22
5. 37
2. 92
5. 26
4. 16
5. 03
4. 22
5. 72
5. 02
5. 12
3. 83
                       E-10

-------
of heavy metals, sediment moisture and hexane extracts.  The rest of





the  sample was  brought back to the  laboratory and kept hydrated in





anaerobic condition in the cold room at  4° C (Bricker,  1975).  This





sediment sample was used as experimental material in fish bioassay.





Non-toxic fuller's earth was used as a reference material.










Sea water of five ppt salinity, about the  mean salinity of the Harbor water





(Garland, 1952; Skelly, 1973), was  made by mixing synthetic sea salts





with dechlorinated, aged  tap water.   This water was used as diluting





water for the sediments and control water in the study.










Two species of fish and one  species of clam found  in Chesapeake Bay





were used as test organisms.  They were mummichogs (Fundulus





heteroclitus), spot (Leiostomus xanthurus) and soft-shell clams (Mya





arenaria).   Mummichogs  were collected from the Patuxent River estuary





about five miles upstream from Solomons,  Maryland,  Spot were collected





from the Patuxent River about a quarter mile downstream from the





Rt.  321 bridge.   Soft-shell  clams were  also collected from the Patuxent





River near Solomons  by Dr. R. Morgan and had been held in a Bay





water circulation tank for nearly a year at Chesapeake Biological





Laboratory.
                                 E-ll

-------
These three test  species were brought back to the laboratory and





acclimated in 5 ppt synthetic sea water for a week prior to the experi-





ments.  Acclimation temperature was 25°C for mummichogs and spot





and 21°C for shoft-shell clams.  The sizes of the test organisms were




43. 05 t 1. 39 mm (mean 1 standard errors) for  mummichogs,  64. 95 I





4. 19 mm for spot, and 31. 08 t 0. 72 mm for soft-shell clams.










Four sets of static bioassay apparatus, each in 4' x 8' x 18" water bath,





were set up.  Each set had  six 10-gallon test  tanks.  Each tank contained





a 6" x  10" x  12" screen basket with a quarter-inch mesh to hold the test




organisms  and a ——   horsepower submerged pump to stir the  sediment-





water mixture during the experiments.  There was a space of about an





inch between the bottom of the  basket and the  bottom of the tank.  The




pump was located at one end of the tank outside of the screen basket.





In order to prevent sediment settlement on the tank bottom,  the mixture





was shot from the pump along the tank bottom surface to the other end




of the tank and then the mixture flowed upward and backward into the





screen basket. The test temperatures were the same as the acclimation




temperature.
                                 E-12

-------
When a sediment sample at a station was to be used,  the total sample





was taken out of the cold room and stirred with a wooden paddle.  After





it was homogeneously mixed, about 10 gallons  of the  sediment was





removed and mixed with 20 to 30  gallons of the synthetic sea water to





make a stock sediment-water mixture.  For  each experiment, five dif-





ferent concentrations  of the test sediment-water mixture were made from





this stock sediment-water mixture by mixing to the desired dilution with





the synthetic sea water in five test tanks.   The sixth  tank was filled -with





synthetic sea water and  used as the control.  Each tank contained 22 liters





of the  sediment-water mixture.  The test  sediment-water mixture and




control water were stirred and aerated for at least 24 hours until the





color of the mixture changed from black into grayish brown to eliminate





high oxygen demands and to maintain an adequate dissolved oxygen level





in the  mixture for the test organisms.   Ten fish or clams were trans-




ferred from the acclimation tank into each test tank.   Mortality in each





tank was checked at least every 12 hours over  a 48-hour period.  For





each sediment station, at least two complete series  of experiments were





conducted.  Criteria  for death of  mummichogs and spot were cessation





of opercular  movement and no response to poking.  The death of soft-





shell  clams was indicated by open shells or no sign of closing shells when





poked  or resisting the pressure of opening shells with fingernails.
                                  E-13

-------
In the beginning and at the end of the 48-hour experiment, dissolved





oxygen, pH,  temperature, salinity,  suspended solids, dissolved solids,





total solids,  and turbidity of the test sediment-water mixture in each





tank were determined. Dissolved  oxygen,  pH, temperature, salinity





and turbidity were determined by meters.  Suspended solids and dissolved





solids were determined by standard methods (American Public Health





Association,  1971).  Water quality  and mortality data of  the test organ-





isms in this  study are presented in Tables E-] 0 through E-37,  located




at the back of this appendix.





E. 4      RESULTS







E.4.1    Pollutants in Bioassay Sediment /Samples







For  each of the nine bioassay stations,  the Harbor sediment samples were





analyzed for  moisture, hexane extracts, and heavy metal concentrations




(bulk analyses).  Their averages,  standard deviations, and coefficients





of variation were calculated (Table E-2).   There was a wide variation among




the stations in the contents of these chemicals.  Moisture was highest at




Station 8 and followed in decreasing  order  by Stations 9,  5,  2,  4,  1, 6,





and 10.   Compared to the  other parameters, moisture was least variable





from one station to another.  The quantity of soluble material extracted




by hexane was highest at  Station 5  followed in decreasing order by





Stations 2, 4,  1, 10, 8,  6, 9,  and  7.  PCB concentration was also highest
                                  E-14

-------
TABLE E-2

Station
No.
1
2
3/4
5
6
7
8
9
10
Moisture
%
67.65
87. 33
75. 62
90.47
65.31
66.59
95; 21
94.46
58.90
Average Dl
77. 95
Standard Deviatio
14. 05
	
Coefficient of Var
18.02
MOISTURE, HEXANE EXTRACTS, PCB's AND HEAVY METAL CONTENTS
(BULK ANALYSES) DETERMINED FOR BALTIMORE HARBOR SEDIMENT
SAMPLES USED IN BIOASSAY, AND MUMMICHOG 24 HR-TLm VALUES
FOR SUSPENDED SOLIDS

Hexane
Extracts
mg/Kg
.9, 600
17, 600
10, 600
21,500
2,900
2, 300
3, 500
2, 500
6, 500
8,555.55
n (d)
7, 001.81
iation 1—
X
81.84
PCB's
mg/Kg
-
1,26
0.84
2. 10
0. 10
<0. 05
0. 16
0.41
0.21
0.64
0.53
100)
82.8
Metals, mg/Kg
As
229
75
53
71
13
44
29
42
31
65.22
64.52
98.93
Hg
2. 65
2.78
0.85
1. 15
0.45
0.47
0.32
0.27
0. 53
1. 05
0.98
\
90.48
Cd
7
15
43
45
2
2
2
2
4
13.55
17.77
131.14
* Sediment sample taken from the cores at the depth of 5
Cr
1, 810
1,460
470
4., 300
200
490
490
160
190
1, 063. 33
1, 347.42
126.72
cm.
Cu
580
1,830
2, 300
580
150
200
140
140
65
665.00
824.43
125.87
Mn
320
510
570
560
710
680
650
1, 500
180
631. 11
363.73
57.63
Ni
79
190
63
93
81
82
60
56
62
85. 11
41. 28
45.50
Pb
510
620
460
800
340
310
120
81
170
379. 00
241.06
63. 60
Zn
1, 010
1,400
430
5, 500
1, 070
1, 080
470
330
680
1, 385. 55
1,577.99
113.89

Mummichog
24 Hr-TLm
Values
11. 79
4,,93
4.65
0. 63
25.96
79.08
24. 64
-
8.44
20.22
25. 60
127.87

-------
at Station 5 followed in decreasing order by Stations 2,  4,  9,  10,  8, 6,




and 7.   Of the heavy metals,  Zn had the highest average concentration





followed in decreasing order by Cr,  Cu, Mn,  Pb, As,  Ni,  Cd, and





Hg.  Coefficients of variation indicate that Cd, Cr,  Cu, Zn,  As, Hg,





and PCB concentrations were more variable among the stations than





Pb, Mn and Ni.   The highest concentrations for any station were Cd,  Cr,





Zn, Pb,  and PCB at Station 5; As, Hg, and Ni at Station 1; Cu at Station 4





and Mn at Station 6.  It was clear from the analyses that the  sediment at





Station 5 was the most contaminated, and material  from Station 7 was




probably the least contaminated.










Correlation analyses were conducted to determine the  relationships





between chemical parameters determined for the nine  stations




(Table E-3). Hexane extracts, PCB,Pb, Cr, Zn,  and Cd were significantly





and positively correlated.  A significant positive correlation was  also





found between Hg and  Pb,  Ni and As, and Cr and Cu, but the correlation




coefficients were low.  In contrast,  Mn had a statistically  insignificant





negative correlation with hexane extracts,  PCB and all heavy metals: it





correlated with moisture positively,  still at an insignificant level.





Moisture was independent from all parameters studied.  Because hexane





mostly extracts non-polar  organic materials from sediments,  PCB and





heavy metals which show a high degree of correlation with the hexane
                                  E-16

-------
                                                  TABLE E-3

                CORRELATIONS AMONG HEAVY METAL CONTENTS,  HEXANE EXTRACTS, PCB's,
                 MOISTURE, AND MUMMICHOG 24 HR-TLm VALUES FOR BALTIMORE HARBOR
               	SEDIMENTS STUDIED AT NINE STATIONS	


	1	2	3	4      5	6	7	8	9	10     11      12      13
  1.  Hexane Extracts

  2.  PCB's            0.96*

  3.  Pb               0. 90*  0. 88*

  4.  Cr               0.84*  0.91*  0.84*

  5.  Zn               0.77*  0.83*  0.78*  0.93*

  6.  Cd               0.76*  0.82*  0.72*  0.64   0.69*

  7.  Hg               0.63   0.62   0.66*  0.45   0.17   0.18

  8.  Ni               0.60   0.47   0.58   0.32   0.22   0.12   0.72*

  9.  Cu               0.55   0.47   0.53   0.13   0.07   0.66*  0.50   0.48

 10.  As               0.31   0.75   0.41   0.40   0.09   0.07   0.77*  0, 14   0.15

 11.  Mn              -0.37  -0.15   -0.39  -0.25  -0.17  -0.18  -0.43  -0.21  -01.9  -0.33

 12.  Moisture         0.29   0.45   0.07   0.31   0.25   0.23   0,00   0.17   0.13  -0.13    0.56

 13.  Mummichog     -0.65  -0.60   -0,42  -0.39  -0.21  -Q. 52  -0,41  -0.18  -0.43  -0.22    0.46   -0.29
     24 Hr-TLm
   Significant at 5% level (P  0. 05).

-------
extracts such as Pb,  Cr, Zn,  and Cd might relate with occurrence of this





organic fraction of the sediments.  Moisture was least variable among





stations and -was independent from heavy metals and hexane extracts.





It seems that moisture has  no  relationship -with heavy metal concentra-





tions in the Harbor sediments.  In other words,  the dissolved form of





metals in the interstitial water of the sediments is  perhaps so low com-





pared to the particulate form in the  sediments that  the sediment moisture




(interstitial water) is not a  factor affecting bulk  concentration of heavy





metals in the sediments.










E.4.2    Properties of  Bioassay Sediment-Water Mixtures







It is known that  sediments in the scoured deposited condition  can have





high biological oxygen demands from deposited nutrients (Morton,  1976;





Saila, et al,  1972) and high chemical oxygen demands from various iron





sulfides and other chemicals (Slotta, 1974).  When  the sediments have





been exposed to oxygenated water, the sediment oxygen demands have





been known to increase eight to seventeen fold (Isaac,  .1965; Reynolds,





et al, 1973).   In order to maintain an adequate dissolved oxygen level in





the  sediment-v/ater mixture for the  test organisms, the Harbor sediment-





water mixtures  in this  study were stirred and aerated continuously for





at least 24 hours prior to and during the experiments.  As a result of





the  stirring and aerating processes, iron  sulfides were changed to iron






                                 E-18

-------
oxides and oxidized sulfur compounds (Slotta, 1974).   The oxidation of





sulfides increased the mobility of metals such as silver,  lead and zinc





from the sediments  (Thomson,  et al,  1973; Gordon, et al, 1972). The





pH values of the mixture decreased as the results of organic oxidation





and production of oxidized sulfur compounds.  Therefore, the properties





of the sediment -water mixture in the bioassay were different from those





of the undisturbed deposited sediments.










Dissolved oxygen concentrations in the Harbor  sediment-water mixture





and fuller's earth-water mixture in the bioassay remained consistently





above 5 mg/1,  except in a  few cases when the concentrations were slightly





lower (Tables E-10 - E-37).  Turbidity,  suspended solids, dissolved  solids,





and pH varied 'according to sediment concentrations and  among different





stations.  In order to compare these parameters between experiments





with fuller's earth and the Harbor  sediments, and also among the stations,





the  relationships between  suspended solids and the other two parameters,





turbidity, and pH, were considered.










The relationship between turbidity and suspended solid concentrations for





fuller's earth  is different from those observed  for the Harbor sediment-





water mixtures (Figure E-Z).  It is evident that the turbidity produced by





a unit weight of suspended solids is much lower for fuller's earth-water
                                 E-19

-------
    100
  err
  «T

  IS

  "o
  W>

  TJ
  0)
  T3
  C
  0
  a
  (A
10
      0.1
        100
                             I
                                          L
                     1000              10000

                         Turbidity, J.T.U.
    I
100000
Figure E-2  Relationship between turbidity and suspended solid concentrations

           for fuller's earth-water mixture (F) and Baltimore Harbor

           sediment-water mixture (Stations 1-10).
                                    E-20

-------
mixture than that for Harbor sediment-water mixture.  The difference




among Harbor samples suggests that physical properties of suspended




solids  may differ between fuller's  earth and the Harbor sediments,  and




among the sediments at the nine stations.










The relationship between pH values and suspended solid concentrations




is shown in Figure E-3. For fuller's earth-water mixture, the pH value




decreased very slightly as suspended solid concentration increased.




The mixture always remained basic  and its pH remained at 7. 2 or higher.




For the Harbor sediment-water mixture,  the pH value decreased very




rapidly as suspended solid concentration increased and reached the




minimum at a concentration of about 20-30 g/1 suspended solids  for all




stations.  This fact might suggest  that a  factor related to suspended




solids  controlled the change of chemical  equilibrium in the  mixture,  and




this change  was stabilized at this suspended solid concentration.  If the




release of toxic chemicals from the  sediments into the mixture was




involved in this chemical equilibrium,  the dissociation of toxic chemicals




from the sediments may have  reached  a maximum level at approximately




20-30  g/1.  The concentration of suspended solids  may,  therefore, be




one of  the important factors controlling the release of toxic  chemicals




in the  sediment-water mixture.  There were differences in the rate of




pH reduction and in the pH minimum among the stations.  The stations
                                 E-21

-------
ro
IS)
                                                                             120     140
                                     Suspended   Solids, 9/j
    Figure E-3   Relationship between suspended solid concentrations and pH values for fuller's earth-water

                mixture (F) and sediment-water mixture of Baltimore Harbor (Stations 1-10,  except 9).

