EPA-905A-79-OH
Chemistry Laboratory Manual
for
Bottom Sediments and Elutriate Testing
U.S. Environmental Protection Agency
Surveillance and Analysis Division
Region V
Central Regional Laboratory
536 South Clark Street
Chicago, Illinois 60605
March 1979
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TABLE OF CONTENTS
PAGE NUMBERS
FORWARD
Description of Field Sampling and Laboratory Handling Procedures 1-2
Parameter Determinations
Total Residue (CRL Method 444) 3-4
Total Volatile Solids (CRL Method 447) 5
Percent Moisture (CRL Method 445) 6-7
Density (CRL Method 446) 8
Specific Gravity (CRL Method 448) 9
Settling Rates (CRL Method 486, CRL Method 441 (See Below) 10 - 11
Grain Size Analysis (Wet Sieving) (CRL Method 483) 12 - 15
Grain Size Analysis (Dry Sieving) (CRL Method 485) 16 - 19
Fluoride (CRL Methods 380 and 378) 20-24
Cyanides {CRL Methods 366, 360, and 357) 25 - 35
Ammonia-N (CRL Methods 324 and 312) 36 - 42
Total Kjeldahl Nitrogen (CRL Methods 468 and 465) 43 - 50
Total Phosphorus (CRL Methods 435 and 465) 51 - 53
Chemical Oxygen Demand (CRL Methods 351 and 342) 54 - 59
'Mercury (CRL Methods 393 and 390) 60 - 68
Total Metals (by Plasma) (CRL Methods 571-598, 504-570) 69 - 76
'Total Metals (by AA) (CRL Methods 595-601, 594-600) 77 - 89
Phenols (CRL Methods 417, 408, and 414) 90 - 102
Oil and Grease (CRL Method 739) 103 - 104
The Elutriate Test (CRL Method 305) 105 - 107
PCB's, Pesticides, Phthalates 108 - 139
(CRL Methods 198-207 and 144-183, 651-732, 210-219)
Method of Analysis for Priority Pollutants 140 - 151
Suspended Solids (CRL Method 441) 152 - 153
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FORWARD
This manual contains the physical and chemical analysis procedures for
bottom sediments and related process waters in partial fulfillment of
the requirements of Section 404 (b) of Public Law 92-500, The Federal
Water Pollution Control Act Amendments of 1972.
Most of the procedures in this manual are based on established standard
methods, while others were developed (some published) by Region V, United
States Environmental Protection Agency, Central Regional Laboratory
personnel.
These procedures represent interim ones at best, but nevertheless pro-
vide some indication of the general chemical composition and pollutional
nature of sediments.
The pollutional nature of bottom sediments, supplemented by results
from elutriate testing are generally sufficient to enable managers and
district engineers to decide whether the sediments should be "confined"
or "open-lake" disposed.
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-1-
Description of Field Sampling and
Laboratory Handling Procedures
Sampling
1. Bottom sediment samples are generally collected by field personnel
in such a manner that they are representative of the site from
which they were collected. Petersen or Shipek-type collected samples
are generally drained of excess water. Hopper-dredge collected
samples generally contain more water than Petersen and other clam-
type dredge-collected samples. Periodically, samples are collected
using a core sampler.
2. Since the laboratory is now analyzing for trace organics, the sample
should be collected either with a glass sampler or stainless steel one
(no copper) manually mixed in the field, placed in a glass container
and stored at 4°C (iced) until analysis. Sample containers should
be filled only 3.4 full to prevent cracking when frozen.
3. If it is impossible to collect one sample for organics and inorganics,
then it is acceptable to collect the trace organic samples with a
metal sampler placed in a glass jar, and collect the inorganic sample
with a plastic sampler and place in a plastic jar. This system may
arouse questions of representativeness of sample, however.
Laboratory Handling
1. Preservatives are not added to the sample, but the sample is kept
between 2 and 4°C at all times in a walk-in refrigerator.
2. When the analyst is ready to proceed, the iced sample is allowed
to thaw to 15-25°C. It is then manually mixed in a large flat
bake-like or other contaminant-free containers and different
fractions are weighed for the analysis listed in the schematic
shown on the Figure. It is left up to the judgement of the analyst
whther the sample should be sieved prior to weighing aliquots for
analysis. If the sample does require sieving, it is passed through
a #10 polypropylene sieve by forcing it through the screen with a
glass beaker. A portion of the sieved sample is also taken for
total solids, any material retained by the sieve will be dried
weighed and included in the total solids calculation as a dilution
factor.
Under no conditions is the sample for PCB's, phthalates and pesti-
cides sieved. The total solids result from the unsieved sample is
used to calculate dry weight for the unsieved trace organics.
3. All results are reported in milligrams per kilograms dry basis
except solids, which are reported in percent.
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Schematic Analysis of Sediment
(Sediment Sample From the Field In Glass Jar)
Manual Mixing In L
Fluoride ^.
10 g
Ammonia-N
TKN
TP
COD
Mercury
Homogeni
, 1-3 a
1-3 g
,1-2
:ation
5 ml of
20%
Preser
Storage
.at
5 ml
Preservative
Grain Size
Analysis x 100-150 g
(Wet Sieving
or
Grain Size
Analysis t
(Dry Sieving
/at Lve
rge Flat Container
V
20 g
1-2 g. Phenol
2-5
(2 ml
5 ml IN NaOH Preservative
40
,,„
20
250-300 g
Pesticides
Phthalates
Oil & Grease
Density or
Specify
Gravity
50 ml Sediment
>
Elutriates
200 ml Process Water
Oven Dry at 105°C Ovenight
1.00 g
| separate dry sample Total Metals
Total Solids
Iqnite Residue at 550-600°C For 1 Hour
Total Volatile Solids
Figure
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-3-
Determination of Total Residue of Sediments
CRL Method No. 444
Scope and Application
This method is applicable to the determination of percent residue in sediments
and other solid samples.
Summary of Method
A portion of the unsieved sample is added to a tared evaporating dish and dried
to constant weight at 105°C.
Equipment
Drying oven
Desiccator
Evaporating dishes
Five significant place blanace, 200 g capacity
Muffle furnace
Procedure
1. Tare the evaporating dishes by igniting them in the muffle furnace for one
hour at 550 + 50°C. Cool and place in a desiccator for a minimum of one hour.
2. Weigh the empty dishes to five figures (example - 90.345).
3. Place 10 to 20 grams of wet, well mixed sediment sample into the tared
evaporating dishes (include all sticks and stones if the sample is not
sieved). Record the weight of the sediment sample plus the evaporating
dish. If the sample is sieved for other tests, use the weight of the
sample which includes sticks and stones for final calculations.
4. Dry the sample at 105°C overnight or until constant weight is obtained.
5. Cool, place in desiccator for a minimum of 1 hour, then weigh.
Quality Control
A duplicate of one of the sediments is analyzed with each group of samples. If
twenty or more samples are analyzed, a mininum of two duplicates are analyzed.
The analytical balance is calibrated and set to zero before each sample is weighed.
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Calculations
Total Residue (%)
= (Init wt. of sample and dish-final wt. of sample and dish-prig, sample wt.) x 100
(Original Sample Weight)
REFERENCE
Standard Methods for the Examination of Water and Wastewater, 14th ed.,
1975, APHA, AWWA, WPCF, Washington, D.C. p. 91-92.
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-5-
Determination of Total Volatile Solids in
Sediments and Other Solids
CRL Method No. 447
Scope and Application
This method is an estimate of those inorganic and organic compounds which
are lost from the sample when ignited to 550 + 50°C.
Summary of Method
The volatile and fixed components remaining after the sample has been dried
at 105°C are determined by igniting the dried sample in a muffle furnace
at 550 + 50°C. The loss in weight represents the amount of volatile matter
in the sample.
Equipment
Porcelain evaporating dishes
Muffle furnace
Analytical balance (4 to 5 significant places)
Desiccator
Procedure
1. Record the weight of the sample and dish determined for total solids.
2. Ignite the residue from the total solids determination in a muffle
furnace at 550 + 50°C for one hour.
3. Remove carefully from the furnace, air cool for about one minute on
a hard fire-proof finish (not the counter top) and place in a desiccator
for a minimum of 15 minutes or until constant weight is obtained.
4. Ascertain whether constant weight has been attained by weighing the
sample to 5 significant figures (examples 85.235) with no change in the
fourth place.
Quality Control
A duplicate of one sample in each group of samples is analyzed. When there
are twenty samples or more, a minimum of two duplicates are analyzed. The
analytical balance is calibrated and set to zero before each sample is weighed.
Total Volatile Solids (%) _ [wt. of dried solids - weight of ash] x 100
[weight of dried solids]
REFERENCE
1. Standard Methods for the Examination of Water and Wastes, 14th ed., 1975,
pp. 95-98.
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Determination of Percent Moisture of Sediments
CRL Method No. 445
Scope and Application
This method is applicable to the determination of moisture in sediments
and other solid samples.
Summary of Method
A portion of the unsieved sample is added, to a tared evaporating dish and
dried to constant weight at 105°C.
Equipment
Drying oven
Desiccator
Evaporating dishes
Five significant place balance, 200 g capacity
Muffle furnace
Procedure
1. Tare the evaporating dishes by igniting them in the muffle furnace for
one hour at 550 + 50°C. Cool and place in a desiccator for a minimum
of one hour.
2. Weigh the empty dishes to five figures (example - 90.345).
3. Place 10 to 20 grams of wet, well mixed sediment into the tared
evaporating dishes and record the weight of the sediment sample plus
the evaporating dish.
4. Dry the sample at 105°C for 24 hours or until constant weight is obtained.
5. Cool, place in desiccator for a minimum of one hour, then weigh until
constant weight is obtained.
6. Cool, place in desiccator for a minimum of one hour, then weigh.
Quality Control
A duplicate of one of the sediments is analyzed with each group of samples.
If twenty or more samples are analyzed, a minimum of two duplicates are
analyzed.
The analytical balance is calibrated and set to zero before each sample
is weighed.
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-7-
Calculations
Percent moisture = initial wt. of sample S dish - final wt. sample and dish x 100
Net weight of initial sample
or total residue in % - 100 = % moisture
REFERENCE
1. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
1975, a PHA, AWWA-WPCF, Wash., D.C. pp. 91-92.
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-8-
Determination of Density of Sediments and
Other Solids
CRL Method Number 446
Scope and Application
This method is applicable to all sediments and solids which contain visible
amounts of water.
Summary of Method
A measured volume of the sediment-water is weighed on an analytical balance.
Density is determined by the weight of the measured volume of the sample.
Equipment
Four or five significant place balance, 250 ml Erlenmeyer flask or bottle.
Procedure
1. Calibrate a 250 ml Erlenmeyer flask, by measuring 250 ml of distilled
water into it and marking the 250 ml graduation level with a felt tip pen.
2. Shake all of the water out of the flask, and weigh the calibrated flask
to the nearest 0.1 g.
3. Fill the flask completely to the marked graduated level with unsieved
sample, record the weight. The volume is considered 250 ml. (If the
sample does not flow readily, add as much sample to the flask as possible,
and weigh. After weighing, mark the level to which the sample was poured,
empty and rinse the flask. Refill the flask with distilled water to the
marked level and re-weigh).
Quality Control
A duplicate of one of the samples is analyzed for each group of samples. If
twenty or more samples are analyzed, a minimum of two duplicates should be
analyzed.
The analytical balance is calibrated and set to zero before each sample is
weighed.
Calculations
Density _ [weight of sample and flask - weight of flask]
[volume of sample]
REFERENCE
1. Standard Methods for the Examination of Water and Wastes, 14th ed., 1975,
p. 121.
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Determination of Specific Gravity of Sediment and
Other Solids
CKL Method No. 448
Scope and Application
This method is applicable to all sediments and solids which contain visible
amounts of water.
Summary of Method
A weighted volume of sample is compared to an equal volume of distilled water.
Equipment
Four or five significant place balance, 250 ml Erlenmeyer flask or bottle.
Procedure
1. Weigh to the nearest 0.1 g, an empty wide mouth flask or bottle of
about 250 ml capacity.
2. Fill the container completely with distilled water and weigh again.
3. Discard the distilled water and shake all of it out of the flask. Fill
the flask or bottle completely with unsieved sample and re-weigh. (If
the sample does not flow readily, add as much sample to the flask as
possible, and weigh. After weighing, mark the level to which the sample
was poured, empty and rinse the flask. Refill the flask with distilled
water to the marked level and re-weigh).
Quality Control
A duplicate of one of the samples is analyzed for each group of samples. If
twenty or more samples are analyzed, a minimum of two duplicates should be
analyzed.
The analytical balance is calibrated and set to zero before each sample is
weighed.
Calculations
Specific Gravity _ [wt. of sample and flask - wt. of flask]
[wt. of distilled water and flask - wt. of flask]
REFERENCE
1. Standard Methods for the Examination of Water and Wastes, 14th ed.,
1975, p. 121.
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Determination of Settling Plates of
Sediments and Other Solids
CRL Method No. 486
Scope and Application
This method is applicable to sediments, sludges and solid samples.
Summary of Method
The settling rate is obtained by measuring the suspended solids content
of a 10 ml aliquot withdrawn from the original sample at 1, 3, 5, 10,
20 minutes/ etc., time intervals. The suspended solids curve is
determined and the values are plotted against time intervals. The settling
rate is obtained from the slope of the linear portion of the curve. The
Oden curve could also be obtained by plotting % suspended solid versus
time.
Equipment
Timer.
Oxford pipett (10 ml capacity) with disposable tips.
Settling jar vessel long enough to hold 1-2 liter capacity with a wide
mouth.
Filtration apparatus: suitable for the type of filter selected, with
suction flask of 500 ml capacity and filter holder.
Glass filter disks:
Oven adjusted to 105°C.
Procedure
Weigh exactly 50-100 grams of well mixed sediment.
Transfer the sediment sample to the settling jar.
Add 1 liter of distilled water or preferably 1 liter of the natural
(process) water [lake, river, lagoon] from which the sediment samples
were taken.
Recap the jar and shake the sample by turning the jar upside down
several times until a homogenous distribution is obtained.
Return the jar or vessel to an upright position. Open the lid and
start the timer.
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With the Oxford pipett equipped with special filter tips/ [cut the narrow
end of the tip to minimize filtration effect] withdraw a 10 ml aliquot
from the middle of the sample bulk. [Withdrawal point could be fixed by
allowing the Oxford pipett to descend to a certain length, already marked
on the other pipett and aligned with vessel mouth.]
Transfer the aliquot to a 100 ml measuring cylinder with a glass cap.
Determine the suspended solids content of the sample using CRL Method
number 441.
Construct an arithmetic plot of mg/1 of suspended solids versus time
and draw a line of best fit through the linear portion of the curve.
The negative slope of such line will be the settling rate in mg/l/min.
Quality Control
To plot the Oden curve, calculate the % suspended solids by using the
following formula:
% sus. solids = [sus. solids of aliquot-susp.solid of blk in mg/1]
wt. of original sample (gm) x 10
Plot % sus. solids versus time.
REFERENCES
1. Sedimentation Engineering Report, the American Society of Civil
Engineers Manual, 1975.
2. American Society for Testing and Materials, "Method for Grain Size
Analysis of Soil", D422-63, part 11, 1966, pp. 193-201.
3. Standard Methods for the Examination of Water and Wastewater, 14th ed,
Amer. Public Health Association, New York, 1975, pp. 129-132.
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Grain Size Analysis by Washing
(Approximate Estimation)
(Wet Sieving)
CKL Method #483
Scope and Application
This method is a fast and approximate estimation of grain sizes and
applicable only to mud, sediments and clay samples.
Summary of Method
A sample is thoroughly homogenized and the excess water is poured off and
drained. A wet weight of the sample is washed through a set of pre-weighed
sieves and the % retained on each sieve is recorded (water content of
sample is included.)
Apparatus
Top loading balance (1500 gram capacity)
A series of U.S. Standard sieves sizes 10, 20, 60 and 200.
Procedure
1. Remove non representative objects from the sample, such as large stones,
debris, leaves, etc.
2. Drain the water accumulated on the top of the sample (as much as you can)
3. Thoroughly mix the sample, (use a metal spatula).
4. Weigh a 100 gm of sample (in a beaker).
5. Select the nest of sieves to be used. Weigh them and record the
weight as sieve # tare weight.
6. Arrange them in descending order (pore size), with #200 at the bottom.
7. Transfer the sample to the top sieve and wash the sample with tap water
until separation is complete.
8. Separate the sieves and let them stand for some time to drain the
excess water.
9. Re-weigh the sieves with the particles retained on it.
Quality Control
A duplicate of one of the sediments is analyzed with each group of samples.
If twenty or more samples are analyzed, a minimum of two duplicates are
analyzed. A precision study by wet sieving technique is attached.
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Calculations
The percent of material by weight retained on the various sieves is computed
as follows:
% retained _ sieve # weight - sieve # tare weight x 100
Total amount of sample
% passed #200 _ total amt. of sample - amt. retained on all sieves x 100
Total amount of sample
Reference
United States Environmental Protection Agency, Region V, Central Regional Laboratory,
Chicago, Illinois, 1976, unpublished.
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UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
iTE: February 23, 1977
,'CT: Precision Study of Sieve Test on Sediments
IOM: Harvey Montgomery, Chemist
Inorganic Chemistry Section, CRL
TO: Files
Four determinations of the sieve test were made on sediment samples
from Les Chenaux Harbor. The samples of sediment were thoroughly
homogenized for each test. Approximately 100 grams was weighed to
the nearest gram. Number 10, 20, 60, and 200 sieves were placed in
the sink. The samples was washed into the #10 sieve, thru #20, thru
#60, and finally the #200 sieve, and then down the drain. Care was
taken to avoid any material being washed over the side of the sieve.
The sample was pressed by my fingers so as much material was made to
go through the sieve as possible. The sieves were weighed with an
average amount of water on the sieve. This weight is constant. The
sieves were weighed after the sample was washed. The amount of
sample x 100 divided by the total weight is the percent retained.
The variation observed in percent retained is caused by several factors.
The material is composed of rocks, organic material, clay, and sand.
Enclosure (data of study)
cc: B. Fairless, CRL
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SIEVE TEST
1/19/77
STD % RETAINED STD
SAMPLE # AVE. DEV NO. 10 AVE. DEV
13597 3
13597 52 621
13597 6
13598 4
13598 73 922
13598 9
13599 2
13599 53 811
13599 6
13601 2
13601 43 721
13601 2
STD %RETAINED STD
AVE DEV NO. 200 AVE DEV
13597 25
13597 19 6 14 63 7
13597 18
13598 14
13598 10 4 7 61 8
13598 9
13599 20
13599 18 2 16 69 2
13599 19
13601 24
13601 23 2 21 61 5
13601 25
% RETAINED
NO. 20 AVE.
Kl
2 11
2
5
Kl 19
Kl
Kl
2 6
Kl
Kl
3 10
1
%PASSED
NO. 200
55
69
66
53
63
63
71
67
71
66
56
63
STD % RETAINED
DEV NO. 60
17
5 9
8
24-
4 16
19
7
2 7
4
8
2 13
10
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Grain Size Analysis (Dry Sieving)
CRL Method No. 485
Scope and Application
This method is applicable to sand, clays, sediments and soil samples. The
method also covers the determination of materials finer than No. 200 sieve
(by washing).
Summary of Method
A sample is dried and certain weight of the sample is first washed through
#200 sieve. The loss in weight, resulting from the wash treatment, is
calculated and is reported as the % passing #200. The amount retained on
the #200 sieve is passed through a nest of sieves and the percentage of
material retained at each sieve is calculated from the weight of material.
Definition
Grain size analysis is a process in which the percentage of material of each
grain size present in given soils is determined by passing a known amount of
the material through a set of sieves in order to separate the different
particle sizes.
Apparatus
A series of U.S. standard sieves, 3/8, 4, 10, 16, 28, 50, 100, 200 bottom and
cover plate (additional sieve #'s could be added).
Sieve shaker: a mechanical device to shake the sample with certain amplitude,
usually equipped with a timer. (Model Fritsch Analysette or comparable to it)
Top load balance (1500 gm capacity) (0.1 gm sensitivity).
Soft wire brush.
Mortar and rubber covered pestle.
Oven adjusted to 105°C.
Procedure
1. Sample Preparation
Thoroughly mix the sample (use metal spatula), remove non representative
objects, such as large stones, debris, leaves, etc., add small amount of
water to homogenize the sample if necessary.
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2. Weigh 150-200 gm of the sample into a pre-weighed clean, dry crucible.
3. Oven dry the sample at 105°C to a constant weight (preferably overnight).
4. Allow to cool.
5. Transfer the sample to a piece of heavy paper. Loosen the aggregates
with hands or use the Mortar and Rubber pestle if necessary.
6. Weigh 100 grams of the dry sample (use clean porcelain dish or beaker).
7. Transfer this amount to #200 sieve other than the one to be used
with the nest of sieves.
8. Wash the sample with tap water in order to pass through those particles
which are finer than the #200 sieve; then with distilled water.
9. Oven dry the amount of sample retained on the #200 sieve (the #200
sieve with the material can be placed directly into the oven at 105°C).
10. Transfer the amount retained on #200 sieve to a pre-weighed beaker by
turning the sieve over and brushing the back with the wire brush (use
a funnel if necessary.
11. Weigh this amount and record as total amount retained by #200.
12. Select a nest of sieves, weigh them and record the tare weights as
sieve # tare weights.
13. Place the nest of sieves in the shaking machine in the following descending
order: 3/8, 4, 10, 16, 50, 100, 200 and the bottom plate.
14. Psur the amount retained on #200 sieve on the top sieve (3/8). Secure
the cover plate (tighten screws).
15. Adjust timer to 15 minutes.
16. Turn on the shaker with an amplitude of 10.
17. After the shaking time is over, remove the nest of sieves from the
shaker. Beginning with the top sieve, weigh it on the balance and
record the weights as sieve # weight.
Quality Control
A duplicate of one sample is analyzed with each group of samples. For
twenty or more samples, a minimum of two duplicates are analyzed.
The analytical top load balance is set to zero before each weighing.
Experimental recovery data are attached for the dry sieve procedure.
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Calculations
The percent of material by weight retained on the various sieves is computed
as follows:
Percent retained _ sieve # weight - sieve tt tare weight x 100
TOTAL amount of sample
Percent passed #200 _ TOTAL amount of sample - total amt. ret. #200 x 100
TOTAL amount of sample
REFERENCES
1. American Society for Testing and Materials (ASTM), "Standard Method or
Test for Sieve or Screen Analysis of Fine and Coarse Aggregates",
Designation C 136-71, American National Standard A378, Sept. 1971,
pp. 87-88
2. American Society for Testing and Materials (ASTM), "Standard Method or
Test for Materials Finer than No. 200 (75-um) Sieve in Mineral
Aggregates by Washing", Designation C117-69 American National Standard
A374, 1970, October 1969, pp. 68-69.
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Sample # % Rtd % Rtd % Rtd % Rtd % Rtd % Rtd % Rtd % Rtd % passed % Recovery
#3/8 # 4 # 10 #16 * 28 * 50 * 10° * 20° Pass 20° TOTAL
GLSB
(169)
72-6753 0 0 0.65 0.65 0 0.65 0.65 76.2 21.2
72-6756 0 6.1 9.6 7.6 23.3 13.1 16 6.9 11.5
72-6757 0 3.2 12.3 6.6 14 . 30 19.8 6.9 5.9
72-6763 19.8 8.2 16 5.8 16.9 9 7.2 3.8 11.3
100
94.1
98.7
98
GLSB
(170)
EGS01 3.6 6.6 6.2 3.4 4.9 7.4 28 20 18.4
EGS02 0.0 0.3 4.7 2.8 6.4 7.7 28 23 26
EGS03 0 3 9.5 11 17 2.6 .4 .2 55.3
EGS04 4.8 4.5 8.6 11.9 22.4 5.7 2.1 1 38
EGS05 0 0.3 8 9.5 23.6 6.3 1.5 .5 48.3
EGS06 0 0 1.9 3.3 5.5 1.3 .4 1.7 85.8
98.5
98.9
99
99
98
99.9
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Determination of Fluorides in Sediments
and Other Solids
CRL Method #380
Scope and Application
This method is applicable to the measurement of fluoride in sediments
and other solids (other than glass fiber filters).
Summary of Method
Fluoride is determined by manual distillation of the sediment sample
at 180°C from 50% sulfuric acid solution followed by potentiometric
analysis using a fluoride selective ion electrode.
Equipment
500 ml or 1000 ml flat bottom distilling flask equipped with a thermometer
adaptor and Graham or other condenser.
Erlenmeyer Flask
Analytical Balance
Specific Ion Meter (See CPL Method #378, Attached)
Fluoride Specific Ion Electrode (See CRL Method #398, Attached)
Reagents
Sulfuric Acid, Concentrated
Buffer Solution (See CRL Method #378, Attached)
Procedure
1. In a 500 ml boiling flask, carefully add with stirring 100 ml of
concentrated sulfuric acid to 200 ml of distilled-deionized water.
2. Distill into an Erlenmeyer flask until the contents of the boiling
flask reaches 180°C. Discard the distillate.
