Screening Inorganic Arsenic in Rice by Visible and Near-Infrared Spectroscopy

Rafael Font,
1*
Dinoraz Vlez,
2
Mercedes Del Ro-Celestino,
1
Antonio De Haro-Bailn,
1
Rosa Montoro
2
1
Instituto de Agricultura Sostenible (CSIC). Alameda del Obispo s/n. 14080, Crdoba,
Spain.
2
Instituto de Agroqumica y Tecnologa de Alimentos (CSIC), Apartado 73, 46100,
Burjassot (Valencia), Spain.
*Corresponding author: telephone (+34) 957499211; fax (+34) 957499252; e-mail:
font@cica.es.
/var/www/apps/conversion/tmp/scratch_2/223766629.doc
1
Abstract
The potential of near infrared spectroscopy (NIRS) for screening the inorganic arsenic
(i-As) content in commercial rice was assessed. Forty samples of rice were freeze-dried
and scanned by NIRS. The i-As contents of the samples were obtained by acid
digestion-solvent extraction followed by hydride generation atomic absorption
spectrometry, and were regressed against different spectral transformations by modified
partial least square (MPLS) regression. Second derivative transformation equation of
the raw optical data, previously standardized by applying standard normal variate
(SNV) and De-trending (DT) algorithms, resulted in a coefficient of determination in
the cross-validation (1-VR) of 0.65, indicative of equations useful for a correct
separation of the samples in low, medium and high groups. The standard deviation
(S.D.) to standard error of cross-validation (SECV) ratio, shown by the second
derivative equation, was similar to those obtained for other trace metal calibrations
reported in NIRS reflectance. Spectral information related to starch, lipids and fiber of
the rice grain, and also pigments in the caryopsis, were the main components used by
MPLS for modeling the selected prediction equation. This pioneering use of NIRS to
predict the i-As content in rice represents an important reduction in labor input and cost
of analysis.
Key words
Near-infrared spectroscopy (NI!"# inor$anic arsenic# %rown rice# mi&&ed rice
2
Introduction
ice is the dominant stap&e food crop in deve&opin$ co'ntries( partic'&ar&y for the h'mid
tropics across the $&o%e )1*. +&most 96, of rice is prod'ced and cons'med in in
deve&opin$ co'ntries )1* and contri%'tin$ over 7-, of ener$y to the dai&y inta.e )2*.
/he component of protein in rice( at 7 0 9, %y wei$ht( is re&ative&y &ow )3*( %'t it is a
ma1or so'rce of protein (2-," for these rice-cons'min$ peop&e )2*.
3or a food with s'ch a hi$h cons'mption it is cr'cia& to have information a%o't to4ic
trace &eve&s( in order to esta%&ish the potentia& effects on h'man hea&th. +rsenic (+s" and
its chemica& species +s(III" and +s(5"( co&&ective&y .nown as inor$anic +s (i-+s"( are
the contaminants of interest in this wor.. /ota& diet st'dies indicate that +s
concentrations in rice are hi$her than those in other prod'cts of ve$eta%&e ori$in )6(2*.
Nat'ra& processes and h'man activities are the two principa& factors responsi%&e for the
introd'ction of arsenic into the rice-$rowin$ environment. Nat'ra& processes of
introd'ction invo&ve soi&/water chemistry and c&imate. 3arm mana$ement activities s'ch
as ferti&i7ation practices( crop rotation and her%icida&/insecticida& 'ses a&so act to
introd'ce arsenic. 3or inor$anic arsenic( soi& properties and 'ses of pesticides are
ass'med to %e the most important interactive inf&'ences that determine its fina&
concentration )6*.
8ata on +s contents in samp&es of rice co&&ected in arsenic-endemic areas s'ch as
/aiwan( 9est :en$a& and :an$&adesh show that the +s content ran$es %etween -.-6
and -.76 ;$/$ )7-9*. In non-arsenic-endemic areas( the hi$hest va&'e reported is -.776
;$/$ )2(1-(11*. /he very few st'dies on i-+s contents in rice show concentrations that
vary %etween -.-21 and -.26- ;$/$ )2(6(7(1-(12*. <va&'atin$ the contri%'tion of rice to
i-+s inta.e is( in o'r view( a necessary tas. in order to ma.e a more rea&istic assessment
3
of the ris. of e4pos're to this to4in( especia&&y in arsenic-endemic areas and deve&opin$
co'ntries.
The standard methodologies for trace metal determination offer a high level of precision
but have some handicaps, such as high cost of analysis, slowness of operation,
destruction of the sample, and use of hazardous chemicals. In contrast, Near Infrared
Spectroscopy (NIRS) is a valuable technique that offers speed and low cost of analysis,
and also the sample is analyzed without using chemicals. The spectral information can
be used for simultaneous prediction of numerous constituents and parameters of the
samples, once appropriate calibration equations have been prepared from sets of
samples analyzed by both NIRS and conventional analytical techniques. After
calibration, the regression equation permits accurate analysis of many other samples by
prediction of results on the basis of the spectra.
NI! has %een app&ied to ana&ysis of meta& content most&y in the environmenta& fie&d(
and to a &esser e4tent in the a$ro-food fie&ds. In environmenta& st'dies vario's a'thors
have reported the ana&ysis of heavy meta&s in &a.e sediments )13*(

