IN THE

MATTER

OF:

WASTE

WATER

PRETREATMENT

UPDATE,

USEPA

AMENDMENTS

(January)

1, 2007

through

June

30, 2007

SDWA

UPDATE,

USEPA

AMENDMENTS

(January

1, 2007

through

June 30,

2007 and

June

2, 2007)

SDWA

UPDATE,

USEPA

AMENDMENTS

(July

1, 2007

through

December

31,

2007

1)17

NOV

)

R08-5

)

(Identical-Substance

STATE

OF

IL.UNOIS

)

)

Rulemaking-Pubic

Supply

Water

OllUtiOfl

Control

Board

)

)

R08-7

)

(Identical-in-Substance

)

Rulemaking-Public

Water

)

Supply

)

R08-13

)

(Identical-in-Substance

)

Rulemaking-Public

Water

)

Supply

NOTICE

OF FILING

John

Thenjault,

Clerk

Illinois

Pollution

Control

Board

James

R.

Thompson

Center

100

W.

Randolph,

Suite

11-500

Chicago,

IL

60601

Matt

Dunn,

Environmental

Bureau

Chief

Office

of the

Attorney

General

69

West

Washington

Street,

Suite 1800

Chicago,

IL

60602

General

Counsel

Illinois

Dept.

Of Natural

Resources

One

Natural

Resources

Way

Springfield,

IL

62702-1271

PLEASE

TAKE

NOTICE

that

I have

filed with

the

Office of

the Clerk

of the

Pollution

Control

Board

the Illinois

Environmental

Protection

Agency’s

Comments

in

the above

captioned

matter,

a

copy

of

which

is

herewith

served upon

you.

Date:

November

7, 2008

1021 North

Grand Avenue

East

Springfield,

Illinois

62794-9276

(217)

782-5544

ILLINOIS

ENVIRONMENTAL

PROTECTION

AGEN

j

BfliflJL

efanie

N.

Diers

1/

/ssistant

Counsel

tMivision

of Legal

Counsel

ILLINOIS

POLLUTION

CONTROL

BOARD

LERc

8

OPFICE

)

)

THIS FILING

IS SUBMITTED

ON

RECYCLED

PAPER

---

ILLINOIS

POLLUTION

CONTROL

BOARD

IN

THE

MATTER OF:

)

WASTEWATER

PRETREATMENT

)

R08-5

UPDATE,

USEPA

AMENDMENTS

(January)

)

(Identical-Substance

1,

2007

through

June

30, 2007

)

Rulemaking-Pubic

Water

)

Supply)

)

SDWA

UPDATE,

USEPA

AMENDMENTS

)

R08-7

(January

1,

2007

through

June

30,

2007

and

)

(Identical-in-Substance

June

2, 2007)

)

Rulemaking-Public

Water

)

Supply)

)

)

SDWA

UPDATE, USEPA

AMENDMENTS

)

R08-13

(July

1,

2007

through

December

31,

2007

)

(Identical-in-Substance

)

Rulemaking-Public

Water

)

Supply)

ILLINOIS

ENVIRONMENTAL

PROTECTION

AGENCY’S

COMMENTS

Now

comes

the

Illinois

Environmental

Protection

Agency

(“Illinois

EPA”

or

“Agency”)

by

and

through

its

attorney

and

hereby

submits

the

following

comments

in

the

above

captioned

cases.

Illinois

EPA

respectfully

states

as follows:

COMMENTS

WITH

RESPEST

TO

THE

BOARD’S

ORDER

AUGUST

7,

2008

1.

Typo’s

occur

on

the

following

pages:

84(611.350),

90(611.351),

93(611.353),

97(611.354), 110(611.355),

129(611.356),

135(611.357),

139(611.358),

140(611.359a),

147(611.360)

and

234(611.884).

These

are in

the

BOARD

NOTE

parts

where

(October

12,

2007)

needs

to

be changed

to

(October

10,

2007).

2.

There

is

a

typo

on Page

94

at

611.354

b) 1)

G3

- this

needs

to

be

changed

to

3C.

3.

Omission

on

Page

140 at

61 1.359(a)(2)(D)

— second

line,

change

to

read

“.

. .described

in

subsection

(a)(2)

(a)(1)

of

this

Section.”

---

4.

Typo on

Page

194, Section

611.61

1(a)(18)(E),

BOARD

NOTE,

next

to last

line:

change

“200”

to

“2000”.

5.

Typo

on Page

224,

Section

611.720(a)(10)(B),

BOARD

NOTE,

third line

from

top:

“Method

Method”

change

to a single

“Method”.

6.

Omission

onPage235,

Section

611.1004(b)(4),

BOARD

NOTE:

last

full

line,

change

to

read:

“. . .Examination

of

Water

and

Wastewater,

20’

edition,

Method

9222D

and

G”.

Reason

for

change:

This

will

be

consistent

with other

citations

to

Standard

Methods

and

the

federal

regulation.

COMMENTS WITH

RESECT

TO THE

BOARD’S

OPINION

7.

On Page

11,

in the

header:

“Revisions

to the

Lead

and

Copper

Rule...”

add

611.360

to

the

series

of

listings

as this

was

omitted.

8.

The

following

is

in response

to

questions

on

Pages

10 and

11

of the

Board

Opinion.

A.

Is

there

any

reason the

Board

should

include

references

to

Standard

Methods

Online,

where the

same

version

of the

Standard

Method

is available

in

the

printed

21st

edition

of

Standard

Methods,

considering

that

a

Board

note

appended

to

the incorporation

of

Standard

Methods

cites

to Standard

Methods

Online

for

purchase

of individual

methods?

Answer:

The

Agency

has

no

objections

to the

Board proposal.

B.

Can

USEPA,

the

Agency,

or anyone

in

the regulated

community

provide

the

Board

with

a

copy

of the

method

entitled

“The

Determination

of

Radium-226

and

Radium-228

in

Drinking

Water

by Gamma-ray

Spectrometry

Using

HPGE

or

Ge(Li)

Detectors,” Revision

1.2,

December

2004,

cited

by

USEPA

as available

from

the

Environmental

Resources

Center

at the

Georgia

Institute

of Technology?

Answer:

The

Agency

has

obtained

a copy

of the

Georgia

Radium

Method

from

US

EPA

Region

V and

is attaching

a copy

of

that

document

with

these

comments.

C.

Can

USEPA,

the

Agency,

or anyone

in the

regulated

community

provide

the

Board

with

a copy

of Waters

Method

D6508,

revision

2, entitled

“Test Method

for

Determination of Dissolved

Inorganic

Anions

in Aqueous

Matrices

Using

Capillary

Ion

2

---

Electrophoresis

and Chromate

Electrolyte,”

cited

by

USEPA as

available

from

Waters

Corporation?

Answer:

The Agency

received

correspondence

(attached)

from Waters

Corp.

regarding

Waters

Method

D6508

in

which

it

is

stated,

the

INSTRUMENT

technology

described

therein

(CE/CIA/CIE)

is

NO

LONGER

AVAILABLE

from

Waters,

having

been

discontinued

in mid-2001,

and

obsolete

at the end

of 2005.

For those

customers

who

operate

an

existing

system, the

Agency

continues

to offer

some of

the electrolyte

solutions

referred

to in the

method.”

Included

with

the

note

is a copy

of ASTMD

6508 —

00

which the

Agency

takes

to mean

Waters Method

6508.

D.

Can or should

the Board

substitute

the

easily

located

method ASTM

D6508-

00(2005)e2

in place of the

Method

cited

as

Waters

Method

D6508,

revision

2

by USEPA,

which

the

Board

could not

locate

from

the

listed

source?

Answer:

Based on the

correspondence

noted

in item

C

above,

the Agency

would

have

no objection

to

the Board

adopting

ASTM D6508-00(2005)e2

in

light

of

the

instrumentation

being discontinued.

E.

Did the

Board

take

an

acceptable

approach

to the approved

equivalent

methods,

which

USEPA

codified

as appendix

A

to

40

C.F.R.

141, by combining

them

with the

methods

that

US

EPA

approved by

rulemaking

within

the text

of the regulations?

Answer:

The

Agency

believes that

the

Board

has

taken the

appropriate

steps

by

incorporating

the

equivalent

methods

within

the

text

of the regulations.

COMMENTS

WITH

RESPECT

TO

SECTION

611.355

(A-G)

9)

With

respect

to the public

education

materials

found

in Section

611.355

(A-G),

Illinois

EPA

respectfully

disagrees

with

language

proposed

by the

Board.

The

current

procedures

for

reviewing

and approving

public

education

(PE) materials

works

effectively

and

has

never

been an issue

for

the

many years

the

Agency

has

been

3

---

implementing

the Lead

and Copper

Rule.

The language

proposed

by

the

Board

is

not

needed

nor is it

required

to be included

in

the regulations.

The

federal

regulation

rightly

places the burden

on the Community

Water

Supply

(“CWS”)

to

generate

and distribute

compliant

PE materials.

