DEPARTML i
OCEAN ENGINEERING

37

NSWC/WOL/TR 7535

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WHITE OAK LABORATORY

A CHEMICAL MONITORING PROGRAM OF THE EXPLOSION PRODUCTS IN UNDERWATER
EXPLOSION TESTS

BY

Ming G. Lai

NAVAL SURFACE WEAPONS CENTER
WHITE OAK LABORATORY
SILVER SPRING, MARYLAND 20910

• Approved for public release; distribution unlimited.

4 APRIL 1975

(

NAVAL SURFACE WEAPONS CENTER

WHITE OAK, SILVER SPRING, MARYLAND 20910

5H5-

it'll

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READ INSTRUCTIONS
BEFORE COMPLETING FORM

I. REPORT NUMBER

NSWC/WOL/TR 75-3 5

2. GOVT ACCESSION NO

3. RECIPIENT'S CATALOG NUMBER

4. TITLE (and Subtitle)

5. TYPE OF REPORT & PERIOD COVERED

A Chemical Monitoring Program Of The
Explosion Products In Underwater
Explosion Tests

6. PERFORMING ORG. REPORT NUMBER

7. AUTHORfsJ

8. CONTRACT OR GRANT NUMBERfaJ

Ming G. Lai

9. PERFORMING ORGANIZATION NAME AND ADDRESS

Naval Surface Weapons Center

White Oak, Silver Spring, Maryland 20910

10. PROGRAM ELEMENT, PROJECT, TASK
AREA » WORK UNIT NUMBERS

62760N, F53554,

SF-53554-301

SEA 33200520024

II. CONTROLLING OFFICE NAME AND ADDRESS

12. REPORT DATE

4 April 1975

13. NUMBER OF PAGES

61

14. MONITORING AGENCY NAME & ADORESS(lf dllterent (torn Controlling Office)

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Approved for Public Release; Distribution unlimited

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19. KEY WORDS (Continue on reverae aide If neceaaary and Identify by block number)

Underwater explosion, explosion product, chemical monitoring,
pollution

20. ABSTRACT (Continue on reverae aide It neceaaary and Identify by block number)

A chemical monitoring program of the explosion products in
underwater explosion tests is described. The objective of the
program is to monitor water quality chemically after underwater
explosion tests. The program consists of sampling and preserva-
tion of water and sediment samples, separation, concentration,

DD | jan 73 1473 EDITION OF 1 NOV 65 IS OBSOLETE

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20. and determination of various explosion products. General
concepts, procedures, and equipment needed for each phase of
the program are presented. Guidelines and recommendations for
the overall program are also given.

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NSWC/WOL/TR 75-3 5

NSWC/WOL/TR 75-3 5 4 April 1975

A CHEMICAL MONITORING PROGRAM OF THE EXPLOSION PRODUCTS IN
UNDERWATER EXPLOSION TESTS

The Navy has been conducting underwater explosion tests in fresh
waters and marine waters for many years. Although the tests, based
on qualitative information, are believed to contribute no adverse
effects on the environment, factual data are still needed for the
quantitative assessment of the probable environmental impact from
the tests. In addition, new explosive compositions have products
that may be less acceptable than the products of compositions
frequently used in the past. This report has been prepared to
institute a chemical monitoring program of the explosion products in
underwater explosion tests, to determine monitoring parameters, and
to provide procedures and methodology for the program.

Because of the complexity of underwater explosion testing, this
report is aimed to serve as a general guide for several common types
of explosives used in the tests. Parameters for other specific
operations should be further formulated as requirements arise.

In order to specify procedures adequately, it has been necessary
occasionally to identify commercial materials and equipment in this
report. In no case does such identification imply recommendation or
endorsement by the Navy, nor does it imply that the material or
equipment identified is necessarily the best available for the
purpose .

The preparation of this report was sponsored by the Naval Sea Systems
Command under Task SEA-SF53554-301 .

Lj^^^^

JOHN B. WILCOX
By direction

NSWC/WOL/TR 75-3 5

TABLE OF CONTENTS

Page

I . INTRODUCTION 5

1.1 BACKGROUND 5

1.2 OBJECTIVE AND SCOPE 6

1.3 WATER QUALITY MONITORING PROGRAM 6

II. EXPLOSION PRODUCTS 7

2.1 PHYSICAL FORMS 7

2.1.1 Gases 7

2.1.2 Suspended Solids 9

2.1.3 Sediment 9

2.1.4 Dissolved Constituents 9

2.2 CHEMICAL COMPOSITIONS 10

2.2.1 Dissolved Gases 10

2.2.2 Suspended Solids 10
2.3.2 Sediment 13
2.4.2 Dissolved Constituents 13

III. SAMPLING AND PRESERVATION 13

3 . 1 WATER SAMPLING 13

3.1.1 General Concepts of Water Sampling 13

3.1.2 Sampling Techniques 15

3.1.3 Samplers 17

3.1.4 Filtration of Water Samples 22

3.1.5 Storage of Water Samples 23

3.2 SEDIMENT SAMPLING 2 5

3.2.1 General Concepts of Sediment Sampling 25

3.2.2 Sampling Techniques 27

3.2.3 Samplers 28

3.2.4 Storage of Sediment Samples 32

IV. DETERMINATION OF EXPLOSION PRODUCTS 3 2
4.1 DESIGN OF MEASUREMENT SYSTEM 32

4.1.1 Objective of Analysis 33

NSWC/WOL/TR 75-3 5

Page

4.1.2 Parameters for Analysis 33

4.1.3 Methods of Analysis 3 5

4.2 SPECIFIC CONSIDERATIONS 3 5

4.2.1 Fresh Water vs Seawater 3 5

4.2.2 In-situ Analysis 36

4.2.3 Concentration and Separation 3 7

4.3 PROCEDURES 39

4.3.1 Dissolved Gases

4.3.2 Dissolved Constituents

4.3.3 Suspended Solids

4.3.4 Sediment

4.3.5 Non-specific Measurements

48
54
56
58

V. CONCLUSIONS AND RECOMMENDATIONS 60

ILLUSTRATIONS
Figure Title

1 Sequence of Steps for Laboratory 8

Instrumental System for Water
Quality Monitoring

2 Van Dorn Water Sampler 18

3 Non-metallic Niskin Water Sampler 20

4 Non-metallic Kemmerer Plus Water 21

Sampler

5 Dissolved Gas Sampling Bottle 26

6 Shipek Sediment Sampler 29

7 Phleger Core Sampler 31

8 Schematic Diagram of System for 41

Dissolved Gas Analysis

9 Chromatogram of Dissolved Gas 42

Mixture in Water

10 Diagram of System for Hydrocarbon 44

Determinat ion

NSWC/WOL/TR 75-35

TABLES

Table Title Page

1 Gaseous Products of Confined 11

Explosions

2 TNT Products in a Surface Pool 12

3 Parameters for Analysis 34

4 Concentration and Separation 38

Techniques for Water Analysis

5 Sensitivity of Atomic Absorption 48

NSWC/WOL/TR 75-35

I
INTRODUCTION

1 . 1 BACKGROUND

The U. S. Navy is engaged in an intensive effort to minimize
or eliminate pollution of all kinds. This overall effort to combat
undesirable environmental effects extends to the manufacture and
testing of explosives and of weapons. The aspect of the work of
concern here is underwater testing, which is vital to the mission
of the Navy.

The majority of people with expert knowledge of underwater
explosion phenomena believe that the effects of any test on the
environment are localized and short-lived and cause no
irreversible changes in the general ecology of a natural body of
water. Longer range effects are minimal and can be estimated on
the basis of existing information, but these estimates are
qualitative because most of the previous work has been directed
toward the predictions of the early-time, close-in phenomena of
military interest.

In order to assess the probable environment impact of the
underwater explosion tests, it is necessary to assemble a body
of factual information regarding the effects of the tests on the
marine environment. Based on this information standards and guide-
lines can be implemented for future underwater explosion test
programs .

NSWC/WOL/TR 75-3 5

1.2 OBJECTIVE AND SCOPE

One of the major effects of an underwater explosion on the
environment is the dispersion of the explosion products after the
detonation takes place. The ultimate disposition, of course, depends
on whether the product is gaseous or a solid, and whether it is
readily soluble in water or remains in a particulate form. Since
some of the explosion products (described in Section II) are toxic
and could produce adverse physiological effects to aquatic life and
wildlife, if present in sufficient concentration levels, field
surveys are needed to obtain adequate data on biological, chemical,
and physical water quality for the determination of the nature and
extent of these effects resulted from the underwater explosion tests.

The purpose of this report is to formulate a chemical monitoring
program for underwater explosive testing, determine monitoring para-
meters, and provide information on the methodology involved. The
biological and physical monitoring programs will not be included in
this report.

1.3 WATER QUALITY MONITORING PROGRAM

Most of the work in water monitoring has been performed by wet
chemical analysis. However, in recent years, the combined needs for
rapid, frequent, and trace analysis demand increasing use of instru-
mental methods, preferably those which can be automated and are
continuous in operation.

Instruments for water quality monitoring can be classified in
many ways. It is convenient to separate them as follows: continuous
samplers, semi-continuous samplers, and laboratory analyzers.
Continuous sampler instruments measure a constituent or physical
parameter on an uninterrupted basis; these instruments may be used
in the field or in the laboratory. Semicontinuous samplers measure
a pollutant on an interrupted or discrete sample basis; the analysis
is then performed on this sample. Semicontinuous sampling analyzers
are utilized in both field and laboratory application. Laboratory
analyzers ordinarily operate in the laboratory owing to the con-
straints of operation intervention, operational environment, and
fragility or high-maintenance requirements.

Despite the large advances in instrument automation, the
majority of water monitoring information is still obtained with
manually operated laboratory analyzers. Manual operation implies
human involvement to progress from one step in the analysis to another,

NSWC/WOL/TR 75-3 5

All water quality parameters can be monitored with laboratory-
analyzers. In trace analysis laboratory analyzers offer better
sensitivity and accuracy. In addition, the overall cost of analysis
is generally lower.

In view of these advantages, laboratory analyzers are
recommended for the water monitoring system in the explosive testing
program. Figure 1 shows a sequence of steps for the laboratory
instrumental system.

II

EXPLOSION PRODUCTS

A considerable amount of knowledge has been acquired concerning
the chemistry of explosives and the shock wave and bubble phenomena
of underwater explosions, but only limited attention has been given
to the dispersion of the explosion products after the detonation
takes place. The ultimate disposition, of course, depends on whether
the product is gaseous or a solid, and whether it is readily soluble
in water or remains in a particulate form. The size of the pool
containing the explosion products depends on the charge weight of
the explosive used, and the distribution of explosion products
depends on the maximum bubble radius and the depth of the explosion.
Most of these phenomena have been discussed in detail in a publication
by Yount . - 1 -

In this section, a brief summary of the explosion products
involved in the monitoring program is given. Only the chemical
products of a bare explosive charge will be discussed. Materials
from the case, fuzing mechanism, and any other detonation devices
will not be considered, as they probably bear no major significance
to the impact of pollution.

2.1 PHYSICAL FORMS

2.1.1 Gases

The majority of the explosion products are in the form of gases.
Initially, the products are contained in a large spherical bubble
that pulsates and migrates toward the surface. Most of the gaseous

Young, G. A., "The Physical Effects of Conventional Explosions on
the Ocean Environment", Naval Ordnance Laboratory, NOLTR 71-120
3 Aug 1971.

NSWC/WOL/TR 75-35

SAMPLING

SITE

SELECTION

SAMPLING
PRESERVATION

CONCENTRATION

sbrAhH i iuim

DATA
PROCESSING

INSTRUMENTAL
MEASUREMENT

CHEMICAL

REACTION(S)

FIG .1 SEQUENCE OF STEPS FOR LABORATORY INSTRUMENTAL SYSTEM
FOR WATER QUALITY MONITORING

NSWC/WOL/TR 75-3 5

products will escape to the atmosphere unless an explosion is
exceptionally deep, but some are soluble in the water. Only the
soluble gases will be considered in this report, since they present
a more significant impact to the marine environment.

