Motor Contagion during Human-Human and Human-Robot Interaction
Human Exposure to Antimony. III. Contents in Some Human Excreted Biofluids (Urine, Milk, Saliva)
54
This article was downloaded by: [Laurentian University] On: 06 February 2013, At: 06:36 Publisher: Taylor & Francis Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK Critical Reviews in Environmental Science and Technology Publication details, including instructions for authors and subscription information: http://www.tandfonline.com/loi/best20 Human Exposure to Antimony. III. Contents in Some Human Excreted Biofluids (Urine, Milk, Saliva) Montserrat Filella a b , Nelson Belzile c & Yu-Wei Chen c a Institute F.-A. Forel, University of Geneva, Versoix, Switzerland b SCHEMA, Rameldange, Luxembourg c Department of Chemistry and Biochemistry, Laurentian University, Sudbury, Ontario, Canada Accepted author version posted online: 12 Jan 2012.Version of record first published: 05 Feb 2013. To cite this article: Montserrat Filella , Nelson Belzile & Yu-Wei Chen (2013): Human Exposure to Antimony. III. Contents in Some Human Excreted Biofluids (Urine, Milk, Saliva), Critical Reviews in Environmental Science and Technology, 43:2, 162-214 To link to this article: http://dx.doi.org/10.1080/10643389.2011.604257 PLEASE SCROLL DOWN FOR ARTICLE Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions This article may be used for research, teaching, and private study purposes. Any substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any form to anyone is expressly forbidden. The publisher does not give any warranty express or implied or make any representation that the contents will be complete or accurate or up to date. The accuracy of any instructions, formulae, and drug doses should be independently verified with primary sources. The publisher shall not be liable for any loss, actions, claims, proceedings, demand, or costs or damages whatsoever or howsoever caused arising directly or indirectly in connection with or arising out of the use of this material.
-
Upload
independent -
Category
Documents
-
view
0 -
download
0
Transcript of Human Exposure to Antimony. III. Contents in Some Human Excreted Biofluids (Urine, Milk, Saliva)
This article was downloaded by: [Laurentian University]On: 06 February 2013, At: 06:36Publisher: Taylor & FrancisInforma Ltd Registered in England and Wales Registered Number: 1072954 Registeredoffice: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Critical Reviews in EnvironmentalScience and TechnologyPublication details, including instructions for authors andsubscription information:http://www.tandfonline.com/loi/best20
Human Exposure to Antimony. III.Contents in Some Human ExcretedBiofluids (Urine, Milk, Saliva)Montserrat Filella a b , Nelson Belzile c & Yu-Wei Chen ca Institute F.-A. Forel, University of Geneva, Versoix, Switzerlandb SCHEMA, Rameldange, Luxembourgc Department of Chemistry and Biochemistry, Laurentian University,Sudbury, Ontario, CanadaAccepted author version posted online: 12 Jan 2012.Version ofrecord first published: 05 Feb 2013.
To cite this article: Montserrat Filella , Nelson Belzile & Yu-Wei Chen (2013): Human Exposure toAntimony. III. Contents in Some Human Excreted Biofluids (Urine, Milk, Saliva), Critical Reviews inEnvironmental Science and Technology, 43:2, 162-214
To link to this article: http://dx.doi.org/10.1080/10643389.2011.604257
PLEASE SCROLL DOWN FOR ARTICLE
Full terms and conditions of use: http://www.tandfonline.com/page/terms-and-conditions
This article may be used for research, teaching, and private study purposes. Anysubstantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,systematic supply, or distribution in any form to anyone is expressly forbidden.
The publisher does not give any warranty express or implied or make any representationthat the contents will be complete or accurate or up to date. The accuracy of anyinstructions, formulae, and drug doses should be independently verified with primarysources. The publisher shall not be liable for any loss, actions, claims, proceedings,demand, or costs or damages whatsoever or howsoever caused arising directly orindirectly in connection with or arising out of the use of this material.
Critical Reviews in Environmental Science and Technology, 43:162–214, 2013Copyright © Taylor & Francis Group, LLCISSN: 1064-3389 print / 1547-6537 onlineDOI: 10.1080/10643389.2011.604257
Human Exposure to Antimony. III. Contentsin Some Human Excreted Biofluids
(Urine, Milk, Saliva)
MONTSERRAT FILELLA,1,2 NELSON BELZILE,3 and YU-WEI CHEN3
1Institute F.-A. Forel, University of Geneva, Versoix, Switzerland2SCHEMA, Rameldange, Luxembourg
3Department of Chemistry and Biochemistry, Laurentian University, Sudbury,Ontario, Canada
Humans are exposed to antimony through a variety of natural andanthropogenic sources. Even though the real value of the approachis still uncertain, it has become common practice to use excretedbiofluids (i.e., urine, milk, saliva) to diagnose pollutant exposuredue to the noninvasive nature of sampling these fluids. In this thirdreview of the series on human exposure to antimony, the authorspresent a critical discussion of the available literature, focusing onantimony concentrations in urine, milk, and saliva, while main-taining their three specific objectives: (a) objective evaluation ofpublished data in consideration of the methodology, (b) establish-ment of a range of reasonable values for antimony concentrationsin the biofluids covered in the review, and (c) assessment of the use-fulness of the data in assessing environmental and occupationalexposure. The authors observed that most data collected are notsupported by the analysis of certificate reference materials, a largenumber of papers have reported concentrations that are close to thedetection limit of the analytical techniques used, and recent studiesusing more sensitive techniques report lower concentration values.When these methodological limitations are taken into account, itbecomes difficult to establish a reliable antimony background valuefor human urine from healthy unexposed individuals; though anupper limit of 0.1 μg L−1 can be suggested. Using antimony con-tent in urine appears justified when examining occupational andenvironmental exposure to nearby localized sources (e.g., mines,
Address correspondence to Montserrat Filella, Institute F.-A. Forel, University of Geneva,10 route de Suisse, CH-1290 Versoix, Switzerland. E-mail: [email protected]
162
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 163
smelters) studies, but its usefulness is less clear for assessing theeffect of diffuse pollution. The very limited number of studies onhuman milk and saliva does not allow any solid conclusions to bedrawn.
INTRODUCTION
Human biomonitoring is defined as the direct evaluation of people’s expo-sure to environmental or occupational contaminants by measuring the latteror their metabolites in blood, urine, hair, or other specimens. Biomonitoringdoes not reveal routes of exposure, nor does it provide any insight into thetoxicokinetic processes that take place after the compound’s intake. How-ever, it provides an integrative measure of the internal dose received by anindividual from all routes of exposure in his or her lifestyle; it might this beuseful information, supplementing other types of environmental monitoring.
The approach is based on the hypothesis that, once inside the body,any element is transported and distributed through the blood into organsand, totally or partially, removed from the organism through different ex-cretory pathways, such as sweat, hair, urine, and feces. The trait that theconcentration of an element in the specimen analyzed responded noticeablyto variations in exposure is sought. Blood and urine are the most widelyanalyzed human biofluids.
One of the difficult issues in human biomonitoring is the need to knowreference concentration values (i.e., concentrations that are expected to bepresent in the general population in the absence of occupational exposure)for the different substances of interest. In principle, such reference valuesneed to take into account the wide normal range of concentration exhibitedby the general population, which might include substantial differences inindividual susceptibility. Although clear procedures for determining them doexist (see, for instance, International Union of Pure and Applied Chemistryguidelines in Poulsen et al., 1997), their establishment for many substanceshas been hampered so far by the lack of reliable data on concentration.The inconsistency of concentration values in the literature for many traceelements in biological samples and the negative impact of this when trying totrack environmentally and occupationally derived variability is a recognizedproblem (i.e., Parr et al., 1991).
In this study, published values of antimony concentrations in urineand other noninvasive liquid matrices have been compiled and reviewed.Although antimony is not used in large quantities, it is used extensivelyfor many purposes. It is well known that it has been used since antiq-uity as a drug to induce emesis and to treat other conditions, as well asin cosmetics. Main current uses include as grid metal in lead storage bat-teries and as antimony oxide in fire retardants, but there are many others
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
164 M. Filella et al.
(e.g., solder, sheet and pipe metal, type metal, castings, ammunition andpewter, glass for cathode ray tubes, in pigments, stabilizers and catalystsfor plastics, cable covering) that might result in extensive human exposure.Therefore, methods capable of measuring exposure from diffuse sources(i.e., the uses mentioned previously as well as recycling and incinerationof antimony-containing compounds) such as urine and milk analysis, areparticularly interesting for this element.
The objectives of this study were to (a) evaluate published data froma methodological point of view, (b) establish a range of plausible valuesfor antimony concentrations in human excreted biofluids, and (c) assess theutility of using antimony concentrations in urine in medical, occupational,and environmental studies. This study complements previous publicationswhere we have reviewed different aspects of antimony behavior in the envi-ronment (Belzile et al., 2011; Filella, 2010; Filella et al., 2002a, 2002b, 2006,2009) and, in particular, the use of hair and nails in human biomonitoring(Filella et al., 2011).
METHODS
A systematic search of our database of studies related to antimony thatcurrently comprises more than 3,300 articles has been supplemented withsearches using various search engines (Web of Science, SciFinder, andPubMed; keywords: antimony, milk, saliva, semen, sweat, tears, urine). Allarticles in our database were individually examined. The result of our searchcan be considered to be comprehensive but not exhaustive. Only articleswritten in Chinese, English, French, German, Italian, Portuguese, and Span-ish were included. Secondary sources were avoided as much as possible and,in particular, values uncritically reproduced in books have been excluded.
RESULTS AND DISCUSSION
Urine
Urine is the second most commonly used biofluid for human biomonitoring(Esteban and Castano, 2009), its main advantage arising from being a nonin-vasive matrix. A total of 74 studies containing antimony data were collected.Publication dates range from 1954 to 2011. The values collected are pre-sented in Table 1. This table also includes information on the geographicalorigin of the samples, number of subjects sampled, type of urine samples,and analytical methodology applied (i.e., storage, pretreatment, and measur-ing analytical method). When available, information related to the quality ofthe analytical procedure (i.e., limit of detection, use of certificate referencematerials) is also included. It is important to point out that, unfortunately,
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
1.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s.Publis
hed
valu
esofan
timony
conce
ntrat
ions
Val
ue
range
or
Pre
trea
tmen
tSa
mple
Num
ber
of
Typ
eof
oth
erst
atis
tical
and
origi
na
indiv
idual
surine
Units
bM
ean
cErr
ord
Med
ian
ein
form
atio
nf
dig
estio
ng
Tec
hniq
ueh
CRM
?iRef
eren
ce
Work
ers
expose
dto
air
conta
inin
gab
out
3m
gSb
m−3
113
(tota
l);not
clea
rhow
man
ypro
vided
urine
sam
ple
s
mg
L−1
0.8–
9.6
NI
Fred
eric
k,19
41N
MB
rieg
eret
al.,
1954
Work
ers
met
allu
rgic
alw
ork
s,CZ
4μ
gL−
1pea
ksat
1500
,13
75,
3500
,33
90N
IG
oodw
inan
dPag
e,19
43N
MK
luci
kan
dK
emka
,19
60Controlin
ast
udy
on
bilh
arzi
asis
Sbtrea
tmen
t2
ng
mL−
16.
23.
1st
ora
ge:N
IN
AA
NM
Man
sour
etal
.,19
67
Work
ers
Sbpro
cess
ing
indust
ry,U
S28
spot
μg
L−1
7–10
20N
IN
IN
MCooper
etal
.,19
68
Hyp
erpar
athyr
oid
ism
pat
ients
:24
hr
μg
day
−1st
ora
ge:–2
0◦C
NAA
NM
Bost
rom
and
Wes
ter,
1969
-untrea
ted
40.
6–6.
0-5
day
saf
ter
oper
atio
n1
4.6
(0.6
bef
ore
)-6
day
saf
ter
12.
3(6
.0bef
ore
)-10
day
saf
ter
12.
6(4
.5bef
ore
)-17
day
saf
ter
11.
4(1
.5bef
ore
)Control
23.
0–4.
0“N
orm
alco
nce
ntrat
ions”
μg
L−1
<0.
05lit
erat
ure
valu
esSc
hro
eder
and
Nas
on,19
71m
gday
−1<
0.07
Hyp
erte
nsi
vepat
ients
trea
ted
with
chlo
rthal
idone
μg
day
−1st
ora
ge:N
IN
AA
NM
Wes
ter,
1973
-bef
ore
trea
tmen
t14
1.5
0.57
0.52
–2.6
-during
trea
tmen
t14
1.4
0.58
0.58
–2.7
Hyp
erte
nsi
vepat
ients
trea
ted
with
hyd
rala
zine
μg
day
−1st
ora
ge:N
IN
AA
NM
Wes
ter,
1975
-bef
ore
trea
tmen
t5
2.0
0.52
1.3–
2.6
-during
trea
tmen
t5
1.6
0.57
0.67
–2.0
Ital
ian
popula
tion
NM
μg
day
−1<
0.3
ster
ilize
dN
AA
NM
Cle
men
te,19
76(C
onti
nu
edon
nex
tpa
ge)
165
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
1.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s.Publis
hed
valu
esofan
timony
conce
ntrat
ions
(Con
tin
ued
)V
alue
range
or
Pre
trea
tmen
tSa
mple
Num
ber
of
Typ
eof
oth
erst
atis
tical
and
origi
na
indiv
idual
surine
Units
bM
ean
cErr
ord
Med
ian
ein
form
atio
nf
dig
estio
ng
Tec
hniq
ueh
CRM
?iRef
eren
ce
Four
groups
Ital
ian
popula
tion:
allfo
r3–
5day
sμ
gday
−1no
pre
vious
trea
tmen
tN
AA
NB
Sorc
har
dle
aves
:N
RS
Cle
men
teet
al.,
1977
-A,m
ounta
ins,
pollu
tion
Hg
10<
0.5
<0.
1–92
5
-B,se
a,m
ediu
msi
zeto
wn,in
dust
ries
10<
0.1
<0.
1–1.
0
-C,m
ediu
msi
zeto
wn
10<
0.1
<0.
1–0.
16-D
,la
rge
tow
n10
0.1
0.1–
0.14
Ital
ian
popula
tion
49al
lfo
r3–
5day
sμ
gday
−1<
0.1
no
det
ails
give
nN
AA
NB
Sorc
har
dle
aves
:N
RS
Cle
men
teet
al.,
1978
Adult
valu
esco
mpila
tion
μg
day
−1<
70,1.
50,3.
50lit
erat
ure
valu
es(S
chro
eder
and
Nas
on,19
71;
Wes
ter,
1973
;Bost
rom
and
Wes
ter,
1969
)
Iyen
gar
etal
.,19
78
Work
ers
Pb-S
bin
dust
ry,G
B:
24-h
rμ
gL−
1st
ora
ge:
refr
iger
ator
afte
rac
idifi
catio
nno
dig
estio
n
SE(A
PD
C-
IBM
K)
+ET-A
AS
NM
Smith
and
Griffi
ths,
1982
-ex
pose
dper
sons
poole
d43
.80.
7416
52.5
10–2
20-unex
pose
dper
sons
18≤1
(11
per
s.)
2(2
per
s.)
3(3
per
s.)
4(1
per
s.)
5(1
per
s.)
Origi
nunkn
ow
nμ
gL−
12.
626
%co
llect
ion
ove
rco
nce
ntrat
ion
HCl
filtr
atio
n2×
mem
bra
ne
filte
rs
resi
n+
HG
-ICP-E
S(0
.07)
only
for
SeFo
dor
and
Bar
nes
,19
83
Origi
nunkn
ow
n3
μg
L−1
1.12
0.32
(n=
10)
pre
trea
tmen
tan
dst
ora
ge:N
IH
ClO
4-H
2SO
4hot
open
dig
estio
n
ASV
NM
Rat
etal
.,19
851.
150.
20(n
=8)
1.22
0.38
(n=
12)
166
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Work
ers
inPb
and
Sbpro
cess
ing
indust
ry,G
B10
NM
μg
L−1
29
12–6
4st
ora
ge:N
Ino
dig
estio
nSE
(APD
C-
IBM
K)
+ca
ndolu
min
es-
cence
NM
Cla
rkan
dPat
el,
1986
Indiv
idual
sw
ith3
NM
μg
mL−
10.
0014
,0.
001,
All
n=
6st
ora
ge:4◦
CN
AA
NB
SW
ard,19
86norm
alfo
od
and
0.00
13,
0.00
009,
or
direc
tdee
p(0
.000
4μ
gm
L−1)
1577
drink
inta
ke0.
0008
0.00
007
free
zing
Tw
o-d
ayst
arva
tion
10.
0012
0.00
01B
efore
0.00
140.
0001
Gla
ss-p
roduci
ng
indust
ryw
ork
ers,
DE:
end
ofsh
ift
μg
L−1
stora
ge:N
IH
NO
3-H
2SO
4
ashin
g
HG
-AAS
NM
Luder
sdorf
etal
.,19
87-al
l10
91.
90.
2–15
.7-m
elte
r32
0.9
0.2–
2.9
-bat
chm
ixer
455.
01.
5–15
.7-cr
afts
man
80.
90.
4–3.
7-gl
ass
was
her
241.
20.
6–6.
3Control
80.
40.
2–0.
7H
ard-m
etal
indust
ry30
morn
ing
ng
g−1
ww
<4.
8fr
oze
n–8
0◦C
RN
AA
NM
Nic
ola
ou
work
ers,
IT24
hr,
etal
.,19
87Control
3<
3.2
lyophili
zed
48hr
dig
estio
n:H
NO
3
min
eral
izat
ion
afte
rirra
dia
tion
Hea
lthy
nonex
pose
d5
NM
μg
L−1
0.6
0.3–
1.3
stora
ge:N
Isu
bje
cts
HN
O3-H
ClO
4-
H2SO
4dig
estio
nIE
+SE
+G
F-AAS
NB
S15
71K
obay
ashian
dIm
aizu
mi,
1989
Hea
lthy
popula
tion,
Lom
bar
dy,
IT36
0N
Mμ
gL−
10.
790.
