Beruflich Dokumente
Kultur Dokumente
17–31 (2009)
MJCCA9 – 530 ISSN 1857 – 5552
Received: February 19, 2009 UDC: 663.2:543.421
Accepted: April 9, 2009
Rewiev
This article reviews methods for the determination and identification of trace elements in wine by using atomic
absorption spectrometry (AAS). Wine is one of the most widely consumed beverages and strict analytical control of
trace elements content is required during the whole process of wine production from grape to the final product. Le-
vels of trace elements in wine are important from both points of view: organoleptic – Fe, Cu, Mn and Zn concentra-
tions are directly related to the destabilization and oxidative evolution of wines, and toxicological – toxic elements
content should be under the allowable limit, wine identification. The identification of metals in wine is subject of in-
creasing interest since complexation may reduce their toxicity and bioavailability. AAS is one of widely used me-
thods for routine analytical control of wine quality recommended by the International Organization of Vine and
Wine. Two main approaches – preliminary sample digestion and direct instrumental measurement combined with
AAS for trace element determination in wines are reviewed and discussed. Procedures for various sample pre-
treatments, for trace element separation and preconcentration are presented. Advances in metal identification studies
in wines based on AAS are presented.
grapevine in the final stages of berry ripening. significantly higher concentration of lead com-
High K levels affect the stability of wine with re- pared to juice and wine stored in stainless steel.
spect to the potassium hydrogen L-(+)-tartarate Moreover fining with bentonite or filtering with
precipitation. diatomaceous earth contributes further to final Pb
concentration, while fermentation, both primary
Calcium is a natural component of wine al-
and secondary, removed Pb [15]. In another study
though the concentration of calcium in wine can be
measurements of 7000 wines were used to identify
affected by the traditional practices of deacidi-
possible sources of Pb in wine and these showed
fication (CaCO3 addition) or plastering (CaSO4
that atmospheric–related contamination (leaded
addition). Elevated calcium levels can lead in
gasoline) was not responsible for elevated Pb lev-
some wines to calcium L-(+)-tartarate precipita-
els in wine. It was also shown that the presence or
tion. It should be pointed that total calcium content
absence of tin-lead capsules as well as the stare of
in wine is not informative enough to predict the
tin-lead capsule corrosion had only a very minor
stability of wine and data for the free metal con-
influence on the Pb concentration in wine. It was
centration are required [14].
concluded that brass is the main contamination
Aluminum is found in grape juice, but the source for elevated Pb content in wine [16].
concentration in both juice and wine is elevated
Cadmium levels have been determined during
because of the use of bentonite, and to a lesser ex-
wine making in 21 locations in France. During the
tent from contact with aluminum surfaces. It has
alcoholic fermentation Cd elimination is almost
become apparent that aluminum is strongly com-
complete with losses between 87 to 100% [17].
plexed in wine which affects its bioavailability
from one side and makes haze formation unlikely An interesting study for statistical evaluation
from the other side. of aroma and metal content in Tokay wine answered
the question – how qualitative and quantitative rela-
At low concentration iron plays an important tions of volatile organic and metal components
role in metabolism and fermentation processes as present in traditional wines depend on the vintage,
an enzyme activator, solubilizer and functional the location on which it is grown, as well as the
component of proteins. Above trace levels, iron type of wine grape, and to what extent these are
has other roles: altering redox system of the wine characteristics of wines of given type and vintage
in favor of oxidation, participating in the forma- [18]. A study revealed the correlation between
tion of complexes with tannins and phosphates trace element content, total antioxidant capacity,
thus resulting in instabilities. total phenolic content, hystamine concentrations
and fruit origin of wine [19]. Wines from Jordan
The same can be said for copper: in trace have been characterized for pesticides and trace
amounts is an important inorganic catalyst for metals contents and it was deremined that heavy
metabolic activities of microorganisms; at high lev- metals showed higher values in grapes than in
els it plays an important role in catalyzing oxidation wines which is attributed to the removal of solids
of wine polyphenols. It should be pointed out that during wine preparation processes [20]. The influ-
copper and copper complexes are more active than ence of copper application on the copper content
iron and its complexes [14]. However for both ele- in grape and wine from Italian wine-farms was
ments copper-induced and iron-induced spoilage studied during the harvest of 2003. It was con-
are not related to the total metal concentration. For cluded that copper content in grape depends more
copper, the free active metal concentration is im- strongly on the total dose applied than on the
portant and for iron the valence state determines number of applications, and that the copper residue
the potential for iron-induced oxidation. level in wine does not depend on the quantity ap-
Sources of lead in wine were inferred from plied in the vineyard [21].
