SEPA
United States
Environmental Protection
Agency
National Training
and Operational
Technology Center
Cincinnati OH 45268
Water
Methods for the
Determination of
Chemical
Contaminants
EPA-430/1-80-006
April 1980
Training Manual
-------
March 1980
PARTICIPANTS HANDBOOK
for
METHODS FOR THE DETERMINATION OF CHEMICAL
CONTAMINANTS IN DRINKING WATER
This Participants Handbook was developed by the Environ-
mental Protection Agency, National Training and Operational
Technology Center with the Technical Support Division in
response to a request from the Office of Drinking Hater.
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
-------
DISCLAIMER
Reference to conmercial products, trade names, or
manufacturers is for purposes of example and illustration.
Such references do not constitute endorsement by the
Office of Water Program Operations, U.S. Environmental
Protection Agency.
-------
METHODS FOR THE DETERMINATION OF CHEMICAL CONTAMINANTS IN DRINKING WATER
INTRODUCTION
Course Instructional Objectives:
This course is designed to meet the needs for training those persons who will
be involved in analysis of potable waters for contaminants listed in the
Interim Primary Drinking Water Regulations. The course can be used by either
State or Federal personnel. Should the course be offered by a State, the
contents should be thoroughly checked to see if discrepancies exist between
the outlines prepared under the Federal regulations and what is required in
the State's Drinking Water Act.
After successfully completing this course, the trainee should have sufficient
information to carry out the various analyses. The trainee will perform analysis
in the laboratory under the supervision of the offering authority's chemist.
The trainee will be observed by the instructors and judged on the competence
of laboratory technique and will be given a test upon completion of the course.
The course will cover the analytical methodology used to analyze for metals,
organics, nitrates and fluoride. Additional topics covered will include
sample handling and discussions on laboratory certification and the Act itself.
Although all parameters, inorganic and organic, are contained in this manual,
caution is advised in several areas. First there is a provision in all acts,
both Federal and State, to allow alternate test procedures. This provision can
be carried out again on a Federal or State level. Consequently, the users of
this manual should inquire of their appropriate authority as to the existence
of any additional methodology which has been approved.
Secondly, from time to time the Primary Drinking Water Regulations will be
amended and new parameters which must be analyzed for added. This will create
a need for constant revision of the manual on the part of the user to keep
it current. Another thought should be considered here and that is the Secondary
Regulations. These will be issued on esthetic principles and will not be manda-
tory. However, the methodology that should be used is listed in these regulations
and analysts might wish to examine these.
The exact make-up of the manual has been designed in such a way as to allow
maximum flexibility in determination of course content. Options have been
provided so as to allow the course director to select the final content.
For a brief overview of the course, the content covered, and the schedule, turn
to the Agenda.
A word about the handbook itself is in order. The handbook is designed to be
used by you from the time you receive it throughout the course, and when you
are back on the job. At the outset, there are some tasks the participant should
complete prior to attending the course. During the course, the handbook will
be referred to daily or with each set of units and presentations. It spells
out for you what you will learn, how, when, under what conditions, and when
you will know if you have learned what is intended. The instructors will
use this same material, with some variations depending on the situation,
participant needs, or scheduling requirements.
A-l
-------
The handbook is assembled in this loose-leaf form to allow the instructor some
flexibility in unit selection or sequencing. Also, it allows you to insert
your notes from the daily sessions next to the corresponding unit. Should
the instructor or a fellow-participant provide additional information (a paper,
articles, etc.) not envisioned for the course but relevant and useful, it can
be inserted in the handbook.
A-2
-------
CONTENTS
METHODS FOR THE DETERMINATION OF CHEMICAL CONTAMINANTS IN DRINKING WATER
PARTICIPANTS HANDBOOK
Introduction A
Table of Contents B
Pre-Course Activities C
Pre-Test Cl
Biographic Statement C2
Participant Survey C3
Course Agenda D
Instructional Units E
Introduction
General Topics
Regulations Concerning the Safe Drinking Water Act El
Sample Handling and Preservation E2
Basic Statistics E3
Quality Control E4
Safety E5
Inorganic Parameters
Silver E6
Extraction Techniques for Cd, Cr, and Pb E7
Mercury E8
Arsenic and Selenium E9
Nitrate
Cadmium Reduction E10.A
Brucine E10.B
Fluoride
SPADNS Ell.A
Electrode Ell.B
Distillation Ell.C
Barium El 2
Chlorine and Turbidity E13.A
Measurement of Free Chlorine Utilizing the DPD Kit E13.B
Determination of Turbidity E13.C
Reserved for Future Expansion E14 - E19
Organics
Pesticides E20
Chlorophenoxys E21
Elective/Optional Units F
B-l
-------
METHODS FOR THE DETERMINATION OF CHEMICAL CONTAMINANTS IN DRINKING WATER
PRE-COURSE ACTIVITIES
Each of the following forms to be completed by you concern activities you are
asked to complete prior to the course itself. Those are the Pre-test, Bio-
graphic Statement, and Participant Survey. They are explained in detail in
the introduction to each form.
A fourth sub-section is entitled Pre-Course Preparation. It is simply those
materials or activities the instructor may appropriately deem important to
read or carry out prior to arriving for the course. This part of the hand-
book is optional and for the instructor to include or exclude.
-------
Course Pre-Test
Dear Participant:
As your first action in relation to this course, we are asking you to complete
a short pre-test and return it to us before coming to the course. It is im-
portant to have this information in order to measure how effectively the course
is meeting its objectives. This, plus the post-test given upon completing
the course, will help us with this measurement.
Note, we talk of "measuring the course," not measuring you in the sense of
pass or fail. While learning is the primary responsibility of the learner,
we recognize that course design, content, methodology, instructor, learning
environment, etc., all play a role. This measurement plus other feedback
the instructors will get, will assist us with future design and delivery.
You are encouraged to take this test without any outside help from books or
individuals. This test is designed to answer only the question of have you
improved your knowledge by taking this course. It will also give some indica-
tion on course design and instructor teaching. No grade will be assigned nor
is any other use intended.
Cl-1
-------
Pre-Test
1. The analytical methods to be used in the analyses of Drinking Water Samples
are set down in the
a. Interim Primary Drinking Water Regulations
b. Safe Drinking Water Act
c. Clean Water Act
2. Organic samples are collected in containers.
a. glass or plastic
b, glass only
c. plastic only
3. The maximum holding time recommended for metals is
a. 14 days
b. 180 days
c. 30 days
4. A statistical measurement for precision is
a, percent recovery
b. central tendency
c. standard deviation
5. Minimum quality control requires that daily checks of a standard curve
be within of the original curve.
a. + 10%
b. + 5%
c. j- 2%
6, Safety practices should be carried out
a. at al1 times
b. only when hazardous materials are being used
c. only when the supervisors are watching
7. The required analytical method, published in the Interim Primary Regulations,
for silver is
a. dithizone
b. silver diethyldithiocarbamate
c. standard atomic absorption techniques
8. The MCL for silver was based on considerations.
a. cost
b. aesthetic
c. health
-------
9. The oxidant and fuel gases used when silver is determined are
a. air-acetylene
b. nitrous oxide-acetylene
c. argon-hydrogen
10. In order to determine cadmium, chromium and lead at their MCL's, the
sample needs to
a. be solubilized
b. extracted and concentrated
c. both
11. The oxidant and fuel gases used to determine cadmium, chromium and lead
are
a. air-acetylene
b. nitrous oxide-acetylene
c. argon-hydrogen
12. The extraction technique
a. necessitates doing each metal (cadmium, chromium, lead) separately
b. allows all metals (cadmium, chromium, lead) to be done with one extraction
c. need a preliminary colorimetric procedure.
13. The determination of mercury is carried out by
a. normal atomic absorption techniques
b. colorimetricly
c. a flameless atomic absorption technique
14. The oxidant and fuel gases used to determine mercury
a. are air-acetylene
b. nitrous oxide-acetylene
c. air only
15. The organic forms of mercury are to convert to metallic form.
a. difficult
b. easy
c. impossible
16. The oxidant and fuel gases used to determine arsenic and selenium
are
a. air-acetylene
b. nitrous oxide-acetylene
c. argon-hydrogen
17. Organic forms of arsenic are analyzed by the gaseous hydroxide
method.
a. directly
b. after an oxidation step
c. colorimetricly
Cl-4
-------
18, The zinc slurry provides in the gaseous hydride procedures
for arsenic and selenium.
a. for the reduction
b. the hydrogen for the flame
c. the hydrogen to form the hydride
19, Nitrate is determined in the cadmium reduction method.
a. as nitrate
b. as nitrite
c, as cadmium
20. Nitrate samples for the reduction column should not be preserved
with
a. sulfuric acid
b. refrigeration at 4°C
c. mercuric chloride
21, The nitrate sample for the cadmium reduction method is filtered to remove
turbidity which could
a. react with the nitrate
b. oxidize the nitrate to nitrite
c. restrict flow through the column
22. The brucine test analyzes nitrate as
a. nitrate
b. nitrite
c. brucine
23. One extremely important control in the brucine test is
a. size of the particles
b. concentration of nitrite
c. temperature
24. The brucine-nitrate test is a test.
a. colorimetric
b. atomic abosrption
c. titrametric
25. For drinking water samples must precede the SPADNS test.
a. filtration
b. use of the electrode
c. distillation
26. Fluoride samples are preserved by the addition of
a. nothing
b. nitric acid
c. mercuric chloride
Cl-5
-------
27. The SPADNS method for fluoride is a procedure.
a. colorimetric
b. atomic absorption
c. titrametric
28. The distillation procedure works by
a. distilling over the interferences and leaving the F behind
b. distilling over the F" and leaving the interferences behind
c. forming a color with the interferences
29. A new batch of acid/water mix must be used
a. with each sample
b. after three samples
c. when the solution turns brown
30. If the temperature is allowed to go beyond 180°C
a. the fluoride is not distilled
b. the iron carries over
c. sulfate is carried over
31. For drinking water samples must precede the electrode method.
a. nothing
b. distillation
c. filtration
32. The electrode must be connected to for the F~ determination.
a. pH meter with expanded scales
b. specific ion meter
c. either of the above
33. The electrode itself and the account for the small number
of interferences.
a. distillation
b. the TISAB buffer
c. the complexone
34. Barium is determined by
a. colorimetry
b. atomic absorption
c. titrametry
35. The barium samples are preserved by adding
a. nitric acid
b. sulfuric acid
c. mercuric chloride
Cl-6
-------
36, In order to express the value of'total" barium, a step
must be performed.
a. filtration
b. weighing
c. solubilization or digestion
37. The approved method for residual chlorine determination for water supply
samples is the
a. o-tolidine
b. phenol red
c. DPD
38. The kit form of the approved method
a. can be used
b. cannot be used
c. must be applied for under alternate test procedures
39. Chlorine samples
a. can be preserved overnight
b. can be held for 48 hours
c. cannot be preserved
40. The turbidity sample must be taken
a. in the plant
b. at an entry point to the distribution system
c. in the distribution system
41. The reason for the MCL on turbidity is because
a. it may interfere with disinfection
b. it makes water look bad
c. it makes water taste bad
42. Turbidity measurement must be carried out
a, a number of times based on population served
b. once a week
c. once a day
43. The Interim Primary Drinking Water Regulations
a. become effective in December of 1977
b. became effective in December of 1975
c. became effective in June of 1977
44. The Interim Primary Drinking Water Regulations include maximum contaminant
levels (MCL's) as well as monitoring frequencies for
a. chemical, bacteriological, radiological contaminants
b. chemical, bacteriological contaminants
c. chemical contaminants
Cl-7
-------
45. The maximum holding time for the chlorinated hydrocarbons samples is
a. 14 days
b. 7 days
c. none
46. The pesticides which are to be monitored are
a. endrin, aldrin, lindane, methoxychlor, toxaphene
b. endrin, lindane, methoxychlor, aldrin
c. toxaphene, methoxychlor, lindane, endrin
47. The pesticides are extracted from the sample using
a, hexane
b. petroleum ether-ethylether
c. hexane-methylene chloride
48. The chlorphenoxy herbicides to be monitored for are
a. 2,4, D; 2,4,5 TP; 2,4,5 T
b. 2,4, D; 2,4,5 T
c. 2,4, D; 2,4, 5 TP
49. The herbicides are extracted from the sample using
a. hexane
b. hexane-methylene chloride
c, ethylether
50. The maximum holding time for herbicide samples is
a. 14 days
b, 7 days
c. none
Cl-
P
-------
BIOGRAPHIC STATEMENT
Dear Participant:
We ask that you answer and complete the following items as briefly as
possible. The purpose is simple: to acquaint the instructor with his/
her students prior to the course.
1) Name: (please print) 2) Date:
3) Address:
4) Date of Birth;
5) Present Position or Job Title:
6) Major job functions or responsibilities:
7) Courses or study undertaken in relation to job:
C2-1
-------
PARTICIPANT SURVEY FOR THE METHODS OF ANALYSIS FOR
INORGANIC CONTAMINANTS OF POTABLE WATERS
1. Identify the experience you have with each method for the various
contaminants covered in the course (give approximate length of
experience).
2. How much experience do you have in atomic absorption?
3. Do you have sufficient basic laboratory skills to carry out necessary
laboratory procedures (use student skills checklist)?
4. List the goals which you wish to achieve in attending this course.
5. Will there be a need for you to pass on the information attained in this
course to others?
C3-1
-------
Name
Employer
STUDENT SKILLS CHECKLIST
To assist us in processing applications, please check YES or NO for each of the
following items:
YES NO
I have operated a laboratory gas burner
I have operated a laboratory hotplate/stirrer ___
I have operated an autoclave
I have operated a laboratory drying oven
I have used a vacuum source to filter liquids
I have used a desiccator _
I have weighed items on an analytical balance
I have weighed items on a double pan balance .....
I have used a graduate to measure liquids __
I have used a volumetric pipet to measure liquids
I have used a graduated pipet to measure liquids .
I have used a pipet bulb to fill a pip^t
I have used mouth suction to fill a pipet
I have used an inoculating loop to transfer small amounts of liquid ___
I have used disinfectant to sterilize a lab bench work area ....
I have poured liquid from a container into glass test tubes .... __
I have prepared media used for coliform tests
I have used chromic acid to clean glassware .
I have operated a laboratory safety shower
I have operated a laboratory eye washer
I have operated a fume hood
I have prepared manganous sulfate solution
I have made out labels for bottles or reagents
I have used a buret _
I have used starch as a chemical change indicator
I have titrated one solution against another to a color change end
Point
I have recorded a reading at a meniscus
I have recorded laboratory data in a laboratory notebook
I have entered laboratory data on a pre-printed form .......
I have recorded information about samples on record sheets . . . .
I have located required purchase information in a catalog of
laboratory equipment
I have written a purchase order for chemicals to be used in the lab
-------
Name
Employer
YES NO
Volume means space occupied by a solid, liquid, or gas . . . .
mg/1 means milligrams per liter ....
Normality (N) is a way to express concentration in a solution
1 kilogram equals 0.001 gram
1 inch equals 2.54 cm
1000 ml equals 1 liter . . . ,
85 times 4.1 equals 42.5
7 minus 2 divided by 0.02 equals 250
3.26 rounded to the nearest tenth is 32.6
84.55147 rounded to the nearest thousandth is 84.551 . . . . ,
C3-4
-------
INSTRUCTIONAL UNITS
INTRODUCTION
The material covered in this section represents the core of the course. All the
parameters listed in the Interim Primary Regulations are covered. Where more
than one analytical procedure has been permitted, all are included here. The
analyst will have to make the choice as to which will be used. The material has
been written in a format that allows the trainee to utilize the outline as the
analysis is carried out. The step-by-step outline proceeds in the same order as
an analyst must proceed. Each step is given and if warranted, additional informa-
tion is given in the next column. The student should be cautioned to read each
step and the material, if any, in the information column before doing the step.
Also included in the outline is an equipment list which lists capital, reuseable
and consumable items necessary to perform the analysis. Where more than one
analysis is being performed, the equipment lists will have duplication and the
trainee must purchase only what is needed.
The level of training required to perform each analysis varies. For example, the
outlines on residual chlorine and turbidity need little formal chemical educational
background to be performed. However, the atomic absorption and gas chromatographic
analysis require considerable background to perform. The later two analyses should
be performed only by experienced chemists or done under their supervision.
As new persons enter into the laboratory and assume responsibility for certain
analyses, this manual or sections of it can be used to acquaint or refresh the
analyst with the methodology for which he is responsible.
E-l
-------
REGULATIONS CONNECTED WITH THE SAFE DRINKING WATER ACT
I. Introduction
The primary interest of the Safe Drinking Water Act was to produce potable
water for the consuming public. It is estimated that there are 240,000
water supplies in the United States. That is about 40,000 community supplies
and about 200,000 non-community water supplies. The Safe Drinking Water Act
required that limits be set down for those materials which, when found in
natural waters, would pose a health hazard. From this requirement a document
was drawn up and published for public comment. This was the Proposed
Interim Primary Regulations. After the comments were received and acted
upon, the Interim Primary Regulations were published in the Federal Register.
These Interim Primary Regulations listed the health related agents to be
monitored for in the nations drinking waters. A monitoring frequency was
set down for the community and non-community supplies and a "Maximum
Contaminant Level" (MCL) for each was set. In addition, a list of "approved"
methods for the analysis of each parameter was given.
The "Act" stipulated that a study was to be made by the National Academy
of Science (NAS) on the parameters that were included in the Interim
Primary Regulations. This study was to look at other compounds to in-
clude, if some parameters should be excluded, if the MCL were right and
suggest changes and areas of research. After the NAS report was finished
the Interim Primary Regulations were to be revised and published for public
comment and then promulgated.
The Environmental Protection Agency was to publish a list of parameters and
methods to analyze for these parameters which a treatment facility might
wish to monitor for. These parameters were to be based on aesthetic values
and were not to be of an enforceable nature. These "Secondary Regulations"
were to follow the route of the Primary in that they were to be proposed
and sent out for public comment.
In addition the the Primary regulations, EPA was called on to issue any
additional parameter it felt might endanger the health of the consuming
public. These additional parameters after being commented on would be
a part of the already published Primary Regulations. As with the other
parameters analytical methodology and monitoring frequencies would be
published for the new parameters.
After publication of the analytical methodology in the Primary Regulations,
any new methods could be used after being ajudged comparable to those already
published. A review panel and an approved mechanism was to be set up
to supervise the requests for "Alternate Test Procedure Approval." If the
new method was found to be comparable, it could be approved on a national
or regional area level.
II. National Interim Primary Drinking Water Regulations
Section 1412 of the Safe Drinking Water Act requires the Environmental
Protection Agency to publish proposed national interim primary drinking
water regulations. These regulations were to be proposed 90 days after
the enactment of the Safe Drinking Water Act. Public comments were to be
solicited on the proposed Interim Primary Drinking Water Regulation and
these regulations were to be promulgated 180 days after enactment.
AT.WMP.4.3.80
Fl-1
-------
The Proposed Interim Regulations were issued on March 14, 1975, and promul-
gated on December 25, 1975. Since the Act states that these regulations
should become effective 18 months after promulgation, they became effective
June 24, 1977. These Interim Primary Regulations will be revised on an as
needed basis as well as at least every three years.
Since the Interim Primary Regulations are based on health hazards to the
consuming public, these regulations contain a list of Organic and Inorganic
materials and a maximum contaminant level for each. These levels are based
upon possible health hazards that may occur after a lifetime of consuming
approximately two liters of water per day. The regulations set down what
must be done by a water supply should one of these maximum contaminant
levels (MCL) be surpassed. Also, a part of the regulations is a list of
approved methods for the analysis of the parameters listed. The parameters,
their levels and methods are listed in Table 1.
Also included in the regulations are the sampling and monitoring frequencies
for the published parameters. This sets down how often samples must be
analyzed and for which of the parameters. Microbiological parameters are
also listed in the Interim Regulations. The limits and sampling frequencies
are covered in other manuals. The chemical sampling and monitoring require-
ments are listed in Table 3.
Under the microbiological sections in the Interim Primary Regulations a
supply may substitute residual chlorine determinations for a portion of
the microbiological tests. The level of free chlorine that must be main-
tained is 0.2 mg/1. The analytical method to determine this is the DPD
colorimetric or titrimetric method. It was the intent to allow the use
of the color comparator kits for this analysis. Due to the inability
to preserve a free chlorine sample it is expected that the operator him-
self will perform this test.
On July 19, 1979, a proposed amendment to the National Interim Primary
Drinking Water Regulations was published. As with any proposed rule it
calls for public comment after which they will be promulgated and become
an addition to the NIPDWR.
The analytically significant areas in these proposed regulations are the
publication of alternative analytical techniques approved for nationwide
use. These are shown in Table 5. In addition, the community supplies
are required to monitor for sodium, at least annually for systems utilizing
surface water sources and at least every three years for systems solely
utilizing ground waters sources. Analyses for sodium are to be carried
out by either flame photometric or atomic absorption methods, the references
for which are given in Table 5.
Some supplies when so notified by the State will be required to initiate
a corrosion control program. This is designed to protect the drinking
water from possible corrosion products as lead, cadmuim, asbestos and
organic compounds. The proposed rules suggest three ways to calculate
some form of corrosion index and a suggested limit for each method of
calculation. When these proposed rules are commented on, it is hoped
some decision can be made on this point.
El-2
-------
Some changes connected with non-community supplies only are suggested in
the proposed armiendments. These would extend for an additional year the
nitrate monitoring deadline and allow up to 20 mg/1 of nitrate in some
systems at the discretion of the State.
In addition to the proposed amendments, a final regulation concerning the
Control of Trihalomethanes in Drinking Water were published on November
29, 1979. These regulations set an MCL of 0.1 mg/1 of total trihalomethane
(TTHM). This is the arithmetic sum of the concentrations of chloroform,
dibromochloromethane, bromodichloromethane and tribromomethane, rounded
to two significant figures.
These regulations would effect, at the present time, only those supplies
serving populations greater than 10,000 persons. There is a phase in
approach for both monitoring and an effective date for the MCL for supplies
of different sizes. The initial monitoring frequency would be four samples
per quarter taken all on the same day at different locations in the distri-
bution systems. The analytical methods that may be used are the purge and
trap technique or the liquid-liquid extraction technique, both of which
are published in the Federal Register along with the regulations. In
addition, the following references are given.
1) "The Analysis of Trihalomethanes in Finished Waters by the
Purge and Trap Method," Method 501.1 EMSL, EPA, Cincinnati,
Ohio 45268.
2) "The Analysis of Trihalomethanes in Finished Waters by the
Liquid/Liquid Extraction Method," Method 501.2, EMSL, EPA,
Cincinnati, Ohio 45268.
III. National Academy of Science Study
After publication of the Proposed and Interim Primary Regulations the EPA
is required by the Act to enter into arrangements with the National
Academy of Sciences to conduct a study. This study should determine the
maximum contaminants levels which should be recommended under the revised
primary regulations in order to protect the health of persons from any
known or anticipated adverse effects, and the existence of any contaminants -
the levels of which in drinking water cannot be determined but which may
have an adverse effect on the health of persons.
The study was to be presented to Congress no later than 2 years after the
date of enactment of the Act. EPA will use this study in deciding whether
to include any such contaminants in a revised Primary Drinking Water
Regulations.
In conducting its study the National Academy of Sciences is directed to
consider only what is required to protect public health, not what is
technologically or economically feasible or reasonable. Based on the results
of the NAS study, EPA may specify additional contaminants with adverse
health effects. It may establish new maximum contaminants levels. It may
prescribe a list of known water treatment techniques which will reduce the
concentration of any contaminant for which no maximum contaminant level is
established (e.g., viruses, organics, asbestos), or it may establish
requirements for operation and maintenance.
El-3
-------
TABLE 1
Parameter
Inorganic -
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Nitrate
Selenium
Silver
Turbidity
Fluoride
Limit
mg/1 iter
Other than Fl
0.05
1.00
0.01
0.05
0,05
0.002
10.00
0.01
0.05
1.0 TU
Temp. Dep.
See Table 2
Method
uoride
Atomic Absorption
(gaseous hydride)
Atomic Absorption
(Std, Conditions)
Atomic Absorption
(Std. Conditions)
Atomic Absorption
with Chelation Ext.
Atomic Absorption
with Chelation Ext.
Flameless Atomic
Absorption
Brucine (Co 1 or i metric)
Cadmium Reduction
(Colorimetric)
Atomic Absorption
(gaseous hydride)
Atomic Absorption
(Std. Conditions)
Nephelometric
Electrode
SPADNS (Colorimetric)
with distillation
EPA1
95-96
97-98
101-103
105-106
112-113
118-126
201-206
145
146
295-298
65-67
59-60
Reference
Std. Meth. (13th) ASTM5
210-215
210-215
210-215
210-215
396-402
461-464
210-215
350-353
172-174 342-344
171-172 340-342
174-176
El-4
-------
TABLE I (Cont'd.)
Parameter
Organic
Chlorinated
Hydrocarbons
Endrin
Lindane
Methoxychlor
Toxaphene
Chlorophenoxys
2.4-D
Si 1 vex
Limit
mg/ liter
0.0002
0.004
0.1
0.005
0.1
0.01
Method
Gas Chroma tography
Gas Chroma tography
Reference
ASTM
*3
EPA Method J 609-624
EPA Method 4 595-602
1
2
Methods for Chemical Analysis of Water and Wastes, EPA, Office of Technology
Transfer, Cincinnati, Ohio 45268.
Standard Methods for the Examination of Water and Wastewater, 13th Edition,
1971, APHA, 1015 18th St., NU, Washington, DC 20036,
Method for Organochlorine Pesticides in Industrial Effluents, EMSL, EPA,
Cincinnati, Ohio 45268.
Method for Chlorinated Phenoxy Acid Herbicides in Industrial Effluents, EMSL,
EPA, Cincinnati, Ohio 45268.
Annual Book of ASTM Standards, 1977. Part 31.
Temperature °C
12.0 and below
12.1 to 14.6
14.7 to 17.6
17.7 to 21.4
21.5 to 26.2
26.2 to 32.5
TABLE 2
Fluoride MCL
MCL mg/1
2.4
2.2
2.0
1.8
1.6
1.4
-------
TABLE 3
Type of
Contaminant
Inorganic
Organic
Turbidity
Water
Source
Surface
Ground
Surface
Ground
Surface
Public Water Supply
Sampling Requirements
Sampling Period
Ini tated by^ Conclude By
Community Water Supplies
6/24/77 6/24/78
6/24/77
6/24/79
6/24/77 6/24/78
To be specified by
State
6/24/77
Sampling Frequency
Thereafter
at yearly intervals
every three years
If MCL is
Exceeded
collect 3
additional
samples in
one month
every three years or
as required by State
To be specified by State
must measure daily
resample
within one
hour
Inorganic-
Nitrate only
Turbidity
Non-Community Water Supplies
Surface 6/24/77 6/24/79
and
Ground
Surface 12/24/77
To be specified by
State
must be measured
daily
collect 3
additional
samples in
one month
resample
within one
hour
Report to State any violations within 48 hours, including violation of monitoring
requirements.
Report to State tests results within 40 days.
El-6
-------
IV. National Secondary Drinking Water Regulations
The Safe Drinking Water Act, Section 1412 C, required the EPA to propose
national secondary drinking water regulations. These regulations were to
be propsoed within 270 days after the enactment of the Safe Drinking Water
Act. Again, public comment was to be requested and acted upon before
promulgation of the secondary regulations. These secondary regulations
are to be based on contaminants that tend to make water disagreeable to
use, but that do not have any particular adverse public health effect.
The secondary regulations were proposed on March 31, 1977, and appeared in
final form on July 19, 1979, and included the following:
TABLE 4
Contaminant
Chloride
Color
Copper
Corrosivity
Foaming Agent
Iron
Manganese
Odor
Li mi t
250 mg/1
15 Color Units
1.0 mg/1
Non-Corrosi ve
0.5 mg/1
0.3 mg/1
0.05 mg/1
Method
Reference
EPA 14th Std, Meth,
Potentiometric
Platinum-Cobalt
Atomic Absorption
Reserved
Methylene Blue
Atomic Absorption
Atomic Absorption
3 Threshold Odor Consistent Series
Number
Sulfate
TDS
Zinc
6.5 - 8.5
250 mg/1
500 rng/1
5 mg/1
Glass Electrode
Turbidimetric
Total Residue
Atomic Absorption
36-38
108-109
157-158
110-111
116-117
287-294
239-240
277-278
270-271
155-156
306
64
144
600
144
144
75
460-465
496
91
144
These secondary regulations are applicable to all public water systems, but
are not enforceable on the Federal level and are intended as guidelines for
the states. However, depending on their legislation, may be enforceable
by the State.
El-7
-------
V. Alternate Test Procedures Approval
Section 141.27 of the National Interim Primary Drinking Water Regulations
permitted the establishment of a procedure for Approval of Alternate
Analytical Methods. On March 10, 1977, this procedure was established.
are allowed, a case by case procedure and a
Alternative analytical techniques
be published as amendments to the
Two parallel approval chains
procedure for national approval.
approved for nationwide yse will
Interim Primary Regulations in the Federal Register.
Several alternate methods have been approved for nationwide use and have
been published in the Federal Register.
TABLE 5
Measurement
Arsenic
Arsenic
Barium
Cadmium
Chromium
Fluoride
Fluoride
Fluoride
Fluoride
Method
1
1
Flameless Atomic Absorption, Graphite Furnace
Technique. Method 206.2.
Silver Diethyldithiocarbamate Method, Ref:
"Methods for Chemical Analysis of Water and
Wastes," pp. 9-10, EPA, Office of Technology
Transfer, 1974. Method 206.4.
Flameless Atomic Absorption, Graphite Furnace
Technique.
Flameless Atomic Absorption, Graphite Furnace
Technique.
Flameless Atomic Absorption, Graphite Furnace
Technique.
Automated Alizarin Fluoride Blue, Ref: "Standard
Methods for the Examination of Water and Wastewater,"
14th, pp. 614-616, 1975.
?
"Zirconium-Eriochrome Cyanine R, Ref: "Methods for
Collection and Analysis of Water Samples for
Dissolved Minerals and Gases," USGS, Book 5, Chapter
A 1, pp. 90-93.
Modified Automated Alizarin Fluoride Blue. Ref.
"Fluoride in Water and Wastewater Industrial Method
#129-71W" December 1972, Technicon Industrial Systems,
Tarrytown, Hew York 10591.
Automated Electrode Method. Ref: "Fluoride in Water
and Wastewater," Technicon Industrial Method #380-75WE."
February 2, 1976. Industrial Systems, Tarrytown,
New York 10591.
El-8
-------
Measurement
Lead
Mercury
Nitrate
Method
1
Nitrate
Organics
Organics (Pesticides)
Organics (Herbicides)
Selenium
Selenium
Silver
Turbidity
Sod ium
1
Flameless Atomic Absorption, Graphite Furnace
Technique.
Automated Cold Vapor Technique, Ref: "Methods
for Chemical Analysis of Water and Wastes,"
pp. 127-133, EPA, Office of Technology Transfer,
1974.
Automated Hydrazine Reduction, Ref: "Methods for
Chemical Analysis of Water and Wastes," pp. 185-
194, MERC, Analytical Quality Control Laboratory,
1971.
Automated Cadmium Reduction, Ref: "Methods for
Chemical Analysis of Water and Wastes," pp. 207-
212, EPA, Office of Technology Transfer, 1974.
?
"Gas Chromatographic, Ref: "Methods for Analysis of
Organic Substances in Water," USGS, Book 5, Chapter
A3, pp. 24-39.
"Standard Methods for the Examination of Mater and
Wastewater." 14th ed. 1975. Qrganochlorine Pesti-
cides, Part 509A, pp. 555-564.
"Standard Methods for the Examination of Water
and Wastewater." 14th ed. 1975. Chlorinated
Phenoxy Acid Herbicides, part 509B, pp. 565-569.
?
"Hydride generation - atomic absorption spectro-
photometry, USGS, Method, 1-1667-77, 1976.
Flameless Atomic Absorption, Graphite Furnace
Technique, Ref: Atomic Absorption Newsletter.
11, No. 5, pp. 100-116, 1975.
Flameless Atomic Absorption, Graphite Furnace
Technique.
j
Nephelometric method with styrene Divinylbenzene
Polymer Standards.
"Standard Methods for the Examination of Water and
Wastewater," 14th ed., pp. 250-253 or "Methods for
Analysis of Water and Wastes, p. 147.
The various furnace devices are considered to be atomic absorption techniques-
Methods of standard addition are to be followed as noted on p. 78 of "Methods
for Chemical Analysis of Water and Wastes," EPA, Office of Technology Trans-
fer, 1974.
E1-9
-------
2
Copies available from: Water Quality Branch, National Center, U.S.
Geological Survey, 112201 Sunrise Valley Drive, Reston, VA 22092.
3
Only the six pesticides named in the Interim Primary Drinking Water
Regulations are included: Endrin, Lindane, Methoxychlor, Toxaphene;
2,4-D; and 2,4,5-TP (Silvex). Federal Register, Vol. 40, No. 248,
pp. 59570-59571, December 24, 1975.
4
Additional information on this method is available from the Environmental
Monitoring and Support Laboratory. Commercial products of Amco-AEPA-1
Polymer are available from AMCO Standards International, Inc., 230 Polaris
Ave., No. C, Mountain View, California 94043.
El-10
-------
VI. Certification
Section 1401 (1) of the Safe Drinking Water Act defines "Primary Drinking
Water Regulations" to include "quality control and testing procedures" to
insure compliance with maximum contaminant levels. Pursuant to the Act,
the National Interim Primary Drinking Water Regulations, Section 141 and
142 require that for compliance purposes, "samples" will be considered
only if they have been analyzed by a laboratory approved by the State,
except that measurement for turbidity and free chlorine residual may be
performed by any person acceptable to the State, and the State must
establish and maintain a program for certification of laboratories
conducting measurement of drinking water contaminants.
A "Manual for the Interim Certification of Laboratories Involved in
Analyzing Public Drinking Water Supplies" has been compiled. This manual
describes how the Environmental Protection Agency will carry out a tentative
program for interim approval and certification of its ten Regional labora-
tories and principal State laboratories. States without certification
programs are encouraged to use this program as a model; States with equi-
valent or better certification programs are encouraged to continue and
improve.
The manual describes evaluation procedures and minimum technical requirements
recommended for certifying laboratories analyzing public drinking water
supplies. In addition to identifying requirements that are critical to
generation of valid data, optional certification requirements have been
included as guidance.
El- 11
-------
SAMPLING
I. INTRODUCTION
With the intent of the Safe Drinking Water Act being the insurance of
proper drinking water quality, meaningful analysis of the water is im-
perative to know if the water meets the standards. This analysis can
only be meaningful if it is performed on a samole that is representative
of the water to be analyzed. Consequently, the proper sampling technique,
use of proper containers, proper preservation and adherence to the set
frequency of sampling must be carefully observed.
In many instances the laboratories themselves will not be responsible
for sampling. However, it is necessary that all laboratories be aware of
what constitutes a representative, properly taken sample. It is the re-
sponsibility of all laboratories sampling for parameters under the Safe
Drinking Water Act to call for a resample if the sample does not meet proper
sampling procedures. To analyze a sample which has been doubtfully taken
is to present data which is dubious in meaning. If the laboratory is
responsible for taking the samples, it is doubly important that the persons
in the laboratory be aware of proper techniques.
There is at this time under development a "Handbook for Sampling and Sample
Preservation of Water and Hastewater" by the U.S. Environmental Protection
Agency. When this book is available it will serve as a good reference
source on the topic of sampling.
The Sampling section of the Criteria and Procedures Document for Laboratory
Certification spells out the mandatory requirements that must be adhered to
for the drinking water sampling. It is attached here for student reference
as this outline is read.
It has been suggested that one of the certification team members be from
the staff of the regional water supply staff. This individual would be
responsible to assess the following:
A. Choice of sampling location
B. Proper sampling procedures
C. Sample identification
D. Prompt sample transport to the laboratory
E. Sampling frequency
F. Bad-sample follow-up
G. Dissemination of data by the laboratory and use of the data
by the water supply supervision program
II. MONITORING REQUIREMENTS
A. Inorganic
1. Analysis for all community water systems utilizing surface water
sources shall be completed within one year following June 1977.
These analyses shall be repeated at yearly intervals.
2. Analysis for all community water systems utilizing only ground
water sources shall be completed within two years of June 1977.
These analyses shall be repeated at three year intervals.
CH.MET.33. 3.30
E2-1
-------
3. For non-community water systems, whether supplied by surface or ground
water sources, analysis for nitrate shall be completed within two years
of June 1977. These analyses shall be repeated at intervals determined
by the state or other regulatory agency.
Sample collecting, handling, and preservation — mandatory requirements
Parameter
Arsenic
Barium
Cadmium
Chromium
Lead
Mercury
Nitrate
Selenium
Silver
Fluoride
Chlorinated
hydrocarbons
Chlorophenoxys
Preservative
Cone HN03 to pH<2
Cone HNCL to nH<2
Cone HN03 to pH<2
Cone HN03 to pH<2
Cone HN03 to pH<2
Cone HN03 to pH<2
Cone
to pH<2
Cone HN03 to pH<2
Cone HN03 to pH<2
None
Refrigerate at 4°C
as soon as possible
after collection
Refrigerate at 4°C
as soon as possible
after collection
Container^- '
P or G
P or G
P or G
P or G
P or G
G
P
P or G
P or G
P or G
P or G
nth foil or
Maximum
holding time
6 months
6 months
6 months
6 months
6 months
38 days
14 days
14 days
6 months
6 months
1 month
14 days^
(2)
Teflon-1ined cap
G with foil or
Teflon-lined can
(1) P = Plastic, hard or soft, G = Glass, hard or soft
(2) In all cases, samples should be analyzed as soon after collection as
possible.
(3) Well-stoppered and refrigerated extracts can be held up to 30 days.
(4) If a laboratory has no control over these factors, the laboratory director
must reject any samples not meeting these criteria and so notify the authority
requesting the analyses.
(5) If nitric acid cannot be used because of shipping restrictions, sample may be
preserved by icing. Upon receipt in the lab, the sample must be acidified with
cone. HN07 to pH>2. At time of analysis, sample container should be thoroughly
O
rinsed with 1:1 nitric acid washings added to the sample to be processed for
subsequent analysis.
E2-2
-------
4. When the maximum contaminant level is surpassed, the frequency of
resample shall be designated by the state and shall continue until
the maximum contaminant level has not been exceeded in two successive
samples or until a monitoring schedule as a condition to a variance,
exemption or enforcement action shall become effective,
B. Organic
1. For all community water systems utilizing surface water sources,
analysis shall be completed within one year of June 1977, Samples
analyzed shall be collected during the period of the year designated
by the state as the period when contamination bv pesticides is most
likely to occur. These analysis shall be reoeated at intervals
specified fay the State, but in no less frequency than at three
year intervals,
2. For community water systems utilizing only ground water sources,
analysis shall be completed by those systems specified by the
State.
3. If the results of an analysis indicate that the level of any con-
taminant exceeds the maximum contaminant level, the supplier of
water shall report to the State within 7 days and initiate three
additional analyses within one month.
4, When the average of four analyses exceeds the maximum contaminant
level the supplier of water shall report to the State. Horn'toring
after public notification shall be at a frequency designated hy
the State and shall continue until the maximum contaminant level
has not been exceeded in two successive samples or until a moni-
toring schedule as a condition to a variance, exemption or enforcement
action shall become effective,
III. SAMPLE CONTAINERS
A. Types
Generally two types of containers are acceptable; these are glass and
plastic. Plastic is the more convenient from a shipping standnoint;
however, plastic ray not be used for the organic parameters. The glass
containers should preferably be made from a hard borosilicate glass
(Klmax or Pyrex; however, other forms may be used).
All these various materials have certain advantages and disadvantages.
The hard glass is inert to most materials. Conventional polyethylene
is to be used when plastic is acceptable because of reasonable cost
and less adsorption. Disposable type plastic containers, such as the
molded polyethylene "Cubitainer," are convenient to use.
Usually, a wide mouth container is praferred. This allows easy sample
removal and easier cleaning.
Depending on the State or Regional requirements, three or four con-
tainers will be needed for a complete analysis. Usually, a one qallon
or equivalent size plastic type container will suffice for the metals
analyses. A one quart or equivalent plastic container is needed for
E2-3
-------
the nitrate sample. A glass container holding about a quart with a
foil or Teflon lined screw cap is required for analyses of the
organics, and finally, a one quart plastic type container will be
needed for the fluoride parameter.
Considering the section on frequency of monitoring, the following
are needed for each public water supply in one years time:
1. One 1 gallon plastic container
2. Two 1 quart plastic container
3. One 1 quart glass container
Additional containers would be needed for resampling needs. A non-
community supply would probably need one 1 quart plastic container
each year unless resampling is to be carried out.
In addition to the containers themselves, some type of shipping
container must be provided for each sample container. These shipping
containers can usually be purchased from the supplier of the actual
sample container.
B. Preparation and Shipment of Containers
Individual responsibility to provide, maintain and clean sample con-
tainers is dependent on how the State has elected to carry out the
certification program. The laboratory or the authority could purchase
in large lots and make available sets of containers to each supply or
the State may elect to require the supply to provide their own con-
tainers. Generally speaking, the clastic containers should not be
reused for any trace analyses, that is, the metals. The qlass
containers should follow the suggested cleaning procedure, including
muffling at 400°C for about 15 minutes. Once cleaned, these containers
should be stored and shipped in such a manner as to prevent recontamination,
Should the decision to reuse plastic containers be made, they should
be cleaned carefully before reuse. There are several cleaning methods
available. Choosing the best method involves careful consideration
of the nature of the sample and of the constituent(s) to be determined.
1. Traces of dichromate cleaning solution will interfere with metal
analyses. Use 1:1 nitric acid wash.
2. Traces of nitric acid may interfere with the nitrate analysis.
Use detergent with thorough rinses with tap and distilled water.
Shipping the containers to the sampling locations should take into
consideration the numbers to be shipped and eliminate any contamination
chances. The shipping containers to be used in transporting the sample
itself to the laboratory must be provided either as a container for
the empty sample container or in bulk form.
-------
One item that must be given consideration is the preservative. Postal
regulations will not permit mailing of acids, particularly nitric
acid. Consequently, these materials must be purchased locally or
shipped by truck or other common carrier. If the materials are to be
purchased locally, the purity must be riqidly controlled to assure no
contaminants are present to effect results.
Even when the preservative nitric acid has been added and diluted by
the sample, postal restrictions may preclude the use of the mails.
Therefore, a special footnote has been added to the certification
procedures allowing an alternate icing followed by acidification upon
receipt of the sample in the laboratory.
When shipping the sample to the laboratory for analysis, sufficient
time should be allowed to assure that the holding times are not sur-
passed. Alternate forms of transportation should be checked out before-
hand to allow use if needed. The sample container must be protected
from physical damage in shipment and sufficient coolant added to the
ice chest or other form of insulated container to last through the
duration of shipment. Caps should be checked when the sample is taken
to assure that they will not leak. Upon receipt in the laboratory,
any deviation from the mandatory sampling requirements, i.e., preservative,
holding times, should be noted and, if necessary, a resample ordered
immediately.
IV. SAMPLE COLLECTING
According to the National Interim Primary Drinking Hater Regulations,
section 141.2(c), the sampling location is the "free-flowing outlet of
the ultimate consumer." Since this represents a minimal effort, one
sample can be taken at any point in the distribution system and fulfill
the regulation. Some States may require more frequent samples at randon
locations, or a single composite sample taken at various locations.
The exception to this sampling location is the turbidity sample which
must be taken at the point of entry of the water into the distribution
system.
When collecting the sample, the tap should be run to assure that the
water collected is from the distribution system and not from the private
pipes. The sample container should be flushed two or three times before
the actual sample is taken. The container should not be filled completely
to allow extra volume for effects of temperature during transit. The
preservative, if any, should be carefully added to the container, the
container capped and the sample shaken.
If the sample is to be cooled during shipment, the sample container
should be placed in an insulated container and sufficient coolant added
to last during shipment.
The sample should be labeled to identify it during future analyses. The
information should include:
A. Date, place and time of sampling; name of person collecting the
sample .
-------
B. Identification of the sample as to whether it is a routine distribution
system sample, check sample, raw or process water sample, or other
special purpose sample.
C. Analysis to be run on the sample as well as any preservative added and
what amount has been added.
D. Any other remarks that the sampler thinks is necessary.
This information should be affixed to the sample container in such a way
as to assure that it will not become separated in later handlings.
The Criteria and Procedures Document for Laboratory Certification states
that chain of custody procedures must be carried out on all samples taken
for potential enforcement actions only. The exact procedure and directions
on this procedure should be obtained from the appropriate certification
authority.
V. FIELD MEASUREMENTS
As set down in the act, there are two types of analysis which may be
carried out in other than certified laboratories. These are the analysis
for residual chlorine and turbidity. These measurements may be carried
out in the field. In addition, should any other information about the
sample be required, such as pH, temperature, etc., these should also be
carried out in the field. It is not the scope of this outline to discuss
the procedures involved in these analyses. Procedures on the residual
chlorine and turbidity have been included in this manual for information
purposes only and may be found under Tab E.
State regulations may require additional procedures to be carried out by
the person taking the sample. The Interim Primary Reflations do not.
VI. SUMMARY
Proper sampling is the foundation of meaningful analytical results. Con-
sequently, a laboratory should know what constitutes a meaningful sample
in order to judge wiien a resample is necessary due to improper sampling,
preservation or handling techniques.
The preservative to be added, the type of container and the holding times
are spelled out in the Criteria and Procedures Document in a mandatory
section.
The laboratory Certification Officer must evaluate whether or not the
laboratory is conducting a proper sample receipt procedure and, if it has
the responsibility, a proper sampling of the v/ater supplies.
-------
STATISTICS FOR CHEMISTS
I INTRODUCTION
A Statistics may be defined, for our purpose,
as a collection of methods which have been
developed for handling numerical data
pertaining to samples or portions of entire
populations.
B The statistical methods with which we will
concern ourselves deal with the presentation
and analysis of numerical data from samples.
H FREQUENCY
A Definitions
1 Frequency - indicates how many times
a particular score occurs in a collection
of data
Frequency table - a tabular arrange-
ment of data, ranked in ascending or
descending order of magnitude,
together with the corresponding
frequencies
Frequency histogram - a set of
rectangles having bases on a horizontal
axia with centers at the given scores
and heights equal to the corresponding
frequencies (See Figure 1)
Frequency polygon - a line graph of
frequencies plotted against scores
(can be obtained by connecting mid-
points of tops of rectangles in the
frequency histogram) (See Figure 1)
Figure 1
Frequency Histogram & Frequency Polygon
Frequency
— to w *» cj
11 1 1 1
X
X
X
X
^
X
^
/
/
/
S~
/v
t
•s
^N
S
"V
\
\
\
i,
\
\
V
1 I 1 I I
98 99 100 101 102
Chloride
ST. 25b. 11. 77
E3-1
-------
Statistics For Chemists
B Application
Consider the application of the above
definitions to the following set of data,
obtained from twelve determinations for
chloride in water.
Results (ujE/1)
100 101 99
101 100 100
99 102 100
SB 101 102
number of observations the median is
H
2
Xn + X
, the average of the
middle two scores,
4 Mean - arithmetic average of all the
values in the sample distribution, de-
noted by X, The formula for calcula-
ting the sample mean is
x -
Table 1
Frequency Table
Chloride (]tg/l) _ ____________ Frequency
98
99
100
101
102
1
2
4
3
2
III MEASURES OF CENTRAL TENDENCY
A Definitions
1 Central tendency - the tendency of
values to cluster about a particular
value in the distribution
2 Mode - that value which occurs most
frequently
3 Median - midpoint of an array of
scores. If there is an odd number of
observations, n, the median is
X!L±JL where Xn + 1
2
2
n+ 1
represents
the •'•' J value in the frequency
distribution. If ^ere is ^ even
where there are n number
of values.
B Aids in calculation of the mean
Application of the following two statements
can reduce errors and amount of time
apent in calculating the mean of a
distribution.
1
Adding or subtracting a constant to or
from each score in a distribution is
equivalent to adding or subtracting the
same constant to or from the mean of
the distribution. Thus the following
formula:
X H X± C
where the X^'s are the
values in the distribution with mean X,
and the Xj ± C's are the_values in the
distribution with mean Xc.
2 Multiplying or dividing each score in
B distribution by a constant is equivalent
to multiplying or dividing the mean of
the distribution by the same constant.
Thus the following formulas:
(1) Xc = CX
or
xc =
where the X.'s are the
values in the distribution with mean X,
-------
Statistics for Chemists
and the CX^s or the
's are the
in the distribution with mean
C Application
Consider the application of the above
definitions to the previously mentioned
set of data, obtained from twelve deter-
minations for chloride in water, shown
in Table 1.
1 Mode = 100
2 Median =
100 + 100
2
= 100
X =
c
Denote the mean of the distribution in
Table 1 by X . If we add 100 to each
score in the distribution in Table 2, we
obtain the scores in the distribution in
Table 1; likewise if we add 100 to the
mean, X, of the distribution in Table 2,
we obtain the mean, X , of the distri-
bution in Table 1.
Thus X = X + 100
c
X =-
c n
100
l(-2) + 2(-l) + 4(0) + 3(1) + 2(2)
12
+ 100
X = .25 + 100 - 100.25
3 Mean =
n
98 + 2 (99) + 4 (1DO[ + 3 (101) 4- 2 (102)
12
= 100.25
4 Aid in Calculation
Consulting Table 1 and observing that
the values are in the neighborhood of
100 we might subtract 100 from each
score and obtain the following distribution:
Table 2
Frequency Table
Chloride C{*g/l) Frequency
-2 1
-1 2
0 4
1 3
2 2
IV MEASURES OF DISPERSION
A Definitions
1 Dispersion - spread or variability of
observations in a distribution
2 Range - the difference between the
highest value and the lowest value
R - max - min
3 Average deviation - the sum of the
deviations of the values from their
mean, without regard to sign, divided
by the total number of data values (n)
The formula for calculating the average
deviation is:
d.
E3-3
-------
Statistics for Chemists
Average deviation of the mean (D) -
the average deviation of Individual
data items from the mean (d) divided
by the square root of the number of
data items (n)
The definition of the average deviation
of the mean can be expressed by the
formula:
d
D = , — -
•J n
Variance - the sum of the squares of
the deviations of the values from their
mean divided by the total number of
data values (n) minus 1
The definition of the- variance can be
expressed by the following formula:
n - 1
Standard deviation - the square root
of the variance
The definition of the standard deviation
can be expressed by the following
formula;
However, the formula commonly used
because of its adaptability to the hand
calculator is the following:
where there are
n number of values.
The definition of the standard
deviation of the mean can be
expressed by the formula:
S =
B
/ n
Relative standard deviation - the
standard deviation (s) expressed as
a fraction of the mean, s
The relative standard deviation is
often expressed as a percent. It is
then referred to as the coefficient
of variation (V):
V = ~ X 100 = %
X
The relative standard deviation is
particularly helpful when comparing
the precision of a number of deter-
minations on a given substance at
different levels of concentration.
B Aids in Calculation
Application of the following statements
can reduce errors and amount of time
spent in calculating the variance or
standard deviation of a distribution.
1
Adding or subtracting a. constant to or
from each score in a distribution
doesn't affect the variance or standard
deviation of the distribution.
Thus the following formulas:
(D
(2)
2 2
8 = S
C
n - 1
Standard deviation of the mean (S) - the
standard deviation of individual data
items (s) divided by the square root of
the number of data items (n)
S « S
C
where the X.'s are the values in
the distribution with variance s
and standard deviation s, and the
Xj +•' C's are the values in the
distribution with variance s ^
and standard deviation s . C
E3-4
-------
Statistics for Chemists
2 Multiplying or dividing each score in
a distribution by a constant is equivalent
to multiplying or dividing the variance
of that distribution by the square of the
same constant.
Thus the following formulae:
(1) 82 = C2S2
where the X;'s are the values in
o
the distribution with variance s ,
"V"
and the CX.'s or the ..... _ i 's are
the values in the distribution with
variance s ,
3 Multiplying or dividing each score in a
distribution by a constant is equivalent
to multiplying or dividing the standard
deviation of that distribution by the
same constant.
Thus the following formulas:
(1) s = Cs
or c
(2) .-£
where the Xj's are the values in
the distribution with standard
deviation s, and the CX.'s or the
"V" »
r;| 's are the values in the
C
distribution with standard
deviation s ,
C Application
Consider the application of the above
definitions to the previously mentioned
set of data, obtained from twelve
determinations for chloride in water,
shown in II B, Table 1.
1 Range =» 102 -98 * 4
~ X 1
4
n
1
2
4
3
2
Average aeviat;
Xi
98
99
100
101
102
X = 100.25
. _j:fXi~ x|
ion - Q -
|Xt- X|
2. 25
1.25
. 25
. 75
1. 75
11. 50
n
njXj^Xl
2. 25
2. 50
1.00
2.25
3. 50
11.50
- . 9fi
12
3 Average deviation of the mean -
Using calculations from number 2,
D . d * 0.96 = 0.96 = Q 2fl
,— .__. 3.46
•J n s/12
n
1
2
4
3
2
.2 .
Xt
98
99
100
101
102
Xi-X
-2. 25
-1. 25
- .25
+ . 75
+1. 75
I- X)2
n-1
(Xi- X)2
5.06
1.56
. 06
. 56
3. 06
16.22
n(Xi- X)2
5.06
3. 12
. 24
1. 68
6. 12_
16.22
A1
n- i
E3-5
-------
Statistics for Chemists
/
n Xj nXi X ,
1 98 98 9604
2 99 198 9801
4 100 400 10000
3 101 303 10201
2 102 204 10404
1203
/ 2
/120617--i222. /
_ - / 12 /120617
° V 11 4U
n - 1
nx!i
;:: .- AV-sf.ynr . ,„
7 n v/
40000 v n - 1
30603
20808 7 Standard deviation of the mean -
120617 s s
120801 Using calculations from number G,
1
s =
..21
3.46
6 Aid in calculation
Recalling that adding or subtracting a
constant to each score in the distri-
bution doesn't affect the variance or
the standard deviation of the distribu-
tion we can simplify the computations
by first subtracting 100 from each
score in the distribution, thus obtain-
ing the frequency distribution shown
in Table 2.
n
1
2
4
3
2
xrc n(xrc) oq-c)2 n(xrc)2
EX-
*
n - 1
8 Relative standard deviation expressed
as a percent (coefficient of variation)
V « -2- X100
X
Using calculations from number 6 for
s = 1. 22 and from number 2 for
X = 100.25,
Figure 2
Normal Distribution Curve
Quantity Measured
E3-6
-------
Statistics for Chemists
INTRODUCTION TO NOHMA L
DISTRIBUTION CURVE
Statistics deals with theoretical curves
which are smoother than frequency
polygons, obtained from experiments in
real life. However, frequency distribu-
tions or frequency polygons of experimental
data often approximate a mathematical
function called the "normal" distribution
curve. (See Figure 2)
As shown in Figure 3, the frequency polygon
for the 12 determinations for chloride in
water is a fairly good approximation of the
normal curve. If, however, in the chloride
determinations we had obtained 103 instead
of 98 and 104 instead of 99 this distribution
would not have- been a good approximation of
the normal curve, as is shown in Figure 4.
Figure 3
Comparison of Normal Curve and Frequency Polygon
o
a
a*
in
•
97
98 99 100 101
Chloride wg/l
102
Figure 4
Comparison of Normal Curve and Frequency Polygon
E3-7
-------
for Chemists
B If a frequency distribution is a good
approximation of the normal curve, we
can use some facte about the normal
curve to give us information about the
frequency distribution.
Figure 5 shows the normal distribution
in terms of the population mean u, and
the standard deviation of the population
o , and gives the percent of area under
the curve between certain points.
Figure 5
Normal Distribution Curve
Figure 6
Frequency Distribution Polygon
o
c
0)
3
O"
Q)
l-f
/Tv
/
1
/ i'
^L f
' P !
-2s I -Is
98
/
/
i
i
99
>
1(
'
1
r
)0
I
101
J N
1 f.
1 j\
i it
+ ls * +2 a
102
k
V
\
Chloride ng/1
E3-8
-------
Statistics for Chemists
We may check the distribution of sample
data to see if it is a "normal" distribution
in the following manner. Substitute the
value of the sample mean (X) for the value
of the midline and substitute the value of
the sample standard deviation (s) for the
limits of the value spans where we might
expect certain percentages of the data
items to occur. Then we can check the
number of data items which actually do
occur within these value spans.
Figure 6 demonstrates this application
using the chloride data values from Table 1.
The data values are marked on the hori-
zontal line and the frequency of the
occurrence of each value is marked on the
vertical. The midline of the distribution
is marked at the value of the sample mean
GT = 100, See HI C 3). The value of the
sample standard deviation (s = 1.21, See
IV C 5) is used to mark value areas under
the curve where different percentages of
data values will probably occur. Thus,
for the area X + IB, X - Is = 98. 79 and
X + 1 s = 101.21. Therefore, according
to the normal distribution curve shown in
Figure 5, we might expect about 68% of the
data items to have values between 99 and
101. (The values are rounded to whole
numbers since the data values are thus
recorded).
Consulting Table 1, we find that 75% or 9
of the 12 data items have values in this
range. This percentage is shown in
Figure 6 by the frequency polygon for the
data shown earlier in Figure 3.
Likewise assuming a normal distribution,
we would expect 95% of the observations
to lie within +2 g 's from the population
mean. In fact, 100% of the observations
were within + 2 s's from the sample mean.
In both cases the observed percentages are
reasonably close to the expected percentages.
Other tests exist for determining whether
or not a frequency distribution might
reasonably be assumed to approximate
the normal distribution.
It would be good to become as familiar as
possible with the normal distribution since
an underlying normal distribution is
assumed for many statistical tests of
hypothesis.
REFERENCES
1 Bennett, C.A. and Franklin, N. L.
Statistical Analysis in Chemistry and
the Chemical Industry. John Wiley
& Sons, Inc., New York. 1954,
2 Crow, E. L., Davis, F.A., and Maxfield,
M.W. Statistics Manual. Dover
Publications, Inc., New York. 1960.
3 Dixon, W.J. and Massey, F.J,
Introduction to Statistical Analysis.
McGraw-Hill Book Co., Inc., New
York. 1957.
4 Ostle, B. Statistics in Research. The
Iowa State University Press, Iowa.
1963.
Youdon, W.J.
Chemists.
New York.
Statistical Methods for
John Wiley & Sons, Inc.,
1951.
This outline was prepared by L. A, Lederer,
Statistician, formerly with Analytical
Reference Service, Training Program,
NCUIH, SEC. Revised by Audrey D.
Kroner, Chemist. National Training and
Operational Technology Center, MOTD, OWPO
USEPA, Cincinnati, Ohio 45268.
Descriptors: Graphic fVJethods, Quality Control,
Statistical Methods. Statistics
E3-9
-------
QUALITY CONTROL
I. INTRODUCTION
The purpose of the Safe Drinking Water Act is to assure the public of an
adequate supply of safe water. To achieve this, maximum levels of certain
contaminants were proposed along with the prescribed methodology for analyz-
ing for these parameters. When a laboratory performs these analyses, the
laboratory should practice quality control to assure that the results being
reported are true values and not in error.
Data developed from these examinations must be reliable and beyond reproach.
The data can be used for making judgments on technical operations in water
treatment or in legal actions involving public health hazards. For these
reasons the U.S. Environmental Protection Agency in its Manual for the
Interim Certification of Laboratories Involved in Analyzing, Public Water
Suppl ie's has set down some required and some optional quality control
procedures.
The entire section contained in the "Manual for Certification" document is
considered as the minimum acceptable program on quality control that a
laboratory can carry out and still expect reliable results. Most labora-
tories will want to go beyond these minimum requirements and include more
quality control.
This outline will cover the minimum quality control procedures, then go
into the optional portions and proceed further into some ideas not in the
Manual for Certification document. The reasons for going further are to
acquaint laboratory certification personnel with sufficient information
to be able to evaluate whether the laboratory has complied with the mini-
mum sections and allow the Certification Officer to recommend further
procedures. The topic of quality control from all aspects in a laboratory
is well covered -in the Handbook for An^y_tJ£aJ^Qu._a_1 vty Control in Water and
Wastewater Laboratories produced by the EPA and available from the Office
of Technology Transfer. The Certification Officer should keep in mind that
technical assistance to the laboratory he is evaluating is of prime impor-
tance because through this assistance he can upgrade the laboratory to
produce better results.
Assistance to state Certification Officers can be obtained from the regional
certification authority, the Analytical Quality Control Officer in the region,
or from Environmental Monitoring and Support Laboratory in Cincinnati, Ohio.
The Quality Control section of the Criteria and Procedures document has been
attached for the use of the trainee.
II. QUALITY CONTROL FOR CHEMICAL ANALYSIS
A. Minimum Requirements
1. All quality control data must be available for inspection.
CH.MET.con.8a.10.78
E4-1
-------
2, Laboratory must analyze an unknown performance sample (when
available) once per year for parameters measured. Results must
be within the control limits established by EPA for each analysis
for which the laboratory wishes to be certified. If problems
arise, appropriate technical assistance will be provided, and a
follow-up performance sample should be analyzed.
3. Minimum Daily Quality Control
a. After a standard reagent curve composed of a minimum of a reagent
blank and three standards has been prepared, subsequent standard
curves must be verified by use of at least a reagent blank and
one standard at or near the MCL. Daily checks must be within +_ 10
percent of original curve.
b. If 20 or more samples per day are analyzed, the working standard
curve must be verified by running an additional standard at or
near the MCL every 20 samples. Checks must be within +_ 10 per-
cent of original curve.
B. Optional Requirements: The following quality control requirements are
optional.
1. Current service contract is in effect on all balances.
2. Class S weights are available to make periodic checks on balances.
3. Thermometer certified by the National Bureau of Standards (or one
of equivalent accuracy) is available to check thermometers in ovens,
etc.
4. Color standards or their equivalent are available to verify wave-
length settings on spectrophotometers.
5. Chemicals dated upon receipt of shipment and replaced as needed or
before shelf life has been exceeded.
6. Criteria have been established for a laboratory analyzing supply
samples other than its own:
a. Laboratory should perform on a known reference sample (when
available) once per quarter for the parameters measured. The
measured value should be within the control limit established
by EPA for each analysis for which the laboratory wishes to be
certified.
b. At least one duplicate sample should be run every 10 samples, or
with each set of samples, to verify precision of the method.
Checks should be within the control limits established by EPA
for each analysis for which the laboratory wished to be certified.
c. Standard deviation should be calculated and documented for all
measurements being conducted.
d. Quality control charts or a tabulation of mean and standard
deviation should be used to document validity of data on a
daily basis.
E4-2
-------
C. The Minimal Requirements
1. All quality control data must be available for inspection. This
statement assures the availability of the data. The person certifying
the laboratory might wish to make use of these data to assure himself
that the laboratory is practicing quality control and to what extent.
After an amount of data have accumulated, it can serve as a record of
a continuing type of quality control rather than a sporadic, hit or
miss type. At any time, should there be questions on the reliability
of any data, the quality control records will be available to show the
reliability of the data produced during the time period in question.
The guidelines for data reporting recommend that the records of chemical
analyses should be kept by the laboratory for not less than three years.
It would seem prudent that all quality control data be kept for a like
period of time.
Data required would include a record of the results of the yearly per-
formance sample, a standard curve for each method the laboratory has been
certified for, the records showing a check of this curve daily or each
time the analysis is carried out. If the laboratory analyzes 20 or more
samples per day, records should include the value of a standard run after
every 20 samples. Again, this is for a minimal program and it would be
well for laboratories to adopt at least the recommended procedures listed
in the Manual for Certification document.
2. Laboratory must perform on an unknown performance sample once per year
for parameters measured,
In a minimal program this yearly check sample would be the first
external indication of a problem in a laboratory to the certifying
authority. The required daily quality control data would not be
sent to the certifying authority. If unacceptable answers were
obtained for one or more parameters, the laboratory would be asked to
analyze a follow-up performance sample. If continued problems existed,
the certifying authority could offer some form of technical assistance
to rectify the problem. If the data is borderline or perhaps sporadic
in nature, the Certifying Officer might wish to schedule his next visit
at a time when the questionable analytical method is being performed.
The principal state laboratory, as well as local laboratories, will be
required to analyze an unknown performance sample. This sample will
be provided by the regional authority which will certify that labora-
tory in each state. The U.S. Environmental Protection Agency also
plans to make available to states samples which can be used as per-
formance samples for local laboratories which the state has responsi-
bility for certifying. The performing laboratory will be given results
of their analysis in terms of being within or out of the acceptable
1imits.
Results must be within the control limits established by EPA for each
analysis for which the laboratory wished to be certified.
The laboratory will be informed if they have or have not complied with
this requirement by the authority supplying the performance sample.
E4-3
-------
3. A standard curve must be prepared and kept for each parameter the
laboratory analyzes for. This curve must be prepared with a minimum
of blank and three standards. The references for the analytical methods
will provide the laboratory with the range of the test. Good procedure
would dictate choosing the three standards to cover this entire range.
A high, low and mid-range standard would be best to run. In order to
assure good coverage the laboratory should be encouraged to run more
than the minimal requirements as listed above. A good recommended
procedure is to prepare the initial curve with a blank and eight
standards covering the entire range.
If more than one analyst will run the same test, it would be wise to
have each analyst check their procedural technique by checking the
standard curve.
After the initial curve has been established, it should be verified
by the use of at least a reagent blank and one standard which has a
concentration at or near the MCL of the contaminant. Again, the Certi-
fication Officer should encourage more than the required minimum
daily check. The recommendation for good technique recommends a
blank and two standards, one high and one low concentration.
These required daily checks of the standard reagent curve should
be within +_ 10% of the original concentration value. For example,
if the MCL was 0.50, a standard at this level analyzed as an un-
known should fall between 0.55 and 0.45. If not, the analyst
should check in the following order:
a. Any variable instrument parameters
b. Rerun check sample
c. Prepare new standard
d. Prepare all reagents fresh
e. Check shelf life of chemicals
f. Check instrument.
If the value persists at the new value through all this, then the
analyst should prepare a new standard curve.
The laboratory Certification Officer should check to see if the
daily records indicate that the curve has been checked (blank and
1 standard) and verified after each 20 samples with a standard run.
D. Guidelines
The following items are classed in the Criteria and Procedures document
as recommended. However, a certain amount of importance must be attached
to each item. The committee preparing the document felt strongly enough
about these items to keep them in the document. Common laboratory
practice would assure that these items be carried out.
E4-4
-------
1. Current Service Contract on All Balances
The analytical balance is of great importance in a laboratory. As
reagents are weighed on this piece of equipment, care must be taken
to assure that it is in good working order. The laboratory Certi-
fication Officer should question the head chemist as to the existence
of a service contract on the balances. Should the laboratory Certi-
fication Officer need additional information on proper care of a
balance there is a section in the Handbook for Analytical Quality
Cgnt_rp1_m Water and Wastewater Laboratorjes,.
2. Class S Weights Available to Make Periodic Checks on Balances.
This could be included as part of the routine service contract or
a set purchased and shared with the bacteriological laboratory
which will also have need for them. A very complete set of directions
for checking the performance of a balance is contained in Part 30 of
ASTM Standards.
3. NBS - Certified Thermometer Available to Check Thermometers in Ovens, etc.
Again this item could be a shared item between chemical and bacteriological
laboratories. The Certification Officer could carry this item with him
and provide this service to the smaller type laboratories. Since this
item is only recommended, the Certification Officer can only question
if this thermometer is avaialble and used.
4. Color Standard or Their Equivalent Available to Verify Wavelength
Settings on Spectrophotometers.
The spectrophotometer like the balance is a very important piece of
laboratory equipment. The Certification Officers should make them-
selves thoroughly aware of the proper techniques for care, use and
calibration of a spectrophotometer. Again the Handbook for Analytical
Quality Control is a good place to start.
Spectrophotometers should be checked for wavelength alignment. If a
particular colored solution is to be used at a closely specified wave-
length, considerable loss of sensitivity can be encountered if the
wavelength control is misaligned. In visual instruments, an excellent
reference point is the maximum absorbance for a dilute solution of
potassium permanganate, which has a dual peak at 526 mu and 546 my.
On inexpensive graphing instruments, which possess less resolution
than the prism instruments, the permanganate peak appears at 525 to
550 my as a single flat-topped spike.
Another point that should be mentioned is the care and use of spectre-
photometric absorption cells. If possible, the Certification Office
should observe the techniques of the laboratory in the use of the
cells. Good techniques here could indicate good technique in all
the colorimetric procedures.
