STUDIES O F THE EFFECTS OF INDUSTRIAL POLLUTION IN THE LOWER PATAPSCO RIVER AREA"
1. The Curtis Bay Region, 1941

R. A. OLSON

H. F. BRUST
STATE OF MARYLAND DEPARTMENT OF RESEARCH A N D EDUCATION

WILLIS L. TRESSLER

Commissioners:
Lloyd M. Bertholf, Chairman...Westminste Julian D. Corrington.... Chestertown E. N. Cory.... College Pa Crisfiel John T. Handy.... B. H. Willier.... Baltimo

Director:

R. V. Truitt.... College Par
Chesapeake Biological Laboratory:
G. F. Beaven, M.A., Associate Biologist, Resident Manager Evelyn S. Beaven, M.A., Assistant, Librarian Esther E. Dodd, Secretary Ralph C. Hammer, B.S., Assistant Biologist, Hatcheries Harvey Mister, Captain, In Charge of Boats R. A.-?!s?n, Ph.D., Associate Biologist, In Charge of Hydrography a
Harry Stern, B.S., Assistant Chemist Willis L. Tressler, Ph.D., Planktologist R. V. Truitt, Ph.D., Biologist
Industrial effluents in the lower Patapsco area, which constitutes the navigable portion of the river and includes Baltimore Harbor, are many and include waste acid, distillery wastes, tannery wastes and copperas (ferrous sulphate) from pigment and steel industries. Preliminary studies have shown the last named waste to be most extensive. The red brown precipitate, Fe(OH), resulting from copperas disposal, is prevalent in Curtis Bay and can be seen in surface waters extending from Leading Point to the junction of Marley Creek and Furnace Branch, its 'extent and intensity depending upon variable conditions of tide and disposal. T h e source of the Fe(OH), is a paint pigment plant situated just inside the entrance of Curtis Bay opposite Sledds Point and from which it is discarded in the manufacture of titanium dioxide. On the north side of the Lower Patapsco area, originating in Humphreys Creek, copperas in pickling liquor from the steel industry produces a similar effect in Bear Creek and its tributaries (see frontispiece and Fig. 1). Also, on the north side of the area copperas is discharged by another plant which manufactures titanium pigment. It has be,en possible to conduct an intensive study of the effect of copperas and its decomposition products on the biological productivity of Curtis Bay and nearby waters through the cooperation o the f officials of the plants concerned and the data they have ~ r o v i d e d the on the effluents and the conditions of their disposal. exact nature This apes, polluted by copperas, is more extensive than other similarly polluted areas in the region and, moreover, its surrounding shore line has a contour that facilitates the study of suc'h a problem.
*This is the first of a series of reports on a comprehensive and continuing hydrographic and pollution study program for the Patapsco River (Baltimore) region of Maryland. Dr. Olson is a Laboratory staff member. Mr. Brust 1s associated with the Department of Chemistry at the University of Pennsylvania. Dr. Tressler is Assistant Professor of Zoology, University O Maryland, and Planktologist, Chesapeake Biological Laboratory. f

ACKNOWLEDGEMENTS

Acknowledgement is made to the following named persons who have made available data, tables, etc., which have been used in this report: Mr. J. H. Hawley, Acting Director, U. S. Coast and Geodetic Survey, Washington, D.C.; Mr. G. R. Cantwell, Plant Manager, Krebs Plant, E. I. duPont de Nemours and Co. and Mr. R. A. Kaiser, succeeding Plant Manager, Krebs Pigment Plant. Mr. F. M. Kip Harbor Engineer, City of Baltimore, and the Maryland Department of Tidewater Fisheries who supplled boats and crews on a number of occasions during the course of this work. Those in charge of the program are grateful for this cooperation. Thanks also are extende to Dr. R. A. Littleford, of Marquette University, who did much the early sampling and conducted a large numbei of toxicity expe ments, and to N. E. White, University of Pennsylvania, J. H. McLain, Johns Hopkins University, and F. W. McNall, Cornell University, who assisted in certain chemical determinations and sampling tions. Mr. L. A. Bruns, at the time a staff member of the Labor assisted in the construction of certain of the equipment used, did of the field sampling, carried out biological tests, and aided in che cal analysis of samples, for which thanks are offered. T h e success the program has been due, in a large measure, to the interest a support of Mr. L. A. Helfrich, Production Manager, U. S. Industri Chemical Corporation; Mr. Elmer Heubeck, Vice-president, D Chemical Corporation, and Mr. J. F. Daley, Production M Krebs Pigment Department of the E. I. duPont de Nemours Company. Acknowledgenlent is made to Dl. C. L. Ne formerly I n Charge of Research at the Laboratory, for early inter in this study. Dr. R. V. Truitt, Director, Chesapeake Biologi Laboratory, offered continued helpful suggestions and advic solution of the problenl and encouraged the work fully within t limits o his office. f
the frequent passage of conlnlercial craft stir up the bottom and produce atypical conditions. T h e ten stations shown in Figure 1 were used in all of the work reported herein. Approxinlate distances in miles, by water, from each to the source of copperas disposal are as