systematic assay of grapes must and wine during The influence of Fe, Cu and Mn on wine oxi-
winemaking. It was found that Pb concentration in dation was studied and it was found that these three
fermenting must vary during vinification. Lead cations intervene ‘somehow’ the evolution of differ-
concentration increased significantly in open-top ent compounds: anthocyanins, tannins, total phenol
vessels, in holding bins, and during pressing. Juice content and acetaldehyde which are sensitive to
and wine stored in concrete or waxed wood have oxidation. Iron catalyzes acetaldehyde combina-
tion with phenolic compounds [22].
METHODS FOR TRACE ELEMENT was applied by Chuachuad et al. for Cd determina-
DETERMINATION IN WINES BASED tion in wines by flow injection cold vapor AAS
ON SAMPLE DIGESTION FOLLOWED (CVAAS) [42, 55] and Pb determination by
BY AAS HGAAS [43] after wine MW digestion by mixture
of HNO3+H2O2. A volatile derivative was formed
The sample preparation step (e.g. preliminary on passage of an acidified cadmium solution
digestion of wine sample) was included to destroy through a strong anion-exchange resin (Amberlite
the organic matrix and/or to extract the metal ions IRA-400) in the tetrahydridoborate(III) form and
bound in inorganic and organic complexes. In the atomized in a quartz T-atomizer [42] or graphite
wine industry dry ashing dates from very begin- furnace [55]. Strong anion-exchange resin (Am-
ning of wine analysis: it involves the complete re- berlist A-26) in the tetrahydridoborate(III) form as
moval of organic matter, although volatilization reductant was used for Pb determination in wines
losses at high temperatures are not always easy to in the presence of K3Fe(CN)6 [43]. Ozone treat-
assess and low recoveries have been observed at ment as wine pre-treatment procedure was applied
trace analytes levels [23]. Comparison between for Hg determination in wine by CV AAS [56]. It
two mineralization methods - microwave (MW) is known that ethanol as main volatile component
digestion versus dry ashing for Pb determination in is a serious depressant in HGAAS and recently has
wines does not result in noticeable differences, but been shown that simple ethanol evaporation is ef-
authors have been inclined to the microwave di- ficient for wine pre-treatment before As determi-
gestion due to the more reproducible results and nation by HGAAS [28].
considerable gain of time [24]. Acid wet digestion Although direct ETAAS is used for trace
is the preferred pretreatment procedure, but re- elements determination in wines, reliable results
agent blanks for some elements are close to their for elements like As and Sb cannot be obtained
natural contents in wine [25–33]. In some cases va- without preliminary wine digestion [26, 27, 57,
nadium pentaoxide was added as a catalyst to im- 58]. Very strong matrix interferences leading to
prove completeness of sample digestion [34–36]. In strong signal depression by 40–60 % have been
order to prevent analyte losses, PTFE bombs [37] observed in direct determinations, even in the
or Savillex vessel [25] have been used. As an al- presence of suitable modifier. It was suggested that
wine organic matter as well as high phosphate and
ternative, microwave oven digestion offers advan-
sulfate contents [57] are responsible for the ob-
tages such as reduced losses due to volatilization,
served interference. As far as phosphate and sulfate
low reagents consumption, fast and complete ma- contents do not change after wine digestion, re-
trix mineralization [2, 34, 38–46]. On-line MW markable depression still exist and requires standard
sample digestion was used in flow injection addition method to be used for calibration [27, 58].