See

40

C.F.R.

141.85(a)(1)

and

(b)(2). When

the

Agency

initially

notifies

the

CWS

that its

lead

action

level

has

been

exceeded,

a

comprehensive

PE packet

is sent

which includes

a self-assessment

checklist

of

requirements,

fill-in-the

blank

PE template(s),

and a

PE-preparation

guidance

document.

The

CWS prepares

the

PE,

distributes

the

materials

to the

consumers

and

sends

the

Agency

a copy along

with completed

forms attesting

that

the required

PE

requirements

were

met.

As soon

as time and

resources

allow,

the

Agency

reviews

the

PE information

submitted,

determines

compliance,

and issues

a response

to

the

CWS.

Due

to the

amount

of information

initially

provided to

the CWS,

the response

most

often

indicates

100%

compliance.

If

there are

minor

issues, then

the

CWS

can correct

these

during any

repeated

notices.

If there

are

major issues,

the

Agency

would

require

re-issuance.

The

language

proposed

by the Board

is shifting

the

burden to

the Agency

and

such

a

shift

is

unnecessary

and

burdensome.

Therefore,

the

Agency

respectfully

request

that

the

proposed

language

in

Section 61

1.355(3)(A-G)

be

stricken in

its entirety.

4

---

10)

As stated

above,

the

Agency

would

prefer

that

Section

611.355

(3)(A-G)

be

stricken.

However,

if

that

is unacceptable

to

the

Board,

the

Agency

offers

the

following

suggestions

with

respect

to

the language

proposed

in 61

1.355(3)(A-G):

The

supplier

must

submit

all written

public

education

materials

to the

Agency

for

review

at least

60

days

after

the

end of

the

sampling

period.its

planned

date

for

delivery

of the

materials

to

the

public.

By

striking

some

of

the

language

proposed

by

the

Board

it

will allow

the

Agency

a

tracking

method

concerning

the

sampling

periods.

If

the Agency

determines

that

the form

and content

of

the

supplier’s

written

public

education

materials

is adequate,

it may

issue

a

SEP

pursuant

to

Section

611.110

that

expressly

approves

the

materials.

A

supplier

may

immediately

distribute

its

written

public

education

materials

after

receipt

of a SEP

or a

revised

SEP

that

expressly

approves

those

materials.

If the

Agency

determines

that

the

form

or content

of

the

written

public

education

materials

submitted

by

the

supplier

does

not

comply

with

the

requirements

of

this

Sections,

it must

issue

a SEP

pursuant

to

Section

611.110.

The

Agency

may

issue

a

revised

SEP

that

expressly

supersedes

a

SEP

previously

issued

under

this

subsection

(a)(1).

Any

SEP

or

revised

SEP

issued

by the

Agency

must

identify

any

deficiencies

in the

written

public

education

materials

with

specificity

sufficient

to

guide

the

supplier

to correct

the

deficiencies

in

a

way

that

would

address

the

Agency’s

concerns. The revised

SEP

shall

be

submitted

to the

Agency

within

30

days

after

being

notified

of

the

deficiencies.

)

The

Agency

must

issue

any

SEP

or

revised

SEP

under

subsection

(a)(3)(D)

of

this

Section

no later

than

90

3f’ days

after

the

date

on

which

it

received

a

copy

of the

supplier’s

prospective

written

public

education

materials,

unless

the

Agency

and

the

supplier

have

agreed

to

a later

date

pursuant

to subsection

(a)(3’KF)

of

this Section.

The

Agency

and

the

supplier

may

agree

to a

longer

time

within

which

the

Agency

may

issue

a

SEP

or

a

revised

SEP,

in

which

case

the

Agency

must

issue

the SEP

or

revised

SEP

before

expiration

of

the

agreed

upon

extension

agreed

longer

time.

5

---

If

the

supplier

has

not

received

a SEP

from

the

Agency

within

45

days

after the

date

on

which

the Agency

received

its

written

public

education

material,

those

materials

are

deemed

approved,

and the

supplier

may

immediately

distribute

them.

The

Agency

respectfully

disagrees with

having

the

automatic

approval

process

and

proposes

this

paragraph

be

stricken

altogether.

This

language

is not

needed

based

on the

Agency’s

comments

and

such

a requirement

is

not found

in

the

federal

regulations.

Furthermore,

the Agency

is

of

the opinion

that

US EPA

may

not approve

an automatic

approval

based

on how

they

have

developed

precise

content

and

delivery

of the

PE.

Also,

once

a

default

approval

is

issued,

the

wrong

information

is in

front

of the

public

which

could

be contrary

to the

actions

they

should

be

taking.

Trying

to

rescind

the

PE would

only

lead

to more

confusion,

leading

to

a

delay in

getting

the right

information

before

the public

while

an

enforcement case or

law

suit

against

the

Agency

is

being processed.

However,

should

the

Board

determine

that

that

611.355

(A-G)

is

necessary

and

that

an

automatic

approval

is consistent

with

the federal

rules, the

Agency

suggest

a

longer

timeframe

for

Agency

review

before

an

automatic

approval

is

granted.

Once

the

supplier

has

revised

its

written

public

education

materials

exaçjy

as described

by

the Agency

in

a

SEP

issued

under

subsection

(a)(3)(D)

of

this

Section,

those

materials

are deemed

approved,

and

the

supplier

shall

may immediately

proceed

to distribute

them.

6

---

11)

It should

be

noted

that

if the

Board

should

determine

that

an automatic

approval

is

not

appropriate,

the

Agency

suggest

that

that

last sentence

in

611.3

55(a)(

1)

should

rewritten

as

follows:

The

supplier

must

submit

all

written

public

education

materials

prior

to

delivery.

as

required

by

subsection

(a)(3)

of this

Section.

12)

The

following is the

Agency

response

to

the

Board

request

for

comments

on

the

numbered questions

on Page

17

pertaining

to Section

611.355(a)(1).

A.

Is requiring

written

Agency

action

only

where

the

Agency

determines

that

deficiencies

exist

the

best

option

for

Agency

review

of the

materials?

Answer:

Requiring

written

action

by

the

Agency

only where

the Agency

finds

deficiencies is not

the best

option

to review

the

materials.

The

Agency

believes

that

approval

or

deficiencies should

be

addressed

in writing.

Currently,

this

is how

the

Agency

address

this

situations.

B.

Is

the provision

that

deems

the materials

approved

and

which

allows

the

supplier

to proceed

and

distribute

the materials in

the absence

of an

Agency

response

workable?

Answer:

The

Agency

disagrees

with

the

45

day

period

set

by

the Board

for

approvals.

This

timeframe

is burdensome

on

the

Agency

and

does

not recognize

the

uniqueness

of

every

review.

Also,

the

federal

regulations

do

not require

a 45

day

review.

C.

Do

the

times

required

for

submission

to

the

Agency

and

provided

for

Agency

review

work

for the

purpose?

Answer:

The

Agency

is

not

sure

the

time

line

for submissions

to

the

Agency

and

the

review

of

work

is doable

based

on our

previous

comment.

D.

Does

the

provision

that

requires

the

Agency

to describe

the

deficiencies

it

has

found

appear

adequate

and

workable

to

assure

that

the

supplier

is

given

a clear

indication

of

those

deficiencies?

Answer:

The

Agency

can

describe

the deficiencies

to

the suppliers.

7

---

E.

Does

the requirement

that allows

the

supplier

to proceed

and

distribute

its

materials after

it has

addressed

the

Agency-determined

deficiencies

appear

adequate

and

workable

to

assure

that

the

Agency

concerns

are

addressed

and

that

publication

occurs

as

rapidly

as

possible?

Answer:

The

Agency

agrees

with

the

requirements

that

allows

the

supplier

to

proceed

and

distribute

the

materials

after

the

Agency’s

concerns

are addressed.

F.

Is it necessary

to set

forth

express

provisions

for

Agency

issuance

of a

revised

SEP,

and

does

such

an

express

provision

provide

for

the

timeliest

resolution

of any

issues

that

might

arise

in the

course

of Agency

review

of a

supplier’s

public

education

materials?

Answer:

The

Agency

is

not

sure how

to

address

the

issuance

of

a

revised

SEP.

The

process

described

by

the

Board

seems

confusing,

so

it

would

probably

be

best

not

to

set

forth

express

provision

concerning

the

Agency’s

review.

However,

if the

Board

believes

such

language

the

Agency

can issue

a

revised

SEP

but

it is

not

clear

what

the

timelines

would

be once

a

revision

is required.

The

Agency

suggestions

that

if a

revision

is required

that

the

supplier

make

the

necessary

changes

within

30

days.

COMMENTS

WITH

RESPECT

TO THE

BOARD’S

SEPTEMBER

4, 2008

SUPPLEMETNAL

OPINION

AND

ORDER

13)

Illinois

EPA

notes

that

on Page

22

of

the Board’s

Opinion

the

Board

Note

should

be

changed

from

40

CFR

141.601(c)

to

40 CFR

141.601(b).