07j
0.1–
3.6
stora
ge:–2
◦ Caf
ter
acid
ifica
tion
dilu
tion
or
dig
estio
n:N
M
ET-A
AS,
ICP-E
S,N
AA
BCR
194,
NB
S26
70,84
19:al
lN
RS,
com
mer
cial
Min
oia
etal
.,19
90
(Con
tin
ued
onn
ext
page
)
167
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
1.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s.Publis
hed
valu
esofan
timony
conce
ntrat
ions
(Con
tin
ued
)V
alue
range
or
Pre
trea
tmen
tSa
mple
Num
ber
of
Typ
eof
oth
erst
atis
tical
and
origi
na
indiv
idual
surine
Units
bM
ean
cErr
ord
Med
ian
ein
form
atio
nf
dig
estio
ng
Tec
hniq
ueh
CRM
?iRef
eren
ce
“Occ
upat
ional
lyex
pose
dpopula
tions:
”N
Mμ
gL−
1st
ora
ge:N
Idilu
tion,no
dig
estio
n
ICP-M
S(<
1ng
mL−
1 )M
ulli
gan
etal
.,19
90
-Sa
mple
114
-Sa
mple
238
-Sa
mple
317
6Le
ishm
ania
sis
10μ
gL−
1Sb
(III):
1.6
0.1
1.4–
1.8
pre
trea
tmen
t,H
G-A
AS
NIS
T15
41Pet
itde
Pen
apat
ients
,prior
totrea
tmen
tw
ithG
luca
ntim
eSb
(V):
1.8
0.1
1.5–
2.0
stora
ge:
Burg
uer
aet
al.,
1990
no
dig
estio
n
(0.2
)et
al.,
1990
Work
ers
expose
dto
Sb(V
)in
anonfe
rrous
smel
ter:
20bef
ore
,μ
gg−
1CRT
stora
ge:N
Inotcl
ear
whet
her
sam
ple
sw
ere
dig
este
d
GF-
AAS
NM
Bai
llyet
al.,
1991
afte
rsh
ift
-w
etpro
cess
-bef
ore
shift
8.2
3.9
-af
ter
shift
12.3
5.0
-dry
pro
cess
-bef
ore
shift
58.4
62.5
-af
ter
shift
110
76W
ork
ers
inSb
pro
duct
fact
ory
(Hunan
,CN
)12
μg
mL−
10.
030–
0.66
0(G
F-AAS)
0.03
1–0.
641
(colo
rim
etry
)
stora
ge:N
Ino
dig
estio
nCom
par
ison
GF-
AAS
with
5-Br-
PAD
AP
colo
rim
etry
Chen
etal
.,19
92
Leis
hm
ania
sis
pat
ients
,prior
totrea
tmen
tw
ithG
luca
ntim
e
5μ
gL−
1Sb
(III):
BD
Lpre
trea
tmen
t,st
ora
ge:B
urg
uer
aan
dBurg
uer
a,19
84
HG
-AAS
(0.2
)U
sem
entio
ned
,no
det
ails
give
n
Burg
uer
aet
al.,
1993
Sb(V
):BD
L
168
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Art
glas
sin
dust
ry30
end
ofsh
ift
μg
L−1
6.8
0.1–
35st
ora
ge:N
IH
G-A
AS
NIS
T26
76c,
Apost
oli
etal
.,w
ork
ers,
ITdig
estio
n:N
M16
43c:
1994
Control
250.
8BD
L-3
NRS;
com
mer
cial
Clo
isonne
work
ers:
urine
during
μg
L−1
stora
ge:N
IFl
amel
ess
NB
Soys
ter
Ara
iet
al.,
-gl
aze
49w
ork
ing
2.93
1.28
2.56
–10.
26dig
estio
n:hot
AA
Stis
sue:
1994
-si
lver
-pla
ting
16hours
2.72
0.64
2.56
–5.1
3H
NO
3(2
.5)
NSb
RS
-pla
ntoffi
ce5
2.56
02.
56–2
.56
Control
622.
710.
582.
56–5
.13
Ref
eren
ceco
nce
ntrat
ions
from
publis
hed
dat
aμ
gL−
10.
19–1
.8Li
tera
ture
valu
es(E
linder
and
Frib
erg,
1977
)
Car
oli
etal
.,19
94
Per
sonal
sele
ctio
nof
liter
ature
dat
a—
μg
g−1
ww
1Li
tera
ture
valu
esH
amilt
on
etal
.,19
94SA
Sdat
a(W
alke
r,19
92),
GB
μg
L−1
0.2–
1.1
Ref
eren
ceG
Bva
lues
μg
L−1
1Le
adbat
tery
pro
duct
ion
indust
ry:
end
last
shift
μg
g−1
CRT
stora
ge:N
Idirec
tan
alys
isH
G-A
AS
NM
Ken
tner
etal
.,19
94ofw
ork
ing
wee
k-ca
ster
s7
3.9
2.8–
5.6
-fo
rmer
s14
15.2
3.5–
23.4
Sbsm
elte
rw
ork
shop
(Guiz
hou,CN
)sp
ot
μg
L−1
stora
ge:N
Idig
estio
n:N
Ico
lorim
etry
Huo
etal
.,19
95
air
Sb2O
3(m
gm
−3):
-<
5.0
3516
8.0
182.
00–
544
-5.
1≤
16.7
039
281.
023
618
.0–7
24Controlpopula
tion
192
12.6
2.0
0–60
.0(C
onti
nu
edon
nex
tpa
ge)
169
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
1.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s.Publis
hed
valu
esofan
timony
conce
ntrat
ions
(Con
tin
ued
)V
alue
range
or
Pre
trea
tmen
tSa
mple
Num
ber
of
Typ
eof
oth
erst
atis
tical
and
origi
na
indiv
idual
surine
Units
bM
ean
cErr
ord
Med
ian
ein
form
atio
nf
dig
estio
ng
Tec
hniq
ueh
CRM
?iRef
eren
ce
Refi
ner
yw
ork
ers
74μ
gL−
10.
08–3
2.6
stora
ge:–2
0◦C
SECom
mer
cial
Smith
etal
.,19
95Chem
ical
man
ufa
cture
rs11
20.
1–36
.1no
dig
estio
n(c
upfe
rron-
IBM
K)
+ET-A
AS
(0.6
9)
Bat
tery
man
ufa
cture
rs36
1.5–
149.
2Control(lab
ora
tory
work
ers)
200.
810.
18–2
.16
Hea
lthy
fres
hm
enuniv
ersi
tyst
uden
ts,CN
:12
8m
orn
ing
μm
olL−
10.
08–8
.13
stora
ge:N
Idig
estio
n:hot
Flam
eAAS
Qin
etal
.19
96
-m
ale
67%
3.12
1.48
HN
O3-H
ClO
4
-fe
mal
e33
%2.
872.
22Ir
ish
infa
nts
<1
year
old
(203
)an
ddea
d(<
2ye
ars)
(17)
210
μg
L−1
0.05
G<
0.02
–0.9
00.
02–0
.11
(25–
75)
stora
ge:–7
0◦C
(Irish
),–2
0◦C
(London)
dilu
tion,no
dig
estio
n
ICP-M
S(0
.01)
BCR
185,
NIS
T15
77a,
1566
aD
elve
set
al.,
1997
London
infa
nts
:-pre
term
new
born
s26
0.28
G0.
03–1
.70.
15–0
.51
(25–
75)
-te
rm13
20.
07G
<0.
02–3
.00.
05–0
.16
(25–
75)
Hea
lthy
infa
nts
:st
ora
ge:–2
0◦C
dilu
tion,no
dig
estio
n
ICP-M
S(0
.004
)N
MD
ezat
eux
etal
.19
97-pre
term
new
born
s26
μg
L−1
ng
mg−
1CRT
0.28
G2.
250.
19–0
.41
1.49
–3.3
9-fu
llte
rm,8
wee
ksold
74μ
gL−
1
ng
mg−
1CRT
0.05
G0.
480.
04–0
.07
0.36
–0.6
5-fu
llte
rm,1
year
old
58μ
gL−
1
ng
mg−
1CRT
0.08
G0.
400.
05–0
.14
0.25
–0.6
5In
fants
dia
gnose
dLR
Iw
ithw
hee
ze43
μg
L−1
ng
mg−
1CRT
0.12
G0.
480.
06–0
.24
0.37
–1.2
5
170
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Unex
pose
dper
sons,
DE
1424
hr
μg
L−1
0.08
20.
077
0.01
2–0.
17st
ora
ge:–4
◦ Caf
ter
acid
ifica
tion
dilu
tion,no
dig
estio
n
ICP-M
S(0
.03)
notuse
dSc
hra
mel
etal
.,19
97
Ran
dom
lyse
lect
edhea
lthy
infa
nts
firs
tye
aroflif
e,IE
:97
(all)
μg
L−1
ng
mg−
1CRT
0.1
70.0
40.
09–0
.25
(mea
n±
SD)
stora
ge:fr
eezi
ng
dilu
tion,no
ICP-M
S(0
.01
μg
L−1 )
NM
Culle
net
al.,
1998
0.42
-2–
6w
eeks
17μ
gL−
10.
160.
03dig
estio
n-8–
16w
eeks
160.
160.
03-20
–18
wee
ks18
0.18
0.04
-33
–41
wee
ks22
0.17
0.05
-48
–56
wee
ks27
0.18
0.04
“Unex
pose
d”
adults
inLo
wer
Saxo
ny,
DE
4724
hr
μg
day
−11.
611.
23<
0.5–
4.74
BD
L:7
sam
ple
sst
ora
ge:–2
0◦C
afte
rac
idifi
catio
nG
F-AAS
(0.5
μg
L−1 )
NM
Geb
elet
al.,
1998
a
Geo
genic
ally
expose
dad
ults
innorther
nPal
atin
ate,
DE
891.
030.
60<
0.5–
5.35
BD
L:40
sam
ple
sno
dig
estio
n
Geo
genic
ally
expose
dad
ults
innorther
nPal
atin
ate,
DE:
24hr
μg
day
−1st
ora
ge:N
Mno
dig
estio
nG
F-AAS
(0.5
μg
L−1 )
Com
mer
cial
Geb
elet
al.,
1998
b
-m
an88
1.12
0.66
BD
L-4.
73-w
om
an10
80.
650.
34B
DL-
4.62
“Unex
pose
d”
adults
inLo
wer
Saxo
ny,
DE
75μ
gday
−11.
531.
11B
DL-
5.86
stora
ge:–2
0◦C
afte
rac
idifi
catio
nno
dig
estio
n
GF-
AAS
(0.5
μg
L−1 )
NM
Geb
elet
al.,
1998
c
Geo
genic
ally
expose
dad
ults
innorther
nPal
atin
ate,
DE
196
0.86
0.46
BD
L-4.
73
(Con
tin
ued
onn
ext
page
)
171
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
1.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s.Publis
hed
valu
esofan
timony
conce
ntrat
ions
(Con
tin
ued
)V
alue
range
or
Pre
trea
tmen
tSa
mple
Num
ber
of
Typ
eof
oth
erst
atis
tical
and
origi
na
indiv
idual
surine
Units
bM
ean
cErr
ord
Med
ian
ein
form
atio
nf
dig
estio
ng
Tec
hniq
ueh
CRM
?iRef
eren
ce
Ref
eren
cem
anre
eval
uat
ion
μg
day
−1<
0.1
–5?
liter
ature
valu
esIy
enga
r,19
98Child
ren
from
Rom
e,IT
30m
orn
ing
μg
L−1
0.06
<0.
01–0
.53
stora
ge:–2
8◦C
dig
estio
n:
HN
O3-H
2O
2+
UV
irra
dia
tion
Q-I
CP-M
S(0
.012
)sp
iked
NIS
T26
70K
rach
ler
etal
.,19
98a
U.S
.re
siden
ts(N
HA
NES
III,
1988
–199
4)49
6μ
gL−
11.
300.
74G
<0.
3–4.
17(2
5–95
)73
.5%
AD
L0.
38–2
.82
(25–
95)
stora
ge:–2
0◦C
dilu
tion,no
dig
estio
n
ICP-M
S(0
.3)
NIS
T26
70Pas
chal
etal
.,19
98
μg
g−1
CRT
1.00
0.67
GIn
fants
dyi
ng
from
SID
S,IE
8ng
mg−
1CRT
0.56
0.02
–3.9
1BD
L:1
sam
ple
stora
ge:–7
0◦C
pre
trea
tmen
t:IC
P-M
S(0
.01
μg
L−1 )
NM
Culle
net
al.,
2000
Control,
IE4
0.67
0.24
–1.2
1D
elve
set
al.,
1997
U.S
.re
siden
ts15
27ra
ndom
,24
hr
μg
L−1
BD
L:96
%ofra
ndom
,82
%of24
-hr
stora
ge:N
Idilu
tion,no
dig
estio
n
ICP-M
S(1
)N
MK
om
arom
y-H
iller
etal
.,20
00
Nonex
pose
dper
son
Asp
ot
μg
L−1
<0.
12st
ora
ge:4◦
Cdig
estio
n:hot
HG
-AAS
NIS
T26
70;
com
mer
cial
Kra
chle
ran
dEm
ons,
2001
Nonex
pose
dper
son
B<
0.12
H2SO
4+
HN
O3
+H
ClO
4+
HF
Exp
ose
dper
son
A8.
30.
3n
=5
Exp
ose
dper
son
B5.
10.
4n
=5
Nonsm
oki
ng
unex
pose
dhea
lthy
subje
cts
19m
gL−
10.
116
0.06
10.
116
0.01
2–0.
223
stora
ge:
refr
iger
ator
dilu
tion,no
dig
estio
n
SF-I
CP-M
S(0
.004
)Com
mer
cial
Rodush
kin
and
Odm
an,20
01
Endem
icar
senis
mpat
ients
(Guiz
hou
pro
vince
,CN
)16
morn
ing
μg
g−1
CRT
4.8
G1.
2–97
.3st
ora
ge:fr
oze
nH
NO
3-H
2O
2
mic
row
ave
dig
estio
n
ICP-M
SN
MX
ieet
al.,
2001
Control
162.
3G
0.5–
6.4
172
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Sb2O
3hig
h-e
xposu
reoper
ators
:24
beg
innin
g,μ
gL−
1st
ora
ge:–2
0◦C
dig
estio
n:
HR-ICP-M
S(0
.03)
Com
mer
cial
Iavi
coli
etal
.,20
02en
dofsh
ift
-beg
innin
gsh
ift
0.39
0.26
0.16
–1.3
7H
NO
3-H
2O
2
0.34
G1.
7G
+U
V-en
dsh
ift
0.46
0.32
0.16
–1.7
7irra
dia
tion
0.41
G1.
6G
Sb2O
3je
toper
ators
15-beg
innin
gsh
ift
0.18
0.10
0.09
–0.4
80.
16G
1.5
G-en
dsh
ift
0.18
0.06
0.10
–0.2
90.
17G
1.4
GA
lloper
ators
-beg
innin
gsh
ift
390.
310.
240.
10–1
.37
0.25
G1.
8G
-en
dsh
ift
0.36
0.29
0.13
–1.7
70.
29G
1.8
GControl
15m
orn
ing
0.10
0.06
<0.
03–0
.24
0.07
G2.
0G
Controlin
ast
udy
on
Glu
cantim
etrea
tmen
tof
leis
hm
ania
sis
10m
gg−
1CRT
0.00
2st
ora
ge:N
Idilu
tion,no
dig
estio
n
Q-I
CP-M
SCom
mer
cial
Mie
kele
yet
al.20
02
NY
Cfire
figh
ters
,U
Sμ
gL−
1st
ora
ge,
pre
trea
tmen
t:N
M
no
met
hod
give
n,only
8re
fsfo
r11
0ch
emic
als
NM
Edel
man
etal
.,20
03-in
WTC
fire
and
collp
ase,
Sep
2001
321
0.20
3G
-offi
cedutie
s(c
ontrol)
470.
165
GPopula
tion
from
Ensc
hed
e,N
Laf
ter
ala
rge
fire
work
explo
sion
4466
μg
L−1
0.11
95%
per
centil
e:0.
35st
ora
ge:–3
0◦C
dilu
tion,no
dig
estio
n
Q-I
CP-M
S(0
.11)
Com
mer
cial
de
Boer
etal
.,20
04
EU
hea
lthy,
nonex
pose
dpopula
tion
6324
hr
μg
L−1
0.08
10.
037
GQ
L–1
.30.
07–0
.18
(60–
95)
stora
ge:5◦
Caf
ter
acid
ifica
tion
ICP-M
SQ
L=
3.5
×D
LCom
mer
cial
Hei
tland
and
Kost
er,20
04BQ
L=
32%
dilu
tion,no
=0.
021
BQ
Lva
lues
=Q
L/2
dig
estio
n(C
onti
nu
edon
nex
tpa
ge)
173
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
1.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s.Publis
hed
valu
esofan
timony
conce
ntrat
ions
(Con
tin
ued
)V
alue
range
or
Pre
trea
tmen
tSa
mple
Num
ber
of
Typ
eof
oth
erst
atis
tical
and
origi
na
indiv
idual
surine
Units
bM
ean
cErr
ord
Med
ian
ein
form
atio
nf
dig
estio
ng
Tec
hniq
ueh
CRM
?iRef
eren
ce
Opto
elec
tronic
sin
dust
ry,
TW
:m
orn
ing
ppb
stora
ge−2
0◦C
HN
O3
ICP-M
S(0
.003
)N
MLi
aoet
al.,
2004
-unex
pose
doffi
cew
ork
ers
670.
300.
002
G0.
431.
68m
icro
wav
edig
estio
n-ex
pose
dw
ork
ers:
103
(all)
0.46
0.00
2G
0.22
1.88
-m
ainte
nan
ce15
0.49
0.00
2G
0.64
1.64
-dope
film
520.
330.
002
G0.
421.
88
-en
ginee
rs36
0.35
0.00
2G
0.44
1.64
Poole
d(3
0–35
indiv
idual
spec
imen
s),SW
3ng
L−1
70–1
20pre
trea
tmen
tan
dst
ora
ge:N
Idilu
tion,no
dig
estio
n
SF-I
CP-M
S(0
.004
)Com
mer
cial
Rodush
kin
etal
.,20
04
Cer
roG
rande
Fire
,U
S:sp
ot
μg
g−1
CRT
stora
ge:fr
eezi
ng
ICP-M
SN
MW
olfe
etal
.,20
04-fire
figh
ters
770.