E4-5
-------
5, Chemical Dated Upon Receipt of Shipment and Replaced as Needed or
When Shelf Life is Exceeded.
It should not be necessary to store clean glassware or chemicals
on bench tops. Floor length cabinets or above bench cabinets should
be available for storage. Chemicals themselves should be of analytical
reagent grade to assure good quality. Dating the chemical upon receipt
will give the chief chemist an Indication of the amounts to order and
if the chemical can still be relied on to have its initial quality.
6. Laboratories Analyzing Water Supply Samples Other Than Its Own
Should Carry Out Additional Quality Control. This section covers
. additional optional items for the larger laboratories.
a. Laboratory should perform on a known reference sample (when
available) once per quarter for the parameters measured.
Since the yearly known performance sample will not indicate to
the laboratory how well it is doing, other than pass or fail,
a known sample will show how the laboratory compares in precision
and accuracy to that given for the various methods. Analysis of
the known sample will allow comparsion and show any trend of the
quality control of the laboratory. These data should be available
to the Certification Officer for inspection.
This known quality control check sample should be available to
the laboratory from the principal state laboratory. If not, a
synthetic sample prepared by the head chemist can be used. This
control can be a large sample from a natural source known to
contain the constituents of concern or a synthetic sample prepared
in the laboratory from chemicals of the highest purity grade. In
either case, if the control is to be kept, it should be stabilized
by addition of a suitable preservative. See the section on
sampling for the choice of preservative.
b. The measured value should be within the control limits established
by EPA for each analysis for which the laboratory wishes to be
certified.
Precision data can be found in one or the other standard
references. That is
1) Standard Methodsforthe Examinationof Water and Wastewater,
13th Edition (1971).""~
2) Manual of Methods for the Chemical Analysis of Waterand Wastes,
1974 Edition.
These data have been accumulated in Table I. If this data does
not fulfill the need of the Certification Officer, he may write to
the U. S. Environmental Protection Agency, EMSL, Cincinnati, Ohio
45268 and request additional information on accuracy and precision.
E4-6
-------
c. At least one duplicate sample should be run every 10 samples,
or with each set of samples, to verify the precision of the
method. Checks should be within the control limits established
by EPA for each analysis for which the laboratory wishes to be
certified.
In order to document that reproducible results are being obtained
(i.e. precision of the method), it is necessary to run duplicate
samples. Although the frequency of such replicate analysis is,
by nature dependent on such factors as the original precision
of the method, the reliability of the instrumentation involved
and the experience of the analyst, good laboratory technique is
to run duplicate analysis at least ten percent of the time.
The resulting data should be within the control limits established
by EPA. If the data do not agree, the system is not under con-
trol, and results are subject to question.
d. Standard deviation should be calculated and documented for all
measurements being conducted.
This calculation will provide the upper and lower control limits
for the test. Analysts can then determine whether or not the
data produced is acceptable. This data can be calculated on
seven replicate determinations for initial comparsion. However,
as additional determinations are performed, they should be added
to existing data and the precision data recalculated. Twenty
or more runs tend to present better statistical data.
Standard deviation calculations should be determined for each
analyst to carry out the analysis. However, the data should
not be collected until the analyst is familiar with the pro-
cedure. The concentration used to calculate the standard
deviation should be at the level expected in the sample for those
laboratories doing only their own water. For laboratories
doing determinations other than their own supply it would be
best to have the standard deviation calculated at several
concentrations. However, for a minimal effort, the concentration
should be chosen at or close to the maximum contaminant level
for the parameter.
In order to assure this data is collected, the standard run after
each 20 samples could be at the concentration used to determine
the standard deviation. This would produce a constant flow of
this data for inclusion in future updates of the standard devia-
tion calculation.
e. Quality control charts or a tabulation of mean and standard
deviation should be used to document the validity of data on
a daily basis.
If the upper and lower control limits of t 2 standard deviations
are calculated, the analyst will have some idea as to the
acceptability of each determination as the results are obtained.
When outliers are found the analyst can reschedule these for
analysis to assure themselves of the result before action is
taken to call for a resample of the supply.
F4-7
-------
Production of quality control charts and subsequent graphing
of the charts of data obtained in the laboratory will give
pictorial representation of the control of the method. Ten-
dencies toward one or the other control limit will indicate
loss of control of the method.
How to produce quality control charts and a discussion of these
statistical tools is covered in the Basic Statistics outline
and in the Handbook for Analytical Quality Contrpj inWater and
Wastewater Laboratories.
E4-8
-------
TABLE I
Maximum
Contaminant
Level ug/1
50
1000
10
50
50
2
10
50
10,000
Varies with
Temperature
Parameters
Arsenic
{Gaseous Hy-
dride)
Barium
(Standard
cond, )
Cadmium
(Extracted)
Chromium
(Standard
cond.)
Lead
(Extracted)
Mercury
(Flameless
AA Inst.)
Selenium
(Gaseous Hy-
dride)
Silver
(Standard
cond.)
Nitrate
(Brucine)
Cadmium Red
Fluoride
(SPADNS
with
Distil)
Electrode
Relative
Standard Standard
Cone. Deviation Deviation
W9/1 s ug/1 RSDf Reference
20.0 + 1.1
10.0
40.0 43
1000
500
10
50
74 29
50
50
50
50
3.4 1.49
0.4
10 1.1
10
50
5000
1040 10
5000
570
570 1 30
750
900
750 36
6.0
8.9
10.0
72.8
43.8
26.4
26.4
23.5
23.5
21.2
11.0
17.5
15.4
9.2
17.2
4.8
2.9
E.P
Std
E.P
Std
Std
Std
Std
E.P
Std
Std
Std
Std
E.P
Std
E.P
Std
Std
Std
E.P
Std
Std
E.P
Std
Std
E.P
.A. Methods - 95 9
. Methods (14th) 146^
.A. Methods - 98
. Methods (13th) 215
. Methods (14th) 146
. Methods (13th) 213
. Methods (14th) 148
.A. Methods - 106
. Methods (13th) 215
. Methods (14th) 146
. Methods (13th)
. Methods (14th)
.A. Methods - 125
. Methods (14th)
.A. Methods
. Methods (14th)
. Methods (13th)
. Methods (13th)
.A, Methods - 206
. Methods (13th) 464
. Methods (13th)
.A. Methods - 59
. Methods (13th)
. Methods (13th)
.A. Methods -67
Where more than one concentration and Standard Deviation is given in the same
reference the closest to the maximum contaminant level has been given.
Although not an official reference, data included here.
E4-9
-------
III. SUMMARY
the quality control items in the Criteria and Procedures document identify a
minimal effort for all types of laboratories. Since quality control is for
the benefit of the laboratory in assuring valid data, it would seem wise for
all laboratories to practice a good deal more quality control than set down
in the Criteria Procedures document.
This section has discussed the quality control steps to be taken to assure
proper analytical performance in the laboratory. However, a complete picture
of quality control would include adherence to proper sampling techniques, in-
cluding collection, preservation and handling; use of acceptable methods, and
proper reporting of data to be considered. It must be recognized (and practiced),
however, that quality control begins with collection and does not end until
resulting data are reported.
E4-10
-------
LABORATORY SAFETY PRACTICES
I INTRODUCTION
A Safe Use, Handling and Storage of Chemicals
I Chemicals in any form can be safely
stored, handled, and used if their
hazardous physical and chemical
properties are fully understood and the
necessary precautions, including the
use of proper safeguards and personal
protective equipment are observed.
2 The management of every unit within a
manufacturing establishment must give
wholehearted support to a well integrated
safety policy.
B General Rules for Laboratory Safety
1 Supervisory personnel should think
"safety, " Their attitude toward fire
and safety standard practices is reflected
in the behavior of their entire staff.
2 A safety program is only as strong as
the worker's will to do the correct
things at the right time.
3 The fundamental weakness of most
safety programs lies in too much lip
service to safety rules and not enough
action in putting them into practice.
4 Safety practices should be practical and
enforceable.
5 Accident prevention is based on certain
common standards of education, training
of personnel and provision of safeguards
against accidents.
II LABORATORY DESIGN AND EQUIPMENT
A Type of Construction
1 Fire-resistant or noncombustible
2 Multiple story buildings should have
adequate means of exit.
3 Stairways enclosed with brick or
concrete walls
4 Laboratories should have adequate exit
doors to permit quick, safe escape in
an emergency and to protect the
occupants from fires or accidents in
adjoining rooms. Each room should be
checked to make sure there is no
chance of a person being trapped by
fire, explosions, or release of dangerous
gases.
5 Laboratory rooms in which most of the
work is carried out with flammable
liquids or gases should be provided
with explosion-venting windows.
B Arrangement of Furniture and Equipment
1 Furniture should be arranged for
maximum utilization of available space
and should provide working conditions
that are efficient and safe.
2 Aisles between benches should be at
least 4 feet wide to provide adequate
room for passage of personnel and
equipment.
3 Desks should be isolated from benches
or adequately protected,
4 Every laboratory should have an eye-
wash station and a safety shower.
C Hoods and Ventilation
1 Adequate hood facilities should be
installed where work with highly toxic
or highly flammable materials are used.
2 Hoods should be ventilated separately
and the exhaust should be terminated
at a safe distance from the building,
3 Make-up air should be supplied to
rooms or to hoods to replace the
quantity of air exhausted through the
hoods.
PC.SA.lab. 1. 11.77
E5-1
-------
Laboratory Safety Practices
4 Hood ventilation systems are best
designed to have an air flow of not less
than 60 linear feet per minute across
.the face of the hood, with all doors open
and 150, if toxic materials are involved.
5 Exhaust fans should be spark-proof if
exhausting flammable vapors and
corrosive resistant if handling corrosive
fumes.
6 Controls for all services should be
located at the front of the hood and
should be operable when the hood door
is closed,
7 All laboratory rooms should have the
air changed continuously at a rate
depending on the materials being
handled,
D Electrical Services
1 Electrical outlets should be placed
outside of hoods to afford easy access
and thus protect them from spills and
corrosion by gases.
2 Noninterchangeable plugs should be
provided for multiple electrical services.
3 Adequate outlets should be provided and
should be of the three-pole type to
provide for adequate grounding.
E Storage
1 Laboratories should provide for adequate
storage space for mechanical equipment
and glassware which will be used
regularly,
2 Flammable solvents should not be stored
in glass bottles over one liter in size.
Large quantities should be stored in
metal safety cans. Quantities requiring
containers larger than one gallon should
be stored outside the laboratory,
3 Explosion proof refrigerators should be
used for the storage of highly volatile
and flammable solvents.
4 Cylinders of compressed or liquified
gases should not be stored in the
laboratory,
F Housekeeping
1 Housekeeping plays an important role
in reducing the frequency of laboratory
accidents. Rooma should be kept in a
neat orderly condition. Floors, shelves,
and tables should be kept free from
dirt and from all apparatus and chemi-
cals not in use.
2 A cluttered laboratory is a dangerous
place to work. Maintenance of a clean
and orderly work space is indicative of
interest, personal pride, and safety -
mindedness.
3 Passageways should be kept clear to all
building exits and stairways.
4 Metal containers should be provided for
the disposal of broken glassware and
should be properly labeled.
5 Separate approved waste disposal cans,
should be provided for the disposal of
waste chemicals.
6 Flammable liquids not miscible with
water and corrosive materials, or
compounds which are likely to give off
toxic vapors should never be poured
into the sink,
G Fire Protection
1 laboratory personnel should be
adequately trained regarding pertinent
fire hazards associated with their work.
2 Personnel should know rules of fire
prevention and methods of combating
fires.
3 Fire extinguishers (CO type) should
be provided at convenient locations and
personnel should be instructed in their
use.
4 Automatic sprinkler systems are
effective for the control of fires in
chemical laboratories.
E5-2
-------
Laboratory Safc;ty Practices
H Alarms
An approved fire alarm system should
be provided.
Wherever a hazard of accidental release
of toxic gases exists, a gas alarm
system to warn occupants to evacuate
the building should be provided.
Gas masks of oxygen or compressed air
type should be located near exits and
selected personnel trained to use them.
Ill HANDLING GLASSWARE
A Receiving, Inspection and Storage
1 Packages containing glassware should
be opened and inspected for cracked or
nicked pieces, pieces with flaws that
may become cracked in use, and badly
shaped pieces.
2 Glassware should be stored on well-
lighted stockroom shelves designed and
having a coping of sufficient height
around the edges to prevent the pieces
from falling off.
B Laboratory Practice
1 Select glassware that is designed for the
type of work planned,
2 To cut glass tubing or a rod, make a
straight clean cut with a cutter or file
at the point where the piece is to be
severed. Place a towel over the piece
to protect the hands and fingers, then
break away from the body.
3 Large size tubing is cut by means of a
heated nichrome wire looped around the
piece at the point of severance.
4 When it is necessary to insert a piece
of glass tubing or a rod through a
perforated rubber or cork stopper,
select the correct bore so that the
insertion can be made without excessive
strain.
5 Use electric mantels for heating
distillation apparatus, etc.
6 To remove glass splinters, use a
whisk broom and a dustpan. Very
small pieces can be picked up with a
large piece of wet cotton.
IV GASES AND FLAMMABLE SOLVENTS
A Gas Cylinders
1 Large cylinders must be securely
fastened so that they cannot be dis-
lodged or tipped in any direction.
2 Connections, gauges, regulators or
fittings used with other cylinders must
not be interchanged with oxygen
cylinder fittings because of the possi-
bility of fire or explosion from a
reaction between oxygen and residual
oil in the fitting.
3 Return empty cylinders promptly with
protective caps replaced.
B Flammable Solvents
1 Store in designated areas well
ventilated.
2 Flash point of a liquid is the temperature
at which it gives off vapor sufficient to
form an ignitible mixture with the air
near the surface of the liquid or within
the vessel used.
3 Ignition temperature of a substance is
the minimum temperature required to
initiate or cause self-sustained com-
bustion independently of the heating or
heated element.
4 Explosive or flammable limits. For
most flammable liquids, gases and
solids there is a minimum concentration
of vapor in air or oxygen below which
propagation of flame does not occur on
contact with a source of ignition.
There is also a maximum proportion of
vapor or gas in air above which
E5-3
-------
Laboratory Safety Practices
propagation of flame does not occur.
These limit mixtures of vapor or gas
with air, which if ignited will just
propagate flame, are known as the
"lower and higher explosive or flammable
limits."
Explosive Range. The difference
between the lower and higher explosive
or flammable limits, expressed in
'terms of percentage of vapor or gas in
air by volume is known as the "explosive
range,"
Vapor Density is the relative density
of the vapor as compared with air.
Underwriter's Laboratories Classification
is a standard classification for grading
the relative hazard of the various
flammable liquids. This classification
is based on the following scale:
Ether Class 100
Gasoline Class 90 - 100
Alcohol (ethyl) Class 60- 70
Kerosene Class 30 - 40
Paraffin Oil Class . . 10 - 20
8 Extinguishing agents
V CHEMICAL HAZARDS
A Acids and Alkalies
1 Some of the most hazardous chemicals
are the "strong" or "mineral" acids
such as hydrochloric, hydrofluoric,
sulfuric and nitric.
2 Organic acids are less hazardous
because of their comparatively low
ionization potentials. However, such
acids as phenol (carbolic acid),
hydrocyanic and oxalic are extremely
hazardous because of their toxic
properties.
3 Classification of acids
B Oxidizing Materials
1 Such oxidizing agents as chlorates,
peroxides, perchlorates and perchloric
acid, in contact with organic matter
can cause explosions and fire.
2 They are exothermic and decompose
rapidly, liberating oxygen which reacts
with organic compounds.
3 Typical hazardous oxidizing agents are:
Chlorine Dioxide
Sodium Chlorate
Potassium Chromate
Chromium Trioxide
Perchloric Acid
C Explosive Power
1 Many chemicals are explosive or form
compounds that are explosive and
should be treated accordingly.
2 A few of the more common examples
of this class of hazardous materials are;
Acetylides
Silver Fulminate
Peroxides
Peracetic Acid
Nitroglycerine
Picric Acid
Chlorine and Ethylene
Sodium Metal
Calcium Carbide
D Toxicity
1 laboratory chemicals improperly
stored or handled can cause injury to
personnel by virtue of their toxicity.
2 Types of exposure. There are four
types of exposure to chemicals:
a Contact with the skin and eyes
b Inhalation
c Swallowing
d Injection
E5-4
-------
Laboratory Safety Practices
VI PRECAUTIONARY MEASURES
A Clothing and Personal Protective Equipment
1 'Chemical laboratories should have
special protective clothing and equipment
readily available for emergency use and
for secondary protection of personnel
working with hazardous materials.
2 Equipment should be provided for adequate:
a Eye protection
b Body protection
c Respiratory protection
d Foot protection
e Hand protection
B Bodily Injury
1 Burns, eye injuries, and poisoning are
the injuries with which laboratory
people must be most concerned.
2 First emphasis in the laboratory
should be on preventing accidents.
This means observing all recognized
safe practices using necessary personal
protective equipment and exercising
proper control over poisonous sub-
stances at the source of exposure.
3 So that a physician can be summoned
promptly, every laboratory should have
posted the names, telephone numbers,
and addresses of doctors to be called
in an emergency requiring medical care.
REFERENCES
Guide for Safety in the Chemical Laboratory,
the General Safety Committee of the
Manufacturing Chemists Association, Inc.,
Van Nostrand. New York (1954).
This outline was prepared by Paul F. Hallbach,
Chemist, National Training and Operational
Technology Center, MOTD, OWPO, USKPA,
Cincinnati, Ohio 45268
Descriptors: Safety, Laboratory, Practices
Safety, Laboratory Design Chemical Storage,
Gas Cylinders, Flammable Solvents
E5-5
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for
DETERMINATION OF SILVER (Ag+)
as applled in
WATER AND WASTEWATER TREATMENT FACILITIES
and in the
MONITORING OF EFFLUENT WASTEWATERS
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.HE.ag.lab.WMPJ.il.77
E6-1
-------
WATER MONITORING PROCEDURE: Determination of Ag+
1. Analysis Objective:
To determine the silver concentration of a water sample.
2. Brief Description of Analysis:
The sample is digested with concentrated nitric acid and evaporated to
dryness. The residue is treated with hydrochloric acid, silicates and
other insoluble material are removed by filtration and the sample is
analyzed for the total metal of interest by atomic absorption spectro-
photometry.
3. Applicability of this Procedure:
The method works for both potable and wastewater.
a. Range of Concentration - The method is recommended for use in the
range of 0.1 to 4.0 mg/1. The detection limit is 0,01 mg/1.
b. Pretreatment of Sample - Digestion in acid pH to assure solubilization -
See Section A.
c. Treatment of Interferences in the Sample - None listed for these
conditions.
Source of Procedure: Methods for Chemical Analysis of Water and Wastes, 1974,
Environmental Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio, p. 146
E6-3
-------
WATER MONITORING PROCEDURE: Determination of Ag+
Operating Procedures:
A. Sample Digestion
B. Reagent Preparation
C. Instrument Calibration
D. Instrumental Analysis
E. Calculations
E6-4
-------
WATER MONITORING PROCEDURE: Determination of Ag+
General Description of Equipment and Supplies Used in the Process
A. Capital Equipment
1. Balance, analytical - sensitivity 0.1 milligram
2. Atomic absorption spectrophotometer and recorder
3. pH meter
4. Hot plate, 110 V
B. Reusable Supplies
1. Flasks, volumetric, 100 ml, 1000 ml
2. Pipets, volumetric, 50 ml, 3 ml, 1 ml
3. Reagent bottles, glass with glass stopper
4. Anion and cation exchange resin cartridges
5. Beakers, 150 ml
6. pH paper
7. Watch glass
8. Funnel, 80 mm diameter
9. Ring stand and 3 inch ring
10. Graduated cylinders 100, 50, 10 ml
C. Consumable Supplies
1. Reagents
Silver Nitrate (analytical reagent grade)
E6-5
-------
WATER MONITORING PROCEDURE: Determination of Ag+
E6-6
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
A. Sample Digestion
for Total Silver
1. Transfer 100 ml of sample
into a clean 150 ml beaker
2, Check the pH using
pH paper
3. Add 5.0 ml of 1:1
hydrochloric acid (HC1)
4. Place the beaker on a hot
plate
5. Heat at 95° C for 15 min
6. Remove the beaker from the
hot plate. Allow it to
cool to room temperature
7. Wash down the beaker walls
with distilled water
8. Filter the sample through
Whatman $42 filter paper
into a clean 100 ml
volumetric cylinder
9. Dilute the volume to 100
ml with distilled water
la. Use a 100 ml graduated cylinder
2a. The pH should be 2.0, If the sample was not
acidified upon collection, add 1:1 nitric acid
dropwise until the pH is adjusted to 2.0
3a. Use a 5 ml pipet. Use a rubber bulb on the pipet
4a. Adjust the hot plate for medium heat
5a. Make certain that the sample does not boil
7a. Use a plastic wash bottle
B. Reagent Preparation
1. Dei om* zed
Distilled Water
1. Prepare by passing
distilled water through a
mixed bed of cation and
anion exchange resions
la. Use deionized distilled water for the preparation
of all reagents, calibration standards and as
dilution water. i
-------
WATER MONITORING PROCEDURE; Determination of Ag+
OPERATING PROCEDURES
STEP SEQUENT
INFORMATION/OFF RAT ING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
2. Nitric Acid
Concentrated
(HN03)
3. Hydrochloric Acid
(HC1) 1:1
4. Silver Stock
Standard Solution
5. Fuel and Oxidant
1. Commercially available
reagent grade
1. Prepare a 1:1 solution of
reagent grade hydrochloric
acid by adding 25 ml of
commercially available
reagent grade hydrochloric
acid to 25 ml of deionized
water
1, Carefully weigh 1.575
grams of silver nitrate
(analytical reagent grade)
on an analytical balance
2. Transfer into a 1000 ml
volumetric flask
3. Dissolve in distilled
water
4. Add 10 ml concentrated
nitric acid
5. Dilute to mark with
distilled water
1. Commercial grade acetylene
is generally acceptable
la. Use a 50 ml graduate
la. Use a plastic weighing boat and an analytical
balance
2a. Use a powder funnel
2b. Use a plastic wash bottle to rinse the weighing
boat and funnel into the flask
4a. Use a graduate cylinder
4b. Use caution with the acid
5a. One ml equals 1 mg Ag+(1000 mg/liter)
E6-7
-------
MATER MONITORING PROCEDURE: Determination of Ag+
E6-8
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
Air may be supplied from a
compressed air line, a
laboratory compressor, or
from a cylinder of
commercial air.
2a. Caution: Air supply must be free from oil
or other contaminants
C. Instrument Calibration
1 . Turn on air supply
2. Turn on acetylene supply
3. Turn on instrument and
ignite flame
4. Turn on power to hollow
cathode lamp
5. Select wave length for
appropriate metal
6. Prepare a series of stand-
ard solutions for silver
as follows:
Silver
Transfer 1.0 ml of stock
silver solution into a
100 ml volumetric flask
and dilute to the mark
with deionized distilled
water and shake well
3a. See instruction manual for your particular
instrument
4a. Select lamp for proper metal analysis
5a. Silver (328.1 nm)
-------
WATER MONITORING PROCEDURE: Determination of Ag+
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Instrument Calibration
(Continued)
6. Continued
Transfer 0.0, 0,2, 0.4,
0.6, 0.8, and 1.0 ml of thi
diluted standard solution
into each of six 100 ml
volumetric flasks re-
spectively. Dilute to the
mark with deionized dis-
tilled water and shake we!
The concentration of these
solutions will be 0.00,
0.02, 0.04, 0.06, 0.08, and
0.10 mg/1 respectively
7. Ignite flame and aspirate
standard solutions into
the flame
8. Prepare a calibration curv
by plotting the concentra-
tion of the respective
metals against the respons
for each concentration
Use a 1 ml micro pipet graduated in 0.1 ml
8a. Record the response on a recorder or use the
readout provided on the instrument
D. Instrumental Analysis
1. Aspirate the unknown solu-
tion into the instrument
immediately following the
aspiration of the standard
2, Record the response
la. Flame characteristics and instrumental settings
should be the same for standards and unknowns.
E6-9
-------
WATER MONITORING PROCEDURE: Determination of Ag+
E6-10
OPERATING PROCEDURES
STCP SEQUENCE:
[JJFORKATION/OPCRATiriG GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Calculations
Determine the concen-
tration of the metal in the
sample by substituting the
observed instrumental re-
sponse on the appropriate
calibration curve.
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
DETERMINATION OF TOTAL CADMIUM, CHROMIUM AND
LEAD BY ATOMIC ABSORPTION
as applied in
WATER TREATMENT PLANTS
and in the
MONITORING OF DISTRIBUTION SYSTEMS
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.ME.lab.WMP.la.A.SO
E7-1
-------
WATER MONITORING PROCEDURE: Determination of Total Cadmium, Chromium and
Lead by Atomic Absorption
1. Analysis Objectives:
The user of the attached procedure will determine the cadmium, chromium
and lead content of a drinking water sample, including sample preparation
and atomic absorption.
2. Brief Description of Analysis
If suspended or settleable matter is present, the sample is treated with
acid and heat to assure complete solubilization of metals. To determine
total chromium, trivalent chromium is oxidized to the hexavalent form.
The metals are chelated and extracted with pyrrolidine dithiocarbamic
acid (PDCA) in chloroform. An acidified water solution of the metals
is aspirated into an atomic absorption spectrophotometer.
3. Applicability of the Procedure:
a. Range of concentration:
This procedure should be carried out if the concentrations in the
sample are below:
0.-.P2CL JffiL/1 jfor cadmium
0.~Q"5Q mg/1 for_chrom1um_
0.200 mg/V for Tead
b. Pretreatment of samples:
This is covered in the procedure. Generally it is to lower the pH of
the sample to below pH 2 with nitric add for preservation. A solubiliza-
tion procedure for "total" metals if particulates are in the sample
is also covered.
c. Treatment of interferences in samples:
The method contains steps to remove interferences, i.e., chelation
and extraction. A section about interferences to atomic absorption
spectrophotometry (chemical, dissolved solids, ionization and
spectral) can be found in the Source of Procedure.*
*Source of Procedure: Methods for Chemical Analysis of Water and Wastes, 1974
and 1979, U.S. Environmental Protection Agency, Environmental Monitoring and
Support Laboratory, Cincinnati, Ohio 45268, Metals (Atomic Absorption Methods)
E7-3
-------
WATER MONITORING PROCEDURE: Determination of Total Cadmium, Chromium and
Lead by Atomic Absorption
A. Glassware Preparation
B. Sample Preservation and Handling
C. Reagent Preparation
D. Instrument Set-up
E. Solubilization for "Total" Metals (If necessary)
F. Preparation of Standard Dilutions
G. Oxidation for Total Chromium
H. Extraction of Metals
I. Instrument Calibration
J. Calculations
K. Instrument Shut-Down
L. Maintenance
E7-4
-------
WATER MONITORING PROCEDURE:
Determination of Total Cadmium, Chromium and
Lead by Atomic Absorption
Equipment and Supply Requirements
A. Capital Equipment:
1. Atomic absorption spectrophotometer: Any commercial atomic absorption
instrument having an energy source, an atomizer burner system, a
monochromator, and a detector is suitable
2. Balance, analytical with a 0.1 milligram sensitivity
3. Hollow cathode lamps - cadmium, chromium, lead
4. Hot plate, capable of holding at least ten 250 ml beakers
5. pH meter with single, combination electrode - optional for pH adjustment
6. Pressure regulator valves:
a. Two stage regulator designed to deliver acetylene with an
inlet CGA 510 connector
b. Two stage regulator designed to deliver air with an inlet
CGA 1340 connector
7. Recorder: One compatible with the electronics of the atomic
absorption instrument is acceptable
8. Steam bath for up to 9 - 100 ml beakers
(sample, spike, duplicate, standards).
determined,
9, Still - borosilicate glass distillation apparatus or another source
of good distilled water
10. Stop watch
or 250 ml beakers
Required if chromium is to
B. Reusable Supplies:
2.
3.
18 or 36
(sample,
beakers, 9 or 13
spike, duplicate
100
- 4
ml,
- 100 ml, 9 - 250 ml size, graduated,
, standards)
ml size, 2 brown glass, 4 clear
clear glass, 1000 ml capacity,
clear glass, 100 ml
three
Six dropper bottles -
Eight Reagent bottles
one brown glass, 1000
4. Cylinders - graduated
1 500 ml
1 250 ml
2 100 ml
1 25 or 50 ml
1 10 ml
9 or 18 10 ml stoppered, wide base (sample, spike, duplicate, standard)
5. Flask, volumetric, glass stoppered
1 1000 ml
1 100 ml
6. Funnel, very small to filter 365 ml, glass
1 (sample, spike, duplicate, standard)
7. Funnel, separatory, glass stoppered, teflon stopcock, 250 ml,
1,9, or 18 (sample, spike, duplicate, standards)
8. Pi pets, graduated, mohr type
1 5 ml
2 10 ml
E7-5
-------
WATER MONITORING PROCEDURE: Determination of Total Cadmuim, Chromium and
Lead by Atomic Absorption
8. Volumetric type (continued)
4 1 ml
2 2 ml
1 3 ml
4 5 ml
5 10 ml
1 20 ml
9. Instrument and manufacturer's operation manual
10. Safety glasses
11. Separatory funnel rack
12. Wash bottle, plastic, squeeze type
13. Watch glasses, 3 (sample, spike, duplicate), 3.5 inches in diameter
C, Consumable:
1. Deionizing column - mixed bed type
2. Gases
Fuel, acetylene (C2H-) - for use with the atomic absorption Instrument,
purified grade, 380 Cf, CGA 510
Oxidant, air - for use with the atomic absorption instrument,
dry grade, 2200 cf, CGA size 1340
3. Filter paper - Whatman #40
4. Plastic weighing boats - about 12
5. Labels
6. Marking pencil
7. Reagents
Ammonium hydroxide
Nitric acid
Hydrochloric acid
Cadmium sulfate (3 CdSQ^SH-O)
Chromium trioxide
Lead nitrate
Potassium permanganate
Pyrrolidine dithiocarbamic acid*
Carbon disulfide
Chloroform
Sodium azide
for pH adjustment - only if the indicator is to be used:
95% ethyl alcohol
Bromophenol blue
*AvaiTable from Aldrich Chemical Co., 940 West St. Paul Avenue,
Milwaukee, Wisconsin, 53233 (414/273-3850).
E7-6
-------
HATER HUN1TQRING PROCEDURE: Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
A, Glassware Preparation
B. Sample Preservation
and Handling
1. Wash In tap water with
detergent and brush.
2. Rinse well with tap water.
3. Rinse with 1:1 nitric acid,
4. Rinse well with tap water.
5. Rinse with 1:1 hydrochloric
acid.
6. Rinse well with tap water.
7. Rinse well with delonlzed
distilled water.
B. If possible, reserve all
glassware used in metal
analyses for that purpose
only.
1. Collect at least a 1 liter
sample.
2. Add 5 ml of concentrated
nitric acid per liter
of sample.
3. The sample may be kept for
6 months before analysis.
la. Do not use chromic acid to clean this glassware.
Ib. This procedure also applies to sample containers,
Ic. Quality control checks may verify that some of
these cleaning steps are not necessary.
2a. Remove all detergent.
8a. Contamination from other reagents is less likely
this way.
la. A quart sample container may be used.
Ib. The sample container should have been cleaned
using the procedure above.
2a. The pH must be less than 2.
2b. The nitric acid should be checked for metals
content before use.
2c. More acid may be necessary for samples with
higher total dissolved solids.
3a. Good practice would dictate analysis of a sample
as soon after collection as possible.
E7-7
-------
HATER MONITORING PROCEDURE: Determination of Total Cadmium, Chromium and Lead by
' Atomic Absorption
E7-8
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
1. Delonized
Distilled Water
2. Nitric Add,
Concentrated
3. Nitric Acid (1:1)
4. Hydrochloric Acid,
Concentrated
Prepare approximately ten
(10) liters of deionlzed
distilled water.
No preparation is necessary
if metals of Interest are
absent.
Pour add into a 100 ml
dropper bottle.
Add SO ml of water to a
100 ml graduated cylinder.
Add 50 ml of concentrated
nitric acid to the same
graduated cylinder.
Allow to cool.
Transfer into tightly-
stoppered bottle for
storage.
Label bottle 1:1 nitric
acid.
No preparation is necessary
if metals of interest are
absent.
la. Prepare by passing distilled water through a
mixed bed of cation and anion exchange resins.
Ib. Use deionlzed distilled water for preparation
of all standards, reagents and dilutions and
also for the washing of equipment.
la. Run a reagent blank to check purity. If results
show necessity, remove impurities by distilling
1:1 acid in an all glass (borosilicate) still. The
redistilled acid (68.0%) is essentially as
concentrated as non-redistilled (69.0 - 71.0%)
acid.
la. Deionlzed distilled water.
2a.
2b.
2c.
2d.
2e.
la,
Caution: Do not reverse this order of addition.
Use safety glasses.
Heat may be generated.
Prepare in a well-ventilated area.
Larger amounts may be prepared. Use equal
amounts of water and acid.
Run a reagent blank to check purity. If
necessary, remove impurities by distilling 1:1
acid in an all glass (borosilicate) still. The
resulting redistilled acid is 20.2% HC1 (~6N)
in contrast to the usual 36.5-38% (-12N)
reagent grade acid.
-------
MAItK HUHllUMNli HHUIUJUW,: uecennuiaLiun ui
Atomic Absorption
DERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
5. Hydrochloric Add
(1:1)
6. Hydrochloric Add
(2.5* v/v)
7. Ammonium Hydroxide
(NH.OH)
Concentrated
1. Add 50 ml of water to a
100 ml graduated cylinder.
2. Add 50 ml of concentrated
hydrochloric acid to the
same graduated cylinder.
3, Allow to cool.
4. Transfer Into tightly-
stoppered bottle for
storage.
5. Label bottle 1:1 hydro-
chloric acid.
1. Add about 50 ml water to
a 100 ml volumetric flask.
2. P1pet 2.5 ml concentrated
HC1 to the flask.
3. Cool and dilute to 100 ml
with water.
1. Pour the concentrated
NH.QH into a glass
dropper bottle.
la. If you have redistilled hydrochloric acid
(C.4.1a), It is~-6N and this preparation 5
Is not necessary.
Ib. This preparation requires a well-ventilated area,
2fl- Caution: Do not reverse this order of addition.
2b. Use safety glasses, Heat may be generated.
2a. See C.4.1a.. If you have redistilled hydro-
chloric acid, It Is a -6N. Accordingly,
you need 5 ml of redistilled acid for this step.
3a. Store in dropper bottle (about 100 ml vol.) This
is used to adjust pH.
la. Use a hood to prevent Inhalation of fumes. Avoid
contact with skin. Wear protective equipment.
Ib. Only some drops of this are needed for the pH
adjustment of acidified samples.
Ic. A brown glass dropper bottle conserves the
stability of this reagent.
E7-9
-------
HATER MONITORING PROCEDURE:
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
E7-10
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
8. Aninonium Hydroxide
(NH^OH) 2N
9. Bromophenol Blue
Indicator
10. Pyrrolidine
dithiocarbamic
acid (PDCA) -
chloroform
solution
1. Dilute 13 ml
trated NH.OH
water.
of concen-
to 100 ml with
1. Dissolve 0.1 g of the solid
in 100 ml of 50% ethyl
alcohol.
1. Add 500 ml chloroform to
a liter flask.
2. Add 18 ml of analytical
grade pyrrolidine.
3. Add 15 ml of carbon
disulfide (CS^) in small
portions with swirling.
4. Dilute to 1 liter with
chloroform.
la. This reagent should be prepared In the hood to
prevent inhalation of fumes. Avoid contact
with skin. Wear protective equipment.
lb. This Is used to adjust pH.
Ic. Use a brown dropper bottle to store.
la. A platform balance can be used for weighing.
lb. In order to prepare this solution 95% ethyl
alcohol should be diluted in half (i.e., 50 ml
alcohol to 50 ml water).
Ic. This solution Is stable Indefinitely so long as
It is kept In a tightly-stoppered dropper bottle
to prevent evaporation.
Id. This solution is not necessary if a pM meter
is used for pH adjustments.
la. This reagent should be prepared in a well ven-
tilated area (or hood)
lb. Measure 500 ml with graduated cylinder.
2a. Pipet with a graduated plpet.
2b. Generates heat -- cool before proceeding.
2c. For supplier, see chemical list.
2d. CAUTION -- reagent Is flammable, toxic and
corrosive.
3a. Carbon disulfide is very odorous. Prepare In
hood or well ventilated area.
3b. Use a measuring pi pet.
3c. CAUTION - Heat generated - cool before proceeding
4a. This solution can be stored for several months
if stored in a brown bottle in a refrigerator.
-------
MATER HUfllTORING PRDCEDURF: Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
11. Potassium
Permanganate
Solution
(KMn04) 0.1 N
12. Sodium Azide
Solution (NaNj
1. Weigh out 3.20 grams of
potassium permanganate.
2, Add about 500 ml of water
to a 1000 ml volumetric
flask.
3. Transfer the potassium
permanganate to the flask.
4. Dilute to the mark.
5. Mix thoroughly.
6. Store in a tightly-stop-
pered reagent bottle.
1. Weigh out 100 mg sodium
azide (NaN3).
2. Add about 50 ml of water
to a 100 ml volumetric
flask.
3. Transfer the sodium azide
to the flask.
4. Swirl to dissolve.
5. Dilute to the mark.
6. Stopper and mix thoroughly
7. Store In a tightly-stop-
pered bottle.
la. Prepare 1f chromium 1s to be determined.
Ib. Use a trip balance and a plastic weighing boat.
3a. Hash the weighing boat with water and add the
washings to the flask.
6a. Label with concentration and preparation date.
6b. When using, transfer a portion to a 100 ml
dropper bottle.
la. Prepare 1f chromium 1s to be determined.
E7-11
-------
E7-12
>r/ATER MONITORING PROCEDURE: Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
13. Stock Cadmium
Solution
14. Stock Chromium
Solution
1. Weigh out 2.282 grams of
cadmium sulfate
(3CdSOy8H20).
2. Add about 500 ml of water
to a 1000 ml volumetric
flask.
3. Transfer the cadmium sul-
fate to the volumetric
flask.
4. Add 2.0 ml of concentrated
nitric acid.
5. Dilute to the mark.
6. Mix thoroughly.
7. Store in a tightly-stop-
pered bottle,
1. Weigh out 1.923 grams of
chromium trioxide (CrO_).
2. Add about 500 ml of water
to a 1000 ml volumetric
flask.
3. Transfer the chromium
trioxide to the volumetric
flask.
la. Use an analytical balance and a plastic weighing
boat.
3a. Use a wash bottle and rinse the weighing boat
with water three times,adding each wash to the
flask.
4a. Use a 5 ml graduated pi pet.
5a, The solution contains 1000 rag Cd/llter
(1 ml = 1 rng Cd).
7a. Label with concentration and preparation date.
7b. Store in a refrigerator.
la. Use an analytical balance and a plastic
weighing boat.
3a. Use a wash bottle and rinse the weighing boat
with water three times,adding each wash to the
flask.
-------
WATER MONITORING PROCEDURE: Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
15. Stock Lead
Solution
4» Add 2.0 ml of concentrated
nitric acid.
5, Dilute to the mark.
6. Mix thoroughly.
7. Store in a tightly-stop-
pered reagent bottle
1. Weigh out 1.599 grams of
lead nitrate (Pb(N03)2).
2. Add about 500 ml of water
to a 1000 ml volumetric
flask.
3. Transfer the lead nitrate
to the volumetric flask.
4. Add 10 ml of concentrated
nitric acid.
5. Dilute to the mark.
6. Mix thoroughly.
7. Store in a tightly-stop-
pered reagent bottle.
4a. Use a 5 ml graduated plpet.
5a. The solution contains 1000 mg Cr/liter
(1 ml = 1 mg Cr).
7a. Label with concentration and preparation
date.
7b. Store In a refrigerator.
la. Use an analytical balance and a plastic weighing
boat.
3a. Use a wash bottle and rinse the weighing boat
with water three times adding each wash to the
flask.
4a. Use a 10 ml graduated pipet.
5a. With water.
5b. The solution contains 1000 mg Pb/liter
(1 ml « 1 mg Pb).
7a. Label with concentration and preparation date.
7b. Store in a refrigerator.
E7-13
-------
WATER MONITORING PROCEDURF:
Determination of Total Cadmium, Chromium and Lead, by
Atomic Absorption
E7-14
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D, Instrument Set-up
1. Pre Warm-up
Prepare the Instrument for
Initial operation.
2. Lamp Installation
1. Install appropriate hollow
cathode lamp.
2. Align the lamp
intensity.
for maximum
3. Set appropriate wavelength,
la. Reference 1s made to the manufacturer's manual of
operation.
Ib. Check power requirements and availability.
Ic. Provide adequate ventilation, including a vent
over instrument burner.
Id. Provide adequate space for instrument and work
area,
le. Provide drain facility for the Instrument.
la. Hollow cathode lamps for lead, chromium and
cadmium must be available.
Ib. If the instrument 1s a single beam type, some
method of warm-up for the hollow cathode lamps
should be available.
Ic. Do not exceed the maximum current rating for the
lamps as this can seriously affect Its life
and stability.
Id. Refer to the instrument manufacturers manual for
proper Installation procedure.
2a. Check instrument manual for proper procedure.
3a. Pb, 283.3 nm; Cd, 228.8 nmi Cr, 357.9 nm.
-------
H- •_>.«_ i iiiiiiu
tuiai
Atomic Absorption
luruinium ana teaa oy
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D, Instrument Set-up
(Continued)
3. Burner
Optimization
1. Install the burner head.
2. Attach the necessary gasses
to the Instrument.
3. Align the burner to obtain
optimum absorption.
4. Check Aspiration
Rate
1. Optimize the aspiration
rate.
la. The usual burner head for direct aspiration Is
the three slot Bollng head. For aspiration of
organic solvents a conventional head with a
single slot 7.6 cm (3 Inches) is used.
2a. For this procedure, acetylene and air are used.
Use purified grades of the gasses.
2b. Attach a pressure regulator to the tanks. Use a
CGA fitting of 510 for the acetylene and a 590
or 1340 for the air.
2c. Connect cylinders through the regulator to the
Inlet part of the Instrument with plastic
pressure tubing,
2d. All cylinders should be securely fastened to
prevent them from tipping over.
3a, The analysis of lead 1s exceptionally sensitive
to turbulence and absorption bands in the flame.
Therefore, some care should be taken to position
the light beam In the most stable, center, portion
of the flame. To do this, first adjust the
burner to maximize the absorbance reading with a
lead standard. Then aspirate a water blank and
make minute adjustments 1n the burner alignment to
minimize the signal.
la. Aspirate a standard Into the burner and adjust the
aspiration rate until optimum absorbance is ob-
tained.
V.D.3.2a
(P. 32)
VII.D.3.3a
(P- 33)
VII.D.4.la
(P. 33)
E7-15
-------
WATER MONITORING PROCEDURF:
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
E7-16
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Sol utilization for
"Total" Metals,
IF NECESSARY
1. Acidify the entire sample
at the time of collection
with cone, nitric acid,
5 ml/liter
2. Proceed with the rest of
these steps only if
necessary.
3. Transfer 200 ml or more
of the well-mixed sample
to a graduated beaker
of appropriate size.
4. Add 5 ml 1:1 hydrochloric
acid for each 100 ml
of sample to be treated.
5. Heat the acidified sample
In the beaker on a steam
bath or a hot plate until
the volume has been
reduced to 15-20 ml. Make
certain the sample does
not boil.
6. Remove the beaker and
allow contents to cool.
la. For metals other than Cd, Cr and Pb, consult
the source of this procedure for possible
modifications of this procedure.
Ib. The acid may have to be redistilled before use.
See C.2. for details.
2a. For drinking water samples, this entire
solubilization procedure Is necessary only
If the samples contain visible suspended
and/or settleable matter.
3a. 200 ml is a usual sample volume for metal
concentrations less than 100 ixj/liter. Choose
a volume appropriate to the expected level of
metal concentration. Cadmium and lead can be
analyzed from the same sample aliquot. A
separate sample aliquot is recommended for
chromium.
3b. Additional volumes will be required to provide
sufficient final volumes for additional runs
of the sample, e.g. as a duplicate, a spike,
analysis for several elements, etc.
4a. IF THE SAMPLE IS BEING PREPARED FOR FURNACE
ANALYSIS, do not add the 1:1 hydrochloric acid.
4b. The acid may have to be distilled before
use. See C.4. and 5. for details.
VII.E.2.2a
(p. 33)
VII.E.3.3a
(p. 34)
VII.E.3.3b
(p. 35)
-------
WAItK MONITORING PKULEDUKK:
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Solubilization for
"Total" Metals,
IF NECESSARY
(Continued)
7. Wash down the beaker
walls with deionized
distilled water.
8. If necessary, filter
the sample Into a 250 ml
separatory funnel If
cadimium and/or lead Is
to be determined. Use
a 250 ml graduated beaker
as a receiver if chromium
is to be determined.
9. Adjust the volume of the
treated sample according
to the requirements of
the subsequent analytical
procedure.
10. Continue with Procedure F,
Preparation of Standard
Dilutions
7a. Use a small volume of the water.
8a. Filter If the sample Is turbid, If you see
particles or If past experience with the
sample source Indicates that you should.
(Filtration removes particles that could clog
the atomizer of an atomic absorption Instrument)
8b. If filtration 1s not necessary, go to the next
step.
9a. If the sample Is to be directly aspirated, the
final volume may be a reduction of the original
to effect up to a 10X concentration of the
sample.
9b. If the sample is to be treated by a chelation -
extraction procedure to determine Cd or Pb, the
sample should be quantitatively transferred to
a 250 ml separatory funnel and brought to the
volume of the standards used to establish the
standard curve. The final volume used in this
write-up Is 200 ml.
9c. To determine total chromium, the sample should
be brought to the volume to be used for the
standards. In this write-up, the final volume
is 200 ml to be contained in a 250 ml beaker
for use In Procedure G.
9d. If the sample is to undergo furnace analysis,
the treated sample should be adjusted back to
the volume of the aliquot used for this
Solubilization procedure.
lOa. Calibration Standards must be analyzed with the
same procedures as are applied to samples.
__
I.E.9.9a
(p. 30)
-------
WATER MONITORING PROCEDURE;
E7-18
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Preparation of
Standard Dilutions
1. Primary Dilution
2. Intermediate
Dilution
1. Add about 500 ml of water
to a 1000 ml volumetric
flask.
2. Add 5.0 ml of concentrated
nitric acid.
3. Pipet 10 ml of the stock
solution(s) of the metal (s)
of Interest into this
volumetric flask.
4. Dilute to the mark with
water,
5. Mix thoroughly and label.
1. Add about 100 ml of water
to a 200 ml volumetric
flask.
2. Add 1.0 ml of concentrated
nitric acid.
3. Pipet 20 ml of the pri-
mary dilution of the
metal(s) of Interest Into
the flask.
4. Dilute to the mark with
water.
5. Mix thoroughly and label.
la. Estimate the amount.
2a. Use a 5 ml graduated plpet.
2b. Use safety glasses
3a. Use a 10 ml volumetric plpet for each measurement
3b. It saves time and glassware to prepare a mixture
of the metals at this stage 1f more than one
metal 1s of Interest.
5a. The solution contains 10 mg/liter of Cd and/or
Cr and/or Pb.
5b. Ideally, this solution should be prepared at the
time of use.
la. Estimate the amount.
2a. Use a graduated pipet.
3a. Use a 20 ml volumetric pipet,
5a. The solution contains 1 mg/liter of Cd and/or
Cr and/or Pb.
I.F.
(P- 30)
-------
WATER HUIIITORING PROCEDURE;
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Preparation of
Standard Dilutions
(Continued)
3.
Calibration
Standards
1. Prepare a blank and a
series of calibration
standards.
5b, This solution should be prepared at the time
of use.
la. Prepare a blank and standards using volumetric
pipets (1, 2, 5, 10, 20 ml) for measuring the
intermediate dilution and a graduated cylinder
for the water.
Ib. To determine Cd and/or Pb, prepare one series of
standards in six labeled, 250 ml separatory
funnels so they are ready for the extraction
procedure (H). Columns A and B in the Table on
E7-20 are to be used to prepare 200 ml volumes.
(Make sure the stopcock on each funnel 1s
closed before you add solutions to 1t).
Ic. To determine Cr, prepare a separate blank and
series of standards in six labeled, 250 ml
beakers so they are ready for the oxidation
procedure (G). The volumes in Columns A and B
In the table E7-20 are to be used to prepare
200 ml volumes.
Id. Calibration standards should be prepared fresh
for each run of samples.
le. The standards are used to prepare a standard
curve.
If. Once the standard curve has been determined, it
need not be redone each time the analysis is
carried out. However, it should be verified
by running a blank and a calibration standard at
the HCL. Standards at the MCL are included in
the Table on the next page:
-For Cd, 2.0 ml Intermediate Dilution
-For Cr, 10.0 ml Intermediate Dilution
-For Pb, 10.0 ml Intermediate Dilution
VII.F.3.Lib
(P. 35)
VII.F.3.Lie
(P. 34)
E7-19
-------
WATER MONITORING PROCEDURF:
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
E7-20
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Preparation of
Standard Dilutions
(Continued)
G. Oxidation for
Total Chromium
Ig. Table for preparing standards:
B
D
2. To determine Cr, continue
with Procedure G, oxida-
tion. To determine Cd
and/or Pb, continue with
Procedure H, Extraction
of Metals.
1. 200 ml volumes of sample(s)
and of standards should
be in 250 ml beakers at
this stage of the analysis.
2. If necessary, adjust the
pH of each to 2.0 or less.
3. Add 0.1 N potassium per-
manganate (KMnO.) drop-
wise to each solution
until a faint pink color
persists.
4. Heat on a steam bath for
20 minutes, adding
mrs of
Inter.
Diln.
1.0
2.0
5.0
10.0
20.0
mi's of
Water
200
199
198
195
190
180
Cone.
(mg/1)
200 ml
In
0.000
0.005
0.010
0.025
0.050
0.100
Cone.
(mg/1) in
Final 10 ml
0.00
0.10
0.20
0.50
1.00
2.00
Instrument
Reading
la. If It was not necessary to solublllze the sam-
ple(s) (Procedure E), at this time:
-measure 200 ml of each well-mixed sample into
a labeled, 250 ml beaker.
-measure 200 ml of one of the samples to run as
a duplicate (in a 250 ml beaker).
-measure 200 ml of one of the samples and spike
It (in a 250 ml beaker).
2a. Use a pH meter to check pH.
2b. Use cone, nitric acid dropwlse to adjust the pH.
3a. The extraction procedure (H) will extract only
hexavalent chromium. To determine total
chromium, you add potassium permanganate to
oxidize any trlvalent chromium to the hexavalent
species.
3b. If volume becomes a problem, use a more con-
centrated solution of KMnO..
4a. A slight excess of KMnO. must be maintained.
VII.F.3.1.1g
(p. 33)
VII.G.I
(p. 34)
VII.G.I.la
(p. 35)
-------
WATtK HONITQRING PROCEDURE:
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
6. Oxidation for
Total Chromium
(Continued)
additional drops of 0.1 N
KMnO. to any solution in
whicn the faint pink color
disappears.
5. While still on the steam
bath, add sodium azide
solution (0.1%) to each
solution dropwise until
the faint pink color of
the KMnO, Just disappears.
6. Continue heating the solu-
tions for 5 minutes after
adding the last drop of
sodium azide solution.
7. Transfer the beakers to a
water bath and cool to
room temperature.
8. If necessary, filter the
solution(s) Into a 250 ml
separatory funnel(s).
If filtration was not
necessary, quantitatively
transfer the sample(s)
and standards to 250 ml
separatory funnels.
5a. Potassium permanganate can interfere with
subsequent processing.
5b. Heat for about 2 minutes after each addition
of sodium azide. Avoid adding any excess.
8a. Use Whatman No. 40 or equivalent filter paper
to filter any solution with a brownish preci-
pitate or coloration which may Interfere with
the pH adjustment 1n the extraction procedure
(H). If a pH meter is used in procedure H,
you do not need to filter even if a solution
is colored at this stage.
9a. Label each funnel to Identify the contents.
9b. Keep rinse volumes as small as possible during
the transfer.
VII.G.9
(p. 35)
E7-21
-------
WATER MONITORING PROCEDURE:
E7-22
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
H. Extraction of Metals
1. pH Adjustment
200 ml volumes of sam-
ple(s) and of standards
should be in 250 ml
separatory funnels at this
stage of the analyses.
1. Use a pH meter and hydro-
chloric acid (2.5* v/v) to
adjust the pH to 2.3 in
each solution. Then
continue at H.2., Chela-
tion and Extraction.
2. Add 2 drops of bromophenol
blue Indicator to each
sample and to each
Standard.
3. Mix well.
4. Add ammonium hydroxide
dropwlse until a very
pale blue color persists.
5. Add 2.5% v/v hydrochloric
acid dropwise until the
blue color just disappears
la. If it was not necessary to solubilize
(Procedure E) or to oxidize (Procedure G)
the sample(s), at this time:
-measure 200 ml of each well-mixed sample into
a labeled 250 ml separatory funnel.
-measure 200 ml of one of the samples to run
as a duplicate (in a 250 ml separatory funnel).
-measure 200 ml of one of the samples and spike
it (in a 250 ml separatory funnel).
la. A single combination electrode should be used
so the adjustment can be done in the separatory
funnels.
Ib. If the pH meter and single combination electrode
are not available, use steps 2-6 to do the pH
adjustment using bromophenol blue indicator.
3a. If any solution Is pale blue, skip step 4.
4a. Use concentrated NH.OH for acidified samples and
standards made with 10 or more ml of acidified
intermediate dilution solution. Use 2
for more dilute standards.
4b. The reagents should be in glass dropper bottles
for this addition. Use a hood.
N NH4OH
5a. Use a glass dropper bottle for this addition.
5b. A pale yellow color may appear.
I.II.
(P.30)
VII.H.I
(P- 34)
VII.H.I.la
(p. 35)
-------
WATER MONITORING PROCEDURE:
OPERATING PROCEDURES
H. Extraction of Metals
(Continued)
2, Chelation and
Extraction
STEP SEQUENCE
6. Add 2.0 ml 2.5% v/v
hydrochloric acid.
Stopper and shake.
1. Add 5.0 ml pyrrolidine
dithiocarbamlc acid (POCA)
reagent to the sample(s)
and to each standard.
2. Shake each vigorously for
2 minutes
3. Allow the PDCA reagent to
settle to the bottom of
the separatory funnel.
4. Open the stopcock and
slowly drain off the lower
reagent phase of each into
a 100 ml beaker.
5. If total chromium is to be
extracted, re-adjust the
pH of the aqueous phases
in the separatory funnels
back to 2.3 before con-
tinuing. Omit this step
if only Cd and/or Pb is
to be extracted.
INFORMATION/OPERATING GOALS/SPEC IFICATIONS
6a. Use a 2.0 ml volumetric pipet.
6b. The pH at this point is 2,3
la. Use a 5.0 volumetric pipet for this step.
Ib. This reagent should be allowed to come to room
temperature before pipetting, since it will be
stored in a refrigerator,
Ic. The bottle should be restoppered immediately
after use and returned to the refrigerator to
prolong usefulness,
2a. CAUTION: Use proper technique with the separatory
funnel. The reagent contains volatile solvents
and pressure Is formed which is released by
opening the stopcock periodically.
3a. Enough time should be allowed for complete
separation of the two phases.
3b. It may take up to 3 minutes.
4a. Hark each beaker with the number of ml used to
prepare the standard or with the sample
identification code.
5a. Use the steps in Procedure H.I., pH Adjustment
(above), to adjust the pH back to 2.3 in each
solution.
TRAINING
GUIDE NOTES
E7-23
-------
HATER HUN1TORING PROCEDURE:
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
E7-24
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
H. Extraction of Metals
(Continued)
3. Recovery of
Complex
4. Digestion of
Complex
6. Add a second 5.0 ml of
PDCA reagent to each
separatory funnel.
7. Shake each vigorously for
two minutes.
8. Allow the reagent to
settle and separate.
9. Open the stopcock and
slowly drain off the
lower reagent phase into
the beaker containing the
reagent phase from the
first 5.0 ml extraction
of the sample or standard.
1. Evaporate each combined
extract to dryness on a
steam bath 1n a hood.
2, Remove and cool 2 minutes.
1. Add 2 ml concentrated
nitric acid (HNOJ to
each residue.
6a. The same volumetric pipet can be used for all
additions of POCA to all samples and standards
provided caution Is used to prevent contamina-
tion.
7a. CAUTION: Use proper technique. Open the stop-
cock periodically to release pressure.
Ba. It should take about 2-4 minutes for complete
separation of the two phases.
9a. A pale pink color may show In extracts.
la. The residue Is a light color with possible pale
green or blue tinges.
Ib. Do not "bake" the residue,
Ic. Should take about 10-15 minutes.
la. Best carried out in a hood. This is a violent
reaction with boiling and dark brown fumes given
off at the beginning.
Ib. Hold the beaker at a 45 degree angle. Use a
measuring pipet for the acid and add the acid
down the walls, dropwise at first while rotating
the beaker. When most of the residue has
dissolved, the acid can be added at a faster rate
Ic. The concentrated HNO., must be a good grade as any
metals in the acid will be concentrated along
with the sample.
-------
HATER MONITORING PROCEDURE:
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
H. Extraction of Metals
(Continued)
5. Dissolving the
Residue
2. Place the beakers on a
low temperature hot plate
or steam bath and eva-
porate just up to dryness.
3. Remove from hot plate and
cool for 2 minutes.
1. Add 2 ml of 1:1 nitric
acid (HNOj to each
beaker.
2. Return each to the low
temperature hot plate or
steam bath and heat for
1 minute.
3. Cool and quantitatively
transfer each solution to
a labeled 10 ml volu-
metric flask.
4. Bring each to the final
10,0 ml volume with
deionlzed distilled water.
5. Stopper each and mix well.
6. The sample(s) and standards
are now ready for aspira-
tion into the atomic
absorption instrument.
2a. Care should be taken to remove each beaker when
only a very small amount of deep brown liquid
remains in the beaker.
2b. The evaporation takes about 8 minutes.
la. Use a measuring pi pet.
Ib. Down inside walls at first.
2a. Both standards and samples should be carried
through this step at the same time as It could
affect the final concentration of add.
3a. A stirring rod and a plastic wash bottle con-
taining deionlzed distilled water should be used
to wash the beaker and transfer the solution.
3b. A wide base 10 ml volumetric flask Is suggested
or place the volumetric flask in a beaker to
prevent tipping it over. A 10 ml stoppered
graduated cylinder can be used instead of a
volumetric flask.
3c. Mark the flask or cylinder with the number of ml
used to prepare the standard or with the sample
identification code.
4a. You might use a dropper to add the final amount
of water.
E7-25
-------
HATER MONITORING PROCEDURE:
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
£7-26
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
I. Instrument
Calibration
1. Turn on power to instru-
ment and lamps.
2. Check and adjust to
optimum settings all
instrumental operational
parameters.
3. Aspriate the blank to
finalize the zero setting.
4. After the standard series
has been prepared (Section
F), oxidized (Section G)»
and extracted (Section H),
begin with the lowest
standard and aspirate the
series Into the atomic
absorption instrument.
5. Measure and record the
peak height, in milli-
meters, obtained on the
records.
6. Check all results before
proceeding.
la. If the power has been turned off.
2a. Set wavelength to one of the settings given
earlier (D).
2b. Install proper lamp.
2c. Adjust current to the lamp as listed by
manufacturer.
2d. Set slit width.
2e. Ignite flaw.
2f. Adjust fuel and oxidant flows to produce a
blue flame.
2g. Adjust zero on recorder.
2h. See operational manual for directions.
3a. After extraction.
4a. If the instrument Is to be adjusted to read
directly in concentration It may be necessary to
start with the highest standard to set the slope
of the absorbance. The instrument manufacturers
manual will describe the procedure.
Sa. The various instrument operational settings
should be recorded for the record.
5b. Repeat the aspiration of the standards and blank
a sufficient number of times to secure a reliable
average reading for each. The finalized readings
could be recorded in column E on the Table in
F.3.1.1g
-------
HATER HUHITORING PROCEDURE;
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
I. Instrument
Calibration
(Continued)
7, Plot the standard curve,
J, Calculations
K. Instrument Shut-Down
7a. Plot a curve for each metal.
7b. Plot on linear graph paper,
7c, Plot the peak height, 1n millimeters against the
concentration, 1n mg metal per liter, before
extraction. - See Column C on the Table, F,3,l.lg
7d. To check a standard curve, run at least a blank
and one standard at or near the MCL. This check
should be done with each sample or set of samples.
The check should be within +_ 10% of the original
value. If not, a new standard curve should be
prepared.
VII.I.7.7d
(p. 35)
1, Read the metal concentra-
1n each sample In mg/liter
from the appropriate
calibration curve (1.7).
la. So long as 200 ml portions of sample are used,
the calibration curve can be used directly to
obtain mg/Hter concentrations for samples.
Ib. If a sample was diluted to a 200 ml volume,
multiply the curve reading by an appropriate
dilution factor.
Ic. If multiples of 200 ml volumes of a sample were
processed and extracts combined, multiply the
curve reading by the appropriate factor.
Vll.J.l.lb
(p. 34 )
VII.J.l.lc
(p. 34)
1. If a flame Is burning.
aspirate water for about
15 seconds.
2. Close the acetylene
cylinder valve.
3. Close the air cylinder
valve.
4, Depress necessary switches
to off.
la. This will prevent build-up of solids in the
capillary.
2a. The flame will automatically extinguish Itself,
leaving about 9 psig in the acetylene supply line.
4a. CAUTION: Exercise care In touching the burner
head and vent area. These will be hot enough
to cause serious burns.
E7-27
-------
l!ATF,n. MONITORING PROCEDURE:
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
L. Maintenance
1. Clean the instrument
regularly.
2. Insure the drain cup is
filled each day prior to
ignition.
la. A regular program of care and maintenance will
prolong the life-time and maximize Its utility.
Such items as filters in gas lines, air intakes,
burner compartment, burner, and nebulizer should
be cleaned.
2a. See the instrument manufacturer's manual for
exact procedures.
E7-28
-------
TRAINING GUIDE
SECTION TOPIC
I* Introduction
II Educational Concepts - Hathematics
HI Educational Concepts - Science
IV Educational Concepts - Communications
V* Field and Laboratory Equipment
VI Field and Laboratory Reagents
VII* Fteld and Laboratory Analysis
VIII Safety
IX Records and Reports
*Training guide materials are presented here under the headings marked*.
These standardized headings are used through this series of procedures.
E7-29
-------
WATER MONITORING PROCEDURES:
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
INTRODUCTION
Section I
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
F.
H.
E.9.9a
The National Interim Primary Drinking Water Regu-
lations listed ten inorganic parameters which are
required to be analyzed for by a public water
supplier. Along with this list, a level was set for
the amount of that parameter permitted to be in the
water. This was the "Maximum Contaminant Level or
MCL." The MCL's for the metals included in this
procedure are:
Cadmium - 0.010 mg
Chromium - 0,05 mg
Lead - 0.05 rag per
per liter
per liter
liter
The range for calibration standards in this write-
up is based on the MCL concentrations. The set
to be prepared will provide at least one standard
above and one below the HCL for cadmium or chromium
or lead, thus bracketing the concentration of
interest.
At such low levels as the MCL's an extraction pro-
cedure is usually the recommended method to con-
centrate samples so an instrument can detect the
metal. Extraction levels recommended for these
three metals are:
Cadmium - 0,020 mg per liter
Chromium - 0.050 mg per liter
Lead - 0.200 mg per liter
Accordingly, this write-up includes an extraction
procedure using PDCA - chloroform reagent.
Another way to concentrate metals in samples is to
evaporate a large volume of a sample at a low pH
and then directly aspirate. Up to a 10X concen-
tration of a sample by evaporation is permissable
if these three conditions are met:
1. The total dissolved solids in the original sam-
ple do not exceed 500 mg/liter.
2. The determination is corrected for non-specific
absorbance.
3. There is no loss by precipitation.
(CONTINUED)
Methods for Chemical
Analysis of Water and
Wastes, 1979, EPA-EMSL,
Cincinnati, Ohio 45268,
Metals Section
Ibid
E7-30
-------
WATER MONITORING PROCEDURES; Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
INTRODUCTION
Section I
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
The results obtained by this short-cut should be
checked thoroughly before reporting. The total
solids would cause light—scattering effects
producing high results. The sample absorbance
should be checked at a non-absorbing wavelength.
If absorbance is still obtained at this wavelength,
then the scattering effect is contributing to the
sample value and the extraction procedure must be
carried out.
Sulfates tend to suppress the absorbance of energy
by lead causing low readings. With a standard
concentration at the MCL accompanying all samples,
this interference could be detected.
£7-31
-------
MATER MONITORING PROCEDURES: Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
Field and Laboratory Equipment
Section V
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
0.3.2a
As acetylene (CHCH) is packed dissolved in acetone
(CH3COCH3)» cylinders should be stored only in an
upright position. The acetone content of the gas
typically depends on the cylinder temperature and
pressure. Avoid introducing acetone into the in-
strument. Should this occur, the normal flame ob-
tained will have a slight pink tinge and yield an
abnormally high background signal. To reduce
acetone carry-over, ft is desirable to allow
acetylene cylinders to stand undisturbed for at
least twenty-four (24) hours before use. Replace
the cylinder when the cylinder reaches 50 psig.
Instrumentation Laboratoi
Incorporated.
Instrumentation Handbook
113 Hartwell Avenue
Lexington, MA 02173
E7-32
-------
WATER MONITORING PROCEDURES:
Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
Field and Laboratory Analysis
Section VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
D.3.3a
D.4.1a
F.3.1.1g
E.2.2a
After the extraction procedure in this analysis,
the volume of the calibration standards for any
of these metals is only 10 ml. You will need
additional amounts of a high and low standard
to use in setting up the AA instrument. Column D
in table F.3.1.1g. gives the range of the con-
centrations of the standards after extraction
when they are ready for aspiration into the
AA instrument. You can prepare comparable
standards by further diluting the primary
dilution solution described in F.lTIFor
example, two nils of primary dilution further
diluted to a 200 ml volume has a concentra-
tion of 0.10 mg/liter. (The 200 ml volume
should also contain 20 ml concentrated nitric
acid so the acid content is comparable to the
extracts). Later, use the extracted blank and
standards for a final check.
If particulates are in the sample, Procedure E
1s carried out in order to solubiHze any of the
metal 1n the particles. If particulates are
present and you do not carry out Procedure E,
filter the sample through a 0.45 micron filter,
extract, aspirate and report the value as
"dissolved" metal.
E7-33
-------
WATER HONITOP.ING PROCEDURES: Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
Field and Laboratory Analysis
Section VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
E.3.3a
F.3.I.1C
E.3.3a
G.I
H.I
J.l.lb
J.I.Ic
If chromium is the metal of interest, the
standards, samples, duplicate and spike should
be treated as a totally separate determination.
There is no problem in using a mixture of metals
in the preparation of the chromium standards.
However, problems can be caused if the reagents
in the oxidation procedure for chromium introduce
contamination in regard to metals other than
chromium in the final solutions to be aspirated
into the AA. The alternative is to run blanks
on the oxidation reagents along with "mixed"
standards if you want to use one sample for all
three of the metals.
200 ml is a usual sample volume for the extraction
procedure for metal concentrations less than
100 ug/liter. If use of 200 ml of sample gives
results too high to be on scale, consult the
source of procedure about doing a direct aspira-
tion of the sample. Alternatively, a smaller
sample aliquot can be used and diluted to the
200 ml volume used for the standards to establish
a calibration curve for the extraction procedure.
The final calculation becomes:
mg/liter metal _
in sample ~
l C '
where:
A»mg/l of metal in diluted sample obtained
from a calibration curve
B=ml deionized distilled water used for
dilution
C=ml of sample aliquot
E7-34
If use of a 200 ml sample gives too low results,
more than one sample aliquot can be treated and
the extracts combined"me final calculation
becomes:
mg/liter metal. ,/B<
in sample " ^C~
where:
A=mg/l of metal in sample obtained from a
calibration curve.
B=volume in ml of each of the standards' used
to develop the curve.
C=total volume in ml of sample aliquots whose
extracts were combined.
-------
WATER MONITORING PROCEDURES: Determination of Total Cadmium, Chromium and Lead by
Atomic Absorption
Field and laboratry Analysis
Section VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
E.3.3b
G.I.la
H.I.la
F.3.1.1b
G.9.