2.1.2 Suspended Solids

The insoluble solids or particulates are formed during the
explosion either by the oxidation of the inorganic components in
the explosive mixture or by the reduction of the organic components.
The resulting oxides and carbon exist either as fine particulates or
colloid, which may remain suspended in the water for an indefinite
period of time.

The unconsumed explosives, which are generally insoluble in
water, also can disperse in the water as suspended solids. In addi-
tion, after the explosion some of the finer bottom particles will be
carried upward with the bubbles. It also seems likely that a
turbidity cloud of disturbed bottom material will remain in the
vicinity of the burst for some period of time. This material would
be mixed with the carbon or other particulate explosion products in
the surface pool.

2.1.3 Sediment

The solid explosion products together with the bottom particles
will begin to settle after the explosion and finally deposit on the
bottom in the vicinity of the explosion area. In the case of a deep
explosion on a rigid bottom, the bubble tends to pulsate at the
bottom before it floats upward. It seems likely that a portion of
the solid products will remain in the crater created by the explosion.
Most of the particulates will also eventually settle to the bottom.
Therefore, an accumulation of the solid explosion products in the
sediment near the explosion area is likely.

2.1.4 Dissolved Constituents

The soluble explosion products will dissolve in the water
immediately after the explosion. Solutions are usually defined in
water chemistry as any chemical species which pass through a 0.45y
membrane filter. Therefore, the dissolved constituents can be
easily separated from the suspended solids by the filtration of the
mixture through a 0.45y membrane filter. The soluble species exist
as ionic or complex forms in the solution. Some of them will undergo
hydrolysis to form colloids.

NSWC/WOL/TR 75-35

2.2 CHEMICAL COMPOSITIONS

The explosives most commonly used for underwater explosions are
organic nitrated compounds with a chemical formula of the type
(C-H-N-O) such as TNT, HMX, RDX, Tetryl, and PETN. 2 Currently
several new explosives are also being used in Navy programs. These
explosives consist of mixtures of different organic explosives or
mixtures of these with metallic components.

In this section the chemical composition of the explosion
products from several explosives listed above will be discussed.
Information on other specific explosives may be found in the
literature.

2.2.1 Dissolved Gases

The gases formed by several explosives are presented in Tables
1 & 2. 3 All the gases are soluble in water at various degrees.
The solubility depends on the temperature, pH, and salinity of the
water. It is possible that the concentrations of gases in water may
temporarily exceed their solubilities. This supersaturation creates
excessive total dissolved gas pressure causing undesirable effect
to the marine life.

Most of the gases in the explosion products are considered
non-toxic, except carbon monoxide (CO) , hydrogen cyanide (HCN) ,
chlorine (CI2) , and ammonia (NH3) , which produce adverse effects to
marine life even at low concentrations.

2.2.2 Suspended Solids

Many explosive compositions currently in use consist of metallic
compounds. For example, aluminum is frequently incorporated into
HBX-1, resulting in the formation of aluminum oxide (AI2O3) particles,
Zr M-4 contains zirconium metal and lead nitrate which form
zirconium oxide (Zr0 2 ) and lead oxide (PbO) after the explosion.
Carbon particles are the major suspended solid after a TNT explosion,

2 Cole, R. H., "Underwater Explosions", Princeton University Press,
Princeton, New Jersey, 1948.

Young, G. A., "Guide-Line for Evaluating the Environmental Effects
of Underwater Explosion Tests", Naval Ordnance Laboratory, NOLTR
72-211, 13 Feb 1973.

10

NSWC/WOL/TR 75-35

TABLE 1

GASEOUS PRODUCTS OF CONFINED EXPLOSIONS
(values in percentage by weight)

Prod

uct

Explosives

Name

Symbol

PETN

HMX

TNT

Carbon
Dioxide

co 2

46.22

28.53

24.22

Carbon
Monoxide

CO

14.26

10.02

24.42

Nitrogen

N 2

17.28

34.81

16.28

Water

H 2

20.97

19.34

12.69

Hydrogen

H 2

0.22

0.20

0.41

Ammonia

NH

0.30

3.42

1.21

Methane

CH 4

0.02

0.21

0.70

Hydrogen
Cyanide

HCN

-

0.07

0.24

Ethane C 2 H£ - 0.01 0.05

11

NSWC/WOL/TR 75-35

TABLE 2
TNT PRODUCTS IN A SURFACE POOL

Product

Concentr;

at ion (mg/1)

Name

Symbol

Pool

Ocean

Carbon
Dioxide

co 2

0.215

0.631

Carbon
Monoxide

CO

0.217

28.8 x 10

Carbon

c

0.172

28

Nitrogen

N 2

0.145

14.3

Water

H 2

0.113

-

Hydrogen

H 2

3

.64 x 10'

-3

-

Ammonia

NH 3

1

.08 x 10-

-2

-

Methane

CH 4

6

.22 x 10"

-3

40.9 x 10

Hydrogen
Cyanide

HCN

2

.13 x 10 -

-3

-

-2 H 6

-6

-6

Ethane C H A 4.44 x 10~ 4 1.49 x 10~ 6

12

NSWC/WOL/TR 75-3 5

remaining visible in a surface pool of blackened water. The
unconsumed explosives which are insoluble in water, can also disperse
in the pool as suspended solids.

Although the disturbed bottom material is part of the suspended
solids generated during the explosion, it will not be considered
chemically as an explosion product because it does not originate
from the explosive.

2.2.3 Sediment

The chemical composition of the explosion products in the
sediment will be similar to that of the suspended solids in water.
The concentrations, however, are expected to be higher because of
localization and accumulation. The amount of solid explosion pro-
ducts deposited on the bottom depends on particle size of the solids,
water current, physical characteristics of the sediment, and the
depth of the explosion. 3

2.2.4 Dissolved Constituents

Some of the other explosion products are soluble in water. In
PBXW-104, 15% hydrochloric acid (HCl) is produced during the explo-
sion, and HCl is readily soluble in water. Other soluble explosion
products include nitrates, perchlorates , chlorides, and a complex
of metallic ions such as Al, Pb, Zr, Li, and Hg, which are
incorporated in various explosive compositions.

Most of the explosives have low solubilities in water; therefore,
the concentration of soluble explosives after the explosion are
expected to be small. The toxicity levels of various explosives in
water are currently being investigated.

Ill

SAMPLING AND PRESERVATION

3 . 1 WATER SAMPLING

3.1.1 General Concepts of Water Sampling

There is no universal procedure for sampling applicable to all

3

Young, G. A., op cit, pg 9

13

NSWC/WOL/TR 75-3 5

kinds of natural waters. The most important requirements for a
satisfactory sample are that it be both valid and representative.
For a sample to be valid, it "has to be one which has been collected
by a process of random selection. Any method of sampling that
sacrifices random selection will impair statistical evaluation of
the analytical data.

A satisfactory sample is not only randomly drawn, but also is
representative. This means that the composition of the sample should
be identical to that of the water from which it was collected; the
collected sample should have the same physiochemical characteristics
as the sampled water at the time and site of sampling.

Planning for a sampling program should be guided by the overall
objectives of analysis. Major factors of concern for any sampling
program are: (a) frequency of sample collection, (b) total number
of samples, (c) size of each sample, (d) sites of sample collection,
(e) method of sample collection, (f) data to be collected with each
sample, and (g) transportation and care of samples prior to analysis.

Frequency of sampling will depend to a large extent upon the
frequency of variations in composition of the water to be sampled.
There are two principle types of sampling procedures commonly used
for analysis of natural waters. The first type is that which yields
instantaneous spot or grab samples, while the second type yields
integrated continuous or composite samples. A grab sample is a
discrete portion of water taken at a given time; a series of grab
samples reflects variations in constituents over a period of time.
The size of such individual samples will depend on the objectives
and methods of analysis, and on the required accuracy. The total
number of grab samples should satisfy the statistical requirements
of the sampling program.

Composite samples are useful for determining average conditions.
A composite sample is essentially a weighted series of grab samples,
the volume of each being proportional to the rate of flow of the
water at the time and site of sample collection. Samples may be
obtained over any time period such as 4, 8, or 24 hours, depending
the purposes of analysis.

Selection of sampling sites should be made with great care.
A field survey is often useful in planning for site selection.
Special consideration should be given to sources of discharge,
dilution by tributaries, and changes in surrounding topography.

14

NSWC/WOL/TR 75-3 5

Sampling can be accomplished by either manual or automatic
means, again depending on the purpose or analysis and method of
sampling. A grab sample is usually collected manually. When it
is necessary to extend sampling over a considerable period of time,
or when a continuous (repetitive) record of analysis at a given
sampling point is required, automatic sampling equipment is commonly
used.

The maintenance of a complete record regarding the source of
the sample and the condition under which it has been collected is an
inherent part of a good sampling program. This is of particular
importance in field or river surveys, where a great number of samples
are collected from different sources and under variable conditions.
The U.S. Geological Survey has defined the minimum data required for
samples of surface waters as follows^:

Name of water body

Location of station or site

Point of collection

Date of collection

Time of collection

Temperature of the water

Name of collector

Weather and other natural or other man-made

factors that may assist in interpreting the

chemical quality

3.1.2 Sampling Techniques

Various techniques have been developed by oceanographers for
sampling waters of the seas at various depths. These include, for
example, the Nansen bottle, the Niskin bottle, and the Van Dorn
Sample (described in 3.1.3). However, sampling of the sub-surface
water affected by an explosion would require accurate placement and
control of sampling devices and would also involve an appreciable
number of stations to insure success. In addition, it would be
necessary to employ a sensitive tracer to provide assurance that a
sample was, in reality, affected by the explosion.

Several types of tracers have been used during the past for
monitoring purposes. Chemical tracers, such as lithium chloride and

4 U.S. Department of Public Works, Public Work 85, 1954,

15

NSWC/WOL/TR 75-3 5

cobalt chloride, were incorporated in an explosive charge of TNT. 5
The amount of tracer in the water samples was analyzed chemically.

Radioactive tracers were employed in the HYDRA-IIA series
sponsored by the Naval Radiological Defense Laboratory during the
early 60' s. The radioactive tracers used on HYDRA-IIA were
Lutetium-177 and Xenon-133, which provided excellent results in
following the history of the explosion products, because extremely
low concentrations of radioactive materials are detectable. The
disadvantages of using radioactive tracers are (1) difficulty in
handling due to high level of radiation, (2) a source of pollution
affecting the marine environment, and (3) relatively expensive.

Fluorescent dyes are used frequently by oceanographers for the
study of diffusion processes and as tracers for sewage and other
pollutants. They do not have the undesirable features of radioactive
tracers. A container of fluorescein dye, mixed with water, can be
attached to the supporting cable directly above the charge. A
ratio of one lb of dye to 100 lb of explosive should provide
visibility for at least one-half hour. 3

With the help of the tracers, sampling can be done by locating
the pool and traversing it with a small boat. If the approximate
location of the pool can be predicted beforehand, an array of fixed
sampling stations can also be set up before the explosion. Samples
can then be collected at a time sequence and at various depths.

Dye concentration can be measured in-situ or in sampling bottles
with a fluorometer. Dye concentration can also be determined from
an aerial photographic negative with a photodensitometer . This
method has the advantage of providing data for the entire surface
pool at selected times.

Young, G. A., op cit, pg 9

5 Young, G. A., "Effects of the Explosion of 45 Tons of TNT Under
Water at a Depth Scaled to Test Baker", Naval Ordnance Laboratory,
NAVORD Report 2891, 1953.

6 Ichiye, T. and Plutchak, N. B., "Photodensitometric Measurement of
Dye Concentration in the Ocean", Limnology and Oceanography, l±,
No. 3, 364 (1966) .

16

NSWC/WOL/TR 75-3 5

3.1.3 Samplers

The essential requisite of a satisfactory water sampler is that
it should capture a truly representative sample of the water at the
sampling depth and bring it to the surface unaltered. This necessi-
tates rapid filling with the water surrounding it when open, and
perfect sealing when closed. The interior of the sampler should be
resistant to corrosion and should not contaminate the sample. Where
serial sampling is to be carried out at various depths, it is advan-
tageous for the sampler to be light in weight so that sampling can
be carried out over the normal range of depth with one cast.