090.
07G
max
:0.
31dig
estio
n:N
M
-ge
ner
alpopula
tion
131
0.13
0.10
Gm
ax:0.
56
Hea
lthy
subje
cts
from
central
IT:
50(a
ll)N
Mng
L−1
66.6
55.4
G39
.060
.811
.3–1
7924
–119
(10–
90)
stora
ge:–3
0◦C
dilu
tion,no
Q-I
CP-M
S(1
.09)
NM
Alim
onti
etal
.,20
05
-m
ale
2580
.069
.8G
38.8
80.0
16.5
–179
30.6
–130
(10–
90)
dig
estio
nSF
-ICP-M
S(0
.43)
-fe
mal
e25
53.3
43.9
G35
.139
.211
.3–1
4621
.8–1
06(1
0–90
)U
.S.re
siden
ts(N
HA
NES
1999
–200
0)22
76N
Mμ
gL−
10.
13G
0.05
–0.4
2(1
0–95
))st
ora
ge:–2
0◦C
dilu
tion,no
dig
estio
n
ICP-M
S(0
.04)
NM
Cal
dw
ellet
al.,
2005
Hea
lthy
volu
nte
ers,
FR10
0sp
ot
μg
L−1
0.04
0.02
–0.0
8(5
–95)
stora
ge:N
Idilu
tion,no
dig
estio
n
ICP-M
S(0
.003
)Com
mer
cial
Goulle
etal
.,20
05
174
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
U.S
.popula
tion
≥40
year
sold
(fro
mN
HA
NES
1999
–200
0)
725
spot
μg
L−1
0.11
GBD
L-0.
29(1
0–90
)m
ax:5.
70BD
L:9.
0%sa
mple
s
see:
Cal
dw
ellet
al.,
2005
ICP-M
S(0
.04)
NIS
T26
70:N
RS
Nav
as-A
cien
etal
.,20
05
Effec
tofM
CP
on
hea
lthy
adults
,Cal
iforn
ia,U
S:8
24hr
μg
day
−1st
ora
gean
ddig
estio
n:N
MIC
P-M
SCom
mer
cial
Elia
zet
al.,
2006
-day
00.
120.
13-day
10.
100.
13-day
60.
160.
16A
achen
,Erk
elen
z,B
rem
en,
DE:
morn
ing
stora
ge:5◦
Caf
ter
acid
ifica
tion
dilu
tion,no
dig
estio
n
ICP-M
SQ
L=
3.5x
DL
=0.
021
Com
mer
cial
Hei
tland
and
Kost
er,20
06m
iddle
stre
am-ch
ildre
n72
μg
L−1
μg
L−1
μg
g−1
CRT
0.06
3Q
L-0.
72BQ
L=
21%
0.05
–0.1
4(6
0–95
)0.
041
G0.
034
G-ad
ults
87μ
gL−
1
μg
L−1
μg
g−1
CRT
0.06
3Q
L-0.
57BQ
L=
21%
0.04
5–0.
18(6
0–95
)BQ
Lva
lues
=Q
L/2
0.03
9G
0.03
7G
Hum
anurine,
origi
nunkn
ow
n1
NM
ng
mL−
1Sb
(V):
0.94
0.02
n=
3no
pre
trea
tmen
tm
entio
ned
CPE
ETV-ICP-E
SN
MLi
etal
.,20
06Sb
(III):
ND
(Con
tin
ued
onn
ext
page
)
175
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
1.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s.Publis
hed
valu
esofan
timony
conce
ntrat
ions
(Con
tin
ued
)V
alue
range
or
Pre
trea
tmen
tSa
mple
Num
ber
of
Typ
eof
oth
erst
atis
tical
and
origi
na
indiv
idual
surine
Units
bM
ean
cErr
ord
Med
ian
ein
form
atio
nf
dig
estio
ng
Tec
hniq
ueh
CRM
?iRef
eren
ce
Opto
elec
tronic
sin
dust
ryex
pose
dw
ork
ers,
TW
103
morn
ing
ppb
0.36
0.46
stora
ge:–2
0◦C
pre
trea
tmen
t:Li
aoet
al.,
2004
ICP-M
SLi
aoet
al.,
2006
Control
670.
300.
43Res
iden
tsofZla
taId
ka,SK
(vill
age
close
toan
aban
doned
min
ing
area
)
116
μg
L−1
18.8
14.3
1.3–
87.7
no
det
ails
give
nG
F-A
AS
NM
Rap
antet
al.,
2006
Bra
zilia
nhea
lthy,
nonex
pose
dsu
bje
cts
412
morn
ing
μg
L−1
0.2
0.03
–2.1
4(5
–95)
stora
ge:in
itial
:4◦
C;fr
oze
n–8
0◦C
afte
rac
idifi
catio
ndilu
tion,no
dig
estio
n
Q-I
CP-M
SN
IST
2670
ahig
han
dlo
wle
vel
Bat
ista
etal
.,20
09
Child
ren
(3–1
4ye
ars
old
)in
DE
1729
NM
μg
L−1
0.11
<0.
01–1
.00.
11–0
.31
(50–
95)
AD
L≥
99.9
Ref
valu
e=
0.3
Bec
ker
etal
.,20
08B
ecke
ret
al.,
2008
Bec
ker
etal
.,20
08K
om
mis
sion
”Hum
an-
Bio
monito
ring“
,20
09;Sc
hulz
etal
.,20
09
176
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
NH
AN
ES,
1999
–200
4,U
S:61
10μ
gL−
1st
ora
ge:
refr
iger
atio
nor
free
zing
dig
estio
n:N
I
ICP-M
SN
MRic
hte
ret
al.,
2009
-ove
rall
popula
tion
0.11
G-non
smoke
rs:
-unex
pose
d0.
10G
-lo
wex
posu
re0.
11G
-hig
hex
posu
re0.
12G
-sm
oke
rs0.
13G
Can
adia
npopula
tion
(6–7
8ye
ars
old
),20
07–2
009
5492
μg
L−1
0.08
0.01
BD
L=
22.4
0%st
ora
ge:–2
0◦C
dilu
tion
(0.5
%H
NO
3),
no
dig
estio
n
ICP-M
SN
MH
ealth
Can
ada,
2010
0.04
G0.
01G
Eva
luat
ion
ofSb
exposu
refr
om
Sb-c
onta
inin
gpan
ts:
spot
μg
g−1
CRT
stora
ge:dry
ice
met
hod:
Cal
dw
ellet
al.,
2005
ICP-M
S(0
.032
)N
Mde
Per
ioet
al.,
2010
-fire
dep
artm
entA
(no
pan
tsla
st4
month
s)11
20.
063
G0.
027–
0.28
5
-fire
dep
artm
entB
(pan
tspre
cedin
gtw
ow
eeks
)
960.
054
G0.
017–
0.36
6
Unex
pose
dpre
gnan
tw
om
en,
Toky
o,JP
(200
7,20
08)
78sp
ot
μg
g−1
CRT
All
BD
Lst
ora
ge:–2
0◦C
dilu
tion
and
filtr
atio
n,no
dig
estio
n
ICP-M
S(0
.21)
Com
mer
cial
Shirai
etal
.,20
10
Adults
,Puch
unca
vıva
lley,
CL
(clo
seto
anin
dust
rial
com
ple
x)
8sp
ot
μg
L−1
AD
L:6,
6.3
BD
L:6
sam
ple
sst
ora
ge:4◦
Cdilu
tion
and
filtr
atio
n,no
dig
estio
n
HPLC
-HG
-AFS
(0.1
)N
MQ
uiroz
etal
.,20
11
(Con
tin
ued
onn
ext
page
)
177
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
1.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s.Publis
hed
valu
esofan
timony
conce
ntrat
ions
(Con
tin
ued
)V
alue
range
or
Pre
trea
tmen
tSa
mple
Num
ber
of
Typ
eof
oth
erst
atis
tical
and
origi
na
indiv
idual
surine
Units
bM
ean
cErr
ord
Med
ian
ein
form
atio
nf
dig
estio
ng
Tec
hniq
ueh
CRM
?iRef
eren
ce
NH
AN
ES,
1999
–200
4,U
S:-19
99–2
000
-20
01–2
002
-20
03–2
004
-20
05–2
006
-20
07–2
008
2276
2690
2558
2576
2627
μg
L−1
95%
confiden
cein
terv
al:
0.12
0–0.
145
0.12
6–0.
142
k
0.06
6–0.
081
0.05
7–0.
066
Ric
hte
ret
al.,
2009
Ric
hte
ret
al.,
2009
LD:0.
04,0.
04,
0.07
,0.
032,
0.03
2,re
spec
tivel
y
Ric
hte
ret
al.,
2009
NH
AN
ES,
2011
0.13
2G
0.13
4G
k
0.07
3G
0.06
1G
Not
e.Val
ues
are
give
nin
chro
nolo
gica
lord
er.
a Inte
rnat
ional
country
codes
follo
wth
eIS
O31
66co
nve
ntio
n.
bThe
origi
nal
units
are
alw
ays
give
nin
ord
erto
avoid
unnec
essa
ryer
rors
.Rem
ember
that
:μ
gg−
1=
ng
mg−
1 ,μ
gL−
1=
ng
mL−
1 ,an
dm
gL−
1=
μg
mL−
1 .c B
ydef
ault,
arith
met
icm
ean.G
eom
etric
mea
nw
hen
the
valu
eis
follo
wed
by
G.In
som
eca
ses,
both
mea
nva
lues
are
give
n.W
hen
the
valu
eap
pea
rsin
italic
s,it
has
bee
nca
lcula
ted
by
us
from
publis
hed
valu
es.
dBy
def
ault,
stan
dar
ddev
iatio
n.
Geo
met
ric
stan
dar
ddev
iatio
nw
hen
the
valu
eis
follo
wed
by
G.
Rel
ativ
est
andar
ddev
iatio
nw
hen
the
valu
eis
follo
wed
by
aper
centa
gesi
gn.
e When
the
valu
eap
pea
rsin
italic
s,it
has
bee
nca
lcula
ted
by
us
from
publis
hed
valu
es.
f By
def
ault,
mea
sure
dra
nge
.Fi
gure
sin
bra
cket
sfo
llow
ing
the
quote
dva
lues
are
per
centil
es.
g NI=
notin
dic
ated
.hW
hen
give
n,th
eva
lue
ofth
edet
ectio
nlim
itis
quote
din
bra
cket
sunder
the
tech
niq
ue.
i NM
=notm
entio
ned
;N
RS
=no
resu
ltssh
ow
n(n
eith
erfo
ran
timony
nor
for
oth
erel
emen
ts);
NSb
RS
=no
Sbre
sults
show
n(b
utre
sults
for
oth
erel
emen
tsgi
ven).
See
Tab
le2
for
listofCRM
and
corr
espondin
gan
timony
valu
es.
j σ/n
1/2 t
valu
ew
her
eσ
=st
andar
ddev
iatio
n,n
=num
ber
ofobse
rvat
ions,
t=
Fisc
her
coef
fici
entfo
rn
–1
(p=
0.05
).k N
otca
lcula
ted:pro
portio
nofre
sults
bel
ow
limit
ofdet
ectio
nw
asto
ohig
hto
pro
vide
ava
lidre
sult.
178
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 179
not every study contained all the information needed for a valid assessmentof the quality of the data reported.
Results are reported in their original units and only original parameters(arithmetic or geometric mean, median, error, range) are quoted. Only ina very few cases did we calculate median values from published valuesfor comparison purposes; the corresponding values appear in italics. Somestudies investigated a very limited number of samples. In these cases, thestatistical meaning of the results may be limited. Moreover, strictly speaking,mean and standard deviation values can be calculated only when data arenormally distributed but these parameters are sometimes published withouttesting for normality. The median and the 95th percentile should also bequoted, but this is not always the case.
Two different types of urine samples can be collected, spot and 24-hrsamples. The collection of spot samples is easier but they have the disadvan-tage of varying volume and chemical concentration. Most of the publishedantimony values are spot samples (only 12 studies of 72 reported 24-hr dataonly).
Concentrations in urine are usually expressed as mass of substance perunit volume of urine. To take into account the variability derived from thevariability in urine volume, creatinine normalization (i.e., dividing the urinaryconcentration of the substance of interest by the urinary creatinine concen-tration) is often applied, particularly to spot urine samples (Barr et al., 2005;Poulsen et al., 1997). However, the use of creatinine-based values has beensubject to controversy (Alessio et al., 1985; Boeniger et al., 1993; Green-berg and Levine, 1989). The World Health Organization (1996), in its 1996guidelines on biological monitoring at the workplace, recommended theuse of creatinine only as an exclusion criterion (i.e., to include in occu-pational studies only urine samples with a creatinine concentration in therange of the excretion rate of the adult working population). More recently,the Human Biomonitoring Commission of the German Federal EnvironmentAgency (2005) recommended determining the creatinine content of urinesamples but only for the purpose of orientation. Creatinine excretion is sig-nificantly lower in children and the elderly in particular, and some authorsthink that creatinine correction can be used in homogeneous populationsbut that variability across levels in multiple demographic groups may behigh (Barr et al., 2005; Fried et al., 1995). For all these reasons, creatinine-corrected values are included in Table 1, but have not been taken accountof in the discussion that follows. It must be pointed out that only eight stud-ies contained creatinine-only data; usually when creatinine-based values aregiven, they accompany uncorrected ones.
Any analysis includes several well-known steps: sampling, stor-age, pretreatment (e.g., digestion/dilution), and measurement. Antimonydetermination-related issues will be discussed subsequently following thisorder.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
180 M. Filella et al.
Unfortunately, information about the conditions of sampling and sam-ple conservation is most often missing from published studies. Avoidingcontamination during the sampling step is a prerequisite in any analyticaldetermination. However, in the case of human urine, this might be par-ticularly difficult because samples are mostly taken in hospitals and notalways under well-controlled conditions. More than 10 years ago, Delveset al. (1997) measured antimony released from materials used in handlingand storage of body fluids and tissues and advised that attention be paidto preanalytical factors in order to avoid contaminating the samples withantimony. It should also be mentioned that antimony trioxide is extensivelyused by the polymer industry as a polycondensation catalyst in the produc-tion of polyethylene terephthalate (PET) and release of antimony from PETcontainers has been demonstrated (Shotyk et al., 2006; Shotyk et al., 2005).Apart from its possible toxicological implications, these results suggest thatsample contamination in the laboratory by antimony-bearing containers andsample-handling equipment could be more widespread than generally as-sumed. Migration of antimony has also been observed from PET containersinto orange juice (Hansen and Pergantis, 2006) and from food trays or PETmaterials to food (Fordham et al., 1995; Haldimann et al., 2007). The possibleimplications for sample conservation and treatment of clinical samples havenot been studied.
Preservation procedures are designed to ensure the stability of theanalyte in the samples from sampling to measurement. Little informa-tion is available about the stability of antimony species in matrices suchas urine samples. Freezing is possibly the most common method usedto preserve urine samples and, for this reason, it has been widely ap-plied to the samples considered here (Table 1). However, very recently,Quiroz et al. (2011) checked the stability of antimony species in spikedurine samples at 4 ◦C and –70 ◦C and their results revealed that antimonyspecies were highly unstable at –70 ◦C, probably due to coprecipitationreactions. Previous results by Lindemann et al. (2000), who spiked NIST2670 reference material with Sb(III) and Sb(V) (20 and 5 μg L−1, respec-tively), concluded that urine samples should be analyzed immediately aftercollection.
Most of the older determinations were performed by neutron activationanalysis (NAA), a technique that does not require digestion of the sample.However, the rest of the techniques require prior digestion of the sample,particularly in samples such as urine with a high organic content. Never-theless, a digestion step always introduces the risk of contamination and, inthe case of antimony, the additional risk of losing the element as its volatilechloride (Gorsuch, 1962). The use of a method where no hydrochloric acid isadded is recommended and care has to be taken to evaporate acidic samplesthat naturally contain chlorides, such as urine.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 181
Direct determination, without digestion of the sample, has sometimesbeen preferred when applying inductively coupled plasma mass spectrom-etry (ICP-MS). However, various authors recommended sample digestionbecause ICP-MS may suffer from a significant decrease in detection powerduring the analysis of imperfectly digested biological samples, and sampleswhere the organic matrix of biological samples has been completely oxi-dized produce more accurate and reproducible results. For instance, Schram-mel et al. (1999) stated that the spectral and nonspectral interferences aredistinctly reduced and long-term stability of the ICP-MS is considerably im-proved when samples are digested to destroy the organic matrix. But, accord-ing to these authors, the demands placed on sample digestion are normallynot very stringent, as there is sufficient thermal energy in the ICP systemto ensure complete destruction of the organic matter if this has not alreadybeen achieved by sample digestion. A comparison of the effect of digestionversus dilution and UV irradiation can be found in Krachler et al. (1998a).These authors recommended Sb be determined by Q-ICP-MS after 1:10 di-lution with high purity water of centrifuged samples. However, the sameauthors used a harsh digestion method (hot digestion involving H2SO4 +HNO3 + HClO4 + HF) in a later study (Krachler et al., 2001). As is the casefor dilution (Table 2), digestion methods and conditions used in the studieswhere antimony has been determined are rarely the same. They are detailedin Table 3. It should finally be mentioned that dilution of the samples mayalso underestimate antimony concentrations if samples are not adequatelymixed and urine sediment is not uniformly sampled, although, according toKrachler et al. (1998a), urine sediment does not contain antimony at levelsaffecting the final results.