-------
which had the faster rates in pH reduction had the  lower pH minima.





The fastest rate in the pH reduction and the lowest value in pH minimum





were at Station  5 (pH minimum about 3. 5) followed in order by Stations





2, 4,  1,  8,  10,  6,  and 7  (pH minimum about 4. 7).  The differences may





be due to the difference in quality and/or quantity  of chemicals, including





toxic substances, released from the sediments.










The exception was  Station 9.  The sediment-water mixture was basic;





and the pH values ranged between 8. 9 to 9. 3, higher than those of control





water and of fuller's earth-water mixture (Table E-15).   This  is





notably different from the other sediment water mixtures.  The reason





for the high pH  values  of Station 9 was not known.  The sediment of this




station was black like those from other stations, but contained many white





clay-like lumps ranging  in size from a  millimeter to about 7. 5 centimeters





When the sediment-water mixture was made, these lumps were broken




into pieces and  mixed well with the sediments.  According to personal





communication  with Dr.  Raymond Morgan, Chesapeake Biological  Labor-





atory,  these lumps may have been a kind of paint binder.  It was suspected





that these clay-like lumps might strongly affect the sediment-water mix-





ture properties.
                                   E-23

-------
E.4.3    Time-Concentration Relationship







Median survival time is the length of the period between the time when





the organisms are: initially exposed to a test solution and the time when




50 percent mortality of the test population has occurred.  This time was





calculated from the  equation describing the  relationship between exposure





time and probits  (Finney,  1971) of cumulative mortality for each species





at each concentration (Bliss,  1937).  Then the relationships between




median survival time and suspended solid concentrations were plotted





for each species  for fuller's earth and for the Harbor sediments at





each station (Figure E-4). Generally,  the median survival time  increased





as suspended solid concentration decreased, but the rate of the increase





differed among the three species tested.










For spot, the rate of increase in median survival time as suspended solid





concentration decreased was  so fast that at  all stations the median sur-





vival time approached infinity after 1440 minutes or 24 hours (Figure E-4).





This suggests that spot will be able to survive indefinitely in the sediment-





water mixture if they can survive for 24 hours.  For mummichogs,  the




increase in the median survival time as  suspended solid  decreased was





slower than that of spot (Figure E-5).   It appears that most of the mummi-




chogs will be able to survive  indefinitely in  the sediment-water mixture
                                  E-24

-------
      c
      8
      >
     *>
      2*
      c
      8
H
                5.000
                  500
                                                                                            1
                                0.5
10
50   TOO
                                             Suspended  Solids,g/l
     Figure E-4   Relationship between suspended solid concentrations and median survival time for spot
                 exposed to fuller's earth-water mixture (F) and the sediment-water mixture of Baltimore
                 Harbor (Stations 1-10).

-------
H
t
DO
                                                             5      1
                                             Suspended   Solids, g/l
     Figure E-5 Relationship between suspended solid concentration and median survival time for mummichogs
                exposed to fuller's earth-water mixture (F) and the sediment-water mixture of Baltimore
                Harbor (Stations 1-10).

-------
if they can survive for 24 hours.  Some of them will die after 24 hours.





For soft-shell clams, the median survival time increased very slowly as





suspended solid concentration decreased, a relationship very different





from that for  the two fish species tested (Figure E-6).










On the basis of median survival time,  Station 5 was most toxic for all





species, followed in decreasing order with small variations by Stations





2,  4,  10, 1, 8, 6,  and 7.  The fuller's earth-water mixture was dis-





tinctly less toxic than any sediment-water mixture from Baltimore Harbor.










E.4.4    Mortality-Concent rat ion Relationship







The data on water quality and mortality of the three species of test





organisms obtained in the bioassay are listed in Tables E-10 - E-37.





For mummichogs and spot,  the 24-hour and 48-hour percent mortality




was transferred into  probits and their relationship with suspended solid





concentrations was established for  each station.  On the basis of the





relationship equations, their 24-hour and 48-hour TLm values (median





tolerant levels, the concentrations  at which 50 percent of a test popula-





tion was killed by the  exposure for  24  hours and 48 hours respectively)





for suspended solids  were calculated for fuller's earth-water mixture





and for the Harbor sediment-water mixture at eight stations.  Because
                                  E-27

-------
      500
0)

£
• ••
I-


"o
>

*>
k.
3
 c

 0
 • if*

 •3
100
 50
                                                              10
                                        aKggC*5*Sg;
                                  Suspended  SoJsds,
  Figure E- 6 Relationship bet-ween suspended solid concentration and median survival

             time for soft-shell clams exposed to fuller's earth-water mixture (F)

             and the sediment-water mixture of Baltimore Harbor (Stations 1-10).
                                          E-28

-------
of limitations in the capacity of the aerating and stirring systems and





the  high tolerance of the soft-shell clams to the sediments, it was





impossible to make  a sediment-water mixture  concentrated enough to





obtain 24-hour and 48-hour TLm for the clams in fuller's earth-water





mixture and the Harbor sediment-water mixture at Stations 6, 7,  and 8.





Therefore, a  96-hour bioassay was conducted for them.  The TLm values





obtained for the soft-shell clams in this study were for exposure times of





24 hours and 48 hours for Stations 1,  2,  4, 5,  and 10; 48 hours and 72





hours for Station 8;  and 72 hours and 96 hours  for Stations 6 and 7 and





fuller's earth. The TLm values for suspended solids obtained for the





three species of test organisms are shown in Table E-4.










When 24 hour TLm values and 48-hour TLm values for suspended  solids





were compared for each of the three species at each  Harbor sediment





station, it was found that there was a very strong positive correlation





(r = 0. 99) between the two values (Figure E-7).  The results  of analyses of





convariance indicated that the slope of the regression line for soft-shell





clams is similar to  that of spot (P> 0.20), about  1,  but different  from





that of mummichogs  (P>  0. 005).  The elevation of the regression  line for





soft-shell clams  is substantially different from that  of both spot and mum-





michogs  (P >  0. 005).  It is evident that the 24-hour TLm and 48-hour TLm





increased proportionally for the three  species  of test organisms.   In
                                 E-29

-------
M
TABLE E-4
TLm VALUES (SUSPENDED SOLIDS, 81e) FOR MUMMICHOGS, SPOT
AND SOFT-SHELL CLAMS EXPOSED TO BALTIMORE HARBOR SEDIMENT-WATER
AND FULLER'S EARTH-WATER MIXTURE
Station
No.
1
2
4
5
6
7
8
10
fuller1 s
earth
* Values
Mummichogs
24
11
4
4
0
25
79
24
8
107
hr.
.79
.93
.65
.63
.96
.08
.64
.44
.48
48
9
4
3
0
22
66
20
7
103
hr.
.72
.21*
.74
.58*
.96
.78
.59
.23
.29
calculated from the formula
24
9
5
6
0
24
31
18
8
Spot
hr.
.36
.78
.05
.74
.99
.89
.89
.44
50. 61
in Figure
48
9
5
5
0
24
29
18
8
50
4-
Soft-- Shell Clams
hr. 24 hr. 48 hr. 72 hr. 96 hr.
.31 160.98 136.82
.22 53.65 16.96
.86* 84.56 57.88
.60 33.30
.92 - - 149.94
.12 - - 120.28 96.94
.04 - 111.08 93.99
.40 156.76 125.50
.61 - - 188.58 137.20
6.

-------
         150
o
 v»
V)
"U
*M

"o
U)
 C
 O
 Q.
 V)
 3
         100
0


E
          50
             0
                               50
100
150
                   24  hr-Ylm  Values (Suspended Soiids,
 Figure E-7  Relationship between 24-hour TLm and 48-hour TLm values of mummichogs

            (solid circles; Y = 0. 043 + 0. 82 X, n = 7,  r = 0. 99),  spot (open circles;

            Y = -0. 0058 + 0. 98 X, n =  7, r - 0. 99), and  soft-shell clams (stars;

            Y = -36. 72 + 1. 06 X, n = 4, r = 0. 99) for  suspended  solids of Baltimore

            Harbor sediments.
                                         E-31

-------
other words, the two values are mutually convertible for the three species





when exposed to Harbor sediments.  The  results also suggest that for





soft-shell clams the 24-hour TLm values are,  on the average, about





37 g/1 higher than 48-hour TLm values.   For spot there is no significant




difference between 24-hour TLm values and 48-hour TLm values.  For





mummichogs 24-hour TLm values increased at a  slightly faster rate





than 48-hour TLm values.  There  is, therefore, species specificity in




mortality response to the Harbor sediment-water mixture.










For  comparison of sediment susceptibility among spot, mummichogs,





and soft-shell clams, 24-hour TLm values of mummichogs were plotted





on the abscissa and the 24-hour  TLm values  of the three species  were





plotted respectively on the ordinate in Figure E-8.  The mummichogs1 rela-




tion  line  is a straight line passing  through the origin of the graph at





45 degrees.  The spot relation line is curvilinear, and it departs from





the mummichogs'  line at Stations 6,  8, and 7.  The  soft-shell clams' line




is also curvilinear,  but it bends to the opposite direction of that for the





spot at the low TLm values of Station 5 and especially at the high TLm





values of Stations  6 and 8.  It is evident that  spot are more susceptible





than mummichogs to  fuller's earth and Harbor sediments at Station 7,





for which the TLm values are high; whereas both species  of fish have





similar susceptibility to the Harbor  sediments at Stations  1,  2,  3,  4,
                                  E-32

-------
  100
   50
 o
73
toi
•8 10
 C
 0)
 &
 VI
 3   5
 li
   0.5
           0.5
               5     10

24  hr-TLm  (Suspended

              Mummichog
       50    100

Solids,g/l)
Figure E-8  Comparison of 24-hour TLm values among mummichogs (solid circles),

           spot (open circles), and soft-shell clams (stars) for fuller's earth (F)

           and Baltimore Harbor sediments (Stations 1-10).
                                      E-33

-------
5,  6,  8,  and 10 where TLm values are low.  On the basis of the 24-





hour TLm values, the susceptibility of spot to fuller's earth and to the





sediments at Station 7 was 42 percent and 48 percent,  respectively,





more than those of mummichogs.  It appears that spot are more suscep-





tible than mummichogs to suspended solids, but both species have similar





susceptibility to toxic  materials released from Harbor  sediments.  For





soft-shell clams,  the Harbor sediments at Stations 1,  2, 4,  5,  and 10





were toxic enough to produce 50 percent mortality within 24 hours.





The sediment susceptibility of the clams was much less than that of





mummichogs, ranging between 53 times less at Station 5 and 13 times





less at Station 2.  At Station 6, 7,  and 8 and for fuller's earth,  soft-shell




clams were so tolerant to the suspended solids that there was little or





no mortality in 24 hours.  Accordingly, as compared to spot and mummi-





chogs, soft-shell  clams were very tolerant to toxic materials and  even




more tolerant to  suspended solids contained the Harbor sediments.





Soft-shell clams  can contract to reduce the surface area exposed to toxicants





or reduce the rate of pumping  water through their gills as parts of their




defense mechanisms in an extremely unfavorable environment.  This may





have been the case in the highly toxic solution of Station 5 sediment and





in the highly concentrated suspended solid mixtures of fuller's earth and





of Stations 5,  8,  and 7 sediments so that their survival time increased





and the mortality  rate was reduced.
                                  E-34

-------
It is interesting to note that the relation lines for spot and soft-shell





clams  increase their curvature and deviate farther from the mummichog





relation line at about 20 g/1 suspended solids (Figure E-8).  This concen-





tration coincides approximately to that  of the sediment-water mixture





at which pH values approach the minimum (Figure E-3).  This evidence





further supports the possibility that the amount of toxicants  released





from the Harbor sediments into the mixture was proportional to the sus-





pended solid concentration until the mixture reached about 20 g/1 of





suspended solids.  At approximately this  concentration, the chemical





dissociation and content of toxic chemicals in the mixture may reach the





maximum.  With further increase in the sediments in the mixture, the





toxic constituents of chemicals in the mixture might  remain fairly constant,





while the  suspended solid concentration increases and becomes a more





important factor for fish mortality.
                                 E-35

-------
E. 5      DISCUSSION







E. 5. 1    Gross Toxicity of Baltimore Harbor Sediments







Because the 24-hour TLm values and 48-hour TLm values were mutually





convertible and there was no important difference in the order  of sedi-




ment susceptibility among the three  species at eight  stations, the mum-





michog 24-hour TLm value for  suspended solids in this study was  selected





as the  index of gross toxicity for  Baltimore Harbor sediments.   On the




basis of this index, Station  5 was most toxic, followed  in decreasing





order by Stations 4, 2,  10,  1,  8,  and 6;  and Station 7 was the least toxic.





This is the same order found in the study of the time-concentration




relationship.  The difference in gross toxicity between the two  extreme





cases at Station 5 and Station 7  was about 125 times ^n  terms of 24-hour





TLm.   It is evident that a wide  range exists in the gross toxicity of





Harbor sediments among different locations.  The fuller's earth-water





mixture was about  18 percent less toxic than the sediment-water mixture





from Station 7.










