eS

TOTAL DRY WEIGHT, mg/m?

100

T |
(ole)
SEAWEED O
Po
10 -— a ° >
ia (ome)
a ° fe)
o x °
x x
a XxX Oo an
a
x
x x?
a x *
fe)
10-1;,— 4
oO © OVER OUTFALLS
Qo % AWAY FROM QUTFALLS
10-2 CONTROL AREAS
_ | | | | |
107" 103 1072 To-1 1 10 Too
HEXANE EXTRACTABLES, mg/m2
Figure 23. Comparison of Total Dry Weight With HEM


Rise of Large Particulates in the Vicinity of the L Diffuser

Figure.18.

July, 1973

of the JWPCP Outfalls:

éL

“eco ‘Aine

3S82P[NILQUeq BHue7] JO uolqzisodwoy) pLoy Az3e4 “GL aunBLy

(r)

(€)

(2)

(1)

- ; tr777, LA
ond bya a oan |
y
YW "| Og y VA j Z
Wi Yee VA y r
Y Y / y,

—IVA A Zt

eauy
[ouquo9

MN UO PL
dodMe

SLLEJINO
ABAD

quan{j33
paureays

0s

00L

NOILISOdWOD INIDUSd

119


dt

DEPTH, m

TEMPERATURE, ©

Cc

TEMPERATURE, °C

1 12 ~«213:«14«21S Sidi 1106120«213:s«s14sid5 sGC‘?'”Ssé=«‘dK'Ci*COTSD
oT TT TT TT TSI
To LL [_
20 =
30 | =
40 =
50 L—
CONTROL AREA
Station 4 (11 July 1973-o—Bottom at 54 m
Station 3b (13 1975) —o- Bottom at 80 m Station 5 (12 July 1973+e-Bottom at 63 m
OL | |i tt tt {| | | | | | 4

Figure 6. Temperature Profiles Observed at Sampling Stations: July 1973


RESEARCH REPORTING SERIES

Research reports of the Office of Research and
Monitoring, Environmental Protection Agency, have
been grouped into five series. These five broad
categories were established to facilitate further
development and application of environmental
technology. Elimination of traditional grouping
was consciously planned to foster technology
transfer and a maximum interface in related
fields. The five series are:

1. Environmental Health Effects Research
2. Environmental Protection Technology
3. Ecological Research

4. Environmental Monitoring

5. Socioeconomic Environmental Studies

This report has been assigned to the ECOLOGICAL
RESEARCH series. This series describes research
on the effects of pollution on humans, plant and
animal species, and materials. Problems are
assessed for their long- and short-term
influences. Investigations include formaticn,
transport, and pathway studies to determine the
fate of pollutants and their effects. This work
provides the technical basis for setting standards
to minimize undesirable changes in Living
organisms in the aquatic, terrestrial and
atmospheric environments.

EPA REVIEW NOTICE

This report has been reviewed by the Office of Research and
Development, EPA, and approved for publication. Approval
does not signify that the contents necessarily reflect the
views and policies of the Environmental Protection Agency,
nor does mention of trade names or commercial products
constitute endorsement or recommendation for use.


the flask vere then added approximately 12 mg of K2CO3 (powdered and dried at
103°C) followed by 10 me of acetone( flano Grade®) and 0.1 mg of 5 percent
a-bromo-2,3,4,5,6-pentafluorotoluene (BFT) dissolved in absolute ethanol.
The flask was then connected to a condenser, the ground glass fitting wetted
with acetone, and the open end of the condenser covered with aluminum foil.
The mixture was refluxed for one hour and cooled in a 20°C water bath for
approximately 10 minutes before disconnecting the flask from the condenser.
(Note: Any water present in the sample grossly inhibits this reaction.)
The acetone was removed on the rotary evaporator as before and the reacted
sample was then quantitatively transferred with hexane to a 10 m2 volumetric
flask.

Chromatography

One micro-liter samples were then injected into two gas chromatographs.
Model 1200 Varian Aerographs were employed in the study, both equipped with
concentric tube electron capture detectors ( H; 250 mCi). Two different
analytical GLC columns were used, one in each chromatograph. The columns
were 1/8 inch by 6 ft Pyrex® glass packed with 2.5 percent QF-1 on Varaport
30 (80/100 mesh) and 5 percent QF-1 plus 3 percent DC 200 on Chromosorb Q
(80/100 mesh). The use of both columns permitted resolution of the fatty
acids into saturated and unsaturated components and provided presumptive evi-
dence for identification of compounds by comparison of retention times with
standards. The carrier gas (purified No) was maintained at approximately
50 m2 min; and the injector, column, and foil temperatures were 230°C,

190°C, and 200°C, respectively, in both chromatographs.

CHLORINATED HYDROCARBON ANALYSES

The cleanup of hexane extracts for chlorinated hydrocarbon analysis was
conducted with liquid chromatography in Florisil as described by Reynolds
[18] and Veigh [19]. The media was purchased from Varian Aerograph in the
purified and activated (at 650°C) form and kept at 730°C prior to use. The
column was 25 mm o.d. with a narrow discharge neck at the bottom fitted
with hexane extracted glass wool and a 250 mz solvent reservoir at the top.

113


Table 11. MASS EMISSION RATES OF PARTICULATE HEM FROM
TREATMENT PLANTS

Plant Day kg of HEM/day
Hyperion IV-7-71 190
Hyperion VIII-31-71 390
JWPCP VII-11-73 880

where Q), is the effluent flow rate, Cy the concentration of HEM in the
effluent, c the concentration of HEM on the ocean surface, U the surface
current, and b the width of the diffuser projected normal to the direction
of U. The product Wey is the plant emission rate given in Table 11.

The main problem with this approach is determing U. Surface drogues were
used to measure the drift over the outfalls (see Figures 7 to 15) but those
drogues were set to a 2m depth, and experiences of the tracer survey of
December 9, 1971 (Figure 11) showed that such drogues did not move with
pellets placed on the ocean surface. Even so, for want of better data, the
drifts measured by the drogues were used to compute U. These estimates
together with computed and observed concentrations of HEM are shown in
Table 12.

Considering all the assumptions which had to be made, the agreement between
computed and observed concentrations of HEM over the outfalls was good, and
the differences were in the right direction (the observed being less than the
computed). Some difficulty was encountered in computing the concentration
over the JWPCP outfalls in 1973 because the current measured by the drogue
was remarkably low (0.11 m/s) which in turn gave a remarkably high computed
concentration (114 mg/m2). Obviously if the current was this small, other
factors such as plume spread would increase the dispersion and reduce the
concentration from that obtained with the continuity equation.

The results of these analyses indicated that most of the particulates screened

from the effluents reached the ocean surface. Their residence time on the
ocean surface may have been remarkably short, a matter of a day or so, Their

62


el

a

| T | ]
80 4
50 11
40 |}— fo) /
30 ;— OVER HYPERION OUTFALL 7% wo —

SIZE,»

T
Ne
x

\

|

/
aL oY” oa CONTROL AREA

a Avi is

1 2 5 10 20 30 4050 60 70 80 90 95 98 99
PERCENT EQUAL TO OR LESS THAN

Figure 27. Cumulative Frequency Distribution of Clumps of Debris Collected By The Nylon Netting:
August-September, 1971.


III. INTRODUCTION

The general objective of the first year of this study was to develop sampling
and analytical techniques suitable for the evaluation of flotage at the sur-
face of marine waters. Only a minimum of ocean work was to be carried out,
primarily to determine the feasibility of the techniques developed and to
obtain data for an initial assessment of the surface pollution problem.
Emphasis was placed on the following items:
1. The development and evaluation of sampling and analytical techniques
for surface films.
2. The development and evaluation of sampling and analytical techniques
for floating particulates.
3. The development and evaluation of sampling and analytical techniques
for other components of the flotage.
4. Evaluation of ocean data obtained in order to provide an initial
assessment of the surface pollution problem.

The second year of the study was to be devoted primarily to ocean studies,
the specific objectives of which were:

1. The measurement of flotage found in the vicinity of a marine outfall
and comparison with that from a region free of water surface
pollution.

2. Investigation of the mechanisms responsible for the concentration
and movement of flotage on the sea surface during the periods of
sampling.

The study objectives were also to include suggestions for the establishment
of water surface quality requirements to be used for control of ocean surface
and beach pollution.

The terms of the award made by the Environmental Protection Agency to The
Regents of the University of California included the following conditions:
1. Both screen and trawled particulates will be characterized.


3. The concentration of floating particulates of waste origin on the water
surface shall not exceed 1.0 mg dry weight/m? more than 50 percent of the
time, nor 1.5 mg dry weight/m? more than 10 percent of the time. (The
samples shal] be taken in areas of maximum probable impact.)

In this study the dry weight of the sewage types generally was not determined
separately from that of the natural types. Over the outfalls the HEM repre-
sented about 50 percent of the total dry weight when pieces of seaweed, tar,
etc. were not prevalent (see Figure 23). The requirement therefore implies
limits on HEM about half those stated for dry weight, or about half the
level recommended herein for HEM.

If the experiences of this study are valid, the above requirement would be
difficult and expensive to enforce with primary effluents because dry weight
is not the appropriate analysis for grease and wax particulates, yet they
were found to be the predominant sewage type in all of the traw] samples taken
during the study. The requirement could be used to control the emission of
non-extractable sewage types (plastic, rubber, etc.) but no reasonable
criterion can be suggested based on the results of this study because the
non-extractable sewage types were encountered relatively infrequently.
Obviously the requirement should be rewritten in terms of HEM, not dry
weight. Stipulations on dry weight should specify the types of non-extractables
to be weighed; making it possible to pick such objects out of the sample and
to clean and weigh them without the services of an expert or the expenditure
of a great amount of effort.

68


v2

Nautical Mile 118°30!

Wind swt k
330
Stati on/

Slicks 5 sec
0700 Wind E0.5k — onbgue pri ft
0.34 k
Sludge Outfa1l 5 pug. ST, 1971
Slick
4 ( 7 stick
ie £

JL ges

—T7 Drogue Drift

0.38 k
Sept. 1, 1971
Wind E 3k

Station
1 />« Swel] NW 2

Figure 9.

lft, 4 sec

Surface Conditions in Hyperion Outfall Region: August 31 and September 1, 1971



Tables 21 and 22 show that the stearic acid proportion of the HEM decreased
from 2.0% in the effluent pan samples to 0.33% in the control area. Assuming
that the stearic acid proportion would have been 2.0% over the JWPCP outfalls
if all of the HEM had been derived from wastewater micro-particulates, the
following ratios of wastewater HEM to total HEM are observed.

Table 24, ESTIMATED CONCENTRATION OF HEM OF WASTEWATER ORIGINS
IN CLOTH SCREEN SAMPLES

Proportion of HEM (ug/m?)
. wastewater Wastewater
Location origin origins Background
Over JWPCP outfalls 0.75 690 230
14 km NW of JWPCP 0.22 90 320
Control area 0.16 34 177

Using this information and the computational methods shown in Figure 26, the
mass of HEM in the study area was estimated to be 312 kg, or about the same
order of magnitude as the HEM derived from the trawled particulates.

The surface materials collected by the cloth samplers proved of pollutional
significance in terms of the PCB compounds and coliform bacteria as well as
the above. All of the remarks made in Section V concerning the coliform
bacteria found in the trawled particulates apply here as well, only more so,
because the particulates carrying the bacteria were much smaller (100 y» or
less in size) and generally more dispersed on the ocean surface.

CONTROL OF SURFACE POLLUTION

The requirements of the California State Water Quality Control Plan for Ocean
Waters of California [7] specify that the concentration of hexane extractables
on the water surface shall not exceed 10 mg/m2 more than 50% of the time, nor
20 mg/m2 more than 10% of the time. The methods of sampling and analysis
were not specified. It was decided in Section V of this report that this
requirement was much too liberal to control adequately trawled grease and

97


le

118°30' W
WIND WEST AT
5K
35°30' N
SWELL NW 100
1.5 ft 4 sec oa 50

SLICKSSx_S
at 0830. Sf

SANTA

CATALINA

‘

ISLAND

Nautical Miles
T

50
100 fathoms hoa

Figure 14. Surface Conditions in Control Area: July 13, 1973


The overall geometric mean value for those areas was 12,000 organisms/mg of
HEM. The coliform bacteria were not derived from the ocean bulk water
because water samples taken 10 cm underneath the ocean surface never indicated

the presence of any of those bacteria.

HEM Concentrations on the Ocean Surface

The average concentration of HEM varied grossly from station to station as
shown below.

Table 9. MEAN CONCENTRATIONS OF val IN TRAWLED PARTICULATES
(ug/m2

Location April, 1971 | Aug.-Sept., 1971 | July, 1973
Hyperion 10,800 2,000
JWPCP 2,200 15,000
3.7 km N of

Hyperion 340 130
14 km NW of

JWPCP 36
Control (3a) 25
Control (3b) 1.2 2.1

These data ae much too few to estimate accurately the total mass of HEM of
wastewater origin present on the ocean surface at any given time. Still,
it is believed that even a crude estimate is better than none at all,

so a concentration distribution of HEM was assumed and the total mass of

HEM computed as shown in Figure 26.

The concentration distribution shown in that figure was estimated by sub-
tracting an assumed background concentration of HEM of 5 ug/m2 from the
average values presented in Table 9. (The HEM data of Aug.-September, 1971
were not used because of the unfavorable winds existing at the time of
sampling.) The zones of highest concentration about the outfalls were
arbitrarily assumed to be about 3.5 km in diameter but they could have been
much more, or much less extensive than that.

58


Le

Nautical Mile

5 1

Manhattan
Beach

," Fathoms|

co
oO
n
&
“e* Hermosa
s Beach
s AY eed Slick
2 -
%y,
K/\ 2 * °
%
2 Swell Redondo
e, W1.5 fp 4 sec d Beach
%
mn i O 33°50!
2 NU ae
©}. ~\ se >
° ——-- nn
» 1971

Figure 11.

Transport of Flotage Study: December 9


2. The sampling method was improved in 1973 by pumping a portion of
the JWPCP effluent through a screen identical to that used in the surface
trawl. The screen approach velocity was 0.8 m/s, the same as used in sur-
face trawling. A maximum of 18 2 of the JWPCP effluent could be passed
through the screen before serious clogging occurred. The material collected
was then extracted with hexane in a soxhlet apparatus. The average HEM
concentration of 5 such samples collected through the day on July 13, 1973
is presented in Table 6.

This method could have been improved further by resuspending the captured
particulates in clean sea water and separating again in a funnel of the
type used in 1971 before extracting with hexane. In this way only those
particulates which float in sea water would have been extracted. It is

believed that such an improvement would not have altered the results
grossly.

The emission rates of HEM from the treatment plants were estimated by
multiplying the effluent concentrations of HEM by the plant flows existing
at the time of the ocean surveys (Table 2). The results, shown in Table 11,
indicate that a metric ton or so of HEM was being released daily to the
study area. Comparing this with the mass found on the ocean surface

(840 kg) indicates that either the residence time of the particulates on

the ocean surface was very short (order of a very few days), or the HEM
found in the effluents did not attain the surface. Other alternatives

might be a rapid decay in the particulates, which seems highly unlikely
because the grease and wax particulates were large and they obviously had
persisted for some period of time when stuck to kelp; erosion into smaller
particulates missed by the trawl screen; or concentrating in regions not
sampled in this study.

To determine if all of the HEM sampled in the plant effluents actually attained
the ocean surface a local mass balance was made about the outfalls using the

steady state continuity equation jn the form
Qcy = ¢ Ub

61


wax particulates of sewage origins, and that it probably was intended to
control concentrations of surface film materials.

Table 15 shows that only one cloth sample out of the many taken had a HEM
concentration in excess of 10 mg/m?, and even a primary effluent diluted

17 times with sea water produced a surface concentration of only 1.49 mg/m?
after an hour of agitation (Table 21). An HEM concentration of 10 mg/m? can
be encountered only with: 1) a chance encounter with a large grease and
wax particulate, or 2) a duplex film. It represents very gross surface
pollution indeed.

The HEM analysis, as performed in this study, proved not to be a sensitive
measure of the pollution collected by the glass cloth screens. Coliform
bacteria and massive concentrations of PCB compounds were found over the
outfalls at HEM concentrations ranging from 0.9 to 3.9 mg/m? on the average,
and a similar range in HEM concentration was observed in the control areas
(0.16 to 2.0 mg/m2). Also, the HEM concentrations tended to vary grossly
from survey to survey, indicating either a poorly developed method of
analysis or unknown seasonal effects.

It could be that further development of analytical methods

(cloth sample acidification, for example) would improve the reliability of
the HEM determination. A few experiments on cloth acidification (data not
shown) indicated that the HEM may not be increased grossly, however, although
the fatty acids increased appreciably.

If the HEM analysis cannot be used to control the type of pollution collected
by the cloth screens (except in the case of duplex films) then the question
remains as to what type of measure might be appropriate. Free stearic acid
may indicate micro-particulate pollution but little experience has been
obtained with this measure and the analysis is not easily performed. The
coliform bacteria analysis, however, is both definitive and easily performed
and the results can be judged to some extent in terms of their pollutional
significance. Considering the accessibility of this type of pollution to the

98


8€

Table 3 (continued). SUMMARY OF SURFACE TRAWLS

Traw1s Counts Fatty Acids
% Dry Aes the-
. Sta. Area | % in Sewage | Wt. HEM % | % |tic
Location No. Date No.| m2 |Slicks] No./m2| Type | mg/m2 | ug/m2 |ug/m2 | Cig [Cre [Rating
sweep 162 | NLR. 0.36 | 27 |o.36 | 58 | 34
, a 213 | NR. 0.29 | 38 |46 | 47 | 48
14 km NW 5 | VIT-12-73 | 4 | 479 | "98 0.22 | 16 |2:7 | 47 | 46
263 | 25 0.50 | 54 {1.1 | 38 | 54] 1.0
200 | 100 | 0.20 | 5 3.6 24
200 | 100 | 0.96 | 10 8.5 73
3a | V8] 4 | 06 | too | 0.22 | 18 0.13 | 22
526 6 | 0.13} 1.5 | 0.024] 8
Control Areas, 391 | 60 | 0.054) 26 0.25 0.1 |0.009} 67 | 33
Santa a | e271 4 | 314 {| 40 | 0.070) 14 0.59 3° 10.078] 40 | 36
Catalina Is. 229 | 100 | 0.13 | 3 3.3 {1160 |2.0 | 100] 0
2a2| 50 | 0.10 | 4 0.44 0.6
161 | NAR. 6.0 3.4 |0.43 | 48 | 40
187 | “10 223 4.6 |0.72 | 46 | 36 | 0
3b] VEI-1S-73 ) 4 | 999 | a0 14 0.4 }0.068) 62 | 27
263 | N.R. 0.033 | 1.0 |o:087| 47 | 34

Note: N.R. means not recorded.

aaverage of judgments of aesthetic appearance made by the sampling crews. The higher the rating
number, the poorer the appearance (see Table 7).


Fatty Acids (FA)

Table 16 lists the overall weights of the long-chain fatty acids (C,5-Cy.)
found in the cloth screen samples collected in the July 1973 survey. The
ranking of the observations is identical to that presented for HEM concen-
trations in Table 15, so direct comparisons can be made if so desired. No
significant background of FA existed in the glass cloth screens.