As mentioned previously, most of the older determinations were per-formed by NAA (10 studies, period 1967–1990). However, the use of thistechnique to detect antimony in urine has not been as widespread as forother matrices, such as hair (Filella et al., 2011). Reported NAA-based valuestend to be higher than more recent values obtained by using other tech-niques. According to Versieck and Cornelis (1989) a possible reason mightbe the use of quartz vials as an irradiation container and the inevitable blankthey contribute to the sample. As long as the quartz material used containsmeasurable amounts of antimony, doubt will persist according to these au-thors. Nowadays, ICP-MS is largely the technique of choice. First appliedby Mulligan et al. (1990) to urine in 1990, it has since been employed inmore than 30 studies. Atomic absorption (AAS) based techniques have alsobeen relatively used, with graphite furnace (10 articles) and hydride gener-ation (HG; six articles) being those most applied. Hydride generation hasalso been used on one occasion coupled with ICP-ES and once with atomicfluorescence spectroscopy (AFS).
Not all studies use certificate reference materials (CRM) to check forthe accuracy of the analytical method. CRM mentioned in the published
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
182 M. Filella et al.
TABLE 2. Examples of dilution methods employed in Sb determinations in human urine
Method Reference(s)
1 + 9 with 2% (v/v) HNO3 Mulligan et al., 1990;Caldwell et al., 2005
Direct analysis Kentner et al., 1995200 μL urine + 2.6 mL water Delves et al., 19978.9 mL urine + 0.5 mL HCl + 0.1 mL internal standard
(dilution factor: 1.124)Schramel et al., 1997
“Aqueous dilution of 200 μL volumes” Cullen et al., 19981–50-fold dilution with water after urine centrifugation
(conditions not given)Krachler et al., 1998a
500 μL urine + 500 μL 15% HNO3, mixing and dilution to5 mL with water
Komaromy-Hiller et al.,2000
0.5 mL urine made up to 10 mL with 0.14 M HNO3 Rodushkin and Odman,2001
Dilution (1:10 or 1:100) with water Miekeley et al., 2002Five times dilution with 1% (v/v) HNO3 de Boer et al., 20041 mL urine (already acidified when sampling) + 100 μL conc.
HNO3, filling up to 5mL with waterHeitland and Koster,
2004, 20061 mL specimen + 9 mL 2% HCl Rodushkin et al., 20041+ 9 (v/v) with 1% HNO3 Alimonti et al., 20050.4 (or 0.6) mL urine, addition 3.6 (or 2.3) mL solution 0.65%
(w/v) HNO3 + 0.01% (v/v) Triton + 0.5% (v/v) butanolGoulle et al., 2005
500 μL urine (already acidified when sampling) in 10 mL0.5% (v/v) HNO3 + 0.005% (v/v) Triton X-100
Batista, 2009
1 mL urine + 0.3 mL conc. HNO3, filling up to 10 g andfiltration (0.45 μm)
Shirai et al., 2010
TABLE 3. Examples of digestion methods employed in Sb determinations in human urine
Method Reference(s)
HNO3-H2SO4 ashing Ludersdorf et al., 1987100–200 mL urine in a Teflon beaker, addition of 30 mL
HNO3 + 3.3 mL H2SO4 + 2 mL HClO4; time not givenKobayashi and Imaizumi,
19895 mL urine in a tight Teflon container, addition of
2.5 mL conc. HNO3, placement in a hot-air circulatingdesiccator at 130◦C for 90 min
Arai et al., 1994
10.0 mL urine + 10.0 mL 3:1HNO3-HClO4, hot digestion(100–150◦C) until colorless
Qin et al., 1996
- 2 mL urine in a Teflon vessel, addition of 1 mL conc.HNO3 + 0.5 mL 30% H2O2, placement in a microwaveoven (250–800 W) for less than 30 min
Krachler et al., 1998a
- 5 mL urine + 2 mL H2O2 + 1 mL HNO3, irradiation byUV (500 W lamp) for 90 min
3 mL urine in an open glassy C vessel, addition of 0.5 mLH2SO4 + 3 mL HNO3 + 0.5 mL HClO4 + 0.1 mL HF,placement in an Al heating block; time not given
Krachler et al., 2001
1 mL urine + 0.4 mL conc HNO3 + 0.2 mL H2O2 in amicrowave oven; time not given
Xie et al., 2001
1 mL urine + 0.25 mL 65% HNO3 + 0.5 mL 30% H2O2,irradiation by UV (500 W Hg lamp) for 90 min
Iavicoli et al., 2002
5 mL urine + 65% HNO3 in a microwave oven (300 W)for 4 min
Liao et al., 2004; Liao et al.,2006
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 183
TABLE 4. CRM used in the studies reported in Tables 1 and 6a
Reference MaterialCertified Sb
concentration Other Sb concentrations
BCR 063 skim milk powder none noneBCR 150 skim milk powder,
spikednone none
BCR 185R bovine liver none noneBCR 194 bovine blood none noneIAEA A-11 cow milk powder none noneNBS 1571 orchard leaves (2.9 ± 0.3) μg g−1
NBS 1577 bovine liver none 0.005 μg g−1 (not certified)NBS 1633b constituents elements
in coal fly ashnone 6 mg kg−1 (not certified)
NBS 2670 toxic metals infreeze-dried urine
same as NIST 2670 none
NBS 8419 inorganic constituentsin bovine serum
none none
NBS must beNIST 1566
oyster tissue
NIST 1541 iron foil for MossbauerNIST 1547 peach leaves none 0.02 μg g−1 (not certified)NIST 1549 nonfat milk powder none 0.00027 μg g−1 (information
value)NIST 1566a oyster tissue none 0.010 μg g−1 (information
value)NIST 1566b oyster tissue none 0.01 mg kg−1 (reference
value)NIST 1577a bovine liver none 0.003 μg g−1 (not certified)NIST 1577b bovine liver none 0.003 μg kg−1 (not certified)NIST 1640 trace elements in
natural water(13.79 ± 0.42) μg kg−1
NIST 1643c trace elements in water none noneNIST 2670 trace elements in
freeze-dried urinenone none
NIST 2670alow level
toxic elements infreeze-dried urine
(0.971 ± 0.033) μg L−1
NIST 2670ahigh level
toxic elements infreeze-dried urine
(0.824·± 0.070) μg L−1
NIST 2676c metals on filter media(atmosphericparticles)
none none
aCRMs IAEA H-4 (animal muscle), IAEA HM-1 (human milk) and NIES 153 (unknown) are mentioned invery few articles (see Table 6) but it has proved impossible to trace whether they had a (certified or not)antimony concentration value when they were available.
studies are listed in Table 4. A brief inspection reveals that most of themhave no certified value for antimony and that, in the very few cases where aconcentration is known, it largely exceeds antimony concentrations in urine.Thus, the accuracy of published antimony concentration values in urineremains an open question. It should be mentioned that a characteristic featureof this type of analysis is the use of commercial reference materials, the use
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
184 M. Filella et al.
of which is completely unknown in the analysis of other matrices (e.g.,waters, soils and sediments, Filella et al., 2002; hair and nails, Filella et al.,2011). A wide range of commercial materials are used, including: ClinRep(RECIPE Chemicals & Instruments, GmbH, Munich, Germany; Iavicoli et al.,2002), Lyphocheck Urine Metals Control and Lyphocheck Quantitative UrineControl (Bio-Rad Laboratories, different countries; Apostoli et al., 1998; Eliazet al., 2006; Gebel et al., 1998b; Heitland and Koster, 2004; Smith et al.,1995), Clincheck Urine Control (Recipe, Munich, Germany; Heitland andKoster, 2004); Medisafe Urine Control (Medichem, Steinenbronn, Germany;Heitland and Koster, 2004, 2006), Seronorm (Nycomed AS, Oslo, Norway;Krachler and Emons, 2001; Miekeley et al., 2002 (spiked); Minoia et al.,1990; Rodushkin et al., 2004; Rodushkin and Odman, 2001), Seronorm (SeroAS, Billingstad, Norway; De Boer et al., 2004; Goulle et al., 2005; Heitlandand Koster, 2006). Whether all these commercial materials contain knownamounts of antimony or whether they have been used to check for otherelement concentrations in multielemental studies is not known.
Antimony is present in low concentrations in urine of nonexposed indi-viduals, often close to the detection limit (DL) of the techniques commonlyused. In many studies, antimony was not detected in all of the samples. Thisinformation and the way the below detection limit (BDL) samples are takeninto account in calculating the mean or median values themselves are notalways detailed. When BDL values are excluded, published concentrationsoverestimate real values. The effect that the technique DL has on the resultsobtained was clearly shown by Caldwell et al. (2005). These authors analyzed2,276 samples by ICP-MS with a DL = 0.04 μg L−1 and found a geometricmean = 0.13 μg L−1; when they had analyzed 496 samples some years be-fore by ICP but with a DL = 0.3 μg L−1, they had found a geometric mean of0.74 μg L−1. The values collected in Table 1 show a clear decrease of reportedconcentrations over time for nonexposed populations as more recent studiesusing more sensitive analytical techniques. The clear implication is that allvalues obtained in the past by using methods with higher DL than currentICP-MS apparatus probably overestimate antimony concentrations, at least inthe case of nonexposed individuals. Recent values (Caldwell et al., 2005; Cen-ters for Disease Control and Prevention, 2011; Health Canada, 2010; Heitlandand Koster, 2006b; Richter et al., 2009; Schulz et al., 2009), obtained usinglow DL analytical techniques and based on a high number of individuals, arein the range of 0.06–0.13 μg L−1. They make it possible to conclude that an-timony concentrations in the urine of nonexposed individuals do not exceed0.1 μg L−1. Concentration values considered normal by public bodies, whichare based on older—and thus higher—concentrations, probably need to bereconsidered.
In relation to concentrations measured by ICP-MS, it should be men-tioned that, since ICP often involves a multielement determination, less at-tention may be paid to elements present in very low concentrations, such
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 185
as antimony, especially when they are not the primary object of the study(which, for antimony, is often the case) and are simply added to the packagebecause the technique is capable of measuring them.
In Table 5, published studies are classified according to the objective ofthe work, using the following categories: nonexposure values (21 studies),analytical (20), medical (13), environmental (9), and occupational exposure(17). Please note that some articles may fall into two categories.
One of the oldest reasons for the detection and determination of anti-mony in human urine has been to follow up on its excretion after antimony-containing drugs were administered, mainly for the treatment of tropicaldiseases and, in particular, leishmaniasis. The classic article by Goodwin andPage (1943) contains a comprehensive table listing older studies where anti-mony excretion during the treatment of tropical diseases was either detectedor determined quantitatively. The first paper mentioned dates from 1916 (DiCristina and Caronia, 1916). Publication of such studies continued steadilythrough the 1950s (e.g., Chakravarti and Sen Gupta, 1950; Chatterjee et al.,1954; Chatterji et al., 1956; Gellhorn et al., 1947) up to the present (e.g.,Zaghloul et al., 2010). Results related to antimony excretion kinetics afteradministration of antimony-containing drugs used to treat tropical diseasesare not included in this study; only values of antimony concentrations inurine for untreated patients are quoted in Table 1 when given in this type ofstudy (classified as Medical in Table 5).
Illnesses and drug administration may have an effect on the excretionof trace elements from the human body. For this reason, the trace elementcomposition of urine has often been monitored in order to assess sucheffects. However, very few published studies contain antimony data (sevenarticles) and those that do have also been classified as Medical in Table 5.They seem to suggest that antimony excretion in urine is not affected bymedical conditions and treatments but there are scant data and their quality isnot always easy to assess in order to be able to reach any general conclusions.
As mentioned in the Introduction, the many different uses of antimonymakes it particularly interesting to be able to follow antimony exposure inan integrated way. However, studies published in the field of environmentalexposure to antimony are not abundant (nine articles, three of which are bythe same authors and probably contain the same data) and results are farfrom conclusive.
Finally, urinary excretion of antimony has been monitored in the con-text of occupational studies. In fact, some of the oldest studies that containurinary data belong to occupational work (e.g., Brieger et al., 1954; Klucikand Kemka, 1960). In particular, workers’ exposure to antimony levels in-doors has been followed in different types of industries (Apostoli et al., 1994;Bailly et al., 1991; Kentner et al., 1994; Ludersdorf et al., 1987) and positivecorrelations have been found between airborne and urinary antimony con-centrations in some cases (Apostoli et al., 1994; Bailly et al., 1991; Kentner
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
5.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s
Typ
eofst
udy
Study
des
crip
tion
Corr
elat
ion
found?/
Oth
erco
mm
ents
Multi
elem
ent?
Ref
eren
ce
No
nex
po
sure
valu
es“N
orm
alco
nce
ntrat
ions”
Lite
ratu
reva
lues
butex
actso
urc
enot
clea
rye
sSc
hro
eder
and
Nas
on,19
71Ital
ian
popula
tion
Dai
lyex
cret
ion
yes
Cle
men
te,19
76B
DL
Ital
ian
popula
tion
Dai
lyex
cret
ion
Man
yva
lues
BD
Lye
sCle
men
teet
al.,
1977
Ital
ian
popula
tion
Dai
lyex
cret
ion
yes
Cle
men
teet
al.,
1978
BD
LA
dult
valu
esco
mpila
tion
Lite
ratu
reva
lues
,th
ree
refe
rence
sye
sIy
enga
ret
al.,
1978
Est
ablis
hm
entofre
fere
nce
valu
esin
Ital
ian
subje
cts
(hea
lthy
popula
tion,
Lom
bar
dy)
0.79
μg
L−1ye
sM
inoia
etal
.,19
90
Ref
eren
ceco
nce
ntrat
ions
Lite
ratu
reva
lues
,only
one
sourc
e(a
seco
ndar
yso
urc
epublis
hed
16ye
ars
bef
ore
)
yes
Car
oli
etal
.,19
94
Ele
men
tre
fere
nce
valu
esfo
rth
eG
Bpopula
tion
Lite
ratu
reva
lues
:1
μg
L−1ye
sH
amilt
on
etal
.,19
94
Hea
lthy
univ
ersi
tyst
uden
ts,CN
Val
ues
too
hig
hSb
only
Qin
etal
.19
96Ran
dom
lyse
lect
edhea
lthy
infa
nts
firs
tye
aroflif
e,IE
“Antim
ony
conce
ntrat
ions
inurine
wer
eunre
late
dto
the
age
or
sex
ofth
ein
fant,
pat
ernal
soci
alcl
ass
or
occ
upat
ion,m
edic
alco
vera
gest
atus
of
the
fam
ily,or
the
type
ofm
attres
suse
d”
Sbonly
Culle
net
al.,
1998
186
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Ref
eren
cem
anre
-eva
luat
ion
Lite
ratu
reva
lues
yes
Iyen
gar,
1998
U.S
.popula
tion
(NH
AN
ES
III19
88–1
994)
1.30
μg
L−1ye
sPas
chal
etal
.,19
98U
.S.popula
tion
Most
sam
ple
sB
DL
yes
Kom
arom
y-H
iller
etal
.,20
00H
ealth
ysu
bje
cts
from
central
ITK
olm
ogo
rov-
Smirnov
test
:norm
aldat
afe
mal
es<
mal
es(p
<0.
01)
yes
Alim
onti
etal
.,20
05
U.S
.popula
tion
(NH
AN
ES
1999
–200
0)0.
13μ
gL−1
Low
erD
Lre
sults
inlo
wer
conce
ntrat
ions
com
par
edw
ithpre
vious
surv
ey(P
asch
alet
al.,
1998
)
yes
Cal
dw
ellet
al.,
2005
Child
ren
and
adults
inD
E0.
063
μg
L−1
“Most
ofth
ege
om
etric
mea
nco
nce
ntrat
ions
ofth
eel
emen
tsar
ehig
her
for
child
ren
than
for
adults
”but
no
stat
s
yes
Hei
tland
and
Kost
er,
2006
b
Hea
lthy,
nonex
pose
dsu
bje
cts,
BR
0.2
μg
L−1
Influen
ceofsm
oki
ng,
alco
hol
consu
mptio
n:ap
par
ently
no
effe
cton
Sbbutno
dat
ash
ow
nan
dno
stat
s;ef
fect
ofag
ean
dge
nder
:no
diffe
rence
(p>
0.05
)
yes
Bat
ista
etal
.,20
09
Ref
eren
ceva
lues
child
ren
(3–1
4ye
ars
old
)in
DE
Ref
eren
ceva
lue
(95t
hpopula
tion
per
centil
eofth
edis
trib
utio
nof
conce
ntrat
ions)
=0.
3μ
gL−1
(med
ian
=0.
1μ
gL−1
)
yes
Kom
mis
sion
“Hum
an-
Bio
monito
ring”
,20
09;Sc
hulz
etal
.,20
09(C
onti
nu
edon
nex
tpa
ge)
187
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
5.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s(C
onti
nu
ed)
Typ
eofst
udy
Study
des
crip
tion
Corr
elat
ion
found?/
Oth
erco
mm
ents
Multi
elem
ent?
Ref
eren
ce
Can
adia
npopula
tion
(6–7
8ye
ars
old
),20
07–2
009
95th
popula
tion
per
centil
eofth
edis
trib
utio
nofco
nce
ntrat
ions
=0.
18μ
gL−1
(geo
met
ric
mea
n=
0.04
μg
L−1)
yes
Hea
lthCan
ada.
2010
Unex
pose
dpre
gnan
tw
om
en,Toky
o,JP
(200
7,20
08)
All
sam
ple
sB
DL
yes
Shirai
etal
.,20
10
U.S
.popula
tion
(NH
AN
ES
2007
–200
8);
valu
esfo
rpre
vious
year
sal
sogi
ven
95th
popula
tion
per
centil
eofth
edis
trib
utio
nofco
nce
ntrat
ions
=0.