3. Cool the acid mixture remaining in the flask to 90°C.
4. Add 2 to 5 grams of wet, well mixed sediment sample.
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5. Mix throughly and distill until the temperature reaches 180°C.
Do not exceed 180°C to prevent Sulfate carryover.
Note: If the sample is known to have a high chloride content,
add silver sulfate to the fask at the rate of 5 mg Ag2SO4 per
milligram of chloride in the sample.
6. Place 25 ml of the distillate in a 100 ml beaker and add 25 ml
of buffer. Place on a magnetic stirrer and mix at medium speed.
Immerse the probe in the solution and observe the meter reading
while mixing (See CRL Method #378, Attached).
7. Allow the probe to remain in the solution for at least three (3)
minutes or until the reading has stabilized. (At lower concentra-
tions below 0.50 ppm, it sometimes takes 5 minutes to reach a stable
meter reading.
8. Read the fluoride level of the sample directly in mg/1 on the fluoride
scale.
Quality Control
A field reagent blank (which contains 200 ml of distilled-deionized
water and 100 ml of Cone. H2S04), one or two F~ standards and a
duplicate of one of the samples are distilled and analyzed for each
group of samples. If twenty are more samples are analyzed a minimum
of two field blanks, F~ standards and duplicates are distilled and
analyzed.
The analytical balance is set to zero before each weighing.
The manufacturer's instructions are followed concerning operation of
the specific ion meter.
Calculations
mg/kgF~ (dry basis) = mg/1 Reading from Method #378 x ml of sample used
Qrig. wet wt. in grams x decimal fraction % solids
References
1. "Standard Methods for the Examination of Water and Wastewaters,
p. 171, Method No. 121 A, Preliminary Distillation Steps (Bellack),
13th Edition, 1971.
2. Manual of "Methods for Chemical Analysis of Water and Wastes", Office
of Technology Transfer, Washington, DC, 1974, p. 65.
-------
-22-
Fluoride (Electrode) in Waters
CKL Method No. 378
Scope and Application
This method is applicable to the measurement of fluoride in drinking,
surface, and saline waters, domestic and industrial wastes.
Concentrations of fluoride from 0.10 up to 1000 mg/1 may be measured.
The Bellack distillation must be performed on industrial waste samples
prior to electrode analysis.
Summary of Method
The fluoride is determined potentiometrieally using a selective ion
fluoride electrode in conjunction with a selective ion meter having
a direct concentration scale for fluoride.
The fluoride electrode consists of a lanthanum fluoride crystal across
which a potential is developed by fluoride ions.
Interferences
A high pH interferes; sample pH should not be greater than 10. polyvalent
cations of Si+4, Fe+3, B+3, and Al+3 interfere by forming complexes with
fluoride. The degree of interference depends upon the concentration of
the complexing cations, the concentration of fluoride and the pH of the
sample. The addition of a pH 5.0 buffer (described below) containing a
strong, chelating agent, preferentially complexes aluminum (the common
interference), iron, and eleminates the pH problem.
Apparatus
Specific ion meter such as the Orion model 407.
Fluoride combination electrode, such as Orion no. 96-09-00.
Magnetic mixer, Teflon coated stirring bars.
Reagents
Sulfuric acid, concentrated.
Buffer solution, pH 5.0 - 5.5: To approximately 500 ml of distilled water
in a 1 liter beaker add 57 ml of glacial acetic acid, 58g of sodium chloride
and 2g of sl,2-cyclohexylene dinitrilo tetraacetic acid (CDTA) (Mathieson,
coleman & Bell, Cat. No. P8661) or cyclohexane diamine tetraacetic acid
(Merck-Titriplex IV or Baker Cat. No. G083). Stir to dissolve and cool to
room temperature. Adjust pH of solution to between 5.0 and 5.5 with 5N
sodium hydroxide (about 150 ml will be required). Transfer solution to a
1 liter volumetric flask and dilute to volume with distilled water. For
work with brines, additional sodium chloride should be added to raise the
-------
-23-
chloride level to twice the highest expected level of chloride in the sample.
Sodium fluoride/ stock solution: Dissolve 0.2210g of sodium fluoride in
distilled water and dilute to 1 liter in a volumetric flask. 1.0 ml = 0.1 mg
fluoride. Store in polyethylene. Sodium fluoride, standard solution: Dilute
50 ml of sodium fluoride stock solution to 500 ml with distilled water. 1.0 ml
=0.01 mg/ml fluoride.
Calibration
Check zero adjustment: With the Function Switch in the off position, the needle
should point to exactly center scale (1.0). If not, turn the zero adjust screw
until the needle is exactly on center scale.
Check batteries: Turn Function Swith to the battery position. If the needle does
not stop in or to the right of the green battery ok area on the meter, replace
batteries. However, the meter is line operated in the laboratory.
Prepare three standards containing 0.40, 1.0 and 4.0 mg/1 by pipetting 20,50 and
200 ml of standard fluoride solution into three 500 ml volumetric flasks and make
up to volume with distilled water. Store standards in polyethylene bottles and
store at room temperature. These standards are stable at room temperature.
Pipette 25 ml of each of the standards into a 100 ml beaker and add 25 ml of buffer
solution. Place the 1 mg/1 standard on the magnetic stirrer, the probe in the
solution and stir for five minutes. If the meter does not read 1 mg/1, adjust by
means of the calibration control knob to read 1 mg/1.
Follow same procedure for the 0.40 mg/1 standard. If the meter does not read 0.40
mg/1, turn temperature compensator knob until the needle points to 0.40 mg/1. Move
the slope indicator until the arrow of the temperature compensator points to the
temperature of the solution.
Follow same procedure for the 4.0 mg/1 standard. The meter should read very close
to 4.0 mg/1 or within 0.10 or 0.20 mg/1.
Procedure
Waste Samples:
1. Place 400 ml of distilled water into a one liter distilling flask and add
200 ml of concentrated sulfuric acid, with stirring. Distill until the
contents of the flask reaches exactly 180°C. Discard the distillate. This
process serves to remove fluoride contamination and adjust the acid-water
ratio for subsequent distillations.
2. After cooling the acid mixture remaining from the steps outlined in step 1, or
previous distillations, to 90°C or below, add 100. ml of sample, mix thoroughly,
and distill as before until the temperature reaches 180°C. To prevent sulfate
carry-over, do not permit the temperature to exceed 180°C.
3. Use the sulfuric acid solution repeatedly until the contaminants from the samples
accumulate to an extent that recovery is affected or interferences appear in the
distillate. Check suitability of the acid periodically by distilling standard
fluoride samples.
-------
-24-
4. Place 25 ml of the distillate in a 100 ml beaker and add 25 ml of buffer. Place
on a magnetic stirrer and mix at medium speed. Immerse the probe in the solution
and observe the meter reading while mixing. The probe must remain in the solution
for at least three minutes or until the reading has stabilized. At concentrations
under 0.50 mg/1, it may require as long as five minutes to reach a stable meter
reading. Head the fluoride level in the unknown directly in mg/1 on the fluoride
scale.
5. Drinking and surface waters.
Place 25 ml of sample in a 100 ml beaker and add 25 ml of buffer solution. Then
follow the procedure described in step 4.
Quality Control
A blank and duplicate of one of the samples is analyzed with each group of
samples. If twenty or more samples are analyzed, a minimum of two blanks
and standards ar analyzed.
Precision
The precision between-runs is 0.04 mg/1.
The precision within-runs is 0.03 mg/1.
These precision values were taken from Quality Control Data for the period
February 2, 1975 thru June 2, 1975 consisting of eighteen analyses.
Calculations
Reading is directly in mg/1 on the specific ion meter providing 25 ml of
sample is used.
References
Manual of Methods for Water and Wastes, U.S. Environmental Protection Agency,
Office of Technology Transfer, Washington, DC, 1974, pp. 65-67.
-------
-25-
Determination of Tbtal Cyanides
in Sediment and Other Solids
CRL Method No. 366
Scope and Application
This method is applicable to the determination of cyanide in sediments
and other solids.
Summary of Method
Cyanide is released from its compounds and converted to HCN by means of
a reflux-distillation catalyzed by copper chloride which decomposes metallic
cyanide complexes. The cyanide is absorbed in a 0.2 N NaOH solution and
analyzed spectrophotometically using an automated system. The color
reaction is based on reaction of cyanide with chloramine-T to form
cyanogen chloride (CNC1~) followed by reaction of the CNC1" with
pyridine-barbituric acid to form at red color at 578 nm.
Equipment
Reflux distillation apparatus consisting of one liter or 500 ml boiling
flask with inlet tube and condenser.
Technicon AA II System (See CRL Method No. 360, Attached)
Heating Mantles or Burners
Analytical Balance
Reagents
6N NAOH
Cuprous Chloride, 2%, Acid Washed (See CRL Method 360)
Sulfuric Acid Concentrated
Chloramine-T Solution - (See CRL Method No. 360)
Pyridine-Barbituric Acid Solution
Procedure
1. Weigh 2-5 g of wet, well mixed sediment.
2. Transfer to the distillation flask.
3. Add 500 ml of distilled water and 5 ml of 6 N NaOH to the flask.
-------
-26-
4. Add 50 ml of 1.25 NaOH to the gas absorbing tube and dilute until
the spiral is cover.
5. Connect the boiling flask, condenser and absorber, turn on the
condenser cooling water and heating mantle.
6. Slowly add 25 ml of cone. H2S04 through the air inlet tube.
Rinse, allow 3 minutes for the acid to mix with the sample,
then pour 10 ml of copper chloride (Cu2 Cl2> solution into
the inlet tube and rinse with distilled water.
7. Heat the solution to boiling, taking care to prevent the
solution from backing up into the air inlet tube.
8. Reflux for one hour.
9. Turn off the heat and continue the air flow for 15 minutes.
After cooling the boiling flask, disconnect the absorbes and
turn off the vacuum. ,
10. Drain the solution from the absorber into a 250 volumetric
flask. Rinse the distillation train into the flask and
dilute to 250 ml.
11. - Store under refrigeration until colorimetric analysis is
conducted using CRL Method 360, (Attached).
Quality Control
One field reagent blank (which contains 5 ml of 6N NaOH), one
standard and one duplicate are distilled and analyzed with each
group of samples. If twenty samples are analyzed, a minimum of
two blanks, standards and duplicates are distilled and analyzed.
The balance is set to zero before each sample is weighed.
The manufacturer's instructions are followed for operation of
the Technicon Autoanalyzer.
Calculations
mg/kg CN~ (dry basis) = mg/1 (from curve using Method 360) x 250
(orig. wet wt of sediment in grams)xdecimal fraction
of % solids)
Reference
1. Manual of "Methods for Chemical Analysis of Water and Wastes",
United States Environmental Agency, Office of Technology Transfer
1974, Washington, DC, pp 40-46.
-------
-27-
Total Cyanide
CRL Method No. 360
(Automated Pyridine-Barbituric Acid With Manual Distillation)
Scope and Application
This method is applicable to the determination of cyanide in drinking, surface,
saline, domestic and industrial waste waters.
Summary of Method
Cyanide is released from its compounds and converted to HCN by means of a reflux-
distillation. It is absorbed in a solution of NaOH. This solution is then analyzed
spectrophometrically using an automated system.
In the spectrophotometric determination, the cyanide reacts with chloramine-T at a
pH of <8 to form CNC1. Addition of a pyridine - barbituric acid reagent produces a
red color which absorbs at 578 nm.
Sample Handling and Preservation
Samples are collected in new polyethylene bottles.
Samples are preserved at the time of collection by the addition of 5 ml of 6N NaOH/1
of sample (pH >\2). Samples are immediately cooled to 4°C for storage.
Samples should be analyzed as soon as possible after collection.
Interferences
Interferences are eliminated or reduced by following the distillation procedure
described in step 1.
Sulfides adversely affect the colorimetric procedure. After distillation, samples
are treated with a small amount of cadmium carbonate. If the sample contains sulfide,
as indicated by a precipitate of yellow cadmium sulfide, additional cadmium carbonate
is added just until precipitation is complete. Only the supernatant is taken for
analysis.
If residual chlorine is present in the sample, an excess of NaAs02 is added to reduce
the chlorine before distillation.
Equipment
Reflux distillation apparatus consisting of 12 boiling flask with inlet tube and
condenser, plus a gas absorber.
Heating mantles.
-------
-28-
Powerstats, 10 amps & 120 volts.
Technicon Auto Analyzer II (3)
Sampler III or IV
Pump II or III
Cyanide cartridge
Colorimeter with 15 mm flowcells and 570 nm filters.
Recorder
Digital Printer
Reagents
1.25 $ sodium hydroxide: Dissolve 50 g of NaOH in distilled water. Cool and
dilute to 12,.
Cadmium carbonate: powdered reagent.
Sodium arsenite: powdered reagent.
Cuprous chloride: Weigh 20 g of finely powdered CU2 Cl2 into an 800 ml beaker.
Wash twice with 250 ml portions of (1:49) H2SC>4 and then twice with distilled
water. Add 250 ml of distilled water and then 120 ml of cone HC1. Continue to
add HC1 as necessary for dissolution. Dilute to 1H with distilled water and
store in a tightly stoppered bottle or flask containing copper metal which extends
the entire length of the container.
Sulfuric acid: Concentrated
Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g of KOH in 1 £ of distilled
water. Standardize with 0.0192 N AgNO3 as described in Standard Methods (2).
Dilute to the appropriate concentration so that 1 ml = 1 mg CN.
Standard cyanide solution (intermediate): Dilute 10 ml of Stock cyanide solution
plus 10 g of NaOH to 100 ml with distilled water (1 ml = 0.1 mg CN). Store at 4°C.
Working standards: Dilute 0, 0.5, 1.0 and 2.0 ml of intermediate standard plus
10 g of NaOH to 1A with distilled water for standards of 0, 0.050, 0.100 and
0.200 mg CN/1. Store at 4°C.
Standard silver nitrate solution, 0.0192 N: Prepare by crushing about 5 g of
AgN03 crystals and drying to constant weight at 40°C. Dissolve 3.2647 g of dried
in distilled water and dilute to l£ (1 ml = 1 mg CN).
-------
-29-
Rhodanine indicator: Dissolve 20 mg of p - dimethyl - amino - benzalrhodanine
in 100 ml of acetone.
Phosphate buffer: Dissolve 138 g of NaH2 PO4"H2O in distilled water and dilute
to l£. Add 0.5 ml of Brij-35. Store at 4°C.
Chloramine - T solution: Dissolve 0.4 g of chloramine - T in distilled water and
dilute to 100 ml. Prepare daily.
Pyridine - barbituric acid solution: Transfer 15 g of barbituric acid into a 11
volumetric flask. Add about 100 ml of distilled water and swirl the flask. Add
75 ml of pyridine and mix. Add 15 ml of cone HC1 and mix. Dilute to about 900 ml
with distilled water and mix until the barbituric acid is dissolved. Dilute to l£
with distilled water. Store at 4°C.
Sampler Wash: Dissolve 10 g of NaOH in distilled water and dilute to 1 liter.
Procedure
Manual distillation
1. Add 50 ml of 1.25N NaOH to the gas sabsorbing tube and dilute with distilled
water until the spiral is covered.
2. Measure 500 ml of sample into the boiling flask. Also distill one blank, one
standard, and one duplicate with each set.
3. Connect the boiling flask, condenser, and absorber. Turn on the condenser water.
4. Start a slow stream of air entering the boiling flask by adjusting the vacuum
source. Adjust the vacuum so that about one bubble of air per second enters
the boiling flask through the air inlet tube. NOTE: The vacuum will need to
be readjusted occasionally to maintain this rate.
5. slowly add 25 ml of cone H2SO4 through the air inlet tube. Rinse the tube with
distilled water. Allow the acid to mix with the sample for 3 min. Then pour
10 ml of Oi2Cl2 reagent into the inlet tube and rinse the tube with distilled
water.
6. Heat the solution to boiling, taking care to prevent the solution from backing
up into the air inlet tube. Reflux for one hour. Turn off the heat and continue
the air flow for 15 min. After cooling the boiling flask disconnect the absorber
and turn off the vacuum.
7. Drain the solution from the absorber into a 250 ml volumetric flask. Wash the
absorber with distilled water and add the washings to the volumetric flask.
Dilute to 250 ml. Samples may be stored for future spectrophotometric analysis.
8. Set up the Auto Analyzer II as shown in the diagram.
9. Calibrate the system using standards of 0.200, 0.100, 0.050 and 0 mg CN/1.
Analyze control standards CS1 and CS2, then analyze the distilled samples.
-------
-30-
Detection Limit
The detection limit is 0.005 VgCN/1.
Quality Control
A blank, one standard and a duplicate are distilled with each sample set. The
results are recorded in the QC book.
Control standards CS1 and CS2/ a blank, and one duplicate are analyzed every •
40 samples. They must be within control limits if the data is used. The results
are recorded in the QC book.
The date of preparation of all reagents and standards is recorded in the QC book.
Calculations
The concentrations of calibration standards and control standards in ug/1 are
obtained directly from the Digital Printer.
Twice the concentration of the distilled sample in yg/1 is obtained from the
Digital Printer. (The concentration factor of 2 is the result of having
distilled 500 ml of sample into 250 ml). The results obtained on the print-out
must be divided by two.
The cyanide concentration must be reported as mg CN/1. This is obtained by
dividing the yg/1 concentration by 1000.
References
1. "Manual of Methods for Chemical Analysis of Water and Wastes",
U.S. Environmental Protection Agency, Cincinnati, OH, 1975, p. 40.
2. "Standard Methods for the Examination of Water and Wastewater", 14th ed.,
American Public Health Association, New York, N.Y., 1975, p. 361.
3. Technicon industrial method no. 315-74W, Technicon Industrial Systems,
Tarrytown, N.Y., 1974.
-------
CYANIDE MANIFOLD
WASTE
190-0051-03
A10
TO F/C
PUMP TUBE
COLORIMETER
570 nm
15 ran F/C
199-B023-06
EB
RECORDER
PRINTER
RANGE 200
A10
170-0103-01
WASTE 4-
TO SAMPLER 4.
30/HR
4:1
(0.32)AIR
(1.00)
5 TC 116-0489-01
(0.42) Bl
(0.10) Cl
(1.00) r
SAMPLER
BARBITURIC ACID
(0.10) WATER
(1.00) FROM F/C
(3.40) WASH
-------
-32-
Determination of Cyanide
in Water and Wasteswater
(Completety Automated Procedure)
CRL Method No. 357
Scope and Application
The procedure is applicable to cyanide in water and wastewater. It is
generally used at this laboratory only following the elutriate test and
for the analysis of lake waters. Presently, it is not used for the
analysis of wastewaters which are governed by the National Pollution Discharge
Elimination System (NPDES) Permit.
Summary of Method
Cyanide is determined using a completely automated system. A UV digestion
is incorporated in the automated distillation step which converts complex
cyanides to simple cyanides. The solution is acified to form HCN which
reacts with chlorantine-T to form cyanogen chloride, followed by reaction
with pyridene-barbituric acid to form a red-colored complex, which is read
at 570 nanometers. An average 30 samples per hour can be analyzed in the
range from 5 to 200 micrograms per liter.
Equipment
Technicon AA II system, equipped with UV digestor, Sample IV, Pump III or IV,
and Colorimeter.
Reagents
Distillation Reagent
(Technicon No. 501-5017)
Phosphoric Acid, 85% (H3PO4) 250 ml
Hypophosphorus Acid 50 ml
Distilled Water, q.s. 1000 ml
Preparation: Carefully add 250 ml of 85% phosphoric acid and 50 ml of hypophosphorus
acid to 700 ml of distilled water and dilute to one liter with distilled water.
Phosphate Buffer, pH 5.2
Potassium Dihydrogen Phosphate
(KH2PO4) 13.6 g
Disodium Hydrogen Phosphate
(Na2HPO4) 0.28 g
Distilled Water, q.s. 1000 ml
Brij-35* (Technicon No T21-0110) 0.5 ml
Preparation: Dissolve 13.6 g of potassium dihydrogen phosphate and 0.28 g of disodium
phosphate in 900 ml of distilled water and dilute to one liter. Add 0.5 ml of Brij-35
and mix.
-------
-33-
Chloramine-T
Chloramine-T * *
(C7H7CINO2SNa . 3H20) 2.0 g
Distilled Water 500 ml
Preparation:
Dissolve 2.0 g of chloramine-T in 500 ml of distilled water.
Pyridine Barbituric Acid Reagent
Barbituric Acid (€4114^03) 15 g
Pyridine (C5H5N) 75 ml
Hydrochloric Acid, cone. (HCl) 15 ml
Distilled Water, q.s. 1000 ml
Preparation:
Place 15 g of barbituric acid in one liter beaker and add enough water (about 100 ml)
to wash the sides of the beaker and wet the barbituric acid. Add 75 ml of pyridine and
mix. Add 15 ml of HCl (sp. gr. 1.19) and mix. Dilute to about 900 ml with distilled
water and mix until all the barbituric acid has dissolved. Transfer the solution to a
one liter flask and dilute to volume with distilled water.
Standards
Stock Standard A, 100 mg/1
Potassium Cyanide (KCN) 0.250 g
Sodium Hydroxide, 0.IN
(NaOH), q.s. 1000 ml
Preparation: Dissolve 0.250 g of potassium cyanide in 800 ml of 0.1 N sodium hydroxide
and dilute to one liter with 0.1 N of sodium hydroxide.
WARNING: AVOID SKIN CONTACT WITH POTASSIUM CYANIDE.
Stock Standard B, 10 mg/1
Dilute to 100 ml of stock A to one liter with 0.1 N sodium hydroxide.
Working Standards
ml Stock B
1
2
3
Preparation: Pipette stock B into a 100 ml volumetric flask and dilute to volume with
0.01 N sodium hydroxide.
-------
-34-
Procedure
1. Set temperature of the heating bath at 150°C.
2. Set the flow rate of the cooling water through the distillation
apparatus at approximately 750 ml per minute at 14°C. (See
Instruction Manual TA1-0213-00 for operation of distillation
head).
3. Position the controls of the Modular Printer as follows:
Control Position
Mode Switch Normal
Sampling RATE Switch 30
Range Switch 200
Decimal Swith 000
(See Technical Publication No. TAl-0278-10)
4. Do not use the Modular Printer without a Linearizer. (The chemistry
is linear up to 200 ug/1 Int a linearizer is needed for a linear
response over the whole range).
5. Alternate ranges may be obtained by utilization of the Std. Cal. Control
on the Colorimeter.
6. Make sure enough sodium hydroxide is added to the waste containers to keep
the highly toxic HCN from escaping.
7. Analyze the samples using the attached manifold with a 0.01 N NaOH wash.
8. When installing replacement light source in QV Digestor, allow burn-in of
12 to 24 hours to permit new UV lamp to equilibrate. (New lamps may
generate undesirable levels of ozone, which may cause lower cyanide results.
Quality Control
A field reagent blank and duplicate are analyzed with each group of samples. If
twenty or more samples are analyzed a minimum of two blanks and duplicates are
analyzed.
The Technicon Company Instructions are followed for operation of the instrument.
Calculations
mg/1 CN~= Value read of the printer x dilution factor (if any)
Reference
1. Industrial Method No. 315-74W", Technicon Industrial Systems, Tarrytown, NY,
August 1974.
-------
-35-
CYANIDE IN WATER & WASTEWATER (UV DIGESTION + DISTILLATION)
(RANGE: 0-500 ^g/l)
MANIFOLD NO. 116-D539-01
SAMPLER IV
30/Hr
4:1
HEATING BATH &
DISTILLATION COIL
183-B010-01
UV DIGESTOR
188-B097-01
To Sampler IV
Wash Receptacle
194-8005-02
0000
PUR/ORN (3.40) WATER
/-yGRN/GRN (ZOO) SAMPLE
116-0489-01
To Waste
DISTILLATION
ORN/ORN (0.42) REAGENT
ORN/ORN (0.42)
10 Turns
157-0251
0000
To Waste
20 Turns 5 Turns
157-B089 170-0103-01
0000 AIO DODO
YEL/YELO.20)
BLK/BLK (0.32) AIR
ToF/C
Pump Tube
COLORIMETER
570 nm
15 mm F/C x 2.0 mm ID
199-B023-06
MOTE: FIGURES IN PARENTHESES
FLOW RATES IN ML/MIN.
x-yGRY/GRY (1.00) RESAMPLE
116-0489-01
C3
ORN/ORN (0.42) BUFFER
^"VORN/GRN (O.IO)CHLORAMINE-T
"^-^ PYRIDINE-
BARBITURIC
j^GRY/GRY (1.00) ACID REAGENT
To Waste
SIGNIFY
• 0.050 KEL-F1 (562-3014-01)
•• aiOO ACIDFLEX (116-0538-17)
••• 0,034 POLYETHYLENE (562-2004-011
«••• 8EE OPERATING NOTE 8.
tTRADEMARK OF 3-M COMPANY.
