EPA-R2-73-177
MARCH 1973 Environmental Protection Technology Series
Adsorption of Chlorinated
Hydrocarbons from Seawater
by a Crosslinked Polymer
Office of Research and Monitoring
U.S. Environmental Protection Agency
Washington, D.C. 20460
-------
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 ENVIRONMENTAL
PROTECTION TECHNOLOGY series. This series
describes research performed to develop and
demonstrate instrumentation, equipment and
methodology to repair or prevent environmental
degradation from point and non-point sources of
pollution. This work provides the new or improved
technology required for the control and treatment
of pollution sources to meet environmental quality
standards.
-------
EPA-R2-T3-1TT
March 1973
ADSORPTION OF CHLORINATED HYDROCARBONS PROM
SEAWATER BY A CROSSLINKED POLYMER
By
George R. Harvey
Project 16020 GCQ
Project Officer
Dr. Earl Davey
National Marine Water Quality Lab.
P. 0. Box 277
West Kingston, Rhode Island 02892
Prepared for
OFFICE OF RESEARCH AND MONITORING
U.S. ENVIRONMENTAL PROTECTION AGENCY
WASHINGTON, D.C. 20460
For sale by the Superintendent of Documents, U.S. Government Printing Office. Washington, D.C. 20402
Price 55 cents domestic postpaid or 40 cents GPO Bookstore
-------
EPA Review Notice
This report has been reviewed by the Environmental
Protection Agency 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 recommenda-
tion for use.
-------
ABSTRACT
A synthetic resin, Amberlite XAD-2, has been evaluated as an adsorp-
tion medium for chlorinated hydrocarbons dissolved in seawater. The
resin was found to be very efficient and the method was developed into
a routine analytical procedure for the monitoring of seawater.
This report was submitted in fulfillment of project number 16020
GCQ under the sponsorship of the Office of Research and Monitoring,
U. S. Environmental Protection Agency.
-iii-
-------
CONTENTS
Section : Page
I Conclusions 1
II Recommendations 2
I'll Introduction 3
IV Evaluation of Resin 4
V Experimental ^
VI Discussion 12
VII Acknowledgements
VIII References 15
IX Appendix 1. Polychlorohiphenyls in North 17
Atlantic Ocean Water
-iv-
-------
FIGURES
Page
1. XAD-2 Column Efficiency ^
2. Adsorption Apparatus for 20-100 Liters 9
of Seawater
-------
TABLES
Page
1. Typical PCB and I DDT Concentrations in 13
Woods Hole Seawater by XAD-2 Ad-
sorption
-vi-
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SECTION I
CONCLUSIONS
1. Amberlite XAD-2 resin is an excellent adsorbant for hydrophobia
chlorinated hydrocarbons dissolved in coastal and off-shore seawater.
2. Adsorbed compounds such as DDT and its metabolites, dieldrin and
polychlorobiphenyls can be quantitatively eluted from the resin.
3. This resin has definite advantages over other solid sorbants now in
use.
-------
SECTION II
RECOMMENDATIONS
1. Amberlite XAD-2 resin should be the material of choice for monitor-
ing coastal seawater for chlorinated hydrocarbon'contaminants.
2. The resin should be evaluated for its adsorption properties toward
petroleum hydrocarbons in natural waters.
,2*
-------
SECTION III
INTRODUCTION
The objective of this work was to develop a working, analytical method
for adsorbing and recovering low concentrations of chlorinated hydro-
carbons (CHCs) such as pesticides and polychlorinated biphenyls (PCBs)
from seawater using Amberlite XAD resins CRohm & Haas Co., Philadelphia).
The objective has been achieved and this report will describe this new
analytical method.
The use of solid absorbants to concentrate CHCs, as well as other classes
of chemicals of interest, has two significant advantages over the
usual solvent extraction: 1. Very large volume samples are possible,
i.e., 20-2000 liters, without any significant change in the apparatus;
2. The ratio of total water volume sampled to volume of solvent used for
final isolation is very large. Thus, solvent impurities are minimized
and the limit of detectability is reduced to ca. 1 part per trillion
Cppt) or less.
When this work commenced only charcoal was in wide use as a solid absor-
bent for CHCs, in spite of the poor and variable recovery characteristics
of this material Cu- In addition, a short communication by Riley (2)
described the use of Amherlite XAD-1 resin for adsorbtion of C^-DDT from
seawater. Unfortunately, only one liter was used in those experiments
and no conditions were given. We believed that the resin had promise as
an analytical tool, but an analytical method had to be researched. The
research presented in this report substantiates that belief.