240
μg
L−1(g
eom
etric
mea
n=
0.06
1μ
gL−1
)
yes
NH
AN
ES,
2011
An
aly
tica
lD
eter
min
atio
nby
sorb
entex
trac
tion
+ET-A
AS
with
com
par
ison
ofw
etdig
estio
nan
ddirec
tex
trac
tion
Rec
om
men
ded
:no
dig
estio
nSb
and
Pb
only
Smith
and
Griffi
ths,
1982
Det
erm
inat
ion
by
resi
nco
mple
xatio
nco
mbin
edw
ithH
G-I
CP-E
S—
yes
Fodor
and
Bar
nes
,19
83D
eter
min
atio
nby
ASV
—Sb
only
Rat
etal
.,19
85D
eter
min
atio
nby
candolu
min
esce
nce
afte
rso
lven
tex
trac
tion
—Sb
only
Cla
rkan
dPat
el,19
86
Det
erm
inat
ion
by
GF-
AA
Saf
ter
ion
exch
ange
separ
atio
nan
dso
lven
tex
trac
tion
—Sb
only
Kobay
ashian
dIm
aizu
mi,
1989
Tes
ting
anal
ysis
by
ICP-M
Sw
ithout
sam
ple
dig
estio
n—
Sbonly
Mulli
gan
etal
.,19
90
188
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Dev
elopm
entofa
spec
iatio
nm
ethod
by
HG
-AA
S—
Sbonly
Pet
itde
Pen
aet
al.,
1990
Det
erm
inat
ion
solv
entex
trac
tion
+ET-A
AS
—Sb
only
Smith
etal
.,19
95
Det
erm
inat
ion
by
dilu
tion
and
ICP-M
S—
Sbonly
Del
ves
etal
.,19
97D
eter
min
atio
nby
dilu
tion
and
ICP-M
S—
yes
Schra
mel
etal
.,19
97Com
par
ison
ofpre
trea
tmen
tpro
cedure
s(d
ilutio
n,U
Virra
dia
tion,m
icro
wav
edig
estio
n)
Rec
om
men
ded
:w
ater
1:10
dilu
tion
of
centrifuge
dsa
mple
san
ddet
erm
inat
ion
by
Q-I
CP-M
S
yes
Kra
chle
ret
al.,
1998
a
Dev
elopm
entofa
spec
iatio
nm
ethod
by
HPLC
-ICP-M
S—
Sbonly
Kra
chle
ran
dEm
ons,
2001
Applic
atio
nofSF
-ICP-M
Sto
the
sim
ulta
neo
us
det
erm
inat
ion
of42
elem
ents
inurine
—ye
sRodush
kin
and
Odm
an,20
01
Dev
elopm
entofa
scre
enin
gm
ethod
for
rapid
anal
ysis
ofa
grea
tnum
ber
of
sam
ple
s,bas
edon
dilu
tion
and
Q-I
CP-M
S
—ye
sde
Boer
etal
.,20
04
Dev
elopm
entan
dte
stofa
routin
em
ulti
elem
entdet
erm
inat
ion
met
hod
bas
edon
the
use
ofIC
P-M
Sw
ithout
sam
ple
dig
estio
n
—ye
sH
eitla
nd
and
Kost
er,
2004
(Con
tin
ued
onn
ext
page
)
189
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
5.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s(C
onti
nu
ed)
Typ
eofst
udy
Study
des
crip
tion
Corr
elat
ion
found?/
Oth
erco
mm
ents
Multi
elem
ent?
Ref
eren
ce
Applic
atio
nofSF
-ICP-M
Sto
the
sim
ulta
neo
us
det
erm
inat
ion
of20
elem
ents
atultr
a-trac
ele
vels
inurine
—ye
sRodush
kin
etal
.,20
04
Com
par
ison
ofQ
-ICP-M
San
dSF
-ICP-M
S;an
alys
is—
yes
Alim
onti
etal
.,20
05
Val
idat
ion
offo
ur
ICP-b
ased
met
hods
—ye
sG
oulle
etal
.,20
05D
evel
opm
entofa
spec
iatio
nm
ethod
by
on-lin
ecl
oud
poin
tex
trac
tion
and
ETV
-ICP-E
S
—Sb
only
Liet
al.,
2006
Dev
elopm
entofa
spec
iatio
nm
ethod
by
HPLC
-HG
-AS
—Sb
only
Quiroz
etal
.,20
10
Med
ical
Controlin
ast
udy
on
bilh
arzi
asis
Sbtrea
tmen
t—
Sbonly
Man
sour
etal
.,19
67
Hyp
er-p
arat
hyr
oid
ism
pat
ients
No
clea
rco
ncl
usi
on
yes
Bost
rom
and
Wes
ter,
1969
Hyp
erte
nsi
vepat
ients
trea
ted
with
chlo
rthal
idone
Pai
red
tte
stN
osi
gnifi
cantdiffe
rence
(p>
0.05
)ye
sW
este
ret
al.,
1973
Hyp
erte
nsi
vepat
ients
trea
ted
with
hyd
rala
zine
Pai
red
tte
stN
osi
gnifi
cantdiffe
rence
(p>
0.05
)ye
sW
este
ret
al.,
1973
Effec
tofst
arva
tion
(all
studie
del
emen
ts)
and
anore
xia
ner
vosa
(notfo
rSb
)“T
he
conce
ntrat
ion
ofSb
does
notva
rysi
gnifi
cantly
”butno
stat
istic
sye
sW
ard,19
86
Controlin
asp
ecia
tion
study
prior
and
afte
rtrea
tmen
tofle
ishm
ania
sis
pat
ients
with
Glu
cantim
e
—Sb
only
Pet
itde
Pen
aet
al.,
1990
Controlin
asp
ecia
tion
study
prior
and
afte
rtrea
tmen
tofle
ishm
ania
sis
pat
ients
with
Glu
cantim
e
—Sb
only
Burg
uer
aet
al.,
1993
190
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Sbin
urine
ofin
fants
(<2
year
sold
)“D
ata
sugg
estth
atfo
etal
assi
mila
tion
may
be
grea
ter
than
post
nat
alupta
ke”
Sbonly
Del
ves
etal
.,19
97
Sbin
urine
ofin
fants
(<2
year
sold
)—
Sbonly
Dez
ateu
xet
al.19
97In
fants
dyi
ng
from
SID
San
din
fants
dyi
ng
from
oth
erca
use
sN
osi
gnifi
cantdiffe
rence
sbet
wee
nin
fants
dyi
ng
from
SID
S,in
fants
dyi
ng
from
oth
erca
use
san
dhea
lthy
infa
nts
(Culle
net
al.,
1998
),st
ats
Sbonly
Culle
net
al.,
2000
Controlin
ast
udy
on
Glu
cantim
etrea
tmen
tofle
ishm
ania
sis
—Sb
only
Mie
kele
yet
al.20
02
Met
als
inurine
and
per
ipher
alar
terial
dis
ease
(PA
D)
“PA
Drisk
incr
ease
dsh
arply
atlo
wle
vels
ofSb
and
rem
ained
elev
ated
bey
ond
0.1
μg
L−1”
(only
when
nonlin
ear
model
sap
plie
d)
yes
Nav
as-A
cien
etal
.,20
05
Effec
tofM
CP
on
urinar
yex
cret
ion
of
trac
eel
emen
tsSt
uden
t’st
test
or
Wilc
oxo
nsi
gned
-ran
kte
stdep
endin
gon
dat
anorm
ality
(chec
ked
by
the
Shap
iro-W
ilkW
test
)“N
osi
gnifi
cantch
ange
sin
the
excr
etio
nofSb
obse
rved
”
yes
Elia
zet
al.,
2006
En
viro
nm
enta
lex
po
sure
Geo
genic
ally
expose
dad
ults
com
par
edto
“unex
pose
dones
”,D
EU
test
(tw
o-s
ided
)U
nex
pose
dgr
oup
hig
her
Sbco
nce
ntrat
ions
(p<
0.00
1);no
corr
elat
ion
with
soil
conce
ntrat
ions
Pro
bab
lysa
me
dat
aas
inG
ebel
1998
b,
1998
c
Sbonly
Geb
elet
al.,
1998
a
(Con
tin
ued
onn
ext
page
)
191
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
5.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s(C
onti
nu
ed)
Typ
eofst
udy
Study
des
crip
tion
Corr
elat
ion
found?/
Oth
erco
mm
ents
Multi
elem
ent?
Ref
eren
ce
Geo
genic
ally
expose
dad
ults
,D
EM
ale
hig
her
conce
ntrat
ions
than
wom
en(p
<0.
01)
Pro
bab
lysa
me
dat
aas
inG
ebel
1998
a,19
98c
yes
Geb
elet
al.,
1998
b
Geo
genic
ally
expose
dad
ults
com
par
edto
unex
pose
dones
,D
EU
test
(tw
o-s
ided
)N
osi
gnifi
cantco
rrel
atio
nw
ithso
ilco
nte
nts
;unex
pose
dgr
oup
hig
her
Sbco
nce
ntrat
ions
(p<
0.00
1);yo
unge
r18
year
s“l
ow
erurinar
ySb
”(p
<0.
001)
;no
corr
elat
ion
with
smoki
ng,
seaf
ood
consu
mptio
nPro
bab
lysa
me
dat
aas
inG
ebel
1998
a,19
98b
As
and
SbG
ebel
etal
.,19
98c
Pat
ients
suffer
ing
from
chro
nic
As
pois
onin
g,CN
Studen
t’st
test
with
pre
vious
dat
alo
gtran
sform
atio
nbec
ause
dis
trib
utio
nposi
tivel
ysk
ewed
No
sign
ifica
ntdiffe
rence
(p>
0.05
)
yes
Xie
etal
.,20
01
Popula
tion
inEnsc
hed
e,th
eN
L,fo
llow
ing
ala
rge
fire
work
explo
sion
—ye
sde
Boer
etal
.,20
04
Urinar
ym
etal
conte
nts
follo
win
gex
posu
reto
ala
rge
fore
stfire
,Cer
roG
rande
Fire
,U
S
Noth
ing
on
Sb,ex
cepturine
valu
esye
sW
olfe
etal
.,20
04
Res
iden
tsofa
villa
gecl
ose
toan
aban
doned
min
ing
area
,SK
Spea
rman
’sco
rrel
atio
nco
effici
ent
No
control;
corr
elat
ion
with
Sbin
soil
not
stat
istic
ally
sign
ifica
nt(p
>0.
05)
yes
Rap
antet
al.,
2006
Study
ofth
eex
posu
reto
tobac
co(N
HAN
ES,
1999
–200
4,U
S)t
test
“Sm
oke
rshad
hig
her
antim
ony
leve
lsth
annon
smoke
rs”
(p<
0.00
1)
yes
Ric
hte
ret
al.,
2009
192
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Occ
up
atio
nal
exp
osu
reW
ork
ers
expose
dto
air
conta
inin
gab
out
3m
gSb
m−3
,U
SN
one
Sbonly
Brieg
eret
al.,
1954
Met
allu
rgic
alw
ork
ers,
CZ
Follo
w-u
pfo
rper
iods
of8
and
11day
s.Res
ults
,only
give
nin
grap
hic
alfo
rm,
show
stro
ng
tem
pora
lva
riab
ility
Sbonly
Klu
cik
and
Kem
ka,
1960
Sbpro
cess
ing
indust
ryw
ork
ers,
US
No
consi
sten
tpat
tern
ofab
norm
aliti
esSb
only
Cooper
1968
Gla
ss-p
roduci
ng
indust
ryw
ork
ers,
DE
Man
n-W
hitn
eyte
stSb
valu
esfo
rbat
chm
ixer
shig
her
than
controls
and
any
oth
ersu
bgr
oup
(p<
0.05
)N
oco
rrel
atio
nw
ithex
posu
rebec
ause
air
sam
ple
sB
DL
Blo
od
vs.urine
corr
elat
ion,
r=
0.21
Sban
dPb
only
Luder
sdorf
etal
.,19
87
Har
dm
etal
indust
ryw
ork
ers,
ITA
ppar
ently
BD
L,no
com
men
tsY
esN
icola
ou
etal
.,19
87W
ork
ers
expose
dto
Sb,B
EPosi
tive
corr
elat
ion
bet
wee
nlo
gof
airb
orn
eSb
and
log
ofSb
inpost
shift
urine
sam
ple
s(r
=0.
83,
p<
0.00
01)
Sbonly
Bai
llyet
al.,
1991
Work
ers
inSb
-conta
inin
gpro
duct
fact
ory
,CN
None
Sbonly
Chen
etal
.,19
92
Art
glas
sm
anufa
cturing
work
ers,
ITD
ata
notnorm
ally
dis
trib
ute
d(K
olm
ogo
rov
test
);lo
gco
nce
ntrat
ions
use
din
com
par
isons
“Urinar
yco
nce
ntrat
ions
hig
her
inex
pose
dvs
.co
ntrolsu
bje
cts”
butno
stat
s;Sb
inurine
corr
elat
edw
ithai
rSb
(r=
0.82
butno
pva
lue
give
n)
Yes
Apost
oli
etal
.,19
94
(Con
tin
ued
onn
ext
page
)
193
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
5.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anurine
sam
ple
s(C
onti
nu
ed)
Typ
eofst
udy
Study
des
crip
tion
Corr
elat
ion
found?/
Oth
erco
mm
ents
Multi
elem
ent?
Ref
eren
ce
Clo
isonne
work
ers,
JPW
ilcoxo
nte
stN
ost
atis
tical
sign
ifica
ntdiffe
rence
bet
wee
nw
ork
ers
and
controls
Yes
Ara
iet
al.,
1994
Lead
bat
tery
pro
duct
ion
indust
ryw
ork
ers,
GE
Sbhal
f-liv
esw
ere
of93
.2hr
for
cast
ers
and
95.1
hr
for
form
ers
Posi
tive
corr
elat
ion
bet
wee
nai
rborn
eSb
vs.urine
Sb(r
=0.
75,
p<
0.05
)
Sbonly
Ken
tner
etal
.,19
94
Sbsm
elte
rw
ork
shop
work
ers,
CN
None
Sbonly
Huo
etal
.,19
95W
ork
ers
expose
dto
antim
ony
trio
xide
leve
ls,IT
tte
stSi
gnifi
cantdiffe
rence
sbeg
innin
gsh
iftvs
.co
ntrolan
den
dsh
iftvs
.co
ntrolfo
ral
lw
ork
ers
(p<
0.00
1);no
sign
ifica
nt
diffe
rence
sbeg
innin
gvs
.en
dsh
iftfo
rboth
hig
her
exposu
rean
dje
tw
ork
ers
Sbonly
Iavi
coli
etal
.,20
02
NY
Cfire
figh
ters
,U
Sin
WTC
fire
and
colla
pse
,Se
p20
01O
f11
0ch
emic
als
test
ed,only
6fo
und
inco
nce
ntrat
ions
sign
ifica
ntly
hig
her
than
inco
ntrols
,one
ofw
hic
hSb
(p<
0.01
)Conce
ntrat
ions
infire
figh
ters
pre
sentat
colla
pse
(148
)hig
her
than
those
pre
sentday
s1–
2(1
42),
fire
figh
ters
insp
ecia
loper
atio
ns
com
man
d(9
5)hig
her
than
oth
erfire
figh
ters
(195
)(p
<0.
01)
Yes
Edel
man
etal
.,20
03
194
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Opto
elec
tronic
indust
ryw
ork
ers,
TW
tte
stap
plie
dto
diffe
rence
sbet
wee
nto
tals
,one-
way
anal
ysis
ofva
rian
cete
stto
diffe
rence
sbet
wee
ngr
oups
No
sign
ifica
ntdiffe
rence
sw
ithco
ntrols
and
among
groups
Pea
rson
rblo
od
vs.urine
Sb=
0.29
1(p
<0.
05)
Yes
Liao
etal
.,20
04
Urinar
ym
etal
conte
nts
follo
win
gex
posu
reto
ala
rge
fore
stfire
,Cer
roG
rande
Fire
,U
S
Noth
ing
on
Sb,ex
cepturine
valu
esY
esW
olfe
etal
.,20
04
Opto
elec
tronic
indust
ryw
ork
ers,
TW
Pro
bab
lysa
me
dat
aas
inLi
aoet
al.,
2004
Yes
Liao
etal
.,20
06Eva
luat
ion
ofSb
exposu
refr
om
Sb-c
onta
inin
gpan
ts,U
St
test
applie
dto
log
conce
ntrat
ions
bec
ause
log
dat
anorm
ally
dis
trib
ute
dN
osi
gnifi
cantdiffe
rence
sbet
wee
nfire
figh
ters
wea
ring
and
notw
earing
Sb-c
onta
inin
gpan
ts(p
=0.
31);
both
sign
ifica
ntly
low
erth
ange
ner
alpopula
tion
(p<
0.00
1)
Yes
de
Per
ioet
al.,
2010
Not
e.Cla
ssifi
catio
nofth
epublis
hed
studie
sac
cord
ing
toth
eobje
ctiv
eofth
est
udy.
See
text
fordet
ails
on
the
crite
ria
applie
d.The
entrie
sar
eth
esa
me
asin
Tab
le1.
195
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
196 M. Filella et al.
et al., 1994). However, the American Conference of Governmental IndustrialHygienists, a private organization that publishes biological exposure indicesthat “generally indicate a concentration below which nearly all workers maybe repeatedly exposed without adverse health effects” (American Conferenceof Governmental Industrial Hygienists, 2011a), estimates that developing bio-logical exposure index values for antimony is not currently feasible owing toinadequate scientific data (American Conference of Governmental IndustrialHygienists, 2011b).
A key question in biomonitoring is to know how well the concentrationin the measured matrix reflects bodily exposure. In the case of elementswith more than one oxidation state, the rate of assimilation and excretionmight differ depending on the redox state, and this appears to be the casefor antimony. Based on animal studies, it has long been known that pentava-lent antimony is mostly excreted in urine and trivalent antimony mainly infeces (Brieger et al., 1954; Edel et al., 1983; Goodwin and Page, 1943; Ottoand Maren, 1950; Rees et al., 1980); pentavalent antimony is also excretedfaster (Goodwin and Page, 1943). It should be pointed out, however, thatthese observations were made after injecting relatively high doses of thecorresponding compounds and, therefore, in conditions far removed fromthose of diffuse environmental exposure to much lower concentrations ofantimony compounds. Such studies usually assume that there is no redoxtransformation of antimony after intake.
However, interesting additional information might be furnished by de-termining the redox state of antimony in urine. Unfortunately, only a fewstudies giving this information have been published, and they focus mostlyon developing the necessary analytical techniques rather than on measuringthe concentration of antimony species in a large number of individuals. Theyare briefly detailed subsequently.