.GRY/GRY (1.00) FROM F/C
OG Water, dilution
TECHNICON INDUSTRIAL SYSTEMS / TARRYTOWN. NEW YORK 10591
A DIVISION OF TECHNICON INSTRUMENTS CORPORATION
-------
-36-
Determination of Ammonia-Nitrogen in
Sediments and Other Solids
CRL Method No. 324
Scope and Application
This procedure is applicable to those ammonia compounds which are readily
leachable from sediments and other solids.
Summary of Method
Five ml of 20% sulfuric acid are added to 2 grams of wet sample. Following
standing and the addition of water, the sample is homogenized, settled and
stored at 4°C overnight and a portion is pipetted out for analysis using the
automated colorimetric phenate method for ammonia-nitrogen (CRL method tt 312).
Alkaline phenol and hypochlorite react with ammonia in the presence of sodium
nitroprusside to form indophenol blue. The intensity of the blue color is
proportional to the concentration of ammonia.
Equipment
Mettler PR 700 balance
360 ml high density polyethylene bottles
Self-sticking labels (yellow)
Tekmar SDT homogenizer
Technicon AA II system (see CRL Method # 312, Attached)
Reagents
Twenty percent H2SO4 . See CRL Method # 312, Attached)
Procedure
1. Place self-sticking labels on the sample bottles and write the sample
numbers and date prepared. Label one bottle "blank" and date it.
2. Tare a polyethylene bottle on the PR 700 balance.
3. Weigh 1.5 to 2.0 g of homogenized bottom sediment directly into the
bottle. Weigh out the larger amount for sandy samples, the lesser
amount for samples with large amounts of humic material.
4. Record the weight of the sample on the bottle label.
5. Add 5 ml of the 20% H2S04 solution to the yellow labeled bottle.
6. Shake the sediment-preservative mixture and let stand for 5 minutes,
add 245 ml of distilled-deionized water to each bottle and shake.
-------
-37-
7. Homogenize all samples with the Tekmar SDT instrument for 1 minute at
high speed. Rinse the shaft and generator between samples with
distilled-deionized water and wipe dry with a Kim-Wipe.
8. Store the sulfuric acid-preservated samples at 4°C overnight (but
not longer than 24 hours if possible).
9. Fill the autoanalyzer sampling cup with each sample using an Eppendorf
pipet (usually 7-10 ml or a dilution of the sample).
10. Proceed with ammonia analysis using CRL Method # 312 (Attached).
Quality Control
Prepare every tenth sample in duplicate or one duplicate per sample set
if the set contains less than 15 samples.
Prepare a reagent blank for the H2SC>4 preservative every day samples are
prepared.
The PR 700 balance is set at zero and re-calibrated for each weighing.
Calculations
mg/kg (dry) NH3 _ mg/1 from AA x 1000 g/kg
g/1 (dry wt)
dry wt (g/1) = % solids(decimal fraction)x wet wt. x 4 (if 250 ml orig. volume was used)
References
1. Methods of Soil Analysis, ASA Monograph No. 9 part 2, 1965, "Inorganic
Forms of Nitrogen" by J.M. Bremner, Chapter 84, pp. 1179-1206.
2. "EPA Methods for Chemical Analysis of Water and Wastes", 1974, Office
of Technology Transfer, Wash., D.C., pp. 168-171.
-------
-38-
Ammonia Nitrogen
(Automated Colorimetric Phenate Method)
CRL Method No. 312
Scope and Application
This method is applicable to surface and waste waters. The range is from 0.03 to
10.00 mg/1 NH3~N. Forty samples can be analyzed per hour.
Summary of Method
Alkaline phenol and hypochlorite react with ammonia in the presence of sodium
nitroprusside to form indophenol blue. The intensity of the blue color is
proportional to the concentration of ammonia.
Sample Handling and Preservation
Samples are collected in polyethylene bottles, and are preserved with 1 ml H2S04
per liter of sample. Reagent blanks of 1 ml H2SC>4 per liter of distilled water
are collected and analyzed with the samples.
Interferences
The complexing reagent of potassium sodium tartrate plus sodium citrate prevent the
precipitation of alkaline earth and heavy metals from occurring.
The pH of the final solution must maintained between 11.4 and 11.6. This method
compensates for the acid used for preservation.
Sample turbidity may interfere. These samples can be decanted or filtered prior
to analysis.
Colored samples which absorb at 630 nm result in a positive interference.
Metal ions in concentration up to 100 mg/1 do not significantly interfere.
Nitroprusside is present to stabilize the formation of indophenol blue and avoid an
irregular response in samples containing heavy metals.
Equipment
Technicon AA II system consisting of:
Sampler IV
Proportioning Pump II
Manifold with 1/5 dilution loop and 55°C internal heating bath
Colorimeter with 15 mm flowcell and 630 nm filters.
Recorder
Digital Printer
-------
-39-
Reagents
Distilled water: NH3 - free. All reagents must be made with NH3~free water
Wash water: Add 1 ml. HSO to 1 liter distilled water.
Sulfuric acid (5N): Air scrubber solution. Carefully add 139 ml of cone.
H2SO4 to about 500 ml of distilled water. Cool and dilute to 1 liter with
distilled water.
Sodium phenolate: In a 1 liter beaker containing about 500 ml distilled water
dissolve 83 g phenol and 36 g NaOH. Transfer the solution to a liter volumetric
flask. Cool and dilute to 1 liter.
Sodium hypochlorite solution: Dilute 200 ml of a bleach solution containing 5.25%
available chlorine (eg. Clorox) to 1 liter with distilled water.
Complexing reagent: Dissolve 33 g of potassium sodium tartrate and 24 g of sodium
citrate in about 500 ml of distilled water. Add 7.6 ml of 10% NaOH solution and
dilute to 1 liter. Add 0.25 ml Brij.-35.
Sodium nitroprusside: Dissolve 0.5 g of sodium nitroprusside in 500 ml of distilled
water and dilute to 1 liter.
Stock standard solution A: Dissolve 3.819 g of anhydrous ammonium chloride, dried
at 105°C, in distilled water. Add 1 ml of H2S04 and dilute to 1 liter 1.0 ml =
1.0 mg NH3~N.
Stock standard solution B - Add 1 ml of H2SO4 to 100 ml stock standard solution A.
Dilute to 1 liter. 1 ml = 0.1 mg NH3-N.
Working standard solutions. Prepare the following standards by diluting suitable
volumes of stock standard solution A to 1 liter with distilled water. (One ml
must also be added) :
NH3-N mg/1
_ ml std soln. B/l
3.00 3.00
5.00 5.00
10.00 10.00
Procedure
Set up manifold as in fig. 1. Allow the colorimeter, recorder, and printer to warm
up for at least 15 minutes. Synchronize the spans of the 3 instruments with a range
of 0.00 to 10.00 on the printer. A stable baseline should be obtained with all
reagents in about 15 min.
-------
-40-
Arrange standards and samples in the sampler tray. To avoid contamination, an
Oxford pipet with disposable tips should be used to dispense samples. The following
pattern is suggested for use without the computer:
5.0 std
5.0 std
10.0 std
10.0 std
3.0 std
3.0 std
BLK (1 ml H2SO4/1 dist. H2O
BLK
Control std A.
Control std B.
BLK
- 39. samples and sample blanks (A blank always precedes a sample blank)
40. Duplicate of a sample around position 20
Note: Calibration standards are used in the first wheel only. Control standards,
blanks, and duplicates are used in every wheel.
Turn on sampler and begin analysis. Only the standards in the first wheel are
used to calibrate the instrument.
Quality Control
The concentrations of the control standards and the second of each pair of blanks
are recorded in the AQC book. The duplicate values and standard cal. reading are
recorded.
If more than one item of quality control data falls outside of the set control limits
(usually +3 standard deviations), the data for that wheel must be discarded.
When running without the computer, the baseline may be reset during the run when a
pair of blanks is analyzed. However, only minor adjustments should be made.
Control limits:
blank 0-0.03 mg/1
Control A 3.88-4.12 mg/1
Control B 4.88-5.12 mg/1
Difference in duplicates 0.03 mg/1 or 3%
Calculations
The NH3-N concentration is obtained directly from the Digital Printer in mg/1.
References
1. Methods for Cehmical Analysis of Water and Wastes, (1974), p. 168.
2. Technicon Industrial Method No. 154-71W/Tentative (1971).
-------
-41-
Modification for Low Level Ammonia
CRL Method No. 315
Scope and Application
This method is applicable to surface and lake waters. The range is from 0.003 to
1.000 mg/1 NH3-N. Forty samples can be analyzed per hour.
Equipment
Technicon AA II system consisting of:
Sampler IV
Proportioning Pump III
Manifold with internal heating bath
(Bypass the dilution loop.)
Colorimeter with 15 mm. flowcell and 630 nm filters.
Recorder
Digital Printer
Reagents
Working standard solutions: Prepare the following standards by diluting suitable
volumes of stock standard solution B to 1 liter with distilled water. (One ml
must also be added.):
NH3-N mg/1 ml std. sol'n B/l
_ 2.0
0.2 6.0
0.6 10.0
1.0
-------
-42-
Figure 1.
Qgg/
TRAV
-TRANS.
E—O
At*.
<.6»o "biu. cooP SOL'*
0,4 A Sft MPL £
r—0
O.«/3 PfStfHPLgl
Use dilution loop
for high level only,
AX |
I I
AMMONIA IN WATER AND SEAWATER
RANGE- °*10 ^9at N/l
" ' 0-140^9 N/l (ppb)
UANtFOLO NO. 116-D223-01
To Sampler IV GRN/GRN (2.00) WATER
Wash Receptacle ^g Q
20 Turns 20 Turns
(0.32) AIR
COVPLEXING REAGENT
ORN/OPN (0.421 SAMPLE
SAMPLER IV
60/HR
6:1
ORN/ORN (0.42) ALKALINE PHENOL
BLK/BLK (0.32) SODIUM HYPOCHLORITE
ORN/ORN (0.42) SODIUM NITROPRUSSIDE
BLU/BLU (1.60) FROM F/C
COLORIMETER
(30 run
SO mm F/C I
1^ mm 10
19S-B023-01
To F/C '
Pump Tube
Control
Mode
Sampling Rate
Decimal
NOTE: FIGURES IN PARENTHESES
SIGNIFY FLOW RATES IN
ML/MIN.
High Level Low Level
Position Position
normal normal
40 40
0.00
000
-------
-43-
Determination of Total Kjeldahl Nitrogen in
Sediments and Other Solids
CRL Method No. 468
Scope and Application
This method is applicable to the determination of TKN from nitrogen components
of sediments such as amino acids, proteins and peptides which are converted to
ammonia by strong acid-catalyzed digestion. Some industrial wastes such as
amines, nitro compounds, hydrazones, oximes, semicarbazones and some refractory
tertiary amines may not be converted to ammonia, hence low TKN values will result.
Summary of Method
The homogenized sample is digested with a concentrated solution of sulfuric acid-
potassium sulfate-mercuric oxide, to 303 fumes and until the solution becomes
colorless or pale yellow. The residue is cooled diluted to volume, centrifuged
and analyzed by the automated colorimetric method for ammonia-nitrogen (CRL Method
No. 312). Alkaline phenol and hypochlorite react with ammonia in the presence of
sodium nitroprusside to form indophenol blue. The intensity of the blue color is
proportional to the concentration of Ammonia.
Equipment
Mettler PR 700 Balance
Pyrex test tubes (1" x 8" heavy walled, See CRL Method 465, Attached)
360 ml high density polyethylene bottles
Self-sticking labels (yellow)
Tekmar SDT homogenizer
Technicon AA II system (See CRL Method 465, Attached)
Automatic pipetter
Reagents
20% H2SC>4 Solution.
Digestion Solution: Dissolve 2.0 grams of HgO in 25 ml of 6N f^SO^ In a
separate beaker, add 200 ml of concentrated H2SO4 carefully to 500 ml of
water. Then add 134 grams of potassium sulfate to the hot solution. After
the potassium sulfate has dissolved add the HgO solution, cool and dilute to
one liter. Store above 20°C.
Other Reagents (See CRL Method 465, Attached)
Procedure
1. Place self-sticking labels on the sample bottles and write the sample
number and date prepared. Label one bottle for the reagent blank and
one for duplicates; date the bottles.
-------
-44-
2. Tare each polyethylene bottle on the PR 700 balance.
3. Weigh 1.5 to 3.0 grams of homogenized sediment directly into the bottle.
Weigh the larger amount for sandy samples, the least amount for samples
with large amounts of humic material.
4. Record the weight of the sample on the bottle label and lab sheet.
5. Add 5 ml of the 20% H2SC>4 to samPle i-n tne yellow labeled bottle.
6. Shake the mixture/ let stand for 5 minutes then add 245 ml of distilled-
deionized water to each bottle and shake.
7. Blend (homogenize) for 1 minute at high speed. Sandy samples require less
time, mud samples more time. Rinse the shaft and generator between samples
with distilled-deionized water and wipe dry with a Kim-Wipe or other tissue.
8. Store the sulfuric acid-preserved samples at 4°C.
9. In a test tube rack, place 3 teflon boiling chips (which were acid rinsed in
1:1 HCl) into each clean, empty 1" x 8" test tube.
10. Reblend the sample in the bottle. Take a representative aliquot usually 10 ml
or less (or as determined from ammonia analysis values. Generally if ammonia
was high, TKN will also be high) and pipet into the tube containing boiling
chips. Dilutions should be made with a blank solution which contains 2 ml of
concentrated H2S04 per liter of water. If the pen goes off scale, a smaller
sample must be taken.
11. To each sample tube, pipet 2 ml of digestion solution.
12. Put each tube in the Technicon BD40, Block Digestor at low temperatude
(200°C) and digest samples for a minimum or 1 hour or until all liquid
has evaporated.
13. Transfer to the high temperature block digester and digest at 370°C while sulfur
trioxide (SO3) fumes are being emitted. After SO3 evolution has stopped, digest
for 30 to 40 minutes more at 370°C.
14. Cool for approximately 5 to 7 minutes (not longer, otherwise, a solid, insoluble,
hard mass will result).
15. Add 10 ml of distilled-deionized water to each tube and cover the rack with foil.
16. Proceed with analysis using the manifold in CRL Method No. 465, Attached).
-------
-45-
Quality Control
One field reagent blank containing preservative and digestion solution and one
duplicate are analyzed for each group of samples. If twenty or more samples are
analyzed two blanks and duplicates are analyzed.
The autoanalyzer is calibrated according to the manufacturers specifications.
The PR 700 balance is set zero and recalibrated for each weighing.
Calculations
ug/kg (dry) TKN = mg/1 from method 465 curve x 1000 g/kg
g/1 (dry wt. of original sample)
dry wt. (g/1) = % solids (decimal fraction) x wet wt. x 1000 (orig. volume).
250
References
1. "EPA Methods for Chemical Analysis of Water and Wastes", 1974, Office of
Technology Transfer, Washington, DC, p. 175-181.
2. "Ultramicro Semi-Automated Method For the Simultaneous Determination of
Total Phosphorus and Total Kjeldahl Nitrogen in Wastewaters", Jirka, A.M.,
Carter, M.J., May, D., and Fuller, F.D., Environmental Science and Technology
Vol. 10, 1976, p. 1038-1043.
-------
-46-
Determination of Total Kjeldahl (TKN) Nitrogen
and Total Phosphorus (TP) in Water and Wastewater
CRL Method #465
Scope and application
This method is an ultramicrotechnique for the digestion of organic nitrogen and
phosphorus compounds in a variety of wastewater samples. The digest is analyzed
simultaneously for phosphate and ammonia in the range of 0.2 - 4.0 mg/1 and
0005 - 10 mg/1 at a rate of 30 samples per hour.
Summary of Method
The samples are digested with sulfuric acid containing potassium sulfate and
mercuric oxide as catalyst. Then, in heavy walled pyrex tubes, the tubes are
heated in a technicon BD-40 Block digestor. The digested samples are then
automatically analyzed for TKN and TP using the Technicon AA II system.
Equipment
Technicon BD-40-Block digestor.
Technicon Autoanalyzer II consisting of
Sampler IV with 30/hour 2:1 cam, proportionating pump III with a dilution manifold.
Phosphate manifold
Ammonia manifold
Colorimeter equipped with 15 mm flow cell, S10 phototube, 630 run interference filter
for TKN.
Colorimeter equipped with 50 mm flow cell, S]_ phototube and 880 run interference filters
for TP.
Dual pen recorder
Dual channel digital printer
Tekmar Model SDT homogenizer
Oxford 5-10 ml adjustable pipett
Teflon boiling chips
Vortex genie mixer
Precision vari-hi speed centricore centrifuge
-------
-47-
Reagents
All chemicals are ACS reagent grades
Digestion Solution: Dissolve 2.0 gm of HgO in 25 ml of 6N 112804.
Add 200 ml of cone. H2SO4 carefully to 500 ml water. While the strong acid
solution is still Hot, 134 gm of K2SO4 was dissolved in it. Add the HgO
solution to sulfuric acid - sulfate solution, allow to cool and dilute to one
liter, and store above 20°C to avoid precipitation of
Reagents for automated dilution manifold: sample wash solution
Add 35 ml of cone. H2SO4 to 500 ml of H2O and dilute to 1 liter with distilled
water.
Dilution Solution: Dilute 12.5 ml of 10 N NaOH to 1 liter with distilled water.
Reagents for automated ammonia manifold: Complexing reagent:
Dissolve 33 gm of sodium tartrate, 24 gm of sodium citrate in 900 ml of distilled
water, and dilute 1 liter and add 0.25 ml of Brig 35 wetting agent.
Alkaline Phenol Solution: Dissolve 83 gm of Phenol and 36 gm of NaOH in 900 ml
of distilled water, dilute to one liter. Store at 4°C.
Sodium Hypochlorite Solution: Dilute 200 ml of "Chlorox" to 1 liter with distilled
water.
Sodium nitropusside reagent: Dissolve 0.5 gm of sodium nitroprusside in 900 ml
of water and dilute to 1 liter. Store at 4°C.
Reagents for Automated Phosphate Manifold
Sodium Chloride Solution: Dissolve 5 gm of sodium chloride in 900 ml of distilled
water, dilute to one liter. Add 0.25 ml of Levor IV wetting agent.
4.9N Sulfuric Acid: Add 136 ml of cone H2SO4 to 500 ml of distilled water, cool
and dilute to one liter.
Ammonium Molybdate Solution: Dissolve 40 gm of (NH4)6 MO7O24 4H2O in 900 ml of
distilled water and dilute to one liter.
Store at 4°C.
Ascorbic acid solution: Dissolve 18 gm of ascorbic acid in 900 ml of water and
dilute to one liter. Store at 4°C.
Antimony Potassium Tartrate: Dissolve 3.0 gm of K(SbO) 04^05.1/2 H20 in 900 ml
of distilled water and dilute to 1 liter. Store at 4°C.
-------
-48-
Combined Color Reagents for TP
Add 15 ml of Amm. Molybdate solution to 30 ml of ascorbic acid solution then add
5 ml of antimony potassium tartrate. This reagent has to be prepared fresh before
each run.
Standards: Stock nitrogen standard [0.1 mgN/ml]: Dissolve 1.05 gm of glutamic acid
[dried at 105°C for one hour] and in 900 ml of distilled water, add 2 ml of cone
H2SO4 and dilute to one liter.
Stock phosphorus standard [0.1 mgP/ml]
Dissolve 0.4394 gm of K H2PO4 [dried at 105°C for one hour], in 900 ml of distilled
water, add 2 ml cone. H2SC>4 and dilute to 1 liter.
Combined Standards: Prepare the following standards
ml P. Stock ml N. Stock
0.4 mg P/l + 2.00 mgN/1 4 20
2.00 mg P/l + 5.00 mgN/1 20 50
4.00 mg P/l + 10.00 mgN/1 40 100
Dilute each combination to one liter [add 1 ml cone. I^SC^ for preservation before
diluting to one liter].
Blank Solution: Add 1 ml of H2SO4 to 900 ml of distilled water and dilute to one
liter.
Procedure
1. All glassware should be rinsed with 1:1 HC1 to prevent phosphorous contamination.
Rinse the digestion tubes with hot water followed by 1:1 HC1 and finally with
distilled water. The tubes should be rinsed immediately after usage with hot water
to prevent hardening of any deposits.
2. Follow this loading pattern in filling the tubes in the rack: set standard,
followed by 3 blanks, 3 calibration standards, 2 control standards, field blanks,
samples then finally a duplicate at position 40.
3. Any non-uniform samples such as sewage, paper mill waste, farm wastes etc.,
should be blended for 30 seconds and aliquots withdrawn imtnediatly after blending.
4. Fill the rack with the digestion tubes.
5. Add a few teflon boiling chips or stones.
6. A representative 10 ml aliquot of standards, blanks, Q.C. standards and samples
is delivered to the digestion tubes using the Oxford pipette with the disposable
tips. Follow the loading pattern discribed in 2 above.
7. Add 2 ml of digestion mixture to each tube.
8. Place the rack of tubes in Block Digestor A [adjusted to 200°C] for 1/2 hour
to allow evaporation of the samples.
-------
-49-
9. Transfer the rack of tubes to Block digestor B [adjusted to 370°C] for another
1/2 hour. The digestion should be complete by then.
10. Remove the rack and allow the tubes to cool to room temp.
11. Add 10 ml of distilled water to each tube and mix the sample with the vortex
mixer. Centifuge if necessary. Suspended, dark materials present after digestion
indicate incomplete digestion and the sample should be discarded.
12. Transfer each sample to a clean 15 x 85 mm test tube and place in the technicon
sample tray in the same loading pattern described.
13. Set up the manifold and reagents as shown in Figs. 1, 2, 3 and allow the colori-
meter, recorder and printer to warm up.
14. Feed all reagents through the lines with the sample probe at the wash cycle.
15. Check the zero and full scale set on the colorimeter.
16. Switch to normal mode and adjust the baseline below the zero line on the recorder
to faciliate zeroing the instrument later with the blanks.
17. Start the analysis. Synchronize the instrument with the set standard, then
set the zero baseline with the 1st blank and calibrate the instrument with the
1st calibration standard [a midscale or a full scale standard could be used].
The instrument is recalibrated for every 40 sample set.
18. Samples following an off scale sample(s) should be rerun at the end of the
wheel to correct for carryover effects.
Quality Control
A minimum of two duplicates, field reagent blanks, and 2 quality control standards
are run with every 40 samples or set.
Calculations
The TP and TKN concentrations in mg/1 are obtained directly from the digital
printer, times any dilution factor if necessary.
References
Jirka, Andrea M., Carter, Mark J., May, Dorothy, and Fuller, Fredrick D.,
"Ultramicro-Semi-Automated Method For the Simultaneous Determination of
Total Phosphorus and Total Kjeldahl Nitrogen in Wastewaters", Environmental
Science and Technology, Volume 10, 1976, p. 1038-1043.
-------
-50-
D
»TMb«g
f2 K\ Strntt* *•» So1"
»32IA»
-sSffis
H CO) Muuon Uoe Sol n
(TO MM, I
Flgura1.Au
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in
_J*r-i6
SmMtIV
af phoaphonat and total K)elctah< narogen dHubon
OQfTMpond to flow nto of pun^tubos fn
Nwnbars adjacant to glan ooH* and flttlnat ire Tachnkxm Corp. part num-
bars
Flgura 2. Automated ammonia rmnrfoW, 0.06-10.00 mg N/l. For ex-
ptanatkxi of manltotd numbers, see Figure 1
(0,32) AIB
J. Automated phosphate mantfoM, 0.02-2.00 mg P/l. For ex-
planation of manHoid numbers, aav Figure 1
-------
-51-
Determination of Total Phosphorus in
Sediments and Other Solids
CRL Method No. 435
Scope and Application
This method is applicable to the determination inorganic and organic phosphorus
forms in sediment and other solid samples.
Summary of Method
The sample is digested with a strong sulfuric acid - potassium sulfate - mercuric
oxide solution to sulfur trioxide fumes (803) and for 30-40 minutes longer. The
solution is cooled, diluted, and an aliquot analyzed by the automated molybdate
reaction. Ammonium mobybdate and antimony potassiumtartrate react in an acid medium
to form an antimony - phospho - molybdate complex. This complex is reduced to an
intensely blue-colored complex by ascorbic acid. The color is proportional to the
phosphorus concentration.
Equipment
Pyrex test tubes (1" x 8:", heavy walled) see CRL Method 465 - Attached to CRL
Method 468.
Technicon AA II System (see CRL Method 465, Attached to CRL Method 468)
Automatic Pipetter
Mettler PR 700 Balance
360 ml high density polyethylene bottles
Self - Sticking labels (yellow)
Tekmar SDT homogenizer
Reagents
20% H2SO4 Solution.
Digestion Solution: Dissolve 2.0 grams of Hgo in 25 ml of 6N E^SOg. In a
separate beaker, add 200 ml of concentrated H2SO4 carefully to 500 ml of
water. Then add 134 grams of potassium sulfate to the hot solution. After
the potassium sulfate has dissolved add the HgO solution, cool and dilute
to one liter. Store above 20°C.
Other Reagents (See CRL Method 465, Attached to CRL Method 468)
Procedure
1. Place self-sticking labels on the sample bottles and write the sample numbers
and date prepared. Label one bottle for the reagent blank and one for dupli-
cate. Date the bottles.