In 1970-1971,  the Center for Environmental and Estuarine Studies (1974)





conducted a comprehensive biological study of Baltimore Harbor,  including





benthic invertebrates,  crabs, fish eggs and larvae, and adult fish.  In.





the study of benthic invertebrates, 28 sampling  stations were designed,
                                 E-36

-------
and at each station four samples were collected with a van Veen grab




in March,  June,  September,  and December of 1970.   In this study; the




species diversity index of each sample was calculated using Margalef's



               S- 1
formula, d =	,  where S is the number of species and N is the total
             Log N



number of individuals (McErlean and Mihursky,  1968).  The average




index was  obtained from the four samples for each station.  Of these




stations, Station 17 (18), 15,  3, 26, 23,  7,  and 20 were either almost




identical or near to the sediment stations 2, 4,  5, 6,  7, 8, and 10 of




this  study.  When mummichog 24-hour TLm values for suspended solids




were plotted against  average  species diversity indexes of the seven stations,




it was found that there is a somewhat sigmoid relationship between the two




values (Figure E-9).   When Station 7 and Station 5, with exceptionally high




and low toxicity, are not included in consideration, there is a generally




linear relationship for the remaining five stations.  According to this




straight line relation formula in Figure  E-9,  the average  species diversity




indexes at 28  stations for benthic invertebrates could be converted into




mummichog 24-hour  TLm values for suspended solids.  Using these




mummichog 24-hour  TLm values as the  indexes  of gross toxicity, the




distribution of the sediment gross toxicity in Baltimore Harbor could




be mapped on the basis of arbitrary limits (Figure E-10).  According to




the sediment gross toxicity,  the Harbor  sediment can be divided into




four toxic  zones:  a highly toxic zone where mummichog 24-hour  TLm
                                  E-37

-------
           5.0
 X

 £
 x
 4-
 • KB
 0)
 5

.2
 o
 Q.
            i.o
           0.5
                                                            6

                       1.0
                                        5.0     10
SO
                      24-hr Tim (Suspended  Solids,
Figure E-9  Relationship between mummichog 24-hour TLm values for suspended
           solids and species diversity indexes of benthic invertebrates at seven
           stations in Baltimore Harbor.  The regression equation of solid line
           is Log10Y =  -0.5678 +  0.4782 Log10X (n = 5, r-0.89).
                                        E-38

-------
  TOXIC   ZONE
                    //
          *4>
Figure E-10  Distribution of toxic zones and mummichog 24-hour TLrn values for
             suspended solids in Baltimore  Harbor (numbers in squares,  real values
             obtained from the bioassay; numbers not in square obtained from con-
             version of species diversity indexes of benthic invertebrates).
                                           E-39

-------
values are less  than 8 g/1 suspended solids;  a moderately toxic zone

where the TLm  values are between 8 g/1 and 20 g/1; a low toxic zone

where the TLm  values are between 20 g/1 and 40 g/1,  and a slightly

toxic zone where the TLm values are higher than 40 g/1.  This zoning,

with obvious imprecision, provides a useful display of the areas with

greatest degradation and permits an estimation  of the  area of sediment

which must be considered in efforts to correct or improve sediments  of

various toxicities in Baltimore Harbor (Figure E-10).
E. 5.2   Relationship Between Biota and Sediment Toxicity
         in Baltimore Harbor
Thirty species of benthic invertebrates belonging to six phyla were

found in Baltimore Harbor in the  1970 study by the Center for Environ-

mental and Estuarine Studies (1975).  The distribution of species diversity

indexes at 28  stations in. the Harbor is shown in Figure E-ll.  The index

decreased from the slightly toxic  zone to the highly toxic zone and was

related to the distribution of sediment toxicity as noted in establishing

the zones. Of the six phyla, Arthropoda,  Mollusca, and  Annelida were

dominant  groups of benthic  invertebrates in the Harbor.   They were

almost equal in  number  of species in the slightly toxic zone.  The number

of species in Mollusca and Arthropoda,  particularly the  latter,  decreased

at the stations where sediment toxicity increased.  In the highly toxic
                                 E-40

-------
     SPECIES  DIVERSITY  INDEX

          >1.50
Figure E- 11  Distribution of species diversity indexes for benthic macro-invertebrate
             community in  Baltimore  Harbor (based on data from H. T. Pfitzenmeyer,
             Center for Environmental and Estuarine Studies,  1975).
                                           E-41

-------
zone, they were either absent or nearly absent,  while Annelida became





a dominant group in the zone (Figure E-12).  It is evident that Mollusca and





Arthropoda are more sensitive than Annelida to  the sediment toxicity.





The  other three phyla  -- Coelenterata, Nemertea, and Insecta -- were





rare in the Harbor  and limited in the sediments  mostly in the low and





slightly toxic zones.  Relative abundance of the species in the six phyla





in the four toxic zones is shown in  Table E-5.  Most species decreased in





abundance from the slightly toxic zone to the highly toxic zone, except





some species of Annelida: Limnodrilus sp. ,  Heteromastus filiformis,





Scolecolepides  viridis, and Streblospio benedicti, which  increased in





abundance in the low and/or moderately toxic  zones.











The  relative abundance of blue crabs at the 12 stations studied in 1970





(Center for Environmental and Estuarine Studies, 1975) is shown in





Figure E-13.  They were abundant at the mouth of the Harbor and tended





to decrease toward the Inner Harbor.  As the crabs are semi-benthic





organisms, according  to Lippson and Miller (Center for  Environmental





and Estuarine Studies, 1975), their abundance seems  not to relate to the





sediment  toxicity alone,  but also to the physical  type of the bottom.





They were abundant at the stations where bottoms were composed of mud





and rocks and were rare at the stations where the bottoms were covered





with oil and grease-like  substance.
                                  E-42

-------
              Annelida
       o
              Arthropoda
              Mollusca
Others
Figure E-12  Percentage species composition of three phyla,  Annelida, Arthropoda,
             and Mollusca in Baltimore Harbor (Based on data from H.  T. Pfitzen-
             meyer, Center for Environmental and Estuarine Studies,  1975).
                                           E-43

-------
TABLE E-5
RELATIVE ABUNDANCE OF BENTHIC INVERTEBRATES
IN THE TOXIC ZONES OF BALTIMORE HARBOR, 1970

(Based on data from H. T. Pfitzenmeyer in Center
for Environmental and Estuarine Studies, 1975)
Phylum
Coelenterata
Nemertea
Annelida
Arthropeda
Insecta
Mollusc a
Species
Fagesia lineata
Diadumene leucolena
Micrura leidyi
Limnodrilus sp.
Heteromastus filiformis
Scolecolepides viridis
Streldospio benedicti
Eteone heteropoda
Nereis succinea
Hypaniola grayi
Polydora ligni
Balanus amphitrite
Neomysis americana
Cyathura polita
Edotea triloba
Monoculodes edwardsi
Janimarus sp.
Carinogammarus mucronatus
Melita nitida
Cymadusa compta
Leptochierus plumulosus
Corophium lacustre
Rithropanopeus harrisi
Chironomus atlenuatus
Procladius sp.
Brachiodonte recurvus
Congeria leucophaeta
Macoma balthica
Macoma phenax
Rangia cuneata
Toxic Zones
Slightly
++
+ +
!r
L
+
+++
Low
+
++
H;:
i

-
Moderately

+
;r
+
+
r+
Highly


T
-
*
++++ Very Abundant
+++ Abundant
""""" Common
+ Rare
Absent or nearly absent
E-44

-------
  NUMBER OF  CRABS  COLLECTED
         >75
Figure E-1 3  Number of blue crabs collected in seven samples at  1Z stations in
             Baltimore Harbor (Data from R. L. Lippson and R.  W. Miller,
             Center for Environmental and Estuarine Studies, 1975).
                                          E-45

-------
Fish are free moving organisms, and their habitats change through





their life history.  Their occurrence and abundance in  the Harbor are





influenced strongly by tidal cycles,  weather, seasons,  water quality,





food availability, fish behavior,  and stages of life history.  Food avail-





ability and water quality are often influenced by sediment toxicity.





Therefore, the species diversity and abundance of the fish in the Harbor





may be affected by the degree  of sediment toxicity.  In the 1970 study,





fish were sampled by three methods:  50-foot shore seine with 1/2-inch





mesh,  25-foot semi-balloon otter trawl with  1/2-inch mesh, and one-





meter  plankton net with mesh opening of 0. 4  by 0. 6 mm.  In this study





the fish data  were rearranged  in order to find the relationship between





fish and s'ediment toxicity.  The distribution  of species diversity sampled





by the  three methods is shown in Figures E-14 - E-16.  Their relative abun-





dance  is shown in Tables E-6 - E-8. For the  fish sampled by  shore seine and




trawl,  there  was a trend of reduction in species diversity index from the




slightly toxic  zone to the highly toxic zone, but the  trend was  not so





obvious as that of the benthic invertebrates.  For the fish sampled by





the plankton net in the Harbor  channel, the species diversity index appears




to be little related to the sediment toxicity.   For the  fish collected by





the three methods,  relative abundance  of most species  tended to decrease





as sediment toxicity increased (Table E-6).   Exceptions were silversides




in water near the shores and white perch, rock fish,  and alewife in the
                                 E-46

-------
     SPECIES  DIVERSITY  INDEX

         >0.70
Figure E-14  Distribution of species diversity indexes of fish sampled by a 50-foot
             shore seine in Baltimore Harbor (based on data from M. L. Wiley,
             Center for Environmental and Estuarine Studies, 1975).
                                          E-47

-------
       SPECIES  DIVERSITY   INDEX
            >  0.80
Figure E- 1 5    Distribution of species diversity indexes  of fish sampled by a 25-foot
               semi-balloon otter trawl in Baltimore Harbor (based on data from
               W. L.  Wiley, Center for Environmental and Estuarine Studies, 1975).
                                            TO-48

-------
        SPECIES  DIVERSITY  INDEX
Figure E- 1 6 Distribution of species diversity indexes of fish sampled by a. one-meter
            plankton net in Baltimore Harbor (based on data from M.  L. Wiley,
            Center for Environmental and Estuarine Studies, 1975).
                                           E-49

-------
                              TABLE  E-6
              RELATIVE ABUNDANCE OF SHORE FISH
        IN THE POLLUTED ZONES OF BALTIMORE HARBOR
             (Based on data from M.  L. Wiley, Center for
              Environmental and Estuarine Studies,  1975)
           Species
                                            Toxic Zones
                             Slightly    Low    Moderately
            Highly
Menidia menidia               +++
Morone americana             +++
Fundulus  heteroclitus          +++
Cyprinus  carpio               ++
Fundulus  diaphanus            ++
Alosa aestivalis               +
Alosa pseudoharengus          +
Morone saxatilis               +
Dorosoma cepidianum          +
Lepomis  gibbosus              +
Fundulus  majalis               +
Anchoa mitchilli               +
Hyporhamphus unifasciatus     +
Menidia berglina               +
Perca flavescens               +
Ictalurus  catus                 +
Anguilla rostrata               +
-t-
++
++++    Very abundant
+++     Abundant
+ +      Common
+       Rare
        Absent or nearly absent
                                      E-50

-------
                             TABLE E-7
       RELATIVE ABUNDANCE OF FISH COLLECTED BY A
         12-FOOT SEMI-BALLOON OTTER TRAWL WITH A
       1/2-INCH STRETCH MESH IN THE POLLUTED ZONES
       OF  BALTIMORE HARBOR, APRIL TO DECEMBER 1970
            (Based on data from M.  L. Wiley, Center for
             Environmental and Estuarine Studies, 1975)
      Species
                                             Toxic Zones
                                   Low
                                              Moderately
Highly
Morone americana
Morone saxatilis
Alosa pseudoharngus
Anchoa mitchilli
Ictalurus  catus
Lepomis gibbosus
Perca flavescens
Alosa aestivalis
Anguilla rostrata
Menidia sp.
Trinectes maculatis
Pomatomus saltatrix
Cyanoscion regalis
Leiostomus xanthurus
Opsanus tau
Fundulus  heteroclitus
                                  -H+
++++    Very abundant
+++     Abundant
++      Common
+       Rare
        Absent or nearly absent
                                      E-51

-------
                              TABLE E-8

     RELATIVE ABUNDANCE OF FISH EGGS,  FISH LARVA, AND
   JUVENILE FISH COLLECTED WITH 1-METER PLANKTON NET
        IN THE TOXIC ZONES OF BALTIMORE HARBOR,  1970
            (Based on data from M.  L. Wiley in Center for
              Environmental  and Estuarine Studies, 1975)
           Species
                                           Toxic Zones
                             Slightly
Low    Moderately
Highly
                                     LARVA AND JUVENILES
Alosa sp.
Anchoa mitchilli
Menidia sp.
Gobiosoma bosii
Morone americanus
Dorosoma cepediunum
Lepomis gibbosus
Brevoortia tyrannus
Fundulus sp.
Notropis hudsonius
Chasmodes bosquianus
Anchoa mitchilli
Trinectus maculatus
                                               EGGS
+++  Abundant
++   Common
+    Rare
     Absent  c?r nearly absent
                                      E-52

-------
off-shore water.  These fish were abundant in all zones and their distri-





bution appears to be unrelated to  sediment toxicity.  Some bottom dwelling





or bottom feeding species, such as winter flounders, Atlantic croaker,





and hogchoker were absent in the Harbor.










The use of Baltimore Harbor as  a spawning ground of fish was very





limited.   Only the eggs of Bay anchovy were found in both slightly and





low toxic  zones  during the late spring and summer.  The  eggs  of the hog-





choker were found only in the Outer Harbor of the  slightly toxic zone in





July.










Bowman (1974) made biweekly samplings of phytoplankton at  seven





stations in Baltimore Harbor and two stations in Chesapeake Bay in the





vicinity of the entrance to the Harbor.  A total of 68 genera was found.