While this work was in progress, two other adsorption methods for
seawater became available: Reversed liquid-liquid partition chromato-
graphy (3), and the use of polyurethane foam (4). Both of these methods
have disadvantages which restrict its use to particular applications.
The method described in this report should be of general applicability
and usefulness.
We originally intended to develop a method for the DDT family, Dieldrin,
Chlordane, etc. in seawater. However, it soon became obvious that the
major CHCs in coastal New England waters were PCBs. Thus, we were forced
to evaluate the resin against those compounds, as well as the pesticides.
-3-
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SECTION IV
EVALUATION
General Characteristics of Amberlite XAD-2 Resin CXAD-2). (5)
XAD-2 is a synthetic polymer of styrene and divinyl benzene which is
further crosslinked and formulated into 20-50 mesh white beads. The
surface area is 300 m2/g and the mean pore diameter is 85-95 A. It is
heat stable to at least 200°C. On one occasion we lowered several grams
of XAD-2 to 1000 m in the sea and observed no compression of the beads.
This property will allow the resin to be used in in situ sampling pumps
lowered to the desired depth. This is a major advantage over polyur-
ethane foam which is highly compressible. For the present objectives
the most valuable property of XAD-2 is its ability to adsorb dissolved
hydrophobic compounds from water, presumably by hydrophobic bonding
which is thermodynamically favored by the entropy increase in the water.
Cleanup of Resin
The commercial product, as received, is very contaminated and contains
PCBs, as well as other materials. After much experimentation the follow-
ing procedure was adopted:
1. Wash resin with several portions of tap water by slurry-
ing and decanting.
2. Put resin in a metal container having a 60 mesh screen
bottom and wash out the fines with 20 bed volumes of tap
water, followed by a distilled water rinse.
3. Extract the resin in a Soxhlet apparatus with pesticide
grade acetonitrile for 18 hours. Change the solvent and
repeat for another 18 hours.
4. Rinse the resin free of acetonitrile with ten bed volumes
of distilled water.
5. Store the resin in tightly sealed glass jars covered with
distilled water until use.
Large batches can be prepared in this way. It need not be repeated
after using the resin since the elution procedure is sufficient for
immediate re-use.
-------
Adsorption of Total Dissolved Organic Carbon
Falmouth seawater, containing 2.1 rng/1 of dissolved organic carbon
was run through an 8 cc bed of resin at flow rates of 1.4, 0.7,
0.3 and 0.1 bed vol/min. The effluent at the first three flow rates
had 1.7, 1.4 and 1.3 mg C/l, or about 80%. At the low flow rate the
resin saturated after one liter indicating secondary adsorption. These
preliminary results led to two valuable conclusions:
1. Coastal seawater contains about 20% hydrophobic organic
matter.
2. At higher flow rates the resin will preferentially
adsorb only hydrophobic material from water,while at low
flow rates discrimination is lost and all the organic
matter is adsorbed causing the resin to saturate prematurely.
Preparation of Spiked Seawater Solution
Unfiltered, Falmouth seawater (19 liters) was spiked with acetone
solutions of DDT, DDE, Dieldrin and PCB (Aroclor 1254} to a concen-
tration of 5-10 ppb. The water was stirred for 48 hours before
vacuum filtration through a 0.3 y glass fiber filter. An aliquot of
the filtered water was extracted with 6% ether in hexane and analyzed
by gas liquid chromatography (glc). The resulting concentration was
generally between 1 and 3 ppb. The major portion of the chlorinated
hydrocarbons remained on the filter. These spiked solutions were
used to evaluate many of the parameters of the analytical system.
However, the concentrations varied daily in an irregular manner,
leading to many erroneous conclusions. Therefore, the final testing
of parameters was done with, unspiked seawater using the ambient levels
of these materials (.10-30 parts per trillion PCB, 1-4 ppt DDT) as
determined by solvent extraction.
Capacity of XAD-2 for Chlorinated Hydrocarbons
Saturation of the resin with chlorinated hydrocarbons was never achieved,
however, the capacity of the resin is large enough to be of no concern
for large volume sampling. For example, seawater solution containing
1.6 ppb DDE, 3.1 ppb dieldrin and 2.3 ppb DDT was passed through a
5 cc column of resin at 5 ml/min gravity flow. After 65 liters had
passed the column clogged, although adsorption was still efficient.
