IS 3025-42: Methods of sampling and test (physical and chemical) for water and wastewater, Part 42: Copper

13 Pages·1992·1.2 MB·English

by  Bureau of Indian Standards

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“The Right to Information, The Right to Live” “Step Out From the Old to the New”
IS 3025-42 (1992): Methods of sampling and test (physical
and chemical) for water and wastewater, Part 42: Copper
[CHD 32: Environmental Protection and Waste Management]
“!ान $ एक न’ भारत का +नम-ण”
Satyanarayan Gangaram Pitroda
““IInnvveenntt aa NNeeww IInnddiiaa UUssiinngg KKnnoowwlleeddggee””
“!ान एक ऐसा खजाना > जो कभी च0राया नहB जा सकता हहहहै””ै”
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“Knowledge is such a treasure which cannot be stolen”

IS 3025 (Part42) : 1992
(Reaffirmed2003)

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Indian Standard
METHODS OF SAMPLING AND TEST
(PHYSICAL AND CHEMICAL) FOR
WATER AND WASTEWATER
PART 42 COPPER
(First Revision)
- -
Fourth Reprint SEPTEMBER 2007
(IncludingAmendment No.1)
UDC 628.1/.3 :543 (546.56)
e
BIS 1992
BUREAU OF INDIAN STANDARDS
MANAK Bl-IAVAN, 9 BAHADUR SHAH ZAFAR MARG
NEW DELHI 110002

Price Group 3
AMENDMENT NO. 1 MAY 2004
TO
IS 3025(PART 42) : 1992 METHODS OF
SAMPLING AND TEST (PHYSICAL AND CHEMICAL)
FOR WATER AND WASTEWATER
PART 42 COPPER
(FintRevision)
( Page 1. claus« 5.2. line 3 ) - Insert the words 'suspended solids' in
between the words 'organicmatter"and 'sulphide'.
(CHD32)
Printedat-PrabhatOfIaetPress.NewDelhi·2
Environmental Protection Sectional Committee, CHD 012
FOREWORD
This Indian Standard ( First Revision) was adopted by the Bureau of Indian Standards, after
the draft finalized by the Environmental Protection Sectional Committee had been approved by
the Chemical Division Council.
Copper is found mainly as a sulphide, oxide or carbonate in the minerals. Copper enters the
water system through mineral dissolution, industrial effluents, because ofits use as algicide and
insecticide and through corrosion of copper alloy water distribution pipes. It may occur in
simple ionic form or in one of many complexes with groups, such as cyanides, chlorides,
ammonia or organic ligands. The test for copper is essential because dissolved copper salts
even in low concentrations are poisonous to some biota. Desirable limit for copper in potable
water is 0·05 mgll maximum which can be relaxed in the absence of better alternate source to
1·5 rna/I.
In the preparation ofthis standard, considerable assistance has been derived from American
Society for Testing and Materials, USA ( ASTM Annual Book Section 11, 1983).
In reporting th results ofa test or analysis made in accordance with this standard, ifthe final
value, observed or calculated, is to be rounded off, it shall be done in accordance with
IS 2: 1960 'Rules for rounding offnumerical values (revised )9.
IS 3025( Part 42 ) : 1991
Indian Standard
METHODS OF SAMPLING AND TEST
(PHYSICAL AND CHEMICAL) FOR
WATER AND WASTEWATER
PART 42 COPPER
( First Revision)
with dilute nitric acid ( 6 N ) prior to the final
1 SCOPE
rinsing with water. The water samples should
1.1 This standard prescribes four methods for be collected and stored for 24h preferably in
determination ofcopper as follows: polypropylene or chemically resistant 81asl
containers. For preservation, the samples
a) Neocuproine method,
should be acidified with concentrated nitric
b) Atomic absorption method ( direct ), acid (2 ml of AR grade nitric acid to 1
litre just to brlng down the pH below 2).
c) Atomic absorption method ( chelation
Unacidifled samples should be analysed on the
extraction ), and
same day while the acidified samples may be
d) Difrerential pulse anodic stripping volt-
stored for a few days in a refrigerator.
ammetry.
or .- QUALITY OF REAGENTS
1.2 The choice the method depends upon
the concentration range and interference. 4.1 Unless specified otherwise, pure chemicals
When the concentration levels are below shall be used.
SOO ./1, pre-concentration is carried out either
by chelation and extraction prior to atomic NOTE - -Purechemical.·shall meanchemicaIIthat
do not contain impuritiel which affect the results
abiorptioD spectrophotometer (AAS) or by
ofanalysis.
as
depolltina in differential pulse anodic
Itrippins voltammetry method. For dissolved 4.2 Double distilled water with a specific
copper content filteration through 0·45 lim conductivity less than 1 p,s/cm shall be used
membrane ftl~eris required. for preparing the standard and reagent
solutions.
