non-organic micropollutants of the environment …aei.pitt.edu/41051/1/a5143.pdf · 2013-03-19 ·...
TRANSCRIPT
COMMISSION OF THE
EUROPEAN COMMUNITIES
Directorate-General for Social Affairs
Health Protection Directorate
V/F/I
V/F/1966/74 e
NON-ORGANIC MICROPOLLUTANTS OF THE ENVIRONMENT
Volume 4
METHODS OF ANALYSIS
REPORT OF A WORKING GROUP OF EXPERTS
Prepared for the Commission of the European Communities
Rapporteur: J • BOUQUIAUX
(Institut d'Hygiene et d'Epidemiologie; Ministere de la Sante Publique,
de la Famille et de 11Environnement, Bruxelles, Belgique)
Luxembourg July 1974
NON-ORGANIC MICROPOLLUTANTS OF THE
VOLUME 4 Method~ o6 anaty~i~
S U M M A R Y
LIST OF EXPERTS
A. FOREWORV
B. PRESENTATION OF THE VOCUMENT
C. VESCRIPTION OF METHOVS (~ee at~o table 1, p. 12
Re6eJtenc.e-6
ENVIRONMENT
Page
9
1 1
1 4
56
COUNTRY
=============
BELGIUM
VENMARK
NAME
LIST OF EXPERTS
AVRESS
--------------------------J. BOUQU IAUX ( RappoJtteuJt)
A.VENTENEER
P. HERMAN
J.EXSTEVL
M.JURISSE
L.PATERNOTTE
F.BRO-RASMUSSEN
B.KOCH
E. POULSEN
J.STEENSBERG
=================================
In~titut d'Hygiene et d'Epidemiologie Mi~.teJte de la Sante pu.bUqu.e, de la FamUle e.t de l' Env.btonne.men:t 14 Jtu.e Ju.Ue.tte Wyuman 1050 BRUXELLES
Eeonom~ehe Zaken Montoyet~tnaat,3 1040 BRUSSEL
In~Utu:t de ReeheJteh~ eiU.m-i..qu.u M-i..~.teJte de l' AgJt-i..eu.UWte 5 MoleMtlta.a.-t 198 0 TERVUREN
Mi~.teJte de l'Emplo-i.. e.t du. TJtavail 51/53 Jtu.e B~d 1040 BRUXELLES
Mi~.teJte de la Sante pu.bUqu.e, de la FamUle e.t de l' Env.btonne.men:t CUe adm-i..~tlta.tive de l' E.ta.t Qu.cvr..Uet v e~ale 1010 BRUXELLES
Admi~t!tation de l'Hyg-i..ene e.t de la Medeeine du. TJtavail 53 Jtu.e BeWmtd 1040 BRUXELLES
National Food 1Mtitu:te M¢Jtkh¢j Bygade 19 2860 S~BORG
Ageney o6 Enviltonmen:tal PJto.tec.Uon 41 S.toJte KongeMgade 1264 COPENHAGEN
In~Utu:te o6 Toxieology Nat-tonal Food In~titute M¢Jtkh¢j Bygade 19 2860 S~BORG
Ag eney o6 Enviltonmen.tal PJto.teeUon 41 S.toJte Kongen~gade 1264 COPENHAGEN
Meeting~ n°1 - 1 Veee.mbeJt 1912 n°2 - 20-21 MaJteh 1913 n°3 - 14-15-16 Nove.mbeJt 1913
2
PRESENT AT THE MEETING N° ===========
1-2-3
2
1-2-3
2
2
2-3
3
2
3
3
COUNTRY NAME AVRESS PRESENT AT THE MEETING N°
============= ============= ================================= =========··
FRANCE P.ANNE Exp0tt eon¢ultant C.C.E. 2-3 In¢titut national de la Reeh0tehe
GERMANY
M.C.VlJCHESNE
B.FESTY
J.GREFFARV
Y. THIBAUD
J .GREINER
KLEIN
H.MUHLECK
R.MUSCHE
H. ROHLEDER
Mee;ting¢ n ° 1-n02-
n°3-
ag~onomique -Station d'Ag~onomie 28 ~ue de H~~heim 68 COLMAR
MirU.-6tVt.e de £. 'Ag~eui:tuJLe S0tviee de¢ F~aude¢ 42bi¢ ~e de Bo~gogne PARIS 1eme
Labo~ato-Vt.e d 'Hygiene de £.a VW.e de Po.Jti¢ 1 b-<A ~ue de¢ Ho¢pita.UVt.e¢ Sain:lGeJtvai¢ 15004 PARIS 4eme
~eau ReeheJtehe¢geo£.ogique¢ et miniVt.e¢ 14 ~ue de la Fed~ation PARIS 15
In¢titut de Peehe¢ m~e¢ La Noe - Route de !a JoneUVt.e 44 NANTES
&Lndumini¢te!t.i.wn 6iilt W-iA.t6eha6t Po¢t6aeh 53 BONN-VUISVORF
&Lnde¢an¢ta.U 6ii!t G~¢eJtk.wtde KweJtin AugMta-An!agen 15/11 V 54 KOBLENZ
&Lndumini¢t~um de¢ InneJtn Rheindo~6eJt s~. 798 V 53 BONN
Bunde¢mini¢t. 6ii!t Jugend Fami!ie und Ge¢undheit ( Bunde¢g e¢undheillamt) Po¢t6aeh I BERLIN 33
In¢titut 6iilt Ok.o£.ogi¢ehe Chemie delL GSF St. AugMlin 1 V 5201 SCHLOSS BIRLINGHOVEN
1 VeeembeJt 1912 20-21 Mo.Jteh 1913
14-15-16 NovembeJt 1913
2
1-2
1-3
1-2-3
2
2
2
2-3
3
. I.
4
COUNTRY NAME AVRESS PRESENT AT THE MEETING N°
============= ============= =========================•======= ===========
GERMANY E.SCHMIVT Bunde~mi~t.6~ Jugend,Famitie und 3 G~undheit(Bunde~ge~undh~amt)
IRELAND
ITALY
LUXEMBOURG
O.SORENSEN
P. P. VONOVAN
S. ANNUNZIATA
Po~t6ac.h I BERLIN 33
Hygiene-In~titut d~ Ruhtgebiet~ Abbendic.k.weg 12 465 GELSENKIRCHEN
PubUc. Analy~t Vepa!ttment o6 Health C~tom Ho~e VUBLIN
VA.ltezione GeneJtale Igiene AUme.n.talte N~zione.-Viv~ione. Addltivi 2 4 , Piazza Ma!tc.o ni ROMA
F. COTTA-RAMUSINO I~tituto Supeltio!te di SanLta Viale Regina Elena, 299
P.HANSEN
M.MOLITOR
PRUV'HOMME
R.WENNIG
ROMA
M..in~tVr.e. de la Sante pubUque. I~tULLt d 'Hygiene e.t de .ea. Sante pubUque 1 a Jtue AugMte Lum.iVr.e LUXEMBOURG
Admin~:tJta;t,ton d~ Eaux et Fo!tW 34 avenue de ia Po!tte Neuve LUXEMBOURG
VA.ltec.tion de. .ea. Sante pubUque ( I~ pec.Uo n d~ PhaJUnac.ieh) 31 Jtue F. L~zt LUXEMBOURG
Mi~tVr.e de l.a. Sante pubUque. In~titut d 'Hygiene et de Sante pubUque 1 a Jtue Aug ~te Lum.iVr. e LUXEMBOURG
Meeting~ n° 1 - 1 Ve.c.e.mb~ 1912 n°2 - 20-21 Ma!tc.h 1913 n°3 - 14-15-16 Novemb~ 1913
2
1-2-3
2-3
1-2-3
2-3
2
1-2
5
COUNTRY NAME AVRESS PRESENT AT THE MEETING N°
============= ============= ================================= ===========
NETHERLANVS A.G.VE MOOR Min.voo~ de Volk~gezondheid en 1-2-3 MiUeuhygiene Leid~hendam
H.W.KROES
P.LEEUWANGH
A.MINVERHOUV
P .SCHULLER
J.J.STRIK
J.SUURLAND
p/ a 1 e Vanden Bo~c.h Stfta.a;t 4 VEN HAAG
Min.voo~ de Voi~gezondheid en MiUeu.hygiene v~. RujeJt~~tlt 8 LEIVSCHENVAM
In~titu.u.t Vet.F~ac.oiogie g Toxic.ologie Bitt6 tltaat 112 UTRECHT
Rij~i~titu.u.;t voo~ de Vol~gezondheid P.O. Box 1 BILTHOVEN
Rijk~i~:tUu.u.;t voott de Vol~gezondheid P. 0. Box 1 BILTHOVEN
I~titu.u.t Vet.F~mac.ologie g Toxic.ologie Bi.i;U tltaat 12 UTRECHT
Min.voo~ de Volk~gezondheid en MiUeuhygiene Vo k:teJt R eyeJt~~tltaa.t 1 0 LEIVSCHENVAM
F. VAN VER KREEK Mi~te!tie van Vol~g ezondheid Vo k:teJt R eye!t.6tltaa.t 1 0 LEIVSCHENVAM
3
1-3
1-2-3
1-2
1-2-3
H.VAN GENVEREN In~titu.u.:t voo~ VeteJtian~y,Ph~ac.ology 3 and Toxic.ology 112 BilUtltaa.t UTRECHT
Meeting~ n°1 - 1 Vec.embe!t 1912 n°2 - 20-21 M~c.h 1913 n°3 - 14-15-16 Novembe!t 1913
6
COUNTRY NAME AVRESS PRESENT AT THE MEETING N°
============= ==========•== =====····=============•======•=== ===========
UNITEV KINGVOM R.BUXTON Vept.o6 Health and Soc~ Se~y 3 AlexandeJt Flem-ing Hou.-6 e
M.COHEN
G.COLLINS
P.S.ELIAS
J.RUZICKA
A. TOLAN
Meeting-6 n. 0 1 -
Vl.0 2 -
Vl.0 3 -
Elephant a.nd Ca..o.tte LONDON
M-irt-iAtlty o6 Ag!t-ieu..ltulte, F -i-bheltiu and Food- Plant Pathology La.bo~a.to~y HARPTENVEN,HERTS
La.bo~a.to~y o6 the GoveJtnment Chem.i-bt Coru.«tU Hou.-6e, Sta.n6o~d St!tee,t LONVON SEI 9NQ
Vept.o6 H~ Soc~ Se~y Alexa.ndeJt F lemlng Hou.-6 e LONDON SEI
La.bo~a.to~y o6 the GoveJtnme.nt Che.m-i-bt Coru.«tU Hou-be, Stam6o~d St!teU. LONDON SE I 9 NQ
M-irt-iA tit y o 6 Ag!t-iCLLU.ult e, 6-i.-6 h eltiu a.nd Food G~ea.t Wu:tm-in-6telt Hou-6 e Hou-6e6eMY Road LONDON SWI
1 VecembeJt 1912
20-21 MMch 1913
14-15-16 Novembelt 1913
1-2-3
2
2-3
COUNTRY
==•=•========
COMMISSION OF THE EUROPEAN COMMUNITIES
1
NAME AVRESS PRESENT AT THE MEETING N°
============= =====•=•============•====•===•=== ======•====
J.SMEETS V.G. A66~e6 Socia!e6 1-2-3 ( C ha1Junan.) PJto tec..ilo n. SaYL-it.tUJL e VI F I 1
C en.tlt. e Lou. v ,{g n.y
R.AMAVIS ( S ec..Jt etaAy)
A. BERLIN
A. BONINI
P.BONNET
0 .VEMINE
E. VI FERRANTE
LUXEMBOURG
V.G. A66~e~ ~oc..~e6 PJtotec..tion. ~aYL-it.tU!te V IF I I C en.tlt.e Lou.v,{gn.y LUXEMBOURG
V.G. A66~e6 ~ocia!e~ PJtotec..ti.on. ~aYL-it.tU!te V IF I 1 C en.tlt.e Lou.vign.y LUXEMBOURG
V.G.A66ai!te6 ~oc..iale~ PJtotec..tion. ~an.UcU.Jte V IF I 1 Cen.tlt.e Lou.v,{gn.y LUXEMBOURG
SeJLvic..e de l' En.v,iAon.n.emen.t PJto tec..ti.o n. d e6 Co~ ommateWL~ 200, Jtu.e de la Loi 1040 BRUXELLES
V • G • AgJtic..u.itwt e. 200, Jtu.e. de. ta Loi 1 040 BRUXELLES
V.G. Rec..heJLc..he,Sc..ien.c..e et Educ..ation. 200,Jtue de ta Loi 1040 BRUXELLES
Meeting~ n. o 1 - 1 Vec..embeJL 1 912
n. 0 2 - 20-21 MaJtc..h 1913
n. 0 3 - 14-15-16 NovembeJL 1913
1-2-3
1-2-3
1-2-3
3
COUNTRY NAME
::::::::::::: :::::::::::::
COMMISSION OF R.MAGNAVAL THE EUROPEAN COMMUNITIES
H.OTT
P.RECHT
G.SERRINI
M. Th. VAN VER VENNE
M ee.ting.6 n ° 1 -n°2 -n°3 -
AVRESS
::::•:::::::::::::::::•:•::::====
A.6.6ociation EURATOM /C.E.A. PJtotec..tio n .6arr..UcU!Le BoZte po.6tale n°6 FONTENAY AUX ROSES (F!tanc..e)
V.G.Rec..h~c..he Scienc..e et Educ..ation 200 Jtue de fa Lo~ 1040 BRUXELLES
V. G .A6 6a.htu .6oc..l.a1e.6 PJtote~on .6anli.aA.Jr..e CenVte Louvigny LUXEMBOURG
CenVte ~ommun de Rec..h~c..he 21020 ISPRA -V~ehe-
V • G • A 6 6 aJ.Jt e.6 .6 o uale.6 PJtotection .6arr..UcU!Le V/F/1 C mtlte Louvigny LUXEMBOURG
7 Vec..emb~ 7972
20-21 Ma!l.c..h 7973
14-15-16 Novemb~ 7973
8
PRESENT AT THE MEETING N° =====·=···
3
2
3
3
3
NON - ORGANIC MICROPOLLUTANTS OF THE ENVIRONMENT
A. FOREWORD
This report has been prepared by the working group on the
consequences for man and his environment, of environmental pollution due
to non-organic micropollutants; it is part of the outline of actions
that have to be undertaken at Community level in the domain of reduction
of pollutions and nuisances. These actions are included in a comprehen
sive programme of the European Communities in the field of environment
that has been accepted by the Council of Ministers on the 19th of
July 1973.
Non-organic micropollutants are listed in the first category
of pollutants of the environment which have to be considered primarily
because of their toxicity and of the present state of knowledge concer
ning their sanitary and ecological importance.
The objective evaluation of risks being the aim of the general
programme a knowledge is required of the level of these pollutants in
the environment as well as a study and analysis of the undesirable effects
which would result from exposure of the target to a given pollution or
nuisance.
At a meeting held on December 7th 1972, the working group de
cided to prepare an inventory of the data available since 1968 on the
levels of non-organic micropollutants in the environment. The report
has been compiled by Mr BOUQUIAUX from information supplied by dele
gates of the various Member States. The list of micropollutants was
examined at the meeting of December 7th, 1972. The final date agreed
by the rapporteur for receipt of information was May 15th 1973.
_!]
A first draft of the report was examined at the meeting of
March 20th and 21st 1973. The final text was discussed at the meeting on
November 14th-16th 1973 and was agreed by the experts present except
for Volume 4 which was written by Mr BOUQUIAUX after the last meeting.
It should be remembered that 2 important non-organic micropol
lutants were studied in depth at the Symposium "Problems of contamina
tion of man and his environment by Mercury and Cadmium" organised by
the Commission of the European Communities in Luxembourg on 3-Sth Ju-
ly 1973.
The whole report appears in 4 volumes entitled:
Volume - general presentation;
Volume 2 - detailed listing of levels present in the
environment;
Volume 3 - synthesis of data;
Volume 4 - methods of analysis.
B. PRESENTATION OF THE VOCUMENT .
The method~ u~ed 6o~ the mea~u~ement o6 non-o~ganic mic~opollu
tant~ o6 the envi~onment a~e much va~ied . Ve~c~iption~ o6 the method~ u~ed have been ~ent by the delegation~ o6 di66e~ent Membe~-Count~ie~ with the analytical
~e~ult~ . The~e de~c~iption~ a~e ~ometime~ 6ull o6 detail~ o~ ve~y b~ie6
o~ el~e, they ~e6e~ to method~ given in the litte~atu~e .