st'dies concernin$
the chemica& characteri7ation of soi&s )16*(

and the determination of heavy meta&s and
arsenic %y NI! in p&ant tiss'es )12(16*. ecent&y( in the a$ro-food fie&d the feasi%i&ity
of this techni='e for meas'rin$ >( Na( ?$( and @a in white wines was demonstrated
)17*. In the speciation fie&d( NI! has %een 'sed for predictin$ merc'ria& species in the
mem%rane constit'ents of &ivin$ %acteria& )1A* ce&&s( and i-+s in cr'staceans of
commercia& interest )19*. !o far( however, no reports have been published on the use of
NIRS for predicting arsenic species in rice.
/he o%1ectives of this wor. wereB (i" to test the potentia& of NI! for predictin$ the i-+s
content in rice samp&es( and (ii" to provide a mechanism to e4p&ain why NI! is capa%&e
of predictin$ i-+s in this species.
6
Experimental
Samples. Samples of commercial rice were selected at different markets in Valencia
(Spain) on the basis of the type of rice (brown or milled, long or medium grain). This
criterium was based on the fact that rice is marketed usually without regard to
geographic origin and specific cultivar type. In addition, previous studies demonstrated
that any differences in concentrations of arsenic are not anticipated to be distinctive
enough to establish geographic origin, rice variety, or other source attributes produced
under normal growing circumstances [20]. Rice samples were ground and freeze-dried
before determination of the i-As content by the reference method, and NIRS analysis.
Determination of inorganic arsenic. The methodology applied was developed
previously by Muoz et al. [21]. Deionized water (4.1 mL) and concentrated HCl (18.4
mL) were added to 0.5 g of freeze-dried sample. The mixture was left overnight. After
reduction by HBr and hydrazine sulfate, the inorganic arsenic was extracted into
chloroform, and back-extracted into 1 mol/L HCl. The back-extraction phase was dry-
ashed and the i-As was quantified by flow injection-hydride generation atomic
absorption spectrometry (FI-HG Perkin Elmer FIAS-400; AAS Perkin Elmer Model
3300). The analytical characteristics of the method were: detection limit = 0.013 g/g
dry weight (dw); precision = 3-5%; recovery As(III) 99% and As(V) 96%.
NIRS equipment and software. Near infrared spectra were recorded on an NIRS
spectrometer model 6500 (Foss-NIRSystems, Inc., Silver Spring, MD, USA) in
reflectance mode equipped with a transport module. The monochromator 6500 consists
of a tungsten bulb and a rapid scanning holographic grating with detectors positioned
for transmission or reflectance measurements. To produce a reflectance spectrum, a
ceramic standard is placed in the radiant beam, and the diffusely reflected energy is
measured at each wavelength. The actual absorbance of the ceramic is very consistent
2
across wavelengths. In this work, each spectrum was recorded once from each sample,
and was obtained as an average of 32 scans over the sample, plus 16 scans over the
standard ceramic before and after scanning the sample. The ceramic and the sample
spectra are used to generate the final Log (1/R) spectrum. The whole time of analysis
took about 2 min., approximately. Mathematical transformations of the spectra and
regressions performed on the spectral and laboratory data were obtained by using the
GLOBAL v. 1.50 program (WINISI II, Infrasoft International, LLC, Port Matilda, PA,
USA).
NIRS procedure: recording of spectra and processing of data. Freeze-dried, ground
samples of rice were placed in the NIRS sample holder (3 cm diameter) until it was full
(weight 3.50 g), and were then scanned. Their NIR spectra were acquired at 2 nm
intervals over a wavelength range from 400 to 2500 nm (visible plus near infrared
regions).
Samples of rice were recorded as an NIR file, and were checked for spectral outliers
[spectra with a standardized distance from the mean (H) > 3 (Mahalanobis distance)],
by using principal component analysis (PCA). The objective of this procedure was to
detect and, if necessary, remove possible samples whose spectra differed from the other
spectra in the set [22].
In the second step, laboratory reference values for i-As, as obtained from the reference
method, were added to the NIR spectra file. Calibration equations were computed in the
new file by using the raw optical data (log 1/R, where R is reflectance), or first or
second derivatives of the log 1/R data, with several combinations of segment
(smoothing) and derivative (gap) sizes. The use of derivative spectra instead of the raw
optical data to perform calibration is a way of solving problems associated with
overlapping peaks and baseline correction [23]. A first-order derivative of log (1/R)
6
results in a curve containing peaks and valleys that correspond to the point of inflection
on either side of the log (1/R) peak, while the second-order derivative calculation results
in a spectral pattern display of absorption peaks pointing down rather than up, with an
apparent band resolution taking place [24]. In addition, the gap size and amount of
smoothing used to make the transformation will affect the number of apparent
absorption peaks.
To correlate the spectral information (raw optical data or derived spectra) of the samples
and the i-As content determined by the reference method, modified partial least squares
(MPLS) was used as regression method, using wavelengths from 400 to 2500 nm every
8 nm. Standard normal variate and De-trending (SNV-DT) transformations [25] were
used to correct baseline offset due to scattering effects (differences in particle size and
path length variation among samples).
Cross-validation. Cross-validation is an internal validation method