Elution with 20 ml of acetonitrile gave recoveries of 125, 108 and 92
percent. This amounts ot 70 yg/cc of resin. When a pump was used
to run the column no reduction in flow rate was observed, even after
100 liters. As a safety margin we have used no more than 13 liters
-------
of seawater per cc of resin. This is clearly not a serious restriction.
Column Dimension
By using a constant volume of resin,(5 cc) and varying the dimensions of
the cylindrical column Oength/i.d.} we were able to measure the per-
cent bleed of DDE at a flow rate of^10 ml/min.> The percent bleed, at
1/1.d. = 7, was 9 and increased as .the 1/i.d. ratio increased to 24% at
1/i.d. - 122. The longer columns are clearly less efficient and we
recommend a column of 1/i.d. = 7.
Optimum Flow Rate
Seawater spiked with one ppb of PCB and DDT was passed through several
10 cc columns of XAD-2 (l/i-d. = 7I at different flow rates. A total
of five liters was passed through each column, followed by 40 cc of
acetonitrile for elution. The results are shown in Figure 1. Five
bed volumes per minute is the maximum flow rate for complete adsorp-
tion of the chlorinated hydrocarbons. The slightly lower efficiency
at two bed vol/min is probably due to the phenomenon discussed in
General Characteristics of the XAD-2 Resin.
The above parameters were checked by passing several liters of Woods
Hole seawater through the same columns at five bed vol/min, eluting
and quantifying. The results were compared several times with solvent
extraction of the same water (6% ether-hexane). In all cases the
results were the same, i.e., the same quantity of DDT, Dieldrin and
PCB by either method, usually 4, 10 and 30 ppt respectively.
Elution and Regeneration
In preliminary experiments and from theoretical considerations it was
obvious that a water miscible organic solvent was required for pene-
tration of the wet resin. Acetonitrile and ethanol were evaluated
and found to be quite satisfactory. Four bed volumes of either solvent
is passed through the resin at 0.2 bed vol/min. After two bed vol.
more than 90% of the chlorinated hydrocarbons have been eluted. An
alternate method is to pour four bed vol. of either solvent, boiling
hot, through the resin at full gravity flow. Recovery in both cases
is 100%. The solvent is washed off the column with four bed vol.
of water and the column is ready for the next sample. We have re-
used the same column 15 times with no change in its efficiency.
-------
100
80
a
60
40
K
2°
6 8 10
BED VOLUMES/win.
12
Figure 1. XAD-2 Column Efficiency
-------
PreflUratlon
Amberlite XAD-2 resin can adsorb only from the dissolved phase. Chlorinated
hydrocarbons adsorbed on participate matter smaller than 20 mesh will
pass through the column undetected. Thus, only a small plug of glass
wool in front of the column to trap large particulates is needed. This
plug is removed before elution of the column.
-8-
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SECTION V
EXPERIMENTAL
Reagents
Amberlite XAD-2 resin (supplied
by Eastman Kodak)
Acetonitrile
Ethanol
Hexane
Water
Glass Wool
Sodium Sulfate
Preparation
See Evaluation - Section A
Pesticide grade, or reagent
grade redistilled in all glass
still
CSI pharmaceutical grade
Pesticide grade, or reagent grade
redistilled from sodium metal
in all glass still
Distilled or pre-analyzed tap or
seawater
Heat at 350° for 48 hours in
vented oven and store in glass
jars.
Anhydrous reagent, treated as
glass wool.
Apparatus
A suggested apparatus is diagrammed in Figure 2.
Procedure
A brass or glass column is packed with a 50 cc bed of XAD-2 resin
and fitted with a 5 cm pre-column of glass wool tFig. 2). Seawater is
pulled through, the column with a peristaltic pump at a rate of 250
nil/mi n until 20 to 100 liters have been extracted. The pre-column
or filter and other fittings are removed. Hot acetonitrile or
ethanol is poured through the column (200 ml) at full gravity flow
into a 1 liter separatory funnel fitted with a Teflon stopcock.
Water (500 ml) is poured through the column into the same separatory
funnel. The column is now ready for immediate re-use. The aqueous
acetonitrile or ethanol (700 ml) is extracted with 2 x 50 ml of hexane.
