103

Analytlca Chumca Acta, 262 (1992) 103-115

Elsevler Science Publishers B V , Amsterdam

The determination of the chromium speciation in sea

water using catalytic cathodic stripping voltammetry
Marc Boussemart I, Constant M G van den Berg * and Mohammed Ghaddaf 2
Oceanography Laboratory, Earth Sciences Department, Vnrversltyof Lwerpooh Lwerpool L69 3BX (UK)

(Received 5th November, revised manuscnpt received 30th January 1992)

Abstract
A voltammetnc procedure to determine chronuum m aqueous solution using cathodic stnppmg voltammetly
(CSV) preceded by adsorptive collection of complex species with diethylenetnannnepentaacetlc acid (DTPA) on a
hangmg mercury drop electrode LSoptlmlzed for sea water The optmuzed conditions Include a pH of 5 2 and a
DTPA concentration of 2 5 mM Comparison of the chemical speclafion of DTPA m sea water and chstdled water
with the CSV senslttvlty mdicated that the adsorptwe species IS a complex of chrommm(II1) wtth H,DTPA The
sensltmty of the CSV procedure for chrommm(VI) m sea water ISa decade lower than m dlstdled water due to major
cation cornpetItion (of c&urn and magnesium) for DTPA m the sea water The hmlt of detection for chrommm(VI)
m sea water IS0 1 nM at a deposition tune of 2 mm Chrommm(VI) produces a stable peak using the optmnaed CSV
procedures, whereas the peak due to chrommm(III) IS unstable due to probable conversion of the chrommm(II1)
complex to an electrochenucally mert complex over a penod of = 30 mm The chfferent behavlours of chronuumCVI1
and -(III) were utdlzed to devise a procedure to determme reactnre chrommm(III) and chrotmum(VI) m sea water
samples Experiments with an added chelator indicated that the reactive chrommm(III) concentration does not
mclude complexes with organic matenal The total &solved chrommm concentration was determined after UVuradlation of the sample at Its ongmal (neutral) pH Storage expenments indicated that neither the redox spectation
of chronumn nor Its total dissolved concentration m sea water could be stored The CSV method was applied
successfully to certified sea water samples and to the ship-board determination of chrommm(V1) and <III) in the
water column of the NW Mechterranean
Keywords Catalyhc methods, Stnppmg voltammetry, Chrommm, Sea water, Waters

Chromium occurs naturally m two oxldatlon

states, chrommm(VI) and chrommm(II0, m natural waters (see eg [1,2]) At the natural pH of sea
water the predommant species of chrommm(VI)
1s CrOf- whereas of chrommm(II1) It 1s Cr(OH),
and Cr(OH)i [3] Previous mvestlgatlons have
shown that the predominant oxldatlon state of
chrornmm 1schrommm(V1) m oxygenated sea water whereas it 1s chrornmm(II1) m anoxlc condl-

tlons [l] The oxldatlon state of chromium 1s

readily changed m the natural system as
chrommm(II1) IS oxldlzed for mstance by MnO,
[41and H202 [51
The usual determmatlon of chromium m natural waters 1s by means of atormc absorption spectrometry with preconcentratlon by coprecrpltatlon on lron(II1) hydroxide [2] Only chrommm(II1) adsorbs on the lron(II1) hydroxide
whereas chrommm(VI) 1s preconcentrated separately after reduction with lron(II) However,

Present address RhBne-Poulenc Agriculture Ltd , Fyfield

Rd , Ongar, Essex CM5 OHW, UK
* Present address Marme Science Centre, Aden, Yemen

other

preconcentratton

techntques

include

ad-

sorption of complexed chrommm(II1) on macroporous resin 161and hqmd-liquid extraction [7j

0003-2670/92/$0.5 00 0 1992 - Elsevler Science Pubhshers B V All rights reserved

104

Chrommm can be determined directly m water

(without previous extraction) using anodlc stnpping voltammetry [81or polarography [9] A more
Fen&we procedure consists of cathodic stripping
voltammetry (CSV) preceded by adsorptive collection of the complex of chrommm(II1) with
dlethylenetrrammepentaacetlc aad (DTPA) [lo]
or with trlethylenetetraammehexaacetlc
acid
0THA) ill1 on a hanging mercury drop electrode (HMDE)
The CSV method is here adapted for the determination of chrommm(VI) and total dissolved
chrommm m sea water It will be shown that total
dissolved chromium can be determined m sea
water after W-irradiation of the sample, whereas
chrommm(IV) can be determined speclflcally m
the untreated sample after a suitable reaction
period to eliminate interference by chromlum(III) The chrommm(II1) concentration can
then be calculated by difference The reactive
(morgamc) chrommm(II1) concentration can also
be determined directly by measuring the peak
height produced mnnedlately upon the addition
of DTPA to the untreated sample
Comparative expernnents were carried out usmg TTI-IA as adsorptive chelating agent for chrommm(III), the results usmg this compound were
generally similar to DTPA but no advantage was
obtained with this hgand so only the results with
DTPA are reported here