Fatty acids were not determined on the samples collected in the April 1971

survey and the fatty acid composition was not fully evaluated in the
August-September 1971 survey. The average values of total fatty acid con-
centration found in the latter survey are presented in terms of percent of

HEM in Table 17, (The means listed in Table 17 do not always compare with

those given in Table 15 because not all of the HEM samples were analyzed for FA.)

Coliform Bacteria

Surface coliform bacteria were collected independently with the nylon net
sampler as described previously in Section VI. Bulk water samples for
coliform organisms were collected 10 cm underneath the surface screen
samples with the aid of a sterile Cornwall continuous pipetting device.

The bacteria were separated and incubated on membrane filters in accord
with Standard Methods [5]. Bacteria samples were not collected in the 1973
survey.

The screen samples were always taken in slick areas in tandem with the glass
cloth samples except in the region of the JWPCP outfalls on September 3,
1971 when no sea slicks were visible. The results of these observations are
presented in Table 18.

PCB Compounds
Glass cloth samples collected in a given region were pooled to obtain suffi-

cient HEM to analyze for PCB compounds and pesticides. Small quantities
of such pesticides as DDE and DDT were observed frequently but their concen-

trations were always very much less than the PCB compounds so their magnitudes
were not ascertained. The results of the pooled screen samples are presented

in Table 19.

81


for the use of their facilities during the 1973 study is likewise deeply
appreciated.

The advice and most generous assistance of Dr. Fred K. Kawahara, Special
Consultant - Oi] Identification, Analytical Quality Control Laboratory
(Environmental Protection Agency), Cincinnati, Ohio, in the development of
the fatty acid analysis for hexane extractables is recognized and appreciated
fully.

xii


TABLE OF CONTENTS

Abstract 2. ee
List of Figures ..........00.- wee ee ee eee
List of Tables 2... ee ee
Sections

I. CONCLUSIONS 6. ww ee ee
Trawled Particulates . 2... . 2. ee eee eee
Micro-Particulates 2... 2 ee eee ee eee
Surface Screen Samples 2... 1... eee ee eee
Il. RECOMMENDATIONS . 2... ww. ee ee ee
III. INTRODUCTION 2. 1... ee ee
IV. DESCRIPTION OF OCEAN SURVEYS . 2... 2... 2. ee eee
Effluent Plume Submergence ..........008.
Surface Conditions During Surveys ..........
Discussion 2... ee
V. TRAWLED PARTICULATES .. 2... 2. 1 ee ee ee ee eee
Description of Trawls ... 2... 6.2.2.0 0200-6
Results of Surveys . 2... 1. ee ee ee ee ee

Proof of Wastewater Derivation of Particulates
Measurement of Surface Pollution ..........
Significance of Surface Pollution... .......
Control of Surface Pollution ............
VI. MICRO-PARTICULATES . 2... 2... . ee eee ee ee ee

10
12
20
29
34

39
44
46
54
65
69


ge

a“

57
— +] 6" —
__>S>_== Plon View
{| 8"dia. Float —_—__

Plastic Cod SS pa
Z Bridle of

1/4" line

| |— Wood Fairing

Fe |
te vy Si
a

ave

500 ppore
# Size Net. ys

a!

jl Tow Line
il Canvas

Screen Sampler
500 ppore Size

Convas ee
: ) 8'dio. Float |)
Stabilizer ——————— ."
lio—
f— 20172" 52"
ee | mn 7
pe] =e a
eee Pk
nae:
— Profile View: -

FIGURE 16. TRAWL NET SAMPLER


reasonable limit might be 1 mg/m?, about 50 times greater than the detectable
limit and 33 times less than the maximum concentration observed.

This recommendation may now be compared with the requirements of the Cali-
fornia State Water Quality Control Plan for Ocean Waters of California,
1972 (7).

Chapter II A
B. Physical Characteristics

1. Floating particulates and grease and oi] shall not be visible.

Floating particulates at the Marineland sampling station (14 km NW of the
JWPCP outfalls) were judged visible but not unsightly by the rating panel
used in this study (see Table 3). The HEM concentration was only 0.054
mg/m2, yet the fatty acid analyses showed that some of the HEM must have been
derived from wastewater outfalls (see Figure 19). If taken literally, the
above requirement is very strict. Its intent probably was to control gross
emissions of floatage of obvious wastewater origin over the outfall diffusers.
(Grease and oi] slicks are discussed in a subsequent section of this report.)

2. The concentration of grease and oi] (hexane extractables) on the water
surface shall not exceed 10 mg/m? more than 50 percent of the time,
nor 20 mg/m2 more than 10 percent of the time, (The samples shall be
taken in the areas of maximum probable impact.)

The method of sampling is not specified in this requirement and in some
cases natural surface film concentrations may build up appreciably,
necessitating the use of rather liberal HEM limits. This requirement
probably was intended to control concentrations of surface film materials.
It is nearly useless in controlling large grease and wax particulates, being
much tea liberal.

67


VII. SURFACE SCREEN SAMPLES

SAMPLING PROCEDURE

Surface films have been collected on solid surfaces and metal screens for
years. A solid surface dipped vertically through a surface film will collect
one coat of film material on the way down and another on the way up. The
thickness of the coating will depend on the speed with which the solid is
passed through the film and the ability of new film to move into the areas
of film depletion. This makes a quantitative estimate of the surface concen-
tration of the film difficult, if not impossible.

Métal screens are an improvement because the closely spaced solid surfaces
insure that most of the film contained between the wires will be collected
while at the same time they inhibit the movement of new film into the area
being sampled. Metal screens have the drawback of not being easily extracted
from grease and oil, and they tend to sag from the center no matter how
tightly stretched. Cloth screens, first used in this study, could be
extracted relatively easily with hexane by folding and inserting into a
soxhlet apparatus. They also tended to conform to the ocean surface and
could be handled easily at sea. Their major disadvantage was that most
fabrics could not be stripped of their background of hexane extractables
even after hours of extraction [10]. Glass fabrics could be cleaned rela-
tively easily. and they were used to collect surface film samples

for HEM analysis. The glass cloth utilized had a 0.003-inch (7.6 u) thread
diameter, a 40 x 39 warp and fill, and a 2.12 oz/sq yd (72 gm/m2) weight
when purchased new. It was commonly used in the construction of fiberglass
boat decks and generally referred to as "deck cloth."

Individual sampling cloths were cut to an area of 0.1 m2. The cloths were
cut slightly oversized because they shrank slightly when subjected to the
initial cleaning procedures. Once cleaned, the cloths released grease and
oi1 collected from the water surface easily, and they were reused until they

76


660/3-74-016

1974
Ecological Research Series

The Significance And Control of
Wastewater Floatables

In Coastal Waters

TED S74>,
ss &

SZ

K
AL paore?

anoulang.
0)
WN aGenct

>
%

Office of Research and Development

U.S. Environmental Protection Agency
Washington, D.C. 20460


IX. GLOSSARY
Band Slicks - Long, narrow sea slicks running parallel with each other.

Floatables or Flotage - All foreign substances collected from the water
surface by the sampling devices developed herein.

Grease - A general term used to designate the hexane extractables found in
domestic wastewater or in a polluted sea slick.

Langmuir Cell - One pair of alternating (right and left) series of longitu-
dinal vortices at the water surface with their horizontal axes parallel to
the wind. Generally such vortices are produced at wind speeds in excess of
3.4 m/sec.

Micro-Particulates - Microscopic particulates captured by the nylon netting
sampler. Generally these particulates were less than 100 u in size.

Slick - Flotage so concentrated that capillary waves are dampened visibly
(or the surface tension is depressed significantly). A slick may contain
the surface film material proper, particulates, plankton, debris, froth,
foam, etc.

Surface Film - A collection of foreign molecules on the water surface.

Trawled Particulates - Particulates larger than approximately 0.5 mm in
diameter collected by the trawl] net.

102


ABSTRACT

The significance of flotage derived from submerged primary effluent plumes
in the Southern California Bight is evaluated in terms of three components:
particulates 2 0.5 mm in size, particulates <s 0.1 mm in size, and surface
film materials. The sampling methods utilized to collect the flotage from
the surface are described in detail. The surface film and micro-particulates
were captured by fabric screen samplers developed during the course of the
study.

It was found that the large particulates penetrated the ocean thermocline
and gathered on the surface in profusion. The grease and wax portions of
the particulates could be measured reliably with hexane extraction, with the
mass of HEM of sewage origin being in the order of a metric ton on the water
surface within the study area. Such particulates contained considerable
numbers of coliform bacteria but little PCB compounds or pesticides.

The surface film materials and/or micro-particulates contained significant
concentrations of coliform organisms and PCB compounds, but not pesticides.
The HEM derived from this type of flotage may have amounted to 300 kg on
the water surface within the study area in July 1973.

Regulations for controlling the concentration of flotage on the ocean surface
are suggested after considerable discussion.

This report was submitted by the Sanitary Engineering Research Laboratory
of the University of California, Berkeley, in fulfillment of Grant Number
R-800373, under the sponsorship of the Office of Research and Development
of the Environmental Protection Agency.


APPENDIX A

MISCELLANEOUS TABLES

103


2

Nautical Mile

Station

118°30!

MARINA

7 DEL REY

April 7 p.m. gt
Sea Swell a
W 2-3 ft, 4 sec

Wind SW @ 4-10 k. oa

\
2 \., Apparent Slic| 2
\’ Movement
1,000/nr
Sludge Outfall “
© 10 Fathoms
Drogue wuent out fa —,
N \ Recovery effTue _—_
~ ° 6
Station (0:33 kT april 7 a.m, 33°55"
1 Swell NW 2-4 ft a
4 sec
/ Wind Light and Variable

Figure 7.

Surface Conditions in Hyperion Outfall Region: April 7, 1971


€8

Table 17.

MEAN CONCENTRATIONS OF CLOTH SCREEN HEM AND FATTY ACIDS
(concentration in mg/m?)

April, 1971 Aug.-Sept., 1971 July, 1973
. a No. of % | No. of % No. of %
Location Type Samples | HEM | FA | Samples | HEM | FA Samples | HEM FA
Hyperion Ss 4 3.9 - 5 1.8 | 12
outfall NS 3 1.5
S 8 1.13 | 8.4
aie eeais LLNS 6 0.91 | 9.3
L| s 6 0.52 114.3
NS gb 17 | 14 5 1.06 | 9.2
Hyperion, S 4 2.7 | - 1.7 [14
3.7 km N NS 3 1.4 415
JWPCP, S 7 0.64 | 3.2
14 km NW NS 9 0.23 | 3.7
Control S 4 2.0 | - 1.3 113 14 0.26 | 1.8
areas NS 1 21 13 0.16 | 4.6

8g = slick and NS = non-slick.

b

Windy day - no slicks.



These approaches measured insoluble duplex films adequately. A vegetable
oil composed primarily of unsaturated Cy¢ and Cyg fatty acid esters was
dissolved into hexane and spread on clean sea water at 20°C. The hexane

was allowed to evaporate and the average surface concentration was computed
to be 71 mg/m2. The film was sampled with a 0.1 m? glass cloth and extracted
with hexane. The results indicated a surface concentration of 76 mg/m*,
within 7% of that computed.

A duplex film is also created in oil] spills and is commonly thought of as
being surface pollution. Natural sea slicks are formed by films one molecule
thick, and such monolayers are not well understood.

Palmitic acid (saturated Cyg) was added to the surface of distilled, care-
fully cleaned water employing the classical procedures of Langmuir [11] and
Adam [12]. The bulk water had a pH of 5.5 and astable monolayer was formed
having an area of 19.7 A? per acid molecule (slightly less than the commonly
accepted value of 20.5 A2 for any normal saturated fatty acid). The layer
was sampled with 0.1 m2 glass cloths with the reduction in the surface area
of the film being measured after each sampling. The reduction in area
averaged 0.095 m2? with a coefficient of variation of 3.7%. This indicates
that the cloths consistently collected 95% of the palmitic acid monolayer.
Stearic acid (saturated C,g) would undoubtedly have behaved in the same way.

The pH of sea water is normally relatively high and only tiny fractions of
the fatty acids will remain undissociated in the bulk water phase. Depending
on the concentrations involved, the dissociated acids can form insoluble
salts with the divalent cations present in the sea water. Magnesium salts
probably would predominate because their solubility products are the

smallest of all the cations commonly encountered in sea water. Such insoluble
salts can move to the water surface to aid in the formation of sea slicks.
The stability of fatty acid salt films seems to be dependent on the
concentrations and proportions of cations and acids present. Fatty acid

salt films are poorly understood and have been investigated little in the
past.

78


in 20% of the samples taken. This level corresponds to a volumetric concen-
tration of at least 1000 organisms/100 mz. No coliform bacteria were found
in 100 mg bulk water samples collected 10 cm underneath the ocean surface,
nor in regions well removed from the marine outfalls.

6. The average surface concentration of free stearic acid (Cyg) was esti-
mated to be 4.0 g/m? (or 27 ug/2) in the study area in July 1973. The
concentration was 20 times higher over the JWPCP outfalls than in the control
area, or more than three times the average study area value. The proportion
of free stearic acid in the HEM decreased from 1.4% over the JWPCP outfalls
to 0.33% in the control area. The bulk ocean water concentration of stearic
acid (salts and free) 0.5 m below the surface was approximately constant at
1.0 yg/e, regardless of location.

7. Very little free stearic acid was recovered from JWPCP effluent diluted
with sea water in a pan in July 1973. The diluted effluent contained 150 ug/%
of stearic acid for a total of 5.4 mg, but only 0.3% of this free stearic
acid was recovered in six cloth samples taken consecutively from the water
surface. The free stearic acid comprised on the average about 2.0% of the
surface HEM.

8. In light of No. 6 and 7 above it was concluded that the free stearic
acid was recovered primarily from micro-particulates which inhibited the
salting out of this acid. This conclusion conforms to theory as well as
such theory is known.

9. Using the free stearic acid as a tracer of micro-particulates of wastewater
origin, the surface HEM derived from wastewater emissions was estimated to
be 300 kg in the study area in July 1973.

10. The HEM determinations proved of little value in ascertaining surface
pollution of wastewater origin, or the reason for the existence of sea slicks.
The observed concentrations were highly variable, ranging from 0.9 to 3.9
mg/m2 over the marine outfalls and from 0.16 to 2.0 mg/m? in the control areas.


From this it was deduced that most of the particulates classed as sewage
types correlated well with each other, Because the concentrations of these
types were much higher over the outfalls than elsewhere (see Table 5) it
may be safely assumed that most of them were derived from the wastewater
discharges.

Hexane Extractable Materials (HEM)

The HEM of the samples correlated closely with the numbers of grease and

wax particulates found in the samples in all cases where tar was not excessive
as shown in Figure 21, At first glance this is surprising but the size
distribution of the grease and wax particulates did not vary significantly
from location to location, and if most of the HEM were derived from those
particulates then the correlation should be good.

Figure 21 also shows a 1 to 1 correspondence between the number of parti-
culates and the mg of HEM. This would arise only if most of the grease and
wax particulates dissolved into the hexane as explained below:

Table 5 shows that the mean size of the grease and wax particu-
lates was 1.3 mm. Their mean volume, therefore, must have been on the
order of 1 x 1073 mg and with a specific gravity close to one their
mean weight must have been on the order of one mg per particulate.
Consequently, a 1 to 1 ratio would be obtained only if most of the
grease and wax was dissolved by the hexane.

The significance of Figures 20 and 21 should not be overlooked. They show
that most of the grease and wax was probably derived from the wastewater
discharges, that most of the HEM was derived from the grease and wax parti-
culates (exclusive of tar), and that most of the grease and wax dissolved
into the hexane and that there is possibly a background threshold of non-
extractable particulates classified as "sewage types." The HEM is, of
course, relatively easily determined in a soxhlet apparatus.

48


HEM and Fatty Acids

The HEM and fatty acid results were much less amenable to analysis than were
the PCB or coliform results. The variations were so great it was difficult
to judge if the differences found in average concentrations were truly signi-
ficant. When a sufficient number of observations were taken, the differ-
ences proved significant as shown in Figure 29 for the HEM concentrations
found in the slick and non-slick areas of the control station in July 1973.

The HEM and fatty acid concentrations did decrease markedly with distance
from the JWPCP outfalls in the July 1973 survey as shown in Table 17. No
such pronounced decrease was observed in the August-September 1971 survey.,
Again the causes of this are unknown. In nearly all cases the observed
HEM concentrations were surprisingly low in sea slick areas.

A free fatty acid occupies approximately 20.5 Re of surface area in a stable
monolayer. Palmitic acid, for example, would produce a surface concentration
of 2.08 mg/m? as HEM under such circumstances. Most of the observed HEM and
fatty acid concentrations were much lower than this.

To understand the role of wastewater fatty acids in the formation of sea
slicks, 2 2 grab samples of the JWPCP effluent were collected on July 13,
1973 and added to an aluminum pan containing clean sea water. The effluent
was added in sufficient quantity to give an overall sea water dilution of
18, about 5 times less than that being achieved over the outfall diffusers.
The depth of the diluted effluent in the pan was 17 cm and the pan had a
surface area of 0.224 m?. The contents of the pan were agitated gently with
magnetic stirrers and six cloth screen samples were taken at approximately
20 minute intervals of time after an initial waiting period of about one
hour. Bulk samples were taken from the undiluted effluent and from the pan
mixture after completion of the surface screening and acidified. Surface
tension was also measured during the course of the experiments. The results
of one such experience is presented in Table 21 and discussed in detail below,
with the results of all the experiments being essentially the same.

90


VI. MICRO-PARTICULATES

SAMPLING PROCEDURE

Nylon netting was used to collect coliform bacteria from the ocean surface.
At the request of the Southern California Coastal Water Research Project,
who had furnished some of the funds and sampling craft used in the 1971
ocean surveys, the netting was also used to collect samples for neuston
(surface plankton). Upon analyzing the neuston samples it was observed that
the samples contained debris, some being colored and of an obvious artifi-

cial nature. Particulates captured in this manner are called “micro-particulates"
in this report.

The nylon netting used in this type of sampling had a two-filament knit with
0.75 to 1 mm openings when purchased new. A sample was obtained by spreading
the netting carefully over the water surface and collecting the surface
layer into the cloth via capillary action. Being coarsely woven, this
netting lost the water collected easily so it had to be lifted from the
water surface and inserted into the sample container with great care. Even
so, much of the water was lost in the process. Laboratory tests conducted
under ideal conditions showed that the netting collected a surface layer
averaging 0.1 mm deep from sea water at 22°C when no water was lost from

the cloth. This information was used to compute the surface area sampled

at sea by dividing the volume of sample collected by 0.1 m.

The nylon netting was used to collect the coliform bacteria and neuston
because the organisms had to be separated from the cloth for further analysis,
and laboratory tests showed that this netting released such organisms readily
upon repeated washing. The organisms could then be collected on a membrane
filter by passing the water released from the cloth together with the wash
water through the filter. Samples for coliform bacteria were then incubated
in accord with Standard Methods [5] while the neuston and micro-particulate
samples were examined directly on the filter with the aid of a microscope.