There are at least two dozen different water sampling bottles
in major use, each serving a particular purpose. Bottles are
usually opened in-situ by means of weights, or messengers, dropped
down the supporting hydrographic wire. Owing to the danger of
contamination, metallic samplers should not be used if samples are
to be analyzed for trace metals. For such work, the use of plastic
water bottles is essential.

Three types of sampling bottles are recommended here:

(1) Van Dorn Water Sampler Model XRB-13
(Hydro Products, San Diego, California) - Fig. 2

Specifications

Sample size: 3 liters

OD of sample tube: 5.5 inches

Length of sampler: 12 inches

Weight in air: 5 3/4 lbs

Weight in water: 2 lbs

Weight with sample: 15 lbs

Price $175

The Hydro Products XRB series water sampler design is an
improved version of the classic Van Dorn design. The main body of
the sampler is a chemically inert, rugged PVC tube which offers free
flushing feature to assure that the water sample is that of the
particular depth at which it was triggered, not a mixture of surface
and intermediate waters.

Operation is a one-operator job, even in rough waters. The
sampler can be rapidly affixed to a hydrographic wire. The unit is
cocked using a fast, simple operation. When the sampler is triggered
by a messenger at a desired depth, the PVC end caps are released and

17

NSWC/WOL/TR 75-35

HYDROGRAPHIC MESSENGER

FIG. 2 VAN DORN WATER SAMPLER

18

NSWC/WOL/TR 75-35

snap snugly into the angled end faces on the end of the sample tube.
After removal from the wire, the water sample can be drained from
the valves to other containers for analysis.

(2) Nonmetallic Niskin Water Sampler Model 1010-1.7
(General Oceanics, Miami, Florida) - Fig. 3

Specifications

Capacity: 1.7 liters

Overall length: 25 inches

Outside diameter: 3.5 inches

Empty weight: 5.3 lbs

Full weight: 9 lbs

Price: $180

The General Oceanics Model 1010 Niskin Sampling Bottles are
general purpose, nonmetallic water samplers suitable for a wide
range of oceanic and inland water sampling applications. The bottle
features all plastic (PVC or polycarbonate) construction and a free
flushing design to yield samples with greater purity and lower
self-contamination than those taken with traditional metal bottles.

For on-wire operation, the bottle end stoppers are held open by
a cocked trigger mechanism until the bottle has been lowered to the
desired depth. A messenger dropped down the wire from the surface,
strikes the trigger mechanism and releases the end stoppers for
closure. The bottles are designed to release a second messenter
down the wire below the bottle to actuate a series of bottles along
the wire with a single messenger dropped from the surface. Water
may be drained from the bottles by opening an O-ring-sealed, non-
metallic stopcock at the lower end. The stopcocks are designed to
accept rubber tubing in order that samples may be drawn off with
minimal exposure. Reversing thermometer assemblies are available as
standard accessories.

(3) Kemmerer Plus Nonmetallic Water Sampling Bottles
(Wildco Wildlife Supply Co., Saginaw, Michigan) - Fig. 4

Specifications

Full weight: 14 lbs

Sample volume: 3.2 liters

Overall length: 2 7 inches

Outside diameter: 4.5 inches

Empty weight: 6 lbs

Price: $175

19

NSWC/WOL/TR 75-35

FIG. 3 NON-METALLIC NISKIN WATER SAMPLER

20

NSWC/WOL/TR 75-35

FIG. 4 NON-METALLIC KEMMERER PLUS WATER SAMPLER

21

NSWC/WOL/TR 75-3 5

The Kemmerer Plus Nonmetallic Bottles are specially designed
for trace metal sampling and pesticides or chlorinated hydrocarbon
sampling. This is accomplished by constructing the Kemmerer Plus
bottle out of materials that cannot contaminate the sample for the
types of sampling. Specifically the rubber end seals, valve washer,
and the closer have been constructed of materials which will not
release trace metal ions or chlorinated hydrocarbons to the sample.

The unique Kemmerer design assures complete flushing of the
bottle as it is lowered into the water. Closing of the Kemmerer
causes much less agitation disturbance of the sample than the Van
Dorn design. Utilizing a specially designed automatic locking
device, the stoppers are locked open before the unit is lowered into
the water. The valves are closed by dropping a messenger. A drain
in the bottom stopper allows the water contained in the sampler to
be drawn off for analysis.

For use on explosion tests, special arrangements are required.
One approach that has been used successfully is to place a sampler
just below the surface at a downstream distance where the explosive
effects are not damaging. A dye tracer is added to the explosive
and the movement of the surface pool is observed visually. The
sampler is activated by wire when the pool arrives. The events are
recorded photographically.

3.1.4 Filtration of Water Samples

Natural water contains two principle types of suspended matter
(i) inorganic particulate matter resulting from rock weathering and
from precipitation, and (ii) marine organisms, their decomposition
products and other organic detritus. In explosion tests, particu-
lates such as aluminum oxide particles, unconsumed explosives, and
carbon are generated. Since trace metals and organic components
from the explosion products can be liberated rapidly from, or be
taken up by particulate matter, it is advisable to separate the
particular matter immediately after collection.

The suspended matter, after it is separated from water samples,
can be saved and analyzed. The separation may be carried out either
by centrifugation, or more conveniently, by filtration.

In the selection of a filtering medium the following criteria
should be satisfied.

(1) The filter should have a reproducible and uniform pore size
The most commonly used pore size is 0.45M.

22

NSWC/WOL/TR 75-3 5

(2) The rate of filtration should be high, and the filter
should not clog easily.

(3) The suspended matter should not penetrate into the filter,
but should be retained on its surface, so that it can be readily-
recovered .

(4) The filter should not absorb trace elements.

(5) In order to prevent contamination of the water sample, it
should have a low ash content. This also enables the inorganic
components of the suspended matter to be recovered by ignition or
wet ashing with minimum contamination.

(6) It should contain no loose fibers since these may
contaminate the water or suspended matter.

The most satisfactory type of filter for the filtration of
water samples for analytical purpose is the molecular membrane
filters. These filters are composed of incompletely cross-linked
high polymers of partially substituted cellulose acetate and
cellulose nitrate, and are approximately 0.15 mm in thickness.
They are commercially available in pore sizes ranging from 10 my -
5. Op (Millipore Corporation Inc., Bedford, Massachusetts). The pore
sizes show a high degree of uniformity. There is little interconnec-
tion of adjacent pore channels, and the pore volume is about 80% of
the total volume of the filter, thus allowing a very high rate of
filtration. The ash weight of the filters is extremely small and
amounts to only 0.0001% of the original weight. Filtration is
carried out with suction. A low-cost, hand operated vacuum/pressure
pump (Cole-Parmer Instrument Co., Chicago, Illinois) is suitable for
field operation. The filter must be supported on a sinstered glass
plate or a fritted teflon support. A filtration apparatus of this
type is available from Wildco Wildlife Supply Co., Saginaw, Michigan,

3.1.5 Storage of Water Samples

One of the most important aspects of the sampling process is
the care and preservation of the sample prior to analysis. A water
analysis is of limited value if the sample has undergone physio-
chemical or biochemical changes during transportation or storage.
These changes are time dependent, but they usually proceed slowly.
In general, the shorter the time that elapses between collection of
a sample and its analysis, the more reliable will be the analytical
results .

23

NSWC/WOL/TR 75-35

Although it is obviously desirable to analyze water samples
immediately after collection, this is not always possible, either
because of shortage of time or because of lack of facilities on
board ship. Rapid changes may occur in the concentrations of micro-
components and trace elements unless measures are taken to stabilize
them, and to prevent contamination arising from the storage vessel.

In the storage of water samples for trace element analysis, it
is necessary to guard against contamination and against losses
cause by adsorption. Contamination by the element to be determined
may arise by solution or desorption from the walls of the storage
container. Contamination arising from the storage vessel is parti-
cularly serious if soft glass bottles are used, but may also be
appreciable even with borosilicate glass. Polyethylene has been
demonstrated to contain extremely low concentrations of trace
elements , and at present, must be considered the best container
material. (Teflon has slightly lower concentration of most trace
elements but is very expensive) . The risk of contamination of
samples by polyethylene containers is generally small, but it is
important that new bottles should be treated with diluted hydro-
chloric acid to remove traces of metals left during the manufacturing
process .

Very serious losses of trace elements can occur through
adsorption onto the walls of the container. Glass and most plastics
are supercooled liquids, which, because of their distorted and
broken bonds, have greater surface energy than crystalline substances,
This leads to the adsorption of ions from solution and to the forma-
tion of bonds between the surface and the absorbed ions. The loss
is likely to be greatest with transition elements and with elements
which are hydrolysed at pH 7-9, such as iron. Generally, acidifica-
tion of the sample prevents, or reduces adsorption of trace elements
by the container. It will often be found that acidified samples
(at a pH value of 1.5) can be stored for several months in
polyethylene bottles without change. Before any type of container
is used for the storage of samples for trace element analysis, it
should be tested to determine whether it adsorbs the element under
examination.

Robertson, D. E., "Role of Contamination in Trace Element Analysis
of Sea Water", Anal. Chem. 40, 1067 (1968).

Q

Robertson, D. E., "The Adsorption of Trace Elements in Sea Water
on Various Container Surfaces", Anal. Chem. Acta, 42_, 553 (1968).

24

NSWC/WOL/TR 75-35

Little is known about the preservation of water samples which
are to be analyzed for their organic content. Water samples are
generally either acidified to pH 1 or stored in a refrigerator. The
samples must be stored in glass bottles since appreciable amounts
of organic material can be dissolved from polyethylene.

Changes in temperature and pressure may result in the escape of
certain gaseous constituents (e.g. CU , C0~, CH 4 ) or the dissolution
of some atmospheric gases. Polyethylene vessels should not be used
for storage of such samples on account of their permeability to
gases. Weimer 9 found that the method of sample collection and
storage greatly affected the reproducibility of the concentration of
dissolved methane. Samples stored in 250-ml, glass-stoppered reagent
bottles gave variable results. Because of the poor reproducibility
obtained with this storage method, a dissolved gas sampling bottle
was designed 10 to eliminate contact of the water sample with the
atmosphere after the initial sample collection was completed. The
dissolved gas sampling bottle is shown in Fig. 5.

Water from a water sampler is added through the neck of the
dissolved gas sampling bottle; three bottle volumes are first allowed
to flush through the neck and the stopcock. The stopcock is closed,
allowing water to fill completely the neck of the bottle. The
plunger is inserted (about 0.5-1 inches into the neck) with the
stopcock of the bottle open to expel some of the water from the
exit post. The stopcock is then closed. The dissolved gas sampling
bottle is fitted with a Male Leur tip at the stopcock for the
introduction of the water sample into a gas stripping chamber.

3.2 SEDIMENT SAMPLING

3.2.1 General Concepts of Sediment Sampling

The same philosophy and practice applied to water sampling
should also be applied to sediment sampling. However, sediment

9 Weimer, W. C. , "Some Considerations of the Chemical Limnology of
Lake Mary, Vilas County, Wisconsin", M.S. Thesis, Water Chemistry
Program, University of Wisconsin, Madison, Wis., 1970.

10 Weimer, W. C. and Lee, G. F., "Method for the Storage of Samples
for Dissolved Gas Analysis," Environ. Sci. Technol. 5_, 1136 (1971)

25

NSWC/WOL/TR 75-35

PLUNGER (FROM
BECTON, DICKINSON
AND CO., RUTHERFORD,
NEW JERSEY) -
50 ml "PLASTIPAK"
DISPOSABLE SYRINGE

/ /

/

VOLUME OF NECK = 60 ml
VERTICAL SCALE: 1/4" = 1 cm
HORIZONTAL SCALE: 3/8" = 1 cm

TO GAS STRIPPING
CHAMBER

BOTTLE VOLUME = 300 ml

SAMPLE OUTLET

JIL

SAMPLE
LOOP

AEROGRAPH
VALVE

TEFLON
STOPCOCK

SAMPLE
LEUR | NLE T

TIP

CARRIER GAS

FLOW IN

XT

t

FIG. 5 DISSOLVED GAS SAMPLING BOTTLE

26

NSWC/WOL/TR 75-35

sampling in reality is much more complicated than water sampling
because of the following reasons:

(1) Sediment sampling is performed at or near the bottom of
the sampling site, which may be deep and inaccessible. Sampling
requires elaborate and heavy equipment.