Respectfully

submitte

Stefi

e

N.

Diers

As

is

t Counsel

Dated:

November

7,

2008

1021

North

Grand

Avenue

East

P.O.

Box

19276

Springfield, Illinois

62794-9276

217-782-5544

8

---

ATTACHMENTS

---

INTERNATIONAL

Designation:

D 6508

— 00

(Reapproved

2005)d1

Standard

Test

Method

for

Determination

of Dissolved

Inorganic

Anions

in

Aqueous

Matrices

Using

Capillary

Ion

Electrophoresis

and

Chromate

Electrolyte’

This standard

is

issued

under

the

fixed designation

D 6508;

the number

immediately

following

the designation

indicates

the year of

original adoption

or, in

the

case

of

revision,

the

year

of

last revision.

A

number

in parentheses

indicates

the

year

of last reapproval.

A

superscript

epsilon

(e)

indicates

an

editorial change

since

the last

revision

or

reapproval.

e’

Nom—Warning

notes were

moved into

the text in

January 2005.

1. Scope

1.1

This test

method

cover

the determination

of the

inor

ganic

anions

fluoride,

bromide,

chloride,

nitrite,

nitrate,

ortho

phosphate,

and

sulfate

in

drinking

water,

wastewater,

and

other

aqueous

matrices

using

capillary

ion

electrophoresis

(CIE)

with

indirect

UV

detection.

See

Figs

.1-6.

1.2

The

test method

uses a

chromate-based

electrolyte

and

indirect

UV

detection

at 254

nm.

It is applicable

for

the

determination

or

inorganic

anions

in

the range

of 0.1

to 50

mg/L

except

for fluoride

whose

range

is 0.1 to

25

mg/L.

1.3

It is

the

responsibility

of the user

to ensure

the validity

of

this test

method

for other

anion concentrations

and untested

aqueous

matrices.

NOTE I—The

highest

accepted

anion

concentration

submitted

for

precision

and

bias

extend the

anion concentration

range for

the following

anions:

Chloride

to

93

mgJL,

Sulfate

to

90

mgIL,

Nitrate to

72 mg/L,

and

ortho-phosphate

to 58

mg/L.

1.4 This

standard

does not

purport

to

address

all

of

the

safe/v

concerns,

if

any,

associated

with

its

use. It is

the

responsibility

of

the

user of this

standard

to

establish

appro

priate safety

and

health

practices

and

deterntine

the

applica

bility of

regulatory

limitations

prior

to use. For

specific

hazard

statements,

see Section

9.

2. Referenced

Documents

2.1

ASTM

Standards:

2

D

1066

Practice

for Sampling

Steam

D

1129

Tenninology

Relating

to Water

D Il

93

Specification

for

Reagent

Water

D 2777

Practice

for Determination

of

Precision

and

Bias

of

This

test

method

is under the

jurisdiction

of ASTM

Committee

D19 on Water

and

is the direct

responsibility

of

Subcommittee

D19.05

on

Inorganic

Constituents

in

water.

Current

edition

approved

Jan. 1. 2005.

Published

April

2005.

Originally

approved

in

2000. Last

previous

edition

approved

in

2000 as

D6508—00.

°

For

referenced

ASTM

standards,

visit the

ASTM

websile,

www.astm.org,

or

contact

ASTM Customer

Service

at

aervice@astm.org.

For Annual

Book

of ASTM

Standards

volume

information,

refer to the

standard’s Document

Summary

page

on

the

ASTM website.

Applicable

Test

Methods

of

Committee

D19

on

Water

D

337(>

Practices

for Sampling

Water

from

Closed

Conduits

I)

3X56

Guide

for

Good

Laboratory

Practices

in

Laborato

ries

Engaged

in

Sampling

and

Analysis

of

Water

[)58

10

Guide

for

Spiking

into

Aqueous

Samples

Copyright ©

ASTM

International,

100

Barr

Harbor

Drive, PC

Box C700,

West

Csnshohocken,

PA

19428-2959,

United States.

Anion

Standard in

mg/I

1

Chloride

= 2

7

Fluoride

= 1

2

Bromide = 4

8

Formate

S

SNitrite

4

9Phosptrate4

4Sulfate

4

lOCarbonate

8

5 Nitrate

=

4

II

Acetate

= 5

11

V

3.000

3.500

.

4,000

4.500

Mmutes

FIG.

1

Electropherogram

of

Mixed

Anion Working

Solution

and

Added Common

Organic

Acids

I Chloride

2

Bromide

3 Nitrite

4

Sulfate

5 Nitrate

6 Fluoride

7 Phosphate

FIG. 2

Electropherogram

of 0.2

mgJL Anions

Used

to

Determine

MDL

---

D

6508

— 00

(2005)d1

- 000

35O0

4OO0

Minutes

FIG.

3

Electropherogram

of

Substitute

Wastewater

ter

Anions

in mqIl_

No

Dilution

I

Chloride

93.3

2

Nitrite

= 0.48

3 Sulfate

60.3

4 Nitrate

= 40.8

5 Carbonate

= Natural

3. Terminology

3.1

Definitions—For

definitions

of tenns

used in

this

test

method,

refer

to

Terminology

D 1129.

3.2

Definitions

of

Terms

Specific

to This

Standard:

3.2.1

capillary

ion electrophoresis,

n—an

electrophoretic

technique

in which

a

UV-absorbing

electrolyte

is

placed

in

a

50

im

to 75

urn

fused

silica

capillary.

Voltage

is

applied

across

the

capillary

causing

electrolyte

and

anions

to

migrate

towards

the

anode

and

through

the capillary’s

UV

detector

window.

Anions

are

separated

based

upon

the

their

differential

rates

of

migra

tion

in

the

electrical

field.

Anion

detection

and

quantitation

are

based

upon

the

principles

of

indirect

UV

detection.

iso

0

3.2.2

electrolyte,

n—a

combination

of

a UV-absorbing

salt

and

an electroosmotic

flow modifier

placed

inside

the

capillary,

used

as

a

carrier

for

the

analytes,

and for

detection

and

quantitation.

The

UV-absorbing

portion

of

the salt

must

be

anionic

and

have

an

electrophoretic

mobility

similar

to

the

analyte

anions

of

interest.

3.2.3

electroosmotic

flow

(EOF,),

n—the

direction

and

ve

locity

of

electrolyte

solution

flow within

the

capillary

under

an

applied

electrical

potential

(voltage);

the velocity

and

direction

of

flow

is determined

by electrolyte

chemistry,

capillary

wall

chemistry,

and

applied

voltage.

3.2.4

electroosinotic

flow

modifier

(OFM,

n—a

cationic

quatemary

amine

in

the

electrolyte

that dynamically

coats

the

negatively

charged

silica

wall

giving

it a

net

positive

charge.

This

reverses

the

direction

of the

electrolytes

natural

dcc

troosmotic

flow

and directs

it towards

the

anode

and

detector.

This

modifier

augments

anion

migration

and

enhances

speed

of

analysis.

Its

concentration

secondarily

effects

anion

selectivity

and

resolution,

(see

Fig.

7).

3.2.5

electrophoretic

mobility,

n—the

specific

velocity

of

a

charged

analyte

in

the

electrolyte

under

specific

electroosmotic

flow

conditions.

The

mobility

of

an analyte

is

directly

related

to the

analyte’

s

equivalent

ionic

conductance

and

applied

voltage,

and

is the

primary

mechanism

of

separation.

3.2.6

electrophe,vgrain,

n—a

graphical

presentation

of

LIV-

detector

response

versus

time

of

analysis;

the

x

axis

is

D

AnionS

in

m/L,

1:20

Dilution

I Chloride

24.2

2

Sulfate

= 3.77

3

Phosphate

= 0.89

4 Carbonate

= Natural

ii

D

Anions

in

m/L,

No

Dilution

I Chloride

= 2.0

2 Nitrite

1.6

3 Sulfate

= 34.7

4 Nitrate

=

16.5

3.500

Minutes

4.000

FIG.

6

Electropherogram

of Industrial

Wastewater

Anions

In mg/L,

No

Dilution

I Chlore

20.2

2

Sulfate

= 7.5

3 Nitrate

=1.6

4 l’luoride

= 0.06

5 Carbonate

= Natural

3.000

i,aoo

4.ooo

FIG.

4

Electropherogram

of

Drinking

Water

3.000

3,500

Minutes

4.000

4.500

FIG.

5

Electropherogram of Municipal

Wastewater

Treatment

Plant

Discharge

D

5847

Practice

for

Writing

Quality

Control

Specifications

for

Standard

Test

Methods

for

Water

Analysis

D

5905

Practice

for

the Preparation of Substitute

Wastewa

F

488

Test

Method

for

On-Site

Screening

of

Heterotrophic

Bacteria

in

Water

2

---

D

6508 —

00

(2005)d1

Cathode

//

“\

High

Mobility

Anion

c:Dl

(

1.0w Mobility

Anion

(te)

I

I

I

Neutrals &

Water

\

J

<—

(

All

Catlon

EOF

>

\

J+++++++++++.++++++++.+++÷÷+

Anode

Injection

Side

/

U

0

\

Detection

Side

L_

1

__..___

jiSLc2i_jiji

—ji

0.