82

\

118°20' w

33°45' N

POINT
VINCENTE

N

Ny

SA
LACSD OUTFALLS

i

SWELL W STATION 4 0.22 k
1 FT 4 SEC
4 WIND W 3k
SLICKS AT
0815
Nautical Miles
50
0 1 2
250 FATHOMS
Figure 12. Surface Conditions Over JWPCP Outfalls: July 11, 1973

N PEDRO
BAY

a


Table 5 . CONCENTRATION AND SIZES OF PREVALENT TRAWLED PARTICULATES
(no./100 m2 trawled)

lv

JWPCP Hyperion, (Summer, 1971 only)
Hyperion outfall | outfalls 3.7 km N Control areas Particulate size
Particulate Median M M,
type TV-7-71 | VET-31-71 | 1X-3-71 | IV-7-71} 1X-1-71 | 1V-8-71 | 1xX-2-71 | UETIAN Naan NaN.
Sewage types
Grease & wax| 573 60 234 16 52 0.48 <0.08 1.0 1.3 10
Seeds 85 7.4 VW 7.0 20 0.29 0.08 (All 2 to 3 mm)
Plastic 4.4 4.7 88 0.3 1.0 0.10 0.25 | (Most 2 to 5 mm)50
Other 54 9 9 8.4 4 1.8 0.53
Natural
Tar 32 4.0 13 1.7 3.5 1.8 0.84 1.5 1.9 35
Kelp 22 0.3 23 1.7 16 14 0.51 2.54 4.08 1508
7.5) 16D 1505

ant Hyperion, 3.7 km N for IX-1-71.
bat OWPCP outfalls.
“The mean is the arithmetic mean.



SAMPLES

TRAWL BULK FILM
—___[
I
DRY
ACID DRY |
WEIGH
HEXANE FILTER
WEIGH
DILUTE
GRIND FATTY
DILUTE Acrd
IT COLIFORM
POLYCHLORO
COLIFORM
BIPHENYL MICROSCOPIC
EXAMINATION
400-430 X
MICROSCOPIC
EXAMINATION
10-100 X

Figure 31. Analytical Approach to Characterizing Flotage and Bulk Samples

W


Lb

100

=
o

Jom!

GREASE AND WAX PARTICULATES, no. /m?

°
1
nN

1073
10-%

Figure 20,

I |
@ OVER OUTFALLS /
Z\ AWAY FROM OUTFALLS y
m CONTROL AREAS 2 _
\v__ INDICATES ¢ oy e
. oe
e Ka ~T
Ye
ALe
Le!’
e
A
a
A @
o / =
| | |
1073 10-2 10-} 1 10 100

OTHER "SEWAGE TYPES" OF PARTICULATES, no/m2

Comparison of Grease and Wax Particulates with Non-Extractable Sewage Types


ra

10

rt | | TTT TT TT [| A
po e je)
= LA -
E |__ _
. e
tw
nN TAR
n
GREASE AND WAX
a eo oom
O5;b-¢ fo) —
0.3 || Lf | | ft ft | | | ft 4
2 5 10 20 30 40 50 60 70 80 90 95 99 99.8
PERCENT EQUAL TO OR LESS THAN
Figure 17. Cumulative Frequency Distribution of Grease and Wax, and Tar Particulates:

August-September, 1971.


September survey, on the other hand, were not noticed at all in the April

survey.

The particulates forming the clumps of debris observed in the second survey
of 1971 were packed too tightly together to permit individual counting or
typing. The sizes of the clumps were distributed in a log-normal manner as
shown in Figure 27. The size distributions changed from location to location
but not from slick to non-slick areas at a given location. The black parti-
culates evidenced similar trends in sizes.

The nylon netting can sample at best only 0.1 m2 of water surface area.
For the analytical procedures used in this study a given type of particu-
late would have to have a surface concentration in excess of approximately
1000/m2 to be counted. Figure 27 shows that for the prevalent clumps of
debris particulates, at least 99% of the particulates were smaller than 100 y.
Thus, a gap existed in the sampling and analytical techniques

employed in this study to characterize the particulates. Particulates
greater than 0.5 mm in size were collected by the surface traw] and

those smaller than 0.1 mm and in concentrations greater than 1000/m? were
collected with the nylon netting. Particulates smaller than 0.5 mm and in
concentrations less than 1000/m2 generally were missed.

Tables 13 and 14 summarize the results of the micro-particulate studies
made in the August-September 1971 survey. The tables show that their
concentrations were surprisingly great, and that their average volume/m2
may have been greater than that observed for the trawled particulates
during the same survey (assuming that the specific gravity of the trawled
Particulates was close to one). The predominant type of micro-particulate
found in the August-September 1971 survey was the clumps of debris. The
black particulates were also very prevalent.

72


Table 16. CONCENTRATION OF CLOTH SCREEN FATTY ACIDS: JULY, 1973
(conc. in ug/m2)

Over JWPCP JWPCP
Outfalls 14 km NW Control
Type VII-11-73 VII-12-73 | VII-13-73

31.0 17.3 5.9

lost 13.3 1.0

160.2 73.1 8.6

a 47.5 12.1 1.2
128.2 14.2 15.8

49.4 8.4 8.9

26.3 2.4 6.4

Slick 223.0 1.4
28.1 -

112.4 1.3

114.5 1.2

> 45.3 3.0

82.9 6.1

94.3 2.9

| 61.4
Mean 86 20.1 4.6
20.2 4.7

87.3 10.1 12.4

- 68.7 20.0 9.7

ae 11.4 7.6

S14 wi 11.7 3.6
lon- Slick 49-7 14.5 5B
100.5 3.1 5.2

65.8 1.3 1.7

139.5 - 12.5

> 90.5 3.5

62.5 14.3

1.8

5.7

11.9
Mean 91 8.5 7.4

82


DESCRIPTION OF TRAWLS

The extent of each trawl is listed in Tables 3 and 4. Conditions at the
time of trawling are described briefly below.

April, 1971

All trawling at the Hyperion outfall was performed within the standing
slick shown in Figure 7. The trawling at Station 2, 3.7 km to the north,
was undertaken during a period of increasing wind. The slicks were destroyed
at that site before the final two trawls could be made. In the control

area (Station 3a) all the trawls except the last were made in the large
slick lying in the lee of Santa Catalina Island.

August-September, 1971

In this survey the trawls were duplicated as much as possible at a given
site with one being taken for coliform bacteria analysis and the other for
all the remaining analyses deemed necessary.

The trawling over the Hyperion outfall was commenced in the afternoon when
the wind was relatively strong. The sea slicks, ill-defined at best, were
destroyed as the trawling progressed. The trawls were conducted progressively
eastward commencing over the center of the Y diffuser and ending 700 m to
the east. The data shown in Tables 3 and 4 are listed in that order. At
Station 2, 3.7 km to the north, trawling was conducted during a period of
relative calm.

No slicks were observed over the JWPCP outfalls during the 1971 survey. The
order of trawling, as listed in Tables 3 and 4, was progressively westward
commencing near the seaward end of the L diffuser (see Figure 10). Three
of the four pairs of trawls were taken parallel with the L diffuser and the
last west of the Y diffuser. Trawls in the control area (Station 3b) were
made during a period of well-defined sea slicks.

duly, 1973

No trawls were collected for coliform bacteria analysis during this survey.
All trawling was conducted in the morning when some rather ill-defined slicks

36


Table 28.

3.7 KM N OF HYPERION OUTFALL

(no./100 m2 trawled)

DESCRIPTION OF PARTICULATES:

IV-7-71

IX-1-71

Trawl No. 1

2

Sewage Types

Grease and wax } 3

Seeds

Misc. tissue

Wood

Plastic

Fiber

Rubber

Unidentified
debris 0.3

Natural Types

Tar 2.3
Insects 11
Charcoal 1
Kelp 4
Eel grass 16
Surf grass
Pumice 0.7
Feathers
Eggs
Crab
Mysid
Siphonophore
Copepod 0.7
Isopod
Hydroid
Sponge
Larvae
Barnacle
part. (7?)
Others@

oO PANO
N wn

=
POO © CO =| an = COOono=1
N wry COO YM AND a OCwWww

0.9
0.3

C900WwNn
ODADH

0.6
1

f=)
wo

Oo SGO9D0ONTD0O0
Ww WAHMWHOAW

38
5.5

1.8
2.7

0.9

ny
AOnMN
Onn

=o
io

1.8

2.7

Pw
or

0.6
0.6

a
eo Ow

_

0.6

0.6

77
25

Bom

NPN

90
69

1.5

2.9

Total 93

55

30

88

36

149

163

Pollen, fish, sea spiders, etc.

107



Hyperion, September 1, 1971

JWPCP, July 11, 1973

Figure 15. Photographs of Sea Slicks Over Hyperion and JWPCP Outfalls

117


EPA-660/3-74-016
January 1974

THE SIGNIFICANCE AND CONTROL OF WASTEWATER

FLOATABLES IN COASTAL WATERS

By

Robert E, Selleck
Lloyd W. Bracewell
Ralf Carter

Contract No. R-800373
Program Element 1BA025
Roap/Task 21 AIS 16

Project Officer

Walter F. Rittall
U.S. Environmental Protection Agency
National Environmental Research Center
Corvallis, Oregon 97330

Prepared for

OFFICE OF RESEARCH AND DEVELOPMENT
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, DC 20460


10.

i.

12.

13.

VITI. REFERENCES

The Ecology of the Southern California Bight: Implications for Water
Quality Management. Final Report. Southern California Coastal Water
Research Project. TR 104. March 1973.

Brooks, N. H. Conceptual Design of Submarine Outfalls - 1. Jet Diffusion.
Program VII, Water Resources Engineering Educational Series. University
of California, San Francisco. January 1970.

Newton, J. R. Factors Affecting Slick Formation at Marine Sewage Out-
falls. Conference on Pollution Criteria for Estuaries, University of
Southhampton, England. July 19, 1973.

Langmuir, I. Surface Motion of Water Induced by Wind. Science. 87:
119-123, 1938.

Standard Methods for the Examination of Water and Wastewater, 12th
edition. APHA, AWWA, WPCF, 1965.

Hahn, G. J., and S. S. Shapiro. Statistical Models in Engineering.
New York, John Wiley and Sons, 1967.

Water Quality Control Plan: Ocean Waters of California. State of
California Water Resources Control Board. July 1972.

Determination and Removal of Floatable Material from Wastewater.
Engineering Science, Inc. Public Health Service Contract 120-64,
November 1965.

Selleck, R. E., and R. Carter. Surface Phenomena Study. Sanitary
Engineering Research Laboratory, University of California, Berkeley.
Report No. 72-9. June 1972.

The Significance and Control of Wastewater Floatables in Coastal Waters.
Interim Report for the Environmental Protection Agency. Grant No.
16070 FKO. Sanitary Engineering Research Laboratory, University of
California, Berkeley. July 1971.

Langmuir, I. Fundamental Properties of Solids and Liquids, II.
J. American Chem. Soc. 38:1858-1898, 1917.

Adam, N. K. The Physics and Chemistry of Surfaces. Dover edition,
New York, 27-33, 1968.

Rizwanul, H., D. W. Schmedding, and V. H. Freed. Aqueous Solubility,
Adsorption, and Vapor Behavior of Polychlorinated Biphenyl Arochlor 1254.
Environmental Science and Technology. 8:139-142, 1974.

100


The results indicate a surprisingly smal] total mount of HEM of wastewater
origins on the ocean surface, only 840 kg or so. Even if this estimate is
in error by a factor of 10, the total amount of HEM still remains small.
To comprehend this more fully, the amount of HEM being discharged daily to
the area must be known. Two different methods of effluent sampling were
employed to obtain this information. They were:

1. In the surveys of 1971, 1.5 % of composited effluent were mixed
with clean sea water and the flotage was separated in a specially designed
funnel. The separated flotage was then extracted with hexane in a soxhlet
apparatus. The details of this method are given in Ref. [8] and the results
for the Hyperion effluent are shown in Table 10. The results of this approach
are questionable because particulates with sizes greater than 0.5 mm were
relatively scarce in the effluents studied, and the flotage derived from a
sample as small as 1.5 2 could have been composed primarily of particulates
smaller than 0.5 mm,

Table 10. ANALYSES OF 24-HR COMPOSITE SAMPLES OF HYPERION EFFLUENT
DURING OCEAN SURVEYS OF 1971

April 6-7 | Aug. 30-31
Measure 1971 1971
Measured by Hyperion staff
Grease and oi] 12 mg/2 9 mg/&
Suspended solids 64 mg/2 81 mg/%
Vol. suspended solids 50 mg/z 76 mg/2
Coliform organisms@
AM 260 ,000/m& | 430 ,000/m%
PM 186 ,000/m2 | 930,000/m2
Measured by this project staff
Bulk hexane extractables 10.7 mg/2 8.2 mg/%
Dry weight of floatables 4.8 mg/z 3.1 mg/2
Hexane extractables in floatables 0.15 mg/z 0.30 mg/2

Determined from grab samples.

60


Table 6

EXPLANATION OF FIGURE 19
FATTY ACID COMPOSITION OF LARGE PARTICULATES

Bar No. of
ho. Location Date observations HEM FA % FA
(1) Stpepee VII-13-73 5 0.65 0.12 18
mg/2 mg/2
effluent $ 9/
(2) | Over JWPCP | VII-11-73 4 15 1.3 9
outfalls mg/m2 | mg/m2
(3) es xm MN VII-12-73 4 36 2.2 6
0 /m2 /m2
outfalls “ “
(4) | Control VII-13-73 4 2.1 0.29 14
ug/m? | g/m?

unsaturation was not determined. Otherwise, those results were nearly
identical in all respects to those presented and discussed above.

MEASUREMENT OF SURFACE POLLUTION

Several different analyses were used in this study to evaluate the surface
flotage. The best means of measuring these particulates derived from
wastewater effluents is discussed below.

Visual Typing

The grease and wax particulates correlated fairly well with other non-
extractable "sewage types" as shown in Figure 20. The rapid drop off in
grease and wax particulates with low concentrations of the other types
indicates that either the grease and wax particulates did not spread as far
as the other types, or the other types had sources other than wastewater
discharges. The figure indicates a natural background of non-extractable

"sewage types" in the order of one particulate every 100 to 1000 m2.

45


Bulk ocean water samples collected 0.5 m underneath the surface were also
analyzed for HEM and fatty acids with the average results being shown in
Table 23. Those samples were acidified at the time of collection.

Table 23. FATTY ACID COMPOSITION OF BULK OCEAN SAMPLES: UY, 19738
(concentrations in yg/2)

Stearic acid

% of |Palmitic | | % of

Location HEM FA HEM acid Conc. | HEM

We aercer omy) | 54] 6-4 | 12 2.7 | 0.92 | 1.7
14 km NW of JWPCP 51 9.1 18 3.6 0.92 1.8
Control area 31 3.3 WW 1.1 11 3.6

samples taken 0.5 m beneath ocean surface and acidi fied for preservation.

The table shows that the bulk water concentrations of palmitic and stearic
acid were nearly constant in the study area during the July 1973 survey.
Stearic acid had an average concentration of only 1 ug/z or so, and palmitic
2.5 ug/g. Even so, a water depth of only one or two meters would be suffi-
cient to produce a fatty acid slick at those concentrations if the acids
could attain the water surface. A direct comparison cannot be made between
the acids found in the bulk water and in the screen samples because the bulk
samples were acidified and the screen samples were not.

The change in the fatty acid composition of the cloth screen samples with
distance from the JWPCP outfalls in the July 1973 survey tended to parallel
that noted for the trawl particulates captured at the same time (Figures 19
and 30). The major differences were a greater proportion of the lighter
acids and a smaller proportion of unsaturated Cy, acids in the screen samples.

95


Table 1. CHARACTERISTICS OF OUTFALLS SAMPLED

Hyperion JWPCP outfalls
0
144 90" 120"

Outfall

Diameter, m 3.66 2.29 3.05

Length, m 8000 2600 3600
Diffuser

Length, m . 2414 732 1353

Shape Y Y L

Av. depth, m 59 63 56

No. of ports 168 100 740
Effluent _(av. for 1971)

Flow, m3/s 14,72 | 5.26¢ 11,0¢

HEM, mg/2 19 70

BODs, mg/2 120 320

SS, mg/g 73 330

VSS, mg/2 55 210

3pata from Ref.

Dag m3/s of secondary effluent mixed with 10.3 m3/s of primary
effluent.

Primary effluent split between two outfalls, Flows in each

- estimated.
The figures show that extensive ocean stratification existed during those
surveys with the overall change in temperature being at a minimum duréng
the April 1971 survey. With respect to the outfall stations, the vertical
profiles were always measured in the Y of the Hyperion outfall diffuser.
At the JWPCP outfalls the profile was measured at the seaward end of the
L shaped diffuser in the summer of 1971, and alSO in the July 1973 survey.
Only a few discrete water samples were collected for salinity measurements
in the summer survey of 1971, so the density structure shown in Figure 5
is only approximate except at the data points shown. A density structure
was estimated for the July 1973 survey using the salinity pattern observed
in August-September 1971.

The daily flows existing in the outfalls during the various survey periods
are shown in Table 2. Again the split of flow between the 90 and 120 inch

18


DEPTH, m

1,
i
H
10 4 ot
20 +
30 4
40 +
50 -
60 4
Station Ocean Bottom
1 ——o—— April 7, 1971
4 2 —ao— April 7, 1971 1
3a —---e —-- April 8, 1971 777777
——- T TT T
25 26
oO;

Figure 3. Water Density Profiles: April, 1971

14



public, it seems logical to restrict the surface bacteria to concentrations
of 1000 organisms/100 mz or less as total coliforms, or 1000 organisms /m2
assuming a sampling depth of 0.10 mm with the nylon netting screens. This
might raise havoc with present ocean outfall disposal methods, necessitating
the disinfection of the entire effluent prior to release even when the
effluent plume is well submerged beneath the ocean thermocline. Also, it

is not known if the bacteria present in the micro-particulates would be
killed even with effluent disinfection, and it may be that even a disinfected
surfacing secondary effluent plume would not meet this requirement. For
these reasons the requirement suggested above for coliform bacteria is offered
with considerable trepidation.

PCB concentration requirements could also be established, regardless of the
source of the compounds. These investigators are unable to judge what an
environmentally safe level of such compounds might be at the ocean surface.
Concentrations on the order of one mg/g as Aroclor 1254 appear excessive,
however, and such a level was approached in some samples collected over the
Hyperion outfall in 1971.

99


92

Nautical Miles

| nn |

N

Figure 10.

San Pedro

LACSD
Outfalls

Slick
Sample” @
“4 Wind E 7k

well W 3'6 sec Drift
0.4k
Station 4
S A N P EDR OO C H AN NEL
Nons lick
Samples

Surface Conditions Over JWPCP Outfalls: September 3, 1971


APPENDIX B

ANALYTICAL METHODS

109


Coliform Bacteria

This method of analysis is easily performed and it can be used to ascertain
the origins of at least a portion of the flotage. It is sensitive but not
precise. For this reason it does not provide an adequate means for computing
mass balances on wastewater flotage.

Dry Weight

The State of California Water Quality Plan for Ocean Waters [7] places
restrictions on the dry weight of wastewater flotage which can be found
over a marine outfall. Such limits are necessary to control non-extractable
flotage of wastewater origin such as rubber or plastic. In this study the
grease and wax particulates always predominated, so it is not known what
the safe limits on such objects might be, aesthetic or otherwise.

The total dry weight of all the particulates gave a poor correlation with
HEM as shown in Figure 23. This might be expected because the samples
contained varying amounts of non-extractables, some natural and some of
wastewater origins. The types of particulates classed as "sewage types"
were not separated and weighed independently in this study. Such a task would
have been difficult because some of the grease particulates were extremely
sticky. It appears that if this had been done a good correlation with HEM
would have been obtained because the grease and wax particulates correlated
well with other sewage types as well as the HEM. This would be an extremely
onerous task and is not advised in normal circumstances.