2. Tare each polyethylene bottle on the PR 700 balance.
3. Weigh 1.5 to 3.0 grams of homogenized sediment directly into the bottle. Weigh
the larger amount for sandy samples, the lesser amount for samples with large
amounts of humic material.
-------
-52-
4. Record the weight of the sample on the bottle label and lab sheet.
5. Add 5 ml of the 20% H2SO4 to sample in the yellow labeled bottle.
6. Shake the mixture, let stand for five minutes then, add 245 ml of distilled-
deionized water to each bottle and shake.
7. Blend (homogenize) for one minute at high speed. Sandy samples require less
time, mud samples more time. Rinse the shaft and generator between samples
with distilled-deionized water and wipe dry with a Kim-Wipe or other tissue.
8. Store the sulfuric acid-preserved samples at 4°C,
9. In a test tube rack, place three teflon boiling chips (which were acid rinsed
with 1:1 HC1) into each clean, empty 1" x 8" test tube.
10. Reblend the sample in the bottle. Take a representative aliquot, (usually
10 ml for colorimetric analysis. If an aliquot smaller than 10 ml is taken,
dilutens should be made with a blank solution which contains 2 ml of concen-
trated H2SC>4 per liter of water.
11. To each sample tube, pipet 2 ml of digestion solution.
12. Put each tube in the Technicon BD40 Block Digestor at low temperatude (200°C)
and digest samples for a minimum or one hour or until all liquid has evaporated.
13. Transfer to the high temperature block digester and digest the samples at 370°C
while sulfur trioxide (803) fumes are being emitted. After 303 evolution has
stopped, digest for 30 to 40 minutes more at 370°C.
14. Cool for approximately five to seven minutes (not longer, otherwise a solid,
insoluble, hard mass will result).
15. Add 10 ml of distilled-deionized water to each tube and cover rack with foil
or other cover.
16. Proceed with analysis using the manifold in CRL Method No. 465, (Attached to CKL
Method 468).
Quality Control
One field reagent blank containing preservative and digestion solution and one
duplicate are analyzed for each group of samples. If twenty or more samples are
analyzed, two blanks and duplicates are analyzed.
The autoanalyzer is calibrated according to the manufacturer's specifications
The PR 700 balance is set to zero and recalibrated for each weighing.
-------
-53-
Calculations
mg/kg (dry) Total P = mg/1 from Method 465 curve x 1000 g/kg
(g/1 (dry wt. of original sample)
dry wt. (g/1) = % solids (decimal fraction) x wet wt. x 1000 (orig. volume)
250
References
1. "EPA Methods for Chemical Analysis of Water and Wastes", 1974, Office of
Technology Transfer, Washington, DC, p. 249-255.
2. "Ultramicro Semi-Automated Method For the Simultaneous Determination of
Total Phosphorus and Total Kjeldahl Nitrogen is Wastewaters", Jirka, A.M.,
Carter, M.J., May, D., and Fuller, F.D., Environmental Science and Technology,
Vol. 10, October 1976, p. 1038-1043.
-------
-54-
Determination of Chemical Oxygen
Demand in Sediments and Other Solids
CRL Method No. 351
Scope and Application
This method is applicable to sediments and other solids. It is a
measure of the quantity of oxygen required to oxidize organic matter
in sediments and solids under specific conditions of oxidizing agent,
temperature and time.
Summary of Method
Organic substances in the sample are oxidized by potassium dichromate
in 50% sulfuric solution at reflux temperature. Silver sulfate is
used as a catatyst and mercuric sulfate is added to remove chloride
interference. Following digestion, an automated spectrophometric
measurement of the appearance of chromium III at 600 nm is used to
determine the Chemical Oxygen Demand (COD) of the sample.
Equipment
Screw cap, teflon-lined culture test tubes (See CRL Method No. 342, Attached).
Technicon AA II System with Sample IV, and Pump III (See CRL Method 342, Attached)
Oven
Reagents
20% Sulfuric Acid
Digestion Solution - Dissolve 10.2169 of K2Cr2O7, 167 ml of cone.
H2SO4and 33.3 g of HgSO4 in 500 ml of water and dilute to 1 liter.
Catalyst Solution - Dissolve 22 g of Ag2SO4 in a 9 Ib. bottle of H2SO4.
Other Reagents - See CRL Method 342, Attached);
Procedure
1. Place self-sticking labels on the sample bottles and write the
sample numbers and date prepared. Label one bottle for the
reagent blank and one for duplicates; date the bottles.
2. Tare each polyethylene bottle on the PR700 balance.
-------
-55-
3. Weigh 1.5 to 3.0 grains of homogenized sediment directly into
the bottle. Weigh the larger amount for sandy samples, the
lesser amount for samples with large amounts of humic material.
4. Record the weight of the sample on the bottle label and lab sheet.
5. Add 5 ml of the 20% H2SC>4 to sample in the yellow labeled bottle.
6. Shake the mixture, let stand for 5 minutes then add 245 ml of
distilled-deionized water to each bottle and shake.
7. Blend (homogenize) for 1 minute at high speed. Sandy samples
require less time, mud samples more times. Rinse the shaft
and generator between samples with distilled-deionized water
and wipe dry with a Kim-Wipe or other tissue.
8. Store the sulfuric acid-preserved samples at 4°C.
9. Wash all of the culture tubes and caps with 20% 112804 to prevent
contamination.
10. Shake the sample which was stored in the bottle and withdraw
2.5 ml of sample into the culture tube.
11. Add 1.5 ml of digestion solution and 3.5 ml of catalyst solution
carefully down the side of the tube so that the acid forms a
layer on the bottom of the tube.
12. Cap tightly and mix by shaking.
13. Prepare blanks and standards of KHP in the same manner (See CRL
Method 342, Attached).
14. Heat in an oven for 2 hours at 150°C (making sure that the sample
is refluxing).
15. Cool, remove from the oven and place in the Technicon Autoanalyzer
sampling tray.
16. Proceed with the colorimetric analysis using the manifold shown
in CRL Method 342, (Attached).
-------
-56-
Quality Control
One field reagent blank (which includes 5 ml of 20% I^SC^ diluted
to 250 ml) and a duplicate of one of the samples are analyzed for
each group of samples. If twenty or more samples are analyzed, a
minimun of two duplicates are analyzed.
Calculations
mg/kg (dry) COD = mg/1 COD from CRL Method 342 x 1000 gAg
orig. wt of sample in grams per liter
dry wt. = (g/1) = decimal fraction of % solids x wet wt. x 1000
250
Reference
1. "Micro Semi-Automated Analysis of Surface and Wastewaters for
Chemical Oxygen Demand", Jirka, Andrea M., Carter, Mark J.,
Analytical Chemistry, Vol. 47, July 1975, p. 1397.
-------
-57-
Determination of Chemical Oxygen Demand in Water
and Wastewater
CRL Method #342
Scope and Application
This method is applicable to waste water, lake water, drinking water, industrial
wastes, raw and finished sewage.
Summary of Method
The semiautomated procedure for the determination of COD combines a micro sample
digestion technique with an automated procedure based on the spectrophotometric
measurement of Cr+++ at 600 nm: The sample is combined with an acid potassium
dichromate, Mercuric sulfate and an acid silver sulfate solution in a specially
capped culture tube. It is then digested in a 150°C oven for two hours and the
concentration of Cr+++ is measured at 600 nm in a 50 mm flow cell. The range is
3-900 mg/1 COD.
Equipment
Technicon Autoanalyser II consisting of
Sampler IV with 40 x 3/1 cam
Proportionating pump IV with a dilution manifold
Recorder II
Single channel digital printer corning No. 9949 16 x 100 mm. Screw cap
(Cap No.No. 9989) Culture Tubes
Tekmar Model SDT Homogenizer
Oven
Reagents
Digestion solution: Add 10.216 gm of K2Cr207, 167 ml of cone. H2S04 and
33.3 gm of HgS04 to 500 ml of water and dilute the cooled solution to
1 liter.
Catalyst Solution: Dissolve 22 gm of Ag2S04 in a 9-lb bottle of cone. H2S04.
Sampler Wash Solution: 50% sulfuric acid by volume.
Standards: Dissolve 8.5 gm of a dried portion of NBS standard reference
material (84h) in water and dilute to 1 liter. The strength of this
solution is 10 gm/1. Working standards of 50, 200, 500, and 800 mg/1 are
prepared by taking the proper dilutions.
-------
-58-
Procedure
1. Wash all culture tubes and screw caps with 20% H2S04 before use.
2. Place 2.5 ml of sample, and 1.5 ml of digestion solution into tubes.
3. Carefully add 3.5 ml of catalyst solution down the sides of the culture
tube .
4. Cap the tube tightly and then shake to mix the contents.
5. Prepare five blanks, a set of standards and Quality Control Standards
CSl, CS2 with each rack.
6. Heat all samples, blanks and standards in the oven at 150°C for two hours.
7. Set the analytical manifold and reagent as shown in Fig. (1) with a glass
capillary as a sample probe.
8. Set the standard calibration control at 228.
9. Adjust the zero and full scale setting.
10. With all reagents passing through the lines and the sample probe in the
wash cycle, turn the colorimeter to the proper damping and adjust the
baseline below the zero line on the recorder.
11. Start the analysis and with the blanks, zero the baseline.
12. Check the preset - calibration (std. cal. at 228) and slightly adjust if
needed with the 500 mg/1 standard.
Quality Control
One field reagent blank and a duplicate of one of the samples is analyzed with
each group of samples. If twenty or more samples are analyzed, a minimum of
two blanks and two duplicates are analyzed.
Calculations
The COD values of the unknown samples are obtained by direct printout in mg/1
times any dilution factor applicable.
References
"Micro Semi-Automated Analysis of Surface and Wastewaters for Chemical Oxygen
Demand", Jirka, Andrea M., Carter, Mark J., Analytical Chemistry, Vol. 47,
No. 8, July 1975, p. 1397.
-------
TO SAMPLER IV
gr/gr (2.00)
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50 mm F/C x 1.5 mm ID
, 199-B007-01
NOTE; FIGURES IN PAUKNTHMSES SIGNIFY
FLOW RATES IN HL/M1N.
*ACIDFLEX
**KEL-F TUBING
***GLASS TRANSMISSION TUBING
Fig. 1 Manifold for Chemical Oxygen Demand
-------
-60-
Determination of Total Mercury
in Sediments and Other Solids
CRL Method No. 393
Scope and Application
This method is applicable to the determination of inorganic and organic
forms of mercury in sediments of virtually all types (clean, sandy,
silty, clay, oozy, and organic-rich sludge) in the ranges from 0.1 mg/kg
to 2 mg/kg (without dilution) and higher.
Summary of Method
Aqueous suspensions of homogenized sediment samples are automatically
analyzed using the cold-vapor detection method following a persulfate
oxidation and stannous chloride. Samples are analyzed at the rate of
30 per hour with a routine detection limit of 0.1 mgHg/kg of sample and
an average relative standard deviation of 6% at a level of 20-30 mg/kg
of mercury.
Equipment
Mettler PR?00 Balance
360 ml high density polyethylene bottles
Self-Sticking labels
Tekmar SDT homogenizer
Pipets (wide tipped)
Mercury-free glassware (See CRL Method 390, Attached)
Spectro Products Mercury Analyzer With Perkin Elmer Model 56 Recorder
(See CRL Method 390, Attached)
Technicon AA II System (See CRL Method 390, Attached)
Reagents
Preservative: To 500 ml of distilled water, add 250 ml of cone. HNO3
and 25 g of potassium dichromate (K2Cr207) and dilute to 1 liter.
1. Potassium Persulfate
2. Hydroxylamine Hydrochloride - Sodium Chloride
3. Stannous Chloride
In items 1, 2, and 3, see CRL Method 390 (Attached)
-------
-61-
Procedure
1. Place self-sticking labels on the sample bottles and write the
sample numbers and date prepared. Label reagent blank and
duplicate sample bottles and date them.
2. Tare a polyethylene bottle on the PR 700 balance.
3. Weigh approximately 1.0 gram of homogenized sediment sample into the
tared 360 ml polyethylene bottle. For sandy samples, slightly larger
amounts may be used (1.5 to 2 grams). Larger sample sizes however
often result in settling and clogging in the manifold. Pulverizing
to a finer mesh allows usage of a larger sample size.
4. Record the weight of the sample on the bottle label.
5. Add 5 ml of preservative solution to the sample. If the I^jC^Oy
is reduced, (as evidenced by a green color), add an additional
amount of preservative solution until the suspension color remains
yellow. Let stand for 5 minutes or until foaming subsides (usually
sulfides and other gases are driven off).
6. If 5 ml of preservative was sufficient, add 245 ml of distilled-
deionized water and homogenize at high speed for 1 minute, followed
by manual shaking for another minute. If more than 5 ml of preser-
vative are added, reduce the volume of distilled deionized water
accordingly (final volume 250 ml is desired).
7. Rinse the shaft and generator between samples with distilled-deionized
water and wipe dry with a kirn-wipe tissue.
8. Store the sample overnight. (If a green color develops on standing,
add more preservative to a yellow color and note the final volume) .
9. Shake the sample and fill the autoanalyzer sampling cup. (Note-the
autoanalyzer contains a cylindrical sterrer which keeps the sample
in suspension) .
10. Proceed with mercury analysis using CRL Method No. 390 (Attached).
Quality Control
One field reagent blank (which includes the J^SC^-^C^Oy preservative)
and a duplicate of one of the samples are analyzed for each group of
samples. If twenty or more samples are analyzed, a minimum of two
duplicates are analyzed.
-------
-62-
Calculations
mgHg/kg (dry basis) = ugHg/1 (from curve using Method 390) x 25
(Orig. wt. in grams of sediment)x(decimal fraction of % solids]
Reference
1. "An Automated Method for the Determination of Mercury in Sediments",
Jirka, Andrea M. and Carter, Mark J., Analytical Chemistry, Vol. 50,
January 1978, p. 91.
2. "Automated Method for the Determination of Total and Inorganic Mercury
in Water and Wastewater Samples", EL-Awady, Miller and Carter, Analytical
Chemistry, Vol. 48, No. 1, January 1976.
-------
-63-
Total and Inorganic Mercury in
Water and Wastewater Samples
CRL Method No. 390
Scope and Application
This method is applicable to drinking water, wastewater, effluents, and a
variety of environmental water matrices. Samples are analyzed at the rate
of 20 per hour, with a routine detection limit of 0.1 ug/1 and a working
range of 0.1-2 ug/1.
Summary of Method
Samples are automatically analyzed using the cold-vapor detection method
following a persulfate oxidation and stannous chloride reduction. The
mercury vapor aerated from solution passes through a cell positioned in the
light path of a spectrophotmeter mercury analyzer. Absorbance (peak heights)
is measured as a function of mercury concentration.
Apparatus
Spectro products mercury analyzer, model HG-2.
Perkin Elmer model 56 multi-range chart recorder.
Harmonically smoothed voltage stabilizer.
Technicon Auto Analyzer unit consisting of
a. Sampler IV
b. Proportioning pump III
c. Heating bath with heating coil (20 ft. long 2.4 mm id)
Absorption cell Fig. 1
Gas liquid separator Fig. 2
A rotameter to measure the rate of air flow in the gas liquid separator.
A Tekmar model SDT homogenizer.
Reagents
Preservative solution - add 250 ml of cone. HNO3, 25 gm of K2Cr2O7 to 500 ml
of distilled water and dilute to 1000 ml.
Sulfuric acid cone. - reagent grade, suitable for mercury determination.
Three percent hydroxylamine hydrochloride/hydrochloric acid reagent. Dissolve
30 gm of Nad, 30 gm of hydroxylamine hydrochloride in one liter of distilled water.
Four percent potassium persulfate reagent. Dissolve 40 gm of K2S207 salt
in one liter of distilled water.
-------
-64-
Stannous chloride/hydrochloric acid reagent. Add 225 ml of HC1 to 500 ml of
distilled water, add 10 gm of SNC12 and dilute to 1 liter.
Stock mercury solution - 1000 pm mercuric chloride ion methyl mercuric chloride
could be used (reagent grade).
Working mercury standard. Prepare 0.1, 0.5, 1, 1.5, and 2 mg/1 standards by taking
the appropriate dilution of the 1000 mg/1 stock solution.
Nitric acid was solution - add 100 ml of concentrated HN03 to 500 ml of distilled
water and dilute to one liter.
Procedure
1. Set up manifold as in Fig. 3.
2. Feeding all the reagents through the system with acid wash solution through
sample line, the vapor liquid separator disconnected, adjust heating bath to
150°.
3. Turn on the cooling water for the jacket mixer.
4. Adjust the nitrogen gas flow to 4 to 5 division on the scale.
5. Turn on the mercury analyzer and adjust the "B" lamp to read 100% full scale.
6. Allow 15-20 minutes for warm-up period and readjust the 100% scale for
the "B" lamp.
7. Turn on the "Age" if the meter deflects from the 100% reading, readjust using
the "Age" adjuster knob.
8. Balance the "B" lamp by increasing the power to the "A" lamp until 0% reading
is obtained.
9. Turn on the 10X (scale expansion) and with the zero fine adjuster readjust the
zero reading.
10. Turn on the recorder and monitor the baseline for 10 minutes or until a stable
baseline is obtained.
11. Connect the gas separator to the absorption cell and monitor the baseline for
5 minutes.
12. Run 2, 1.0, 1, 0, 0.5, 0.1 ug/1 standards, blanks. Prepare standard curve by
plotting peak heights of processed standards against concentration values.
13. Analyze the samples and determine the mercury content from the standard curve.
14. After the analysis is completed, disconnect the gas separator and put all the
lines in the washing solution, to wash out the system.
-------
-65-
15. Turn off the recorder, the mercury analyzer and the nitrogen gas
16. Turn off the autoanalyzer pump and remove the plate.
17. Unplug the heating bath.
18. Turn off the cooling water.
Quality Control
One field reagent blank (which includes the f^SC^-^C^Oy preservative, and a
duplicate of one of the samples are analyzed for each group of samples. If
twenty or more samples are analyzed a minimum of two duplicate are analyzed.
Calculations *
ug/1 mercury = ug/1 (from curve) x dilution factor (if any)
*A computer program is also used frequently for calculations. It involves
calculations of the peak heights versus standard values using the best square fit.
Reference
"Automated Method for the Determination of Total and Inorganic Mercury in Water
and Wastewater Samples", El-Awady, Miller and Carter, Analytical Chemistry,
Vol. 48, No. 1, January 1976.
-------
-66-
AIR AND
SOLUTION
IN
0.4 cm 10
l4cm
SOLUTION
OUT
FIGURE 1. VAPOR LIQUID SEPARATOR
-------
0)
M
g,
VD
I I
-------
-68-
Figure 3
(2.00) air
Sampler IV
20/HR
1:2
(0.80) air
HBC
DO
SMC
(0.80) air
(3.90) sample
KO
Al Al
(3.80) sample
(3.90) sample
G3
(1.89) H2S
ACIDFIEX
(2.50) K?S208
DO
(0.32) NH,OH HCi/NaCI
JMC
(2.00) SnCI2 /HC!
DO
•LMC
DO
SMC
(3.90) wash
to Sampler
GO
(3.80) wash
(3.90) wash
!GO
V
\
*hase
r_ — ^ wasti
Separator
Scrubber
S
#
i
F
s
253.7 nm
0
^g II Analyzer
Recorder
-------
-69-
Determination of Total Metals in
Sediments and Other Solids
CRL Method Nos. 571 to 598
Scope and Application
This procedure is applicable to the determination of calcium, magnesium,
sodium, potassium, aluminum, barium, beryllium, boron, cadmium, chromium,
cobalt, copper, lead, manganese, molybedenum, mickel, silver, thallium,
tin, titanium, vanadium, ytrium and zinc in sediments and other solids.
It is not applicable to mercury, which is very volatile.
Summary of Method
One gram of the dried sample is digested with 8N nitric acid and 30%
hydrogen peroxide, followed by heating with 25 ml of a strong nitric-
hydrochloric acid solution to solubilize transition and noble metals.
The sample and washings are diluted to 100 ml and a portion of the sample
is analyzed for all metals by Inductively Coupled Argon Plasma Atomic
Emission (ICAP) spectrometry or by atomic absorption spectrometry.
Equipment
Jarrell-Ash Plasma Atom Comp. 750 equipped with exit slits for spectral
lines of the elements listed under Scope and Application. Plasma Assembly-
Composed of Cross Plow Nebulizer, spray chamber, torch, coupling box and
1.3 kilowatt power supply.
or Atomic Absorption Spectrometer
Beakers
Hotplates (non-metallic)
Mettler PR 700 balance
Reagents
50% 8N HNO3 (Redistilled)
30% H202
Cone HC1
Procedure
1. The dried sample from the total solids determination is ground with
a porcelain mortar and pestle until the entire sample passes through
a number ten mesh polypropylene sieve. The sieved sample is placed
in a two ounce polypropylene bottle, capped and labeled.
2. One (1.00) gram of the sample is weighed into a 300 ml acid-washed
tall form beaker. The beaker is placed in the hood.
3. 0.5 ml of 30% hydrogen peroxide and 20 ml of 8N (50%) re-distilled
nitric acid are added to the beaker. A ribbed watch glass is placed
on the beaker.
-------
-70-
4. After heavy foaming subsides, the mixture is swirled to aid mixing,
then placed on a hot plate and gently heated to dryness (at 95°C or less).
5. The beaker is removed from the hot plate, cooled and 25 ml of a mixture
containing 50 ml of concentrated HC1, 200 ml of concentrated HNO3 and
750 ml of deionized water is added.
6. The sample and acid mixture are heated for 15 minutes and cooled.
7. The contents of the beaker transferred are filtered through a
quantitative grade filter paper such as Schlichter and Schnell
white label paper, into a clean 100 ml volumetric flask. The empty
beaker and watch glass are rinsed with deionized water and a clean
(rubber usually contains zinc) rubber policeman is used to remove any
deposits. The washings are transfered to the filter and allowed to
filter into the volumetric falsk. The flask is diluted to the mark,
capped, and shaken.
8. Approximately 50 ml of the sample is poured into one clean labeled
2 ounce (60 ml) polyethelene bottle and the other 50 ml into another
clean, labelled 2 ounce polyethylene bottle. (One of the 2 ounce
bottles are saved in case of re-checking at a later date).
9. The bottle contents are analyzed directly by aspiration into the ICAP
(CRL Method Nos. 504 to 570 attached) or by AA. The ICAP procedures
enable 21 metals to be determined simultaneously with about 10-12
ml of sample. If the same number of samples are done by AA, a much
greater volume is required.
10. Some samples will require dilution from 1 to 10, 1 to 100 and even
greater.
11. Results for calcium, magnesium, sodium and potassium are reported in
milligrams per gram (mg/g) dry basis, whereas results for all other
metals are reported as mg/kg (same as ug/g) dry weight basis.
Quality Control
A blank, duplicate and spike for every ten samples are carried through the
same procedures as the samples.
The manufacturers instructions are followed for both the ICAP and AA
procedures.
The balance is set to zero before and after each reading.
Calculations
Using the ICAP
mg/kg (ug/g) dry basis = lg/100 ml x ICAP Reading in ug/1
10
-------
-71-
References
1. Manual of Methods for Chemical Analysis of Water and Wastes, United
States Environmental Protection Agency, Office of Technology Transfer,
1974, pp.78-155.
2. "Simultaneous Multielement Analysis of Liquid Samples by Inductively
Coupled Argon Plasma Atomic-Emission Spectroscopy", United States
Environmental Protection Agency, Region V, Central Regional Laboratory,
Chicago, IL (unpublished).
3. "Analysis of Sediment Samples for Cadmium, Chromium, Copper, Iron,
Manganese, Nickel, Lead and Zinc using Inductively Coupled Argon
Plasma (ICAP) Detection", Kirkpatrick, James C., Morris, John V.,
United States Environmental Protection Agency, Region V, Central
Regional Laboratory, Chicago, Illinois, November 1978 (unpublished).
-------
-72-
Determination of Total Metals in Water
and Wastewaters by Plasma Spectrometry
CRL Method Nos. 504-570
Scope and Application
This procedure is applicable to the determination of calcium, magnesium,
sodium, potassium, aluminum, barium, berylium, boron, cadmium, chromium,
cobalt , copper, lead, manganese, molybdenum, nickel, silver, thallium,
tin, titanium, vanadium, ytrium and zinc in water and industrial municipal
wastewaters.
Summary of Method
The sample is digested with 8 N nitric acid to near dryness followed by
additional heating with HC1 to solubilize transition and noble metals.
The sample is cooled, diluted to 50 ml and analyzed using Inductively
Coupled Argon Plasma Atomic Emission Spectrometry (ICAP). The alkali
metals concentrations are expressed in milligrams per liter, whereas
concentrations for other metals are expressed in micrograms per liter.
Twenty-two metals are routinely analyzed.
Equipment
Jarrell Ash Atomcomp 750. Inductively coupled argon plasma emission
spectrometer consisting of:
a. RF generator
b. Plasma housing
1. Water-cooled induction coil
2. Quartz torch
3. Cross-flow nebulizer
4. Spray chamber
c. Direct reading spectrometer
1. Entrance slit
2. Refractor plate at entrance slit
3. Grating
4. Exit slits
5. Phototubes.
d. Computer for instrument control
e. Data output device.