O

0.

0

0.

O

0.

OH

LL

+

+

+

+

L

+

N

FIG. 7

Pictorial

Diagram

of Anion

Mobility

and

ElectroOsomotic

Flow

Modifier

migration

time, which

is

used to

qualitatively

identify

the

anion,

and

the

y

axis

is

UV

response,

which

can

be

converted

to

time corrected

peak

area

for quantitation.

3.2.7 hydrostatic

sampling,

n—a

sample

introduction

tech

nique

in which

the

capillary

with electrolyte

is

immersed

in the

sample,

and

both

are

elevated

to

a specific

height,

typically

10

cm, above

the

receiving

electrolyte

reservoir

for

a preset

amount

of

time,

typically

less

than

60 s. Nanolitres

of sample

are siphoned

into

the capillary

by

differential

head pressure

and

gravity.

3.2.8

indirect

UV

detection,

n—a form

of

UV

detection

in

which

the analyte

displaces

an

equivalent

net charge

amount

of

the

highly UV-absorbing

component

of

the electrolyte

causing

a

net

decrease

in background

absorbance.

The

magnitude

of the

decreased

absorbance

is

directly

proportional

to

analyte

con

centration.

Detector

output

polarity

is

reversed

in

order to

obtain a

positive

mV

response.

3.2.9

midpoint

of

peak

width, n—CIE

peaks

typically

are

asymmetrical

with

the

peak

apex

shifting

with increasing

concentration,

and

the

peak apex

may

not be

indicative

of

true

analyte

migration

time.

Midpoint

of

peak width

is

the midpoint

between

the

analyte

peak’s start

and

stop

integration,

or the

peak

center

of gravity.

3.2.10

migration

time,

n—the

time

required

for a

specific

analyte

to

migrate

through

the

capillary

to

the

detector.

The

migration

time in

capillary

ion

electrophoresis

is

analogous

to

retention

time in

chromatography.

3.2.11

time

corrected

peak

area,

n—normalized

peak

area;

peak

area

divided

by

migration

time.

CE

principles

state that

peak

area is

dependent

upon

migration

time,

that

is, for

the

same

concentration

of

analyte,

as migration

time

increases

(decreases)

peak

area

increases

(decreases).

Time

corrected

peak

area accounts

for

these changes.

4.

Summary

of Test

Method

4.1

Capillary

ion electrophoresis,

see

Figs.

7-lU,

is

a

free

zone

electrophoretic

technique

optimized

for the

determination

of

anions with

molecular

weight

less

than 200.

The

anions

All

Cations

Miaration

Time

MT 0

Hioh

Mob

lily

Low Mohilitv

MT>7

mm

—

p

Anions

Anions

FIG.

8 Selectivity

Diagram

of

Anion Mobility

Using

Capillary

Ion

Electrophoresis

/AnaMe

ion (A) c5splaces

electrolyte

len (a)

°

El Cr01

e

yt

g

\

/

charge ror

charge

or

transfer

ratio

causing

\

/

a

net decrease

ri background

abscrbanca.

g

\

/

The change

in absorbance

is

directly

\/

related

to Analyte

concentration.

FIG.

9

Pictorial

Diagram

of Indirect

UV Detection

electrolyte

when

an

electrical

field

is applied

through

the open

tubular fused

silica

capillary.

The

electrolyte’s

electroosmotic

low modifier

dynamically

coats

the inner

wall

of the

capillary

changing

the

surface

to

a net positive

charge. This

reversal

of

wall charge

reverses

the

natural

EOE

The modified

EOF

in

Inorganic

Divalent

Anions

Org

Acids.

Monovalent

Water

Cl. Br.

Oxymetals.

Organic

and

All

NO..

SQ

4

F.

P0

3

.

Acids

Neutral

NO,

ClO

Ci0

3

,

C

2 thru

C

5

Organics

SQ,

S

203

Formate

tie

e

tie

A

A

A e

tie

tie

e

e

ee

eeeeeAAAAeeeeee

tie

eeeeeeAAAAe

tie ee

tie

e

e

eeeeAAAAee

tie

eeee

migrate

and

are

separated

according

to

their

mobility

in

the

combination

with

a

negative

power supply

augments

the

---

D

6508

— 00

(2005)E1

Capillary

with

Polyimlde

Coating

Removed,

Cell

Window

UV Detector

at

254

nm

FIG.

10 General

Hardware

Schematic

of

a

Capillary

Ion

Electrophoresis

System

mobility

of the analyte

anions

towards

the

anode

and

detector

achieving

rapid

analysis

times.

Cations

migrate

in the opposite

direction

towards

the

cathode

and are removed

from

the sample

during

analysis.

Water

and

other

neutral

species

move toward

the

detector

at the

same

rate

as the EOF.

The

neutral

species

migrate

slower than

the

analyte

anions

and

do

not interfere

with

anion

analysis

(see

Figs.

7 and

8).

4.2 The

sample

is

introduced

into

the

capillary

using

hydro

static

sampling.

The

inlet of

the capillary

containing

electrolyte

is

inrnersed

in the

sample

and the

height

of

the sample

raised

10 cm

for 30

s

where

low

nanolitre

volumes

are siphoned

into

the

capillary.

After

sample

loading,

the

capillary

is immediately

immersed

back

into

the

electrolyte.

The

voltage

is applied

initiating

the

separation

process.

4.3

Anion

detection

is based

upon

the princip]es

of

indirect

UV

detection.

The

UV-absorbing

electrolyte

anion is displaced

charge-for-charge

by

the

separated

analyte

anion.

The

analyte

anion

zone

has

a net

decrease

in background

absorbance.

This

decrease

in

UV

absorbance

in quantitatively

proportional

to

analyte

anion

concentration

(see

Fig.

9).

Detector

output

polarity

is

reversed

to provide

positive

mV response

to

the data

system,

and

to

make

the

negative

absorbance

peaks

appear

positive.

4.4

The

analysis

is complete

once

the last

anion of

interest

is

detected.

The

capillary

is

vacuum

purged

automatically

by

the

system

of

any

remaining

sample

and replenished

with

fresh

electrolyte.

The

system

now is

ready

for

the

next

analysis.

5.

Significance

and Use

5.1

Capillary

ion

electrophoresis

provides

a simultaneous

separation

and

determination

of

several

inorganic

anions

using

nanolitres

of

sample

in a

single

injection.

All

anions

present in

the

sample

matrix

will be

visualized

yielding

an anionic

profile

of

the sample.

5.2

Analysis

time is

less than

5 minutes

with

sufficient

sensitivity

for

drinking

water and

wastewater

applications.

Time

between

samplings

is

less than

seven

minutes

allowing

for

high

sample

throughput.

5.3

Minimal

sample

preparation

is

necessary

for

drinking

water

and

wastewater

matrices.

Typically,

only

a dilution

with

water is

needed.

5.4

This test

method

is intended

as

an alternative

to

other

multi-analyte

methods

and various

wet

chemistries

for

the

detennination

of

inorganic

anions in

water and

wastewater.

Compared

to other

multi-analyte

methods

the major

benefits

of

CIE

are

speed

of

analysis,

simplicity,

and

reduced

reagent

consumption

and operating

costs.

6.

Interferences

6.1

Analyte

identification,

quantitation,

and

possible

comi

gration

occur

when

one anion

is in significant

excess

to

other

anions

in the

sample matrix.

For

two

adjacent

peaks,

reliable

quantitation

can

be

achieved

when the

concentration

differen

tial is

less than

100:1.

As the resolution

between

two

anion

peaks

increase

so does

the tolerated

concentration

differential.

In samples

containing

1000 rng/L

Cl,

1 mg/L

SO

4

can

be

resolved

and quantitated,

however,

the

high

Cl

will

interfere

with

Br and NO

2

quantitation.

6.2

Dissolved

carbonate,

detected

as HC0

3

’,

is

an

anion

present

in

all aqueous

samples,

especially

alkaline

samples.

Carbonate

concentrations

greater

than

500 mg/L

will

interfere

with

P0

4

quantitation.

6.3 Monovalent

organic

acids,

except

for

formate,

and

neutral

organics

commonly

found

in wastewater

migrate

later

in

the electropherogram,

after

carbonate,

and

do

not

interfere.

Formate,

a common

organic

acid

found

in

environmental

samples,

migrates

shortly

after

fluoride

but

before

phosphate.

Formate

concentrations

greater

than

5 mg/L

will

interfere

with

fluoride

identification

and

quantitation.

Inclusion

of

2

mg/L

formate

into

the mixed

anion

working

solution

aids

in

fluoride

and formate

identification

and quantitation.