I.7.7d
As a check on precision, you should measure a
second aliquot of at least one sample 1n a set,
and process it in exactly the same manner as
the first. Ideally, the results from the two
aliquots should agree within the range of two
(three maximum) standard deviations as established
by the analyst.
As a check on accuracy, you should prepare a
spiked aliquot of a chosen sample in a set
and process it in exactly the same manner as
the unspiked sample To determine the amount of
spike to add, you must have some knowledge of the
concentration of the unspiked sample either by
analyzing it or from previous experience. Add
enough spike to about double a concentration
at the lower end of the standard curve concen-
trations. If the sample is at the intermediate
part of the curve, add sufficient spike to bring
the concentration to about 7S% of the curve
range. You can use either the primary or the
intermediate dilutions in Procedure F for spiking,
depending on the concentration you choose to add
and keeping in mind that added volumes should be
minimal. One ml of primary dilution adds 0.05
mg/liter in a 200 ml sample volume. One ml of
intermediate adds 0.005 rag/liter to a 200 nil
volume. The Table in F.3.1.1g. can be a useful
guide. After running the unspiked and spiked
samples, calculate the % recovery. Check the
% recovery for the analysis as established by
the analyst.
Larger volume funnels may be used. Also, if this
number of separatory funnels is not available,
the standards can be prepared and held in other
type containers prior to the actual extraction
procedure. Take care that the solutions do not
get contaminated during the holding time.
When a daily check of the standard curve falls
outside the W% limit of the procedure, reagents
prepared since the last check and any recently
purchased chemicals should be checked before
doing a new curve. If possible, some old chemical
should be retained when a new batch is purchased.
Consequently, the new may be checked against the
old, should doubt arise in its purity.
Handbook for Analytical
Quality Control,
USEPA-AQCl, 1972,
Cincinnati, Ohio 45268,
Chapter 6
E7-35
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
DETERMINATION OF MERCURY USING THE FLAMELESS
ATOMIC ABSORPTION (COLD VAPOR) TECHNIQUE
as applied in
WATER AND WASTEWATER TREATMENT FACILITIES
and in the
MONITORING OF EFFLUENT WASTEWATERS
National Training and Operational Technoloqy Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.ME.hg.lab.WMPJ.il.77
E8-1
-------
WATER MONITORING PROCEDURE: Determination of Mercury Using the Flame!ess
Atomic Absorption (Cold Vapor) Technique
1. Analysis Objectives:
The learner will use the attached WMP to prepare a sample for analysis in-
cluding reagent and sample preparation. A description of the instrumentation
will be presented. However, the learner should consult the manufacturer's
direction for operation of any equipment.
2. Brief Description of Analysis:
This procedure is a three step procedure which 1) chemically vaporizes the
sample, 2) introduces the mercury and 3) determines the mercury by flameless
atomic absorption techniques.
3. Applicability of the procedure:
This method is applicable to drinking, surface, and saline waters; domestic
and industrial wastes.
a. Range of Concentration - The method is recommended for use in the range
of 0.2 wg Hg/liter using a 100 ml sample; the upper limit can be varied
by instrument expansion or dilution.
b. Pretreatment of the Sample - No pretreatment is necessary as the chemical
digestion procedure inherent in the method is sufficient.
c. Treatment of interferences - High chlorides will require additional permanga-
nate (as much as 25 ml). Then additional hydroxylamine sulfate is needed
(25 ml) and the dead air space of the sample container swept out by air
before addition of the stannous sulfate.
Some volatile organics can interfere but can be removed by a preliminary
run without reagents.
d. Source of the Method - Manual of Methods for Chemical Analyses of Water
and Wastes, 1974 ed., p. 119; U.S. EPA Technology Transfer, Cinti., OH 45268.
E8-3
-------
WATER MONITORING PROCEDURE: Determination of Mercury Using the Flameless
Atomic Absorption (Cold Vapor) Technique
Operating Procedures:
A. Equipment Preparation
B. Instrument Set-up
C. Reagent Preparation
D. Sample Handling and Preservation
E. Calibration
F. Sample Determination
G. Calculation
E8-4
-------
WATER MONITORING PROCEDURE: Determination of Mercury Using the Flameless
Atomic Absorption (Cold Vapor) Technique
Equipment and Supply Requirements
A. Capital Equipment:
1. Atomic absorption spectrophotometer - Any commercial atomic absorption
instrument is suitable if it has an open burner head area in which to
mount an absorption cell, and if it provides the sensitivity and
stability for the analyses. Also instruments designed specifically
for the measurement of mercury using the cold vapor technique are
commercially available and may be substituted,
2. Mercury hollow cathode lamp
3. Recorder - Any multi-range variable speed recorder that is compatible
with the UV detection system is suitable.
4. Absorption cell - See Figure 4. The cell is constructed from glass
or plexiglas tubing 25.4 mm O.D. x 114 mm (Note 1). The ends are
ground perpendicular to the longitudinal axis and quartz window
(25.4 mm diameter x 1.6 mm thickness) are cemented in place. Gas
inlet and outlet ports (6.4 mm diameter) are attached approximately
12 mm from each end. The cell is strapped to a support and aligned
in the light beam to give maximum transmittance,
5. Analytical balance, 200 gram capacity
6. Trip balance, 500 gram capacity
7. Water bath, capable of maintaining 95°C temperature
B. Reusable Supplies;
1. Air pump - Any peristaltic pump, with electronic speed control, capable
of delivering 1 liter of air per minute may be used. (Regulated com-
pressed air can be used in an open one-pass system.)
2. Six BOD bottles (plus one bottle is needed per sample)
3. Volumetric flasks
Six 1000 ml
Four 100 ml
One 250 ml
4. Pi pets
Five 10 ml graduated
Two 1 ml graduated
One 1 ml volumetric
One 2 ml volumetric
Three 10 ml volumetric
One 5 ml volumetric
5. One 100 ml graduated cylinder; two 25 ml graduated cylinders
6. One Laboratory apron or coat
7. One pair safety glasses
8. One spatula
9. One pipet bulb
10. One wash bottle for distilled water
11. One glass stirring rod (about 6 inches long)
Note 1: An all glass absorption cell, 18 mm O.D. by 200 iron, with inlet 12 mm
from the end, 18 mm O.D, outlet in the center, and with quartz windows has
been found suitable.
-------
WATER MONITORING PROCEDURE: Determination of Mercury Using the Flameless
Atomic Absorption (Cold Vapor) Technique
Equipment and Supply Requirements (Continued)
12. One powder funnel
13. Rubber stoppers - two size #2 (for drying tube)
14. Fifteen feet of Tygon tubing
15. One glass tubing - 6 inches x 3/4 inch diameter
16. One Rotometer (any unit capable of measuring air flow of 1 liter/min.)
17. One set cork hole borers
18, One brush (for cleaning balance)
The following equipment is needed depending on which method is chosen to trap
the mercury,
1. Liquid trap
a. Straight glass frit, coarse porosity, such as Corning #404260
b. Filtering flask, such as Corning #40058
c. Rubber stopper, one hole to accept frit
d. Reagents, KMn04 and H2S04
2. Solid trap
a. Activated carbon such as Barnebey and Cheney #580-13 or #580-22
from: Barnebey and Cheney
E. 8th Avenue & Cassidy Street
Columbus, OH 43219
or
Coleman Instruments
42 Madison St.
Maywood, IL 60153
Item #50-160
b. Glassware - Can be assembled similar to the drying tube (Figure 3).
3. Closed System
The following equipment is needed when using the closed system with a
trap.
a. Two position valve, or stopcock, such as Corning #442838
b. Glass "Y" shaped tubing connecter
c. Pinch clamp, type used for stopping flow in tubing
C. Consumable Supplies:
1. Sulfuric acid (H?SO.) concentrated
2. Nitric acid (HN03) concentrated
3. Potassium permanganate, KMnQ*
4, Potassium persulfate, K0S000
C. C O
5. Sodium chloride, NaCl
E8-6
-------
WATER MONITORING PROCEDURE; Determination of Mercury Using the Flameless
Atomic Absorption (Cold Vapor) Technique
Equipment and Supply Requirements (Continued)
6. Hydroxylamine sulfate (HONH2)-H2S04 or
Hydroxylamine hydrochloride NFLOH-HCl
7, Stannous sulfate, SnSO. or stannous chloride, SnCl^
8. Mercuric Chloride, HgCl2
9. Hydrochloric acid concentrated
10. Magnesium perchlorate, Mg(C10.)2 for drying tube, 20 g.
11. Distilled water
12. Sponges (for cleaning laboratory table tops)
13. Notebook for recording weights and readings
14. Two pieces of glass tubing (5 mm diameter, about two inches long) for
the drying tube
15. Glass wool (for drying tube)
16. Plastic weighing boats (about 10)
17. Pen or pencil
Ffl_7
-------
WATER MONITORING PROCEDURE: Determination of Mercury Using the Flame!ess
Atomic Absorption (Cold Vapor) Technique
Sample
Chemical Sample Preparation
a. Oxidation of all mercury to mercuric form
b. Reduction of all mercuric mercury to metallic mercury
Aeration
The metallic mercury is ciruculated as a vapor through
the system
Flame!ess Atomic Absorption
Absorption of energy at 253.7 nm from a hollow cathode
lamp measured by a photodetector
E8-8
-------
WAFER MONITORING PROCEDURE:
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
OPERATING PROCEDURES
A. Equipment Preparation
1. Cleaning of
Glassware
2. Balance Preparation
Instrumental Set-up
1. Flow System
STEP SEQUENCE
1. Wash with detergent.
2. Rinse with tap water.
3. Rinse with 1:1 nitric acid.
4. Rinse with tap water.
5. Rinse with 1:1 hydrochloric
acid,
6, Rinse with tap water.
7. Rinse with distilled water.
1. Check all balances for
cleanliness and proper
operation.
1. Before operation of the
instrument, four additions
to the system should be
considered (Figure 1).
lnFfiRMATION/OP£RATING GOALS/SPECIFICATIONS
la. Cleaning should be carried out in this order.
lb. Care should be taken to insure clean glassware,
Ic. If possible glassware should be reserved for
mercury analysis only and separated from other
glassware.
3a. Add 500 nil concentrated nitric acid (HNO,) to
500 ml distilled water. J
5a, Add 500 ml concentrated hydrochloric acid (HC1)
to 500 ml distilled water.
la. There are two ways the flow system can be set up.
It can be operated as a closed or open system.
In the closed system the mercury vapor con-
tinously passes through the system until wasted
in the mercury trap by the operator. In the
open system the vapor passes through the absorp-
tion tube only once and goes directly to the trap.
Which system is chosen will dictate what equipment
is necessary. Figure I shows the choices and the
equipment necessary for each.
TRAINING
GUIDE NOTES
E8-9
-------
WATER MONITORING PROCEDURE:
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
E8-10
OPERATING PRCCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Instrumental Set-up
(Continued)
2. Mercury Trap -
Liquid Type
1. One of the following mer-
cury traps should be in-
cluded in the system.
2. For a liquid type trap,
use a 250 ml side arm
filtering flask.
3. Assemble as shown in
Figure 2.
4. Insert straight gas dis-
persion tube or frit
through the hole so that
the bottom or fritted end
is about one inch above
bottom of the flask.
5. Insert into filtering
flask.
6. Connect tygon tubing to top
end of frit and a second
piece of tygon tubing to
the side arm of filtering
flask.
7. Add 200 ml of 1:1 potassium
permanganate (KMnO.) -
sulfuric acid (H S04)
Reagent (Reagent #10).
la. Because of the toxic nature of mercury vapor,
precaution must be taken to avoid contamination.
The vapor will be held in the trap after it has
been measured.
2a. Use a filtering flask such as Corning #400580
or its equivalent.
3a. Use a #3 cork hole borer to make the hole.
4a. Frit should have a coarse porosity such as
Corning #404260 or equivalent. The frit should
always fall below liquid level in the flask.
Should the level become low add more liquid
(Reagent #10). The nonfritted end should be
lubricated and care taken when the frit is in-
serted through the stopper so as not to break
the frit and injure the worker.
6a. Care should be taken so that the liquid level does
not come close to the opening of the side arm of
the flask. This could flood the instrument if
allowed to do so. If flooding should occur,
dismantle the absorption tube and clean it and
the tubing immediately.
7a. A solution of 0.25% iodine in a 3% potassium
iodide (KI) solution may also be used (Reagent 12)i
7b. Filling the flask can be postponed until all of
the apparatus is assembled.
-------
WATER MONITORING PROCEDURE:
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERA]ING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Instrumental Set-up
(Continued)
2. Mercury Trap -
Solid Type
3. Drying Tube
1. The apparatus can be pre-
pared similar to the dry-
ing tube (B-3) but packed
with 2-3 grams of acti-
vated carbon.
2, The equipment can be pur-
chased with adsorbent as
an option from the
analyzer manufacturer.
1. Construct as shown in
Figure 3.
2. Bore a hole through a
number 2 stopper with a
number 2 cork hole borer.
Repeat with a second
stopper.
3, Insert a 2 inch long piece
of glass tubing (5 mm
diameter) through each
stopper allowing about 1/2
inch protruding from each
end.
4. Fill a 6 inch piece of 3/4
inch diameter tubing with
20 grams of magnesium
perchlorate
la. Locate after 2 position valve in closed system,
Figure 1 (system two) or after the analyzer in
an open system, Figure 1 (system three).
2a. Position as above.
la. Place between sample container and instrument.
3a. Care should be taken when inserting glass tubing.
4a. Other drying agents such as calcium chloride
(Cad,) may be used.
E8-11
-------
WATER MONITORING PROCEDURE:
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
E8-12
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Instrumental Set-up
(Continued)
4. Rotometer
5. Use a small piece of glass
wool in each end of the
tube to prevent loss of
granules.
6. Insert stopper prepared
above in each end of tube.
7, Replace drying agent when
needed.
1. Must be capable of measur-
ing a gas flow of 1 liter
per minute.
Connect one length of
tubing between the sample
container and the drying
tube through the rotometer
to the fitting of the
instrument.
A second length of tubing
should beqin at the out
fitting of the instrument
and proceed to the next
piece of equipment.
5a. The tube should not be packed so tight as to
restrict gas flow.
7a. Replace magnesium perchlorate or any drying agent
regularly. These materials tend to cake and form
a plug when their limit of saturation is ap-
proached. The length of time the material will
last will vary with use and samples. Experience
will dictate a routine.
la. Place between water trap and instrument. See
Figure 1 for location.
Ib. The rotometer may be removed from the circuit
after the instrument pump rate is checked.
lc. The flow rate should be checked periodically to
insure flow rate has not changed.
2a. The connection must be made to the sample con-
tainer by side arm. Reverse tubing connections
may flood the instrument with liquid.
3a. See Figure 1 for gas flow path.
-------
WATER MONITORING PROCEDURE:
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Instrumental Set-up
(Continued)
5. Two Position Valve
6. Recorder
(Optional
7. Instrument
1. A two position valve is
necessary when using a
closed system and a trap.
Use stopcock, Corning No.
442838 or equivalent for
the two way valve or
stopcock.
2. One position of the valve
should go through the
trap to the sample con-
tainer. The other positior
should by-pass the trap
and be connected to the
frit of the sample
container.
1. Any multi-range variable
speed recorder that is
compatible with the equip-
ment is suitable.
1. Follow instrument
manufacturer's directions.
C. Reagent Preparation
1. Sulfuric Acid 0.5 N
2a. It is important to maintain a specific air
volume in the system. Once the system is
calibrated, this volume cannot be changed unless
the system is recalibrated.
la. Use of a recorder or its equivalent for analysis
of potable water samples is strongly recommended,
Add 14.0 ml concentrated
sulfuric acid (H2S04) to
approximately 500 ml water
and mix. Then dilute with
water to 1 liter volume.
la. The concentrated H-SO. should be of low mercury
concentration.
Ib. Unless specified the term water means distilled
water.
Ic. Use a 25 ml graduated cylinder to measure the
sulfuric acid.
E8-13
-------
HATER MONITORING PROCEDURE:
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
E8-14
OPERATING PROCEDURES
STEP SEQUEhCt
INFORMATION/OPERA! ING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
2. Potassium
Permanganate
Solution - 5%
Solution w/v
3. Potassium Persul-
fate Solution -
5% Solution w/v
4, Sodium Chloride -
Hydroxylamine
Sulfate Solution
Solution
122 NaCl
12%
((HQNH2)2-H2SO
5.
Stannous Sulfate
Solution - 10%
Solution w/v
6.
Sulfuric Acid
Concentrated
(H2S04)
1. Prepare 100 ml of solution
containing 5.0 grams
potassium permanganate
(KMn04).
1. Dissolve 5.0 g potassium
persulfate (K0S00Q) in
f. L O
water and dilute to 100 ml
1. Dissolve 12.0 g of sodium
chloride (NaCl) and 12.0 g
of hydroxylamine sulfate
K-H-SO,) in water
and dilute to 100 ml.
1. Add 25.0 g Stannous sul-
fate (SnSOj to about 40
0.5 N sulfuric acid and
dilute with 0.5 sulfuric
acid to 50 ml.
1. No preparation necessary.
la. Should a larger amount of reagent solution be
needed the same ratio should be maintained. For
example: prepare 1000 ml of solution containing
50 grams KMn04-
Ib. Weigh out in plastic weighing boat on a trip
balance.
la. Weigh out in a plastic weighing boat on a trip
balance.
la. Hydroxylamine hydrochloride (NH~OH-C1) may also
be used. It should be prepared in the same
manner.
Ib. Weigh out in a plastic weighing boat on a trip
balance.
la. Stannous chloride (SnCl2'2H?0) may be used and be
prepared in the same manner.
Ib. The acid is reagent no. 1.
Ic. This is a suspension and should be stirred con-
tinuously during use.
Id. Weigh out in a plastic weighing boat on a trip
balance.
la. This should be reagent grade and low in mercury
concentration.
Ib. Caution: this is corrosive.
-------
WATER MONITORING PROCEDURE;
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
OPERATING PROCEDURES
STTP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
7.
8.
Nitric Acid
Concentrated
(HN03)
Stock Mercury
Solution (HgCl.
9.
Intermediate
Mercury Solution -
(HgCl,
Dilution
of Solution 8
1. No preparation necessary.
1. Dissolve 0.1354 g of mer-
curic chloride (HgCl?) in
water.
2. Add 10 ml concentrated
nitric acid
3. Cool to room temperature.
4. Dilute to 100 ml with
water.
1. The intermediate solution
is a dilution of the stock
solution to adjust the
concentration of Hg to
0.1 Kg/ml. Proceed as
follows.
2. Add about 700 ml water to
a 1000 ml volumetric flask
3. Add 0.5 ml concentrated
la. This should be reagent grade and low in mercury
content.
lb- Ca_uti_gn_: this is corrosive.
Ic. If a high reagent blank is obtained, it may be
necessary to distill the nitric acid.
la. Weigh out in a plastic weighing boat on an
analytical balance.
2a. Caution: solution will increase in temperature.
2b. Use a 10 ml graduated pipet.
4a. Concentration of stock solution is now
1 ml = 1 mg Hg.
4b. Stock solution is stable for several months.
la. Prepare fresh before use.
3a. The nitric acid concentration of the dilutions
including the working solution should be main-
tained at 0.15%. This acid should be added to
the flask before addition of the aliquot.
3b. Use a 1 ml pipet graduated in tenths.
E8-15
-------
WATER MONITORING PROCEDURE;
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
E8-16
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
10. Working Mercury
Solution (HgCl2)
Dilution of
Solution 9
Prepare 11 or 12 for a
liquid trap.
11. Potassium
Permanganate 0.1
(KMn04) and
Sulfuric Acid 10%
Solution (for
Mercury Trap)
M
4. Add 10 ml stock Hg
solution.
5. Dilute to 1000 ml mark.
This solution contains
10
1 . Add about 700 ml water to
a 1000 ml volumetric flask
2. Add 1.5 ml concentrated
HN03.
3. Add 10 ml of intermediate
solution (10 yg/ml ) .
4. Dilute to 1000 ml mark.
This is working solution
and contains 0.1 yg/ml .
1. Dissolve .316 g potassium
permanganate (KMnO.) in
100 ml water.
2. Add 10 ml concentrated
sulfuric acid (H^SO.) to
about 80 ml water. Dilute
to 100 ml with water.
3. Mix equal volumes of each
solution; KMN04 (1) and
Hen /9\
oOU. \l).
4a. Use a 10 ml volumetric pi pet.
2a. Use a 10 ml graduated pipet.
3a, Use a 10 ml volumetric pipet.
la. Let stand until following solution is prepared.
Ib. Weigh out in a plastic weighing boat or a trip
balance.
2a. Caution: heat generated.
2b. Should be at room temperature before volume
adjustment.
2c. Use a 10 ml graduated pipet.
-------
WATER MONITORING PROCEDURE:
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
12. Iodine (0.25) in
KI (3%) Solution
D. Sample Handling and
Preservation
1. Measure 250 ml of dis-
tilled water in a gradu-
ated cylinder.
2. Transfer about half the
water to a 500 ml
Erlenmeyer flask.
3. Weigh out 7.5 grams of
potassium iodide (KI).
4. Transfer the potassium
iodide to the 500 ml
Erlenmeyer flask and
dissolve.
5. Weigh out 0.63 grams of
iodine (I).
6. Add to the Erlenmeyer
flask and dissolve.
7. Add the remainder of the
water.
8. Mix well.
3a. A trip balance can be used,
5a. A trip balance can be used,
1. Upon collection, the sample
pH should be lowered to 2
or lower by the addition
of concentrated nitric
acid (HN03).
la. If only dissolved mercury is to be determined,
the sample should be filtered before addition
of the acid. For total mercury the filtration
is omitted.
Ib. If nitric acid cannot be used because of shipping
restrictions, the sample may be initially pre-
served by icing and immediately shipped to the
(Continued)
E8-17
-------
WATER MONITORING PROCEDURE:
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
E8-18
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Sample Handling and
Preservation
E. Calibration
2. Collect samples in
appropriate container.
3. Do not store samples beyonc
the acceptable time.
laboratory. Upon receipt in the laboratory, the
sample must be acidified with concentrated nitric
acid to pH<2.
2a. Samples should be collected in acid-washed glass
or high density polyethylene bottles.
3a. Samples should be analyzed within 38 days if
collected in glass bottles and within 13 days
if collected in polyethylene bottles.
1. Prepare a series of
standards from the working
mercury standard.
la. Prepare as follows:
ml 's of
Standard
0.0
0.5
1.0
2.0
0
10.0
ml's of Water
100.0
99.5
99.0
98.0
95.0
90.0
Concentrated
0.00
0.05
0.10
0.20
0.50
1.00
2. Mix thoroughly.
3. Add 5 ml concentrated
sulfuric aci
each bottle.
sulfuric acid (H9SO.) to
Ib. Use 300 ml BOD bottles.
Ic. Use volumetric pipets to pipet the standards.
Id. A 100 ml graduated cylinder may be used for the
water.
3a. Mix thoroughly.
3b. Use caution when using concentrated acids
3c. Use a 5 ml graduated pipet.
I.E.3
VII.E.3
(p. 22 &
P. 26)
-------
WATER MONITORING PROCEDURE:
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
OPERATING PROCEDURES
E. Calibration
(Continued)
STEP S
4. Add 2.5 ml concentrated
nitric acid (HNO,) to
each bottle.
5. Add 15 ml potassium
permanganate (KMnO*)
(Reagent no. 2).
5. Allow to stand 15 minutes.
7. Add 8 ml potassium
persulfate (K^S^On)
(Reagent no. 3).
8. Heat in a water bath at
95°C for 2 hours.
9. Cool to room temperature.
10. Add 6 ml of the sodium
chloride-hydroxylamine
sulfate (NaCl-(HONH2)2-
HpSO.) (Reagent no. 4).
11. Allow to stand at least
30 seconds.
inFURMATlON/OPERATING GOALS/SPECIFICATIONS
4a. Mix thoroughly.
4b. Use caution when using concentrated acids.
4c. Use a 5 ml graduated pipet.
5a. Shake and add additional potassium permanganate
solution, if necessary, until the purple color
persists for the following standing time.
5b. Use a 25 ml graduated cylinder for the addition,
7a. Use a 10 ml graduated pipet.
8a. The heat step is required for organic mercury
compounds. For standards prepared with dis-
tilled water and mercuric chloride, the heating
step is not necessary.
lOa.
lOb.
lOc.
lla
Shake we!1.
Use a 10 ml graduated pipet.
This reagent should decolorize the solution.
6 ml is not enough, add sufficient extra to
complete the decolorization.
If
Up to this point all samples to be run can be
treated as a group. From this point each must be
done individually as the mercury is liberated
immediately upon addition of the stannous
sulfate.
TRAINING
GUIDE NOTES
E8-19
-------
WATER MONITORING PROCEDURE;
Determination of Mercury Using the Flameless Atomic
Absorption (Cold Vapor) Technique
E8-20
OPERATING PRCCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Calibration
(Continued)
12. Add 5 ml of stannous
sulfate suspension (SnSO.)
(Reagent no. 5).
13. Immediately insert bubbler
into the bottle.
14. Observe reading.
15. Trap the mercury.
16. Continue with the
remaining standards.
17. Plot a standard curve.
12a. Use a 5 ml graduated pipet with a large bore
opening.
13a. The air mover (pump-air, cyl inder, etc.) should be
calibrated before use at 1 liter/minute. It
should be on and allowed to operate continously
when analyzing samples or standards.
13b. The reading will increase and reach a maximum
within one minute.
14a. When a recorder is used, allow the pen to level
off.
15a. In the closed system the valve must be turned to
the trap position until the absorbance returns to
the minimum value. The aeration should be
continued. In the open system wait until the
absorbance returns to the minimum value.
16a. Repeat steps 12-15. Section D.
17a. Plot the peak height (from the recorder plot)
versus the concentration in micrograms of
mercury on arithmetic paper.
VII.E.15
(P. 26)
II.E.17a
(p. 24)
F. Sample Determination
1. Transfer 100 ml of the
sample to a 300 ml BOD
bottle.
la.
Ib.
The sample should not contain more mercury than
the upper limit of the equipment being used. The
range of the method may be varied through
instrument and/or recorder expansion and by using
a larger volume of sample.
The usual range of the procedure is 0.2 to about
10.0 yg Hg/liter (.02 to 1.0 ugHg/100 ml).
-------
WATER MONITORING PROCEDURE:
Determination of Mercury Using the Flameless Atomic
At,sorption (cold Vapor) Technique
OPERATING PROCEDURES
F. Sample Determination
(Continued)
G. Calculations
2. Treat sample(s) with same
procedure used in cali-
bration section steps
3 through 15.
1. Determine the peak height
of the unknown(s) from the
recorder chart and read the
mercury value from the
standard curve,
2, Calculate the mercury con-
centration in the sample.
3. Report mercury concentra-
tion as follows:
Below 0.2 yg/1 as <0.2 yg/1
Between 1.0 and 10.0 yg/1
using one place after
decimal
Above 10.0 yg/1 using only
whole numbers
!NFC
-------
WATER MONITORING PROCEDURE: Determination of Mercury Using the nameless
Atomic Absorption (Cold Vapor) Technique
TRAINING GUIDE
SECTION TOPIC
I* Introduction
II* Educational Concepts - Mathematics
III* Educational Concepts - Science
IV Educational Concepts - Communications
V* Field and Laboratory Equipment
VI Field and Laboratory Reagents
VII* Field and Laboratory Analysis
VIII Safety
IX Records and Reports
*Training Guide materials are presented here under the headings marked*.
These standardized headings are used through this series of procedures.
E8-22
-------
WATER MONITORING PROCEDURES:
Determination of Mercury Using the Flameless
Atomic Absorption (Cold Vapor) Technique
INTRODUCTION
Section I
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
E.3
Theoretical Concepts
The method is based on the method developed by Hatch
and Ott. The mercury in the sample is oxidized to
the mercuric ion with potassium permanganate in a
nitric-sulfuric acid medium. Hydroxylamine sulfate
is then added to remove the excess permanganate,
Stannous sulfate, Is then added to reduce the
mercury to metallic form. Then the mercury is
vaporized and circulated by the bubbler system. Thi
consists of a circulating pump and the bubbler.
Measurement is made with a flameless atomic ab-
sorption spectrophotometer. The energy at the 253,7
nm mercury line emitted by a mercury lamp is ab-
sorbed by the mercury vapor in the flow-through
absorption cell. The change in transmittance is
detected by a phototube.
Analytical Chemistry,
vol. 40, p. 2085,
December 1968.
E8-23
-------
HATER MONITORING PROCEDURES: Determination of Mercury Using the Flameless
" Atomic Absorption (Cold Vapor] Technique
EDUCATIONAL CONCEPTS - MATHEMATICS
Section II
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
E.17a
The standard curve is a reference to a fundamental
law of absorption chemistry known as the Beer-
Lambert law. Simply, this law states that the amount
of energy absorbed by a solution is proportional to
the concentration of the absorbing material in the
solution. Applied to this outline the amount of
energy absorbed at the wavelength of 253.7 nm Is
proportional to the amount of mercury present in a
solution.
If the concentrations of a series of known solutions
(prepared as in step 1 under Calibration) and peak
height are plotted, a straight line should result.
When an unknown sample value is obtained, its mercury
content can be determined from the straight line or
standard curve.
To use the attached graph paper prepare the standards
as in step 1 of the Calibration section and run them
as described. The known concentrations are plotted
along the bottom of the graph. Then plot the peak
heights obtained from the recorder chart plotted on
the left of the graph.
Where the known concentration line intersects with
the appropriate peak height, a mark is made. After
all six standards are plotted, draw a line through
the marks.
E8-24
-------
WATER MONITORING PROCEDURES;
Determination of Mercury Using the Flameless
Atomic Absorption (Cold Vapor) Technique
FIELD AND LABORATORY EQUIPMENT
Section V
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
B.6.1a
The criteria for certification of a laboratory for
analysis of drinking water samples for compliance
rfith the Safe Drinking Water Act (93-523) lists as
nandatory equipment a recorder to be used when
inalyzing for mercury.
E8-25
-------
WATER MONITORING PROCEDURES:
Determination of Mercury Using the Flameless
Atomic Absorption (Cold Vapor] Technique
FIELD AND LABORATORY ANALYSIS
Section VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
E.3
E.15
Loss of mercury may occur at elevated temperature.
However, with the stated amounts of acid the
temperature rise is only about 13°C (25-38°C) and no
losses of mercury will occur.
PA Method Study B» Total
lercury in Water,
PA-600/4-77/012, Feb. 1977,
Be sure to close the valve before running another
sample/standard when using the closed system. Since
the system is being calibrated with the valve in
that position, running a sample/standard in the open
mode will produce a nonacceptable value. This is due
to the change in volume of the system.
Operation in the open mode does not require the
valve. Consequently, the opening and closing will
not have to be done.
E8-26
-------
.7
.61
.5;
.4-;
.2
.1
10
20
3d
40 50
Peak Height
60
70
100
-------
RECORDER
o
MERCURY
TRAP
ROTOMETER
SAMPLE
CONTAINER
(BOD BOTTLE)
SYSTEM ONE: LIQUID MERCURY TRAP CLOSED SYSTEM
RECORDER
-o
WATER UROTOMETER
TRAP
SAMPLE
CONTAINER
(BOD iOTTLE)
SYSTEM TWO: SOLID MERCURY TRAP CLOSED SYSTEM
SAMPLE CONTAINER
(BOD BOTTLE;
SYSTEM THREE: SOLID MERCURY TRAP OPEN SYSTEM
Es-28
Figure 1. FLOW SYSTEMS FOR THE COLD VAPOR
TECHNIQUE FOP MFPrilRY
-------
FROM
MAS-50
RUBBER STOPPER
(size #6)
FILTERING FLASK
(Corning #400580
TYGON TUBING
STOPCOCK
GLASS "Y" SHAPED
TUBING CONNECTOR
TO SAMPLE
CONTAINER
SIDE ARM OF
FILTERING FLASK
CD
I
ro
id
FIGURE 2. ARRANGEMENT OF TWO-POSITION STOPCOCK AND
MERCURY TRAP
-------
oo
i
U)
o
GLASS
TUBING
6 inches
MAGNESIUM PERCHLORATE (20 g)
RUBBER STOPPER GLASS WOOL
(#2 size)
3/4 inch
__^ ^_ 1 Jf_ diameter
GLASS WOOL TYGON
TUBING
FIGURE 3. DRYING TUBE
-------
18 MM
18 MM
JL
10 - 18 CM
FIGURE 4.CELL FOR MERCURY MEASUREMENT
BY COLD VAPOR TECHNIQUE
The length and OD of the cell are not critical. The body of the cell
may be of any tubular material but the end windows must be of quartz
because of the need for UV transparency.
The length and diameter of the inlet and outlet tubes are not important,
but the position of the side arms may be a factor in eliminating recorder
noise. There is some evidence that displacement of the air inlet arm
away from the end of the cell results in smoother readings, A mild
pressure in the cell can be tolerated, but too much pressure may cause
the glued-on end windows to pop off.
Cells of this type may be purchased from various supply houses.
E8-31
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
DETERMINATION OF ARSENIC AND SELENIUM
as applied in
DRINKING WATER TREATMENT FACILITIES
and in the
DISTRIBUTION SYSTEMS OF DRINKING WATER TREATMENT FACILITIES
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.ME.lab.WMP.2.11.77
E9-1
-------
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
General Description of Equipment and Supplies Used in the Process
A. Capital Equipment:
1. Balance, analytical - sensitivity 0.1 milligrams
2. Atomic absorption spectrophotometer - see instrument section
3. pH meter
4. Hot plate, 110 V
5. Magnetic stirrer
6. Pan balance
B, Reusable Supplies:
1. Flasks, volumetric, 50 ml, 100 ml, 1000 ml
2. Flasks, Erlenmeyer, 250 ml
3. Pipet, volumetric, 25 ml 50 ml
4, Pipet, micro, 1 ml graduated 0.1 ml
5. Pipet, measuring, 1 ml, 10 ml
6. Graduated cylinders, 500 ml, 100 ml, 50 ml, 25 nil
7. Beakers, 250 ml
8. Funnel, 80 mm diameter
9. Ring stand and 3 inch ring
10, Watch glass
11. Anion and cation exchange resin cartridges
12. Reagent bottles
13. pH paper
14. Specialized glassware - See apparatus section
C. Consumable Supplies:
1. Reagents, analytical reagent grade
a. Arsenic trioxide
b. Selenium metal
c. Zinc metal (200 mesh)
d. Potassium iodide
e. Stannous chloride
f. Sulfuric acid 18N
g. Hydrochloric acid, concentrated
h. Nitric acid
i. Perchloric acid, 70-72 percent
j. Sodium hydroxide
2. Gases
a. Argon
b. Hydrogen
F9-3
-------
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
1. Analysis Objective:
To determine the arsenic and selenium concentration, as listed in the
Interim Primary Drinking Water Regulations, in water samples from
potable water treatment and distribution facilities.
2. Brief Description of the Analysis:
Samples are prepared to distinguish between inorganic and total (inorganic
and organic) metal by appropriate acid digestion. Either one of the
prepared samples or standards are treated with SnCl^, a reducing agent to
convert the metal to its lowest oxidation state, Zinc is added to the acidi-
fied sample, generating hydrogen and producing the evolution of the metal
hydride which is aspirated into a Argon-Hydrogen flame of an atomic absorption
spectrophotometer. Calculations are made from a standard curve by measuring
the peak heights of the samples and reading the concentration.
3. Applicability of this Procedure:
a. Range of Concentration - From 2 to 20 yg/1 is the working range of the
method.
b, Pretreatment of Samples - Upon collection the pH of the sample should
be lowered to below 2 by the addition of concentrated nitric acid.
The maximum holding time is 6 months.
c. Treatment of Interferences - In analyzing most surface and ground waters,
interferences are rarely encountered. Organic forms of arsenic and
selenium must be oxidized before analysis,
d. Source of Procedure - Methods for Chemical Analysis of Water and Wastes,
1974, Environmental Monitoring and Supply Laboratory, Cincinnati, Ohior.
E9-4
-------
WATER MONITORING PROCEDURE; Determination of Arsenic and Selenium
Operating Procedures:
A. Apparatus and Instrumentation
B. Instrument Calibration
C. Reagent Preparation
D. Sample Preparation
E. Standards Preparation
F. Samples and Standards Treatment
G. Calculations
E9-5
-------
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
E9-6
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
A. Apparatus and
Instrumentation
1. Atomic absorption spectro-
photometer.
2. Hollow cathode lamp.
3. Recorder.
4. Flowmeter.
5. Medicine dropper.
6. Reaction flask.
7. Special gas inlet-outlet
tube.
8. Magnetic stirrer.
9. Drying tube.
la. Any atomic absorption spectrophotometer that
allows the introduction of a gaseous sample;
double-beamed instrument preferred because of
increased stability.
2a. Arsenic or selenium hollow cathode lamp compati-
ble with the spectrophotometer.
3a. Any variable-speed recorder that is compatible
with the spectrophotometer; a chart speed of
10 mm/minute recommended.
4a. A flowmeter capable of measuring 1 I/minute, such
as a Gilmont No. 12 or equivalent used for
auxiliary argon.
5a. A dropper capable of delivering 1.5 ml, fitted
into a size "0" rubber stopper.
6a. A pear-shapped vessel with side arm and 100 ml
capacity, both arms having 14/20 joint
(Scientific Glass JM-5835) or equivalent.
7a. Constructed from a micro cold finger condenser
(Scientific Galss JM-3325) or equivalent by
cutting off the portion below the 14/20 ground
glass joint.
8a. Must be strong enough to homogenize a 50% mixture
of zinc dust and water.
8b. See reagent section.
9a. 100 mm long polyethylene tube filled with glass
wool to keep particulate matter out of the
burner.
-------
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
OPERATING PROCEDURES
A. Apparatus and
Instrumentation
(Continued)
STLF SEQUENCE
10. Apparatus setup: See
schematic.
INFORMATION/OPERATING GOALS/SPECIFICATIONS
lOa. Connect the apparatus with the burner of the
spectrophotometer as indicated in the schematic.
Connect the outlet of the reaction vessel to the
auxiliary oxidant input of the burner with Tygon
tubing. Connect the inlet of the reaction
vessel to the outlet side of the auxiliary
oxidant, argon supply, control valve of the
instrument.
TRAINING
GUIDE NOTES
B. Instrument
Calibration
Prepare atomic absorption
spectrophotometer for
operation.
Install the hollow cathode
lamp for the element being
measured (As or Se) in the
instrument, set the wave-
length dial and align the
lamp in accordance with
the manufacturer's
instructions.
Set the slit width accord-
ing to the manufacturer's
suggested setting for the
element being measured
(As or Se}.
Turn on the instrument and
ajust the current to the
hollow cathode lamp as
suggested by the
manufacturer.
la. It is not possible to formulate instructions
applicable to every instrument but in general
one can follow the step sequence in the
adjacent column and by consulting the instruction
manual for your particular instrument.
2a. Arsenic wavelength 193.7 mm.
Selenium wavelength 196.0 mm.
2b. See instruction manual for your particular
instrument.
4a. Allow the instrument to warm up, usually 10-20
minutes, until the energy source stabilizes.
E9-7
-------
E9-8
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B.
Instrument
Calibration
(Continued)
5. Install a Boling burner
head.
6. Turn on the argon and
adjust to a flow rate of
about 8 1/minute with
the auxiliary argon flow
at 1 1/minute.
7. Turn on the hydrogen,
adjust the flow rate of
about 7 1/minute and
ignite the flame which
will be essentially color-
less.
8. Adjust the burner head
both sideways and verti-
cally in the 1ight path
until maximum response is
obtained by atomizing a
freshly prepared standard
solution for the element
being measured (1.00 ml
equals 1.00 mg (As or Se))
7a. The gas flow rates may require adjustment to
optimize the flame for your particular instrument
8a. The instrument is now ready to run standards and
samples.
C. Reagent Preparation
1. Dionized
Distilled Water
2.
Nitric Acid
Concentrated
(HNOJ
1. Prepare by passing dis-
tilled water through a
mixed bed of cation and
am"on exchange resin.
1. Commercially available
reagent grade.
la. Use deionized distilled water for the preparation
of all reagents, calibration standards, and as
dilution water.
la. If metal impurities are found to be present,
distill reagent grade nitric acid in a
borosilicate glass distillation apparatus.
-------
WATER MONITORING PROCEDURE:
Determination of Arsenic and Selenium
OPERATING PROCEDURES
STLP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
3. Hydrochloric Acid
4. Diluent - Stock
5. Potassium Iodide
Solution
6. Stannous Chloride
Solution
Commercially avialagle
reagent grade.
Add 100 ml 18 N Sulfuric
acid and 400 ml hydro-
chloric acid to 400 ml
deionized distilled water
in a 1 liter volumetric
flask and bring to volume
with deionized distilled
water.
1. Weigh 20 grams potassium
iodide, KI, on a pan
balance.
2. Transfer the reagent into
a 250 ml Erlenmeyer flask
and dissolve with 100 ml
deionized distilled water
Weigh 100
chloride,
balance.
grams
SnCl~,
stannous
on a pan
Transfer the reagent into
a 250 ml Erlenmeyer flask
and dissolve with 100 ml
concentrated hydrochloric
acid, HCL.
la. Use a 100 ml and 500 ml graduate.
Ib. Diluent used for preparation of working standards
la. Use a weighing disk.
2a. Use a 100 ml graduate.
la. Use a weighing disk.
2a. Use a 100 ml graduate.
E9-9
-------
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
E9-10
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
7. Stock Arsenic
Intermediate
Arsenic Solution
1. Weigh 4 grams sodium
hydroxide, NaOH, on a pan
balance.
2. Transfer the reagent to a
250 ml beaker and add 100
ml of deionized water,
allow to dissolve.
3. Weigh 1.3209 grams arsenic
trioxide, As?0_ on an
analytical balance.
4. Transfer the reagent to
the beaker containing the
NaOH solution, allow to
dissolve.
5. After dissolution transfer
into a clean 1000 ml
volumetric flask and
dilute to the mark with
deionized distilled water.
1. Pipet 1 ml stock arsenic
solution (1000 mg/1) into
a 100 ml volumetric flask
and bring to volume with
deionized distilled water
containing 1.5 ml con-
centrated nitric acid per
liter.
la. Use a weighing disk.
2a. Stir if necessary with a glass or plastic rod,
3a. Using a weighing disk.
4a. Stir if necessary.
5a. Use a plastic wash bottle to rinse the beaker
and stirring rod into the volumetric flask.
5b. One ml equals 1.00 mg As (1000 mg/1).
la. One ml equals 10.0 mg As (10 mg/1).
Ib, Use a volumetric pi pet.
lc. This solution is made up fresh at time of use.
-------
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Conti nued)
9. Standard Arsenic
Solution
10. Perchloric Acid
70-725;; HCIO,
Pi pet 10 ml intermediate
arsenic solution in 100
ml volumetric flask and
bring to volume with
deionlzed distilled water
containing 1.5 ml con-
centrated nitric acid per
liter.
Commercially available
grade.
la. One ml equals 1 pg As (1
Ib. Use a volumetric pipet.
Ic. This solution is made up
mg/1).
fresh at time of use,
D. Sample Preparation
1. Inorganic Arsenic
or Selenium
2, Total (Inorganic
and Organic)
Arsenic
1.
To a 50 ml volumetric
flask add 25 ml of water
sample, 20 ml concentrated
HC1 and 5 ml
of 18N H2S04.
1. To 50 ml of water sample
in a 150 ml beaker add
10 ml of concentrated
nitric acid, and 12 ml of
18 N sulfuric acid. This
mixture is evaporated to
SO,, fumes (a volume of
about 20 ml).
2. To maintain oxidizing
conditions add small
amounts to nitric acid
whenever the red-brown
NO- fumes disappear.
la. Allow to cool to ambient temperature.
Ib. Use a 25 ml volumetric pipet,
Ic. Use 10 ml measuring pi pets.
la. Oxidizing conditions must be maintained at all
times to avoid loss of arsenic.
2a. Add nitric acid in
measuring pipet.
1 ml increments using a
E9-11
-------
E9-12
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
0. Sample Preparation
(Continued)
3. Allow to cool slightly,
add 25 ml of deiom'zed
distilled water and 1 ml
perchloric acid, and
again evaporate to SO,
fumes.
4. Allow to cool, add 40 ml
concentrated HCL, trans-
fer the solution into a
100 ml volumetric flask
and dilute to the mark
with deionized distilled
water.
3a. Use a 25 ml graduate. Use a 1 ml measuring
pipet.
4a. Use a plastic wash bottle to rinse the beaker
during the transfer.
4b. Use a 50 ml graduate.
E. Standards
Preparation
Transfer 0, 0.5, 1.0, 1.5
and 2.0 ml standard
arsenic or selenium so-
lution to 100 ml volumet-
ric flasks and bring to
volume with diluent to
obtain a concentration of
0, 0, 10, 15, and 20 pg/1
arsenic or selenium.
la. Use a 1 ml micro pipet graduated in 0.1 ml.
Ib. Refer to reagent preparation section.
F. Samples and
Standards Treatment
Transfer a 25 ml aliquot
of sample prepared as in
(D.I) or 0.2) or standard
prepared as in (E.) to a
reaction vessel.
la. Use a 25 ml volumetric pipet.
-------
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
OPERATING PROCEDURES
STEP SEQUENCE
IMfORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Samples and
Standards Treatment
(Continued)
2. Add 1 ml of 20 percent
potassium iodide to
arsenic samples and
standards only.
3. Add 0.5 ml of 100 percent
stannous chloride
solution.
4. Attach the reaction vessel
to the special gas inlet-
outlet glassware.
5. Fill the medicine dropper
with about 1-1/2 ml of
zinc slurry that has been
kept in suspension with a
magnetic stirrer.
6. Firmly insert the stopper
containing the medicine
dropper into the side
neck of the reaction
vessel.
7. Squeeze the bulb to intro-
duce the zinc slurry into
the sample or standard.
8. When the absorbance
reaches its maximum and
the recorder pen returns
part way to the base line,
remove the reaction vessel
2a. Us a 1 ml measuring pi pet.
2b. Omit potassium iodide for selenium determinations
3a. Use a 1 ml measuring pipet.
3b. Allow at least 10 minutes for the arsenic or
selenium to be reduced to its lowest oxidation
state.
7a. The argon carrier gas will sweep the generated
metal hydride into the burner. The metal hydride
will produce a peak almost immediately.
E9-13
-------
E9-14
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
G. Calculations
1. Draw a standard curve by
plotting peak heights of
standards verus concen-
trations of standards.
2. Using your standard curve
measure the peak heights
of the samples and deter-
mine the concentration
from the curve.
la. Use linear graph paper.
2a. Take in account any dilution factors. In this
case the sample was diluted 1 + 1 with acid,
multiply the concentration obtained from the
curve by two.
-------
WATER MONITORING PROCEDURE: Determination of Arsenic and Selenium
ft
Flow
Meier
JM -33215 -.
Medicmc ^y"-xo
Dropnei in K.. —'--
Size "0" V?~
Rubber \^/
Stopper
tryon
1 . Drying p-*^1
1 TU')C t i .. - A-,
J _
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
DETERMINATION OF NITRATE-NITRITE NITROGEN AND
OF NITRATE NITROGEN, CADMIUM REDUCTION METHOD
as applied in
WASTEWATER TREATMENT FACILITIES
and in the
MONITORING OF EFFLUENT WASTEWATERS
Developed by the
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.N.n/n.EMP.lb.3.80
E10.A-1
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen
and of Nitrate Nitrogen, Cadmium Reduction
Method
This operational procedure was developed by:
NAME Don Roach
ADDRESS Miami-Dade Community College, South Campus, 11011 S.W. 104 Street,
Miami, Florida 33176
POSITION Chairman - Chemistry Department
EDUCATION AND TECHNICAL BACKGROUND
B.S. - Chemistry
M.S. - Chemistry
PhD. - Analytical Biochemistry
1 year Commercial Laboratory Chemist
10 years College Chemistry Instructor
7 years Chemical Consultant to Industry
E10.A-3
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen
and of Nitrate Nitrogen, Cadmium Reduction
Method
1. Objective:
To determine the nitrate-nitrite nitrogen and the nitrate nitrogen content
of an effluent.
2. Brief Description of Analysis:
The procedure converts nitrate nitrogen to nitrite nitrogen when the
nitrate is passed through a column containing copper-cadmium granules.
Nitrate is almost quantitatively reduced to nitrite by this process.
The resulting nitrite is determined by reacting the effluent with sul-
fanilamide and coupling with N - (1-napthyl) - ethylenediamine dihydro-
chloride to form a highly colored dye which can then be determined
colorimetrically. A correction must be made for any nitrite initially
present in the sample since the method determines total nitrite. The
concentration of nitrite originally present in a sample can be determined
by omitting the initial copper-cadmium reduction and carrying out the
remainder of the procedure. Separate nitrate-nitrite values for a sample
may be obtained by analyzing two aliquots of the sample; one with the
copper-cadmium reduction step and one without the initial reduction step.
3. Applicability of this Procedure:
a. Range of Concentration:
0.01 to 1,0 mg N03-NOZ N/liter
(The range may be extended for samples by dilution.)
b. Pretreatment of Samples:
The Federal Register Guidelines do not specify any pretreatment.
c. Treatment of Interferences in Samples:
This procedure includes directions for removal of turbidity and/or of
grease and oil from samples. It also includes addition of EDTA to
eliminate interferences from metals. No other Interferences are noted
in the Source of Procedure.*
* Source of Procedure: Methods for Chemical Analysis of Water and Wastes, 1979,
U.S. Environmental Protection Agency, Enivornmental Flonitoring and Support
Laboratory, Cincinnati, Ohio, page 353.3-1 (Issued 1974).
nn.A-4
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen
and of Nitrate Nitrogen, Cadmium Reduction
Method
FLOW SHEET:
TURBIDITY REMOVAL
(if necessary)
OIL AND GREASE REMOVAL
(if necessary)
ADJUST pH TO BETWEEN 5
AND 9 (if necessary)
REDUCTION OF NITRATE TO
NITRITE BY PASSING THROUGH
CADMIUM REDUCTION COLUMN
COLOR DEVELOPMENT BY REACTION
OF NITRITE WITH SULFANILAMIDE
AND WITH N-(l- NAPTHYL) -
ETHYLENEOIAMINE DIHYDROCHLORIDE
MEASUREMENT OF ABSORBANCE AT
540 nm
RESULTS: NITRATE N PLUS
ORIGINAL NITRITE N
The above procedures determine nitrate N plus nitrite N. The initial nitrite
concentration of the samples could be determined without reduction. Thus,
the nitrate concentration can be determined by:
Nitrate N = Total Nitrite N - Nitrite N without reduction
E10.A-5
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen
and of Nitrate Nitrogen, Cadmium Reduction
Method
Equipment and Supply Requirements
A. Capital Equipment:
1. Balance, analytical, 160 g capacity, precision +^0.1 mg
2. Balance, triple beam, 500 g capacity, precision +_ 0.25 g
3. pH meter/combination electrode, range 0-14 pH
4. Refrigerator, temperature range 2° - 10°C
5. Spectrophotometer, wave length range 325-825 nm
6. Still a,nd de-ionizing cartridges (or other means of distilling and
de-ionizing water)
B. Reusable Supplies:
1. One apron, laboratory
2. One 100 ml beaker
3. Four 250 ml beakers (3 for buffer solutions)
4. One 400 ml beaker
5. One 1 liter beaker
6. One 2 1iter beaker
7. Two bottles, Barnes with stoppers and two droppers, small gauge
8. One 150 ml bottle, dropper
9. One 250 ml bottle, plastic wash
10. One 100 ml bottle, storage with screw-on cap (storage of 6N HC1)
11. Seven 1 liter bottles, storage, brown with screw-on caps or rubber stoppers
12. Two 5 gallon bottles, water with bottom spout
13. One brush, camel hair (cleaning analytical balance)
14. Two brushes, bottle (cleaning glassware)
15. One bulb, propipet type
16. One buret holder, double clamps (reduction column support)
17. Two columns, reduction (see Figure 1 at the end of this section)
18. Three cuvettes
19. One 25 ml cylinder, graduated
20. One 50 ml cylinder, graduated
21. One 100 ml cylinder, graduated
22. One 500 ml cylinder, graduated
23. One 1 liter cylinder, graduated
24. One 50 ml flask, volumetric with stopper (dilution of sample)
25. Twelve 100 ml flasks, volumetric with stoppers (for standards)
26. X 100 ml flasks, volumetric with stoppers (for samples - 1 flask
per sample)
27. Twelve 250 ml flasks, Erlenmeyer with stoppers (for standards)
28. X 250 ml flasks, Erlenmeyer with stoppers (for samples-1 flask per sample)
29. One 1 liter flask, Erlenmeyer, or a large, empty chemical bottle
(for Cd washings)
30. Three 1 liter flasks, volumetric with stoppers
31. Two 2 liter flasks, volumetric with stoppers
32. One filter funnel for 0.45 u filter (turbidity removal)
E10.A-6
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen
and of Nitrate Nitrogen, Cadmium Reduction
Method
B. Reusable Supplies (Continued)
33. One funnel, powder
34. One funnel, large powder with large filter paper (for Cd washings)
35. One 250ml funnel, separatory (oil and grease removal)
36. One pair glasses, safety
37. Two hoses, rubber, 3" strip, 4 cm 1.0. with screw type clamp
38. One notebook (recording data)
39. Two 100 ml volumetric pipets (construction of reduction columns)
40. One C,5 ml pipet, volumetric
41. One 1 ol pipet, volumetric
42. One 2 ml pipet, volumetric
43. One 5 ml pipet, volumetric
44. One 10 ml pipet, volumetric
45. One 25 ml pipet, volumetric
46. One 50 ml pipet, volumetric
47. One rod, stirring (6" or 12")
48. One sieve, 40 mesh
49. One sieve, 60 mesh
50. One spatula (scoopula )
51. Two stands, ring (support funnel, and reduction column)
52. One support, ring, small (support funnel)
C. Consumable Supplies:
1. Glasswool, wad
2. Membrane filter, 0.45 y
3. Notebook (recording data)
4. Pen or pencil (recording data, marking flasks)
5. Soap
6. Sponges (for cleaning)
7. Tissues, soft (wiping cuvettes and electrodes)
8. Towels, paper
9. Twelve weighing boats
10. 26 g ammonium chloride, NH^Cl
*11. 100ml ammonium hydroxide, NH^OH
*12. 150 ml buffer solution, STD pH 4
*13. 600 ml buffer solution, STD pH 7
*14. 450 ml buffer solution, STD pH 10
**15. 25 g cadmium granules, 40-60 mesh
16. 55 ml chloroform, CHCU (Freon or another non-polar solvent may be used.)
17. 20 g copper sulfate, pentahydrate, CuSO^-SH^O
18. 3.4 g disodium ethylenediamine tetraacetate, ^]o^i4^2^a2^8
19. 1 g N-(l-napthyl) - ethylenediamine dihydrochloride, C12H^N2'2HC1
*20. 200 ml hydrochloric acid, concentrated, HC1
21. 100 ml hydrochloric acid, dilute (6N), HC1
22. 100 ml phosphoric acid, concentrated, H3P04
*23. Potassium dichromate (cleaning solution), K^r^Qj
24. 7.218 g potassium nitrate, KN03
E10.A-7
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen
and of Nitrate Nitrogen, Cadmium Reduction
Method
C. Consumable Supplies (Continued)
25. 6.072 g potassium nitrite, KNO«
26, 240 g sodium hydroxide, pellets, NaOH
27. 10 g sulfanilamide, CgHgN^S
*28, Sulfuric acid, concentrated, (cleaning solution) H-SQ^
29. 100 g zinc sulfate, heptahydrate, ZnSO.-7HpO
30. Labels, package, 1 1/2 x 1 inch
31. Paper,,graph 8 1/2 x 11, package
All reagents should be reagent grade.
The above amounts do not allow for spillage or mistakes.
"These amounts will vary
**MCB Reagents . . .
E10.A-8
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen
and of Nitrate Nitrogen, Cadmium Reduction
Method
10 cm
80-85 ml
25 cm
,
•3 cm I.D.
3.5 mm I.D.
Cu/Cd
100 mi
volumetric
pipet
GLASS WOOL PLUG
CLAMP
TYGON TUBING
-Cut
•Cut
Figure 1. Reduction column
E10.A-9
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and of
~~ Nitrate Nitrogen, Cadmium Reduction Method
E10.A-IO
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
DETERMINATION OF NITRATE
A. Equipment
Preparation
1. Glassware Wash-Up
2. Balance Inspection
3. Spectrophotometer
Inspection
NITRITE NITROGEN AND OF NITRATE NITROGEN, mg/liter
1, Clean all glassware in
suitable detergent.
1, Clean balance.
1. Clean spectrophotometer.
2, Turn power on by rotating
the power control
clockwise.
3. Select wavelength by
rotating the wavelength
control knob either
direction until the proper
wavelength is reached.
4. Zero the instrument by
bringing the meter needle
to "0" on the percent
transmittance scale.
5, Use an empty cell and
adjust the light control
to 100% T.
I
(p. 41 )
la. Distilled water drains without leaving any
droplets on surfaces.
Ib. Use chromerge if necessary.
la. Free of dust and dirt.
la. Free of dust and dirt,
2a. Pilot lamp on.
2b. Directions are for Spectronic 20.
3a. 540 nm on the wavelength scale.
4a. Meter needle reads zero.
5a. To be sure that the Instrument can achieve 100% T.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFQRMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
1, Distilled Water
2. Concentrated
Ammonium Chloride
EDTA Solution
1. Prepare approximately ten
(10) liters of highly pure
water.
1. Weigh 26 g of armnonium
chloride, NH.C1, in a
weighing boat and wash
into 2.0 liter graduated
beaker.
2, Weigh 3.4 g of disodium
ethylenediamine tetra-
acetate, C^mM, .NpNa«Oo,
and wash into the sane
beaker.
3, Add enough distilled water
to bring the total volume
to approximately 1800 ml.
4. Use a pH meter to adjust
the pH of the solution to
8.5 by the dropwise addi-
tion of concentrated
ammonium hydroxide,
NH4OH.
5. After the pH has been ad-
justed, transfer the
solution to a 2 liter
volumetric flask.
la
An ion exchange column in conjunction with a still
provides an adequate source of highly pure water.
This water will be used for all reagent prepara-
tion and washing of equipment.
Ic. The pH of the water must be between 5.5-7.5.
Ib
la. Distilled water should be used for all phases of
solution preparation including water used in
washing a solid into a container.
4a. Vix the solution thoroughly by stirring, after
the addition of each drop of NH.OH.
5a. Whenever a solution is transferred, the container
from which the transfer is made should be washed
and the washings added to the container to which
the transfer was made.
E10.A-11
-------
E10.A-12
EFFLUENT MONITORING PROCEDURF: Determination of mtrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
Reagent Preparation
(Continued)
3, Dilute Ammonium
Chloride EDTA
Solution
4, Color Reagent
6. Dilute to volume with
distilled water.
7. Label the bottle in which
the solution is stored.
1. Measure 300 ml of the
concentrated ammonium
chloride-EDTA solution
into a one liter graduated
cylinder,
2. Add distilled mter to
bring the volume to
500 ml in the cylinder.
3. Swirl to mix the
solution.
4. Store in a labeled
container.
1. Add 800 ml of distilled
water to a 1 liter flask,
2. Add 100 ml of concentrated
phosphoric acid, H3PO., to
the same flask.
3. Mix thoroughly.
4. Weigh 10 g of sulfanilamfde
(CgHgN202S) in a weighing
boat.
6a, The solution is stable for several months.
*
7a, Include the name of the solution, your name and
the date of preparation.
4a. This dilute ammonium chloride-EDTA solution is
stable for several months.
la. Use a graduated cylinder.
lb. Use a 1 liter volumetric flask.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
5. Zinc Sulfate
Solution
6.
7.
8.
Use a wash bottle and
funnel to wash the
sulfanilamide into the
1 liter flask containing
phosphoric acid solution.
Weigh 1 g N-(l-napthyl)-
ethylenediamine dihydro-
chloride, Marshall's
Reagent, and wash into
same flask.
Dilute to volume with
distilled water.
Store in a
container.
labeled
1, Weigh 100 g of zinc sul-
fate heptahydrate,
ZnSO.-7ILO, in a weighing
boat.
2,
Wash into a 1
using a wash
funnel.
liter
bottle
flask
and a
8a. Container should be dark 1 liter plastic reagent
bottle,
8b. Store at 4°C when not in use.
8c. Use at room temperature.
8d. The solution is stable for several months.
8e. A very faint pink color may show up in this
color reagent. You may still use the reagent.
If a precipitate forms in the reagent, though,
discard it.
la. This reagent is used if flocculation is employed
as an alternative to filtration if the sample
requires removal of turbidity.
2a. Use a volumetric flask.
3. Add sufficient distilled
water to dissolve all of
the solid.
E10.A-13
-------
HO.A-14
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and of
Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
6. Sodium Hydroxide
Solution (6N)
7. Ammonium
Hydroxide
8. Hydrochloric
Acid, (6N)
4. Dilute to volume with
distilled water.
5. Store in a labeled
container.
1. Rapidly weigh 240 g q,f
solid sodium hydroxide,
NaOH, pellets 1n a 1 liter
graduated beaker.
2. Add 500 ml distilled
water to dissolve the
sodium hydroxide.
3. Dilute to a total volume
of 1 liter.
4. Store in a glass bottle or
jug and stopper with a
rubber stopper.
5. Label the container.
1. A 100 ml supply should be
available.
2. Place in a Barnes
(dropper) bottle.
1. Add 50 ml of distilled
water to a 400 ml beaker.
5a. This solution is stable for at least one year.
la. This reagent is used if flocculation is employed
as an alternative to filtration if the sample
requires removal of turbidity.
Ib. Sodium hydroxide picks up moisture from the air
quite readily.
2a, The water should be added with constant swirling
to avoid fusing. CAUTION: Heat is liberated.
Place Beaker in a pan of cold water.
3a. The solution should be allowed to cool to room
temperature before the dilution is made.
4e. Sodium hydroxide slowly etches glass causing
glass stoppers to stick.
4b. The solution is stable for at least a year.
la. Drop quantities may be required for pH
adjustment.
la. A 100 ml graduated cylinder is suitable for
measuring the volume of the distilled water.
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
9. Copper Sulfate
Solution (2%)
10, Nitrate Stock
Solution
2. Slowly add 50 ml of
concentrated hydrochloric
(HC1) acid (12 N) to the
same beaker.
3. Mix thoroughly.
4, Store in a TOO ml bottle.
5. Label the container.
1. Weigh 20 g of copper
sulfate pentahydrate,
CuSO.-SHpO, in a weighing
boat.
2. Wash copper sulfate into a
two 1iter beaker.
3. Add 500 nil distilled water
and swirl to dissolve the
sol id.
4. Add 500 ml distilled water
and swirl to nix.
5, Store in a labeled
container.
1. Carefully weigh 7.218 g of
potassium nitrate, KNO..,
in weighing boat.
2a. Measure the acid in a 100 ml graduated cylinder.
3a. Use a graduated cylinder to measure 500 ml.
5a. This solution is stable for at least one year.
la. An analytical balance should be used.
E10.A-15
-------
E10.A-16
EFFLUENT MONITORING PROCEDURE.: Determination of Nitrate-Nitrite Nitrogen and of
— Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
11. Nitrate Standard
Solution
2. Transfer the solid to a
1 liter volumetric flask
equipped with a powder
funnel.
3. Use wash bottle to wash
the solid into the flask.
4, Add sufficient distilled
water to dissolve the
solid,
5. Dilute to volume with
distilled water and
thoroughly mix.
6. Store in a labeled glass
bottle.
7. Preserve the solution by
adding 2 ml of chloroform,
CHC13,
1. Carefully pipet 10.0 ml of
nitrate stock solution
into a 1 liter volumetric
flask.
2, Dilute to volume with
distilled water.
2a. This is best achieved by washing the solid onto
the funnel with a wash bottle.
3a. The weighing boat should be rinsed three times
and all of the rinse water should be added to
the flask.
4a. About 500 ml is sufficient.
7a. The solution prepared^stored and preserved in
this manner should be stable for at least
6 months.
7b. The nitrate stock solution contains 1.00 mg of
nitrate nitrogen (NO-j-N) in each 1.00 ml of
solution.
la. This nitrate standard solution should be prepared
fresh for each use.
Ib. The nitrate stock solution should be at room
temperature before using.
Ic. Use a 10 ml volumetric pipet.
-------
EFFLUENTMONITORING PROCEDURE.; Determination of Nitrate-Nitrite Nitrogen and of
~~ Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
12. Nitrite Stock
Solution
3. Store in a labeled
container.
1. Weigh 6.072 g of
potassium nitrite, KNCL,
in a weighing boat.
2. Transfer the solid to a
1 liter volumetric flask
using a powder funnel.
3. Use wash bottle to wash
the solid into the flask.
4. Add sufficient distilled
water to dissolve the
solid.
5. Dilute to volume and mix
thoroughly.
6. Store in a labeled glass
bottle.
7. Preserve the solution by
adding 2 ml of chloroform
for each 1 liter of solu-
tion and refrigerate when
not in use.
3a. Use within two hours of preparation.
3b. The nitrate standard solution contains 0.01 rug
of nitrate nitrogen (NO_-N) in each 1.0 ml of
solution. J
la. An analytical balance should be used for all
weighings involving standards.
3a. The weighing boat should be washed three times
and the washings added to the flask.
4a. About 500 ml is sufficient.
7a. The solution should be stable for at least
3 months when preserved this way and stored
at about 4°C when not in use.
7b. The nitrite stock solution contains 1.00 mg of
nitrite nitrogen (NO?-N) in each 1.0 ml of
solution.
E10.A-17
-------
E10.A-18
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B, Reagent Preparation
(Continued)
13. Nitrite Standard
Solution
1. Pipet 10.0 ml of nitrite
stock solution into a
1 liter volumetric flask.
2. Dilute to volume with
distilled water.
3. Store in a labeled
container.
la. This nitrite standard solution should be prepared
fresh for each use.
Ib. The nitrite stock solution should be at room
temperature before using.
Ic. Use a 10 ml volumetric pipet.
3a. Use within two hours of preparation.
3b. The nitrite standard solution contains 0,01 mg of
nitrite nitrogen (NOj>~N) in each 1.0 ml of
solution.
C. Reduction Column
Preparation
1. Preparation of the
Glass Column
1. Construct a glass column
by joining a 10 cm length
of 3 cm ID glass tubing
with a 25 cm length of
3.5 mm ID tubing using
figure 1 as a guide.
2. Loosely plug the delivery
tip of the column with
glass wool.
la
Ib
Figure 1 is at the end of the Equipment and
Supply Requirements Section.
The column shown in Figure 1 was constructed by
cutting both ends off a 100 ml volumetric pipet
as indicated.
Ic. Fire polish all cut surfaces.
2a. The plug must be firm enough to hold the cadmium
granules in the column, but not so firmly packed
as to slow down the later flow of solutions
through the column.
-------
EFFLUENT MONITORING PROCEDURF: Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reduction Column
Preparation
(Continued)
2. Preparation of
Copperized
Cadmium for
Packing the
Glass Column
1. Weigh about 25 g of
cadmium granules in a
weighing boat.
2. Transfer the cadmium to a
400 ml beaker.
3. Add enough dilute (6N)
hydrochloric acid to
cover the granules.
4. Swirl the contents of the
beaker.
5. Pour off the acid while
retaining the granules
1n the beaker. The
cadmium should be silver.
6. Add enough distilled water
to cover the granules.
la. This will be enough for one column.
lb. Granulated cadmium (40-60 mesh) can be purchased.
Ic. Alternatively, file sticks of pure cadmium metal
(reagent grade) with a coarse metal hand file
(about second cut) and collect the fraction which
passes a sieve with 10 mesh openings and is re-
tained on sieves with 40, then 60 mesh openings.
Id. Handling cadmium is hazardous, thus filing should
be conducted under a hood using rubber gloves and
mask,
2a. A scupula and wash bottle with water is good for
this.
VIII.C.2.Id
(p. 46)
5a. All decanting should be done into a container
equipped with a large funnel and filter paper
so as to catch all the small cadmium particles.
5b. Use this filter paper for any subsequent cadmium
washings.
.A-19
-------
E1Q.A-2Q
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reduction Column
Preparation
(Continued)
7. Pour off the water while
retaining the granules in
the beaker.
8, Repeat steps 6 and 7,
above, two more times so
that the granules receive
a total of three dis-
tilled water washings.
9. Add TOO ml of the 2%
copper sulfate solution to
the granules and swirl for
five minutes or until the
blue color of the copper
sulfate fades.
10. Carefully decant off the
solution leaving the
copperized cadmium
granules in beaker.