(2) Sediment is composed of various types of material with a
large size distribution range. Representative samples are difficult
to obtain.

(3) Sediment sampling requires tedious steps in sample
processing and handling, such as extracting residual moisture from
core samples, transferring samples from samplers to storage con-
tainers, and preserving samples at freezing temperature.
Contamination and loss of samples may occur if they are not handled
properly.

3.2.2 Sampling Techniques

There are three types of sediment sampling, each one serving a
particular purpose:

(1) Suspended-sediment sampling - The purpose of the suspended-
sediment sampling is to obtain a sampling that is representative of
the water-sediment mixture moving in the vicinity of the bottom.

The sample can be collected with a Van Dorn water sampler (Section
3.1.3). The sediment is separated from the water by centrifugation,
and the sample is transferred into a glass container for storage
before analysis.

(2) Grab sediment sampling - Grab sampling of the sediment is
performed by grab samplers which usually have the distinctive feature
of the shapes of an orange-peel or a clamshell. During sampling,

the sampler is lowered to the bottom with its grab opened. The grab
is closed after being triggered by electrical or hydraulic means,
after closure the sampler is lifted to the surface. The sediment
sample is a composite sample of a several inch layer of sediment.

(3) Core sampling - Cylindrical and box corers are used to
remove a vertical tube of sediment at a particular location in as
undisturbed a state as possible. The purpose may be to examine the
historical formation, the interrelationship of the biological
components and their environment, or the accumulation of polluted
materials from a particular source. These extractive devices can
be subdivided by the means utilized in forcing the penetration of

27

NSWC/WOL/TR 75-3 5

the medium: (1) gravity (weight or hydraulic piston), (2) vibrator
(pneumatic and electric), (3) explosive (chemical and electric
spark), (4) rotary (hydraulic and direct mechanical), and (5) scuba
divers inserting cores by hand. Among them, the gravity corer is
most commonly used for general purpose sampling.

The sediment cores collected are immediately extruded and
sliced into sections. Each section is squeezed to remove residual
water and stored in appropriate containers (Section 3.1.5).

3.2.3 Samplers

There are close to one-hundred different sediment samplers
commercially available with price ranging from $30 to $4,000. Many
are designed for specific purposes. Others can be used for general
purposes. Since there is no "ideal" sampler, selection of an
appropriate sampler must depend on the requirements of the program.
Considerations should be given to:

1. Types of sediment to be sampled.

2. Depth of the water above the sampling site.

3. Importance of undisturbed, unwashed samples.

4. Introduction of contaminant to the samples.

5. Size and weight of the samples.

6. Requirements for support equipment on board ship.

7. Ease of removal of the sample from the unit.

8. Cost of the unit.

Three types of sediment samplers are recommended for the
explosive testing program:

(1) Van Dorn Sampler - Van Dorn sampler, normally used as a
water sampler, can be used for sampling suspended and unconsolidated
sediment. The description of the Van Dorn sampler is presented in
Section 3.1.3.

(2) Shipek Sediment Sampler, Model 860
(Hydro Products, San Diego, California) - Fig. 6

Specifications

Size: 18.6 in. x 17.4 in. x 25.1 in.

Weight: 134 lbs

Materials: Sampler: cast iron

Springs: tempered stainless
steel

28

NSWC/WOL/TR 75-35

FIG. 6 SHIPEK SEDIMENT SAMPLER

29

NSWC/WOL/TR 75-3 5

Finish: International Orange epoxy

paint applied over inert
primer coat

Sample size: surface area: 8 in. x 8 in.

depth: 4 inches at center

Price: $900

The Shipek Sediment Sampler is designed for sampling
unconsolidated sediment, from soft ooze to hard-puck coarse sand.
The device is capable of bringing virtually undistrubed, unwashed
samples to the surface from any depth. Basically the unit is composed
of 2 concentric half cylinders. The inner semi-cylinder, or sample
bucket, is rotated at high torque by 2 helically wound external
springs. Upon contact with the bottom it is automatically triggered
by the inertia of a self-contained weight upon a sear mechanism.
At the end of its 180° travel the sample bucket is stopped and held
at the closed position by residual spring torque.

After closure the sample is given optimum protection from
washout during the return trip by the cylindrical configuration of
the unit. Once on deck, the sample bucket may be disengaged from
the rest of the device by releasing two retaining latches at each
end of the upper semi-cylinder. The sample is then readily accessible
for immediate study or transport to off-site laboratory facilities.

(3) Phleger Corer, Model 840-A
(Hydro Products, San Diego, California) - Fig. 7

Specifications

Weight: 13 1/2 lbs

Valve: Naval bronze and neoprene

Cutting nose: Bayonet-detach chromalloy,

precision ground
Core barrel: Steel tubing 25 in. long x 1.5

in. diameter
Core liners: Clear buterate tubing

Sample size: 24 in. long x 1.38 in. diameter

Unit weight: 2 5 lbs, less weights; 75 lbs

including chest
Sea chest

Dimensions: 32 in. x 15 in. x 9.6 in.

Price: $345

30

NSWC/WOL/TR 75-35

O

«

A\

FIG. 7 PHLEGER CORE SAMPLER

31

NSWC/WOL/TR 75-35

The Phleger Corer is a compact, general purpose sampler for
obtaining sediment cores. Core retention is accomplished by a
simple positive-displacement valve arrangement providing closure of
the top of the tube. The resulting vacuum created inside the tube
when it is withdrawn from the sediment holds the core securely in
the buterate core liner. Little wash out is experienced at the
bottom of the sample, and no loss is possible at the top portion of
the core. Upon return to the surface, the clear buterate core
liner is easily removed from the corer. The liners are replaceable
and provide positive support of samplers for permanent storage or
for when it is desirable to split the core container for
cross-section analysis.

3.2.4 Storage of Sediment Samples

The same principles for the storage of water samples should
also be applied to the storage of sediment samples. In addition,
attention must be given to the effect of biological activity on the
sample characteristics in the sediment samples. The concentrations
of micro organic and inorganic components in sediment samples are
liable to change rapidly on storage owing to bacterial or enzymatic
action. If possible, samples should be analyzed within an hour of
collection; if the analysis has to be delayed, they should be placed
in glass bottles and immediately frozen with dry ice on board ship.
The samples can then be brought back to the laboratory and stored in
a deep freeze until analyzed.

IV

DETERMINATION OF EXPLOSION PRODUCTS

4.1 DESIGN OF MEASUREMENT SYSTEM

There are three basic steps in the design of a measurement for
characterization of explosion products in water. These are based
on the answers to the following questions:

(a) Why are the measurements needed? or
"Objectives of Analysis"

(b) What parameters should be sought? or
"Parameters of Analysis"

(c) How should the measurement be made? or
"Method of Analysis"

32

NSWC/WOL/TR 75-3 5

4.1.1 Objective of Analysis

The objectives of explosion products analysis are as follows:

(a) Establish the base of information on the present quality of
water bodies and sediment in the vicinity of the explosion test
area for evaluating future changes in water quality.

(b) Determine the amounts of toxic substances, chemicals,
organic substances or solid wastes introduced into bodies of water
and sediment immediately after the explosion.

(c) Determine the effects of continued testing at a site in
terms of possible long term accumulation of pollutants from the
tests.

4.1.2 Parameters for Analysis

The choice of parameters for analysis depends primarily on the
type of information sought. It is of vital importance to try to
understand the complete problem. The number of tests performed on
such samples should be based on the following considerations:

(a) The analysis should produce valuable data and valid
conclusions can be drawn from it. Tests should be ruled out if they
are insignificant to the objective of the program.

(b) Priority of tests should be established according to their
importance, practicality, and cost. Very often part of the tests
must he abandoned because of lack of time, equipment, and personnel.
Only the more important ones will be processed.

(c) In addition to the tests used for identification of various
types of pollutants (e.g. explosion products), nonspecific tests
(e.g. pH, temperature, total carbon and turbidity) should also be
considered. These tests are frequently used to correlate data in
the whole analysis.

The parameters and the nonspecific tests for several explosives
are listed in Table 3. These are given as a general guideline.
The specific analyses to be performed in a water pollution study will
depend on the types of explosive materials used in the test and the
objective of the program.

In general, it is more important to measure the potentially
harmful products than the harmless ones. However, one that is

33

NSWC/WOL/TR 75-3 5

TABLE 3

PARAMETERS FOR ANALYSIS

DISSOLVED GASES

DISSOLVED COMPONENTS

HCN
NH 3
CO

CH4

C 2 H 6
Cl 2

co 2

N?

SUSPENDED SOLIDS

A1 2 3
PbO
Zr0 2
Explosives
Total Suspended Solids
Particle Size Distribution
Particulate Carbon

Al

Pb

Zr

Li

Nitrate

Chloride

Explosives

SEDIMENT

A1 2 3
PbO
Zr0 2
Explosives
Particulate Carbon
NON SPECIFIC

pH

°2

Turbidity-
Temperature

34

NSWC/WOL/TR 75-35

harmless, but easy to measure, can be used as an indicator of the
presence of others.

4.1.3 Methods of Analysis

Following the establishment of the objectives of the measurement
program and the selection of parameters for analysis, suitable
analytical methods are then selected. There are no prescribed pro-
cedures which are applicable to all situations but the best method
for any given situation must be based upon consideration of many
factors. Some of the more important factors are:

(a

(b
(c
(d
(e
(f

(g

(h
(i

Required sensitivity
Accuracy of method
Presence of interferences
Number of samples to be analyzed
Necessity of field or in situ analyses
Speed of analysis required for results
Availability of required instruments
Number and skill of laboratory personnel
Cost of the analyses

Listings of "standard" and "recommended" analytical methods
for natural waters and marine waters are to be found in a variety of
publications .

For this report a literature survey of these methods was
conducted. Based upon the above considerations, the most appropriate
procedures were selected, refined, combined, and evaluated to
establish their applicability to the analysis of explosion products.
General discussion of the methods will be given and specific analyti-
cal procedures for some explosion products will be presented.

4.2 SPECIFIC CONSIDERATIONS

4.2.1 Fresh Water vs Seawater

Most of the analytical methods used in water analysis can be
applied to fresh water as well as seawater. However, the complexity
of seawater often causes a number of problems in trace analysis in
that medium:

1. The larger quantity of salts present in seawater reduces
the efficiency of some separation techniques, such as ion exchange
and solvent extraction.

35

NSWC/WOL/TR 75-3 5

2. Many conventional techniques used for the measurement of
trace elements in water are complicated by the interference of the
overwhelming quantity of dissolved ions present in the seawater
matrix.

3. In seawater trace elements may exist in many different
complex species which could give erroneous results in analytical
determinations if the method employed is dependent of the chemical
states of the trace elements.

Consequently, many conventional analytical techniques for
analysis of trace elements in water cannot be directly applied to
seawater solutions. Therefore, selection of special procedures are
necessary.

4.2.2 In-situ Analysis

It is practically impossible to handle and process a water
sample without changing its characteristics. The best chance for an
error-free procedure lies in the use of in-situ analyses. In-situ
analysis not only alleviates the problems of sampling, sample
transportation, and storage but also provides analyses continuously
or at short time intervals on a 24 hour basis. The excellent
coverage of fluctuations in water quality by the continuous monitor-
ing systems will often need to be coupled with sampling programs to
define the types of pollutants being introduced and their dispersion
characteristics .

A number of systems are commercially available which are
designed to automatically measure and record water quality parameters
by instrumental methods of analysis. These systems are usually
capable of measuring temperature, conductivity, dissolved oxygen,
turbidity, pH, and chloride. Certain parameters are measured for
specific applications, e.g., the monitoring of fluoride, chlorine,
nitrates, cyanides, and copper in certain waste effluents.