2 UFERENCES
5,'NEOCUPROINE METHOD
2.1 The followin, Indian Standards are the
necessary adjuncts to this standard: 5.1 PriDclple
IS No. Title Copper (II) is reduced to copper (I) by
bJdroxyl amine hydrochloride and the pH of
3025 Methods ofsampling and test
tie solution is adjusted to Sby sodium citrate
( Part 1) : 1986 (physical and chemical) for
solution. Copper ( I ) forms a soluble yellow
water and wastewater: Part I
complex with 2, 9-dimethyl-l, lO-phenan
Samplina
tbrolioe ( neocuproine) suitable for spectro
7022 Glossary ofterms relating to photometric measurement. This method is
( Part 1) : 1973 water, sewage and industrial applicable in the concentration range of O·OS
efBuentl: Part 1 to Smill ofcopper.
7022 Glossary ofterms relatiDS to
( Part 2 ) : 1979 water, sewale and industrial 5.2 Iat.rere.cea
efBuents: Par"t2 Chromium interferes when its concentration
exceedsStimesthatofcopper. The interference
3 SAMPLING AND PRESERVATION
from organic matter, sulphide, cyanide and
3.1 The sampling and storage shall be done as chromium can be eliminated by a preliminary
prescribed in IS 3025 (Part 1) : 1986. The sample treatment as liven in 5.5.1. The other
sample bottles should be cleaned thorouahly commonly present ions do not interfere.
1
IS 3025( Part42 ) : 1"2
5.3 Ap,ara. 5.5 Procedare
5.5.1 Ifinterferill8 substances are present add
5.3.1 Spectrophotometer - Cor use at 457 nm
1 ml of concentrated sulphuric acid and
with 1em cell.
Sml of concentrated nitric acid. Evaporate
the sample to dense white sulphur trioxide
5.4 RealeDt.
fumes on a hot plate. Repeat the treatment
or
5.4.1 Ammonium Hydroxide - Specific sravity with S ml concentrated nitric acid and
5 ml of hydrogen peroxide and evaporate the
0-90.
solution to complete dryness. Dissolve the
5.4.2 Chloroform - AR grade, residue with 80 ml of water, boil, cool and
filter. Adjust the pH with dropwlse addition
5.4.3 Hydrochloric Acid- Concentrated. orammonium hydroxide to 4 to 6. Add 0-2
ml ofhydrochloric acid and dilute to 100 ml.
5.4.4 Hydroxylamine Hydrochloride Solutloll If no interfering substance is present, just boil
the acidified sample and cool.
Dissolve 40 g of hydroxylamine hydrochloride
( NH.OH. He) ) in 200mlofwater. 5.5.2 Extraction
5.4.5 Isopropyl Alcohol Transfer SO ml of the acid-fled sample or filt
rate ( 5.5.1) to a 125 ml separating funnel.
S.4.6 Neocupro;ne Solution Add S ml of hydroxylamine-hydrochloride
solution. 10ml ofsodiumcitrate solution and
Dissolve 0·1 g of neocuproine in SO ml of iso 10ml of neocuproine solution. Shake well.
propyl alcohol. Dilute to 100 ml with double Add 20 ml of chloroform and shake for 1
distilled water. minute. Allow the aqueous and chloroform
layers to separate. Collect the chloroform
5.4.7 Nitric Acid - Concentrated. layer in a dry flask. Repeat with separate
20ml aliquot of chloroform. Combine the
5.4.8 Sulphuric Acid- Concentrated.
extracts and dilute to SO ml with isopropyl
alcohol. Prepare a reagent blank by treating
5.4.9 Sodium Citrate Solution
SO ml ofdouble distilled water in the same way
as described above.
Dissolve 250 g of hydrated aodium citrate
( Na.C.H,O,. 2H.0 ) in water and make up to 5.5.3 Measure the optical density ofthe sample
1000 ml. Add 10 ml each of neocuproine solution at 457 nmagainst the "reagent blank.
solution and hydroxy lamine hydrochloride Treat SO ml portions of standard solutions
solution. Any impurities of copper can be containing 0·05, 0-1, O-S, 1·0, S·O mgll ofcopper
removed by extraction with chloroform, as above. Plot absorbance versus copper
discarding the chloroform layer. concentration ( mill) for the standards to get
a calibration graph. Read the concentration
5.4.10 Copper ( 11) SolutiDns ofcopper in the sample from the calibration
graph,
5.4.10.1 Stock copper ( 11)6olutioll
S.'
Calc.latloD
Dissolve0·2 I ofpure copper metal bywarmin.