The ~ubmitted method~ have been ~tudied clo~ely and a gene~al ~cheme ha~ been d~awn that could be applied to each one . Thi~
~tudy ha~ in 6act d~awn the 6ollowing gene~al ~tep~ that can
be 6ound in all the method~ (even i6 ~orne them a~e ~ometime~ omitted) :
1. P~e-t~eatment;
2. Ve~t~uction o6 o~ganic matte~;
3. Sepa~ation ; 4. Mea~u~ement .
Many po~~ibilitie~ can be 6ound in each ~epa~ate ~tep and, in ~orne o6 them, ~uch a~ p~e-t~eatment and ~epa~ation, ~eve~al po~~ibilitie~ can be a~~ociated . The~e po~~ibilitie~ ane li~ted in table 1 ( p. 72) ,which can
be con~ide~ed a~ a table o6 content~ 6o~ de~cnibing method~ o6 analy~i~ .
1 1
Table 2 ( p. 45 ) give~ a ~umma~y o6 the di66e~ent method~ u~ed in the di66e~ent labo~ato~ie~ which have p~ovided mea~u~ement~ . Thi~ ~umma~y i~ ba~ed upon the ~cheme o6 analy~i~ which i~
u~ed in thi~ ~epo~t .
The method 6o~ the dete~mination o6 methyl-me~cu~y in 6i~h i~ given in an appendix (p. 55 ) .
. I .
TABLE 1. - - - - - - - - - - _,_ - - -
I
ANALYSIS P 0 S S 1 B L E S T E P S . =•==••=•==•======··==····=·==•============····=·····=
1 • 1 • 1
1 • 1 • 2
1 • 1 • 3
1 • 1 • 4
1 • 1 • 5
1 • 1 • 6
1 • 2 • 1
1 • 2 • 2
1 • 2 0 3
1 • 2 • 4
1 • 2 • 5
1 • 2 • 6
2 • 1 • 1
2 • 1 • 2
2 0 1 • 3
2 • 2 • 1
1 • 1
1 • 2
2 • 1
2 • 2
2 . 2 • 1 • 1
2.2.7.2
2.2.7.3
2.2.1.4
2 . 2 • 1 • 5
2.2.7.6
2 • 2 . 2
1. PRE-TREATMENT
WateJt
FiltJtation
Ac.idi6ic.ation
Con~eJtvation at low tempeJtatuJte
Oxidation with pe!t~ul6ate Addition o6 a t!tac.e!t Evapo!tation
Biologic.al ~ample~ and ~ediment~
GJtanulometJtic. ~epa!tation (~ediment~)
Con~eJtvation at low tempe!tatuJte
Sampled pa!tt (biologic.al ~ample~)
VJtying
Homogeni~ation
NeutJton ac.tivation
2. DESTRUCTION OF ORGANIC MATTER
Wate.Jt
No de~t!tuc.tiort
Ve~t!tuc.tion with pota~~ium pe.Jtmanganate
Ve.~tJtuc.tion with b!tomine
Biologic.al ~ample~ and ~ediment~
We.t dec.ompo~ition Ve.~tJtuc.tion with HN03 and H2S04 , with oJt without the aid o6 HCl04 oJt H202
Ve~tJtuc.tion with HN03 and H2S04 , with the aid o6 a c.ataly~t
Ve~tJtuc.tion with HN03 and HCl04
Ve~t!tuc.tion with KMn04 and H2S04 ,with oJt without .the aid o6 HN03
Ve~tJtuc.tion with H202 and H2S04 No de~tJtuc.tion . Acid ~olubili~ation
V!ty dec.ompo~ition (a~hing)
1 2
Page
1 4
1 4
1 4
1 5
1 6
1 6
7 7
1 7
7 8
1 8
1 9
1 9
1 9
20
20
2 1
2 1
2 1
2 1
2 2
22
23
23
25
25
25
27
28
29
. I .
3 • 7 • 7
3 • 7 • 2
3 • 2 • 1
3 • 2 • 2
3 • 2 • 3
3. 2 • 4
3. 2 • 5
3 • 7
3. 2
3 • 3
3. 4
3. 5
3. 6
3. 1
3 • 8
3 • 9
4 • 7
4. 2
4. 3
4. 4
4. 5
4. 6
4. 1
3. SEPARATION
Solid-liquid ext~a~tion
Cationi~ ~e~in~ (Metal~)
Anionic ~e~in~ (Me~~u~y)
Liquid-liquid ext~a~tion
Ext~a~tion o6 lead Ext~a~tion o6 ~admium
Ext~a~tion o6 ~admium and lead
Ext~a~tion o6 metal~ 6~om wate~
Ext~a~tion o6 me~~u~y
Ch~omatog~aphy (Men~u~y)
Vi~tillation (Me~~u~y halide~)
I~otopi~ ex~hange (Me~~u~y)
Vepo~ition on metal (Me~~u~y)
Pne~ipitation (A~~eni~,mangane~e)
Redu~tion - Me~~uny
Redu~tion - A~~enic
4. MEASUREMENT
Atomi~ ab~o~ption ~pe~t~ophotomet~y
Flamele~~ atomi~ ab~o~ption
Spe~t~ophotomet~y (~olo~imet~y)
Radioa~tive ~ounting
Polanog~aphy
UV - ~pe~tnog~aphy
x-~ay 6luo~e~~ence
Page
30
30
30
30
31
31
32
32
32
34
34
34
34
35
36
36
31
38
38
39
39
40
41
41
42
7 3
I
C. DESCRIPTION OF METHOVS
1. PRE-TREATMENT
=· ===·=====··===
A p~e-t~eatment i~ gene~ally needed to in~u~e the con~e~vation
o6 the ~ample, to i~olate the pa~t o6 the ~ample that mu~t be analy~ed, o~ ta p~epa~e the ~ample be6o~e analy~i6.
1 • 1 - WATER
Mo~t autho~~ have pointed out that 6u~6ace wate4 wa~ 6ilte4ed (o4 cent4i6uged ) and I o~ acidi6ied acco4ding to di66e4ent
method~ be6o4e analy~i~
1.1.1 FILTRATION
Seve4al p4oeedu~e~ have been u~ed :
- Filt4ation alone ( without any indicated acidi6ication) (41);
- Cent4i6ugation o6 ~ample when 4eceived in the labo4ato4y
6ollowed by 6u4the4 aeidi6ication ( 11,41,16) ;
- Filt4ation made on the ~ampling plaee (21) ; - Filt4ation and aeidi6ieation made on the ~ampling place(79); - Filt4ation and analy~i~ made on the ~ampling place
(30.2, Cu , eolo4im.) ;
- Filt4ation &allowing aeidi6ication (46).
The amount o6 ~u~pended matte4 in wate4 depend~ on many
6aeto~~ mainly ~elated with the pe4tu4bution~ o6 the wate4 6to~m~, 6lood~, e~o~~ing o6 boat~, velocity o6 the 4ive4,etc ... In the~e condition~, bottom ~ludge~ a4e o6ten put into ~u~pen~ion . The~e ~u~pended matte4 ~t4ongly di~tu4b the eon~tancy
o4 4~p~odueibility o6 the analy~i~ ~e~ult~, ~pecially 6o4 non-o4ganie mie~opollutant~ . Mo~eove~, they a4e in 6aet a pha~e quite di66e4ent 64om the
aqueou~ pha6e . It ~hould then be neee~~a~y to ~epa4ate
them p~eviou~ly by eent~i6ugation o~ 6ilt~ation and to analy~e
them ~epa~ately .
. I .
14
The ~epa~ation o6 ~u~pended matte~ ~hould alway~ be ca~~~ed out on the ~ampling place ~o a~ to avoid the t~an~6o~matian
o6 the ~u~pended matte~ du~ing t~an~po~tat~an and con~e~vat~an.
Howeve~ thi~ method i~ ~ubject to many di66icultie~ which can
only be dealt with on boat~ o~ in moving labo~ata~ie~ p~avided with a good equipment
Cent~i6ugation appea~~ to be bette~ than 6ilt~at~an becau~e
it ha~ no e66ect an mechanical and elect~ical behav~au~ o6
callo~d~ . Mo~eove~, cent~i6ugatian can deal with ~t~angly
~ha~ged wate~~ .
Filt~ation, on the athe~ hand, ~eem~ to be mo~e adequate 6o~
t~eatment o6 la~ge volume~ o6 wate~ with ~light amount in ~u~pended matte~ .
1 • 1 • 2 ACIVIFICATION
The ~ample i~ 6~equently p~e~e~ved by acidi6icatian at pH 5
by mean~ o6 hyd~ochlo~ic acid (79) o~, in a mo~e gene~al way , at pH 1 o~ 2 by mean~ o6 hyd~ochlo~ic o~ nit~ic acid(15,16,
27,41,45,46,50,76 ) .
The 6ilte~ed o~ cent~i6uged ~ample ha~ to be p~e~e~ved by
mean~ o6 acidi6ication ~o a~ to avoid p~ecipitation~ and lo~~e~ in metal~ due to depo~ition on the containe~~ wall~ .
The~e depo~it~ can occu~ even in pla~tic bottle~ . Acco~ding to Butte~wo~th et al. (79), Ma~tin (7968) ha~ ~tated
that pla~tic ~u~6ace~ can develop ion exchange capacity with
con~equent plating out o6 t~ace metal~ . The~e autho~~ have examined thei~ pla~tic collecting ve~¢el¢
6o~ plating 6~om ~aw ~ea wate~ and 6ound that a con¢ide~able
p~opo~tion o6 the zinc and lead we~e lo~t in thi~ way . Howeve~,
when the pH wa¢ adju¢ted to 5.0 with nit~ic acid an collection
no lo~~ in thi~ way could be detected .
The ve~~el~ mu~t o6 cou~~e and nece~~a~ily be wa¢hed with acid be6o~e they ean be u¢ed .
. I .
1 5
\
1 • 1 • 3 CONSERVATION AT LOW TEMPERATURE
Sample~ a~e ~ometime~ kept at tow tempe~atu~e 6o~ p~e~e~va:tion
- in the 6~eeze~ (21,between 6itt~ation made on the ~ampling·
pta~e and a~idi6i~ation made at the tabo~ato~y ); - in the ~e6~ige~ato~ (50 ) •
Con~e~vation o6 wate~ ~ample~ at low tempe~atu~e i~ ~pe~ially
intended 6o~ avoiding the t~an~6o~ma:tlon o6 nit~ogenou~ and o~gani~ ~ompound~ when thei~ dete~mination i~ ~a~~ied out
in the ~arne ~ample a~ non o~gani~ mi~~opollutant~ . Bu:t the
a~idi6i~ation o6 wate~ make~ thi~ way o6 p~oceeding pu~po~e
te~~ whe~e metal~ a~e ~on~e~ned .
1 • 1 • 4 OXIVATION WITH PERSULPHATE
A~~o~ding to Fond~ and Vanden E~ho6 (16), an oxidation ~tep
i~ ne~e~~a~y be6o~e the liquid -liquid ext~a~:tion o6 a ~e~le~
o6 metal~ 6~om wate~ .
The~e autho~~ u~e the 6ottowlng method :
-Add 0.5 mt 65% HN03 and 5 mt 50% (NH4) 2S20g ~olutlon to
500 mt (~ent~i6uged ) ~u~6a~e wate~ o~ d~lnklng wate~ and
b~ing to boiling . - Boil 6o~ 10 mlnute~,~top boiling and a6te~ 1 minute ~ooting
add 25 mt 5% (NH4)2S20g ~olution . - Bolt down to 350 mt.
Coot to 20°C and add 5 mt 10% a~~o~bi~ a~id ~otution, mix and
allow to ~:tand 6o~ 10 minute~ .
Thi~ method l~ 6otlowed by the liquid-liquid ext~a~tion de~~~ibed at pa~ag~aph 3.2.4.2.
Oxydation o6 the wate~ ~ample i~ ~e~tainly u~e6ut in o~de~
to b~ing the metal~ to an ioni~ ~tate ~uitable 6o~ ext~a~tion with o~gani~ comptexing ~eagent~.
Howeve~ , :thl~ ~tep i~ gene~atty omitted,:the ~ample being
~imply a~idl6led .
. I .
1 6
\: ....
1 • 1 • 5 AVVITION OF A TRACER
A ~ad~oaet~ve t~aee~ can be added to cheek the y~eld o6 the chemical ~epa~ation~ . Ex. : 203Hg (76).
The add~t~on o6 a ~ad~oaetive t~aee~ can be u~e6ul to check the y~eld o6 a new method . Howeve~ it ~~ ~eldom nece~~a~y ~n ~outine method~ and only when the method~ u~ed 6o~ ~epa~ation cannot be ~ep~odueed ea~ely.
1 • 1 • 6 EVAPORATION
Wate~ ~ample~ can be evapo~ated at 110°C and ealcinated at a tempe~atu~e o6 < 450°C . Thi~ p~oeedu~e ha~ been u~ed be6o~e UV-~peet~og~aphy (32).
+
+ +
The elabo~ated p~e-t~eatment u~ed by P~e~ton et at. (21) i~
given he~e a~ an example :
" Su~6ace ~ample~ we~e collected u~ing a polyp~opylene bucket and ~ope; ~ub~u~6aee collection~ we~e made by d~awing the
1 1
wate~ th~ough a2.5cm diamete~ PVC ho~e (~ein6o~eed with b~aided te~ylene) with the aid o6 an eleet~ieally-d~~ven pump,eon~t~ucted ent~~ely 6~om polyp~opylene and PTFE except 6o~ a ~mall ca~bon ~ha6t-~eal. No ~~gni6ieant va~iat~on between the method~ o6 ~ampling ha~ been detected.
" It wa~ decided that ~orne 6o~m o6 ~epa~at~on o6 the ~ample into 'mainly ~olid' and 'mainly liquid' pha~e~ wa~ e~~ent~al
the ehie6 ~ea~on being the eon~ide~able va~iat~on in ~u~pended load due to weathe~ condition~; Mill~po~e eellulo~e acetate 6ilte~ pape~~ (142mm d~amete~, 0.2 ~m po~e ~~ze)mounted ~n a PTFE 6~lte~ p~e~~ we~e u~ed to e66eet thi~ ~epa~at~on ~apididly ~n p~e6e~ence to eent~i6uging, beeau~e o6 the
. I .
di66iQulty in Qa~~ying out the latte~ ope~ation on boa~d
~hip . The Qontamination p~oblem 6~om the Millipo~e 6i~te~~ i~ well known (Robe~t~on,1968 ) and mueh wo~k ha~ been Qa~~ied out at thi~ labo~ato~y on the p~oblem~ o6 the leaehing o6 impu~itie~ 6~om the pape~ . The 6ilt~ate wa~ Qolleeted i~ a polythene eontaine~ ,~apidly 6Aozen and ~to~ed at -20°C until ~equi~ed 6oA analy~i~ - thi~ p~oeeduAe
ha~ been ~hown to be ~ati~6aQto~y and doe~ not ~equi~e the u~e o6 QOnQent~ated acid~ at ~ea . The ~ample~ weAe le6t 6~ozen until the ~ta~t o6 the analy~i~, when they weAe thawed and aQidi6ied to pH 2 with ~edi~tilled hyd~oQhlo~ie
'aQid to en~u~e that i~on wa~ in a 6o~m ~uitable 6o~ ~ub~equent analy~i~ . The 6ilteA memb~ane and 6ilte~ we~e
~toAed in a 5 in (app~ox.13 Qm) poly~tyAene petAi di~h
until AequiAed 6 oA analy~i~ ".
1.2- BIOLOGICAL SAMPLES ANV SEVIMENTS.
1 • 2 • 1 GRANULOMETRIC SEPARATION (SEVIMENTS).
A~ heavy metal~ o6 ~ediment~ a~e met p~e6e~entially in ~mall pa~tiQle~ (6.2) , many authoA~ ope~ate a gAanulomet~iQ ~epa~a
tion and expAe~~ theiA Ae~ult~ only 6oA a given ~ize o6 paAtiQle~ QOn~ide~ed a~ being the mo~t Aep~e~entative one
EX. 6~aQtion
6~aQtion
6~aQtion
<16 1-1m (6.2,30.1) <21-1m (44);
80-me~h(26).
Othe~ autho~~ don't opeAate thi~ gAanulometAiQ ~epaAation and exp~e~~ thei~ ~e~ult~ on dAy matte~ ( 9, 15,19, 22, 41, 53,62)
o~ on wet matte~ (76) .
. I .
1 8
1 • 2 • 2 CONSERVATION AT LOW TEMPERATURE
When b~olog~~al ~ample~ ane not analy~ed d~~e~tly , they a~e
alway~ kept at low tempe~atu~e, e~then ~n a 6~eeze~ at -15°C
to -20°C ( 77,79,20,22,27,32,59) on ~n the ~e6~~ge~ato~. The ~arne p~o~edu~e ~~ ~omet~me~ u~ed 6o~ ~ed~ment~ (45, 53) .
1 • 2 • 3 SAMPLEV PART (b~olog~~al ~ample~,6ood p~odu~t~)
Fo~ 6ood and b~olog~~al ~ample~, the analy~~~ ha~ nea~ly
alway~ been made on the ed~ble po~t~on o6 the ~ample a~ p~e
~ented o~ ~old ~n ~hop.