11. Repeat steps 9 and 10
until a brown colloidal
(very fine) precipitate
of metallic copper does
form.
12. Wash the copper-cadmium
at least 10 times with
distilled water.
13. Place the washed copper-
cadmium on the 60 mesh
sieve.
9a. A brown colloidal (very fine) precipitate of
metallic copper should form.
lOa. Also decant off through the filter paper any
precipitate that formed.
lOb. The cadmium should have a black color.
lla. If a brown colloidal precipitate is formed in
step 9, and the cadmium is black, do not repeat
steps 9 and 10.
12a. All of the brown precipitated copper should be
removed by washing 10 times but continue to
wash if any remains.
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reduction Column
Preparation
(Continued)
14. Pour water over the
granules at least three
times so that al1 the
small particles will
wash through the 60 mesh
screen.
15. Return meshed granules to
the beaker.
16. Decant off excess water
used to transfer the
cadmium.
17, Close the clamp on the
column delivery tube.
18. Fill the column with liq-
uid, using about 60 ml
DILUTE ammonium chloride-
EDTA solution.
19. Loosely fill the reduction
column with copper cadmium
granules to a level about
2 cm below the broad,
cup-like section as shown
in Figure 1 page 9.
14a. Hold the sieve over the filter paper during
these washings.
15a. Use a scupula and the wash bottle.
18a. Use a graduated cylinder and very slowly pour the
solution down the inside wall of this column so
air pockets do not form.
19a, Avoid tight packing of granules by allowing the
granules to "float" down through the solution
of ammonium chloride-EDTA.
19b. A glass stirring rod may be used to transfer the
cadmium to the column.
E10.A-21
-------
EFFLUENT HUNITORING PROCEDURE.: Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
E10.A-22
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reduction Column
Preparation
(Continued)
20. Open the screw clamp and
measure the flow rate of
ammonium chloride-EDTA
solution through the
column. The flow rate
must be between 7 ml and
10 ml/minute before you go
to the next step. Keep a
record if you add more di-
lute ammonium chloride-
EDTA solution.
21. Rinse the column with up ta
140 ml dilute ammonium
chloride-EDTA solution,
draining until the solutior
is about 2.5 cm above_ the
top of the granules." Then
close the screw clamp.
20a. To calculate the flow rate, place a 50 or 100 ml
graduated cylinder under column and measure the
amount of fluid collected in one minute
20b. The flow rate should be between 7 ml and 10 ml/
minute. DO NOT let the column go dry.
20c. If the flow rate is too fast, tighten the screw
clamp. If the clamp must be so tight that contra
is lost, add more copper-cadmium granules to the
column.
20d. If the flow rate is too slow, decrease the length
of the copper-cadmium column until a flow rate of
7-10 ml/minute is achieved.
21a. There is to be a 200 ml rinse with this solution.
You used about 60 ml in Step 18 and may have
added more in Step 20. Now add the balance
to total 200 ml.
21b. It is convenient to add a second clamp to shut
off the flow so the flow-regulating clamp can re-
main undisturbed.
21c. When the column is not in use, the granules
should be covered with solution so they do not
dry out.
D. Removal of
Interferences
1. Turbidity Removal
(If necessary)
1. Prior to analysis, remove
turbidity from samples by
filtering through a 0.45 u
membrane filter.
VI.D
(p. 42)
la. If the turbidity is not removed by filtration,
proceed as follows: Add 1 ml of the zinc sulfate
solution to 100 ml of sample. Add enough 6 N
sodium hydroxide to bring the pH to 10.5 (about
8 to 10 drops is usually sufficient). Let the
treated sample stand for 15 minutes. Filter
through a 0.45 y membrane filter.
Ib. Suspended solids can clog the reduction column.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Removal of
Interferences
(Continued)
2. Oil and Grease
Removal (If
Necessary)
1. Prior to analysis,
measure 100 ml of the
sample (filtered sample
if the original sample
was turbid) into a 400 ml
beaker.
2. By dropwise addition, add
sufficient concentrated
hydrochloric acid (12 N)
to bring the pH down to 2,
3, Place the sample in a
250 ml separatory funnel.
4. Add 25 ml of chloroform.
5. Shake gently to extract
the oils and grease into
the chloroform layer.
6. Allow the separatory
funnel to stand until all
of the chloroform layer
settles to the bottom.
7. Open the stopcock and
allow the bottom (chloro-
form) layer to pass into
a 400 ml beaker.
la. Oil and grease can clog the reduction column
and coat the Cu/Cd granules.
2a. Use a pH meter in adjusting the pH to 2,
2b. Standardize using standard buffer of pH = 4.00.
4a. Freon or another non-polar solvent may be used.
5a. Carefully release the pressure after shaking
gently so that no sample is lost. This can be
accomplished by inverting the separatory funnel
and slowly opening the stopcock away from face
and other people.
6a. Place funnel in ring stand.
6b. Remove stopper while layer is settling.
7a. Grease and oils are extracted into chloroform
layer leaving a grease-oil free sample which is
used for analysis.
E1Q.A-23
-------
E10.A-24
EFFLUENT MONITORING PROCEDURE; Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
D. Removal of
Interferences
(Continued)
E. Preparation of
Nitrate Working
Standards
1. Nitrate Working
Standards
*
STEP SEQUENCE
8. Repeat steps 4, 5, 6, and
7 with 25 ml of fresh
chloroform.
1. Prepare nitrate working
standards by respectively
pipetting the following
volumes of nitrate
standard solution into
each of six 100 ml
volumetric flasks.
Add This For This
Volume of Concentra-
Nitrate tion of
To Flask Standard N03-N in
No. Solution mg/1
1 0.0 ml 0,00
2 0.5 ml 0.05
3 1.0 ml 0.10
4 2.0 ml 0.20
5 5.0 ml 0.50
6 10.0 ml 1.00
2. Dilute each of the flasks
to volume with distilled
water.
3. Stopper and mix thoroughly
by inversion.
INFORMATION/OPERATING GOALS/SPECIFICATIONS
8a. The second chloroform extract is added to the
same beaker as the first extract.
la. Label flasks.
Ib. Use appropriate volumetric pipets (0.5 ml, 1.0 ml,
2.0 ml, 5.0 ml , 10.0 ml).
Ic. The 0.00 solution which contains no nitrate (or
nitrite) serves as the reagent blank for the
nitrate samples and standards which are passed
through the reduction column.
TRAINING
GUIDE NOTES
-------
EFFLUENTMONITORING PROCEDURE
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E, Preparation of
Nitrate Working
Standards (Continued)
4. Use the working standards
inrmediately after their
preparation.
F. Reduction of Nitrate
to Nitrite
1. Adjustment of pH
2. Activation of
Column
Use a pH meter to adjust
the pH of each of the
working standards to
between 5 and 9 either
with concentrated hydro-
chloric acid or with
concentrated armonium
hydroxide.
1. Pipet 25.0 ml of working
standard 16 to a small
Erlenmeyer flask.
2. Add 75 ml of the CON-
CENTRATED ammonium chlo-
ride-EDTA solution to
the sane flask.
3. Mix the working standard
thoroughly by swirling
the contents of the flask
4. Place a 250 ml beaker
under the reduction
column.
la. Use a beaker small enough for this volume of
standard to cover the pH electrode(s).
Ib. **ake sure that the pH meter is calibrated within
this range.
Ic. Use buffer solutions pH 4, pH 7, pH 10 to
calibrate and check the meter.
Id. This pH adjustment is necessary to insure that
the pH is approximately 8.5
(No pH adjustment is necessary if the pH is
already between 5 and 9.)
la. Activation of column is necessary to prepare
surfaces of Cu-Cd granules for reduction process,
Ib. This standard is 1.00 mg NO,-N/liter
concentration.
Ic. A 25C ml flask is good for this purpose,
2a. A 100 ml graduated cylinder is good for this
purpose.
E10.A-25
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Reduction of Nitrate
to Nitrite
(Continued)
5. Check that the level of
ammonium chloride-EOTA
solution in the column is
near to the top of the
granules.
6, Pour the prepared nitrate
working standard into the
reduction column.
7. Using the screw clamp
(see Figure 1) adjust the
collection rate to
7-10 ml per minute.
8. Collect the reduced
working standard until
the level of solution is
one cm above the top of
the granules.
9. Close the screw clamp to
stop the flow.
10. Discard the entire re-
duced working standard.
11- Measure about 40 ml of
DILUTE ammonium chloride-
EDTA solution,
12. Pour the 40 ml into the
column.
5a. If the level is too high, drain the excess into
the beaker.
6a. Since the column will not hold the total amount,
add the solution in portions.
7a. The clamp should be slowly opened until a
collection rate of 7-10 ml per minute is
achieved.
7b. A collection rate of 7-10 ml of solution per
minute should be carefully maintained throughout
the collection process to assure complete re-
duction of nitrate in the sample.
lOa. The column is now activated.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
I TRAINING
3UIDE NOTES
F. Reduction of Nitrate
to Nitrite
(Continued)
3. Reduction of
Working Standards
13. Collect the solution until
the level of the solution
is one cm above the top of
the granules. Then close
the screw clamp to stop
the flow.
14. The column should be ready
to use.
1. Pipet 25.0 ml of the lowest
concentration of nitrate
working standard into a
small Erlenmeyer flask.
2. Add 75 ml of the CONCEN-
TRATED ammonium chloride-
EDTA solution to the same
flask.
3. Mix nitrate working stand-
ard thoroughly by swirling
the contents of the flask.
4. Place a short graduated
cylinder under the reduc-
tion column.
5. Pour the prepared nitrate
working standard into the
reduction column.
6. Using the screw clamp (see
Figure 1) adjust the col-
lection rate to 7-10 ml
per minute.
13a. You can check for "carry over" by collecting
about 5 to 10 ml of the final effluent in a
clean receiver and adding a few drops of the
nitrite color reagent to verify that no color
develops after 10 minutes. (A very faint pink
color is negligible). Repeat steps 11 through
13 if significant color develops in this check
procedure.
la. A 250 ml flask is good for this purpose,
Ib. Label the flask.
Ic. Begin with the 0.00 mg/liter solution.
2a. Use a 100 ml graduated cylinder,
4a. You need to measure 25 ml of solution in the
graduate.
5a. Since the column will not hold the total amount,
add the solution in portions.
6a. The clamp should be slowly opened until a collec-
tion rate of 7-10 ml per minute is achieved.
6b. A collection rate of 7-10 ml of solution per min-
ute should be carefully maintained throughout the
collection process to assure complete reduction of
the nitrate in the nitrate wor king sTandard.
E10.A-27
-------
E10.A-23
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and of
—^— N-jtr0gen> cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Reduction of Nitrate
to Nitrite
(Continued)
7, Discard the first 25 ml
of solution which is
collected,
8. Replace the graduate with
the rinsed,air-dried
flask used for this
standard,
9. Collect the remaining
portion of the reduced
standard in the original
flask,
10, Analyze the reduced
standard IMMEDIATELY
after collection from
the reduction column.
11. Repeat steps 1 through 10
for each of the prepared
working nitrate standards,
7a. This discard portion serves to "wash off"
solution remaining in the column from any
previous pass-through.
8a. The solution originally in the flask should now
be in the column so you can thoroughly rinse it.
A different flask may also be used.
9a. Close the screw clamp when the level of solution
is about one cm above the granules.
9b. About 70 ml should be in the flask.
lOa. While one solution is passing through the column
you should proceed to color development of the
previous solution that has already been reduced.
Color development (Section G) MUST BEGIN WITHIN
15 MINUTES after reduction.
lla. Proceed from the least concentrated to the most
concentrated standard.
lib. Label each receiver flask.
G. Color Development of
Reduced Nitrate
Working Standards
1. Use a 50.0 ml
remove a 50.0
from flask #1
liter N03-N).
pi pet to
ml aliquot
(0.00 mg/
la. By using a propipet the aliquot can remain in
the pipet during the next two steps.
Ib. Aliquots of each of the working standards should
have been passed through the reduction column as
described in the previous section (Section F).
Ic. The reduced working standards should be analyzed
as soon as possible after the reduction and in.
no case, should they be allowed to stand for more
than 15 minutes after reduction before color
development is begun.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
G. Color Development of
Reduced Nitrate
Working Standards
(Continued)
2. Discard the remainder of
the nitrate reduced
working standard.
3, Shake flask dry.
4. Add the 50.0 ml working
standard back to same
flask from which it was
removed.
5. Add 2.0 ml of the color
reagent to the 50.0 ml
of working standard.
6. Mix thoroughly by
swirling.
7. Allow the working standard
to stand until color
develops.
8. Repeat steps 1 through 7
for each of the reduced
working standards.
3a. Do not rinse the flask.
4a. If you find the technique in steps 1-4 too
difficult, transfer the 50.0 ml to a different
flask.
5a. Use a 2.0 ml volumetric pipet.
7a. The reduced working standard should be allowed
to stand for at least 10 minutes but NOT MORE
THAN TWO HOURS before doing Procedure L,
Spectrophotometric Measurements.
8a. Start with least concentrated solution and
proceed to most concentrated.
8b. Rinse the 50.0 ml pipet thoroughly after each
standard.
H. Analysis of Samples
for Nitrate Reduced
to Nitrite
1. Dilution of
Samples (if
necessary)
Pipet 25.0 ml of unknown
sample into 50 ml volu-
metric flask.
la. Potable water samples will usually require no
dilution, while sewage samples may require
dilution.
no.A-29
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
E10.A-30
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
H
Analysis of Samples
for Nitrate Reduced
to Nitrite
(Continued)
2. Adjustment of pH
3. Reduction of
Nitrate to Nitrite
in Samples
4, Color Development
in Samples
2. Dilute to volume with
distilled water.
Use a pH meter to adjust
the pH of each sample to
between 5 and 9 either
with concentrated hy-
drochloric acid or with
concentrated ammonium
hydroxide.
1. Aliquots of each of the
samples should be passed
through the reduction
column as described in
Procedure F.3, "Reduction
of Working Standards."
1. Follow the steps fn
Procedure G, "Color
Development."
2a. If you need to dilute a sample, you must apply a
dilution factor to the concentration found from
a standard curve.
la. Put the 50 ml of sample in a small beaker so
the pH electrode(s) is covered with solution.
Ib. Hake sure that pH meter is calibrated within
this range.
Ic. Use buffer solutions pH 4, pH 7, pH 10 to cali-
brate and check the meter.
Id. This pH adjustment is necessary to insure that
the pH is approximately 8,5
(No pH f.rljustpent is necessary if the pH is
already between 5 and 9.)
VII.H.I.2a
(P. 44 )
I. Preparation of
Nitrite Working
Standards
1, Nitrite Working
Standards
Prepare nitrite working
standards by respectively
pipetting the following
volumes of nitrite stand-
ard solution into each of
six 100 ml volumetric
flasks.
la,
Ib,
Ic.
Label flasks.
Use appropriate volumetric pipets (0.5 ml, 1.0 ml,
2.0 ml, 5.0 ml, 10.0 ml).
The 0.00 solution which contains no nitrite (or
nitrate) serves as the reagent blank for the
nitrite standards and samples that are jipt passed
through the column.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
I. Preparation of
Nitrite Working
Standards
(Continued)
2, Adjustment of pH
o Flask
No.
1
2
3
4
5
6
Add This
Volume of
Nitrite
Standard
Solution
0.0 ml
5 ml
0 ml
0 ml
0 ml
10.0 ml
For This
Concentra-
tion of
NOz-N in
mg/1
0.00
0.05
0.10
0.20
0.50
1.00
2. Dilute each of the flasks
to volume with distilled
water.
3. Use the working standards
immediately after their
preparation.
1. Use a pH meter to adjust
the pH of each of the
working standards to
between 5 and 9 either
with concentrated hydro-
chloric acid or with
concentrated ammonium
hydroxide.
la,
Ib,
Ic.
Id.
Use a beaker small enough for this volume of
standard to cover the pH electrode(s).
Make sure that pH meter is calibrated within this
range.
Use buffer solutions pH 4, pH 7, pH 10 to
calibrate and check the meter.
This pH adjustment is necessary to insure that
the pH is approximately 8.5
(No pH adjustment is necessary if the pH is
already between 5 and 9.)
E10.A-31
-------
E10.A-32
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
J. Color Development of
Nitrite Working
Standards
1. Pipet 25.0 ml of each of
the nitrite working
standards into each of
six clean 250 ml
Erlenmeyer flasks,
2. Add 75 ml of CONCENTRATED
ammonium chloride-EDTA
solution to each of the
nitrite working standards,
3. Mix each thoroughly by
swirling each flask.
4. Use a 50.0 ml pi pet to
remove a 50.0 ml aliquot
from flask #1 {0.00 mg/
liter N02-N),
5. Discard the remainder of
the standard from the
flask.
6. Shake the flask dry,
7, Add the 50.0 ml nitrite
working standard back to
the same flask from which
it was removed.
8. Add 2.0 ml of the color
reagent to each nitrite
working standard.
9. Mix thoroughly by
swirlfng.
la. Use a 25,0ml volumetric pipet.
Ib. Label each flask.
Ic. The nitrite working standards are not passed
through the reduction column.
2a. Use a 100 ml graduated cylinder.
4a. By using a propipet the aliquot can remain in the
pipet during the next two steps.
6a. Do not rinse the flask.
7a. If you find the techniques in steps 4-7 too
difficult, transfer the 50.0 ml to a different
flask.
8a. Use a 2.0 ml volumetric pipet.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
J, Color Development of
Nitrite Working
Standards (Continued)
10. Allow the working stand-
ards to stand until color
develops.
11. Repeat steps 4 through 10
for each of the nitrite
standards.
lOa. At least 10 minutes but NO MORE THAN 2 HOURS
should be allowed before doing Procedure L,
Spectrophotometric Measurements.
lla. Proceed from the least concentrated to the most
concentrated standard.
lib. Rinse the 50.0 ml pipet thoroughly after each
standard.
K. Analysis of
Non-reduced
Samples for
Nitrite
1. Dilution of
Samples (if
necessary)
2. Adjustment of pH
3. Color Development
1. Pipet 25.0 ml of unknown
sample into 50 ml volu-
metric flask.
2. Dilute to volume with
distilled water.
1. Use a pH meter to adjust
the pH of each sample to
between 5 and 9 either
with concentrated hydro-
chloric acid or with
concentrated ammonium
hydroxide.
1. Pipet 25.0 ml of sample
into a clean 250 ml
Erlenmeyer flask.
la. NOTE: Potable water samples will usually
require no dilution, while sewage samples
may require dilution.
2a. If you need to dilute a sample, you must apply a
dilution factor to get a final answer.
la,
Ib,
Ic.
Id,
VII.K.l.Za
(P. 44)
Put the 50 ml of sample in a small beaker so the
pH electrode(s) is covered with solution.
Make sure that pH meter is calibrated within
this range.
Use buffer solutions pH 4, pH 7, pH 10 to
calibrate and check the meter.
This pH adjustment is necessary to insure that
the pH is approximately 8.5. (No pH adjustment
is necessary if the pH is already between 5 and 9)
la. Use a 25.0 ml volumetric pipet.
Ib. Label the flask.
Ic. The sample is not passed through the reduction
column.
E10.A-33
-------
E10.A-34
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
K. Analysis of
Non-reduced
Samples for
Nitrite (Continued)
2. Add 75 ml of the con-
centrated ammonium
chloride-EDTA solution to
the same flask.
3. Mix the sample thoroughly
by swirling.
4. Use a 50.0 ml pipet to
remove a 50.0 ml aliquot
from flask,
5, Discard the remainder of
the solution from the
flask.
6. Shake flask dry.
7. Add the 50.0 ml of sample
back to same flask from
which it was removed.
B. Add 2.0 ml of the color
reagent to the same flask
9. Mix the sample thoroughly
by swi rli ng.
10. Allow the sample to stand
until color develops.
11. Repeat steps 1 through
10 for each sample.
Ha. Use a 100 ml graduated cylinder.
4a. By using a propipet the aliquot can remain in
the pipet during the next two steps.
6a. Do not rinse the flask.
8a. Use a 2.0 ml volumetric pipet.
lOa. At least 10 minutes but NO MORE THAN 2 HOURS
should be allowed before doing Procedure L,
Spectrophotometric Measurements.
lla. Rinse the 50.0 ml pipet thoroughly after each
sample.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING COALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
L. SpectrophotometHc
Measurements
1. Adjusting the
Instrument
2. Reduced Nitrate
Standards and
Sample(s)
3. Non-reduced
Nitrite Stand-
ards and
Sample(s)
1, Consult the manufacturer's
instructions for cali-
brating your particular
instrument.
2. Adjust the wavelength to
540 nm.
3. Check to make sure that
the instrument reads
infinite absorbance with
no sample cell in the
instrument.
1. Use the reduced nitrate
reagent blank to adjust
the instrument to zero
absorbance.
2. Measure and record the
absorbance of each re-
duced nitrate working
standard.
3. Measure and record the
absorbance for each
reduced sample.
1. Use the nitrite reagent
blank (non-reduced) to
adjust the instrument to
zero absorbance.
la. Instrument must be warmed up for at least
10 minutes.
Ib. There is an EMP on "Use of a Spectrophotometer."
3a. If it does not read infinite absorbance with no
sample cell in it, adjust the instrument so that
it does read infinite absorbance (see manu-
facturer's instructions),
3b. Use calibration knob to calibrate infinite
absorbance.
la. Use 0.00 nitrate working standard reagent blank
which has been passed through the column.
Ib. Adjust to zero absorbance using the calibration
knob.
2a. Use the nitrate working standards which have
been passed through the column.
2b. Use data sheet provided.
3a. Use data sheet provided.
la. Use 0.00 nitrite working standard reagent blank.
Ib. Adjust to zero absorbance using the calibration
knob.
IX.L.2.2b
(p. 47)
E10.A-35
-------
E10.A-36
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
1. Spectrophotometrlc
Measurements
(Continued)
2. Measure and record the
absorbance of each non-
reduced nitrite working
standard.
3. Measure and record the
absorbance for each non-
reduced sample.
2a. Use data sheet provided.
3a. Use data sheet provided.
IX.L.3.2a
(p. 47)
M. Preparation of
Calibration Curve
1. Obtain an 8 1/2 x 11 inch
piece of graph paper.
2, Label the longer side as
the concentration axis.
3. Label the shorter side
as the absorbance axis.
4. Use the absorbance value
and its corresponding ni-
trate concentration for
each of the nitrate working
standards to make a plot of
absorbance versus
concentration.
5. On another piece of graph
paper follow steps 1, 2, 3,
and 4 using absorbance val-
ues and the corresponding
nitrite concentrations for
each of the nitrite working
standards.
2a. See Training Guide for an example of labeling
the axis on a calibration curve.
4a. Use the absorbances and concentrations recorded
on the data sheet in Column B, "Total N02+N03-N."
4b. This will be the standard curve for reduced
samples.
5a. Use the absorbances and concentrations recorded
on the data sheet in Column D, "NCL-N."
5b. This will be the standard curve for non-reduced
samples.
VII.M.2a
(p. 45)
IX
(p. <8)
IX
(p. 48)
-------
EFFLUENT MONITORING PROCEDURE.: Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
N. Checking Column
Efficiency
1. Divide the absorbance
value for the 1.00 rug/
liter NITRATE (N03)
working standard by the
absorbance for the 1.00
mg/liter NITRITE (N02)
working standard to
obtain the column
efficiency as follows:
abs of 1.00 Big/liter N03std x 100 = % efficiency
abs of 1.00 mg/liter N02std
la. The abbreviation, abs is used to stand for
absorbance.
2. Divide the absorbance
values for each of the
other NITRATE (N03)
working standards by the
absorbance value for the
corresponding NITRITE
(NO*) working standard to
obtain a column efficiency
value in each case as was
done in the previous step.
3. Calculate the average
value for the column
efficiency.
2a.
At least one reduced nitrate standard should be
compared to a nitrite standard of the same con-
centration to check column efficiency, calculated
as given in Step 1. If series of the standards
are run, you can calculate the average column
efficiency using this Step 2 and then Step 3.
3a.
3b.
The average value for the column efficiency
should be between 96% and 1041. If the average
% efficiency does not fall in this range,
another cadmium reduction column should be
prepared and tested until the average column
efficiency does fall in this range.
For regeneration of a column, see Training
Guide,
VII.N.3b
(p. 43)
E10.A-37
-------
E10.A-38
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
0. Determination of
mg/liter Nitrite
Nitrogen Plus Nitrate
Nitrogen in a Sample
Use the absorbance for
the reduced sample and
the standard curve for
reduced samples ("Total
N02+N03-N") to obtain
the mg/liter of nitrite-N
plus nitrate-N in the
sample and record it in
Column (A) on the data
sheet provided.
la.
Ib,
If the sample was not diluted (25 ml of sample
is used), the ing/liter result is read directly
from the nitrate standard curve.
If the concentration of nitrate in the sample
is too high for analysis, the sample must be
diluted. The procedure is described in H.I and
involves diluting the sample to a 50 ml volume.
In this case, the mg/liter result from the nitrate
standard curve must be multiplied by a dilution
factor which would be:
IX.O.la
(p. 47)
Dilution Factor =
50ml
ml sample used in dilution
Ic,
Id.
The reduction process converts the nitrate-N
initially present in the sample to nitrite
nitrogen and the species analyzed is nitrite
nitrogen.
Any nitrite nitrogen initially present in the
sample remains as nitrite nitrogen after the
reduction. Thus the total nitrite analyzed is
the sum of the nitrite initially present and
the nitrite which has been formed by reduction
of nitrate.
VH.O.lb
(p. 44)
P. Determination of
mg/liter Nitrite
Nitrogen in a Sample
1. Use the absorbance for
the non-reduced sample
and the standard curve
for non-reduced samples
("N02-N") to obtain the
mg/liter of nitrite-N in
the sample and record it
in Column (C) on the data
sheet provided.
le. If the sample was not diluted (25 ml of sample is
used), the mg/liter result is read directly from
the nitrite standard curve.
Ib. If the sample was diluted to a 50 ml volume (as
given in K.I), the mg/liter result read from the
nitrite standard curve must be multiplied by a
dilution factor which would be:
IX.P.la
(p. 47)
VII.P.Ib
(P- 44)
Dilution Factor =
50 ml
ml sample used in dilutTorf
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and of
Nitrate Nitrogen, Cadmium Reduction Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
Q, Calculation of
mg/liter Nitrate
Nitrogen in a Sample
Subtract the mg/liter of
nitrlte-N in the sample
from the mg/1iter of
nitrite-N plus nitrate-N
In the sample to obtain
the concentration of
nitrate-N.
la. Since the procedure measures the total nitrite
concentration in a sample, the nitrite concen-
tration of samples must be determined with
reduction and without reduction. The nitrate
concentration of a sample is then determined by:
NO.-N = (NOp+NO^-N) TOTAL - (NO.-N) WITHOUT
WITH REDUCTION
RE-
DUC-
TION
These concentrations were recorded on the data
sheet in Columns (A) and (C) respectively.
2, Record the answer in
Column (E) on the data
sheet provided.
IX.Q.la
(P- 47)
R. Calculation of
mg/liter Nitrate
in Sample
1. Multiply the value found
for nitrate-nitrogen
(N03-N) by a factor of
4.43.
2. Record the answer in
Column (F) on the data
sheet provided.
la. (NC3-N) x (4.43) = mg/liter Nitrate in sample.
Ib. NO,-N value was calculated in Procedure Q and
recorded in Column (E).
IX.R.lb
(p. 47)
S. Calculation of
mg/liter Nitrite
in Samples
1. Multiply the value found
for nitrite-nitrogen
(N02-N) by a factor of
3.29.
2. Record the answer in
Column (G) on the data
sheet provided.
la. (N02-N) x (3.29) = ing/liter Nitrite in sample.
Ib. NO»-N value is found by using the calibration
curve for non-reduced samples as in Procedure P
and recorded in Column (C).
IX.S.lb
(p. 47)
E10.A-39
-------
TRAINING GUIDE
SECTION TOPIC
I* Introduction
II Educational Concepts - Mathematics
III Educational Concepts - Science
IV Educational Concepts - Communications
V Field and Laboratory Equipment
VI* Field and Laboratory Reagents
VII* Field and Laboratory Analysis
VIII* Safety
IX* Records and Reports
*Training guide materials are presented here under the headings marked*.
These standardized headings are used throughout this series of procedures.
Fin A-
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and Nitrate
Nitrogen, Cadmium Reduction Method
INTRODUCTION
Section
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
The cadmium reduction procedure for nitrate-nitrite
nitrogen provides a sensitive method for the deter-
mination of nitrate singly, or nitrite and nitrate
combined in drinking, surface, and saline waters.
The method is commonly used to determine both
nitrate-N and nitrite-N in water samples.
The procedure described in this EMP is applicable
for range of 0.01 to 1.0 ing/liter of nitrate-
nitrite nitrogen. However, the range may be
extended by appropriate sample dilution.
The test described in this instruction can be found
in the 1979 EPA Methods Manual on p. 353.3-1, entitled1
Nitrogen, Nitrate-Nitrite (Cadmium Reduction Method).
Another reference which contains an acceptable
test for NPDES monitoring is on page 423 of the 14th
edition of Standard Methods.
The major sources of nitrogen entering the environ-
ment are: through the heavy application of nitrogen-
ous fertilizers which cause agricultural runoffs, as
the end products of aerobic stabilization of organic
nitrogen, in domestic sewage, through animal and
plant processing wastes, in animal manure, through
the atmosphere and fn various types of industrial
effluents.
While nitrogen is essential to our survival (as in
the make-up of amino acids and proteins), when it
exists as nitrate and nitrite it can be toxic. A
limit of 10 mg/1 nitrate-N and 1 mg/1 nitrite-N is
recommended for public water sources. The desirable
criteria is virtually 0 mg/liter.
In ruminant animals (i.e. cows) nitrates may be
internally reduced by bacteria present in the rumen
to nitrites. The nitrites have been found to be tox-
ic to these animals. Dr. Joptha E. Campbell, (Chief,
Food Chemistry Unit, Milk and Food Research, Environ-
mental Sanitation Program, Public Health Service,
U.S. Department of H.E.W., Cincinnati, Ohio, 1968)
has reported methemoglobfnemia in cattle receiving
water containing 2.790 mg/liter of nitrate.
Nitrates in high concentrations have also been found
to stimulate vegetative growth under favorable con-
ditions. Heavy undesirable growth in fresh water can
lead to eutrification of important waterways.
1. Methods for Chemical
Analysis of Water and
Wastes, 1979, EPA-
EHSL, Cincinnati,
Ohio 45268, p. 353.3-1.
2. Standard Methods for the
Examination of Water and
Wastewater, 14th ed.,
1976, APHA, New York,
New York, p. 423.
Federal Water Pollution
Control Administration
Water Quality Criteria.
U.S. Sovernment Printing
Office, Washington, D.C.
1968.
E1D.A-41
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and Nitrate
Nitrogen, Cadmium Reduction Method
FIELD AND LABORATORY REAGENTS
Section VI
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
D.
Samples should be analyzed for nitrate nitrogen as
soon as possible after sampling to avoid any change
in nitrogen balance due to biological activity. If
analysis can be made within 24 hours, the sample
should be preserved by refrigeration at 4°C.
Samples should be preserved with sulfuric acid if
they are to be held more than 24 hours. To pre-
serve samples for analysis, add 2.0 ml of con-
centrated sulfuric acid per liter of sample and
store at 4°C.
E10.A-42
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and Nitrate
Nitrogen, Cadmium Reduction Method
FIELD AND LABORATORY ANALYSIS
Section yil
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
N.3b
Check the column efficiency when it is suspected
that column efficiency is decreasing, as indicated
by suspected low concentration levels. Prepare
working standard nitrate solutions, and pass them
through the column. (Begin at E. Preparation of
Nitrate Working Standards.) If the absorbance for
the known concentration does not give an average
between 96% and 104% of your standard curve value
for reduced nitrate standards of equivalent concen-
tration, the column must be reactivated.
REACTIVATION OF COLUMN
1. Empty cadmium granules from column into a clean
beaker.
2. Wash with distilled water 3 times.
3. Add enough dilute HC1 to cover granules.
4. Swirl contents.
5. Decant HC1.
6. Wash with distilled water 3 times.
7. Add 100 ml CuSO. solution to granules.
8. Swirl contents of beaker for approximately 5
minutes until the blue color fades to colorless.
9. Decant liquid leaving the granules.
10. Repeat steps 7, 8, and 9 until a very fine
brown-red precipitate forms.
11. Wash granules with distilled water (approximately
10 times) until precipitate is removed.
12. Place granules on the 60 mesh sieve.
13. Shake to remove the small particles (the particles
which remain on the sieve are the ones you want.)
14. Repack column (packing must be loose).
15. Activate the column (See F.2).
16. Standard curve using nitrate v/orking stadards
must be re-established.
17. Check column efficiency as described in N,
Checking Column Efficiency.
E10.A-43
-------
EFFLUENT MONITORINGPROCEDURE: Determination of Nitrate-Nitrite Nitrogen and Nitrate
Nitrogen, Cadmium Reduction Method
FIELD AND LABORATORY ANALYSIS
Section VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
H.1.2a
K.l.Za
O.lb
P.lb
to
Since a dilution is only part sample, when the
absorbance reading obtained for 1t Is converted
a concentration using a calibration curve, the
concentration obtained 1s only that of the dilution.
To obtain the mg/Hter concentration of the sample,
the mg/liter concentration of the dilution must be
multiplied times the amount of dilution (must be
multiplied times the dilution factor). For a 1/2
dilution (25 ml sample/50 ml total volume) the
dilution factor would be 2 (the dilution is only half
sample). For a 1/5 dilution (10 ml of sanple/50 ml
total volume) the dilution factor would be 5. Below
is a table of some dilution factors when the sample
is diluted to a 50 ml volume.
ml of Sample per
50 ml Total Volume
25
10
5
1
0.5
0.05
Amount of
Dilution
1/2
1/5
1/10
1/50
1/100
1/1000
Dilution
Factor
2
5
10
50
100
1000
The dilution factor for any dilution may be calcu-
lated by dividing the ml of sample used 1n the
dilution into 50:
Dilution Factor =
50 ml
ml sample used in dilution
Ex. 2 ml of sample diluted to 50 ml
50 -
The dilution factor for this dilution would be 25.
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and Nitrate
Nitrogen, Cadmium Reduction Method
FIELD AND LABORATORY ANALYSIS
Section VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
M.2a
A calibration curve is prepared by plotting the
measured absorbance of each of the workinq
standard versus the concentration in the working
standard as shown below.
CONCENTRATION OF N03 or N02 - N. mg/Iiter
E10.A-45
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite Nitrogen and Nitrite
Nitrogen, Cadmium Reduction Method
SAFETY
Section VIII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
C.Z.ld
Cadmium metal is highly toxic thus caution must be
exercised in the use of cidmium. Cadmium metal
should never be handled directly since cadmium has
been shown to have cumulative effects. Rubber
gloves should be used whenever cadmium must be
handled. A mask should be worn during the filing of
cadmium and the filing should be done in a hood.
The waste cadmium should be disposed of in an
appropriate manner which conforms to Federal, State
and local pollution control regulations.
cm fl.
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and Nitrate
Nitrogen, Cadmium Reduction Method
RECORDS AND REPORTS
Section IX
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
L.2.25
H.4a
L.3.2a
M.5a
O.la
P.la
Q.la
R.lb
S.lb
You will need the following Key to use the Example
Data Sheet found on the next page:
KEY TO DATA SHEET
(B) Record the absorbances of the column-reduced
nitrate working standards and of the column-
reduced sample(s) in Column (B).
(D) Reccrd the absorbances of the non-reduced
nitrite working standards and of the non-reduced
sample(s) in Column (D).
(A) Read the mg/liter (concentration) of
Total NOj+NOj-N in the column-reduced sample(s)
from the corresponding calibration curve and
record the answer(s) in Column (A).
(C) Read the mg/Hter (concentration) of NO--N in
the non-reduced sample(s) from the corresponding
calibration curve and record the answer(s) in
Column (C).
(E) Subtract: Value (A) - Value (C) = Value (E)
(F) Multiply: Value (E) x 4.43 = Value (F)
(G) Multiply: Value (C) x 3.29 = Value (G)
E1Q.A-47
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Nitrite Nitrogen and Nitrate
Nitrogen, Cadmium Reduction Method
RECORDS AND REPORTS
Section IX
EXAMPLE DATA SHEET
See Key on Page No. 7-47
SAMPLE
NUMBER
mg/liter
TOTAL
N02+N03-N
(A)
Reduced Nitrate
Working Standards
2
3
4
5
6
0.05
0.10
0.20
0,50
1,00
Reduced Sample (s)
Non-reduced Nitrite
Working Standards
2
3
4
5
6
\ /
\ /
X
/ \
/ \
Non-reduced Sarnple(s)
\ /
X
/ \
ABSORBANCE
OF TOTAL
N02+NQ3-N
(B)
\ /
\ /
X
/ \
/ \
\ /
X
mg/Hter
N02-N
(C)
\ /
\ /
X
/ \
/ \
\ /
X
/ \
0.05
0.10
0.20
0.50 '
1.00
•J
ABSORBANCE
N02-N
(D)
\ /
\ /
X
/ \
/ \
\ /
X
/ \
mg/liter
N03-N
(E)
0.05
0.10
0.20
0.50
1.00
\ /
X
/ \
\ /
\ /
X
/ \
/ \
mg/ liter
N03
(F)
0.22
0.44
0.89
2.22
4.43
\ /
X
y \
\ /
\ /
X
/ \
/ X
mg/Hter
N02
(G)
\ /
\ /
X
/ X
/ \
\ /
X
/ X
0.16
0.33
0.66
1,65
3.29
E10.A-48
-------
ABSORBANCE
p p — '
00 O
o o o
0.40
0.20
i
|
I
0.00"
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate-Ni
. Cadmium Reduction Method
RECORDS AND REPORTS
DETERMINATI
(Reduced Ni
SIGNATURE 0
DATE GRAPH
4 ,{{.,_
.- i. . 4
- *. . i . |
" i ' ! . ; ; i ;
. i . t . - \ '
. i . . ..
* 4 ' ! • I •
. i . . . I . i . .
* . ; - } . i . i
i . - . i * i . j .
: ; i ::::•!
t . i . i . .
trite Nitrogen and of Nitrate Nitrogen,
SECTION
ON OF TOTAL NO^NO^M
trate Standards)
CALIBRATION GRAPH
F PREPARER:
WAS PREPARED
- J - * • t - • •
, i .-,,.,.,,
... , i . . .
... , . , i ,
, f » S . . * | .
: . ^ { , ^ i . .
.4 ..4 . - - f - *
- - • • » - i • *
, , | - . . i . t
iiil
. v , i . ,.
,i:|:L
-
-
,
*
k— i
-1
i_
. i.
•|
, ,
. .
• •
i
i ,
i •
1 •
....
i • i •
! • t •
4 ' ' 1
, . . ,
* f T
f"~
•
-
r
t
_a,
'
.j
*— i
*
1
-
. i . t .
t
i
*~~i
• r ;
;:i
. t
.
:
; : : i ; : :
. . | : i . ...
H~
i
i
i
r
-4—
•
1 ,
.
*
i
J
i
— *—
;
«-
,
' >
•
i
i
~
•
i
—
...
t • t
r • i •
• I
. . . ,
T
1 < -t
,
•i;
— •—• t *
T"
-l
-
„.'
*•
-
•
'
1
i
.
;
' '
+ f -*
•
' t
i
f
-
-
•-
IX
-M
.4 -
..... r .
-^•* ' • : J
_
\
-;
r
1
I
-H
. .
1 -
.1
•
i_j
r
1
^1
+ * * -,
•* - f-
••- * — i — j —
: !• • ;
4fF
I*'
—
i .
...
i
i
•
:
r
1 !
— L
"
-.
^
u
f t
-
•
-
1
1
!'
+
f
•f
•
r
ij
i
i
t
•
*
. t-.
. . .
* -i
i
* t
+ -* <
r *
t *
v -
f"
— *— »
* *
1
t •
t
; ;
f
i !
i
id
0.10
0.20
0.30 0.40 0.50 0.60 0.70
CONCENTRATION OF NITRATE NITROGEN, mg/liter
0.80
0.90
1.0C
E10.A-49
-------
E10.A-50
1.00
0.80
f.
CO
C£
O
1/1
S 0.60
0.40 —
0.20
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate-Nitrite
Cadmium Reduction Method
RECORDS AND REPORTS
DETERMINATION OF HO^-N
(Non-reduced Nitrite Standards)
J CALIBRATION GRAPH
SIGNATURE OF PREPARER:
DATE GRAPH HAS PREPARED
I i 4. 1 . j . 1 . 1 . i . I . | .. .
U - i 1 i » J . I . i . .- .
i . i I i '
. f -T r } , 4 . i | i . ; .
L....f; .}
f - — f * - j-
* - + i -•- » i
1
i
*
.,!....
-;•-:•- J ; r * ; ; ; ; i
L i _| . } . . t
i * * * * 1
, ~[ * j • i
. , - *
r i ; ' ' :
*+.{...
. : i . , . ,
-
*
1 1 :
i
j
I
4 *• -k-
• : i : i :_,
* -
1 s |
> i . > ' > *
I ' f ' 1 ! *> i j
j r it
i !* : ; '
T f * * f f - ' '
i 4 . . . | . . ,
>. - - . ,- i 4 ,
L: :;:;::
-_i:l:i:.
i- } : .
f :i ! i : : :
I * 1 . i i j .
1 , . 4 . i -
1 I '11'"
4
'
i
4-
*
f
•
'
•
T - f 4 r
1 -
i
'
t -
4- -
•
r • j
,
-
•
*
•
f
1
^
-
j
,
<
-
*
_.
:
•
•
•
i
1 !
t
•
|
*
>-
..,,...
*• • * * r }
*
4
-
'
"1
t
-
>
•
.
•
.:
. i 1
'
_*
_
-
-
-.
r
•
|
. i
i
\ *
; {
•
.
Nitrogen and of Nitrate Nitrogen,
*
•
•
-
i
t I
1
I
•
-
J
*
.
t
J
"
!
.
-4
SECTION IX
t f
:
-t
-
1
'.
1
t
•
-
-
\
:.
-
-
-
-
-
-
-
•
-
-
-
-
-
-
-
-
.
;
i
•
j-
t
i
t
-•
j
^
f
K~*~
i
•
-
--
1
^
-
f
-*
I
\;
t-
4
i™™+_
t
i
0.10
0.20 0.30
0.40 0.50 0.60 0.
CONCENTRATION OF NITRITE NITROGEN, mg/liter
70
0.80
0.90
1.00
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
DETERMINATION OF NITRATE IN DRINKING WATER
AND WASTEWATERS BY THE BRUCINE METHOD
as applied In
WATER TREATMENT FACILITIES
WASTEWATER TREATMENT FACILITIES
and in the
MONITORING OF EFFLUENT WASTEWATERS
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.N.n/n.lab.WMP.1.11.77
E10.B-1
-------
Effluent Monitoring Procedure: Determination of Nitrate in Drinking Water
and Wastewaters by the Brucine Method
1. Analysis Objectives;
The learner will determine the nitrate content of a sample of drinking
water or wastewater effluent.
2. Brief Description of Analysis:
Brucine sulfate-sulfanilic acid color reagent is added to a series of
nitrate standards and to the sample. The yellow color which develops
is read in a spectrophotometer at 410 nm. A calibration graph is
prepared, and the nitrate nitrogen content of the sample is determined
from the graph.
3. Applicability of the Procedure:
The method works well in waters having salinities which range from
that of fresh water to sea water.
a. Range of Concentration:
The method is recommended for use in the range of
0.1-2.0 mg of nitrate nitrogen/1.
b. Pretreatment of Sample:
Filtration through a 0.45 pm membrane in the
case of samples which are turbid or contain solids.
See C.2.
c. Treatment of Interferences 1n the Sample:
Chlorine is an interference and is removed by addition
of sodium arsenite solution. See C.e.
4. Source of Procedure:
Standard Methods for the Examination of Water and Wastewater, 14th ed.,
pg. 461, Method 213C, 1975.
E10.B-3
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate in Drinking Water and Wastewaters
i^——-^^— by the Brucine Method
E10.B-4
OPERATING PROCEDURES
STEP SEQUENCE
IMFORMATION/CPr.RATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
A. Equipment Preparation
1. Cleaning of
glassware
2. Balance Inspection
B. Reagent Preparation
1. Distilled Water
2. Stock Nitrate
Solution
1. Clean all Glassware and
rinse with tap and
distil led water.
1. Check all balances for
cleanliness and proper
operation.
V.A.1.1.
(P. 16)
la. Consult the manufacturer's manual if the balance
does not operate properly.
1. Prepare approximately five
liters of distilled water
for use in this procedure.
la,
Ib.
Either distill the water, or obtain distilled
water from some other source.
Throughout the remainder of this procedure, unless
otherwise stated, the term water means distilled
water.
1. Add about 500 ml of water
to a 1 liter volumetric
flask.
2. Weigh 0.721B g of
anhydrous potassium nitrate
3. Transfer it to the flask.
4. Swirl the flask.
5. Add water to the 1000 ml
mark.
6. Thoroughly mix the contents
of the flask.
la. Estimate the 500 ml.
2a, Use an analytical balance.
4a. To dissolve the solid.
6a. The concentration of this solution is 0.1 mg N/ml.
-------
EFFLUENT MONITORING PRUCEDURF: Determination of Nitrate in Drinking Water and Wastewaters
by the Bruclne Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
3. Standard Nitrate
Solution
4. Brucine Sulfate-
Sulfanilie acid
Solution
7. Transfer the solution to a
1 liter glass stoppered
bottle.
1. Pipet 10.0 ml of the stock
nitrate solution into a
1 liter volumetric flask.
2, Add water to the 1000 ml
mark.
3. Thoroughly mix the contents
of the flask.
4. Transfer the solution to a
1 liter glass stoppered
bottle.
1. Weigh 1,0 g of brucine
sulfate.
2. Weigh 0.1 g of sulfanilic
acid.
3. Measure 70 ml of water.
4. Transfer it to a 250 ml
Erlenmeyer flask.
5. Heat the water to almost
bo iling.
6. Transfer the brucine
sulfate and sulfanilic acid
to the flask.
la. Prepare this solution just prior to use.
Ib. Use a volumetric pipet.
2a. Use a trip balance
3a. The concentration of this solution is 1.0 vg N/ml
la.
Caution: this material is extremely toxic. If any
is spilled, wipe it up with damp tissues, discard
the tissues, and wash your hands thoroughly.
Ib. Use a trip balance.
3a. Use a 100 ml graduated cylinder.
E10.B-5
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate in Drinking Water and Wastewaters
by the Brucine Method
E10.B-6
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
1. Reagent Preparation
(Continued)
5. Sulfuric acid
Solution
7. Measure 3 ml of concentra-
ted hydrochloric acid, HCl.
8. Add it to the flask.
9. Swirl the flask.
10. Allow the solution to cool
to room temperature.
11. Measure 30 ml of water.
12. Transfer it to the flask.
13. Thoroughly mix the contents
of the flask.
14. Transfer the solution to a
100 ml glass stoppered
bottle.
1. Measure 125 ml of water.
2, Transfer it to a 1 liter
Erlenmeyer flask.
3. Measure 500 ml of
concentrated sulfuric acid,
H2S04.
4. Pour about 100 ml of the
acid into the Erlenmeyer
flask.
7a. Use a 10 ml graduated cylinder.
9a. To dissolve the solids.
lla. Use a 100 ml graduated cylinder.
13a. Caution: this solution is also extremely toxic.
la. Use a 100 ml graduated cylinder.
3a. Use a 500 ml graduated cylinder.
4a. Pour it down the sides of the flask.
-------
EFFLUENT MONITORING PROCEDURE; Determination of Nitrate in Drinking Water and Wastewaters
by the Brucine Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
6. Sodium Chloride
Solution
5. Thoroughly mix the contents
of the flask.
6. Repeat steps 4 and 5 until
all of the acid has been
added.
7, Allow the solution to cool
to room temperature.
8. Transfer the solution to a
1 liter glass stoppered
bottle.
1. Add about 70 ml of water.
2. Transfer it to a 250 ml
Erlenmeyer flask which
has a mark at the 100 ml
level.
3. Weigh 30 g of sodium
chloride, NaCl.
4. Add it to the flask.
5. Swirl the flask.
6. Add water to the 100 ml
mark.
7, Thoroughly mix the contents
of the flask.
5a. Caution: a large amount of heat will be generated
la. Prepare this solution only if the sample is known
to contain chloride. Two ml of it are needed per
sample and standard.
lb. Estimate the 70 ml.
5a. To dissolve the solid.
E10.B-7
-------
E_F_F_LUE_NT_ MUNI TOR ING PROCEDURE: Determination of Nitrate in Drinking Water and Wastewaters
by the Brucine Method
E10.B-8
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
7. Sodium Arsenite
Solution
C. Sample Pretreatment
1. Storage and
Preservation
8. Transfer the solution to a
100 ml glass stoppered
bottle.
1. Add about 50 ml of water to
a 100 ml volumetric flask.
2. Weigh 0.5 g of sodium
arsenite, Na
3. Transfer it to the
volumetric flask.
4. Swirl the flask.
5. Add water to the 100 ml
mark.
6. Thoroughly mix the contents
of the flask.
7. Transfer it to a 100 ml
<]lass stoppered bottle.
la. Prepare this solution only if the sample is known
to contain chlorine.
Ib. Estimate the 50 ml.
2a. Caution: this material is extremely toxic. If any
is spilled, wipe it up with damp tissues, discard
the tissues, and wash your hands thoroughly.
2b. Use a trip balance.
4a. To dissolve the soid.
6a. Caution: This solution is also extremely toxic.
1. Start the nitrate
determination promptly
after sampling.
la. Standard Methods offers three preservation
techniques when needed:
i) Concentrated sulfuric acid, 0.8 ml/liter of
sample. If this technique is used, the sample
must be neutralized to a pH of about 7 just
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate in Drinking Water and Wastewaters
- - -- by the Brucine Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Sample Pretreatment
(Continued)
2. Solids, Turbidity
3. Chlorine
before beginning the determination.
ii) Mercuric chloride, 54 ing/liter of sample.
iii) Chilling to just above the freezing point.
b. For later convenience in handling the chlorine
interference, filter 1 liter of sample.
1. If solids and/or turbidity
are present in the sample,
filter it through a 0.45 \im
membrane filter.
1. Determine the free and com-
bined chlorine content of
the sample in mg/1.
2. For each 0.1 mg of chlorine
(free and combined), add 1
drop of the sodium arsenite
solution.
The filter will be plugged quickly by
sample. However, only about 20 ml of
needed for the determination.
3. For each 50 ml of sample,
add 1 drop of the sodium
arsenite in excess.
solids in the
filtrate is
. For samples of wastewater effluent, two methods are
approved: amperometric or titrimetric. For samples
of drinking water, one method is approved: N,
N- Diethyl-Phenylenediamine (DPD). See the
appropriate Effluent Monitoring Procedures (EMP's).
2a. Example calculation:
0.1 = mg of free chlorine per liter of sample
1.0 = mg of combined chlorine per liter of sample
Then 1.1 = mg of free and combined chlorine per
1iter of sample.
Therefore add 11 drops of the sodium arsenite for
each 1 liter of sample. Only about 10 ml of sample
will actually be needed for the determination, but
it is convenient to actually collect a larger
volume such as 1 liter.
E10.B-9
-------
_EFFUJIENT_MUMTOR1N6 PROCEDURE: Determination of Nitrate in Drinking Water and Wastewaters
by the Brucine Method
E10.B-10
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Sample Pretreatment
(Continued)
D. Procedure
1. Sample
4. Thoroughly mix the contents
of the sample container.
1. Assemble 9 large test tubes
in a wire rack.
2. Pipet 1.0 ml of sample
into a large test tube,
3. Pipet 9,0 ml of water into
the same tube.
4. Mix the contents of the
tube.
5. Pipet 5.0 ml of the same
sample into a second large
test tube.
6. Pipet 5,0 ml of water into
the same tube.
7. Mix the contents of the
tube.
:. Pipet 10.0 ml of the same
sample into a third large
test tube.
la. There must be an empty rack space next to each
tube.
2a. Use a graduated pipet.
3a. Use a graduated pipet.
4a. This is a 10% sample dilution.
5a. Use the same pipet as in 2a.
6a. Use the same pipet as in 3a.
7a. This is a 50% sample dilution.
8a. Use the same pipet as in 2a.
8b. This is an undiluted, or 100%, sample.
Be. Use a clean graduated pipet to measure volumes of
different^ samples.
8d. The idea of preparing three sample dilutions is
that one of them will give a result within the
applicable range of the test. Once experience
with the sample source is gained, it will not be
necessary to do more than one sample dilytion.
-------
EFFLUENL MU NIT C RIM G PRUlEDU R F: Determination of Nitrate in Drinking Water and Wastewaters
by the Brucine Method
OPERATING PROCEDURES
D. Procedure (Continued)
2. Standards
3. Sodium Chloride
STEP SEQUENCE
1. Pipet standard nitrate
solution (B.3) and water
into the six remaining
large test tubes.
1, Place the rack in a tray
containing tap water or
cold water from a fountain.
2, Add about 6 ice cubes to
the tray.
3. Pipet 2.0 ml of the sodium
chloride solution into each
of the 9 tubes.
INFORMATION/OPERATING GOALS/SPECIFICATIONS
la. So as to obtain the following solutions:
Cone, of
Nitrate
Tube ml of Standard ml of Nitrogen in
Number Nitrate Solution Water mg/1
1 0.0 10.0 0.0
2 1.0 9.0 0.1
3 2.0 8.0 0.2
4 4.0 6.0 0.4
5 7.0 3.0 0.7
6 10.0 0.0 1.0
Ib. Use one 10 ml graduated pipet for the standard
nitrate, and a second for the water.
la. The water level should be about half-way up the
tubes.
2a. If cold water is used, step 2 is unnecessary.
3a. Use a 10 ml graduated pipet only if the sample
contains Cl~.
TRAINING
GUIDE NOTES
E10.B-11
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate in Drinking Water and Wastewaters
~™—•——^—^——^—^^^^~~ by the Brucine Method
E10.B-12
OPERATING PROCEDURES
D. Procedure (Continued)
4. Sulfuric Acid
5. Turbidity
STEP SEQUENCE
4. Thoroughly mix the contents
of each of the 9 tubes.
1. Pipet 10.0 ml of the sul-
furic acid solution into
each of the 9 tubes.
2. Thoroughly mix the con-
tents of each of the
9 tubes.
3. Allow the tube contents to
cool to room temperature.
1. Check the three sample
tubes for turbidity.
2. Turn on the Spec 20 and
allow it to warm up.
3. "Zero" the instrument
using tube number 1.
4. Measure and record the
absorbancies of those
sample tubes whose contents
are turbid.
INFORMATION/OPERATING GOALS/SPECIFICATIONS
4a. By hand swirling.
4b. Do not use a vortex-type mixer.
la. The rack is still in the cold water.
Ib. Use a 10 ml graduated pipet.
2a. By hand swirl ing.
2b. Do not use a vortex-type mixer.
3a. The ice cubes or cold water will probably have to
be replaced.
3b. Do this step only if the sample is known to con-
tain chloride.
la. If more than one type of sample is being run,
there may be more than three sample tubes. Check
all the sample tubes for turbidity.
Ib. If no_ turbidity is present, proceed to D.6,
Color Development.
Ic. If turbidity j_s_ present, do steps 2, 3, and 4
below.
3a. At 410 urn.
TRAINING
GUIDE NOTES
-------
EFFLUENT MONITORING PROCLDURF: Determination of Nitrate in Drinking Water and Wastewaters
by the Brucine Method
OPERATING PROCEDURES
STEP SEQUENCE
ENFORMATION/OFFRATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
0. Procedure (Continued)
6. Color Development
7. Color Measurement
1, Pipet C.5 ml of the bru-
cine sulfate-sulfani1ic
acid reagent into each of
the 9 tubes.
2. Thoroughly mix the con-
tents of each of the 9
tubes.
3. Place the rack of tubes in
the hot water bath.
4. If the Spec 20 has not been
used prior to this step,
turn it on now and allow
it to warm up.
5. After exactly 20 minutes
remove the rack from the
hot water and place it
back into the cold water.
1. Remove the rack from the
cold water bath.
2. Dry the outside of the
large test tubes.
3. Zero the Spec 20 using
tube 1 as a "blank."
4. Record the absorbanices for
tubes 2 through 6.
5. Record the absorbancies
for all sample tubes.
la. The rack is still in the cold water,
Ib. Use a 10 ml graduated pipet.
2a. By hand swirling.
2b. Do not use a vortex-type mixer.
3a. Ninety-five degrees C.
5a. The ice cubes or cold water may have to be
replaced.
5b. The contents of the tubes should be at room
temperature.
4a. These six tubes are the standards to be used in
preparing the calibration graph.
E10.B-13
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Nitrate in Drinking Water and Wastewaters
by the Brucine Method
E10.B-14
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Calculations
1. Prepare a calibration
graph using the absorban-
cies and concentrations
for tubes 1 through 6.
2. If any absorbancies due
to turbidity were recorded
for any of the sample
tubes, subtract those
absorbancies from the
appropriate absorbancies
obtained in D.7.5 above.
3. Determine the mg of
nitrate nitrogen per liter
of sample for each
different sample.
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate in Drinking
Water and Wastewaters by the Brucine Method
TRAINING GUIDE
SECTION TOPIC
I Introduction
II Educational Concepts - Mathematics
III Educational Concepts - Science
IV Educational Concepts - Communications
V* Field and Laboratory Equipment
VI Field and Laboratory Reagents
VII Field and Laboratory Analysis
VIII Safety
IX Records and Reports
*Training Guide materials are presented here under the headings marked*.
These standardized headings are used through this series of proceudres.
E10.B-15
-------
EFFLUENT MONITORING PROCEDURE: Determination of Nitrate in Drinking Water and Wastewaters
• gruci-ne Method
FIELD AND LABORATORY EQUIPMENT
Section V
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
A.I.I
If the glassware is especially dirty and cannot be
cleaned with ordinary detergents, chromic acid
cleaning may be required.
1. Pour 35 ml of distilled water in a 250 ml beaker.
2. Add about 1/8 teaspoon (simply estimate this
quantity) of sodium dichromate, Ha-Cr^O^. to
the water.
3. Swirl the beaker until the sodium dichromate has
dissolved.
4. Keep repeating steps 2 and 3 until no more
sodium dichromate will dissolve.
5. Pour the solution into a 2 liter beaker.
6. Slowly pour 1 liter of concentrated sulfuric
acid, hLSO^, into the 2 liter beaker.
Caution: Use eyeglasses and
protective clothing.
7. Stir the mixture thoroughly.
8. Store it in a glass stoppered bottle.
9. The cleaning solution should be at a temperature
of about 50 C when it is used.
10. It may therefore be necessary to warm the
cleaning solution,
11. When using the warm cleaning solution, fill the
piece of glassware with the solution.
12. Allow it to soak for 2-3 minutes (or longer).
13. Pour the cleaning solution back into the storage
bottle.
14. Rinse the piece of glassware ten times with
tap water.
15, The cleaning solution may be reused until it
turns green.
16, It should then be discarded.
14th Standard Methods,
p. 336, section 2.c,2)
E10.B-16
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
DETERMINATION OF FLUORIDE IN POTABLE AND
WASTEWATERS USING THE
SPADNS COLORIMETRIC PROCEDURE
as applled in
WATER TREATMENT FACILITIES
WASTEWATER TREATMENT FACILITIES
and in the
MONITORING OF EFFLUENT WASTEWATERS
National Training and Operational Technology Center
Municipal Permits and Operations Division
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.HAL.f.lab.WMP.1.11.77
Ell.A-1
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride in Potable
and Waste Waters Using the SPADNS
Colorimetric Procedure
1. Analysis Objectives:
The learner will determine the fluoride content of a water or wastewater
sample using the SPADNS Colorimetric Procedure.
2. Brief Description of Analysis:
After distillation to remove interferences the sample is treated with the
SPADNS reagent. The amount of color remaining after the reaction of the
fluoride and reagents is read on a spectrophotometer. This reading is a
function of the fluoride concentration.
3. Applicability of this procedure:
a. Range of Concentration: from 0.05 to 1.4 mg F liter.
b. Pretreatment of Sample:
The Bellack distillation procedure must be carried out on all samples before
determination by the SPADNS procedure. The method is applicable to the
measurement of fluoride in drinking, surface, and saline waters, domestic
and industrial wastes. The distillation procedure is covered in a separate
EMP.
c. Treatment of Interferences in the Sample:
The distillation will remove all interferences when carried out properly.
For a list of interferences consult the training guide notes (VII.B.2.a).
4. Source of Procedure:
Standard Methods for the Examination of Water and Wastewater; 14th
Edition 1975. pg 393.
Ell.A-3
-------
FLUORIDE ANALYSIS FLOW SHEET
L
SAMPLE
Potable Water
Waste Water
DISTILL
ELECTRODE
METHOD
SPADNS
COLORIMETRIC
METHOD
SPADNS
COLORIMETRIC
METHOD
DISTILL
ELECTRODE
METHOD
AUTOMATED
COMPLEXONE
METHOD
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride in Potable
and Waste Waters Using the SPADNS
Coloritnetric Procedure
Equipment and Supply Requirements
A. Capital Equipment;
1. Spectrophotometer, for use at 570 nm providing a light path of
at least 1 cm. with cells.
2. Analytical balance; capable of weighing to 0.1 mg
3. Still or Ion Exchange column or other source of distilled water
4. Still for distilling sample - see EMP on Fluoride Distillation
5. Trip balance - 500 gram capacity
B. Reusable Supplies:
1. Beakers - 500 ml glass - 1 each
2. Flasks - Erlenmeyer - 125 ml - 8 each
3. Flasks - Erlenmeyer - 500 ml - 1 each
4. Flasks, volumetric - 50 ml - 8 each
5. Flasks, volumetric 100 ml - 2 each
6. Flasks, volumetric 1000 ml - 2 each
7. Graduated Cylinder - 500 ml - 1 each
8, Pipets, volumetric - 10 ml - 3 each
9. Pipets, volumetric - 50 ml - 8 each
10. Powder funnel - 1 each
11. Saftey glasses - 1 pair
12. Spatula - 1 each
13. Thermometer 0-100 C - 1 each
14. Wash bottle - plastic - 1 each
C. Consumable Supplies
1. SPADNS - Reagent 4,5-dihydroxy-3 [(p-sulfophenyl)azo-2.7 napthalene
disulfonic acid, trisodium salt.
Baker Cat No. 5189 — 10 grams
Eastman Cat No. 7309 — 25 grams
2. Zirconyl chloride - Reagent ZrOCl-
Baker Cat No. X720 — 500 grams
Fisher Cat No. Z-80 — 1 Ib.
3. Sodium Fluoride-NaF-Reagent
Baker Cat No. 3688 — 1 Ib.
Fisher Cat No. 5299 — 1/4 Ib.
or
Sodium Fluoride Stock Solution
Ell.A-5
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride in Potable
and Waste Waters Using the SPADNS
Colon'metric Procedure
C. Consumable Supplies (continued)
3. Orion Research Inc. Cat No. 94-06-07
Hach Chemical Co.
4. Sodium Arsem'te NaAsOp Reagent
Baker Cat No. 3487 — 1 Ib.
Fisher Cat No. S-225 — 1 Ib.
5. Hydrochloric acid HC1 Reagent
Baker Cat No. 9535 — 1 pt
Fisher Cat No. A-144 -— 1 pt
6. Weighing boats-plastic disposable - 60 each
7. Pen or Pencil
8. Notebook
D. Addresses of Suppliers Mentioned
J. T. Baker, Chemical Co.
1 Public Square
Cleveland OH 44113
Eastman Organic Chemicals
Eastman Kodak Co.
1187 Ridge Road W.
Rochester, NY 14650
Fisher Scientic Co.
5481 Creek Rd.
Cincinnati, OH 45242
Hach Chemical Co.
P. 0. Box 907
Ames,Iowa 50010
Orion Research Inc.
380 Putnam Ave,
Cambridge, MA 02139
Ell.A-6
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride Using the SPADNS Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
A. Sample Collection
1, Collect a minimum of 300 ml
in a plastic or hard qlass
container.
B. Sample pretreatment
1. Add 1 drop (0.05nl) sodium
arsenite (NaAs02) solution
for every 0.1 mg residual
Cl.
2. Distill the sample.
C. Equipment Preparation
1. Glassware
2. Spectroohotometer
Insoection
1. Rinse all glassware
immediately after use with
taowater.
2, Rinse several times with
distilled water.
1. Clean spectroohotometer.
la
Ib.
Ic
Id,
la
Ib.
2a,
2b.
2c.
Do not rinse the container in tap water for its
final rinse. Tap water usually contains some
fluoride even if the source is not fluoridating.
For distillation a volume of 300 ml is required.
For the SPADNS procedure 50 ml of the distillate
is used.
No special requirements are necessary for
preservation.
Polyethylene bottles are preferred, hard glass
(Pyrex, Kimax) is acceptable
Chlorine will bleach the color and is therefore
a definite interference.
Caution: This solution (Reagent D.6.) is toxic.
Take care not to injest any.
For total or total dissolved Fluoride the sample
must be distilled.
If interferences are present the sample must be
distilled.
The distillation procedure is covered under a
separate EMP.
la. If detergent is used care should be taken to
rinse thoroughly to remove any phosphate,
2a. All tap water contains traces of Fluoride and
could also contain about 1.Omg/1 if fluoridated.
la. Free of dust and dirt.
Ib. Consult manufacturer's instructions.
i.e.2
(p. 18)
VII B.2a
(p. 20)
Ell.A-7
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride Usinq the SPAONS Method
Ell.A-8
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Reagent Preparation
1. Distilled Water
2. SPADNS Reagent
1, Prepare about six liters of
distilled water.
This water should be free
from fluoride.
1. Weigh out 0.958q of SPADNS
dye.
2. Add about 200 ml of
distilled water to a
1 liter volumetric flask.
3. Transfer the SPADNS dye to
the 1 liter volumetric
flask, using a powder
funnel.
4. Dissolve the SPADNS dye
in distil led water.
5. Weigh out 0.133 gm
zirconyl chloride
octahydrate.
6. Dissolve in about 200 ml
distil led water.
7. Transfer the airconyl
chloride to the 1 liter
flask with the SPADNS dye.
la. Use a still or pass tap water through an ion-
exchange column containing a strongly acidic
cation exchange resin mixed with a strongly
basic anion exchange resin.
la. i.e., 2.(para sulfophenylazo) -1,8-dihydroxy
-3,6- nanhthalene disulfonate, also called
45 dihydroxy -3-(parasulfophenylazo) -27-
napthalene disulfonic acid trisodium salt.
Ib. Use an analytical balance and a plastic weighing
boat.
3a. Use a wash bottle to wash the solid into the
flask. The weighing boat should be washed
three times and the washings added to the flask.
5a. Use a plastic weighing boat on the analytical
balance.
6a. A 500 ml beaker may be used.
6b. Use a wash bottle to wash the solid into the
flask. The weighing boat should be washed three
times and the washings added to the flask.
7a. Care should be taken to rinse the beaker with
distilled water.
-------
LFFLULNT MONITORING PROCEDURE: Determination of Fluoride Using the SPADNS Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
2. SPADNS Reagent
(Continued)
3. Sodium Fluoride
(NaF) stock
solution - 100mq,F~/l
Add 350 ml concentrated
hydrochloric acid (HC1),
9. Mix well.
10. Dilute to the 1 liter mark
with distilled water.
11. Mix well.
1?. Label.
1, Weigh out 0.2210 grams of
sodium fluoride.
2. Add about 500 ml of dis-
tilled water to a 1 liter
volumetric flask.
3, Transfer the solid to the
1 liter volumetric flask
using a powder funnel.
4. Use a wash bottle to wash
solid into flask.
5. Dissolve the solid.
6. Dilute to the mark and
mix thoroughly.
'. Label
8a. Caution: When using the concentrated acid, use
eye protection.
8b. Solution may increase in temperature, cool to
room temperature before proceeding.
lla. Solution stable for at least 2 years.
la. Use an anlytical balance
Ib. Use a plastic weighing boat.
Ic. Solution can be purchased from Orion Research
Inc; Cat No. 94-06-07 or Hach Chenieal Co.;
Cat No. 232-11.
4a. The weighing boat should be washed three times
and the washings added to the flask.
6a. Solution contains 0.1 mg F /l.O ml (i.e. 100 ppm
n,
6b. Keep in a plastic container. Solution is stable
for at least 6 months.
Ell.A-9
-------
EFFLUENT MONITORING PRQCCDURF: Determination of Fluoride Using the SPADNS Method
Ell.A-10
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
4. Sodium Fluoride
(NaF) Solution
10 mg F"/l.