-------
60 mesh ss screen
PERISTALTIC PUMP
17x2 cm brass
50ccXAD-2
5xlcm
brass
Reducing bushing
Glass wool
1/4"copper tubing
Water
Figure 2. Adsorption Apparatus for 20-100 Liters of Seawater
-10-
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The combined hexane extracts are washed with 25 ml of water, dried with
3-5 g of sodium sulfate and concentrated to an appropriate volume for gas
chromatographic analysis, or silica chromatographic separation of PCB
from the DDT family (6). No florisil or sulfuric acid cleanup of the
hexane extract was necessary before gc analysis in our work including
both inshore and open-ocean seawater.
Gas Chromatographic Conditions Used in This Work
•••'!• i •',:•'
Column: 2m x 2mm glass packed with 8% QF-1 and 2% OV-17 (1:1) on Ana-
krome (100 - 120 mesh).
Temperatures: Injector - 240
Column - 190°
Manifold - 220°
Detector - 250°
Gas: 5% methane in Argon at 40 ml/min.
Detector: Ni-63 in pulse mode.
Any standard methods for separation of the pesticides from the PCB1s,and
their quantitation can be used (61. Some typical results are shown in
Table 1 and Appendix 1.
-------
SECTION IV
DISCUSSION
Amberlite XAD-2 resin, as described in this report is an excellent ad-
sorbent for chlorinated hydrocarbon contaminants in seawater. The
resin should work quite well with freshwater, but the "salting out"
effect of seawater probably makes the high flow rates possible. XAD-2
resin has two advantages over polyurethane foam (4) and reversed phase
liquid-liquid chrdmatography (3). Firstly, there is no organic coating
on the XAD-2 so that after elution of the column it is ready to be re-
used. Secondly, the XAD-2 has excellent pressure resistance, so it
can be used in in situ columns at depth. We have tested XAD-2 at 1000 m
and observed no compression of the spheres.
The system described in this report should be sufficiently flexible for
any natural water monitoring of ambient levels of chlorinated hydro-
carbons. In connection with another project, we have used XAD-2
resin to monitor the water of the open - North Atlantic Ocean (Table 1,
Appendix 1). In that work, 20 - 80 liters of seawater was pumped through
the 50 cc column described here. The efficiency of the column was
checked several times by simultaneous solvent extraction and was found
to be >95%.
The column conditions described in this report were given to Drs. Donald
C. Gordon and Rodney A. Badger of the Bedford Institute of Oceanography,
Marine Ecology Laboratory, Dartmouth, Nova Scotia. They evaluated our
parameters by using C^4 labelled DDT. They found the resin to be 97.5%
efficient at a flow rate of 5 bed volumes/rain, and the recovery was 100%.
These results will not be published and are mentioned here as an inde-
pendent confirmation of our observations.
One use of the resin which should be exploited for coastal monitoring is
in situ sampling from a ship underway. If a flow meter was attached to
a weighted column set in a "fish" it could be towed while other work was
in progress. Furthermore, a more representative, or integrated sample
would be obtained.
-12-
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TABLE 1
TYPICAL PCB AND zDDT IN WOODS HOLE SEAWATER BY XAD-2 ADSORPTION
Date
4-7-72
4-13-72
5-4-72
5-11-72
6-14-72
10-4-72
11-14-72
CPCB]a
7.1
10.3
b
b
b
35
7.2
CsDDT)3
<.l
0.7
1.3
3.3
3.3
0.3
2
Volume (A
4
4
4
4
18.5
12
96C
a) Reproducibility is ± 10%; verified by ether-hexane extraction.
Values given in parts per trillion.
b) Not calculated due to very poor chromatographic matching
with standard, commercial PCB mixtures.
c) By immersion of water intake tube below the surface of the sea
at the Woods Hole dock.
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SECTION VII
ACKNOWLEDGEMENTS
The analytical, mechanical and intellectual efforts to this work by
Mr. William G. Steinhauer have been major, and they are responsible
for the success of the project.
Without the generous support of the Office of Research and Monitoring,
Environmental Protection Agency, this work would have been impossible.
The assistance of Dr. Earl Davey, Project Officer is appreciated.