Figure 23 also shows that commonly nearly half of the total dry weight of the
flotage collected over the outfalls could be extracted, whereas this proportion
became very small and erratic in the control regions.

Recommendations

These studies indicate that HEM is by far the best analysis for ascertaining
the extent of surface pollution created by floating particulates having sizes
greater than 0.5 mm. The source of the HEM can be checked by the following

52


Table 27. DESCRIPTION oF Te PARTIAULATES: OVER OUTFALLS
100 m? trawled
Station 1 Station 4
1V-7-71 VIII-31-71 IX-3-71
Trawl No. 1 2 3 1 3 5 7 2 4 6 8
Sewage Types
Grease and wax | 380 233 1270 2.5 | 46 85 WI 14 23 213° | 557
Seeds 43 27 209 12 6.9] 11 5.7] 0.9 6 27
Misc. tissue 31 2.6 69 2.7 5
Wood 13 7 31 1.2 4
Plastic 3.5 0.7 11 8 4.1 6.5] 2.9| 4.2] 54 238
Fiber 3.5} 0.4 3.1414 2.7 14 1.7 2
Rubber 1.8 1
Unidentified
debris 6.7| 12 6.1/1] 4.1 0.9 8.9
Natural Types
Tar 6.7} 31 52 1.2 1.4 3.2} 2.9] 0.9} 15 27
Insects 14 12 62 1.2 | 2.7 4.1 1
Charcoal 1.2 2
Kelp 2.6 5.6 63 1.2 2.9} 1.7| 29 47
Eel grass 0.9 0.8 0.9
Surf grass 0.9 1.5 3
Sea lettuce 0.4 1.6 4 3.7
Pumice 1.7
Feathers 0.6) 2.5] 1.4 4.1 2.9
Eggs 1.1 1.2
Crab 0.3 1.2
Mysid 0.8
Siphonophore 0.9 0.8 0.6
Copepod 2.6 0.3 2.5 36 1
Sponge 0.9. 1.8
Nauplius
Dinoflagel late 1.7
Barnacle
part. (?) 2.6 4.9
Eucarida 2.5 34 4.2 3.7
Diatom 5.5 1.6
Others? 1.4 1.4 3.2 1.7
Total 417 337 1790 {37 78 115 139 80 75 345 903

®pollen, fish, sea spiders, etc.

106



At first the cloths used to collect the neuston and micro-particulates had
an area of 0.4 m2 but this size proved awkward to handle at sea. All of the
cloths were reduced to a uniform area of 0.1 m2 in the August-September 1971
survey. (The cloths used to collect the bacteria samples were always 0.1 m2
in area.) Neither coliform bacteria nor micro-particulate samples were col-
lected in the July 1973 survey.

ANALYTICAL PROCEDURE

The resolution employed to count and identify the neuston and micro-particulates
in the April 1971 survey was 200X, and approximately 0.3% of the membrane
filter area was examined. One sample was collected in slick areas at each
station and the average volume of water collected was 36 mz. Thus, the

area of sea surface actually examined was approximately 0.0011 m2 per

sample. This gives a least count of approximately 1000 particulates of a

given type/m2.

The area of the cloths was reduced to 0.1 m2 and the magnification increased
to 430X in the August-September 1971 survey. In this case the netting was
spread over the water surface several times at a given location until a
sample volume deemed sufficient was collected. Eight independent samples
were collected at most of the stations; four in slick areas and four in
non-slick areas. The average volume of water collected per sample was 32 me,
about the same as collected in the April survey.

The proportion of the filter examined was reduced to 0.1% from the 0.3%

used in the April survey. Thus, the area of the sea surface actually analyzed
was approximately 0.0003 m2 per sample. The results presented in Table 13
represent the average of four such samples; consequently the actual coverage
was approximately the same for both surveys.

RESULTS

The composition and concentration of the micro-particulates varied grossly
between the two surveys. The differences in concentration can be explained,

70


appeared to be less than those obtained for the summer 1971 survey but the
latter computations have to be considered as being very approximate.

In most cases the initial dilution may have been nearly 100-fold over the
outfalls, checking with some of the observations of water quality made in
the Southern California Coastal Water Research Program Study [1].

The significant finding of all this is that the wastewater effluent plumes
were submerged beneath the pycnocline during the times when flotage was
collected from the ocean surface. A minimum submergence of 12 m may have
existed in the Hyperion area in April 1971. These computations check well
with visual observations of the sea surface made during the ocean surveys
as discussed below.

SURFACE CONDITIONS DURING SURVEYS

The success of a program of ocean surface sampling is dependent on the weather
conditions encountered. By far the most significant influence is the wind.

A strong wind will disrupt and disperse sea slicks quickly and eventually
submerge even fairly large floating particulates. A light breeze is not detri-
mental in some respects but the sea slicks become invisible quickly either
because the wind is insufficient to ripple areas not covered by a surface
film, or because the film itself has an opportunity to form across the

entire surface. Sea swell makes accurate surface sampling more difficult

but it has little effect on the sea slicks. The effects of water density
stratification and internal waves on sea slick visibility remains to be
ascertained. Because the wind plays a significant role in surface sampling

a detailed description of the wind conditions encountered during each survey
is given below.

April, 1971

The best wind conditions were encountered in the very first survey of April
7-8, 1971. Numerous well-defined slicks were observed despite an appreciable
sea swell. A 10 knot (5 m/s) wind did break up the slicks in the afternoon
of April 7.


1973. Daily composites of the JWPCP effluent were also collected for this
study during the week of July 6-12, 1973. These samples were acidified and
extracted in a liquid-liquid extraction apparatus for three hours with hexane
followed by separation on an activated silica column, The output on the GLC
column was gross, and the typical PCB patterns were masked by large
quantities of unidentified compounds. Further separation and identification
procedures were not pursued.

A grab sample of the JWPCP effluent was taken in the afternoon of July 13,
1973 and diluted 17 times with clean sea water, extracted and analyzed for
PCB. In this case Aroclor 1254 patterns were distinct on the GLC output and
a concentration of 6.5 ug/2 was indicated after correction for dilution and
sea water background. This was for only a single grab sample, but

the analysis was deemed accurate because of the unusual care taken in the
liquid-liquid extraction and separation procedures. Using this concentration
and those reported in the SCCWRP study the wastewater effluent PCB mass
emission rate was found to range from 3.3 to 9.6 kg/day to the study area,
depending on whose data were used. These results indicate that the wastewater
mass emission rate of PCB was considerably greater than the rate of atmos-
perhic fallout in the study area.

Four 4.5 2 bulk ocean water samples were collected 0.5 m beneath the ocean
surface at each station occupied in the 1973 survey. The average results
are compared with the surface screen samples in Table 20.

Table 20. COMPARISON OF OCEAN WATER AND SURFACE CONCENTRATIONS
OF AROCLOR 1254: JULY, 1973

Cloth Screen
Samples
. Bulk Samples a Concentrating
Location ug/2 ug/m2 | ug/2 Effect
JWPCP outfalls 0.1036 4.8 | 32 310
14 km NW of JWPCP 0.025 2.1 13.7 540
Control area 0.018 1.2 8.0 440

aAS suming a sampling depth of 0.15 mm.
BL diffuser.

88


I, CONCLUSIONS

The following applies to primary (or a combination of primary and secondary)
wastewater effluent plumes submerged 12 to 30 m beneath the ocean surface.

TRAWLED PARTICULATES (20.5 mm in size)

1. Grease and wax particulates always predominated over all other sewage
types. The mean grease and wax particulate found over the marine outfalls
had the following characteristics:

Size = 1.3 mm

Hexane Extractable Materials (HEM) = 1.0 mg

Coliform Bacteria ~ 2 x 10% organisms

Composition of HEM

PCB < 0.10%
Free Fatty Acids = 10%
Fats = 20%

Alkanes = 20%

Unidentified Long-Chain Organics = 10%

Bound Water = 40%
Their size remained constant regardless of distance from the outfalls but
their free fatty acid composition altered significantly.

2. The number of grease and wax particulates found in a sample usually
correlated directly with the mg of HEM extracted from the sample, regardless
of location. Interferences in the correlation were caused by pieces of tar.

3. The mass of HEM on the water surface within the study area may have
averaged approximately 840 kg during the surveys of 1971 and 1973. The concen-
tration of HEM ranged fron a maximum of approximately 33 mg/m? over the outfalls
to a minimum of 0.001 mg/m2 in the control areas.

4. The free fatty acid compositions of particulates strained from the JWPCP
effluent and collected over the outfalls at the same time were nearly identical.


table 13. COMPOSITION AND CONCENTRATION OF PARTICULATES CAPTURED BY

THE CLOTH SCREEN SAMPLER
(concentrations in thousands/m2)

— —= soy
April, 1971 (200X) Aug.-Sept., 1971 (430X)
No. No.
. of of
Location | Type jobs.} Aj B} Cj] D] E]obs.| D F G H
Hyperion Ss 1 46 | 15 2 | 6.5 |1635 | 299
outfall
NS 410 328 | 42 )1.7
awecp@ s
outfalls NS 8 | 2.6 | 260} 21 10.3
Hyperion, Ss 1 | 37 11 4 | 1.8 } 310] 20
3.7 km N NS 4} 3.2 | 411] 30
Control Ss 1 1] 1} 1) 149 4 | 0.7 | 243] 30
areas NS 4 | 5.8 | 560] 35} 1.6
Wi ndy day
Classification Code:
A Blue
B Purple
c Irradiant
D Fibers
E Metallic
F Clumped or flocculated minute debris
G Black
H Other
Ss Slick
NS Non-slick

at least in part, by the differences in magnification employed, but the
particulates found in the August-September 1971 survey should also have
been observed in the April survey, and vice-versa, because the field coverage
was about the same. For example, the large numbers of blue and metallic
appearing particulates found in the vicinity of the Hyperion outfall in
April 1971 did not appear at all in the samples collected in August-September.
The black and clumped particulates observed so frequently in the August-

7


unraveled. Their life could have been prolonged greatly by sewing about
the edges.

The glass cloth was relatively heavy and closely woven. Water, bacteria,
and micro-particulates collected into the fabric were not released easily
when washed with water. For this reason the cloth could not be used to
collect those samples which required easy release to analyze; i.e., coliform
bacteria, neuston, and micro-particulates.

The cloths were applied to the ocean surface with clean wooden tongs and
allowed to rest on the surface under their own weight. Clean fiberglass

rods were then inserted under the center of the cloths as quickly as possible
and they were raised from the surface and rolled about the rods for insertion
into individual sample containers. Some water dripped from the cloths in

the process but measurements showed that most must have remained in the
cloths. The average volume of water held on the 0.1 m2 cloths in the July
1973 survey was 12.8 mg with a coefficient of variation of 11%. Laboratory
tests indicated a pickup of about 15 mg without rolling, but some of this
water could have been excess fluid lying on the surface of the cloth. It
appears that the water was bound tightly in the cloth by surface tension

and the depth of water sampled may have varied between 0.128 and

0.15 mm.

SAMPLING AND ANALYTICAL ACCURACY

The analytical methods utilized paralleled those employed for the trawled
particulates. The glass cloths were first air-dried and extracted with
hexane in a soxhlet apparatus without prior acidification or saponification.
The long-chain fatty acids (Cy2-Co2) present in the HEM were analyzed by
reacting the HEM with the BFT reagent to form fatty acid esters which were
then identified and measured quantitatively by techniques of gas-liquid
chromatography. The PCB compounds and some pesticides were separated from
the HEM in an activated silica column and determined by methods of gas-liquid
chromatography.

77


10.

i.

12.
13.

14,

15.
16.

7.

18.

LIST OF TABLES

Title

Characteristics of Outfalls Samples... . 1...

Calculated Plume Submergence and Dilution Over

Marine Outfalls 2... ee ee ee ee

Summary of Surface Trawls 2... 2.2.05 ee eee

Summary of Surface Trawls - Coliform Bacteria

Concentration and Sizes of Prevalent Trawled

Particulates 2... ee ee

Explanation of Figure 19, Fatty Acid Composition of

Large Particulates 2... . . . eee ee ee ee
Comparison of Aesthetic Impact with HEM .......

Comparison of Coliform Bacteria with HEM .......

Mean Concentrations of HEM in Trawled Particulates

Analyses of 24-Hr Composite Samples of Hyperion

Effluent During Ocean Surveys of 1971 .......-.

Mass Emission Rates of Particulate HEM From

Treatment Plants 2... 2 2 ee ee ee ee ee

Local Mass Balance on HEM of Trawled Particulates ...

Composition and Concentration of Particulates

Captured by the Cloth Screen Sampler .........

Sizes of Prevalent Types of Particulates Captured

by the Cloth Screen Sampler: August-September, 1971 . .

Concentration of Cloth Screen HIM .... 1... 2.4.

Concentration of Cloth Screen Fatty Acids:

duly, 1973 6 we

Mean Concentrations of Cloth Screen HEM and

Fatty Acids 2... ee ee

Concentration of Coliform Bacteria: Cloth Screen

and Ocean Water Samples .......2.00 200200]

ix

19
37
39

41

45
55
57
58

60

62
63

71

74
80

82

83

84


SOL

Table 26. OCEAN CURRENTS IN AUGUST-SEPTEMBER 1971 SURVEY

— ae
Station 2 Station 3b Station 4
Station 1 (10 to 11 a.m., (9:40 to 10:15 (7:41 to 8:21
(7 to 8 a.m., Aug. 31) Sept. 1) a.m., Sept. 2) a.m., Sept. 3)
Depth | Speed | Direction | Speed | Direction | Speed | Direction | Speed j Direction
m knots true knots true knots true knots true
1 30 N +25 W +20 W 40 NW
10 15 SW 30 W +20 NW -20 N
15 15 SW +35 W +20 E +25 NW
20 20 SW 15 NW 05 NW +20 N
30 +20 SW 10 N 20 E 30 N
40 4) SW 20 SW 10 N +20 N
50 10 W +25 SW - - 20 NW
55 - - 10 SW - - 10 N



CONCLUSIONS

The project staff decided to abandon the micro-particulate sampling after
the rather inconclusive results obtained in the August-September 1971 survey.
Obviously the source of the particulates found in that survey could very well
have been atmospheric fallout with the clumped debris being dust blown from
the mainland. The ocean surface appeared very clean in the July 1973 survey
and possibly micro-particulate sampling conducted at that time would have
revealed more about the nature of the micro-particulates. The best that can
be stated at this time is that the numbers and volumes of such particulates
were gross and it appears that some of them were truly derived from the
wastewater effluents as discussed in the following section.

75


14,

15.

16.

7.

18.

19.

A Synoptic Survey of Chlorinated Hydrocarbon Inputs into the Southern
California Bight. Annual Progress Report to the Environmental Protec-
tion Agency. Southern California Coastal Water Research Project, ET
Segundo, California. August 1973.

Kawahara, F. K. Microdetermination of Pentafluorobenzyl Ester Derivatives
of Organic Acids by Means of Electron Capture Gas Chromatography.
Analytical Chemistry. 40:2073-2075, November 1968.

Kawahara, F. K. Gas Chromatographic Analysis of Mercaptans, Phenols,
and Organic Acids in Surface Waters with Use of Pentafluorobenzal
Derivatives. Environmental Science and Technology. 5(3):235-239,
March 1971.

Carter, R. C. Surface Pollution of Coastal Waters. Thesis of University
of California, Berkeley, pp. 151-158, 1973.

Reynolds. L. M. Polychlorobiphenyls (PCB's) and Their Interferences
with Pesticides Residue Analysis. Bulletin Environmental Contamination
Toxicology. 4(3):128-143, 1969.

Veith, G. D. Environmental Chemistry of the Chlorobiphenyls in the
Milwaukee River. Theses of University of Wisconson, 1970.

101


bulk water samples taken 10 cm underneath the screen samples, and any such
concentration had to be less than approximately one organisms/100 me.

The variable nature of the data suggests that the bacteria were contained
in fine debris of wastewater origin. The nylon net sampler collected a
layer about 0.1 mm deep and the maximum size of the particulates captured
was less than 100 yp as shown in Figure 27. It appears that the bacteria
containing debris had sizes of less than 100 yu. If they averaged 100 uy then
the volumetric concentration of bacteria in numbers/100 meg would be equal

to the surface concentration in numbers/m?, If they were smaller then the
volumetric concentration would be proportionately greater.

Figure 28 shows the cumulative frequency distribution of coliform bacteria
found over the outfalls in 1971 in terms of number/100 me (or number/m?).
The frequency distribution was close to exceeding a bathing water standard
of 1000 organisms/100 mg for 80% of the time. These concentrations probably
would be superimposed on those found for the trawled particulates (Figure
25).

PCB_ Compounds

PCB compounds as Aroclor 1254 were highly concentrated in the slick areas
over the outfalls as shown in Table 19. Extraordinary concentrations of
120 and 39 yg/m2 were found over the Hyperion outfall in 1971. These would
be equivalent to volumetric concentrations of 800 and 260 ug/2, respectively,
assuming a sampling depth of 0.15 mm for the glass cloth screens. These
appear well in excess of the solubility of PCB compounds in water [13],
suggesting that the PCB compounds were dissolved in the film material and/
or micro-particulates. With the exception of observations made directly
over the various outfalls the PCB fraction of the cloth screen HEM was
fairly consistent, averaging about 0.58% by weight. In the trawled parti-
culates, the PCB fraction of the HEM was generally less than 0.10%. The
PCB compounds apparently tended to concentrate to a greater degree in the
substances collected by the glass cloth samplers than in the trawled
particulates.


additional analyses; visual identification, fatty acid composition, and
coliform bacteria. In the case where non-extractable wastewater particu-
lates are preponderant, a dry weight analysis might prove to be of greater
benefit.

SIGNIFICANCE OF SURFACE POLLUTION

It has been demonstrated that particulates can reach the ocean surface through
a well defined ocean density structure. The significance of this type of
pollution is now evaluated in terms of HEM, the parameter believed to be

of greatest value in its control.

Aesthetic Impact

In the July 1973 survey it was possible to evaluate the aesthetic impact of
the particulates with a team of 6 to 7 observers composed of sampling personnel
and the ship's crew. (Prior to this time the number of sampling personnel

was too small to make very valid assessments of aesthetic impact.) A rating
sheet of the type shown in Figure 24 was used and the average response was
determined from a scale ranging from 0 to 3 points, with the points increas-
ing as the surface appearance deteriorated. The results are summarized in
Table 3.

It is difficult to relate surface appearance with any quantitative measure
such as HEM because the particulates seemed more objectionable when gathered
in a slick than when free, and any surface trawl tends to strike an average
through zones of both high and low particulate concentration. Even so, the
aesthetic evaluations tended to correlate with the HEM as shown in Table 7.

Remembering that 1 mg/m? of HEM was approximately equivalent to 1 grease
and wax particulate/m?, it is apparent that a relatively high HEM concen-
tration is necessary before the surface becomes aesthetically offensive.

It may be appropriate to maintain an HEM concentration of less than 3 mg/m?
to be on the safe side at all times, however.

54


Fatty Acids (FA

The fatty acids (Cy-Cy2) were determined directly on the HEM without
acidification or saponification. Only free fatty acids could be determined
in this manner.