Only the mu~~le pa~t (ed~ble pa~t) o6 6~~h wa~ ~n gene~al
analy~ed.
Cook~ng o6 whole 6~~h ~n a m~~~owave oven unt~l 6le~h ~~
tende~, allow~ an ea~y ~epa~at~on o6 ed~ble po~t~on 6~om bone
1 9
and othe~ t~~~ue . Th~~ method ha~ been u~ed ~n ~e6.75 ~n ~pe~~a£
~a~e~ 6o~ the dete~m~nat~on o6 me~~u~y . F~~h wa~ ~ooked w~th
~t~ ~k~n ~nta~t to p~event lo~~ o6 mo~~tu~e .
1 • 2 • 4 VR YING
V~y~ng o6 ~ample~ ~onta~n~ng wate~ (at 90 to 105°C ) ~~ ob
v~ou~ly ne~e~~any be6o~e ~al~~nat~on (30.3 ,32,67) .
Howeve~ ,~orne ~ample~ o6 b~olog~~al mate~~al (79,20,27) and
o6 ~ed~ment~ o~ ~o~l have al~o been d~~ed at 70 to 105°C ( genenally 6o~ 24h ) be6one wet de~ompo~~t~on (79,53,62,64) o~ be6one UV-~pe~t~og~aphy on X-nay 6luo~e~~en~e (32).
In one ca~e (6.2) ,~ample~ o6 ~ed~ment~ have been d~~ed at
~0°C be6one dete~m~nat~on o6 me~~u~y by neutnon a~t~vat~on . In ~orne ~a~e~, 6~eeze-d~y~ng ha~ been u~ed 6o~ b~olog~~al
~ample~ and ~ed~ment~ be6o~e detenm~nat~on o6 me~~u~y by neu
t~on a~t~vat~on (76) o~ be6one UV-~pe~t~og~aphy o~ X-~ay
6luo~e~~en~e on b~olog~~al ~ample~ (32) .
. I .
1 • 2 . 5 HOMOGENISATION
It i~ obviou~ly nece~~a~y to take the pa~t that ha~ to be analy~ed 6~om an homogenized ~ample ( 7,28,37,50,59).
Homogeneity o6 biological ~ample~ can be attained with the
help o6 a mixe~ { 77,61) oiL by c~u~hing (15) .
V~ied ~ample~ o6 biological mate~ial oiL ~ediment~ can be
g~inded ( 64) oft c~u~hed { 32,61, 62) .
Contamination o6 ~ample~ by the mateftial o6 the appa~atu~
mu~t be avoided(knive~ o6 the mixeft~, g~inde~~, .•• ).
1 • 2 • 6 NEUTRON ACTIVATION
Some element~ can be mea~u~ed by neutfton activation .
Thi~ technique ha~ been u~ed 6oft meftcufty in biological mateftial and in ~ediment~
(6.2,6.3,6.5 to 6.9, 16,22,23,33,59,14) ;
- mangane~e and zinc in butteft (34);
- ~eve~al metal~ in aift pa~ticulate~ (43).
The neut~on activation method include~ the 6ollowing ~tep~ { 6 2 6 3 (. Z:: r ·r 6 0 • , • ,04.1 ·'\..{_, .1, 33,3-+,14; ;
- int~oduction o6 0.1 to
~ealing o6 the tube
g o6 ~ample into a quatz tube;
- iJtftadiation in a 6lux o6 ~low neutfton~ pftoduced by a
nuclean ~eactoft ; - ~adioactive " cooling " 6oJt a la.p~e o6 time which depend~
on the element that i¢ to be mea~u~ted ; cooling o6 the tube in liquid nit~ogen(74} , to fteduce the
inteftnal pAe~~u~e 6~tom ga~e~ p~oduced by Jtadioly~i~ and
p~event any lo~~ o6 ~ample when opening the tube ; opening
o6 the tube
- addition o6 an inactive caJt~.[e~
de~t~uction o6 o~ganic matte~t . be6o~e oiL dulLing the
. I .
20
The. ne.ut~on activation method i~ a ve.~y ~e.n~itive. and ~eliable.
one. . It can be. u~e.d 6oh a lange va~le.ty o6 ~ample.~ and in
a ve~y la~ge. ~ange o6 c.onc.e.vt.tJtat.(.~uU).
2 • V E S TR U C T I 0 ~J 0 r: 0 r· S ~ N E M A T T E 1\ • = • • ••••• ., • ~ .. !2 1//J .:· ", ..... = ::- 'ii:l -.:: = = ::- = ••• !~ •
2.1- WATER
Except 6o~ the dete~minat~on o6 m~~cuJty, no de~t~~c~ian o6
o~ganic matte.~ i~ pe~6o~med on waten ~ample~(~iven o~ ~e.a
wate~), whateve.~ the. elemert-t .-._·o 1:.,( rrle::r.~teLe.d •
Howe v e~, the ~am p.e, e. i_/!) ruz.a.~ .e. y a .t(,{t(t ~~· 6 .... :2 .t. .. ~Lt 6 i e.d duni n ~:· .r he.
p~e.-t~eatme.nt (~ee 1.1.2 above) . In one ra~e oxidati·Jn wit~
pe.~J.>uephate haJ.> b"e.n calt~..ted out d;;"ci:'t;] t ··:C! p~~--tA-:(•. ,{ <'.•:.1• (-;,
(J.>ee 1.1.4 above).
2 • 1 • 1 NO DESTRUCTION
Even 6o~ me~cu~y, de.J.>t~uction o6 o~ganic matte.~ haJ.> been omitted by one autho~ (16), but the 20-40 l J.>ample. wa~
acidi6ie.d . Me.~cu~y wa~ then J.>epa~ated a~ a chlono-coMpl~x
on anion exchange. ne6in (J.>ee 3.1.2. bela~) .
2 • 1 • 2 DESTRUCTION WITH POTASSIUM i)ER1\:AGANATE ------·--
U e 6 t 't u c..t-~ Vi o 6 o Jig a n.i ~.~ m a:tt e~~ -i.. n wat e~ .o a 1:: ,rJ-C ~ .t, w-i. t !t p D ;ra.::. "·
6ium p~'-frm-.Hganat~·- ha<:t been u.J.>e.d by 6ouJr. au.U~·~~11>6 o .. -t. l:zo~.'
( o n -6 i x ) ( 1 5 , 1 7 , 4 5 )I 4 7 ) 6 on t h e d e t e.n min a Li. o n o 6 m eJt c. u./r. y •
In the method o6 Vavid Smith e.t al. (77), the J.>ample. iG ma.dc. no!Lm~tR ,i_vL 6ulphu.lLic. acJ...d by add,.[ng 50% v/v HzS04; .u·d.
0. 05 rt(;JtHctL -Ln pe~manganate_ by add-ing 5% w/v KMn04 in wa{e-'t;
t h e. ~\ ru : p :. .(· .-5 th l: n !> h a h en. 6 on 1 h . E x c. ~ .. ~ o 6 p 2./L m a n g cu·. a. · ··~ '1. n d
any <Uh~'U..:Lt o6 Mn02 cio,L-me.d a~e ne.duc.ed by adding 30% ~~2-'~) .oo.Eu.-
t.-LO 11 · .. I .
2 1
Acco~d~ng to the autho~~, th~~ t~eatment d~~~olve~ elemental
me~cu~y, me~cu~y ~alt~ 1 and o~gano-me~cu~y compound~ a~ H9 2+ . Me~cu~y ~~ then ~epa~ated by depo~~t~on on an Ag co~£ (~ec 3.6 below).
The othe~ p~ocedu~e~ ane a~ 6o£low~ :
- de~t~uct~on w~th H2S04 1 HN03 and KMn04 (45) ;
- ox~dat~on w~th KMn04 alone (w~thout ac~d~6~cat~on ) 6o~
2 day~ at 4oom tempe~atu~e (41);
- ox~dat~on o6 ac~d~6~ed ~ample w~th pe~manganate to obten~~on o6 a ~table ~o~e (15) •
2 • 1 • 3 VESTRUCTION WITH BROMINE
In one ca~e, wate~ ~ample~ have been t~eated w~th b~om~ne be6o~e the dete~minat~on o6 mencu~y by 6lamele~~ atom~c ab~o~ption ~pect~ophotomet~y (41).
2.2 - BIOLOGICAL SAMPLES ANV SEVIMENTS
Ve~y good de~c~iption~ o6 method~ 6o~ the de~t~uction o6 o~ganic matte~ a~e g~ven in The Analy~t by the Analyt~cal M e tho d ~ C om m ~tt e e ( 8 0 1 8 1 1 8 2 ) . Each method i~ com m e nt ed ~ega~d~ng ~t~ applicab~l~ty 1 advantage~, d~~advantage~ and haza~d~ . The method~ o6 the A.M.C. w~ll ~e~ve a~ a gu~de 6o~ thi~
~epo~-t .
" When o~gan~c matte~ ~~ to be de~t~oyed a~ a p~elimina~y to the dete~mination o6 metallic t~ace~, the choice o6 method w~ll depend (a) on the natu~e o6 the o~gan~c mate~~al and o6 any ~no~gan~c con~t~tuent and (b) on the metal that i~ ~ub~equently to be dete~mined and the method to be u~ed 6o~ ~t~ dete~m~nat~on " (80).
. I .
22
23
2 . 2 . 1 WET VECOMPOSITION
2.2. 1.1- v~~t~uction w~th nit~ic and ~ulphunic acid~, with on
w~thout th~ a~d o6 p~~chlonic acid on hyd~og~n p~noxid~.
Th~ m~thod6 u~~ng ~ulphunic ac~d " ane not n~comm~nd~d in th~
p~~6~nc~ o6 appn~c~able amount6 o6 alkalin~ -~anth m~tal~,
which g~v~ in~olubl~ ~ufphat~~~ 6inc~ th~ in~olubl~ ~ulphat~6
ab~o~b a con6id~~able pnopo~tion o6 t~ac~ m~tal~, pa~t~culanfy
l~ad. In ~uch in6tanc~6 d~compo6ition w~th nitnic and p~~chlo
n~c ac~d 6houfd b~ ~mploy~d " (80) .
2.2. 1. 7.1- ~~P~9:~~~~i~-~~~~~~~~iq~-=~PP~~q~~~-l
Fou~ d~66~~~nt m~thod6 an~ giv~n by th~ A.M.C. (80) ,d~p~n-
ding on th~ n~activity o6 th~ mat~~~al that i~ to b~ d~~t~oy~d.
Th~6~ m~thod6 a~~ 6n~qu~ntly th~ 6in~t ~tep p~ion to a t~eatment
w~th p~nchlo~ic ac~d ( 2.2.7.1.3 ) on hyd~ogen penoxide (2.2.1.1.4) .
2.2.7.7.2- ~~~P~Q:~~~~~~-~~~!~~~~~Q~!-~pg~~q~-~~~~Q~_6q~
~g~~~~y_J~ll!_:~PP~~~~~~-g!
" The pnopo~ed method (a) a66o~d6 a mo~e convenient mean~ o6
adding nitn~c acid to maintain ox~di6ing condition~ du~ing
the decompo~ition, and (b) avoid6 lo66e~ o6 mencu~y th~ough
di~ t~llatio n " ( 8 1 ) .
How~ve~, when the d~tenm~nat.ion o6 mencuny i~ to be ca~~ied out on a ~outine ba6~6, a method 6uch a~ 2.2.1.4 (de~t~uction
with pota~~ium pe~manganate) on 2.2. 1.5 (de~t~uction with
hydnogen penox~de) would centa~nly be mo~e convenient .
Remank : At th~ ~nd o6 the d~6t~uction, the d~ge~tat~ i6
t~eated with hydnoxylamin~ hyd~ochlo~id~ to ~~move oxide6 o6 n~tnog~n .
Method6 v~~y 6imilan to 2.2.7.7.2 hav~ b~~n u6~d 6o~ the
detenminat~on o6 mencuny in biological mate~ial by 6ome o6
. I .
the. au.thoft~ o6 the_ pape_ft~ fte.c.e_ive_d, with (1,41) oft without
(28) addition o6 hydftoxytamine_ hydftoc.htoftide_ .
Method~ ~imitaft to 2.2. 1. 1.1 oft 2.2.1.1.2 have been u.~ed
6oft the de.teftmina.tion o6 meJtc.u.fty by o.the!t au.thoft~ a~ welt
(12,50,58).
24
2.2.1.1.3- ~~?P~9:~~~~~£-~~~~~~£~~q~_jg~g~z~l~ll_l_6~??9~~~
~Y-~~~-~~~~~~q~_Qo_P~~£~{~~~£-~£~~-J~Ql~:~PP~~~~~~-1·
The u.~e o6 a method involving oxidation with pe!tc.htoJtic. ac.id
i~ to be_ avoided 6oft me_ftc.ufty de.teJtmina.tion~ • Hydftoc.hloJtic.
ac.id p!toduc.ed dufting wet oxyda.tion~ with pe!tehtoJtic. ac.id
lead~ to enhanc.ed volatility o6 meJtc.u.fty .
2.2.1.1.4- ~~{p~~=~~~~~£-~~~~~~£~~~~Jg~g~l~l~ll_l6q{?q~~~
~Y-~~~-~~~~~~q~_q6_~y~~qa~~-e~~q~~~~-J~Ql!:~ee~~~~~~-l·
A method o6 that type_ ha~ been u.~ed 6oft .the_ de.te_Jtmina.tion o6 Cd and Pb in biotogic.al mate_Jtiat(41), bu..t a~ a c.on.tinu.a.tion o6 method 2.2. 1. 1.2 (with appaJta.tu~ 2) : the whole dige~.ta.te i~
.tJtan~6efted in an open 6la~k, whe_Jte it -<-~ heated with 0,5ml -poJt.tion~ o6 30% hydJtoge_n pe!toxide added ~eveJtal time~ to the
hot ~otJ.tion .
2.2. 1. 1.s - Q~~~~~£~~~~-~~~~-~~~~~~1-P~~£~?9~~~-~~~-~~~e~~~~£ ac.id~.
Two di66eJten.t method~ a!te_ given by .the_ A.M.C. (80), one o6 them
u.~ing appa!ta.tu~ 3, the otheft u~ing appaJta.tu.~ 1.
Method~ o6 that type have been u.~ed 6oft .the_ de.teJtmination
o6 Cd,Pb,Zn, in biologic.at ma.teJtial (79) , o6 Cu in ~edimen.t~
(30. 1 ) and o6 Mn in neutJton ac..tiva.ted bu..tteJt a6teJt addition o6 inac..tive Mn a~ a c.aftJtie_Jt (34).
. I .
2.2. 1.2- Ve~t~u~tion with nit~i~ and ~uiphu~i~ a~id~,with
the aid o6 a ~ataly~t.
That method i~ not' mentioned by the A.M.C. but ha~ been u~ed
by Cumont et al. (31) 6o~ the dete~mination o6 Hg in 6i~h. The
Qataly~t wa~ vanadium oxide, and the de~t~u~tion wa~ ~a~~ied
out unde~ a ~e6~ige~ated atmo~phe~e.
2.2. 1.3- Ve~t~u~tion with nit~i~ and pe~~hlo~i~ a~id~.
Th~ee di66e~ent method~ a~e de~~~ibed by the A.M.C. (80)
( A p p a~ at u ~ 1 , 4 o fL 5 ) •
A method o6 that type ha~ been u~ed 6o~ the dete~mination
o6 metal~ (Ag,Cd,Cu,Fe,Mn,Ni,Pb,Zn ) in oven-d~ied biologi
~al mateJtial (21).
2.2. 1.4- Ve~t~u~tion with pota~~ium pe~manganate and ~ulphu
~i~ a~id, with o~ without the aid o6 nit~i~ a~id.
Tho~e method~ a~e ~pe~ially u~ed 6o~ the dete~mination o6
me~Qu~y in biologi~al mate~ial.
2.2. 1.4. 1 -The A.M.C. (80} de~c~ibe~ a ~pe~ial method 6o~
me~~u~y whe~e, a~ a 6i~~t ~tep, the de~t~u~tion
i~ ~a~~ied out by boiling with nit~i~ a~id and pota~~ium pe!Lmanganate (Appa~atu~ 6).
Sulphu!Li~ a~id and an ammonia~al hyd~oxylamine
~olution aiLe added a6te~wa!Ld~ and the mixtu~e
i~ allowed to ~tand at ~oom tempe!Latu~e 6o~ at
lea~t 3 hou~~.
The method lead~ to a pa!Ltial oxidation o6 liquid~
~ontaining ~elatively ~matt amount~ o6 o~gani~
matte~ (u~ine and othe!L 6inely minced biological
mate~ial~).
. I.