that like the external
validation approach seeks to validate the calibration model on independent test data, but
it does not waste data for testing only, as occurs in external validation. This procedure is
useful because all available chemical analyses for all individuals can be used to
determine the calibration model without the need to maintain separate validation and
calibration sets. The method is carried out by splitting the calibration set into M
segments and then calibrating M times, each time testing about a (1/M) part of the
calibration set [26].

In this work, the different calibration equations were validated with
7 cross-validation segments, as this was the optimum number of groups automatically
selected by the software as a function of the number of samples employed.
/he prediction a%i&ity of the e='ations o%tained was determined on the %asis of their
coefficient of determination in the cross-va&idation (r
2
" )27* (e=. 1" and standard
deviation (!.8." to standard error of cross-va&idation (!<@5" ratio (C8" )2A* (e=. 2".
7
r
2
D
1
1
2
1
2
" ( " E (

,
_

,
_

n
i
i
n
i
y y y y e=. 1
whereB
yE
D NI meas'red va&'e#
y
D mean FyG va&'e for a&& samp&es#
i
y
D &a% reference
va&'e for the ith samp&e.
C8 D ( )
1
2 / 1
1
1
2
1 " E ( . .

1
]
1

,
_

K N y y D S
n
i
i i
e=. 2
whereB
i
y
D &a% reference va&'e for the ith samp&e#
yE
D NI meas'red va&'e# ND
n'm%er of samp&es( KD n'm%er of wave&en$ths 'sed in an e='ation# !.8.D standard
deviation.
/he statistics shown in e=. 1 and e=. 2( $ive a more rea&istic estimate of the app&ica%i&ity
of NI! to the ana&ysis than those of the e4terna& va&idation( as cross-va&idation avoids
the %ias prod'ced when a &ow n'm%er of samp&es representin$ the f'&& ran$e are
se&ected as va&idation set )27(2A*. /he !<@5 method is %ased on an iterative a&$orithm
which se&ects samp&es from a samp&e set pop'&ation to deve&op the ca&i%ration e='ation
and then predicts on the remainin$ 'nse&ected samp&es. /his statistic indicates an
estimate of the standard error of prediction (!<C" that may have %een fo'nd in an
e4terna& va&idation )29*( and as occ'rred with !<C is ca&c'&ated as the s='are root of the
mean s='are of the resid'a&s for N-1 de$rees of freedom( where the resid'a& e='a&s the
act'a& min's the predicted va&'e.
In this work, cross-validation was computed on the calibration set for determining the
optimum number of terms to be used in building the calibration equations.
Results and Discussion
A
Population boundaries and identification of spectral outliers for rice samples.
Cop'&ation %o'ndaries for spectra of samp&es of rice were determined %y C@+
performed over the entire pop'&ation (3i$'re 1". :y 'sin$ twe&ve C@s( ca&c'&ated on the
second derivative (2( 2( 2( 2# !N5H8/" of the raw spectra( the 9A.26 , of the who&e
spectra& varia%i&ity in the data was e4p&ained. /he $&o%a& H (IJ" of the samp&e
pop'&ation e4tended from -.22 to 2.12 with a mean distance of -.96.
Kne samp&e was shown to %e a IJ o't&ier in C@+. +fter caref'&&y e4amination of the
commercia& description of the prod'ct( it was decided to e&iminate it from the
ca&i%ration set as prod'ct composition was in do'%t.
Inorganic arsenic contents in the rice samples. !amp&es of rice 'sed to cond'ct this
wor. showed mean content and !.8. of 11-.37 and 69.A- n$/$ dw( respective&y (/a%&e
1". /he ran$e of i-+s fo'nd in the samp&es e4tended form 13.- to 26A.- n$/$ dw( these