HGAAS determination of Pb in wine [47]. Simple Relatively low concentration of Pd and Ni modifi-
and very reliable sample preparation method in ers has been recommended for efficient thermal
wine analysis is UV-photolysis which allows low stabilization of As, Sb [27] and Se [57] in wine
blanks with minimal analyte losses [48, 49]. Wine digests. Complete wine decomposition in the pres-
sample digestion is unavoidable and highly rec- ence of HNO3+H2O2 in two different digestion
ommended (OIV) procedure when HGAAS was systems (Tecator and Bethge) was achieved without
applied in wine analysis [50, 51]. Complete diges- any analyte losses before their ETAAS determina-
tion [58]. Recently Llobat-Estelles et al. [59] have
tion of wine organic matter was required in order
shown that even for such "easy" element as Cu pre-
to obtain accurate and reliable results. Flow-
liminary digestion of wine sample is preferable pro-
injection HGAAS with on line MW oxidation was cedure ensuring accurate and reliable results.
used for Pb determination in wines [46, 52]; a mix-
Summary of the methods based on ETAAS
ture of HNO3+HClO4 has been proposed for wine
together with detection limits (LOD) achieved are
digestion in thermostated vessel for Se determina- presented in Table 1. In Table 2, HG and CV meth-
tion by HGAAS [53]; MW digestion with HNO3 ods combined with AAS and ETAAS are presented.
was applied to Hg and Se determination in wines
from Canary Islands [54]. An interesting approach
Table 1
The application of ETAAS in wine analysis
Element(s) Sample pretreatment Modifier(s) LOD Ref.
Al Direct after dilution No modifier 40 μg l–1 60
Al Direct (dilution) Na2Cr2O7 2.8 μg l–1 61
Al Direct after dilution No modifier 1 μg l–1 62
Al Digestion with HNO3+V2O5 Mg(NO3)2 0.4 μg l–1 35
Al Direct No modifier 1.5 μg l–1 63, 64
Al, Cd, Pb Sample dilution with HNO3 (add surfactant,
Triton X-100) NH4H2PO4 1.5 μg l–1 65
Al MW digestion/solid-phase extraction No modifier 0.021 μg l–1 66
Al Dilution No modifier 0.125 μg l–1 67
Ag, Co, Si, Zn Direct 0.20 μg l–1 Ag
1.6 μg l–1 Co
7.9 μg l–1 Si
21 μg l–1 Zn 68
As Digestion with HNO3+H2O2 Pd 5 μg l–1 27
As Digestion with HNO3 Pd 6.6 μg l–1 26
As, Sb Direct/better after digestion Pd(NO3)2 – 58
Cd Digestion/HNO3/V2O5 0.5 pg 37
Cd Digestion with HClO4 and HNO3 – 0.008 μg l–1 29
Cd Direct Pd(NO3)2+HNO3 0.03 μg l–1 69
Cd Direct Pd 0.08 μg l–1 70
Cd, Pb Dilution with HNO3 Pd(NO3)2+Mg(NO3)2 0.03 μg l–1 Cd
0.8 μg l–1 Pb 36
Cd, Pb Microwave digestion with HNO3 NH4H2PO4+Mg(NO3)2 0.1 μg l–1 Cd
1.0 μg l–1 Pb 40
Cd, Cr, Pb Direct 0.5 μg l–1 Cd
1 μg l–1 Cr
3 μg l–1 Pb 71−73
Cd, Cr, Pb MW digestion Pd(NO3)2 for Cd and Pb
Mg(NO3)2 for Cr 74
Cd, Co, Cr, MW digestion Cd: Pd(NO3)2;; Co, Mn, and Cr:
Mn, Pb Mg(NO3)2; Pb: Pd(NO3)2+NH4H2PO4 75
Cr Direct No modifier or Pd 0.1−1 μg l–1 76−78
Cu Direct No modifier 5.75 μg l–1 79
Cu, Fe, Mn Direct No modifier 80
Cu, Pb Direct No modifier 81, 82
Cu, Fe Direct/dilution (1+9) with Milli-Q water No modifier 83
Cu Direct Pd(NO3)2+ Mg(NO3)2 5.0 μg l–1 84
Cu Digestion with HNO3/HClO4 No modifier 30 μg l–1 21
Cu Microwave digestion with HNO3/H2O2 No modifier 59
Hg MW digestion and extraction with APDC into MIBKPd 0.2 μg l–1 85
Ni Direct Pd 1.0 μg l–1 86, 87
Pb Dilution with HNO3 Pd+Mg 15.5 μg l–1 26
Pb Direct after dilution Pd(NO3)2+Mg(NO3)2 19 μg l–1 Pb 60
Pb Interlaboratory study by using ETAAS 88
Pb Direct Pd+Mg(NO3)2 0.9 μg l–1 89