300 ml tall form beakers
Mettler PR 700 Balance
Corning Hot Plates
-------
-73-
Reagents, Water, Glassware and Standards
Redistilled Nitric Acid (1:1-8 Normal).
Hydrochloric Acid (1:1), Reagent Grade.
Glassware: Beakers for digestion, after being run through diswasher, are
rinsed with distilled water and placed in an aqua regia bath for at least two
hours. They are then rinsed thoroughly and allowed to air dry. The chemist
performing the digestion will select his or her beakers and give each a hot
acid wash by following then with 1:1 HCl and placing on the hot plate for at
least one half hour.
The laboratory distilled water is passed through an ultrapure mixed-bed resin
column before use. All water used unless otherwise stated, has been passed
through the mixed-bed resin (Super Q Water).
Standards; All standards are diluted from Fisher 1000 ppm Atomic Absorption
standards with the exception of silver and beryllium (varian) and Yytrium
(made from ytrium nitrate (Y(N03)3).
Standards used for the ICAP Calibration Procedure
SOOO: Mixed-bed resin water (super Q water)
S001: One ppm in all elements except silver and
calcium
AGCA: 1 ppm silver and 10 ppm"calcium, made fresh
daily.
1000: 1000 ppm calcium (Fisher)
XXXX: 1000 ppm iron (Fisher), FFFA matrix only.
Procedure
1. A designated aliquot (usually 50 ml) of well-shaken and preserved
sample (pH<2) is poured off into a 300 ml tall-form beaker. Normal
procedure is to place the beaker on an automatic-tare balance and
deliver 50 g - drawing off excess with a disposable pipet. (This
procedure assumes the sample is of sufficiently low concentration that
the specific gravity is not appreciably greater than one. The purpose of a
mass determination rather than a volume one is to eliminate cross-contamina-
tion). After the addition of 6 ml of 8N redistilled HN03, to the
sample a ribbed beaker cover is placed on the beaker and the sample
is heated to near dryness. (The sample is not taken to complete
dryness to avoid the loss of boron). If the residue is dark colored
after cooling, an additional 6 ml of 8N HN03 is added and the sample
is reheated. This process is continued until no color change is
detected.
2. Following the digestion, 5 ml of 1:1 HCl is added and the residue is
dissolved and/or placed in suspension by warming on a hot plate.
After cooling, the sample is transferred to a pre-tared 2 ounce
polyethylene bottle and diluted up to 50 g. If some solids remain
undissolved, the sample is filtered into a 50 ml volumetric and then
transferred to a polyethylene bottle for subsequent analysis.
-------
-74-
3. Operating Conditions
a. Incident RF power 1.1 kw
b. Reflected RF power minimized (<10 w)
c. Plasma observation height 15 mm above load coil
d. Horizontal observation position...center
e. Aspiration Argon flow rate 0.6 L/min
f. Plasma Argon flow rate 22 L/min
4. ICAP Standardization Procedure and Sample Analysis.
Following startup, the instrument is profiled with the mercury monitor.
The micrometer reading is recorded on the sheet with the interelement
correction values for the day.
The matrix is brought onto core and time and date established. The
available matrices are:
CCAS: correction for calcium
FEAS: correction for calcium and iron
KlAS: correction for calcium and iron and
outputs potassium.
The Q-string QEGGGAB is set for standization. This string of commands
will erase the burn buffers, execute three burns, average them, and
print the average on the teletype.
(It has been found that examining the standards in background mode allows
a better judgement of the noise in a given channel).
5. The standards cited above are run. Once it has been verified that the
standards check, the values for interelement correction for iron and
calcium are recorded and entered via the data base manager. In actual
operation it is possible that these may vary only slightly (5%) from day
to day, in which case they need not be entered.
Upon return to the operating system, the matrix is recalled and the
blank and 1 ppm standard are checked. If these remain with in standard-
zation, an instrument AQC solution is measured. This AQC solution
is simply the waste from the drain of the nebulizer, collected and
held until it is deemed stable. The values for this solution are
recorded in a log book and compared with previous values. This is
a check for gross operator error during standardzation.
6. Once these criteria have been satisfied, the instrument is ready
to run samples. The blank and 1 ppm standard should be checked
every 30-45 min to establish that the instrument has not drifted.
The blank should also be checked if values above detection limits
are found for the field blanks or digested laboratory blanks.
-------
-75-
7. Samples are aspirated for 45 seconds before executing the Q string
QEGC which perform a single burn followed by output in concentration
mode which includes interelement corrections. Longer flush times,
may be desired for samples which follow high (>500 ppm) iron samples
or high (>1000 ppm) sodium samples. No other elements have been
encountered in sufficient quantities in real samples to result in
noticeable memory effects.
8. Duplicates and spikes should be checked against the corresponding
samples before continuing. This is to establish whether deviations
occur in the digestion or measurement of samples on the ICAP. If
it is found that the digestion is not at fault, restandardization
on the ICAP is recommended.
9. Samples at high levels are routinely diluted 10-fold to determine
if results for all elements are valid or the result of intererence
not accounted for by the matrix lECC's.
The paper tape from the teletype is read into the DG NOVA and the
report plus QC check is performed by programs written in BASIC.
Quality Control
Four types of quality control samples are put through the digestion
process at the same time as the samples. In a typical run of forty
samples there are in addition, four blanks, 4 AQC solutions, 2 dupli-
cates, 2 spikes.
1. Blanks: These are simply the laboratory super Q water carried
through the same digestion process as the samples. The blank
data is summarized periodically and is used to determine detec-
tion limits for the method (average and 2 standard deviations).
2. AQC Solutions: A series of solutions were made to cover the
ranges measured for each parameter. These were arranged in
Youden pairs approximately as follows: 10 ppm - 8 ppm? 1 ppm -
800 ppb; 100 ppb - 80 ppb. Two pairs of these solutions are
digested as part of the run. This is separate from the instru-
ment AQC and calibration procedure mentioned earlier.
3. Duplicates: Two samples are chosen to be analyzed as duplicates are
carried through the digestion process. The results for these are
expected to be within 10% of each other for each element, for concen-
trations in the working range (blank one + 10 standard deviations).
4. Spikes: Two samples are chosen to be analyzed as spikes. A table
of spike concentrations in terms of final concentrations is formulated
Spike recoveries are determined if the sample is less than 200% of
the added spike.
-------
-76-
Routine Maintainance
Following four days of operation the torch and nebulization spray chamber
should be acid washed. Before the torch is removed and after it is replaced,
statistical programs are run to determine the standard deviation of all the
lines when aspirating blank water. Dark currents are also examined in this
manner. A reading of the profile meter is taken for each element both before
and after cleaning while aspirating both blank water and the 1 ppm standard.
When the torch is replaced, coarse alignment is made using a 1000 ppm yttrium
standard to center the image on the slit. Pine adjustment of the mirror is
made by maximizing the signal to noise ratio on the lead line.
Once a month, statistical programs are run to maintain an historical record of
intensities obtained on each line for the series of standards.
Calculations
These are done by the computer program (written in basic) including
insertion of dilution factors to give results in mg/1 for calcium,
magnesium and sodium and ug/1 for the other metals.
Reference
1. Manual of "Methods for Chemical Analysis of Water and Wastes",
U.S. Environmental Protection Agency, Office of Technology Transfer,
1974, Washington, DC, pp 78-155.
2. "Simultaneous Multielement Analysis of Liquid Samples by Inductively
Coupled Argon Plasma Atomic - Emission spectroscopy", U.S. Environmental
Protection Agency. Region V, Central Regional Laboratory, Chicago,
Illinois, (unpublished).
-------
-77-
Determination of Total Antimony, Arsenic and
Selenium and Thallium in Sediments and Other Solids by
Flameless Atomic Absorption
CRL Method Nos. 601, 604, 607, and 595
Scope and Application
This method is applicable to the determination of total antimony, arsenic and
selenium and thallium in sediments and other solids.
Summary of Method
One gram of the dried sample is digested with 8N nitric acid and 30% hydrogen
peroxide, followed by heating with 25 ml of a strong nitric-hydrochloric acid
solution to solubilize transition and noble metals. The sample and washings
are diluted to 100 ml and analyzed by atomic absorption, using the graphite
furnace flameless standard additions technique.
Equipment
Atomic absorption spectrometer with graphite furnace attachment and autosampler
hotplates (non-metallic)
Beakers
Mettler PR 700 balance
Eppendorf pipets
Reagents
50% 8N HNO3 (redistilled)
30% H202
Cone HC1
Procedure
1. The dried sample from the total solids determination is ground with a
porcelain mortar and pestle until the entire sample passes through a
number ten mesh polypropylene sieve. The sieved sample is placed in
a two ounce polypropylene bottle, capped and labeled.
2. One (1.00) gram of the sample is weighed into a 300 ml acid-washed
tall form beaker. The beaker is placed in the hood.
3. 0.5 ml of 30% hydrogen peroxide and 20 ml of 8N (50%) redistilled nitric
acid are added to the beaker. A ribbed watch glass is placed on the beaker.
-------
-78-
4. After heavy foaming subsides, the mixture is swirled to aid mixing, then
placed on a hot plate and gently heated to dryness (at 95° or less).
5. The beaker is removed from the hot plate, cooled and 25 ml of a mixture
containing 50 ml of concentrated HC1, 200 ml of concentrated HNC>3 and
750 ml of deionized water is added.
6. The sample and acid mixture are heated for 15 minutes and cooled.
7. The contents of the beaker transferred are filtered through a quantitative
grade filter paper such as Schlichter and Schnell white label paper, into
a clean 100 ml volumetric flask. The empty beaker and watch glass are
rinsed with deionized water and a clean (rubber usually contains zinc)
rubber policeman is used to remove any deposits. The washings are
transfered to the filter and allowed to filter into the volumetric flask.
The flask is diluted to the mark, capped and shaken.
8. Approximately 50 ml of the sample is poured into one clean, labeled
2 ounce (60 ml) polyethylene bottle and the other 50 ml into another
clean, labeled 2 ounce polyethylene bottle. (One of the 2 ounce
bottles are saved in case of re-checking at a later date).
9. A portion of the sample is removed and diluted 1 to 10 prior to analysis.
(This is to lessen the chloride matrix effects in the sample).
10. The sample is analyzed by flameless atomic absorption using the Standard
Additions Technique (CRL Methods 594, 600, 603 and 606, Attached)
11. Generally, 20 microliters of the sample is injected into the furnace
followed by three spikes of sample plus the element of interest.
Quality Control
A field reagent blank and duplicate is analyzed with each group of ten samples.
The standard additions technique involves spiking the real samples to compensate
for matrix effects, therefore, spike and recovery values are received for every
sample. The manufacturers instructions are followed for the instrument. The
balance is set to zero before and after each reading.
Calculations
mg/kg (ug/g) dry basis of metal = 1 g/100 ml x least squares value x dilution factor
10
REFERENCES
1. Manual of Methods for Chemical Analysis of Water and Wastes, United States
Environmental Protection Agency, Office of Technology Transfer, 1974,
pp. 78-155.
-------
-79-
2. "The Determination of Antimony, Arsenic, Berylium, Cadmium, Selenium,
Lead, Silver and Tellurium in Environmental Water Samples by Flameless
Atomic Absorption", Metals Section, United States Environmental Protection
Agency, Region V, Central Regional Laboratory, Chicago, Illinois.
3. "Determining Selenium in Wastes, Wastewaters, Sediment and Sludge by
Flameless Atomic Absorption Spectroscopy", Martin, Theodore D., Kopp,
John P., Atomic Absorption Newsletter, Volume 14, No. 5, September-October
1975.
4. "Quality Control Summary for Graphite Furnace Analysis", Meszaros, Timothy,
United States Environmental Protection Agency, Region V, Central Regional
Laboratory, Chicago, Illinois, June 1977, unpublished.
-------
-80-
Determination of Total Antimony, Arsenic, Selenium
and Thallium in Water and Wastewater by
Flameless Atomic Absorption
CRL Method Number 600, 603, 606, and 594
Scope and Application
This method is applicable to the determination of total antimony, arsenic,
selenium, and thallium in surface and drinking water, wastewaters and
industrial wastes.
Summary of Method
Regular samples are analyzed by Flameless Atomic Absorption followed by equal
volumes of the regular samples spiked with a blank and standards containing
the element of interest to correct results for possible unknown interferences.
Sample values range generally from 2 to 20 ug/1 for the elements (higher ranges
upon dilution of the samples). Recoveries range from 90 to 110% at a concentra-
tion level of 10 ug/1.
Equipment
Perkin Elmer Model 503 Atomic Absorption Spectrometer equipped with an HGA 2100
Graphite Furnace, deuterium background corrector, Strip Chart Recorder Model PE 056
and AS1 Automatic Sampler.
Electrodeless Discharge Lamp (EDL) for Antimony, Arsenic and Selenium
Hollow Cathode Lamp for Thallium
Eppendorf Pipettes (or equiralent)
Disposable 1 ounce plastic cups
Cups to fit AS1 Sampler
Data General NOVA, 840 Minicomputer
Reagents, Standards, Distilled Water and Glassware
Distilled Water: The laboratory distilled water is passed through an ultra-
pure mixed-bed resin column before use. All water used unless otherwise
stated, has been passed through the mixed-bed (super Q) water resin.
Glassware: Beakers and glassware for standards run through dishwasher, are
rinsed with distilled water and placed in an aqua regia bath for at least
two hours. They are than rinsed thoroughly and allowed to air dry. The
chemist performing the test will select his or her beakers and glassware and
give each a hot acid wash by filling them with 1:1 HCl and placing on the hot
plate for at least one half hour.
Redistilled Nitric Acid (1:1), 8 Normal
Hydrochloric Acid, Reagent Grade
-------
-81-
Calibration Standards
Four standards per element are prepared fresh daily from a stock solution
of 1 ppm of the element of interest.
Stock solution: Dilute to 100 ml in a clean volumetric flask 100 ul of 1000 ppm
Fisher standard or equivalent with deionized water from the prep lab column or
equivalent plus 1 ml of 1:1 redistilled HNC>3. For Arsenic and Selenium also
add 1 ml of 1000 ppm Nickel Standard.
Calibration Standards: Calibration standards consist of a reagent blank [a 1%
solution of 1:1 redistilled HNO3 (+ 1 ml 1000 ppm Ni standard if As, Se)] and
three standard solutions for the method of additions spiking. These usually
range from 5 to 80 ppb and are listed for each element under it's conditions
for analysis listed later in this paper. All are appropriate dilutions of the
1 ppm stock solution in 1% 1:1 redistilled HN03 brought to a final volume of
100 ml, 1 ml of 1000 ppm Ni standard is added if As, Se, are to be analyzed.
e.g.: 1000 ul (1 ml) of stock solution (1 ppm) in 100 ml = 10 ppb.
Note: Eppendorf disposable pipettes are used for all additions. Thorough
shaking to mix the solution is required. Acid is always added to the
volumetrics containing some deionized water first before the nickel or
stock solutions.
Control Standards: For arsenic and selenium analysis a lab control standard
is analysed.
The LCS is spiked with only reagent blank plus the two highest calibration
standards on a 500 ul 1:1 basis.
The spectro might appear as: A least squares fit of the peak height versus
spike concentration would produce a negative concentration value, (see section
on calculation of data). In actuality, negative concentration values are what
one wants, the absolute value is reported.
Lab control standards (LCS) have "known" values
Arsenic: 26 ug/1
Selenium: 26 ug/1
Note: Historical data on the selenium LCS has averaged 19-20 ug/1 after
more than a year of analysis. LCS results are also kept and tabulated,
as statistical analysis on the results will be used later in quality
control.
Instrument Operational and Standardization Instructional Procedures
1. Turn on the PE 056 strip chart power to amp.
Reserve setting to serve until ready to record peaks.
2. Turn on the HGA 2100 Power.
3. Torn on the 503 AA Power.
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-82-
4. Turn on the Supply.
By turning valve from overhead gas columns clockwise, check to make sure
gas is on by opening valve on HGA Power Supply and observing flowrate
setting of 40. Once argon is on, close valve on HGA Power Supply to
save on argon use. Check argon supply before daily run by noting
supply in the mechanical room.
5. Turn on water.
6. Turn on Hollow Cathode or Electrodeless Discharge Lamp {see Table 1 for
Instrumental Settings).
HCL - Set current to lamp at rated amperage
EDL - Set power setting to approximately 1.5 watts below recommended
power setting on lamp.
Note: Once power supply is turned on lamp is not necessarily on.
Lighted match or other source of light if placed in front of
lamp will usually initiate EDL lighting. *
If power control on supply is slowly turned clockwise, meter
may show increase in power to lamp then suddenly increase,
signifying lamp has lit or meter may even decrease at five
below the zero point and then suddenly increase.
By setting lamp 1.5 watts below recommended power setting,
will allow lamp warm-up drift ( .5 watts) until steady
power output is attained (by noting deviation of meter on
503 AA in Reverse Mode).
Althrough still 1 watt below recommended setting, this is at
first acceptable, since at the higher recommended setting
the Deuterium Arc Lamp cannot always balance the energy of the
EDL.
Options - Element of Choice
7. While waiting for the HCL or EDL to warm up 15 minutes and approximately
1.5 hours several instrumental parameters may be set.
8. Slit width
9. HGA 2100 Program
Time for the three segments of cycle
Temperatures
Atomisation time temperature and charring (ashing)
Furnace parameters used in this laboratory are given in Table I.
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-83-
Drying time, temperature and notably charring time are a function of sample
type. A sample with high particulate matter, especially of an organic nature
may be better analyzed if charred for a longer time. Smoke and thus light
scatter will be minimized. The limiting factor is loss of the element of
interest by removing the matrix in which the metal is contained. The list at
end of paper lists time and temperature which provide adequate sensitivity for
routine analysis.
10. Aliquot volume: The AS-1 at present has two pump sizes - 20 ul and 50 ul
The choice of these is based upon the sensitivity required.
11. Strip chart range: Once the lamp (HCL or EDL) is sufficiently stable (EDL's
drift notoriously during warm-up) the following parameters can be set.
Wavelength: With 503 AA in Reverse Mode (observing energy of lamp on AA Energy
meter) adjust wavelength to maximize energy reading.
One may not notice any fluctuation on meter if the meter is on the low end.
Increasing gain until a midscale reading is attained will allow observation
of meter deflection (in Reverse Mode!).*
Lamp Position: Again, we want to maximize the lamp energy reaching the detector.
Remain in Reverse Mode and adjust vertical and horizontal lamp positions until
maximum meter reading is achieved.
Energy Maximization:
A. Set meter needle to fixed reference point on the scale using the gain
control knob while remaining Reverse Mode, (preferably in the green area
of the scale).
B. Release Reverse Mode and adjust Deuterium Arc Lamp energy (now being
observed on the meter, using the push buttons on the D2 lamp power
supply) to the reference point on the scale to which the HCL or EDL
energy had previously been set. This is balancing the sample and back-
ground beams energies.
More often than not, the D2 lamp energy cannot be balanced at the same
level as the EDL or HCL if the EDL, HCL is set at it is recommended
value. This can be rectified in two ways.
a. Decreasing EDL power or HCL current. Note: earlier it was
recommended that the EDL's be set at 1.5 watts below nominal
power setting. After 0.5 watt drift upward, the lamp can
usually be left at this setting and still balance the beam
energies.
b. Sometimes if a high EDL or HCL energy level is desired for
which the D2 lamp energy cannot be balanced, the line source
energy may be set at a reference point within the energy may
be set at a reference point within the energy meter's given
area and the D2 lamp energy set as high as possible. This is
usually necessary when operating with an older lamp which
requires higher energy output to offset baseline noise.
-------
-84-
Note: Be careful not to allow the dark portion of the neutral density
filter into the optical path. This can be checked blocking off
the light from the line source and observing the light from the 02
lamp with the mirror held at the end of the furnace.
C. Points A and B have to be repeated at regular intervals due to drift.
Once the line source reference point is reset and the best effort made
with the 02 lamp, press the Auto Zero to reset the baseline.
There are a few days when the beam energies cannot be balanced; This
should not deter one from analyses. Good results can most readily be
obtained despite minimal D2 lamp capabilities.
13. Mechanics of Analysis
At this point calibration standards have been made, line source (EDL or HCL)
has been warmed-up, the energy of the sample and background beams have been
equalized (or best possible) and the baseline is not drifting severely, or
is extremely noisy (may check by having recorder on servo and switching from
Auto to Manual or HGA Power module). Depending on the type of lamp, to attain
all this may take from 30 minutes (HCL operation) to 1.5 hours (good EDL
operation).
A. Sampler alignment (may be done any time before analysis)
1. With AS-1 Box Power off manually lift sampler arm, bring to
position as if to draw sample and take towards furnace.
2. With supplied mirror placed at right end of furnace observe
if sampler arm easily is placed into furnace without hitting
sides or bottom of graphite tube.
3. If out of alignment, release lock under auto sampler and adjust
position with knobs at end of sampler table.
Also if necessary, adjust depth of sampler arm, see manual on
auto sampler position adjustment for placement of controls.
B. Graphite tubes
1. Graphite tubes are always conditioned before analysis begins.
a. Make sure water and argon is turned on.
b. Condition by performing a high temperature "burn" for
approximately 10 seconds.
2. It never hurts to give older tubes a high temperature "burn"
for a few seconds before analysis either, as the graphite may
be contaminated from the previous day's analyses.
Note: New tubes should be used whenever lead is analyzed, due
to lead contamination.
-------
-85-
C. Furnace blank
1. Be sure recorder is on Servo.
2. Manually press Program button on HGA Power Supply to
initiate a burn cycle with its specified temperatures
and times.
3. If the spectro shows a deflection above baseline (a peak)
run another high temperature burn and repeat furnace blank.
14. Mirrors and Glass
Once a month
1. Photometer windows
2. Furnace end windows
(may require periodic cleaning as sample with smoke tend to
leave particulates).
Less Frequently
1. Mirrors - clean with ethanol plus lens tissue, careful not to
move.
Furnace
1. Graphite tube - change often as needed. Note severe cracking at
spots other than the injection port. Also note the function of
sample volumes used, times and temperatures and frequency of high
temperature burns.
2. Graphite contact rings - rarely need replacement. Good for six
months or better. If lead is continously analyzed, change more
often.
D2 Arc Lamp
If severely bad performance of the T>2 arc lamp is encountered, a service
call is usually necessary. The lamp, the small mirror directly above the
lamp housing, and the adjustable slit (not to be confused with the slit in
the monochrometer housing) may need alignment.
Procedure
Reagent blank plus three calibration standards
1. All samples are run using the method of standard additions, whereby a
sample is spiked with varying concentrations of the element of interest.
-------
-86-
2. Using the 1 oz. plastic cups, for the three calibration standards, place
50 ul of each standard with an Eppendorf pipette into three cups being
careful not to lose any standard from "splashing".
3. Place 500 ul of reagent blank into each cup so that there is a 1:1 spike
performed for each standard.
4. Mix well.
5. Begin injections with the reagent blank alone, then the three spiked
standards.
Assuming the Auto Sampler is being used, place 1 ml of the four solutions
into four 2 ml cups in increasing order of spike concentration. Place the
cups on an empty sample wheel and press the start/stop button on the AS-1
box. It is assumed that the AS-1 box has been powered by pressing the red
Power button and noticing the flashing light in the start/stop button has
gone out.. The flashing takes place while the digital electronics are being
set.
6. The resultant run should appear as shown in Figure 1.
Note the linearity of the peak heights. If "perfectly" linear, with no
reagent blank deflection from baseline, the calculation from plotting
peak height versus spike would produce an intercept of zero indicating
zero concentration for the element of interest in the reagent blank.
Unfortunately, due to variation in peak heights from actual contamination
of glassware, graphite tubes, etc. and/or detector response fluctuation,
we often get a reading of either positive or negative concentration. The
calculated result of "reagent blank concentration" are to be kept for cal-
culation of detection limits (X + o).
where: X - the mean calculated concentration
o - the standard deviation from the mean
7. All samples are analysed as the LCS were - method of additions with reagent
blank plus the two highest calibration standards.
8. Prepare ten samples at a time.
9. Inject 500 ul of reagent blank into the first cup beside each sample.
10. Next inject 500 ul of the next calibration standard into the second cup next
to a sample.
-------
Peak Heights —
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-88-
11. Inject 500 ul of the last calibration standards into the third cup next to
each sample.
These procedures save Eppendorf tips and your time.
12. Shake each sample in turn and inject 500 ul of sample into each of the three
cups next to it.
13. After 10 samples are prepared this way, mix each cup's contents by shaking
or in the case of viscous samples, stir with the Eppendorf pipette with a clean
tip.
14. Fill a sample wheel with the 10 samples (30 cups), place on the turntable, check
again for energy beams being balanced and any other conditions, press start/
stop on AS-1 box to begin analysis.
Quality Control
A field reagent blank and duplicate of one of the ten samples are analyzed.