25
'2..'2..1.4.2- The A.M.C. (80) af~o de~c~ibe~ a va~iation o6 the
6o~me~ method intended 6o~ ~t~onge~ biological ma
te~iaf, whe~e ~ulphu~ic acid i~ added be6o~e the
dige~tion unde~ ~e6lux conden~e~ (Appa~atu~ 6) •
'2..2.1 .4.3- Je66u~ et al. (75) give a method whe~e, a6te~
a ~ulpho-nit~ic dige~tion ( a~ de~b~ibed in
2.2. 1. 1.1 but with appa~atu~ 6), pota~~ium pe~man
ganate i~ added, and the ~olution i~ b~ought to
momenta~y boiling . Hyd~oxyfamine hyd~ocho~ide ~o
lution i~ then added to de~t~oy the exce~~ o6
oxidant~.
'2..'2.. 7.4.4 - Thibaut(11) give~ a ve~y ~mooth method whe~e
0,4 to 0,1 g o6 6inely minced 6i~h a~z dige~ted
du~lng '2. houn~ at 50-60°C in an open long neck
6la~k wittt 6 ml ~ufpho-nit~.ic acid (1 pa~t cone.
HzS04 + 1 pa~t conc.HN03 ) . A ~upennatant gnea~y laye~ doe~n't di~tu~b. A6te~
cooling, 16 ~f o6 a 6% pota~~lum pe~manganatl ~o
lutlcn a~e added and the 6fa~k l~ allowed to ~tand
at ~oom tempe~atune 6o~ at lea~t 3 hou~~ . Hyd~ogen
petoxide l~ then added d~opwi~e until decol~~ation.
'2.. '2.. 1. 4. 5 - Foua~/~ln ( 16) doe~n 't u,~e nitn,i.c ac..id 6o~ .the.
dlge~tlon .
One gJtam o6 6l~h l~ dA...ge~ted with 30 rnf o6 concen
tnated 6ulphuJtic.. acid at ~oom tempenatu~e dunlng
7 5 minute~, .then put in a wa.:t e.~ bath at 58 ° C duJting
2 houn~ . A6te~ cooling, the. ~olution i~ diluted
w~th 50 ml bldi~tilfe.d wate~, and oxidized ove.~
High.t at -'t.oom te.mpe.na,tuJte with '2.0 rnl o6 ~atu~a.te.d
pota~~lum pe~maHganate 6olution ( 7%) • Exc.e.~-6
o6 oxidant l~ then de.~t~oye.d with 5 ml o6 a 75%
hydnoxyfamlne hyd~oc.hfo~lde .6olution .
The 6ame pJtoc.edu~e l~ u~ed by the Geme.ln~amen
Komitee F£en6buJtgeJt FBnde (6'2.) 6o~ the. de.~t~uc.tlon
u6 oJtganic. matteJt in ~e.diment~ (1g wet 6e.dlment
. I .
'2.6
+ 4 mt conc.H2S04 , 2h at 58°C ; + 15 ml 5% KMn04 , ovenn~ght at noom tempenatu~e ; + hyd~o
xylam~ne hydnochl.~ol. ; 6~tt~at~on ) .
2.2. 1.4.6- Quent~n (45) openate~ a wet d~ge~t~on o6 n~ven
~ed~ment~ by heat~ng w~th KMn04 and K2S20g ~n
~ulpho-n~tn~c med~um unden ne6iux .
2.2. 1.5- Ve~tnuct~on w~th hydnogen penox~de and ~ulphun~c ac~d.
2.2. 1.s. 1 - ~~~~~~~~~q~-~~~~-~Q~-~Y~~qg~~-e~~Q~~~~ .
The A.M.C. (82) g~ve~ 5 po~~~bte van~at~on~ (depend~ng on
th~ matenial to be de~tnoyed ) o6 a new method u~~ng 50%
hydnogen penox~de and ~ulphun~c ac~d . The method ~eem~ 6ull
o6 pnom~~e .
2.2. 1.s.2- Q~~t~~~tiq~-~i~~-~Q~-~Y~~qg~~-eg~q~~gg ·
Heat~ng w~th 30% hydnogen penox~de and concentnated ~ulphun~c.
ac~d ~n a 6ta~k 6~tted with a ne6lux conden~en (Appanatu~ 6 )
ha~ been u~ed 6on the de~tnuct~on o6 b~ological maten~al
(16,47,61,74) and o6 ~ed~ment~ (74) 6on ~ample~ in wh~ch mencu-
ny had to be mea~u~ed.
27
2. 2. 1. s. 3 - ~~-~-i>!~~~~Q~-~~~~-~Q~_~yg~qg~~-eg~q~i~~-~Q.~-i-~~-f!!g~~Q~·
Henman(32) u~e~ a veny quick method 6on the de~tnuct~on o6
6~~h ~n wh~c.h Hg and Cu have to be mea~uned . Thnee to ten gnam o6 6~6h a~e intnoduced ~n a 250 mt -
c.on~cal 6la6Q 6~tted to a waten-cooled ne6lux conden~en by
mean6 o6 a 6tandand gnound joint (appanatu~ 6).
F~ve mi o6 concentnated 6ulphun~c ac~d ane added thnough the
top o6 the_ conden~en, and ane 6oltowed by 2. 5 ml 30% hydnogen
penox~de . The content o6 the 6la6k i~ heated lightly dun~ng
3 to 4 "' i nut e. 6 { 6 on d e. c. om p o ~ ~ t ~ o n o 6 H 2 0 2 ) . T h e c. o ate d ~ o -tut~on i6 bnought to 100 ml w~th waten in a 100 ml 6la~k .
(At th~6 6tage, an aliquot ~6 taken 6on detenm~nat~on o6
c.oppen by d~nect atomic ab~onption ) .
. I .
A 6ew d~op~ ( ~ 70) o6 a 5% pota~~ium pe~manganat~ ~olution
a~e then added until a ~o~e colo~ation develop~ (de~t~uction
o6 the ~emaining o~ganic matte~ and o6 H202 ) .
2.2. 1.6 -No de~t~uction o6 o~ganic matte~ .Acid ~olubili~ation.
2.2.1.6.1- ~s-~~-~~gg_~~~q~
No de~t~uction (o~ only a pa~tial de~t~uction ) o6 o~ganic
matte~ ha~ been ca~~ied out in ~orne ca~e~ . A ~imple acid di
ge~tion ha~ been u~ed in~tead , e~pecially 6o~ ~ample~ o6
~ediment~ . Boiling with nit~ic acid ha~ been u~ed (Hg in ~ediment~ :50 ;
Cd, C~, Cu, Pb, Zn in ~ediment~ : 62), o~ boiling with hyd~o
chlo~ic acid (6luo~ine in 6oil :64 ) o~ with hyd~ochlo~ic acid
and hyd~ogen pe~oxide (metal~ in ~u~pended matte~ : 21 ) .
In one ca~e (20) ,concent~ated nit~ic acid only ha~ been u~ed
to d~66olve d~ied biological ~ample~ (dete~mination o6 Cd, Pb,Zn).
2.2. 7.6.2- ~Y~~Q6~~2~~~-=e~~s-~{q~~s--~s-~g~-~~gg_~~iq~.
Thi6 p~ocedu~e ha~ been u~ed 6o~ the analy~i~ o6 metal~ in
~ediment~ in only two ca~e~ (79,53) •
2.2. 1.6.3 - ~y~~2D~~q~~s--~~gg_~~iQ~
Thi~ p~ocedu~e ha~ been u~ed fio~ the de~t~uction o6 mine~al
~ample~ containing ~ilicate6 ,be6o~e UV-~pect~og~aphy o~
x-~ay 6luo~e~cence (32) .
. I .
28
2 . 2 . 2 VRY DECOMPOSITION
The Analytical Method~ Committee (80) give~ a good de~c~ipt~on
o6 ~~x method~ o6 d~y a~h~ng o6 o~gan~c matte~ (w~th o~
w~thout a~h~ng aid~ ) .
" V~y a~hing i~ appl~cable to the dete~m~nat~on o6 mo~t c.ommon
metal~, u~ually with the except~on o6 me~cu~y and a~~en~c,
-<-n o~gan~c matte~ " . ( 8 0)
" The d~y-a~h~ng p~ocedu~e .{.~ o6 pa~t~cula~ advantage when
the u~e o6 ~ulphu~~c ac-<-d ~~ object~onable ; 6o~ ~n~tanc.e 1
6o~ the dete~m~nat-<-on o6 lead ~n mate~~al~ c.onta~n~ng app~e
ciable quantit~e~ o6 alkaline ea~th~ , who~e ~ulphate~
occlude lead ~ulphate " . (80}
In gene~al , the tempenatu~e o6 420°C ~hould not be exc.eeded. A6te~ a~h~ng, a~he~ a~e di~~olved ~n an ac.~d .
Vny a~h-<-ng ha~ been u~ed -<-n ~orne o6 the ~ece~ved pape~~~ 6on the detenm--i_nation o6 lead (7,58), o6 lead and z~nc (32} ,
o6 Cu,Fe,Mn,Ni,Pb,Zn (32,67} ~n biolog~c.al mate~~al, and
o6 Cd, Cu, Fe, Mn, Pb , V , Zn in ai~ pa~t~c.ulate~ (63).
In one occ.a~~on(30.3) a Low Tempe~atu~e A~he~ ha~ been u~ed
at a maximum tempe~atu~e o6 60°C 6on the dete~minat~on o6
c.oppe~ .
. I .
29
3. SEPARATION . ==• ·········===
3.1- SOLID- LIQUID EXTRACTION
Re~in6 a~e u6e6ul when ~epakation o6 heavy metal~ 6kom
alkali ~alt~ i~ needed a~ well a~ a concentkation e66ect.
Mokeovek, the volume o6 watek that can be tkeated may be veky
impoktant ( 10 to 40 l ) .
3 • 1 • 1 CATIONIC RESINS
Cationic chelating ke~in~ have been u~ed 6ok the ~epakation
o6 Cd, Cu, Pb, Zn 6kom ~ea ok kivek wateJt (10 l) , the
mea~ukement being made by pul~e polakogJtaphy(24,25 J oJt
atomic ab~okption (25).
Cationic ke6in~ have al~o been u6ed to 6epakate Cd, Pb, Zn
6kom e6tuaky watek (79); a 2 l ~ample wa~ acidi6ied to pH 5 ,
ad6oJtbed on an acid ke6in , and eluted with 2 N nitJtic acid;
the mea6unement wa6 made by polaJtogJtaphy .
3 • 1 • 2 ANIONIC RESINS
Anionic exchange ke6in ha6 been u~ed 6oJt the ad6oJtption o6
meJtcuky a6 a chlono-complex 6nom a 20-40 l ~ample o6 e~tuaJty
waten, acidi6ied to 0,1 N with 6uiphuJtic oJt hydJtochloJtic
ac~d (16). 203Hg i6 added a~ a tJtaceJt duking the pne-tJteatment
(~ee 1. 1.4 be6one).
Mencuny i6 eluted in a ~olution o6 peJtchlokic acid and ethyl
acetate . A6ten nemoval o6 ethyl acetate , meJtcuny i6 extkacted
with dithizone (6ee 3.2.5.below) and mea6uJted coloJtimetJtically .
. I .
30
3 1
3. 2 - LIQUIV-LIQUIV EXTRACTION
Liquid-liquid ~xt~actio~ ha~ b~~~ mai~ly u~~d 6o~ ~~pa~ation
a~d co~c~nt~ation o6 (h~avy) m~tal~ 6~om wat~~ o~ d~~t~uct~d
biological ~amp£~~~ p~io~ to a colo~im~t~ic d~t~~minatio~ o~
a~ atomic ab~o~ption ~p~ct~ophotom~t~y.
3 • 2 . 1 EXTRACTION OF LEAV
3 . 2 • 1 • 1 - Vi t hi z o ~ ~ ~ x tfl. action .
A v~fl.y good d~~cll.iptio~ o6 th~ d~t~~mination o6 l~ad in o~ganic
matt~~ i~ giv~n by th~ A~alytical M~thod~ Committ~~ i~
Th~ Analy~t (77) . L~ad i~ ~xtfl.act~d 6~om the dig~~tat~ o~
acid di~~olv~d a~h by m~an~ o6 dithlzon~ at pH 9.0 to 9.5,
a6t~~ the addition o6 citfl.at~ , and in th~ p~~~~nc~ o6 ~odium
h~xam~tapho~phat~ ~o a~ to p~~v~nt the p~ecipitation o6 ma
gne~ium o~ calcium pho~phat~~. Fo~ ~amp£~~ with a high cont~nt
in catcium, magn~~ium a~d pho~phat~ , a p~~limina~y ~xt~action
6~om acid ~olution with dl~thylammonium diethyldithioca~bamat~
(V.AoV.V.T.C.) i~ ~ub~tltut~d 6o~ th~ h~xametapho~phat~ p~o
c~du~~ .
Lead i~ di66olv~d agal~ in diluted nit~ic acid, and fl.~-~xt~act~d
with dlthizon~ a6t~fl. addition o6 an ammoniacal ~ulphlto-cyanid~
6olutlon . Th~ optical d~~~ity o6 th~ dithizon~ ~xt~act i~
m~a6u~ed .
When con6id~~abl~ bi6muth i~t~fl.6~fl.~nc~ i6 indicat~d, a giv~n
modi6ied pll.oc~du~~ 6hould b~ u~~d.
Th~ method ~~commend~d by th~ A.M.C. ha~ b~en u~~d by on~
autho~ ( 1) .
. I .
,.
3 • 2 • 1 • 2 - A.P.D.C. ext~aetion
Anothe~ autho~ (58) ha~ ~epa~ated lead w~th ammon~um py~olli
dine dith~oea~bamate (A.P.D.C.) , the mea~u~ement be~ng made
by atom~e ab~o~pt~on ~peet~ophotomet~y .
3 • 2 • 2 EXTRACTION OF CADMIUM
32
The Analyt~eal Method~ Comm~ttee g~ve~ a ve~y good de~e~iption
o6 method~ 6o~ the dete~minat~on o6 ~mall amount~ o6 cadmium
~n o~g anie matte~ ( 8 3) •
A 6~~~t method ~~ ba~ed on a double-ext~aet~on w~th d~th~zone
6ollowed by a eolo~~met~~e dete~m~nat~on .
A ~eeond method, ba~ed on anothe~ p~oeedu~e o6 double
ext~aetion with d~th~zone , ~~ 6ollowed by a pola~og~aph~e
dete~m~nat~on .
Anothe~ method ean be 6ound ~n the 066~e~al Standa~d~zed and
Reeommended Method~ o6 Analy~~~ o6 the Soe~ety 6o~ Analyt~eal Chem~~t~y (1963) and ha~ been u~ed ~n ~e6e~enee 1.
3 • 2 • 3 EXTRACTION AF CADMIUM AND LEAD
Ext~aetion w~th ~odium diethyldith~oea~bamate (Na D.D.T.C } and
methyl-i~obutyl-keton (M. I.B.K.) ha~ been u~ed by the
Rijk~in~tituut voo~ de Volk~gezondheid (47} 6o~ the dete~mina
t~on o6 Cd and Pb in de~t~ueted biological ~ample~ . A6te~ baek-ext~aetion with diluted n~t~ic acid, the metal~ a~e mea~u~ed by atomie ab~o~ption .
3. 2. 4 EXTRACTION OF METALS 6~om wate~}
3 . 2 . 4 . 1 - A • P . D . C • e x t~ actio n
Fo~ ~ea wate~, P~e~ton et at. (27) have u~ed an ext~action
in ehlo~o6o~m at pH 6 o6 the ammonium py~ollidine dithioca~
bamate (A.P.D.C.} eomplexe~ . Atom~c ab~o~ption ~peet~ophoto-
. I .
met~y i~ then ~a~~ied out on a ~mall po~tion o6 the ext~a~t
u~ing the tantalum boat te~hnique ( Kahn et al., 7968)
6o~ Cd, Pb and Ag ; the ~emaining po~tion o6 the ~hlo~o6o~m ext~a~t i~ ~onve~ted into a methanoli~ ~olution and a~pi~ated
di~e~tly into an A.A. in~t~ument ( 6o~ Cu,Fe,Mn,Ni, Zn ) .
Fo~ an initial ~ea wate~ volume o6 1 lit~e and 2 X 25 mi
~hio~o6o~m ext~a~t~, the li~ted element~ a~e ext~a~ted with
yield~ ~upe~io~ to 95% , and the u~e o6 methanol a~ a~pi~ant
mean~ that the ext~a~ted ~ample~ ~an be di~e~tly ~ompa~ed with
a mixed element ~tanda~d o6 the metal ~hlo~ide~ di~~olved in
methanol.
Ext~a~tion in methyl-i~obutyl-ketone (M.l.B.K.) o6 the A.P.V.C ~omplexe~ ha~ al~o been u~ed 6o~ ~ive~ wate~ (75) , the M1BK
ext~a~t being mea~u~ed di~eetly by atomi~ ab~o~ption ~pe~t~o
photomet~y 6o~ Cd, Co, C~, Cu, Fe,Ni, Pb . Yield~ o6 700%
a~e attained by adapting the APVC eoncent~ation to ea~h
element .