Pb Direct/dilution (1+4 v/v) Triton X-100 No modifier Not present 90
Pb Dilution with HNO3 NH4H2PO4+Mg(NO3)2 6.2 μg l–1 91
Pb Dilution with HNO3 NH4H2PO4 LOD 4 μg l–1
LOQ 14 μg l–1 92
Pb Digestion with HNO3+UV photolysis NH4H2PO4+Mg(NO3)2 0.12 μg l–1 93
Pb Direct NH4H2PO4 94, 95
Pt Direct and mineralization – 10 μg L–1 96
Se Digestion with HNO3+H2O2 Ni(NO3)2+Sr(NO3)2 1 μg l–1 57
Se Extraction with APDC into MIBK Ag or Ni(NO3)2+Sr(NO3)2 0.2 μg l–1 57, 97
Se Direct Pd + hydroxylamine hydrochloride 9 μg l–1 98
Tl Extraction from 0.5 mol l–1 KI solution into
MIBK Pd+ascorbic acid; Ag 0.05 μg l–1 99
V Direct 4.2 μg l–1 100, 52
Table 2
HG and CV methods with AAS, ETAAS and AFS detection in wine analysis
Element(s) Technique Sample pretreatment Reaction media Reductant LOD Ref.
As(III), HGAAS Direct (ethanol 8 mol l –1 HCl NaBH4 (0.2% or 0.1 μg l–1
As(V) total evaporation) 0.6% m/v) As(III), As(V),
As MW digestion total As 31
–1
Cd FI-CVAAS Digestion 0.2 mol l HNO3; Amberlite IRA-400/
1% m/V thiourea, 1 tetrahydroborate(III)
mg l–1 Co form 0.032 μg l–1 43
Cd FI-CV Digestion 0.2 mol l–1 HNO3; Amberlite IRA-400/
ETAAS 1% m/V thiourea, tetrahydroborate(III)
1 mg l–1 Co form 0.09 μg l–1 58
–1 –1
Hg CVAAS Digestion 1 mol l HCl SnCl2 (20% m/v) 1.0 μg l 42
–1 –1
Hg (white wines) FI-CVAAS Ozonation 1 mol l HCl SnCl2 (20% m/v) 0.5 μg l 59
Pb FI-HGAAS Direct 0.1 mol l–1 HNO3 Amberlite IRA-400/
3% m/V tetrahydrido-
K[Fe(CN)6]3 borate(III) form 3.1−5.2 μg l–1 46
–1
Pb FI-HGAAS Digestion HNO3+H2O2 NaBH4 (6 % m/V) 10 μg l 50
–1
Pb FI-HGAAS Direct HNO3 H2O2 10 μg l 55
Pb HGAAS Direct (dilution with
HCl) HCl H2O2 (7.5%) NaBH4 (21% m/V) 24 μg l–1 101
Sb HG-ETAAS Direct (Pd modifier) HCl+thiourea NaBH4 (1 % m/V) 0.13 μg l–1 Sb 102
–1 –1
Se HGAAS Digestion with HNO3 7 mol l HCl NaBH4 (0.6% m/V) 0.1 μg l Se 42
DIRECT METHODS FOR TRACE ELEMENTS matched standard solutions and La(III) chloride is
DETERMINATION IN WINE used as releasing agent to overcome phosphate
atomization interferences in the determination of
Atomic Absorption Spectrometry in Flame, Ba, Ca, Mg and Sr. Sample dilution with HNO3 is
Electrothermal and Hydride generation modes is recommended for FAAS determination of transi-
particularly suitable for direct determination of tion metals Cu, Fe, Mn and Zn. In order to increase
trace elements in wine. However wine is a com- sample throughput, an automatic flow injection
plex matrix containing ethanol and other organic system based on zone sampling technique has been
compounds which influence the transport proper- developed for the determination of Ca, K, Mg and
ties of the sample toward atomization device due Na in wines [106] as well as a flow injection sys-
to the changes in viscosity and surface tension in tem based on stream splitting for Cu determination
comparison with aqueous standard solutions. Wine in wines [107]. Direct application of HGAAS with
contains high concentrations of K, which acts as quartz tube or quartz burner with Ar/H2 flame as
natural ionization buffer and should be taken into atomizers in wine analysis is limited because of
account in calibration procedures. Inorganic com- drastic ethanol interference [28, 101, 108, 109]. It
ponents in wine like sulphates and phosphates was shown recently that ethanol probably enters as
could interfere with the atomization of elements an aerosol from gas/liquid separator into the atom-
(FAAS) or cause strong background absorption izer, thus interfering with the atomization of hy-