The distribution of diversity indexes of genera calculated from Margalef's





formula is shown in Figure E-17, and relative abundance  of each genus is





shown in Table E-9.  The  difference in genus diversity indexes was small.





between 0. 51  and 0. 71 at the Harbor stations, lower than 0. 85 at the





Bay stations.  The stations in higher toxic  zones tended to have slightly





lower diversity  than those in less toxic zones.  The-total number of





genera which  occurred from March to August  1971 was 39 in the slightly





toxic  zone and low toxic  zone,  52 in the moderately toxic  zone,  and
                                 E-53

-------
   DIVERSITY   INDEX
            >0.7

            >0.6

            >0.5
Figure E-17  Distribution of genus diversity indexes of phytoplankton in Baltimore

             Harbor (based on data from G. A. Brown, 1974).
                                           E-54

-------
                             TABLE  E-9
           RELATIVE ABUNDANCE OF PHYTOPLANKTON
        IN VARIOUS TOXIC ZONES OF BALTIMORE HARBOR,
        	MARCH-AUGUST,  1971	
              (Based on data from G.  A.  Brown,  1974)
      _                                     Toxic Zone
      Genus
                             Slightly    Low    Moderately    Highly
Skeletonema
Scenedesmus
Pediastrum
Exuviella
Chlamydomonas
Dictyosphaerium
Goniaulax
Oscillatoria
Ulothrix
Anabaena
Prorocentrum
Aphanizomenon
Ankistrodesmus
Coelastrum
Oocystis
Tetrustrum
Coscinodiscus
Fragilaria
Melosira
Nitzschia
Chaetoceros
Navicula
Synedra
Cyclotella
Asterionella
Peridinium
Gleocystis
Staurastrim
Amphiprora
Meridion
                                                    Continued.
                                      E-55

-------
                        TABLE  E-9 (Continued)
      Genus
                                            Toxic Zone
                             Slightly
Low     Moderately    Highly
Rhizosolenia
Cocconeis
Diatoma
Cymbella
Tabellaria
Cerataulina
Pleurosigma
Dinobryon
Tribonema
Thallasiosira
Microthamnion
Surirella
Microspora
Synura
Hormidium
Stigeoc Ionium
Ceratium
Crucigenia
Biddulphia
Amphora
Anacystis
Rhopalodia
Actinastrum
Diploneis
Anacystis
Botryococcus
Mallomonas
Kirchneiella
Phormidium
Stephanodiscus
Gymnodinium
Tetraedron
Eudorina
Eutreptia
Gleocapsa


+ + + +  Very Abundant
+++   Abundant
++    Common
+     Rare
      Absent or nearly absent
                                      E-56

-------
49 in the highly toxic zone.  The presence of a low diversity index by

occurrence of high numbers of genera suggests an unstable phytoplankton

community with the high turning over of genera at different times of  the

year in the highly toxic zone.  The phytoplankton  community in the

Harbor was less  diverse than that in the adjacent  Chesapeake Bay,

indicating the stressed condition of phytoplankton  in the Harbor.

Several genera,  such as Coscinodiscus, Fragillaria,  Melosira, Nitzchia,

Schnedesmus,  and Pediastrum, were abundant in  all zones.  Exuviella,

Chlamydomonas,  Pietyosphaerium and some other genera were common

only in the slightly toxic zone, while Navicula, Chaetoceros and Synedra

were commonly in the moderately and highly toxic zones.
E. 5. 3   Ecological Effects of In-Place Pollutants
         in Baltimore Harbor
According to the wide variation in gross toxicity among the sediments

tested,  the in-place pollutants in the Harbor sediments are clearly not

homogeneously distributed but fairly patchy in distribution, perhaps

because of their  sources and local events.   They seem not to be trans-

ported for long distances by water and Harbor activities.   Except for

extreme storm conditions,  they  appear unlikely to be transported in

large quantities from the Inner Harbor to the Outer Harbor or  from the

Harbor to the Bay.  The Harbor  sediments have become a sink or trap
                                  E-57

-------
for much  of the pollutants produced by domestic and industrial activities





of the City of Baltimore.










The present  biotic  structure and distribution in the Harbor resulted from





the combined effects of pollutants in the water column,  derived directly





from the discharges of domestic and industrial wastes,  and of pollutants





accumulated in the Harbor sediments.  The benthic invertebrates and





bottom dwelling fish are in constant contact with the sediments and feed





primarily on foods produced in or on them.  They  have  been the organisms





most seriously affected by toxic chemicals in the sediments.  The pelagic





organisms are influenced  primarily by toxic chemicals  in the water column,




whose  sources are direct  domestic and industrial waste discharge, import





from the Bay,  and,  to some degree,  release from the bottom sediments.










The transfer of contaminants such as heavy metals,  nutrients and





pesticides across the sediment-water interface is  complex and not yet





fully understood.  Morton (1976) reviewed the literature and  identified





several factors important to the process,  such as  sediment clay content,





organic fraction, redox potential, pH, bacteria, sulfur  cycle and  iron





cycle.  The clay particles preferentially sorb heavier metallic ions





(Reynolds, et al, 1973).  Metals which form highly insoluble metal sulfides





have little chance of leaving the sediments.  Relatively  soluble metal
                                  E-58

-------
compounds might migrate up the sediment column until encountering an





aerobic environment which may set the limit of their mobility if they





are converted to insoluble oxide compounds.  On the basis of solubility





product constants for the sulfide compounds of metals,  Pb, Cd, Ni, Hg,





Ag, Cu,  and Zn should remain essentially fixed  in sediments having inter-





stitial water with a  sulfide ion activity of 10~9 moles/liter.  Mn and Fe





will be readily mobilized since MnS and FeS have high solubility





(Thomson, et al,  1973).  Accordingly,  even though there is some trans-





fer of contaminants from the sediments to the water column, the process





will be very  slow and ecological effects on the water column might be minor.










Two likely pathways by -which toxicants enter the food chain in the water





column in the estuary are from the sediments into rooted plants and





ingestion of solid particles with sorbed toxicants by organisms  (Wolfe,





1973).  The in-place pollutants in Baltimore Harbor are indeed  a problem,





particularly  for bottom dwelling organisms, but they exist as a  nearly





immobile reservoir.  A different kind of biological threat is posed by





domestic and industrial wastes which have been  and are discharged to





the Harbor not only to contaminate the Harbor water, but also to "enrich"





pollutants in the bottom sediments.  The input of these  is  still substantial





(Maryland Environmental  Service,  1974).
                                  E-59

-------
The flushing rate of the  open fairway has been found to be relatively





high (Stroupe, et al,  1961).  It is suspected that if the domestic and





industrial waste discharges were suspended, water quality of the water





column in the Harbor would return to a nearly natural condition,  and fish





and other pelagic organisms •would repopulate to form a healthy water





column community in a short period of time.  It would take a longer





time for benthic communities to recover toward natural and healthy con-





ditions, and these might never be reestablished over the more seriously





polluted areas.  If the in-place pollutants alone of the Harbor -were





cleaned up and domestic and industrial wastes were still .discharged into





the Harbor, water quality of the Harbor water column would remain con-




taminated as before; and pelagic biotic communities would remain unhealthy.





The toxicants from the wastes  in the water column would continue to be




trapped by suspended solids  and settle quickly to the  bottom to form




additional toxic sediments.  Accordingly,  the present in-place pollutants





in Baltimore Harbor are of considerable concern,  but they cannot be





fully corrected except through simultaneous treatment and the prevention





of further additions  from domestic and industrial waste  discharges.










Because of the presence of high  concentrations of  persistent pollutants,





particularly heavy metals, in Baltimore Harbor sediments,  concern





exists  about the possible danger of release of these pollutants  into the
                                  E-60

-------
water column and their concentration,  cycling and magnification in the


food web, so-called bioconcentration.  American oysters, Crassostea


virginica, are known to concentrate in ten weeks an amount as much as



50, 000 times  the lead, zinc, copper; 700 times the cadmium and about


500 times the chromium in the surrounding water (Shuster and Pringle,


1969).   Fish are known to accumulate mercury as much as 3, 000 times


that in the surrounding water (Johnels  and Westermark, 1969; Hannerz,


1968).
                                       i-





In the Upper Chesapeake  Bay, this possible bioconcentration of heavy


metals in oysters resulting from spoil disposal of Baltimore Harbor  sedi-


ments  into the Kent Island and other open Bay spoil areas caused concern


in the late 1960's,  and was studied in 1970 (Cronin.  et al,  1974).  The


results of the study indicated that the heavy metal concentrations in the


oysters were  below "alert levels",  and the uptake of metals by the oysters


had no detected  relationship to the concentration of the  metals in surround-


ing water or on  suspended sediments.  Also, the concentration of metals


in the oysters were,  to a high probability, independent  of distance  from


the bottom.   Instead,  uptake rates were related to growth rate and


salinity or some factors coincident with it.  It appears  that the heavy


metal concentration in the water  column and in the bottom sediments did


not cause a  dangerous concentration in the oysters in the Chesapeake Bay
                                  E-61

-------
and also were not factors at all in bioconcentration of the metals in





oysters.  Morgan (1972) exposed clams, Macoma balthica, M.  phenax,





and Rangia cuneata, in Baltimore Harbor water for eight weeks.  It was





found that concentrations of the heavy metals in clams were very minor,




and in some instances there were no significant differences from those





in the control.  Morton (1974) concluded from his literature review that





biological uptake and accumulation by aquatic organisms did not occur




as might be expected in polluted areas.   This has caused a controversy





over the relative significance of bioconcentration.  It  is still impossible





to predict if and to what extent bioconcentration will occur, because the





potential release of toxicants across the sediment-water interface is




complex and not well understood.
                                 E-62

-------
E. 6      SUMMARY








In-place pollutants in Baltimore Harbor are patchy in distribution.





Sediment from the most toxic station sampled was about 125 times as





potent as that from the least toxic.  Among the pollutants determined,





hexane extracts correlated significantly with bulk concentrations of





PCB,  Pb,  Cr, Zn, and Cd, but the sediment moisture had no relation-





ship to heavy metal contents.










For the three species  of estuarine organisms, spot,  mummichogs,  and





soft-shell clams,  24-hour TLm and 48-hour  TLm values for suspended




solids correlated  strongly and, thus,  these two values for each species





were mutually convertible.










Spot -were more susceptible to suspended  solids than mummichogs,  but





both species had similar  susceptibility to toxic chemicals released  from





the Harbor  sediments.  As compared to these two fish species, soft-shell





clams were very tolerant to toxic materials and even more tolerant to





suspended solids.










Based on mummichog  24-hour TLm values for suspended solids used as





the index of sediment gross toxicity, the Baltimore  Harbor sediments
                                 E-63

-------
may be divided into four toxic zones: a highly toxic zone, with TLm





values less than 8 g/1;  a moderately toxic  zone,  with TLm values between





8 g/1 and 20 g/1; a  low  toxic zone, with TLm values between 20 g/1 and





40 g/1; and a slightly toxic  zone,  with TLm values higher than 40 g/1.










The  effects of sediment toxicity on benthic macro-invertebrates,  fish,





and phytoplankton are evaluated.   The community structure and diversity,





and distribution of  benthic macro-invertebrates are related to sediment





toxicity and thus they are mainly  affected by in-place pollutants in the





Harbor sediments.  Pelagic fish and phytoplankton are mainly affected by





pollutants in the water  column and very little,  if present, by the  in-place





pollutants  in the sediments.










The  ecological effects of in-place pollutants in Baltimore Harbor were





evaluated.  These pollutants are of considerable concern, but they cannot





be fully corrected except with simultaneous prevention of further addition




of domestic and industrial waste discharges.
                                  E-64

-------
                     TABLE E-10

 WATER QUALITY AND FISH MORTALITY DATA OF THE THREE
EXPERIMENTS OF MUMMICHOGS SUBJECTED TO THE SOLUTION
       OF BALTIMORE HARBOR SEDIMENT, STATION 10


Exp.
no.

I
1
1
1
1
1
2
2
3
3
3
2
.2
3
3
2

Suspended
solids
9/1
0.1
87.04
52.28
31.07
18.20
16.35
10.64
9.62
8.94
7.18
5.43
6.91
5.05
3.99
3.28
2.36

Dissolved
solids
9/1
5.40
6.43
5.92
5.15
6.10
5.96
5.64
5.26
5.81
5.72
5.43
5.31
4.82
5.83
5.74
4.64

Total
solids
9/1
5.5
93.47
58.20
36.22
24.30
11.6
16.28
15.88
14.75
12.90
10.86
12.22
9.87
7.82
9.02
7.00



Fish

Mortality
Turbidity
JTU
4
43,500
28,000
18,400
9,100
—
6,900
5,800
6,500
5,250
4,250
4,350
3,300
3,500
2,650
1,500
pH

8.3
5.0
4.75
4.8
4.65
5.0
5.2
5.75
4.8
4.9
5.8
6.02
6.5
6.6
7.0
7.1
DO
mg/1
7.2
4.5
6.5
6.5
6.5
6.35
6.4
5.7
6.6
6.5
6.6
6.6
6.6
6.6
6.5
6.5
%
24-hrs
0
100
100
100
100
100
80
70
50
40
10
0
0
0
0
0

48-hrs
0
100
100
100
100
100
100
100
70
60
20
0
0
0
0
0
                              E-65

-------
                      TABLE E-ll
  WATER QUALITY AND FISH MORTALITY DATA OF THE TWO
EXPERIMENTS OF MUMMICHOGS SUBJECTED TO THE SOLUTION
        OF BALTIMORE HARBOR SEDIMENT, STATION 8

Exp.
No.

7
7
7
7
6
6
6
6
6
6
7
Suspended
solids
9/1
34.78
23.65
IS. 70
15.27
12.20
10.57
8.80
7.96
7.56
0.08
0.01
Dissolved
solids
9/1
7.02
7.22
7.16
7.03
7.31
6.94
6.79
7.02
6.89
6.92
6.55
Total
solids
9/1
41.80
30.47
23.86
22.30
19.51
17.51
15.59
14.98
14.45
7.00
6.56
Fish Mortality
Turbidity
JTU
29,000
25,000
16,750
15,000
9,250
8,5OO
7,200
6,750
6,450
2
2
PH

4.8
5.2
5.3
5.3
5.9
5.6
5.8
5.8
6.0
8.2
8.1
DO
mg/1
6.8
7.4
7.4
7.4
7.5
7.1
7.7
7.6
7.6
7.9
7.5
%
24-hrs
100
20
20
0
0
0
0
0
0
0
0

48-hrs
100
50
30
10
0
0
0
0
0
0
0
                              E-66

-------
                      TABLE E-12

  WATER QUALITY AND FISH MORTALITY DATA OF THE TWO
EXPERIMENTS OF MUMMICHOGS SUBJECTED TO THE SOLUTION
   OF BALTIMORE HARBOR BOTTOM SEDIMENT, STATION 7

Exp.
No.

11
11
11
11
10
10
10
10
10
11
10
Suspended
solids
g/i
117.69
86.37
74.14
61.96
61.50
48.54
41.92
26.32
15.41
7.39
0.08
Dissolved
solids
9/1
5.54
6.71
6.70
7.58
6.05
6.27
6.59
6.47
6.40
6.20
6.82
Total
solids
9/1
123.23
93.08
82.84
69.54
67.54
54.81
48.51
32.79
21.81
13.59
6.90
Fish Mortality
Turbidity
JTU
66,000
64,500
58,000
55,000
45,500
37,500
32,500
23,500
15,000
5,800
2
pM

5.9
5.3
5.3
5.5
6.1
5.7
5.7
5.7
5.9
6.8
7.4
DO
mg/1
0.7
6.3
5.4
5.6
5.6
5.9
6.0
6.6
6.6
7.0
6.2

24-hrs
100
90
50
30
10
0
0
0
0
0
0
%
48-hrs
100
80
80
50
30
0
0
0
0
0
0
                             E-67

-------
                        TABLE E-13

    WATER QUALITY AND FISH MORTALITY DATA OF TWO
EXPERIMENTS OF MUMMICHOGS SUBJECTED TO THE SOLUTION
       OF BALTIMORE HARBOR SEDIMENT, STATION 6

Exp.
No.