3.2.4.2 - A.P.V.C.-V.A.V.V.T.C. ext~a~tion
A ve~y elabonated method i~ u~ed at the Rijk~in~tituut voo~
de Volk~gezondheid in Ut~eeht (47) and i~ de~~~ibed by Fond~
and Van den E~ho6 (76) . The yield o6 the ext~a~tion 6o~
Cd, Co, Cu, Mn, Ni, Pb, Zn 6~om d~inking o~ ~ive~ wate~ i~
1 0 0 ~ 0 •
An APVC/MIBK ext~aetion at pH 2 to 2.5 i~ 6ollowed by an
ext~a~tion with diethylammonium-diethyldithio~a~bamate
(V.A.V.V.T.C.) in ~hlo~o6o~m, 6i~~t at pH 3.5, then at pH 6
33
to 7 • The ~ombined ext~aet~ a~e baek-ext~a~ted with diluted
nit~ie a~id . Thi~ la~t ~olution i~ mea~u~ed by atomi~ ab~o~ption
~pe~t~ophotomet~y.
. I .
~
3. 2. 5 EXTRACTION OF MERCURY
Ext~aQt~on o6 m~~Qu~y 6~om th~ d~g~¢tat~ o6 o~gan~Q matte~
d~luted to 0,1 N aQ~d~ty w~th dithizone in Qa~bon tet~aQhlo
~ide i¢ given by the AnaiytiQal Method¢ Committee in The
Analy¢t (87) . A6te~ a baQk-ext~aQtion with 0,1 N hyd~oQhio~iQ
aQid, me~Qu~y i¢ ~e-ext~aQted w~th dithizone and mea~u~ed by
QOlo~imet~y .
A ~imila~ method ha¢ been u¢ed in ~e6.76.
3.3 - CHROMATOGRAPHY
The method o6 Woid~ch et al. (84) ha~ been u~ed 6o4 the dete4mi
nation o6 me~Qu~y ~n b~ological mate~ial (72) • Me4Qu~y i~
ext~acted 6~om the d~g~~tate with d~thizone . The dithizone
complex i¢ pu~i6ied by th~n laye~ Qh4omatog4aphy, and the
me~Qu~y band i¢ ext~aQted w~th methanol . The mea~u~ement
i¢ made by QOlo~imet~y .
3.~ -DISTILLATION
34
V~~t~ffat~On ha¢ been U¢ed 6o~ the ¢epa~ation OQ me~CU~lj Qhlo~ide
o~ b~omide, when neut~on aQt~vation method~ u¢ed (76, 22,
59,14) .
3.5 - ISOTOPIC EXCHANGE
I6otopic cxQhange ha¢ been u¢ed a6t~~ d~~tillation o6 the
me~Qu~y chlo~ide o~ b~om~de .
I¢otopiQ exQhange o6
been u¢ed ~n ~e6.59.
203 Hg on an amalgamated coppe~ ooii ha¢
. I .
35
The p~o~edu~e u~ed by de Goeij (74) , ante~ the wet de~t~u~
tion o6 o~gani~ matte~ , i~ the nollowing :
" The. me.~~u~y i~ volatilized at 200°C by adding hyd~oge.n·
b~omide. and t~appe.d in a ~odium a~e.tate ~olution . An ina~
tive. me.~~u~y d~ople.t i~ added to thi¢ ¢olution and the.
mixtu~e vigo~ou¢ly ¢ti~~ed 6o~ 1 hou~, b~aking the. elemental
me.~~u~y into hund~e.d¢ on d~ople.t¢ thu~ e.n~u~ing a good
i¢otopi~ ex~hange . The me~cu~y metal i~ then ~olle.~te.d
on a ¢inte.~ed gla~¢ 6ilte.~ and wa~hed with wate.~ and with
a~etone . Finally it i~ di¢¢olved in nit~i~ a~id and c.ounte.d".
3. 6 - VEPOSITION ON METAL
Fo~ the. ~e.pa~ation and ~on~e.nt~ation on me~~u~y , Vavid
Smith et al. (77) u¢e_ a p~o~edu~e. whi~h lead~ to a ve.~y
¢e_n~itive method no~ the. dete.~mination on me.~~u~y in wate~ .
Ante~ the oxydation on the ¢ample with KMn04 (~ee 2.7.2 above.),
the p~o~e.du~e. i~ a¢ nollow¢ :
" A ¢ilve~ ~oil 6~e.e.d on me~~u~y by heating wa~ added to ea~h bottle and the bottle¢ ¢hake.n ove.~night .
Up to thi~ ~tage the ~ample¢ ~emained in thei~ ~olle~ting
bottleJ, thu¢ minimizing ~ontamination and lo~~e~ on me~~u~y.
Each ~oil wa¢ ~emoved n~om the ~olution, wa~hed with wate~
and a~etone and d~ied in ai~ . Optimum ~ondition~ no~ the
~e~ove~y on me.~Qu~y we.~e. de.te.~mined u~ing 203Hg t~a~e~.
Me~~u~y amalgamated with the ~ilve~ wa~ d~iven onn by heating
the ~oil to ~oughly 250°C in a ~ili~a tube . The me~~u~y
vapou~ wa¢ pa~¢ed ~n a ~t~eam on nit~ogen th~ough a ~e.ll o6 15 ~m light path, in an atomi~ ab~o~ption ~pe~t~ophotomete~.
Fo~ 1 kg ~ample¢ ..... the ~oe66icient on va~iation at the
0,050 wg/kg level wa¢ 1,8% "
Thi6 method i6 the only case on ~on~ent~ation p~io~ to
6lamele~~ atomic ab~o~pt~on ¢pe~t~ophotomet~y on me.~~u~y .
. I .
3.1- PRECIPITATION
In two ~a~e~, p~e~~p~tat~on ha~ been u~ed 6o~ ~epa~at~on .
3 • 1 • 1 PRECIPITATION OF ARSENIC
A~~en~~ ~~ p~e~ip~tated 6~om wate~ ~ample~ w~th th~onal~de(41).
The p~e~~p~tate i~ 6~lte~ed and de~t~u~ted and A~H3 ~~
6o~med ( ~ee 3.9. below).
3 • 1 • 2 PRECIPITATION OF MANGANESE
In th~~ p~o~edu~e (34) , mangane~e i~ ~epa~ated 6~om the
d~ge~tate o6 neut~on a~t~vated butte~, a6te~ add~t~on o6 a Mn ~a~~~e~ (~ee 2.2. 1.1.5. above).
The d~y ~e~t o6 the d~ge~tate ~~ d~~~olved ~n 150 ml wate~
and 30 g pota~~ium ~hlo~ate i~ added . The ~olut~on ~~ boiled
a 6ew minute~, then le6t 45 to 60 minute~ at ~oom tempe~atu~e
to allow the 6o~mation o6 a p~e~ipitate o6 mangane~e dioxide . The p~e~ipitate i~ 6~lte~ed, d~~ed and ~ounted in a gamma ~pe~t~omete~ .
3.8 - REDUCTION-MERCURY
The dete~mination o6 me~~u~y by 6lamele~~ atomi~ ab~o~pt~on
~pe~t~ophotomet~y 6ollow~ the p~in~iple~ o6 the Hat~h and Ott method . Me~~u~y ~ompound~ a~e ~edu~ed to elemental me~~u~y , the vapo~6 o6 whi~h a~e evolved th~ough a ~ili~a ~ell whe~e ~t i~ mea6u~ed .
The method i~ ~ompo~ed o6 the 6ollow~ng ~tep~ :
36
a. The ex~e~ o6 oxidant6 in the dige~tate i~ de~t~oyed (i6 not
ab~eady done at the end o6 the de6t~u~tion o6 o~gani~
matte~ 6tep) by addition o6 a ~olution o6 hyd~oxylamine
hyd~o~hlo~ide . Thi~ t~eatment may be done ~epahately (18,62,15) o~ in combination with the next ~tep (11,41 ) .
. I .
b. The ~educt~on o6 the me~cu~y compound~ to elementai
me~cu~y ~~ obta~ned by addition o6 a 5 to 20 % ~oiut~on o6 ~tannou~ chio~~de o~ ~uplhate , comb~ned
( 11, 41 ) o~ not w~th the hydtz_ox.ylamine hyd~ochlo~~de
-~ oiut~o n •
The quant~ty o6 ~eagent added va~~e~ ia~9eiy acco~ding
to t h e aut h o ~ -~ ( 0 , 1 to 3 9 o 6 d ~ y ~ e a 9 en t p e~ 9 ~am
o6 o~~g~nal b~otogical ~ample).
The ~cduct~on can al~o be obta~ned by add~t~on o6 2 mi
o6 a 1% ~od~um bo~ohyd~~de (NaBH4 ) ~otution ~n
0,005 N NaOH ( 32).
Bo~ohyd~~de lead~ to a mo~e con~tant ~eduction and
i6 pu~e~ than tin ~alt~ .
c. The elemental me~cu'Ly vapou~~ a~e conducted to the
mea~u~~ng celt w~th the aid o6 a 6low o6 a~~ o~ nit~ogen.
3.9 - REDUCTION -ARSENIC.
Inotz_ganic a~~enic ~~ 'Ledu~ed into a~~~ne,A~H3 , by z~nc ~n
acid 6olution . The a~~~ne i~ then pa~~ed th~ough a ~c~ubbe~
containing gla~~ wool impnegnated wi~h lead acetate ~olution
and into an ab~o~betz_ tube containing oilve~ d~ethyldithioca~
bamate di~~oived in pytz_~dine . In the ab~o~be~, a~~enic ~eact~
with the ~ilve~ ~alt and 6o~m~ a ~oluble ~ed complex which
i~ ~uitable 6ot photomet~ic mea6u~ement .
The method ha~ been u~ed 6o~ the dete~m~nat~on o6 a~~enic
~n wat e,t, a6 te~ p~ ec~p~tatio n tA.J,ith thio nal~d e ( 41 ) , ~n b~o io-
g{cal mate~ial, a6te~ dige~tion (7, 47), and ~n d~y
~ e dime n t ,~ ( 6 2 ) •
. I .
37
4. MEASUREMENT . =•=•==•=======
Table 3 {p. 54) ~ho~~ the app~oximate pe~centage~ o6 ~ample~
anafy~ed by the di66e~ent technique~ available .
4.1 - ATOMIC ABSORPTION SPECTROPHOTOMETRY
Whe~eve~ it wa~ po~~ible to u~e it, atomic ab~o~ption wa~ the
method mo~t 6~equently employed . It ha~ been u~ed 6o~ mo~e
38
tha~ 80% o6 the ~e~ult~ t~an~mitted. Thi~ ~ecent technique,
allowing a quick and ~en~itive mea~u~ement o6 metal~ , i~
p~obably the g~ound 6o~ the development o6 mo~t ~e~ea~che~ in the
6ield o6 non-o~ganic mic~opollutant~ .
The detection limit that can be achieved on wate~ ~ange~ 6~om
1 to 100 ~g/l , acco~ding to the metal mea~u~ed [ 6o~ in~tance A g , C d , C o , C ~ , C u , F e , M n , M o , N i , P b , Z n ) and t h e a p p a~ a -
tu~ employed . A6te~ an ext~action by mean~ o6 a complexing
~eagent in a combu~tible ~olvant ( 6.i. M.I.B.K ) a 6u~the~
~en~itivity 6acto~ 6~om 1 to 50 can ~till be gained acco~ding to
the element taken into account , the 6inal detection limit
being then 1 to 5 ~g/l o~ even bette~ .
Vi66e~ent acce~~o~ie~, e~pecially at the level o6 the element
excitation (g~aphit oven, tantalum boat ) , lead to detection
limit~ ~anging 6~om 0,001 to 0,1 ~g/l 6o~ ~ome metal~ .
Biological ~ample~ and ~olid ~ample~ mu~t inevitably be de~tnoyed and put in ~olution be6o~e injection in the 6lame
thi~ nea~ly alway~ p~oduce~ a dilution 6~om 10 to 100 with
a neducing e66ect on ~en~itivity which i~ ~till ve~y good 6o~
that kind o6 ~ample~ (detection limit ~anging 6~om 0,01 to
5 mg/kg acco~ding to the metal ) .
. I .
39
4.2 - FLAMELESS ATOMIC ABSORPTION.
Thi~ te~hnique i~ p~e~ently the be~t one 6o~ me~~u~y mea~u~ement.
It i~ qui~k and ea~y and ~an be ea~~ied out by mean~ o6 a
t~aditional atomi~ ab~o~ption ~peet~ophotomete~ 6itted with a
~peeial mea~u~ement eell, o~ by mean~ o6 ~pe~ial appa~atu~ ~on
eeived 6o~ me~eu~y mea~u~ement .
The deteetion limit ~eaehed in wate~ i~ about 0,02 ~g/l.
Reduetion in metallie Hg with ~tannou~ ehlo~ide o~ ~ul6ate o~
~odlum bo~ohyd~lde (~ee 3.8 above) i~ p4eeeded by an oxidation
whieh i~ u~ually ea~~ied out with aeid pe4manganate when wate~
i~ ~onee~ned (~ee 2.1. 2 above) , o4 by a mo4e o4 le~~.> elabo-
4ated de~t4u~tion o6 o4ganie matte4 6o4 biologleal ~.>ample~.>
o~ ~.>ediment~ (~.>ee 2.2.1 above) .
One autho~ only (77) p~oeeded to a p4eviou~.> eoneent~ation o6
wate4, by ~etting down me~eu~y on a ~ilve4 eoil . In the~.>e
~ondition~, the eoe66i~ient o6 va~iation at the 0,050 ~g/kg
level wa~ 1,8 % 6o4 1 kg ~ample .
4.3 - SPECTROPHOTOMETRY (COLORIMETRY)
Colo4imet~y ha~.> been u~ed 6o4 the mea~u4ement o6 metal~.> by
di66e~ent labo~ato~ie~ be6o4e they eould be equipped with atomi~
ab~o~ption ~peet4ophotomete4~ , o~ in pa4ti~ula4 ~i~eon~.>tan~e~.> .
It ha~ al~o been u~ed 6o~ the mea~u4ement o6 element~.> whieh
a~e not adapted, o4 we4e not adapted at the time o6 mea~u4ement,
6o~ atomie ab~o4ption : a4~enie , bo4on, molybdene,~.>elenium .
. I .
A~~~ni~ ha~ alway~ b~~n m~a~u~~d by m~an~ o6 ~ilv~~ -di~thyl
dithio~a~bamat~ di~~olv~d in py~idin~ ( 7,47,62).
A ~olo~im~t~i~ m~thod by m~an~ o6 zin~ - dib~nzyl -
dithio~a~bamat~ ha~ b~~n u~~d 6o~ di~~~t ~nd eontinuou~ m~a~u~~
m~nt o6 eopp~~ in wat~~ 6~om a boat (30.2 ) and 6o~ m~a~u~~m~nt
in dig~~t~d ~~dim~nt~ (30.1 ) and (low t 0 - ) a~h~d biological
mat~~ial (30.3) •
Colo~im~t~y ha~ al~o b~~n u~~d 6o~ th~ m~a~u~~m~nt o6 th~
Hg-dithizon~ compl~x ~~pa~at~d by thin-lay~~ eh~omatog~aphy
and di~~olv~d in m~thanol (72,~~~ 3.3 abov~) , and 6o~ th~
m~a~u~~m~nt o6 th~ Hg-dithizon~ eompl~x di~~olv~d in ehlo~o6o~m,
a6t~~ ~~pa~ation o6 th~ ehlo~o-Hg-~ompl~x on an~oni~ ~~~in
(76, ~~~ 3.1.2 abov~) .
U~ually, p~~viou~ ~onc~nt~ation~ o~ ~xt~act~on~ a~~ n~~~~~a~y
wh~n d~t~~tion limit~ ~~mila~ to tho~~ aeh~~v~d by atom~~
ab~o~ption hav~ to b~ p~~6o~m~d in eolo~~m~t~y .
4.4 - RADIOACTIVE COUNTING (AFTER NEUTRON ACTIVATION)
N~ut~on a~tivat~on ~~ a ~~n~~tiv~ and ~~liabi~ t~chniqu~ 6o~
th~ m~a~u~~m~nt o6 many ~l~m~nt~ . It can b~ appli~d to a va~i~ty o6 ~ampl~~ with a wid~ ~ang~ o6 eon~~nt~ation l~vel~.
How~v~~~ in many ~a~~~ , a ~h~mieal ~~pa~ation i~ ~~qui~~d to
~~pa~at~ th~ 6o~m~d ~adioi~otop~~ . Mo~~ov~~ a nuei~a~ ~~a~to~
i~ n~c~~~ay
M~a~u~~m~nt o6 th~ 6o~m~d ~adioi~otop~~ i~ ca~~i~d out mainly
by gamma ~p~ct~om~t~y . M~~eu~y ha~ b~~n m~a~u~~d that way
( a~ Hg 191 ) in biological ~ampl~~ and ~~dim~nt~ a6t~~ d~~t~uc
tion o6 o~ganie matt~~ , ~~pa~ation by di~tillat~on and i~otopic
~xchang~ (~~~ 3.5 abov~ ) (6.2,6.3,6.5 to 6.8, 14) and in
b~ologieai ~ampl~~ ( 2 2, 59) •
. I .