Although in-situ analysis offers a number of advantages, its
use is still limited by the following reasons:

1. The cost of instruments and supporting equipment for the
in-situ analysis is relatively high compared to laboratory analysis.

2. Analyses cannot be repeated because no sample is collected.

3. Problems in sensitivity, interference, and accuracy often
make in-situ analysis unreliable and impractical.

36

NSWC/WOL/TR 75-3 5

4. Trained analysts must be at the site to perform or
supervise the analyses.

In view of the above limitations, it is recommended all the
analyses for the explosive test program to be performed in the
laboratory with the exception of some parameters, (e.g. temperature,
turbidity, and dissolved oxygen), which require in-situ measurements.

4.2.3 Concentration and Separation

Many current methods of water analysis do not permit the direct
determination of elements at low concentrations because of limits
of detectability by certain analytical instruments and because of
interferences from other constituents in the sample. This is
particularly true for seawater analysis, which, as previously
discussed, presents many difficulties in the direct determination.

Before the determination can be made, it is usually necessary
to concentrate the trace element from a large volume of water. After
concentration, the element is separated, where necessary, from other
elements which may also be removed by the concentration procedure,
and determined by a specific and sensitive physico-chemical method.

Concentration and separation techniques have been discussed in
the literature. H* ^ , 13 A SUIT imary of these techniques is presented
in Table 4 .

Although these various separation and concentration techniques
are useful and frequently required, they do introduce another step
into the analytical process. The procedures involved often are time-
consuming and there always exists a possibility of contamination
introduced by the reagents and the manipulation used in the procedures,
Thus, wherever possible, interferences should be removed by masking

Spencer, D. W. and Brewer, P. G., "Analytical Methods in Oceano-
graphy, I. Inorganic Methods", Crit. Rev. Solid State Sci., 1,
409 (1970) .

1 9

Andelman, J. B. and Caruso, S. C. , Handbook of Water and Water
Pollution, L. L. Ciaccio, Ed., Vol. 1, Chapter 13, p. 213, Marcel
Dekker, New York, 1965.

13

Berg, E. W., Physical and Chemical Methods of Separation, McGraw-
Hill, New York 1963.

37

NSWC/WOL/TR 75-3 5

TABLE 4

CONCENTRATION AND SEPARATION TECHNIQUES
FOR WATER ANALYSIS

Technique
Freeze Drying
Carbon Adsorption
Solvent Extraction
Ion Exchange
Cocrystallization
Cooprec ip it at ion
Gas-liquid Chromatography
Thin Layer Chromatography
Membrane Filtration
Centrifugation

Application
organic materials, inorganic ions
organic materials
organic and inorganic ions
organic and inorganic ions
trace elements in seawater
trace elements in seawater
volatile materials, dissolved gases
organic materials
suspended and particular matter
suspended and colloidal matter

38

NSWC/WOL/TR 75-35

techniques, or a sufficiently sensitive analytical procedure chosen
to eliminate the need to concentrate.

4.3 PROCEDURE

4.3.1 Dissolved Gases

4.3.1.1 Gas Chromatographic Methods

The gas chromatographic approach has been recognized as one of
the best methods for the determination of dissolved gases in water.
The method provides rapid and accurate measurement, and data may be
collected easily and routinely on shipboard. The method consists of
stripping the dissolved gases from the test solution with an inert
gas and subsequent separation and detection by gas chromatography.

Stripping is essentially a gas-liquid extraction procedure in
which an inert carrier gas is bubbled through a sample to carry off
the dissolved gases for further separation, concentration, or
detection. Gas transfer efficiency in such systems is dependent on
the gas-liquid interfacial area and on the degree of mixing.

Gas-exchange separation can be carried out as either a batch or
a continuous flow process. In one design, a continuous mixed stream
of sample and carrier gas is forced through an aspirator nozzle
under 50 pounds of pressure. 14 In another design, the dissolved gases

are stripped from the test solution by multiple spinning discs

rotating at high speed.

The gas stream from the exchange unit is then passed through the
gas chromatographic columns. After the chromatographic separation
of the different components, the gas stream is passed through the
detector cells (thermal conductivity or flame ionization) and the
elution curve is recorded by a strip-chart recorder.

14 Dixon, W. S., "Pollution Control by Co»tinuous Dissolved Oxygen
Analysis and Associated Instruments", Proc. Water Quantity
Measurement and Instrumentation, Technical Report, Robert A. Taft
Sanitary Engineering Center, Cincinnati, Ohio (1960).

15 Swinnerton, J. W. , Linnenbom, V. J., and Cheek, C. H., "Dissovled
Gases in Aqueous Solution by Gas Chromatography", Anal. Chem. , 3A_,
483 (1962).

39

NSWC/WOL/TR 75-35

A system based on this method has been developed by Swinnerton
et. all 5 ' 16 for the analysis of CO, CH4, N2 , 2 , and CO2 in seawater,
The equipment consists of an all-glass sample chamber in which the
dissolved gases are stripped from solution by an inert carrier gas

(such as helium), a four-way by-pass valve, a commercially available
gas chromatograph, and a recorder- The stripped gases are dried and
passed to a gas partitioner consisting of two columns. The first

(a 6 ft. x 1/4 in. column of 30% hexamethylphoramide on 60-80 mesh
column pack) separates CO2 from the mixture while the second (a 4 ft.
x 1/4 in. column of 60-80 mesh column pack followed by a 7 3/4 ft.
x 1/4 in. column of 40-60 mesh molecular sieve 13x) resolves the
O2, N2 # CH4, and CO. A thermal conductivity detector is used to
determine the separated gases. A schematic of the system is shown

in Fig. 8. The system is calibrated using determinations on water
saturated with pure gases at a known temperature and pressure.
Sensitivities as low as 0.05 ppm in 30 ml samples can be obtained.
A chromatogram of a dissolved gas mixture in water is shown in
Fig. 9.

Swinnerton and Linnenbom-'-^ have develop an extremely sensitive
gas chromatographic procedure for the determination of very low
concentrations of low molecular weight hydrocarbons in seawater
(C1-C4) . The hydrocarbons are stripped from about 1 liter of sea-
water with helium and after drying, collected in a series of two
cold traps. The first cold trap is a column of activated alumina
at -80°C (acetone-dry ice bath) which traps the C2-C4 hydrocarbons.
The second is a column of activated charcoal, at -80°C, which traps
the methane. Following a stripping period of 15 to 20 minutes the
temperature of the cold traps is raised to 90°C and the gases back
flushed with helium, from the traps into the gas chromatograph.
The methane is passed through a 4 ft. x 1/4 in. column of silica gel
while the C2-C4 hydrocarbons are resolved by either a 4 ft. x 3/16 in,
activated alumina column with 10% paraffin oil or a 10 ft. column
of chromosorb with 20% SF-96 (or SE-30) depending on whether

15

Swinnerton, J. W. , Linnenbom, V. J., and Cheek, C. H. , op cit, pg 37

" Swinnerton, J. W., Linnenbom, V. J., and Cheek, C. H., "Revised
Sampling Procedure for Determination of Dissolved Gases in Solution
by Gas Chromatography", Anal. Chem. , 34, 1509 (1962).

1 7

Swinnerton, J. W., Linnenbom, V. J., and Cheek, C. H.,

"Determination of the C-i to C4 Hydrocarbons in Seawater by Gas

Chromatography", J. Gas Chromatog., 5_, 570 (1967).

40

NSWC/WOL/TR 75 35

SAMPLE
INJECTION

rr.

RUBBER

SERUM

CAP

40
mm

10mm

GLASS

SAMPLE

CHAMBER

COARSE

GLASS

FRIT

2mm
BORE

DRYING
TUBES

4-WAY
VALVE

/

«fc

\

BYPASS
POSITION

r

SEPARATION
COLUMNS

o-

6

THERMAL
CONDUCTIVITY CELL

o— -o

EXHAUST

FLOW
RATE
METER

GASPARTITIONER
TANK He DRYING

(OR N 9 )

TUBE

>— ^*i

RECORDER

PRESSURE
REGULATOR

FIG. 8 SCHEMATIC DIAGRAM OF SYSTEM FOR DISSOLVED GAS ANALYSIS

41

NSWC/WOL/TR 75-35

100 r

o

n

<

C/J

o

LU

t/J

rr

-J

LU

Q

LL

a:

>

O

o

^

50

CO

A

12

10

COMPOSITE

-i

TIME (MINUTES)

FIG. 9 CHROMATOGRAM OF DISSOLVED GAS MIXTURE IN WATER

42

NSWC/WOL/TR 75-3 5

resolution of the higher or lower molecular weight olefins from
normal paraffins is desired. A flame ionization detector is used
and calibration is with gas saturated distilled water. The system is
shown in Fig. 10.

The sensitivity of the system is about 5 x lO -10 ml/1 with a
precision of + 10%. The procedure can also be used for the deter-
mination of very low concentrations of carbon monoxide. The carbon
monoxide, stripped from the seawater, is trapped in a column of one
quarter activated charcoal and three quarters molecular sieve at
-77°C. The gas is back flushed from the cold trap by raising the
temperature to 90°C and separated by the silica gel column. Before
passing to the flame ionization detector, hydrogen is introduced and
the carbon monoxide quantitatively reduced to methane by passing
through a heated tube containing nickel catalyst supported on 30-60
mesh silocel firebrick.

The time required for analyzing 1 liter of seawater for CO,
methane, and other light hydrocarbons is approximately 45 min. The
complete system costs approximately $10K. The cost for analyzing
the dissolved gases is estimated to be $100 per sample.

Precaution must be exercised about doing dissolved gas analysis
by shipping water samples from the point of collection to a labora-
tory for analysis. 18 Methane is probably the most stable gas, but
it can be produced or consumed by various organisms. Carbon monoxide
and ethane can be affected by presence of bacteria and by the
breakdown of dissovled organic matter in the samples. Samples should
be treated with sodium azide (which destroys marine bacteria) and
kept in a cool dark place. There will most certainly be an air
bubble at the top of the water sample when it finally arrives at the
laboratory. This will be the result of degassing due to the changing
temperature and agitation of the water sample. To be sure of the
gas concentration in the water, this air bubble must be analyzed.

4.3.1.2 Specific Ion Electrodes

Two dissolved gases in the explosion products, NH 3 and HCN,
can be conveniently measured by specific ion electrodes. Specific
ion electrodes are basically potent iometric membrane electrodes
systems which operate on a principle similar to that of the glass
electrode for the measurement of pH. The experimental procedure in

18

Lamontagne, R. A., Naval Research Laboratory, Private Comm. (1974)

43

(HELIUM INlT

TOGGLE VALVE

SEA WATER

COLLECTION

BOTTLE

NSWC/WOL/TR 75-35

FROM
G.C.

EXHAUST

FLOW METER

WASTE

ACTIVATED
CHARCOAL
COLUMN

SAMPLING AND STRIPPING

GAS CHROMATOGRAPH

ELECTROMETER

I RECORDER I

DETECTORS
(FLAME)

~0 H 2
-O AIR

HELIUM
-O CARRIER
GAS

FROM

STRIPPING

CHAMBER

ACTIVATED^

ALUMINA

COLUMN

FOR
DETECTORS

■ ,-1-90'C v
WATER >
BATH

t ACTIVATED

'charcoal

COLUMN

INJECTION AND ANALYSIS
FIG. 10 DIAGRAM OF SYSTEM FOR HYDROCARBON DETERMINATION

44

NSWC/WOL/TR 75-3 5

their use is also quite similar to that for the glass pH electrode.
They are used with a reference electrode, such as saturated calomel
or silver-silver chloride, and a high impedance potential measuring
device, such as a pH meter with a millivolt scale. A calibration
plot of voltage versus the logarithm of concentration of the test
ion is made, generally for at least a 10-fold range of concentra-
tion. The voltage for the test solution is measured, and the test
ion concentration is then calculated from the calibration plot. For
on-the-spot, plant or field measurements, a portable, direct-reading
specific ion meter is used (Orion Series 400 specific ion meters) .