EXPERIMENTAL.
Equrpment

Voltammograms were recorded with an Autolab polarograph (Ecochemle, Netherlands) connected to a Metrohm model 663 HMDE (drop
surface area = 0 38 mm*), controlled by an IBMcompatible personal computer with a 80286 mlcroprocessor
Some comparative expenments
were carried out with a PAR 303 HMDE (drop
surface area 2 94 mm2) The voltammetrlc cell
was glass, and solutions m the cell were stirred
usmg a rotating PTFE rod (Metrohm electrode)
or a PTFE coated magnetic stirrer (PAR electrode) Potentials are given Hrlth respect to a
Ag/AgCl, saturated AgCl m 3 M KC1 (SSCE)

M Boussemart et al /Anal

Chtm Acta 262 (1992) 103415

reference electrode Samples were stored m

high-density polyethylene bottles, which were
cleaned usmg standard procedures (soakmg m
50% hydrochloric acid (BDH, AnalaR), followed
by soakmg m 2 M nitric acid, and subsequently
stored partially filled with dlstllled water of pH
2) All sample handling was carried out m a
lammar-flow hood supphed with filtered air
Reagents

Reagents were from BDH (AnalaR quality)

unless indicated differently Water was purified
by reverse osmosis (Mllh-Ro, M&pore) and ionexchange (Mllh-Q) Ammonia was purified by
isothermal dlstlllatlon and hydrochloric acid by
sub-bollmg dlstlllatlon
An aqueous solution of DTPA (Sigma) was
prepared contammg 0 25 M DTPA An acetate
pH buffer was prepared contammg 2 M sodium
acetate (BDH, Anstar) and = 1 M ammonia
Addition of 0 02 M of the acetate solution to sea
water gave a pH of 5 2 A second acetate pH
buffer was prepared contammg = 12 M ammoma gave a pH of 6 2 m dlsttlled water A stock
solution of chrommm(V1) was prepared from
potassmm chromate m water and contamed 1
mM chrommm(VI) This solution was found to be
stable for at least 3 months A stock solution of
chromrum(II1) was prepared from an atomic absorption standard solution for chrommm (BDH)
containing chromium chloride and diluted with 1
M hydrochlonc acid
Contaminating chrommm was removed from
an aqueous solution of 5 M sodium nitrate by
co-precipitation with u-on(III) hydroxide, lron(II>
chloride (0 1 mM) was thereto added to the solution and the pH was adJusted to neutral wrth
ammonia, the lron(II) iron was omdlzed by the
dissolved oxygen to lron(III) and allowed to precipitate The suspension of lron(III) hydroxide
was subsequently filtered to produce the purified
nitrate solution Addition of 0 5 M of the thus
purified nitrate to sea water contributed < 0 03
nM chrommm to the sample
Sea water used for preliminary experiments
originated from the North Sea (salinity = 34 psu)
or the Indian Ocean (sahnlty = 35 psu) (salmltles
are expressed m practical salinity units (psu))

M Boussemariet aL/Anal Chm Acta 262 (1992) 103-115

Estuanne samples were collected from the Mersey

estuary m collaboration with NRA Northwest,
and from the Mediterranean durmg the Cybele
cruise with the research vessel Marion Dufresne,
April 1990 as part of the EROS project supported by the European Commumty The Mersey
samples were filtered m the laboratory through
0 45 PM Oxold cellulose acetate filters The
Mediterranean samples were collected usmg 15-1
Go-Flo bottles The samples were filtered through
0 4 pm Nuclepore membrane filters and analyzed
on-board ship Comparative analyses were carned out m samples which were stored at the
natural pH, frozen at -20C

Procedure to determrne total drssolvedchromium

in sea water

Sea water was W-u-radiated for a penod of 4

h using either a l-kW high-pressure or a 100-W
medium pressure mercury vapour lamp An
ahquot of 10 ml of the sea water was plpetted
mto the voltammetnc cell, then 1 ml of 5 M
KNO, (final concentration of 0 5 M), 100 ~1 of 2
M acetate buffer (final concentration of 0 02 M
glvmg a pH of 5 2) and 100 ~1 of 0 25 M DTPA
(final concentration of 2 5 n&l DTPA) were
added (the reagents can also be pre-mnced to
mmlmlze the plpettmg during the reagent addltlons) The solution was deaerated by purging for
5 mm with oxygen-free, water saturated nitrogen
Then a new mercury drop was made, starting the
adsorption peirod of 60 s whilst the solution was
being stirred Then the stirring was stopped and a
qmescence period of 10 s was allowed Subsequently the potential scan was carried out m a
negative potential direction using the square-wave
modulation, the step height was 2 5 mV wth a
frequency of 100 Hz, the scan rate was 250 mV
s-l Comparative measurements were carried out
using the differential-pulse modulation with a
pulse rate of 10 s-l, a scan rate of 20 mV s-l and
a pulse height of 25 mV The peak corresponding
wth the reduction of the adsorbed DTPA complex of chrommm(II1) appeared at - 122 V The
sensltlvlty was calibrated by addition of chromlum(V1) standard solution sufficient to double the
peak height