In 1990, Petit de Pena et al. (1990) proposed the selective determinationof Sb(III) and Sb(V) species by exploiting the acidic dependence of the evo-lution of stibine (SbH3) on reduction with sodium borohydride in HG-AAS(total Sb determined in 0.5 M H2SO4 and Sb(III) in citric acid, pH 2.5). Whenapplied to the urine of patients with leishmaniasis injected intravenously withGlucantime, they found similar amounts of Sb(V) and Sb(III) in untreatedand treated patients. However, 10 years later, Krachler and Emons (2001),by coupling on-line high performance liquid chromatography (HPLC) to anICP-MS instrument, found that Sb(V) was by far the predominant Sb speciesin human urine and only traces of Sb(III) (and some trimethyl antimony(V)[TMSbCl2]) were sometimes detected. Sb(V), Sb(III), and TMSbCl2 detectedaccounted for 52–78% of total antimony, depending on the sample. Mieke-ley et al. (2002), after intramuscular administration of N-methyl meglumineantimoniate, detected both Sb(III) and Sb(V). Their technique differed fromthat used in previous studies (a Hamilton PRP-100X anion exchange columnwith ethylenediaminotetraacetic acid [EDTA] as the mobile phase, coupled
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 197
to ICP-MS). They found that, although only a small fraction of total anti-mony was present as anionic Sb(V) (<7%) in pure aqueous drug solutions(the remainder being bound to the organic structure of the drug), the Sb(V)fraction increased significantly in urine from patients treated with the drugand, interestingly, a peak of Sb(III) appeared, especially in samples collectedduring the slow drug elimination phase of the drug, suggesting in vivo Sb(V)reduction. Concentrations of antimony species determined by Li et al. (2006)by on-line cloud point extraction combined with electrothermal vaporization(ETV) ICP-MS were too high (2 ng mL−1 = 2000 ng L−1) to be considered re-liable. Very recently, Quiroz et al. (2011) published a HPLC-HG-AFS method(Hamilton PRP-100X column; EDTA, pH 4.5, and phosphate, pH 8.3, as mo-bile phases) but this appears to be useful only for elevated/occupationalexposed urine samples because, when applied to real samples, Sb(V) couldonly be detected in two of the eight samples analyzed. Neither Sb(III) norSbTMSb(V) were detected. Therefore, it can be concluded that redox speci-ation of antimony in urine at nonexposed healthy individual concentrationlevels largely requires further elucidation.
Breast Milk
Breast milk is an additional route of excretion of unwanted substances thathas attracted particular attention because it can be a dangerous source ofintake for newborns (LaKind et al., 2001; Pronczuk et al., 2002). The num-ber of publications that contain data on antimony in breast milk is muchlower than that for urine: only 14 studies have been found, with publicationdates ranging from 1982 to 2008. The information gathered is presented inTable 6, according to the same criteria followed for urine. Concentrationsare sometimes expressed on a mass-basis and sometimes on a volume-basisbut, according to Rossipal and Krachler (1998), the differences in both con-centrations are negligibly small because the density of the different types ofhuman milk is always close to 1 g mL−1 (colostrum: 1.013; transitory milk:1.006; mature milk: 1.015).
Most of the methodological issues discussed in relation to urine (i.e.,risk of contamination, preservation, digestion, and analysis of samples) alsoapply to milk and will not be repeated here. It should perhaps be mentioned,however, that NAA has been more widely applied in milk (eight of 14 studies)than is the case for urine.
It is not possible to draw any conclusions about the utility of antimonymeasurements in milk because of the limited number of studies published.Moreover, it should be mentioned that milk values are subjected to numeroussources of variability. In particular, although in the case of antimony no cor-relation of the amount taken up as lactation progresses could be established(Wappelhorst et al., 2002), it has been observed that the concentration ofsome elements in breast milk changes during the course of lactation (Aquilio
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
6.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anm
ilksa
mple
s.Publis
hed
valu
esofan
timony
conce
ntrat
ions
Sam
ple
origi
na
Num
ber
of
sam
ple
sN
um
ber
of
moth
ers
Units
bM
ean
cErr
ord
Med
ian
Val
ue
range
or
oth
erst
atis
tical
info
rmat
ion
e
Pre
trea
tmen
tan
ddig
estio
nf
Tec
hniq
ueg
CRM
?hRef
eren
ce
Mat
ure
milk
,IT
>13
021
ng
g−1
ww
3.0
0.4
≤0.5
BD
L-12
.9AD
L:49
sam
ple
sst
ora
ge:N
IN
AA
(0.0
5)N
BS
orc
har
dle
aves
:N
RS
Cle
men
teet
al.,
1982
Poole
dhum
anm
ilksa
mple
9ng
g−1
135
n=
18st
ora
ge:N
IIN
AA
NM
Iyen
gar
etal
.,19
82
Ljublja
na,
SIμ
gkg
−1st
ora
ge:
free
ze-d
ryin
gN
AA
IAEA
A-1
1,H
-4K
ost
aet
al.,
1983
-co
lost
rum
100.
50.
30.
1–1.
0-tran
sitio
nal
160.
550.
670.
12–3
.0-m
ature
41.
21.
30.
8–3.
2M
oth
ers,
GB
(most
sam
ple
stran
sitio
nal
milk
)
4219
μg
mL−
1<
0.02
8–0.
169
stora
ge:N
Idilu
tion,no
dig
estio
n
ICP-M
SN
BS
1577
:N
SbRS
Durr
antan
dW
ard,
1989
Guat
emal
a84
μg
L−1
11%
1.0
BD
L-13
.3st
ora
ge:
free
ze-d
ryin
gIN
AA
(≈0.
2)IA
EA
A-1
1,H
M-1
:Sb
resu
ltsonly
for
HM
-1
WH
O,19
89;Par
ret
al.,
1991
Hunga
ry71
10%
1.6
BD
L-7.
7N
iger
ia18
57%
4.1
0.2–
17.7
Phili
ppin
es65
14%
11.0
BD
L-43
.0Sw
eden
3225
%3.
00.
3–22
.9Zai
re69
10%
3.6
BD
L-26
.6Colo
stru
m,m
oth
ers
(22–
26ye
ars
old
),N
agpur,
IN
3ng
g−1
1.02
,0.
93,0.
79st
ora
ge:N
Ipre
trea
tmen
t:ev
apora
tion
by
slow
hea
ting
RN
AA
NIS
T15
49,IA
EA
A-1
1:N
RS
Gar
get
al.,
1993
a
Colo
stru
m3
ng
g−1
0.81
0.05
stora
ge:N
Ipre
trea
tmen
t:ev
apora
tion
by
slow
hea
ting
RN
AA
NIS
T15
77a,
1549
;IA
EA
H-4
,A
-11;
NIE
S15
3
Gar
get
al.,
1993
b
198
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Ref
eren
ceco
nce
ntrat
ions
from
publis
hed
dat
a
μg
L−1
1–4
no
refe
rence
give
nCar
oli
etal
.,19
94
Kaz
akhst
an:
115
ng
g−1
stora
ge:fr
eezi
ng
dig
estio
n:H
NO
3T
and
Pdig
estio
n
ICP-M
San
dN
AA
NIS
T16
33b,
1547
:N
RS
Lutter
etal
.,19
97-Akt
au0.
270.
12–0
.31
-Akt
ubin
sk0.
140.
11–0
.58
-Alm
aty
0.09
BD
L-8.
15-K
hro
mta
u0.
10B
DL-
10.4
4-Pav
lodar
0.11
0.11
–0.8
8-O
ldSe
mip
alat
insk
BD
LBD
L-27
.97
-N
ewSe
mip
alat
insk
BD
LBD
L-6.
9
-U
st-
Kam
enogo
rsk
1.19
0.14
–2.1
8
Gra
z,AT:
46μ
gkg
−1st
ora
ge:–2
0◦C
HN
O3-H
2O
2
mic
row
ave
assi
sted
Pdig
estio
n
ICP-M
S(0
.36)
BCR
063,
150
Kra
chle
ret
al.,
1998
b-co
lost
rum
131.
10.
7B
DL-
6.9
-tran
sito
ry18
BD
LBD
LBD
L-1.
6-m
ature
:BD
L-1.
3-42
–60
d8
BD
LBD
LBD
L-66
–90
d8
BD
LBD
LBD
L-87
–293
d8
BD
LBD
LBD
L-6.
9O
vera
ll55
0.38
BD
LBD
L:73
%sa
mple
sM
oth
ers
24–3
7ye
ars
old
ofch
ildre
n1–
16m
onth
sold
,CZ,
DE,PL
536
19μ
gL−
10.
140.
120.
06–0
.57
stora
ge:
free
ze-d
ryin
gH
NO
3-H
2O
2
mic
row
ave
assi
sted
Pdig
estio
n
ICP-M
SN
IST
1549
:N
RS
Wap
pel
hors
tet
al.,
2002
(Con
tin
ued
onn
ext
page
)
199
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
TA
BLE
6.
Surv
eyoflit
erat
ure
dat
afo
ran
timony
inhum
anm
ilksa
mple
s.Publis
hed
valu
esofan
timony
conce
ntrat
ions
(Con
tin
ued
)
Sam
ple
origi
na
Num
ber
of
sam
ple
sN
um
ber
of
moth
ers
Units
bM
ean
cErr
ord
Med
ian
Val
ue
range
or
oth
erst
atis
tical
info
rmat
ion
e
Pre
trea
tmen
tan
ddig
estio
nf
Tec
hniq
ueg
CRM
?hRef
eren
ce
Raw
alpin
di-
Isla
mab
ad,
PK
23(a
ll)ng
g−1
stora
ge:
free
ze-d
ryin
gRN
AA
(2)
NIS
T15
49,
IAEA
A-1
1N
SbRS
Gill
etal
.,20
03
-lo
w-inco
me
131.
010.
74–1
.3-m
ediu
m-
inco
me
101.
00.
83–1
.3
Moth
ers
24–3
8ye
ars
old
ofch
ildre
n0.
4–16
.4m
onth
sold
,Reg
ion
Nei
sse
(CZ,D
E,
PL)
1295
23μ
gkg
−1w
w0.
180
%st
ora
ge:N
IH
NO
3-H
2O
2
mic
row
ave
assi
sted
Pdig
estio
n
ICP-M
Sm
entio
ned
but
no
info
rmat
ion
give
n
Wunsc
hm
ann
etal
.,20
04
Moth
ers
18–5
0ye
ars
old
ofch
ildre
n4–
80w
eeks
old
,AE
205
μg
L−1
0.35
20.
268
0.50
00.
003–
0.9
stora
ge:–3
0◦C
HN
O3-H
2O
2
mic
row
ave
assi
sted
Tdig
estio
n
ICP-M
SN
IST
1577
b,
1566
b,16
40:
NRS
Abdulraz
zaq
etal
.,20
08
Not
e.Val
ues
are
give
nin
chro
nolo
gica
lord
er.
a Inte
rnat
ional
country
codes
follo
wth
eIS
O31
66co
nve
ntio
n.
bThe
origi
nal
units
are
alw
ays
give
nin
ord
erto
avoid
unnec
essa
ryer
rors
.Rem
ember
that
:μ
gkg
−1=
ng
g−1 .
c By
def
ault,
arith
met
icm
ean.
dBy
def
ault,
stan
dar
ddev
iatio
n.Rel
ativ
est
andar
ddev
iatio
nw
hen
the
valu
eis
follo
wed
by
aper
centa
gesi
gn.
e By
def
ault,
mea
sure
dra
nge
.f N
I,notin
dic
ated
.g W
hen
give
n,th
eva
lue
ofth
edet
ectio
nlim
itis
show
nin
bra
cket
sunder
the
tech
niq
ue.
hN
M=
notm
entio
ned
;N
RS
=no
resu
ltssh
ow
n(n
eith
erfo
ran
timony
nor
for
oth
erel
emen
ts);
NSb
RS
=no
Sbre
sults
show
n(b
utre
sults
for
oth
erel
emen
tsgi
ven).
See
Tab
le4
for
listofCRM
and
corr
espondin
gan
timony
valu
es.
200
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 201
et al., 1996; Casey et al., 1989; Perrone et al., 1993). No correlation of an-timony concentrations with age of infant and age of mother (Abdulrazzaqet al., 2008) or amount of food consumed (Wappelhorst et al., 2002) hasbeen observed.
The extent and rate of transfer from blood to milk for a given substancedepends on several factors such as solubility in liquids, strength of binding toplasma proteins, and molecular mass. In the two studies where food/mother’stransfer factors were evaluated, the values obtained were close: 0.041 d kg−1
(Wappelhorst et al., 2002) and 0.035 d kg−1 (Wunschmann et al., 2004).For comparison, iodine gave a transfer factor of 0.560 d kg−1 (Wunschmannet al., 2004).
Other Biofluids
Saliva is a bodily fluid that can be collected easily and without discomfortto the subject (Esteban and Castano, 2009). This does not, however, meanthat using it is free of complicating factors (i.e., variability in saliva com-position, frequent blood contamination of samples; Koh and Koh, 2007).Despite that, saliva has been used in biomonitoring to estimate environmen-tal and occupational exposure to toxic elements (Costa de Almeida et al.,2009; Nriagu et al., 2006; Wang et al., 2008). However, relatively little isknown about the presence of antimony in this biofluid. Olmez et al. (1988)obtained the following values (units: ppm) by applying instrumental neutronactivation analysis (INAA) to freeze-dried samples of human parotid saliva:0.003 (only observed in one sample from four healthy volunteers, two menand two women); 0.010 (only observed in one sample from three patientswith hypogeusia, two men and one woman); 0.11 ± 0.09 in six patientswith hyposmia; 0.009 in three patients with both, two men and one woman(only observed in one sample). Zaichick et al. (1995) identified (INAA) 21chemical elements, among them antimony, in nonstimulated saliva from 52healthy people and 22 men involved in the cleanup after the Chernobyl acci-dent. Mean antimony values were 1.8 ± 0.2 (ng mL−1) in healthy people and0.381 ± 0.101 (μg g−1 dry weight) in cleaners (0.510 ± 0.080 in controls).Gender, age, and season did not influence the antimony concentration in an-alyzed samples. Chicharro et al. (1999) measured antimony concentrationsin saliva at rest and in postexercise situations. In both cases, they obtaineda value of 0.05 mg L−1. In this study, samples were initially kept at 4 ◦C,centrifuged, and stored at –80 ◦C for 15 days prior to analysis by ICP-MS(DL = 0.03 μg L−1). Obviously, the number of published studies is too low,and the values reported too divergent, to be able to extract any conclusionabout antimony levels in saliva, the possible causes of variability and theutility of such measurements.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
202 M. Filella et al.
Other media for biological monitoring include semen, sweat, and tears.No values of antimony concentrations in these fluids could be found.
CONCLUSIONS
The following main conclusions can be drawn from this review article:
1. The lack of adequate CRM (only one CRM, now out of stock, containscertified antimony concentrations in urine, but the values are too high)seriously hampers the assessment of the accuracy of published antimonyconcentrations in urine.
2. Antimony concentrations in urine are close, and often below, the detec-tion limit of the analytical techniques applied. This may have the effectof overestimating the antimony concentrations reported.
3. A dependence has been observed between values obtained in urine andthe sensitivity of the techniques used for their determination, with lowervalues when using more recent, more sensitive analytical methods. Forthis reason, it is recommended that only state-of-the-art dedicated tech-niques, with low detection limits, be used to determine antimony contentin the urine of nonexposed individuals.
4. On the basis of published values, it is not possible to establish a value forthe contents of antimony in the urine of healthy, nonexposed individuals.It is, however, possible to situate, on the basis of more recent results, aconcentration ceiling at around 0.1 μg L−1.
5. Values quoted in secondary sources (i.e., books) and values taken as nor-mal by public bodies are based on old values and are therefore too high.They need to be reconsidered in the light of more recent determinations.
6. Following up on antimony concentrations in urine might be useful inassessing direct occupational exposure to the element and, probably, en-vironmental exposure to nearby point sources of antimony (e.g., antimonymines) but its value for assessing diffuse antimony pollution is not clear.
7. Redox speciation of antimony in urine requires further elucidation.8. No conclusions can be drawn from published values for breast milk and
saliva because of their limited number.
ACKNOWLEDGMENTS
The authors would like to thank Josef Caslavsky (Brno University of Tech-nology, Czech Republic) for providing the translation of the article by Klucikand Kemka (1960). The authors acknowledge the support of the LaurentianUniversity library, more specifically Diane Tessier, Lina Beaulieu, and Daniel
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 203
Leduc for their help in obtaining research articles and reports through theinterlibrary loan system.
LIST OF ABBREVIATIONS
AAS Atomic absorption spectroscopyACGIH American conference of governmental industrial hygienistsADL Above detection limitAES Atomic emission spectroscopyAFS Atomic fluorescence spectroscopyAPDC Ammonium pyrrolidine dithiocarbamateASV Anodic stripping voltammetryAQL Above quantification limitBCR Community bureau of referenceBDL Below detection limitBEI Biological exposure indexBQL Below quantification limitCPE Cloud point extractionCRM Certificate reference materialCRT CreatinineDL Detection limitEDTA Ethylenediaminotetraacetic acidET-AAS Electrothermal atomic absorption spectrometryETV-ICP-MS Electrothermal vaporization inductively coupled plasma mass
spectrometryGF-AAS Graphite furnace atomic absorption spectrometryHG-AAS Hydride generation atomic absorption spectrometryHG-AFS Hydride generation atomic fluorescence spectrometryHG-ICP-MS Hydride generation inductively coupled plasma mass spec-
trometryHPLC High performance liquid chromatographyHR-ICP-MS High resolution inductively coupled plasma mass spectrome-
tryIAEA International atomic energy agencyIBMK Isobuthyl methyl ketoneICP-ES Inductively coupled plasma emission spectrometryICP-MS Inductively coupled plasma mass spectrometryIE Ion exchangeISO International organization for standardizationINAA Instrumental neutron activation analysisLRI Low respiratory tract illnessMCP Modified citrus pectinNAA Neutron activation analysis
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
204 M. Filella et al.
NBS National bureau of standards (NIST since 1988)NHANES National health and nutrition examination surveyNI Not indicatedNIST National institute of standards and technologyNM Not mentionedP Pressure5-Br-PADAP 2-(5-Bromo-2 pyridylazo)-5-diethylaminophenolPET Polyethylene terephthalatePTFE PolytetrafluoroethyleneQ-ICP-MS Quadrople inductively coupled plasma mass spectrometryQL Quantification limitRNAA Radiochemical neutron activation analysisSE Solvent extractionSF-ICP-MS Sector field inductively coupled plasma mass spectrometryT TemperatureTMSb(V) Trimethyl antimony(V)WHO World health organisation
REFERENCES
Abdulrazzaq, Y.M., Osman, N., Nagelkerke, N., Kosanovic, M., and Adem, A. (2008).Trace element composition of plasma and breast milk of well-nourished women.J. Environ. Sci. Heal. A, 43, 329–334.