The major advantages of specific ion electrodes for use in
water analyses are their speed and ability to be used for in-situ
monitoring. Minimal sample and reagent preparation prior to analysis
are required. The method also offers a wide concentration range,
and a precision and accuracy comparable to other accepted methods.
The system is relatively inexpensive. A portable, direct-reading
specific ion meter costs $450 and prices of individual specific ion
electrodes range from $150 to $300. The cost for analysis is
approximately $10 per sample.

a. Ammonia

The use of an ammonia specific ion electrode in the
determination of ammonia in surface waters, sewage samples, and
saline waters has been recently developed. 19 The electrode is an
Orion Model 95-10 gas sensing electrode, incorporating an internal
reference electrode and a diffusion-type membrane.

Dissolved ammonia from the sample diffuses through a highly
gas-permeable membrane until a reversible equilibrium is established
between the ammonia level of the sample and the internal filling
solution. Hydroxide ions are formed in the internal filling solution
by the reaction of ammonia with water,

NH 3 + H 2 « NH4 + +OH-

The hydroxide level of the internal filling solution is measured by
the internal sensing element and is directly proportional to the
level of ammonia in the sample. The electrode potential is

19 Thomas, R. F. and Booth, R. , "Selective Electrode Measurement of
Ammonia in Water and Wastes", Environ. Sci. Technol., 1_, 523 (1973)

45

NSWC/WOL/TR 75-3 5

essentially Nernstian with respect to the ammonia level and
approximately follows the equation:

E = Eo - S log (NH 3 )

E = electrode potential in millivolts

Eo = approximately 180 mv (varies slightly from
electrode to electrode)

S = the Nerst slope, 58 mv/decade at 2 9°C

The ammonia electrode is almost totally interference free.
Anions, cations, and common gases (carbon dioxide, sulfide, cyanide,
and sulfur dioxide) do not interfere. Sample color, turbidity, and
the presence of suspended solids do not affect the measurement.
Used with an expanded scale pH/mv meter, the electrode is capable
of precision equal to the best color imetric methods for ammonia.
The sensitivity is approximately 10 _ 6 moles/liter (20 ppb) .

b. Cyanide

The cyanide specific ion electrode has been used for rapid,
direct measurement of cyanide ions in waste waters. The cyanide
electrode uses a membrane of silver sulfide and silver iodide.
Cyanide ion in the sample reacts with the silver iodide in the
membrane to release iodide into the solution. The iodide at the
membrane surface is proportional to the level of cyanide and is in
turn sensed by the electrode:

2CN~ + Agl „ Ag(CN)~ + I~

As a consequence the electrode responds to cyanide with Nernstian
behavior :

E = Eo + S log(CN~)

where S is the electrode slope (about 59 mv for a ten-fold increase
in the cyanide level at 25°C) . The lowest level of cyanide that can
be measured is about 50 ppb.

20

Riseman, J. H., "Electrode Techniques for Measuring Cyanide in

Waste Waters", Am. Lab., 4, 63 (1972).

46

NSWC/WOL/TR 75-35

Cyanide can be present as free cyanide ion and as dissolved
HCN gas. The cyanide electrode responds only to the free cyanide
ion, so the sample must be adjusted to the corrected pH range before
measurement .

Sample pH adjustment before measurement is effected by adding
concentrated NaOH to the sample to make it . 1 M in hydroxide ion.
This will make the sample pH about 13, insuring that substantially
all the HCN is converted to free cyanide ion. A calibration curve
for the cyanide electrode is made using a series of standardizing
solutions of different concentrations. Each standard solution is
made 0.1 M in hydroxide ion so that the NaOH treated samples and
standards will have about the same ionic strength and pH.

The electrode does not respond to most common ions in water,
such as fluoride, chloride, nitrate, sulfate, phosphate, carbonate,
sodium, potassium, and ammonium. Sulfide and iodide ions are the
only major interferences.

4.3.1.3 Colorimetric Method

Chlorine in water may be present as free available chlorine
(in the form of hypochlorous acid and/or hypochlorite ion) or as
combined available chlorine (chloramines and organic chloro deriva-
tives) . Chlorine in aqueous solution is not stable, and the chlorine
content of samples, particularly weak solutions, will rapidly
decrease. Exposure to sunlight or other strong light or agitation
will accelerate the reduction of chlorine present in such solutions.
Therefore, it is recommended that chlorine determinations be started
immediately after sampling, avoiding excessive light and agitation.

Several methods have been described for the determination of
free or combined available chlorine in water. 21 The colorimetric
method using orthotolidine appears suitable for field use. In this
method, the water sample is mixed with a 2N HCl solution containing
0.15% orthotolidine (the ratio by weight of orthotolidine to chlorine
must be at least 3:1). A yellow holoquinone color is developed, and
the color intensity is immediately measured with a portable colori-
meter (Hach Chemical Co., Ames, Iowa; Model DR-EL, $330). The
minimum detectable concentration of chlorine is approximately 10 Vg/l.

"? 1

Standard Method for Examination of Water and Wastewater, 1971, 13th

Edition, American Public Health Association, Washington, D. C.

47

NSWC/WOL/TR 75-3 5

4.3.2 Dissolved Constituents

4.3.2.1 Metallic Ions

Determination of metallic ions in water from the dissolved
explosion products can be accomplished by many methods. A recent
study shows that atomic absorption appears to be the best technique
for the analysis of trace metals in marine waters. ^2 Th e method is
simple, rapid, and applicable to a large number of metals in surface
waters, domestic and industrial wastes, and saline waters.

However, the concentration of the metals in the water samples
may be below the practical limits of detection by atomic absorption
(Table 5) . Although the recently developed graphite furnace technique
has increased the limits of detection by several orders of magnitude,
severe problems have been encountered in the direct analysis of trace
metals in seawater with this technique. Therefore, when trace metals
are present in low concentration, they must be concentrated in some
manner before analysis by atomic absorption analysis (see Section
4.2.3) .

Table 5

SENSITIVITY OF ATOMIC ABSORPTION

AA

Optimum

Toxicity

Sens it ivity**

Concentration

Metal

Limit* (mq/1)
1.5

(mg/1)

Range (mg/1)

Al

1.0

10-50

Pb

0.03

0.5

4-20

Zr

N.A.

10

100-800

Li

N.A.

0.035

0.4-2

*The maximum permissible concentration in water without constituting
a hazard in the marine environment.

**The concentration that produces an absorption of 1%.

22

Lai, M. G., "Evaluation of Analytical Techniques for the Determina-
tion of Trace Elements in Marine Waters", Naval Ordnance Laboratory,
NOLTR 74-116, 24 July 1974.

48

NSWC/WOL/TR 75-3 5

a. Sample handling

For the determination of dissolved constituents the sample
should be filtered through a 0.45 y membrane filter as soon as
practicable after collection. Acidify the filtrate with 1:1 HNO3
(3 ml per liter). Normally this amount of acid will lower the pH to
2 or 3 and should be sufficient to preserve the sample indefinitely.

b. Concentration

Aluminum

A method for the concentration of Al in water has been

developed by Hsu and Pipes. 23 i n their method, a benzene solution

of diphenylthiocarbazone (0.1% by wt.), 8-quinolinol (0.75% by wt . ) ,

and acetylacetone (20% by vol.) is used to extract Al from water.
The optimum pH for extraction is about 5. An extraction ratio as

high as 200 (1000 ml aqueous sample and 5 ml benzene solution) can

be conveniently used. A sensitivity of 9 yg/1 can be attained by
this method.

Lead

A procedure has been developed by Brooks et al for the
extraction of Pb from saline waters. 24 The procedure should be
applicable to fresh waters as well. In the procedure samples of
seawater (750 ml) are placed in 1000 ml Erlenmeyer flasks and 35 ml
of methyl isobutyl ketone (MIBK) are added to each flask followed by
7 ml of 1% ammonium pyrollidine dithiocarbomate (APDC) solution. The
samples are then equilibrated for 30 min. on a mechanical shaker.
The phases are separated by means of a separatory funnel and the
organic phases are stored in polyethylene bottles. With this
procedure a sensitivity of 2 Ug/1 can be attained.

9 -j

Hsu, D. Y. and Pipes, W. 0., "Modification of Technique for

Determination of Aluminum in Water by Atomic Absorption
Spectrophotometry", Environ. Sci, Technol., 6, 654 (1972).

24 Brooks, R. R., Presey, B. J., and Kaplan, I. R. , "APDC-MIBK

Extraction System for the Determination of Trace Elements in Saline
Waters by Atomic-Absorption Spectrophotometry", Talanta, 14, 809
(1967) .

49

NSWC/WOL/TR 75-35

Lithium

Lithium in seawater may be directly determined by atomic
absorption without separation and concentration.

Zirconium

Any zirconium introduced into the natural waters will be
rapidly hydrolyzed at the pH of the waters (seawater and fresh water)
to a colloidal hydrous oxide which will be readily precipitated.
Therefore, the concentration of soluble Zr is expected to be extremely
low. The co-precipitation technique with iron hydroxide at a pH of
9.0 to 9.5 described by Slowey et al^ is used for the concentration
of Zr in water. Each sample previously filtered through 0.45y filter
is co-precipitated three times by the addition of 12 mg of Fe + ^ per
liter of sample. The pH is then adjusted to 9 by the addition of
ammonium hydroxide. The sample is filtered through Millipore filters.
The precipitate is dissolved in 9N HCl and the iron extracted with
d iisopropylether . The sample is then evaporated to almost dryness
and diluted to 10 ml with 2% HF. With this procedure a sensitivity
of 0.1 ppm can be attained.

Direct analysis of metals by atomic absorption generally costs
$15 per element. The cost will increase several times if concentra-
tion procedures are required.

4.3.2.2 Explosives

Very few reliable methods for the analysis of explosives at low
concentration (parts per million) in water and in sediment have been
developed. Procedures for several common types of explosives (TNT,
RDX, Tetryl, and ammonium perchlorate) were established by Hoffsommer
et al at NAVS URFWPNCEN based on the use of gas chromatography and the
ion specific electrode. A method for the analysis of HMX in water

25

Slowey, J. F., Hayes, D. , Dixon, B. and Hood, D. , "Distribution

of Gamma Emitting Radionuclides in the Guld of Mexico", Symposium

on Marine Geochemistry, University of Rhode Island, Occasional

Publication No. 3, Aug 1965.

Hoffsommer, J. C. , Glover, D. J., and Rosen, J. M., "Analysis of
Explosives in Sea Water and in Ocean Floor Sediment and Fauna",
Naval Ordnance Laboratory, NOLTR 72-215, 11 Sept 1972.

50

NSWC/WOL/TR 75-35

was also developed based on the thin-layer chromatography .^ Methods
for the analysis of any other explosives used in t he underwater
explosion program would have to be developed.

TNT, RDX, Tetryl

A 100-ml water sample is extracted with 30 to 40 of
benzene; the benzene is evaporated to a small volume and injected
into a gas chromatograph equipped with a high temperature nickel-63
electron capture detector. Chromatographic traces of the water
extracts are compared to chromatographic traces of standard solutions
of TNT, RDX, Tetryl. Retention times and areas of peaks are measured
by means of an automatic digital integrator to an accuracy of + 1
sec. for retention time and an integration area count of approximately
9 counts/mm 2 . Detection levels for TNT, RDX, and Tetryl have been
determined to be 2, 5, and 20 parts per trillion, respectively, under
normal routine working conditions.

HMX

A 100-ml water sample is extracted with four 2 5-ml portions
of benzene. The combined benzene extracts are evaporated under
reduced pressure (17 mm/20°C) with a water aspirator to dryness.
The residue is taken up in 1.0 ml of acetone. A total of 20- 1 are
spotted in four 5- 1 portions as one spot with drying between spott-
ing onto a 0.3 mm silica gel HF-254 thin-layer glass plate. Standard
solutions of HMX are similarly spotted to the right and to the left
of the unknown, and the thin-layer plate is developed in an ascending
manner with benzene/acetone, 4:1, as eluent. After air drying, the
TLC plate is placed in a ultraviolet cabinet, and zones for HMX are
located as dark spots under 254 mm radiation.