6.4

Divalent

organic

acids

usually

found

in

wastewater

migrate

after

phosphate.

At high

concentrations,

greater

than

10

mg/L,

they

may interfere

with

phosphate

identification

and

quantitation.

Constant

Temperature

Compartment,

25-30°C

Silica

Capillary

.———.

•._i--...

7

•

tandards

•

E

Vaccum

Purge

Mechanism

I

lectrolyte

High

Voltage

UPIY

4

---

D

6508 — 00

(2005)d1

6.5

Chlorate

also migrates

after phosphate

and

at concen

trations

greater

than

10

mg/L

will interfere

with

phosphate

identification

and

quantitation.

Inclusion

of 5 mgfL

chlorate

into

the

mixed

anion working

solution

aids in phosphate

and

chlorate

identification

and quantitation.

6.6 As

analyte concentration

increases,

analyte

peak shape

becomes

asymmetrical.

If

adjacent

analyte

peaks

are not

baseline

resolved,

the data system

will drop

a

perpendicular

between

them

to

the baseline.

This causes

a

decrease

in

peak

area

for both analyte

peaks

and

a low bias for

analyte

amounts.

For

optimal

quantitation,

insure

that

adjacent

peaks

are

fully

resolved,

if

they are not,

dilute

the

sample

1:1 with

water.

7.

Apparatus

7.1 C’apillaiy

Ion Electrophoresis

System—the

system

con

sists

of the following

components,

as shown

in

Fig. it)

or

equivalent:

7.1.1 High

Voltage Power

Supply, capable

of

generating

voltage

(potential)

between

0 and

minus

30 kV relative

to

ground

with

the

capability

working

in

a constant

current

mode.

7.1.2

C’overed

Sample

Carousel,

to

prevent

environmental

contamination

of the samples

and

electrolytes

during

a multi-

sample

batch analysis.

7.1.3

Sample

Introduction

Mechanism,

capable

of hydro

static

sampling

technique, using

gravity, positive

pressure, or

equivalent.

7.1.4

Capillary

Purge

Mechanism,

to

purge

the

capillary

after

every

analysis with

fresh

electrolyte

to eliminate

any

interference

from the previous

sample

matrix, and

to clean

the

capillary

with other reagent,

such as

sodium hydroxide.

7.1.5

UV Detector,

having

the capability

of

monitoring

254

nm, or equivalent,

with

a

time constant

of

0.3

s.

7.1.6 Fused

Silica

Capillary—A

75

im

(inner

diameter)

x

375

pm (outer diameter)

x

60 cm (length)

having

a

polymer

coating

for flexibility,

and

noncoated

section

to

act as

the cell

window

for

UV detection.

3

7.1.7

C’onstant

Temperature

Cotnpartment—To

keep

the

samples,

capillary,

and

electrolytes

at constant

temperature.

7.2

Data

System—A

computer

system that

can

acquire

data

at 20

points/s minimum,

express

migration time

in minutes

to

three

decimal places,

use

midpoint

of the analyte

peak

width,

or center

of gravity,

to

determine

the analyte

migration

time,

use

normalized

migration

times

with respect

to a reference

peak

for qualitative

identification,

use time corrected

peak

area

response

for analyte

quantitation,

and express

results

in con

centration

units.

3

NOTE

2—It

is recommended

that

integrators

or

standard

chromato

graphic

data

processing

not be

used with this

test method.

7.3 Anion

Exchange

Cartridges

in the Hydroxide

Form.

3

’

4

7.4 Plastic

Syringe, 20-mL,

disposable.

The sole

source

of

supply

of

the

apparatus known

to the committee

at this

time

is

Waters

Corp.,

34

Maple St.,

Milford,

MA 01757. If

you are

aware

of alternative

suppliers,

please

provide

this

information

to ASTM

International

l-leadquarters.

Your comments

will receive

careful

consideration

at a meeting

of

the responsible

technical

committee

,

which

you

may

attend.

The sole source

of

supply of the

apparatus

known

to

the

committee

at this time

is Alltech

Associates,

P/N

30254, 2051

Wsukegan

Rd.,

Deerfield,

IL,

60015.

7.5

Vacuum

Filtration Apparatus,

capable

for

filtering

100

mL of

reagent

through

a

0.45

pm

aqueous

filter.

8.

Reagents

and

Materials

8.1 Purity

of Reagents—Unless

otherwise

indicated,

it

is

intended

that all

reagents

shall

conform

to the

reagent

grade

specification

of the Analytical

Reagents

of the

American

Chemical

Society,

where

such

specifications

are

available.

5

Other

grades

may be used,

provided

it is first

ascertained

that

the

reagent

is

of sufficient high

purity

to permit

its

use

without

lessening

the

performance

or accuracy

of

the

determination.

Reagent

chemicals

shall

be

used for

all tests.

NOTE

3—Calibration

and detection

limits

of this test

method

are biased

by

the purity

of

the reagents.

8.2

Purity

of Water—Unless

otherwise

indicated,

references

to

water shall

be understood

to mean

Type

I

reagent

water

conforming

or exceeding

specification

1)

1193.

Freshly

drawn

water

should

be

used

for preparation

of

all

stock

and

working

standards,

electrolytes,

and solutions.

6

Performance

and detec

tion

limits

of this

test method

are

limited

by

the

purity

of

reagent

water,

especially

TOC.

8.3 Reagent

Blank—Reagent

water,

or any

other

solution,

used to

preserve

or dilute the

sample.

8.4 Individual

Anion Solution,

Stock

NOTE 4—It

is

suggested

that

certified

individual

1000

mg/L

anion

standards

be purchased for

use

with this

test method.

NOTE

5—All

weights

given

are for anhydrous

or

dried

salts.

Reagent

purity

must

be accounted

for in order

to calculate

true value

concentration.

Certify

against NIST traceable

standards.

8.4.1

Bromide

Solution,

Standard

(1.0

mL

= 1.00

nag

Bromnide)—Dry

approximately

0.5

g

of

sodium

bromide

(NaBr)

for

6

h

at

150°C and cool

in

a

desiccator.

Dissolve

0.128

g

of the

dry salt

in a 100 mL

volumetric

flask

with

water,

and fill

to mark with

water.

8.4.2

Chloride

Solution,

Standard (1.0

,nL

=

1.00

mg

Chloride)—Dry

approximately

0.5

g

of

sodium

chloride

(NaCl) for

1

h at

100°C and

cool

in

a

desiccator.

Dissolve

0.165

g

of

the

dry

salt in

a

100

mL a volumetric

flask

with

water, and

fill

to mark

with

water.

8.4.3 Fluoride

Solution,

Standard

(1.0

niL

1.00

mg

Fluoride)—Dry

approximately

0.5

g

of sodium

fluoride

(NaF)

for

1 h at

100°C and

cool

in

a desiccator.

Dissolve

0.22

1

g

of

the dry salt

in a 100

mL volumetric

flask

with

water,

and fill

to

mark with

water.

8.4.4

Formate

Solution,

Standard (1.0

mnL

=

1.00

mg

Formate)—Dissolve

0.151

g

of sodium

formate

in

a

100-mL

volumetric

flask

with water,

and

fill

to

mark

with

water.

Reagent

Chemicals,

American Chemicat

Society

Specifications,

Am.

Chem.

Soc., Washington,

DC.

For suggestions

on the testing

of reagents

not

listed

by

the

American

Chemical Society,

see

A,ialar

Standards far

Laborata?y

Chemicals,

BDH

Ltd.,

Poole, Dorset,

U.K., and

the

United

States

Pharmacopeia

and

National

Formuirny,

U.S.

Pharmacopoeia

Convention,

Inc.

(USPC),

Rockville,

Md.

Although

the

reagent water

may exceed

Specification

1)

1193.

the

reagent

water

needs

to be periodically

tested

for bacterial contamination.

Bacteria

and their

waste

products

may adversely

affect

system

performance.

As

a

guide,

ASTM

Type

IA

water

specifies

a total bacteria

count of 10 colonies/L.

Refer

to Test

Method

F

455

for analysis

procedure.

5

---

I111Jfr

D

6508

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00

(2005)1

8.4.5

Nitrate

Solution,

Standard

(1.0

mL =

1.00

ing

Nitrate)—Dry

approximately

0.5

g

of

sodium

nitrate

(NaNO

3

)

for 48

h at 105°C

and

cool

in

a desiccator.

Dissolve

0.137

g

of

the

dry

salt in

a 100-niL

volumetric

flask

with

water,

and

fill

to

mark

with

water.

8.4.6

Nitrite

Solution,

Standard

(1.0

mL

= 1.00

nig

Nitrite)—Dry

approximately

0.5

g

of sodium

nitrite

(NaNO

2

)

for

24

h in a

desiccator

containing

concentrated

sulfuric

acid.

Dissolve

0.150

g

of

the

dry

salt in

a

100-mL

volumetric

flask

with

water,

and fill

to

mark

with

water.

Store

in a

sterilized

glass

bottle.