due to radicals formed in ETAAS. FAAS is most drides [28, 108]. The magnitude of this interfer-
widely used and easily accessible technique for the ence strongly depends on the type of the atomizer
determination of Ag, Ca, Fe, K, Mn, Mg, Na and used – it is not observed if hydride trapping in
Zn in wines [31, 65, 103−105]. Conventional ioni- graphite furnace or inductively coupled plasma are
zation buffers (CsCl) and ethanol are added to the employed as atomizers. This fact is well docu-
calibration solution in order to obtain matrix- mented as successful direct determination of Sb in
wine using HGAAS with hydride trapping into the determined in wine samples by ETAAS moreover
graphite furnace was reported [102]. Sample dilu- that ETAAS is an official method of analysis for
tion [101, 108] or flow injection mode [109] are Cd and Pd in wine by European regulations [71,
proposed to overcome ethanol interference and to 72, 111]. Typically sample dilution with HNO3 is
achieve accurate determination of As in wine sam- the only sample pretreatment and the chemical
ples. Recently sample matrix-assisted photo- modifiers used for thermal stabilization of both
induced chemical vapor generation has been pro- elements in wine samples are Pd(NO3)2 [34, 69,
posed for ultrasensitive detection of Hg in wines 74, 89], Pd(NO3)2+Mg(NO3)2 [35, 77], NH4H2PO4
[110]. Ethanol e.g. wine matrix component under [92, 94, 95], and NH4H2PO4+Mg(NO3)2 [91].
UV-irradiation reduces mercury compounds or Method of standard addition is frequently recom-
ions to atomic mercury thus playing a role of re- mended as calibration procedure for Cd and Pb
ductant for CVAAS determination of Hg. The ap- quantification in wines. An alternative approach is
plication of direct hydride generation with differ- presented by Jorhem and Sundstrom [90]: Pb is
ent detectors is summarized in Table 2. determined in wine without any modifier by utiliz-
ETAAS permits determination of toxic trace ing relatively low atomization temperature. It
elements in wine samples much below their per- should be mentioned that the wine matrix contains
missible limits (OIV, national legislation) and by itself enough phosphate and Mg to act as a
therefore is widely used for wine quality control. thermal stabilizer ("internal modifier"). Successful
The choice of efficient modifier for trace element simultaneous determination of Cd and Pb in wines
thermal stabilization, optimal temperature program was reported in the presence of Pd(NO3)2 as modi-
for the graphite furnace and suitable calibration fier and by using two stage ashing to avoid forma-
method are the most popular topics of investiga- tion of carbonaceous residue inside the atomizer
tion. An advantage of ETAAS is the possibility to [35]. Although it is not very typical for ETAAS, Bi
develop accurate direct methods for trace element as an internal standard has been proposed for Pb
determination in wine without any sample pre- determination in wine [89]. The employment of
treatment. Expected matrix interferences are asso- internal standard could minimize absorbance varia-
ciated with wine organic matter which may cause tions due to changes in experimental conditions
high values of nonspecific absorption and ethanol such as atomizer temperature, integration time,
content in wine sample which impairs sample de- graphite tube surface, sample composition etc.