va&'es %ein$ simi&ar to those contents previo's&y reported in white rice from the Lnited
!tates of +merica )6*. Inor$anic arsenic contents were norma&&y distri%'ted in the
occ'rrence ran$e (3i$'re 2".
Spectral data pre-treatments and equation performances. /he app&ication of the
second derivative and !N5H8/ a&$orithms to the raw spectra (Mo$ 1/" (3i$'re 3"(
res'&ted in s'%stantia& correction (3i$'re 6" of the %ase&ine shift ca'sed %y differences in
partic&e si7e and path &en$th variation. Cea.s and tro'$hs in 3i$'re 6 correspond to the
points of ma4im'm c'rvat're in the raw spectr'm( and it has a tro'$h correspondin$ to
each pea. in the ori$ina&. /he increase in the comp&e4ity of the derivative spectra
res'&ted in a c&ear separation %etween pea.s which over&ap in the raw spectra.
/he 'se of the second derivative transformation (2( 2( 2( 2# !N5H8/" of the raw optica&
data performed over the entire se$ment (6---22-- nm"( yie&ded a hi$her prediction
a%i&ity e='ation in cross-va&idation than any other of the vario's mathematica&
9
treatments 'sed. ?CM! re$ression res'&ted in an e='ation that presented fo'r terms and
showed a &ow standard error of ca&i%ration (!<@ D 2-.19 n$/$ dw" and hi$h coefficient
of determination in the ca&i%ration (
2
D -.A-" (/a%&e 1". In cross-va&idation the se&ected
e='ation showed an r
2
of -.62 (meanin$ that the 62, of the chemica& varia%i&ity in the
data was e4p&ained"( which was indicative of e='ations 'sef'& for a correct separation of
samp&es with &ow( medi'm and hi$h contents )27* (3i$'re 2". In accordance with the
C8 va&'e (1.67" shown %y the hi$hest prediction a%i&ity e='ation o%tained( and
considerin$ the &imits for C8 recommended %y @han$ et a&. )3-*( and 8'nn et a&. )31*(
this e='ation was accepta%&e for i-+s prediction in rice.
/he 'se of the coefficient of determination in the eva&'ation of an NI e='ation
invo&vin$ trace e&ements and minera& species has received some criticism )12(32*. In
addition( the interpretation of the va&'e of the coefficient of determination as it was first
reported %y !hen. and 9esterha's )27* for a$ric'&t'ra& prod'cts( pro%a%&y needs to %e
revised for e&ement ana&ysis. Kn the other hand( whi&e m'ch effort has %een app&ied to
the deve&opment of ca&i%ration of ='a&ity components in the a$ro-food fie&d( no critica&
&eve&s of the C8 statistic have %een set for trace e&ements and minera& species in these
prod'cts. :y this reason( those st'dies reported on minera& composition of soi&s )3-(31*
show a specia& re&evance at the time of esta%&ishin$ s'ita%&e &imits of C8.
:'t in spite of the a%ove considerations( a'thors c'rrent&y researchin$ NI! for
environmenta& ana&ysis and food safety sti&& %ase their decisions on these statistics for
rapid fie&d and &a%oratory meas'rements )19(33(36*( to re&ate chemistry and apparent
a%sorption of NI spectra.
Bron and milled rice reflectance spectra. /he avera$e second derivative (2( 2( 2( 2#
!N5H8/" spectra of those samp&es that were c&ear&y identified as %rown (nD 16" and
mi&&ed rice (nD 16" were o%tained. +s it can %e o%served in 3i$'re 6( mi&&ed rice showed
1-
hi$her a%sorptions than %rown rice at wave&en$ths 916 and 9A6 nm( which have %een
assi$ned to @-J stretchin$ third overtone of @J
2
$ro'ps and K-J stretchin$ second
overtone of starch )32*( respective&y. /he re&ative hi$her starch content of mi&&ed rice