Statlon

o water as influ'enced by astronomical conditions only. However, in f the upper Chfesapeake Bay and tributaries the effect of astro'nomical influences o n tid'e are frequ,ently almost ~ b l i t e r a t ~ eby such meteorod logical conditions as wind and precipitation. This is shown in Figure 2 by th,e mark'ed difference bsetw'een the prediceed tide h'eights and th~e actual.tide heights, as measure,d by th'e automatic tide gage maintained by the Coast and Geodetic Surv,ey at Fort McH,enry. Even greater differmences.than those indicated are frtequent, th,e actual heights o tide f being entir,ely unpredictable. Records of the ti'de gage, operated continuously at Fort McH'enry, w.ere made availabl'e to this study, and from them it was possible to co'rrelate tidal height, therefme current variations with sampling data.

-- - - - PREDICTED

L TlDE

" 2 MAY

24 HOURS 1 5

FIGURE 2.

U. S. I.-U. S. Industrial Chemical Corporation. DAVISON PLT.-Davison Chemical Corporation.
instruments operated by a.large group of work'ers over a long pe of tim,e, their general trend and th'e time of their maxima can low and high water every day at nearby Fort XIcHenr~,Balt is predict,ed for each year by the Coast and Geodetic Survey. values ar~e predicted.from harmonic constants and represent the he
Copperas results at the Krebs pigment plant as a waste product in the manufacture of.titanium dioxide, a white paint pigment. T h e pigment is extracted from ilmenite, ferrmous titanate (FeTiO,), by using sulphuric acid to diss.01r.e out the iron, and the ferrous sulphate which occurs is discarded. Since copperas has not yet found any marketab1.e use, and is of little commcrcial value (Hodges, 1939) it i s dumped into Curtis Creek along with a small amount of titanium dioxide and a variable amount of unclaimed frese acid. T h e rat'e of disposal of copperas in Curtis Bay was increased during I940 to the point where the average sometimes exceeds 150 tons per
day. Records of rates of disposal supplied by the plant authorities were correlated in every case with the time of sampling, the effect of tide, and the results of analyses. A typical record of disposal rate i s shown in Table I.
TABLEI COPPERAS DISPOSAL Pounds Accumulated by Shifts*

150,870 163,710

X variable amount of free acid sometimes finds its way into Curtis Creek From the Davison Chemical plant situated o n Sledd's Point, and infrequently a discharge of oxygen-consuming distillery waste results fllom the U. S. Industrial Chemical plant near Cabin Branch. Since these effluents are not discharged daily their effects are atypical for the region and are thereby easily detected.