5. Sodium Fluoride
(NaF) Solution
1.0 mg F"/liter
6. Sodium Arsenite
(NaAsO,,) Solution.
1. Add approximately 50 ml of
distilled water to a 100
ml volumetric flask.
2. Pipet 10 ml of the stock
fluoride solution (reagent
3) into the flask.
3. Dilute with distilled water
to the mark.
4. Mix thoroughly.
5. Label
1. Add approximately 50 ml of
distilled water to a 100 ml
volumetric flask.
2. Pipet 10 ml of the fluoride
solution (reagent 4) into
the flask.
3. Dilute with distilled water
to the mark.
4. Mix thoroughly.
5. Label
1. Weigh out 2.5 grams of
sodium arsenite.
2. Transfer the solid to a
500 ml Erlenmeyer flask.
2a. Use a 10 ml volumetric pipet.
3a. Solution contains 0.01 mg F/l.0 ml (i.e. 10 ppm),
4a. Keep in plastic container.
4b. Solution stable for at least 6 months.
2a. Use a 10 ml volumetric pipet.
3a. Solution contains 0.001 mg F~ per 1.0 ml (i.e.
1.0 ppm F~).
4a. Solution should be prepared fresh daily.
la. A trip balance can be used.
-------
EFFLUENT KUNITQRING PROCEDURE: Determination of Fluoride Using the SPADNS Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORKATION/OPERA~ING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
6. Sodium Arsenite
(NaAs02) Solution
(Continued)
E. Calibration
By use of a
standard curve.
3. Measure out 500 ml
distil led water.
4. Dissolve the sodium
arsenite in about half of
the distil led water.
5. Add the rest of the 500 nil
portion.
3a. Use a graduated cylinder.
1. Turn on spectrophotometer
and allow to warm up.
2. Calibrate the
spectroohotometer.
Preoare a series of
standard solutions usinq
the lOmq F'/liter sodium
fluoride solution (Reagent
D.4).
la. Refer to manufacturer's manual for warm up time.
However usually one-half hour is sufficient
2a. This can be carried out in two ways; by use of a
calibration qraoh or by calculation of the un-
known. Section E.I covers the calibration graph
and Section E.2 covers the calculation.
3a. The series of standards should be prepared in
50 ml volumetric flasks by pipetting with a
graduated pioet the indicated amount of Reagent
D.4 into a 50 ml volumetric flask and diluting
to the volume mark,
VII E.I
(p. 21)
Ell.A-11
-------
EFFLUENT MONITORING PROCEDURF: Determination o* Fluoride Using the SPADNS Method
E11.A-12
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
£. Calibration
(Continued)
3b. The following table can be used to prepare a
series of standards containing from 0 to 1.4
mg F~/liter.
ml of Reaqent D.4
0.00
1.00
2.00
3.00
4.00
5.00
6,00
7.00
Cone, when diluted to
50 ml_,_ mg F /11 ter_
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
. Transfer the entire 50 ml of
the standards just prepared
into 125 ml Erlenmeyer
flasks.
5. Add 10 ml SPADNS Reagent
(Reagent D.2.).
6. Mix thoroughly.
7. Determine the absorbance at
570 nm.
4a. All eight standards can be prepared at the same
time.
5a. Use a 10 ml volumetric pipet
5b. Caution: This volume is critical; take care to
add exactly 10 ml.
6a. Unless nixed, the solution can layer giving false
readings.
7a. The manufaturer's manual on operation of the
soectrophotometer should be consulted for proper
instrument operation.
m.E.i.
(p. 22}
5b
V.E.1.7a.
(p. 19)
-------
EFFLUENT HUUITORING PROCEDURE: Determination of Fluoride Using the SPADES Method
OPERATING PRCCEDURLS
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Calibration
(Continued)
2. Bv Calculation
8, Prepare a calibration
curve.
9. Analyze the sample
10. Obtain concentration usinq
the graph prepared here.
1. Turn on spectrophotometer
and allow to warm up.
2. Adjust the wavelength to
570 nm.
3. Prepare two standards.
4. Pipet 50 ml of each sample
to be run into a series of
125 ml Erlenmeyer flasks.
5. Pipet 10 ml of SPADN'S
Reagent to all flasks.
6. Mix al1 thoroughly.
7. With nothing in the meter
adjust the left side of the
absorbance scale to read
its maximum,
8. Fill a sample cell with
0 mg F /liter standard.
8a. Use the attached graph paper.
8b. Refer to: Effluent Monitoring Procedure: Prepara-
tion of Calibration Graphs.
9a. Operating Procedure F.
V.E.I.8
IX.E-l.8a
(p. 19)
3a. Prepare as follows: 0 mg F"/liter (pioet 50 ml of
distilled water into a 125 ml Erlenmeyer flask):
1 mq F~/liter (pipet 50 ml of reagent D.5 into a
125 nl Erlenmeyer flask).
4a. Label each flask with sannle identification.
5a. This includes both standards (including 0 mg
F /I) and samp!es,
7a, This is the maximum (marked as infinity <»).
Ell.A-13
-------
EFFLUENT MONITORING PRUCEDURF: Determination of Fluoride Using the SPADNS Method
Ell.A-14
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
2. By Calculation
(Continued)
9. Place the cell in the cell
compartment,
10. Adjust the slit control so
that a reading of 0.5 is
obtained on the absorbance
scale.
11. Fill a sample cell with
1.0 mg F~/liter standard.
12. Place in the cell
compartment.
13. Read the absorbance value.
14. Read all samples without
changing any adjustment
controls.
15. Calculate the concentration
of the unknown.
lOa.
This is to set the portion of the scale to be
used.
13a,
This reading should read about 0.25 to 0.27. If
this reading is not obtained the make up of the
reagent and standard used should be checked.
13b. Use Operating Procedure F
15a. Use the equation: X =
"
__
AQ - A,
X = concentration of the unknown in mg F"/liter
A = Absorbance reading of the 0 mgF"/l.
This is set in steo 10 at 0.5
VII.E.Z.lOa.
(p. 22)
-------
EFFLUENT MONITORING PROCEDURE.: Determination of Fluoride Using the SPADNS Method
OPERATING PROCEDURES
STEP SEQUENCE
INFORKATION/OPCSATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
?. By Calculation
(Continued)
F. Procedure
1. After calibration the
samples are tested as
follows.
15a, (continued)
A. = Absorbance reading of the 1.0 mg F~/liter
(usually 0.25 to 0,27)
Ay = Absorbance reading of the unknown.
15b. Example: If the sample absorbance value
obtained from the spectrophotometer was 0.32
X =
then
0.5-0,32
0.18
0.5-0.25 " 0.25
X = 0,72 ng F~/liter
If more than one sample were run the only number
that would change would be the 0.32. A
calculation must be performed for each sample.
2. Add 50 ml of satrple to a
125 rr] Erlenmeyer flask.
3. Add 10 ml SPADNS Reagent,
4. Mix thoroughly.
la. If the calibration graph was used (E.I.), two
standards should be used each time to verify that
the calibration curve is still valid. (Al.O mg F~
/liter and a 0.2 mg F~/liter).
Ib. If the calculation procedure was used, the 0 and
1.0 oom standards rust be run with each batch of
samples run.
?a. Use a 50 rrl volumetric pipet.
3a. Use a 10 ml volumetric pipet.
Ell.A-15
-------
EFFLUENT MONITORING PROCEDURE.: Determination of Fluoride Usinq the SPADNS Method
Ell.A-16
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/CREATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Procedure (Continued)
5. Read the absorbance value
at 570 nm.
6. Dilute sample if
concentration is not be-
tween 0.0 to 1.4 mq
F"/liter.
6a. If the calibration graph is used.the absorbance
value for a concentration of 1.4 mg F~/liter has
been ploted do not use absorbance values
corresponding to values greater than 1.4 mg
F"/liter.
6b. If the calculation procedure is used, obtain the
absorbance value and calculate if the value
calculated is above 1.4 mg F~/liter dilute the
sample.
-------
TRAINING GUIDE
SECTION TOPIC
I* Introduction
II Educational Concepts - Mathematics
III Educational Concepts - Science
IV Educational Concepts - Communications
V* Field and Laboratory Equipment
VI Field and Laboratory Reagents
VII* Field and Laboratory Analysis
VIII Safety
IX* Records and Reports
*Training Guide materials are presented under the heading marked *. These
standardized headings are used throughout this series of procedures.
Ell.A-17
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride Using the
SPADNS Method
INTRODUCTION
Section
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
I.
The basis for the SPADNS procedure is the
reaction between zirconium and the SPADNS dye
(SPADNS is an abbreviation of sodium 2-(p-sulfo~
phenylazo)-!,8-dihydroxy 3.6-napthlene disulfonate).
The color of the reaction mixture (water sample plus
reagent) varies from very deep red in the absence of
fluoride to light red when the concentration of
fluoride is high. The change in color caused by
small changes in fluoride concentration is not
discernable by eye, but can be readily detected by a
photometric instrument. The better the instrument,
the better the sensitivity to small changes of
f1uoride.
Distillation is not required if comparability
data on representative effluent samples are on file
to show that this preliminary distillation step is
not necessary. However, manual distillation will be
required to resolve any controversies.
For drinking water samples analysis to comply
with requirements as listed in the National Interim
Primary Drinking Water Regulations (F. R. Part IV,
12/24/?5-para. 141.23f,10-pg59573\ distillation is
necessary.
Distillation of the calibration standards is
not necessary should sample require distillation.
Ell.A-18
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride Using the
SPAONS Method
FIELD AND LABORATORY EQUIPMENT
Section
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
E.1.7a
E.l.i
Should the analyst be using a Bausch and lornb
Spectronic "20" Spectrophtometer there is an EMP,
"Use of a Spectrophototneter" availble. It would be
of value to the analyst to consult this procedure,
There is an EMP "Preparation of Calibration
Graphs" that would be of value to the student.
Ell.A-19
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride Using the
SPADNS Method
FIELD AND LABORATORY ANALYSIS
Section
VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
,2.a
Other ions, particularly phosphate, iron and
aluminum can cause significant errors. The table
below gives some indication of this error. Should
any of these interferences be present in the sample
at concentrations that will cause error, the sample
must be distilled. The numbers given show the
concentration in mg/liter that will cause an error
of plus or minus 0.1 mg/liter at 1.0 mg F*/l.
Substance Cone
Type Error
Alkalinity
(CaC03)
Aluminum
(Al + )
Chloride
(Cl")
Iron,
(Fe+3)
Hexametaphosphate
(CNaP03]g)
Phosphate
Sul
Chlorine
Color &
Turbidity
5000
0.1"
7000
10
1.0
16
200
Must be completely
Removed with Arsenite
Must be Removed or
Compensated for.
Fluoride Determination in
Water, E.P.A., Training
Manual NTOTC, Cincinnati,
OH 45258.
*Above figure is for immediate reading. Allowed to
stand two hours tolerance is 3.0 mg/liter, four hours
tolerance is 30 mg/liter.
Ell.A-20
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride Using the
SPADNS Method
FIELD AND LABORATORY ANALYSIS
Section
VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
B.2.&.
Continued
E.l.Za
The temperature of the samples and standards
must be the same before carrying out the test.
Consequently if a difference in temperature exists,
allow both to sit at room temperature for about one
hour before proceeding with the test.
Analytical results obtained with the SPADNS
reagent are limited to a range of 0 to 1.4 mg F"/
liter. Samples which approach or exceed the limit of
the range must be diluted. The dilution must be
made before addition of reagent, since subsequent
dilution will affect the concentration of dye,
zirconium and acid.
The first method to calibrate the spectrophoto-
meter is to prepare a calibration graph. Calibration
graphs are commonly used in absorbance measurements.
In this type measurement energy is absorbed by some
chemical constituent in the solution by means of a
calibration graph.
Two things must be done in order to prepare a
calibration graph. A series of standards must be
prepared. A standard is a solution which contains
a known amount of the same chemical constituent
which is being determined in the sample. Secondly,
the absorbance of these standards must be measured.
This is done by carrying the standards through
the test procedure and measuring the amount of energy
absorbed. This value is graphed against the known
concentration and a line drawn through the points
produced. This line is the calibration graph.
When an unknown sample is run, its absorbance value
is determined and using the calibration graph, its
concentration can be determined.
The second method used in the SPADNS uses the
fact that a straight line will be formed between 0
and 1.4 mg F/liter. Then the equation for a straight
line is used to calculate the unknown concentration
after values for two standards have been run.
This is carried out as follows. Two standards
are prepared, usually 0 and 1 ppm. These are used to
set the instrument, thus obtaining values for their
absorption. These two knowns can be used to
calculate the unknown by the equation. Both methods
are shown in the EMP.
Ell.A-21
-------
EFFLUENT MONITORING PROCEDURE;
Determination
SPADNS Method
of Fluoride Using the
FIELD AND LABORATORY ANALYSIS
Section
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
E.l.Bb
E.Z.lOa
The addition of the highly colored SPADNS
reagent must be done with utmost accuracy because
the fluoride concentration is measured as a
difference of absorbance in the standard and the
sample. A snail error in reagent addition is the
most prominent source of error in this test after
the interferences.
The absorbance scale is logarithmic. This
means that the distance between numbers varies. The
meter distance between numbers is larqe on the right
side of the meter while the distance between numbers
is small on the left side. For example the distance
between 0 and 0.5 is over half the scale while from
1 to 2 is less than a quarter of the total distance.
Consequently the right side of the scale can
be read with a much hinher degree of sensitivity and
accuracy.
The ratio of fluoride concentration and absorb-
ance is inverse, that is the higher the fluoride
concentration the lower the reading and the lower
the fluoride concentration the higher the reading,
Thus by setting the lowest concentration of fluoride
possible, i.e., 0 mg F~/1iter, at 0.5 absorbance
units this means that no reading can go higher.
This restricts all readings to the most sensitive
section of the scale.
Methods for Chemical
Analysis of Water and
Wastes 1974, E.P.A.
Environmental Monitoring
and Support Laboratory
Cincinnati, OH 45268.
Ell.A-22
-------
TYPICAL LABORATORY DATA SHEET Section IX
Sample Collection:
1. Name of Plant:___ ,
2. Sampling Location:
3. Type of Sample:__ „ ,
4. Date and Time Collected:
5. Sample Collector:
SampleAnalysis:
1. Name of Laboratory:
?.. Date and Time Collected'
3, Sample Designation:
4. Method Used:
5. Was Sample Distilled:
6. Concentration of F~ Determined (in ing/liter):
Ell.A-23
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
DETERMINATION OF FLUORIDE IN POTABLE AND WASTEWATERS
USING A SELECTIVE ION ELECTRODE
as applied in
WATER TREATMENT FACILITIES
WASTE WATER TREATMENT FACILITIES
and in the
MONITORING OF EFFLUENT WASTEWATERS
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.HAL.f.lab.WMP.2.11.77
Ell.B-1
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
This operational procedure was developed by:
NAME John D. Pfaff
ADDRESS USEPA, OWPO, National Training and Operational Technology Center
Cincinnati, Ohio 45268
POSITION Chemist - Instructor
EDUCATION AND TECHNICAL BACKGROUND
B.A. Chemistry
3 years Research Chemist
14 years DHEW, ECA, EPA - Chemist
Ell.a-3
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride in Potable
and Waste Waters Using a Selective Ion Electrode
1. Analysis Objectives:
The learner will determine the fluoride content of a water or wastewater
samole using a selective ion (fluoride) electrode.
2. Brief Description of Analysis:
The nH of the samole is adjusted to between 5 and 5.5 by use of
buffer solution. Then the electrodes are immersed in the solution and
the fluoride content determined using the meter. If an expanded scale
pH meter is used the concentration is read from a standard curve. If a
specific ion meter is used the concentration can be read directly from the
face of the meter. Other acceotable methods not covered in this outline
are the SPADNS and automated complexone procedures.
3. ADD!icability of this procedure:
a. Range of Concentration:
from Q.I to 1000 mg/1
Information is qiven so the same stepwise procedure can be used for
fluoride concentrations UD to 1000 mg/liter.
b. Pretreatment of Samples:
Distillation is not necessary for potable water samples. However,
the guidelines for MPDES procedures soecify distillation of waste
water samples must be carried out. (See training quide note VII .B.I.la.).
The distillation procedure is not included but is covered in another EMP
on Fluoride Distillation.
c. Treatment of Interferences in Samples:
Interferences are few when the buffer is used with the electrode,
The polyvalent cations of si ", fe , al , interfere but can be
tolerated up to 5,0 mq/1 with use of the buffer. Extremes of pH
can cause problems but adjustment of pH with the buffer negates
this problem.
Additional information is given in the training guide note VII.E.4.
*Source of Procedure: Methods of Chemical Analysis of Water and Wastes, 1974,
Environmental Protection Agency, Environmental Monitoring and Support Laboratory,
Cincinnati, Ohio 45268, p.65.
Ell.B-4
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Equipment and Supply Requirements
A. Capital Equipment:
1. Expanded scale pH meter or selective ion meter
Examples: Beckman: Expandomatic Model 76007
Coleman: Model 37A
Corning: Model 12
Fisher Accumet Model 320
Leeds & Northrup Model 7405 - A 2.
Orion Model 407A portable
Hach pH/Fluoride meter No. 12330
No.12320 - portable
2. Sleeve-type reference electrode
Examples: Beckman: No. 40463
Coleman: No. 3-721
Corning: Mo. 476012
Fisher: No. 13-639-62
Orion: No. 90-01
3. Fluoride Electrode
Example: Beckman: 39600
Coleman: 3-803
Corning: 476042
Orion: 94-09
Orion: 96-09
Hach: 13034-00
4. Trip balance, 500 gram capacity.
5. Magnetic stirer and teflon covered stir bar, about 2.5 cm long.
6. Water still or other source of distilled water.
Ell .B-5
-------
EFFLUENT MONITORING PROCEDURE:
B, Reusable Supplies:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
1. One stop watch, clock or watch (with second hand).
2. One thermometer, glass 0 to 100 C.
3. One elastic squeeze bottle
4. One stirring rod, glass about in inches lonq.
5. One pair, safety glasses
6. One powder funnel, glass about 3 inch diameter
7. One laboratory aoron
8. Five weighing boats, plastic (2-3 inches square),
9. One note book (for recording data)
10. One pen or pencil
11. One Flask volumetric 1000 ml volume.
12. Two Flask volumetric 100 ml volume
13. Ten Flasks 50 ml volume (for use with pH meter only)
14. One Cylinder graduated 500 ml volume
15. One Cylinder graduated TOO ml volume
16. Seven Pipet volumetric 10 ml
17. Two Pipet graduated 10 ml
18. Four Beakers, plastic 100 ml volume
19. One Pipet Bulb
20. One spatula
The following will be needed in addition to the above only if the buffer is
prepared rather than purchased.
21, One Erlenmeyer flask, 500 ml volume
22. One Beaker, 1000 ml volume
23. One Flask volumetric, 1000 ml volume
24. One pH electrode
C. Consumable Supplies:
1. a. Sodium Fluoride -NaF Reagent grade powder - 4 oz.or
b. Sodium Fluoride Stock Solution -
Orion Research Inc. 380 Putnam Ave. Cambridge, Mass 02139, Cat. Mo.
94-06-07
Hach Chemical Co, P.O. Box 907 Ames Iowa, 50010, Cat. No. 232-11
2. Adjustment buffer
a. Total Ionic Strength Adjustment Buffer (TISAB)
Orion Research Inc. 380 Putnam Ave, Cambridge, Mass. 02139 Cat. No.
94-09-09
b. Fluoride Adjustment Buffer, Formula - 2589
Hach Chemical Co. P.O. Box 907 Ames Iowa, 50010 Powder - Cat. No.
2589.01
Pillows - Cat. No.
2509-99
Ell.B-6
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
C. Consumable Supplies (Continued):
3. The following are needed if the adjustment buffer is prepared instead
of purchased,
a. Acetic Acid, Glacial, CH,COOH. Reaqent qrade - 1 pt
b. CDTA* (1,2. cyclohexylene dinitrilotetraacetic acid) 25 q.
Matheson, Coleman A Bell Cat. No. CX - 2390
c. Sodium Chloride, NaCl, Reagent grade - 1 oound
d. Sodium Hydroxide, NaOH, Reagent grade - 1 oound
* Also listed as 1,2~cyclohexylene" diaminetetraacetic acid Baker Cat. No. G083,
Ell.B-7
-------
FLUORIDE ANALYSIS FLOW SHEET
E11.B-8
Sample
Potable Water
Waste Water
Distill
Electrode
Method
SPADMS
Colorimetric Method
SPADf.'S
Colorimetric
Method
Automated
Complexone
Method
-------
EFFLUENT MONITORING PROCEDURE.:
Determination of Fluoride in Potable and Waste Water
Ion Electrode
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
A. Sample Collection
B. Sample pretreatment
C. Equipment Preparation
1, Glassware
2. Electrometer
(pH meter or
selective ion meter
1. Collect a minimum of 300
ml in a plastic or hard
glass container.
la. Polyethylene bottles are preferred
Glass bottles are satisfactory provided they have
not previously contained high-fluoride solutions.
Ib. No special requirements are necessary for
preservation.
Ic. Chlorine does not interfere so no precautions are
necessary.
1, Distill sample
la. Distill wastewater sample for total or total
dissolved fluoride.
Ib. Use the EMP covering the distillation procedure
for Fluoride.
Ic. Distillation is not required for drinking water
samples.
1. Clean all glassware and
plastic beakers in
detergent.
2. Rinse with distilled water
1. Check meter zero.
2. Check power supply.
3. Check connection of
electrodes to meter,
la. Most instruments have a mechanical screw
adjustment to center the pointer of the meter face
2a. Check correct connection to voltage source for
line operated meters. Check batteries on all
portable and some line operated models. See
instrument manual for directions.
3a. There should be two connecting pins that attach
to the meter. The longer one from the measuring
electrode, is the fluoride electrode, and the
smaller one is from the reference electrode.
Ell.B-9
-------
EFFLUENT MONITORING PROCEDURE
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Ell.B-10
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
3. Reference Electrode
D. Reagent Preparation
1. Distilled Water
Sodium Hydroxide
NaOH, 5N
(for use in
preparation of
buffer)
3. Buffer Solution
(preparation
optional - can
he purchased)
1. Check Internal
solution.
fillinq
3b. Some connections are spring loaded and must be
held in the socket until clamped with a screw.
3c, Combination electrodes are two electrodes placed
one inside the other. This electrode will still
have two connecting pins.
la. Before usinq the reference electrode make sure the
internal filling solution has been added. This
solution is provided with the electrode and must
be used.
Ib. Fill about half the electrode with the solution.
Prepare about six (6)
liters of distilled water.
This water must be free
from fluoride.
1. Weigh out 40 grams of
sodium hydroxide (NaOH)
2. Dissolve the sodium
hydroxide in 200 ml of
water in a 500 ml
Erlenmeyer flask.
1. Add approximately 590 ml
of distilled water to a
1 liter beaker.
la. Use a still or pass tap water through an ion-
exchange column containing a strongly acidic
cation exchange resin mixed with a strongly
basic anion exchange resin.
la. Use a trip balance.
Ib. Put sodium hydroxide in a plastic weighing boat
for weighing.
2a. Use a graduated cylinder to measure the 200 ml of
water.
2b. Caution: heat given off.
la. This solution can be purchased already prepared.
Sources are listed in the front of the EMP.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Reagent Preparation
3. Buffer Solution
(Continued)
2. Add 57 ml of glacial
acetic acid.
3. Weigh out 58 grams of
sodium chloride (Nad)
4. Add sodium chloride
(NaCl) to the 1 liter
beaker,
5, Weigh out 4 grams of CDTA.
6. Add CDTA to the 1 liter
beaker.
7. Stir to dissolve.
8. Place beaker in a cool
water bath.
9. Insert calibrated pH
electrode into solution.
2a, Use a graduated cylinder.
2b. Caution: Use in a well ventilated area.
2c. Use safety glasses.
3a. Use a trip balance.
3b. Put sodium chloride in a plastic weighing boat
for weighing,
3c. For work with brines additional Nad should be
added to raise the chloride level to twice the
highest expected level of chloride in the sample,
4a. That is the same beaker to which the glacial
acetic acid has been added.
5a. The E.P.A. Methods Manual 1974, calls for 2 grams
however, STD Methods 14th and the Orion manual
both call for 4 grams.
5b. Use trip balance-
5c. Put CDTA in a plastic weighing boat for weighing.
5d. CDTA - 1,2 cyclohexylene diamine tetraacetic
acid.
8a. Cool to room temperature.
9a. The sane meter that will be used for the fluoride
measurement can be used for this.
9b. Consult EMP on pH measurement.
E11.B-11
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Usinn a Selective Ion Electrode
Ell.B-12
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING COALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Reagent Preparation
3. Buffer Solution
(Continued)
4. Sodium Fluoride
(NaF) stock
solution 100 mg
F"/liter
10. Add 5N Sodium hydroxide
(Reagent D2) (NaOH) to the
solution until meter reads
5.0 to 5.5 pH.
11. Allow solution to reach
room temperature.
12. Transfer solution to a 1
liter volumetric flask.
13. Dilute to volume and mix
thoroughly.
1. Weigh out 0.2210 grams of
sodium fluoride.
2. Add about 500 ml of
distilled water to a 1
liter volumetric flask.
3. Transfer the solid to the
1 liter volumetric flask
using a powder funnel.
4. Use wash bottle to wash
the solid into flask.
5. Dissolve the solid.
6. Dilute to volume and mix
thoroughly.
lOa. Reagent 2.
lOb. About 150ml will be needed.
ICc. Use a 100 ml graduated cylinder to add the sodium
hydroxide until the pH nears 5.0. Then add from
a pipet dropwise until the range of 5.0 to 5.5
is reached.
12a. Use wash bottle and rinse beaker with small
amounts of distilled water, transferring this
wash water to the volumetric flask.
la. Use analytical balance.
Ib. Use plastic weighing boat.
Ic. Solution can be purchased from Orion Research
Inc., Cat NO. 94-06-07 or Hach Chemical Co., Cat.
No. 232-11
2a. Approximately \ full.
4a. The weiging boat should be washed three times
and the washings added to the flask.
6a. Solution contains 0.1 mg F~ per 1.0 ml
(i.e. IOC ppm F")
-------
EFFLUENT MONITORING PROCEDURE!: Determination of Fluoride in Potable and
'~ Waste Waters Using a Selective Ion Electrode
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING COALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Reagent Preparation
4. Sodium Fluoride
(NaF) stock
solution 100 mg
F~/liter
(Continued)
5. Sodium Fluoride
(NaF) Solution
10 mg F~/liter
6. Sodium Fluoride
(NaF) solution
1.0 mg F"/liter
E. Meter and Electrode
Check
7. Label container.
1. Add approximately 50 ml
distilled water to 100 ml
volumetric flask.
2. Pipet 10 ml of the (NaF)
stock solution (reagent
C.4.) into the flask.
3. Dilute with distilled water
to the mark.
4. Mix thoroughly.
1. Add approximately 50 ml of
distilled water to a 100
ml volumetric flask.
2. Pipet 10 ml of reagent 5
(10 mg F~/l) 1iter into
the flask.
3. Dilute with distilled
water to the mark.
4. Mix Thoroughly.
6b. Keep in plastic. Stable for 6 months.
2a. Use a 10 ml volumetric pipet.
3a. Solution contains 0.01 mg F~ Der if) m] i.e.,in
ppm. Label solution.
2a. Use a 10 ml volumetric pipet.
3a. Solution contains 0.001 mg F~ per 1.0 ml i.e.,
1.0 ppm.
4a. Label
1. Turn on Meter
Ell .B-13
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Ell.B-14
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Meter and Electrode
Check (Continued)
2. Allow to warm up.
3. Pipet 10 ml of Reagent 6
into a 100 ml plastic
beaker.
4. Add 10 ml of buffer i.e.,
Reagent 3.
2a. If battery powered, no warm up necessary.
3a. Use a 10 ml volumetric pipet.
4a.
4b.
4c.
4d.
5. Place a stirring bar into
the beaker.
6. Place beaker on stir plate
7. Lower electrode or
electrodes into solution.
7a,
7b.
8. Turn on stir plate.
8a.
8b.
9. Turn meter on to a
millivolt reading position
Use a 10 ml volumetric pipet.
Any volume of sample or standard and buffer can
be used, provided equal volumes are used. For
example 10 ml of sample plus 10 ml of buffer.
Use of powdered buffer (Hach Co.) eliminates the
dilution of sample or standard and therefore
eliminates possible error.
Volume should be sufficient to cover the electrode
or electrodes to a depth of about 1 inch.
VII.E.4
VII.E.4b
(pp. 27
& 28)
Care should be taken that the stirring bar does
not hit the electrode.
Before using the reference electrode make sure
the internal filling solution has been added.
This solution is provided with the electrode and
must be used. Fill about half the electrode with
the solution.
For best results stirring should be at a rate
that will not cause a vortex.
Insulate with cardboard or styrofoam between
sample and stir plate to reduce possibility of
sample temperature change. Not so thick as to
stop the stirrer.
9a. The meter should be used in the expanded scale
mode.
V.E.7.
(p. 26)
-------
EFFLUENT MONITORING PROCEDURE:
Dctonnination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Meter and Electrode
Check (Continued)
10. Record reading in
mil 11 volts.
11. Turn meter to standby
position or off position,
12. Raise electrodes from
solution.
13. Rinse electrodes with
disti11ed water.
14. Blot dry with soft tissue.
15. Pipet 10 ml of Reagent 5
into a clean 100 nil plastic
beaker.
16. Add 10 ml buffer.
17. Place a stirring bar into
the beaker.
18. Place beaker on stir
plate.
19. Lower electrodes into
solution.
20. Turn meter on at a
millivolt reading position
lOa. The electrodes must remain in the solution for at
least three minutes or until the reading has
stabilized. At concentrations under 0.5 mg
F /liter it may require as long as five minutes
to reach a stable meter reading. Higher
concentrations stabilize more quickly.
lla. Depends on type meter being used.
15a. Use a 10 ml volumetric pipet.
16a.
16b.
19a,
Use a 10 ml volumetric pipet.
Samples and standards should be at the same
temperature. A 1°C difference in temperature
will give rise to about a 2 X error.
Care should be taken that the stir bar does not
hit the electrode.
Ell.6-15
-------
EFFLUENT MONITORING PROCEDURE
Determination of fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Ell.B.16
OPERATING PROCEDURES
E. Meter and Electrode
Check (Continued)
F. Calibration
1 . Using a pH meter
STEP SEQUENCE
21. After 3 minutes record the
reading in mil 1 ivol ts.
22. Determine the difference
between the first and
second millivolt reading.
1. Turn on meter and allow to
warm up.
2. Prepare a series of
standards using Reagent 5.
3. Pipet 10 ml of a standard
into a 100 ml plastic
INFORMATION/OPERATING COALS/SPECIFICATIONS
21a. Or until the meter
stabil izes .
22a. Correct electrode operation is indicated by a
difference of about 58 millivolts, assuming the
solution temperature is between 20°C and 25 C.
22b. If the change is not within + 2 millivolts,
consult the electrode manual.
2a. The following table can be used to prepare a
series containing from 0 to 2.0 mg F /liter by
diluting appropriate volumes to 50 ml.
ml of Reagent 5
0.00
1.00
2.00
3.00
4.00
5.00
6.00
7.00
8.00
10.00
Cone, when diluted to
50 ml in mg F~/l iter
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
1.60
2.00
2b. Use a 10 ml graduated pipet.
3a. Any volume can be used provided equal amounts of
sample or standard and buffer are used.
TRAINING
GUIDE NOTES
III. E. 22
(p. 25)
beaker.
-------
EFFLUENT MONITOR ING PROCEDURE: Determination of Fluoride in Potable and
" Waste Waters Using a Selective Ion Electrode
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F, Calibration
1. Using a pH meter
(Continued)
2. Using a selective
Ion Meter
4. Add 10 ml of buffer.
5. Add a stir bar to the
beaker.
6. Lower the electrodes into
the beaker.
7. Turn on stir plate.
8. Turn on meter.
9, Allow meter to stabilize.
10. Record millivolt reading.
11. Turn meter to off or
standby position,
12. Raise electrodes.
13. Rinse the electrodes.
14. Blot dry.
15. Repeat steps 3-13 for each
standard,
16. Prepare a standard curve.
1. Pipet 10 ml of Reagent 6
into a 100 ml plastic
beaker.
3b. Use a 10 ml volumetric pipet.
4a. Use a 10 ml volumetric pipet.
7a. Do not allow stir bar to hit electrode.
7b. Stir at a rate that will not cause a vortex.
8a. Use expanded mode.
8b. Use millivolt mode.
9a. About 3 minutes.
lla. Always go to either position, depending on meter,
before raising the electrodes from the solution.
13a. With distilled water.
Ha. With soft tissue.
15a. Repeat for each standard until all are run,
recording the millivolt reading.
16a. Plot on two cycle semilog paper.
la. Use a 10 ml volumetric pipet.
VII F.l.lSa
Ell.B-17
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
m.B-18
OPERATING PROCEDURES
F. Calibration
2. Using a selective
Ion Meter
(Continued)
STEP SEQUENCE
2. Pipet 10 ml of buffer into
the beaker.
3. Place a stirring bar into
the beaker.
4. Place beaker on stir plate.
5, Lower electrodes into
beaker.
6. Turn on stir plate.
7. Turn meter to the mono-
valent anion position.
8. Using the calibration con-
trol adjust the meter to
read at center scale.
9. Turn meter to off.
10. Raise the electrodes.
11. Rinse electrodes with
distil led water.
12. Blot dry with soft tissue.
13. Pipet 10 ml of Reagent 5
into a clean plastic 100 ml
beaker.
INFORMATION/OPERATING GOALS/SPECIFICATIONS
lb. Any volume can be used provided equal amounts of
sample or standard and buffer are used.
2a. Use a 10 ml volumetric pipet.
5a. Do not allow stir bar to hit electrode.
6a. Stir at a rate that will not cause vortex.
7a.
7b.
8a.
8b.
This may be marked as X or F .
Allow three minutes before reading.
Use the logrithmic scale on the meter.
This adjustment makes the_instrument read a
concentration of 1.0 mg F~/liter at center scale.
13a.
13b.
Use a 10 ml volumetric pipet.
This solution will be a 10 mg F~/liter standard.
TRAINING
GUIDE NOTES
VII.F.2.8a.
(p. 29)
-------
EFFLUENT MONITORING PROCEDURF:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING COALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Calibration
2. Using a selective
Ion Meter
(Continued)
14. Add 10 ml of buffer.
15. Place stir bar into
beaker.
16. Place beaker onto stir
plate.
17. Lower electrodes into
solution.
18. Turn meter to monovalent
anion position.
19. Allow to stir for three
minutes.
20. Use Temperature
compensator to adjust
meter needle to the last
number on far right of log
scale.
14a. Use a 10 ml volumetric pipet.
17a. Do not allow stir bar to hit electrodes.
19a. Or until meter stabilizes.
20a. The temperature of all samples and standards
should be the same. If sample is not the same
temperature, allow to stand at room temperature
for about one hour.
20b. This adjustment makes the meter read a con-
centration of 10.0 mg F~/liter at far right
scale.
20c. The entire scale now can be used to read directly
concentrations from 0.1 rig F /liter to
10.0 mg F~/liter.
20d. This calibration should be checked about every
1 to 2 hours by repeating procedure F2. If the
temperature changes, recalibrate more often.
20e. The log scale may be located at various positions
on the meter face. Consult the manufacturers
manual to point out which to use if in doubt.
Ell.B-19
-------
EFFLUENT MUKITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Ell.B-20
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Calibration
2. Using a selective
Ion Meter
(Continued)
G. Procedure
21, Turn meter off.
22. Raise electrodes.
23. Rinse electrodes with
distil 1ed water.
24. Blot dry with soft tissue
1. After the calibration of
the meter has been com-
pleted, test all samples
by doing the following.
2. Turn on meter for warm up.
3. Pipet 10 ml of sample into
a clean plastic 100 ml
beaker.
4. Add 10 ml of buffer.
5. Place stir bar into beaker.
6. Place beaker on stir plate.
7. Lower electrode.
8. Turn on stir plate.
9. Adjust stir plate to a
rate that will not form
vortex.
10. Turn on meter.
2a. If necessary.
3a. Any volume can be used provided equal amounts of
sample or standard and buffer are used.
3b. Use a 10 ml volumetric pipet,
4a. Or same volume as used for sample.
8a. Do not allow stir bar to hit electrode.
lOa. To monovalent am'on position.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
G. Procedure
(Continued)
1. Stir for three minutes, or
until meter stabilizes.
2. Read value.
H. Storage
1. Reference
Electrode
2. Fluoride?
Electrode
12a. For pH meters read at millivolt scale and use
millivolt vs concentration curve to determine
F~ concentration in sample.
For selective ion meter read concentration
12b.
13. Turn meter off.
14. Raise electrodes.
15. Rinse and dry electrodes.
Store in the 1.C mg F /
1iter standardizing
solution or distilled water
if the electrode is to be
used in a short time or
next day.
Clean thoroughly and store
dry if storing for long
period of time.
Store in air or in a
standardizing solution.
I. Calculations
1. pH meter
1. Use the constructed
standard curve.
directly from logarithmic scale.
la. If using separate electrodes, i.e. reference
and fluoride, this section applies to the
reference only. If a combination electrode is
being used the precautions for the reference
electrode section should be used.
2a. Before reuse add internal filling solution.
la. No specific storage precautions necessary.
la.
When the reading of millivolts is obtained
this value to convert to concentration in
T -; -*- ~ ~
obtained use
mg F" liter.
Ell.B-21
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Ell.B-22
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
I. Calculations
1. pH meter
(Continued)
2, Specific Ion
Meters
Read concentration scale
(logarithmic directly to
obtain sample mg F /liter.
Ib. Using the graph paper attached. Look at the
bottom of the graph and find the millivolt
reading for the sample. Move upward until the
curve is contacted then move horizontally left
until the edge of the paper is reached. Read
this intersection in mg F~/ liter.
Ic. If additional instruction on the use of a
calibration graph is needed, consult the EMP,
Preparation of Calibration Graphs.
la. All data reported in mg F"/liter.
-------
TRAINING GUIDE
SECTION TOPIC
I* Introduction
II Educational Concepts - Mathematics
III* Educational Concepts - Science
IV Educational Concepts - Communications
V* Field & Laboratory Equipment
VI Field & Laboratory Reagents
VII* Field & Laboratory Analysis
VIII Safety
IX* Records & Reports
*Training guide materials are presented here under the headings marked*.
These standardized headings are used through this series of procedures.
Ell.B-23
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
INTRODUCTION
Section
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
The basis for this
electrode itself,
fluoride solution;
crystal doped with
method is in the fluoride
Most electrodes contain a
at the tip of the electrode is a
fluoride ions. The crystal acts
as an ion-exchange membrane, so that when the
fluoride concentration outside of the electrode is
higher than that inside, ions move toward the inside
setting up a voltage potential proportional to the
difference in fluoride concentration. Conversaly
when the fluoride concentration on the outside is
lower than that on the inside, a proportional
potential of opposite sign is set up. In most
fluoride electrodes, the internal solution is about
10 molar in fluoride, so concentrations below
19 mg F~/liter result in positive voltage readings.
Some electrodes contain no internal solution, but the
principle of operation is similar. However, in the
solid electrodes the potential developed by a
particular fluoride solution is independent of a
filling solution but rather depends entirely on the
characteristics of the particular crystal used in the
electrode manufacture.
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Educational Concepts - Science
Section
III
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
1.22
Theory of operation of a fluoride electrode predicts
a behavior that is expressed by the Nernst equation.
Consequently the difference in millivolt readings
between two concentrations of fluoride that differ
by a factor of ten should be between 55 and 60
mil 1ivolts,
If one knows concentration of fluoride, for example
1 mg/liter, is expressed on a meter in millivolts anc
then a second concentration differing by a factor of
ten, for example 10 mg/liter, is expressed on the
same meter in millivolts, the difference between
these millivolt values will be about 58 millivolts.
This fact can be used to check on whether the system
is operating properly. How this is carried out will
depend on the type of meter and electrode being used.
Ell.B-25
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Field & Laboratory Equipment
Section
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
E.7
The fluoride electrode must be used in conjunction
with a standard single junction sleeve-type
reference electrode. If smaller volumes of sample
are to be run for convenience sake, a combination
electrode is available. This appears to be a single
electrode. However, in actuality, it is two
electrodes, one inside the other. This allows the
electrode to be inserted into smaller diameter
containers and also makes for easier use.
Ml
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Field & Laboratory Analysis
Section
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
1.1,la,
E, 4.
For potable waters to comply with requirements as
listed in the National Interim Primary Drinking
Water Regulations (F.R. Part IV - 12/24/75-§10 - pg
59573), distillation is not necessary.
However, for surface and saline waters or domestic
and industrial wastes to comply with NPDES
requirements distillation if necessary unless
sufficient data exists to prove that distillation is
not necessary. Manual distillation will be required
to resolve any controversy.
Interferences connected with the electrode can be
1 is ted as being:
a) PH
b) temperature
c) other ions
d) total ionic strength
In acid solutions below pH 5, hydrogen can complex
fluoride by forming the undissociated acid
hydrofluoric HF. This will not allow the electrode
to sense the fluoride concentration, thus tied up,
Hydroxide ion can also interfere when concentration
of this ion are about 10"^ Molar. Addition of the
buffer solution will adjust most samples into the
range of 5.0 to 5.5 pH where no interference of pH
is found. For samples high in pH, i.e., pH 11, the
volume of buffer added may not be sufficient.
These samples should have their pH adjusted by the
addition of IN HC1 to adjust the pH to about 8 before
addition of the buffer.
So long as the temperature of the standards and
samples are the same, temperature will not affect the
readings. However a variance between standard and
sample of 1 C can cause a 2% error for a concentra-
tion of 19 mg F/l.
Other ions, particularly, iron and aluminium can
cause significant errors. The table below gives
some indication of this error. The numbers given
show the concentration that will affect the
electrode after addition of buffer.
Ell.B-27
-------
EFFLUENT MONITORING PROCEDURE:
Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Field & Laboratory Analysis
Section
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
E.4
.Continued)
E.4.b.
F.1.15a.
INTERFERENCES FOR THE ELECTRODE
Concentration of substance, in mg/liter required to
cause an error of plus or minus 0.1 mg/liter at
1.0 mg F/liter.
SUBSTANCE
Alkalinity
Aluminum
Chloride
Iron
Hexametaphosphate
Phosphate
Sulfate
Chlorine
luoride Determination in
^ater, E.P.A. Training
"lanual, National Training
and Operational Technology
Center, Cincinnati, Ohio
5268
7,000 (+)
4 (-)
20,000 (-)
200 (-)
>50,000
>50,000
50,000 (-)
>5,000
From this, it can be seen that with the use of the
buffer, very few ions normally used in the treat-
ment of water will interfere.
Variations in ionic strength can interfere but again
the make-up of the buffer will adjust this to a
point where interferences are eliminated.
All samples are actually diluted in half by the
addition of an equal volume of buffer solution.
Since this same dilution ratio of equal volumes is
carried out for all samples and standards the
original concentration is used. Thus if a 1.0 mg/
liter solution is diluted with buffer and is
actually 0.5 mg/liter it is read as 1.0 mg/liter.
Plot the concentration of fluoride in mg/1 on the
log axis and the millivolt reading on the linear
axis. Figure one has a piece of 2 cycle semi log
paper with the concentration values in the EMP
marked.
The graph will have a negative slope; i.e., there
will be a lowering of the millivolt reading as the
concentration increases. The line will be straight
from 0.1 to over 100 ppm.
rii D oo
-------
EFFLUENT MONITORING PROCEDURE: Determination of Fluoride in Potable and
Waste Waters Using a Selective Ion Electrode
Field & Laboratory Analysis
Section
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
F.2.8a.
A selective ion meter usually has several scales on
the meter face. One is divided into 14 equal
divisions is the pH scale; another is divided into
unequal divisions and usually repeats itself at
least twice. How it is numbered varies with each
manufacturer. This scale is the logarithmic scale
and should be used to read the concentration of
selective ions in mg/1.
Since the units, i.e. how it is numbered, vary the
concentration range of the scale can be arbitrarily
set. This scale is usually repeated; for example,
if the first number on the left is marked as .1 and
at the middle of the scale is 1 and the last number
on the right is 10 this gives two complete
repetitions. Concentration wise this could mean
that the concentration at center can be adjusted to
read 1.0 mg/1 and at far right as 10.0 mg/1. This
would then allow concentrations of from 0.1 to 1.0
to 10.0 to be read directly from the meter face.
Ell.B-29
-------
Section IX
TYPICAL LABORATORY DATA SHEET
Sample Collections:
1. Name of Plant:
2. Sampling Location
3. Type of Sample
4. Date and Time Collected
5. Sample Collector
Sample Analysis:
1, Name of laboratory
2. Date and Time Collected
3. Sample designation
4. Methods Used
5. Was Sample Distilled
6. Concentration of F~ determined
(in mg/liter)
Standard Cone.
mg j^yiHer Millivolt reading
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
2.0
Ell.B-30
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
PRELIMINARY DISTILLATION PROCEDURE FOR
FLUORIDE ANALYSIS OF POTABLE AND WASTEWATERS
as applied in
WATER TREATMENT FACILITIES
WASTEWATER TREATMENT FACILITIES
and in the
MONITORING OF EFFLUENT WASTEWATERS
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.HAL.f.lab.HMP.l .11.77
Ell.C-1
-------
WATER MONITORING PROCEDURE; Preliminary Distillation Procedure for Fluoride
Analysis of Potable and Wastewaters
1. Analysis Objectives:
The learner will remove interferences to the fluoride analyses by a pre-
liminary distillation of the sample.
2. Brief Description of Analysis:
The sample is added to a previously adjusted acid water mixture. The
fluoride is liberated in the strongly acid mixture as the fluoride ion F~.
This reacts with the excess hydrogen ion H+ to form hydrofluoric acid HP.
This material leaches silica from glass and forms hydrofluorsilic acid
HoS,Fg) which distills over as an aqueous solution. All impurities remain
behind.
3. Applicability of this procedure:
a. Range: When high-fluoride samples are distilled (greater than 10 mg F /I),
all of the fluoride may not be distilled over. Repeat the distillation
with 300 ml distilled water.
b. Pretreatment: None required
c. Treatment of Interferences: None required
Ell.C-3
-------
o
I
FLUORIDE ANALYSIS FLOW SHEET
Potable Water
Waste Water
Distill
Distill
Electrode
Method
SPADNS
Colorimetric
Method
SPADNS
Colorimetric
Method
Automated
Complexone
Method
-------
WATER MONITORING PROCEDURE:
Preliminary Distillation Procedure for Fluoride
Analysis of Potable and Wastewaters
Equipment and Supply Requirements
A. Capital Equipment:
Water still or other source of distilled water
B. Reusable Supplies:
1. One adaptor - offset with outer ground glass joint 24/40 at top and inner
ground glass joint 24/40 at the bottom, with opening with rubber glove
connector for thermometer.
1. One burner, natural - gas type (or for other type gas used in lab)
3. One boiling flask - 1 liter, Pyrex or Kimax, round bottom, with 24/40
outer ground glass joint
4. Two clamps - to hold boiling flask and condenser to ring stand. One
should be covered with asbestos or fiberglas to withstand heat.
5, One condenser - 40 cm long, double jacket, outer ground glass 24/40
joint at top
6. One connecting tube - with two inner ground glass 24/40 joints
7. One cylinder - volumetric, 500 ml
8. One flask - Erlenmeyer, 300 ml
9. Twelve glass beads - (not hard glass, i.e., Pyrex or Kimax)
10. One tube grease - silicone stopcock
11. One ring stand and rod
12. One thermometer - 0 to 200°C, 24" long
13. Tubing, Tygon - enough to reach water supply and drain
C. Consumable:
1. Distilled water - about 6 liters
2. Silver sulfate - crystals (for removal of chloride concentration greater
than 2000 rng/1)
3. Sulfuric acid
4. Detergent
Ell .C-5
-------
Ell.C-6
WATER MONITORING PROCEDURE:
Preliminary Distillation Procedure for Fluoride
Analysis or Potable and Wastewaters
OPERATING PROCEDURES
STEP SEQUENCE
ION/OPERA:ING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
PRELIMINARY DISTILLATION
A. Sample Collection
B. Equipment Preparation
C. Reagent Preparation
1. Distilled Water
2. Sulfuric Acid
0. Still Preparation
1. Connect the sti 11
FOR FLUORIDE ANALYSIS:
1. Collect a minimum of 300 ml
in a plastic or hard glass
container.
1. Clean all glassware in
detergent.
2, Rinse with distilled water,
1. Prepare about six (6)
liters of distilled water.
This must be free fron
fluoride.
1. Concentrated; no pre-
paration required.
1. As shown in Fig. I.
2. The ground glass joints
should be greased with
silicons stopcock grease.
3. The thermometer must be
capable of reading about
200°C.
la.
Ib.
la.
2a.
Polyethylene bottles are preferred to glass
bottles and are satisfactory provided they have
not previously contained high-fluoride concen-
tration solutions.
No special requirements are necessary for
preservation.
on: Tap waters can contain fluoride.
la. Use a still or pass tap water through an ion-
exchange column containing a strongly acidic
cation exchange resin mixed with a strongly
basic anion exchange resin.
Leave the joint between the adaptor and connecting
tube open.
Very small amounts are used. One way to do this
is to coat the joint then lightly wipe the grease
off with a soft tissue.
-------
WATER MONITORING PROCEDURE:
Preliminary Distillation Procedure for Fluoride
Analysis of Potable and Wastewaters
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Still Preparation
(Continued)
2. Add the Reagents
3. Close the Still
4. Heat the Still
1. Place 400 ml of distilled
water in the boiling flask
2. Carefully add 200 ml con-
centrated sulfuric acid.
3. Add about 10 to 12 glass
beads.
4. Shake the flask by swirling
to mix the two liquids.
1. Connect the joint between
the adaptor and the
connector tube.
2. Check all joints to assure
tightness.
1. Turn on water to the
condenser.
la. Use a 500 ml graduated cylinder.
2a. Caution: Heat is generated, also use protective
eye covering.
3a. These serve a two fold purpose: first to act as
boiling stones to prevent superheating of the
mixed liquids and secondly to serve as a source
of silica for a chemical reaction in the flask.
F" + H •+ HF + Si •+ H,SiFc
L b
If the glass beads are not present, the silica
will be taken from the boiling flask and will
considerably shorten its useful life.
4a. Hold the ring stand top and rotate in circular
fashion. The mixing must be complete or the
liquid can superheat. If the flask is observed
closely while mixing, gradient lines (wavy lines)
can be seen. Mix until no more are seen.
la. Consult Figure I.
2a. Fluoride will be lost through any joints that
are not tight.
la. The water should enter at the bottom of the
condenser.
Ib. The flow of water should be maintained at such a
rate that condensation does occur in the upper
third of the condenser.
VIII.2.D.4
(p. 15)
Ell.C-7
-------
MATER MONITORING PROCfcOURr: Preliminary Distillation Procedure for Fluoride
Analysis of Potable and Wastewaters
Ell.C-8
OPFRATING FRCCFDURES
D. Still Preparation
(Continued)
SUP SEIJLNCE
2. Turn on and ignite the
burner.
3. Place a 300 ml Erlenmeyer
flask under the condenser,
4, Begin to heat slowly.
5. When boiling begins, heat-
ing nay be increased.
6. Continue heating until the
temperature reaches 180°C,
7. Remove heat.
8. Discard distillate.
INFRMATION/CPLPJTING COALS/SPECIFICATIONS
2a. A heating mantle may be used; however, it is in-
convenient to use. The temperature must be
stopped at 180°C and it is hard to do with a
mantle. If a mantle is used, it can be turned off
at a somewhat lower temperature, allowing the
residual heat to carry the temperature to 180°C.
How early should be determined by practice since
all mantles very.
4a. If bumping occurs, mixing has not been completed.
5a. Adjust the flame to prevent it from contacting the
distilling flask above the liquid level. Super-
heating of the vapor results in high sulfate
carryover which causes a sulfate interference.
6a. Distillation must be stopped when the temperature
reaches 180°C. Higher temperatures result in
excessive sulfate carryover.
6b. About 45 minutes.
7a. Turn off burner.
8a. Discard this distillate, since it contains traces
of fluoride from the acid and glassware. This
preliminary procedure also serves to adjust the
acid-water ratio for subsequent distillations.
8b. This preliminary distillation need be repeated
only if new acid is used or obvious contamination
occurs or if the operator has doubts as to
contamination.
8c. The resulting acid-water ratio can be used over
and over for samples until a brown color pre-
dominates and 180°C is hard to obtain.
8d. The amount of distillate should be 300 ml.
TRAINING
GUIDE NOTES
-------
i-.!ATER MONITORING PROCEDURL: Preliminary Distillation Procedure for Fluoride
Analysis of Potable and Wastewaters
OPERATING PRCCEDURES
E. Procedure
1, Sample Addition
2. Distill sample
STEP SEQUENCE
1, Allow the still to cool
until the temperature
drops to 120°C or lower,
2. Disconnect the joint be-
tween the adapter and
connecting tube.
3, Remove high levels of
chloride in the sample.
4. Add 300 ml sample.
5. Mix thoroughly.
6. Close joint between
adapter and connecting
tube.
1. Place a 300 ml Erlenmeyer
flask under condenser.
2. Turn on water to the
condenser.
3. Ignite burner.
IHFCPMATICu/CPlRAYING GOALS/SPECIFICAFIONS
la. Caution: The glass is hot; touch with care.
2a. The connecting tube may be lifted clear of the
adapter and condenser.
3a. Add silver sulfate to the sample at the rate of
5 mg per milligram of chloride when high-chloride
samples are distilled.
3b. Most potable waters will not have high-chlorides.
Sea water and brackish waters may have. As a gen-
eralized guide, about 2000 rng/1 chlroide should be
a starting point for adding the silver sulfate.
4a. Use a 500 ml graduated cylinder.
4b. Pour into adapter.
5a. Caution: Improper mixing may cause super-heating
and bumping,
5b. Use support ring and swirl in circular manner.
2a. If it has been turned off.
TRAINING
GUIDE NOTES
Ell.C-9
-------
WATER MONITORING PROCEDURE:
Preliminary Distillation Procedure for Fluoride
Analysis of Potable and Wastewaters
Ell.C-10
OPERATING PROCEDURES
STEP SLQUtfXE
INFORMATION/OPIATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Procedure (Continued)
3. Remove Distillate
4. Begin to heat slowly.
5. Increase temperature.
6. Heat to 180°C.
7. Remove heat.
1. Retain distillate for
analysis of the fluoride.
F. Fluoride Determinatior
1. Chose an approved method.
2. Determine the fluoride
concentration.
4a. Until boiling begins.
5a. Cautiori: Do not allow flame to go above liquid
level.
7a. When temperature reaches 180°C.
la. When high-fluoride samples (> 10 mg F~/Hter) are
distilled, repeat the distillation using 300 ml
of distilled water. If substantial amounts of
fluoride appear in the second distillate, add the
amount to that obtained initially and flush
(300 ml of water) the still again. Quantities of
less than 0.1 mg/1 F~ may be disregarded.
la. For wastewater the SPADNS-electrode or automated
complexone methods are approved after
distillation.
Ib, For potable water the SPADNS or electrode methods
are approved. Distillation is not required for
the electrode method.
Ic. Consult the appropriate EMP on the procedures.
-------
WAiER MONITOR 1NG PROCEPURL: Preliminary Distillation Procedure for Fluoride
: Analysis of Potable and Wastewaters
fPERATINr, PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
G. Storage
1. The Still
2. The Acid
1. Store the glass still in
such a manner as to pre-
vent physical damage.
1. Store in the sti11.
la. This acid may be reused until the buildups of
impurities discolors or prevents the temperature
from being obtained.
lb. The time is dependent upon content of impurities
in the water sample.
Ic. A good practice would be to occasionally run a
known standard to assure complete distillation
of fluoride.
Ell.C-11
-------
CONNECTING TUBE
12mm. I.D.
THERMOMETER
RUBBER SLEEVE
S 24/40
JOINTS
4J ADAPTER
1000 ml. BOILING FLASK
f 24/40 JOINT
BURNER
CONDENSER
300 ml. ERLENMEYER
FIGURE 1. DISTILLATION APPARATUS
Ell.C-12
-------
WATER MONITORING PROCEDURE: Preliminary Distillation Procedure for Fluoride
Analysis of Potable and Wastewaters
TRAINING GUIDE
SECTION TOPIC
I* Introduction
II Educational Concepts - Mathematics
III Educational Concepts - Science
IV Educational Concepts - Communications
V Field and Laboratory Equipment
VI Field and Laboratory Reagents
VII Field and Laboratory Analysis
VIII* Safety
IX Records and Reports
*Training Guide materials are presented here under the headings marked*.
These standardized headings are used through this series of procedures.
Ell.C-13
-------
WATER MONITORING PROCEDURES:
Preliminary Distillation Procedure for Fluoride
Analysis of Potable and Wastewaters
INTRODUCTION
Section I
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
The Guidelines Establishing Test Procedures for the
Analysis of Pollutants lists three approved analyti-
cal methods for fluoride. It 1s mandatory to pre-
cede each by the preliminary distillation procedure,
unless comparability data is available on a repre-
sentative effluent sample to show that this pre-
liminary distillation Is not necessary.
The National Interim Primary Drinking Water Regu-
lations lists two approved analytical methods for
fluoride. It is mandatory to precede only the
coloritnetric (SPAONS) method by the preliminary
distillation procedure.
The Preliminary Distillation step required to be
used is the method utilizing a distillation from
suIfuric acid.
Federal Register, Part II,
Wednesday, Dec, 1, 1976,
page 52782, Parameter 20.
Federal Register, Part iy,
Wednesday, Dec. 24, 1975,
page 59573, Parameter 10.
Standard Methods for the
Examination of Water and
Wastewater. 13th ed.,
page 171. 14th ed.,
page 389.
Ell.C-14
-------
WATER MONITORING PROCEDURES:
Preliminary Distillation Procedure for Fluoride
Analysis of Potable and Wastewaters
SAFETY
Section VIII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
D.Z.4
Care should be taken to assure complete mixing
between the acid and water or sample. Incomplete
mixing will result in a violent bumping of the still
which can throw the acid mixture out of the distill-
ing flask and possible damage to the still, analyst
and loss of sample.
Ell .C-15
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
DETERMINATION OF BARIUM (Ba++)
as applied in
WATER AND WASTEWATER TREATMENT FACILITIES
and in the
MONITORING OF EFFLUENT WASTEWATERS
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.ME.ba.lab.WMP.l .11.77
E12-1
-------
WATER MONITORING PROCEDURE: Determination of Barium (BA++)
1. Analysis Objectives:
The learner will be instructed on how to determine the barium content of a
sample.
2. Brief Description of Analysis:
The sample is first digested with acid to assure all metals are in a soluable
form. After which a portion of the sample is aspirated into an atomic ab-
sorption spectrophotometer utilizing an acetylene-nitrous oxide flame.
3. Applicability of the Procedure:
The method works for both potable and wastewaters.
a. Range of Concentration - The method is recommended for use in the range
of 1.0 to 20 mg of barium/liter. The detection limit is 0.03 mg/1.
b. Pretreatment of the sample - Digestion in acid pH to assure solubil ization.
See Section B.
c. Treatment of Interferences in the sample - The use of the nitrous oxide-
acetylene flame virtually eliminates chemical interferences; however,
barium is easily ionized in this flame and potassium must be added to
standards and samples alike to control this effect.
d. Source of Procedure - Manual of Methods for Chemical Analysis of Water
and Wastes; 1974 ed., p. 97; USEPA Technology Transfer, Cinti., OH 45268.
E12-3
-------
WATER MONITORING PROCEDURE; Determination of Barium (BA++)
Operating Procedures:
A. Equipment Preparation
B. Reagent Preparation
C. Standard Preparation
D. Sample Pretreatment
E, Instrument Calibration
F. Sample Analysis
G. Calculations
El 2-4
-------
WATER MONITORING PROCEDURE: Determination of Barium (BA++)
Equipment and Supply Requirements
A. Capital Equipment:
1. Atomic absorption spectrophotometer
2. Recorder - compatible with the instrument
3. Nitrous oxide burner head
4. Barium - hollow cathode lamp
5. Pressure regulators two stage for
Acetylene - CGA inlet 510 connector
Air - CGA inlet 1340 connector
Nitrous oxide - CGA inlet 1320 connector
6. Balance - analytical with a 0.1 milligram sensitivity
7. Still - borosilicate glass or equivalent
B. Reusable Supplies:
1. Trip balance - 100 gram capacity
2. Pen or pencil
3. Twelve inch ruler
4. Hot plate
5. Five reagent bottles - clear glass, glass stoppered 500 ml cap
6. Six beakers - glass, 150 ml size
7. Six cylinders - graduated, 100 ml size
8. Three flasks - volumetric, 1000 ml volume
9. Six flasks - volumetric, 100 ml volume
10. One pipet - graduated, 1 ml
11. Two pi pets - graduated, 10 ml
12. One pipet - volumetric, 1 ml
13. Two pipets - volumetric 5 ml
14. One pipet - volumetric 10 ml
15. One pipet - volumetric 20 ml
16. One funnel - powder, glass
17. One funnel - filtering
18. Pipet bulb
19. Safety glasses
20. Wash bottle - plastic
Consumable Supplies:
1. Deionizing column - mixed bed type
2. Gases
Acetylene - purified or commercial grade
Air - dry grade
Nitrous oxide - technical grade
3. Detergent
4. Nitric Acid - ACS grade
5. Hydrochloric acid - ACS grade
6. Barium chloride
7. Potassium chloride
E12-5
-------
WATER MONITORING PROCEDURE: Determination of Barium
Equipment and Supply Requirements (Continued)
8. pH paper - capable of measuring pH 2 (pHydrion)
9. Filter paper - Whatman #42
10. Graph paper
11. Wax marking pencil
12. Plastic weighing boats, ^ 12 each
E12-6
-------
+ +^
WATER MONITORING PROCEDURE: Determination of Barium (Ba )
OPERATING PROCEDURES
STEP StQUENCE
INFORMATION/OPE RAT ING GOALS/SPEC IFICATIONS
TRAINING
GUIDE NOTES
A. Equipment Preparation
1. Cleaning of
Glassware
2. Balance Inspection
3. Instrument
Inspection
1. Wash with detergent.
2. Rinse with tap water.
3. Rinse with 1:1 nitric acid
4. Rinse with tap water.
5. Rinse with 1:1 hydro-
chloric acid.
6. Rinse with tap water.
7. Rinse with distilled water
1. Check all balances for
cleanliness and proper
operation.
1. Check all items of the
instrument to assure
proper optimization and
operation.
la. Cleaning should be carried out in this order.
Ib. All glassware should be kept covered after
cleaning.
3a. Add an equal volume of acid to an equal volume of
distilled water. (Example: 500 ml of acid added
to 500 ml of water.
3b. Caution: Always add acid to water not the
reverse.
5a. Add equal volume of HC1 to an equal volume of
distilled water.
la. Consult the manufacturer's manual if the balance
does not operate properly.
la. Consult the manufacturer's manual.
E12-7
-------
+-K
WATER MONITORING PROCEDURE: Determination of Barium (Ba )
E12-8
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
1. Distilled
Deionized Water
2. Nitric Acid
Concentrated
(HN03)
3. Nitric Acid 1:1
4. Hydrochloric Acid
Concentrated (HC1)
5. Hydrochloric Acid
1:1
6. Barium Stock
Solution
1. Prepare by passing dis-
tilled water through a
mixed bed of cation and
anion exchange resins.
1. Commercially available
reagent grade.
1. Prepare a 1:1 solution from
reagent grade nitric acid
by adding an equal amount
of the acid to an equal
amount of distilled water.
1. Commercially available
reagent grade.
1
Prepare a 1:1 solution from
reagent grade hydrochloric
acid by adding an equal
amount of the acid to an
equal amount of distilled
water.
Carefully weigh 1.7787
grams of barium chloride
la. Use deionized distilled water for the preparation
of all reagents, calibration standards and as
dilution water.
la. If a high reagent blank is obtained, it may be
necessary to distill the acid or purchase a
better purity.
la. Caution: add the acid to water; not the reverse.
la. Caution: add the acid to water; not the reverse.
(BaCl.
•2H20)
(analytical
reagent grade).
2. Transfer Into a 1000 ml
volumetric flask.
la. Use a plastic weighing boat and an analytical
balance.
2a. Use a powder funnel.
2b. Use a plastic wash bottle to rinse weighing boat
and funnel into the flask.
-------
WATER MONITORING PROCEDURE: Determination of Barium (Ba1
OPERATING PROCEDURES
STEP SEQUENCE
INFOKMATION/OPERA! If,G G00L.S/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
7. Barium Standard
Solution
8. Potassium Chloride
Solution (KC1)
9. Fuel and Oxidant
3. Dissolve in distilled
water.
4. Dilute to the mark with
distilled water.
1. Transfer about 50 ml of
distilled deionized water
to a 100 ml volumetric
flask.
2. Pipet 1 ml of barium stock
solution (Reagent 6) into
the flask.
3. Dilute to the mark with
distilled deionized water.
1. Weigh 95 grams of potassium
chloride (KC1) (analytical
reagent grade).
2. Transfer into a 1000 ml
volumetric flask.
3. Dissolve in distilled
water.
4. Dilute to the mark with
distilled water.
1. Commercial grade acetylene
is generally acceptable.
4a, One ml equals 1 mg Ba (1000 mg/liter)
la. This volume need not be measured exactly.
2a. Use a 1 ml volumetric pipet.
3a. This solution contains 10 mg Ba/liter,
(1 ml = 0.01 mn Ba)
la. Use a plastic weighing boat on a trip balance.
2a. Use a powder funnel.
2b. Use a plastic wash bottle to rinse the weighing
boat and funnel into flask.
4a. One ml = 50 mg K = (50,000 mg/liter)
El 2-9
-------
HATER MONITORING PROCEDURE: Determination of Barium (Ba )
E12-10
OPERATING PROCEDURES
STfP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
2. Reagent grade nitrous
oxide (N~Q) is required.
3. Air - dry grade.
3a. Air may be supplied from a compressed air line,
a compressor or cylinder.
3b. Air is used to ignite the burner initially on
most instruments, then the flame is switched
over to the nitrous oxide. This reduces the
possibility of flash back occurring.
3c. Caution: The air supply must be free from oil
or other contaminants.
C. Standard Preparation
1. Collect 5 clean 100 ml
volumetric flasks.
2.
Add about
distilled
flask.
50 ml
water
deionized
to each
3. Add 0.2 ml concentrated
nitric acid.
4. Add 5.0 ml of concentrated
hydrochloric acid.
5. Add 2.0 ml of the potassiun
chloride solution (Reagent
8)
2a. This volume is not critical—just fill flask
about half full.
3a. The calibration standards should be prepared
using the same type of acids (HC1 and HNO-) and
at the same concentrations as the samples for
analysis.
3b, Nitric acid will have been added to the sample
for preservation.
3c. Use a 1 ml pi pet graduated in tenths.
3d. Use caution when pipetting concentrated acids.
3e. Use a pipet bulb and safety glasses.
4a. Use a 10 ml graduated pipet.
5a, Use a 10 ml graduated pipet.
VI.C.5
(P. 17)
-------
WATER MONITORING PROCEDURE: Determination of Barium (Ba
OPERATING PRCCEDURES
5T£- SEQUENCE
I:NFGKMAT ION/OFF BATING GOALS/SPEC IFICATIONS
TRAINING
GUIDE NOTES
C. Standard Preparation
(Continued)
D. Sample Pretreatment:
for Total Metal
6. Transfer 0.0, 5.0, 10.0,
15.0, 20.0 ml of the
barium standard solution
(Reagent 6) to each of the
five volumetric flasks
respectively.
7. Dilute each flask to the
volume mark with de-
ionized distilled water.
8. Mix thoroughly.
1. Transfer 100 ml of
sample into a clean 150 ml
beaker.
2. Check the pH.
3. Adjust pH to below 2 if it
has not been adjusted
during sampling.
4. Add 5 ml of 1:1 hydro-
chloric acid.
5. Heat the sample at 95°C
for 15 minutes.
6. Cool to room temperature.
7. Wash down walls of the
beaker with distilled
water.
6a. Use volumetric pipets for the transfer.
6b. The blank (the 0.0 flask) will not need to be
pipetted.
7a. The solutions contain 0.0, 0.5, 1.0, 1.5, and
2.0 mg Ba/liter of solution.
la. Use a 100 ml graduated cylinder.