(7A," in comparison to that of %rown rice (66," )36*( as a conse='ence of removin$
the %ran and em%ryo fractions in the a%rasive mi&&in$( e4p&ain these differences in
apparent a%sorption %etween %oth spectra.
/he same phenomenon( %'t of inverse si$n( can %e o%served at wave&en$ths 177A and
236A nm( re&ated to @-J stretchin$ first overtone of ce&&'&ose( and @J
2
symmetric
stretchin$ p&'s D@J
2
deformation )32(37* $ro'ps of oi& and fi%er (3i$'re 6". ?ost non-
starch constit'ents are removed d'rin$ mi&&in$( with fi%er showin$ the most dramatic
drop( fo&&owed %y other n'trients e4cept protein )36*. es'&ts reported on distri%'tion of
n'trients in %rown rice( s'pports the idea that on&y a 27, of the tota& ce&&'&ose( a 21, of
the &i$nin and a%o't a 2-, of the non-starch &ipids (ether-so&'%&e" are present in the
mi&&ed rice )3A*( %ein$ the rest of them removed d'rin$ mi&&in$.
/he visi%&e se$ment of the spectr'm simi&ar&y showed a%sorption %ands that differed in
intensity %etween %rown and mi&&ed rice. /he fact that pi$ments in co&o'red rices are
&ocated in the pericarp or the seed coat( which are removed d'rin$ mi&&in$( e4p&ains
these differences shown %y spectra (3i$'re 6". /he conspic'o's %and at 66A nm is
disp&ayed %y %oth types of rice( %'t with &itt&e hi$her intensity in %rown than in mi&&ed
rice. /his %and( which has %een re&ated previo's&y to some %ran component )39* is
diffic'&t to e4p&ain here as %ein$ ca'sed on&y %y the o'ter &ayers of the $rain %eca'se its
'%i='ity in the different types of rice.
!orrelation plot of i-As "s a"elength. /he corre&ation p&ot for i-+s vs wave&en$th
a%sor%ance for the standardised (!N5H8/" optica& data in disp&ayed in 3i$'re 7. ?ost
re&evant feat'res shown %y the corre&ation p&ot were the ne$ative corre&ation %etween i-
11
+s and a%sorption e4istin$ in those wave&en$ths which have %een assi$ned to starch
(aro'nd 9A6 nm( and a&so from 22-- to 2226 nm" and protein (2-22 nm" )32(37*.
Crevio's st'dies reportin$ e&ement distri%'tion in rice demonstrated a hi$her i-+s
concentration in the %rown rice than in mi&&ed rice )36*. + considera%&e portion of the
rice caryopsis ash is acco'nted for %y phosphor's. /h's( mi&&in$ res'&ts in &oss of
different essentia& e&ements. +&tho'$h severa& st'dies have %een reported concernin$ the
e&ement distri%'tion in the mi&&in$ fractions of rice )6-*( data avai&a%&e on arsenic
concentration in this species are main&y referred to mi&&ed rice )6*.
Jowever( %eca'se the simi&ar %iochemistry of arsenic with that of phosphor's )61(62*( it
is &o$ica& to thin. that caryopsis acco'nt a&so for most arsenic in the $rain. /his fact
wo'&d e4p&ain %y itse&f the ne$ative corre&ation with starch shown %y i-+s( i.e.( mi&&ed
rice has a &ower concentration of i-+s and a re&ative hi$her percenta$e of starch( and the
opposite for %rown rice.
?ore diffic'&t is to e4p&ain the re&ative hi$h ne$ative corre&ation of i-+s with those
wave&en$ths re&ated to protein a%sorption. /he &ow difference in protein concentration
%etween %rown (7.1-A.3 ," and mi&&ed rice (6.3-7.1," )36* does not 1'stify this fact. It
is pro%a%&y that the m'&tip&e factors contro&&in$ the fina& protein content in rice( or
$eo$raphic &ocation and farm mana$ement activities )6* re&ate %oth( protein and i-+s
contents.
Cositive corre&ations were fo'nd %etween i-+s and a%sorption in wave&en$ths re$ions
re&ated to fi%er and oi& (1722 and 231- nm" and a&so pi$ments (from 672 to 2-6 nm"(