HYDROLYSIS OF FeSO,

28 131,610 121,980 154,080 186,180 112,350 121,980 131,200 182,970 173,340
-Disposal occurs twlce dally one hour after each flood tide.
plant to accumulate copperas throughout the day in large storage bins One hour after each predicted flood tide these bins were flushed ou and their contents discharged into the Bay. This practice was sugproducts of decomposition in Curtis Bay. During 1938-39 this practi was carried out only during the summer months in order to redu
OXIDATION OF FERROUS IRON TO FERRIC
large quantities of exposed copperas on the plant floor led to construction of permanent storage bins and the present regular prac of disposal on ebb tide, throughout the year.
of ferric hydroxide, a yellow brown insoluble precipitate which exists in the colloidal form and through subsequent "salting
FIGURE 3. DECOMPOSITION REACTIONS O F COPPERAS.
flocculation and settling of Fe(OH),. T h e ionic reactions, in c densed form, are represented in Figure 3.
Analysis for dissolved oxygen, salinity, pH, and in some cases total iron, were made on samples taken at the regular stations from Fort Carroll to the head of Malley Creek over a period of two years -during 1938 and 1939. Total iron in bottom muds was also determ-
ined. T h e results showed the degree to which copperas disposal affected the normal characteristics of nearby waters. Under the pre\ailing conditions of disposal the p H and dissolved oxygen anomalies were found to be largely local and effective to the limits of Curtis Bay proper, while total iron ran high as far as Leading Point. Laboratory experiments on the toxicity of coppeias decomposition products also were carried out, and in a number of cases the toxic nature of these substances in concentrations that occur in Curtis Bay was clearly determined. Recent increases in the rate of copperas disposal, however, has extended the limits of detrimental effects i n a degree and manner which wlll be pointed out in this report. Moreoler, a number of problems involving a more detailed study not considered previously are treated herein.

METHODS

Statiop? and Samptpling. T h e ten stations cstablishcd (Fig. 1) were sampled at surface and bottom depths at least once durlng each ten day period except when weather conditions o r other uncontrollable factors made this impossible. Since the depth ranges only from 4-10 meters sampling at intermediate depths was not considered necessary except in special cases. All samples were collected with the Foerst sampler. The analytic work for dissolved oxygen, total iron, soluble iron, insoluble iron, ferrous iron, chlorinity, and pH was done in the field in those cases uhere unstable compounds were involved. Biological determinations were made from 250cc samples preserved with formalin and centrifuged for micro-plankton counts while macroplankton was determined on a semi-quantitative basis by five minute surface tows with a No. 20 plankton net. Transparency was determined with the conventional Secchi disc in earlier work and whenever possible with the submarine spectroradiometer deleloped at the Laboratory. Temperature was measured with the usual reversing thermometers and with new rapld measuring thermoelectric equipment likewise developed during this work. Mud core samples were obtained at each statlon with the Woods Hole type core sampler, the core being cut into two inch vegments for subsequent analysis for total and ferClzemical Annlysis-Dissolved oxygen-Since the widely used Win

10/26/38 11/16/38 12/14/38 1/17/39 3/8/39 4/24/39 5/17/39 6/19/39 8/2/39
Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom

. 10.5..

10.7 10.8 10.9..

31.8 31.6 30.0 29.4 30.1

23.7 20.1 32.0 31.0 29.4 29.3 28.3 20.0 21.1
32.0 31.7 30.3 26.3 27.0 28.2 20.1 21.0 12.8 13.1 5.3 5.4 4.4 4.3 5.5 32.0 31.4 31.0 30.3

31.8 31.4 30.2 28.3

28.3 30.2 20.0 20.4 12.8 13.8 6.8 6.9 4.1 5.0 4.4 12.4

6.2 6.2 6.0 6.0

30.2 18.0 20.4 12.2 13.0 5.3 5.4 3.3 4.0 4.8 29.0 20.0 22.0 12.7 13.2

6.4 3.1 3.1

.. 6.0 5.0..

4.6 5.3 4.7

.. 12.2 12.8... 20.5... 21.2.

.. 30.3 28.2..