Refrigerate

and

prepare

monthly.

NOTE

6—Nitrite

is

easily

oxidized,

especially

in

the

presence

of

moisture.

Use

only

fresh

reagent.

NOTE

7—Prepare

sterile

bottles

for

storing

nitrite

solutions

by

heating

for

1 h

at 170°C

in

an air

oven.

8.4.7

Ortho-Phosphate

Solution,

Standard

(1.0

,nL

= 1.00

mg

o-Phosphate)—Dissolve

0.150

g

of

anhydrous

dibasic

sodium

phosphate

(Na

2

HPO

4

)

in

a

100-mL

volumetric

flask

with

water,

and

fill to

mark

with

water.

8.4.8

Sulfate

Solution,

Standard

(1.0 ,nL

=

1.00

mg

Sulfate)—Dry approximately

0.5

g

of

anhydrous

sodium

sul

fate

(Na

2

SO

4

)

for 1

h

at 110°C

and

cool

in a

dessicator.

Dissolve

0.148

g

of

the

dry salt

in

a

l00-mL

volumetric

flask

with

water,

and

fill to

mark

with

water.

8.5

Mixed

Anion

Solution,

Working—Prepare

at least

three

different

working

standard

concentrations

for

the

analyte

anions

of

interest

bracketing

the

desired

range

of

analysis,

typically

between

0.1

and

50 mgIL,

and

add

2

mg/L

formate

to

all

standards.

Add

an appropriate aliquot

of Individual

anion

stock solution

(see 8.4)

to a prerinsed

100-mL

volumetric

flask,

and

dilute

to

100

mL

with

water.

NOTE 8—Use

100

1

.iL of Individual

anion

stock solution

(see

g.4)

per

100

mL

for 1

mgIL

anion.

NOTE

9—Anions

of

no

interest

may be

omitted.

NOTE

10—The

midrange

mixed

anion

solution,

working

may

be used

for

the

determination

of

migration

times

and resolution

described

in

12.1.

8.6

C’alibration Verification

Solution

(CVS)—A

solution

formulated

by

the

laboratory

of

mixed

analytes

of

known

concentration

prepared

in water.

The

CVS

solution

must

be

prepared

from

a

different

source

to

the

calibration

standards.

8.7

Petformance

Evaluation

Solution

(PES)—A

solution

formulated

by

an

independent

source

of

mixed

analytes

of

known

concentration

prepared

in

water.

Ideally,

the

PBS

solution

should

be

purchased

from

an

independent

source.

8.8

Quality

Control

Solution

(QCS)—A

solution

of

known

analyte

concentrations added

to a

synthetic

sample

matrix

such

as

substitute

wastewater

that

sufficiently

challenges

the test

method.

8.9

Buffer

Solution (100

mM C’HES/l

mM

Calcium

Gluconate)—Dissolve

20.73

g

of

CHES

(2-EN-

Cyclohexylamino]-Ethane

Sulfonic

Acid)

and

0.43

g

of cal

cium

gluconate

in a I -L

volumetric

flask

with

water,

and dilute

to I

L

with

water.

This

concentrate

may

be stored

in

a

capped

glass

or

plastic

container

for up

to

one

year.

8.10

C’hromate

Concentrate

Solution

(100

mM

Sodium

Chroniate)—Dissolve

23.41

g

of

sodium

chromate

tetrahydrate

(Na

2

CrO

4

.4

H

2

0)

in a

1-L

volumetric

flask

with

water,

and

dilute

to I

L with

water.

This concentrate

may

be

stored

in

a

capped

glass

or

plastic

container

for

up

to

one

year.

8.11

OFM

‘oncentrate

Solution

(100

mM

Tetradecyltrim

ethyl

Animonium

Bromide)—Dissolve

33.65

g

of

Tetradecylt

rimethyl

Ammonium

Bromide

(TFABr)

in

a

I -L

volumetric

flask

with

water,

and

dilute

to

1 L

with

water.

Store

this

solution

in a

capped

glass

or

plastic

container

for

up to

one

year.

NOTE 1

l—TTABr

needs

to

be

converted

to

the

hydroxide

form

(FfAOH)

for

use

with

this test

method.

TfAOH

is

commercially

available

as 100 mM

TFAOH,

which

is

an

equivalent

substitute.

8.12

Sodium

Hydroxide

Solution

(500

mM

Sodium

Hydroxide)—Dissolve

20

g

of

sodium

hydroxide

(NaOH)

in

a

1-L

plastic

volumetric

flask

with

water,

and

dilute

to

1

L with

water.

8.13

Electrolyte

Solution,

Working

(4.7

mM

C’hromate/4

mM

?TAOH/10

mM

CHES/0.1

mM

Calcium

Gluconate)

3

’

7

—

Wash

the anion

exchange

cartridge

in the

hydroxide

form

(see

7.3)

using

the

20-mL

plastic

syringe

(see

7.4)

with

10

ml..

of

500mM

NaOH

(see

8.12)

followed

by

10

mL

of water.

Discard

the washings.

Slowly

pass

4-mi..

of

the 100

mM

TTABr

solution

(see

8.11)

through

the

cartridge

into

a

lOO-mL

volumetric

flask.

Rinse

the

cartridge

with

20

mL

of

water,

adding

the washing

to

the

volumetric

flask.

NOTE 12—The

above

procedure

is

used

to

convert

the

Tl’ABr

to

TI’AOH,

which

is

used

in the

electrolyte.

If

using

commercially

available

100 mM

TTAOH,

the

above conversion

step

is

not necessary;

substitute

4

mL

of 100

mM

TTAOH

and continue

below.

8.13.1

Into

the

100-mi..

volumetric

flask

add

4.7

mL

of

chrornate

concentrate

solution

(see

8.10)

and

10

mL

of buffer

solution

(see

8.9).

Mix

and dilute

to

100

mL

with

water.

The

natural

pH

of the

electrolyte

should

be

9

±

0.1.

Filter

and

degas

using

the

vacuum

filtration

apparatus.

Store

the

any

remaining

electrolyte

in

a capped

glass

or

plastic

container

at

ambient

temperature.

The

electrolyte

is stable

for

one

year.

9.

Precautions

9.1

Chemicals

used

in

this test

method

are

typical

of many

useful

laboratory

chemicals,

reagents,

and

cleaning

solutions,

which

can be

hazardous

if

not handled

properly.

Refer

to

Guide

0

3856.

9.2

It

is the

responsibility

of the

user to

prepare,

handle,

and

dispose

of chemical

solutions

in accordance

with

all

applicable

federal,

state, and

local

regulations.

(Warning—This

capillary

electrophoresis

method

uses

high

voltage

as

a

means

for

separating

the

analyte

anions,

and

can

be

hazardous

if not

used

properly.

Use

only

those

instruments

that have

all proper

safety

features.)

10.

Sampling

10.1

Collect

samples

in

accordance

with

Practice

D

3:370.

10.2

Rinse

sample

containers

with sample

and

discard

to

eliminate

any

contamination

from

the

container.

Fill

to

over

flowing

and cap

to exclude

air.

The

sole source

of supply

of the

apparatus

known

to the

committee

at

this

time

is

Waters

Coip..

34 Maple

St., Milford,

MA

01757,

as tonSelect

High

MobilityA

nion Electrolyte,

P/N 49385..

6

---

411Jfr

D

6508

—

00

(2005)E1

10.3

Analyze

samples,

as

soon

as

possible,

after

collection.

For

nitrite,

nitrate,

and

phosphate

refrigerate

the

sample

at

4°C

after

collection.

Warm

to

room

temperature

before

dilution

and

analysis.

10.4

At

the

laboratory,

filter

samples

containing

suspended

solids

through

a

prerinsed

0.45

pm

aqueous

compatible

mem

brane

filter

before

analysis.

10.5

If

sample

dilution

is

required

to

remain

within

the

scope

of

this

test

method,

dilute

with

water

only.

11.

Preparation

of

Apparatus

11.1

Set

up

the

CE

and

data

system

according

to

the

manufacturer’s

instructions.

11.2

Program

the

CE

system

to

maintain

a

constant

tem

perature

of

25

±

0.5°C,

or

5°C

above

ambient

laboratory

temperature.

Fill

the

electrolyte

reservoirs

with

fresh

chromate

electrolyte

working

solution

(see

8.13),

and

allow

10

minutes

for

thermal

equilibration.

11.3

Condition

a

new

capability

(see

7.1,6)

with

500mM

NaOH

solution

(see

8.12)

for

5

minutes

followed

by

water

for

5

minutes.

Purge

the

capillary

with

electrolyte

(see

8.13)

for

3

minutes.

11.4

Apply

15

kV

of

voltage

and

test

for

current.

The

current

should

be

14

±

1

pA.

If

no

current

is

observed,

then

there

is

a

bubble,

or

blockage,

or

both,

in

the

capillary.

Degas

the

chrornate

electrolyte

working

solution

and

retry.

If

still

no

current,

replace

the

capillary.