It was believed that acidification, which is not easily accomplished with
soxhlet extraction, would not increase the yield of HEM appreciably because
the grease and wax particulates appeared to extract readily as discussed
previously and because little residue was Teft over in the soxhlet thimble.
Saponification increased the yield of the fatty acids considerably when

an experiment was conducted on one trawl] sample collected over the JWPCP
outfalls in July 1973. The results indicated that 12% of the HEM was composed
of free fatty acids and 18% of fats. The saponifiable fatty acids contained
large fractions of saturated C,, and C,s acids while those extracted directly
were preponderantly unsaturated C;g acids (see Figure 19). Carbon, hydrogen,
oxygen analyses indicated that 38% of the remaining HEM was simply bound
water, 21% alkanes (paraffins) and 10% unidentified long chain organic
compounds. Thus, the visual description was apt, the sewage particulates
were composed primarily of grease and wax.

Figure 22 shows that the total weight of the unsaponified fatty acids com-
prised about 10% of the HEM on the average. This proportion varied rather
grossly at times but no trend was evidenced with distance from the outfalls.
Thus, the FA analysis could be used as well as the HEM to measure the grease
and wax particulates but the results would be considerably less reliable.

The composition of the fatty acids altered considerably with distance from
the outfalls as shown in Figure 19. The proportion of Cig acids increased

at the expense of the Ci, acids, but the proportion of saturated free stearic
acid remained approximately constant at 10 to 20%.

50


IV, DESCRIPTION OF OCEAN SURVEYS

This study was conducted in the San Pedro Channel and Santa Monica Bay
regions of the Southern California Bight as shown in Figure 1. Sampling
Stations 1 and 4 were located over the marine outfalls of the Hyperion

Plant of the City of Los Angeles and the Joint Water Pollution Control Plants
(JWPCP) of the County of Los Angeles, respectively. Station 2 was located
3.7 km north of the Hyperion outfall and Station 5 west of the Palos Verdes
Peninsula at the latitude of the Marineland of the Pacific. This station
will be called "Marineland" at times in this report and it was located
approximately 14 km northwest along the coast from the JWPCP outfalls.

Stations 3a and 3b were selected as control areas. They were located at the
northern end of Santa Catalina Island and out of the main surface circula-
tion pattern of Santa Monica Bay. This region was approximately 44 km south
of the Hyperion outfall and 33 km southwest of the JWPCP outfalls.

Three field surveys were conducted in 1971. The objectives of the first two,
performed on April 7-8 and August 31-September 3, were to evaluate various
means of sampling the water surface for flotage, the identification of sur-
face pollution, and the significance of sea slicks in concentrating the flotage.
The third survey of December 9 was for the purpose of tracing the movement

of flotage on the sea surface.

The data procured from the 1971 surveys were analyzed and a fourth survey
of the study area was made on July 11-13, 1973. The major emphasis of that
survey was placed on surface film sampling because the results of the 1971
surveys were inadequate in some respects for this type of sampling.

The two outfall systems sampled, JWPCP and Hyperion, had about equivalent
flows and contributed together about 71 percent of the total wastewater
flow released to the California Bight in 1971 [1]. The two other major
dischargers , Orange County and San Diego, were located many kilometers south
of the study area. The dimensions of the outfalls sampled are presented

10


wastewater origin; consequently, they were called "sewage types." Included
in this category were such objects as pieces of grease and wax, plastic,
fiber, rubber, wood, seeds (several kinds), and unidentifiable tissue and
debris. The grease and wax particulates were always predominant, and the
seeds and plastic were usually prevalent.

Other types of particulates were obviously of natural origin. Pieces of
kelp and tar were the most prevalent in this category. In some samples the
kelp predominated over all the other types of particulates.

The particulates captured in the August-September survey of 1971 were measured
with the aid of a dissecting microscope and the size distributions of the
more prevalent types were determined. The mean sizes of each type showed
some tendency to vary from location to location but the trends were not
Pronounced except in the case of the kelp. Consequently, all of the size
data except kelp were lumped together without regard to sampling location,
with the results shown in Table 5 and Figure 17.

Two types of size distributions were obtained; log-normal and uniform. The
sizes of the grease and wax particulates, the tar, and the kelp were distri-
buted log-normally; implying a process of natural erosion [6]. The seeds
and pieces of plastic were more or less uniform in size although an occasional
large piece of plastic was recovered.

The side netting and collector screen used in the surface trawl had a pore
size of 0.5 mm; consequently, it might be expected that objects less than
0.5 mm would not be captured. Generally this proved to be the case but
Figure 17 shows that 15% of the grease and wax particulates captured had
sizes equal to or less than 0.5 mm. Some of these particulates were very
sticky, and they tended to adhere to everything in sight. They

seemed to favor the kelp, and in some instances the kelp had grown partially
or even completely around the grease. This proves that their association
did not always result from the sampling method utilized, and that those
particulates had persisted for some time in the environment. It also

40


that was the limit of detectability for PCB at that time. These fractions
were disproportionately small in comparison to those found in the ocean
film materials and the analysis was not pursued further. Pesticides, if
present, also were minute. These tests were not conducted on the non-
extractable particulates such as plastic.

PROOF OF WASTEWATER DERIVATION OF PARTICULATES

Proof that some of the trawled particulates were derived from wastewater

discharges is as follows:

1. The particulates could be seen rising to the ocean surface within the
vicinity of the marine outfalls. Photographic evidence is presented
in Figure 18. (See page 119)

2. Coliform bacteria were found in the particulates collected over and
near the outfalls, but not in the control area.

3. Figure 19 shows that the fatty acid compositions of the particulates
collected over the JWPCP outfalls on July 11, 1973 and those screened
from the JWPCP wastewater effluent on July 13, 1973 were nearly identical;
whereas the acid compositions in the Marineland and control areas were
grossly different. For example, the proportion of unsaturated Cig
acids decreased from approximately 60% in the effluent particulates
to 25%.or less in the control area particulates, and the proportion
of Cyg acids increased from approximately 30% in the effluent particulates
to 65% in the control area. (See page 119)

Table 6 presents data pertinent to Figure 19. It shows that the average
concentration of HEM strained from the JWPCP effluent on July 13, 1973 was
0.65 mg/2. Both the HEM and the total fatty acid concentrations decreased
about 5000 times from the outfall area to the control area. Not all this
decrease may be ascribed to the wastewater discharges because the natural
background may have been higher close to the mainland.

The fatty acid composition of the HEM was also determined in the samples
collected in the August-September survey of 1971 but the degree of


Table 14. SIZES OF PREVALENT TYPES OF PARTICULATES CAPTURED BY THE
CLOTH SCREEN SAMPLER: AUGUST-SEPTEMBER, 1971

Hyperion JWPCP Hyperion, | Control
outfall outfalls | 3.7 km N area
Clumps of debris
Median size, u 5.5 2.5 3.5 2.5
Mean size, u 12 6.5 8.2 6.5
Concentration ,k/m2 581 260 363 388
Black particulates
Median size, u 4 4 4 3
Mean size, u 5.5 5.5 5.5 4.1
Concentration ,k/m2 92 21 25 33

The particulates tended to increase in numbers over the Hyperion outfall
(Table 14), but those collected over the JWPCP outfalls had about the same
concentrations as observed in the control area, and north of the Hyperion
outfall. (It should be recalled that samples were collected over the
JWPCP outfalls on a windy day.) Again with the exception of the-samples
collected over the Hyperion outfall, no significant differences in the
concentrations of particulates were found between slick and non-slick areas
(Table 13).

The sizes of the micro-particulates tended to decrease with distance from

the Hyperion outfall (Table 14) but again the samples collected over the
JWPCP outfalls contained micro-particulates whose sizes were nearly equal

to those found in the control area. No significant differences in particulate
size were noted between slick and non-slick areas at a given location.

74


11. The HEM analysis can be used only to control surface pollution resulting
from duplex (of1) films or unusually high concentrations of wastewater micro-
particulates. It is too gross a measure to control any pollution existing
in the form of surface monolayers.

12, At the present time only the coliform bacteria analysis can be used to
reliably control surface pollution derived solely from wastewater discharges.
A criterion of 1000 total coliform organisms per m2 of ocean surface is
suggested but with reservation because such a criterion could prove to be
extremely difficult to meet.


60

GREASE AND WAX PARTICULATES, No./m2

100

[

107 1)—

10-27 —

1073

| | | I

@ OVER OUTFALLS
ZX AWAY FROM OUTFALLS
m= CONTROL AREAS
\V__ INDICATES <

ad

SEAWEED
fe

SEAWEED ??

@
ae/ ©

4 ¥ @ TAR
| 4 ‘ | |

1o"#

10-3 10-2 to! J
HEXANE EXTRACTABLES, mg/m?

10

Figure 21. Comparison of Grease and Wax Particulates With

HEM

100


TABLE OF CONTENTS (Continued)

Section Page

Sampling Procedure. 2... ee. eee ee 69

Analytical. Procedure .. 1... eee eee eee 70

Results 2. ee ee ee 70

Conclusions 2... ee ee 7%

VII. SURFACE SCREEN SAMPLES .. 1... 1 1 ee ee ee eee 76

Sampling Procedure 2... 1.1 eee eee ee es 76

Sampling and Analytical Accuracy .......2-0-- 77

Results of Surveys... 1... ee ee ee ee 79

Discussion of Results . 2... ee ee eee eee 85

Origins of Cloth Screen Fatty Acids ......... 96

The Significance of the Surface Pollution ...... 96

Control of the Surface Pollution ........2. 97

VIII, REFERENCES 6 ww. ee ee 100

IX, GLOSSARY we ee ee 102
APPENDICES

A, Miscellaneous Tables 2... 1. eee eee ee es 103

B. Analytical MethodS 2.2... . eee ee ee ee ee 109

vi


small, or there would be insufficient space to hold the particulates.
Figure 17 shows that about 99% of the grease and wax particulates captured
in 1971 had sizes equal to or less than 5 mm. It was assumed somewhat arbi-
trarily that a depth less than this would exclude a significant portion of
the grease and wax particulates.

It was found that 1 mg of HEM contained a median of 12,000 coliform bacteria
(Table 8 and subsequent discussion). Allowing for a depth of 0.5 cm, approxi-
mately 4 mg/m? of HEM would give a median volumetric concentration of 1000
organisms/100 me ([1000/100 me] x [5,000 me/m?] x [1/12,000/mg] = 4.2 mg/m2),
Figure 25 shows that the 80% value of the cumulative frequency distributions
for surface coliform concentrations was about twice that for the 50% value;
consequently, a median of about 2 mg/m2 of HEM would be necessary to insure
that 1000 organisms/100 mz would not be exceeded in 80% of the samples.

Intuitively, one feels that a coliform standard for floating parti-

culates should be more strict than for the bulk sea water. For example, one
grease and wax particulate may contain 12,000 coliform bacteria. This would
be equivalent to 1.2 2 of seawater at a concentration of 1000 bacteria/100 me.
No individual would swallow 1.2 2 of seawater voluntarily, but he might ingest
relatively easily a small floating grease particulate. Also, Table 8 indi-
cates that no appreciable coliform die-away occurred in the particulates
collected 3.7 km north of the Hyperion outfall. This is not too surprising
because the particulates may shield the bacteria and any pathogens present
against the rather hostile ocean environment. Some decay must occur but
apparently it is much less than that demonstrated for coliform organisms

in bulk seawater. Thus, the relatively rapid rate of bacterial decay usually

used in ocean outfall design cannot be relied upon in the case of floating
particulates,

The results of these studies indicated that wastewater pollution may be
detected to concentrations as low as 0.02 mg/m2 of HEM (Figure 26), The
maximum concentration observed was approximately 33 mg/m2 (Table 3). Both
the aesthetic ratings and coliform bacteria analyses indicated that a
reasonable concentration should be something less than 3 mg/m2 of HEM. A

66


Table 2 . CALCULATED PLUME SUBMERGENCE AND DILUTION
OVER MARINE OUTFALLS

Daily Plume Initial
flow submergence | dilution
Outfall Date m/s m
Hyperion | IV-7-71 14.9 12 100
VIII-31-71 | 15.2 21 90
JWPCP
90" IX-3-71 5.4 33 100
VII-11-73 5.1 7 (a)
120" IX-3-71 11.3 33 70
VII-11-73 10.6 15 (a)

No submarine currents measured.

outfalls of the JWPCP facility was estimated. Using these data plus the
density gradients measured or estimated at each outfall, the rise of the
effluent plumes above the diffusers was estimated using the methods of
Brooks [2]. In the case of the two older Y shaped diffusers it appeared
that the jets derived from the rather widely spaced ports would rise more

or less independently without much overlap, but the jets from the L shaped
diffuser would soon overlap giving continuous curtains of rise. The results
of these computations in terms of plume submergence are presented in Table 2.

Initial dilutions over the outfalls were also estimated using the methods
of Brooks [2] as well as the continuity equation in those cases where the
currents had been measured with depth. In general the continuity approach
yielded the lesser initial dilution values and those estimates are presented
in Table 2 along with the estimates of plume submergence. The current data
utilized for this purpose are tabulated in Tables 1 and 2 of Appendix A.

The results shown in Table 2 indicate a minimum plume submergence over the
Hyperion outfall on April 7, 1971; being at a depth of only 12 m or so.
Maximum submergences of 20 m or greater may have occurred in the summer
survey of 1971. The plume submergences computed for the July 1973 survey

19


disappearance most likely was not caused by rapid bacterial decomposition
but rather some mechanism of removal from, or transport out of the entire
study area. For example, the particulates could have been filtered out on
the kelp, consumed by aquatic birds, or transported to the coast by the
wind or internal waves. All of these factors were observed in operation
during the various ocean surveys.

Transport Study

An attempt was made to measure the movement of large polyethylene pellets
(average size of 4 mm and a specific gravity of 0.985) on the ocean surface
on December 9, 1971. As usual the weather was not particularly conducive
for such work with the wind being onshore and in excess of 3.6 m/s in the
morning. This was sufficient to destroy any slicks which might have existed
in the study area.

The wind did decrease around 2 pm, however, and band slicks formed in the
area as shown in Figure 11. At 2:40 pm, 400 g of the pellets were seeded
along 12.5 m of the shoreward edge of a band slick at a density of approxi-
mately 900 pellets/m of slick. A surface drogue set for a 2 m depth was
also released at that location.

The pellets were followed for a period of 80 minutes and they remained more
or less undispersed along the shoreward side of the slick. The slick moved
shoreward with an average speed of 0.20 m/s while the wind steadily decreased
to values of less than 2.8 m/s. The drogue was not followed but it ended up
well southward and seaward of the pellets.

There was a comparatively slight amount of stratification in the water to a
depth of 80 m but internal waves were present [9] and the band slicks appeared
to be associated with the internal waves. Unfortunately, these observations
had to be terminated with the early onset of dusk (5 pm), and it is not clear
if the pellets and band slick were being moved shoreward by the onshore wind
or the internal waves. Also it would have been interesting to record the
fate of the pellets in the surf zone, and if pellets added between the

slick bands would eventually be incorporated into one of the slicks,

64


200 | | | | | | J 4 | 20
Hyperion
— A
% April 7, 1971 9 os
=< =
aan _| Ss
geo mee
es 4 Ls
g - §
bat aa —— a
3 a
S 50 L-5 5
Ss O uo
2 ~~] a n
=I a
= z
2 7)
PJ —_S -— D>
= 2
- e
o(1.4)
20 2
PoP T TT TT T

5 10 20 30 40 50 60 70 28 90 95
PERCENT EQUAL TO OR LESS THAN

Figure 25. Cumulative Frequency Distributions of Coliform Bacteria
Surface Concentration: 1971

Table 8. COMPARISON OF COLIFORM BACTERIA WITH HEM

HEM Coliform bacteria
mg/m2 no. /m2
Location Date (average) (median) No./mg of HEM
-7- a 4
Hyperion IV-7-71 10.8 150 ,000 1.4 x 10
VIII-31-71 2.0 3,000 1.5 x 103
JWPCP IX-3-71 2.2 63,000 2.9 x 10"
3.7 km N IV-7-71 0.34 6,4504 1.9 x 104
of Hyperion | ty.4-71 0.13 2,500 1.9 x 104
(3a) IV-8-71 0.025 <0.0043 <0.2
Control (some atypical)
(3b) IX-2-71 0.0012 <0 .00070 <0.6

3One trawl sample only.

57


in Table 1 together with the average 1971 flows and effluent quality
characteristics.

The JWPCP outfall system was complicated, consisting of three separate
outfalls. Most of the flow was released from ejther the 90 inch (2.29 m)
or 120 inch (3.05 m) outfalls, with the split between the flows shown in
the table being an estimate.

The JWPCP effluent was a primary effluent containing significant portions

of industrial wastewater [1]. Table 1 shows that it was relatively strong
in terms of grease, BOD, and other routine measures of wastewater quality.
The Hyperion effluent, on the other hand, stemmed almost entirely from
domestic sources and a portion of it received secondary treatment (activated
sludge). Its quality was better than that of a normal primary effluent,
reflecting its domestic nature and the influence of the secondary treatment.

Commonly both effluents were chlorinated during periods of effluent plume
surfacing. No chlorine was being added to the effluents during the surveys
of 1971, but it was being added to the JWPCP effluent in July 1973. All
effluent samples collected at that facility were taken beyond the chlori-
nation process.

EFFLUENT PLUME SUBMERGENCE

Of great practical significance is the depth of effluent plume submergence
occurring during the field surveys. The depth of the effluent plumes were
not measured directly in this study but water temperature and salinity were
measured with depth at all the stations occupied during the first two sur-
veys. The results showed that most of the density structure resulted from
temperature variation and only the observed temperature and computed density
profiles are shown in Figures 2, 3, 4, and 5. Water temperatures only were
measured during the July 1973 survey with the results being presented in
Figgre 6. ;

12


to the coast but some paralleled the coast, suggesting two independent slick
Patterns with one moving across the other. The wind increased to 7 knots
(3.5 m/s) by noon and the slick patterns disappeared.

On the following day an easterly morning wind was much too strong to permit
sea slick formation in the JWPCP outfalls area, but the land mass of the
Palos Verdes Peninsula sheltered the waters lying to the west of the
peninsula and a series of band slicks were found at the Marineland station
shown in Figure 13. The wind in this region was from the east, approximately
steady at 6 to 7 knots (3 to 3.5 m/s}, and theslicks were broad and il1-
defined, with some running normal and others parallel to the coast. By

noon the slicks had been broken up and dispersed by the easterly wind.

A break in the wind pattern occurred on July 13, 1973 when unsteady westerly
winds dropped from an average of about 6 knots (3.m/s) in the early morning
hours to 4 knots ( 2 m/s) by noon. A series of band slicks were

observed in the control area northwest of Santa Catalina Island (Station
3b) as shown in Figure 14. No interfering slick band patterns were observed
and the slicks tended to run normal to the coast.

Photographs of the sea slicks observed in the summer 1971 and July 1973
surveys are shown in Figure 15 for the areas over the Hyperion and JWPCP
outfalls. Unfortunately, photographs were not taken of the large standing
slick found over the Hyperion outfall on April 7, 1971. (See page 117)

DISCUSSION

Very little information exists in the literature concerning the mode of
formation or significance of wastewater sea slicks. One recent paper by
Newton [3] describes the prevalence of sewage slicks in an estuary and some
attempts were made to procure a mass balance on amounts of fats released
and the extent of the resulting surface sewage films. Unfortunately, there
exists orders of magnitude differences between that study and this, where
the grease content of the effluentswere grossly less and the effluent
plumes remained submerged beneath the ocean thermocline.