105
RESULTSAND DISCUSSION

Catalytrc CSV of chromrum m sea water

The CSV scan of chrommm(VI) m sea water

(using the standardized conditions) produced a

peak at - 122 V, at the bottom of the hydrogen
wave The reduction current 1s due to the reduction of chrommm(II1) to chrommm(I1) and 1s
enhanced by a catalytic effect m the presence of
nitrate ions owmg to the chemical reoxldatlon of
chrommm(I1) to chrommm(III) which 1s subsequently re-reduced at the electrode surface [lo]
The scan was preceded by adsorptive collection
of chromlum(II1) complexes with DTPA The
chromnun(II1) 1s produced freshly during the adsorption step by reduction of the dissolved
chrommm(V1) at the electrode surface durmg
deposition at - 10 V (chrommm(VI) 1s reduced
to chrommrn(II1) at potentials < -0 05 V, the
reduction potential of chrommm(VI)), and subsequently forms a complex with the DTPA which
adsorbs on the mercury drop
Addition of chronuum(II1) to the solution produced the same reduction peak at - 122 V mdlcatmg that the adsorptive complex 1s also produced when chrommm(II1) 1s present m solution
However, the reduction current of the dissolved
complex of chrommm(III) was not stable and
gradually dunmrshed m height, disappearing altogether m approxunately 30 mm (discussed below)
The CSV sensltlvlty for chrommm(II1) unmedlately upon the DTPA addition was less (ca 30%)
than that for the same concentration
of
chrommm(V1) probably as a result of slower dlffusion of the dissolved chromnnn(III)-DTPA
complex than of the uncomplexed chrommm(V1)
to the mercury surface
Comparative experiments m distilled water and
sea water showed that the sensltlvlty for
chromuun(V1) differed considerably bemg 20-fold
lower m the sea water The analytical conditions
for the determmatlon of chronuum m sea water
using CSV were therefore optmnzed
Optlmuatwn of the anulyttcalcond1tlon.sDTPA,
pH, deposztwnpotentuzl, and competrng cations

Several parameters affecting the CSV sensltlvlty were vaned whilst the reduction current of the

M Boussemartet al /Anal Chrm Acta 262 (1992) 103-115

106

chrommm(III)-DTPA
complex was monitored
after 60 s adsorptlon at - 1 V from sea water of
pH 5 2 contauung 2 5 mM DTPA, 0 5 M NO;
and 10 nM chrommm(V1) unless indicated otherwise The results are summarized m Fig 1
Vanatlon of the DTPA concentration showed
that the peak height for chromuun mcreased untrl
2 5 mM DTPA whereafter a small decrease was
apparent (Fig 1A) The optunal DTPA concentration of 2 5 mM for analytical purposes 1sslightly
smaller than that (5 mM DTPA) required m fresh
water [lo], this fmdmg 1s unexpected m view of
the competition by the major ions m the sea
water for DTPA The decrease of the peak height
for chromium at higher concentrations of DTPA
m sea water may be due to the formation of
higher order complexes such as chrommm(III)DTPA,
The adsorption of the chrommm(III)-DTPA
complexes was found to be strongly dependent on
the deposition potentral (Fig 1D) reaching mmmum adsorption at - 1 V The adsorption was
very low at potentials more positwe than - 0 5 V
where the charge on the mercury drop electrode

IS positive

m electrolytes contammg chlonde ions

such as sea water [12], suggesting that the adsorbmg chrommm(III)-DTPA complex has a posltme
charge
Vanatlon of the pH showed that a pH between 5 0 and 5 3 1s optimal for the determmatlon of chrommm m sea water The optimal pH
range 1slower than for fresh water where a pH of
6 4 1s optimal [lo] which produces poor sensltlvlty
m sea water pH values near 5 m sea water and
near 6 m fresh water can both be conveniently
buffered usmg acetate pH buffer due to calcuun
and magnesium competition for the acetate Ions
m sea water, so the same pH buffer can be used
for fresh water and sea water analysis of
chrommm although the actual pH values differ
Comparative measurements showed that the
CSV sensltlvlty m sea water of pH 5 2 was conslderably lower than m fresh water of pH 6 4 Vanatlon of the concentrations of calcmm and magneslum m dlstllled water showed that the CSV peak
height for chromium decreased with increasing
concentration of these major cations, at the same
time shlftmg the peak potential to more positive

Collection potential WI

Fig 1 The effect of varymg the DTPA concentration (A), the pH (B), the magnesmm Ion concentrabon (0 and the deposItIon
potential (D) on the CSV peak height for chrommm m sea water (A, B and D) and cbstdled water (C) Standard conchtlons are used
unless Indicated differently The chrommm concentration was 2 nM as chrommm(VI)