M
with 6 ml of I : 1 nitric acid. Add 1 ml of Copper,mgll = y X 1000
concentrated sulphuric acid and evaporate the
solutlon to dryness. Dilute the lolution to I where
litre with distilled water. 1 ml =- 200 pi of M -= mass in mg of copper in the
Copper ( II ).
sample, and
5.4.10.2 Intermediate copper ( 11) lolulloll V t= volume of sample in mi.
Dilute 100ml ofstock solution to 1 litre with 6 ATOMIC ABSORPTION METHOD
(DfRKef )
diltilled water. 1ml - 20 ".1/1.
6.1 Prladple
5.4.10.3 Sttllldardcopper ( II) 10/""011
The copper content of the sample is deter
Dilute 1ml ofintermediate stock solution to mined by atomic absorption spectrophoto
SOml with distilled -water. 1ml 0·4 PI/I. metry. Por dissolved copper, the filtered
:::II
Prepare diluted solutions daily. .ample is directly aspirated Into the atomizer.
2
IS 3025 ( Part41 ) : 199:Z
Por total recoverable copper, an acid digestion acid ( 1: 500) and repeat as above. Asprirate
procedure is carried out prior to aspiration the solutions and measure the absorbance.
ofthe sample. This method is applicable in
the range 0(0·02 to 5mg/l. 6.6 C.lculatioDI
6.2 Interferences Construct a standard calibration graph by
plotting the absorbance versus copper concen
Cadmium, lead, nickel, 'line, cobalt, manganese tration ( mg/l ) for each standard. Read the
and chromium up to 10mg/l do not interfere. concentration ofthe sample from the graph:
Alkali and alkaline earth metals can be tole
~l
rated up to 5000mg. Iron does not interfere Copper, mg/l = V x 1000
upto 1000 mg/l.
where
6.3 Apparatus
M = mass (in g) of copper in the
6.3.1 Atomic Absorption Spectrophotometer sample, and
withair-acetylene flame. V == volume ofsample in mi.
6.3.1 Copper Hollow Cathode Lamp - for use at
7 ATOMIC ABSORPTION METHOD
324·7 om.
( CHELATION-EXTRACTION)
6.4 Reageats 7.1 Principle
6.4.1 Hydrochloric Acid- Concentrated.
Copper (II) is chelated with pyrrolidine
dithiocarbamic acid and extracted with MIBK.
6.4.1 Nitric Acid- Concentrated.
The extract is treated with hot nitric acid
6.4.3 Dilute Nitric Acid- 1: 500. after evaporating to dryness, then dissolved in
hydrochloric acid and diluted with water. An
6.4.4 Dilute Sulphuric Acid- 1: 1_ aliquot. is aspirated into the air-acetylene flame
ofthe spectrophotometer. For total recover
6.4.5 Copper ( II ) Solutions able copper an acid digestion procedure is
carried out prior to aspiration of the sample.
6.4.5.1 Stock copper ( II ) solution
This method is applicable for the concentra
Soo
tion range of2 to ug/l.
Dissolve 1·0 I of pure copper metal in 30 ml
of( 1: 1) nitric acid and add 4 ml of ( 1: I ) 7.1 Interference -- Same as in 6.1.
sulphuric acid and heat until sulphur trioxide
fumes evolve. Cool the solution and dilute to 7.3 Apparatus - Same as in 6.3.
1 litre with distilled water. I ml = 1·0 mg of
copper- 7.4 ReageDts
7.4.1 Hydrochloric Acid- Concentrated.
6.4.5.1 Standard copper ( II ) solution
7.4.1 Dilute Hydrochloric Acid- 1 : 2.
Dilute 100ml of copper stock solution to I litre
=
with distilled water. I ml 0-1 mg ofcopper. 7~4.3 Nitric Acid- Concentrated.
6.5 Procedure 7~4.4 Pyrrolidine Dithiocarbamic Acid- Methyl
isobutyl ketone ( MIBK) reagent
6.5.1 If total recoverable copper is to be
determined, add S ml of concentrated hydro Mix 36 ml ofpyrrolicine with 1 litre of MIBK.
chloric acid and evaporate the solutionto ISto Cooland add 30 ml of carbon disuJphide in
small fractions with continuous stirring.
20 ml. Cool and filter the sample through acid
washedfilter paper. Make up to 100 ml in a Dilute with 2 litres ofMIBK. Store in a cool
volumetric flask, aspirate the solutionand mea and dark place- The reagent so prepared is
stable for at least six months.
sure the absorbance at 324·7 om using copper
hollow - cathode lamp- Aspirate nitric acid NOTE- AscompODents ofthis mixture aro hipl,
( 1: 500) prior to sample aspiration. toxic and ftammable. prepare anel use in •
fumebood.