In order to determine the HMX present, the dark areas are
marked with a needle and photographed with a polariod camera with
transparency film. The developed film is projected by means of a
lantern slide projector onto a sheet of white paper 3 to 4 feet away,
and the area for the HMX spots traced with a pencil. The standard
and sample area are measured by means of a precision planimeter.
The weight of HMX in the unknown spot is calculated from the
following :

27 Glover, D. J. and Hoffsommer, J. C. , "Thin-Layer Chromatographic
Analysis of HMX in Water", Bull. Environ. Contaim. Texicol. 10 ,
302 (1973).

51

NSWC/WOL/TR 75-3 5

Log wt / log wt STD-1 - log wt STD-2] 4*5 A h \

HMX =[" j\ HMX STD-1 l+log wt STD-2

^A } 2 " A^

STD-1 STD-2

A = the area of the respective spots.

Ammonium Perchlorate

The analytical procedure for the determination of ammonium
perchlorate is based on the use of a specific ion electrode which
develops a potential across a thin porous inert membrane.

The potential measured is a function of perchlorate
concentration. A reference curve is prepared using a standard sea-
water to which is added known amount of perchlorate. Differences
in seawater samples may contribute to a small uncertainty in the
measurement, particularly at low concentrations. For clear seawater,
the method gives satisfactory results in the 1 ppm range, using a
research pH meter.

4.3.2.3 Nitrate

The nitrate electrode allows nitrate to be quickly and easily
determined in fresh waters. However, the nitrate electrode will not
operate in the presence of high levels of other ions, so it cannot
be used to measure nitrate in concentrated salt samples such as
seawater.

Nitrate can be reduced to ammonia, allowing the ammonia electrode
to be used for nitrate analysis, without interference. The reduction
procedure is as follows:

1. Place in a round-bottom flask 100 ml of (neutral) sample
and a magnetic stirring bar. To the sample, add 1 ml of concentrated
HC1 and about one-half gram of NaF . Stir vigorously. Add about
0.1 g of finely divided aluminum powder. Wait until the evolution
of hydrogen stops, then add 1 ml of 10 M NaOH. Pour the contents
into a beaker and measure the ammonia concentration by the ammonia
electrode (see 4.3.1.2).

Samples which may already contain ammonia must be measured
first. The background level of ammonia is subtracted from the value
found after reduction.

52

NSWC/WOL/TR 75-35

The above method will give better than 90% conversion of the
sample nitrate. It is recommended that a recovery study be used to
determine the conversion efficiency in the type of sample being
measured .

4.3.2.4 Chloride

Two methods are presented for the determination of chlorides.
The colorimetric method is suitable for use in clear samples with
relatively low chloride concentration, and the potent iometric method
is suitable for colored or turbid samples with high chloride
concentrat ion .

In the colorimetric method, chloride is determined by reacting
the sample with mercuric thiocyanate which forms unionized mercuric
chloride and thiocyanate ions. The thiocyanate is reacted with
ferric ion producing highly colored ferric thiocyanate proportional
to the chloride in the original sample.

2C1" + Hg(SCN) 2 — *-HgCl 2 + 2SCN~ H±± — „Fe(SCN) +2

The color intensity is then measured with a spectrophotometer at a
wavelength of 480 mm. There are no significant interferences in the
analysis .

In the potent iometric method, chloride is determined by
potent iometric titration with silver nitrate solution using a glass
and silver-silver chloride electrode system. During titration, an
electronic voltmeter is used to detect the change in potential
between the two electrodes. The end point of the titration is that
instrument reading at which the greatest change in voltage has
occurred for a small and constant increment of silver nitrate added.

Ferric ion interferes if present in an amount that is
substantially higher than the amount of chloride. Chromic ion,
ferrous iron, and phosphate do not interfere. Iodide and bromide
also are titrated as chloride.

Grossly contaminated samples usually require pre-treatment .
Where contamination is minor, some contaminants can be destroyed
simply by the addition of nitric acid.

53

NSWC/WOL/TR 75-3 5

4.3.3 Suspended Solids

4.3.3.1 Suspended Metals

For the determination of suspended metals a representative
volume of sample should be filtered through a 0.45y membrane filter.
Transfer the membrane filter containing the particulate matter to a
beaker and add 3 ml of HNO3 . Cover the beaker with a watch glass and
heat gently. The warm acid will soon dissolve the membrane. Increase
the temperature of the hot-plate and digest the material. When the
acid has evaporated, cool the beaker and add another 3 ml of HNO3 .
Cover and continue heating until the digestion is complete. Add
1:1 HCl (2ml) to the dry residue and again warm the beaker to
dissolve the material. Filter the sample to remove silicates and
other insoluble material. The sample is now ready for analysis by
atomic absorption.

4.3.3.2 Suspended Explosives

A representative volume of sample is filtered through a . 5 y
solvent-resistant filter (membrane or glass fiber) . The particulate
matter collected on the filter is washed with several small portions
of benzene which is drawn through the filter after each washing.
The combined benzene extracts are analyzed for explosives using
procedures described in Section 4.3.2.2.

4.3.3.3 Non-filterable Solids

a. Total Non-filterable Solid

Total non-filterable solids are defined as those solids
which are retained by a standard membrane filter and dried to
constant weight at 103-105°C.

A known volume of sample is passed through a weighed filter
(0.8U). The filter is carefully removed from the filter funnel
assembly, placed in a drying oven, and dried at 103-105°C to constant
weight.

b . Particle Measurement

Particle measurement of the suspended solids can be made by
manual microscope methods, but they are tedious and time consuming.
Other indirect measuring techniques such as light scattering, sedi-
mentation, and electrical field effect are limited by lack of
precision. A recently developed Millipore riMC System (Millipore

54

NSWC/WOL/TR 75-35

Corp., Bedford, Massachusetts) offers both speed and precision in
counting particles, in determining size distributions and in
characterizing shapes. It can rapidly and accurately measure such
parameters as diameter, longest dimension, or area.

Samples forTTMC measurement are prepared by Millipore filtration.
This results in a random distribution of particles. The filters are
made transparent with various clearing techniques and mounted on
glass slides. The sample is ready for measurement.

The sample is placed on the microscope stage and the
illumination and focus are adjusted while the operator is viewing
the sample. The camera scans the microscope image and converts its
contents into a video signal which is sent to the computer. The
computer receives the video signal and applies the logic necessary
to count and measure particles in the field of view. The video
signal then goes to the viewing monitor where the field of view is
reconstructed. Measurements are displayed instantly in micrometers
or square micrometers and can be made on individual particles as
well as entire fields of view.

4.3.3.4 Particulate Carbon

To determine the particulate carbon in water a Dohrmann total
organic carbon analyzer (Envirotech Corp., Santa Clara, Calif., $8, 000)
can be used. In the analysis a 30yl acidified water sample is
injected into a sample boat containing an oxidizer at room tempera-
ture. The boat is then advanced to the 90°C vaporization zone where
H2O, CO2 (from dissolved CO2 , carbonates and bicarbonates) and
organic carbon materials which are volatile at 90°C are swept into
the by-pass column. Here volatile organic carbon (VOC) is trapped
on a Porapak Q column at 60°C while the H2O and CO2 are swept through
the switching valve and vented to atmosphere.

After sample vaporization, the valve is automatically switched
to the pyrolyze position and the boat is then advanced to the
pyroysis zone. Residual organic carbon (ROC) materials left in the
boat react with the oxidizer at 850°C to produce C0 2 . At the same
time the by-pass column is backflushed at 120°C thus sweeping the
VOC material through the pyrolysis zone. Both the VOC and the C0 2
(from the ROC) are swept by helium into the hydrogen enriched nickel
catalyst reduction zone where all carbon is converted to methane at
350°C.

The reduction product is swept through the switching valve,
the water detention column and into the flame ionization detector

55

NSWC/WOL/TR 75-35

which responds linearly to methane. The detector output is
integrated and displayed in milligrams per liter (mg/1) on the
digital meter.

4.3.4 Sediment

4.3.4.1 Metals

Metals in the sediment samples can be determined by a simple
procedure essentially described by Iskandar and Keeney.28 Each sedi-
ment sample is mixed thoroughly, and a subsample is dried at 105°C
in a forced-air oven. The dried sample after discarding large
pebbles, twigs, shells, bugs, etc, is ground with a porcelain mortar
and pestle until fine ( 100-mesh) .

A subsample (1-2 grams) is placed in a 70-ml Pyrex digestion
tube and predigested at room temperature for 16 hours by reaction
with 5-10 ml of concentrated HNO3 . Subsequently, the sample is
digested on an hot plate at 120°C for 3 hours. After it is cooled,
3 ml of concentrated HCIO4 are added, and the mixture is heated at
210-220°C until HCl fumes are evolved. The cooled digest is then
filtered through a 0.45u Millipore filter and brought to a 2 5-ml
volume with distilled water. The metals in the solution are
determined by atomic absorption.

4.3.4.2 Explosives

The analyses of explosives in sediment samples are generally
more involved than in water samples. First, the explosives are
extracted from the sediment with the appropriate solvent. Then, the
explosives in the extract are separated by thin- layer chromatography
and finally analyzed by gas chromatography.

TNT, RDX, Tetryl

Seventy-five to 100 grams of the sediment sample are stirred
with 50 ml of benzene. The benzene extract is decanted into a 100-ml
round-bottom flask for vacuum evaporation.

28

Iskandar, K. I., Keeney, D. R., "Concentration of Heavy Metals in

Sediment Cores from Selected Wisconsin Lakes", Environ. Sci.

Technol., 8, 165 (1974).

56

NSWC/WOL/TR 75-35

After evaporation of the benzene extract under reduced pressure
( 17-20mm/20°C) , the flask is rinsed with 1.0 ml of pesticide quality
benzene and transferred to a 5.0 ml test tube. The benzene is again
completely removed under reduced pressure. A total of 0.050 ml of
benzene is added to the residue and 0.025 ml of this solution are
spotted along a narrow band in 5 separated spots onto a ChromAr 500
TLC sheet. Simultaneously, a standard mixture of TNT, RDX, and
Tetryl in benzene is spotted to the right of this band, as a guide.

The fluorescent ChromAr sheet is developed in an ascending
manner with hexane/acetone :45/5 as eluent. After air-drying the
ChromAr sheet for 5 minutes, zones for the standard TNT, RDX, and
Tetryl are located as dark spots under 254 mm UV light. Correspond-
ing areas to the left of these standards are cut out and transferred
to a 5-ml beaker. These ChromAr discs are extracted 3 to 4 times
with a total of 1.0 to 1.5 ml of benzene. The benzene extracts are
combined into a 2.0 ml sample tube with a tapered bottom and the
benzene completely removed under reduced pressure. A total of 50 y 1
of benzene is added to the tapered tube together with 5^ 1 of
o-dinitrobenzene (4.5 x 10~1° g/ 1) as internal standard. After
thoroughly mixing, a 5 to 6y 1 injection of this solution is placed
into the gas chromatograph. At this point, the procedure follows
that reported in Section 4.3.2.2.

HMX

HMX is extracted from the sediment sample by the same procedure
used in TNT, RDX, and Tetryl. After extraction HMX is determined by
the procedure described in Section 4.3.2.2.

Ammonium Perchlorate

A sediment sample is stirred with distilled water for several
hours, after which the sediment is removed using a centrifuge.
Ammonium perchlorate in the solution is measured by the specific
ion electrode.

4.3.4.3 Particulate Carbon

The particulate carbon in the sediment can be determined with an
organic carbon analyzer (Section 4.3.3.4). The sediment sample is
first suspended in water, and an aliquot is then withdrawn for the
analysis. Samples with sediment and high dissolved solids content
pose no problem. However, the analysis is subject to some degree of
error if the organic content other than the particulate carbon is
relatively high.