M Bouweman et al /Anal Chmt Acta 262 (1992) 103-115

potentials The results for magnesium are shown

m Fig 1C This fmdmg suggests that major cation
competition for DTPA 1sresponsible for the lower
sensltlvlty m sea water as well as for the lower
stab&y of the adsorbed chronuum(III)-DTPA
complexes
Vanatlon of the mtrate concentration (not dnplayed) showed that the CSV peak height for
chrommm m sea water mcreased lmearly with the
nitrate concentration until 0 5 M mtrate and nonlmearly thereafter until approxnnately 12 M mtrate whereafter the peak height started to dnnmlsh probably due to dllutlon of the DTPA concentration m the solutlon (a correction was made for
the dllutlon of the chrommm concentration) The
optunal nitrate concentration (12 M) is somewhat higher than that observed previously in fresh
water (0 5 M) The hnear relationship of the
sensitivity with the nitrate concentration at mtrate concentrations below ca 1 M 1s m lme with
expectation as the reduction current depends on
dlffuslon of the oxidant to the electrode surface
durmg the scan
A nitrate concentration of 0 5 M was used by
us for the optumzed analytical conditions as the
solublhty of sodnun nitrate m the stock solution 1s
lmuted to ca 5 M at room temperature, so the
chrommm m the sample becomes slgmflcantly
diluted when a concentration greater than 0 5 M
1s used unless the nitrate would be added as the
salt
The specmon of DTPA
The chemical speclatlon of DTPA (total concentration 2 5 mM) was calculated as a function
of the pH for a solution snmlar to sea water
(contammg 53 mM Mg*+) and fresh water m
order to investigate which species is responsible
for the formation of the adsorptive complex with
chromnun(II1) and to explain the dtierent behavlours m sea and fresh water The following
equlhbrmm constants for DPTA and its chelates
were used 1131 pK,, = 182, pK, = 2 66, pK, =
4 3, pK, = 8 59, pK, = 10 55 and log K,,, =
= 5 84 (Y = unprotonated DTPA)
9 3, log K,,
It can be seen m Fig 2 that the concentration of
the H,Y species reaches a maximum at pH 6 45
m fresh water and at pH 5 05 m sea water These

107
3

FRESH WATER
HZY

Ia

SEA WATER

H3Y

00

20

40

HZY

80

60

100

120

PH

Fig 2 The protonatlon of 2 5 mM DTPA as a function of the

pH m fresh water (top) and sea water (bottom) Note the
different vertical (concentration)

scales

pH values agree very well with the optnnal senatlvltles obtained at pH 6 4 m fresh water [lo] and
at pH 5 0 m sea water (Fig lB), suggestmg that a
complex of H,Y with chrommm(II1) adsorbs on
the mercury drop
Assuming that the H,Y speaes of DTPA
(DTPAH,) is indeed responsible for the formation of the adsorptive complex with chrommm(II1)
the calculated speclatlon explams that the optlma1 pH IS lower in sea water as a result of major
cation competition for DTPA Further it can be
seen that the H,Y concentration m sea water
(= 1 PM) 1s much lower than m fresh water
(= 2 5 n&I) at the optimal pH values due to the
major cation competition m the sea water, clanfymg why the maxunal sensltlvlty m sea water 1s
lower than m fresh water The stab&y constant
for the formation of the chrommm(III)-DTPAH,

108

M Boussemarret al /Anal ChumActa 262 (1992) 103-115

__

03
Trkon X 100

02

04

lppml

05

08

Fig 3 The interference of Trlton X-100 m the determmatlon

of 6 nM chrommm(V1) m UV-xradlated
sea water at two
different adsorptlon times (60 s and 120 s)

complex (log K value) 1s 3 67 [14] lllustratmg that

the stability of this complex is not high m sea
water where the dissolved concentration of
DTPAH, 1s particularly low The actual degree
of complexatlon of chrommm(II1) by the DTPA
can not be calculated as the effective DTPA
concentration at the mercury drop surface 1s mcreased by adsorption of the DTPA on the mercury
Interferences

Interferences m adsorptive CSV include competitive adsorption of surface active compounds

or of other metal complexes on the mercury drop
electrode The potential interference by surfactants was tested by addmg Trlton X-100, a nonlomc surfactant which 1s often used to model
effects of surfactants occurring in natural waters
[15,16], to sea water and monitoring the peak
current using CSV Natural waters typically contam 02-2 kg ml- of compounds with a
surface-active effect similar to that of Trlton X100 [15] It can be seen in Fig 3 that the sensitivity 1s strongly affected by addltlon of even low
concentrations of surfactant, the peak being completely inhibited m the presence of 0 4 ppm Tnton X-100 at an adsorption time of 120 s Addltlon of humlc acid (Fluka) to the sea water also
dmumshed the sensitivity, completely eliminating
the peak for 10 nM chrommm(V1) at a level of 5