29


FATTY ACIDS, mg/m?

10

1 © OVER OUTFALLS 0
x AWAY FROM OUTFALLS
— CONTROL AREAS O
107? 0 _
of
o-? x © SEAWEED _
TAR
10-3 _
1o"# y Oo og —
10-5 lA | | | | |
10-4 10-3 10-2 10-1 1 10 100
HEXANE EXTRACTABLES, mg/m2
Figure 22, Fatty Acid Proportion of HEM

51


SL

DEPTH,

1 Meter Observation Interval

104

20-

507

Sept. 2, 1971

———-— Sept. 3, 1971

12.13 14 «+15 16 17
TEMPERATURE, °C

Figure 4.

T
1819 20 W112 13 «14 «15 1 17
TEMPERATURE, °C

L 1 | 1 i 4 4
Yo
t
/
7
/
/
- L 4
c .
Station 1 Aug. 31, 1971 Station 3b
Station 2 ------ Sept. 1, 1971 t 4 Station 4
' 1
— 77
Station 3b Bottom 100 meters
I 7 1 r T r T r 1 : 1 7 r

T T
18 #19 20

Temperature Profiles Observed at Sampling Stations: August-September, 1971

21



v8

Table 18.

CONCENTRATION OF COLIFORM BACTERIA: CLOTH SCREEN
AND OCEAN WATER SAMPLES

Cloth Screenings

Bulk Water@

No. No. Total No.
of meb No. of No. No. | of me of No.
Location Date Samples | Filtered | Colonies 00 mg m2 |Samples | Sampled | Colonies 00 me
4.7 41 880 880
IV-7-71 4 4.7 34 720 720 4 75 none <1.3
4.5 none <22 22
Hyperion 7.2 none <14 <14
outfall 14.9 none <7 <7
VITI-31-71 4 1.94 100 5150 5150 4 400 none <0.25
10.0 none <10 <10
4.8 none <2] <21
5.2 21 405 405
JWPCP IX-3-71 4 5.4 none <19 <19 4 400 none <0.25
outfalls 5.1 none <20 <20
5.4 30 555 555
IV-7-71 4 33.2 none <3 <3 4 100 none <]
: total
Hyperion,
3.7 km N IX-1-71 4 35.1 none <3 <3 4 400 none <0.25
total
IV-8-71 4 33.9 none <3 <3 4 200 none <0.5
Control total
areas
IX-2-71 4 38 8. none <3.5 <3.5 4 400 none <0.25
otal

collected 0.10 m under ocean surface.
One of sample actually filtered, not me of sample collected.



Le

Table 3. SUMMARY OF SURFACE TRAWLS
One m2 of Traw] Equals 30 2 of Strained Water
Traw1s Counts Fatty Acids
xy 4 % Dry Aes the-
Sta. No. Area slicks No./m? | Sewage We. HEM | mg/m? aa Pa tic a
Location No. Date Type |mg/m2 |mg/m2 16 /*18 IRating'
we | wo | 5.2 | 92 |12
IV-7-71 3 | 268] 100 | 3.4 | 82 5.7 | 2.8 3
yperton , 163} 100 | 18 go | 4a 24
outfall zo | 30 | 0.37 | 78 0.15 | 0.06 |o.001] 36 | 42
74 | 30 | 0.78 | 94 0.95 | 0.39 |0.27 | 22 | 73
VIEI-31-71 | 4 | 53 0 | 1.2 | 82 2.4 | 0.91 |0.22 | 27 | 67
62 0 | 1.4 | 93 [25.3 | 6.6 |0.80 | 26 | 52
35 | none | 0.80 | 46 0.46 | 0.15 |0.01 | 32 | 53
Ke3-71 4 | 118 | none | 0.75 | 41 4.7 | 0.15 |0.02 | 29 | 61
101 | none | 3.4 | 85 | 36 2.8 {0.01 | 31 | 39
JWPCP 4 108 | none | 9.0 | 91 9.0 | 4.4 }0.66 | 16} 79} 2
outfalls
245 | 100 24 12 1 21 | 76
318 | 20 51 32.5 |2.8 | 34] 61 2.3
VII-11-73 | 4 | 9537 | 29 26 9.0 |1.1 | 25] 68] 1.5
276 | 20 6.6 | 1.7 |o.10 | 27 | 67
304. | 48 | 0.93 | 61 1.4 | 0.89
IV-7-71 3 | 320 | none | 0.55 | 49 1.0 «| 0.11
Hyperion, , 320 | none | 0.30 | 37 0.13 | 0.021
3.7 km N 110 | 100 | 0.88 | 56 0.94 | 0.15 |0.05 | 64] 31
Mele71 4 | 159] 23 | 0.36 | 83 0.38 | 0.10 }o.01 | 31} 61
yaa { 100 | 1.5 | 73 2.6 | 0.07
68 | 43 | 1.6 | 99 1.7 | 0.31 |o.o1 | 42 | 44



In summary, it is believed that the glass cloth sampler collected insoluble
duplex and stable monolayer surface films accurately. The divalent acid
salts probably were not extracted to any significant extent with the hexane
because the samples were not acidified. Alkanes, fats, free fatty acids,
alcohols, etc. were extracted to become a part of the HEM but only the free
fatty acids were analyzed because the fatty acid esters were not decomposed
first by saponifying. Acidification and saponification were not easily
performed on the minute quantities of material collected in the cloth screens,
and every additional analytiéal step introduced the spectre of more back-
ground contamination. It should also be recalled that micro-particulates
were found in great profusion on the sea surface and that they also would

be captured by the glass cloth sampler; consequently, it was difficult to
assess which portions of the HEM or fatty acids were derived from the surface
film and which from the micro-particulates.

RESULTS OF SURVEYS

Hexane Extractable Materials (HEM)

Four individual glass cloth samples were collected at each station in the
April 1971 survey. These samples were taken in slick areas only. The
sampling was extended to both slick and non-slick areas in the August-
September 1971 survey with rather inconclusive results. The sampling
frequency was then increased greatly in the July 1973 survey as shown in
Table 15.

The table shows that the HEM concentrations were extremely variable and that
they decreased grossly on the average from 1971 to 1973. That decrease
might have been caused in part by increasing analytical precision in the
second year, but it could have stemmed as well from actual seasonal and
weather effects. Some of the HEM concentrations found in the 1973 survey
were so low they approached the background levels still existing in the
glass cloths (0.10 mg/m2 or less). Those particular observations are
indicated by dashes in Table 15. (The 1973 observations were corrected for
a background of 0.10 mg/m2 which stemmed from the glass cloth screens

employed. )
79


Bacteria

Table 4 lists the results of the bacterial analyses. All of these analyses
were made in 1971 when the effluents were not being chlorinated. An oppor-
tunity was missed to evaluate the effect of chlorination when these analyses
were eliminated in the 1973 survey.

The hacteria were collected on membrane filters and incubated in differen-
tiating media in accord with Standard Methods [5]. Only typical coliform
bacteria colonies were counted and recorded (green metallic sheen) but

many more atypical colonies appeared on the filters. The atypical colonies
were highly concentrated over the outfalls but a few were found in the
samples collected on the northeastern side of Santa Catalina Island (Station
3a) in the spring of 1971. As a result, the control area was shifted to the
seaward side of the island in the summer survey where no bacterial colonies

of any type developed On the membrane filters.

Figure 25 shows the cumulative frequency distributions of the coliform
bacteria surface concentrations found over the various outfalls in 1971.
The median values of the surface concentration varied widely, with that
observed over the Hyperion outfall in August 1971 being significantly less
than the others. All of the trawls of the August-September survey were
conducted during periods of high wind, when the sea slicks had

been, or were on the verge of being destroyed. Undoubtedly the counts would
have been higher during a calm spell when all of the particulates would
have been present at the air-sea interface.

The coliform samples were collected and analyzed independently of all the
other particulate analyses. Even so, an approximate relationship appears
to exist between the coliform organisms and the HEM as shown in Table 8.

Aside from the observations made over the Hyperion outfall in August 1971,

the table shows that the number of organisms found per mg of HEM was
remarkably consistent in the samples taken over or near the marine outfalls.

56


Table 15.

(conc. in mg/m2)

Concentration of Cloth Screen HEM

Hyperion, JWPCP Control Areas
Hyperion Outfall JWPCP Outfalls 3.7 km N 14 km NW 3a 3b 3b
Type | IV-7-71 | VITI-31-71| IX-3-71 | VII-11-73 | IV-7-71 | IX-1-71 | VII-12-73 | IV-8-71 } IxX-2-71 | VII-13-73
12.60 1.60 0.35 2.10 1.25 0.33 1.30 0.80 0.23
0.25 2.15 1.50 5.75 0.80 0.40 2.65 0.75 -
1.40 1.55 1.00 1.20 1.45 1.95 2.80 2.25 0.32
1.35 3.05 0.40 1.70 3.30 0.54 1.40 1.60 0.29
0.85 0.64 0.12 0.36
0.32 0.64 0.38
. 0.38 0.47 -
Slick 1.29 -
0.71 0.15
3.41 0.23
0.82 0.58
0.73 0.18
0.60 0.62
1.00 0.27
0.45
Mean 3.90 1.84 0.91 2.69 1.70 0.64 2.04 1.35 0.26
0.30 1.454 0.26 0.12 0.75 - 1.05
1.20 1.80 0.45 1.40 0.20 3.35 0.40
2.12 1.10 0.41 1.05 0.25 1.30 0.16
1.30 0.95 0.23 1.85 0.24 - 0.35
0.50 3.96 0.34 0.06
Non- 2.30 0.60 0.25 0.08
Tick 3.60 1.08 0.47 0.13
site 1.50 1.10 0.21 0.13
0.65 1.03 0.13 0.20
3.10 0.82 0.25
0.82 0.12
0.08
0.10
Mean 1.23 1.70 0.98 1.26 0.23 1.43 0.16

aWindy conditions, no slicks present.

5

See Table 16 for location over diffusers.



solution, rinsed with distilled water, baked out at 103°C, and purged with
nitrogen gas while still hot. Blanks were run frequently on reagents and
glassware for contamination monitoring.

The fiberglass cloth samplers were washed in distilled water and then air
dried in a hood. The cloths were then soaked in a 60°C dichromate and acid
cleaning solution (heated initially only) for twenty four hours after which
they were removed, washed with tap water, rinsed with distilled water and
then air dried as before. The cloths were then placed in a 4 liter bottle of
hexane with a few pellets of KOH in the bottom, a reflux condenser fitted

to the bottle's tapered glass joint and the hexane refluxed on a hot plate
for 4 hours. The cloths were then extracted in soxhlet extractors, 2 to a
soxhlet for 4 hours with hexane plus a few pellets of potassium hydroxide.
Fresh hexane, distilled in glass from pesticide quality hexane was then used
to extract the cloths for 2 more hours (no potassium hydroxide present).

The extracts from 6 soxhlets were then combined, dried, and weighed to deter-
mine the cleanliness of the extracted cloths. The hexane residue was then
reacted with BFT and the fatty acids present determined by GLC to determine
cloth background tevels.

115


SELECTED WATER 1. Report No] 2.
RESOURCES ABSTRACTS

INPUT TRANSACTION FORM Ww

5. Report Date

"The Significance and Control of Wastewater Floatables

in Coastal Waters." & Performing Organization
Report No.

bad

Selleck, Robert E., Lloyd W. Bracewell, and Ralf Carter

1BA025
Sanitary Engineering Research Laboratory :
College of Engineering & School of Public Health 800373
University of California, Berkeley 15. Type f Repost and

Period Covered

32, Sponsorin’ Organ’ ation

Environmental Protection Agency Report No. EPA 660/3-74-016, January 1974

Significance of flotage derived from submerged primary effluent plumes in
the Southern California Bight is evaluated in terms of three components: particulates >
0.5 mm in size, particulates <0.1 mm in size, and surface film materials. The sampling
methods utilized to collect the flotage from the surface are described in detail. The
surface film and micro-particulates were captured by fabric screen samplers developed
during the course of the study.

It was found that the large particulates penetrated the ocean thermocline and gath-
ered on the surface in profusion. The grease and wax portions of the particulates could
be measured reliably with hexane extraction, with the mass of HEM of sewage origin being
in the order of a metric ton on the water surface within the study area. Such particu-
lates contained considerable numbers of coliform bacteria but little PCB compounds or
pesticides.

The surface film materials and/or micro-particulates contained significant concen-
trations of coliform organisms and PCB compounds, but not pesticides. The HEM derived
from this type of flotage may have amounted to 300 kg on the water surface within the
study area in July 1973. Regulations for controlling the concentration of flotage on
the ocean surface are suggested after considerable discussion.

This report was submitted by the Sanitary Engineering Research Laboratory of the
University of California, Berkeley, in fulfillment of Grant No. R-800373, under the spon-
sorship of the Office of Research & Development of the Environmental Protection Agency.

Ma Deseriptars

Water pollution, ocean outfalls, surface floatables, surface films, surface slicks,
waste water disposal, collection methodology

California, ocean outfalls, surface pollution

O5A, O5B, 05C

19. Security Class. | 21. No.of | send To:
{Repor.) Pages
20. Security Coss, 2 Pree WATER RESOURCES SCIENTIFIC INFORMATION CENTER

U.S. DEPARTMENT OF THE INTERIOR
(Page) WASHINGTON. D.C. 20240



£2

Slicks

Wind east % °
at 5 k A

© 0800

2 September 1971

Nautical Miles

F icks Y
ta 0.2 korift SP
50 OOO
if fo

1?
,.
Ne Santa

Catalina
Island

Slicks not to scale

Figure 8.

0

=

100 Fathom.

Surface Conditions in Control Areas: April 4 and September 2, 1971


ACKNOWLEDGMENTS

The continued interest and assistance of Dr. Donald J. Baumgartner, Program
Chief of the National Coastal Pollution Research Program, Environmental
Protection Agency, and Mr. Walter F. Rittall, Grant Project Officer, is
acknowledged with thanks. Also, the aid of Dr. Joseph Blazevich of the
Corvallis, Oregon Laboratory in supplying standards and suggestions for
methods of analysis is recognized and fully appreciated.

Professor Robert E. Selleck was the faculty investigator of the project,
acting in behalf of The Regents of the University of California, and

Dr. Ralf C. Carter was the project director during the 1971 studies and

Mr. Lloyd Bracewell during the 1973 work. Professor Pat Wilde, co-faculty
investigator, was primarily responsible for the conduct of the various oceano-
graphic studies and Professor David I. Jenkins aided in the development of
the analytical techniques.

Under the direction of Dr. George Hlavka, SCCWRP supplied the means for
conducting the survey work off the coast of Southern California in 1971.
The assistance of Mr. Chen-Shyong Young, Sanitary Engineer of SCCWRP,
during that time is especially acknowledged.

Mr. Al Leipzig, Chief Engineer, and Mr. William Garber, Assistant Chief
Engineer, and the staff of the Hyperion Wastewater Treatment Plant aided
the 1971 study greatly by collecting and analyzing samples of their
wastewater effluent during the field surveys, and by making arrangements
with the City of Los Angeles for the use of the survey boat "Marine
Surveyor" in the 1973 program of studies. The generosity of the City
Council of Los Angeles in permitting the use of their survey boat without
compensation in the 1973 survey is also gratefully acknowledged.

The cooperation of Mr. Roger Beeken, Plant Engineer of the County of Los
Angeles JWPCP, and staff in the collection of effluent samples and permission

xi


Table 4 . SUMMARY OF SURFACE TRAWLS — COLIFORM BACTERIA
One m2 of Traw? Equals 30 2 of Strained Water

Trawls Coliform Bacteria
; Sta. Area % in
Location No. Date No.| a | slicks |No./m2 |No./100 me
IV-7-71 1 26.6 100 | 150,000 500
H .
yeerel | 16] 30 | 1,400 5
1 VIII-31-71! 4 161 30 2,500 8
74 0 6,700 22
49 0 3,000 10
wpe ie none | 130,000 430
=e 05 none 43 ,000 140
outfalls 4) Aes 4 | 95 | none | 74,000 247
195 none 41,000 137
IV-7-71 14) 114 22 6,450 22
Hyperion, ie 100 19,000 63
3.7 km N 2. | 1X-1-71 4 none 260 1
160 100 11,000 37
184 35 1,300 4
3a | IV-8-71 1 | 232 100 none
Control areas,
Santa Cata- 533 30 none
lina Is. 304 40 none
3p | Tk-2-71 4 | 242 100 | none
350 50 none

were visible. The first trawl listed in Table 3 for the JWPCP outfalls
station was taken 400 m north of the seaward end of the L diffuser, the
second parallel to the L diffuser, and the remaining two over the Y diffuser.
Trawls taken at the remaining two sampling stations were always made normal
to the band slicks visible at the time.

RESULTS OF SURVEYS

Visual Typing
Tables 3 through 5 of Appendix A give the numbers of each type of particulate
captured in the trawls made in 1971. Some types seemed likely to be of

39


LIST OF TABLES (Continued)
Table Title Page
19, Concentration of Cloth Screen PCB Compounds... .... 85

20. Comparison of Ocean Water and Surface Concentrations
of Aroclor 1254:° July, 1973 2... ee eee ee ee 88

21. Pan Data for JWPCP Effluent .........6. ee 92

22, Fatty Acid Composition of Cloth Screen Samples:
July 19973. ee ee we eee ee 98

23. Fatty Acid Composition of Bulk Ocean Samples:

July 19973 .....0. Se ee ee ee 95
24, Estimated Concentration of HEM of Wastewater Origins

in Cloth Screen Samples ......2..2.0005 wee 97
25. Ocean Currents at Hyperion Outfall ..........2. 104
26. Ocean Currents in August-September 197] Survey ..... 105

27. Description of Trawled Particulates: Over Outfalls ... 106

28. Description of Particulates: 3.7 KM N of Hyperion
Outfal] 2. 2 ee ee ee ee we we «(WOT

29. Description of Particulates Collected: Control Area... 108


A review of the state of visibility of the sea slicks and wind speeds recorded
in this study indicates that the slicks became invisible when the wind was less
than approximately 1/2 to 1 m/s. Speeds in excess of 5 to 6 m/s quickly
destroyed the slick patterns and formed surface mixing cells in accord with
the concepts of Langmuir [4].

The wind seldom permitted the sea surface in the Southern California Bight
to attain any state of equilibrium. Strong winds mixed the surface flotage
with the upper ocean layer, and once they ceased the flotage reformed. Winds
with speeds of 3 to 4 m/s may not disrupt a slick pattern quickly but if
given sufficient time the evidence indicates that the slicks will eventually
disappear. Finally, a non-surfacing wastewater plume may form a sea slick
if the thermocline is located sufficiently close to the ocean surface

(approximately 12 m for an outfall releasing 6.2 2/s of effluent per meter
of outfall diffuser length).

33


Twenty grams of Florisil were added to the column topped with ten grams of
anhydrous sodium sulfate for removal of possible trace water present in

the extract. The column was washed with 70 mg hexane which was discarded,
followed by 20 mg hexane used as a blank. The extract was then placed on

the column and eluted with 200 mz hexane to recover DDE and PCB primarily.

A second fraction was then collected by eluting with 20 mg of 20 percent

ethyl ether in hexane to obtain DDT, dieldrin, and other more polar chlorinated
hydrocarbons. If the hexane extract had been reacted with BFT, these esters
were also eluted in the second fraction. Control showed that PCB's were not
affected during the BFT reaction.