9
9
9
9
12
12
12
12
12
9
12
Suspended
solids
9/1
71.26
58.93
47.08
34.91
31.34
27.38
21.05
20.39
17.74
0.08
0.05
Dissolved
solids
9/1
6.73
7.18
6.99
6.97
6.95
6.89
6.95
7.21
6.87
6.82
7.05
Total
solids
9/1
77.99
66.11
54.07
41.88
38.29
34.27
28.00
27.60
24.61
6.90
7.10
Fish Mortality
Turbidity
JTU
50,500
44,000
35,000
28,500
28,500
25,500
18,000
19,000
16,000
2
3
PH

5.0
5.0
5.1
5.2
5.5
5.7
5.4
5.9
5.9
7.4
7.5
DO
mg/1
5.1
5.3
6.2
6.2
7.5
7.3
6.2
7.4
7.4
6.2
7.3

24-hrs
100
100
100
90
70
60
30
20
0
0
0
%
48-hrs
100
100
100
100
90
80
30
40
0
0
0
                                 E-68

-------
                         TABLE E-14

   WATER QUALITY AND FISH MORTALITY DATA OF THREE
EXPERIMENTS OF MUMMICHOGS SUBJECTED TO THE SOLUTION
        OF BALTIMORE HARBOR SEDIMENT. STATION 5

Exp.
No.

14
14
15
15
15
15a
15
15a
15a
15a
14
15
15a
14
Suspended
solids
9/1
3.36
3.10
2.34
2.21
1.44
1.44
1.40
1.13
0.92
0.77
0.48
0.38
-0.08
0.09
Dissolved
solids
g/i
7.46
7.42
6.87
6.87
6.87
6.85
7.11
6.87
7.12
6.76
7.02
7.26
7.20
6.37
Total
solids
g/i
10.82
10.52
9.21
9.08
8.31
8.39
8.51
8.00
8.04
7.63
7.80
7.64
7.12
6.49
Fish Mortality
Turbidity
JTU
3,000
2,750
2,700
2,400
1,800
1,800
1,400
-
1,300
1,100
590
465
6.5
3
pH

4.2
4.2
3.8
4.7
5.0
5.0
6.2
6.2
5.6
6.4
6.9
6.5
7.5
7.5
DO
mg/1
6.5
6.5
6.5
6.6
6.5
6.5
6.5
6.5
6.6
6.5
6.75
6.6
6.6
6.5

2 4-hr s
100
100
100
100
100
100
90
100
80
50
0
0
0
0
%
48-hrs
100
100
100
100
100
100
100
100
90
70
0
0
0
0
                                  E-69

-------
                        TABLE E-15

    WATER QUALITY AND FISH MORTALITY DATA OF TWO
EXPERIMENTS OF MUMMICHOGS SUBJECTED TO THE SOLUTION
        OF BALTIMORE HARBOR SEDIMENT, STATION 9

Exp.
No.

8
5
5
4
4
5
5
4
5
4
4
5
4
Suspended
solids
9/1
33.79
16.95
15.02
14.32
13.09
11.46
11.09
10.99
8.77
8.60
7.01
0.10
0
Dissolved
solids
9/1
9.02
8.00
8.03
7.00
6.90
7.70
7.58
6.85
7.44
6.50
6.76
6.61
6.54
Total
solids
9/1
42.81
24.95
23.09
21.32
19.92
19.16
18.67
17.85
16.21
15.10
13.77
6.72
6.54
Fish Mortality
Turbidity
JTU
19,000
8,300
7,450
6,900
5,850
5,400
4,450
5,250
4,400
4,350
3,550
3.7
2.5
pH

9.0
8.9
8.9
9.3
9.3
8.9
9.3
9.3
8.9
9.3
9.2
8.2
8.2
DO
mg/1
5.6
7.5
7.7
8.3
8.2
7.7
7.8
8.4
8.9
8.2
8.2
9.2
8.3

24-hrs
20
0
0
20
10
0
0
10
0
20
10
0
0
%
48-hrs
30
0
0
50
70
10
10
20
0
30
20
0
0
                                E-70

-------
                        TABLE E-16

     WATER QUALITY AND FISH MORTALITY DATA OF AN
EXPERIMENT OF MUMMICHOGS SUBJECTED TO THE SOLUTION
        OF BALTIMORE HARBOR SEDIMENT, STATION 4

Exp.
no.

18
18
18
18
18
18
16
Suspended
solids
g/1
8.09
4.93
3.74
2.68
2.08
0.81
-0.25
Dissolved
solids
g/1
5.65
7.21
6.91
7.33
7.01
7.02
6.73
Total
solids
g/1
13.74
12.05
10.70
10.00
8.59
7.83
6.48
Fish Mortality
Turbidity
JTU
9,000
4,300
3,200
2,300
1,800
565
2.5
PH

5.2
5.7
6.0
6.3
6.75
7.2
7.6
DO
mg/1
6-9
7.1
7.1
7.0
7.0
7.0
7.1
%
24 hrs.
100
60
20
0
0
0
0

48 hrs
100
90
50
0
0
0
0
                                E-71

-------
                         TABLE E-17
    WATER QUALITY AND FISH MORTALITY DATA OF TWO
EXPERIMENTS OF MUMMICHOGS SUBJECTED TO THE SOLUTION
       OF BALTIMORE HARBOR SEDIMENT,  STATION 2

Exp.
No.

16
20
20
20
20
20
16
16
16
16
16
Suspended
solids
g/1
20.94
10.48
9.41
8.43
7.58
6.70
4.94
3.82
2.45
1.19
-0.26
Dissolved
solids
g/1
7.66
6.95
6.16
7.26
6.78
7.08
7.05
7.00
7.02
'6.98
6.51
Total
solids
g/1
28.60
17.43
15.57
15.69
14.36
13.78
13.99
10.82
9.50
8.17
6.25
Fish Mortality
Turbidity
JTU
17,000
6,000
5,700
5,400
4,800
4,200
3,400
2,700
1,800
740
3
pH

4.2
4.4
4.4
4.4
4:6
4.9
5.7
6.0
6.75
7.2
7.5
DO
mg/1
6.1
6.5
6.5
6.6
6.6
6.7
6.5
6.5
6.5
6.5
6.6
%
24 hrs.
100
100
100
100
80
70
50
0
0
0
0

48 hrs
100
100
100
100
100
80
70
0
0
0
0
                                  E-72

-------
                        TABLE E-18

 WATER QUALITY AND FISH MORTALITY DATA OF THE THREE
EXPERIMENTS OF MUMMICHOGS SUBJECTED TO THE SOLUTION
        OF BALTIMORE HARBOR SEDIMENT,  STATION 1

Exp.
No.

17
21
21
21
21
24
24
24
24
17
17
17
17
17
21
Suspended
solids
g/1
21.14
22.41
18.43
17.10
13.92
11.08
9.29
8.56
7.38
5.01
3.54
2.60
2.14
0.79
- 0.06
Dissolved
solids
g/1
6.22
7.82
7.61
7.43
7.46
7.55
7.55
7.64
7.50
6.91
7.04
6.96
7.07
7.01
6.97
Total
solids
g/1
27.36
30.23
26.04
24.53
21.38
18.58
16.83
16.20
14.90
11.96
10.57
9.56
9.30
7.80
6.91
Fish Mortality
Turbidity
JTU
20,000
16,000
14,000
12,000
8,000
6,650
5,850
5.250
4,850
3,700
2,750
2,150
1,600
565
3
PH

4.5
4.5
4.6
4.6
4.7
5.9
5.8
5.9
6.2
6.5
6.7
6.8
7.2
7.6
7.8
DO
mg/1
6.0
6.2
6.2
6.5
6.6
6.6
6.9
6.9
6.7
6.9
6.9
7.0
6.9
6.7
6.7

24-hrs
100
100
100
100
100
40
30
10
10
0
0
0
0
0
0
&
48-hrs
100
100
100
100
100
60
60
40
10
0
0
0
0
0
0
                                 E-73

-------
                 TABLE  E-19

 WATER QUALITY AND FISH MORTALITY DATA
OF THE THREE EXPERIMENTS OF MUMMICHOGS
   EXPOSED TO FULLER'S EARTH SOLUTION

Exp.
No.

26
26
26
26
26
25
25
25
25
23
23
23
23
23
25
23
26
Suspended
solids
9/1
123.45
114.15
104.14
97.82
77.33
61.05
49.16
42.15
24.57
26.25
19.48
16.33
14.90
11.98
0.04
0
0.04
Dissolved
solids
9/1
9.95
9.18
8.10
9.20
9.41
9.78
9.65
9.62
9.69
8.44
8.44
8.37
8.29
8.28
9.39
8.79
9.34
Total
solids
9/1
133.40
123.33
121.24
107.02
86.74
71.83
58.81
51.77
34.26
34.69
27.92
24.70
23.19
0.26
9r43
8.79
9.38
Fish Mortality
Turbidity
JTU
31,000
25,000
25,000
29,500
21,000
17,000
15,000
12,000
5,950
5,650
4,600
4,400
3,700
3,150
3
2
2
PH

7.3
7.6
7.7
7.5
7.6
7.3
7.6
7.7
7.9
7.8
7.9
7.9
7.9
8.0
8.1
7.9
7.9
DO
mg/1
5.3
5.1
5.9
6.1
7.2
6.5
7.0
7.3
7.1
7.3
7.4
7.5
7.5
7.1
7.4
7.1
7.5

24-hrs
90
70
20
20
10
0
0
0
0
0
0
0
0
0
0
0
0
%
48-hrs
100
70
60
30
10
0
0
0
0
0
0
0
0
0
0
0
0
                          E-74

-------
                TABLE  E-20

WATER QUALITY AND FISH MORTALITY DATA
    OF THE FOUR EXPERIMENTS ON SPOT
  EXPOSED TO FULLER'S EARTH SOLUTION

Exp.
No.

29
29
29
35
29
35
36
36
36
35
35
36
27
27
Suspended
solids
9/1
122.06
98.84
77.20
75.08
74.73
74.48
70.30
67.89
66.48
64.34
51.52
49.60
26.37
-0.01
Dissolved
solids
9/1
9.63
9.18
8.70
10.69
8.43
9.82
11.31
11.79
12.06
10.90
9.78
10.70
9,73
9.29
Total
solids

131.69
108.02
85.90
85.76
83.57
84.30
81.61
79.67
78.54
75.24
61.30
60.30
18.05
9.28
Fish Mortality
Turbidity
JTU
33,000
26,000
24,000
23,000
24,000
21,000
25,000
27,000
26,000
20,000
16,000
20,000
6,100
2
DO
mg/1
5.6
5.5
5.5
6.5
6.2
6.3
5.9
5.4
6.6
6.3
6.1
6.1
6.9
7.2
pH

7.4
7.7
7.6
7.5
7.7
7.6
6.5
7.4
7.5
7.7
7.7
7.5
7.9
8.1

24-hrs
100
100
100
100
90
100
90
70
80
80
50
50
0
0
%
48-hrs
100
100
100
100
100
100
90
70
80
80
50
50
0
0
                         E-75

-------
                     TABLE E-21
      WATER QUALITY AND FISH MORTALITY DATA
  OF THE TWO EXPERIMENTS ON SPOT EXPOSED TO THE
SOLUTION OF BALTIMORE HARBOR SEDIMENT, STATION 10

Exp.
No.

30
30
32
30
32
30
30
32
32
32
Suspended
solids
g/i
17.30
15.75
10.30
8.74
6.67
6.38
2.71
6.30
4.11
-0.23
Dissolved
solids
9/1
8.66
8.56
8.24
8.71
7.67
8.61
8.60
7.59
7.84
8.96
Total
solids
9/1
25.97
23.78
18.54
18.45
14.33
14.97
11.31
13.90
11.95
8.73
Fish Mortality
Turbidity
JTU
12,500
9,000
6,200
6,000
4,800
3,975
1,375
4,500
3,350
2
DO

6.6
6.7
7.2
6.9
7.4
6.8
7.2
6.7
7.2
7.5
PH

5.3
4.9
5.6
5.2
5.6
5.9
7.4
5.9
6.5
8.1
%
24-hrs
100
100
90
30
0
0
0
0
0
0

48-hrs
100
100
100
60
3-0
0
0
0
0
0
                               E-76

-------
                    TABLE E-22

     WATER QUALITY AND FISH MORTALITY DATA
OF THE TWO EXPERIMENTS ON SPOT SUBJECTED TO THE
SOLUTION OF BALTIMORE HARBOR SEDIMENT, STATION 8

Exp.
No.

31
31
31
31
34
34
34
34
34
31
31
Suspended
solids
9/1
53.93
46.68
29.29
21.97
20.39
17.46
16.60
16.53
15.79
14.09
0.25
Dissolved
solids
g/i
8.68
8.82
8.07
8.42
10.02
9.27
9.31
9.70
9.24
8.34
8.15
Total
solids
9/1
62.61
55.50
32.36
30.39
30.41
26.73
25.91
27.23
25.03
22.43
8.30
Fish Mortality
Turbidity
JTU
39,500
36,500
26,500
19,000
18,500
17,000
14,750
15,250
14,500
12,000
2

DO
5.9
6.6
6.1
6.6
6.8
5.3
5.5
5.5
6.4
5.5
6.6

PH
4.4
4.5
4.7
5.0
5.2
5.3
5.4
5.5
5.6
5.5
8.0
%
24-hrs.
100
100
100
100
80
20
10
10
0
0
0

48-hrs
100
100
100
100
90
40
20
40
40
0
0
                              E-77

-------
                      TABLE E-23

      WATER QUALITY AND FISH MORTALITY DATA
 OF THE TWO EXPERIMENTS ON SPOT EXPOSED TO THE
SOLUTION OF BALTIMORE HARBOR SEDIMENT  STATION 7

Exp.
No.