40
In that way al~o, mangane~e ha~ been mea~u~ed in butte~ a~
Mn 56, a6te~ ~epa~ation o6 the Mn02 p~eeipatate (34, ~ee 3.1.2
above) and zinc in butte~, a~ Zn 65, without any ~epa~ation
( 3 4) •
Beta counting o6 Hg 203 ha~ been u~ed 6o~ mea~u~ement o6 Hg
~n b~ological ~ample~ and ~ediment~, a6te~ de~t~uction o6 o~ganic matte~, di~tillation a~ the chlo~ide, and 6u~the~
~adiochemical pu~i6ieation (76) .
A ~en~itivity 6~om 0,1 to 1 ~g /kg ean be achieved 6o~ me~eu~y 6o~ ~ample~ o6 1 g o6 wet matte~ .
4.5 - POLAROGRAPHY
Pola~og~aphy ha~ been u~ed by 6ive autho~~ 6o~ wo~k on ~ive~
and ~ea wate~~( 13,19,24,25,50 ) and by one (55) 6o~ mea~u~ing
Cu in 6~uit . Pul~e pola~og~aphy ha~ been u~ed by two o6 them (24,25 } 6o~
mea~u~ement o6 Cd,Cu,Pb,Zn on ~ive~ and ~ea wate~, a6te~ eon
eent~ation on eationie ~e~in (~ee 3.7.7 above} .
Pul~e pola~og~aphy i~ a ~en~itive method, but ~equi~ing ~kii6ul
teehn~eian~ .
4.6 - U.V-SPECTROGRAPHY
U.V-~pect~og~aphy wa~ u~ed by one autho~ 6o~ wo~k on ~ive~
and ~ea ~ed~ment~, ~oil~ and plant~ (15,32) .
The mate~ial to be anaiy~ed i~ 6i~~t b~ought up in d~y powde~
6o~m :
. I .
41
6o~ b~o~og~~al ~ampl~~ , bu lyophili~ation ( 6~uit,6~~h )o~
d~y~ng at <10°C o~ a~hing at <450°C.
6o~ mine~al ~ampl~~~ by d~ying at <105°C o~, 6o~ ~ili~eou~
mat~~~al, by t~~atment with hyd~o6luo~i~ a~id ( ~ee 2.2.1.6.2 abov~) , d~ying and a~hing at <450°C .
- 6o~ wat~~ ~ampl~~~ by ~vapo~ation to d~yne~~~ and a~hing at
<450°C (p~ev~ou~ po~~ible ~on~ent~ation on ~e~in ) .
Th~ g~ound ~~~idu~ i~ intnodu~~d in a g~aphit~ el~~t~ode
Th~ ~x~itation i~ giv~n by mean~ o6 a ~ontinuou~ a~e, the
~p~~t~um i~ photog~aph~d .
Thi~ m~thod i~ a d~lieate on~; th~ making o6 ~tanda~d~ in
mat4ixe~ ~imila~ to tho~e o6 the ~ample i~ u~ually ~equi~ed
and th~ ~ta66 mu~t b~ well t~ain~d . It~ application i~ advan
tag~ou~ only 6o~ la~ge ~~nie~ o6 ~ample~ . Wh~n the~~ ~ondition~ a~~ 6ul6ill~d, thi~ m~thod allow~ the
m~a~u~ement o6 a ~~~i~~ o6 element~ on the ~am~ ~ample, with
d~t~~tion limit~ 4anging 6~om 1 to 100 ~g pe~ g o6 analy~ed
p~odu~t . Anoth~~ advantage i~ that th~ ~ample i~ eoneent~ated
( d~ying o~ a~hing ) while in wet method~, the ~ample i~
u~ually dilut~d . How~v~n , th~ a~eu~aey, whi~h i~ about 10% in the mo~t e66eetive
ea~e~, i~ u~ually not ~o good a~ in th~ othen method~ .
4.1 - X-RAY FLUORESCENCE
X-~au 6luo~e~~ene~ wa~ u~~d by only two autho4~ 6o~ mea~uning
Fe, T~ , and Sn ~n ~oil~ and plant~ ( 32 ) and 6o~ Cd, Pb,
N~ ~n a~n pant~eulat~~ and in na~n (43) .
. I .
42
The ~ample~ i~ p~epa~ed a~ in U.V-~peetnognaphy (32 , ~ee 4.6
above J then ~et on a eeilulo~e tablet on any othen eonvenient
~uppo~t .
Ain 6ilte~~ ean be analy~ed dineetly .
X-~ay 6iuo~e~eence i~ mone aecu~ate and ~ep~odueible than
U.V-~pect~ognaphy ; the ~en~itivity i~ ~imilan and both
method~ have the ~arne pnobiem~ with matnixe~ .
One advantage i~ that the method i~ a non-de~tnuctive one .
43
A P P A R A T U S .
=====•==================
1 • 2.
~in r
B
D
3. ConicaL 6la~k wlth ~lto~t ~e6lux tube exten~lon, elect~lcal hot p.e.at e ;
5. La!Lge bo-i.ling tube ( 40 mm X 230 mm) ;
6. Round - bottommed 6la~k o~ conical 6ia~k 6ltted by
mean~ o6 a ~tanda~d g~ound joint to a long wate~ - cooled ~e6lux conden~e~ .
44
T A
B L
E
2.
~~;~;~
~~~~~~
~r~;~~
~;;~~~
~~~r~~
~~~~~~
~~~,~~
~~~~;~
~~~~~~
~~~~ --
----
----
----
----
----
----------------------~----------------------
DES
TRU
CTI
ON
SE
PAR
ATIO
N
MEA
SURE
MEN
T --
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
Hg
I EJ.>
.tu.a
/Ly
I.O:L
te!t
11
F ~.
'1 • 1
• 1 •
H2S
04
V e.
po -6
..it
io n
+
KM
n04
2•1
•2•
A
it
3.6.
F
.t.A
.A.
4.2
. A
c.-id
•
1 • 1
• 2 •
OYI
. g
C.O
Hg
I Riv
eJt
LO:L
te/t
15
Ac.
-id.
1.1
.2.
KMn0
4 2
.1.2
. R
e.du
c.. S
n.C£
.2
3.8
. I
F.£.
.A.A
. 4
.2.
Hg
I v un
.tu
ng
45
A
c.id
. 1
.1.2
. H
2S04
+HN
03
2.1
.2.
Re.d
uc..?
3.
8.?1
F.
£..A
.A.
4.2
. I.O
:Lte
Jt
+
KMn.
04
Hg
Riv
eJL
I.O:Lt
e.Jt
46
Ac.
-id.
1.1
.2.
? I
Re.
duc.
.?
3.8.
?1
F.£.
.A.A
. 4
.2.
Fil:t
!t.
1.1
.1.
Hg
Wat
:eJt
41
Fi
l:t!t
. 1
.1.1
. KM
n04
2 . 1
• 2 . I
R e.
duc.
• ?
3.8.
?1
F.£.
.A.A
. 4
.2.
Hg
I Riv
eJt
utt
.teJ
t I
50
I A
c.id
. 1
.1.2
. ?
I R
e.du
c..?
3.
8.?1
F
.t.A
.A.
4.2
. a
tlo
w t
0 1
.1.3
.
Hg
I Riv
ell
t.lt
tte!
t I
41
I Fi
l:t!t
. 1
.1.1
. &
2 2.
1. 4
. I
R ed
uc..
Sn.
Ci2
3
.8.
I F
.t.A
.A.
4.2
. A
c.id
. 1
.1.2
.
Hg
I Bio
i.
I 1
I H
omog
. 1
.2.5
. S
ulp
ho
-2 •
2 . 1
• 1 • 2
. I R
e.du
c.. S
n.SO
4
3.8
. I
F.t.
A.A
. 4
.2.
nit
ltic
.
Hg
I Bio
t.
I 28
I
Hom
og.
1.2
.5.
I Su
lph
o-
nit
Aic
. 2.
2. 1
. 1 • 2
. I
Red
uc.. S
n.C£
.2
3.8
. I
F.t.
A.A
. 4
.2.
Hg
I &L
ot.
I
41
I ?
I Su
lph
o-
nit
ltic
. 2
.2.1
.1.2
.1 R
e.du
c..S
n.C
£.2
3.8
. I
F.t.
A.A
. 4
.2.
. I.
j ..
·~
----
----
----
----
----
----
---
----
----
----
---
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
__
__
__
__
__
__
__
__
__
_ J~-
ELEM
ENT
MEV
IUM
R
EFER
ENC
E PR
E-TR
EATM
ENT
DE
STR
UC
TIO
N
SE
PA
RA
TIO
N
MEA
SUR
EMEN
T
----
----
----
----
----
----
---
----
----
----
---
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
--
Hg
Bio
i.
50
VJt
ying
1
.2.4
. S
ulp
ha
-2
.2.1
.1.1
. R
educ
..?
3.8
.?
F.R
..A.A
. 4
.2.
Hom
og.
1.2
.5.
rU:t
!tic
. OJ
t 2
.2.1
.1.2
.
Hg
Bio
R..
58
? S
ulp
ha
-2
.2.1
.1.1
. R
educ
.. Sn
.C£.
2 3
.8.
F.R
..A.A
. 4
.2.
rU:t
!tic
. O
ft 2
• 2 •
1 • 1
• 2 •
Hg
Bio
R..
3 7
Hom
og.
1.2
.5.
H2S
04
2.2
.1.2
. R
e.du
c. •
Sn.C
R. 2
3
.8.
F.R
..A.A
. 4
.2.
+V
ox.
Hg
Bio
R..
11
FJte
.e.z
ing
1.2
.2.
Su
lph
a-
Hom
og.
1.2
.5.
rU:t
!tic
.,
2.2
.1.4
.4.
Re.
duc.
.Sn.
S04
3
.8.
F.i.
A.A
. 4
.2.
KMn0
4
Hg
Bio
i.
75
Hom
og.
1. 2
. 5.
S
ulp
ha
-rU
:t!t
ic.,
2
.2.1
.4.4
. R
educ
.. Sn
.SO
4
3.8
. F
.i.A
.A.
4.2
. KM
n04
Hg
Bio
i.
78
? H
2S04
, 2
.2.1
.4.5
. R
e.du
c.. S
n.C
i2
3.8
. F
.i.A
.A.
4.2
. KM
n04
Hg
S ed
i.m.
( tiv
e!Z. }
62
?
H2S
04
' 2
.2.1
.4.5
. R
edu.
c.. S
n.C
i2
3.8
. F
.i.A
.A.
4.2
. KM
n04
Hg
S ed
i.m.
( tiv
e!Z. }
45
Lo
w t
0 1
.2.2
. S
ulp
ha
-rU
.:t/r.
A_c.
' 2
.2.1
.4.6
. R
e.du
.c..?
3
.8.?
F
.i.A
.A.
4.2
. K
Mn0
4,
K2S
208
. I.
----
----
----
----
----
----
---
----
----
----
---
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
--EL
EMEN
T M
EVIU
M
REFE
RENC
E PR
E-TR
EATM
ENT
VEST
RUCT
ION
SEPA
RATI
ON
MEA
SURE
MEN
T
----
----
----
----
----
----
---
----
----
----
---
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
--
Hg
Rio
t.
41
? H
2S04
2
.2.1
.5.2
. R
educ
..?
3.8.
? F
.t.A
.A.
4.2
. +
H
202
Hg
Rio
t.
61
? H
2S04
2
.2.1
.5.2
. R
e.du
c..?
3.
8.?
F.t
.A.A
. 4
.2.
+
H20
2
Hg
B.io
l. T
32
FJ
te.e
.zing
1
.2.2
. H
2S04
2
.2.1
.5.3
. R
educ
.. Na
BH 4
3
.8.
F.t
.A.A
. . I
+
H20
2 4
.2.
Hg
Se.d
-iln.
50
VJ
ty-i..n
g 1
.2.4
. HN
03
2.2
.1.6
.1.
Red
uc..?
3.
8.?
F.t
.A.A
. 4
.2.
Hom
og.
1.2.
5.
Hg
Riv
e/1.
. an
d 16
A
c.id
. 1
.1.2
. A
nion
Jte
-bin
3
.1.2
. C
oloi
L-im
. 4
.3.
.6 e.a
. «X
tt e
ll
TJta
c.ell
1.1.
4 •
V -U
:h-(_
zo ne
. 3
.2.5
.
Hg
B.io
l. 81
H
omog
. 1
.2.5
. Su
lpho
-2
.2.1
.1.2
. V
.U.h
izon
e.
3.2
.5.
Col
o!U
.m.
4.3
. rU
.:tJU
c.
Hg
Bio
i.
12
? Su
lpho
-2
.2.1
.1.1
. C
hlto
ma.
.to •
3.3
. C
oloi
Um
. 4
.3.
rU.:t
JUc.
OJt
2 • 2
• 1 • 1
• 2 •
d-U
:h-(_
zona
te.
Hg
Rio
t. ,
.6 e.d
..im.
14
N e..
u:tlt
o n a
c..t.
1
.2.6
. H
2S04
2
.2.1
.5.2
. V
.iA
UU
. bJto
m.
3.4
. y-
.6pe
.c;tJ
r..om
. 4
.4.
+
H20
2 1.
6o.to
pic.
.e.x
c.h.
3
.5.
. I.
____
____
____
__ [ __
____
____
___
----
----
----
---
----
----
----
----
----
----
----
----
----
----
--EL
EMEN
T M
EVIU
M
REFE
REN
CE
PRE-
TREA
TMEN
T D
ESTR
UC
TIO
N
----
----
----
----
----
----
---
----
----
----
---
----
----
----
----
----
----
----
----
----
----
--
Hg
1 R
iot.
, ;.,
e.cLi.
m.
6.2
,6
.3,
Ne.
ut!t
on
ac.t
. 1
.2.6
. ?
6.5
:to
6.8
F Jt
e. e. z
ing
1
.2.2
. Hg
1 B
ioi.
I
59
1 H
omog
. 1
.2.5
. W
et M
hin
g
? Ne
.uJJ
r..on
ac
.t.
1.2
.6.
Hg
1 B
ioi.
I
22
FJt
e.e.
zing
1
.2.2
. W
et M
hin
g
? I
Ne.
ut!t
on
ac.t
. 1
.2.6
.
Hg
1 B
iol.
, ;.,
edim
. I
76
I V
Jtyi
ng
1.2
.4.
H2S
04
2.2
.1.5
.2.
N e.
ut!t
o n
act.
1
.2.6
. +
H
202
A;.,
I Wa.
.te!t
I 41
I
Fil
VL
. A
c.id
. 1
.1.1
. I
1.1
.2.
A;.,
I Bio
i.
I 1
I Lo
w t
0 I
Su
lph
a-
2.2
.1.1
.2.
1.2
.2.
nit
!t' -<-C
.
A;.,
Bio
i. ,
;., e
.dim
. 41
?
I ?
A;.,
Sed.
im.
62
VJt
ying
1
.2.4
. I
Hom
og.
1.2
.5.
----
----
----
----
----
--1-
----
----
----
----
----
-SE
PARA
TIO
N
MEA
SURE
MEN
T
----
----
----
----
----
----
----
----
----
----
----
V-<
At)
1(. b
ltom
. 3
.4.
I cA
Jz.
4. 4
. I;
.,oto
p-ic
. e.
xc.h
. 3
.5.
Y -
;.,pe
. om
.
V-L
6t)1
(.
3.4
. I
c.:tA
I;
.,oto
pic.
e.
xc.h
. 3
.5.
Y -
;.,pe
. om
. 4
.4.
I V
-L6t
)1(.
3
.4.
I y
-;.,p
e.c.
t!to
m.
4.4
.
V-L
6t)1
(. c
.hlo
Jt.
3.4
. I
S -c.ou~y
4.4
.
P!t
e.u
pU
. 3
•1·7
. I
c l!
t.
4.3
. R
e.du
c.. A
J.> H
3 3
.9.
0 0
-<.m
.
Redu
c..AJ
.>H
3 3
.9.
Col
oJti
m.
4.3
.
Re.d
uc..A
J.>H
3 3
. 9.
Col
oJt.i
m.
4.3
.
I Re
.duc
..AJ.>
H3
3 • 9
. I
C ol
oJU
.m •
4.3
.
. I.
.c: 0
----
----
----
----
----
----
---
----
----
----
---
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
--EL
EMEN
T M
EVIU
M
REF
EREN
CE
PRE-
TREA
TMEN
T VE
STR
UC
TIO
N
SEPA
RAT
ION
M
EASU
REM
ENT
----
----
----
----
----
----
---
----
----
----
---
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
--
Cu
Bio
i.
Low
t0
1.2
.2.
Su
lph
o-
2.2
.1.1
.2.