Alessio, L., Berlin, A., Dell’Orto, A., Toffoletto, F., and Ghezzi, I. (1985). Reliabilityof urinary creatinine as a parameter used to adjust values of urinary biologicalindicators. Int. Arch. Occup. Environ. Health, 55, 99–106.
Alimonti, A., Forte, G., Spezia, S., Gatti, A., Mincione, G., Ronchi, A., Bavazzano,P., Bocca, B., and Minoia, C. (2005). Uncertainty of inductively coupled plasmamass spectrometry based measurements: an application to the analysis of uri-nary barium, cesium, antimony and tungsten. Rapid Commun. Mass Sp., 19,3131–3138.
American Conference of Governmental Industrial Hygienists. (2011a). 2011 TLVsand BEIs. ACGIH publication #0111.
American Conference of Governmental Industrial Hygienists. (2011b). Chemicalsubstances and other issues under study. Retrieved from http://www.acgih.org/tlv/CSBEIStdy.htm
Apostoli, P., Giusti, S., Bartoli, D., Perico, A., Bavazzano, P., and Alessio, L. (1998).Multiple exposure to arsenic, antimony, and other elements in art glass manu-facturing. Am. J. Ind. Med., 34, 65–72.
Aquilio, E., Spagnoli, R., Seri, S., Bottone, G., and Spennati, G. (1996). Trace elementcontent in human milk during lactation of preterm newborns. Biol. Trace Elem.Res., 51, 63–70.
Arai, F., Yamamura, Y., Yoshida, M., and Kishimoto, T. (1994). Blood and urinarylevels of metals (Pb, Cr, Cd, Mn, Sb, Co and Cu) in cloisonne workers. Ind.Health, 32, 67–78.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 205
Bailly, R., Lauwerys, R., Buchet, J.P., Mahieu, P., and Konings, J. (1991). Experimentaland human studies on antimony metabolism: their relevance for the biologicalmonitoring of workers exposed to inorganic antimony. Brit. J. Ind. Med., 48,93–97.
Barr, D.B., Wilder, L.C., Caudill, S.P., Gonzalez, A.J., Needham, L.L., and Pirkle, J.L.(2005). Urinary creatinine concentrations in the U.S. population: implicationsfor urinary biologic monitoring measurements. Environ. Health Perspect, 113,192–200.
Batista, B.L., Rodrigues, J.L., Tormen, L., Curtius, A.J., and Barbosa, F. (2009). Ref-erence concentrations for trace elements in urine for the Brazilian populationbased on q-ICP-MS with a simple dilute-and-shoot procedure. J. Braz. Chem.Soc., 20, 1406–1413.
Becker, K., Mussig-Zufika, M., Conrad, A., Ludecke, A., Schulz, C., Seiwert, M.,and Kolossa-Gehring, M. (2008). German Environmental Survey for Children2003/06 –GerES IV- Human biomonitoring. Levels of selected substances in bloodand urine of children in Germany. WaBoLu-Hefte 01/08, ISSN 1862–4340. Fed-eral Environment Agency, Dessau-Roßlau.
Belzile, N., Chen, Y.-W., and Filella, M. (2011). Human exposure to antimony I.Sources and intake. Crit. Rev. Environ. Sci. Technol., 41, 1309–1373.
Boeniger, M.F., Lowry, L.K., and Rosenberg, J. (1993). Interpretation of urine resultsused to asses chemical exposure with emphasis on creatinine adjustment: Areview. Am. Ind. Hyg. Assoc. J., 54, 615–627.
Bostrom, H., and Wester, P.O. (1969). Pre- and postoperative excretion of traceelements in primary hyper-parathyroidism. Acta Endocrinol. (Copenhagen), 60,380–388.
Brieger, H., Semisch, C.W. III, Stasney, J., and Piatnek, D.A. (1954). Industrial anti-mony poisoning. Ind. Med. Surg., 23, 521–523
Burguera, J.L., and Burguera, M. (1984). Determination of cadmium in human urineby extraction with dithizone in a flow injection system. Anal. Chim. Acta, 153,207–212.
Burguera, J.L., Burguera, M., Gallignani, M., and Alarcon, O.M. (1990). A comparativestudy of methods for determining selenium in biological materials. Acta Cient.Venez., 41, 5–10.
Burguera, J.L., Burguera, M., Petit De Pena, Y., Lugo, A., and Anez, N. (1993). Se-lective determination of antimony(III) and antimony(V) in serum and urineand of total antimony in skin biopsies of patients with cutaneous lesih-maniasis treated with meglumine antimonate. Trace Elem. Med., 10, 66–70.
Caldwell, K.L., Hartel, J., Jarrett, J., and Jones, R.L. (2005). Inductively coupled plasmamass spectrometry to measure multiple toxic elements in urine in NHANES1999–2000. At. Spectrosc., 26, 1–7.
Caroli, S., Alimonti, A., Coni, E., Petrucci, F., Senofonte, O., and Violante, N. (1994).The assessment of reference values in human biological tissues and fluids: Asystematic review. Crit. Rev. Anal. Chem., 24, 363–398.
Casey, C.E., Neville, M.C., and Hambidge, K.M. (1989). Studies in human lactation:secretion of zinc, copper, and manganese in human milk. Am. J. Clin. Nutr., 49,773–785.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
206 M. Filella et al.
Centers for Disease Control and Prevention. (2011). Fourth National Report on hu-man exposure to environmental chemicals. Retrieved from http://www.cdc.gov/exposurereport
Chakravarti, R.N., and Sen Gupta, P.C. (1950). Urinary excretion of antimony af-ter administration of methyl glucamine antimoniate. Preliminary observations.Indian Medical Gazette, 85, 388–391.
Chatterjee, A., Werner, G., and Sen Gupta, P.C. (1954). Urinary excretion of antimonyin kala-azar patients. Bulletin of the Calcutta School of Tropical Medicine, 2,53–54.
Chatterji, A., Chatterjee, M.L., and Sen Gupta, P.C. (1956). Further observations onthe urinary excretion of antimony in kala-azar patients. Bulletin of the CalcuttaSchool of Tropical Medicine, 4, 7–8
Chen, S., Zhu, A., and Chen, J. (1992). Direct determination of antimony in hu-man urine by graphite furnace atomic absorption spectrometry with the L’vovplatform. Guangpuxue Yu Guangpu Fenxi, 12, 63–65.
Chicharro, J.L., Serrano, V., Urena, R., Gutierrez, A.M., Carvajal, A., Fernandez-Hernando, P., and Lucıa, A. (1999). Trace elements and electrolytes in humanresting mixed saliva after exercise. Br. J. Sports Med., 33, 204–207.
Clark, E.R., and Patel, M. (1986). Determination of antimony in urine by candolumi-nescence spectrometry. Analyst, 111, 415–417.
Clemente, G.F. (1976). Trace element pathways from environment to man. J. Ra-dioanal. Chem., 32, 25–41.
Clemente, G.F., Ingrao, G., and Santaroni, G.P. (1982). The concentration ofsome trace elements in human milk from Italy. Sci. Total Environ., 24, 255–265.
Clemente, G.F., Rossi, L.C., and Santaroni, G.P. (1977). Trace element intakeand excretion in the Italian population. J. Radioanal. Chem., 37, 549–558.
Clemente, G.F., Rossi, L.C., and Santaroni, G.P. (1978). Studies on the distributionand related health effects of the trace elements in Italy. Proc. Univ. Miss. Annu.Conf. Trace Subst. Environ. Health, 12, 23–30.
Cooper, D.A., Pendergrass, E.P., Vorwald, A.J., Mayock, R.L., and Brieger, H. (1968).Pneumoconiosis among workers in an antimony industry. Am. J. Roentgenol.Radium Ther. Nucl. Med., 103, 495–508.
Costa de Almeida, G.R., Umbelio de Freitas, C., Barbosa, F. Jr., Tanus-Santos, J.E.,and Gerlach, R.F. (2009). Lead in saliva from lead-exposed and unexposedchildren. Sci. Total. Environ., 407, 1547–1550.
Cullen, A., Kiberd, B., Devaney, D., Gillan, J., Kelehan, P., Matthews, T.G., Mayne, P.,Murphy, N., O’Regan, M., Shannon, W., and Thornton, L. (2000). Concentrationsof antimony in infants dying from SIDS and infants dying from other causes.Arch. Dis. Child., 82, 244–247.
Cullen, A., Kiberd, B., Matthews, T., Mayne, P., Delves, H.T., and O’Regan, M. (1998).Antimony in blood and urine of infants. J. Clin. Pathol., 51, 238–240
De Boer, J.L.M., Ritsema, R., Piso, S., van Staden, H., and van den Beld, W. (2004).Practical and quality-control aspects of multi-element analysis with quadrupoleICP-MS with special attention to urine and whole blood. Anal. Bioanal. Chem.,379, 872–880.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 207
De Perio, M.A., Durgam, S., Caldwell, K.L., and Eisenberg, J. (2010). A health hazardevaluation of antimony exposure in fire fighters. J. Occup. Environ. Med., 52,81–84.
Delves, H.T., Sieniaswska, C.E., Fell, G.S., Lyon, T.D.B., Dezateux, C., Cullen, A.,Variend, S., Bonham, J.R., and Chantler, S.M. (1997). Determination of antimonyin urine, blood and serum and in liver and lung tissues of infants by inductivelycoupled plasma mass spectrometry. Analyst, 122, 1323–1329.
Dezateux, C., Delves, H.T., Stocks, J., Wade, A., Pilgrim, L., and Costeloe, K. (1997).Urinary antimony in infancy. Arch. Dis. Child., 76, 432–436.
Di Cristina, G., and Caronia, G. (1916). Terapia della leishmaniosii [Therapy ofleishmaniasis]. Malar. Mal. Paesi Caldi, 7, 245–253.
Durrant, S.F., and Ward, N.I. (1989). Multi-elemental analysis of human milk byinductively coupled plasma-source mass spectrometry: Implications for infanthealth. J. Micronutr. Anal., 5, 111–126.
Edel, J., Marafante, E., Sabbioni, E., and Manzo, L. (1983). Metabolic behaviour ofinorganic forms of antimony in the rat. Proc. Heavy Metal Environ. Int. Conf.,1, 574–577.
Edelman, P., Osterloh, J., Pirkle, J., Caudill, S.P., Grainger, J., Jones, R., Blount, B.,Calafat, A., Turner, W., Feldman, D., Baron, S., Bernard, B., Lushniak, B.D.,Kelly, K., and Prezant, D. (2003). Biomonitoring of chemical exposure amongNew York City firefighters responding to the World Trade Center fire and col-lapse. Environ. Health Perspect., 111, 1906–1911.
Eliaz, I., Hotchkiss, A.T., Fishman, M.L., and Rode, D. (2006). The effect of modifiedcitrus pectin on urinary excretion of toxic elements. Phytother. Res., 20, 859–864.
Ellinder, C.G., and Friberg, L. (1977). Antimony. In L. Friberg, G. F. Nordberg, V.B. Vouk (Eds.), Toxicology of metals, volume 2 (pp. 26–42). Springfield, VA:National Technical Information Service.
Esteban, M., and Castano, A. (2009). Non-invasive matrices in human biomonitoring:A review. Environ. Internat., 35, 438–449.
Filella, M. (2010). Alkyl derivatives of antimony in the environment. Met. Ions LifeSci., 7, 267–301.
Filella, M., Belzile, N., and Chen, Y.-W. (2002a). Antimony in the environment: areview focused on natural waters. I. Occurrence. Earth-Sci. Rev., 57, 125–176.
Filella, M., Belzile, N., and Chen, Y.-W. (2002b). Antimony in the environment: areview focused on natural waters. II. Relevant solution chemistry. Earth-Sci.Rev., 59, 265–285.
Filella, M., Belzile, N., and Chen, Y.-W. (2012). Human exposure to antimony. II.Contents in some human tissues often used in biomonitoring (hair, nails, teeth).Crit. Rev. Environ. Sci. Technol., 42, 1058–1115.
Filella, M., Belzile, N., and Lett, M.-C. (2007). Antimony in the environment: a reviewfocused on natural waters. III. Microbiota relevant interactions. Earth-Sci. Rev.,80, 195–217.
Filella, M., Williams, P.A., and Belzile, N. (2009). Antimony in the environment:knowns and unknowns. Environ. Chem., 6, 95–105.
Fodor, P., and Barnes, R.M. (1983). Determination of some hydride-forming ele-ments in urine by resin complexation and inductively coupled plasma atomicspectroscopy. Spectrochim. Acta B, 38B, 229–243.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
208 M. Filella et al.
Fordham, P.J., Gramshaw, J.W., Crews, H.M., and Castle, L. (1995). Element residuesin food contact plastics and their migration into food simulants, measuredby inductively-coupled plasma–mass spectrometry. Food Addit. Contam., 12,651–669.
Fredrick, W.G. (1941). Estimation of small amounts of antimony with Rhodamine B.Ind. Eng. Chem. (Anal. Ed.), 13, 922–924.
Fried, P.A., Perkins, S.L., Watkinson, B., and McCartney, J.S. (1995). Associationbetween creatinine-adjusted and unadjusted urine cotinine values in childrenand the mother’s report of exposure to environmental tobacco smoke. Clin.Biochem., 28, 415–420.
Garg, A.N., Weginwar, R.G., and Chutke, N.L. (1993a). A comparative study of minorand trace elements in human, animal and commercial milk samples by neutronactivation analysis. J. Radioanal. Nucl. Chem., 172, 125–135.
Garg, A.N., Weginwar, R.G., and Chutke, N.L. (1993b). Radiochemical neutron ac-tivation analysis of Fe, Co, Zn, Sb and Se in biomedical and environmentalsamples. Sci. Total Environ., 139/140, 421–430.
Gebel, T., Claussen, K., and Dunkelberg, H. (1998a). Human biomonitoring of anti-mony. Int. Arch. Occup. Environ. Health, 71, 221–224.
Gebel, T., Suchenwirth, R.H.R., Behmke, C., Plessow, A., Claussen, K., Schulze,E., and Dunkelberg, H. (1998b). Biomonitoring-Untersuchung bei Personenin Wohngebieten mit erhohten Bodenwerten an Quecksilber, Arsen und An-timon [Human biomonitoring study of persons geogenically exposed to ele-vated levels of mercury, arsenic and antimony]. Gesundheitswesen, 60, 580–585.
Gebel, T.W., Suchenwirth, R.H.R., Bolten, C., and Dunkelberg, H.H. (1998c). Hu-man biomonitoring of arsenic and antimony in case of an elevated geogenicexposure. Environ. Health Persp., 106, 33–39.
Gellhorn, A., Rose, H.M., and Culbertson, J.T. (1947). The plasma antimony concen-tration and the urinary antimony excretion in man during therapy with organicantimony compounds. J. Trop. Med. Hyg., 50, 27–31.
Gill, K.P., Zaidi, J.H., and Ahmad, S. (2003). Radiochemical neutron activation analy-sis for trace elements evaluation of human milk. Radiochim. Acta, 91, 547–551.
Goodwin, L.G., and Page, J.E. (1943). A study of the excretion of organic antimonialsusing a polarographic procedure. Biochem. J., 37, 198–209.
Gorsuch, T.T. (1962). Losses of trace elements during oxidation of organic materials.The formation of volatile chlorides during dry ashing in presence of inorganicchlorides. Analyst, 87, 112–115.
Goulle, J.-P., Mahieu, L., Castermant, J., Neveu, N., Bonneau, L., Laine, G., Bouige, D.,and Lacroix, C. (2005). Metal and metalloid multi-elementary ICP-MS validationin whole blood, plasma, urine and hair. Reference values. Forensic Sci. Int.,153, 39–44.
Greenberg, G.N., and Levine, R.J. (1989). Urinary creatinine excretion is not stable:A new method for assessing urinary toxic substance concentrations. J. Occup.Med., 31, 832–838.
Haldimann, M., Blanc, A., and Dudler, V. (2007). Exposure to antimony frompolyethylene terephthalate (PET) trays used in ready-to-eat meals. Food Ad-dit. Contam., 24, 860–868.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 209
Hamilton, E.I., Sabbioni, E., and Van der Venne, M.T. (1994). Element referencevalues in tissues from inhabitants of the European Community. VI. Review ofelements in blood, plasma and urine and critical evaluation of reference valuesfor the United Kingdom population. Sci. Total Environ., 158, 165–190.
Hansen, H.R., and Pergantis, S.A. (2006). Detection of antimony species in citrusjuices and drinking water stored in PET containers. J. Anal. At. Spectrom., 21,731–733.
Health Canada. (2010). Report on human biomonitoring of environmental chem-icals in Canada. Results of the Canadian Health Measures Survey Cycle 1(2007–2009).
Heitland, P., and Koster, H.D. (2004). Fast, simple and reliable routine determinationof 23 elements in urine by ICP-MS. J. Anal. At. Spectrom., 19, 1552–1558.
Heitland, P., and Koster, H.D. (2006). Biomonitoring of 30 trace elements in urineof children and adults by ICP-MS. Clin. Chim. Acta, 365, 310–318.
Human Biomonitoring Commission. (2005). Standardisation of substance con-centrations in urine – creatinine. Retrieved from http://www.umweltdaten.de/gesundheit-e/monitor/Creatinine.pdf
Huo, X., Huang, L., Zhang, J., and Zhang, A. (1995). Analysis of antimony in bi-ological material from smelter workers. Gongye Weisheng Yu Zhiyebing, 21,375–376.