pg ml- The interfermg effect is less at an

adsorption time of 60 s (Fig 3) lllustratmg that it
may be possible to nnprove the sensltlvlty by
lowering the adsorption time when the analysis is
subject to interference by natural surface active
compounds The interference by natural surface
active compounds was found to be ehmmated by
UV-irradiation of the sample
Other metals can interfere if they form adsorptive electroactlve complexes with a peak potential near to that for chromium No mterfermg
effect was observed by the addition of cobalt (5
nM), mckel(50 nM), zmc (100 nM), tltamum (100
nM), manganese011 (100 nM) and rron(II1) (1
PM)
A kmetlc effect was produced by higher iron
additions The sensltlwty for chromium was found
to dnnmlsh gradually by the addition of 10 PM
lron(III), showing a 90% decrease m 10 mm and
dsappearmg altogether m 15 mm, presumably as
a result of competition for DTPA The chromium
peak did not reappear upon addition of
chrommm(VI) mdlcatmg that perhaps a DTPA
complex of lron(II1) adsorbed on the mercury
drop and mterfered with the adsorption of the
chromium complex 10 FM levels of iron do not
normally occur in sea water from coastal or
oceanic origin but can occur m mterstmal waters
of sediments
The chromium concentration can be determined accurately also m the presence of low
levels (sub hg ml-) of surface active compounds
or high levels of non by using internal standard
additions of chromium
It was found that high levels of hydrogen peroxide and nitrite interfered with the CSV determination of chromium by producing a broad peak
positive of the chronuum peak and overlappmg
with that of chromium respectively Hydrogen
peroxide 1s sometnnes added (e g [lo]) to lmprove the W-irradiation treatment, and our experiments indicated that this hydrogen peroxide
was not destroyed d the radiation was carried out
at a low temperature (ca 30C) perhaps because
the irradiation was carried out at neutral pH
which increases the thermodynamic stabdlty of
hydrogen peroxide somewhat Nitrite was found
to be produced by UV-irradiation of samples

M Boussemnrt et al /Anal Chum Acta 262 (1992) 103-115

which had been stored after ac&flcatlon

mtnc acid

109

Limit of detectwn and Hnear range of the determmatwn of chromuun(V7) m sea water

with

CSV of chromnun added to UV-lrradlated sea

water showed that the peak height increased lmearly with the chrommm concentration up to 20
nM (adsorption tune 60 s) and non-hnearly thereafter (Fig 4A) This linear range IS much greater
than the range of chrommm concentrations occurring m sea water (normally well below 10 nM)
The peak height for 6 nM chromnun 111sea
water was found to increase lmearly with the
deposition time up to 4 mm and non-linearly
thereafter, the peak height after a deposition
time of 15 mm betng 11 times greater than after
one of 1 mm The non-lmeanty ISprobably caused
by saturation of the drop surface with adsorbed
complexes CSV scans for low levels of chrommm
m sea water from which the chrommm had been
removed by co-preapltatlon usmg lron(IIl)hydroxlde (added as iron(
are shown m Fig 4C
The scans were carried out using the square-wave
modulation at a frequency of 100 Hz
Variation of the square-wave frequency showed
that the sensltlvlty increased with the frequency

Contammatwn from reagents

The contnbutlon of chronuum from freshly

prepared reagents to the sea water was approxlmately 0 3-O 5 nM It was observed that this
contribution dlmuushed upon storage of the
reagent solutions and was found to be due to
chrommm(III) and chromuun(VI) present 111the
nitrate solution It was found that this chromuun
could be readily removed by addltlon of 0 1 mM
lron(I1) chloride to the nitrate stock solution and
neutrallzatlon with ammoma, followed by oxldatlon of the lrodl1) iron to lron(III) hydroxide by
the dissolved oxygen Hrlth concomitant reduction
of chrommm(VI) to chrommm(III) and the subsequent copreclpltatlon of all chrommm(II1) with
the lron(III) hydroxide (this procedure 1s ldentlcal to that used for the preconcentratlon of
chrommm from sea water [l]) The preapltate
was removed by fdtratlon (0 45 km Mdhpore
filter) The contrlbutlon of chrommm from the
thus pursed reagents was less than 0 03 nM

151

__

5,

li:.:..:-:
1 In,

0
0

5-

5o

Cr VI

(do0

150

3O

50

100

150

SW Frequency (Hz)

200

250

0'

I
11

12

13

14

Potential (VI

Fig 4 CSV of chrommm(VI) m sea water The lmear range at two deposlhon times, 60 s and 120 s (A), the effect of varymg the
square-wave frequency (B), and scans for low levels of chrornmm(Vl) m punfied sea water (deposItIon time 60 s), the
chrommm(VI) concentrations are mdxated on the drawmg

110

levelhng off at frequencies between 50 and

100 Hz, whilst the sensltlvlty dlrmnlshed at higher
frequencies probably due to poor electrochemical
reverslblhty of the reduction step (Fig 4B)
The standard devlatlon of a determmatlon of 3
nM chrommm m sea water usmg the optlmlzed
conditions was 3% (n = 6) The sensltlvlty was 5 8
nA nW nun- A hmlt of detection of 0 1 nM
wth a deposmon time of 2 mm can be calculated
from 3 x the standard deviation of this detennation This lumt can be reduced to ca 0 02 nM
m UV-Irradiated sea water by mcreasmg the adsorption time to 15 mm The voltammetric scans
for low levels of chrommm m punfled sea water
are shown m Fig 4C It can be seen that the lnmt
of detection 1s not determined by electronic noise
but by the slope of the baseline as the chrommm
peak 1s located at the bottom of the hydrogen
wave The actual reduction current 1slarge due to
the catalytic effect of the mtrate
unttl

Chromrum (III)

Addition of chrommm(II1) to the sea water

produced a peak which decreased with time, dlsappearing altogether after a period of approxlmately 30 mm (Fig 5) leaving only the peak due
to the chrommm(V1) which was orlgmally present
m the sea water The same effect has been shown
to occur m distilled water 1171