A.A
. 4
. 1
• ni
:t!U
..c.
Cu
Bio
i.
32
Low
t0
1.2
.2.
H2S
04
2.2
.1.5
.3.
A.A
. 4
. 1.
+
H20
2
Cu
R-iv
eJL
tOO
..ieJt
30
.2.
Fil
.tlt
. 1
.1.1
. C
oiot
r.l.m
. 4
.3.
HN03
+
A
.A.
4.
1.
Cu
S ec
l-im
( JL
.iv e
ll )
30.
1.
VJty
-i.ng
1
.2.4
. H
2S04
+
2
.2.1
.1.5
. ?
c.o io
!t-im
• 4
.3.
HC
i04
oJt
Cu
Bio
i.
3 0. 3
. VJ
ty-i.
ng
1.2
.4.
Low
t0
2.2
.2.
? Q
oioJ
t-im
. 4
.3.
Mh
-in
g
F S
oil
64
? Ac
.-i.d.
2.2
.1.6
.1.
? Sp
e.c.
-i.6-
ic.
e.le
.c.V
tod
HN
03
+
Mn
But
i:e!
t 34
N
eJ.J.
Vto n
a.c
.t.
1.2
.6.
HC
i04+
2
.2.1
.1.5
. P
Jte
.up
li. M
nO 2
3
.1.2
. y-
.6pe
.c..t
ltom
. 4
.4.
H2S
04
Pb
Bio
i.
32
Low
t0
1.2
.2.
Cal
c..
2.2
.2.
? A
.A.
4.
1 •
./.
r---
----
----
---
----
----
----
---
----
----
---
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
---
----
----
----
----
----
-EL
EMEN
T M
EVIU
M
REF
EREN
CE
PRE-
TREA
TMEN
T D
ESTR
UC
TIO
N
SE
PA
RA
TIO
N
MEA
SURE
MEN
T
----
----
----
----
----
----
---
----
----
----
---
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
---
----
----
----
----
---
Pb
&W
l.
58
? C
alc.
. 2
.2.2
. L
iqu
-id
-3
.2.1
.2.
A.A
. 4
. 1
• liq
uA..d
ex
..tlta
c:ti.
.on.
Su
iph
o-
L{.
q.-
Pb
&W
l.
Low
t:.0
7.2
.2.
ni..tJ
L.,L
c. 2
.2.1
.1.2
. 3
.2.1
.1.
Col
o!U
.m.
4.3
. OI
L c.
a.ic
.-i.n
• 2
.2.2
. L
Lq.
exbt
ac.t:
..
Zn.
&W
l.
32
Low
t:.0
1.2
.2.
Ca
lc..
2
.2.2
. ?
A.A
. 4
. 1.
Zn.
Bu.
t:te!
t 34
N
eu.-t
lr. on
. a
d.
1.2
.6.
y-.6
pec.
tltom
. 4
.4.
Mn,
Zn
R-iv
. un.
teJt.
15
Ac.
i..d.
1
.1.2
. A
.A.
4.
1.
Su
lph
o-
Liq
.-C
d, P
b &
i..ol
. 41
?
nitA
-i.e
2
.2.1
.1.2
. U
q. ed
Jla.
c. •
3.2
.3.
A.A
. 4
. 1.
+
H
202
2.2
.1.1
.4.
Cu
,Fe
,Mn
, F
il.i:
!t.
1.1
.1.
Liq
.-S
ea
un.te
Jt
21
Low
t:.0
1.1
.3.
3.2
.4.1
. A
.A.
4.
1.
N-i,
Pb
A
c.i.d
. 1
.1.2
. L-
i.q.
ex~c
..
./.
:~;~~~~:
:::::1:~
~~~~::::
::1:~~~~
~~~:::1:
~~~~~~~~
~:::::::
: ----
----
----
----
----
------------------------~----------------------
DES
TRU
CTI
ON
SE
PAR
ATIO
N
MEA
SURE
MEN
T
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
----
--A
g,
Cd,
Zn
I S e. a
«n.
teJL
Cd
,Co
,C!t
,Cu,
R
iv . «
n.te
.JL
Fe
.,N
i,Pb
Cd,
Co,
Cu,
Fe, lwat~
Mn,
Ni,
Pb,
Zn
Cd,
Pb,
Zn
Cd,
Pb,
Zn
Cd,
CJL
,Cu,
P
b,Z
n
Cu,
Fe.
,Mn,
N
i,
Zn
I Bio
i.
Bio
i.
Se.d
-Un.
SU-6
p. m~elt
FiU
/t.
I 21
I
Low
~o
Ac.
id.
75
Ac.
id.
1 4
1.
16
1
C en
:t/1..<
.6 •
Ac.
i.d.
Oxid
ati
on
I 79
Lo
w ~
o
I V
Jtyi
ng
20
Low
t0
VJL
ying
62
VJL
ying
H
omog
.
21
?
1.1
.1.
1.1
.3.
1.1
.2.
1.1
.2.
1.1
.1.
1.1
.2.
1.1
.4.
1.2
.2.
HN
03
+
1.2
.4.
HC
i04
+
H2S
04
1.2
.2.
HN
03
7 .2
.4.
1 • 2
. 4.
I H
N03
1
.2.5
.
HC
i +
H
202
Liq
.-U
q •
ex.tn
ac. .
Liq
.-Li
q.e.
x.V
tac.
.
Liq
.-U
q.e
.xV
tac.
.
2.2
.7.7
.5.1
2.2
.7.6
.7.1
2.2
.7.6
.7.1
2.2
.1.6
.1.
3.2
.4.1
.1
A.A
. (T
a bo~)
4.
1 •
3.2
.4.1
.1
A.A
. 4
. 1
•
3.2
.4.2
.1
A.A
. 4
. 1
•
? I
A.A
. 4
. 1
•
? I
A .A
. 4.
1.
? I
A.A
. 4
.l.
? A
.A.
4.
1.
./.
c..n
------------------------------------------~----------------------,----------------------~-------------------·-------------------------
ELEM
ENT
I M
EVIU
M
I R
EFER
ENC
E I
PRE-
TREA
TMEN
T I
DE
STR
UC
TIO
N
I S
EP
AR
ATI
ON
I
MEA
SUR
EMEN
T
----
----
----
----
----
----
---·
----
----
----
-· -
----
----
----
----
----
-·--
----
----
----
----
----
·---
----
----
----
----
---·
----
----
----
----
----
--A
g ,C
d, P
b Su
.6 p
. ma.
.tteJ
L 21
?
Cd
,Pb
,Zn
I
Sed-
i.m.
I 79
I
VJt
yin.
g
Me:
to.i.
A I
Se.d~.
I 53
Lo
w :
t0
I Vl
llJ in
g
• I
1 Lo
w :
t0
He.
avy
me.t
a.t6
~ B
ioi.
21
V
!tyi
ng
Cu,
Fe,
Mn,
1
Bio
i.
I 61
I V
Jtyi
ng
Ni,
Pb,
Zn
1-fo
mog
.
Cd,
Cu,
F e,
Mn,
I A
i.ll.
pa!r
...tic
. P
b,V
,Z
n
• I
63
I ?
Me:
to.i.A
( o
:theJ
t th
an
I A
i.Jr..
pa!t
ti.c.
. I
43
I N
e.u.
tlto
n a.
c.:t.
C
d,N
-i,P
b )
I I
I
HC
i +
H20
2
1.2
.4.
I H
F+H
Ci0
4
1•2
•2•
I H
F+H
Ci0
4 1
.2.4
.
1. 2
. 2. I H
N03
+
1.
2. 4
. H
Ci0
4
1. 2
. 4.
I C
al.
1.2
.5.
c..
I C
ai.c
..
7.2
.6.
I I
2.2
.1.6
.1.
2.2
.1.6
.2.1
2.2
.7.6
.2.1
2.2
.7.3
.1
2.2
.2.1
2.2
.2.1
? I I
? A
.A.
(Ta.
boa.
:t)
4.
1.
? I
A.A
. 4.
1.
? I
A.A
. 4
. 1.
? I
A.A
. 4
. 1.
? I
A.A
. 4.
7.
? I
A.A
. 4
. 1.
? I
y-.6
pe.c
tltom
. 4
.4.
I ./
.
IJ'
N
----
----
----
---
----
----
----
----
----
----
---
----
----
----
----
----
ELEM
EMr
MEV
IUM
R
EFER
ENC
E PR
E-TR
EATM
ENT
----
----
----
---
----
----
---
----
----
----
---
----
----
----
----
----
Cu,
Pb,
Zn
Riv
. wa.
teJt
25
?
Cd,
Pb,
Zn
I W
a..te.
Jt I
79
I F
il-t
!t.
7.1
.1.
Ac.
id.
1.1
.2.
C d
, C u
, Pb
, Z n
Sea
un.
te.J
t 24
?
Me
:tw
W
ate!
t 32
E
vapo
!t.
1.1
.6.
Me
..tw
I
Bio
i.
I 32
I
V~ty
ing
1.2
.4.
Hom
og.
1.2
.5.
Me,
t.a.i,
6 I
Sed
im.
I 32
I
V~ty
ing
1.2
.4.
Hom
og.
1.2
.5.
Mda
..t6
I M
ine.
Jtal
.6 ,
Sil
ic.a
tu
I 32
I
Cd
,Ni,
Pb
I
A-it
pa
lt.t.
I
43
I ?
----
----
----
----
----
--D
ESTR
UC
TIO
N
----
----
----
----
----
--? . ?
Ca.
lc..W
. 2
.2.2
.
O!t
Ca
.lc.in
. 2
.2.2
. H
omog
. 1
.2.5
.
HF
2.2
.1.6
.3.
Ca.
lc..{
n.
2.2
.2.
I ?
I ----
----
----
----
----
----
----
----
----
----
----
-S
EP
AR
ATI
ON
I
MEA
SUR
EMEN
T
----
----
----
----
----
----
----
----
----
----
----
Ca.
t. !te
A in
3
.1.1
. A
.A.
4.1
o!t P~e.
Pol
alr..
. 4
.5 •
Ca
t. Jt
e.-6-
Ut.
3.1
.1.
Po
la!t
o.
4.5
.
Cat
.Jte
.-6-in
. 3
.1.1
. Pu
£.,6 e
. po
R..a
lto •
4
.5.
UV
-.6p
e.ct
lt.
4.6
. OI
L X
-ILa
lj 6l
. 4
.1.
UV
-.6pe
.c:tJ
L.
4.6
. OI
L X
-Jr..
a.tj
6l.
4.1
.
u v-.6
p e.
c.Vt •
4
.6.
O!t
X-J
tay
6l.
4.1
.
uv-.6
pe
.ctlt
. 4
.6.
OIL
X-!
talj
6l.
4.1
.
? I
X-IL
alJ
6l.
4.1
.
<..rt
~
Met;~:d
i~~~il
l-~:-
·:'~
~a:~
p.te
ll •
AA
I 81
____
___ j
____
_
Cct
. 8.
5
It/A
1 10
0
Pc.e.
2
t:V
7. 5
X
_____ j
___ _
All
Sa
98 2
100
ee
T A
8
L E
3
.
App~oximate pe~centage~
d.i6
6 e~ent
o6 ~amp!e~ mea~u~ed
met
hod4
8.i
B
8ll
Cd -~:
T~:-
Cu
F
Fe
Pb
l.fn
1 oo I
7 o
o 81
14
I
80
83
61
93
90
IS
2.5
6 25
0.
5
7 00
12. 5
I
77
2.5
1
6 6
4
by
the
Hg
Mo
92
0.1
111.
5
I 72
.5
15
0.1
I 9
12.5
0.
251'
2.5
10
10.1
<0.
1 0.
1 <
0.1
N.i
Se
Ag
93
100
15
25
1
0 .1
·
Sic. ~:
-F~-
100.
1
----·-
-----
-
90
10
100
-t ,.. m
r- "" \N
v Zn
z.t
3.51
8-1
91
6 s
5.51
51
10
0 I
____
., ___
.... ___
_ ~
____ . _
_____ _
_j
V"'
~
A PPENV IX
·················===
METHYL- MERCURY IN FISH .
The method~ u~ed 6o~ the dete~mination o6 methyl-me~~UAy in 6~~h a~e de~ivation~ o6 the We~too method (85) . The method ha~ been ~tanda~dized by the No~di~ Committee on Food Analy~~~ (86) .
, The methylme~eu~y in the homogenized ~ample i~ libe~ated 6~om the p~otein~ by hyd~oeh£o~ie aeid,and the methylme~eu~y ehlo~ide 6o~med i~ ext~aeted with benzene. Fat~, pho~pholipid~, and lipop~otein~ a~e eo-ext~aeted into the benzene pha~e . The methylme~eu~y i~ 6u~the~ i~olated by ext~aetion with a wate~ ~olution o6 ey~teine ~lightly a~idi6ied with a~eti~ aeid . Exee~~ o6 hyd~o~hlo~ie aeid i~ added and methylme~eu~y ehlo~ide i~ ~e-ext~aeted into benzene. The benzene ext~aet i~ d~ied and analy~ed u~ing a ga~ eh~omatog~aph with eleet~on ~aptu~e deteeto~ " .
The ~en~itivity i~ o6 the o~de~ o6 0,02 mg methylme~eu~y pe~ kg 6i~h.
Re~ult~ have been given 6o~ methyl-me~eu~y by 6ou~ autho~~
oney (6.4, 6.1, 6.8, 69).
55
R E F E R E N C E S .
(7) VONOVAN,P.P., Publi~ Analy~t·~ Labo~ato~y, Galway Regional Ho~pital, Galway ,!~eland .
(2) HTLL,F., Citlj Labo~ato~y, Vublin, !~eland .
(3) TO NUZZOLTLLO,F., Limite di eontaminozione dame~~u~io dei p~odotti itti~i.
( 4)
( 5)
Mini~te~io della Sanita, Vi~ezione gene~ale pe~ l'igiene degli alimenti e la nut~ozione, Viv.TV bi~, Roma, Italy .
H20 ~ (7913) 2.
H20 ~ (7913) 73.
(6) Kwik in het Nede~land~e milieu, TNO-nieuw~ 26 (7917).
(6. 7.) FONVS ,A.W., Me~~u~y in Vut~h Su~6aee Wate~~~ p.315.
(6.2.) VE GOEIJ,J.J.M., ZEGERS,C., VE GROOT,A.J., Me~~u~y in the Sediment~ o6 the Rive~~ Rhine and Em-6, p.318.
(6.3.) HETVTNGA,M.C., KOEMAN,J.M., VE GOETJ,J.J.M., ZEGERS,C., VERWEY,J.P.M., VAN VRTEL,W., VE GROOT,A.J., The A~~umulation o6 Me~~u~y in the Winte~-bed o6 the Rhine, p.382.
56
(6.4.) ROSKAM,R.Th., Me~~u~y in Fi~h-Vut~h F~e~h Wate~ Fi-6he-6, p.390.
(6.5.) GROVE,P.A., WI,S.L., Me~~u~y in Fi~h-Tota.l Content in F~e-6hwa.te~ and Ma~ine Fi-6he-6, p.395.
(6.6.) VE GOEIJ,J.J.M., ZEGERS,C., Me~~u~y in Fi~hTmpo~ted Tinned Fi~h, p.400~
(6.1.) KOEMAN,J.H., CANTON,J.H., WOUVSTRA,A., PEETERS,W.H.M., VE GOETJ,J.J.M., ZEGERS,C., VAN HAAFTEN,J.L., Me~~u~y in the Vut~h Litto~al Envi~onment, p.402.
(6.8.) FUCHS,P., VE VOS,R.H., ZWTERS, J.H.L., Me~~u~y in Owl~ and Bi~d-6 o6 P~ey, p.413.
. I .
s'!if .·
(1) SCHULLER,P.L., VERJAAL,A.J., v.BEKKUM,W.,.SMITS,C.A.W., TOLSMA,K., Ond~~zo~R naa~ h~t g~halt~ aan kwik ,load ~n cadmium in va~R~n~ni~~~n,~und~~ni~~~n ~n kipp~l~v~~~. RijR~ In~tituut voo~ d~ VolR~g~zondh~id, Int~~im ~appo~t no. 159112 LCLO. Ond~~zo~R g~v~aagd doo~ d~ V~t~~inai~ Hoo6din~p~et~u~ d ~ M 0 OR , A • G •
(8) VAESSEN,H.A.M.G., BREMER,H.C.R., A~~~~ng~halt~ ~n d~ ni~~ van h~t va~R~n ~n h~t ~und . RijbJ.>iM:tituut voo~ d~ VolR~g~zondh~id , 1nt~~im ~appo~t no.169l12 LCLO. Ond~~zo~R g~v~aagd doo~ d~ V~t~~inai~ Hoo6din~p~et~u~ d~ MOOR, A.G.