which can %e e4p&ained %y the main &ocation of these components in the o'ter &ayers of
the $rain( where hi$her concentrations of i-+s are s'pposed to %e fo'nd.
#odified partial least square loadings. ?CM! re$ression red'ces the spectra&
information of the samp&es %y creatin$ a m'ch sma&&er n'm%er of new ortho$ona&
12
varia%&es (factors"( which are com%inations of the ori$ina& data( and which retain the
essentia& information needed to predict the composition. /he ro&e p&ayed %y the NI
a%sor%ers (or$anic and inor$anic mo&ec'&es" present in the samp&es( in mode&&in$ the
ca&i%ration e='ations for i-+s( can %e interpreted %y st'dyin$ the %ands of the ?CM!
factors (&oadin$ p&ots". /hese &oadin$ p&ots show the re$ression coefficients of each
wave&en$th re&ated to the e&ement (i-+s" %ein$ ca&i%rated( for each factor of the
e='ation. /he wave&en$ths represented in the &oadin$ p&ots as participatin$ more hi$h&y
in the deve&opment of each factor are those that have $reater spectra& variation and
%etter corre&ation with the e&ement in the ca&i%ration set.
It has %een stated that the s'ccess of estimation via NI! of specific minera& e&ements
in some $rasses and &e$'mes is 's'a&&y dependent on the occ'rrence of those e&ements
in either or$anic or hydrated mo&ec'&es )12*. +t the very &ow concentrations in which i-
+s is fo'nd in the rice samp&es 'sed in this wor. (meanD 11- n$/$ dw"( any prediction
of this e&ement has to %e done on the %asis of secondary corre&ations with p&ant
components )26(36*. /his phenomenon is s'pported %y data from ?CM! &oadin$s
(3i$'re A" in this wor. for the se&ected e='ation for i-+s. It can %e conc&'ded from
3i$'re A( that @-J (912 nm" and a&so K-J (9A6 nm" $ro'ps of starch hi$h&y inf&'enced
the first three ?CM! &oadin$s for this e&ement. In addition( @-J $ro'ps of oi& and fi%er
(23-A and 236A nm" a&so participated to mode&( main&y( the first term of the e='ation.
In the visi%&e re$ion of the spectr'm( cromophores &ocated in the caryopsis (a%sorption
at 672 nm and shorter wave&en$ths" a&so participated active&y in constr'ctin$ the first
terms. In spite of the &ow r va&'e shown %y the %and at 912 nm (3i$'re 7"( this %and was
se&ected to hi$h&y participate in the first three terms of the e='ation for i-+s( d'e to the
hi$h varia%i&ity in a%sor%ance disp&ayed %y it (3i$'re 6".
13
Crediction res'&ts o%tained from cross-va&idation showed for the first time that NI!
can %e emp&oyed with speciation p'rposes in rice( and that this techni='e is a%&e to
predict the i-+s concentration in samp&es of this species with s'fficient acc'racy for
screenin$ p'rposes in spite of the &ow i-+s &eve&s shown in this wor.. /h's( NI! can
%e 'sed for identifyin$ those samp&es havin$ &ow( medi'm and hi$h i-+s contents. In
the second step( the e4act va&'e of i-+s of the samp&es se&ected %y the researcher as
%ein$ of interest( can %e o%tained %y the reference method. NI! can( therefore(
decrease the n'm%er of ana&yses in the &a%oratory needed for monitorin$ the i-+s
content in screenin$ pro$rams.
References
16
)1* ?. Jossain( Mon$-term prospects for the $&o%a& rice economy( 3+K ice
@onference. ome( Ita&y( 12-13 3e%r'ary 2--6.
)2* /. 8. Ch'on$( C. 5. @h'on$( 8. /. >hiem( !. >o.ot( <&ementa& content of
5ietnamese rice Cart 1. !amp&in$( ana&ysis and comparison with previo's st'dies(
Analyst $%%%( 124( 223.