Rg 5 The decay of the peak height obtamed by CSV for 10

nM chrommm(II1) m the presence of 5 nM chrommm(VI) m
sea water pH 8 Each scan was preceded by 60 s adsorptlon
on the mercury drop

M Boussemart et al /Anal

Chum Acta 262 (1992) 103-115

Measurement by atomic absorption spectrometry of the total dissolved chromuun(II1) concentration added to dlstllled water showed that the
maJor part of the added chrommm was still m
solution after the voltammetrlc peak had dlsappeared, suggesting that the dunmlshmg peak
height was not due to adsorptlon of the chrommm
on the cell wall Apparently the electroactlve
DTPA complex which is formed immediately
upon the reactlon of the DTPA with chrommm(III) 1s gradually converted to an electro-inactive
complex One posslblhty IS that chrommm IS hydrated m the first complex whereas It loses part
or all of its hydration sphere m the second type
Another posslblhty 1s that the second type of
complex 1s polynuclear and does not adsorb on
the mercury drop surface due to stereohmdrance
The reaction mechanism of the chrommm(II1)
which 1s freshly produced from chrommm(V1) at
the electrode surface could be qmte different
from that which 1s orlgmally present m the solution as the freshly produced chrommm(II1) 1s
known to be electrochemlcally very reactive [18]
The peak due to chrommm(III) freshly produced
from dissolved chrommm(V1) was found to be
much more stable decreasmg only very slowly by
ca 02% mm- m sea water of pH 5 2 This
decrease was found to be due to the chemical
reduction of chrommm(VI) by mercury waste m
the voltammetrlc cell, this effect was stronger
when a PAR303A electrode was used with a large
mercury drop (drop area 2 9 mm) than using the
Metrohm mercury drop electrode with a surface
area of 0 8 mm2 (thus producmg less mercury
waste) Chrommm(V1) 1s known to be reduced by
metalhc mercury [ 191
Additions of chrommm(II1) to sea water
showed that the CSV sensitivity was 3 3 nA nM_
mm- immediately after the addition Measurements by CSV of chrommm(III) added to sea
water indicated that it 1s possible to determine
the concentration of reactwe chromzum(ZII) by
measuring its peak height by CSV at pH = 5
immediately after the reagent addltlon to the
sample The sensmvlty was calibrated by a standard addltlon of chromlum(II1) after a reactlon
time of = 30 mm to allow the slgnal to stablhze
Prellmmary experiments were carried out to

M Boussemartet al /Anal Chm Acta 262 (1992) 103-115

mvestlgate the Influence of complexatlon of

chrommm(lI1) by organic hgands other than
DTPA on the CSV sensltlvlty Addition of 0 5
mM citrate (added as citric acid) to sea water
containing 2 5 mM DTPA and acetate buffer (pH
5 2) was found to decrease the CSV sensitivity for
10 nM chrommm(V1) by 20% Slmllarly the CSV
sensltlvlty for 10 nM chrommm(lI1) m purified
sea water (contammg 0 8 nM chrommm(V1)) was
dlmmlshed by 20% by the addition of citrate (and
the peak gradually dlmuushed m height as usual)
However, no CSV peak was produced by 10 nM
chrommm(II1) when the citrate was added to the
sea water and complexatlon of the chrommm(II1)
by the added citrate was completed by heatmg
the sample to = 60C for 30 mm m a mlcrowave
oven, prior to the addition of the DTPA, mdlcatmg that the chromnun(II1) was complexed by the
citrate and was either not released to the DTPA
or was released to form the electro-inactive complex This result suggests that chrommm(II1)
complexed by organic material present m sea
water samples would not be part of the reactive
chrommm(110 concentration

The determmatlon of reactive chromaun(VI) m

sea water

The concentration of reactive chrommm(V1)

can be determined m the presence of chrommm
(III) without prior treatment of the sample by
allowmg the sample to react for a short period
(30 mm> with added DTPA as Illustrated m Fig
5 Experiments at different pH values indicated
that the contrlbutlon of the dissolved chrommm(III) to the reduction peak dlmlmshed more
rapidly at higher pH values whereas the stability
of the chrommm(V1) towards reduction by mercury waste improved Thus the disappearance of
the contnbutlon from chromlum(II1) was completed m a period of approximately 15 mm at pH
6 8 whereas the decrease m the peak height due
to chrommm(V1) was negligible at that pH
Probably all chrommm(VD orlgmally present
m the sample 1s determined
as reactive
chrommm(V1) as its major species 1s anionic
CrO,Z- which 1s unlikely to undergo any strong
mteractlons with organic complexmg hgands