-14-
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REFERENCES
1. Breidenback, A. W., et al., The Identification and Measurement of
Chlorinated Hydrocarbon Pesticides in Surface Waters, Federal Water
Quality Administration, No. WP-22, Gov't. Printing Office, Washington,
D. C., 1966.
2. Riley, J. P. and D. Taylor, The Analytical Concentration of Traces of
Dissolved Organic Materials from Seawater with Amber!Ite XAD-1 Resin,
Anal. Chim. Acta, 46_, 307 (.I960]. "~
3. Ahling, B. and S. Jensen, Reversed Liquid-Liquid Partition in De-
termination of PCB and Chlorinated Pesticides in Water, Analytical
Chem., 42, 1483 0970).
4. Uthe, J. F.9 J. Relnke and tL. Gesser, Extraction of Organochlorine
Pesticides from Water by Porous Polyurethane Coated with Selective
Absorbent. Environmental Letters, 3, 117 (.1972).~~
5. Araberlite XAD-2, Technical Bulletin, Ion Exchange Dept., Rohm and
Haas Co., Philadelphia, Pa. 19105, April 1970.
6. Fishbein, L., Chromatographlc and Biological Aspects of Polychlorinated
Biphenyls, J. Chromatogr., 6^, 345 11972).
-15-
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GLOSSARY
DDT or zDDT - The family of the pesticide DDT and its major metabolites,
ODD and DDE.
PCB - The class of industrial chemicals composed of a mixture of poly-
chlorinated biphenyls.
Chlorinated Hydrocarbon - Any organic compound composed of only carbon,
hydrogen and chlorine.
Amberlite - A trademark of Rohm and Haas Co., Philadelphia, Pa. for
their class of exchange resins.
-16-
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APPENDIX I
-17-
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POLYCHLOROBIPHENYLS IN NORTH ATLANTIC OCEAN WATER
George R. Harvey
William G. Steinhauer
John M. Teal
Woods Hole Oceanographic Institution
Woods Hole, Massachusetts 02543
SCIENCE, 1973
(in press)
-18-
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Abstract
Concentrations of polychlorobiphenyls (PCBs) have been measured
in the water of the North Atlantic Ocean from surface and various
depths between 26° and 63° North latitude. The concentrations average
twenty parts per trillion and amount to an estimated 2 x ICr tons of
PCB in the upper 200 m. The surface water of the Sargasso Sea contains
average PCB concentrations which are lower than the northern North
Atlantic.
-19-
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Seawater is the most abundant solvent available for trapping hydro-
carbons, such as the RGBs, released into the environment. The volume
of the oceans (1021 liters) is sufficient to dissolve all the PCBs which -
have been made (1). Relatively few PCB measurements have been made in
open-ocean water to determine the extent to which it functions as a
solvent trap (2). Most analyses have been confined to organisms (3)
which comprise less than 1 ppm of the total volume.
During the summer of 1972 we analyzed open-ocean water from the eastern
and western North Atlantic between 26°N and 63°N. The stations are
marked in Figure 1 and the analyses are tabulated in Table I (4).
Samples 1 to 9 and 13 were analyzed by extracting 19 liters of seawater
(5) with 6% ether-hexane, followed by concentration and electron capture
gas chromatography (ECGC). The other samples were analyzed by pumping
19 to 80 liters of water through a 50 cc brass or glass column (length/-
diameter = 6) of Amber!ite XAD-2 resin (6) at 250 ml/min. The PCBs
were eluted from the column with 300 ml of hot acetonitrile at full gravity
flow. The acetonitrile was diluted with one liter of water (distilled1
or seawater) and extracted with h&xane. The hexane was treated as above.
It was found that no cleanup of the extract was required prior to ECGC.
Unfiltered seawater samples collected and analyzed simultaneously with
water filtered through a 0.3 p glass fiber or a glass wool plug revealed
a maximum of 10% more PCB. All analyses were completed on shipboard
within four hours of sampling (.7).
Three observations can be made from the data:
1. Concentrations of PCBs in the northern North Atlantic average
35 ng/kg (ppt) in surface waters, and 10 ppt at 200 m.
2. PCB concentrations do decrease with depth.
3. The surface waters of the Sargasso Sea have slightly lowered
surface levels of PCBs (27 ng/kg) than other parts of the North
Atlantic.
The widespread distribution of PCBs in the open-North Atlantic supports
previous observations that the atmosphere must be the predominant mode
of transport (3). The wide range of concentrations observed (< 1-150 ppt),
in some cases only 50 miles apart (Stations 29 and 33), may be due to
sea slicks (2), localized rainfall or discharges from other ships. No re-
lationship between PCB concentration and proximity to land was observed.