2a. pH paper can be used (pHydrion).
2b. pH must be
-------
WATER MONITORING PROCEDURE: Determination of Barium (Ba )
EU'-12
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Sample Pretreatment:
for Total Metal
(Continued)
8. Filter the sample through
a filter paper into a
100 ml graduated cylinder.
9. Adjust the volume to
100 ml.
8a. A paper such as Whatman #42 should be used.
9a. The sample is now ready for analysis.
E. Instrument Calibration
1. Install the nitrous oxide
burner head.
2. Assure that the barium
lamp is in the light path.
3. Adjust the wavelength to
the proper setting.
4. Select the proper slit
arrangement,
5. Set the lamp current con-
trol to its lowest
position.
6. Turn on the power to the
instrument.
7. Adjust the lamp current
control until the proper
mill lamps are applied to
the lamp.
la. Follow the manufacturer's directions for in-
stallation. Usually no tools are required and
the installation is not difficult.
2a. Depending on the instrument, the analyst may
have to place the lamp into the lamp compartment
or revolve the turret.
3a. 553.6 nm for barium.
4a. Consult the manufacturer's specifications or
procedures manual.
5a. Consult the manual for location on your
instrument.
6a. Consult the manufacturer's manual for location.
6b. Allow warm up time for single beam instruments.
7a. Consult the lamp for proper operating current.
-------
WATER MONITORING PROCEC'JRF.: Determination of Barium (Ba )
OPERATING PROCEDURES
E. Instrument Calibration
(Continued)
F. Sample Analysis
STLP SEQUENCE
8. Turn on the master valves
for the air, acetylene
and nitrous oxide.
9. Ignite flame.
10. Aspirate the standard
solution prepared in
Section C.
11. Prepare a calibration
curve by plotting the
concentration, in mg Ba/
liter, of the standards
against the response for
each concentration.
1. Each sample must be pre-
treated to assure that all
materials which might
contain barium are in
soluble form.
2. Add 2 ml of the potassium
chloride solution (Re-
agent 8).
3. Aspirate the unknown
solution(s) into the
instrument immediately
following the aspiration
of the standards.
IfiFCRMATICN/OPEPATING GOALS/SPEC I PI CAT IONS
8a. The pressure setting for the gases should be set
to the manufacturer's recommendations.
9a. Using air-acetylene: after ignition, switch to
nitrous oxide.
9b. Adjust the acetylene for maximum absorption.
9c. See instruction manual for your particular
instrument.
lOa. Record the response on a recorder or its
equivalent.
la. Steps are in Section C.
2a. Use a 10 ml graduated pipet.
3a. The standard curve produced under Section E must
be verified each time barium is to be analyzed.
3b. The flame characteristics and instrument
settings should be the same for standards and
unknowns.
TRAINING
GUIDE NOTES
E12-13
-------
WATER MONITORING PROCEDURE: Determination of Barium (Ba )
E12-14
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Sample Analysis
(Continued)
G. Calculations
4. Record the response.
Determine the concentra-
tion of barium in the
sample by substituting the
observed instrumental re-
sponse on the calibration
graph.
2.
Express all values
mg Ba/liter.
as
la. Consult the outline in Section F concerning
"Calibration Graphs."
Ib. Some instruments can be calibrated to read
directly in concentration. This should be used
only after the analyst is assured that correct
responses can be attained.
-------
WATER MONITORING PROCEDURE: Determination of Barium (Ba++)
TRAINING GUIDE
SECTION TOPIC
I Introduction
II Educational Concepts - Mathematics
III Educational Concepts - Science
IV Educational Concepts - Communications
V* Field and Laboratory Equipment
VI* Field and Laboratory Reagents
VII* Field and Laboratory Analysis
VIII Safety
IX Records and Reports
*Training Guide materials are presented here under the headings marked*.
These standardized headings are used through this series of procedures
£12-15
-------
•H-,
WATER MONITORING PROCEDURES: Determination of Barium (Ba )
FIELD AND LABORATORY EQUIPMENT
Section V
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
D.4.1a
B.9.2
As acetylene (CgH2) is packed dissolved in acetone
(CH3COCH3), cylinders should be stored only in an
upright position. Acetone can be introduced into
the flame if the cylinder has been stored lying on
its side or if used below 75 psig. Acetone entrain-
ment usually produces a slight pink tinge and ab-
normally high background signals.
The use of a nitrous oxide-acetylene flame is
recommended for the determination of barium. This
flame virtually eliminates chemical interferences.
However, if nitrous oxide is not available an air-
acetylene flame can be used.
E12-16
-------
WATER MONITORING PROCEDURES: Determination of Barium (Ba
FIELD AND LABORATORY REAGENTS
Section VI
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
B.8
B.7
C.5
Barium is easily ionized in the nitrous oxide flame.
lonization will produce incorrect results. In order
to suppress the ionization effect potassium is added
to standard and sample alike. The concentration in
the standards and samples should equal 1000 mg
K/1000 ml of solution. For the concentration used
in the preparation, 2 ml of the potassium solution
should be added per 100 ml of standard or sample.
If the nitrous oxide flame is not availabe and the
acetylene-air flame is used, phosphate, silicon
and aluminum will severely depress the barium
absorbance. This may be overcome by the addition
of 2000 mg La/liter. This solution is prepared as
follows: Dissolve 58.65 g lanthanum oxide (La?0_)
in 250 ml of concentrated hydrochloric acid
(Caution: reaction is violent; use a hood). Dilute
to 500 ml volume. This solution contains 100 mg La/
ml. Add 2 ml of this solution to each 100 ml of
standard and/or sample. This gives a final con-
centration of 2000 mg La/1000 ml of solution.
£12-17
-------
WATER MONITORING PROCEDURES: Determination of Barium (Ba )
FIELD AND LABORATORY ANALYSIS
Section VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
F.3a
In order to comply with the quality control section
of the "Criteria and Procedures for Water Supply
Laboratory Certification," the minimum requirement
is to run a validation of the standard curve con-
sisting of at least a reagent blank and one standard
at or near the maximum contaminant level of
1.0 mg Ba/liter. This should be done daily or with
each batch of samples.
If 20 or more samples are run daily, the standard
curve must be verified by running an additional
standard of midrange every 20 samples.
All checks must be within +_ 10 percent of the
original curve. If not, a new standard curve must
be prepared.
The control recommended for water pollution analysis
as listed in the Handbook for Analytical Quality
Control in Water and Wastewater Laboratories is
to verify the standard curve by two standards, one
high and one low concentration.
Criteria and Procedures for
Water Supply Laboratory
Certification. Office of
Research and Development,
U.S. EPA, Washington, DC
20460.
Handbook for Analytical
Control in Water and
Wastewater Laboratories.
U.S. EPA Technology
Transfer, Cinti., OH 45268.
E12-18
-------
RESIDUAL CHLORINE AND TURBIDITY
I. INTRODUCTION
The Interim Primary Drinking Water Regulations (Federal Register, December 24,
1975) permits the options of substitution of up to 75 percent of the bac-
teriological samples with residual chlorine determinations. Any community
or non-community water system may avail themselves of this option with
approval from the State based upon results of sanitary surveys. Residual
chlorine determinations must be carried out at the frequency of at least
four for each substituted microbiological sample.
Since many potable water plants carry out their own microbiological deter-
minations, it will be necessary that these laboratories be certified for
the bacteriological parameters. Residual chlorine determinations may be
carried out by any person acceptable to the State and the analytical
method and techniques used must be evaluated in some manner to assure that
reliable information is obtained.
Since the presence of high turbidity can interfere with the disinfection
capability of chlorine, a maximum allowable limit has been set for turbidity
as follows:
A. One turbidity unit (TU) as determined by a monthly average except
that five or fewer turbidity units may be allowed if the supplier
of water can demonstrate to the State that the higher turbidity
does not
1. Interfere with disinfection,
2. Prevent maintenance of residual of disinfectant throughout
distribution system, or,
3. Interfere with microbiological determinations.
B. Five turbidity units based on an average of two consecutive days.
The Criteria and Procedures Document for Water Supply Laboratory Certifi-
cation suggests that some quality control guidelines be instituted for
the residual chlorine and turbidity measurements at the State level for
the purpose of ensuring data validity for these critical measurements.
In response to public comments regarding the proposed Primary Regulations
(Federal Register, December 24, 1975) it is stated that operators per-
forming residual chlorine and turbidity analyses "....be certified,
approved, or at least minimally trained to perform the analytical tasks
before a State could accept their analytical determinations...."
CH.TURB.3.9.77
E13.A-1
-------
II. RESIDUAL CHLORINE
Since residual chlorine analysis would be carried out in "field" conditions
or in the small laboratories of treatment plants, perhaps by unskilled
operators, it is necessary to keep the analytical method as simple as
possible. For a number of years, operators had utilized the orthotolidine
technique in a kit form to determine the chlorine residual. Recent
studies and regulatory guidelines have dictated against this test procedure.
The acceptable test procedure is-now the DPD Test (13th Ed., Standard Methods
for the Examination of Water and Nastewater. pgs. 129-132), for which kits
are available" fromat least two companies and which meet requirements for
accuracy and reliability. These kits are capable of measuring both free
and combined chlorine of which only the free chlorine is measured to meet
compliance requirements. Kit procedures call for a premeasured single
powder or tablet reagent added to the test cell with the sample and a
resultant color development measures by comparison the standardized colors
within one minute. Standard^ Methods includes cautions regarding temperature
and pH control regardfng "th~Ts~test parameter and this test procedure, the
DPD Test, is least effected by temperature and the pH is adjusted by the
added reagents. The only interfering substance, oxidized manganese, can
be determined in a preliminary step and compensated for in the final test
value.
III. TURBIDITY
Turbidity has long been used in the water supply industry for indicating proper
operational techniques. Turbidity should be clearly understood to be an ex-
pression of the optical property of a sample which causes light to be scattered
and absorbed rather than transmitted in straight lines through the sample.
The standard method for the determination of turbidity has been based on the
Jackson candle turbidimeter. However, the lowest turbidity value which can
be measured directly on the Jackson turbidimeter is 25 units which is well
above the monitoring level. Because of these low level requirements, the
nephelometric method was chosen and procedures are given in StandardMethods
(13th Ed., 1971).
IV. NEPHELOMETRIC MEASUREMENTS FOR COMPLIANCE MONITORING
The subjectivity and apparatus deficiencies involved in visual methods of
measuring turbidity make each unsuitable as a standard method.
Since turbidity is an expression of the optical property of scattering or
absorbing light, it was natural that optical instruments with photometers
would be developed for this measurement.
(1 6)
The type of equipment specified for compliance monitoring* '' utilizes
nephelometry.
A. Basic Principle^7'
The intensity of light scattered by the sample is compared (under defined
conditions) with the intensity of light scattered by a standard reference
solution (formazin). The greater the intensity of scattered light, the
greater the turbidity. Readings are made and reported in NTUs (Nephelometric
Turbidity Units).
E13.A-2
-------
B. Schematic
Lamp
I
LJ
Meter
Photoceli(s) fC
ns
1
1 r~
-1
/"''
, i
f •
furbidity P
^v/Scallei tig
\ «^
**
^
Sample Cell
(Top View)
Figure 2 NEPHELOMETER
(90° Scatter)
Light passes through a polarizing lens and on to the sample in a cell.
Suspended particles (turbidity) in the sample scatter the liqht.
Photocell (s) detect light scattered by the particles at a 90° angle to the
path of the incident light. This light energy is converted to an electric
signal for the meter to measure.
1. Direction of Entry of Incident Light to Cell
a. The lamp might be positioned as shown in the schematic so the
beam enters a sample horizontally.
b. Another instrument design has the light beam entering the sample
(in a flat-bottom cell) in a vertical direction with the photocell
positioned accordingly at a 90° angle to the path of incident light,
2. Number of Photocells
The schematic shows the photocell(s) at one 90° angle to the path of
the incident light. An instrument might utilize more than one photo-
cell position, with each final position being at a 90° angle to the
sample liquid.
3. Meter Systems
a. The meter might measure the signal from the scattered light in-
tensity only.
b. The meter might measure the signal from a ratio of the scattered
light versus light transmitted directly through the sample to a
photocell.
E13.A-3
-------
4. Meter Scales and Calibration
a. The meter may already be calibrated In NTLJs. In this case,
at least one standard is run in each instrument range to be
used in order to check the accuracy of the calibration scales,
b. If a pre-calibrated"scale is not supplied, a calibration curve
is prepared for each range of the instrument by using appropriate
dilutions of the standard turbidity suspension.
C. EPA Specifications for Instrument Design^ '
Even when the same suspension is used for calibration of different
nephelometers, differences in physical design of the turbldimeters will
cause differences in measured values for the turbidity of the same sample.
To minimize such differences, the following design variables have been
specified by the U. S. Environmental Protection Agency.
1. Defined Specifications
a. Light Source
Tungsten lamp operated at not less than 85% of rated voltage
and at not more than rated voltage.
b. Distance Traveled by Light
The total of the distance traversed by the incident light plus
scattered light within the sample tube should not exceed 10 cm.
c. Angle of Light Acceptance of the Detector
Detector centered at 90° to the incident light path and not to
exceed ± 30° from 90°.
(Ninety degree scatter is specified because the amount of scatter
varies with size of particles at different scatter angles).
d. Applicable Range
The maximum turbidity to be measured is 40 units. Several ranges
will be necessary to obtain adequate coverage. Use dilution for
samples if their turbidity exceeds 40 units.
2. Other EPA Design Specifications
a. Stray Light
Minimal stray light should reach the photocell(s) in the absence
of turbidity.
E13.A-4
-------
3.
Some causes of stray light reaching the photocell(s) are;
1) Scratches or imperfections in glass cell windows.
2) Dirt, film or condensation on the glass.
3) Light leakages in the instrument system.
A schematic of these causes is shown in Figure 3.
Photocell!*)
Light laokage from
Tronimitted tight
Light Scatter by glass lube
(Top View)
Figure 3 NEPHELOMETER
SOURCES OF STRAY LIGHT
Stray light error can be as much as 0.5 NTU. Remedies are
close inspection of sample cells for imperfections and dirt,
and good design which can minimize the effect of stray light
by controlling the angle at which it reaches the sample.
b. Drift
The turbidimeter should be free from significant drift after a
short warm-up period. This is imperative if the analyst is
relying on a manufacturer's solid scattering standard for setting
overall instrument sensitivity for all ranges.
c. Sensitivity
In waters having turbidities less than one unit, the instrument
should detect turbidity differences of 0.02 unit or less.
Several ranges will be necessary to obtain sufficient sensitivity
for low turbidities.
Examples of instruments meeting the specifications listed in 1 and 2
above include:
a. Hach Turbidimeter Model 2100 and 2100A.
b. Hydroflow Instruments DRT 100, 200, and 1000.
E13.A-5
-------
4. Other turbidimeters meeting the listed specifications are also
acceptable.
D. Sources of Error
1. Sample Cells
a. Discard scratched or etched cells.
b. Do not touch cells where light strikes them in instrument,
fo\
c. Keep cells scrupulously clean, inside and out. '
1) Use detergent solution.
2) Organic solvents may also be used.
3) Use deionized water rinses.
4) Rinse and dry with alcohol or acetone.
2. Standardizing Suspensions^ '
a. Use turbidity - free water for preparations. Filter distilled
water through a 0.45um pore size membrane filter if such filtered
water shows a lower turbidity than the distilled water.
b. Prepare a new stock suspension of Formazin each month,
c. Prepare a new standard suspension and dilutions of Formazin
each week,
3. Sample Interferences
a. Positive
1) Finely divided air bubbles
b. Negative
1) Floating debris
2) Coarse sediments (settle)
3) Colored dissolved substances
(absorb light)
E13.A-6
-------
E. Reporting Results^ '
NTU RECORD TO NEAREST
0.0-1.0 0.05
1-10 0.1
10-40 1
40-100 5
100-400 10
400-1000 50
>1000 100
F, Precision and Accuracy' '
1. In a single laboratory fEMSL), using surface water samples at
levels of 26, 41, 75 and 180 NTU, the standard diviations were
+0.60, +0.94, +1.2 and +4.7 units, respectively.
2. Accuracy data is not available at this time.
V. STANDARD SUSPENSIONS AND RELATED
One of the critical problems in measuring turbidity has been to find a
material which can be made into a reproducible suspension with uniform sized
particles. Various materials have been used.
A. Natural Materials
1. Diatomaceous earth
2. Fuller's earth
3. Kaolin
4. Naturally turbid waters,
Such suspensions are not suitable as reproducible standards because
there is no way to control the size of the suspended particles.
B. Other materials
1 . Ground glass
2. Microorganisms
3. Barium Sulfate
4. Lates spheres
Suspensions of these also proved inadequate.
E13.A-7
-------
Formazin
1. A polymer formed by reacting hydrazine sulfate and hexamethylenete-
tramine sulfate.
2. It is more reproducible than previously used standards. Accuracy
of + one percent for replicate solutions has been reported.
3. In 1958, the Association of'Analytical Chemists initiated a standard-
ized system of turbidity measurements for the brewing industry by:
a. Defining a standard formula for making stock Formazin solutions
and
b Designating a unit of measurement based on Formazin, i.e.i the
Formazin Turbidity Unit (FTU).
4. During the 1960's Formazin was increasingly used for water quality
turbidity testing. It is the currently recognized standard for
compliance turbidity measurements.
D. Units
1. At first results were translated into Jackson Turbidity Units (JTU).
However, the JTU was derived from a visual measurement using con-
centrations (mg/liter) of silica suspensions prepared by Jackson.
They have no direct relationship to the intensity of light scattered
at 90 degrees in a nephelometer.
2. For a few years, results of nephelometric measurements using specified
Formazin standards were reported directly as Turbidity Units (TUs).
3. Currently, the unit used is named according to the instrument used for
measuring turbidity. Specified Formazin standards are used to calibrate
the instrument and results are reported as Nephelometric Turbidity
Units (NTUs).
VI. SUMMARY
The importance of residual chlorine determination can be seen in its possible
effect on the health of the consumers. The Criteria and Procedures for
Laboratory Certification suggests that some form of quality assurance should
be instituted on a state level to assure valid data for both the chlorine and
turbidity measurements. The comments on the public responses to the proposed
Interim Primary Regulations also suggests some form of quality assurance on
the state level to be instituted. Consequently, the Regional Certification team
should point out to the principal laboratories the importance of some kind of
effort being instituted. States might wish to offer some kind of formal
training effort as part of the approval mechanism for the operators doing
the chlorine and/or turbidity measurements.
E13.A-8
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
MEASUREMENT OF FREE CHLORINE UTILIZING THE DPD KIT
as applied in
DRINKING WATER TREATMENT FACILITIES
and in the
DISTRIBUTION SYSTEMS OF DRINKING WATER TREATMENT FACILITIES
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.HAL.cl.lab.WMP.1.11.77
E13.3-1
-------
WATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing
the DPD Kit
1, Analysis Objectives:
The actual use of a kit form of the DPD method for chlorine is so simple
a procedure, it need not be written. However, the permanent standards,
whether liquid or solid, must be calibrated. This unit sets down a method
that can be used to accomplish this. The method is applicable to drinking
waters only for compliance purposes.
2. Brief Description of Analysis:
The kit usually contains a comparator which is a holder of sorts to support
the sample cell and the standard in such manner as to allow the operator to
see both colors and compare their intensities. The operator adds a single
reagent to the water to be analyzed. The color is formed immediately and
a comparison is made between the sample and standards.
3. Applicability of this Procedure:
a. Range of concentration - 0.0 to about 3.0 mg chlorine/liter or whatever is
the highest standard supplied with the kit.
b. Pretreatment - the sample may not be preserved; it should be run as soon
as possible or within one hour after being taken.
c. Treatment of Interferences in Samples: The procedure includes instructions
for the determination of the interference caused if oxidized manganes is
present. Other interferences are suppressed by the make-up of the reagents,
Source of this procedure: Standard Methods for the Examination of Water
and Wastewater, 13th ed., pp. 129-132 or 14th ed. pp. 329-334.
E13.B-3
-------
WATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing
the DPD Kit
Equipment and Supply Requirements
A. Capital Equipment:
Analytical balance capable of weighing to 0.1 mg (.0001 g) under
a 200 g load.
B. Reusable Supplies:
1. Chlorine Test Kit {DPD method) such as:
a. Model CN-66
Hach Chemical Company
PO Box 907
Ames, IA 50010
b. Model LP-1
LaMotte Chemical Products Company
Cbestertown, MD 21620
2. Eight beakers, 50 ml size
3. Two flasks, volumetric with stoppers, 1000 ml size
4. Ten flasks, volumetric with stoppers, 100 ml size
5. One pipet, volumetric, 100 ml size
6. One pipet, volumetric, 50 ml size
7. One pipet, volumetric, 20 ml size
8. Three pipets, volumetric, 10 ml size
9. One dropper bottle, 100 ml size
10. Two rubber stoppers - to fit comparator cells {if stoppers are not
supplied by manufacturer)
C, Consumable Supplies:
1. Distilled water, about 1 gal, or 3.8 liters
2. Graph paper, arithmetic, 10 x 10 divisions
3. Pencil or pen
4. Wash bottle, plastic squeeze type
5. Weighing boat, plastic, disposable
6. Potassium Permanganate (KMnO.)
7. Potassium Iodide Crystals (KI)
8, Sodium Arsenite (NaAsQ-)
9. DPD - Reagent (Usually a supply is provided with the kit.)
E13.B-4
-------
U'ATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing the DPD Kit
OPERATING PROCEDURES
STEP SFQUENCt
IilF(;RMATION/OPESATIf,5 COALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
A. Reagent Preparation
1. Stock Potassium
Permanganate
Solution
1. Weigh out 0.891 grams of
potassium permanganate
(KMN04).
2. Transfer the potassium
permanganate to a 1000 ml
volumetric flask,
3. Wash the weighing boat
4. Pour the washing into the
volumetric flask.
5. Repeat washing two more
times.
6. Add enough water to fill
the flask about half full.
7. Swirl until the potassium
permanganate is dissolved.
8. Dilute to the mark on the
volumetric flask.
9, Stopper and mix by re-
peated inversions.
la. Use an analytical balance.
lb. Use a plastic weighing boat.
3a. With distilled water.
3b. Use a plastic squeeze type wash bottle.
3c. The wash should be about 10 to 20 ml.
5a. The idea is to assure complete transfer of the
potassium permanganate into the volumetric flask,
Since potassium permanganate has a strong color,
wash until no color is seen in the weighing boat
containing water.
7a. If a magnetic stirrer is available, this can be
used to save time.
8a. There is a single ring etched around the neck of
the flask. When the flask is filled to this
mark, it will contain the volume stated on the
flask.
L13.B-5
-------
WATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing the DPD Kit
E13.B-6
OPERATING PROCEDURES
STEP SEQUENT
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
A. Reagent Preparation
(Continued)
2. Intermediate
Potassium
Permanganate
Solution
3. Standard Potassium
Permanganate
Solution
4. Potassium Iodide
Crystals
5. Sodium Arsenite
(NaAs02)
1. Transfer 10.00 ml of the
stock potassium permanga-
nate solution into a 100ml
flask.
2. Dilute to the mark with
distilled water.
3. Stopper and mix by re-
peated inversions.
1. Transfer 10.00 ml of the
intermediate potassium
permanganate solution to a
1000 ml volumetric flask.
2. Add distilled water to the
flask to the mark.
3. Stopper and mix by re-
peated inversions.
1. No preparation necessary.
1. Weigh out 0.500 grams of
sodium arsenite.
2. Transfer the sodium
arsenite to a 100 ml
volumetric flask.
la. Use a 10.0 ml volumetric pipet.
2a. Add water from a plastic squeeze bottle.
3a. This solution has a chlorine equivalent of
1.00 mg/1 in the DPD reaction.
la. Use a trip balance or an analytical balance.
Ib. Use a plastic weighing boat.
Ic. CAUTION: TOXIC - take care to avoid injestion.
-------
MATER MONITOR!N6 PROCEDURE: Measurement of Free Chlorine Utilizing the DPD Kit
OPERATING PROCEDURES
STEP SEQUENCE
I'lFCRMATION/OPEaATING COALS/SPECIFICATIONS
TRAINING
GUIDL NOTES
A. Reagent Preparation
(Continued)
6. Preparation of the
Standard Series
3. Rinse the weighing boat.
4, Add the rinses to the
volumetric flask.
5. Add enough distilled water
to fill the flask about
half full.
6. Swirl until the sodium
arsenite is dissolved.
7. Dilute to the mark on the
volumetric flask.
8. Stopper and mix by re-
peated inversion.
9. Transfer to a dropper
bottle, and label.
1. Prepare a series of dilu-
tions of the standard
potassium permanganate
solution in 100 ml
volumetric flasks.
3a. With distilled water.
3b. Use a plastic squeeze bottle.
7a. There is a single ring etched around the neck of
the flask. When the flask is filled to this
mark, it will contain the volume stated on the
flask.
9a. Label "Sodium Arsenite."
la. The series should contain several concentrations
below and above the expected values.
Ib. The expected value for drinking water would be
near 0.2 mg/1 of free chlorine.
Ic. The series can be prepared as follows:
E13.B-7
-------
E13.B-8
WATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing the DPD Kit
OPERATING PROCEDURES
A. Reagent Preparation
(Continued)
B. Calibration of the
Kit Standards
STEP SEQUENCE
1. Fill the reference tube
with distilled water.
2. Rinse the sample cell with
the water to be tested.
3. Fill the cell with the
water to be tested to the
mark.
4. Add the manufacturer's
DPD reagent.
INFORMATION/OPERATING GOALS/ SPECIFICATIONS
Col. 1
ml of
Std. KMnO.
0
10
20
30
40
50
70
100
Col. 2
ml of
Water
100
90
80
70
60
50
30
0
Col. 3
Cone.
Cl"
mg/I
0.0
0.1
0.2
0.3
0.4
0.5
0.7
1.0
Col
. 4
Comparator
Values
mg C
a
r/i
b
Col. 5
*~ Avg. Value
a + b
2 mg/1
la. Not all kits have a reference tube.
Ib. Follow the manufacturer's directions for per-
forming a test with their comparator.
2a. In this case, one of the standards.
2b. Read from low to high on the
3a. Most kits have a line around
series.
the tube. This
indicates a calibrated volume. The cells should
always be filled to this mark.
4a. This is usually in the form of a powder or a
tablet.
4b. This reagent contains both the DPD indicator
and the buffer as prescribed
in the DPD method
In the "Standard Methods" references.
TRAINING
GUIDE NOTES
-------
WATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing the DPD Kit
OPERATING PROCEDURES
STEP SEQUEhCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Calibration of the
Kit Standards
5. Stopper the cells.
6. Mix by inversion.
7. Place cell in comparator.
8. Hold comparator up to the
light.
9. Obtain a match between
color in cell and
standard.
10. Record the value obtained
from the comparator.
11. Discard the solution.
12. Rinse the cell with the
next standard to be run.
13. Discard.
14. Fill to the line with the
next standard.
15. Repeat steps 4 through 11
for al1 standards.
16. Rinse the tube with the
first standard read.
5a. Most manufacturers provide stoppers. If not,
procure two rubber stoppers. The diameter of
the tubuler cells varies so check the size needed
6a. One inversion will do.
8a. Rotate disc and/or compare color in tube with
the standard colors.
9a. Where the comparator has only specific values
such as 0.2, 0.4, 0.6, etc. If the color is not
an exact match the mid-point value between the
two closest colors is used.
lOa. Along with the known concentration
16a. The entire series should be read again to obtain
a second value.
16b. The values should be recorded in Column 4 of
Table A.6.1c.
E13.B-9
-------
WATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing the DPD Kit
E13.B-10
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
Calibration of
Kit Standards
(Continued)
the
C. Interference
Determination
17. Fill with solution.
18. Add the reagent.
19. Obtain a value.
20. Repeat steps 16-19 for the
remaining standards.
17a. Do not add more water or standard.
19a. Steps 5 through 9.
20a. By comparing standards of known concentrations to
the sealed/permanent visual standards and plot-
ting a comparison on graph paper, a correction
factor can be derived and applied to all future
results obtained on the now calibrated apparatus.
?0b. This calibration should be carried out at least
every 6 months and checked by running one or two
concentrations whenever new reagent (powder or
pill) is purchased.
1. Fill the reference tube
with the clear water to be
tested.
2. Rinse the sample tube with
the water to be tested.
3. Discard this rinse.
4. Fill the cell to the mark
with sample.
5. Add one small crystal of
potassium iodide.
6. Add one drop of sodium
arsenite solution.
7. Stopper the tube and mix
by inverting several
times.
la. This procedure must be carried out until it is
determined that the interference is not present,
then this section may be omitted.
4a. Do not overfill; the reagents are based on this
volume.
6a. Reagent 5.
-------
HATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing the DPD Kit
OKRATING PROCEDURES
STEP
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Interference
Determination
(Continued)
D. Sample Analysis
8. Unstopper and add the
manufacturer's reagent.
9. Stopper and mix by
inversion.
10. Place cell in comparator.
11. Hold comparator up to the
light.
12. Match any red color in the
sample with the standard.
13. Record the value.
14. Subtract this value from
the value obtained in
section D.
1. Fill the reference tube
with the clear water to be
tested.
2. Rinse the sample tube with
the water to be tested.
3. Discard this rinse.
4. Fill with water to be
tested.
5. Add the reagent.
6. Stopper and mix by
inversion.
8a. This is the DPD reagent and buffer.
14a. Step D.10.
la. If a reference tube is used in the kit.
4a. Fill to the mark on the tube. Do not over fill;
the reagents are based on this volume.
E13.B-11
-------
MATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing the DPO Kit
E13.B-12
OPERATING PROCEDURES
0. Sample Analysis
(Continued)
E. Calculations
STEP SEQUENCE
7. Insert into the comparator
8. Hold the comparator up to
the light.
9. Match the color developed
in the sample with the
standard colors.
10. Check the calibration
graph.
1. Average the values ob-
tained for each standard.
2. Record averages in
Column 5.
3. Plot the known value
(Column 3) vs. the average
in Column 5.
INFORMATION/OPERATING GOALS/SPECIFICATIONS
IQa. If no deviation has been noted, the concentration
can be determined directly from the comparator.
la. Use the formula at the top of Column 5 in
Table A.b.lc.
3a. Use an arithmetic paper.
3b. See example paper attached.
TRAINING
GUIDE NOTES
-------
c
\- -
_100
i / i "> 6m IQ • i
oo
" O
^*
^
• -CNJ
-------
WATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing
the DPD Kit
DPD KITS
The DPD N.N-diethyl-p-phenylene diamine method was chosen because it is a
relatable test and there is a test kit for it. It is specifically mentioned
in the comments to the Interim Primary Drinking Water Regulations (p. 59580),
The kit can be used for many of the forms of chlorine. However, the only
form which must be measured and reported is the free chlorine. The kit
requires the addition of a solid reagent to the sample, mixing and comparison
of the reading with standard colors, the color generated by the free chlorine
and the DPD reagent is formed immediately.
Any kit using the DPD reagent is acceptable for the measurement. Both the
Hach Chemical Company and the LaMotte Chemical Company make kits that can
be used.
The permanent color standards provided with the kit should be calibrated
initially and thereafter periodically to assure correct readings are obtained,
These kits are not to be used to monitor chlorine under the permit system
for the National Pollutant Discharge Elimination System (NPDES). This kit
is approved only for analysis of chlorine in drinking waters under the
National Interim Primary Drinking Water Regulations.
E13.B-14
-------
WATER MONITORING PROCEDURE: Measurement of Free Chlorine Utilizing
the DPD Kit
TRAINING GUIDE
SECTION TOPIC
I Introduction
II Educational Concepts - Mathematics
III Educational Concepts - Science
IV Educational Concepts - Communications
V Field and Laboratory Equipment
VI Field and Laboratory Reagents
VII* Field and Laboratory Analysis
VIII Safety
IX Records and Reports
*Training Guide materials are presented here under the headings marked*.
These standardized headings are used through this series of procedures.
F13.B-15
-------
WATER MONITORING PROCEDURES:
Measurement of Free Chlorine Utilizing
the DPD Kit
FIELD AND LABORATORY ANALYSIS
Section VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
C.I.la
The only interfering substance likely to be en-
countered 1n water is oxidized manganese. Conse-
quently an operator should determine If this
interfering substance is present or not. If not,
the procedure may be omitted. If it is present,
the procedure must be carried out prior to each
determination.
E13.B-16
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
DETERMINATION OF TURBIDITY
as applied in
WATER AND WASTEWATER FACILITIES
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.TURB.lab.WMP.1.11.77
E13.C-1
-------
WATER MONITORING PROCEDURE: Determination of Turbidity
1. Analysis Objectives:
The user of the attached material will learn how to use a nephelometric
type turbidimeter to measure the turbidity of a sample.
2. Brief Description of Analysis:
The method is based upon a comparison of the intensity of light scattered
by the sample under defined conditions with the intensity of light scattered
by a standard reference suspension. The higher the intensity of scattered
light, the higher the turbidity.
A person using this outline should have the basic skills used in a laboratory
such as:
a. Preparation of standards
b. Use of volumetric glassware
3. Applicability of this Procedure:
a. Range - From 0 to 40 nephelometric turbidity units or with appropriate
dilutions higher than 40 units.
b. Pretreatment of Samples - The sample should be run as soon as possible.
Preservation is not recommended.
c. Treatment of Interferences - (1) Floating debris should be removed before
analysis, (2) air bubbles should be allowed to dissipate before reading,
(3) with finished waters no other interferences are noted.
Source of Procedure: Methods for Chemical Analysis of Water and Wastes, 1974,
Environmental Protection Agency, Office of Technology Transfer, Cincinnati,
Ohio 45268. Page 295.
E13.C-3
-------
WATER MONITORING PROCEDURE: Determination of Turbidity
Equipment or Supply Requirements
A. Capital Equipment:
1. Turbidimeter, Nephelometrie - see list of acceptable instruments meeting
the following criteria:
a. Light source - Tungsten lamp operated at not less than BS% of rated
voltage or more than rated voltage.
b. Distance traveled by incident light and scattered light within the
sample tube: total not to exceed 10 cm.
c. Angle of light acceptance of the detector: centered at 90° to the
incident light path and not to exceed + 30° from 90°.
d. Maximum turbidity to be measured: 40 units.
Acceptable Instruments*
- Hach Model 2100
Model 2100 A
- HF Instruments
Model DRT- 15
-100
-150
-200
Hach Chemical Co., 713 S. Duff Ave.,
PO Box 907, Ames, IA 50010
HF Instruments, ltd.* 105 Healey Rd.,
Bolton, Ontario, Canada
- Turner Model 40-002 (for drinking water) Turner Designs, 2247A Old Middlefield
40-005 (for waste waters) Way, Mountain View, CA 94043
• Bausch & Lomb - An attachment for their "Spectronic mini 20" Spectrophotometer.
This can be obtained from any company that sells Bausch and Lomb
Spectrophotometers,
2. Trip balance (or platform) or analytical balance: with 0.01 gram
sensitivity
3. Distillation equipment - all glass still or ion exchange cartridges
4. Standard Turbidity Suspensions (optional) - if none supplied with the
Instrument
B. Reusable Supplies:
1. One brush, bottle
2. One flask, side arm filtering, 500 ml size
3. Six flasks, volumetric, 100 ml size with stoppers
4. One funnel, membrane filter funnel and holder
5. Two pi pets, volumetric, 5 ml size
Three pipets, volumetric, 10 ml size
6. Pipet bulb
7. Wash bottle, squeeze type, 500 ml
+Also sold by: Fisher Scientific Co., 711 Forbes Ave., Pittsburgh, PA 15219
*This list is not meant to be complete. It covers those known by the author
at the time of writing this material.
E13.C-4
-------
WATER MONITORING PROCEDURE: Determination of Turbidity
C. Consumable Supplies:
1. Distilled water
2. Detergent
3. Membrane filters, 0.45 micron pore size
4. Tissues
5. Weighing boats, plastic disposable, about 12
6. Reagents
Hexamethylenetetramine, reagent grade - can be purchased from:
J. T. Baker Chemical Co. Cat. No. N145
Fisher Scientific Cat. No. H289
MC/B or Sargent-Welch Cat. No. HX-0280
A. H. Thomas Co. Cat. No. C389
Hydrazine Sulfate, Reagent grade - can be purchased from:
J. T. Baker Cat. No. 2177
Fisher Scientific Cat. No. H-320
MC/B or Sargent-Welch Cat. No. HX-0575
A. H. Thomas Co. Cat. No. C393
E13.C-5
-------
MA1ER MONITORING PROCEDURE: Determination of Turbidity
E13.C-6
OPERATING PROCEDURES
A. Glassware
1. Volumetric
2. Cells
B. Sample Pre-treatment
STEP SEQUENCE
1 . Wash with brush and
detergent.
2. Rinse with tap water.
3. Rinse with turbidity free
water.
1. Rinse with tap water.
2. Rinse with turbidity free
water.
3, Handle and dry with soft
tissue.
1. Measure turbidity as soon
as possible after
sampl ing.
INFORMATION/OPERATING GOALS/SPECIFICATIONS
la. The glassware used for the formaline preparation
may have some polymer adhering to the glass.
Consequently, the brush should be used to clean
this off.
la. Use care in handling the cells at all times Do
not touch them where the light strikes them.
Ib. Consult the instrument manual to determine the
area where the light strikes the cells. In Hach
instruments, it is the bottom of the cell; in
the DRT and Turner, it is the side of the cell.
2a. See section C.I .
la. Preservation of samples is not recommended.
Ib. Within one hour.
TRAINING
GUIDE NOTES
ifii.B.i
Sp- 21)
-------
WATER MONITORING PROCEDURE: Determination of Turbidity
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
1. Turbidi ty Free
Water
2. Hydrazine Sulfate
Solution
1. Read the turbidity of the
distilled water.
2. Filter a quantity of
distil led water.
3. Read the turbidity of the
filtered water.
4. If the filtered distilled
water shows a lower tur-
bidity value, treat all
water used in this pro-
cedure by filtration.
1. Weigh out 1.00 grams of
hydrazine sulfate.
2. Transfer the hydrazine
sulfate to a 100 ml
volumetric flask.
3.
4.
Swirl the flask until
hydrazine sulfate has
dissolved.
the
Dilute with water to the
100 ml mark.
la. Use directions under "Sample Analysis" Section.
2a. Filter using a vacuum membrane filter apparatus
like that used in the membrane filter technique
for bacteriological analysis.
2b. The membrane filter should have a pore size of
0.45 micrometer.
4a. If the values are the same, use the distilled
water without filtration.
4b. Check the distilled water periodically by fil-
tration to assure absence of turbidity.
la. A trip balance can be used.
Ib. Use a plastic weighing boat.
2a. Use a plastic wash bottle and rinse the weighing
boat with distilled water.
2b. Add the washings to the volumetric flask.
2c. Rinse three times with about 15 mi's of water.
E13.C-7
-------
WATER MONITORING PROCEDURE: WATER MONITORING PROCEDURE
E13.C-8
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPE .WING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
3. Hexamethylenetetra
mine Solution
4. Stock Turbidity
Suspension
(400 units)
1. Weigh out 10.00 grams of
hexamethy1enetetramine.
2. Transfer the hexamethy lene-
tetramine to a 100 ml
volumetric flask.
3. Dilute to the mark with
distil led water.
1. Pipet 5.0 ml's of the
hydrazine sulfate solution
into a 100 ml volumetric
flask.
2. Pipet 5.0 ml's of the
hexamethylenetetramine
solution into the same
100 ml volumetric flask.
3. Mix by swirling the flask.
4. Stopper.
5. Allow to stand 24 hours.
6. Remove the stopper.
7. After standing, dilute to
the 100 ml mark.
8. Stopper.
la. A trip balance can be used.
Ib. Use a plastic weighing boat.
Ic. Also called Methenamine.
2a. Use a plastic distilled water wash bottle and
rinse the weighing boat three times.
2b. Add the washings to the volumetric flask.
2c. Each washing should be about 15 mi's.
la. Use a 5 ml volumetric pipet.
Ib. Always pipet with a pipet bulb. These chemicals
are toxic.
2a. Use a second 5 ml volumetric pipet.
5a. The temperature should be between 22°C (72°F) and
28°C (82°F).
5b. The formazine polymer forms during this time.
7a. With distilled water.
-------
KATER MONITORING PROCEDURE: Determination of Turbidity
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C, Reagent Preparation
(Continued)
5. Standard Turbidity
Suspension
(40 units)
6, Standard Turbidity
Suspension
(4 units)
9. Mix well.
1. Mix the stock suspension
wel 1.
2. Pipet 10 ml of the stock
turbidity suspension into
a 100 ml volumetric flask.
3, Dilute to the TOO ml mark.
4. Stopper and mix well.
1. Mix the 40 unit standard
thoroughly.
2. Pipet 10 ml of the 40 unit
standard into a 100 ml
volumetric flask.
3. Dilute to the mark.
4, Stopper and mix.
9a. Invert the flask several times while holding the
stopper in.
9b. This suspension has 400 turbidity units.
9c. This suspension can be kept (when stoppered) for
one month,
la. This material will settle out rapidly.
2a. Use a 10 ml volumetric pipet.
2b. Pipet with a pipet bulb.
3a. With distilled water,
4a. This suspension is defined as 40 turbidity units.
4b. This suspension can be kept (when stoppered) for
one week.
4c. Never pour the suspension back into the flask
after use.
la. By inverting the stoppered flask.
2a. Use a 10 ml volumetric pipet.
2b. Use a pipet bulb.
3a. With distilled water.
4a. This suspension contains 4 turbidity units.
4b. This suspension can be kept (when stoppered) for
one week.
4c. Never pour the suspension back into the flask
after use.
E13.C-9
-------
WATER .MONITORING PROCEDURE: Determination of Turbidity
E13.C-1Q
OPERATING f'FCCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Reagent Preparation
(Continued)
7. Standard Turbidity
Suspension
(0.4 units)
D. Instrument
Calibration
5. Label the volumetric flask.
1. Mix the 4 unit standard
thoroughly.
2. Pipet 10 ml of the 4 unit
standard into a 100 ml
volumetric flask.
3. Dilute to the mark.
4. Stopper and mix.
la. By inverting the stoppered flask.
2a. Use a 10 ml volumetric pipet.
2b. Use a pipet bulb.
3a. With distilled water.
4a. This suspension contains 0.4 turbidity units.
4b. This suspension can be kept (when stoppered) for
one week.
4c. Never pour the suspension back into the flask
after use.
5. Label the volumetric flask.
1. Check the meter needle to
see that it is on the
zero mark.
2. If it is not, zero it by
turning the small screw
located on the meter
frame.
3. Turn on the power switch.
la. This is done before the instrument is turned on.
V.D.I
(p. 20)
3a. This will sometimes be a separate switch or the
instrument is turned on by moving the range
selector switch to one of the ranges.
-------
HATER MONITORING PROCEDURE: Determination of Turbidity
OPERATING PROCEDURES
STEP SEQUENCE
IMFCRMATION/OPERATING GOALS/SPECiKICATIONS
TRAINING
GUIDE NOTES
D. Instrument
Calibration
(Continued)
4. On battery powered in-
struments, check the
batteries.
5. Allow sufficient warm-up
time.
6. Set the range selector
on the 0-1 scale.
7. Shake the 0.4 unit
standard suspension.
8. Wait until large air
bubbles disappear.
9. Pour into cell.
10, Wipe the cell sides and
bottom with a soft tissue.
11. Insert the cell into cell
compartment.
12. Cover cell compartment.
4a. All battery powered instruments have a battery
check position.
4b. See the manufacturer's manual.
5a. This time will vary with the type instrument.
Follow the manufacturer's manual.
5b. Line operated instruments should be left on if
they are to be used regularly.
7a. Leave the stopper in place and invert gently
several times.
8a. Oo not wait too long or suspension will settle,
usually only several seconds.
9a. With the Hach instruments the volume must be 25 ml
+ 1 ml, On other instruments the volume is not
as critical so long as the cell is filled to about
3/4 of its total volume.
9b. Take care when handling the cell. Do not touch
the bottoms of the Hach cells or the lower half
of other type cells. Handle all cells by holding
the top edges.
Ida. Take care that it is not scratched.
la. Handle near the top section only.
V.D.10
(p. 20)
E13.C-11
-------
E13.C-12
WATER MONITORING PROCEDURE: Determination of Turbidity
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Instrument
Calibration
(Continued)
13. Allow instrument to
stabilize.
14. Turn reference adjust knob
until the 0.4 mark is
reached.
15. Turn the range adjust
switch to the 0-100
scale.
16. Uncover cell compartment.
17. Remove standard suspension
18. Wipe off sides and bottom
of the manufacturer's
standard with a soft
tissue.
19. Insert the manufacturer's
reference suspension.
20. Cover the cell compartment
21. Turn range adjust switch
to 0-1 scale.
22. Allow the instrument to
stabilize.
23. Read the turbidity.
13a. Usually in less than one minute.
13b. Stabilization is attained when the needle no
longer drifts.
I4a. The meter faces vary in how they are marked off.
The user will have to determine which mark repre-
sents 0.4 units.
15a. This step will keep the meter needle from bouncing
off the ends of the meter scale.
15b. May be termed the xlO scale.
17a. Handle near the top of the container.
17b. Retain this standard for future use.
19a. If more than one, use the suspension that is
nearest to 0.4 units.
19b. Handle near the top section only.
V.D.19a
(p. 20)
23a. If a discrepancy with the expected reading exists,
take note of this reading and proceed.
-------
U'ATER MONITORING PROCEDURE: Determination of Turbidity
OPERATING PRCCLDURES
SEQUENCE
INFGRMATION/CPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Instrument
Calibration
(Continued)
24. Turn the range switch to
the 0-100 scale.
25. Uncover cell compartment.
26, Remove manufacturer's
standard,
27. Shake formazine standard.
28. Wipe with tissue.
29, Insert into cell
compartment.
30. Cover compartment,
31. Allow instrument to
stabilize.
32, Turn range switch to 0-1
scale.
33, Read the turbidity.
27a, The standard used in step 11.
63b.
If it still reads 0.4 units, there is a dis-
crepancy between the formazine and the manufac-
turer's standard. Note should be taken of how
much and whenever the manufacturer's standard is
used to calibrate the instrument, this discrepancy
should be added or subtracted from its value.
If it no longer reads 0.4, use the reference ad-
just knob and recalibrate by turning the reference
adjust knob until the 0.4 mark is reached. Then
repeat these steps beginning at step 15.
Rinse the cell with the next material to be read.
When finished, rinse with turbidity free water.
Store as manufacturer suggests.
E13.C-13
-------
HATER MONITORING PROCEDURE; Determination of Turbidity
L13.C-14
OPERATING PROCEDURES
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Instrument
Calibration
(Continued)
E. Sample Analysis
34, The formazine standards
should be used at least
once/week to monitor
manufacturer's standard
for change.
35. For future calibration of
the 0-1 scale, the manu-
facturer's standard can be
used.
35a. Taking care to allow for any discrepancy noted
in step 33.
35b. All ranges on the instrument must be calibrated
in this same manner.
1. Turn on the instrument.
2. Allow warm up time.
3. Check batteries.
4. Fill a cell with the
sample.
5. Wipe side and bottom of
cell.
6. Allow bubbles to disperse.
7. Set the range selector
on 0-100 scale.
8. Insert cell into cell
compartment.
9. Cover the cell compartment
3a. If the instrument is battery operated.
4a. Fill about three fourths of the capacity.
6a. A light tapping with a finger will speed up
this procedure.
-------
UATIR MONITORING PROCEDURE: Determination of Turbidity
OPERATING PROCEDURES
STEP SEQUENCE
INrtRMATinN/OFEPATIKG GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E, Sample Analysis
(Continued)
10. Select the range that will
keep the sample's reading
on scale and read the
turbidity.
11. Note which scale is used.
lla.
Ib.
12. Set range selector on 0-10C
range.
13. Uncover cell compartment.
14, Remove sample.
15. Select a manufacturer's
standard.
16. Wipe off side and bottom.
17. Insert into cell
compartment.
18. Cover cell.
19, Allow instrument to
stabilize.
20. Select range used in
step 10,
If the value is greater than 40 units, the sample
must be diluted before it can be read.
All samples below 40 units should be read on the
scale that gives the greatest movement of the
meter needle and remains on scale.
5a.
Depending on the manufacturer, the standard could
be a simple standard or a set of standards.
Choose the standard that will be in the same range
as the sample.
E13.C-15
-------
MATER MONITORING PROLLDiM,: Determination of Turbidity
E13.C-16
OPERATING r
E. Sample Analysis
(Continued)
HI, Adjust reference adjust
knob until standard's
value is obtained.
2?. Turn range selector to
0-100 scale.
23. Uncover cell compartment.
24. Remove standard.
25. Insert the cell containing
the sample.
26. Cover the cell compartment
27. Set scale on range used in
step 10 and 20.
28. Allow instrument to
stabilize.
29. Read turbidity,
30. Repeat steps 15 through ?0,
31. Turn range selector to
0-100 scale.
32. Uncover cell compartment.
33. Remove eel 1.
KATri:, GOALS/SPECIFICATIONS
21a. Make any change of standard concentration found
necessary in step D.33.
25a. Care should he taken not to touch the cell except
at the top. If it has been touched anywhere
else, wipe the cell off.
30a. If the instrument has drifted, from the value set
in step 21, recalibrate by adjusting the reference
adjust knob and reread the samples turbidity,
beginning at step 21.
TRAINING
GUIDE NOTES
-------
HATER MONITORING PROCEDURE; Determination of Turbidity
OPERATING PROCEDURES
STEP SLQttNCL
INFQSMATION/OPiRATI !\G GOALS/SPEC IFI CAT IONS
TRAINING
GUIDE NOTES
E. Sample Analysis
(Continued)
F, Calculations
34, Insert next sample or if
no more samples are to be
read, continue on,
35. Cover compartment.
36. Turn off instrument.
37. Wash out cells with
turbidity free water.
38. Dry cells with soft
tissue.
39. Store cells as manufactur-
er recommends.
34a.
36a,
1. Calculate the turbidity
of the sample.
la,
Ib,
If more samples are to be analyzed, repeat
steps 4-10, checking for instrument drift by
checking standardization occasionally.
If line operated, leave power on if instrument
is to be used within a reasonable time.
Calculation is necessary only where the sample
was above 40 units and had to be diluted.
If no dilution was performed, then the turbidity
of the sample is read directly from the face of
the meter.
IX.F.Zc
(p. 22)
E13.C-17
-------
MATER •••QKITQ_R!N_G PROCEDURE: Determination of Turbidity
E13.C-18
OPERATING PhCCLL-URES
S1EP SCQUFNCt
GCALS/SPLCIFICATIONS
TRAINING
GUIDL NOTES
F. Calculations
(Continued)
2. Multiply scale reading
times the dilution
factor.
3. Report the results.
2a. That is A x (B+C)
C
Where B = volume of turbidity free water used
to dilute the sample (mi's)
C = the volume of sample used (mi's)
A = the turbidity units of the dilution
read on the meter scale
2b, Example:
If 2 rnl's of sample were diluted to 10 mi's with
turbidity free water and the dilution had a
scale reading of 30 units, then
A = 30
B = 8
C = 2
x 30 = 150 turbidity units (TU's)
3a. Report as follows:
TURBIDITY RANGE
NTU or TU
0-1.0
1-10
10-40
40-100
100-400
400-1000
>1000
RLCORD TO THE
NEARESTNTU or TU
0.05
0.1
1
5
10
50
100
-------
WATER MONITORING PROCEDURE: Determination of Turbidity
TRAINING GUIDE
SECTION TQPJX
I Introduction
II Educational Concepts - Mathematics
III Educational Concepts - Science
IV Educational Concepts - Communications
V* Field and Laboratory Equipment
VI Field and Laboratory Reagents
VII* Field and Laboratory Analysis
VIII Safety
IX* Records and Reports
*Training Guide materials are presented here under the headings marked*.
These standardized headings are used through this series of procedures.
E13.C-19
-------
WATER MONITORING PROCEDURES: Determination of Turbidity
FIELD AND LABORATORY EQUIPMENT
Section V
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
D.I
D.10
D.19a
Calibration of any nephelometric turbidimeter should
be done using the standard turbidity suspensions
prepared as described in the Reagent Preparation
Section. Many manufacturers provide secondary
standards with purchase of these instruments. It is
well to check this by comparing it to a dilution of
the standard turbidity suspension.
Since the maximum contaminant level is usually one
turbidity unit, dilutions of the standard turbidity
suspension should be made and calibration of the
instrument carried out on the scale near this value.
However, each scale of the turbidimeter and each
secondary standard should be calibrated against the
standard suspension (formazine).
The sample cells to be used with the instruments
must be of clear colorless glass. They should be
kept scrupulously clean both inside and out, and
discarded when they become scratched or etched.
Some manufacterers claim scratched cells are not a
problem, however, this should be verified. They
must not be handled at all where the light strikes
them, and should be long enough so that they may be
handled by the top.
This procedure will calibrate the 0-1 scale and
those standards provided by the manufacturer that
can be read on that scale. If other scales are to
be used, insert a standard suspension (fonnazine)
that was made up in the Reagent Preparation Section
that can be read on the scale of interest and set
the reference adjust knob to the value.
El 3.C-20
-------
WATER MONITORING PROCEDURES: Determination of Turbidity
FIELD AND LABORATORY ANALYSIS
Section VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
B.I
Turbidity is one of the parameters classed as a
health limit in the Interim Primary Drinking Water
Regulations. Public water systems are required to
measure for turbidity daily. The consents to the
Interim Primary Regulations (p. 59581) indicate
that turbidity measurements were intended to be
carried out by the operators of the public water
system. This intent was due to the fact that
preservation of the sample was not possible.
The location at which the sample is to be taken is
listed in the Interim Primary Regulations as the
point of entry to the distribution system.
E13.C-21
-------
WATER MONITORING PROCEDURES: Determination of Turbidity
RECORDS AND REPORTS
Section IX
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
F,2c
The faces of the meters are labeled as NTU, TU and
FTU. These are:
NTU - Nephelometric Turbidity Units
TU - Turbidity Units
FTU - Formazine Turbidity Units
These units are considered as being the same,
Express all values obtained as TU's for drinking
waters and as NTU's for wastewaters.
E13.C-22
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE ANALYTICAL PROCEDURES
for the
DETERMINATION OF CHLORINATED HYDROCARBON PESTICIDES
as applied in
POTABLE WATER TREATMENT FACILITIES
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.PES.lab.WMP.l .11 .77
E20-1
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
Operational Procedures
A. Glassware
B, Reagent Preparation
C. Instrument Set-up
1. Gas Connection
2, Detector Installation
3. Leak Check
4. Column Conditioning
D. Instrument Calibration
E. Standardization of the Sodium Hydroxide
F. Florisil Preparation
1. Laurie Acid Value Determination
2. Testing for Proper Elution Pattern
G. Sample Extraction
1. Pretreatment
2. Extraction
3. Concentration
H. Sample Clean-up
I. Sample Analysis
J. Calculations
E20-3
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
1. Objective:
To determine the concentration of the chlorinated hydrocarbons, as listed
in the Interim Primary Drinking Water Regulations, in water samples.
2. Description of the Analysis:
A measured water sample is extracted with an organic solvent. This
chlorinated hydrocarbon containing solvent is then concentrated to a
volume of 1 ml. A small volume (10 yl) is injected into a gas chromato-
graph and the amount of chlorinated hydrocarbon present is quantitated.
Should there be interferences presents a method is given to separate the
chlorinated hydrocarbon from the interferences. The equations for cal-
culating the pi/liter concentration of chlorinated hydrocarbon are given.
This method is recommended for use only be experienced pesticide analysts
or under the close supervision of such qualified persons.
The person attempting to use this outline should have a basic knowledge of
gas chromatography. Among these skills should be
a. proper injection technique
b. proper quantisation technique of the peaks
c. knowledge of retention times and relative retention times
d. basic knowledge of the theory and operation of a gas chromatograph
e. basic chemical skills, such as pipetting, solution preparation, etc.
3. Applicability of this Procedure:
a. Range of Concentration
Many of the chlorinated hydrocarbons can be detected at .001 nig/liter
quantities. Of those listed in the Interim Primary Drinking Water
Regulations, Lindane, Endrin and Methoxychlor can be determined at this
level. Using the concentration inherent in the procedure this level can
be lowered. Toxaphene, also listed in the Interim Primary Regulations, can
be determined but is somewhat more difficult.
b. Pretreatment of Samples
Upon collection of the sample temperature should be lowered to 4-° C with
ice and maintained at this temperature until analyzed. The maximum holding
time is 14 days.
E20-4
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
3, Applicability of this Procedure (Continued)
c. Treatment of Interferences
This outline includes a clean-up procedure involving separation on a
Florisil Column, Inclusion of method blanks during all runs will
indicate interferences due to impure solvents and reagents.
Source of Procedure: "Method for Organochlorine Pesticides in Industrial
Effluents, EMSL, National Environmental Research Center, Cincinnati, Ohio
45268."
E20-5
-------
Detm .
Det. Limit
Extract
Sample
Inject
Sample
Compare with
Std, Curves
P re pa re
Elution Column
Detm. Laurie
Acid Value
Elute
Sample
Inject
Eluates
Calc.
Cone.
If no interf.
calc. cone.
E20-6
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
Equipment and Supply Requirements
A. Capital Equipment:
1. Gas Chromatograph equipped with
a. Glass lined injection port
b. Electron capture detector - tritium or nickel 63
c. Recorder - potentiometric strip chart (10 in - 25 cm) compatible
with the detector
2. Gas Chromatographic Column (best purchased from gas chromatographic supply house)
a. Tubinq - Pvrex (180 cm lonq (6 ft.) x 4mm ID)
b. Glass Wool - Silanized
c. Solid Support - Gas Chrom Q (100 - 120 mesh)
d. Liquid Phase - Expressed as weight percent coated on solid support
1) OV-1, 3%
2) OV-210 5%
3) OV-17/1.5% plus QF-1, 1.95%
4) QF-1, 6% plus SE-30, 41
3. Hot Water Bath - Capable of keeping temperature at 50° - 100° C
4. Source of high quality distilled water
5. Rotometers - If the instrument is not equipped with meters to monitor
the flows of gases, these should be purchased as options
6. Analytical Balance - With a 0.1 milligram sensitivity
7. Trip or Platform Balance - With a 0.1 or 0.01 gram sensitivity
8. Oven - Capable of maintaining 130° C
9, Stop Watch - Capable of measuring at least 1/2 hour, the 60 second cycle
divided to 1/5 second
10. Cylinder of Argon-methane (95 + 5%) for use with pulsed mode detector OR
Nitrogen - Purified grade, moisture and oxygen free, for use with a DC
mode detector
11. Pressure Regulator - Two stage with a CGA 580 fitting for Nitrogen or a CGA
350 fitting for Argon-methane
12. Filter - For carrier gas - molecular sieve type
13. Micro Syringes - 5, 10, 50 ul sizes
14. pH Meter - With pH electrode
E20-7
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
Equipment and Supply Requirements (Continued)
15. Magnetic Stirrer with Teflon coated bar
16. Oven (optional) - Forced air capable of heating to 400° C
17. Trap - for oxygen
B. Reusable Supplies:
1.
2.
3.
4.
5.
10.
11
12,
13.
Beaker, 150 ml - One for
Beaker, 500 ml - One for
Buret, 10 ml graduations
Buret, 25 ml graduations
each sample - duplicate
each sample - duplicate
- One
- One
blank
blank
Chromatographic Column - Chronaflex (400 mm long x 19 mm ID) vnth coarse
fritted plate on the bottom and Teflon stopcock and a 250 ml reservoir
bulb at the top of the column with a flared out funnel shape at the top
of the bulb, (special order Kontes Glass - K-420540-9011) - One for each
sample - duplicate - blank
6. Chromatographic Column - Pyrex (about 400 mm long x 20 mm ID) with coarse
fritted plate on bottom - One for each sample - duplicate - blank
7. Cylinders, graduated
10 ml - One
50 ml - Three
100 ml - Two
250 ml - Two
1000 ml - One
8. Dropper Bottle, with dropper, 75 ml - One
9. Flasks, Erlenmeyer
25 ml, glass stoppered
125 ml, glass stoppered
glass stoppered
glass stoppered
, glass stoppered
volumetric
Five
Three
One
- Two
- One
- One
- One
for each sample - duplicate - blank
250 ml,
500 ml,
1000 ml,
Flasks,
10 ml -
100 ml -
500 ml - Three
Funnels, Separatory, with Teflon stopcock, 200 ml - One for each sample -
duplicate - blank
Glassware, Kuderna-Danish (K-D), order
a. Concentrator Tube, 10 ml calibrated,
Size 1025
b. Snyder Column, three ball, 150 mm long, #K503000, Size 121
c. Snyder Column, one ball, 150 mm long, #K5690Q1, Size 1/19
d. Flask, 500 ml volume, #K570001
e. Stoppers for flask, f Size 19/22, #K850500
One for each sample - duplicate - blank
Pipets, graduated
1 ml - Two
10 nl - One
from Kontes Glass Company
f joint 12/22 female, IK570050,
E20-8
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
Equipment and Supply Requirements (Continued)
14. Pipets, volumetric
1 ml - One
5 ml - One
10 ml - Two
20 ml - One
15, Reagent Bottles, glass, glass stoppered
100 ml - One
500 ml - Four
1000 ml - One
16, Ring stand with ring and clamp and base - One for each sample - duplicate -
blank
17. Ruler, divided in millimeters, about 30 cm long
18. Stirring Rod, glass, 12 in, long
19. Safety Glasses
20. Bottle, glass, wide-mouth, with glass stopper, 500 ml - One
21 Desiccator
C. Consumable Supplies;
1. Alcohol, ethyl, U.S.P. or absolute, neutralized to phenolphthalein (see
Reagent Preparation Section)
2. Ethyl ether, Nanograde, pesticide quality
3. Florisil, PR Grade (60-100 mesh), purchase activated at 1250° F. Store
in the dark in glass containers
4. Hexane, Nanograde, distilled in glass
5. Laurie Acid, purified, CP
6. Methylene Chloride, Nanograde, distilled in glass
7. Pesticide Standards, reference grade
8. Petroleum Ether, (boiling range 30-60° C) Nanograde (98+ % pure)
9. Phenolphthalein Indicator
10, Soap Solution, any liquid soap mixed 1:1 with water
11. Sodium Hydroxide, ACS
12. Sodium Sulfate, ACS, Granular, anhydrous
13. Sulfuric Acid, ACS
14. Distilled Water
15. Weighing Boats, plastic disposable
16. Chart Paper, for the recorder
17. Notebook, bound
18. Paper, graph
E20-9
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-10
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
A. Glassware Preparation
B. Reagent Preparation
1. Ethyl Ether (6%)
in Petrn]ptm
1. Clean all Glassware.
2. Wash with soap and water.
3. Rinse with tap water.
4. Rinse with distilled water
5. Muffle at 400° C for 15 to
30 m1n.
6. Cool to room temperature.
7. Store until used.
3a. At least 10 times,
4a. At least 10 times.
5a. Volumetric glassware should not be muffled.
5b, Plastic ware and cap liners for sample containers
should not be muffled.
5c. The glassware may be rinsed with redistilled
acetone followed by a rinse with pesticide
quality hexane in place of the muffling.
7a. Store inverted or cover mouth with aluminum foil.
7b. Sample containers should be stored capped.
1. Use caution with this
solvent.
2. Add about 100 ml of
petroleum ether to a 250
ml graduated cylinder.
3. Pipet 12 ml of ethyl ether
into the graduated
cylinder.
4, Dilute to 200 ml with
petroleum ether.
la. Prepare and use in a well ventilated area.
Ib. Prepare just before use.
4a. In the graduated cylinder.
-------
MATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURE:
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
Reagent Preparation
(Continued)
2, Ethyl Ether (151)
in Petroleum Ether
3. Alcohol - Ethyl
Neutralized to
Phenolphthalein
4. Phenolphthalein
Indicator
5. Mix with a long glass
stirring rod.
1. Use the above directions
except in Step 3, pipet
30 ml of ethyl ether.
1. Measure 500 ml of alcohol
into a 1 liter Erlenmeyer
flask.
2. Add 3 drops of phenol-
phthalein indicator.
3, Titrate with 0.05 N Sodium
Hydroxide until a pale red
color is obtained.
4. Store in glass stoppered
reagent bottle.
1. Weigh out 1,0 g of the
Phenolphthalein indicator.
2. Transfer to a 100 ml
volumetric flask,
3. Dissolve in about 50 ml
ethyl alcohol.
4. Dilute to the mark with
distilled water.
5a. Do not store this solution.
immediately.
Prepare and use
la. For water supply monitoring for the pesticides
listed in the Interim Primary Regulations only
the 6^ and 15% should be needed. However, if
wastewaters are being monitored a 50% eluate will
have to be prepared and used.
Ib. Do not store this solution.
la. Use a trip balance.
E20-11
-------
WATLR MONITORING PROCEDtR!"- Determination of Chlorinated Hydrocarbon Pesticides
L20-i2
OPERATING PROCEDURES
INFCRMATiON/OPtkAI J.V3 GQALi/SPLOU ICATIONS
TRAINING
GUIDE NOTES
B, Reagent Preparation
(Continued)
5. Laurie Acid
Solution (2% W:V)
6. Methylene Chloride
(IBS) in Hexane
(V:V)
1. Weigh out 10.000 g of
lauric acid.
2. Add about 250 ml hexane to
a 500 ml volumetric flask.
3. Transfer the lauric acid
into the 500 ml volumetric
flask.
4. Wash the weighing container
with several small portions
of hexane and add to the
volumetric flask.
5. Dissolve the lauric acid.
6. Dilute to the mark with
hexane.
7. Mix thoroughly.
8. Store in a glass stoppered
bottle.
1. Add about 200 ml hexane
to a 500 ml graduated
cyl inder.
2. Measure 75 ml of methylene
chloride.
3, Add the methylene chloride
to the hexane.
la. Use an analytical balance.
2a. Just add hexane to the volumetric flask until
half full.
6a. 1 ml =20 nig lauric acid.
2a. With a graduated cylinder.
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
!. Reagent Preparation
(Continued)
7. SuIfuric Acid
(HS0) 1:1 (V:V)
8. Sodium Hydroxide
(NaOH) 10 N
4. Dilute to the mark with
hexane.
5. Mix.
6, Store in a glass, qlass
stoppered bottle.
1. Add about 25 ml of
distilled water to a 100
ml volumetric flask.
2, Measure 50 ml concentrated
sulfuric acid in a 100 ml
graduated cylinder.
3. Add the sulfuric add to
the volumetric flask.
4. Dilute to the mark.
5. Cool.
6. Check to assure the volume
is still on the mark.
7, Store in a glass stoppered
bottle.
1. Weigh out 40 g of Sodium
Hydroxide.
2, Measure 100 ml of water.
2a. Caution: Use safety glasses.
2b, Do not add water to acid; follow the procedure.
3a. The solution will get hot; cool to room tempera-
ture before proceeding.
4a. With distilled water.
6a. If not, add water to mark.
la. Use a trip balance.
Ib. Weigh out in a 250 ml Erlenmeyer flask.
2a. In a graduated cylinder.
E20-13
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-14
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
i. Reagent Preparation
(Continued)
9. Sodium Hydroxide
(NaQH) 1.0 N
10. Sodium Hydroxide
(NaOH) (0.05 N)
3. Add the water to the
Erlenmeyer flask.
4. Swirl to dissolve.
5. Stopper the flask with
a rubber stopper and
label.
1, Weigh out 20 g of sodium
hydroxide,
2. Transfer the NaOH to a 500
ml Erlenmeyer flask.
3. Measure 500 ml of water,
4. Add the water to the
Erlenmeyer flask.
5. Swirl to dissolve.
6. Stopper the flask with a
rubber stopper and label.
1. Add about 250 ml distilled
water to a 500 ml
volumetric flask.
2. Transfer 25 ml of the 1.0 N
NaOH to the volumetric
flask.
3a. The solution will get hot; cool under cold water.
3b. Use safety glasses.
4a. Do not stopper and invert to mix.
4b. Use a stirring rod or magnetic stirrer and
Teflon coated bar.
5a. Do not stopper unless cool,
la. Use a trip balance.
Ib. Weigh out in a plastic weighing boat.
3a. Us? a 500 ml qraduated cylinder.
4a. The solution will get hot; cool under
cold water.
4b. Use safety glasses.
5a. Do not attempt to stopper and mix by inversion,
use a stirring rod or a magnetic stirrer and
Teflon coated bar.
6a. Do not stopper unless cool.