6.5.2 Prepare a reagent blank and series of
standards containing 0, 0-02, 0·1, 0-5, 1,2, 5 7.4.5 Sodium Hydroxide Solution
mill ofcopper by diluting a suitable volume Dissolve 100g ofsodium hydroxide in distilled
ofthe standard solution with 100ml of nitric water and dilute to 1 litre.
IS 3025( Part42) : 1tf2
7.~.' Metllyll.rolJutylbtoM (MIBK) the residue by dropwise addition of2 ml of
concentrated nitric acid by holding the beaker
Rea,ent grade Cor trace analysis purify MIBK at an anile. Again evaporate to dryness and
by redistillation or by subboilins distillation. add 2 ml ofhydrochloric acid ( 1 : 2 ) and heat
for 1minute. Cool and make up the solution
7.~.'.1 WilIerIllIIJdllrdMIBK in a 10ml standard flask. Aspirate the sample
and measure the absorbance.
Mix one part of purified MIBK with one part
or
of water in a separatory funnel. Shake 30 7.5.2 Prepare a reagent blank and a series
times and let separate. Discard aqueous layer. standards containing 0, 10, 20, SO, 100, 200,
Save MIBK layer. 500pa/1 ofcopperby diluting a suitablevolume
ofthe standards solution. Treat the standards
7.4.7 BromophenolBI". ["dlclltor a~o/u,'o"
in the same manner as the sample. Aspirate
the MIBK extracts and measure the
Dissolve O·lS ofbromophenol blue in 100 ml absorbance.
or
50percent ethanol or isopropanol.
7.'
7.4.8 Cop,., (11) Solllt;oIU CalcalatloD
7.4.1.1 Stock cop,., ( 11) '0/,,'101I - Same as 7.'.1 Construct a standard calibration graph
in '.4.5.1. by plotting the absorbance versus the concen
tration of copper ( 1'1/1). . Read the
concentration ofthe sa·mplefrom the curve.
7.4.1.2 1lItetmedltll. copp~,(11)101ull01l
Add 1ml orconcentrated nitric acid to 10 ml Copper 1£8/1 == ."M..x I 000
ofstock solution and dilute to I litre with t
distilled water. 1ml =- 0·01 rna of copper.
where
7.4.1.3 Stillldilrdcopper ( II) ,olut;on M == mass in ,,8 ofcopper in the sample
V =- volume ofthe sample in mi.
Dilute 10ml of copper intermediate solution
to 100ml with distilled water. Prepare daily • DIFFERENTIAL PULSE ANODIC
for use. 1ml = 1".1ofcopper. . STRIPPING VOLTAMMETRY
7.5 Procedmae
8.1 Scope ud ApplicatioD
7.5.1 If total recoverable copper is to be deter
Copper is deposited on a hanging mercury drop
mined, add S ml of concentrated hydrochloric
at a negative potential of -0·4 V versus
acid and evaporate the solution to 15 to 20
saturated calomel electrode. Then the copper
mi. Cool and filter the sample throulh acid
is stripped back into the solution by applying
washed filter paper. Make up to 100ml in a
or a positive potential scan. The anodic current
volumetric flask. Add 2 drops bromo
peak which is measured represents the copper
phenol blue indicator solution and mix. Adjust
concentration in the sample. For total
the pH by adding sodium hydroxide solution
dissolved copper the sample is filtered through
till a blue colour persists. Add dilute hydro
• Whatman No.·4Ofilter paper prior to acidi
chloric acid ( 1: SO) drop by drop until the
fication analysis.
colourjust disappears. Then add 2·5 ml of
dilute hydrocbloric acid to briDI thepH to 2·3
to 2-5. Add 10ml ofpyrrolidincditbiocarbamic This method is applicable in the concentration
acid-MIBK realent and shake well. After the ranle of0·1 - 1001Jt,/1 ofcopper.
phases separate out, collect the MIBK phase
or
by lakinS care to avoid any trace water 8.2 laterfereaeel
in the flask. Repeat the cxtractioD twice
with 6 to 1 ml of MIBIC. and combine the Iron interferes when present at levels greater
extract.. Aspirate the orpnic extract than the copper. This can be overcome by
directly into the flame ( broiDI instrument on subtracting the anodic peak current for a
a water staturated MIBK blank) aad record voltammoffam without deposition from that
absorbanees. To avoid problems' aSlociated Cor the atrlppins vcltammcgram. The presence
or
with instability of extracted metal complexes any neighbouring stripping peaks which is
determine immediately after extraction. Bva les. tban 100mV from tbat of copper will
porate the solutionjust to drynesl aDd dissolve interfere.