38
38
38
38
38
39
39
39
39
Suspended
solids
9/1
38.25
36.76
31.67
29.31
27.81
21.19
14.79
12.87
7.74
Dissolved
solids
9/1
10.42
10.98
10.63
10.43
10.20
9.86
9.96
10.14
9.94
Total
solids
9/1
48.67
47.74
42.30
39.74
38.01
31.05
24.75
23.01
17.68
Fish Mortality
Turbidity
JTU
36,500
33,500
29,000
27,000
26,000
17,500
14,500
13,000
9,000
DO

6.7
6.6
6.8
6.6
6.7
6.1
6.5
6.5
5.8
PH

5.4
5.4
5.5
5.5
5.6
5.4
5.9
6.3
6.1
i
24-hrs
90
90
60
20
0
0
0
0
0
fc
48-hrs
100
90
90
20
0
10
0
0
0
                              E-78

-------
                      TABLE  E-24

      WATER QUALITY AND FISH MORTALITY DATA
 OF THE TWO EXPERIMENTS ON SPOT EXPOSED TO THE
SOLUTION OF BALTIMORE HARBOR SEDIMENT, STATION 6

Exp.
No.

40
40
39
40
40
39
39
39
39
Suspended
solids
9/1
36.10
31.46
28.57
27.66
24.69
21.19
14.79
12.87
7.74
Dissolved
solids
g/i
10.95
10.62
9.89
10.43
10.44
9.86
9.96
10.14
9.94
Total
solids
9/1
47.05
42.08
38.46
38.09
35.13
31.05
24.75
23.01
17.68
Fish Mortality
Turbidity
JTU
26,000
25,000
25,000
24,000
21,500
17,500
14,500
13,000
9,000
DO

5.6
6.1
6.0
6.6
6.5
6.1
6.5
6.5
6.1
PH

5.1
5.2
5.3
5.2
5.4
5.4
5.9
6.3
5.8

24-hr.
100
100
80
60
50
0
0
0
0

48 -hr.
100
100
90
70
50
10
0
0
0
                               E-79

-------
                                                 TABLE  E-25
               WATER QUALITY AND FISH MORTALITY DATA OF THE EXPERIMENTS WITH SPOT

                SUBJECTED TO THE SOLUTION OF BALTIMORE HARBOR SEDIMENT, STATION 5
00.
o

Expt.
No.

43
43
43
43
43
45
45
45
51
45
Suspended
Solids
9/1
2.13
1.96
1.66
1.63
1.43
1.02
0.99
0.89
0.62
0.57
Dissolved
Solids
g/i
11.28
11.32
11.12
10.96
11.00
22.06
11.04
7.02
13.46
11.14
Total f
Solids'
9/1
13.41
13.28
12.78
12.59
12.43
12.08
12.03
7.90
14.08
11.71
Turbidity
JTU

1700
1500
1300
1275
975
780
1100
950
545
678
PH


5.9
5.7
5.6
5.7
5.7
5.9
5.8
5.8
6.5
6.2
DO


6.5
6.6
7.0
7.1
7.5
6.1
6.6
6.5
6.2
6.6
Fish Mortal
24-hrs

100
100
100
100
100
100
100
90
10
0
ity %
48-hrs

100
100
100
100
100
100
100
100
60
0

-------
                                TABLE E-26

WATER QUALITY AND FISH MORTALITY DATA OF AN EXPERIMENT WITH SPOT
SUBJECTED TO THE SOLUTION OF BALTIMORE HARBOR SEDIMENT, STATION 4

Expt.
No.

52
52
M
1
oo 52
52
52
Suspended
Solids
9/1
10.04
6.90


6.41
5.92
4.05
Dissolved
Solids
g/i
11.18
11.53


11.47
11.72
12.13
Total
Solids
9/1
21.22
18.43


17.88
17.64
16.18
Turbidity
JTU

7700
6100


5500
5250
4000
PH


4.7
4.8


5.1
5.7
5.6
DO
mg/1

6.1
6.2


6.4
6.0
6.5
Fish Mortal
24-hrs

100
100


100
10
0
ity %
48-hrs

100
100


100
10
0

-------
                                  TABLE  E-27

WATER QUALITY AND FISH MORTALITY DATA OF THREE! EXPERIMENTS WITH SPOT
  SUBJECTED TO THE SOLUTION OF BALTIMORE HARBOR SEDIMENT, STATION 2

Expt.
No.

46
46
46
H
co 46
tv
49
49
42
42
42
Suspended
Solids
g/i
8.41
7.47
7,34

6.01
5.83
5.61
3.53
2.38
1.03
Dissolved
Solids
g/i
11.77
11.59
11.87

11.39
12.08
11.77
10.82
10.48
1.073
Total
Solids
g/i
20.18
19.06
19.21

17.40
17.91
17.38
14.35
12.86
11.76
Turbidity
JTU

5300
5100
4900

4450
4650
4200
2550
1600
900
PH


5.4
5.3
5.5

5.5
6.0
6.0
6.6
6.8
7.1
DO


6.5
6.4
6.5

6.3
6.6
6.3
6.9
6.7
6.8
Fish Mortal
24-hrs

100
90
80

80
60
50
0
0
0
ity %
48 hrs

100
100
100

90
90
70
0
0
0

-------
                                                 TABLE E-28
CO
OJ
                WATER QUALITY AND FISH MORTALITY DATA OF TWO EXPERIMENTS WITH SPOT
                 SUBJECTED TO THE SOLUTION OF BALTIMORE HARBOR SEDIMENT, STATION 1

Expt.
No.

47
50
50
50
47
47
50
50
Suspended
Solids
9/1
13.66
11.23
9.77
8.99
7.91
6.13
6.28
4.48
Dissolved
Solids
g/i
10.49
10.79
11.41
10.81
9.42
10.31
11.09
9.13
Total
Solids
9/1
24.15
22.02
21.18
19.80
17.40
16.44
17.37
13.61
Turbidity
JTU

8200
7350
6550
5800
5200
4200
4000
3700
PH

5.6
6.0
6.2
6.5
6.1
6.9
6.5
6.9
DO

6.4
6.8
7.1
6.9
6.6
6.9
6.8
7.1
Fish Mortal
24-hrs

100
100
70
30
20
10
0
0
ity %
48 hrs

100
100
80
30
20
20
0
0

-------
                            TABLE E-29

WATER QUALITY AND CLAM MORTALITY DATA OF THE EXPERIMENTS
      WITH SOFT-SHELL CLAMS SUBJECTED TO THE SOLUTION
           OF BALTIMORE HARBOR SEDIMENT,  STATION 1

Expt.
No.

62
62
H
OD 59
62
59
62
Suspended
Solids
g/1
129.51
106.27

39.09
33.32
16.04
0.14
Dissolved
Solids
g/1
15.59
14.88

13.17
13.81
13.28
12.50
Total
Solids
9/1
145.10
121.15

52.26
47.13
29.32
12.64
Turbidity
JTU

67,000
57,000

29,000
27,000
13,500
2
PH


4.3
4.3

5.0
4.9
6.4
7.5
DO


3.4
6.1

7.1
7.5
7.1
6.3
Clam Mortal
24-hrs

30
10

0
10
0
0
ity %
48 hrs

50
40

20
30
0
0

-------
                         TABLE E-30

WATER QUALITY AND CLAM MORTALITY DATA OF EXPERIMENTS
    WITH SOFT-SHELL CLAMS SUBJECTED TO THE SOLUTION
         OF BALTIMORE HARBOR SEDIMENT, STATION 2

Expt.
No.

58
57
W 58
oo
^ 57
58
58
58
Suspended
Solids
9/1
49.49
49.20
48.25

47.33
34.11
17.00
-0.02
Dissolved
Solids
g/i
13.15
12.36
13.12

12.28
12.12
12.07
11.05
Total
Solids
g/i
62.64
61.56
61.37

59.61
46.23
29.07
11.03
Turbidity
JTU

34,000
32,000
31,000

30,750
25,000
13,000
4
PH

4.6
4.3
4.8

4.4
5.0
5.3
7.4
DO

6.5
5.2
6.5

5.8
6.4
6.8
6.8
Clam Mortal
24-hrs

50
50
30

40
30
10
0
ity %
48-hrs

100
90
80

90
100
50
0

-------
                            TABLE E-31
WATER QUALITY AND CLAM MORTALITY DATA OF EXPERIMENTS
    WITH SOFT-SHELL CLAMS SUBJECTED TO THE SOLUTION
         OF BALTIMORE HARBOR SEDIMENT, STATION 4

Expt.
No.

60
61
H
k 6°
60
61
cZ
Suspended
Solids
9/1
39.40
38.06

37.87
23.69
22.21
0.14
Dissolved
Solids
9/1
12.50
13.50

12.13
11.79
12.45
12.50
Total
Solids
9/1
51.90
51.56

50.00
35.48
34.66
12.64
Turbidity
JTU

35,000
34,000

35,000
21,500
20,500
2
PH


3.9
4.8

3.8
4.9
5.2
7.5
DO


6.6
6.1

6.2
6.8
7.0
6.3
Clarn Mortal
24-hrs

10
40

10
10
0
0
ity %
48-hrs

50
40

40
50
30
0

-------
H
i
oo
                                              TABLE  E-32



                      WATER QUALITY AND CLAM MORTALITY DATA OF TWO EXPERIMENTS

                             WITH SOFT-SHELL CLAMS EXPOSED TO THE SOLUTION

                                  OF BALTIMORE HARBOR SEDIMENT, STATION 5

Exp.
noo

70
70
70
63
70
63
70
63
70
Suspended
solids
g/I
66.86
45.09
30.15
22.13
19.85
10.74
8.72
0.10
0.06
Dissolved Total
solids solids
g/1
20.82
18025
I5o96
14.39
14.61
12.47
13.01
11.42
12.14
g/1
87.68
63.38
46.11
36.52
34.46
23.21
21.73
11.52
12.20
Turbidity pH
JTU
54,000
35,000
27,000
20,000
17,500
10,000
6,050
3
3

3.5
3.6
3.8
4.2
3.5
3.7
4.5
7.5
7.8
DO
mg/1
4.8
6.3
7.5
5.7
7.4
6.3
7.7
8.0
7.5
Clam mortality($)

24 hrs
80
60
50
40
40
30
20
0
0

48 hrs
90
80
100
80
90
80
90
0
0

-------
w
I
oo
                                                TABLE  E-33

                    WATER QUALITY AND CLAM MORTALITY DATA OF TWO EXPERIMENTS
                           WITH SOFT-SHELL CLAMS EXPOSED TO THE SOLUTION
                                OF BALTIMORE HARBOR SEDIMENT, STATION 6

Exp.
no.
Suspended
solids
g/1
74
67
74
67
67
67
150.
139.
135.
131.
130.
- 0.
75
77
4l
94
05
07
Dissolved Total
solids solids
g/1
13.53
11.61
12.95
11.4o
11.33
12.39
g/1
164.28
151.38
148.36
143.34
141.38
12.32
Turbidity pH
JTU
91,000
100,000
95.500
87,000
81,000
2

4.2
4.3
4.4
4.3
4.3
7.6
DO -
mg/1
6.4
6.6
6.8
7.8
5.1
7.4
Clam mortality (%)




24 hrs 48 hrs 72 hrs 96 hrs
0
0
0
0
0
0
40
10
40
0
0
0
60
20
80
10
20
0
100
100
100
100
100
0

-------
H
i
CO
                                               TABLE E-34

                    WATER QUALITY AND CLAM MORTALITY DATA OF TWO EXPERIMENTS
                          WITH SOFT-SHELL CLAMS EXPOSED TO THE SOLUTION
                                OF BALTIMORE HARBOR SEDIMENT, STATION 7

Expo
no.

77
77
85
72
85
68
85
77
Suspended Dissolved Total
solids solids solids
g/1
173.21
167.21
1^7.26
137.71
121.75
108.82
103.61
0.06
£/l
13.97
13.14
14.67
11.69
16.58
10.86
12.79
12.14
g/1
187.18
180.35
161.93
149.40
138.33
119.28
io6.4o
12.20
Turbidity
pH
JTU
175
150
150
98
94
77
75

,000
,000
,000
,500
,000
,000
,000
3
4.7
4.8
4.9
4.7
4.8
4.8
4.9
7.8
DO
mg/1
6.6
6.5
6.5
6.1
606
7.2
6.3
7.5
Clam mortality ($)




24 hrs 48 hrs 72 hrs 96 hrs
0
0
0
0
0
0
0
0
30
60
30
20
0
0
0
0
100
100
100
50
50
20
10
0
100
100
100
100
100
60
60
0

-------
H
^
o
                                               TABLE E-35

                   WATER QUALITY AND CLAM MORTALITY DATA OF TWO EXPERIMENTS
                          WITH SOFT-SHELL CLAMS EXPOSED TO THE SOLUTION
                               OF BALTIMORE HARBOR SEDIMENT, STATION 8

Exp0
uoe

76
76
76
69
69
76
Suspended Dissolved Total
solids solids solids Turbidity jJfi
g/1
113.80
101.98
96.15
84.39
68.42
0.06
g/1
13.34
13.23
13.09
10.88
8.64
12.14
g
127.
115.
109.
95.
77.
12.
;/i
14
21
24
27
06
21
JTU
85,000
73,ooo
70,000
68,000
52,500
3

4.7
4.4
4.5
4.5
4.7
7.8
DO
mg/1
6.8
6.2
6.4
6.5
6.7
7,5
Clam mortality ($)
24 hrs 48 hrs 72 hrs 96 hrg
10
20
0
0
0
0
60
40
20
0
0
0
100
90
70
0
0
0
100
100
100
20
40
0

-------
w
                                              TABLE  E-36

                  WATER QUALITY AND CLAM MORTALITY DATA OF TWO EXPERIMENTS
                         WITH SOFT-SHELL CLAMS EXPOSED TO THE SOLUTION
                              OF BALTIMORE HARBOR SEDIMENT, STATION 10

Exp0
nOo

80
80
81
8l
81
8l
Suspended
dolids
S/l
156o48
152.39
150.8?
lM.91
132.39
0.25
Dissolved Total
solids solids
g/1
14.28
16. 03
15.66
14.48
13.8?
13.34
g/1
170,76
168.42
166.53
159.39
l46026
13.59
Turbidity pH
JTU
97,000
81,000
83,000
83,500
75,000
2

3.8
3.8
3.8
3.8
3.9
7.4
DO •
mg/1
6.0
5.8
5.6
5.7
5.4
7.7
Clam mortality (.%}



24 hrs 48 hrs 72 hrs
40
20
30
30
0
0
80
90
90
70
60
0
100
100
100
90
100
0

-------
xO
                                                TABLE  E-37

                   WATER QUALITY AND CLAM MORTALITY DATA OF THREE EXPERIMENTS
                    WITH SOFT-SHELL CLAMS EXPOSED TO SOLUTION OF FULLER'S EARTH

Exp.
noo

78
86
78
83
83
78
78
86
86
Suspended
solids
g/1
202,
176.
144.
127.
1240
119.
78.
66.
0.