19.7 26.3 26.1

20.5 26.0 25.4 29.4 28.3

19.2 26.3 26.0

18.8 27.3 26.4 31.1 28.1

23.0 27.2 25.4 30.2 29.3
ranged from 2C. during January and F'ebruary to 29C. in July, but surface waters show a wider variation. During February ice covere,d the entire region with th'e ,exception of th'e ship channmels, which were kept open. Unfortunat,ely, no samp1,es could be obtainled at this time. Surface water during July frequently reached a temperature o'f 33C. and high,er. Th'e additional effect of ,this upper and warmer layer, thus low oxygen water, in retarding th'e oxygen saturation of the underlying waters is obvious. Chlorinity-Ther,e is but little difference in chlorinity with respect to station lo,cation, since th,e run off from the Marley Creek drainage ar,ea, itself small, is influenced mainly by local precipitation and is meager except during the spring thaw. Only a slight gradient exists iEroniStation I to Station X, comprising less than one part per thousand chloride ion. Typical seasonal changes are indicated in Table 1. 0 these values ranged from 2.0/00 in March to 8.0/os in
Seasonal changes in temperature at each depth and at all stati
T h e chlorinity stratification with depth is marked only at the deeper stations located in isolated areas where a minimum of turbulence and mixing occurs. Such is the case at Stations 111, IV, and VI, where a difference of more than l.OO/oooften occurs between surface and bo'ttom. O'th'er stations, except in rare cases, show a surfacebottom difference of less than 0.3O/00. Chlorinity, as a regional factor affecting the intensity and ext,ent of p o l l ~ t i ~ o n effects, cannot be considered as important in view of the slight differences experienced. As a seas'onal factor it influences the rate of Fe(OH), flocculation by "salting o'ut" the colloidal particles. As an indicator 0.f salinity, chlorinity shows the tr'en'd of the buff'ering action o'f th'e waters and, hence, their capacity to tolerat'e the contribution of add,ed H ions. Perhaps the most significant indication from chlorinity determinati'ons is that of the relative mixing and vertical movements of water at different depths. There are two or three instanc'es wher'e, in deep places, pro-

average water temperature for each set of measurelnents and the saturation value for that temperature is also given.
TABLE IV Dissolved Oxvgen At Each Station in ec. Per Liter -- -
Date 1/20/38 3/22/38 5/6/38 7/15/38 9/15/38 11/16/38 1/17/39 3/8/39 6/19/39 7/10/39
A v e r. 0,Sat. Temp. 7.1 11.0 19.9 31.5 28.6 13.0 4.4.4.6 26.2 30.1 8.48 7.32 6.00 4.95 5.20 1.08 8.55 8.51 5.43 5.05
Depth Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Bottom Surface Rottom Surface Bottom Surface Bottom Surface Bottom

4.82 3.21 3.37 1.81

VII VIII
1.04. 6.93. 6.62. 6:72 4.85 5.91.. 6.27.. 5.87 5.: 3 4.35 4.12 4.42 4.20 6.01. 5.46 4.93 4.87 6.40. 5.43. 7.03. 7.10 4.95 5.90 8.01 S.06 7. M 4.55 4.91. 0.00. 3.96

620 6.13

6.49 5.74 5.82 5.69 4.53 2.55 5.20 4.55 5.18 4.26 6.18 6.11
7.44 4.02 0.33.. 5.33. 1.97
5.84 2.07 5.99 2.71. 5.73 3.47 5.91 3.59 4.20 0.14 1.80 5.:4 4.11. 6.18. 2.35 5.96 4.61 2.01. 6.61 5.81 6.09. 3.12.. 3.62. 4.97. 1.85
. 6. 6.49 1.28. 1.97 3.47 5.63. 2.71 4.00 5.66 5.77 5.84 5.41 1.51.. 1.45 1.16 5.11 5.71 5.50 1.21 3.31 5.04 0.42. 3.56 6.63 6.10. 2.72. 3.46. 4.81 5.24 5.17. 3.12 4.10 4.20. 6.21 6.61 7.41 4.56 0.00 2.31 4.41

7.56 6.60 2.18 6.11 2.63

6.18'. 3.62.. 0.76.. 6.44. 1.26

6.18 4.25 1.16 6.85 6.72

tions, or by th,e vertical mixing that normally accompanies temperatu changes in the annual turnover, th'e water in such areas b'ecomes dilute

TABLE I11

It can be seen that harmful low values occur in Curtis Cre'ek very frequently thro,ughout the year, whil'e during th,e summer months wh'en the water temperatures are above 25C. low values often occur over tm entire region. he Th,e lower values have been more intense and more frequent as the disposal rate of copperas has increasmed during 1939-1940 and during the summ'er months of 1940 (Table V) extremely low values wer'e observed at Station I. Wh,eth,er th,ese ,effects are to be found beyond this station as yet have not been determined. I t is obvious, however, that at these high'er water temperatures (25-3O0),when even fully air-