2a, Use a 25 ml volumetric pi pet.
-------
WATER MONITORING PROCEDURE; Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP
IflFCRK-'JlON/OPESATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
8. Reagent Preparation
(Continued)
11. Sodium Sul fate
3. Dilute to the mark,
4. Mix thoroughly.
5. Store in a glass, rubber
stoppered, bottle.
1. Weigh out 1.0 gram of the
sodium sulfate.
2. Add enough methylene
chloride - Hexane
(Reagent 6) to cover the
sodium sul fate.
3. Mix.
4. Decant reagent.
5. Inject 10 pi of the solvent
into the gas chromatograph.
6. If contaminated proceed as
below,
7. Weigh out about 100 g of
sodium sulfate in a 500 ml
beaker.
8. Place beaker and sodium
sulfate in an oven.
9. Heat the sodium sulfate
for 4 hours at 400° C.
la.
Ib.
Use a trip balance.
Weigh in a 150 ml beaker.
4a.
5a.
Take care not to include any sodium sulfate.
After retention times and optimization have been
determined.
Contamination is shown peaks of 1 times the
noise level are obtained.
6a
7a. Use a trip balance, weigh in the beaker.
8a. The oven should be preheated to 400° C.
E2Q-15
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-16
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
12. Pesticide Standards
10. ReTOve from oven and place
in a desiccator and allow
to cool.
11. Transfer to a wide-mouth
glass stoppered bottle.
12. Store in the bottle in a
desiccator.
1. Consult Tables 1 and 2
lOa. Use tongs to handle the hot beakers.
lOb. Be sure the desiccant is activated.
la. In order to properly calibrate the instrument
both qualitatively (Retention Values) and
quantitatively (Detection Limits) single
standard and a mixture containing all the
pesticides of interest should be made.
Ib. The amount weighed out to each compound was
kept at 10 mg in order to have a weight which
could be accurately weighed yet using the
smallest amount of compound possible.
Ic. After weighing out 10 mg and preparing 10 ml of
the stock solution of each pesticide, proceed
toward the right of the table and make two
dilutions as directed.
Id. Use Table 2 for preparing two mixtures. Mixture
1 is used to prepare the column. Mixture 2
will be used to determine the standard curves.
I.B.12
-------
DIRECTIONS FOR DILUTION TABLE
In order to properly calibrate the instrument both qualitatively (Retention
Values) and quantitatively (Detection Limits) a single standards and a mixture
containing all the pesticides of interest should be made.
The amounts weighed out of each compound was kept at 100 mg in order to have
a weight which could be accurately weighed yet using the smallest amount of
compound possible.
After weighing out and diluting the stock solution of each pesticide, proceed
toward the right of the chart. Making dilutions as directed.
Use Table 2 for preparing two mixtures. Mixture 1 is used to prepare the
column. Mixture 2 will be used to determine the standard curves.
E20-17
-------
TABLE 1
E20-18
Compound
Lindane
Endrin
Methoxychlor
Aldrin
Toxaphene
Stock
10 mg
10 ml* ;
10 mg
100 ml* 1
10 mg
10 ml** 1
i
1
10 mg
10 ml*
10 mg ;
10 ml* ;
Dilution 1
4 ml stock
100 ml**
2 ml stock
100 ml**
1 ml stock
1 100 ml**
1 ml stock
100 ml**
5 ml stock
1 100 ml**
Cone, mg/1
;
1
40
i
20 |
i
10 j
10
50 j
1
Dilution 2
i
1 ml Oil. 1
100 ml
1 ml Oil. 1
100 ml
None
1 ml Oil. 1
100 ml
1 ml Oil. 1
100 ml
Cone, mg/1
0.4
0.2
None
0.1
0.5
i
* Make stock solutions in 2.2.4 Trimethyl pentane (Isooctane)
** Use hexane for all dilutions of the stock.
-------
TABLE 2
Use Hexane for all dilutions
Compound
Lindane
Endrin
Methoxychlor
Aldrin
Toxaphene
Add to th
Amount ml .
1 .0
1.0
1.0
1.0
1.0
Mixture 1
e same 5 ml vo
Dilution Ho.
Stock
Stock
Stock
Stock
Stock
. flask
Cone, mg/1
200
200
200
200
200
Add ti
Amount ml .
1
1
1
1
1
Mixture 2
3 the same 100 ml vol .
Dilution No.
1 (40 mg/1)
1 (20 mg/1)
Stock (1000 mg/1)
1 (10 mg/1)
1 (50 mg/1)
flask
Cone, mg/1
0.4
0.2
10.0
0.1
0.5
E20-19
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-20
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERAT ING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Instrument Set-up
1, Gas Connection
2. Detector
Installation
3. Carrier Gas Leak
Check
1. Remove cylinder cap from
cylinder of carrier gas.
2. Install the pressure
regulator.
3. Connect the cylinder to
the instrument.
1. Install the electron
capture detector.
1. Open master valve on the
cylinder,
2. Adjust regulator control,
3. Close carrier gas control
valve on the instrument.
4. Turn off master cylinder
va1ve.
la. The tank should be chained to the wall or lab
bench.
Ib. Use Argon-methane for pulsed mode detector or
Nitrogen for detector operated in a DC mode.
Consult the manufacturer's manual.
2s. The regulator should have a CGA 350 fitting
for Argon-methane or for Nitrogen.
2b. Fitting should be tight to a CGA 350 fitting
to prevent leaks.
3a. Use teflon tape on all metal threads to prevent
leaks.
3b. Polethylene (1/8" diameter) tubing can be used.
3c, If plastic tubing is used, nylon ferrules
should be used with the connector fittings.
la. This can be of the tritium or nickel 63 type.
Ib. See the manufacturer's manual on procedures for
installation.
2a. To about 65 psig and allow to stabilize (about
1 minute).
V.C.I
(p- 45)
-------
WATERMONITOR!NG PROCEDURE.: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STLP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Instrument Set-up
(Continued)
4. Column
Conditioning
5. Observe gage on the
cylinder.
6. Use soap solution and
check for leaks at the
injection port and column
connections.
1. Install packed column in
the oven by connecting
only the column inlet.
5a. Pressure should not drop more than a few psig.
5b. If the pressure does drop use soap solution to
locate leak.
5c. Correct leak and check again.
2. A flow of carrier gas
should be started through
the detector.
3. Begin a low flow of
carrier gas through the
column.
4. Wait 5 minutes.
la. These columns should be purchased and meet the
specifications as listed under the equipment
section.
Ib. Column conditioning is essential to eliminate
column bleed and to provide acceptable analysis.
Ic. Do not connect the column to the detector.
Id. If in doubt as to column installation refer to
the manufacturer's manual.
2a. Use the purge gas line or in dual column oven
by connecting an unpacked column to the detector,
2b. In some systems it may be necessary to
temporarily connect the carrier gas to the air
or hydrogen inlet in order to get a flow to the
detector. The manufacturer's manual should be
consulted.
3a. Less than 60 ml/min.(N40-50).
3b. Removes oxygen and other trapped gases.
3c. This will be two separate flows. The column
should not be connected to the detector.
E20-21
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP SEQUENCE
If,FORMAT10N/CP£?ATING GOAL^/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Instrument Set-up
(Continued)
5. Turn on power to the oven
6. Adjust column temperature
to near the maximum re-
commended temperature for
the liquid phase being
used.
7. Continue heating for
2 hours,
8. Reduce temperature to
about 40° C below
maximum temperature.
9- Allow column temperature to
equi1ibrate.
10. Check carrier gas flow.
5a. Consult manufacturer's manual for location and
necessary steps.
6a.
Column
Max. Temp.
0 C
OV-17 & QF-1 250
OV-210 275
OV-1 350
QF-1 & SE-30 250
8a. See table above (6a).
9a. Minimum of 3C minutes.
9b. Caution: Bleed off of the liquid phase will
occur if the column temperature is not fully
equilibrated.
lOa. About 50 ml/nrin.
lOb. If the instrument does not come equipped with
rotometers to monitor the flow rate of the
carrier gas this should be purchased as an
option.
lOc. The pressure regulator on the cylinder should
be set at 65 psig.
lOd. The electron capture detector must be installed,
II. Allow to remain at
temperature and flow for
one hour.
v.c.e.b
(p. 45}
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP SLQUEfiCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Instrument Set-up
(Continued)
12. Increase temperature to
about 20° C above
operating temperature.
13, Continue the same flow of
carrier gas.
14. Allow to equilibrate for
24-48 hours.
15. Turn off oven and allow
to cool to room
temperature.
16. Adjust carrier gas flow to
method flow rate.
17. Connect column to the
detector.
18, Turn on oven and adjust to
method column temperature.
19. Allow the instrument to
equilibrate at least one
hours.
12a. This is operation temperature not maximum
temperature.
12b. These temperatures would be
200° C for the OV-17 and qF-1 and the
QF-1 & SE-30
OR
200° C for the OV-210 and the OV-1.
14a. Caution: Do not exceed maximum recommended
temperatures. See 6a. this section.
16a. 60 rnl/min. for the OV-17 & QF-1 and QF-1 & SE-30.
70 ml/min. for the OV-210 and OV-1.
17a. Check connection with soapy solution.
18a. 200° C for the OV-17 & QF-1 and the QF-1 & SE-30,
180° C for the OV-210 and the OV-1.
19a. Preferably overnight.
E20-23
-------
MATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-24
OPERATING PROCEDURES
STEP SEQ'JENCt
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Instrument
Calibration
1. Optimization
2. Retention Time
Determination
1. Check instrument operating
conditions after the
instrument has been set-up
2. Inject 5 ul of standard
mixture 2.
3. Adjust the operating
parameters to achieve
optimum results.
1. Inject 5 yl of dilution
2 (Table 1) of the
standards one at-a-time.
la. The oven temperature should be stabilized.
Ib. The flow rate constant.
Ic. The column conditioned.
Id. The flow system checked for leaks.
2a. This standard mixture was prepared from the
stock standards (Table 2).
2b. The actual volume of material injected should be
kept constant. That is, the same for standards
and samples.
2c. The standard mixture 2 can be used to optimize
the instrument initially and thereafter monitor
its performance.
3a. Best resolution (separation of peaks) and
retention times can be achieved by adjusting
the column temperature and/or the carrier gas
flow rate.
3b. Compare results with the standard chromatograms
attached.
3c. Caution should be taken to allow the instrument
to equilibrate after any changes.
3d. Optimum results would include good separation of
the peaks, good sensitivity, good reproducibility,
la. The individual standards lindane, endrin,
methoxychlor, aldrin, and toxaphene should be
used.
Ib. Dilutions of the individual standards can be
prepared from the stock solutions as in Table I.
Ic. Injection is a technique which must be learned
and practiced in order to make accurate and
reproducible injections.
Id. The analyst should consult a text on gas
chromotography or a syringe manufacturer's
1iterature.
V.D.1.3a
(p. 45)
VII.D.4
(p. 46)
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Instrument
Calibration
(Continued)
3. Detection Limit
of the Instrument
2. With a stop watch measure
the time elapsed between
the first appearance of
the solvent peak and the
peak of the known
standard.
3. Repeat steps 1 and 2 six
more times.
1 . Inject 5 ul of a single
pesticide standard.
Continue with each standard
by diluting the last
standard concentration
run in half and injecting
5 ul portions unti1 a
detection limit is obtainec
The peak height in milli-
meters should be used and
plotted against the known
concentrations to produce
a standard curve.
2a.
2b.
This time is called the retention time.
After the retention times have been obtained
using single standards, the mixtures should
be used to determine that no changes in retention
time occur.
3a.
At least 7 repeat times should be obtained and
the mean value obtained for each pesticide.
3b. If in subsequent injections, the retention times
vary significantly (+ 2%) the system should be
checked over.
la. Begin with Dilution 2, Table 1 of each.
Ib. The standards need not be carried through
the extraction and concentration steps to
develop a standard curve.
2a. The detection limit is usually considered as a
standard whose peak is 2 times the highest peak
caused by noise and is run at the most sensitive
setting of the instrument.
3a. The curve produced can be used to select the
concentration of standard to be injected to
calculate the concentration of an unknown. See
calculation of results section.
3b. To select the concentration to be used to
calculate the unknown, first note the peak height
of the unknown. Second refer to this standard
curve and find a concentration which gave the
same peak height and inject it into the
instrument. This should provide a standard
very close to the sample peak height to use in
the calculations.
V.D.3.2
(p. 45)
E20-25
-------
WATER MONITORING PROCEDURE!: Determination of Chlorinated Hydrocarbon Pesticides
E20-26
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Standardization of
Sodium Hydroxide
F. Florisil Preparation
1. Laurie Acid Value
Determination
1. Weigh out TOO mg of lauric
acid.
2. Quantitiatively transfer
to a 125 ml Erlenrneyer
flask.
3. Dissolve with 50 ml
ethyl alcohol.
4, Add 3 drops phenolphthaiein
5. Titrate with (0.05 M)
sodium hydroxide.
6. Calculate mg lauric acid/
ml 0.05 fl NaOH.
la. On an analytical balance.
3a. Neutralized to phenolphthalein (See B.3).
5a. See reagent section for preparation.
5b. Until a pink color persists.
6a. ma lauric acid
ml of" 0.05 t; JiaOH =
100 mg Jaurjc acid
number of ml needed
to titrate (from Step 5]
6b. See calculation section J.I for use.
1. Place 2.000 grams of
Florisil in a 25 ml glass
stoppered Erlenmeyer flask.
2. Cover the flask loosely
with foi1.
3. Heat overnight at 130° C.
4. Stopper and cool to room
temperature.
la. Weigh on an analytical balance,
VII.F.I
(p. 46)
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPLRATiNG PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Florisil Preparation
(Continued)
5, Remove stopper and add
20.0 ml of lauric acid
solution (reagent 5).
6. Stopper the flask.
7. Swirl intermittently for
15 minutes.
8. Allow the florisil to
settle.
9. Pipet 10.0 ml of the
supernatant into a 125 ml
Erlenrneyer flask.
1C. Add 5C ml ethyl alcohol.
11. Add 3 drops of
phenolphthalein indicator,
12. Titrate with 0.05 N NaOH
to a permanent red color.
13. Calculate the amount of
lauric acid absorbed by
the florisi1.
Sa, Use a 20 ml volumetric pi pet.
7a. A gentle swirling of the flask is sufficient.
7b. This is to assure contact of the florisil with
the lauric acid solution.
9a. Use a 10 ml volumeteric pi pet.
9b. Supernatant is the clear liquid standing above
the settled absorbent.
9c. Avoid inclusion of any florisil.
lOa. Neutralized to phenolphthalein.
lOb. See reagent section for preparation.
lla. The solution should remain colorless.
12a. Those individuals not familiar with procedures
for titration should consult a procedure on the
use of a buret.
13a. The calculation will be found under the
calculation section of this procedure.
13b. This lauric acid value must be obtained for each
new batch of florisil purchased. Then an
equivalent weight of the new batch can be
calculated to obtain values similar to the old
batch.
E20-27
-------
WATER MONITQRINS PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
£20-28
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPE PAT ING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Florisil Preparation
(Continued)
2. Testing for Proper
Elution Pattern
14. Store the rest of the
florisil.
1. Weigh out the determined
amount of florisil.
2. Pour the florisil into the
chroma tographic column.
3. Tap the column lightly to
settle the florisil and to
level its surface.
4. Add about one-half inch
of sodium sulfate to the
top of the florisil in
the column.
5. Add 40-50 ml of petroleum
ether to the top of the
column.
6. Time and rate of passage
of the petroleum ether
through the column.
7. Remove the container used
to collect the petroleum
ether.
14a. In glass bottle with glass stopper kept in the
dark in an oven at 130C C,
la. Determined from the 1 auric acid value of the
batch of fIon'si 1.
Ib. Usually about 10 to 15 grams.
Ic. See the calculation section (J.2).
2a. The column should meet the specifications listed
in the equipment section.
3a. The column should not be packed so tight as to
impede solvent flow.
4a. This should be the anhydrous, granular, ACS grade
4b. Should be pre-conditioned by heating at 400° C
for four hours (See B.ll).
5a. This is used to pre-wet the column.
5b. The column may generate heat as it is wet by the
solvent. Let cool to room temperature before
proceeding,
5c. This solvent can be collected in any type of
container and need not be saved.
6a. This elution rate should be set at about 5 ml
per minute.
6b. Use a 10 ml graduated cylinder and a stopwatch.
7a. This should be done while a small level of
solution is still above the sodium sulfate
layer.
VII.F.2
(p. 46)
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERA:ING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Florisil Preparation
(Continued)
8. Place a clean 500 ml K-D
flask equipped with a 10
ml graduated ampul under
the column,
9. Just prior to the exposure
of the sulfate layer to
the air add 10 ml of
mixture 2.
10. Rinse container with 10 ml
of petroleum ether.
11, Add 200 ml of the 6« ethyl
ether in petroleum ether
solution.
12. Collect the 200 ml
13. Add 200 ml of the 15% ethy
ether-petroleum ether
solution,
14. Immediately replace the
500 ml K-D flask with
another clean one.
8a. Some portion of the petroleum ether will be
collected.
8b. K-D is a Kuderna-Oanish.
9a. See the reagent preparation section (B.12, Table
2).
9b. The sulfate surface should not be allowed to dry
between additions of the mixture and the
following eluates.
lOa. Add the rinse to the column.
lla. Measure in a graduated cylinder.
lib. If prepared just prior to use by the directions
given in the reagent preparation section, only
200 ml will be prepared and can be completely
transferred to the column.
lie. Add small portion slowly to bring liquid level
to the top of the florisil column then add the
rest.
12a. Close the column's stopcock before the sulfate
layer is exposed to the air.
E20-29
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
[20-30
OPERATING PROCEDURES
STEP SEQUENC!
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Florisil Preparation
(Continued)
15. Collect the 151 eluate.
16. Just prior to the sulfate
layer being exposed add
200 ml of ethyl ether.
17. Immediately replace the
500 ml K-D flask with
another clean one.
18. Collect the ethyl ether
elution.
19. Insert a Snyder column
into each flask.
20. Concentrate each elution.
21. Remove the flask from the
ampul .
22. Rinse the walls of the
ampul .
23. Stopper the ampul.
15a,
16a.
There will be a small overlap; in this case a
small portion of the 6% will be collected in the
15% flask. Again close the stopcock to prevent
exposure of sulfate layer to the air.
For wastewater or if other pesticides are to be
monitored other than those listed in the Interim
Primary Regulations, a 50% ethyl ether in
petroleum ether elution would be carried out
at this time followed by the straight ethyl
ether elution.
203,
21a,
22a.
22b.
Use the procedure under sample concentration, G.3,
1 through 6.
Rinse bottom of flask and lower glass joint into
the ampul.
Rinse to a final volume of 10 ml.
Use a 5.0 cc glass syringe.
-------
HATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STLP StgbENCE
HiFORMATIO'.'/OPF.SATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Florisil Preparation
(Continued)
24. Inject 5 pi of the
fractions.
25. Compare retention times
with standards run in
Section D.5.
G. Sample Extraction and
Concentration
1. Pre-Treatment
2. Extraction
1. Blend the sample.
2. Adjust pH to 6.5 - 7.5
1. Measure out 1 liter of
sample.
2. Transfer to a 2 liter
separatory funnel.
24a. The pattern will be 6K eluate
Aldrin-Lindane-Methoxychlor-Toxaphene, 15% eluate
Endrin, Ethyl ether and anytning left on the
column.
25a. If agreement is not attained, check the instrument
operational parameters (Section D.I).
la. This is usually not required for drinking waters.
2a. Use 50?t sulfuric acid or 1.0 N sodijm hydroxide.
2b. Use a pH meter to measure the pH.
2c. Usually not necessary for drinking waters.
la. Use a 1 liter graduated cylinder.
Ib. Experience witn tie sample source will indicate
if smaller volumes should be used. If smaller
volumes are used they should be diluted to 1
liter volume before extraction.
Ic. A 1 liter volume of distilled water should be
carried through the entire procedure along with
each sanple batch to serve as a metnod blank.
Id. The standard mixture 2 to be used as a check on
the curve (D.3.3) must also be carried through
this procedure.
le. Duplicate analysis of the samples are recommended
to be carried out.
If. Surface waters sometimes require larger volumes.
2a. Use a 2 liter size in order to have room to
obtain proper mixing.
VII.G.2.If
6)
(P.
E20-31
-------
MATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-32
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
G. Sample Extraction and
Concentration
(Continued)
3. Add 60 ml of the methylen«
chloride-hexane mixture
(Reagent 6) to the
separatory funnel.
4. Shake vigorously for two
minutes.
5. Return to holder and allow
mixtures to separate.
6. Prepare the anhydrous
sodium sulfate column.
7. Remove the stopper from
the separatory funnel.
8. Drain the water layer into
a one liter Erlenmeyer
flask.
3a. Use the 60 ml to rinse the sample container (if
empty) and the graduated cylinder.
4a. Pressure may build up in the separatory funnel.
Invert, with stopper tightly in place, open
stopcock slowly to relieve pressure, do this
several times during shaking.
5a. The water layer will be on the bottom and the
methylene chloride - hexane on top.
5b. The holder is some type support, such as a ring
clamped to s ring stand.
6a. Add 3 to 4 inches of anhydrous sodium sulfate to
the chromatographic column (Pyrex, approximately
400 mm long x 20 mm I.D. with a coarse frit on
the bottom).
6b. The column should be placed in a support such as
a clamp attached to a ring stand.
6c. Position the bottom of the column well into the
neck of a 500 ml Kuderna-Danish flask with a 10
ml graduated ampul attached to the stand.
6d. The sodium sulfate should have been heated at
400° C for four hours in an oven (Section B.ll).
8a. Keep the water layer for further extractions
-------
MATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
G. Sample Extraction and
Concentration
(Continued)
9. Pour the organic
(methylene chloride-
hexane) layer into the
sodium sulfate column.
10, Collect the organic layer
after it has passed
through the column in a
500 ml Kuderna-Danish
(K-D) flask with a 10 ml
ampul attached,
11. Return the water phase to
the separatory funnel,
12. Rinse the Erlenmeyer flask
with a second 60 ml
portion of the methylene
chloride-hexane solvent.
13. Transfer the second
portion of the methylene
chloride-hexane solvent
to the separatory funnel.
14. Put stopper in place.
15. Shake vigorously for two
minutes.
16. Repeat steps 5 and 7
through 11.
9a. Pour from the top of the separatory funnel.
9b. Use a funnel at the top of the column to help
transfer sample into column.
15a. Release pressure periodically.
16a. Step 6 does not have to be done again. Use the
same column.
16b. Collect the second organic layer (methylene
chloride-hexane) in the same K-D flask.
E20-33
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-34
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
G. Sample Extraction and
Concentration
(Continued)
3. Concentration
17. Perform the extraction
procedure with a third
portion of the methylene
chloride-hexane solution,
18. Rinse the sodium sulfate
column three times with
10 ml volumes of
methylene chloride-hexane.
1. Insert a condenser into
the K-D flask.
2. Place K-D flask in a
holder above a boiling
water bath.
3. Add small boiling chip.
4, Lower the ampul into the
water.
17a. Steps 12 through 17.
17b. All three 60 ml organic extraction portions are
combined in the K-D flask.
18a. Collect in the K-D. flask.
la. Condenser - Snyder column - three ball
4a. The water level should be maintained below the
lower joint (where the ampul connects to the
flask). The lower rounded surface of the flask
should be bathed in steam.
4b. Surrounding the flask with aluminum foil will
help.
4c. The evaporation must not go to dryness. The
analyst should stay with the flask.
Water
- -
Level
-------
UATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP SEQUENCE
If.'FORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDL NOTES
G. Sample Extraction and
Concentration
(Continued)
5. Allow the solvent to
evaporate.
6. Concentrate to about 1 ml
volume.
7. Remove from the bath.
8. Remove the three ball
condenser from the flask.
9. Rinse the lower joint of
the column into the ampul.
10. Insert a micro Snyder
column (one ball) into the
ampul.
11. Return to the water bath.
12. Boil and reduce the volume
to about 0.2 to 0.5 ml.
13. Cool .
14. Remove the micro column.
5a. Evaporation should be adjusted so that the
solvent vapors are rushing through the condenser.
5b. Carry out the evaporation in a hood.
5c. There should be no splashing at the top of the
column or flooding of the chambers.
6a. This will be in the ampul. However, after
cooling solvent that has remained in the Snyder
column will drain back into the ampul and raise
the volume to above 1 ml.
9a. Rinse with hexane.
lla. Caution: When using the micro column, the analyst
should constantly watch the samples as they are
heated. They must not go to dryness.
12a. Do not allow to go to dryness.
12b. After cooling the volume will increase by about
0.1 ml by the solvent draining back into the
ampul.
E20-35
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-36
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATION!
TRAINING
GUIDE NOTES
G. Sample Extraction
Concentration
(Continued)
and
15.
16.
Rinse the lower joint of
the column into the ampul.
Dilute to
of 1 ml.
the final volume
17. Stopper to prevent further
evaporation.
18. Inject 5 ul of this
concentration into the gas
chromatograph.
19. If interferences are
present proceed to the
clean-up section.
20. If no interferences are
present and pesticides are
determined, proceed to the
calculation section.
15a. Use a 10 ul syringe.
15b, The rinse should be about 0.1 to D.2 ml.
15c. Caution: Do not go above 1 ml.
16a. With hexane.
16b. This would include samples, check standards,
duplicates and method blanks.
18a. This chromatogram will provide the analyst with
the information for further need of concentration
or clean-up.
18b. Interferences in the form of distinct peaks and/
or high background will indicate further clean-up
is necessary.
19a. See next section (Section H).
20a. If a standard of a concentration at the drinking
water MC has been carried through the procedure
and gives quantitatdble peaks, the analyst can
express his value as less than his detection
limit if he has obtained no peaks in the sample.
20b. Both the sample and duplicate should produce the
same results.
20c. Section J.
/II.G.3.16
[p. 46)
I.B.12
(p- 44)
-------
kATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPE RAT ING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
H. Sample Clean-Up
1. Weigh out the determined
amount of florisil.
2. Pour the florisil into the
chroma tographic column.
3. Tap the column lightly to
settle the florisil and to
level its surface.
4. Add about one-half inch of
sodium sulfate to the top
of the florisil in the
column.
5. Adjust the sample(s)
volume to 10 ml.
6. Add 40-50 ml of petroleum
ether to the top of the
column.
7. Time the rate of passage
of the petroleum ether
through the column.
8. Remove the container used
to collect the petroleum
ether.
la. Determined from the lauric acid value for this
batch of florisi1.
lb. Usually about 10 to 20 grams.
Ic. See calculation section (J.2).
2a. The column should meet the specifications listed
in the equipment section.
3a. The column should not be packed so tight as to
impede sol vent flow.
4a. This should be the anhydrous, granular, ACS grade
4b. Should be pre-conditioned by heating at 400° C
for four hours (See B.ll).
5a. A column must also be prepared for the method
blank, the standard check and each duplicate
being run.
5b. Use hexane.
6a. This is used to pre-wet the column
6b. The column may generate heat as it is wet by the
solvent. Allow to cool to room temperature
before proceeding.
6c. This solvent can be collected in any type of
container and need not be saved.
7a. This elution rate should be set at about 5 ml
per minute.
7b. Use a 10 ml graduated cylinder and a stopwatch.
8a. This should be done while a small level of
solution is still above the sodium sulfate layer.
E20-37
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-38
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
H. Sample Clean-Up
(Continued)
9. Place a clean 500 ml K-D
flask equipped with a 10
ml ampul under the column.
10. Just prior to the exposure
of the sulfate layer to
the air quantitatively
transfer the sample
extract into the column.
11. Rinse container with 10 ml
of petroleum ether.
12. Add 200 ml of the 6% ethyl
ether in petroleum ether
solution.
9a.
lOa.
lOb.
13. Collect the 200 ml
H. Add 200 ml of the 15% ethyl
ether-petroleum ether
solution.
15. Immediately replace the
500 ml K-D flask with
another clean one.
Some portion of the petroleum ether will
collected.
be
The sulfate should not be allowed to dry between
additions of the sample or future eluates.
Wash the ampul with three 5 ml portions of
petroleum ether and transfer each wash into the
column.
11 a. Add the rinse to the column.
12a. Measure in a graduated cylinder.
12b. If prepared just prior to use by the directions
given in the reagent preparation section, only
200 ml will be prepared and can be completely
transferred to the column.
12c. Add small portion slowly to bring liquid level
to the top of the florisil column then add the
rest.
13a. Close the column's stopcock before the sulfate
layer is exposed to the air.
-------
WATER MONITORING PROCEDURE; Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/CPFRAT1NG GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
H. Sample Clean-Up
(Conti nued)
16. Collect the 15% eluate,
17. Just prior to the sulfate
layer being exposed add
200 ml of ethyl ether.
18. Immediately replace the
500 ml K-D flask with
another clean one,
19. Concentrate the elution
volumes in their
respective flasks.
20. Remove the flask from the
ampul.
21. Rinse lower portion of
the flask and glass joint.
22. Obtain a final volume of
10 ml.
23. Stopper the ampul.
24. Inject 5 pi of the
fractions.
16a. There will be a small overlap; in this case a
small portion of the 6% will be collected in the
15?= flask. Again close the stopcock to prevent
exposure of sulfate layer to the air.
17a. For wastewater or if other pesticides are to be
monitored other than those listed in the Interim
Primary Regulations, a 501 ethyl ether in
petroleum ether elution would be carried out
at this time followed by the straight ethyl
ether elution.
19a. Use the procedure under Sample Concentration,
(G.3), Steps 1 through 6.
24a. See F,23a.
E20-39
-------
HATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-40
OPERATING PROCEDURES
STLP SEQUENCE:
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
I. Sample Analysis
1 . Check instrument
parameters.
2. Inject 5 yl of standard
mixture 2.
3. Determine if response has
changed for the standards.
4. Inject 5 yl of the method
blank.
5. Determine if impurities
are present which will
interfere.
6. Inject 5 yl of the sample.
7. Compare with standard
curve (Step I.2.).
8. Inject 5 yl of a known
standard mixture that is
very close to that of the
sample.
9. Calculate the amounts of
the pesticides present.
- 70
- 70
la. Column Temp.
OV-17 & QF1 - 200°
OV-210 - 180°
OV-1 - 180°
QF1 - SE30 - 200°
Ib. These conditions should be
analyst during operation.
Ic. If the instrument was off,
equilibrate overnignt.
Flow
- 60 ml/min.
ml/min.
ml/min,
C - 60 ml/min. -
monitored
Detector
220° C
200° C
200° C
220° C
by the
turn on and allow to
2a. Reagent Preparation Section.
3a. Check retention times as well as peak heights
for the known concentrations.
4a. Continue the chromatogram until the retention
time for the last peak has passed.
6a. Time the retention time; from first sign of the
solvent until the top of the peak, for each peak.
7a. Retention times and numbers of peaks will
indicate further actions.
8a. Measure the peak area or peak height in
mil 1imeters.
9a. See the Calculation Section.
VII.1.7.7a
(p. 47)
-------
WATER MONITORING PROCEDURE; Determination of Chlorinated Hydrocarbon Pesticides
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING COALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
J. Calculations
1. Laurie Acid Value
Use the following steps
to calculate the lauric
acid value.
la. The calculation formula is
Lauric Acid Value = mg lauric acid
gm florisil
for
= 200 - (ml required
titration x
mg lauric acid
ml 0.05N NaOHj
the mg lauric Ac1d
ml T.05N NaOH"
comes from the standardization of the NaOH
(See Section on Standardization of Sodium
Hydroxide).
2. Amount of Florisil
to be Used in the
Column
1. Calculate the amount
of florisil to be used in
the columns.
la.
Ib.
The calculation formula
Amount of florisil
to be used = 110
is
x 20 grams
Lauric Acid Value
The 110 value is a value abritrarily assigned
as the desired adsorptive capacity.
Milis, P.A.,
Variations of
Florisil
Activity:
Simple Method
for Measuring
Adsorbent
Capacity and
its Use 1n
Standardizing
Florisil
Columns;
JAOAC, 51 29
(1968)
E20-41
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
E20-42
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
J. Calculations
(Continued)
3. Calculation of
Results
1. Calculate the micrograms
of pesticide per liter of
sample.
VT * V
la. The calculation formula is
micrograms _ A x B x V^
liter"
where
A = ng standard (obtained in Sample Analysis
standard area Section, Step 8)
B = Sample Aliquot Area (obtained in Sample
Analysis Section,
Step 7)
V^ = Volume of total extract (i.e. the volume
to which the
extract was
concentrated)
in microliters
Vi
= Volume of extract injected in microliters
$ = Volume of water (sample) extracted in
mil 1 iters.
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Hydrocarbon Pesticides
TRAINING GUIDE
SECTION TOPIC
I* Introduction
II Educational Concepts - Mathematics
III Educational Concepts - Science
IV Educational Concepts - Communications
V* Field and Laboratory Equipment
VI Field and Laboratory Reagents
VII* Field and Laboratory Analyses
VIII Safety
IX Records and Reports
*Training guide materials are presented here under the headings marked*.
These headings are used through this series of procedures.
E20-43
-------
WATER MONITORING PROCEDURES: Determination of Chlorinated Hydrocarbon Pesticides
INTRODUCTION
Section I
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
B.12
When the Interim Primary Drinking Water Regulations
were promulgated they contained the requirement
that all Public Water Supplies be monitored for
pesticide contamination. Certain nonitoring
frequencies and analytical methods were prescribed.
A level beyond which public notification and other
steps were to take effect was set and termed the
"Maximum Contaminant Level" (MCI). The MCL's for
the Chlorinated Hydrocarbon Pesticides are as
follows:
Endri n
Lindane
Methoxychlor
Toxaphene
0.0002 mg/liter
0.004 mg/liter
0.1 mg/liter
0.005 mg/liter.
E20-44
-------
WATER MONITORING PROCEDURES: Determination of Chlorinated Hydrocarbon Pesticides
FIELD AND LABORATORY EQUIPMENT
Section V
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
C.I
C.6.b
D.I.3.a
D.3.2
Use of high grade carrier gases are recorrmended.
However, occasionally bad cylinders of the Argon-
Methane gas can be obtained. Before attaching to
the instrument,a slight sniff of the gas should be
taken; if a "fishy" ordor is noted, the tank may
be contaminated. Use of the gas will produce an
off scale peak and very noisy base line. If
contaminated gas is used in the instrument, remove
from use as soon as it is determined and replace
all traps and purge with a good gas.
OV-210 may be substituted for the QF-1 . The OV-210
is a purified version of the QF-1 and does not
bleed as much as the QF-1.
Because of the many variables inherent in gas
chromatographs, the column packing, column oven
temperature and carrier gas flow rate may have to
be adjusted to different settings than those given.
The analyst should strive to reproduce the retent-
ion times given in the body of the paper as guides.
The two things which must be obtained are
reproducibility and resolution. When these are
adequate the system is suitable.
The analyst must know what the detection limit is
in his procedure. The concentrations are so low
in drinking water that frequently the results
will be non-detectable. In this case the analyst
should express the value as "non-detectable,"
below the detection limit of
This detection limit must be at least below the
Maximum Contaminant Level for the compound as
listed in the Interim Primary Drinking Water
Regulations.
E20-45
-------
WATER MONITORING PROCEDURES: Determination of Chlorinated Hydrocarbon Pesticides
FIELD AND LABORATORY ANALYSES
Section
VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
D.4
F.
F.2
G.Z.lf
G.3.16
Lindane, Endrin, and Methoxychlor are quantitated
using one peak for each. However, toxaphene has
many peaks and should be quantitated by averaging
the peak height (in millimeters) of as many peaks
as possible. Use only those peaks which are
identical in the standard and sample by retention
and peak height ratio.
The more peaks used in this average, the closer
this number will come to the true value. However,
when other chlorinated hydrocarbons are present
the peaks of toxaphene in areas not affected by
the other chlorinated hydrocarbons should be
averaged. From running the standards separately
these areas can be found.
When the peaks of the other chlorinated hydrocarbons
are influenced by the presence of toxaphene they
should be separated by another technique, i.e.
another absorption column or liquid chromatography
etc.
Different batches of florisil have varying adsorp-
tive capacities. In order to obtain elution of
the various pesticides in the same fractions, this
adsorptive capacity must be known. A rapid method
for determining this adsorptive capacity is to
measure the amount of lauric acid adsorbed from
hexane solution by a measured amount of florisil.
This is referred to as the lauric acid value.
This procedure need be carried out only once with
each batch of florisil. As a new supply is
purchased, the lauric acid value and this procedure
should be determined again, using this same
procedure.
Samples up to 3 liters can be extracted to increase
the sensitivity. However, larger volumes of
extraction solvent (methylene chloride-hexane)
will be needed. Use 100 ml portions in place of
the 60 ml. The separatory funnel size will also
need to be increased to a 6 liter size.
Samples containing small quantities of pesticides
(low nanogram amounts) are concentrated to 1 ml.
Should the concentrations allow, it is possible
to concentrate to 10 ml for higher values. In
this case the initial concentration with the Snyder
Column will reduce the volume to 5 to 6 ml and the
E20-46
-------
WATER MONITORING PROCEDURES: Determination of Chlorinated Hydrocarbon Pesticides
FIELD AND LABORATORY ANALYSES
Section yil
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
G.3.16
(Continued)
I.7.7a
walls of the
give a final
flask and glass joint can be washed to
volume of 10 ml.
Major peaks not matching those of the standards
along with increased peak heights on some peaks
will indicate the presence of interfering
compounds. If this is the case, the florisil
column clean-up should be used. If no
interferences are present, identify and quantitate
the peaks.
E20-47
-------
TABLE 3
RETENTION RATIOS OF VARIOUS ORGANOCHLORINE PESTICIDES RELATIVE TO ALDRIN
Liquid Phase
Column Temp.
Argon/Methane
Carrier Flow
Pesticide
Lindane
Aldrin
Endrin
Methoxychlor
Aldrin
(Min absolute)
1.5% OV-17
+
1.95% QF-1
200° C
60 ml/min.
RR
0.69
1.00
2.93
7.6
3.5
5%
OV-210
100° C
70 ml/min.
RR
0.81
1.00
3.56
6.5
2.6
3%
OV-1
180° C
70 ml/min.
RR
0.44
1.00
2.18
5.7
4.0
6% QF-1
+
4% SE-30
200° C
60 ml/min.
RR
0.60
1.00
2.42
4.60
5.6
All columns glass, 180 cm x 4 mm ID, solid support Gas-Chrom 0 (100/120 mesh)
E20-48
-------
X
O
I
T
25
20 15 10
RETENTION TIME IN MINUTES
ro
c
FIGURE 1. COLUMN PACKING: 1.5% OV-17 + 1.95% QF-1, CARRIER
GAS: ARGON/METHANE AT 60ML/MIN, COLUMN
TEMPERATURE: 200 C, DETECTOR: ELECTRON CAPTURE.
-------
10 5 0
RETENTION TIME IN MINUTES
FIGURE 2. COLUMN PACKING: 5% OV-210, CARRIER GAS:
ARGON/METHANE AT 70ML/MIN, COLUMN
TEMPERATURE: 180 C, DETECTOR: ELECTRON
CAPTURE.
E20-50
-------
DC
O
X
O
i
25
20 15 10
RETENTION TIME IN MINUTES
O
•
en
FIGURE 3. COLUMN PACKING: 6% QF-1 -I- 4% SE-30, CARRIER GAS:
ARGON/METHANE AT 60/VU/MIN, COLUMN TEMPERATURE;
200 C, DETECTOR: ELECTRON CAPTURE.
-------
IN)
O
I
Ul
PO
O
_J
<
z
O
oc.
O
U
I
CO
25
FIGURE 4
20 15 10 5
RETENTION TIME IN MINUTES
COLUMN PACKING: 3% OV-1, CARRIER GAS:
ARGON/METHANE AT 70 ML/MIN, COLUMN
TEMPERATURE: 180 C, DETECTOR: ELECTRON
CAPTURE.
J
0
-------
A PROTOTYPE FOR DEVELOPMENT OF
ROUTINE OPERATIONAL PROCEDURES
for the
DETERMINATION OF CHLORINATED PHENOXY ACID HERBICIDES
as applied in
POTABLE WATER TREATMENT FACILITIES
National Training and Operational Technology Center
Office of Water Program Operations
U.S. Environmental Protection Agency
CH.PES.lab.WMP.1.11.77
E21-1
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
Operational Procedures
A. Glassware Preparation
B. Reagent Preparation
C. Standard Preparation
D. Instrument Set-Up
1. Gas Connection
2. Detector Installation
3, Carrier Gas Leak Check
4. Column Conditioning
E. Instrument Calibration
1. Optimization
2. Retention Times
3. Detection Limits
F. Sample Treatment
1. Pre-Treatment
2. Hydrolysis
3. Esterification
G. Sample Analysis
H, Calculations
L21-3
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
Equipment and Supply Requirements
A. Capital Equipment:
1. Gas chromatograph equipped witn
a. Glass lined injection port
b. Electron capture detector - tritium or nickel 63
c. Recorder - potentiometric strip chart (10 in.-25 cm) compatible
with the detector
2. Gas chromatographic column (best purchased from gas chromatographic
supply house)
a. Tubing - Pyrex (180 cm long (6 ft.) x 4 mm ID)
b. Glass wool - silanized
c. Solid support - gas chrom Z (100-120 mesh)
d. Liquid phase - expressed as weight percent coated on solid support
1) OV-210, 5%
2) OV-17, 1.5% plus QF-1, 1.95%
3. Hot water bath - capable of keeping temperature at 50°-100° C
4. Source of high quality distilled water
5. Rotometers - If the instrument is not equipped with meters to monitor the
flows of gases, these should be purchased as options.
6. Analytical balance - with a 0.1 milligram sensitivity
7. Trip or platform balance - with a 0.1 or 0.01 gram sensitivity
8. Oven - capable of maintaining 130° C
9. Stop watch - capable of measuring at least 1/2 hour, the 60 second
cycle divided to 1/5 second
10. Cylinder of Argon-methane (95 + 51) for use with pulsed mode detector OR
Nitrogen - purified grade, moisture and oxygen free, for use with a DC mode
detector
11. Pressure regulator - two stage with a CGA 580 fitting for nitrogen or a CGA
350 fitting for Argon-methane
12. Filter - for carrier gas, molecular sieve type
13. Micro syringes - 5, 10, 50 yl sizes
14. pH meter (optional)
E21-4
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
Equipment and Supply Requirements (Continued)
15. Desiccator
16. Muffle furnace (optional) - capable of heating to 400° C
17. Source of Vacuum
18. Trap for oxygen
B. Reusable Supplies:
1, Beaker - 100 ml, I/sample, duplicate, blank, standard
2. Cylinders, graduated
2, 25 ml
2, 100 ml
1, 250 ml
1, 1000 ml
3. Cylinder, graduated - glass-stoppered
1-25 ml/sample, duplicate, blank, standard
4. Flasks, Erlenmeyer
1, 125 ml/sample, duplicate, blank, standard
1, 250 ml/sample, duplicate, blank, standard
1, 1000 ml/sample, duplicate, blank, standard
Erlenmeyer - glass-stoppered
1, 250 ml/sample = I 19/22
5. Flasks - volumetric
4, 100 ml
6, 10 ml
6. Funnel, 1 - 50 mm diameter top/sample, duplicate, blank, standard
7. Funnel - separatory (with Teflon stopcock)
1, 2000 ml/sample, duplicate, blank, standard
1, 60 ml/sample, duplicate, blank, standard
8. Glass stirring rod, about 10 cm long
9. Glassware brush
E2t-;
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
Equipment and Supply Requirements (Continued)
10. Kuderna-Danish (K-D), order from Kontes Glass Corporation
5 plus 2/sample, concentration ampul, 10 ml calibrated 5 19/22 female
#1(5-70050, size 1025
I/sample, Snyder col., three section, 150 mm long, IK503000, size 121
I/sample, Snyder col., one section, #K569Q01, size 1-19
I/sample, flask, 250 ml size, #K570001
About 6/pr., springs, 2/set-up, #K662750
I/ampul, stoppers for concentrator ampul, #K850500, size 19/22
11. Pipets
1 box, Pasteur, disposable (140 mm long x 5 mm ID)
4 - graduated, 1 ml
5 - volumetric, 1 ml
3 - volumetric, 2 ml
2 - volumetric, 10 ml
12. Pipet bulb
3 ml size for Pasteur type pipets
Rubber type for pipets
13. Reagent bottles (glass-stoppered, storage)
5 - 150 ml size
1 - 500 ml size
1 - 1000 ml size
14. Rack for separatory funnel
15. 3 - ring stand and clamp
16. 1 ruler - divides in millimeters
17. Safety glasses
18. 1 timer (60 min.)
C. Consumable Supplies
1. 1 box aluminum foil
2. 1 bottle - boiling stones (rinse with hexane)
3. 1 box detergent
4. 25 liters distilled water
5. 1 box glass wool (filtering grade, acid washed)
E21-6
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
Equipment and Supply Requirements (Continued)
6. 1 pack graph paper (arithmetic, 10 x 20)
7. 1 roll pH paper (for acid pH)
8. 12 labels
9. 1 note book (bound)
10. 1 pencil or pen
11. 12 weighing boats, plastic, disposable
12. 1 bottle soap solution (any liquid soap mixed with water)
13. Chart paper for records
14. Reagents
a. Acetone - ACS grade
b. Alcohol - ethenol, 95%, ACS grade
c. Benzene - nanograde, distilled in glass
d. Borontrifluoride - methanol, esterification reagent, 14% BF3 by weight*
e. Ethyl ether - nanograde, distilled in glass
f. Florisil - pesticide residue grade (60-100 mesh), purchase activated at
1250° F and store at 130° C
g. Herbicide standards, reference grade
h. Hexane, nanograde, distilled in glass
i. Potassium hydroxide (KOH), ACS grade
j. Potassium iodide (KI), ACS grade
k. Sodium sulfate, ACS, granular
1. Sulfuric acid, ACS, concentrated
*Available already prepared from: Applied Sicence Laboratories
PO Box 440
State College, PA 16501
E21-7
-------
HATER MONITOR!?^ PROCEDURE; Determination of Chlorinated Phenoxy Acid Herbicides
E21-8
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
A. Glassware Preparation
B. Reagent Preparation
1. Distilled Water
2. Sulfuric Acid (25%)
1. Clean all glassware.
2, Wash with soap and water.
3. Rinse with tap water.
4. Rinse with distilled water.
5. Muffle at 400° C for 15 to
30 minutes.
6. Cool to room temperature.
7. Store until used.
3a. At least 10 times.
4a. At least 10 times,
5a, Volumetric glassware should not be muffled.
5b. Plastic ware and cap liners for sample containers
should not be muffled.
5c. The glassware may be rinsed with redistilled
acetone followed by a rinse with pesticide quality
hexane in place of the muffling.
7a. Store inverted or cover mouth with aluminum foil.
7b. Sample containers should be stored capped.
1. Distill water.
1. Add 50 ml of water to a
100 ml graduated cylinder.
2. Add 25 ml of concentrated
sulfuric acid.
3. Cool to room temperature.
4. Add water to the 100 ml
mark.
la. Use an all glass still.
Ib. Extract a volume of distilled water, equal to the
sample size used, to check purity. This reagent
blank should be analyzed with each set of samples
2a. Measure in a 25 ml graduated cylinder.
2b- CAUTION: Temperature will rise.
-------
HATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
3. Sodium Sulfate
Solution (5%)
(Na2S04)
4. Potassium Iodide
(10%) (KI)
5. Transfer to a reagent
bottle.
6. Store in freezer section
of a refrigerator.
1. Weigh out 5.0 grains of
sodium sulfate.
2. Transfer to a glass-
stoppered reagent bottle.
3. Measure out 100 ml water.
4. Use a small amount of water
to wash the weighing boat.
5. Add remaining water to a
reagent bottle.
6. Mix and label.
1. Weigh out 10.0 grams of
potassium iodide.
2. Transfer to a glass-
stoppered reagent bottle.
3. Measure out 100 ml water.
4. Use small amount of water
to wash weighing boat.
5. Add remianing water to
reagent bottle.
6. Mix and label.
la. Use a trip balance and a plastic weighing boat.
Ib. This is not the acidified sodium sulfate (B.8).
2a. A 150 ml size.
3a. In a graduated cylinder.
4a. Add washing to reagent bottles.
la. On a trip balance in a plastic weighing boat.
2a. A 150 ml size.
3a. In a graduated cylinder.
4a. Add wash to reagent bottle.
E21-9
-------
WATER MONITORING PROCfDLRE: Determination of Chlorinated Phenoxy Acid Herbicides
E21- 10
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
5. Potassium Hydroxide
(w:v) (KOH)
6. Diethyl Ether
1. Weigh out 37.0 grams of
potassium hydroxide
pellets.
2. Transfer to a glass-
stoppered reagent bottle.
3. Measure out 100 ml water.
4. Use small amount of water
to wash the weighing boat.
5. Add remaining water to
reagent bottle.
6. Mix and label.
1. Test for peroxides.
2. Rinse a 25 ml glass-
stoppered graduated cylin-
der with ethyl ether.
3. Add 10 ml ether to the
cylinder.
4. Add 1 ml freshly prepared
potassium iodide (KI)
solution.
5. Mix by inverting.
2a. A 150 ml size.
3a. In a graduated cylinder.
4a. Add washing to reagent bottle.
5a. CAUTION: Temperature will rise.
la. Purchase distilled in glass or nanograde.
Ib. Ether must contain 2% alcohol and be free of
peroxides as follows.
2a. Discard the rinse.
4a. Use a 1.0 ml volumetric pipet.
5a. Two or three times. Open stopper to allow
pressure out.
-------
WATER M.pNJTORINjj PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PRCCLDURiS
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B. Reagent Preparation
(Continued)
7, Ethyl Ether -
Hexane Mix (1:1
8. Sodium Sulfate
(Acidified)
6, Let stand one minute.
7, No yellow color should be
observed in either layer.
7a.
7b.
If yellowing occurs, the peroxides can be decomposed
by adding 40 ml of 30% ferrous sulfate solution
to each liter of ether. (CAUTION: Reaction may
be violent if ether contains a high concentration
of peroxides). Then distill.
If this is needed, an alternate source for a
better product should be sought.
8. Discard tested ether.
9. Add 20 ml of 95% ethanol
to one liter of ether.
0. Store in refrigerator.
1. Mix equal amounts of the
hexane and ethyl ether,
2. Store in glass-stoppered
reagent bottles.
1. Weigh out 100 grams of
sodium sulfate.
2, Add ether to just cover the
sodium sulfate.
3. Add 0.1 ml of concentrated
sulfuric acid.
4. Swirl to mix.
lOa.
lOb.
la.
2a.
la.
Ib.
3a.
3b.
Storage of all flammable solvents should be in
an explosion proof refrigerator.
Store in reagent bottle glass-stoppered (1 liter
size).
Example: Add 250 ml hexane to 250 ml ether.
Use a 500 ml size.
Use a trip balance.
Use a 250 ml Erlenmeyer flask.
Use caution when working with concentrated
acids.
Use safety glasses.
E21- 11
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
E21-12
CPtRATING PROCEDURES
STLP SEQUENCE
INFRMAT ION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
B, Reagent Preparation
(Continued)
5. Remove ether with vacuum.
6. Weigh 1.0 gram of the
dried sodium sulfate.
7. Add 5 ml of distilled
water.
8. Swirl to mix.
9. Check pH of the solution.
10. Discard the solution.
11. Store the remaining sodium
sulfate at 130° C in glass
bottles in an oven.
Standard Preparation
1. Stock 2,4 Dichloro-
phenoxyacetic acid
(2,4-D)
1. Weigh out 0.100 grams of
2,4-D.
2. Measure out 60 ml of
ethyl ether.
3. Pour 40 ml of ethyl ether
into a glass-stoppered
100 ml volumetric flask.
6a, On a trip balance,
6b. In a 50 ml beaker.
7a. Use a 5 ml graduated pipet.
9a. Solution should have a pH below 4.
9b. If not, repeat steps 2 through 9.
9c. Use a pH meter or paper that can distinguish
a pH below 4.
lOa. Prepared in step 9.
lla. Or activate overnight at 130° C before use,
storing in a desiccator.
la. Prepare standard as shown in the accompanying
chart,
Ib. Weigh on an analytical balance,
lc. Use a plastic weighing boat.
Id. Carry out this procedure in a hood or well
ventilated area.
2a. In a 100 ml graduated cylinder,
2b- CATION: Ether is extremely flammable.
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING COALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Standard Preparation
(Continued)
2. Stock Silvex
3. Working Standard
2,4-D
4. Working Standard
Silvex
4. Transfer the 2,4-D into
the volumetric flask.
5. Use the remaining ether
to wash the weighing
boat.
6. Dissolve the 2,4-D.
7. Dilute to the mark with
hexane.
8. Stopper and label.
1. Perform steps 1 through 8
above using si 1 vex.
1. Add about 50 ml of the
ethyl ether:hexane mixture
(reagent 7) to a glass-
stoppered 100 ml volumetric
flask.
2. Pipet 10.0 ml of the stock
2,4-D into the flask.
3. Dilute to the mark with
the ether:hexane mixture.
4. Stopper and label.
1. Add about 50 ml of the
ethyl ether:hexane mixture
(reagent) to a glass-
stoppered 100 ml volumetric
flask.
7a. Solution contains 1 mg/ml
la. Solution contains 1 mg/ml
la. Just estimate this amount.
2a. Use a 10.0 ml volumetric pipet.
3a. Solution contains 100
ml
E21-13
-------
HATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
E21-14
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OFtRATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Standard Preparation
(Continued)
5. Esterification of
Standard for
Chromatography
2,4-D
2, Pipet 1.0 ml of the stock
si 1 vex into the flask.
3. Dilute to the mark with
ether:hexane mixture.
4. Stopper and label.
1. Turn on water bath and
steam bath.
2. Pipet 1.0 ml of the working
standard into a 10 ml
concentrator ampul.
3, Add 0.5 ml of Benzene.
4. Insert a two chamber
evaporative column.
5. Place assembly into ring
stand and support with
clamp.
6. Place over steam bath.
7. Lower volume to 0,4 ml.
8. Remove from steam bath and
allow to cool.
9. Remove the evaporative
column.
3a. Solution contains 10
ml
la. Allow water bath to reach 50° C,
Ib. Allow steam bath to boil.
2a. Use a 1.0 ml volumetric pipet.
2b. See equipment section, K-D concentrator ampul
3a. Use a 1 ml graduated pipet.
4a. See equipment section,
4b. Be sure to attach springs.
VII.5.1
(p. 38)
6a. The height above the steam bath will have to be
adjusted to speed up or slow down the evaporation.
The analyst should not allow the material to go
to dryness.
-------
WATER HnNITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Standard Preparation
(Continued)
6. Esterification
of Standard for
Si 1 vex
Chroma tography
7. Esterification of
Standard Mixture 1
10. Add 0.5 ml of the
borontri f1uori de-methanol
reagent.
11. Replace the evaporative
column.
12. Lower into a preheated
50° C water bath.
13. Heat for 30 minutes.
14. Remove from water bath.
15. Allow to cool to room
temperature.
16. Remove column.
17. Wash walls of concentrator
ampul with benzene until a
total volume of 5 ml is
reached.
18. Stopper and mix.
1. Repeat steps 1-7 above
using silvex working
standard in place of the
2,4-D. in step 2.
1, Pipet 2.0 ml of each work-
ing standard (for 2>4~D.
and silvex) into a 10.0 ml
concentrator ampul.
12a, This is not a steam bath.
12b. The water bath should be preheated to 50° C and
checked with a thermometer.
17a. Solution contains 200 ng esterified 2 4-D per
10 pi. '
la. These esterified standards are at the level of
the sample containing the MCL's after it has
been concentrated. That is the MCL in 5 ml.
Ib. Solution contains 40 ng silvex/ 10 pi.
la. Use two 2 ml volumetric pipets.
E21-15
-------
WATERMONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
E21- 16
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
C. Standard Preparation
(Continued)
2, Add 1.0 ml of benzene.
3. Insert a two chamber
evaporative column.
4. Place assembly into ring
stand and support with
clamp.
5. Place over steam bath.
6. Lower the volume to 1.0 ml.
7. Remove from steam bath.
8. Remove evaporative column.
9. Add 1.0 ml of the boron-
trifluoride rnethanol
reagent.
10. Replace the evaporative
column.
11. Lower into a preheated
50° C water bath.
12. Heat for 30 minutes.
13. Remove from water bath.
14. Allow to cool.
2a.
3a.
Use a 1 ml graduated pipet.
Attach springs.
5a.
The height above the steam bath will have to be
adjusted to speed up or slow down the evaporation
rate. The analyst should not allow the solution
to go to dryness.
12a.
The bath must be at temperature before lowering
the assembly.
-------
HATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
STEP SEQUENCE
JHFORMATION/CFERAriNG GOALS/SrECIFICATIONS
TRAINING
GUIDE NOTES
C. Standard Preparation
(Continued)
8. Dilutions
15. Remove evaporative column.
16. Wash walls of concentrator
ampul until a total volumn
of 5.0 ml is reached.
17. Stopper and mix.
1, Prepare dilutions of this
mixture labeled Mix 2 and
3 as shown in Table 1.
16a. Solution contains 400 ng 2,4-D/lO yl and
40 ng silvex/10 pi.
E21-17
-------
WATER MONITORING PROCEDURE; Determination of Chlorinated Phenoxy Acid Herbicides
STANDARD PREPARATION
TABLE I
2,4-D
100 mg
Stock 100 ml
Working ml
1 ml
10/100 dilution
0.1 mg 100 yg 2 ml 2,4-D -
or
ml
1/5 dilution
Esterification 100 yg 200 ng
Jingle Std. 1 5 ml ° 10 pi
1/2 dilution
100 ng
Standard 2 10 yl
1/2 dilution
50 ng
Standard 3 10 pi
2.4,5-TP - Silvex
1 mg _ 100 mg
1 ml ~ 100 ml Stock
1/100 dilution
10
2 ml Silvex ]p ]
ml
2/5 dilution
and
Esterification
of Mixtyre
400 ng M. , 40 nc
-iQ-J Mlx ] Tori
1/2 dilution
_
10
1/2 dilution
100 ng
TO yl
_ 0.01 mg_
ml Working
1/5 dilution
20 ng 10 yg Esterification
TOyl y 5 ml Single Std. 1
1/2 dilution
20 ng
10 yl Standard 2
1/2 dilution
50 09
T0~yl Standard 3
F11x 3
10 ng
10 yl
E21-18
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
STEP SEQUENCE.
Itif CRMATlQN/OP'iRAT I KG GOAL S/SPEC IFICAT IONS
TRAINING
GUIDE NOTES
D. Instrument Sep-Up
1. Gas Connection
2. Detector
Installation
3. Carrier Gas Leak
Check
1. Remove cylinder cap from
cylinder of carrier gas.
2. Install the pressure
regulator.
3. Connect the cylinder to
the instrument.
1. Install the electron
capture detector.
1. Open master valve on
instrument.
2. Adjust regulator control
3. Close carrier gas control
valve on the instrument.
4. Turn off master cylinder
valve.
5. Observe gage on the
cylinder.
la. Tank should be chained to wall or lab bench.
Ib. Use Argon-methane for pulsed mode detector or
use nitrogen for a detector operated in a DC mode.
Consult the instrument manufacturer's manual.
2a, The regulator should have a CGA 350 fitting for
Argon-methane or a 580 fitting for nitrogen.
2b. Fitting should be tight to prevent leaks.
3a. Use Teflon tape on all metal threads to prevent
leaks.
3b. Polyethylene (1/8" diameter) tubing can be used.
3c. If plastic tubing is used, nylon ferrules should
be used with connector fittings.
la. This can be of tritium or nickel 63 type.
Ib. Requires license from Atomic Energy Commission.
Ic. See the manufacturer's manual on procedures for
installation.
2a. To about 65 psig and allow to stabilize
(about 1 minute).
5a. Pressure should not drop more than a few psig.
5b. If pressure does drop, use soap solution to
locate leak.
5c. Correct leak and check again.
V.D.I
(P. 37)
E21-19
-------
UATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
E21-20
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OP[RATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
D. Instrument Set-Up
(Continued)
4. Column Conditioning
6. Use soap solution and check
for leaks at the injector
port and column connections,
1. Install packed column in
oven by connecting only the
column inlet.
2. Start a flow of carrier gas
through the detector only.
3. Begin a low flow of
carrier gas through the
column.
4. Wait 5 minutes.
5. Turn on the power to the
oven.
6. Adjust column temperature tc
near maximum recommended
temperature for the liquid
phase being used.
7. Continue heating for 2
hours.
la. These columns may be purchased and meet the speci-
fications as listed under the equipment section.
lb. Column conditioning is essential to eliminate
column bleed of packing materials and to provide
acceptable analysis.
Ic. Do not connect the column to the detector.
Id. If in doubt as to column installation, refer to
the manufacturer's manual.
2a. Use the purge gas line or in a dual column oven
by connecting an unpacked column to the detector.
2b. In some systems it may be necessary to temporarily
connect the carrier gas to the air or hydrogen
inlet in order to get a flow of carrier gas to
the detector. The manufacturer's manual should
be consulted.
3a. Less than 60 ml/min. (^0-50).
3b. To remove oxygen and other trapped gasses.
3c. This will be two separate flows. The column should
not be connected to the detector.
5a. Consult manufacturer's manual for location
and necessary steps.
6a. Still no flow of carrier gas through the column.
5b. Column Max. Temp. °C
OV-2'TO (5%) -275
OV-17 (1.5%) and QF-1 (1.95%) 250
V.D.6.6b
(p. 37)
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PRCCFDURES
D. Instrument Set-Up
(Continued)
STEP SEQUENT
9.
Reduce temperature to
about 40° C below maximum
temperature.
Allow column temperature
to equilibrate.
10. Check carrier gas flow.
11. Allow to remain at temper-
ature and flow for one
hour.
12. Increase temperature to
about 20°C above operating
temperature.
13. Continue the same flow of
carrier gas.
14. Allow to equilibrate for
24 to 48 hours.
15. Turn off oven and allow to
cool to room temperature.
INFORMATION/OPERATING GOALS/SPECIFICATIONS
fla. See table above (6b).
9a. Minimum of 30 minutes.
9b- CAUTION; Bleed off of the liquid phase will
occur if the column temperature is not fully
equilibrated.
lOa.
TOb.
lOc.
lOd.
12a.
12b.
At about 50 ml/minute.
If the instrument has not come equipped with
rotometers to monitor the flow rate of the
carrier gas, this should be purchased as an
option.
The pressure regulator on the cylinder should be
set at 65 psig.
The electron capture must be installed but the
column connection should not be made.
This is operating temperature not maximum
temperature.
The temperatures would be:
220° C for OV-17 and QF-1
200° C for OV-210
CAUTION: Do not exceed maximum recommended
temperature. See 6b this section.
TRAINING
GUIDE NOTES
£21-21
-------
HATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
L21- 22
OPERATING PROCEDURES
D. Instrument Set-Up
(Continued)
E. Instrument Calibration
1. Optimization
STEP SEQUENCE
16. Connect column to the
detector.
17. Adjust the carrier gas
flow to the method flow
rate.
18. Turn on oven and adjust
to method column
temperature.
19. Allow the instrument to
equilibrate at least one
hour.
1. Check instrument operating
conditions after the in-
strument has been set up.
2. Inject 5
mixture.
yl of standard
3. Adjust the operating
parameters to achieve
optimum results.
INFORMATION/OPERATING GOALS/SPECIFICATIONS
16a, Check connection with soapy solution.
17a. 70 ml per minute.
18a. 185° C.
19a. Preferably overnight.
la.
Ib.
Ic.
The oven temperature should be stabilized at the
method temperature of 185° C.
The flow rate constant on 70 ml/minute.
The column conditioned.
Id. The system checked for leaks.
2a. This standard mixture was prepared from the
stock and esterffied.
2b, The actual volume of material injected should be
kept constant. That is, the same volume for
standards and samples.
2c. The standard mixture 2 can be used to optimize
the instrument initially and thereafter to
monitor its performance.
3a. Best resolution (separation of peaks) and
retention times can be achieved by adjusting the
column temperature and/or the carrier gas flow
rate.
TRAINING
GUIDE NOTES
-------
WATER MONITORING PROCFDURF: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
5TFP SEQUENCE
INFORMATION/OPIATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
E. Instrument Calibration
(Continued)
2. Retention Time
Determination
3. Detection Limit of
the Instrument
1. Inject 5 ul of standard 1
of 2,4-0 and Silvex one at
a time.
With a stop watch, measure
the time elapsed between
the first appearance of the
solvent peak and the peak
of the standard.
3. Repeat steps
more times.
1 and 2 six
1. Inject 5 ul of the
herbicide standards.
2. Continue with standards 2
and 3 of the 2,4-D and
then si 1 vex and determine
the detection limit of
each herbicide.
3b. Compare results with the standard chroma tograms
attached (Figure I).
3c. Caution should be taken to allow the instrument
to equilibrate after any changes,
3d, Optimum results would include good separation of
peaks, good sensitivity, and good reproducibility.
la. The individual standards of the 2,4-0 and silvex
should be run. Not mixtures.
Ib. Injection is a technique which must be learned
and practiced in order to make accurate and
reproducible injections.
2a. This time is called the retention time.
2b. After the retention times of the single standards
have been obtained, the mixtures should be
chromatographed to determine that no changes in
retention times occur.
3a, At least 7 repeat times should be obtained and
the mean value obtained for each peak.
3b. If in subsequent injections the retention times
vary signficiantly, the system parameters
(E.l.la-d) should be checked over.
la. Begin with standard 1 Table 1 of each herbicide
and continue with standard 2 and 3.
Ib. The standards must be esterified.
2a. Always inject 5 ul,
2b. The detection limit is that concentration of a
standard whose peak is twice the highest peak
caused by instrument noise and is run at the
most sensitive setting of the instrument.
VII.E.Z.lb
(p. 38)
¥.E.3.2b
(p. 37)
E21-23
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
E21-24
OPERATING PRCCEPURES
INFORMATION/OPERATING GOALS/SPtCIFICATIONS
TRAINING
GUIDE NOTES
E. Instrument Calibration
(Continued)
F. Sample Treatment
1. Pretreatment
2, Extraction
The peak height measured
in millimeters should be
plotted against the known
concentrations to produce
a standard curve.
1. Blend the sample.
2. Adjust pH to 2 or below.
1. Measure out 1 liter of
sample.
2. Transfer to a 2 liter
separatory funnel.
3. Add 150 ml of ether to the
separatory funnel.
3a. The curve produced can be used to select a con-
centration that produces a response (peak height)
close to a unknown sample's peak height. This
concentration will be used to calculate the
unknown concentration. See the calculation
section.
la. If suspended matter is present. This is usually
not required for drinking waters.
2a. Use concentrated sulfuric acid.
2b. Use a pH meter or indicator paper to measure pH.
2c. Usually not necessary for drinking waters.
la. Experience with the sample source will indicate
if smaller volumes of sample can be used. If
smaller volumes are used, they should be diluted
to one liter before extraction.
Ib. A volume of distilled water equal to the sample
volume used should be carried through the pro-
cedure every time to act as a method blank.
Ic. Analyze one duplicate sample with each run as a
quality control check.
Id. One ml each of working dilution of 2,4-D and
si 1 vex should be diluted to 1 liter and should be
carried through the procedure to check on the
standard curve and to assure the analyst of
proper operation of the wet and instrumental
sections of the method.
2a. Use a 2 liter funnel in order to have room to
shake.
3a. If the sample container has been emptied, use the
ether to wash the container and cylinder used for
transfer.
-------
HATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
STEP SLQULNU
INFORMATION/OPERATING GOALS/SPECIFICATION'S
TRAINING
GUIDE NOTES
F. Sample Treatment
(Continued)
4. Shake virorously for one
minute.
5, Place in holder and allow
phases to separate for at
least 10 minutes.
6. After separation of the
phases is completed, drain
the water phase into a
one-liter Erlenmeyer flask
7. Add 2 ml of the 37% aqueous
potassium hydroxide solu-
tion (reagent 5) to a
250 ml ground glass
stoppered Erlenmeyer flask.
8. Drain the ether layer from
the separatory funnel into
the Erlenmeyer containing
the potassium hydroxide
solution.
9. Close the stopcock and pour
the aqueous phase into the
separatory funnel.
3b. Measure in a 250 ml graduated cylinder.
4a. Pressure may build up in the separatory funnel.
Invert, with stopper tightly in place, and open
stopcock slowly to relieve pressure. Then con-
tinue with shaking until one minute is up. Re-
lieve pressure several times during shaking.