57

NSWC/WOL/TR 75-3 5

4.3.5 Non-specific Measurements

4.3.5.1 Turbidity

The turbidity of a water sample can be measured in a
turbidimeter (e.g., Kach Model 2100A Laboratory Turbidimeter, $525),
which is a true nephelometer . The method is based upon a comparison
of the intensity of light scattered by the sample under defined
conditions with the intensity of light scattered by a standard
reference suspension. The higher the intensity of scattered light
the higher the turbidity. The readings are made in the Nephelometric
Turbidity Unit (NTU) .

Samples taken for turbidity measurements should be analyzed as
soon as possible. Preservation of samples is not recommended.

The presence of floating debris and coarse sediments which
settle out rapidly will give false high readings. Finely divided
air bubbles will also affect the results in a positive manner.

4.3.5.2 pH

The pH of most natural waters falls within the range 4 to 9 .
The majority of waters are slightly basic due to the presence of
carbonate and bicarbonate. A departure from the norm for a given
water could be caused by the entry of strongly acidic or basic wastes
(HCl in the explosion products) . pH is the logarithm of the
reciprocal of the hydrogen ion concentration in moles per liter.
The practical pH scale extends from 0, very acidic, to 14, very
alkaline, with the middle value (pH 7) corresponding to exact
neutrality at 25°C.

pH can be measured either colorimetrically or electrometrically.
The color imetric method requires a less expensive investment in
equipment but suffers from severe interferences contributed by color,
trubidity, high saline content, colloidal matter, free chlorine, and
various oxidants and reductants .

Electrometrically pH is measured with a pH meter equipped with
either a glass electrode in combination with a reference potential

(saturated calomel electrode) or a combination electrode (glass and
reference) . A portable pF meter such as the Micro 50 pH meter

(Service Tectonics Instrument, Detroit, Michigan, $125) is convenient
for field pF measurements.

58

NSWC/WOL/TR 75-3 5

4.3.4.3 Dissolved Oxygen

Adequate dissolved oxygen (DO) is necessary for the life of
fish and other aquatic organisms. The DO concentration may also be
associated with corrodibity of water, photosynthet ic activity, and
septic ity. Therefore, it may be desirable to determine the DO in
water after an underwater explosion test.

Membrane electrodes of the polarographic as well as the galvanic
type have been used for DO measurements in la"kes and reservoirs^
and in estuarine and oceanographic studies. 30 Being completely
submersible, membrane electrodes are well suited for analysis in-situ.
Their portability and ease of operation and maintenance render them
particularly convenient for field applications.

Membrane electrodes provide an excellent method for DO analysis
in polluted waters, highly colored waters and strong waste effluents.
They are recommended for use, especially under conditions which are
not expedient for use of other chemical methods.

Membrane electrodes are commercially available in larger variety.
In all these instruments the diffusion current is linearly propor-
tional to the concentration of molecular oxygen in the test solution.

Dissolved organic materials are not known to interfere in the
output from dissolved oxygen membrane electrodes, while inorganic
salts, reactive gases, and temperature affect the performance of
the electrodes.

No specific electrode or accessory is especially recommended as
superior. However, one oxygen analyzer which has been in use and
found to be reliable is the Y.S.I. Model 54 oxygen analyzer (Yellow
Springs Instrument Co., Yellow Springs, Ohio, $535).

4.3.5.4 Temperature, Conductivity, and Salinity

29 Weiss, C. M. and Oglesby, R. T., "Instrumentation for Monitoring
Water Quality in Reservoirs", American Water Works Association,
83rd Annual Conference, New York, 1963.

Duxbury, A. C, "Calibration and Use of a Galvanic Type Oxygen
Electrode in Field Work", Limol. & Oceanogr., 8, 483 (1963).

59

NSWC/WOL/TR 75-3 5

As theory and experimental data both indicate temperature
changes produced in water by explosions are entirely negligible after
a few minutes have elapsed. There seems to be no justification for
attempting to measure this effect for the purpose of monitoring a
test. However, temperature, along with conductivity and salinity, are
often needed data for water quality monitoring.

Conductivity is an important water quality test. Also the
conductivity and temperature measurements can be used to estimate
total dissolved solids. When measuring dissolved oxygen, it is
necessary to correct for the salts dissolved in the water. The
salinity measurement provides the data necessary to make this
correction and is of particular importance in coasted areas.

To facilitate in-situ pollution studies YSI has developed the
Model 33 S-C-T Meter ($250) and Probe ($45) for direct measurement of
salinity, conductivity, and temperature. The meter is operated as
follows :

Estimate total dissolved solids by dropping the unbreakable
plastic probe in water, switching to the appropriate conductivity
scale and reading the answer directly from to 50,000 mhos/cm.
Switch to the temperature scale and read temperature from -2° to
+50°C (accuracy: +0.1°C at -2°C and +0.6°C at 45°C) . Measure
salinity as in estuarian environment by dialing the water temperature
and switching to the salinity scale for direct, temperature
compensated salinity readings from to 40% e (accuracy : +0.9%oat 40%
and + 0.7% o at 20%) .

V

CONCLUSIONS AND RECOMMENDATIONS

It is desirable to cover every parameter in a water quality
monitoring program, if possible. Accurate assessment of the water
quality can be conveniently made if sufficient data have been obtained,
However, very often complete coverage of the monitoring parameters
cannot be achieved because of lack of time, personnel, or funding.
Therefore, priority must be established on the parameters needed to
satisfy the minimum requirement of the monitoring program and on the
number of measurements necessary for a reliable quantitative estimate.

In the chemical monitoring program of explosion products several
basic parameters are recommended:

60

NSWC/WOL/TR 75-35

1. Pre-test conditions

In order to make valid comparisons on water quality data
before and after an explosion test and after an explosion test and
to establish a long-term trend, pre-test conditions of the test
environment should be accurately established. Extensive base-line
data on water quality should be compiled.

2. Post-test conditions

Explosion products which are expected to have the most
adverse effect on the environment should be selected first for
measurement. In addition, explosion products which are pertinent to
the objectives of the test program should also be examined.
Parameters which are relatively unimportant, but their measurements
can be made with very little effort, should be considered. If the
products are in a fixed ratio, measurements of a product that can be
easily obtained, can be used to estimate the quantity of others in
the water.

3. Long-term monitoring

Continuous monitoring of water quality at the test site is
unnecessary because underwater explosion tests are usually conducted
in an unconfined area. Most of the explosion products would have
been diluted and carried away by the water current shortly after the
explosion. However, periodical examination of the sediment in the
vicinity of the test site should be made in order to assess the degree
of long-term accumulation of explosion products in the sediment.
This would be particularly important in a shallow water site.

The minimum number of samples collected for analyses should be
sufficient to fulfill the objectives of the monitoring program.
Multiple sampling, necessary for an adequate characterization of the
water body, can be reduced to single sampling as a trade off between
cost and accuracy. Less expensive analytical methods can be used to
substitute the more expensive ones for the similar purpose.

It should be stressed that the collection of water samples from
underwater explosion tests presents many special problems. For
example, if automatic equipment is placed too close to the explosive,
it may be damaged by the shock wave. However, samplers and other
devices can be strung in a line down-current. Also, a boat can be
used to traverse the pool immediately following the explosion. In
general, the time available for the collection of meaningful data is
only a few minutes.

61

NSWC/WOL/TR 75-35

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630 N. Rosemead Boulevard
Pasadena, California 91107
Attn: Dr. Li-San Hwang

Underwater Systems, Incorporated
World Building, Room B-10
8121 Georgia Avenue
Silver Spring, Maryland 20910
Attn: Dr. Marvin S. Weinstein
Daniel D. Wollston

18

NSWC/WOL/TR 75-3 5

Copies

URS Research Company

155 Bo vet Road

San Mateo, California 94402

Vitro Laboratories

14000 Georgia Avenue

Silver Spring, Maryland 20910

Attn: Seymour J. Finkel 10-2002

Robert Ely

Zimpro

Rothschield, Wisconsin 54474

Battelle

Columbus Laboratories

505 King Avenue

Columbus, Ohio 43201

Attn: James B. Kirkwood
R. Glen Fuller
Ms. Ann W. Rudolph
John B. Brown, Jr.

Chesapeake Bay Institute
The Johns Hopkins University
Baltimore, Maryland 21218

Chesapeake Biological Laboratory

P.O. Box 38

Solomons, Maryland 20688
Attn: Dr. T. S. Y. Koo

Dr. Joseph A. Mihursky
Dr. Martin L. Wiley
John S . Wilson

Dr. William B. Jackson, Director
Environmental Studies Center
Bowling Green State University
Bowling Green, Ohio 43403

Florida State University
Tallahassee, Florida 32306
Attn: R. J. Menzies

19

NSWC/WOL/TR 7 5-35

Copies

Professor George B. Butler
Professor of Chemistry-
University of Florida
232 Leigh Hall
Gainesville, Florida 32601

Dr. Melvin Kaufman
Department of Chemistry
University of Florida
Gainesville, Florida 32611

Dr. Joseph B. Levy
Department of Chemistry
George Washington University
Washington, D.C. 20006

Department of Physics
Harvey Mudd College
Claremont, California 91711
Attn: Dr. Alfred B. Focke

Dr. Robert L. Fisher

Dept. of Biology

Juniata college

Huntingdon, Pennsylvania 16652

Lamont-Doherty Geological Observatory
Palisades, New York 10964
Attn: Mr. Robert Gerard

University of California
Lawrence Livermore Laboratory
P.O. Box 808

Livermore, California 94550
Attn: Milton Finger, L402

20

NSWC/WOL/TR 75-35

Copies

Director

Los Alamos Scientific Laboratory
University of California
P.O. Box 1663

Los Alamos, New Mexico 87544
Attn: Dr. D. P. MacDougall

Report Library

Mortimer Schwartz

R. N. Rogers

Lovelace Foundation for Medical
Education and Research
5200 Gibson Boulevard, S.E.
Albuquerque, New Mexico 87108
Attn: Dr. Clayton S. White

Dr. Donald R. Richmond

Robert K. Jones

John T. Yelverton

University of Missouri - Rolla

Rock Mechanics and Explosives Research Center

Buehler Building

Rolla, Missouri 65401

Attn: Ronald R. Rollins
George B. Clark

Dr. Alf Fischbein

Mount Sinai School of Medicine

Department of Environmental Medicine

Fifth Avenue and 100th Street

New York, NY 10029

Mr. C. T. Sanders

Building 2029

Oqk Ridge National Laboratory

P.O. Box X

Oak Ridge, Tennessee 37830

School of Oceanography
Oregon State University
Corvallis, Oregon 97331
Attn: A. G. Carey, Jr.
Librarian

21

NSWC/WOL/TR 75-3 5

Copies

Sandia Laboratories

P.O. Box 5800

Albuquerque, New Mexico 87115

Attn: Dr. Melvin L. Merritt (9150)
Jack W. Reed (5644)

Sandia Laboratories
P.O. Box 969

Livermore, California 94550
Attn: Code 8151 (H. Krieger)

Code 9361 (M. Hicks)

Code 8151 (Dr. Donald E. Warne)

Director

Scripps Institution of Oceanography
La Jolla, California 92037
Attn: Fred Spiess

Stanford Research Institute
3 33 Ravenswood Avenue
Menlo Park, California 94025
Attn: Dale G. Hendry

Howard M. Peters
Donald L. Ross

Dr. William J. Hargis, Director
Virginia Institute of Marine Science
Gloucester Point, Virginia 23062

University of Washington
College of Fisheries
Fisheries Research Institute
Seattle, Washington 98195
Attn: Dave R. Gibbons

Charles Simenstad, Biologist

Director

Woods Hole Oceanbgraphic Institution
Woods Hole, Massachusetts 02543
Attn: Dr. Bostwick Ketchum

Library

Dr. Gifford C. Ewing

Dr. Earl E. Hays

22

NSWC/WOL/TR 75-35

Copies

Stanford Research Institute
Menlo Park, California 93555
Attn: Robert Shaw
Marion Hill

Director

Defense Documentation Center
Cameron Station
Alexandria, Virginia 22314

12

23

NDW.NSWC(W)-5605/l (Rev. 1-75)

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