The presence of measurable PCB concentrations, even to 3000 meters, sug-
gests that animals which migrate vertically, plus sinking shells, feces
and dead organisms transport PCBs out of the mixed layer (ca. 150 m)
and prevent even higher concentrations from accumulating in the productive
zone.
-------
The Sargasso Sea is an area of high evaporation and low rainfall. We
suggest that PCBs, adsorbed on participates falling into this region,
are partially solubilized by equilibrating with the surface water. Ev-
aporative codistillation then transports some of this material to areas
of higher precipitation.
18
The volume of the upper 200 m of the North Atlantic is 10 liters. If
we assume an average PCB concentration of 2 x 10~8 g/l in that volume
(8) then there is about 2 x 1010 g (.2 x 104 tons) in the water (1, 9).
In 1971 the U. S. manufactured 1.8 x 10^ tons 0)- Thus, a considerable
fraction of the world's 40 year production has been trapped by the North
Atlantic Ocean.
Finally, based on quantitative estimates of production and rates
of losses to the environment a iDDT/PCB ratio of 10 is expected in
the North Atlantic, assuming similar half lives C9). The observed ratio
from our data (and Reference 2) must be less than 0.05 (footnote b,
Table I). Thus, the environmental half life of the PCBs appears con-
siderably greater than the DDT family.
-21-
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TABLE Ia
Concentrations of PCBs in North Atlantic Ocean Water
Position _g
Station North
deg. min.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
f\ f\
29
30
A m
31
f\ ^\
32
f\ A
33
34
35
*s f*
36
37
38
*S A
39
A XS
40
41
52
44
40
36
34
35
34
38
38
38
41
43
43
43
46
52
52
55
57
60
60
60
63
41
39
37
34
35
35
35
36
36
35
34
33
28
26
25
26
28
31
55
00
33
U
02
00
47
20
23
19
09
57
20
16
31
31
35
41
22
04
09
29
03
32
40
12
32
22
17
56
05
24
37
26
41
42
50
56
58
26
13
West
deg. min.
35
30
29
25
22
18
14
11
11
19
20
22
21
21
21
19
19
15
12
06
05
04
02
70
70
68
67
67
68
66
67
68
67
66
65
58
55
54
53
53
53
08
36
16
33
50
59
57
23
11
28
46
13
57
34
43
52
53
02
01
02
36
43
22
40
03
54
01
36
28
34
27
24
49
22
44
39
38
15
57
55
49
Date
(1972)
6/30
7/3
7/5
111
7/9
7/11
7/13
7/15
7/22
7/23
7/24
7/25
7/27
7/29
7/30
8/1
8/2
8/4
8/5
8/6
8/7
8/7
8/8
10/2
9/21
9/22
9/23
9/24
9/24
9/25
9/26
9/27
9/27
9/28
9/28
10/3
10/5
10/6
10/7
10/8
10/9
Depth
(meters)
0
0 -
0 -
0 -
0 -
0 -
0 -
0 -
0 -
0
0
0
0
100 -
0
0 -
1500
0
200
200
0
0
0 -
0
0
0
0
1000
0
0
0
0
0
0
0
0
0
0
0
0
0
200
200
200
200
200
200
200
200
3000
100
200
PCB (x 10 " g/lT
150
35 -
4 -
11 -
30 -
14 -
67 -
19 -
41 -
77
< 1
52
47
> lc
10
45 -
> lc
3
97
42
82
23
21 -
30
29
36
12
1
2
5 '
11
22
9
12
15
26
36
27
42
88
68
10
7
3
6
5
39
2
13
8
7
-22-
-------
(Table I Continued)
a) The limit of detection was 1 x TO"9 g/1 for a 19 liter
sample.
b) The closest matching commercial mixture in all cases was
that containing 54% chlorine. Aroclor 1254 (Monsanto Company)
was used as the standard. Procedural blanks ranged from 0-3 ng/1
and were subtracted from the tabulated concentrations. The DDT
family, if present, was at concentrations less than 1 ng/1.
C) Poor match for Aroclor.
-23-
-------
References and Notes
1. The total U. S. production of PCBs since 1957 is about 3.6 x 1011 g
(data released by Monsanto Company, November 1971) which is estimated
to be about one-half of the total world production.