(9) HANSEN ,P., Labo~atoi~~ d~~ ~aux, 1n~titut d'Hygien~ ~t d~ Sant~ publiqu~, Lux~mbou~g. AnalyJ.>i~ mad~ by th~ Labo~ato~ium d~~ Ruh~v~~band~~~ E ~ ~ ~n •
( 70) HANSEN, P., Labo~atoi~~ d~~ Eaux, 1n~titut d'Hygien~ ~t d~ Sant~ publiqu~, Lux~mbou~g.
(77) THIBAUT ,Y., Labo~atoi~~ d~ Chimi~ analytiqu~ d~ l'In~titut J.>ei~nti6iqu~ ~t t~ehniqu~ d~~ Peeh~~ ma~itim~~, 44- Nant~~,F~ane~.
(72) WENNING,M., Labo~atoi~~ d~~ d~n~~~~ alim~ntai~e~, In~titut d'Hygien~ ~t d~ Sant~ publique,Lux~mbou~g .
(73) Math~matieal Mod~l o6 Pollution in th~ No~th Sea. Commi~~ion int~~mini~t~~i~ll~ de la Politiqu~ ~eienti6iqu~, B~u~~~l~, B~lgium . T~ehnieal ~~po~tJ.> :
( 1 3 • 7 ) G 1 L LA 1 N, 7 911 - C him. ( 73.2} G1LLAIN, 1911I03-Chim.04. (73.3) G1LLA1N, 1912I01-Chim.05. (73.4) GILLAIN, 1912103-Chim.OJ. (73.5) G1LLA1N, 19111Seh~ldt-Chim.05. ( 1 3 • 6) GIL LAIN, 1 912 IS e h ~ldt-C him. 0 3 • (13.1} ELSKENS, 1911101-02-Chim.Ol. (73.8} ELSKENS, 19121Seh~ldt-03-Chim.01.
. I .
(74) Mathematical Model o6 Pollution in the ~ive~ Samb~e. Commi~~ion inte~mini~te~ielle de la Politique ~cienti6ique, B~u~~el~, Belgium. Technical ~epo~t~.
MULKENS, PIRON, BAUGARV,LACOURT,LOQUET.
MS/08-12/C4-001 MS/09-12/C4-008 MS/10-12/C4-009 MS/10-12/C4-011
(75) Invento~y o6 pollutant~ o6 ~u~6ace wate~~. Commi~~ion inte~mini~te~ielle de la Politique ~cienti6lque, B~u~~el~, Belgium.
Rappo~t de ~ynthe~e, nov. 1912. Rappo~t annuel 1912.
In~titut de Reche~che chimique and In~titut d'Hygiene et d'Epidemiologie.
(76) BURTON,J.V., LEATHERLANV,T.M., Me~cu~y in a Coa~tal Ma~ine Envi~onment, Nat u~ e ill 6 ( 1 9 11 ) 4 4 0 .
(11) VAVIV SMITH,J., NICHOLSON,R.A., MOORE,P.J., Me~cu~y in Wate~ ofi the Tidal Thame~, Natu~e 232 8 (1911)393.
58
(18) FOUASSIN,A., Le me~cu~e dan~ le~ poi~~on~ et c~u~tace~ du ma~che beige . Etude ~ub~idiee pa~ l'In~titut belge de !'Alimentation et de la Nut~ition(IBAN) ala demande du Mini~te~e de la Sante publique, 1912.
(79) BUTTERWORTH,]., LESTER,P., NICKLESS,G., V~6t~ibut~on o6 Heavy Metal~ in the Seve~n E~tua~y, Ala~. Po li. Bu ii. 3 5 ( 1 91 2 ) 1 2 .
(20) NICKLESS,G., STENNER,R., TERRILLE,N., Vi~t~ibution o6 Cadmium,Lead and Zinc in the B~i~tol Channel, Ma~.Poll.Bull., 112 (7912) 188.
(27) PEVEN,J.V., CROTHERS,J.H., WATERFALL,C.E.,BEASLEY,J., Heavy metal~ in Some~~ et Ma~ine O~gani.6m~, . Ma~. Poll. Buii. i 1 ( 1 913) 1 .
( 22) Vani~h I~otope Cente~
. I .
(23) Meftc.ufty in Fi~h, 1968-1912, Va.ni~h I~o.tope Cen.teft.
( 2 4) A BV U L LA H, M. I. , R 0 Y L E, L. G. , MORRIS, A. W. , Heavy metal c.onc.en.tfta..tion in Coa.~.ta.l Wa.teft~, N a. .tuft e 2 3 5 7 ( 1 9 1 2 ) 1 5 8 .
( 2 5 ) A BV U L LA H, M. I. , R 0 Y L E, L. G. ,
59
Heavy metal c.onten.t o6 ~orne ftiveft~ and lake~ in Wale~, N a. .tuft e 2 3 8 8 ( 1 9 1 2 ) 3 2 9 •
(26) ELVERFIELV,H., THORNTON,L., WEBB,J.S., Heavy Metal~ and Oy~.teft Cul.tufte in Wale~, M aft . Po ll . Bull . 2 3 ( 1 9 11 ) 4 4 •
(21) PRESTON,A., JEFFERIES,V.F., VUTTON,J.W.R., HARVEY,B.R., STEELE,A.K., Bfti.ti~h i~le~ c.oa.~tal wa.teft~ : The c.onc.en.tfta..tion o6 ~elec.ted heavy metal~ in ~ea. wa.teft, ~u~pen~ed ma.t.teft an biologic.a.l indic.a.toft~ - A pilot ~uftvey.
(28) Woftking Pa.ftty on .the Moni.tofting o6 Food~.tu66~ 6oft Meftc.ufty and Otheft Heavy Metal~ - Fift~.t Repoftt. Suftvey o6 Meftc.ufty in Food . Heft Ma.je~ty'~ S.tationa.fty 066ic.e,London,1911.
( 28a.) Idem- Re~ult~ inc.luded by c.ouft.te~y o6 .the A~~oc.ia.tion o6 Public. Ana.ly~.t~.
( 29) Woftking Pa.ftty on the Moni.tofting o6 Food~.tu66~ 6oft Heavy Metal~ - Sec.ond Repoftt. Suftvey o6 Lead in Food. Heft Ma.je~ty'~ S.ta..tiona.fty 066ic.e, London, 1912.
( 3 0 ) TN 0 - N i e uw ~ 2 1 9 ( 1 9 1 2 ) .
(30.1.) VE GROOT,A.J., ZSCHUPPE,K.M., Coppe!t in Vutc.h Velta., p.431.
(30.2.) BROUWER,W., VAN HOOVEN ,J.A., Rec.oftding~ o6 the c.oppeft c.onten.t o6 ~orne wa.teftwa.y~ deteftmined by mean~ o6 c.on.tinuou~ a.na.ly~i~, p.444.
( 3 0 . 3 . ) V INK, G . J . , Cop p eft in 6 i~ h , p. 4 9 3 •
(30.4.) VE WOLF,P., LEWIS,W.E., A monitofting ~y~tem 6oft heavy metal~ along .the Vu.tc.h c.oa.~.t, p.504.
. I .
(37) CUMONT,G., VIALLEX,G., LELIEVRE,H., BOBENRIETH,P., Contamination de~ poi~~on~ de me~ pa~ le me~cu~e Revue inte~nationale d'oceanog~aphie medicate , Nice, XXVIII (1912) 95.
60
(32) HERMAN,P., In~titut de ~eche~che~ chimique4,B~u~~el~, Special ~epo~t 6o4 E.C.C.
(33) KOEMAN,J.M., VINK,J.A.J., VE GOEIJ,J.J.M., Cau~e~ o6 mo~tality in bi~d~ o6 p~ey and owl~ in the Nethe~land~ in the winte~ o6 1968-1969, A~dea ll (7969) 61.
(34) VE GOEIJ,J.J.M., KROON,J.J., ZEGERS,C., Bepaling van ~po~en mangaan en zink in bote~ met behulp van active~ing~analy~e , I.R.I ~appo~t 133- 10- 03- Inte~unive~~itai~ ~eacto~ in~tituut, Vel6t.
(35) Ak~o analy~i~ ~epo~t .
(36) Unpubli~hed ~e~ult~, Onde~zoek VINK,G.J., Cent~aal lab.TNO, Vel6t.
( 31) Nede~land~e Bote~contJtole~tation~ .
(38) The Nethe~Rand~,ContJtole~tation~ vooJt Melkp~odukten.
(39) The NetheJtland~, GcldeJt~ -OveJtij~el~e Zuivelbond.
(40) SCHULLER,P.L., Rijk~in~tituut voo~ de Volk~gezondheid. The NetheJtland~,LaboJtatoJtium vooJt Leven~mlddelenondeJtzoek.
(47) MINVERHOUV,A., Idem.
( 4 2) PREST ON, A., Heavy Metal~ ,i_n BJt-itiJ.> h wateJr ~, Natu~e 242 Ma!tch (7913) 95.
(43) PEIRSON,V.H., CAWSE,P.A., SALMON,L., CAMBRA-Y,R.S., TJtace Element~ in the Atmo~pheJtic Envi~onment, Na.tuJte 241 1 (1913) 252.
. I .
(44) BANAT,K., FORSTNER,U., MULLER,G., S~hwe~metalle in Sedimenten von Vonau,Rhein,Em~, We~e~ und Elbe ~m Be~eich de~ Bunde~~epublik Veut~~hland, Natu~wi~~en~cha6ten ii (1972) 525.
(45) QUENTIN,H., In~titut 6u~ Wa~~e~ Te~hn.Unive~~itiit, Mun~hen.
(46) In~titut nii~ Wa~~e~-, Boden- und lu6thygiene de~ Bunde~ge~undheit~amt, Be~lin - Vahlem.
(41) RuhltveJtba.nd, Ruh~tal~pe~~enve~ein, Chemi~che~· u.hd. Biologi~ehe~ Labo~ato~ium, E~~en.
( 48) Bunde1>an~talt 6u~ Gewa~~e~kunde, Koblenz.
( 4 9) G e~ ell~ eha6 t 6 u~ K e~n6 o~~ ehung, Ka~l.o~uhe.
(50)
( 5 1 )
Baye~i~~he Biologi~~he Ve~~u~h64n.otalt.
Hygiene In.otitut de~ Joh.Gutenbe~g Unive~.oitit, Mainz.
(52) F~eie Han~e~tadt B~emen, Wa.o.oeJtwiJtt.o~ha6t.
(53) Veut~~he~ hydJtog~aphi~che~ In.otitut.
61
\'
(54) La.nde.oa.n.ota.lt 6u~ Gewii.o.oe~r.ku.nde u.nd Gewii.o.oe~r..ochu.tz NW~
(55) VeJr..ochiedenen chemi.oche Unte~.ou.~hu.ng.oa.n.ota.lten in de~ BRV.
(56) Ba.ye~r.i~che~ La.nde~a.mt 6u~ Unwelt.ochu.tz.
(57) In~titut 6u~ Bodenku.nde delL Teehni.ochen UniveiL.oitiit Be~lin.
(58) Bu.nde~6o~~chu.ng~an~talt 6uiL Get~eideve~a.Jtbeitu.ng, s~hutzenbe~g.
. I.
(59) In~titut 6~~ St~ahlenteehnologie de~ Bunde~6o~~ehung~an~talt 6~~ Leben~mittel6~i~ehhaltung, Ka~l~~uhe .
(60) Bunde~an~talt 6u~ Flei~eh6o~~ehung,Kulmbaeh.
(67) VIETZ, Vie An~eiehe~ung von Sehwe~metallen in ~ubme~~en P6lanzen, GWF - Wa~~e~ /Abwa~~e~ 113 (1912) H.6,269.
(62) Gemein~amen Komitee Flen~bu~ge~ Fo~de, Vandkvalitet~in~titutet,ATV , K~penhavn,Venma~k. ( Vu~ehge6uh~t du~eh FRG).
(63) Unive~~itiit~in~titut 6ii.~ Meteo~ologie und Geophy~ik- Fo~~ehung~au6t~ag Pilot~tation, F~ank6u~t am Main .
(64) BayeJrJtGeologi~he~ Lande~amt, Munehen.
(65) Ge~ell~eha6t 6ii.~ St~ahlen -und Umwelt6o~~ehung m.b.H, Mii.nehen- Neuhe~be~g.
(66) GARVNER,V., RILEY,J.P., Vi~t~ibution o6 Vi~~olved Me~eu~y in the I~i~h Sea, N atu~ e 2 4 1 ( 1 913 ) 52 6 •
(61) CHESTER,R., GARVNER,V., RILEY,J.P., STONER, J., Me~eu~y in Some Su~6aee Wate~~ o6 the Wo~ld Ocean, Ma~. Poll. Bull. 4 2 (7913) 28.
(68) ASTON,S.R., BRUTY,V., CHESTER,R., PAVGHAM,R.C., Me~eu~y in Lake Sediment~ : a Po~~ible Indieato~ o6 Technological G~owth , NatuJt e 2 4 1 2 ( 1 913) 4 50.
(69) Wo~king Pa~ty on the Monito~ing o6 Food~tu66~ 6o~ Heavy Metal~, Thi~d Repo~t . Su~vey o6 Me~eu~y in Food : A Supplementa~y Repo~t. He~ Maje~ty'~ Stationa~y 066iee , London 1913.
(10) Wo~king Pa~ty on the Monito~ing o6 Food~tu66~ 6o~ Heavy Metal~,FouJtth Repo~t. Su~ve~ o6 Cadmium in Food. He~ Maje~ty'~ Stationa~y 066iee, London 1913 •
. I .
62
(10a) Id~m-Re~ult~ i~~lud~d by cou~t~~y o6 th~ City o6 B~i~tol Public A~aly~t.
(77) REYNOLVS,C.V., REYNOLVS,E.B., J.A~~.Publi~.Anal. 9 ( 1 9 1 1 ) 1 1 2 •
(72) GOLWER,A., SCHNEIVER,W., B~la~tu~g d~~ Bod~~~ u~d d~~ u~te~i~di~~he~ Wa~~e~~ du~~hSt~a~~~~v~~k~h~, GWF - Wa~~e~/Abwa~~e~ lli (7973) H.4, 154.
(73) RIEVER,W., SCHWERTMANN,U., Kup6e~a~~~i~h~~ung in hop6~ng~nut~ten Boden de~ Halle~tau, La~dwi~t~~ha6tli~he Fo~~~hung ~ (7972) H.2, 110. .
(14) VE GOEIJ,J.).M., Automat~d ~~pa~atlon~ in ~outine a~tivatio~ ~haly~l~ o6 m~~~u~y, 2d Symp~~ium dn the ~~~ent d~v~lopm~nt~ in ~eut~on analy~i~, Camb~idg~ (7977).
(75) JOFFUS,M.T., ELKINS ,J.s., KENNER,C.T., v~t~~minat~on o6 m~~~u~y in biologi~al mate~ial, J.o6'AOAC. 53 6' (7970) 1112. .
(76) FONQS,A.W., VAN VEN ESHOF,A.J., Bepaling van ~po~en lood; ko~~~~ zihk, ~admium, nikk~l, kobalt, mangaan e~ ijze~ i~ wate~ d.m.v. gelijktijdige ext~a~tie
63
~n atoomab~o~~ie~p~~kt~ophotomet~ie,H20! 78 (7913)465.
(11) Analyti~a~·Method~ Committ~~, The det~~mination o6 fc.ad, Analy~t !j_ (7959) 727.
( 18) AHaiyti.~al Mvthod~ Committee, Note~ on pe~~hlo~i~ ac~d and it6 handli~g in analyti~al wo~k, Anal y ~ t -~ ( 1 9 5 9 ) 2 1 4 .
(79) Analytical Method~ Committ~e, The dete~mination o6 ~mall.amount~ o6 a~~~nic i~ o~gani~ matte~! A naly 6 t ~2 ( 7 9 6 o ) 6 2 9 •
(80) Analyti~al Method~ Committ~~,Method~ 6o~ th~ de~t~u~tion o6 o~gani~ matte~, Analy~t 85 (7960) 643.
. I .
(87) Analytical Method~ Committee, The dete~mination o6 ~mall amount~ o6 me~cu~y in o~ganic matte~, Analy~t J...Q_ (7965) 575.
(82) Analytical Method~ Committee , The u~e o6 50 pe~ cent. hyd~ogen pe~oxide 6o~ the de~t~uction o6 o~ganic matte~, Analy~t i! (7961) 403.
(83) Analytical Method~ Committee, The dete~mination o6 ~mall amount~ o6 cadmium in o~ganic matte~, A naly~ t J.i ( 1 9 6 9) 77 53.
(84) WOIVICH,H., et at., Zeit~ch~i6t 6a~ Leben~mittel U n t e~ ~ u c hung u n d F o Jt ~ c h u n g 1 4 9 1 ( 1 9 1 2 ) •
(85) WESTOO, Ac.ta Chem.Scand. 11_ (7961) 1190.
(86) MethytmeJtc.uJty Compound~.Vete~mination in Fi~h. uvc 541.254.9 : 631.56.N~ 82,2d ed.,7912.
64