The eluants were then concentrated to volumes of 1 mg or 10 me, and one
micro-liter volumes were injected into the same columns used for the fatty
acid analysis.

STANDARDS

Fatty acids of 99+ percent purity were purchased from Applied Science
Laboratories, Inc. These were weighed and reacted with o-bromo-2,3,4,5,6-
pentafluorotoluene, Puriss Grade® (molecular weight 260.99) purchased from
Aldrich Chemical Compnay, Inc. The completion of the reaction and recovery
of the ester was confirmed by comparison with known amounts of similar esters
supplied by Dr. Kawahara of the Analytical Quality Control Laboratory,

EPA in Cincinnati, Ohio.

PCB standards for Aroclor 1242, 1248, 1254, and 1260 were obtained from
Dr. Joseph Blazevich of the EPA Laboratory in Corvallis, Oregon. Chlori-
nated insecticide standards were purchased from Varian Aerograph.

~ CONTROLS

All hexane purchased was of Nano Grade® quality and redistilled in glass
before use. Potassium hydroxide pellets were placed in the distilling flask.
All glassware was cleaned with a hot dichromate in sulfuric acid cleaning

114


118°30'W

a STA. 2 LOS
ZZ O ANGELES
a =
o” oO
oy & STA.
4oO
Zz
a
oO
N ” STA,
=z
el]
fe]
3
- Sy
Pp
po p
CONTROL AREA a y
STA. 3 A Wy
N ey
SANTA CATALINA
ISLAND
Nautical Miles
0 5 10
Figure 1. Study Area

Vv



II, RECOMMENDATIONS

1. A great amount of work remains to ascertain the composition and mode

of formation of sea slicks. Much of this would be strictly of scientific
interest, but it would provide a better means of estimating the proportion
of the surface film material derived from wastewater discharges as well as
its ultimate destination. For example, reliable methods of acidifying and
saponifying the glass cloth samplers should be developed to increase the
yield of HEM and fatty acids. Also, the relationship between the fatty
acids and their salts at the ocean interface has to be more fully understood
with the aid of laboratory studies.

2. Reliable methods of sampling wastewater effluents for surface film
forming substances remain to be developed. Simply screening from the top

of effluent diluted with salt or fresh water yields information on the
composition of the flotage, but not its total amount because an equilibrium
appears to be established between the surface and bulk phase which is quickly
reestablished upon removal of material from the surface. This process appears
to continue indefinitely. It should be pointed out here that the composi-
tion of the flotage may differ appreciably between salt and fresh diluting
waters.

3. The characteristics of the flotage, if any, derived from secondary
effluents remains to be ascertained. It is possible that surfacing secondary
effluent plumes could produce measurable quantities of surface flotage.

4. The effect of wastewater effluent chlorination on coliform bacteria
contained in trawled and micro-particulates remains to be ascertained.

5. To complete the study discussed herein, measurements should be made on
surfacing primary effluent plumes. This would enable a more direct means of
establishing relationships between cause and effect. For example, the
quantities of surface PCB compounds derived from a wastewater effluent
could be determined quantitatively under such circumstances.


Figure
1.

2.

10.

Ni.
12.
13.
14.
1,
16.
7,

18.

LIST OF FIGURES
Title

Study Areas... ee

Temperature Profiles Observed at Samping Stations:

April, 197] 2 we ee
Water Density Profiles: April, 1971 ..........

Temperature Profiles Observed at Sampling Stations:

August-September, 1971 2... 2... 2.2.02. ee eee

Water Density Profiles: August-September, 1971

Temperature Profiles Observed at Sampling Stations:

July 1973

Surface Conditions in Hyperion Outfall Region:

April 7, 971 6 we ee ee

Surface Conditions in Control Areas: April 4 and

September 2, 197] 2... ee eee eee ee ee ee

Surface Conditions in Hyperion Outfall Region:

August 31 and September 1, 1971 ..........20.4

Surface Conditions Over JWPCP Outfalls:

September 3, 1971 2... wee eee ee ee ee
Transport of Flotage Study: December 9, 1971 .....

Surface Conditions Over JWPCP Outfalls: July 11, 1973

Surface Conditions Off Marineland: July 12, 1973 ....

Surface Conditions in Control Area: July 13, 1973

Photographs of Sea Slicks ...........0004

Traw] Net Sampler 2... 1... ee ee ee ee ee ee

Cumulative Frequency Distribution of Grease and
Wax, and Tar Particulates: August-September, 1971

Rise of Large Particulates in the Vicinity of the L

Diffuser of the JWPCP Outfalls: July, 1973 ......

15
16

7

22

23

24

26
27
28
30
31


Table 25. OCEAN CURRENTS AT HYPERION OUTFALL
(6:20 to 7:14 a.m., April 7, 1971)

Depth Speed Bearing
m knots ag.

0-1 0.30 360

10 0.42 180

20 0.30 320

30 0.25 300

40 0.15 Rotating
50 0.07 Reversing
60 0.12 90

104


£9

Table 12.

LOCAL MASS BALANCE ON HEM OF TRAWLED PARTICULATES

Surface current

Diffuser Concentration of HEM, mg/m?
-— length
Direct. b Calculated
Outfalls Date m/s true m c Observed
Hyperion | IV-7-71 0.17 NNE 1100 12 11 (slick average)
Hyperion | VIII-31-71 | 0.18 NE 1800 14 6.6 (eastern-most traw1)
JwPcp? VII-11-73 0.11 NW 800 114 32.5 (western leg of L diffuser)
5.4 (avg. over Y diffuser)

4y and L diffusers considered together.



DEPTH, TM

Station

ly
1 Aug. 31, 1971 _»— \
2 Sept. 1, 1971 —aA— \
40+ 3b Sept. 2, 1971 ---@-- “
4 Sept. 3, 1971 ---m=---
50 | Sta. 1
Sta. 2 Sta. 4
VITITTT 77777
60 | Ocean Sta. 3b
Bottom SS
100 meters
70 ; TI — , T
24 25 26
0,
Figure 5. Water Density Profiles: August-September, 1971

16



5. Local mass balances made about the marine outfalls indicated that an
appreciable portion of the large particulates must have attained the ocean
surface even when the effluent plumes were submerged.

6. Evidence indicates that the grease and wax particulates can persist for long
periods of time in the marine environment. Their ultimate destination was not
ascertained definitively but a study using floating polyethelene pellets indi-
cated that the particulates could move with the band type of sea slicks. The
band slicks formed under wind speeds of less than 3-4 m/s. They always moved
toward the mainland, independent of the wind direction and probably were asso-
ciated with the internal waves, moving with the same speed and in the same
direction as the internal waves. When the wind speed exceeded 4 m/s the band
slicks were destroyed quickly and Langmuir mixing cells formed. The particulates
were then either transported downwind or submerged under the ocean surface.

7. The mass emission rate of particulate HEM from the Hyperion and JWPCP
outfalls was estimated to be approximately 1000 kg/day. In light of No. 3
above this implies a surface residence time of only one day in the study area.
Either the particulates clustered in regions not sampled, or they were moved
quickly out of the study area by wind and band slick influences of the type
described in No. 6 above.

8. The grease and wax particulates contained from 2 x 103 to 2 x 10% coliform
bacteria per mg of HEM within the vicinity of the marine outfalls. The bacteria
were found in particulates captured as far as 4 km from the Hyperion outfall.

9. A suggested surface pollution control requirement for HEM, based on
aesthetic and coliform bacteria considerations, is 1.0 mg/m? or less (exclusive
of tar). This is 10 times lower than the current State of California requi re-
ment for ocean waters. No contro] requirement for nonextractable particulates
is suggested because their concentrations were too small to be aesthetically
objectionable, and their ecological significance was unknown to these investigator

MICRO-PARTICULATES (<0.1 mm in size)

1. The surface concentration of the micro-particulates exceeded a million/m2
at times. Their overall volume per unit surface area may have been greater
than the trawled particulates and their sizes ranged from the minimum
detectable limit of approximately one y to 100 u.


The most outstanding feature of the first survey was a large standing slick
outlining the Hyperion diffuser on the morning of April 7 as shown in
Figure 7. This slick was never observed subsequently. Other types of

sea slicks were also observed in the area including a broad meandering slick
directed more or less downcurrent fron the diffuser and narrow band slicks
running parallel to the coast at Station 2, 3.7 km north of the outfall
diffuser. The slicks at Station 3a in the control area consisted of a large
ill-defined slick lying in the lee of Santa Catalina Island and several band
slicks as shown in Figure 8. The wind speed was ideal at 2-3 knots (1 to
1.5 m/s).

August-September, 1971

The wind was not particularly favorable for surface sampling during the
summer cruise of 1971 and the sea slicks commonly were rather poorly defined.
No wind existed in the Hyperion outfall region on the morning of August 31
and the slicks were nearly invisible. There was the hint of a series of
band slicks moving across the diffuser in the shoreward direction, however,
and these were sampled and called "slick samples." A strong southwest wind
rose in the afternoon destroying any slick patterns which might have existed
in the area.

Conditions were better in the early morning hours of September 1 and well-
defined band slicks were observed 3.7 km north of the Hyperion outfall as
shown in Figure 9. An east wind of 5 to 7 knots (2.5 to 3.5 m/s) existed

at the time but this soon disappeared and the slicks became nearly invisible.
At times the wind would gust briefly and a slick pattern would appear again.
At noon the wind veered to the southwest and increased to 11 knots (5.7 m/s)
and the surface was broken up entirely into downwind mixing cells.

The results of the first survey conducted in the control area on April 8,

1971 indicated that the surface may have been polluted slightly at Station
3a. The windward side of Santa Catalina Island was then selected as the

21


Table 21. PAN DATA FOR JWPCP EFFLUENT
(grab sample of July 13, 1973)

Stearic acid

% of % of
Type of sample HEM FA HEM Conc. | HEM

Bulk effluent? | 71.4 | 29 41 5.8 8.1
(mg/2)

Diluted bulk??? 2.36 0.48 | 20 0.15 6.4
in pan (mg/2)

Glass cloth® 1.49 | 0.10] 6.7 | 0.030 | 2.0
samples (mg/m?)

®acidi fied.
opi luted 17:1 with clean sea water.
Means for 6 cloth samples - cloths not acidified.

The stearic acid was reduced to 6.4% of the HEM and the proportion of all the
fatty acids in the HEM was reduced from an initial 40% to 20% in the diluted
pan sample. In other words, more than half of the fatty acids had disappeared
from the diluted mixture.

After a period of one hour of waiting the surface tension had dropped by
more than 20 dynes/cm, far more than needed to depress capillary waves and
form sea slicks. The glass cloth samples indicated an average surface concen-
tration of HEM of only 1.5 mg/m?, and the concentration of stearic

acid was only 30 ug/m2. By this time the acid comprised only 2% of the HEM
extracted from the glass cloths. The glass cloths were not acidified prior
to extraction, and the acid salts would not be extracted with the

hexane. It is probable that appreciable quantities of the acid were missed
in this way, but exactly how much cannot be estimated from a mass balance
because some of the salts went to the sides of the pan as well as the water
surface, and because new film formed quickly after a cloth sample was taken
from the water surface. Indeed it appeared as if surface sampling could
have been continued indefinitely with significant HEM recovered until all

92


Table 19. CONCENTRATION OF CLOTH SCREEN PCB COMPOUNDS
(concentration in ug/m2 as Aroclor 1254)

Aug.-Sept.,
April, 1971 197] July, 1973
. a % of % of % of
Location Type b | PCB HEM b PCB HEM b | PCB | HEM
Hyperion Ss 1 | 120 0.96 | 4 39 2.2
NS 3 3.3 | 0.23
y | s 5 |8.7 | 0.77
JWPCP NS 6 | 4.
outfalls S eee
L 6 42.5 | 0.49
NS gc 3.1 | 0.18 5 13.2 | 0.30
Hypert on > Ss 4 5.7 | 0.36
of Bn NS 4 | 5.8 | 0.44
siPer S 7 12.0 | 0.31
4 km NW NS 8 | 2.1 | 0.89
Control Ss 1 | <10 (50.83 4 7.5 | 0.60 | 12 11.1 | 0.42
areas
NS 4 6.4 {0.35 | 12 11.3 | 0.80

45 = slick and NS = non-slick.
No. of samples pooled to obtain PCB analysis.
windy day - no slicks.

DISCUSSION OF RESULTS

Coliform Bacteria

The coliform bacteria provided the only direct evidence that some of the
flotage collected by the cloth samplers was derived from the wastewater
discharges. Large numbers of coliform bacteria were found at times in the
nylon net samples collected over the outfalls in the 1971 surveys, but the

results were highly variable with either large numbers being recovered or

none, as shown in Table 18. No coliform organisms were found in the

85


2. The concentrations and types of micro-particulates observed varied

grossly between the two surveys of 1971. Their overall concentration generally
was 2 to 3 times greater over the Hyperion outfall than elsewhere but their
sources or chemical composition were not ascertained. Sampling for micro-
particulates was discontinued after 1971.

SURFACE SCREEN SAMPLES

1. The glass cloth sampler collected duplex and stable monolayer surface
films accurately (within approximately 10% for duplex films and 5% for
monolayers).

2. PCB compounds appeared to be concentrated in the sea slicks found over
the marine outfalls. A volumetric concentration as high as 0.8 mg/g as
Aroclor 1254 was found over the Hyperion outfall in April 1971.

3. The average surface concentration of PCB was estimated to be 2.8 yg/m2
(or 19 ug/2) as Aroclor 1254 in the study area in July 1973. The bulk ocean
water concentration 0.5 m below the surface averaged about 0.050 ug/2.
These data indicate that the PCB compounds were concentrated by a factor of
at least 380 times on the ocean surface.

4. The surface and bulk water concentrations of PCB were four times higher
in the region of the JWPCP outfalls than in the control area in July 1973,
or twice the average values found throughout the study area at that time.
The wastewater mass emission of PCB to the study area may have ranged from 3
to 10 kg/day as Aroclor 1254, but the significance of this material in terms
of ocean surface pollution could not be ascertained because the surface PCB
compounds could have been derived from atmospheric fallout as well as
wastewater discharge. Concentrations of pesticides were always at least

10 times less than the PCB compounds in the 1973 survey.

5. Coliform bacteria were found in the screen samples collected over the
wastewater outfalls in 1971. (No bacterial samples were collected in
1973.) The surface concentration very nearly exceeded 1000 organisms /m?


0.8 +

_ Y [
0.6 ore _
0.5 I
0.4

one) * 7
7 x
0.34 an |

O x —
A A NON-SLICK
x

HEM CONCENTRATION, mg/m2

\

0.05 J L

0.04
l FoT TT ty ft oo Po]
5 10 20 3% 40 5060 70 90 95 98

PERCENT EQUAL TO OR LESS THAN

Figure 29. Cumulative Frequency Distribution of HEM Found in
Cloth Screen Samples in Control Area: July, 1973

The concentration of stearic acid (saturated C,g) was 5.8 mg/2 in the bulk
effluent sample, or 8.1% of the total HEM. This includes the salts of the
acids because the sample was acidified before extraction. The concentration
of the acid in the pan after dilution should have been approximately 0.32 mg/x
instead of the 0.15 ug/2 observed. It appears that some of the stearic

acid salts had migrated from the mixture before the onset of pan screening.

91


ORIGINS OF CLOTH SCREEN FATTY ACIDS

It appears that the fatty acids found in the unacidified and unsaponi fied
screen samples may have been derived primarily from micro-particulates rather
than surface film materials. Some of the reasons for this belief are as
follows: the surveys of 1971 showed that micro-particulates were profuse and
of significant volume, and that the coliform bacteria were distributed in a
spotty manner; the free fatty acid concentrations found at a given site were
highly variable but almost always too small to form a sea slick; differences
in fatty acid concentrations between slick and non-slick areas were usually
relatively minor; the acidified bulk water palmitic and stearic acid concen-
trations were fairly constant in the study area, implying that their surface
concentrations (either free or as salts) should be reasonably uniform, but
the surface concentration of stearic acid decreased 20-fold from the JWPCP
outfalls to the control area; and the methods of analysis employed might make
any free stearic acid very scarce unless protected by being incorporated in
some type of micro-particulate.

THE SIGNIFICANCE OF THE SURFACE POLLUTION

The coliform bacteria and PCB analyses demonstrated clearly that some surface
wastewater pollution existed in the study area. The PCB data could not be
used to trace that type of pollution because of interferences derived from
atmospheric fallout. Only the fatty acid data could be used to obtain such
an estimate, and then only very crudely.

Of all the fatty acids recovered from the ocean surface stearic acid will
salt out the most readily and possibly be the most persistent in the marine
environment. Assuming that this acid was derived primarily from wastewater
micro-particulates and that it was relatively inert inside the micro-parti-
culates, the mass of HEM of wastewater origin could be estimated grossly.
Obviously these assumptions are highly questionable. For example, free
stearic acid could have been contained in the particulates falling from
the atmosphere but no information on such a phenomenon was available.

96


Particulate samples selected for coliform organism analysis were processed
as soon as possible at dockside. The particulates were homogenized in a
sterile buffer solution of known volume, and appropriate aliquots of the
homogenized mixture were filtered through membrane filters in accord with
the procedures described in Standard Methods [5].

BULK WATER SAMPLES

The bulk sewage effluent and ocean samples were acidified with hydrochloric
acid to a pH between 1 and 2 and extracted in a Pearson-Thomas liquid-liquid
extraction apparatus [8]. The 1 liter sewage effluent samples were extracted
for 3 hr and the 4 liter sea water samples were extracted for 9 hr. The
hexane extractables fraction of the bulk samples was concentrated in a tared
vial and weighed following hexane evaporation.

FATTY ACID ANALYSIS

The hexane extractables were characterized for their fatty acid composition
by applying the techniques of electron capture gas chromatography using the
novel esters prepared by reacting a-bromo-2,3,4,5,6-pentafluorotoluene
(BFT) with the fatty acids in the hexane extract residues [15,16,17].

Weighing

The flasks containing the hexane extracts from either soxhlet or liquid-
liquid extraction were concentrated to 1 or 2 m& using a rotary evaporator
with a water bath at 40°C and an applied vacuum of 50 mm of mercury. A
one gram, 1.3 mg, glass, tared vial was heated to 40°C. The concentrated
sample was transferred to the vial quantitatively with hexane using a jet
of high purity nitrogen gas to assist in the evaporation of the solvent in
the vial. After cooling in a dessicator the vial was weighed to + 10 ug.

Reaction

After weighing, the sample was quantitatively transferred back to its
original flask using 10 mz hexane and dried on the rotary evaporator. To

112


JWPCP QUTFALLS

HYPERION OUTFALL

N 300 y
30
3b. 2 3a
Ta
; SANTA CATALINA ISLAND
Kilometers
0 10 20 Contours = ug/m? of HEM
Calculations
HEM Avg. Incremental | Incremental
conc. | Area end area conc. weight
ug/m2 | (km)2 (km)2 g/m kg
0 2300
2300 20 46
20 2300
1500 10 15
30 700
400 270 108
300 90
55 12,200 671
12,500 20
Total 840
Figure 26. Estimate of Mass of Wastewater HEM Present on

Ocean Surface - Traw] Samples

59


CONTROL OF SURFACE POLLUTION

The suggestions made herein apply only to the conditions encountered in this
study; i.e., primary unchlorinated wastewater effluents submerged beneath

an ocean thermocline. Surfacing plumes should give concentrations of parti-
culates at least as great as those found in this study, however. Effects

of chlorination on the coliform bacteria contained in the large particulates
is unknown but it is likely that the particulates will protect the bacteria
from the disinfectant.