Data is only good when it passes quality control measures to assure accuracy.
1. Acceptable data are obtained when peak heights are linear within statistical
limits for calibration on stds. as well as real samples.
2. When Lab Control Standards (LCS) - are run with each group of twenty samples
and are within acceptable limits of variation.
3. Duplicates - agreement should be within limits set in Quality Control Manual
(generally within 10%).
Quality Control and Instrument Logbook
In order to properly keep track of samples analyzed, acquire data for statistical
calculation of quality control parameters and keep record of maintenance of the AA,
a QC and Logbook is kept. The book consists of various sections.
Section 1. is completed at the end of each day.
Section 2. is also entered into each day. The frequency at which the analyst
cares to use the running accumulation of data is left to his or her
discretion.
Section 3. is entered only when notable changes in daily opeation service calls
or operator maintenance occurs.
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-89-
Calculations
Each peak height is measured in millimeters. Provided a sample's peak are
proportionally linear a least squares fit program to calculate the concen-
tration may be used.
Graphically, peak heights are plotted as a function of spike concentration (actually
spike plus sample concentration). The negative concentration axis intercept being
the concentration of the sample. The best fit line of the calibration standards
normally intercepts at the (0,0) point. It is the added absorbance of the sample
which changes the negative concentration axis intercept.
A linear least square fit program accomplishes the same calculation and the present
program on the NOVA is:
ID: AAAl
Name: "Flameless"
Results must at present be transcribed from the CRT screen to paper as no hard copy
report is now written.
A data storage file is not included either so that the raw spectra must be saved to
record data at a later date.
References
"The Determination of Antimony, Arsenic, Berylium, Cadmium, Selenium, Lead,
Silver and Tellurium in Environmental Water Samples by Flameless Atomic
Absorption", Metals Section, United States Environmental Protection Agency,
Region V, Central Regional Laboratory, Chicago, Illinois, (unpublished).
-------
-89A-
Table I
Instrumental Settings For the Determination
of Arsenic, Antimony, Selenium and Thallium
Wavelength, NM
Bandpath, nm
EDL Power, W
Hollow Cathode Lamp, Current
Drying Temp. °C (Time, sec.)
Charring Temp., °C (Time, sec.) 1000(40)
Atomize Temp., °C (Time, sec.) 2700(5)
Argon Gas Flow, ml/min
As
193.7
0.7
8
125(60)
000(40)
700(5)
50
Sb
217.6
0.2
8
125(60)
1000(40)
2200(5)
50
Se
196.0
0.7
6
125(60)
1000(40)
2700(3)
50
Tl
276.8
0.7
20
mil li amps
175(40)
400(40)
2100(8)
40
( interrupt )
-------
-90-
Determination of Phenols in Sediments
and Other Solids
CKL Method 417
Scope and Application
This method is applicable to the determination of phenolic compounds
(except paracresols and similar parasubstituted phenols) in sediments
and other solids.
Summary of Method
Phenolic compounds are manually distilled to remove interferences.
The distillate reacts with buffered ferricyanide and 4 aminoantipyrine
spectrophotometrically at 505 nm. An automated system is used for the
color development and measurement.
Equipment «
Distillation apparatus, consisting of a 500 Pyrex flat-bottom distilling
flask and a Graham condenser.
250 ml or 500 ml Erlenmeyer flasks calibrated at 200 ml.
Technicon Autoanalyzer II System (See CRL Method 408, Attached)
Analytical Balance
Heating Mantles or Burners
Reagents
CuSO4/H3PO4 Solution, 5%
10% H2S04
Other Reagents - See CRL Method 408 (Attached)
Procedure
1. Steam out the distillation flasks before each use by boiling
distilled water in the flasks without water running through
the condenser.
2. Weigh accurately 1 to 2 grams of wet, well-mixed sediment.
-------
-91-
3. Transfer to the distillation flask.
4. Add 100 ml of distilled water and 2 ml of 5% CuS04/H3PC>4 solution.
5. Distill 100 ml of sample (20-35 ml of distilled water may be added
to assure distillation of 100 ml of sample into the erlenmyer flask) .
6. Add 1 ml of 10% H2SC>4 and proceed with analysis using CRL Method
No. 408. (Samples may be stored at 4°C for a maximum of three
weeks if necessary) .
Quality Control
A field blank which contains CuSC>4/H3PO4, one or more standards and a
duplicate of one of the samples, are analyzed with each group of samples.
If twenty or more samples are analyzed, a minimum of two field blanks,
standards and duplicates are analyzed.
The analytical balance is set to zero before each sample is weighed.
The manufacturers instructions are followed for operation of the
Technicon Autoanalyzer .
Calculation
mg/kg Phenol (dry basis) = reading in ug/1 x 1000 from Method 408 x 100 _
(orig. wt. in grains) x decimal fraction of % solids
References
1. "Manual of Methods for Chemical Analysis of Water and Wastes",
United States Environmental Protection Agency, Office of
Technology Transfer, 1974, Washington, DC, p. 241-242.
-------
-92-
Determination of Phenol in
Water and Wastewater ^
(Automated 4-AAP Method With Manual Distillation)
CKL Method No. 408
Scope and Application
This method is applicable to drinking, surface, saline, domestic and industrial
waste waters.
Summary of Method
Phenolic compounds are manually distilled to remove interfering substances. The
distillate reacts with buffered ferricyanide and 4-aminoantipyrine to form a red
complex which is measured spectrophotometrically at 505 nm. An automated system
is used for the color development and spectrophotometric measurements.
Interferences
Interferences from sulfur compounds are eliminated at the time of collection by
acidifying the samples to a pH of less than 4 with H3PO4 and adding Cu 804.
If residual chlorine is present it is removed by the addition of an excess of
NaAsC>2 to reduce the chlorine prior to distillation.
All other interferences are eliminated or minimized by the distillation procedure.
Sample Handling and Preservation
New polyethylene bottles are used for sample collection. (Caps must not contain
phenolic resin).
Samples are preserved with 20 ml of a solution containing 50 g CuSO4.5H20 and 50 ml
H3PO4 per liter of sample.
Samples are stored at 4°C.
Apparatus
Distillation apparatus, consisting of a 500 ml Pyrex flat-bottom distilling flask
and a Graham condenser.
250 or 500 ml erlenmeyer flasks calibrated at 200 ml.
Technicon Auto Analyzer II (3)
Sampler IV
Pump III
Phenol Cartridge
-------
-93-
Colorimeter containing 50 mm flowcells and 505 nm filters.
Recorder
Di gi t al Pr in ter.
Reagents
CuSO4 preservative: Dissolve 50 g of CaSO^.S^O and 50 ml of H3PO4 in distilled
water and dilute to 1 liter. (Use 20 ml/1 sample).
H2 304 preservative: Add 100 ml cone H2 SO4 to 800 ml of distilled water and dilute
to 1 liter. (Use 10 ml/1 sample).
Stock phenol solution: Dissolve 1.00 g of reagent grade phenol in distilled water.
Add 10 ml of H2 SO4 preservative and dilute to 1 liter. (1 ml = 1000 ug). Store at
4°C.
Intermediate phenol solution: Dilute 10 ml of stock phenol solution to 100 ml with
distilled water (1 ml = 100 ug). Prepare fresh daily.
Working phenol standards: Dilute 0, 0.50, 1.00, and 2.00 ml of intermediate phenol
solution to 1 liter with distilled water for blank, 50, 100 and 200 ug/1 phenol
standards.
NOTE: These standards should be preserved with Cu SO4 preservative solution if
they are to be distilled. They should be preserved with H2S04 preservative solution
if they are to be used for instrument calibration.
Ammonia buffer: Dissolve 50 g of NH4 Cl in about 900 ml distilled water. Adjust the
pH to 10.1 using NH4OH. Dilute to 1 liter.
In NaOH: Dissolve 40 g of NaOH in distilled water and dilute to 1 liter.
Potassium ferricyanide solution: Add to 800 ml of distilled water, 2.0 g of K3 Fe(CN)6,
3.75 g of KCl and 44 ml of IN NaOH. Dissolve and dilute to 1 liter. Adjust the pH to
10.1 and add 0.5 ml of Brij-35. Store at 4°C. Filter before each use.
4-aminoantipyrine: Dissolve 0.65 g of 4-aminoatipyrine in distilled water and dilute
to 1 liter. Store at 4°C. Filter before each use.
Sampler wash solution: Dilute 10 ml of H2 SO4 preservative to 1 liter using distilled
water.
-------
-94-
Procedure
Distillation
Steam out the distillation flasks before each use by boiling distilled water in the
flasks with the condenser water off.
Using a graduate, measure 200 ml of sample into each distilling flask. Also measure
out one blank, one standard, and one duplicate for each run. Add 35 ml of distilled
water to each flask.
Distill 200 ml of sample into calibrated erlenmeyer flasks or bottles. Add 2 ml of
H2 804 preservative. The samples may be stored at 4°C for future analysis for a
minimum of three weeks or longer.
Spectrophotometric Analysis
Set up the Technicon AA-II system as indicated in the diagram.
Calibrate the system using standards containing 200, 100, 50 and 0 ug phenol/1.
Also analyze control standards CS1 and CS2 (See paragraph 2 under Quality Control).
Analyze the distilled samples, blanks and duplicates.
Detection Limit
The detection limit is 5 ug phenol/1.
Quality Control
One standard, one blank, and one duplicate are distilled with each sample set.
After calibration of the analytical system, 2 control standards are run. They
must be within control limits if the data is used. Results are recorded in the
AQC book.
The date of preparation of reagents and standards is recorded in the AQC book.
Calculations
The concentration of phenol in ug/1 is obtained directly from the digital printer.
-------
-95-
References
1. "Standard Methods for the Examination of Water and Wastewater", 14th ed.,
American Public Health Association, New York, N.Y., 1975, p. 574.
2. "Manual of Methods for Chemical Analysis of Water and Wastes", U.S.
Environmental Protection Agency, Cincinnati, OH, 1974, p. 241.
3. Industrial Method No. 127-71W, Technicon Industrial Systems, Tarrytown,
N.Y., 1972.
4. Carter, M.J. and Huston, M.T., "Preservation of Phenolic Compounds in
Wastewaters" (unpublished), U.S. Environmental Protection Agency, CRL,
Chicago, IL, 1977.
-------
PHENOL MANIFOLD
RECORDER
PRINTER
RANGE 400
TO SAMPLER
WASTE
157-B089-01
20TC
COLORIMETER TO PUMP
505 NM
50 MM F/C
1.5 MM ID
199 - B023-01
WASTE
SAMPLER
40/HR
6:1
(3.40) WASH
(0.32) AIR
jj 116-0489-01 G001-01 (1.20) SAMPLE
, ^ TO PUMP
WASTE ^ .(0.23) DEBUBBLER
(0.23) BUFFER
(0.23) 4AAP
(0.23) FERRICYANIl
(1.00) FROM F/C
-------
\
vO
•-J
I
-------
-98-
Determination of Phenols in Water
Automated Distillation and Automated Colorimetry
CRL Method 414
Scope and Application
This method is applicable to the determination of phenolic compounds (except
paracresols and similar parasubstituted phenols) in lake, surface, waters,
elutriates and other water mediums which are not governed by the National
Pollution Discharge Elimination System.
Summary of Method
Phenolic compounds are distilled on the autoananlyzer at 150°C to remove
interferences. The distillate reacts with buffered ferricyanide and 4-
aminoantipyrine spectrophotometrically at 505 nm. An automated system is
used for color development and measurement. This method involves the
determination of phenols in the ranges of 30-200 ug/1 using a completely
automated system.
Equipment
Techicon Auto Analyzer II
Sampler IV
Pump II
Phenol Cartridge
Heating Bath With Distillation Coil
Colorimeter With 50 mm Flow Cells and 505 nm Filters
Recorder
Digital Printer
Reagents
Distillation Reagent (Techicon No. T01-5017)
Phosphoric Acid, 85% (H3PO4) 100 ml
Distilled water, q.s. 1000 ml
Preparation: Carefully add 100 ml of phosphoric acid to 700 ml of distilled water.
Dilute to one liter with distilled water.
Buffered Modified Potassium Ferricyanide 2.0
Potassium Ferricyanide (K3Fe(CN)g) 1.0 g
Boric Acid (113603) 3.1 g
Potassium Chloride (KC1) 3.75 g
Sodium Hydroxide, IN (NaOH) 44 ml
Distilled Water, q.s. 1000 ml
Brij-35* (Technicon No. T21-0110) 0.5 ml
Preparation: Add to 800 ml of distilled water, 2.0 g of potassium ferricyanide,
3.1 g of boric acid, 3.75 g of potassium chloride and 44 ml of IN sodium
hydroxide, Dissolve and dilute to one liter with distilled water. Adjust
the pH to 10.1 and add 0.5 ml of Brij-35.
-------
-99-
4-Aminoantipyrine (Technicon No. Tll-0021)
4-Aminoantipyrine 0.65 g
(CH3NN(C6H5)COC(NH2) :CCH3)
Distilled Water, q.s. 1000 ml
Preparation: Dissolve 0.65 of 4-aminoantipyrine in 800 ml of distilled water.
Distilled water.
Standards
Stock Standard A, 100 mg/1
Phenol (C6H5OH) 0.100 g
Hydrochloric Acid, 0.05N, q.s 1000 ml
Preparation: Transfer into a one liter volumetric flask 0.100 g of phenol.
Use 0.05N hydrochloric acid to assist in the transfer and mix until dissolved.
Dilute to volume with 0.0 5N hydrochloric acid.
Stock Standard B, 10 mg/1
Dilute 100 ml of Stock A to one liter with distilled water.
Working Standards
ml Stock B ug/1
1 100
2 200
3 50
Preparation: Pipette stock B into a 100 ml volumetric flask and dilute to
volume with distilled water.
Note: The stock standard B and the working standards are not stable and
should be prepared fresh twice daily.
Procedure
1. Following sample arrival, unpreserved samples should be preserved with
1 ml per liter concentrated sulfuric acid (H2SO4) if analysis is not to
begin immediately.
2. Fill the Technicon Sampler IV cups with sample (usually 8 to 10 ml), blank
and working standards ranging from 30 to 200 ug/1.
3. Use a wash cycle containing 1 ml H2SC>4 per liter.
4. Set the temperature of the heating bath to 150 °C.
-------
-100-
5. Adjust the flow of cooling water through the distillation apparatus to
approximately 750 ml per minute at 14°C (See Technicon Publication Number
TA 1-0213-00 for distillation head operating instructions).
6. Before running the method, position the controls of the Modular Printer as
follows:
Control Position
Mode Swith Normal
Sampling Rate Switch 30
Range Swith 200
Decimal Switch 000
For details of Modular Printer Operation see Technicon Publication Number
TA1-0278-10.
7. If necessary, alternate ranges may be obtained by utilization of the
Std. Cal. control on the colorimeter.
8. The use of multiple working standards is only to establish linearity.
For day to day operation, the 200 ug/1 standard is recommended for
instrument calibration.
9. After calibration, two control standards (separate from calibration
standards) are also analyzed.
Quality Control
A field reagent blank and duplicate of one of the samples are analyzed with
each group of samples. If twenty or more samples are analyzed, a minimum of
two blanks and duplicates are analyzed.
The two control standards are re-analyzed along with a duplicate sample each
hour. Data is only acceptable when the control samples and duplicates are
within the control limits. Results are recorded in the AQC logbook.
The date of preparation of all reagents and standards are recorded in the AQC
book. The Technicon Manufacturer's instruction are followed at all times as well
as the daily readings of the calibration controls.
Calculations
ug/1 Phenol = Reading from the printer in ug/1, times any dilution factor(s)
applicable.
-------
-101-
References
1. "Technicon Industrial Method Number 127-71W", Technicon Industrial System,
Tarrytown, New York, October 1972.
2. Carter, Mark J., Huston, Madeleine T., "Preservation of Phenolic Compounds
in Wastewaters", (Unpublished), Unites States Environmental Protection Agency,
Region V, Central Regional Laboratory, Chicago, Illinois, 1977.
-------
-102-
PHENOL
(Range: 0-500 ,,g/l)
MANIFOLD NO. 116-0115-01
PRE-DILUTION NO. 116-B214-03
HEATING BATH WITH
DISTILLATION COIL
183-B010-01
To Sampler IV
Wash Receptacle
194-8005-02
ECO
PUR/ORN (3.40) WATER
BLK/BLK (0.32) AIR
(2.00) SAMPLE
\ 116-0489-OlVoRN/ORN (0.42) DISTILLATION REAGENT
Waste—£5—Q
ORN/ORN (0.42)
J3t^-
^^
20 Turns Y/aste-
157-BOS9-01
000
pjYEL/YELfl^O)
^BLK/BLK (0.32) AIR
1 XGRY/GRY d.co) RESAMPLE
A2
1 116-0489-01 X°RN/t''HT (0-23) 4-A.MINOANTIPYRINE
i i
COLORIMETER 1
505 nm W *•*•-
50 mm F/C x 1
1.5 mm ID To f/C
199-B023-01 PumP
Tube
XORN/WHT (0.23) BUFFERED POTASSIUM FERRICYANIDE
_ XGRY/GRY (1-00) FROM F/C
^ L^ "•" — —
NOTE: FIGURES IN PARENTHESES SIGNIFY
FLOW RATES IN ML/MIN.
•irci _c /ocroicnreoeri -^c* Ar\t*i A ov r*er ^t« /-*rs \
**.100 ACIDFLEX
»**.034 POLYETHYLENE
TECHNICON INDUSTRIAL SYSTEMS/TARRYTOWN. NEW YORK 10591
A DIVISION OF TECHNICON INSTRUMENTS CORPORATION
-------
-103-
Analysis of Sediments and
Other Solids for Oil and Grease
CRL Method Number 739
Scope and Application
This method is applicable to the measurement of freon extractable matter
from sediments, sludges and other solids which contain relatively non-
volatile hydrocarbons, vegetable oils, animal fats, soaps, waxes, greases
and related compounds.
This method is not applicable to the measurement of light hydrocarbons
that volatilize at temperatures below 70°C. Petroleum fuels from gasoline
through #2 fuel oil are completely or substantially lost in the solvent
extraction process.
This method is applicable in the range from 650 mg/kg to 100,000 mg/kg.
Summary of Method
The acidified sediment or solid sample is dried with magnesium sulfate
monohydrate (avoid heating, which gives low results) and extracted with
freon in a soxhlet apparatus for 4 hours.
Equipment
Extraction apparatus, soxhlet.
Vacuum pump or other source of vacuum.
Extraction thimble, paper.
Reagents
a. Hydrochloric acid, HC1, cone.
b. Magnesium sulfate monohydrate: Prepare MgSO4H2O overnight
c. Freon (l,l,2-trichloro-l,2,2,-trifluoroethan), boiling point
47°C. The solvent should leave no measurable residue on
evaporation; distill if necessary.
d. Grease-free cotton: Extract non-absorbent cotton with freon.
Procedure
In a 150 ml beaker weigh a sample of wet sludge, 20 + 0.5 g of which the
dry-solids content is known. Acidify to pH 2.0 (generally, 0.3 ml cone
HCl is sufficient). Add 25 g MgSO4H20. Stir to a smooth paste and spread
on the sides of the beaker to facilitate subsequent removal. Allow to stand
until solidified, 15 to 30 min. Remove the solids and grind in a porcelain
mortar. Add the powder to a paper extraction thimble. Wipe the beaker and
mortar with small pieces of filter paper moistened with freon and add to the
-------
-104-
thimble. Fill the thimble with glass wool or small glass beads. Extract
in a Soxhlet apparatus, using freon, at a rate of 20 cycles/hr for 4 hours.
If any turbidity of suspended matter is present in the extraction flask,
remove by filtering through grease-free cotton into another weighed flask.
Rinse flask and cotton with freon. Distill the solvent from the extraction
flask in water at 70°C. Place the flask on a warm steam bath for 15
minutes and draw air through the flask by means of an applied vacuum for
the final one minute. Cool in a desiccator for exactly 30 minutes and weigh.
Quality Control
One blank and one duplicate of one of the sediments are analyzed with each
group of samples. If twenty or more samples are analyzed, a minimum of
two duplicates are analyzed.
The analytical balance is calibrated and set at zero before each sample is
weighed.
Calculations
Grease and oil as % dry solids
= gain in weight of flask, g x 100
wt. of wet solids, g x % dry solids
REFERENCES
1. Standard Methods for the Examination of Water and Wastes, 14th ed.,
1975 APHA-AWWA-WPCF, pp. 519-520.
2. EPA Manual, "Methods for Chemical Analysis of Water and Wastes" 1974
Office of Technology Transfer, Wash., D.C., pp. 226-228.
-------
-105-
The Elutriate Test for the Analysis of
Metals, Mercury, Cyanide, TKN, Total
Phosphorus, Ammonia and COD
CRL Method No. 305
Scope and Application
This procedure is an estimate of the amounts of chemical substances which
are exchanged (on a worst-case basis) when a sample of dredged sediment
is shaken with four parts water collected near the sediment.
Summary of Method
One part of the wet sediment is added to four parts of process water
followed by mechanical shaking for 30 minutes at maximum speed. Following
one hour settling, the supernatant solution is centrifuged for 30 minutes,
filtered through a pre-washed 0.45 micron membrane filter, transferred to
a 12 ounce bottle and distributed to different sections of the laboratory
for analysis of metals, mercury, cyanide and nutrients.
Equipment
Plastic bottles (12 02 and 2 oz)
Burrell Fast Oscillating Mechanical Shaker
Analytical Balance
Plastic Centrifuge Bottle
Reagents
See individual water procedures cited earlier in this manual.
Procedure
1. Place 50 ml of the wet well-mixed sediment sample and 200 ml of
process water from the same area into a capped shaking bottle.
2. This mixture is shaken on the Burrell Mechanical Shaker for 1/2 hour
at maximum speed.
3. Settle for 1 hour and pour approximately 200 ml of sample solution
into a conical plastic centrifuge bottle.
4. Centrifuge at 15,000 RPM for 1/2 hour.
5. Filter through a pre-washed millipore 0.45 micron filter and transfer
to a 360 ml plastic bottle.
6. Pour approximately 50 ml of sample into each of four 2 ounce
(60 ml) bottles.
7. Preserve as follows:
-------
-106-
Analysis Preservative
bottle 1 Metals 500 Lamda (A) (0.5 ml) of 8N HNO3
bottle 2 Cyanide 500 Lamda (70 (0.5 ml) of IN NaOH
bottle 3 Mercury 500 Lamda (TO (0.5 ml) of 2.5%
solution
bottle 4 Nutrients 300 Lamda (71) (0.3 ml) of 50% H2S04
'(COD, TKN, TP, NH3)
8. Following are the analysis procedures which are used for the parameters.
These are the same procedures which are attached to CRL sediment procedures
for Metals, Mercury, COD, TKN, TP and Ammonia. The completely automated
cyanide procedure is only used for elutriates, not for sediments, (See CRL
Method Number 357).
Metals - CRL Method Nos. 600, 603, 606 - Arsenic, selenium and antimony
by flameless atomic absorption.
Metals - CRL Method Nos. 504 - 570 - plasma metals b ICAP (22 metals)
Cyanide - CRL Method No. 357 - Total cyanide, automated distillation
and colorimetry, (See pages 32-35 of this manual).
Ammonia - CRL Method No. 312 - Automated phenate method.
TKN/TP - CRL Method No. 465 (micro kjeldahl digestions followed by
automated phenate).
COD - CRL Method No. 342 - automated colorimetric.
9. The process water sample should be filtered, if necessary through a
pre-washed, acid rinsed 0.45 micron filter.
10. It is then preserved according to the procedures in step 7 above or
analyzed immediately using the procedures cited in step 8 above.
Quality Assurance
A blank and duplicate are analyzed with each group of samples. If twenty
or more samples are analyzed 2 blanks and 2 duplicates are analyzed.
The balance is set to zero before and after each sample is weighed.
The manufacturers instructions are followed for all instruments.
Calculations
Same as for water. See individual method calculations.
-------
-107-
REFERENCE
Ecological Evaluation of Proposed Discharge of Dredged or Fill Material
into Navigable Waters, Interim Guidance for Implementation of Section 404
(b) (c) of Public Law 92-500 (Federal Water Pollution Control Act
Amendment of 1972), Environmental Effects Laboratory, U.S. Army Engineer
Waterways, Vicksburg, Mississippi, May 1976, Appendix A, pp. Al to A7.
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-108-
METHOD FOR ANALYSES OF PCB'S, PESTICIDES
AND PHTHALATES IN SOILS AND BOTTOM SEDIMENTS
CKL METHOD NOS. 198 THRU 207
Scope and Application
The adsorption of chlorinated hydrocarbons on soils and muds is well docu-
mented. This procedure incorporates the recommendations of the Environ-
mental Protection Agency's National Research Centers ^-"^ to include the
analyses of 25 pesticides, 2 phthalate esters and 4 polychlorinated biphenols
(PCB) in mixtures. These are listed in Table I with their limits of
detection. This method is recommended for use only by persons experienced
in chromatographic analyses. The mention of trade names or commercial
products here is for illustrative purposes only and does not constitute an
endorsement for use by the Environmental Protection Agency.