Iavicoli, I., Caroli, S., Alimonti, A., Petrucci, F., and Carelli, G. (2002). Biomonitoringof a worker population exposed to low antimony trioxide levels. J. Trace Elem.Med. Biol., 16, 33–39.
Iyengar, G.V. (1998). Reevaluation of the trace element content in Reference Man.Radiat. Phys. Chem., 51, 545–560.
Iyengar, G.V., Kasperek, K., Feinendegen, L.E., Wang, Y.X., and Weese, H. (1982).Determination of Co, Cu, Fe, Hg, Mn, Sb, Se and Zn in milk samples. Sci. TotalEnviron., 24, 267–274.
Iyengar, G.V., Kollmer, W.E., and Bowen, H.J.M. (1978). The elemental compositionof human tissues and body fluids. A compilation of values for adults. Weinheim,Germany: Verlag Chemie.
Kentner, M., Leinemann, M., Schaller, K.-H., Weltle, D., and Lehnert, G. (1995).External and internal antimony exposure in starter battery production. Int. Arch.Occup. Environ. Health, 67, 119–123.
Klucik, I., and Kemka, R. (1960). Vylucovanie antimonu u robotnıkov antimonovejhutee [The excretion of antimony in workers in antimony metallergical works].Pracovnı lekarstvı, 12, 133–138.
Kobayashi, R., and Imaizumi, K. (1989). Determination of antimony in urine bygraphite furnace atomic absorption spectrometry after ion exchange separationand solvent extraction. Anal. Sci., 5, 61–64.
Koh, D.S.-Q., and Koh, G.C.-H. (2007). The use of salivary biomarkers in occupa-tional and environmental medicine. Occup. Environ. Med., 64, 202–210.
Komaromy-Hiller, G., Ash, K.O., Costa, R., and Howerton, K. (2000). Comparison ofrepresentative ranges based on U.S. patient population and literature referenceintervals for urinary trace elements. Clin. Chim. Acta, 296, 71–90.
Kommission “Human-Biomonitoring” des Umweltbundesamtes. (2009). Neue undaktualisierte Referenzwerte fur Antimon, Arsen und Metalle (Blei, Cadmium,
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
210 M. Filella et al.
Nickel, Quecksilber, Thallium und Uran) im Urin und im Blut von Kindernin Deutschland [New and updated reference values for antimony, arsenic andmetals (lead, cadmium, nickel, mercury, thallium and uranium) in the urine andblood of children in Germany]. Bundesgesundheitsblatt – Gesundheitsforschung– Gesundheitsschutz, 52, 977–982.
Kosta, M., Byrne, A.R., and Dermelj, M. (1983). Trace elements in some human milksamples by radiochemical neutron activation analysis. Sci. Total Environ., 29,261–268.
Krachler, M., Alimonti, A., Petrucci, F., Forastiere, F., and Caroli, S. (1998a). Influ-ence of sample pre-treatment on the determination of trace elements in urine byquadrupole and magnetic sector field inductively coupled plasma mass spec-trometry. J. Anal. At. Spectrom., 13, 701–705.
Krachler, M., and Emons, H. (2001). Urinary antimony speciation by HPLC-ICP-MS.J. Anal. At. Spectrom., 16, 20–25.
Krachler, M., Shi Li, F., Rossipal, E., and Irgolic, K.J. (1998b). Changes in the concen-trations of trace elements in human milk during lactation. J. Trace Elem. Med.Biol., 12, 159–176.
LaKind, J.S., Berlin, C.M., and Naiman, D.Q. (2001). Infant Exposure to chemicalsin breast milk in the United States: what we need to learn from a breast milkmonitoring program. Environ. Health Perspect., 109, 75–88.
Li, Y., Hu, B., and Jiang, Z. (2006). On-line cloud point extraction combined withelectrothermal vaporization inductively coupled plasma atomic emission spec-trometry for the speciation of inorganic antimony in environmental and biolog-ical samples. Anal. Chim. Acta, 576, 207–214.
Liao, Y.-H., Hwang, L.-C., Kao, J.-S., Yiin, S.-J., Lin, S.-F., Lin, C.-H., Lin, Y.-C., andAw, T.-C. (2006). Lipid peroxidation in workers exposed to aluminum, gallium,indium, arsenic, and antimony in the optoelectronic industry. J. Occup. Environ.Med., 48, 789–793.
Liao, Y.-H, Yu, H.-S., Ho, C.-K., Wu, M.-T., Wang, C.-Y., Chen, J.-R., and Chang, C.-C. (2004). Biological monitoring of exposures to aluminium, gallium, indium,arsenic, and antimony in optoelectronic industry workers. J. Occup. Environ.Med., 46, 931–936.
Lindemann, T., Prange, A., Dannecker, W., and Neidhart, B. (2000). Stability stud-ies of arsenic, selenium, antimony and tellurium species in water, urine, fishand soil extracts using HPLC/ICP-MS. Fresenius J. Anal. Chem., 368, 214–220.
Ludersdorf, R., Fuchs, A., Mayer, P., Skulsuksai, G., and Schacke, G. (1987). Bio-logical assessment of exposure to antimony and lead in the glass-producingindustry. Int. Arch. Environ. Health, 59, 469–474.
Lutter, C., Iyengar, G.V., Barnes, R., Amarasiriwardena, D., Kotrebai, M., Kru-shevska, A., Chuvakova, T., Kazbekova, G., and Sharmanov, T. (1997). Con-centrations of toxic metals and radionuclides in Kazakhstani breast milk.In Harmonization of health related environmental measurements using nu-clear and isotopic techniques (pp. 405–419). Hyderabad, India: BernanAssociation.
Mansour, M.M., Rassoul, A.A.A., and Schulert, A.R. (1967). Anti-bilharzial antimonydrugs. Nature, 214, 819–820.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 211
Miekeley, N., Mortari, S.R., and Schubach, A.O. (2002). Monitoring of total antimonyand its species by ICP-MS and on-line ion chromatography in biological samplesfrom patients treated for leishmaniasis. Anal. Bioanal. Chem., 372, 495–502.
Minoia, C., Sabbioni, E., Apostoli, P., Pietra, R., Pozzoli, L., Gallorini, M., Nicolaou,G., Alessio, L., and Capodaglio, E. (1990). Trace element reference values intissues from inhabitants of the European community. I. A study of 46 elementsin urine, blood and serum of Italian subjects. Sci. Total Environ., 95, 89–105.
Mulligan, K.J., Davidson, T.M., and Caruso, J.A. (1990). Feasibility of the directanalysis of urine by inductively coupled argon plasma mass spectrometry forbiological monitoring of exposure to metals. J. Anal. At. Spectrom., 5, 301–306.
Navas-Acien, A., Silbergeld, E.K., Sharrett, A.R., Calderon-Aranda, E., Selvin, E., andGuallar, E. (2005). Metals in urine and peripheral arterial disease. Environ.Health Perspect., 113, 164–169.
Nicolaou, G., Pietra, R., Sabbioni, E., Mosconi, G., Cassina, G., and Seghizzi, P.(1987). Multielement determination of metals in biological specimens of hardmetal workers: A study carried out by neutron activation analysis. J. Trace Elem.Electrolytes Health Dis., 1, 73–77.
Nriagu, J., Burt, B., Linder, A., Ismail, A., and Sohn, W. (2006). Lead levels in bloodand saliva in a low-income population of Detroit, Michigan. Int. J. Hyg. Environ.Health, 209, 109–121.
Olmez, I., Gulovali, M.C., Gordon, G.E., and Henkin, R.I. (1988). Trace elements inhuman parotid saliva. Biol. Trace Elem. Res., 17, 259–270.
Otto, G.F., and Maren, T.H. (1950). Chemotherapy of filiariasis. VI. Studies on theexcretion and concentration of antimony in blood and other tissues followingthe injection of trivalent and pentavalent antimonials into experimental animals.Am. J. Hyg., 51, 370–385.
Parr, R.M., DeMaeyer, E.M., Iyengar, V.G., Byrne, A.R., Kirkbright, G.F., Schoch,G., Niinisto, L., Pineda, O., Vis, H.L., Hofvander, Y., and Omololu, A. (1991).Minor and trace elements in human milk from Guatemala, Hungary, Nigeria,Philippines, Sweden, and Zaire. Biol. Trace Elem. Res., 29, 51–75.
Paschal, D.C., Ting, B.G., Morrow, J.C., Pirkle, J.L., Jackson, R.J., Sampson, E.J.,Miller, D.T., and Caldwell, K.L. (1998). Trace metals in urine of United Statesresidents: Reference range concentrations. Environ. Res. A, 76, 53–59.
Perrone, L., Di Palma, L., Di Toro, R., Gialanella, G., and Moro, R. (1993). Traceelement content of human milk during lactation. J. Trace Elem. ElectrolytesHealth Dis., 7, 245–247.
Petit de Pena, Y., Gallignani, M., Burguera, M., Burguera, J.L., Anez, N., and Lugo,Y. A. (1990). Selective determination of antimony(III) and antimony(V) in bloodserum and urine by hydride generation and atomic absorption spectrometry. J.Braz. Chem. Soc., 1, 72–75.
Poulsen, O.M., Holst, E., and Christensen, J.M. (1997). Calculation and application ofcoverage intervals for biological reference values. Technical Report. A supple-ment to the approved IFCC recommendation (1987) on the theory of referencevalues. Pure Appl. Chem., 69, 1601–1611.
Pronczuk, J., Akre, J., Moy, G., and Vallenas, C. (2002). Global perspectives in breastmilk contamination: infectious and toxic hazards. Environ. Health Perspect. 110,A349–A351.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
212 M. Filella et al.
Qin, H.-L., Lei, Z. L., and Hu, W.-D. (1996). Determination of urinary antimonyin healthy adult population by flame atomic absorption spectrometry. GongyeWeisheng Yu Zhiyebing, 22, 240–241.
Quiroz, W., Arias, H., Bravo, M., Pinto, M., Lobos, M.G., and Cortes, M. (2011). De-velopment of analytical method for determination of Sb(V), Sb(III) and TMSb(V)in occupationally exposed human urine samples by HPLC–HG-AFS. Microchem.J., 97, 78–84.
Rapant, S., Dietzova, Z., and Cicmanova, S. (2006). Environmental and health riskassessment in abandoned mining area, Zlata Idka, Slovakia. Environ.Geol., 51,387–397.
Rat, J.C., Debrus, C., and Burnel, D. (1985). Dosage de l’antimoine par polarogra-phie impulsionnelle avec redissolution anodique. Application aux milieux bi-ologiques [Determination of antimony by pulse polarography with anodic strip-ping. Application to biological media]. Annales des Falsifications de l’ExpertiseChimique et Toxicologique, 78, 7–11.
Rees, P.H., Kager, P.A., Keating, M.I., and Hockmeyer, W.T. (1980). Renal clearanceof pentavalent antimony (sodium stibogluconate). Lancet, 316, 226–229.
Rice, D.C., Lincoln, R., Martha, J., Parker, L., Pote, K., Xing, S., and Smith, A.E. (2010).Concentration of metals in blood of Maine children 1–6 years old. J. Expo. Sci.Env. Epid., 20, 634–643.
Richardson, B.A. (1994). Sudden infant death syndrome: a possible primary cause.J. Forensic Soc., 34, 199–204.
Richter, P.A., Bishop, E.E., Wang, J., and Swahn, M.H. (2009). Tobacco smoke ex-posure and levels of urinary metals in the U.S. youth and adult population: TheNational Health and Nutrition Examination Survey (NHANES) 1999–2004. Int. J.Environ. Res. Public Health, 6, 1930–1946.
Rodushkin, I., Engstrom, E., Stenberg, A., and Baxter, D.C. (2004). Determination oflow-abundance elements at ultra-trace levels in urine and serum by inductivelycoupled plasma-sector field mass spectrometry. Anal. Bioanal. Chem., 380,247–257.
Rodushkin, I., and Odman, F. (2001). Application of inductively coupled plasmasector field mass spectrometry for elemental analysis of urine. J. Trace Elem.Med. Biol., 14, 241–247
Rossipal, E., and Krachler, M. (1998). Pattern of trace elements in human milk duringthe course of lactation. Nutr. Res., 18, 11–24.
Schramel, P., Wendler, I., and Angerer, J. (1997). The determination of metals (an-timony, bismuth, lead, cadmium, mercury, palladium, platinum, tellurium, thal-lium, tin and tungsten) in urine samples by inductively coupled plasma-massspectrometry. Int. Arch. Occup. Environ. Health, 69, 219–223.
Schramel, P., Wendler, I., Dunemann, L., Fleischer, M., and Emons, H. (1999). Anti-mony, lead, cadmium, platinum, mercury, tellurium, thallium, bismuth, tung-sten, tin. Analyses of Hazardous Substances in Biological Materials, 6, 79–109.
Schroeder, H.A., and Nason, A.P. (1971). Trace-element analysis in clinical chemistry.Clin. Chem., 17, 461–474.
Schulz, C., Angerer, J., Ewers, U., Heudorf, U., and Wilhelm, M. (2009). Revisedand new reference values for environmental pollutants in urine or blood of
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
Human Exposure to Antimony III 213
children in Germany derived from the German Environmental Survey on Chil-dren 2003–2006 (GerES IV). Int. J. Hyg. Envir. Heal., 212, 637–647.
Shirai, S., Suzuki, Y., Yoshinaga, J., and Mizumoto, Y. (2010). Maternal exposure tolow-level heavy metals during pregnancy and birth size. J. Environ. Sci. Heal.A, 45, 1468–1474.
Shotyk, W., Krachler, M., and Chen, B. (2006). Contamination of Canadian and Eu-ropean bottled waters with antimony from PET containers. J. Environ. Monitor.,8, 288–292.
Shotyk, W., Krachler, M., Chen, B., and Zheng, J. (2005). Natural abundance ofSb and Sc in pristine groundwaters, Springwater Township, Ontario, Canada,and implications for tracing contamination from landfill leachates. J. Environ.Monitor., 7, 1238–1244.
Smith, B.M., and Griffiths, M.B. (1982). Determination of lead and antimony in urineby atomic-absorption spectroscopy with electrothermal atomisation. Analyst,107, 253–259.
Smith, M.M., White, M.A., and Wilson, H.K. (1995). Determination of antimony inurine by solvent extraction and electrothermal atomization atomic absorptionspectrometry for the biological monitoring of occupational exposure. J. Anal.At. Spectrom., 10, 349–352.
Versieck, J., and Cornelis, R. (1989). Trace elements in human plasma or serum.Boca Raton, FL: CRC Press.
Walker, A.W. (Ed.). (1992). Trace element analyses. Clinical and analytical hand-book Royal Surrey County and St Luke’s Hospitals (2nd ed.). Surrey, England:Guildford.
Wang, D., Du, X., and Zheng, W. (2008). Alteration of saliva and serum concentra-tions of manganese, copper, zinc, cadmium and lead among career welders.Toxicol. Lett., 176, 40–47.
Wappelhorst, O., Kuhn, I., Heidenreich, H., and Markert, B. (2002). Transfer ofselected elements from food into human milk. Nutrition, 18, 316–322.
Ward, N.I. (1986). Multi-element analysis of urine by neutron activation analysis:Application to starvation and anorexia nervosa. J. Micronutr. Anal., 2, 211–231.
Wester, P.O. (1973). Trace elements in serum and urine from hypertensive pa-tients before and during treatment with chlorthalidone. Acta Med. Scand., 194,505–512.
Wester, P.O. (1975). The urinary excretion of trace elements before and duringtreatment with hydralazine. Acta Med. Scand., 197, 307–309.
Wolfe, M.I., Mott, J.A., Voorhees, R.E., Sewell, C.M., Paschal, D., Wood, C.M., McK-inney, P.E., and Redd, S. (2004). Assessment of urinary metals following expo-sure to a large vegetative fire, New Mexico, 2000. J. Expo. Anal. Env. Epid., 14,120–128.
World Health Organization. (1989). Minor and trace elements in breast milk. Reportof a Joint WHO/IAEA Collaborative Study. Geneva, Switzerland: WHO.
World Health Organization. (1996). Biological monitoring of chemical exposure inthe workplace. Vol. 1. WHO/HPR/OCH 96.1. Geneva, Switzerland: WHO.
Wunschmann, S., Franzle, S., Kuhn, I., Heidenreich, H., Wappelhorst, O., and Mark-ert, B. (2004). Verteilung chemischer Elemente in der Nahrung und Milch stil-lender Mutter. Teil II: Ag, Au, Ba, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, I, La, Mn, Mo,
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
214 M. Filella et al.
Nb, Ni, P, Pb, Ra, Rb, Re, Ru, Sb, Sr, Te, Th, Ti, U, Y, Zn und Zrr [Distributionof chemical elements in the diet and milk of breast feeding mothers. Part II: Ag,An, Ba, Cd, Ce, Co, Cr, Cs, Cu, Fe, Ga, I, La, Mn, Mo, Nb, Ni, P, Pb, Ra, Rb, Re,Ru, Sb, Sr, Te, Th, Ti, U, Y, Zn, and Zr]. UWSF – Z. Umweltchem. Okotox., 15,168–174.
Xie, Y., Miyamoto, H., Kondo, M., Koga, H., Zhang, A., Ohmichi, M., Inaba, Y., andChiba, M. (2001). Element concentrations in urine of patients suffering fromchronic arsenic poisoning. Tohoku J. Exper. Med., 193, 229–235.
Zaghloul, I.Y., Radwan, M.A., Al Jaser, M.H., and Al Issa, R. (2010). Clinical efficacyand pharmacokinetics of antimony in cutaneous leishmaniasis patients treatedwith sodium stibogluconate. J. Clin. Pharmacol., 50, 1230–1237.
Zaichick, V., Tsyb, A., and Bagirov, S. (1995). Neutron activation analysis of saliva:Application in clinical chemistry, environmental and occupational toxicology. J.Radioanal. Nucl. Chem., 195, 123–132.
Dow
nloa
ded
by [
Lau
rent
ian
Uni
vers
ity]
at 0
6:36
06
Febr
uary
201
3