111

which could render it electro-inactive m sea water

The followmg procedure was therefore followed to determme the concentration
of
chrommm(V1) ongmally present m a sample ammoma was added to the sample m the voltammetnc cell m addition to the usual DTPA-acetate
buffer nuxture to raise the pH to ca 6 8, and a
reaction tnne of 15 mm was allowed whilst the
sample was bemg deaerated Then the pH was
lowered to 5 O-5 2 by addition of hydrochloric
acid equivalent to the ammonia added previously
The dissolved concentration of chrommm(V1)
could then be determined usmg the optlmlzed
CSV procedure Complete conversion of the
chrommm(II1) to an electrochemlcally mert complex was Indicated by stab&y of the peak height
The determmutlon of total dusolved chromrum
in sea water
The chrommm(II1) IS known to be converted

to chrommm(VI) upon UV-madlatlon of the

sample [lo,171 and also by hydrogen peroxide [5]
We found that it was not necessary to add hydrogen peroxide to the sea water m order to obtam
complete conversion to chrommm(VI) by UVirradiation of samples from the North Sea or the
Atlantic Ocean However, samples from estuarme
origin (the Mersey estuary) benefitted from the
addition of hydrogen peroxide (final concentration 0 03%) to the sample to fully destroy the
natural surface active compounds
Tests indicated that not all chrommm(II1) was
converted to chrommm(V0 if the sample was
irradiated at low pH (pH 2) and losses occurred
probably due to adsorption of chrommm(II1) on
the slhca walls, but complete conversion was
achieved if the irradiation was carried out at
neutral pH values (pH 7-8 5, mcludmg the natural pH of the sea water)
The concentration of chrommm(II1) (as total
chrommm(II0, mcludmg complexes wth organic
material) can be calculated from the difference
between the total chrommm and the reactive
chrommm(V1) concentratrons
The accuracy of the CSV method was evaluated by determmatlon of the total dissolved
chromium concentration m certlfled sea water

112

Unfortunately the certified sea water orlgmatmg

from the North Atlantic (NASS-2 [19]>was stablhzed by aadlficatlon to pH 16 wrth mtric acid
which precluded UV-treatment as this produced
mterfermg quantltles of mtrrte It was found that
the chrommm(II1) could be converted quantltatlvely to chrommmW1) by reacting the sea water
with MnO, The conversion efficiency was cahbrated by addltlon of known amounts of
chrommm(II1) and was found to he between 97
and 104% NASS-2 was found to contam a total
chrommm concentration of 3 3 f 0 2 nM (n = 3)
which compares well with a certified value of
3 37 & 0 02 nM A sea water sample ongmatmg
from the North Sea and recently prepared for
certlflcatlon by BCR (Bureau for the Certlflcatlon of Reference Materials of the European
Commumty) was analyzed by the same procedure
and was found to contam 2 03 f 0 2 nM chrommm
(the chrommm concentration has not been certified by BCR 111this sample and this value is given
for information only)
Determrnatwn of the specuztwn of chromwm m
the Mediterranean

The CSV method was applied to samples from

the Mediterranean to test the procedures Measurements of reactwe chrommm(V1) and reactive
chromuun(II1) were carried out on-board ship m
samples from the Mediterranean during the
Cybele cruise m the Gulf the Lyon, April 1990
[20] The results for two statlons @AD1 and
EBB4) are shown m Fig 6 The station locatlons
were 433/55 (RADl) and 403/151 (EBB4)
The station depths were 140 m &AD11 and 1700
m (EBB4) The shipboard analyses were less reproducible than those carried out m the landbased laboratory due to engme vlbratlons Nevertheless clear trends are apparent m the data
It can be seen m Fig 6 that the concentration
of chrommmW1) was around 5 nM at both stations Some varlatlon m the chromlum(V1) concentration was apparent m samples from shallow
depth perhaps due to uptake by orgamsms
The chrommm(V1) concentration could be determined readily without prior UV-treatment of
the samples mdlcatmg that the concentration of
mterfermg surface-active compounds was low

M Boussemart et al /Anal

Chrm Acta 262 (1992) 103-115

Cr InM)

Statm

IUD1

c.m.-

Cr (nM)

Fig 6 The concentrations of chrommm(VI) and reactive

chrommm(III) at stations RADl and EBB4 m the NW
Mediterranean These chrommm concentrations were determined on-board slup reactwe chrommm(II1) was estimated
from the peak height obtamed lmmechately after the addltlon
of the DTPA to the sample

(with an surface-active effect less than that for 0 5

pg ml- Trlton X-100)
The concentration of chrommm(II1) was much
lower than that of chrommm(VI) and could be
detected only m near-surface waters the chromlum(II1) concentration dununshed rapldly from ca
1 nM at the surface to undetectable at 30 m
depth at RADl The chrommm(111) concentratlon was below the lunlt of detection in most
samples from EBB4 except m the surface sample
and a sample from 200 m depth It 1s temptmg to
ascribe the presence of chrommm(II1) m the surface waters to photochemical effects but a more
detailed study has to be carried out to confirm
this observation
The detected levels of chrommm(V1) and -(III)
m the Mediterranean are generally slmdar to
those detected previously (usmg co-precipltatlon
and atomic absorption spectrometry) m samples
orlgmatmg from the Eastern Paafic 1211 The