Hexane extractable materials (HEM) appear to be the best general analysis

for this type of surface pollution. The question remains as to what is a
reasonable and safe upper limit for the HEM on the ocean surface. The only
measures at hand which could aid in this judgment were aesthetic impact
(Table 7) and coliform bacteria (Table 8). Pesticides and PCB compounds

were not of great help because their proportions in the particulates were
very slight (although foraging aquatic birds might have obtained appreciable
doses of the chlorinated hydrocarbons if they consumed enough of the parti-
culates). Fatty acids, fats, and alkanes are benign in the ocean environment,
at least at the rates of emission estimated for the large particulates.

The aesthetic ratings given in Table 7 indicated a maximum safe level of perhaps
3 mg/m2 of HEM (see p. 54). The coliform data presented in Table 8 were far
more difficult to judge, their public health significarce being unknown.

A commonly accepted standard for ocean bathing waters is less than 1000

total coliform bacteria/100 mz 80% of the time, but a surface concentration
cannot be expressed conveniently in terms of a volumetric concentration.

For example, the surface trawl used in this study strained the surface

water to a depth of approximately 3 cm, but the same particulates would

have been captured at a trawl depth of 2 cmor less. Thus, the volumetric
concentration increases in proportion with the decrease in the sampling

depth considered significant. The depth cannot be considered infinitesimally

65


Particulates will be classified according to size.

3. The analysis of inorganic and organic parameters will be conducted
on both film and particulates.

4. Coliform and, if possible, virus concentrations of film and parti-
culates will be enumerated.

5. The wastes sampled in the ocean will be correlated with raw water
samples, preferably by sampling from the same waste volume.

The only one of those conditions which modified substantially the proposed
work was item 4, i.e., "Coliform and, if possible, virus concentrations of
film and particulates will be enumerated." After consultation with the
Project Officer, it was agreed that virus enumerations could not be carried
out without considerable cost and therefore would not be included. Coliform
organism determinations were initiated immediately, however.

Subsequent to the awarding of this grant, the Southern California Coastal
Water Research Project (SCCWRP) requested that the sampling and analytical
techniques developed in the first year of this study be used in fairly
extensive ocean studies of surface conditions in the Southern California
Bight. This was well removed in distance from the sites envisaged originally
for the ocean studies and the costs were increased appreciably. SCCWRP
offered compensation in terms of furnishing the sampling craft and supporting
the personnel needed for the ocean studies. Three separate ocean surveys
were made in 1971 under this arrangement with the pertinent data being
presented and discussed in this report. The ocean work of 1973 was conducted
without any aid from SCCWRP but the studies were continued in the Southern
California Bight area to complement the results of the 1971 work.

The participation of SCCWRP made it possible to collect data in a region

of real concern to the public. Even so, the Southern California Bight region
was not ideal for the development of new sampling and analytical tools
because the large primary effluents were always submerged beneath

the ocean thermocl{ne during the ocean surveys and the region was remote
from the sample processing laboratory. A more orderly procedure would

have been the sampling of surfacing primary and secondary effluents first


of the film forming substances had been removed from the pan.

It is possible that the method of sampling and analysis employed to measure
the surface films altered the fatty acid-salt relationships actually existing
at the air-water interface. For example, the cloths were air-dried prior to
extraction and the sea salts would concentrate as the water evaporated. This
could produce additional fatty acid salts depending on the pH of the evaporat-
ing solution.

In summary, it appears that the ocean fatty acid salts were not extracted
from the screen samples and it may have been that additional salting-out
occurred during the air drying stage. The recovery of saturated long-chain
free fatty acids should be very small therefore, as indicated by the results
of the effluent sampling experiments.

Figure 30 and Table 22 show the mean compositions of the fatty acids ‘found in
the screen samples collected during the July 1973 survey. Palmitic acid
predominated in all areas sampled and stearic acid was relatively prevalent.
The concentrations of both of those acids decreased grossly with distance
from the JWPCP outfalls, with stearic acid decreasing some 20-fold from

the outfalls to the control area. The proportion of stearic acid found in
the HEM decreased from 1.4% over the outfalls to only 0.33% in the control
area.

Table 22. FATTY ACID COMPOSITION OF CLOTH SCREEN SAMPLES: JULY, 1973%
(concentrations in yg/m2)

) Stearic acid

% of | Palmitic % of

Location HEM FA HEM acid Conc. | HEM
JWPCP outfalls 910 88 9.6 27 13 1.4
14 km NW of JWPCP | 410 13.6 3.3 5.2 1.9 0.46
Control area 210 5.9 2.8 1.9 0.69 | 0.33

Weighted means of the data presented in Table 17.

93


€L

0 4 4 1 £5 1 L
-”
’
ws
10 4 L
20 | L
= 30 4 L
x
=
a
a
40 | L
50 7 r
Station 1 ——» —_
Station 2 ---@---
60 4 April 7, 1971 r
T —T T
8 9 10 4 #12 #+%13 14 «15 16

TEMPERATURE, °C

Figure 2.

Bottom at 73 meters

Control Area
Station 3a — 8 April 1971

10

am)

T TT

T
12 13 14:15 «+16 17
TEMPERATURE, °C

Temperature Profiles Observed at Sampling Stations: April, 1971



indicates that the growth of the kelp was not particularly hindered by the
adhering grease.

Graphs like Figure 17 have to be interpreted with care. It might be assumed
that the tar pieces were generally larger than the grease and wax parti-
culates on the ocean surface. This may not have been the case because the
small tar pieces may have slipped through the trawl screens without diffi-
culty whereas the grease and wax particulates tended to stick to the apparatus
or other debris, as described above. If 15% of the tar pieces equal to or
smaller than 0.5 mm in size had stayed in the collector the two size distri-
butions would have been identical.

In summary, Table 5 shows clearly that the grease and wax particulates
captured in the 1971 surveys were predominant in the samples collected over
the outfalls-and north of the Hyperion outfall. Natural types such as tar
and kelp dominated the samples taken in the contro] areas. The table also
shows that the mean size of the grease and wax particulates captured in the
summer survey of 1971 was 1.3 mm, and that the largest particulate had a
length of 10 mm. Most of the plastic pieces ranged from 2 to 5 mm in size
but pieces up to 50 mm in length were taken on occasion.

Dry Weight, HEM, and Fatty Acids

Table 3 summarizes the results of these analyses. The fatty acid analysis
was not conducted on the particulates collected in the first survey of
1971, and the degree of unsaturation was not determined until 1973, The
significance of these analyses will be discussed in detail subsequently.

PCB and Pesticides

A few samples collected in the August-September 1971 survey were analyzed
for PCB and pesticides. Aroclor 1254 was detected in one sample collected
over the Hyperion outfall, but it amounted to only 0.13% of the HEM found
in that sample. PCB was not detected in any of the other samples tested
and it had to amount to less than 0.10% of the HEM in any of them since

43


The results show that the PCB compounds tended to concentrate strongly on
the ocean surface. The concentrating effect remained relatively constant
throughout the study area; or in other words, the bulk and screen concen-
trations of the PCB compounds corresponded fairly closely with each other.
In this regard the PCB results differed greatly from those found for the
fatty acids to be discussed subsequently.

The average bulk water PCB concentration found over the L diffuser of the
JWPCP outfalls was approximately 50 times higher than that reported by
SCCWRP for bulk samples collected in the same area at a depth of 3m in
May 1973 [14]. The reason for such a wide discrepancy is unknown except
that a more efficient hexane extraction technique was employed in this
study.

The approximate computational methods shown in Figure 26 and the data pre-
sented in Tables 19 and 20 were used to estimate the mass of PCB present on
the ocean surface in the surveys of August-September 1971 and July 1973.
The mass computed was 24 and 6.4 kg (as Aroclor 1254), respectively. These
results reflect the greater concentration of PCB found everywhere in the
study area in the 1971 survey; the cause being unknown but possibly due to
restrictions being placed on the use of PCB by the manufacturers after 1970.
The July 1973 results indicate a surface residence time in the order of

13 days if the PCB compounds were derived solely from atmospheric fallout.

The presence of significant atmospheric fallout makes it difficult to
estimate the proportion of surfaced pollution derived from the marine
outfalls. Both the bulk water and surface screen results shown in Tables

19 and 20 indicate that the contribution of the marine outfalls must have
been significant, otherwise the appreciable decrease in the PCB concentrations
with distance from the outfalls could not be logically explained. For this
reason the PCB results were taken as a second proof that some of the
substances collected by the glass cloth screens were derived from the

wastewater discharges.


control area and designated as Station 3b as shown in Figure 8, A steady
2.5 m/s east wind was favorable for sea slick visibility and a number of
narrow well-defined slick bands were observed in the area.

The JWPCP outfalls were sampled on the morning of September 3, 1971 as shown
in Figure 10. The wind averaged only about 7 knots (3.6 m/s) from the east
during that time but no sea slicks were visible. The best that could be

done was to allow the sampling craft to drift over the 90 inch Y diffuser while
collecting film samples

December, 1971

A slick tracing study was conducted on December 9, 1971 as shown in Figure

11. A steady southwest wind in excess of 7 knots (3.6 m/s) persisted until
mid-afternoon when it gradually decreased to a light air by sunset. No

slicks were apparent anywhere along the coast until the wind began to decrease.
A series of sharply-defined band slicks then appeared in the region where

the sampling craft happened to be cruising at the time. Those slicks, shown
in Figure 11, ran parallel to the coast and increased in width as the wind
dropped until by sunset it appeared as if the entire surface was covered

by a single slick.

duly, 1973

Wind conditions were never very ideal during the July 1973 survey. The
weather had been unsettled for weeks prior to the cruise, following a general
pattern of strong winds in the afternoon and evening and mild winds in the
early morning hours. The slicks themselves were always poorly defined and
seemingly on the verge of disappearing.

The wind was calm over the JWPCP outfalls in the early morning hours of
duly 11, 1973 and no slick patterns were visible. Indeed, it appeared that
the entire surface was one large slick. A 2 to 3 knot (1 to 1.5 m/s) west
wind sprung up quickly after 8 a.m. and poorly defined patterns of broad,
diffuse band slicks formed as shown in Figure 12. The majority ran normal

25


to establish firmly cause and effect relationships.

Section IV of this report describes the character of the area sampled in

the ocean surveys as well as the conditions encountered during each survey.
General information on the techniques employed in each survey is also presented
in that section. Sections V, VI, and VII deal almost exclusively with the
three types of sampling techniques evaluated during the study: surface
trawling, nylon netting screens, and glass cloth screens. Wastewater

effluent sampling of concern to each of those techniques is presented at the
appropriate time.


No.:

Date:

Time:
OCEAN SURFACE AESTHETIC SURVEY

Location:

Categories: check one

0. No pollution - water surface appears to be in virgin condition

1. Trace pollution - some evidence of floating material - not
significant

2. Obvious pollution - readily observable amounts of debris -
unsightly

3. Offensive pollution - sufficient quantities of pollutants
present that you wouldn't go in the water

Recorder

Figure 24. Example of Aesthetic Rating Sheet for Evaluating
Ocean Surface Pollution

Table 7. COMPARISON OF AESTHETIC IMPACT WITH HEM

HEM, = mg/m2 Average rating
0.005 ....ee 0 - Water surface in virgin state
0.050 ...... 1 - Some flotage evident but insignificant
3B . eee 3 - Offensive (in standing slick over Hyperion
outfall, April 1971)
9 ve eee 1.5 - Flotage obvious and somewhat unsightly
32.5 ... ae 2.3 - Flotage obvious and unsightly - offensive to
some

55



Table 29.

DESCRIPTION OF PARTICULATES COLLECTED: CONTROL AREA
(no./100 m2 trawled)

Traw1 No.

IV-8-71

IX-2-71

2

4

3

5

Sewage Types

Grease and wax

Seeds

Misc, tissue

Wood

Plastic

Fiber

Unidentified
debris

Natural Types

Tar
Insects
Charcoal
Kelp
Eel grass
Surf grass
Sea lettuce
Red algae
Feathers
Eggs
Crab
Mysid
Siphonophore
Copepod
Isopod
Hydroid
Sponge
Nauplius
Larvae
Barnacle
part. (?)
Coelenterata
Eucarida
Others

0.5

0.5

16
0.5

0.5

nm NMWONO—O
a an aan

Nw

2.5

2.8

0.9

Pp aw

oo
ww

o Oo ONO
eo © LCAw

0.

on

oo

oo
0

wa

ny

2

0.3

0.3

oo
nw

on
no

0.3

a0O-4

0.4

Ow
wo

0.4

1.3

ar)
Ne

0.4

NO
or

Total

20

96

22

13

oa}-oo
P ]wWwo

coloan

wl ao
Pw

9.9

pollen, fish, spiders, etc.
> includes one piece 35 x 15 x 2 mm in size.

108



The ocean surface and bulk samples, and the 24-hour composited bulk effluent
samples, were processed as indicated in the scheme of analyses shown in
Figure 31. Details of sample collection were presented in the appropriate
sections of the report. The processing of samples collected by the various
samplers and the methods of analyses are presented below.

CLOTH SCREEN SAMPLES

The hexane extractables were obtained from the glass cloth screens by removing
the cloths from their containers and allowing them to air dry in a hood.

The cloths were then extracted for one hour in a standard soxhlet apparatus
and concentrated to 5 mg for transfer. The residue was dried under nitrogen
at 40°C and weighed for hexane extractables. This material was retained for
subsequent fatty acid and chlorinated hydrocarbon analyses.

The coliform organisms, surface plankton, and micro-particulates were washed
from the nylon netting screens and filtered. Sterile buffer solution

(150 mg) was used to wash the coliforms from the net screens and appropriate
aliquots were then filtered immediately through membrane filters and incubated
for later counting in the laboratory in accord with Standard Methods [5].

For the surface plankton and micro-particulate determinations, however,

the wash water was filtered sea water and the sampler washing procedure

was repeated twice with the filtered material being counted and identified
directly on the membrane filter.

FLOATING PARTICULATES

The floating particulate samples were washed with distilled water, dried at
35°C,: and weighed. For the first two surveys the particulates were counted
and identified directly under a dissecting microscope. The particulates were
then extracted with hexane for one hour in an alumina thimble in a standard

soxhlet apparatus. The residual was then evaporated and weighed for hexane
extractables.

110


Figure
19.

20.

23.
22.
23.
24,

25.
26.
27.

28.

29.

31.

LIST OF FIGURES (Continued)
Title

Fatty Acid Composition of Large Particulates:

duly, 1973. 2 ee ee ee ee

Comparison of Grease and Wax Particulates With

Non-Extractable Sewage Types ..... rr

Comparison of Grease and Wax Particulates with HEM

Fatty Acid Proportion of HM 2... 1. ee ee ee
Comparison of Total Dry Weight with HEM ........

Example of Aesthetic Rating Sheet for Evaluating

Ocean Surface Pollution .. 2... 1. ee ee ween

Cumulative Frequency Distributions of Coliform

Bacteria Surface Concentration: 1971 .........

Estimate of Mass of Wastewater HEM Present on Ocean

Surface - Traw] Samples ......... wee eee

Cumulative Frequency Distribution of Clumps of Debris
Collected by the Nylon Netting: August-September 1971

Cumulative Frequency Distribution of Coliform
Bacteria Found in Screen Samples Taken Over the

Outfalls: April and September, 1971 ..........

Cumulative Frequency Distribution of HEM Found in

Cloth Screen Samples in Control Area: July, 1973... .

Fatty Acid Composition of Cloth Screen Samples:

July, 973... ee ee ee

Analytical Approach to Characterizing Flotage and

Bulk Samples... ee ee

viii

55

57

59

87

QT

94


To*

PT Tim

103

ll

No./100 me

102

v INDICATES
LESS THAN

|
o<

a a

40 50 60 70 80 90 95 98
PERCENT EQUAL TO OR LESS THAN
Figure 28. Cumulative Frequency Distribution of Coliform Bacteria

Found in Screen Samples Taken Over the Outfalls:
April and September, 1971

An appreciable source of PCB compounds could have been atmospheric

fallout [1]. The fallout along the coast within the study area might

have averaged 0.26 ug/m2-day as Aroclor 1254 during the months of

June and July 1973 [14]. Information concerning decrease in fallout with
distance from the coast was unavailable to this study but DDT compounds
decreased by a factor of about 4 from the coast to Santa Catalina Island.
Assuming a similar decrease in PCB compounds, the fallout may have averaged

approximately 0.5 kg/day on the study area.

Data of the SCCWRP study [14] indicated average concentrations of Aroclor
1254 of 2.0 ug/z or so for the JWPCP effluent during the period July 6-12,
1973, and 0.36 ug/2 for the Hyperion effluent during the week of June 18-24,

87


10 #118° 25'W
REDONDO
BEACH
Wi 33°50!N

FLAT ROCK PT
DRIFT —
0.3K ==>
PAUOS VERDES PT

rr
2' at 5 sec POINT VINCENTE

WIND WEST
AT6 K

Figure 13. Surface Conditions Off Marineland: July 12, 1973
(Note: Figure is only approximate)


06

PERCENT COMPOSITION

100

a
f=)

Over JWPCP Control
—_ Effluent outfall 14 km NW area _
U, ; y Yi
Zine “1,
| 8 %e | WZ |
& Cie 17
“| Cie eb " WMA [-
a _ 2 VM Cie |
IL
Cie Cie Z
Cis
| ne Cis _
Cis C
| TS Cia Ciy * |
“| Cy c |
12 Cio Cro 12

Figure 30.

Fatty Acid Composition of Cloth Screen Samples: July, 1973


V. TRAWLED PARTICULATES

Floating particulates greater than 0.5 mm in size were collected by straining
an ocean surface layer approximately 3 cm deep and 0.87 m wide through a

500 u pore size nylon screen fastened behind a trawling device. The charac-
teristics and dimensions of the trawl used in this study are shown in Figure
16.

The traw] was towed alongside the sampling craft at approximately 0.8 m/s
(1.5 knots). At the termination of a trawl the screen was removed from the
plastic cod and stored in a petri dish under refrigeration until ready for
analysis. The types of analyses conducted on the particulates varied from
survey to survey but included at times, 1) type, size, and number of parti-
culates captured; 2) total dry weight; 3) hexane extractable materials

(HEM) and the composition of the HEM in terms of fatty acids (FA), pesticides,
and polychlorinated biphenols (PCB); and 4) coliform bacteria.

The type, size, and number of particulates were determined visually under-
neath a dissecting microscope. The HEM were obtained by extraction with
hexane in a soxhlet apparatus and the fatty acids by reacting the hexane
extracts with o-bromo-2,3,4,5,6-pentafluorotoluene (BFT) to form fatty
acid esters. The esters were then determined quantitatively by techniques
of gas-liquid chromatography. The PCB and some pesticide compounds were
first separated from the HEM with the aid of an activated silica column,
then measured quantitatively in a gas-liquid chromatograph. The details
of these chemical methods of analyses are presented in Appendix B.

Unfortunately it was not possible to measure the coliform bacteria in a
trawl] sample without destroying the sample. Such samples were first
homogenized in a blender and then filtered through membrane filters in
accord with the techniques described in Standard Methods [5]. For this
reason the coliform samples had to be collected and analyzed independently
of all the other analyses.

34