)3* 3. 3. !hih( +n 'pdate on the processin$ of hi$h-protein rice prod'cts(
Nahrung/Food &''(( 4( 62-.
)6* . 9. 8a%e.a( +. 8. ?c.en7ie( I. ?. +. Macroi4( @. @&ero'4( !. :owe( . +.
Iraham( J. :. !. @onacher( C. 5erdier( !'rvey of arsenic in tota& diet food
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chi&dren. !" A#A$ %nt" $%%(( &( 16.
)2* . +. !choof( M. N. Oost( N. <ic.hoff( <. +. @rece&i's( 8. 9. @ra$in( 8. ?.
?eacher( 8. :. ?en7e&( + mar.et %as.et s'rvey of inor$anic arsenic in food(
Food $he'" (o)icol" $%%%( *( A39.
)6* 9. J. Mamont( @oncentration of inor$anic arsenic in samp&es of white rice from
the Lnited !attes( !" Food $o'+" Anal" &''(( 1&( 6A7.
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drin.in$ water( Hu'" ,col" Ris- Assess" $%%)( 4( 117.
)A* /. oychowdh'ry( / Lchino( J. /o.'na$a( ?. +ndo( !'rvey of arsenic in food
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)9* J. >. 8as( +. >. ?itra( C. >. !en$'pta( +. Jossain( 3. Is&am( I. J. a%%ani(
+rsenic concentration in rice( ve$eta%&es( and fish in %an$&adeshB a pree&iminary
st'y( ,n/iron" %nt" &''*( *.( 3A3.
12
)1-* 8. /. Jeit.emper( N. C. 5e&a( >. . !tewart( @. !. 9estpha&( 8etermination of
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19
)62* +. +. ?ehar$( ?. . ?acnair( +n a&tered phosphate 'pta.e system in arsenate-
to&erant Holcus lanatus M.( New :hytol" $%%', 11&( 29.
2-
-able $. @a&i%ration and cross-va&idation statistics (n$/$( dry
wei$ht" for inor$anic arsenic for the se&ected e='ations (2( 2( 2(
2# !N5H8/"( performed on the ran$e from 6-- to 22-- nm.
!alibration !ross-
"alidation
n range mean S... S/! R
&
RP. r
&
6
-
13.--
26A.-
11-.3
7
69.A
-
2-.1
9
-.A
-
1.67 -.62
nD n'm%er of samp&es in the ca&i%ration fi&e# ran$eD minim'm
and ma4im'm reference va&'es in the ca&i%ration fi&e# !.8.D
standard deviation of the ca&i%ration fi&e# !<@D standard error of
ca&i%ration#
2
D coefficient of determination in the ca&i%ration#
C8D standard deviation to standard error of cross-va&idation
ratio# r
2
D coefficient of determination in the cross-va&idation.
21
0igure !aptions
0igure $. 3irst two principa& component p&ot (C@1 vs C@2" for rice samp&es (nD 6-"
'sed in this wor..
0igure &. 3re='ency distri%'tion of inor$anic arsenic (n$/$ dw" in the samp&es 'sed in
the st'dy (nD 6-".
0igure (. aw spectra (Mo$ 1/" of the rice samp&es 'sed in this wor. (nD 6-"( in the
ran$e from 6-- to 22-- nm.
0igure *. !econd derivative spectra (2( 2( 2( 2# !N5H8/" of the raw optica& data in the
ran$e from 6-- to 22-- nm.
0igure 1. @ross-va&idation scatter p&ot of &a%oratory vs. predicted va&'es %y NI! for
inor$anic arsenic in rice samp&es (nD 6-" (n$/$ dw".
0igure 2. !econd derivative (2( 2( 2( 2# !N5H8/" spectra of a" %rown and %" mi&&ed
rice samp&es 'sed in this st'dy.
Figure 7. @orre&ation p&ot for inor$anic arsenic reference va&'es vs. wave&en$th
a%sor%ance %y 'sin$ !N5H8/ a&$orithms( in the ran$e from 6-- to 269A nm (nD 6-".
0igure ). ?CM! &oadin$ spectra for inor$anic arsenic in the second derivative (2( 2( 2(
2# !N5H8/" transformation. 3rom the top to %ottom( pane&s represent &oadin$s for
factors 1( 2 and 3( respective&y.
22
0igure $.
23
0igure &.
26
0igure (.
22
0igure *.
26
0igure 1.
0 50 100 150 200 250 300 350
50
100
150
200
250
i
n
o
r
g
a
n
i
c

a
r
s
e
n
i
c

(
p
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)
inorganic arsenic (laboratory)
27
0igure 2.
2A
0igure +.
29
0igure ).
3-