Summary of Method
The soil or sediment sample is partially dried, sieved to 20-60 mesh, and
extracted for 16 hours by soxhlet extraction with a mixture of 1:1 acetone/
hexane (v:v). The extract is then concentrated, partitioned thru florisil
and/or silicic acid as necessary for elimination of interferences and separation
of various pesticide mixtures. Quantitative determination is affected via gas
liquid chromatography employing electron capture or electrolytic conductivity
detection and two or more unlike columns. Results are reported in milligrams
per kilogram.
Interferences
The most common interference encountered with soil and sediment samples is
sulfur. This interference can mask a major portion of the gas chromatogram.
A method blank is required to monitor various possible contaminants in
reagents and apparatus.
Apparatus and Materials
1. That outlined in the "Combined Method for Analysis of Pesticides, PCB's
and Phthalates in Aqueous Media". 6
2. Evaporating dishes - pyrex, 80 x 45 mm.
3. Oven-drying - 105°C.
4. Muffle furnace. 51 x 40 x 51 cm chamber size 66 - 1000°C temp range.
5. Desiccator.
6. Soxhlet extraction apparatus capable of holding cellulose extraction
thimbles of 33 x 80 mm.
-------
-109-
7. Distilled water, suitable for pesticide residue analysis.
8. Aluminum pans - approximately 9 x 12 x 2".
9. Aluminum foil.
10. Glass wool.
11. Sieves - meeting ASTM specification for 20 and 60 mesh size.
Procedures
1. Transfer the sediment into an aluminum pan and spread it to dry over
a period of 1-4 days in a fume hood at ambient temperature. Pulver-
ize sediment after drying, using a mortar and pestle.
2. As the final calculations will be made on a dry weight basis, the
inorganic section will determine the percentage of total solids
in each smaple using CRL Method No. 444, and provide the results
to the Organic section.
3. Transfer the air dried sediment into a soxhlet apparatus between two
layers of glass wool. The glass wool should be pre-extracted for 16
hours with 1:1 acetone/hexane (v:v). Extract the sample for 16
hours with 1:1 acetone/hexane (v:v).
4. Concentrate the extract to approximately 5 ml with a Kuderna Danish
apparatus. Remove tube, rinsing joint with n-hexane.
5. The sample is now ready for initial gas chromatographic screening. This
is conducted as described in the corresponding section for analysis of
aqueous media. Colored material usually indicates necessity for florisil
chromatography.
6. Interference appearing as peaks for high background as well as the general
appearance and a knowledge of the sample source will determine whether
treatment of the sample to remove chemical interference (commonly known
as sample clean-up) is required. When these interfere with parameter
measurement or pose a threat to gas chromatographic column life or detector
sensitivity, proceed to section entitled, "Florisil Chromatography in Procedure
for Aqueous Media".
-------
-110-
Quality Control
1. Reagent blank - Beginning with the sample container a reagent blank
is run with each set of 20 or fewer samples. The control limits are
the detection limits listed in Table I listed below.
2. Duplicate and Spiked Samples - One sample is selected from each of
20 or fewer samples and divided into four aliquots after drying and
mixing. Two of the four aliquots are spiked with an acetone solution
(enough to wet the entire sample) containing approximately 10 ppm
concentrations of the compounds of interest and the acetone is
evaporated. All aliquots are then analyzed as real samples. The
control limits are as follows: For duplicate analysis the relative
percent difference (CRPD) should be less than 50% at an average
concentration of 3x the above detection limit. The spike recovery
should be calculated or described in appendix 1 of the CRL QC Manual
and should be between 50 and 120%.
3. Each time a set of samples is run an extraction apparatus is charged with
glass wool for a method blank.
Calculations
2. concentration of Pesticide and Phthalate components in sediments. The
weight (ug) of sample per unit volume of extract (ml) is calculated by
comparing peak areas of the sample chromatogram with that of a standard.
This is accomplished with the aid of a gas chromatographic data system. 7
milligram/kg (A) (B) (V )
E
(Ws) 1000
A = nanogram standard injected = ng
* * —*-~
standard peak area mm"
2
B = sample peack area = mm'1
VI = volume of sample injected (ul)
VE = volume of sediment extract (ul)
from which sample was injected
Ws = weight in kg of sediment sample
3. Concentration of PCB's as Aroclor® mixtures in sediments.8
A. When a simple Aroclor is present, the Aroclor® reference standards
are compared to the sample. The areas of the unknown and correspond-
ing the reference Aroclor are measured with the aid of a gas chromato-
graphic data system. At least five peaks and the ratios are used to
calculate the Aroclor concentration in the following manner:
-------
-111-
n
mg = (Z Ai) CL) (concentration of standard)
(i=l Bi) (n) ( in jjg per ml )
(final volume ) ( 1 ) (% solids)
(of extract in ml ) (sample in gm) ( 100 )
where: Ai = area of sample peak
Bi = area of corresponding standard peak
n = the number of peaks compared
B. For complex situations, the sample chromatogram is compared to
each Aroclor® standard and a portion of the chromatogram is
assigned to areas in which each of the Aroclors® predominate.
The concentration of each PCB mixture in the sample is calculated
using the major peaks in the region after peak areas from the
interfering mixtures are factored out.
-------
-112-
TABLE I
Limits of Detection for PCB's, Pesticides and Phthalates
Compound Detection Limit (mg/kg)
2,4-D-isopropyl ester 5
di-n-butyl-phthalate 10
DCPA 2
Endosulfan I 2
Dieldrin 2
Endrin 3
Endosulfan II 2
di-2-ethylhexyl phthalate 10
Tetradefon 10
Treflan 2
Hexachlorobenzene 2
Lindane 2
beta-BHC 1
Heptachlor 1
Aldrin 1
Zytron 2
Isodrin 2
Heptachlor epoxide 2
gamma-chlordane 2
o,pJ_DDE 2
£,pj_DDE 1
o,pj_DDD 1
o,p_M3DT 3
£,p_M3DD 3
p_,£j_DDT 3
Mirex 3
Methoxychlor 5
Arochlor 1242 2
Arochlor 1248 2
Arochlor 1254 2
Arochlor 1260 2
These limits of detection must be demonstrated for the matrix of interest
to be meaningful. The procedure for this is found in the section on
Quality Control in Part I.
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-113-
QUALITY ASSURANCE
PESTICIDES, PCB'S AND PHTHALATES IN SEDIMENT SAMPLES
1. Reagent blank - Beginning with the sample container a reagent blank
is run with each set of 20 or fewer samples. The control limits are
the detection limits listed in Table I above.
2. Duplicate and Spiked Samples - One sample is selected from each of
20 or fewer sample and divided into four aliquots after drying and
mixing. Two of the four aliquots are spiked with an acetone solution
(enough to wet the entire sample) containing approximately 10 ppm
concentrations of the compounds of interest and the acetone is evaporated.
All aliquots are then analyzed as real samples. The control limits are
as follows: For duplicate analysis the relative percent difference
(CRPD) should be less than 50% at an average concentration of 3x the
above detection limit. The spike recovery should be calculated or
described in appendix 1 of the CRL QC Manual and should be between
50 and 120%.
-------
-114-
AQC SUMMARY SEDIMENTS
Parameter Spike Level Average %
(mg/kg) Recovery
Aroclor® 1254 5 87
Tatradefon 5 55
Di-n-butyl phthalate 8 83
p,p'-DDT 5 74
Endosulfan II 5 71
p,p'-DDD 20 68
o,p'-DDT 3 74
Gamma Chlordane 4 85
p,p'-DDD 10 68
Endrin 3 67
o,p'-DDD 10 74
Dieldrin 10 72
Endosulfan I 10 73
o,p'-DDE 10 113
Heptachlor Epoxide 3 86
DCPA 6 70
di-ethylhexyl phthalate 20 78
Beta BHC 1 98
Lindane 3 77
2,4-D-isopropyl ester 10 101
Treflan 5 79
Aldrin 2 78
p,p'-DDE 3 80
Mirex 5 78
Isodrin 2 77
Heptaclor 1 89
Hexachlorobenzene 1 79
-------
-115-
REFERENCES
1. L.E. Furguson, J.L. Ludbe, J.P. Wood, and J.W. Prather,
J. Miss. Acad. Sci., 11, 219 (1965).
2. G.W. Barley and J.L. White, J. Agr. Food Chem., 12, 324 (1964).
3. M.W. Poirrier, B.R. Bordelon, J.L« Laseter, Environ, Sci and
Technol. 6, 1033 (1972).
4. "Analysis of Pesticide Residue in Human and Environmental Samples"
Environmental Protection Agency, Research Triangle Park, M.C. (1974).
5. T.A. Bellar and J.J. Lichtenberg, "Some Factors Affecting the
Recovery of Polychlorinated Biphenyl from Water and Bottom Samples"
presented at the symposium on Water Quality Parameters, Burlington,
Ontario, Nov. 1973.
6. This procedure is adapted from:
a. Methods for Organic Pesticides in Water and Wastewater 1971 and
EPA publications appeared in Federal Register 38, 2758 (1973).
b. Analysis of Pesticide Residues in Human and Environmental Samples, 1974.
7. J.H. Johnson, E.E. Sturino and S. Bourne, J. Environ. Sc; Health
All. Sci. Eng. 2_, 165 (1976).
8. R.G. Webb and A.C. McCall, J. Chromatogr. Sci., 11, 366 (1973).
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-116-
PCB's PESTICIDES AND PHTHALATES
IN AQUEOUS MEDIA
CRL Method Nos. 144 to 183, 651 to 732 and 210 to 219
Introduction
The procedure is based on Methods for Organic Pesticides in Water and
Wastewatefj 1971 and EPA Publications from the National Environmental
Research Centers.1'2 This procedure differs from the referenced proce-
dures in that the gas chromatographic step has been automated, and it
has been expanded to include 44 pesticides, 5 PCB mixtures, and two
phthalate esters. These parameters are listed in Table I along with
their limits of detection in micrograms per liter. This method is
recommended for use only by persons experienced in chromatographic
analysis. The mention of trade names or commercial products here is
for illustrative purposes and does not constitute an endorsement for
use by the U.S. Environmental Protection Agency.
Summary
The procedure describes an effective co-solvent for efficient sample
extraction. Elimination of non-pesticide interferences and separation of
pesticide mixtures is accomplished with liquid column chromatography1
(see Chart I). Qualitative and Quantitative determination is effected
via gas liquid chromatography using electron capture and flame photometric
detectors and two or more unlike columns. Results are reported in micro-
grams per liter.
Interferences
The analyst must be vigilant for contaminants in solvents, reagents,
glassware, and other apparatus that comes in contact with samples as
they will yield discrete erroneous artifacts in gas chromatograms. As it
is not possible to describe all interferences which may be encountered in
residue analysis, a method blank described herein is used to monitor inter-
ferences.
-------
-117-
Apparatus and Materials
1. Gas Chromatograph equipped with:
a) glass lined injection port
b) electron capture detector
c) flame photometric detector (phosphorous mode)
d) potentiometric strip chart recorder compatible with detectors
2. Gas Chromatographic Materials:
a) tubing - pyrex (81 x 4mm ID)
b) glass wool - salanized
c) solid support - supelcoport (100-120 mesh)
d) liquid phases - expressed as weight percent of solid support:
i) 1.95% SP2250/1.5% SP2401
ii) 4% SE30/6% SP2401
3. Kuderna Danish Glassware:
a) synder columns - three ball
b) evaporative flasks - 500 ml
c) receiver ampule - 10 ml, graduated
d) ampule stoppers
4. Chroma tographic Columns:
Kontes or Ace 400 mm long x 10 mm ID with coarse fritted disc at
bottom and teflon stopcock, 250 ml reservoir bulb at top of column
(Kuderna Danish 250 ml evaporative flask).
5. Capillary pipets disposable (5 3/4 in.) with rubber bulb
6. Beakers, 100 ml and 500 ml
7. Erlenmeyers - 300 ml
8. Micro syringes - 10, 25, and 50 yl
9. Separatory funnel with teflon stopcocks, centrifuge tubes - 15 ml
graduated, Erlenmeyer flasks - 125 ml and 3000 ml, 300 ml glass
stoppered bottle
10. Graduated cylinders - 10 ml, 250 ml, and 1000 ml
11. Florisil - PR grade (60-100 mesh), purchase activated at 1250 F and
store with glass stoppers or foil lined screw caps. Before use, activate
each batch for 4 hrs at 450°C in foil-covered glass container. Deter-
mine elution pattern with parameters of interest before use with samples.
-------
-118-
12. Silica gel - Davidson code 950-08-08-226 (60/80 mesh) or
Bio Rad - Bio Sil A (100/200 mesh)
13. Culture tubes, 16 x 125 mm screw cap culture tubes, borosilicate glass
with teflon-lined screw caps, 14 centrifuge tubes, 15 ml with teflon-
lined screw caps
Reagents, Solvents, and Standards
1. Sodium sulfate - (ACS) granular, anhydrous, conditioned for 4 hours
at 600°C
2. Sulfuric acid - reagent grade - 50% in distilled water
3. Sodium hydroxide solution - reagent grade 10 molar in distilled water
4. Diethyl ether - Nanograde, redistilled in glass, peroxide-free
n-Hexane - pesticide quality (not mixed hexanes)
Acetonitrite & methylene chloride, pesticide quality distilled in glass
5. Pesticide standards - those listed in Table I
Sampling
A. Sample Containers: ' Aqueous samples are collected in clean 1-liter
narrow mouth glass quart bottles. The molded screw cap must have a
teflon liner. Wide mouth glass jars are employed for mud samples.
The caps are lined with aluminum foil previously washed with acetone
and hexane.
B. Sample Collection: Surface water grab samples are taken by immersing
the container and allowing it to fill up. A 500 gm sample of sediment
is sealed in the above mentioned wide mouth jar.
C. Storage: Samples are extracted as soon as possible after collection,
usually within two weeks.
Sample Preparation
1. Blend the sample if suspended matter is present. If organophosphate
pesticides are to be measured, adjust pH to near neutral (pH 6.5-7.5)
with 50% sulfuric acid or 10 normal sodium hydroxide.
2. Quantitatively transfer the sample into a two-liter separatory funnel.
-------
-119-
Extraction
1. Add 60 ml of 15% methylene chloride in n_-hexane (VrV) to the sample
container, replace cap, shake for 1 minute, and pour the contents into
the separatory funnel.
2. Stopper the separatory funnel and shake for 2 minutes.
3. Allow the organic layer to separate from the sample, then draw the
water into the sampling container. Pour the organic layer into a
500 ml erlenmeyer flask containing 5 gm anhydrous sodium sulfate.
Return the aqueous phase to the separatory funnel. Rinse the sample
container with a second 60 ml volume of solvent; add the solvent to
the separatory funnel, and complete the extraction procedure a second
time. Perform a third extraction in the same manner with 60 ml of
n_-hexane.
4. Allow the organic phase to stand over sodium sulfate for at least one
hour.
5. Concentrate the organic extract to approximately 5 ml in a Kuderna
Danish evaporator on a hot water bath. The volume is first reduced
to less than 4 ml using a stream of dry nitrogen, and then diluted to
exactly 4 ml with n_-hexane.
6. If analysis for Organophosphorous pesticides is desired, the concentrated
extract is divided into two 2-ml portions, A and B.
Analysis of Organophosphorous Pesticides (Compounds 1-16)
1. Spike portion A with phorate (2 yg) and inject 3-6 yl into a gas chroma-
tograph equipped with a flame photometric detector.
Gas Chromatographic Condition: An 8 ft x 6 mm OD x 4 mm ID coiled glass
column packed with 4% SE30/6% SP2401 on 100-120 mesh Gas Chrom Q is
used for the original analysis, and a 1.5% SP2250/1.95% SP2401 on
100-120 mesh Supelcoport is used for confirmation. Operating conditions
are: inlet temperature 250 C, transfer unit temperature 250°C, detector
temperature 240°C} and the oven programmed from 200° to 265°C, at 4°
per min, nitrogen carrier at 60 ml/min.
2. The elution patterns relative to phorate are listed in Table 1.
3. Determine pesticide concentration by method outlined in "Calculations"
section.
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Analysis of Organochlorine Pesticides, Phthalate Esters, and PCB's
(Compounds 16-45)
A. Qualitatively analyze the sample.
Approximately 5 yl of the concentrated extract (portion B of organo-
phosphate pesticides are to be analyzed) are injected onto a gas chroma-
tograph equipped with an electron capture detector.
Gas Chromatographic Conditions: A gas chromatograph equipped with a
single inlet to dual column splitter, dual electron capture detectors
and associated electronics, and dual 8 ft x 6 mm OD glass columns
packed with (a) 1.5% SP2250/1.95% SP2401 and (b) 4% SE30/6% SP2401 both
on 100-120 mesh Supelcon AWDCMS is employed. Operating conditions are:
Injector temperature 250°C, column temperature 210°C, detector tempera-
ture 325°C, 5% methane:95% argon carrier with flow rate of 53 ml/min
for column (a) and 50 ml/min for column (b).
Interferences appearing as peaks on high background as well as the
appearance and a knowledge of the sample source will determine whether
treatment of the sample to remove chemical interferences (commonly
known as "sample clean-up") is required. If the parameters of interest
are present with no interferences, proceed with quantitative analysis
according to appropriate parameter as described below. When interfer-
ences complicate parameter measurement or pose a threat to gas chromato-
graphic column life or detector sensitivity, proceed as follows:
B. Florisil Column Adsorption Chromatography
1. Place sodium sulfate into the chromatographic column to one-half
inch.
2. Pour a slurry of 18 grams of Florisil in 80 ml iv-hexane into the
column. After settling the Florisil add one-half inch layer of
sodium sulfate.
3. Pre-elute the column, discard the eluate just prior to exposure
of the sulfate layer, quantitatively transfer the sample extract
(portion B if organophosphate pesticides are to be analyzed) with
subsequent washings of the sample container with n_-hexane. Adjust
the elution rate to about 5 ml per minute and collect two eluates.
4. Perform the first elution with 200 ml of 6% diethyl ether in
-------
-121-
iv-hexane CV:V), and the second with 50% di-ethylether in n_-hexane
(V:V).
5. Compounds 28-50 in the first eluate and compounds 17 thru 27 are
contained in the second eluate.
6. Concentrate the eluates to 5 ml in the Kuderna Danish evaporator.
7. Analyze the second eluate by electron capture gas chromatography
as outlined in "calculation" section. If PCB's and pesticides are
present in the first eluate, proceed with silica gel adsorption
chromatography.
C. Separation of PCB's from Pesticides with Silica Gel Adsorption Chroma-
tography
1. Deactivation of Silica Gel: Place about 8 gm of silica gel per
sample (prewashed with methylene chloride) in a glass dish or
aluminum foil lined pan no deeper than ^ inch. Activate at 180 C
for 16 hours. Transfer the silica gel to a glass stoppered bottle.
When cool, add distilled water 1.0% by weight. Store the well
sealed bottle in a dessicator prior to use. Silica gel can be
effectively stored in this manner for several days.
2. Preparation of Chromatographic Column
a. Fill a Chromatographic column with iv-hexane. Pack the lower
one-half inch section of the column with anhydrous sodium
sulfate.
b. Weigh out 6 gm of silica gel and cover with 60 ml iv-hexane.
c. Carefully add the slurry to the column with gentle tapping
making sure there are no air bubbles in the column.
d. Turn stopcock to maximum flow rate.
e. When the silica gel has settled, add sodium sulfate to form
a one-half inch layer atop the silica gel.
f. Turn off the stopcock just as the hexane enters the sodium
sulfate layer.
The column is now ready for use.
3. Chromatography of Sample
a. Quantitatively transfer the sample (the 6% diethyl ether eluate
(B) in n-hexane) concentrate onto the column with the reservoir
-------
-122-
disconnected. As the last of the sample passes into the
sodium sulfate layer, rinse down the internal wall of the
column twice with ca 0.25 ml portions of iv-hexane used to
wash the sample container. Then assemble the reservoir onto
the column.
4. Determination of Elution Volumes
a. The elution volumes for pesticides and PCB's depend on a
number of factors which are difficult to control; these
include variations in:
i) mesh size of the silica gel
ii) adsorption properties of the particular batch of silica
gel
iii) polar contaminants in sample extract
iv) dimensions of chromatographic column
Hence, the optimum elution volume must be experimentally
determined each time a variable is encountered. It is advis-
able to chromatograph a set of standards prior to each batch
of samples to monitor any change in elution patterns.
b. To determine the elution volumes add standard mixtures of
Aroclors** and pesticides to the column and collect 10 ml
sequential aliquots. Analyze each individual eluate by gas
chromatography and determine the cut off volume for both the
nj-hexane (fraction E) and the acetonitrite, iv-hexane, methylene
chloride eluate (fraction F). At the CKL we find that all
the PCB's are generally eluted in the first 45 ml of n_-hexane
along with hexachloro-benzene, mirex, aldrin, and heptachlor.
Quantitative Determination
Measure the amount of eluateand inject 5-10 yl into the gas chromatograph.
If necessary adjust the volume of eluate to give a response which can be
measured at the same attenuation as that for the standard.
1. Quantitation - Pesticides and Phthalates
Measure the peak heights or areas of the known and the reference
compound and calculate the concentration as follows:
-------
-123-
CA) (B) CVE)
microgram/liter
A = ng standard injected = ng
standard peak area mm2
B-= sample peak area = mm^
V. = volume of sample injected (ul)
V = volume of extract (yl) from which sample was injected
V = volume of water sample extracted CD
Note: 500 ml of sample are used when the organophosphorous pesticides
section is included and one liter when it is not.
At the Central Regional Laboratory, gas chromatograms of pesticides
and phthalate esters are analyzed with the aid of a computerized gas
chromatographic data system.3 This system is readily incorporated
into methods currently recommended by EPA for pesticide residue
analysis and is available upon request.
PCB's
When a single Arochlor" mixture is present, quantitative reference
standards (i.e. Arochloi~ mixture) are compared with the unknown
sample. An internal standard (Dieldriir' and Lindane=*) is added to
monitor the gas chromatographic data system. The retention time
relative to the internal standards and peak areas are calculated by
the data system.3 The concentration of a PCB mixture in the sample
is calculated by comparing at least three individual peaks of the
unknown with corresponding peaks from the standard mixture on each of
the two columns as follows:
nanograms/liter = micrograms/kilogram = V. C D
Vgh D2
V. = final volume of the sample extract (ml) from which the sample is
injected into the gas chromatograph
C = concentration of the Arochloir' standard (ng/ml)
V = size of the sample (grams of soil or liters of water)
S
A^= area of the individual sample peak
B^= area of the corresponding peak from the standard
n = number of pairs of peaks used in the calculation
D = area of the internal standard peak in the sample which does not
-------
-124-
interfere with peaks corresponding to the Arocloi™ of interest
D2 = area of corresponding peak from internal standard in the sample
4. For complex situations, the sample chromatogram is compared to each
Aroclor*^ standard and a portion of the chromatogram is assigned to
areas in which each of the Aroclors*r predominate. The concentrations
of each PCS mixture in the sample is calculated using the major peaks
in that region after peak areas from interfering mixtures are factored
out.
Sulfur is a common interference in the chromatographic fraction E.
Sulfur removal is outlined in Appendix I.
When the concentration of PCB's is less than 100 ng/1, the samples are
subjected to a perchlorination procedure.5 A measured aliquot of the
sample is transferred to a pyrex culture tube (previously muffled at
400 C) and the volume is reduced to 0.5 ml and then diluted with 2 ml
chloroform. This solution is then concentrated to 0.2 ml with a stream
of dry nitrogen at room temperature. A second 2 ml of chloroform is
added and the volume is again reduced to 0.2 ml. This step is then
repeated a third time followed by the addition of 0.5 ml antimony
pentachloride. The tube is sealed with a cap lined with a teflon disc
and heated for overnight at 175°C. The tube is then allowed to cool
to room temperature, carefully vented (caution, HC1 fumes), and slowly
diluted with 6 ml of 2N hydrochloric acid. The aqueous solution is
extracted with three 10 ml portions of hexane. The organic extracts
are combined and back-washed with a 5 ml portion of 2N hydrochloric
acid. The solution is transferred to a centrifuge tube, 5 drops of
methanol are added, and the volume reduced to 2 ml. Hexabromobiphenyl
is added as an internal standard and the solution analyzed by electron
capture gas chromatography using a 6' x V glass column packed with
4% SE-30/6% OV-210 operated at 245°C. This procedure affords greater
sensitivity as the PCS is measured as a single peak. However, this
procedure does not reveal the identity of the Arochlor** mixture or
allow for any biphenyl present in the sample.
-------
-125-
Although the perchlorination procedure is a valuable tool, it is subject
to limitations. The analyst must be aware that biphenyl though not
a PCB per se, can lead to erroneous results at low levels. The analyst
should review the chromatogram of the sample before it is subjected
to the perchlorination procedure. At CKL we express residues in terms
of ppm decachlorobiphenyl when this procedure is used. When the proce-
dure is used for quantitative confirmation, it can be expressed as a
specific Aroclor^when a conversion factor is used.^
DCS peak height of sample mg standard^ /\ _ ng in sample
DCB peak height of standard \ injected /^ ' injection
-------
-126-
QUALITY CONTROL
A. Reagent Blank
A background or blank of each of the reagents or solvents used in this
method are determined for each lot. The conditions to determine the
background or blank must be the same as those used in the analysis.