M Boussemart et al /Anal

Chum Acta 262 (1992) 103-115

113

Sample storage
Prelmunary experunents mdlcated that chrommm(III) 1s removed rapidly Cm a matter of
minutes to hours) from solution by adsorption
onto the contamer walls at neutral pH, whereas
chrommm(VI) IS known to be reduced to
chrommm(II1) by organic material m aadlfled
conditions [2] Several samples were stored frozen
(m high dens@ polyethylene bottles) m an attempt to stabdlze the chrommm speclatlon The
results of later laboratory determmatlons of the
chrommm speclatlon and of total dissolved
chromium can be compared m Table 1 with the
chromium speclatlon determmed on-board ship
munedlately after collection It can be seen that
the chrommmW1) and the total dissolved
chromium concentrations m the stored samples
were much lower than the chrommm(V1) concentrations ongmally present m the samples As
chrommm(VI) does not readdy partlclpate m adsorption reactions at the natural pH of sea water
It IS hkely that some of the chrommm(VI) became
reduced to chrommm(II1) durmg storage and that
some of this was removed from solution by adsorption on the bottle walls or by preclpltatlon
durmg freezmg or thawmg The chrommm(III)
concentration was measured m two of the stored
samples and was found to be much higher (at 15
and 2 1 nM) after storage than before (0 and 0 2
nM chrommm(III)), confummg that some of the

deep water concentrations of chrommmW1) m

the Pack were 4-5 nM, perhaps slightly lower
than m the deep waters from the Mediterranean
where the chrommmW0 concentrations were
around 5 nM The surface concentrations of
chrornmm(VI) m the Pa&c were lower at 3-4
nM [21] but metal concentrations m surface waters are affected by blogeochemlcal reactlons with
temporal variations The absence of a clear reductron of the chrommm(VI) concentrations m
the upper water column of the Mediterranean
may therefore be due to comparatively recent
mlxlng of the water column
The concentration of chrommm(II1) m the Paclflc was between 0 and 1 nM wth a maximum m
the upper water aAnnn 1211, smllar to the
Mediterranean data
The CSV method was sufficiently sensltlve to
detect reactive chrommm(V1) and total dissolved
chrommm m the sea water samples, but not usually sufflclently sensltlve to detect the low levels
of chrommm(II1) occurnng in sea water either
directly (from the peak height unmedlately after
the reagent addition) or by difference (total
chrommm mmus reactive chrommm(VI)) due to
the much higher concentrations of chrommmWI)
Investlgattons are therefore currently underway
to develop a procedure mvolvmg a preconcentratlon step to lower the detectlon hnut for chromlurn(II1)

TABLE 1
Effect of sample storage on the concentrations of chrommm(II1) and (VI) m sea water
(The samples were collected from the Mechterranean (StatIon RADl) and were stored by freezmg)
Sample
depth
(m)

ZQO
140
83
72
30

Analysts on-board

Anaiysls m laboratory

Reactrve
chronuum(VI)

Reactwe
chrommmUI1)

Reactwe
chrommm(VI)

Total
chronuum

Total
chrommm(II1)

(nM)

(nM)

(nM)

(nM)

(M)

490
5 80
448
500
5 10

0
02
0
07
0

2 10

150

280
360
350
260
420

150

270

114

chrommm(VI) had been converted to chrommm

(III) These results illustrate the difficulty of preservmg the dissolved chrommm concentration as
well as the redox speclatlon of chrommm m sea
water

Conclusions
The CSV sensltlvlty

for chrommm m sea water

is approximately a decade poorer than m distilled
water as a result of major cation competition for
DTPA The optlmrzed conditions include a solutlon pH of 5 2 (approximately one pH unit lower
than m freshwater) and a DTPA concentration of
2 5 mM The different sensitivity for chrommm,
and the different optmuzed condltlons, as compared with the situation m fresh water, are due to
competltlon by the major cations, magnesium and
cahum, 111sea water Calculation of the speclatlon of DTPA m sea water and fresh water showed
that (H,DTPA) 1s the hgand of the adsorptive
complex vvlth chromnun(II1)
Reactive chrommm(VI) and total dissolved
chrommm can be determined m sea water using
CSV with a hmlt of detection of ca 0 1 nM with
an adsorptlon time of 2 mm The hmlt of detectlon is higher than m freshwater (ca 0 01 nM)
The total dissolved chromium concentration 1s
determined after UV-lrradlatlon of the sample at
neutral pH The concentration of total chromlum(II1) (reactive morgamc and organically complexed) can then be evaluated by difference
Reactive chrommm(II1) can be determined by
adsorption of the DTPA complexes onto the
HMDE munedlately after the DTPA addition to
the sea water The experiments with citrate mdrcate that orgamc complexes of chrommm(III) do
,not contribute to this chrommm fraction Unfortunately the redox speclatlon of chromium m sea
water cannot be stored, necessltatmg analysis as
soon as possible upon samplmg The determmatlon of chrommm(II1) m oxygenated sea water 1s
dd%cult as Its concentration 1s much lower than
that of chromu.un(VI) Chrommm(II1) m oxygenated sea water IS therefore generally below

M Boussemart et al /Anal

Chm

Acta 262 (1992) 103-115

the limit of detection by the current CSV procedure

The authors are grateful for assistance by Lucla Campos with the chrommm analyses on-board
ship, and for the cooperation of the other sclentests with sample collection during the cruise of
the Marion Dufresne Thus research was fmanclally supported by NERC grant GR3/7247 whilst
the field expenses were sponsored by the EROS
programme of the European Commumty
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