11.5

Set

the

UV

detector

to

254

nm

detection,

or

equivalent.

Zero

the

detector

to

0.000

absorbance.

UV

offset

is

less

than

0.1

AU.

11.6

Program

the

CE

system

for

constant

current

of

14

pA.

11.7

Program

the

CE

system

for

a

hydrostatic

sampling

of

30

s.

Approximately

37

nL

of

sample

is

siphoned

into

the

capillary.

Different

sampling

times

may

be

used

provided

that

the

samples

and

standards

are

analyzed

identically.

11.8

Program

the

CE

system

for

1

minute

purge

with

the

chromate

electrolyte

working

solution

between

each

analysis.

Using

a

15

psi

vacuum

purge

mechanism,

one

60-cm

capillary

volume

can

be

displaced

in

30

s.

11.9

Program

the

data

system

for

an

acquisition

rate

of

at

least

20

points/s.

Program

the

data

system

to

identify

analyte

peaks

based

upon

normalized

migration

time

using

Cl

as

the

reference

peak,

and

to

quantitate

analyte

peak

response

using

time

corrected

peak

area.

NOTE

13—Under

the

analysis

conditions

Cl

is

always

the

first

peak

in

the

electropherogram,

and

can

be

used

as

migration

time

reference

peak.

12.

Calibration

12.1

Determination

of

Migration

Times

(Calibrate

Daily)—

The

migration

time

of

an

anion

is

dependent

upon

the

electrolyte

composition,

pH,

capillary

surface

and

length,

applied

voltage,

the

ionic

strength

of

the

sample,

and

tempera

ture.

For

every

fresh

electrolyte

determine

the

analyte

migra

tion

time,

in

mm

to

the

third

decimal

place,

of

the

midrange

mixed

anion

standard

working

solution

(see

8.5),

described

in

Section

11.

Use

the

midpoint

of

analyte

peak

width

as

the

determinant

of

analyte

migration

time.

NOTE

l4—Analyte

peak

apex

may

be

used

as

the

migration

time

detemiinant,

but

potential

analyte

misidentification

may

result

with

asymmetrical

peak

shape

at

high

analyte

concentrations.

12.2

Analyze

the

blank

(see

8.3)

and

at

least

three

working

mg/L

solutions

(see

8.5),

using

the

set-up

described

in

Section

11.

For

each

anion

concentration

(X-axis)

plot

time

corrected

peak

area

response

(Y-axis).

Determine

the

best

linear

calibra

tion

line

through

the

data

points,

or

use

the

linear

regression

calibration

routine

(linear

through

zero)

available

in

the

data

system.

NOTE

15—Do

not

use

peak

height

for

calibration.

Peak

area

is

directly

related

to

migration

time,

that

is.

for

the

same

analyte

concentration,

increasing

migration

time

give

increasing

peak

area.

12.2.1

The

r

2

(coefficient

of

determination)

values

should

be

greater

than

0.995;

typical

r

2

values

obtained

from

the

inter-

laboratory

collaborative

are

given

in

Table

A2.

1.

12.3

Calibrate

daily

and

with

each

change

in

electrolyte,

and

validate

by

analyzing

the

CVS

solution

(see8.6)

according

to

procedure

in

16.4.

12.4

After

validation

of

linear

multiple

point

calibration,

a

single

point

calibration

solution

can

be

used

between

0.1

and

50

mg/L

for

recalibration

provided

the

quality

control

require

ments

in

16.4

are

met.

13.

Procedure

13.1

Dilute

the

sample,

if

necessary

with

water,

to

remain

within

the

scope

(see

i

.2

and

1.3)

and

calibration

of

this

test

method.

Refer

to

Al

.5.1.

13.2

Analyze

all

blanks

(see

8.3),

standards

(see

8.5),

and

samples

as

described

in

Section

11

using

the

quality

control

criteria

described

in

16.5-16.9.

Refer

to

Figs.

1-6

for

represen

tative

anion

standard,

detection

limit

standard,

substitute

wastewater,

drinking

water,

and

wastewater

electrophero

grams.

13.3

Analyze

all

blanks,

calibration

standards,

samples,

and

quality

control

solutions

in

singlicate.

13.3.1

Optional—Duplicate

analyses

are

preferred

due

to

short

analysis

times.

NOTE

16—Collaborative

data

was

acquired,

submitted

and

evaluated

as

the

average

of

duplicate

samplings.

13.4

After

20

sample

analyses,

or

batch,

analyze

the

QCS

solution

(see

8.8)

If

necessary,

recalibrate

using

a

single

mixed

anion

standard

working

solution

(see

8.5),

and

replace

analyte

migration

time.

NOTE

17—A

change

in

analyte

migration

time

of

the

mixed

anion

standard

working

solution

by

more

than

+5%

suggests

that

components

in

the

previously

analyzed

sample

matrices

have

contaminated

the

capillary

surface.

Continue

but

wash

the

capillary

with

NaOH

solution

(see

8,12)

before

the

next

change

in

electrolyte.

14.

Calculation

14.1

Relate

the

time

corrected

peak

area

response

for

each

analyte

with

the

calibration

curve

generated

in

12.2

to

deter

mine

mg/L

concentration

of

analyte

anion.

If

the

sample

was

diluted

prior

to

analysis,

then

multiply

mg/L

anion

by

the

dilution

factor

to

obtain

the

original

sample

concentration,

as

follows:

Original

Sample

mgfL

Analyte

=

(Ax

SF)

(1)

7

---

D

6508

— 00

(2005)€1

where:

A

=

analyte

concentration

determined

from

the calibration

curve,

in mgfL,

and

SF

=

scale or

dilution

factor.

15.

Report

Format

15.1

The sample

analysis

report

should

contain

the sample

name,

analyte

anion

name,

migration

time

reported

to three

decimal

places,

migration

time

ratio, peak

area,

time

corrected

peak

area, sample

dilution,

and original

solution

analyte

concentration.

15.1.1

Optional—Report

analysis

method

parameters,

date

of sample

data

acquisition,

and

date of

result processing

for

documentation

and

validation

purposes.

16.

Quality

Control

16.1 Before

this

test method

is applied

to the

analysis

of

unknown

samples,

the

analyst

should establish

control

accord

ing

to procedures

recommended

in Practice

D

5847,

and Guide

1)5810.

16.2

The

laboratory

using

this

test

should

perform

an initial

demonstration

of

laboratory

capability

according

to

procedures

outlines

in

Practice D

5847.

NOTE

18—Certified

performance

evaluation

solutions

(PES)

and

QC

solutions

(QCS and

CVS)

are commercially

available

and recommended.

16.3

Initial

Demonstration

of

Peiformance—Analyze

seven

replicates

of a

performance

evaluation

solution

(PES)

(see

6.7).

The

analyte concentration

mean

and

standard

deviation

of

the

seven

replicates

should

be calculated

and

compared

to

the test

methods

single

operator

precision

for

equivalent

concentra

tions

in

reagent

water

given

in Section

17.

16.3.1

Repeat

the

seven

replicate

analysis

protocol

before

using

a freshly

prepared

QVS

solution

(see

8.6) and

QCS

solution

(see 8.6)

for

the

first time.

Calculate

the

standard

deviation

and compare

with

previous

results

using

the

student

t-test.

If no significant

difference

is noted,

then

use

the

combined

standard

deviation

to

determine

the

QC

limits,

generally

the mean

± three

standard

deviations,

for

the

QCV

and QCS

solutions.

16.4 Calibration

Verification—After

calibration,

verify

the

calibration

linearity

and acceptable

instrument

performance

using

a calibration

verification

solution

(see 8.6)

treated

as an

unknown.

If the determined

CVS concentrations

(see 8.6)

are

not

within

±

3 standard

deviations

of

the

known

true

values

as

described

in 16.3.],

the calibration

solutions

may

be

out of

control.

Reanalyze,

and if

analyte

concentration

still

falls

outside

the

acceptable

limits,

fresh

calibration

solutions

(see

8.5)

are

required.

Successful

CVS analyte

concentration

must

be

confirmed

after

recalibration

before

continuing

with the

test

method.

16.5

Analyze

a

reagent blank

(see 8.3)

with

each

batch to

check

for

contamination

introduced

by the

laboratory

or

use of

the

test method.

16.6 Quality

Control Solution—Analyze

one QCS

(see 8,8)

after

20 samples,

or batch.

The analyte

concentrations

for

the

QCS

should

fall

within

±

3 standard

deviations

of

historical

values

for the

equivalent

concentration

and

matrix.

They are

determined

as

described

in 1.6.3.1.

Upper

Control Limit

= Analyte

Mean Value

+ 3 times

the Standard

Deviation

Lower

Control

Limit

= Analyte

Mean

Value

— 3

tines

the Standard

Deviation

16.7

Matrix

Spike

Recovery—One

matrix

spike

(MS)

should

be analyzed

with

each

batch

of samples

to

test

method

recovery.