This is particularly needed with solvents. Sodium sulfate and chroma-
tographic column packings are prone to contain phthalates in high con-
centration .
B. Method Blank
The method blank is determined by following the procedure with 1 L of
distilled water, step by step to include all reagents and solvents,
in the quantity required by the method. When this cumulative blank
interferes with determination, steps must be taken to eliminate the
interference. If this is not possible, the magnitude of the interfer-
ence must be considered when calculating the concentrations of specific
constituents in the samples analyzed and the limits of detection.
One blank is analyzed with each set of ten or fewer samples.
C. Laboratory Control Standards
Laboratory control standards prepared in advance in sample bottles by
adding acetone stock pesticide/PCB solutions (1.0 ml) to distilled water
are analyzed with each set of 10 or fewer samples. The control limits
for these samples are 50-150% recovery (measured) of the "true" value.
The laboratory control standards are prepared separately from the
instrument calibration standards so each audit also compares two sets
of standards against one another.
D. Limits of Detection
These are estimated for each sample depending on chemical interferences
found in that sample but usually the detection limits are less than
10 ng/1 for the chlorinated hydrocarbon pesticides, 1 ug/1 for the
organophosphorus pesticides, 200 ng/1 for PCB's using the traditional
method, and 20 ng/1 for decachlorobiphenyl.
-------
-127-
CHART I.
Flow Chart for Extraction and Cleanup of
PCB's, Pesticides, and Phthalates
Sample
Extraction
1 __^
Portion B Portion A
Florisil Perform GC Analysis
Chromatography for Phosphorous Compounds
I
I i
Fraction C Fraction D
Chromatograph Perform GC Analysis
with Silica Gel for Compound
No. 17 thru 27
No. 29 thru 45
r — ,
E F
Perform GC Analysis Perform GC Analysis
for Compound Nos. for Compound Nos.
2, 17, 6, 5, and 1-4, 7-16, 18
46-50
-------
DETECTOR RESPONSE
I
t-1
K)
I
-------
-128-
Compound
Number
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
TABLE I.
Physical Parameters for Parameters
OV17/OV210
Relative Retention
Time
Name
Treflan
Hexachlorobenzene
Lindane
g-BHC
Heptachlor
Aldrin
Zytron
Isodrin
Heptachlor epoxide
Gamma Chlordane
o,p'-DDE
p,p'-DDE
o,p"-ODD
o,p'-DDT
p,p'-ODD
p,p'-DDT
Mirex
Methoxychlor
2,4-D isopropyl ester
di-n-butyl phthalate
DCPA
Endosulfan I
Dieldrin
Endrin
Chlorobenzilate
Endosulfan II
di-2-ethylhexylphthalate
Tetrafidon
Phorate
Diazinon
Dyfonate
Ronnel
Dursban
Methyl Parathion
Malathion
Ethyl Parathion
DEF
Ethion
Carbonphenthion
Phencaptan
EPN
Azinphos Methyl
Phosalone
Azinphos
Coumaphos
Arochlor 1221
Arochlor 1242
Arochlor 1248
Arochlor 1254
Arochlor 1260
0.44b
0.54b
0.70b
0.77b
0.84b
00b
15b
26b
43b
58b
68b
02b
2.35b
2.80b
3.00b
3.59b
5.58b
6.62b
55b
19b
48b
72b
12b
0.
1.
1,
1.
2,
2.541
54b
3.10b
5.25b
6.02b
1.00
1.3
1.5
2.5
2.9
3.1
3.4
4.1
4.7
5.9
6.1
7.5
8.4
9.1
9.3
9.7
12.3
SE30/OV210
Relative Retention
Time
0.60b
0.50b
0.60b
0.60b
0.84b
1.00b
1.14b
1.20b
1.40b
1.47b
1.71b
1.87b
2.02b
2.20b
2.41b
2.86b
4.07b
4.23b
0.86b
1.17b
1.58b
1.90b
2.29b
2.53b
3.85b
3.87b
5.39b
7.50b
1.0
1.3
1.4
2.0
2.3
2.4
2.5
2.9
3.3
4.0a
4.1a
5.0a
5.5a
5.8a
6.0A
6.2a
7.6a
Limits of
Detection
ug/i
0.004
0.04
0.004
0.004
0.004
0.004
0.01
0.006
0.004
0.004
0.006
0.006
0.006
0.006
0.006
0.006
0.01
0.02
0.04
2
0.006
0.01
0.01
0.006
0.01
0.006
0.02
0.01
2
0.02
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
0.1
0.1
0.1
0.1
0.1
Relative to Phorate
Relative to Aldrin
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-130-
DETECTOR RESPONSE
co
i to
*'»
is
IS CO
CO
70
es
-n
CO
CO
ro
CO
*• •
CO
X
•n
J2B
>x
)27
28
•
-------
-131-
DETECTOR RESPONSE
-------
-132-
REFERENCES
1
Federal Register 38, 2758 (1973) and references cited therein.
^Analysis of Pesticide Residues in Human and Environmental Samples,
Environmental Protection Agency, Research Triangle Park, NC (1974).
3J. H. Johnson, E. E. Sturino, and S. Bourne. J. Environ. Sai. Eealth -
Environ. Sai. Eng. AIK12), 165 (1976).
^Introduction to the G.C. Data System, Stored Method Version, Perkin-Elmer
Corp., Norwalk, Conn. (1971).
5W. J. Trotter, and S. J. V. Young. J. Assoc. Offia. Anal. Chem. 58,
466 (1973).
6J. A. Armour. J. Assoa. Offia. Anal. Chem. 56, 987 (1973).
7Handbook for Quality Control in Water and Wastewater Laboratories,
Environmental Protection Agency, National Environmental Research Center,
Cincinnati, Ohio (1972).
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APPENDIX I.
Sulfur Removal
Add a drop of metalic mercury to the eluate containing PCB's in a
centrifuge tube. Stopper and place on a wrist action shaker. A
black precipitate indicates presence of sulfur. After approximately
20 minutes the mercury may become entirely reacted or deactivated by
the sulfur. Three treatments may be necessary to remove all the sulfur.
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-134-
ANALYTICAL QUALITY CCNTROL
Pesticide Unit, Organic Section
In order to insure validity in the analytical results, analytical
quality control is to be performed not only on the total scheme, but also on
each critical step of the scheme. In the analytical scheme for the chlorinated
pesticides and PCB's given above, four steps may be classified as being the
"critical steps." They are critical because if any of them fails, the whole
scheme fails. The four steps are: 1} extraction, 2) Florisil liquid chro-
matography of the sample extract, 3) silicic acid liquid chromatography of a
fraction collected from the Florisil column, and 4) the gas chromatographic
analysis.
Sample Handling
In order to monitor the status of samples for PCB and pesticide analysis,
all samples will be delivered to one person as assigned by the Section Chief.
A folder will be prepared to contain data pertaining to the samples and to
include: the data request form, and all extraction and chromatographic data.
The samples will be logged in the PCB and pesticide logbook in groups
by the CRL designation number. The sample number and the parameters requested
on the sample label will be checked against those listed on the data request
sheet. Any discrepancies will be reported to the Section Chief and corrected
prior to extraction.
The samples will then be turned over to the person assigned to extract
them. Samples which are not extracted immediately will be stored in the
refrigerator.
-------
-135-
A set number will be assigned to each group of 10 samples and will be
recorded by each sample in the Pesticide/PCB logbook by the person assigned
to perform the extraction.
Th epesticide group leader will prepare a series of 20 reagent blanks
by adding distilled water to CRT, sample bottles and placing these in a
designated area. A second series of 20 samples will be prepared as laboratory
control standards by adding one liter of distilled water and a measured amount
of a pesticide/PCB stock solution to each bottle. These bottles will also be
labeled and stored with the reagent blank samples. The laboratory control
standards should be prepared completely independently of all instrument
calibration standards and should contain all chlorinated hydrocarbon pes-
ticides (20-200 ng/1), all organcphosphorus pesticides (1-5 ygle),and Aroclors
1242 and 1254 (400-2000 ng/1). One reagent blank and one laboratory control
standard should be analyzed with each set of samples.
If possible,reference standards should be run each quarter.
Control Limits
Control limits will be as listed below until further notice.
Reagent Blank:
a) Chlorinated hydrocarbon pesticides 10 ng/1
b) Qrganophosphorus pesticides lyg/1
c) PCB's 100 ng/1
Laboratory Control Standards:
a) Chlorinated hydrocarbon pesticides 75-125% of True Value
b) Organophosphorus pesticides 75-125% of
c) PCB's 30-200% of " "
-------
-136-
Summary of Results
The Pesticide Group Leader should establish audit control limits
based on actual performance data as soon as possible.
Hie Section Chief should be notified about all audits out of control,
and the action taken should be documented.
A suimary of all QA results should be completed and reported to the
CKL QA Coordinator through the Organic Section Chief as each series of 20
reagent blanks and laboratory control samples are about to be (15-17) completed.
-------
-137-
TOIAL PCB'S AS DECaOILOROBIPHENYL
The total (usually 1 liter) is extracted, dried, concentrated/and
purified with florisil as described by the Pesticide/PCB procedure. The
purified extract is then perchlorinated v according to the attached procedure
and the decachlorobiphenyl analyzed.
This method is very technique sensitive. An inexperienced chemist
should not expect to obtain high quality data without considerable (1-2
months) practice with standard solutions.
QUALITy ASSURANCE
1) A reagent blank is analyzed to audit the total procedure. A
second reagent blank is run to audit the perchlorination step. Antimony
Pentachloride is usually contaminated with either biphenyl or PCB's in low
concentrations. The control limit is 50 ng/1.
2) Laboratory control standards containing 1242/1016 and 1254 at
10-200 ng/1 should be run with each set of 10 or fewer samples. The control
limit is 50-150% recovery of measured PCB concentration.
3) One sample from each of 10 or fewer samples should be run in
duplicate. The results should agree to within ± 50% ((difference/Average)
x 100).
4) Since this method is so sensitive the quality assurance data
should always be reported with the sample analytical data.
-------
-138-
Previously the CRL has frequently experienced high reagent blanks when
using this procedure so appropriate steps should be taken (check solvents,
clean glassware, etc.) prior to starting a sample analysis.
Perchlorination Procedure
The solution of the sample to be perchlorinated is placed in a
15 x 85 ram disposable screw top culture tube, which has been muffled for at
least six hours at 600°C. The sample volume is reduced to approximately
one ml, ta*3 mis of chloroform are added, and the volume is again reduced to
0.2 ml - 0.1 ml. Dry air or nitrogen is used to affect these reductions in
volume. The tube must not be heated or allowed to go to dryness during
concentration or the yield of decachlorobiphenyl is reduced. If all of the
hexane is not removed the reaction mixture turns black when the antimony
pentachloride is added. Usually low yields are obtained from these
solutions (50%).
die half ml of antimony pentachloride is added to the sanple using
a volumetric pipet. The culture tube is tightly capped with a teflon lined
cap that has been fitted with an additional teflon disc liner. The tubes
are placed in a Technicon Digestion Block at 175°C for a minimum of 4 hours.
The digestion block is kept behind a safety shield in a fume hood. The tube
must be handled with care as they become pressurized with chloroform vapors
and HC1 gas.
After cooling to room temperature, each tube is carefully opened in
a fume hood. Rubber gloves and safety glasses are required. Two mis of 6 N
(1:1) HC1 are carefully added to the reaction mixture causing the evolution
of HC1 gas.
-------
-139-
After gas evolution is complete and the mixture cools, four additional
mis of 6 N HC1 and two mis of hexane are added. The tube is capped and
placed on a ferris wheel rotator for 15 minutes for shaking. Wte employ a
moving rotator since twenty to thirty samples are usually run simultaneously.
The aqueous phase is extracted a total of three times with two ml portions
of hexane. The hexane extracts are washed one time each with two ml portions
of 2N HC1 and distilled water. A screw cap, 15 ml centrifuge tube is used
for the washing as the lower aqueous phase is easily removed with a pasteur
pipet. The hexane is then dried over anhydrous sodium sulfate. A pasteur
pipet is used to agitate the solution to insure complete drying. The solution
is then quantitatively transferred to a graduated 13 ml centrifuge tube to
which has been added an appropriate amount of hexabrcmobiphenyl as an internal
standard. An ebulation tube and five drops of methanol (to azeotrope and
remaining chloroform) are added and the tube placed in a Kbntes Tube Heating
o
Block maintained at 80 C. The volume is reduced to 0.5 ml to insure complete
distillation of chloroform.The solution is then brought up to an appropriate
volume and analyzed by electron capture gas chrcmatography. A 6' x 1/4"
o
glass column packed with the mixed phase 1.5% OV-17/1.95% 0V 210 at 255 C
and a carrier flow of 35 ml/min provides adequate resolution.
-------
-140-
Method for the Analysis of
"Priority Pollutants" in Solids and Bottom Sediments
CRL Method No. 1003
-------
-141-
Determination of "Non Purgeable" Priority Pollutants in Sediments
Sample Preparation
1. Transfer the homogeneous sediment sample into an aluminum pan and spread
it to dry over a period of 1-4 days in a fume hood at ambient temperature.
Pulverize sediment after drying, using a mortar and pestle and sieve
through 20 mesh sieve into a 60 mesh sieve. Sieve again with 60 mesh
sieve and sediment retained on the 60 mesh screen is used for extraction.
2. As the final calculations will be made on a dry weight basis, it is
necessary to determine the percentage of total solids in each sample.
Weigh ca 5 gm of the homogenous sediment into a tared crucible. Determine
the percent solids by:
a. drying overnight at 105°C
b. allow crucible to come to constant weight in a desiccator before
weighing.
3. Transfer 20 g of the air dried sediment into a soxhlet apparatus between
two layers of glass wool. The glass wool should be pre-extracted for
16 hours with 1:1 acetone/hexane (v:v). Extract the sample for 16 hours
with 1:1 acetone/hexane (v:v).
4. Concentrate the extract to a ca 5 ml with a Kuderna-Danish apparatus.
Remove tube, rinsing joint with n-hexane.
-------
-142-
Separation of Acids from Neutral-Basic Compounds
The concentrated extract is transferred to a one 1 separatory funnel
and extracted three times with 100 ml of l.ON NaOH solution. (The NaOH
solution is pre-extracted with methylene chloride to remove any organic
compounds which may be present in the solution). The organic phase is
dried over anhydrous sodium sulfate, concentrated to 4 ml in a Kuderna-Danish
concentrator and transferred into two GC vials which are labeled as the base-
neutral fraction (BN-I).
The aqueous extracts are returned to the separatory funnel, made acidic
(pH3) with concentrated sulfuric acid and extracted three times each with
100 ml of methylene chloride. The extracts are combined, dried over anhydrous
sodium sulfate, concentrated to 2 ml transferred into a GC vial and labeled
as the acid containing fraction (A-I).
Quantification
The extracts are analyzed by gas chromatography/mass spectroscopy as out-
lined in the method for the analysis of priority pollutants in aqueous
samples.
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-143-
DETERMINATION OF PURGEABLE ORGANICS IN SEDIMENT
David N. Speis, Chemist
U.S. Environmental Protection Agency
Region II, Edison, New Jersey 08817
The analysis of volatile organic compounds in sediment poses
challenging problems. Previous methods have been insensitive to
low concentrations of volatiles in sediments. The reasons, behind
this are twofold. Sediment analysis is usually limited to a 50 gm
sample size for ease of sample handling. A liquid extraction of a
sediment sample this large would be difficult. The large volumes
of solvent required could not be concentrated by any solvent
stripping technique without loss of the organics in question. Head
space analysis is limited to small volume injections of low con-
centration resulting in a minimum detectable limit of 25 ppb
"EMSL, Cincinnati, Ohio" (1977).
By modifying a Tekmar LSC-1 liquid sample concentrator to
accommodate a 15 gram sediment sample and sample chamber heater,
the analyst is able to thermally purge volatile organics from
sediments. With this system, a minimum detectable limit of 0.1
ppb can be attained.
The purge and trap method is useful in the analysis of water
samples for hydrocarbons and halogenated hydrocarbons. An inert
gas (helium) is bubbled through the sample transferring those
compounds favoring the vapor state from the aqueous phase to the
gaseous phase. These gaseous compounds are then concentrated in
a porous polymer trap at room temperature. (Figure 1) The trapped
compounds are thermally desorbed into a gas chromatograph inter-
faced to an electron impact mass spectrometer, electron capture,
or Hall electrolytic conductivity detectors "Bellar, Lichtenberg"
(1974). (Figure 2).
-------
m
CD
cr
;=D
m
m
23
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c
71
o
m
rn
CT)
m
O
m
o
m
•H
m
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DESORB MODE
CARRIER/DESORB GAS AND SAMPLE OUT
CARRIER/DESORB GAS IN
1 SAMPLER
PURGE VALVE
FLOWMETER
PURGE IN
FIGURE 2
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A Tekmar LSC-1 with modified sample container was interfaced
to a Finnigan 3200 electron impact, gas chromatograph/mass spectro-
meter with a Systems Industries data system.
Sediment samples are collected in the field in pre-weighed
Pierce (or equivalent) 20 ml hypovials with uncrimped aluminum
seals and teflon backed septa. These vials have the capability
of holding up to 15 grams of wet sediment. For best results, the
vials should be filed to maximum capacity to reduce the amount
of head space. The aluminum seals are crimped in the field after
sample collection. All samples should be transported and stored
at wet ice temperature and equilibrated to room temperature for
weighing and analysis. Two holes are then drilled into the
septum to allow the snug insertion of two 1/8" glass tubes to be
used as a purge gas inlet and outlet. The purge gas inlet should
be extended to the bottom of the septum vial. The purge gas
outlet should extend 1/2" below the septum (Figure 3). The vial
is wrapped in heating tape and the glass tubes are connected to
the appropriate gas lines. The sample is then heated at 80°C for
five minutes. At the conclusion of five minutes, the sample
chamber is purged with helium for 4 minutes at a rate of 60 ml/min.
This effectively traps volatilized organics on the polymer trap.
The trapped organics are then desorbed onto the chromatographic
column for analysis and data collection.
A pre-selected sediment whose consistency was that of a loose
field soil, was muffled at 600°C to remove any volatile organics.
This sediment served as a media for spiking. A solution of five
volatile organics was prepared in methanol. This solution was
injected directly into an empty septum vials to be used as a
standard. This eliminates any matrix effects caused by the
sediment so that an easy assessment of recovery can be made. Five
dilutions of this standard were prepared in water. Ten mis of the
diluted standard was pipetted into the septum vial containing 10-
15 grams of pre-weighed sediment. The vial was sealed and allowed
to stabilize for four hours. Five replicates of each concen-
tration were analyzed as well as four unspiked sediments and four
empty vials as blanks.
Minimum detectable levels obtained were 1.0 ng/15 grams of
sediment (.07 ug/kg). Mean recoveries were calculated for each
compound in each concentration group. Recoveries ranged from a
high 52% to a low of 24%. The results are summarized in Table 1.
The data was quite linear over the range of operation (Table 2).
The lowest correlation coefficient was .934 for chlorobenzene;
however, three compounds had values greater than .99.
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flODIFIED SAMPLER
PURGE GAS
INLET
PURGE OUTLET
TO TRAP
20 MM TEFLON
BACKED „
SILICON SEPTA
SEDIMENT LEVEL
SEDIMENT
SCALE 2* = 1"
FIGURE 3
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TABLE 1, RECOVERIES
00
CHLOROFORM
Ll/1 TRICHLORETHANE
TOLUENE
TETRACHLOROETHYLENE -
i
CHLOROBENZENE
BLANK
X NG
1,0 ( 1,7)
6,2 ( 2,7)
6.1 (0,17)
1,6 ( 1,6)
3,8 ( 3,3)
.100 UG SPIKE
x RECOVERY
.'12 (.06)
,52 (,05)
,32 (.07)
.32 (.09)
,32 (.08).
,500 UG SPIKE
x RECOVERY
,31 (.10)
,11 (.10)
,13 (,05)
,21 (.06)
.25 (.03)
1,00 UG
SPIKE
x RECOVERY
,11 (.08)
,50 (.01)
,11 (.13)
,37 (,08)
,11 (.11)
2,00 UG
SPIKE
x RECOVERY
,16 (.11)
,50 (.09)
,31 (.07)
,31 (.07)
,28 (,09)
3.0 UG SPIK
x RECOVERY
.39 (.12)
.16 (,10)
.37 (,09)
.39 (.08)
,13 (.15)
H * 5 SAMPLES/COMPOUND CONCENTRATION
( )= STANDARD DEVIATION
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TABLE 2 SPIKE RECOVERIES
3,00 .
o
14J
:*:
CO
2,00 .
1,00 .
,50
.10
,50
CHLOROFORM
LL1 TRICHLOROETHAN
TETRACHLOROETHYLENE
TOLUENE
CHLOROBEN2ENE
1,00
RECOVERY ;JG
i2,00
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-150-
Minimum detectable levels obtained using this sediment
purge and trap procedure represent a 350 fold improvement in
detection limits over that reported for head space analysis
techniques. Although recoveries are on the low side, they are
linear and reproducible. The results indicate that this can be
a reliable method for detecting and determining low levels of
volatile organics in sediments. This soil matrix represented the
type of sample that would be taken as the result of an organic
spill in an uncontaminated area. The matrix used was very
difficult to purge of organics. The muffling served as an
activation of a sediment that, otherwise, might not have held onto
a purgeable compound so tenaciously. Higher recoveries would be
expected from a contaminated unmuffled sediment. Limited avail-
able data on spiked environmental samples gave recoveries of
80-100% using this method.
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References
Bellar, T.A.; Lichtenberg, J.J., and Kroner, R.C., Determin-
ing Volatile Organics in Microgram per Liter levels by Gas
Chromatography. Journal American Water Works Association,
Volume 66, No. 12, December 1974.
Sediment Sampling for Volatile Organics, U.S. Environmental
Protection Agency, Environmental Monitoring and Support
Laboratory, Cincinnati, Ohio, August 2, 1977.
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Residue, Total Non-filterable
(Suspended Solids)
CRL Method No. 441
Scope and Application
This method is applicable to drinking, surface, and saline water, domestic and
industrial wastes.
The practical range of the determination is 10 mg/1 to 20,000 mg/1.
Summary of Method
A well-mixed sample is filtered through a standard glass fiber filter, and the
residue retained on the filter is dried to constant weight at 103-105°C. The
filtrate from this method may be used for Residue, Total Filterable.
Definitions
Non-filterable solids are defined as those solids which are retained by a standard
glass fiber filter and dried to constant weight at 103-105°C.
Sample Handling and Preservation
Non-homogeneous particulates such as leaves, sticks, fish, and lumps of fecal matter
should be excluded from the sample.
Preservation of the sample is not practical; analysis should begin as soon as
possible.
Interferences
Too much residue on the filter will entrap water and may require prolonged drying.
Equipment
Glass fiber filter discs, 4.7 cm or 2.2 cm, without organic binder, Reeve Angel type
934-A or 984-H, Gelman type A, or equivalent.
Filter holder, membrane filter funnel or Gooch crucible adapter.
Suction flask, 500 ml.
Gooch crucibles, 25 ml (if 2.2 cm filter is used).
Drying oven, 103-105°C.
Desiccator.
Analytical balance, 200 g capacity, capable of weighing to 0.1 mg.
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Procedure
Preparation of glass fiber filter disc: Place the disc on the membrane filter
apparatus or insert into bottom of a suitable Gooch crucible. While vacuum is
applied, wash the disc with three successive 20 ml volumes of distilled water.
Remove all traces of water by continuing to apply vacuum after water had passed
through. Remove filter from membrane filter apparatus or both crucible and filter
if Gooch crucible is used, and dry in an oven at 103-105°C for one hour. Remove
to desiccator and store until needed. Weigh immediately before use.
Assemble the filtering apparatus and begin suction. Shake the sample vigorously
and rapidly transfer 100 ml to the funnel by means of a 100 ml volumetric.
Depending upon the suspended solids concentration, a smaller or larger volume may
be filtered. Wash the filter with 100 ml of distilled water.
Carefully remove the filter from the membrane filter funnel assembly. Alternatively,
remove crucible and filter from crucible adapter. Dry at least one hour at 103-105°C.
Cool in a desiccator and weigh. Repeat the drying cycle until a constant weight is
obtained or until weight loss is less than 0.5 mg.
Quality Control
Duplicate samples are analyzed with each group of samples.
Calculations
Calculate non-filterable residue as follows:
Non-filt. residue, mg/1 = (A-B) x 1000
C
where:
A= weight of filter + residue
B = weight of filter
C = ml of sample filtered
Precision and Accuracy
Precision data are not available at this time.
Accuracy data on actual samples cannot be obtained.
Reference
This method is identical to the one in the EPA Manual of Methods for Chemical
Analysis of Water and Wastes, 1974, Office of Technology Transfer, Washington, DC.
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