5a. Holder may be a ring and stand or some form of
separatory funnel rack. Places should be pro-
vided for the blank, duplicate standard and all
samples.
6a. If emulsions form and prevent adequate separation,
drain the aqueous layer that has separated. In-
vert the separatory funnel, and shake rapidly.
Vent the funnel frequently to prevent excessive
pressure buildup.
6b. Assure no water phase remains with the ether.
The water is highly acid and step 7 is to assure
an alkaline condition in the ether.
6c. Remove the stopper before opening the stopcock.
7a. The 5 size of the flask should be capable of
fitting the three ball Snyder columns.
E21-25
-------
MTER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
E21-26
OFERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Sample Treatment
(Continued)
3. Hydrolysis
10. Add 50 ml of ether.
11. Stopper and shake vigor-
ously for one minute.
12. Place in holder and allow
phases to separate for at
least 10 minutes.
13. After separation of the
phases is complete, drain
the water phase in the
one liter Erlenmeyer flask
used in step 6.
14. Combine the other phase
with the first ether
extract.
15. Repeat steps 9-14 with a
third extraction of 50 ml
of ether.
1. Add 15 ml of distilled
water and one small boilinc
stone to the flask con-
taining the ether extract.
2. Insert a 3 section Snyder
column into the flask.
3. Suspend flask and column
over a steam bath.
lOa. Use the ether to rinse out the flask used to
contain the aqueous layer.
lla. Occasionally invert the separatory funnel and
relieve the pressure by slowly opening the
stopcock.
13a. Assure no water phase remains to be collected
with the ether.
la. Use a 25 ml graduated cylinder.
3a. Support with ring stand and clamp.
-------
MATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
STEF SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Sample Treatment
(Continued)
. Heat until ether has
evaporated.
5, Continue heating for a
total of 60 minutes.
6. Remove and allow to cool.
7. Transfer the water con-
centrate to a 60 ml
separatory funnel.
8. Add 20 ml of ether to the
separatory funnel,
9. Stopper and shake one
minute.
10. Place in holder and allow
phases to separate for at
least 10 minutes.
11. Drain aqueous layer into a
100 ml beaker.
12. Drain off and discard the
ether.
13. Return the water to the
separatory funnel.
14. Add 20 ml ether and repeat
steps 9-13.
4a. This should be carried out in a hood,
4b. Do not allow flame in or near the hood.
4c. Ether fumes are extremely flammable.
7a. Use the same support as with other separatory
funnels.
8a. Use a 25 ml graduated cylinder.
8b. Because the solution is basic, the herbicides
will remain in the aqueous phase.
9a. Vent pressure in separatory funnel.
14a. Again discard the ether.
E21-27
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
E21-28
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Sample Treatment
(Continued)
15. Rinse the TOO ml beaker
with a small amount of
water and add to the
separatory funnel,
16. Add 2 ml of cold (4° C)
25% sulfuric acid (reagent
2) to the separatory
funnel.
17. Add 20 ml of ether to the
separatory funnel.
18. Shake one minute.
19. Allow to stand and sepa-
rate for at least 10
minutes.
20. Drain the aqueous layer
into a TOO ml beaker.
21. Add 0.5 grams of acidified
anhydrous sodium sulfate
(reagent 8) to a 125 ml
Erlenmeyer flask.
22. Collect the ether in the
125 ml Erlenmeyer flask.
23. Return the water layer to
the separatory funnel.
24. Add 10 ml ether.
25. Repeat steps 17-22.
15a. Use about 2 ml.
16a. This reagent should have been stored in the
freezer section of a refrigerator (B.2.6).
16b, This will acidify the solution; the herbicides
are now soluable in the organic phase.
22a. The herbicides are in the ether.
23a. Close the stopcock.
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
F. Sample Treatment
(Continued)
4. Esterification
STEP SEQUENCE
26. Extract with another 10 ml
volume of ether.
27. Collect all ether ex-
tractions in the same
125 Erlenmeyer (step 22).
28. Allow the ether extract to
remain in contact with the
sodium sulfate (step 21)
for 2 hours.
29. Turn on water bath and
heat to 50° C.
1. Connect a 10 ml graduated
ampul to a 250 ml Kuderna-
Danish (K-D) evaporative
flask.
2. Clamp flask and ampul to a
ring stand.
3. Plug the stem of a small
funnel with glass wool.
4. Position the funnel stem
into the K-D flask.
5. Transfer the ether extract
from the Erlenmeyer flask
through the funnel and
into the K-D flask.
INFORMATION/OPERATING GOA!S/SPECIFICATICNS
26a. This will be three extractions, one with 20 ml
and two with 10 ml of ether.
26b. On final extraction, rinse the 100 ml beaker used
to collect the aqueous phase with the ether and
then add the ether to separatory funnel.
la. Attach springs.
3a. Should have been washed with acid.
5a. Use a glass stirring rod and crush any caked
sodium sulfate.
5b. The sodium sulfate may be transferred to the
funnel.
TRAINING
GUIDE NOTES
E21-29
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
E21-30
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Sample Treatment
(Continued)
6. Wash the Erlenmeyer flask
and sodium sulfate with
liberal amounts of ether.
7. Add 0.5 ml benzene.
8. Position flask above steam
bath and evaporate to about
5 ml.
9. Rinse the flask with 2 ml
of ether.
10. Remove ampul from flask.
11. Insert the two section
Snyder microcolumn into
the ampul.
12. Return to steam bath and
concentrate to about
0.4 ml.
13. Remove from steam bath and
allow to cool.
14. Remove column.
15. Add 0.5 ml of boron tri-
fluoridemethanol reagent.
16. Return two chamber column
to the ampul.
17. Lower into a preheated
50° C water bath.
7a. Use a 1 ml graduated pi pet.
8a. A condenser column is not necessary.
lla. Attach springs.
12a. All ether should have been evaporated.
17a. Support by a ring stand and clamp.
17b. This is not the steam bath.
-------
lyAT£_R_HQ_N I TORI NG PROCE PURE ; Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
F, Sample Treatment
(Continued)
STFP SEQUENCE
18. Heat for 30 minutes.
19. Remove from bath and cool
to room temperature.
20. Remove column.
21. Add enough sodium sulfate
solution (reagent 3} to
position the interface,
between the benzene and
aqueous sodium sulfate,
into the neck of the K-D
ampul,
22. Stopper the ampul and
shake vigorously for about
one minute.
23. Allow to stand and
separate.
24. Plug a disposable Pasteur
pipet with glass wool,
25. Add florisil absorbant to
the column.
?6. Place on top of the flori-
sil some granular sodium
sulfate.
27. Support the mini-column.
28. Position mini-column into
the neck of a 10 ml gradu-
ated K-D ampul.
INFORMATION/OPERATING GOALS/SPECIFICATIONS
18a. The column acts as an air cooled condenser.
21a. Usually about 4 to 5 ml.
23a. About three minutes.
25a. Add enough to provide about 2.0 cm height (in the
large diameter section on the pipet).
26a. Enough to provide a sodium sulfate length of
2.0 cm.
27s. In a clamp on a stand.
TRAINING
GUIDE NOTES
E21- 31
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
L21-32
OPERATING PROCEDURE:
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
F. Sample Treatment
(Continued)
G. Sample Analysis
29. Pipet the solvent layer
from the neck of the ampul
(step 22) to the top of
the mini-column.
30. Add small amounts of
benzene to the ampul,
shake, allow to separate
and pipet into column.
31. Adjust final volume to
5.0 ml.
32. Stopper the ampul.
29a. Another Pasteur pipet and bulb can be used
(just the pipet no packing).
29b. Collect as little of the aqueous sodium sulfate
as possible.
30a. This is a washing step for the ampul, aqueous
phase and column. Little to no water should be
transferred to the column.
30b. The final volume will be 5.0 ml. Take care not
to wash with volumes of benzene which will sur-
pass this total volume.
32a. This extract if kept well stoppered and refrig-
erated, can be held 30 days.
1 . Check all instrument
parameters.
2. Inject 5 ul of the stan-
dard mix 2.
3. Determine if response has
changed.
4. Inject 5
blank.
of method
5. Inject 5 ;jl of the stan-
dard carried through the
procedure.
la. They should be the same as used to obtain
optimum results (section E.I.3).
2a. Table 1.
3a. Compare results for retention times and response
(peak height) with those obtained in E.I.2.
4a. No significant peaks should be obtained.
5a. From section F.2.1.Id.
-------
MATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
OPERATING PROCEDURES
STEP SEQUENCE
INFCRMATION/OPIRAIING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
G. Sample Analysis
(Continued)
H. Calculations
1. Calculation of
Results
6. Inject 5 ul of the
sample/s.
7. Compare with standard
curve.
8. Choose a standard whose
concentration will produce
a peak that will approxi-
mate that obtained from
the sample.
9. Calculate the amount of
herbicide/s present.
1. Calculate the micrograms
of methyl ester per liter
of sample.
6a. Inject 5 ul of the duplicate sample.
6b. Be sure to time the peaks from the first
appearance of the solvent peak to the top of
each peak.
7a. Step E.3.3,
9a. See the calculation section.
la. Determine the methyl ester concentration by
using the equation below.
micrograms A x B x V
per liter
Vi*V5
where A = 03L standard (obtained in Sample
standard area Analysis section,
step G.8)
B = Sample aliquot area (step G.6)
Vt = Volume of total extract in micro-
liters (the volume to which the
extract was concentrated i.e., 5 ml)
E21-33
-------
HATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
E21- 34
OPERATING PROCEDURES
STEP SEQUENCE
INFORMATION/OPERATING GOALS/SPECIFICATIONS
TRAINING
GUIDE NOTES
H. Calculations
(Continued)
2. Reporting Results
2. Convert to niicrogratns of
acid per liter of sample.
1. Report results in ing per
liter as the acid.
V. = Volume of extract injected in
microliters
V = Volume of water (sample) extracted
in mill liters
Molecular Wt. Acid
Molecular Wt, Ester
jjg acid = ug ester x
Molecular Weight:
2,4-D (acid) = 222.0
2, 4-D (ester) = 236.0
Silvex (acid) = 269.5
Silvex (ester) = 283.5
la. Without correction for recovery data.
lb. Report duplicate and spiked sample results when
analyzed.
-------
WATER MONITORING PROCEDURE: Determination of Chlorinated Phenoxy Acid Herbicides
TRAINING GUIDE
SECTION TOPIC
I* Introduction
II Educational Concepts - Mathematics
III Educational Concepts - Science
IV Educational Concepts - Communications
V* Field and Laboratory Equipment
VI Field and Laboratory Reagents
VII* Field and Laboratory Analysis
VIII Safety
IX Records and Reports
*Training Guide materials are presented here under the headings marked*.
These standardized headings are used through this series of procedures.
E21-35
-------
WATER MONITORING PROCEDURES: Determination of Chlorinated Phenoxy Acid Herbicides
INTRODUCTION
Section I
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
C.I.la
When the National Interim Primary Drinking Water
Regulations were promulgated they contained the re-
quirement that all Public Water Supplies be moni-
tored for herbicide contamination. Certain
monitoring frequencies and analytical methods were
prescribed. A level beyond which public notifica-
tions and other steps were to be carried out was
set and termed the Maximum Contaminant Level (MCL).
The MCL's for the chlorophenoxy herbicides are as
follows:
2,4, Dichlorophenoxyacetic acid (2,4-D) -
0.1 mg/liter
2,4,5-Trichlorophenoxypropionic acid (2,4,5-TP)
0.01 mg/liter
These materials are used extensively for weed
control in lakes, streams and irrigation canals.
Phenoxy acid herbicides are very potent even at
low concentrations.
-------
MATER MONITORING PROCEDURES: Determination of Chlorinated Phenoxy Acid Herbicides
FIELD AND LABORATORY EQUIPMENT
Section V
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
E.1.3a
E,3.2b
D.I
D.6.6b
Because of the many variables inherent in gas
chromatography, the column packing, column oven
temperature and carrier gas flow rate may have to
be adjusted to different settings than those given.
The analyst should strive to reproduce the re-
tention times given in the body of the paper as
guides. The two things which must be obtained are
reproducibility and resolution. When these are
adequate, the system is suitable.
The analyst must determine the detection limit for
each herbicide. If a sample is taken through the
procedure and no peaks are obtained, while peaks
are obtained for a standard carried along with
the sample, then the analyst is assured that
herbicides are not present in concentrations above
his detection limit. Whenever reporting such results
the analyst should report the detection limit and
state that no herbicide is present above that
concentration. The values 200 ng for 2,4-D and
10 pi
20 ng
10 M! for si 1 vex represent the published MCL for
that compound in a 5 ml volume, that is the con-
centration factor of this procedure.
Use of high grade carrier gases are recommended.
However, occasionally bad cylinders of the Sigon-
Methane gas can be obtained. Before attaching it to
the instrument, a slight sniff of the gas should be
taken; if a "fishy" smell is noted, the tank may be
contaminated. Use of the gas will produce an off-
scale peak and very noisy base line. If contami-
nated gas is used in the instrument, remove from use
as soon as detected and replace all traps and purge
with a noncontaminated gas.
OV-210 may be substituted for QF-1. The OV-210 is a
purified version of the QF-1 and does not tend to
bleed as much as the QF-1.
E21-37
-------
WATER MONITORING PROCEDURES: Determination of Chlorinated Phenoxy Acid Herbicides
FIELD AND LABORATORY ANALYSIS
Section VII
TRAINING GUIDE NOTE
REFERENCES/RESOURCES
VII.5.1
Standards may be prepared from the acids or the
methyl esters. If prepared from the methyl esters,
the esteriflcation steps are not necessary. How-
ever, the methyl esters are hard to purchase.
Since samples must be esterified, the standard
should also be esterified. If anything less than
100% conversion of the acid to the ester 1s ob-
tained in the esterification steps, the standards
will not reflect this and an incorrect analytical
result can be obtained.
Consequently, this procedure has been written using
an esterification step for the standards.
E21-38
-------
TABLE 2
RETENTION RATIOS FOR METHYL ESTERS OF SOME CHLORINATED
PHENOXY ACID HERBICIDES RELATIVE TO 2,4-D
Liquid Phase
Column Temp.
Argon/Methane
Carrier Flow
Herbicide
2,4-D
Si 1 vex
2,4-D
(minutes absolute)
1.5% OV-17
+
1.95* QF-1
185° C
70 ml/min.
RR
1.00
1.34
2.00
5%
OV-210
185° C
70 ml/min.
RR
1.00
1,22
1.62
All columns glass, 180 cm x 4 mm ID, solid support Gas Chrom Q (100/120 mesh)
E21-39
-------
E21-40
6420
RETENTION TIME IN MINUTES
FIG. 1 Column: 1.5% OV-17+1.95% QF-1,
Carrier Gas: Argon (5%) /Methane: 70 ml/min.,
Column Temp. 185 C, Defector: Electron Capture.
-------
WEDNESDAY, DECEMBER 24, 1975
PART IV;
ENVIRONMENTAL
PROTECTION
AGENCY
WATER PROGRAMS
National Interim Primary Drinking
Water Regulations
-------
.19500
RULES AND REGULATIONS
Title 40—Protection of Environment
CHAPTER I—ENVIRONMENTAL
PROTECTION AGENCY
SUBCHAPTER D—WATER PROGRAMS
IFBL 464 7)
PART 141—NATIONAL INTERIM PRIMARY
DRINKING WATER REGULATIONS
On March 14, 1975, the Environmental
Protection Agency (EPA) proposed Na-
tional Interim Primary Drinking Water
Regulations pursuant to sections 1412,
1414, 1415, and 1450 Of the Public Health
Service Act ("the Act"), as amended by
the Safe Drinking Water Act ("SDWA,"
Pub. L. 03-523), 40 FE 11990. EPA held
public hearings on the proposed regula-
tions in Boston, Chicago, San Francisco,
and Washington during the month of
April. Several thousand pages of com-
ments on the proposed regulations were
received and evaluated. In addition, the
Agency has received comments and In-
formation on the proposed regulations
from the National Drinking Water Ad-
visory Council, the Secretary of Health,
Education, and Welfare, and from num-
erous others during meetings with repre-
sentatives ol State agencies, public in-
terest groups and others,
The regulations deal only with the
basic legal requirements. Descriptive
material will be provided in a guidance
manual for use by public water systems
and the States.
The purpose of this preamble to the
flnal regulations Is to summarize the most
significant changes made In the proposed
regulations as a result of comments re-
ceived and the further consideration of
available information. A more detailed
discussion of the comments and of
changes In the proposed regulations is
attached as Appendix A.
WATFR SYSTEMS CovrRr.o
The Safe Drinking Water Act applies
to each "public water system," which is
denned Jn Section 1401 <4> of the Act as
"a system for the provision to the public
of piped water for human consumption.
If such system has at least fifteen service
connections or refrularly serves at least
twenty-five individuals." Privately owned
as well as publicly owned systems are
covered. Service "to the public" Is Inter-
preted by EPA to Include factories und
private housing developments.
-------
RULES AND REGULATIONS
These on-site inspections of water sys-
tems are more effective in assuring safe
water to the public than individual tests
taken in the absence of sanitary surveys.
The regulations provide that monitor-
ing frequencies for coliform bacteria can
be changed by the entitv with primary
enforcement responsibility for an Indi-
vidual non-community system, and in
certain circumstances for an individual
community system, based on the results
of a sanitary survey.
MAXIMUM CONTAMINANT LF.VT.IS
Numerous comments were received by
EPA on the substances selected for the
establishment of maximum contaminant
levels and on the levels chosen Congress
anticipated that the initial Interim Pri-
mary Drinking Water Regulations would
be based on the Public Health Service
Standards of 1962. and this Congres-
sional Intent has been followed. Com-
ments received on the various levels did
not contain new data sufficient to re-
quire the establishment of level', differ-
ent from those contained in the Public
Health Service Standards.
WATER CONSUMPTION
The maximum contaminant levels are
based, directly or indirectly, on an as-
sumed consumption of two liters of water
-per day. The same assumption was used
In the 1962 Standards. This assumption
has been challenged because of instances
where much higher water consumption
rates occur. EPA's justification for using
the two-liter figure is that, it already
represents an above average water or
water-based fluid intake. Moreover, while
the factor of safety may be somewhat re-
duced when greater quantities of water
are ingested, the maximum contaminant
levels based on the two-liter figure pro-
vide substantial protection to virtually
all consumers. If, as has been suggested,
a water consumption rate of eight liters
•per day Is used as the basis for maxi-
mum contaminant level, all of the pro-
posed MCL's would have to be divided by
four, greatly increasing ihe monitoring
difficulties, and in some cases challeng-
ing the sensitivity of accepted analytical
procedures. It could be expected, in such
a ease, that the maximum contaminant
levels would be exceeded to a significant
degree, and that specialized treatment
techniques would be required to order
that the contaminant levels would be re-
duced. The economic impact of a move
In this direction would be enormous. It
Is not technically or economically feasi-
ble to base maximum contaminant levels
on unusually high consumption rates.
SAFETY FACTORS
A question was raised about the fact
that different safety factors are con.
talned in various maximum contaminant
levels. The levels are not intended to
have a uniform safety factor, at least
partly because the knowledge of and the
nature of the health risks of the various
contaminants vary widely. The levels set
are the result of experience, evaluation
of the available data, and professional
judgment. They have withstood the test
of time and of professional review, They
are being subjected to further review by
the National Academy of Sciences in con-
nection with development of data for the
Revised Primary Drinking Water Regu-
lations.
MCL's BASED ON TEMPOS'! URE
A question was also raised as to
whether ranges of maximum contami-
nant levels should be established on the
basis of tlie climate in the area served
by the public water system, as was done
with fluoride. EPA believes that the use
of a temperature scale for fluoride is
more appropriate than for other chemi-
cals because of the studies available on
the fluoride-temperature relationship
and because there is a small margin with
fluoride between beneficial levels and
levels that cau.se adverse health effects.
MCL's DELETED
Three proposed maximum contami-
nant levels have been eliminated in the
final regulations because they are not
justified by the avnilable data. One of
these is carbon chloroform extract
(CCE>. which Is discussed separately
below. The others are the proposed levels
for the standard bacterial plate count
and cyanide. In the case of the plate
count, it is believed that the coliform
limits contained in the regulations, com-
bined with the turbidity maximum con-
taminant level, adequately deal with
bacterial contamination. However, EPA
continues to believe that the standard
plate count is a valid indicator of
bacteriological quality of drinking water.
and recommends that it be used in ap-
propriate cases in conjunction with the
coliform tests as an operational tool.
The proposed maximum contaminant
level for cyanide was eliminated because
the possibility of cyanide contamination
can be effectively addressed only by the
use of emergency action, such as under
Section 1431 of the Act. EPA's 1969 Com-
munity Water Supply Study did not
reveal a single instance in which cyanide
was present in a water system at a level
greater than one-thousandth of the level
at which cyanide is toxic to humans.
Available data indicate that cyanide
will be present in water systems at toxic
levels only in the event of an accident,
such as a spill from a barge collision.
Maximum contaminant levels are not
the appropriate vehicle for dealing with
such rare, accidental contamination.
Heptachor, hejstachlor epoxide
and chlordane have also been removed
from the list of maximum contaminant
levels at least temporarily in view of the
pending cancellation and suspension
proceedings under the Federal Insecti-
cide, Fungicide and Rodenticide Act in-
volving those pesticides. When the re-
sults of these proceedings are available,
EPA will again consider whether maxi-
mum contaminant levels should be es-
tablished for those three pesticides.
SODIUM AND SUI.FATES
A number of comments were received
on the potential health effects of sodium
and sulfates. The National Urinking
Water Advisory Council has recom-
mended that consideration be given to
the monitoring of these constituents, but
has not, recommended the adoption of
maximum contaminant levels because
available data do not support the adop-
tion of any specific levels. EPA has re-
quested the National Academy of Sci-
ences to include sodium and sulfates
among the contaminants to be studied
by NAS, and to include information on
the health effects of sodium and sulfates
in the report to be made by NAS in
December 1976.
Since a number of persons suffer from
diseases which arc influenced by dietary
sodium im.ike and since then: are others
who wish to restrict their sodium in-
take, it is desirable that the sodium con-
tent of drinking water be known. Those
affected can, bv knowing the sodium con-
centration in their drinking water, make
adjustments to their diets or, in extreme
case?, seek alternative sources of water
•a be used for drinking and food prepara-
tion. I( is recommended that the States
institute programs [or regular monitor-
ing of the sodium content of drinking
water served tr> the public, and for in-
forming {ihvbjfinns and consumers of the
sodium concentration in drinking water.
A relatively hifh concentration of sul-
fate in drinking water has little or no
known laxative effect on regular users of
the water, but transients using such
water sometimes experience a laxative
effect. It is recommended that the States
institute monitoring programs for stil-
fp.tss, and that transients be notified if
the sulfate content of the water is high.
Such notification should include an as-
sessment of the possible physiological
effects of consumption of the water
PCB's AND ASBESTOS
An inter a,Ten cy comment expressed
concern for asbestos and PCB's in the
environment and noted the need for at
least a monitoring requirement, if not
for MCL's. for these contaminants. EPA
Is also concerned, but for the moment
lacks sufficient evidence regarding ana-
lytical methods, health effects, or occur-
rence in the environment to establish
MCL's The Agency is conducting re-
search and cooperating in research proj-
ects to develop criteria for eslablUhiriK
needed limits as quickly as possible A
monitoring study on a number of organic
chemical contaminants, including PCB's,
for which MCL's are not being estab-
lished at this time, will be contained in
an organic chemical monitoring regula-
tion thai Is being promulgated with these
regulations. Regarding asbestos, HEW
and EPA are sponsoring a number of
studies this year at an approximate cost
of $16 million to establish health effects,
anayltical methods and occurrence
POIXT or MEASUHEMENT
Other comments on maximum con-
taminant levels focused on the proposed
requirement that such levels be tested
at the consumer's tap. Concern was ex-
pressed over the inability of the public
water system to control potential sources
FEDERAL RfClSTfl, VOL. 40, NO. 241—WEDNESDAY DECEMBER 24, 1775
-------
59568
RULES AND REGULATIONS
of contaminants which are under the
control of the consumer.
The promulgated definition of "maxi-
mum contaminant level," | 141,2(d>, re-
tains the requirement that the maxi-
mum contaminant level be measured at
the tap except In the case of turbidity,
which should be measured at the point
of entry to the distribution system. How-
ever, the definition has been expanded
to make clear that contaminants added
to the water by circumstances under the
control of the consumer are not the re-
sponsibility of the supplier of water,
unless the contaminants result from cor-
rosion of piping and plumbing resulting
from the quality of the water supplied.
It should be noted, however, that this
requirement ihould not be Interpreted
at to discourage local, aggressive cross
connection control measures.
ConroHM BACTERIA MCL's
The promulgated MCL's for collform
bacteria are basically the 1962 Public
Health Service Standards, with minor
refinements and clarifications. However,
further changes may be desirable. For
example, the MCL's for the membrane
filter analytical method do not resolve
the question of how many collform bac-
teria are assumed to be present In a
single highly contaminated sample.
Some laboratories assume an upper limit
of 50, while others Reek to continue to
count Individual bacteria to a level of
100 or even higher in a single sample
The upper limit assumed will affect tlie
monthly average which is calculated to
determine compliance with the MCL's.
Another question relating to the coli-
form bacteria MCL's Is the matter of
possible spurious positive samples. As the
regulations are written, all routine sam-
ples taken to determine compliance with
the MCL's must be counted, regardless
of the results of unalysls of any check
samples that may be taken. The reason
for this is that bacterial contamination
la often intermittent or transient, and as
a result negative check samples taken a
day or more after a positive sample can-
not demonstrate that the positive result
was In error. It may be possible, however,
to prescribe a means of dealing with spu-
rious positive results without compro-
mising the Integrity of the MCL's.
A third question concerning the MCL's
for collform bacteria is the relationship
of monthly averages of coliform bacteria
levels to monthly percentages of positive
samples. For example, the monthly av-
erage MCL for the membrane filter
method Is violated if the monthly aver-
age exceeds one collform bacterium per
sample. However, for purposes of deter-
mining whether the monthly-percent-
age-of-positlve-samples MCL Is violated.
a sample Is counted as positive only If it
contains more than four coliform bac-
teria. Thus, It is possible, particularly
when a relatively small number of sam-
ples Is taken, for a system to fail the
monthly average MCL even when no sin-
gle sample taken during the month Is
out of compliance with the limit.
These and other questions concerning
Uie coliform bacteria MCL's will be re-
viewed further by EPA. If review Indi-
cates that changes In the MCL's are
desirable, those changes will be made as
soon as possible but within 8 months, In
time to take effect at the same time as
the Initial Interim Primary Drinking
Water Regulations.
ORGANIC CHEMICALS
The proposed maximum contaminant
levels for organit; pesticides, other than
the three which are the subject of can-
cellation and suspension proceedings,
have been retained. It Is anticipated that
additional organic pesticides will be
added to the regulations If surveys of
pesticides In drinking water being con-
ducted by EPA indicate that this Is
needed.
The proposed regulations also con-
tained a maximum contaminant level for
organic chemicals obtained by the carbon
chloroform extract (CCE) method. It
was anticipated by Congress that organic
chemicals would be dealt with primarily
In the Revised Primary Drinking Water
Regulations because of the paucity of ac-
curate data on the health effects of vari-
ous organic chemicals, the large number
of such chemicals, unccrtHinUles over ap-
propriate treatment techniques, and the
need for addlttoral Information on the
incidence of specific organic chemicals
in drinking water supplies. EPA thought
that the CCE standard might provide an
appropriate means of dealing with or-
ganic chemicals as a class pcndinp action
on the Revised Primary Regulations
Tlie CCE standard was originally de-
veloped as u test for undesirable tastes
and odors Sn drinking water. As concern
developed over the health effects of or-
ganic chemicals, the possibility of using
CCE as a health standard rather than
an esthetic standard was considered,
A« pointed out by numerous comments,
CCE has many failings as an Indicator
of health effects of organic chemicals.
To begin with, the test obtains Informa-
tion on only a fraction of the total
amount of organic chemicals in the water
sampled. Furthermore, there Is serious
question as to the reliability of CCE in
identifying thosn organic chemicals
which are most suspected of adverse
health effects. In addition, there are no
existing data on which a specific level
for CCE can be established on a rational
basis. To establish n maximum contami-
nant level under these circumstances
would almost certainly do more harm
than good. It could give a false sense of
security to persons served by systems
which are within the established level
and a false sense of alarm to persons
served by systems which exceed the level.
It also would divert resources from
efforts to find more effective ways of
dealing with the organic chemicals
problem.
EPA believes that the intelligent
approach to the organic chemicals ques-
tion Is to move ahead as rapidly as pos-
sible along two fronts. First, EPA Is
adopting simultaneously with these reg-
ulations a Subpart E of Part 141, con-
taining requirements for organic chemi-
cal monitoring pursuant to Sections 1445
and 1450 of the Act.
The regulation* require that desig-
nated public water systems collect sam-
ples of raw and treated water for submis-
sion to EPA for organlcs analysis. EPA
will analyze the samples for a number of
broad organic pnrameters, Including car-
bon chloroform extract (CCE), volatile
aiid non-volatile total organic carbon
(VTOC and NVTOO, total organic chlo-
rine (TOC1), ultraviolet absorbancy, and
fluorescence. In addition, monitoring will
be required for probably 21 specific or-
ganic compounds. Selection of the spe-
cific compounds has been based on the
occurrence or likelihood of occurrence In
treated water, toxlclty data and availa-
bility of practical analytical methods.
Laboratory analyses will be used to
evaluate the extent and nature of organic
chemical contamination of drinking
water, to evaluate the validity of the
general organic parameters as surrogates
for measures of harmful organic chemi-
cals, and to determine whether there Is
an adequate basis for establishing maxi-
mum contaminant levels for specific or-
ganies or groups of organlcs.
Second, EPA is embarking on an inten-
sive research program to find answers
to the following four questions:
1. What are the effects of commonly
occurring organic compounds on human
health?
2. What analytical procedures should
be used to monitor finished drinking
water to assure that nny Primary Drink-
ing Water Regulations dealing with or-
ganics are met?
3. Because some of these organic com-
pounds are formed during water treat-
ment, what changes In treatment prac-
tices are required to minimize the for-
mation of these compounds in treated
water?
4. What treatment technology must
be applied to reduce contaminant levels
to concentrations that may be specified
in the Primary Drinking Water Regu-
lations?
This research wiil involve health-
effects and epidemlologkal studies, In-
vestigations of analytical methodology,
and pilot plant and flsld studies of or-
ganic removal unit processes. Some
phases of the research are to be com-
pleted by the end of this year, while
much of the remainder are to be com-
pleted within the next calendar year.
As soon as sufficient Information Is
derived from the monitoring program
and related research, the Interim Pri-
mary Drinking Water Regulations will
be amended so that the organic chemi-
cals problem can be dealt with without
delay. The monitoring process will be
completed within 1 year.
During the Interim period, while sat-
isfactory MCL's for organic contamina-
tion in drinking water arc being devel-
oped, EPA will act in specific cases where
appropriate to deal with organic con-
tamination. If the EPA monitoring pro-
gram reveals serious specific cases of
contamination, EPA will work with StRte
and local authorities to Identify the
source and nature of the problem and to
FEDERAL REGISTER VOl 40, NO. J4J—WEDNESDAY, DECEMBER 34, 1975
-------
iUlES AND REGULATIONS
59569
take remedial action. EPA will also old
the States in identifying additional com-
munity water supplies that require
analysis.
PUBLIC NOTICE
The public notice requirements pro-
posed In § 141.32 dtd not distinguish be-
tween community and non-community
public water systems. They would have
required that public notice of non-com-
pllanre with applicable regulations be
made by newspaper, in water bills, and
by other media for all public water sys-
tems. These requirements are Inappro-
priate and Ineffective In the case of most
non-community water systems. Those
systems principally serve transients who
do not receive water bills from the sys-
tem and who probably are not exposed
significantly to the local media. A more
effective approach would be to require
notice that can inform the transient
before he drinks the system's water, and
thereby both warn the transient and
provide an incentive to the supplier of
water to remedy the violation. Accord-
ingly, Section 141.32 as adopted provides
that in the case of non-community sys-
tems, the entity with primary enforce-
ment responsibility shall require that
notice be given In a form and manner
that will insure that the public using
the public water system is adequately
Informed.
The proposed public notice require-
ments also faiLed to distinguish between
different types of violations of the In-
terim Primary Drinking Water Regula-
tions. Since the urgency and Importance
of a notice varies according to the nature
of the violation Involved, § 141.32 as
promulgated seeks to match the type of
notice required with the type of violation
Involved. Written notice accompanying
a water bill or other direct notice by
mall is required for all violations of the
regulations, including violations of mon-
itoring requirements, and for the grant
of a variance or exemption. In addition,
notice by newspaper and notification to
radio and television stations Is required
whenever a maximum contaminant level
Is exceeded, or wlien the entity with
primary enforcement responsibility re-
quires such broader notice.
QUALITY CONTROL AND TESTING
PROCEDURES
Section 1401(1) of the Act defines
"primary drinking water regulation" to
Include "quality control and testing pro-
cedures." The promulgated regulations
include testing requirements for each
maximum contaminant level, including
check samples and special samples in
appropriate cases. The regulations also
specify the procedures to be followed in
analyzing samples for each of the maxi-
mum contaminant levels. These proce-
dures will be updated from time to time
as advances are made In analytical meth-
ods. For example, references to "Stand-
ard Methods for the Examination of
Water and Wastewater" are to the cur-
rent, 13th, edition, but these references
will be changed to cit* the HtJh edition
when It is available In the near future.
A key element of quality control for
public water systems IE accurate labora-
tory analysis. Section 14128 of tlie regu-
lations provides that analyses conducted
for the purpose of determining com-
pliance with maximum contaminant
levels must be conducted by a laboratory-
approved by the entity with primary en-
forcement responsibility. EPA will de-
velop as soon as possible. In cooperation
with the States and other interested
parties, criteria and procedures for lab-
oratory certification. A Slate with pri-
mary enforcement responsibility will
have'a laboratory certified by EPA pur-
suant to the prescribed criteria and pro-
cedures, and in turn will certify labora-
tories within the State.
Record-keeping requirements and re-
ports to the State also will assist in
quality control efforts.
RECORD-KEEPING
Adequate record-keeping Is necessary
for the proper operation and administra-
tion of a public water system. It is also
Important for providing information to
the public, providing appropriate data
for inspection and enforcement activities
and providing information on \vhich fu-
ture regulations can be based. Accord-
ingly, a new § HI.33 has been added to
the regulations to require that eurh pub-
lic water system maintain records of
sample analvses and of actions to r.rrrect
violations of the Primary Drinking Water
Regulations.
ECONOMIC AMD COST ANALYSIS
A comprehensive economics study has
been ir.ade of the Interim Primary Drink-
Ing Water Regulations. This study esti-
mates the costs of the regulations, evalu-
ates the potential economic Impact, and
considers possible material and labor
shortages. The results of this analysis are
summarized here
Total Investment costs to coinimmily
water systems to achieve compliance
with these regulations arc estimated to
be between $1,050 and $1,765 million. It
Is estimated that non-community sys-
tems will invest an additional $24 million.
The range of the estimate ii due to un-
certainty as to the desipn flow thnt will
be used in installing treatment facilities.
Systems not In compliance will have to
consider sizing their new components to
reflect average daily flow conditions, or
maximum daily now conditions in cases
where system storage is not adequate.
This investment will be spread over
several years. Investor-owned systems
will bear about one-fourth of these rofts,
and publicly-owned systems the remain-
der. It Is not anticipated that, systems will
have difficulty financing these capital re-
quirements.
In annual terms, national costs are ex-
pected to be within the following rungcs:
In millions
.. $146 247
.. 363 .363
17- 36
Capital costs,.
Operation:! and mnJntenancy
Monitdrtisg (roxHlne oni>')
Total - M26-54S
Although these aggregate figures are
large, most water consumers will not be
significantly affected. For those users In
systems servinE 10,000 persons or more,
tl»e average annual treatment cost per
capita may increase from less than $1.00
for systems requiring disinfection and
lead control, to between $15 to $35 for
control of turbidity and heavy metal re-
moval. For systems serving ICEB than 100
persons, the average annual per capita
costs of disinfection, lead control and
fluoride/arsenic removal are estimated to
be between $2.10 and $11.80. However, if
turbidity control or heavy metal removal
were required in' a system of this size
then costs are expected to range from,
$52 to 5237 per year per capita. EPA is
aware of the serious potential economic
Impact on users in these small systems.
However, the legislative history specifies
that the regulations should be based on
costs that can be reasonably afforded by
large metropolitan or regional systems.
Further economic evaluation of these
systems is teing conducted, and realistic
options for these small systems are being
reviewed. Options that will be under con-
sideration include less costly treatment
technologies; formation of regional sys-
tems; and use of alternative water
sources. Ind'.is!,rial and commercial users,
whether providing their own water or
using public, systems, are not expected
to be .MBnifk'jintly aflor.trd by these
regulations.
Possible constraints to the implemen-
tation of the interim primary regula-
tion« were examined. Although there
will be an increase in demand for chem-
icals, manpower, laboratories, and con-
struction of treatment facilities, it is not
anticipated tint any of these factors u-Dl
be a ferious obstacle to implementation
of these regulations over B reasonable
time frame.
For the reasons giver, above. Chapter
4(1 of the Code of Federa! Regulations Is
hereby amended by the addition of the
following new Pan 141. These regula-
tions will tnke effect 18 months after
promulgation.
(II is hereby crrtifird that the economic and
Inflationary lir.pnrts o( these regulations
haTft beer* earefuUf evaluated in accordance
with Executive Order 11821J
Dated: December 10, 1975
RUSSELL E. TRAIN.
Administrator
Subparl A—General
Sec.
141.1 App!i'-»!><:ity
141.2 Definitions
141.3 Cover;. i;r
141 4 Variances &nd exemptions
141 5 Siting rrc|ulrrmei>t«.
141.8 Effective (intr
Subpart D—Maximum Contaminant Levels
141.11 MaXiimiti'. Gor.iiirjilr.&tit level** Jor
Inorganic chenilcals,
141.12 Maximum cont*mln«i;t lew:!* for
organic chemicals.
141.13 Maximum contaminant levels for
turbidity.
141.14 Maximum microbiological contami-
nant levels
Subpart C—Monitoring and Analytical
Require m« n(i
141 Jl Microbiological contamliiaiit sam-
pling fuid analytical requirement*.
FEDEUM IfOtSTIl, VOL. 40, NO, 248—WEDNESDAY, DECIMiH 24, 1975
-------
59570
RULES AND REGULATIONS
s*c.
141.22
141.23
141,24
1*1.27
141.28
141 29
Turbidity aunpllng and analytical
requirements
Inorganic chemical lampltng and
analytical requirements.
Organic chemical sampling and
analytical requirements.
Alternative analytical techniques.
Approved laboratories.
Monitoring of coiistcutKo public
water »ya terns,
Subpirt D—Reporting, Public Notification, and
Hfrcord keeping
141.31 Reporting requirement*.
141.32 Public notification of variances, ex-
emptions, and non-compllanca
with regulations.
141,33 Becord maintenance.
AUTHORITY: 6*CB. 1413, 1414, 1445, »nd 1450
of the Public Health Service Act, B8 8tat. I860
(42 U.S.C. 300g-l, 300g-3, 30QJ-4, and 300J-B).
g 141.1
Subpart A—General
Applicability,
This part establishes primary drinking
water regulations pursuant to section
1412 of the Public Health Service Act, as
amended by the Gate Drinking Water
Act (Pub. L. 93-523); and related regula-
tions applicable to public water systems.
§141.2 Definitions.
As used In this part, the term:
(a) "Act" means the Public Health
Service Act, as amended by the Safe
Drinking Water Act, Pub. L. 83-523
Cb) "Contaminant" means any physi-
cal, chemical, biological, or radiological
substance or matter in water.
(c> "Maximum contaminant level"
means the maximum permissible level of
a contaminant In water which Is de-
livered to the free flowing outlet of the
ultimate user of a public water system,
except In the case of turbidity where the
maximum permissible level Is measured
at the point of entry to the distribution
system Cbntaminants added to the water
under circumstances controlled by the
user, except those resulting from corro-
Blon ol piping and plumbing caused by
water quality, are excluded from this
definition.
(d> "Person" means an Individual,
corporation, company, association, part-
nership, State, municipality, or Federal
agency.
(e) "Public water system" means a
system for the provision to the public
of piped water for human consumption,
II such system has at least fifteen service
connections or regularly serves an aver-
age of at least twenty-five individuals
dally at least 60 days out of the year.
Such term -Includes (1) any collection,
treatment, storage, and distribution fa-
cilities under control of the operator of
such system and used primarily In con-
nection *ith such system, and <2) any
collection or pretreatment storage facili-
ties not under such control which are
used primarily in connection with such
system. A public water system Is either
a "community water system" or a "non-
community water system."
(i) "Community water system" means
a public water system which serves at
least 15 service connections used by year-
round residents or regularly serves at
least 25 year-round residents.
(11) "Non-conununlty water system"
means a public water system that is not
a community water system.
(f) "Sanitary survey" means an on-
site review of the water source, facili-
ties, equipment, operation and mainte-
nance of a public water system for the
purpose of evaluating the adequacy of
such source, facilities, equipment, op-
eration and maintenance for producing
and distributing safe drinking water.
(g) "Standard sample" means the
aliquot of finished drinking water that is
examined for the presence of coliform
bacteria.
(h) "State" means the agency of the
State government which has jurisdic-
tion over public water systems. During
any period when a State does not have
primary enforcement responsibility
pursuant to Section 1413 of the Act, the
term "State" means the Regional Ad-
ministrator, U.S. Environmental Protec-
tion Agency.
Obtains all of its water from, but
Is not owned or operated by, a public wa-
ter system to which such regulations
apply:
Does not sell water to any person;
and
(d> Is not .1 carrier wh'.ch conveys
passengers in interstate commerce.
§ 141.1 Variance1* and exemption*.
Variances or exemptions from certain
provisions of these regulations may be
granted pursuant to Sections 1415 and
1416 ol the Act by the entity with pri-
mary enforcement responsibility. Provi-
sions under Part 142, Notional Interim
Primary Drinking Water Regulations
Implementation—subpart E (Variances)
and subpart F (Exemptions)—apply
where EPA has primary enforcement
responsibility.
§ 141.5 Siting requirements.
Before a person may enter into a fi-
nancial commitment for or Initiate con-
struction of a new public water system
or increase the capacity of an existing
public water system, he shall notify the
State and, to the extent practicable,
avoid locating part or all of the new or
expanded facility at a site which:
(a) Is subject to a significant risk
from earthquakes, floods, flres or other
disasters which could cause a breakdown
of the public water system or a portion
thereof; or
(b) EKcept for intake structures, is
within the floodplaln of a 100-year flood
or Is lower thnn any recorded high tide
where appvopiiate records exist.
The U.S. Environmental Protection
Agency will not seek to override land use
decisions affecting public water systems
siting which are made at the State or lo-
cal government levels.
§141.6 Effective dale.
The regulations set forth In this part
shall take effect 18 months after the date
of promulgation.
Subpart B—Maximum Contaminant Levels
§ 141.11 Masimum contaminant level*
lor inorganic chemicals,
(a) The maximum contaminant level
for nitrate Is applicable to both commu-
nity water systems and non-community
water systems. The level! for the other
Inorganic chemicals apply only to com-
munity water systems. Compliance v*ith
maximum contaminant levels for inor-
ganic chemicals Is calculated pursuant to
i 141.23.
(b) The following are the maximum
contaminant levels for inorganic chemi-
cals other than fluoride:
Levtl,
milligram!
Contaminant per liter
Arsenic - 0.08
Barium — 1.
Cadmium , 0.010
Chromium , 0. OS
Lead - — O.OB
Mercury . 0.003
Nitrate .. .
M.'HOTO.H 1?.7U>21.<.
71).7 to 7!< .'1.. ,, 'Jl.5l«l!ft2
75.3 10 !l0.5 : M-S to 32.!<
2.0
1.8
16
1,4
§ 141.12 Maximum contaminant levels
lor organic clieinirala,
The following are the maximum con-
taminant levels for organic chemicals.
They apply only to community water
systems. Compliance with maximum
contaminant levels for organic chemicals
is calculated pursuant to 0 141,24,
Level.
mtlltgTami
per liter
(H) Chlorinated hydrocarbons:
Endrln (1.2,3,4.13. lo-hesftchloro- 0.0002
6.7-epoxjr-l,4. 4»,5,fl,7,8,8s-oeta-
h;dro-l,4-endo, endo-5,8 - dl'
metbano naphthalene).
Llndana C 1,2,3.4,6,6-Iiexachloro- 0004
cyelohiiane, gamma Isomer).
Methoxychlor (1,1,1-lVlchloro- 0. 1
bis |p melhoxjphenyl)
a, 2 -
ethane) .
Tonnphene
(ClaHttCl,-Technlo«l 0.005
chlorinated camphene, (7-69
percent chlorine).
FEDERAL REGISTER VOL. 40, NO. 748—WEDNESDAY, DECEMBER 14, 1975
-------
RULES AND REGULATIONS
59371
(b) Chlotopheuouys:
2,4 - D, (2,4-Dlehlorophenoxj'aoe- 0- 1
tic acid).
2,4,5-TP Stlvex (2,4,5-Trichloro- 0.01
pheaoxypropkmlc acid).
§ 141,13 Maximum contaminant leveli
fur turbidity.
The maximum contaminant levels for
turbidity are applicable to both commu-
nity water systems and non-community
water systems using surface water
sources In whole or in part. The maxi-
mum contaminant levels for turbidity
In drinking water, measured at a repre-
sentative »ntry point(s) to the distribu-
tion syste.u, are:
. as de-
termined by a monthly average pursuant
to I 141.22, except that five or fewer
turbidity units may be allowed if the
supplier of water can demonstrate to the
State that the higher turbidity does not
do any of the following:
(1) Interfere with disinfection;
<2> Prevent maintenance of an effec-
tive disinfectant agent throughout the
distribution system; or
(3) Interfere with microbiological
determinations.
(b) Five turbidity units based on an
average for two consecutive days pursu-
ant to 5 141.22.
§ 141.14 Maximum niivrukiolugiruT con-
tuminanl levels.
The maximum contaminant levels for
coliform bacteria, applicable to com-
munity water systems and non-com-
munity water systems, are as follows:
(a> When the membrane filter tech-
nique pursuant to § 141.21 is used.
the number of coliform bacteria shall
not exceed any of the following:
(1) One per 100 miililiters as the
arithmetic mean of all samples examined
per month pursuant to i 141.21 or
(«;
(2) Four per 100 miililiters in more
than one sample when less than 20 are
examined per month; or
(3) Four per 100 miililiters in more
than five percent of the samples when
20 or more are examined per month,
(bid) When the fermentation tube
method and 10 mlllillter standard por-
tions pursuant to I 141.21 (a) are used.
coliform bar.teria shall not be present in
any of the following:
(1) more than 10 percent of the por-
tions In any month pursuant to I 141.21
(b) or (c);
(li> three or more portions in more
than one sample when less than 20 sam-
ples are examined per month; or
(iii) three or more portions in more
than five percent of the smnples when
20 or more samples are examined per
month.
(2> When the fermentation tube
method and 100 nitillUter standard por-
tions pursuant to § 141.21(a) are used,
coliform bacteria shall not be present in
any of the following:
(i) more than 60 percent of 'he por-
tions in any month pursuant to § 141.21
or (c);
Ul» five portions in more than one
sample when less than flve samples are
examined per month, or
(iii) flve portions in more than 20
percent of the samples when flve or more
samples are examined per month.
(c) For community or non-community
systems that ore required to sample at a
rate of less than 4 per month, compli-
ance with paragraphs (a), (b)(l>, or
(b> (2) of this section shall be based upon
sampling during a 3 month period, ex-
cept that, at the discretion of the State,
compliance may be based upon sampling
during a one-month period.
Subpart C—Monitoring and Analytical
Requirements
§ 141.21 Microliiotdfic.il rontcminanl
tampling and analytical require-
ment!.
(a) Suppliers of water for community
water systems and non-community water
systems shall analyze for coliform bac-
teria for the purpose of determining
compliance with § 141.14, Analyses shall
be conducted in accordance with the an-
alytical .recommendations set forth in
"Standard Methods for the Examination
of Water and Wastewater," American
Public Health Association, 13th Edition,
pp. 662-688, except that a standard sam-
ple size .shall be employed. The standard
sample used in the membrane fiHer pro-
cedure shall be 100 miililiters. The stand-
ard sample uied in the 5 tube most
probable number *MPNi procedure (fer-
mentation tube method) shall be 5 times
the standard portion. The standard por-
tion Is either 10 milliliU'rs or 100 milli-
liter.s as described in $ 141.14 tb ' and 'c>.
The samples shall be taken at points
which are representative of the condi-
tions within the distribution system.
<\>1 The supplier of water /or a com-
munity water system shall take coliform
density samples (it regular time Inter-
vals, arid in number proportionate to the
population served by the system. In no
event shall the frequency be less than as
set forth below:
on tit
i
2
3
4
6
6
ion b^rved: samples per ?«
25 to 1.000
1.D01 to 2,500 . ......
Z.Mt to 3,300 ..
3,301104,100,. ...
4.:01 t-o 4.90<>
4.901 to 5,800 ,,
5,801 to £,700-_- _ 7
0.101 to ;.BOO .... B
7.8'U to 8,500 .. 9
8.501 to 0,400 .- .- -- 10
9.401 to 10,300 .- 11
10,301 to 11,100.. .- , 12
11.1«)1 to 12.000 13
12,01/1 to 12.900. 14
12,801 to 13.700 15
13,701 to 54,800 .... 18
14,001 to 15,500.. 17
15,501 to :a.aoo is
16,301 to 17.200 ..- 19
17.201 la 18.100 .... 20
18,101 to 18,800 ... 21
18.901 to IB 800 22
19,801 to 20,700 2'J
20,701 to 21.500. - 24
21,601 '.023,300 , 25
22,aOI to 23.200 29
23201 to 24,000 27
24,001 to 24,900 . 28
2»,901 to 25,000 .,„ 2B
25,001 to UB.OOQ .. 30
28,001 to 33.000...
33,001 to 37,000
37,001 to 41,000..
41.001 to 46,000 ......
46001 to 50.000
5O.001 to 54,000
64.001 to 58,000 ..
69.001 to 64.000 _
64.001 to 70.000
70.001 to 76,000
76,001 to 83,000 ...
83,001 to 90.000
90,001 W96.000 ,
86,001 to lll.OOO.
m.QOl to 130,000 _»
130.001 to 160,000 ,
160.001 to 190,000
193.001 la 220.000
220.001 to 250000
250.001 to 290.000 ..
203.00! 10 320.000
320 001 to 380,000
aeo.ooi to 410,000 ...
410.001 to 450,000
450.0O1 to 500.000
500,001 to 550.000 .
550,001 to 500000..
803 U01 to 880.000 ,
860,001 to 720.000
720,001 to 790,000
•78D.DO 1 to BIO 000 -
840,001 to 910.000
910.UOI to 970.000 -
1)70.0-")! to 1.000 000
1.050.30! to 1.140.000 ...
1.140301 to 1.230.000
1.231001 to 1,320000
1,:!JO.;!01 tol,420.000_
1.420,001 lo 1. WO 000
1,020.001 to J .63') 000 ---
1.030.001 to t.7X)Oor>_-
1,730.001 l<» 1 Bir'J.SOO -
1,830.001 '.0 l.UfOO'X) -
l 370.co« t--i a.ofio i;fio
2.0130.0'H lo 2.37.) COO. - --
2.'J7O,t;Q: to !.5:0,OOO -_
2.MO,001 to !,','50000- --
2.750.001 tu J.CK'OOnO
3020.001 to 1.320.000- ,
35
40
45
60
55
BO
65
70
75
80
as
80
B6
100
no
130
130
140
150
180
170
180
190
300
210
220
230
240
350
280
270
230
290
300
310
320
330
340
350
300
370
3§o
390
400
410
420
430
440
450
480
470
480
480
500
Based on a history of no coliform bac-
terial contamination and on a sanitary
survey by the State showing the water
system to be supplied solely by a pro-
tected ground water source and free of
sanitary defect,?, a community water sys-
tem .--crving 2S to 1,000 persons, with
written permission from the State, may
reduce tills sampling frequency except
that in no cose shrill il be reduced to less
than one per quarter,
(c> The .supplier of water for a non-
community water -lysw-m shall .sample for
coliform bacteria in each calendar quar-
ter during which the system provides
water to the public. Such sampling shall
begin within two years after the effective
dale of this part. If the Stale, on the
basis of a sanitary survey, determines
that some other frequency is more appro-
priate, that frequency shall be the fre-
quency required under these regulations.
Such frequency shall be confirmed or
changed on the basis of subsequent
surveys.
(dM 1 > When the coliform bacteria in a
single sample exceed four per 100 miili-
liters ), at least two consecu-
tive daily check samples shall be collected
and examined from the same sampling
point. Additional check samples shall be
collected daily, or at a frequency estab-
,1.320.001 to
1.K20.000.
J <«60 000,
3 620,001 U
3 960.C01 to 4.310 fl<».
4 3IUTI01 to 4.090.000.
4.
-------
RULES AND REGULATIONS
Hshed by the State, until the results ob-
tained from at least two consecutive
check samples show less than one con-
form bacterium per 100 mUlilitera,
<2> When collform bacteria occur In
three or more 10 ml portions of a single
sample (| 141.14(b)(l)), at least two
consecutive dally check samples shall be
collected and examined from the game
sampling point. Additional check samples
shall be collected dally, or at a frequency
established by the State, until the results
obtained from at least two consecutive
check samples show no positive tubes,
(3) When collform bacteria occur In all
five of the 100 ml portions of a single
sample <§ ui.H(b) <2) >, at least two
'dally check samples shall be collected
and examined from the same sampling
point. Additional check samples shall be
collected daily, or at a frequency estab-
lished by the State, until the results ob-
tained from at least two consecutive
check samples show no positive tubes.
(4) The location at which the check
samples were taken pursuant to para-
graphs (d) (1), (2>, or (3) of this section
shall not be eliminated from future sam-
pling without approval of the State. The
results from all collform bacterial analy-
ses performed pursuant to this subpart,
except those obtained from check sam-
ples and special purpose samples, shall be
used to determine compliance with the
maximum contaminant level for collform
bacteria as established in ! 141.14. Check
samples shall not be Included in calculat-
ing the total number of samples taken
each month to determine compliance
with 5 141.21 (b) or Special purpose samples, such as
those taken to determine whether dis-
infection practices following pipe place-
ment, replacement, or repair have been
sufficient, shall not be used to determine
compliance with 5 141.14 or 1141.21 (b)
or (c).
-------
RULES AND REGULATIONS
mental Protection Agency, Office of
Technology Transfer, Washington, D.C.
20460,1974.
(2) Barium—Atomic Absorption Meth-
od, "Standard Methods for the Exami-
nation of Water and Wastewater." 13th
Edition, pp, 210-215, or "Methods for
Chemical Analysts of Water and Wastes,"
pp. 97-98, Environmental Protection
Agency, Office of Technology Transfer,
Washington, D.C. 20460, 1974.
<3> Cadmium—Atomic Absorption
Method, "Standard Methods for the Ex-
amination of Water and Wastewater,"
13th Edition, pp. 210-215, or "Methods
for Chemical Analysis of Water and
Wastes," pp, 101-103, Environmental
Protection Agency, Office of Technology
Transfer, Washington, D.C. 20460, 1974.
(4) Chromium—Atomic Absorption
Method, "Standard Methods for the Ex-
amination of Water and Wastewater."
13th Edition, pp. 210-215, or "Methods
for Chemical Analysis of Water and
Wastes," pp. 105-106, Environmental
Protection Agency, Office of Technology
Transfer, Washington, D.C. 20460, 1874.
(5) Lead—Atomic Absorption Method,
"Standard Methods for the Examina-
tion of Water and Wastewater," 13th
Edition, pp. 210-215, or "Methods for
Chemical Analysis of Water and Wastes,"
pp. 112-113. Environmental Protection
Agency, Office of Technology Transfer,
Washington, D.C. 20460, 1974.
(6) Mercury—Flameless Atomic Ab-
sorption Melhod, 'Methods for Chemical
Analysis of Water and Wastes." pp. 118-
126, Environmental Protection Asenr.y,
Office of TechnoloRv Transfer, Wash-
ington, D.C. 20460,1374.
<7> Nitrate—Brucine Colorimetric
Method. "Standard Methods for the Ex-
amination of Water and Wastewater,"
13th Edition, pp. 461-464, or Cadmium
Reduction Method, "Methods for Chemi-
cal Analysis of Water and Wastes,"
pp. 201-206, Environmental Protection
Agency, Office of Technology Transfer,
Washington, D.C. 20460, 1974.
(8) Selenium—Atomic Absorption
Method, "Methods for Chemical Analysis
of Water and Wastes," p. 145, Environ-
mental Protection Agency, Office of
Technology Transfer, Washington. DC.
20460.1974.
(Si Silver—Atomic Absorption Meth-
od. "Standard Methods for the Ex-
amination of Water and Wastewater",
13th Edition, pp. 210-215, or "Methods
for Chemical Analysis of Water and
Wastes", p. 146. Environmental Protec-
tion Agency. Office of Technology Trans-
fer, Washington, DC, 20460, 1974.
flO> Fluoride—Electrode Method,
"Standard Methods for the (examination
of Water and Wastewater", 13th Edition,
pp. 172-174, or "Methods for Chemical
Analysis of Water and Wastes." pp. 65-
67. Environmental Protection Agency,
Office of Technology Transfer, Wash-
ington, D.C. 20460, 1974, or Colorimetric
Method with Preliminary Distillation,
"Standard Methods for the Examination
of Water and Wastewater," 13th Edition,
pp. 171 -172 and 174-176, or "Methods for
Chemical Analysis of Water and
Wastes," pp. 59-60, Environmental Pro-
tection Agency, Office of Technology
Transfer, Washington, D.C, 20460, 1974,
§ 141.24 Organic chemical fanipling
and analytical r<*i|uSrcmenl9.
(a) An analysis of substances for the
purpose of determining compliance with
I 141.12 shall be made as follows:
(1) For all community water systems
utilizing surface water sources, analyses
shall be completed within one year fol-
lowing the effective date of this part.
Samples analyzed shall be collected dur-
ing the period of the year designated by
the State as the period when contami-
nation by pesticides is most likely to
occur. These analyses shall be repeated
at intervals specified by the State but
in no event less frequently than ?.t three
year intervals.
(2) For community water systems
utilizing only ground water sources,
analyses shall he completed by those sys-
tems specified by the State.
(b) If the result of an analysis made
pursuant to paragraph ia) of this sec-
tion indicates that the level of any con-
taminant listed in 5 Hi.12 exceeds the
maximum contaminant level, the iu:j-
plier of water shall report to the State
within 7 days and initiate three addi-
tional analysts within one month.
(c> When the average of lour analyses
made pursuant to paragraph (b) of this
section, rounded to the .--ame number of
significant figures as the maximum con-
canirmui level for the substance in ques-
tion, exceeds the maximum contaminant
level, the supplier of \vntrr shall report
to thr State pursuant to 5 Ml.31 and give
»ot:re to the public pur.sunnt to ? 141.32.
Monitor):)!: after public notification shall
be at a frequency designated by the State
and slinH CL.-nUr.vie unt:l the maximum
contaminant level has not been exceeded
in two surre'P-ive .iimpU's o: '.ailil n
monitoring «'hc'.iule as a condition to n
Viirjrtiu'o, exemption or enf'irrf-inoii: ;••<•-
tion shall become elfeet:vc>
For the initial anal VMS required
by paragraph ;a> il> and (2- of this
section, data for surface water acquired
within or.o year prior to the effective
date of this part and ti:ua lor ground
water acquired within three yen:s pn<>;
ta the effec.tivtt date of this uu:*. r:;.sy be
substi'.ulrd a; the ai'-er<'Kin of (he St'.ite.
Analyses made to determine com-
pliance with 3141.l2-
chtorine Pesticides in Industrial Efflu-
ents," MDQAKL, Environment! Pro-
tection Agency. Cincinnati. Ohio, Novem-
ber 28. 1973.
(ft Analyses made to iiel•<>'cms, the State may modify the moni-
•or::)B requirements imposed by this
i:?rt w the extent that the interconnec-
:»n of the syseirc.s junfirs treating them
c.< a .'••ingle system for monitoring pur-
J;U-P« Any modified monitoring shall be
conducted pursuant lo a schedule speci-
fied by the SUite a::d concurred in by the
Admini'-trator of the U.S Environmental
Protection Agency,
Cubpart D—Reporting, Public Notification
and Record Keeping
5: 111.31 Kfpnriiiic icijui
'ai Exrept uhi'i'i* a .•.•lurti-r
period is specified in this part, the
supplier ni water shall rfport to the State
uitlur, 40 days fdknuns; a test, measure-
ment or acaiy-15 rinuimi. to be made by
ihS part, the rc-u!t. of that test, nieas-
ur'";ncnt or a:i:ily-it.
' b> Th" st!|.>: I lor <»f v.atf r .s;ial! report
to the h'tate u itiiin :!i houiv-i '.he failure
to comply v,:!h any primary di'i/ukir.K
v.:>tcr n'i;ul:i'.i tti ' incl jdir.g failure to
co:n|i7y ui'Ji miinitorir.g reqairfmenl.-;!
sc' :orth in llii-; iv.rt.
'(•; Ti'.e suppik-r c-f '.va'er is not ve-
ritu'vtl 'o rcpori iHiulvl'.i ;U results to the
SI.;;!" in ca=c-s wlicrt' a State laboratory
;.".vrl.')!'i::s the •.u:a!y:-'i--i and reports the
rc-.ults to the State n;T;re wliich would
nnirially i-fet:n o .--.m-V. notiiication irom
tin- .'".ipplier.
!j JH..12 I'llllilV I>rltrable maximum
<.--.>m.imi:iant level cstal-lished in Subpavt
D, fruls to comply with an applicablR
ti-.itiiig procedure eylabii^hcd In Subpart
C of this part, is granted a variance or
an exemption from an applicable maxi-
mum contaminant levol, fails to comply
with the requirements o:' any schedule
prescribed pursuant to a variance or ex-
cmiJlion, or fails U> perform any moni-
toring required pui'Miant to Section 1445
>'a> of the Act, the supplier of water shall
notify persons served by the system of
the failure or grant by Inclusion of a no-
tice in the first set of water bills of the
system issued after the failure or grant
FEDERAL HIGISIIR, vot. 40, NO. 24i—WEDNESDAY, DECEMBER 1*1, i»?s
-------
59574
•ULES AND REGULATIONS
and In any event by written notice within
three months. Such notice shall be re-
peated at least once every three months
so long aa the system's failure continues
or the variance or exemption remains ID
effect. If the system issues water bills less
frequently than quarterly, or doe's not
Issue water bills, the notice shall be made
by or supplemented by another form of
direct mall.
(b) If a community water system has
failed to comply with an applicable mai-
Imunt contaminant level, the supplier of
water shall notify the public of such fail-
ure. In addition to the notification re-
quired by paragraph (a; of this section,
as follows:
(1) By publication on not less than
three consecutive days In a newspaper or
newspapers of general circulation in the
area served by the system. Such notice
shall be completed within fourteen days
after the supplier of water leams of
the failure,
(2) By furnishing a copy of the notice
to the radio and television stations serv-
ing the area served by the system. Such
notice shall be furnished within seven
days after the supplier of water learns
of the failure,
(c) If the area served by a community
water system Is not served by a dally
newspaper of general circulation, notifi-
cation by newspaper required by para-
graph (b) of this section shall Instead be
given by publication on three consecutive
weeks in a weekly newspaper of general
circulation serving the area. If no weekly
or dally newspaper of general circula-
tion serves the area, notice shall be given
by posting the notice In post offices with-
in the area served by the system,
(d) If a non-community water sys-
tem fails to comply with an applicable
maximum contaminant level established
in Subpart B ot this pert fails to comply
with an applicable testing procedure
established In Subpart C of this part, la
granted a variance or an exemption from.
an applicable maximum contaminant
level, fails to comply with the require-
ment of any schedule prescribed pursu-
ant to a variance or exemption or falls to
perform any monitoring required pursu-
ant to Section 1445'a) of the Act. the
supplier of water shall given notice of
such failure or grant to the persons
served by the system. The form and man-
ner of such notice shall be prescribed by
the State, and shall Insure that the
public using the system Is adequately In-
formed of the failure or grant.
(e) Notices given pursuant to this sec-
tion shall be written In a manner reason-
ably designed to inform fully the users
of the system. The notice shall be con-
spicuous and shall rot use unduly tech-
nical language, unduly small print or
other methods which would frustrate the
purpose of the notice. The notice shall
disclose all material facts regarding the
subject Including the nature of the prob-
lem and, when appropriate, a clear state-
ment that a primary drinking water
regulation has been violated and any pre-
ventive measures that should b« taken by
the public. Where appropriate, or where
designated by the State, bilingual notice
shall be given. Notices may include a bal-
anced explanation of the significance or
seriousness to the public health of the
subject of (be notice, a fair explanation
of steps taken by the system to correct
any problem and the remits of any addi-
tional sampling.
(f) Notice to the public required by
this section may be given by the State on
behalf of the supplier of water.
(g) In any Instance In which notifica-
tion by mall la required by paragraph (a)
of this section but notification by news-
paper or to radio or television stations
la not required by paragraph (b) of this
section, the State may order the supplier
of water to provide notification by news-
paper and to radio and television stations
when circumstances make more immedi-
ate or broader notice appropriate to
protect the public health.
§ 141.33 Record maintenance.
Any owner or operator of a punlic
water system subject to the provisions of
this part shall retain on Its premises or
at a convenient location near Its prem-
ises the following records:
(a) Records of bacteriological analyses
made pursuant to this part shall be kept
for not less than 6 years. Records of
chemical analyses made pursuant to this
part shall be kept for not less than 10
years. Actual laboratory reports may be
kept, or data may be transferred to tab-
ular summaries, provided that the fol-
lowing information Is included:
(1) The date, place, and time of sam-
pling, and the name of the person who
collected the sample;
(2> Identification of the sample as to
whether it was a routine distribution
system sample, check sample, raw or
process water sample or other special
purpose sample;
(3) Date of analysis;
(4) Laboratory and person responsible
for performing analysis;
(5) The analytical technique/method
used; and
<6> The results of the analysis.
(b) Records of action taken by the
system to correct violations of primary
drinking water regulations shall be kept
for a period not less than 3 years after
the last action taken with respect to the
particular violation involved.
-------
TECHNICAL REPORT DATA
(Please read Instructions on th? rererse before completing]
1. REPORT NO.
h'A-430/1-80-006
4. * TLE ANDSUBTITLE
Methods for the Determination of Chemical Contaminants
in Drinking Water Training Manual
|3. RECIPIENT'S ACCESSIOf*NO.
! Fee?' &Q31
jS~ REPORT DATi
April 1980
6. PERFORMING ORGANIZATION CODE
. ALTHCRSSl
John D, Pfaff
8. PERFORMING ORGANIZATION REPORT NO.
9. PEBFORV.!NG ORGANIZATION (SiAME AND ADDRESS
1O. PROGRAM ELEMENT NO.
Environmental Protection Agency
Office of Water Program Operations
National Training & Operational Technology Center
Cincinnati, Ohio 45268
1 1. CONTRACT/GRANT NO,
12. SPONSORING AGENCY NAME AND ADDRESS
Same
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
Supercedes P8 284392/AS
16. ABSTRACT
This laboratory manual is designed to contain analytical procedures for all parameters
listed in the National Interim Primary Drinking Water Regulations (NIPDWR). Some
procedures ray be carried out by operators or laboratory technicians with little or
no experience (chlorine, trubidity, fluoride, nitrate) while other parameters require
understanding and experience in using sophisticated analytical equipment (atomic
absorption, gas chromatography). Parameters included are procedures for silver,
cadmium, chromium, lead, mercury, arsenic, selenium, nitrate, fluoride, barium,
chlorine, turbidity, perticides, herbicides. It is written in a step-by-step format.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
Analysis, Chemical Analysis, Chlorine,
Turbidity, Metals, Silver, Cadmium
Chromium Fluoride, Barium, Pesticides,
Herbicides, Potable Water.
b.lDENTlFlERS/OPSN ENDED TERMS
COSATI Field/Group
07B, 07C, 14B
3. D:S-RIBUT!ON STATEMENT
Release to the public
19. SECURITY CLASS (This Report!
Unclassifi ed
21, MC. OF PAGES
20. SECURITY CLASS (This pate)
unclassi tied
22. PRICE
EPA Form 2220-1 (9-73)
------- |