Spike

a

portion

of one

sample

from

each

batch

with

a

known

concentration

of analyte,

prepared

in accordance

with

Guide

I)

3856. The

% recovery

of the

spike

should

fall

within

%recovery

±

analyst

%RSD

for

an

equivalent

spike

concen

tration

and

matrix

given

in Thbles

1-7.

If it

does

not,

an

interference

may

be

present

and

the data

for the

set

of similar

samples

matrices

must

be qualified

with a

warning

that

the

data

are

suspect,

or an

alternate

test

method should

be used.

Refer

to Guide

1)

581(1.

16.7.1

If the known

analyte

concentration

is

between

15

and

50 rngJL,

then spike

the sample

solution

to increase

analyte

concentration

by

50

%.

16.7.2 If

the known

analyte

concentration

is

less

than

15

mgfL,

then

spike

the

sample

solution

to

increase

analyte

concentration

by 100

%, but not

less

than 2

rngfL.

16.7.3

Calculate

the

percent

recovery

of

the

spike

using

the

following

formula:

where:

%

Recovery

= 100

[A

(V

+

V) —

B VJ/C V

(2)

A

= Analyte

concentration

(mg/L)

in

spiked

sample,

B

= Analyte

concentration

(mgIL)

in unspiked

sample,

C

= Concentration

(rng/L) of

analyte

in spiking

solution,

=

Volume

(mL) of

sample

used, and

V = Volume

(mL)

added

with

spike,

Evaluate

the

performance

according

to Practice

D

5847.

16.8

Method

Precision—One

unknown

sample

should

be

analyzed

in

triplicate

with

each

batch

to test

method

precision.

Calculate

the

standard

deviation

and

use the

F-test

to

compare

with

the single

operator

precision

give in

Tables

1-7

for

the

equivalent

analyte

concentration

and matrix

type.

Evaluate

performance

according

to Practice

D 5847.

16.9 The

laboratory

may

perform

additional

quality

control

as

desired

or appropriate.

17. Precision

and

Bias

17.1

The precirion

and

bias

data

presented

in

this

test

method

meet the

requirements

of Practice

D 2777,

and

are

given in

Tables

1-7.

17.2

This test

method

interlaboratory

collaborative

was

performed

by 11

laboratories

using

one

operator

each.

Four

Youden-Pair

spike

concentrations

for

the

seven

analytes

anions

yielding

eight

analyte concentration

levels.

Test

data

was

submitted

for

eleven

reagent

waters,

eleven

substitute

waste-

waters,

15 drinking

waters,

and

13 wastewater

sample

matri

ces.

17.3

The

precision,

bias, and

matrix

recovery

of this

test

method

per

anion analyte

in four

tested

sample

matrices

are

based

upon

the analyte

true

value,

calculated

using

weight,

volume,

and

purity. True

value

spiking

solution

concentrations

are

given in

Table

A 1.4.

17.4

The bias

and

matrix

recovery

statements

for

less

than

2

mgIL

of chloride,

sulfate,

and nitrate

in

naturally

occurring

sample

matrices

may

be

misleading

due

to

spiking

of

small

analyte

concentration

into

a high naturally

occurring

analyte

---

D 6508

— 00

(2005)d1

TABLE

1

Precision,

Bias,

and

Matrix

Recovery

for

Chloride

Matrx

No.

of

True

Val e

Mean

Bias

Versus

Recovery Versus

Interlab

Interlab

Single

Operator

Analyst

Values

U

Result

True Value

True

Value

Std

0ev S(t)

%RSD

Std

0ev.

S(o)

%RSD

Reagent

water

9

0.50

0.55

0.05

110.0

0.11

19.8

10

0.71

0.69

—0.02

97.2

0.08

11.5

0.05

7.5

10

2.00

1.97

—0.03

98.5

0.14

6.8

9

2.98

2.97

—0.01

99.7

0.11

3.8

0.05

2.1

10

14.92

14.76

—0.16

98.9

0.61

4.2

10

19.91

19.81

—0.10

99.5

0.81

4.1

0.48

2.8

10

39.81

38.58

—1.23

96.9

1.43

-

3.7

10

49.76

48.70

—1.06

97.9

1.94

4.0

1.36

3.1

Substitute

wastewater

9

0.50

0.46

—0.04

92.0

0.51

111.1

9

0.71

0.43

—0.28

60.6

0.69

160.7

0.42

93.8

9

2.00

1.52

—0.48

76.0

0.68

45.0

9

2.98

2.58

—0.40

86.6

0.63

24.5

0.50

24.3

9

14.92

14.29

—0.63

95.8

1.02

7.1

9

19.91

18.93

—0.98

95.1

1.24

6.6

0.60

3.6

9

39.81

37.34

—2.47

93.8

5.44

14.6

9

49.76

47.54

—2.22

95.5

3.13

6.6

4.43

10.4

Drinking water

12

0.50

0.63

0.13

126.0

0.67

106.1

12

0.71

0.75

0.04

105.6

0.34

45.5

0.40

57.2

12

2.00

2.15

0.15

107.5

0.51

23.6

12

2.98

2.95

—0.03

99.0

0.39

13.1

0.47

16.5

12

14.92

14.54

—0.38

97.5

0.71

4.9

12

19.91

19.09

—0.82

95.9

1.11

5.8

0.37

2.2

12

39.81

38.38

—1.43

96.4

1.56

4.1

12

49.76

47.97

—1.79

96.4

2.19

4.6

1.26

3.9

“Real”

Wastewater

9

0.50

0.42

—0.08

84.0

0.34

81.0

10

0.71

0.47

—0.24

66.2

0.34

72.6

0.26

59.3

10

2.00

1.56

—0.44

78.0

0.51

32.7

9

2.98

2.78

—0.20

93.3

0.19

6.8

0.37

17.3

10

14.92

14.29

—0.63

95.8

0.63

4.4

10

19.91

18.83

—1.08

94.6

0.78

4.1

0.46

2.8

9

39.81

37.01

—2.80

93.0

2.78

-

7.5

10

49.76

48.24

—1.52

96.9

3.15

6.5

2.54

6.0

concentration

observed

with

the matrix

blank.

The commonly

with

Millennium

Data

Processing

Software,

and one

laboratory

occurring

analyte

concentrations

observed

in

the sample

matrix

used

a Agilent

CE

System with

Diode

Array

Detector

that

blanks

for

the

naturally

occurring

tested

matrices

are

given

in

provided

equivalent

results.

Table

Al.5.

17.5

The

high nitrate

bias

and

%recovery

noted

for

the

0.5

NOTE 19—Refer

to

reference

B 1.16

and Agilent

(the

former

HP

mg/L

NO

3

spike solution

are attributed

to

the spiking

solution

company)

website

for

recommended

operating

conditions.

containing

50 mgfL

nitrite

and 0.5

mgIL nitrate.

Refer

to Annex

Table

Al.4,

Solution

3.

Some of

the nitrite

converted

to nitrate

18.

Keywords

prior

to analysis.

Similar

NO,,

conversion

effect

is observed

18.1

anion;

capillary

electrophoresis;

drinking

water;

ion

with

the 2-mgfL

nitrate

and 2 mgIL

nitrite

spike,

Solution

7.

analysis;

reagent

water;

substitute

wastewater;

wastewater

17.6 All

collaborative

participants

used

the premade

chro

mate

electrolyte.

7

Ten

laboratories

used a

Waters CIA

Analyzer

9

---

cfr

D

6508

00

(2005)E1

TABLE

2 Precision,

Bias, and

Matrix

Recovery

for

Bromide

No. of

Mean

Values

True Value

Result

10

0.51

0.60

10

0.70

0.83

10

2.00

2.06

10

3.01

2.88

10

14.93

15.00

10

19.91

19.32

10

39.81

39.66

10

49.77

50.04

Sias

Versus

Recovery

Versus

Interlab

True

Value

True

Value

Std

Dev

S(t)

0.09

117.6

0.19

0.13

118.6

0.23

0.06

103.0

0.14

—0.13

95.7

0.23

0.07

100.5

0.58

—0.59

97.0

0.97

—0.15

99.6

1.24

0.27

100.5

2.94

Interlab

%RSD

31.0

28.2

6.6

7.9

3.9

5.0

3.1

5.9

0.08

9.3

0.17

7.0

1.63

9.7

0.48

1.1

Matrix

Single

Operator

Analyst

Std

Dev.

S(o)

%RSD

Reagent

water

Substitute

wastewater

Drinking

water

“Real”

Wastewater

0.10

0.15

0.75

1.61

14.6

6.3

4.4

3.6

0.19

28.8

0.21

21.8

0.22

10.2

0.35

12.8

0.58

3.9

2.62

13.8

1.11

2.9

1.52

3.1

9

0.51

0.67

9

0.70

0.96

9

2.00

2.14

9

3.01

2.72

9

14.93

14.70

9

19.91

18.91

9

39.81

38.76

9

49.77

48.81

13

0.51

0.58

13

0.70

0.83

13

2.00

1.98