Station VII

3.0 4.3 4.2 3.9 4.2 3.9 6.0 3.3 6.6 6.2
6.7 6,4 6.7 6.7 6.6 6.4 6.7 6.3 9.1 3.6 3.8

Station VIII

6.2 6.0 5.6 5.4 5.9 5.8 6.0 6.0 8.7 4.3 4.2

Plant Pier

4.2 5.7 3.9 4.0 4.0 4.0 5.9 5.0 5.0 5.1
3.5 4.6 5.0 4.1 3.5 2.7 3.1 2.8
he T h e d'etrimental effect of copperas disposal in t m summer months at the incraeas'ed rate prevailing during 1940 (300,000 lbs. per day) is, ther'efore, recognizable.
TABLE VII pH of Samples Taken Before and During Shutdown

- - --

Date Before Shutdown
7/7/38 7/8/38 7/9/38 7/10/38 7/11/38 7/12/38 7/13/38 7/14/38

pier-E End

3.2 3.3 3.0

Pier Center

3.3 3.1 3.2

pier-w End

3.2 3.0 3.2

pier-w Center

3.2 3.2 3.1
Stat.ion VII Station VIII 1 s t Bridge 2 n d Bridge

6.7 6.5

3.4 3.3 3.7 3.4 4.7 4.7 6.5 6.7 6.5 6.7 6.8 6.8 6.8
3.2 3.7 3.4 3.4 3.7 3.7 6.7
3.0 3.4 3.2 3.2 3.7 3.7 6.4
3.1 3.7 3.2 3.3 3.7 3.7 6.8
6.7 6.7 6.8 6.6 6.8 6.6 6.6

During Shutdown

7/16/38 7/16/38 7/17/38 7/18/38 ~/19/38 1/20/3S 7/21/38 7/22/38 7/23/38 7/24/38 7/25/38 7/26/38 7/27/38 7/28/38 7/29/38
6.4 6.3 6.4 6.7 6.8 6.8 7.0 6.8 6.6 6.0 6.0

7.0 6.8 6.4 6.8

6.8 5.6 6.4 6.8 6.8 6.8 7.0 7.0 6.8 6.4 6.7
6.4 6.4 6.6 6.7 6.8 6.8 7.2 7.0 6.8 6.4 6.5
6.9 6.5 6.8 6.7 6.9 6.8 6.8 7.0 6.8 6.5 4.5 6.3
pH-Values of p H low enough to inhibit the growth and activity of aquatic life (pH 4.5 and lower) occur locally in Curtis Creek almost 16
*.*; 8 g gX g g oe~* ; 1 z g ; ; 2. -23 &szo: 0 0""Nz ZG r

65 F f $rn

g2 ' 2

' q x"%" ,-sN

that under the conditions existing in Curtis Bay the oxidation Fe++ to Fe+++ does not occur immediately after disposal, but prrsists for some time during which oxygen is continually being removed from the water. T h e fact that ferrous iron is not detected beyond Station 1 may be due to the low sensitivity of the method under field conditions. Nevertheless, results show that oxidation of ferrous iron is nearly complete by the time contaminated waters reach Leading Point and that surface waters become oxidized almost immediately after disposal. Figures for a number of typical conditions are given in Table V and Tabl'e VT.

O m i "N - -

"2%:

:"

: ' " "

i a, 0 A i

P"

"'

I - > l i +

i : : :

".- I

"

g g ~a.

* "

go E :'

"2

"-

N % O ;