07
43
55
85
61
09
68
99
02
Dissolved Total
solids solids Turbidity pH
g/1
10o32
11.76
10.23
12.21
12.09
10.28
10.17
11.21
11.19
g/1
212.39
188.19
154.78
140.06
136.70
129.37
88085
78.20
11.21
JTU
53,000
44,000
36,000
38,500
41,000
28,250
22.250
23.500
2

7.2
7.3
7.3
6.4
7.2
7.4
7.5
7.4
7*3
DO
mg/1
3.8
2.0
5.1
6.3
6.0
7.4
7.0
5.3
8.0
Clam mortality (%}




24 hrs 48 hrs 72 hrs 96 hrs
0
0
0
0
0
0
0
0
0
10
20
0
0
0
0
0
0
0
40
30
30
20
10
20
0
0
0
90
40
90
60
20
90
10
20
0

-------
                   APPENDIX F

SUPPLEMENTARY DATA ON DREDGING,  DISPOSAL,
          AND BLANKETING TECHNIQUES

-------
F. 1    DREDGING AND DISPOSAL


One  of the more  important recent investigations of the effects of dredging

in an estuarine environment is a detailed study of the effects of dredging

and disposal in the San Francisco Bay and Estuary by the U. S. Army

Corps of  Engineers.   This study,  as  reported in July 1975,  reached

a number of conclusions.  Those which are most important  to an under-

standing and consideration of dredging and spoil disposal results of the

San Francisco study final composite environmental  statement are quoted

below:
      "The purpose of this Statement of Findings is to set forth the
      rationale  leading to a recommendation that the maintenance
      dredging for the Federal navigation projects in  San Francisco
      Bay be continued as authorized, and as described in the Final
      Composite Environmental Statement".

      "3.  Rationale and Discussion.  The possible consequences  of
      the navigation projects have been studied for environmental,
      social well-being,  economic effects  (including regional and
      national economic development) and  engineering feasibility.
      In evaluating the projects,  the following points were considered
      pertinent:

           a. Environmental Considerations.

             (1) Bay Estuary - Turbidity  in the upper water column
      from a dredging activity usually lasts less than 15 minutes with
      the highest turbidity values adjacent to  the dredge.  In addition
      to the turbidity  plume created in the upper water column, dredg-
      ing induces  an ill-defined fluff zone in the channel bottom which
      can last up to several weeks.  This fluff zone shifts with the tide
      but is localized to the channel boundaries, and eventually con-
      solidates.
                                   F-Z

-------
    "Material released at open water disposal sites reaches
the bottom relatively intact.  Less than five percent of the
material is dispersed in the upper water  as the material des-
cends.  The  disposed sediments are  subsequently dispersed
within the bottom few feet of the water  column,  diluted, and
follow the circulation pattern of natural sediment distribution
in the Bay.

    Benthic  organisms  experience various amounts of dredging
impact depending on the surface area distributed,  the numbers
and species present, depth of the  cut, and frequency of mainte-
nance.  In San Francisco Bay,  it does not appear that sediments
from disposal operations cause extensive smothering of benthic
organisms because  the disposal areas are high  energy areas
where currents are swift and continuous.   Estuarine fish (includ-
ing anadromous fish) are generally tolerant of relatively high
turbidity and can avoid or move away from immediate areas  of
impact.

    Dredging and disposal have adverse impacts on bottom dwel-
ling organisms  in the immediate work areas. Some  organisms
are destroyed at both the dredging and  disposal site, while others
are transported to the disposal site.  Indications are that,  while
there is some diversity of life at project  and disposal sites,
these areas,  in general, do not have  as great an abundance of
life as those areas outside  the channel  or disposal sites.

    To date,  there  is no indication that dredge  and disposal
operations directly  influence uptake of  toxic constituents although
there is evidence of limited release of  some contaminants  during
sediment  agitation.

    b. Social Well-Being Considerations.

       (1) Historical and Archaeological Sites  - All 20 projects
are areas previously dredged.  Of the five projects involving land
disposal,  only-the Port  of Redwood City has  tentatively chosen a
land disposal site.  The site has been investigated by an archaeol-
ogist  and the  determination has been  made that  no  archaeological
resources  exist and that no historical sites will be affected.  Any
other potential sites for Port of Redwood  City land disposal and
                             F-3

-------
"land disposal sites for other projects will be surveyed by a pro-
 fessional archaeologist, and a supplement to the environmental
 statement will be issued to cover this and other considerations.

        (2)  Demography and Land Use - Most of the 20,400 port-
 related jobs are in core urban areas and help sustain the economic
 health of those  areas.  Maintenance dredging is essential to port
 operations; thus it  strengthens the inner city economies and to
 some extent retards the exodus from  cities to suburbs.

        (3)  Government  - Port activities comprise a vital part
 of socio-economic  structures of city government land use plans.

        (4)  Transportation  - Trucking and rail lines interface
 with waterborne commerce in the Bay area to link water and land
 freight transfer.   Maintenance dredging serves  to continue  this
 efficient and economical land-water freight system.

        (5)  Recreation   Maintenance dredging benefits some
 recreational boaters  in areas such as San Rafael Creek and
 San Leandro Marina as well as  all other marinas  covered under
 Corps permit program.  Cessation of maintenance dredging
 would have a negative social impact on such recreation activities.

        (6)  Scenic Resources -  Land disposal would have an
 aesthetic impact.   If  land disposal is utilized, this impact will be,
 assessed in the appropriate supplemental environmental statement.

      c. Engineering Considerations.

        (1)  Existing Project  The Federal navigation projects
 under consideration have already been constructed.  Hydrographic
 surveys are routinely done to determine when maintenance  dredging
 is required and to estimate the  amount of material to be dredged.

        (2)  Land Disposal - Those projects for which land dis-
 posal is being considered v/ill be subjected to engineering review
 and analysis.  This review and  analysis will  consider such  items
 as seismic hazards,  ground water, runoff, etc.  Supplemental
 environmental statements  for these projects will include these con-
 siderations .
                              F-4

-------
      " (3)  Future Projects - New dredging projects, both Federal
and private requiring a permit,  and expansion of current projects
will be  the subject of engineering review and analysis and will have
separate environmental reports  issued on them.

    d.  Economic Considerations.

        (1) Economy  - Maintenance  of Federal  navigation projects
will have  a positive impact on the San Francisco Bay regional econ-
omy.   Dredging is considered to have beneficial long-term impacts
for maintaining port facilities and navigation commerce, helping
to maintain land values,  public revenues,  and  the provision of com-
munity  services.   Total military and civil port investment in the
Bay-Delta area was  nearly $2 billion through 1973.   Over 4, 500
vessel trips with ships greater than 25-foot draft, requiring dredged
channels for navigation,  passed through San Francisco Bay and over
56 million tons  of cargo were handled in Bay-Delta  ports in 1973.

        (2) Employment - the  Federal navigation projects maintain
channels that serve commercial ports,  private wharves, oil piers,
and military installations that are dependent on Bay access.  Approx-
imately 7; 800 jobs were related to  export in the Bay area.   Numerous
other jobs are indirectly related to waterborne transportation.

    e.  Alternative Considerations.

        (1)  No Maintenance  -  In order to provide  open navigation
channels for  commercial shipping and other purposes in the
national interest, dredging in the Bay area has become a continual
operation and it is doubtful that  maintenance dredging would be
permanently halted.  Two programs of decreasing maintenance
dredging activities,  partial  and  complete moratoriums, would be
extreme measures having severe negative socio-economic  impacts
throughout the Bay region and the nation, as well as both positive
and negative environmental  effects.

        (2)  Alternate Dredging Methods - Present dredging methods
in the Bay include the hydraulic  cutterhead pipeline, the hopper
dredge  and the clamshell dredge.  Each method is uniquely suited
for particular project conditions.  Studies are  being conducted to
develop methods which may reduce impacts on the aquatic environ-
ment without decreasing dredging efficiency.   All methods  are
required to meet the total dredging requirement.
                             F-5

-------
      "(3)  Alternate Disposal Sites  - Alternative proposals for
disposal in the Bay are ocean disposal, land disposal,  and salt
marsh development.  Large scale ocean disposal by hopper and/or
barge is uneconomical and not in line with energy conservation.  A
conceptual plan of a permanent,  self-contained pipeline system to
the ocean disposal site was investigated for economic feasibility,
but appears infeasible in the  short run.  Any ocean  disposal plan
would require a detailed  study in which alternative ocean disposal
plans would be thoroughly assessed prior to approval.  Land dis-
posal is  a short-term alternative and should be considered as an
alternative to aquatic disposal.  Should land disposal be selected
for'a particular project,  a supplemental environmental statement
will be prepared covering all aspects of this  alternative.  Marsh
development studies have shown this to be a  feasible alternative;
however, like other land disposal alternatives, it should be con-
sidered short-term and  of limited applicability.

       (4)  Economic Consideration  for Alternatives -  Economic
analysis of the cost efficiency of alternative dredging and disposal
systems were derived in the following ranking (from least expen-
sive to most expensive):  closest aquatic disposal (no constraints on
disposal), closest aquatic disposal seaward of the dredge site (no
constraints), ocean disposal  (100-fathom  contour),  land disposal
(Petaluma River Area),  delta island reclamation (Sherman Island),
and marshland development (Petaluma River Area).

       (5)  Reduce Shoaling Rate - Studies have been conducted
involving structural plans to either prevent shoaling in the  navi-
gation channels or to increase flushing  of the  channels, and
selection of alternative aquatic disposal sites to  reduce the amount
of sediments returning to the channels.

       (6)  Development in Dredging Technology - Important
factors being considered involve improving the efficiency of dredg-
ing techniques,  acquiring new equipment, applying chemical addi-
tives, and adjusting  the timing,  scheduling, and methodology of
dredging operations.   These factors  are being studied by the Corps.

     f.  Other Public Interest  Considerations.

       (1) Federal Navigation Projects -  Federal navigation projects
planned for the coming year are  announced in a single  public notice.
Revised public notices are issued as required.

                             F-6

-------
      "  (2) Regulatory Permit Actions - Dredging projects for
which a Department of the Army permit is required are announced
by public notice.  For  small volumes (less than 10,000 cubic yards)
involving land disposal above MHHW, no public notice is issued;
however, all concerned agencies are afforded the opportunity to
comment on the project.

        (3) Public Hearings - If requested,  public hearings are
held on both Federal navigation  projects and permit dredging
projects.  These hearings afford concerned agencies and individ-
uals additional opportunity to comment.

4.  Conclusions and Recommendations.  Based on an analysis and
evaluation of the investigation conducted on the proposed Federal
navigation projects,  I find that an interdisciplinary approach has
been used in the preparation of the  Final Composite Environmental
Statement and that all major environmental issues have been addres-
sed.  I find that where the proposed projects have adverse environ-
mental effects,  these effects are limited (based on available study
results),  or are substantially outweighed by other positive con-
siderations.  There are no adverse economic effects with regard
to these  projects.  On the contrary, there  are substantial positive
economic benefits to be gained by the Bay Area,  and a curtailment
of these maintenance projects could,  in fact,  have a major adverse
economic impact.

    Therefore, based on a thorough analysis,  and evaluation, I
recommend that the subject Federal navigation projects be main-
tained as authorized, with the understanding that land disposal will
be analyzed in  supplements.  I further recommend that the Final
Composite Environmental Statement be used to aid in assessing the
impacts  of future permit navigation projects.  I find this  recommenda
tion consistent with national policies, statutes,  and administration
directives.
                                     /si H. A.  Flertzheim
28 November 1975                  H. A.  FLERTZHEIM, JR.
                                    Colonel, CE
                                    District Engineer "
                             F-7

-------
F. 1. 1   Pneuma^ Dredge
The Pneumar^Dredge is a dredging and transport system which has been





developed by Pneuma International S. A. ,  an Italian firm.  The dredge





design uses compressed air for pumping and uses hydrostatic pressure





to remove  materials from the bottom.  The system has  been used in





most  standard dredging applications  and has achieved acceptance, partic-





ularly in stiuations involving the removal  of sediments from channels and





harbor areas.  It is claimed that very little sedimentation is  caused by





the cutting and removal actions of the system.  High  percentages (60 -





90%) of solids are also reported.











The system uses three cylinders grouped  together to form.a pump body.





Special valves for inlet and outlet are installed on each of the three





cylinders.   A distributor functions to automatically control the supply of





compressed air to each cylinder and the exhaust of compressed air from





the cylinder to the atmosphere.  When the pump body is  submerged,





water  fills the pump body after lifting the  inlet valve  in each cylinder due





to the  hydrostatic head. The water,  or  the  material  to be dredged, enters





the pump body through an inlet tube which extends below the  pump body





and to which may be attached various suitably shaped shovels.  When the





pump body has been filled,  the distributor supplies compressed air to
                                  F-l

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the pump body.  The inlet valve closes because the pressure inside the


pump body is now greater than the ambient hydrostatic pressure;  and


the air pressure acts as a piston, forcing the material inside the  pump


body out through a pipe  which extends to the lower portion of the pump


body.  When the cylinder has been almost emptied, the  distributor vents


the air in the cylinder to the atmosphere  and equalizes the cylinder


internal  pressure with atmospheric.   This naturally creates a pressure


differential between the inside  of the  cylinder and the hydrostatic  pres-


sure.  This pressure differential induces  the flow of sedimentary mate-


rials through the inlet tube, lifting the inlet valve and refilling the cylinder.


In order to maintain a continuous  flow rate, the distributor acts on the


three cylinders in turn,  repeating the cycle described above.