2. Olney, C. E. and J. G. Quinn in: Deliberations of the International
Decade of Ocean Exploration Baseline Conference, E. D. Goldberg,
convener, Scripps Institution of Oceanography. May 24-26, 1972.
These workers made PCB measurements in the surface microlayer and from
20 cm below the surface in the North Atlantic. Their subsurface
concentrations agree with our surface measurements, although their
sample size was much smaller.
3a. Harvey, G. R., V. T. Bowen, R. H. Backus and G. D. Grice in: Nobel
Symposium 20: The Changing Chemistry of the Oceans, D. Dyrssen
and D. Jagner, Eds., Almquist and Wiksell, Stockholm, 1972, p. 177.
3b. Deliberations of the International Decade of Ocean Exploration Base-
line Conference, E. D. Goldberg, convener, Scripps Institution of
Oceanography. May 24-26, 1972.
4. Stations 1 to 23 were occupied on cruise 105 of R/V CHAIN; Stations
25 to 41 were occupied on cruise 71 of R/V ATLANTIS II. Station 24 is
the Woods Hole dock.
5. Surface samples were collected in a stainless steel bucket from the
bow of the ship underway. Deep samples were collected in a 120
liter Niskin-type bottle lined with Teflon.
6. Rohm & Haas Co., Philadelphia. The given parameters for using this
resin were developed by the authors in this laboratory. The efficiency
of the adsorptive extraction, when compared with solvent extraction,
is >95%
7. A Packard gas-liquid chromatograph, model 407, equipped with a Ni-63
electron capture detector was used. No motion sensitivity was ob-
served in the instrument's response. The ship's paints, greases
and oils did not contain any PCBs as determined by shipboard analysis.
8. These data and Reference 2. In contrast, PCB concentrations in coastal
northeast Pacific waters average 1 ppt (I. Barrett in Reference 3b).
9. This quantity is remarkably similar to a recently calculated estimate
of PCBs in the N. Atlantic as 1.5 x 10^ tons. No water data was avail-
able at the time of the calculation. I.C.T. Nisbet and A. F. Sarofim,
Environmental Health Perspectives, 1, 21 (1972).
-24-
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10. We thank Dr. R. H. &ackus, chief scientist on R/V CHAIN-105 for
the opportunity to collect those samples and Dr. V. T. Bowen for
making the deep samples available. Supported by NSF Grant GX 35212,
Office of the International Decade of Ocean Exploration, and EPA
grant GQ 16020.
Woods Hole Oceanographic Institution Contribution No. 2798.
-25-
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Figure 1. Water Station Locations in the N. Atlantic Ocean
60"
30'
60° -
-BERMUDA
30° -
t
16
12
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M
23*
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60'
30'
i
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60'
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1
Accession Number
w
5
Q Subject Field & Group
05A
SELECTED WATER RESOURCES
ABSTRACTS
INPUT TRANSACTION FORM
Organization
\df\f\ A f Ur% 1 A A *•» x\-ib\sv«-.uttM.U..?_ T.-_J_»J_..J-»
V I
Woods Hole, Mass. 02543
Title
Adsorption of Chlorinated Hydrocarbons from Seawater by a Crosslinked
Polymer
1 Q Authors)
George R.
Harvey
16
21
Project Designation
EPA #16020GCQ
Note
22
Citation
Environmental Protection Agency report
number, EPA-R2-73-177, March 1973.
23
Descriptors (Starred First)
Adsorption, DDT
Identifiers (Starred First)
PCB, Hydrocarbon
27
Abstract
A synthetic resin, Amberlite XAD-2, has been evaluated as an adsorption
medium for chlorinated hydrocarbons dissolved in seawater. The resin was
found to be very efficient and the method was developed into a routine
analytical procedure for the monitoring of seawater.
This report was submitted in fulfillment of project number 16020 GCQ
under the sponsorship of the Office of Research and Monitoring, U. S. Environ-
mental Protection Agency.
Abstractor
Harvey
Institution
Woods Hole Oceanographic
Institution
WR:102 (REV. JULY 1969)
WRSIC
SEND. WITH COPY OF DOCUMENT, TO: WATER RESOURCES SCIENTIFIC INFORMATION CENTER
U.S. DEPARTMENT Or THE INTERIOR
WASHINGTON, D, C, 20240
* GPO: 1970—389-930
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