Total Iron-Total iron values in waters serve only to trace th,e path of movement and the dilution of pollut'ed waters, and account for all of the iron containing decomposition products of copperas including those that are insoluble. T h e stage of oxidation and the degree of prmecipitation, however, can be determined only by cornparison o f ferrous iron and soluble and insoluble iron. During 1940 total iron values ranged from less than.5 p.p.m., at Station I, to around 25 p.p.m. at those stations near the source of disposal. Typical va1u.e~ given are in Tables VITI, TX, and X, as well as in Figures 4 and 5.
F u r t h e r Results Involving t h e Interaction of Factors-Soluble iron accounts for thos,e decomposition products of copperas that have not yet precipitated out as Fe(OH), in the precipitate or flocculate form. Through comparison of thes'e two valu'es the stage of brseakdown of copperas can be d,etermined. Typical results are shown in Tablmes 111, VTIT and TX. I n Figures 4 and 5 the results of analysis for oxygen, pH, total iron, soluble iron, and insoluble iron are represented in graphic form for two different sampling trips. Transpar,ency determinations were made with the Secchi disc and are, therefore, not absolut,e. They serve to show relative differ,ences in the transparency of the surface layers in order that this may be correlated with the density of flocculent material or insolubl7e iron. This correlation is indicated in Figure 4 and again in Figure 5. I n practically all cases the transparency is a reciprocal function of insolub1.e iron. Slight discrepancies may be caused by titanium oxide in thre vicinity of the plant piers as well as by fertilizer products, refuse, oil, arid other harbor wastes that find their way into the waters of the region, there to alter transparency but to affect other physical or chemical properti'es very slightly. Soluble iron runs high at or near the disposal source and in those more isolated 19

,754 2.530.427.634 1.598 3.690 1.139 4.2.796 1.004 1.201 1.602 1.975 12.3.279 5.025 ,445 2.757

92 S O 110

242,200 103,800

69,200

2,388,000 415,200 1,868,000 1,212,000 2,147,000 242,200 3,290,000* 830,000 7,000,000 2,006,000 1,590,000 3,530,000 69,200 3,810,000 1,970,000 3,220,000 3,560,000

34,600 34,600

1,487,800 449,800 2,076,000 485,000 1,088,000 346,000 1,696,002

1.8 1.8 1.9 1.9 1.9 2.0

I1 I11 IW IV V VI VII VIII

.". *

6.21 5.95 7.1 6.35 6.25 6.63 6.28 6.07 5.87
69,200 69,200 69,200 34,600 34,613; 34,60!*

34,60!

. *.*.
311,400 69,200 207,600 207,600 34,60!
934,000 1,970,000 900,000 623,000
12:10 P.M. 12:30P.M. 1:30 P.M 1:50 P.M. 2:15P.M. 2:35 P.M.
2,076,000 103,800 lj87O,0O@ 761,000 3,220,000 1,800,000

2.1 2.0 1.9 1.9

5.51 5.18

47.4 149.1 71:s

&,'I0 105

346,000 1,140,000

34,600

..*. '

*None observed in twenty counts.
complete dissipation of the pollutant and upon the predominating direction and rate of flow of tidal currents. Since disposal during this period was cariied out so that the whole copperas accumulation (75,000 lbs., or more) was discharged into the Bay over a period of 15-30 minutes the area of immediate contamination was restricted to a limited region or mass of water which was, during its subseqmnt decomposition and dissipation, subject to movement by the variable currents. Knowledge of the exact changes due to oxldation, dilution and other factors that occur during this time, and the rate at which they occur, was deemed necessary in the interpretation of sampling data and in predicting the intensity of effects under various conditions of disposal. For this purpose a number of experiment? on the rate of copperas decomposition at different dilutions was carried out uildeicontrolled conditions in the laboratory. With high concentrations all the oxygen in the small experimental tanks employed in the study was used u p almost immediately and remained at zero concentration for several days. Stirring and aeration shortened this time to a matter of hours, but since the exact deglee of mixing and dilution occu~ring in the field cannot be determined the results of these experiments %.ere not applicable. T h e same is true for rates of hydrolysis and flocculation. However, these experiments served to show that the loxv pH values in Curtis Ray cannot be caused by copperas hydrolysis alone and that oxygen demand of those concentrations existing near- the disposal source is high enough to deplete the waters completely of oxygen. Thus, it was necessary to find some olther means to determine the time sequence and reaction rates in the field. During regular sampling in the Curtis Bay region it has been observed often that sharp lines of demarcation persist between turbid contaminated waters and adjacent unpolluted waters. T h e same has been found in pH, ferrous iron and oxygen determinations. A sample taken o n one side of the boat often differed tremendously from a similar sample taken simultaneously o n the other side of the boat, and if the boat was held over the same mass of water the results were reproducible. From this it appears that the characteristic lack of mixing due to the slow movement of the waters in the area makes for the persistence of distinct horizontally homogeneous bodies of water which are moved as such by the slow tidal currents. If these masses can be followed accurately and sampled periodically the desired information concerning reaction rates may be obtained. Accordingly, a number of submerged-type spar buoys were devised using fourteen foot two- by-