Since there is little mechanical disturbance of the bottom sediments  from
                       \\Ri
the action of the Pneuma Dredge, very little turbidity is produced.
This descriptive material was extracted from a "Test Report on Dredging


by S.I. R.S.I. Pneuma Pump System",  from the abstracts of "The Japan


Dredger Technical Society", Number 82, July 1972, by Y. Takamura,


S. Kasajima and C. Mukai,  all of the Port and Harbor Bureau,  City of


Osaka.
                                   F-9

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F.2    BLANKETING








Blanketing is a technique that has been used to control the turbidity





caused by the disturbance of sea-floor sediments.  In some underwater





work, the reduction to visibility which may persist for some hours after





disturbance is a serious hindrance to continued work by divers.  In order





to deal with this problem, local applications of plastic sheeting,  the pour-





ing of hydraulic mortar and the formation on an in-place plastic film have





been explored.  For one of the  purposes of  this study,  the evaluation of





possible remedial actions to reduce  or eliminate the impact of pollutants





upon the Harbor waters,  it appeared valuable to pursue the possibilities





of a formed-in-place plastic layer.  Successful placement of a plastic





layer couid offer two advantages:  (1) preventing the disturbance  of con-





taminated sediments  and  (2) isolation of the water  column from the in-place





contaminated sediments.











A description of a process  to form such a plastic film in place on the sea





bottom is contained in Technical Note N-1107,  "Chemical Overlays for





Seafloor Sediments", by T. Roe, J.  S. Williams and H. J. Migliore,





June, 1970, published by the Naval Civil Engineering Laboratory, Port





Hueneme,  California.  This Technical Note and United States  patent num-





ber 3,845,003, granted to Thorndyke Roe,  Jr., and assigned  to United
                                  F-10

-------
 States of America as represented by the Secretary of Navy, provide the





 basis for the information which follows.










 The Technical Note and the patent describe the use of the following two





 distinct film-forming chemical solutions, each of which precipitate when





 extruded  through a slit into sea water:








                                                       Parts by Weight







1 .     Polyvinyl butyral resin                               1.0





       2-(2-ethoxyethoxy)  ethanol                           28.4





       Citric acid                                          13.4





       Dibutyl Phthalate                                     7. 9





       Dimethyldicocoammonium chloride 75% active         0. 1







 2.    Polyvinyl butyral resin                               1.0





       2-(2-ethoxyethoxy)  ethanol                           24.6





       Chlorinated Paraffins                                12.0





       Dibutyl Phthalate                                     6.0





       Dimethyldicocoammonium chloride,  75% active        2. 1










 In practice,  these solutions have been found to provide a continuous flex-





 ible non-toxic plastic film capable of covering the ocean floor  sediment
                                    F-ll

-------
and preventing the sediment from becoming disturbed and  suspended in





the sea water.  Also,  these non-toxic plastic films were found to have a





strength sufficient to support light loads and a strength which increased





with deposit time.










Included in the solution is an antistatic agent to reduce the static electri-





city on the extruded plastic film.  This enhances the spreading of the





plastic film by allowing the film to spread in thinner sheets than would





otherwise be possible. The antistatic agent utilized in the present inven-




tion is Dimethyldicocoammonium  chloride, 75% active.










The other significant factor in the formulation is the use of a solvent which





itself is  miscible  and  preferably soluble in sea water.   Consequently, when





the solution initially is exposed to the sea water,  the solvent commences to




dissolve in the sea water permitting the resin  system to precipitate out in





a desired manner. The initial film formed by the  precipitation is suffi-





ciently cohesive to provide a continuous sheet  although the toughness or





strength of the sheet will not be achieved until the  solvent has completely




dissolved in the water.










In the  same period (1967-69) under contract to the Supervisor of Salvage,





U. S, Navy, Battelle Memorial Institute developed a two-component







                                    F-12

-------
overlay method in which sodium alginate containing titanium dioxide as





a weighing agent is insolubilized by treatment with dilute hydrochloric





acid.  The overlay formed instantly and had fair mechanical properties.





Its  surface was quite slippery; and when walked upon, it tended to extrude





or creep out from under one's feet and break up.  It had some resilience





and very low tensile strength.  If a large area is to be covered,  adjacent





layers of this material cannot be  bonded to  one another, but must be over-





lapped or cross-hatched.  Because of its requirement for two  components,





its  marginal mechanical properties and its  inability to bond to itself,  this





method is not recommended for future development.










Pilot-test costs for these overlays were on the order of $1.00 per square





foot (1970).










Experimental runs of fixed-slit dispensers  with candidate overlay solu-





tions were conducted in 25 feet of water off Santa Cruz  Island and in 50





feet of water off Anacapa Island.   These tests indicated that a  chemical





overlay dispensing system could not be entirely diver-operated.  Any





system which requires divers to swim above the  sediment with a dispenser





and attached hose was found to be  impractical because the dispenser and





hose are too cumbersome to be handled in this  manner.   For this reason,
                                   F -13

-------
two dispensing system prototypes were proposed: one to be used on a





Construction Assistance Vehicle (CAV), and a subsequent model to be





used on a deep-water submersible.











The CAV provides a load bed that can support a dispensing-system





prototype.  As the CAV cruises over an intended work site, the dis-





penser, suspended from the  stern, can apply chemical overlay solution





on the  sea floor.   Several parallel runs, overlapped at the edges, would





completely cover the site.  With the CAV in mind, the main features of





the chemical overlay dispensing  system include: (1) 600-gallon capacity;





(Z) at least 100 square feet per minute and 2000 square feet per hour





coverage; (3) storage container to be pressure-compensated; and (4) stip.





ulations to ensure convenience and efficiency in operator control.
                                  F-14

-------
F. 3   APPENDIX F - REFERENCES
      U. S. Army Corps of Engineers, Final Composite Environmental
      Statement, Maintenance Dredging, Existing Navigation Projects,
      San Francisco Bay Region California,  Volume 1,  December 1975.
      (Quoted in section F. 1)

APPENDIX A  - Main Ship Channel (San Francisco Bar)
      Study of the effects of dredging and disposal on the Bar outside of
      the Golden Gate and consideration of optimal procedures.

APPENDIX B  - Pollutant Distribution
      Not yet available.

APPENDIX C  - Water Column
      Observations in the  Bay of the effects of dredging and spoil place-
      ment, with special attention to oxygen demand,  suspended solids,
      mounding or dispersal of deposits and the factors affecting these
      characteristics.

APPENDIX D  - Biological Community
      Detailed survey of the distribution and abundance of infauna at
      11 stations in San Francisco Bay and analysis of the heavy metal
      content  of the biota and of some  environmental conditions.

APPENDIX E  - Material Release
      Not yet  available.

APPENDIX F  - Cyrstalline Matrix
      Sediments from nine sites -were  analyzed for physical,  chemical,
      and mineralogical parameters and the data were analyzed with
      reference to implications for dredge-related activities.  Many
      components  and conditions were  included.
APPENDIX G  -  Physical Impact
      Experimental evaluation of the effects of fine  sediments in suspen-
      sion and of cataclysmic deposition on estuarine macrofauna,  with
      interpretation in redredging activities. Experiments involved effect
      of sediments, temperature,, of depressed oxygen concentrations
                                   F-15

-------
      and of simultaneous variation of all three.  Includes the edible
      mussel,  young striped bass,  a perch, sand shrimp, and others.
      Good literature review.

APPENDIX H  -  Pollutant Uptake
      Report on field experiments in which resident and transplanted
      organisms were observed before,  during, and after near-by dredg-
      ing activity for heavy metal uptake and effects.

APPENDIX I    Pollutant  Availability
      Results of an experimental placement of polluted sediments and
      detailed observations on resident and transplanted benthic species.

APPENDIX J    Land Disposal
      Analysis of the economic,  technical,  and environmental aspects
      of land placement of  materials dredged from San Francisco Bay.

APPENDIX K  -  Marsh Development
      Report on experimental efforts to  create  suitable habitat for marsh
      development and encourage development of California cord grass,
      Spartina foliosa, and pickleweed,  Salicornia sp.  Methods, costs,
      and pollutants for  San Francisco Bay are presented.

APPENDIX L-  -  Dredging  Technology
      Field observations and tank simulation of release patterns of various
      types of sediment  were analyzed to assist in predicting the mounding
      or spreading and other attributes of the release pattern.

      Biological Impacts of Suspensions  of Dredged Material,  Richard
      Peddicord, U.  S.  Army Corps of Engineers,  Waterways Experiment
      Stations, Environmental Effects Laboratory,  Vicksburg, Mississippi,
      Paper presented at WODSON  VII,  World Dredging Conference,  San
      Francisco, California, July 10-12, 1976.

      Effects of Suspended  Solids on San Francisco  Bay Organisms,  R.
      Peddicord, V.  A.  McFarland,  D.  P.  Belfiori,  T.  E. Byrd,
      University of California, Bodega Marine Laboratory, Bodega Bay,
      California.  Paper presented at WODCON VII, World Dredging
      Conference, San Francisco, California, July  10-12, 1976.
                                   F-16

-------
Applications of Predictive Sediment Transport Models, by R.  B.
Krone, University of California, Davis,  California, and C. R.
Ariathurai, Nielson Engineering and Research, Inc.,  Mountain
View, California.

Containment Area Facility Concepts for Dredged Material Separation,
Drying and Handling, by C. W.  Mallory and M. A. Nawrocki of
Hittman Associates, Inc. , for the Dredged Material Research
Program of the Environmental Effects  Laboratory of the U. S. Army
Corps of Engineers  Waterways Experiment Station,  Vicksburg,
Mississippi.

Identification of Relevant Criteria and Survey of Potential  Appli-
cation Sites for Artificial Habitat Creation, Volume 1, Relevant
Criteria for March-Island Site Selection  and  Their Application,
by Coastal Zone Resources Corporation,  Wilmington,  North
Carolina, October 1975.

An Examination of some Physical and Biological Impacts of Dredging
in Estuaries,  Interdisciplinary Studies of the Schools of Engineering
and Oceanography,  Oregon State University,  Corvallis, Oregon
submitted to the Division of Environmental Systems and Resources
(RANN), National Science  Foundation,  Washington, D. C. ,  NSF RANN
GRANT Gl  34346, December, 1974.
                              F-17

-------
 APPENDIX G




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                                      G-4

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                                     G-8

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                                    G-12

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               APPENDIX H





ACKNOWLEDGEMENTS AND PARTICIPANTS

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H. 1
CONTRACT AND CONTRACTORS
This project was undertaken for the Environmental Protection Agency,

Toxic Substances Branch,  401 M Street,  WSM, Washington,  D. C. 20460,

under Contract No. WA 75   R263.



Contractor for the project was Trident Engineering Associates, Inc.,

48 Maryland Avenue, Annapolis, Maryland  21401,  in conjunction with

the Center for Environmental and Estuarine Studies, University of Mary-

land,  Horn Point,  Cambridge, Maryland 21613.
Participants in the project were:


                     Trident Engineering


      Mr.  Richard H.  Wagner

      Dr. John F. Hoffman

      Dr. Raymond P.  Morgan, Jr.,
      Chesapeake Biological Laboratory

      Ms.  Kristen K. Stout
                                Project Manager

                                Project Scientist

                                Trident Associate for
                                PCB Analysis

                                Biologist
                                  H-2

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                   Center for Environmental
                     and Estuarine Studies
      Dr. L. Eugene Cronin,
      Research Professor and
      Associate Director for Research

      Dr. Sheldon Sommer,
      Associate Professor, Geology,
      University of Maryland of College Park

      Dr. Chu-Fa Tsai,
      Research Professor

      Dr. Albert J.  Pyzik

      Ms. Ivis Ailin-Pyzik

      Ms. Justine Welch

      Mr. Blenny Chang

      Mr. John Schaeffer

      Mr. Mark Burke

      Mr. John Paul

      Mr. Jeffrey A. McKee

      Mr. Raymond Rossario

      Captain Martin O'Berry
      and Crew
Project Coordinator
Principal Investigation,
Geochemistry
Principal Investigation,
Bioassay

Geochemistry

Geochemistry

Faculty Research Assistant

Faculty Research Assistant

Biological Aide

Biological Aide

Geochemistry

Student Assistant

Student Assistant

Master, RV AQUARIUS
The firm WAPORA, Inc., 6900 Wisconsin Avenue, Washington, D.  C. ,

performed the  chemical analysis for all parameters of the sediment

samples, filtered water, interstitial water, and the elutriate analysis.
                                  H-3

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The firm Analytical Bio Chemistry Laboratories,  Inc.  (ABC), Columbia,





Missouri, performed the PCB analysis of the sediment samples.










The firm Micromeritics, Norcross,  Georgia, Performed the particle size





and surface area analysis of the sediment samples.
                                 H-4

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                                    TECHNICAL REPORT DATA
                             (Please read Instructions on the reverse before completing)
1. REPORT NO.
  EPA 440/5-77-015a
                                                            3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
  EVALUATION  OF THE PROBLEM  POSED BY IN-PLACE  POLLUTANTS
  IN BALTIMORE  HARBOR AND RECOMMENDATION OF  CORRECTIVE
  ACTION - Appendices
             5. REPORT DATE

             September 1977
            6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
                                                            8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
  Trident Engineering Associates,  Inc.
  48 Maryland Avenue
  Annapolis, Maryland  21401
                                                            10. PROGRAM ELEMENT NO.
               2  BH413
             11. CONTRACT/GRANT NO.
                                                               68-01-1965
12. SPONSORING AGENCY NAME A_ND ADDRESS
  Office of Water Planning and Standards
  U.  S.  Environmental  Protection Agency
  401  M  St.,  S.W.
  Washington, D.C.   20460
                                                            13. TYPE OF REPORT AND PERIOD COVERED
            14. SPONSORING AGENCY CODE
             EPA/700/01
15. SUPPLEMENTARY NOTES
  Prepared in cooperation  with the Center for Environmental and  Estuarine Studies,
  University of Maryland,  Horn Point,  Cambridge, Maryland
16. ABSTRACT
  This report and a companion report,  EPA 440/5-77-0155,  present  the  results of  a
  study of the in-place  pollutants in  Baltimore harbor  and their  effect on water
  quality.  This part  of the report contains the appendices.
                                KEY WORDS AND DOCUMENT ANALYSIS
                  DESCRIPTORS
                                               b.IDENTIFIERS/OPEN ENDED TERMS
                                                                             COS AT I Field/Group
  Environmental  Research
  Sediments
  Water Quality
  Bioassay
 Baltimore harbor
 Pollution
 Dredging
 13B
18. DISTRIBUTION STATEMEI

  RELEASE TO PUBLIC
9. SECURITY CLASS (ThisReport)
 UNCLASSIFIED
21. NO. OF PAGES
                                                :0. SECURITY CLASS (Thispage)

                                                 UNCLASSIFIED
                           22. PRICE
EPA Form 2220-1 (9-73)
                                                      * U.S. GOVERNMENT PRINTING OFFICE  1977 0-720-117/2033

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