r timbers with suspended weights just heavy enough to allow
uppei fourteen foot layer. On August 20, 1940, three of these le X and Figure 6. T h e first buoy ($1) was released as a trial,
oy moved slowly in the direction of the ebbing tide. T h e immediate xidation o n the dischaige of coppeias was shown by complete absence f oxygen at fourteen feet at position C. T h e value of total iron and
White bars represent p ~.
FIGURE 6. REPRESENTATION OF RESULTS OF BUOY STUDY, AUGUST 20, 1940. and White bus represent total iron, the black portion insoluble iron+ and the white portion soluble iron.
Cros'-hatched bars represent dissolved oxygen in ce.,liter, bars represent trnllsparency in decimeters.
able quantity of Fe(OH), had begun. pH, however, had decieased but little at the surface and practically none on the bottom. It appears that undei field conditions hydrolysis is favoiable in the uppei strata unless, of course, some waste acid was simultaneously disposed of. One houi and fifteen minutes late1 at position B, 150 feet further northeast, a somewhat different situation resulted than was expected. T h e total iron had decreased as had the soluble and insoluble iron and the oxygen had more nearly approached the pre-disposal value. This suggested that the highly contaminated waters at position A had settled due to their greater density and had fallen below the lower level of sampling, but the rapid restoration of the oxygen at the 14 foot level was hard to account foi in such slow moving waters. T h e same conclusion could be drawn to account for the still lower value of total, soluble and insoluble iron at position C, 200 feet from ~ o s i t i o n 4 in the same direction, but the increase in soluble iron at 14 feet would, in light of these observations, be difficult to explain. It is mole likely that theie had been some difference in the movements of the water at the two sampling levels and that the buoy had moved with a direction and late which was the resultant of the two components of force. T h e unexpected results at position B of buoy $3 also bear this

out. I n Curtis Bay, water movements are known to be irregular and the possibility of opposing currents at different levels is greater than in the somewhat less restricted waters in the direction of Fort Camoll. Moreover, the t o m of the tide is known to affect bottom and surface currents at a different rate in all bodies of water. It appears that buoys 2 and 3 were moved to positions B further into the disposal mass by stronger surface currents and were retarded by weaker surface currents to a position C lagging behind the now deeper lying and diluted mass. These results do not provide all of the expected information, but they do show the trend of movement of the disposal masses and

SAMPLES

rs being only GOO feet and the shortest distance only 200 feet. T h e Aiculty in following the movements of disposal products is thus
SEGMENTS 0 - 2 INCHES 2 - 4 INCHES

INCHES

6 - 8 INCHES
T h e results of core sampl'e analysis show the degree of ferric droxide accum~~lation the bottom. T h e samples taken during on overnber, 1939, show in Figure 7 the depth of their accumulation at h station during that period. I n the right hand ordinates the values e represented as the per cent weight of apparent ferric hydroxide, the amount of ferric hydroxid'e that would be present if all the tal iron present were in the forin of ferric hydroxide. This, of course, not the case, there being from 2-4y0 iron in normal river muds in region. Nevertheless, comparison of these relative valu,es should e a fairly good indication of accumulation at different levels and at different locations with an error of not much more than 4% weight. It will be seen that total iron values as high as occur at Stati'on I, at a depth of four inches, and decrease to 4% at eight inches. Maxima occur at Station I and Station VSII with values exceeding 3570 for total iron corresponding to over 70% ferric hydroxide. Similar core samples collected during August, 1940, (Fig. 8) show a marked

STATION

FIGURE 7. Results of core sanlple analyscs for November, 1939. Each b a r represents a two-inch segment, the surface segment being represented in each case by the b a r t o the left.
relative rates of the initial reactions. T h e most significant information derived from them is the unexpected slow rate of tidal movement in this small region, the greatest distance covered in two and one-half

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