livery into the graphite furnace. Problems con- Chromium levels in French wine and grapes and in
nected with reproducible sample injection are most Spanish wines were determined by direct ETAAS
frequently solved by injection into a preheated after careful optimization of temperature programs
platform or graphite tube (‘hot injection’), while [76, 78]. Fast temperature programs with high
sample sputtering is avoided by applying two-stage sample throughput were developed for Cu deter-
drying step [60]. The use of Zeeman background mination in wines [84]. Useful models which per-
correction is preferable to overcome high nonspe- mit the detection of possible sources of bias errors
cific absorbance, thus greatly improving the accu- were applied to the determination of Cu in wine
racy of measurements. Stabilized temperature plat- [59]. Manganese, Ni and V levels were defined in
form furnace (STPF) conditions should be fulfilled French wines and grapes from different regions and
in order to obtain accurate and reliable results in Californian wines by using ETAAS [86, 100,
[79]. Aluminum levels in wine are high enough to 112]. Vanadium determination by ETAAS from
permit high dilution factors to minimize matrix the view point of matrix interferences and calibra-
effects and allow for external calibration in assays. tion procedures was discussed [49]. Selenium is an
[63, 65, 67]. For port wine, however, a product essential element, unfortunately present at very
with the most complex matrix which composition low levels in wine. Direct determinations are ham-
differs considerably from traditional table wines, pered by strong matrix interferences [57] and even
potassium dichromate was proposed as modifier by different behavior of both oxidation states [98].
for Al determination together with end-capped Comparison of results obtained for trace ele-
Transverse Heated Graphite Atomizers (THGA®) ments content by ETAAS and ICP-AES with ultra-
[61]. Trace elements (Ag, Co, Si, and Zn) were sonic nebulization shows very good agreement
determined in port wine by ETAAS, and FAAS [29]. Methods for direct trace element determina-
[68]. Cadmium and Pb are elements predominantly tion in wines by ETAAS are complied in Table 1.
traction is used for selective determination of positively charged labile species. The ability of
Fe(II) or Fe(III) and the other form is calculated by plant polysaccharides to bind cations is due to the
the difference from the total Fe content. HPLC presence of a high proportion of negatively char-
with AAS and electrochemical detection is applied ged glycolsyl-residues. Their complexation capa-
for Fe speciation in wines (e.g. determination of cities increase between pH 3 and pH 7 due to the
Fe(II) and Fe(III) bound with wine organic acids) dissociation of the carboxylic acid groups. The
and it was found that both Fe species are in com- total capacity of pectic polysaccharides to complex
plex with tartaric acid. However less than 12 % of metal ions is directly related to their degree of po-
total Fe is found in this fraction, the rest could be lymerization and their glycosyl-residue composi-
bound to other organic compounds of wine [128]. tion [127].
A scheme was presented for fractionation of wine HGAAS is very suitable technique for spe-
components (polyphenols, proteins polysaccha- ciation purposes due to different response obtained
rides) and Fe, Cu and Zn determination in different from different analyte chemical species. Selective
fractions [121]. The resin XAD-8 is used for the hydride generation of different arsenic species
separation of wine polyphenols in complex with (As(III), As(V), DMA, MMA) is achieved by us-
wine proteins and polysaccharides. Around 20–30 ing different reaction media, hence arsenic speci-
% of Fe, 30 % of Cu and 15 % of Zn are found in ation in wine could be performed. Applying this
this fraction. Dowex ion exchange resins were approach it was shown that As(III) is major arsenic
used for the separation of cationic and anionic species in wines [28, 108]. Wifladt et al. [102]
species of Cu, Fe and Zn. As a rule the concentra- showed by using HGAAS that Sb(III) as well
tion of labile Fe(II) is higher than the concentra- Sb(V) are present in wine samples.
tion of labile Fe(III). Less than 5 % of Cu and Fe
Most important procedures recommended for
are bound to wine polysaccharides and around 50
trace element speciation are presented in Table 3.
% of Cu and 60 % of Zn are presented in wines as
Table 3
Speciation analysis of trace elements in wine
Element Species Separation procedure Detection method Ref.
As As(III), As(V), Ion exchange, cation exchange resin AG 50 W-X8;
MMA, DMA anion exchange resin AG1-X8 HGAAS, 1.4% m/V NaBH4 129
As Total, As(III), As(V)As(III), As(V): selective reaction media
Total: wine MW digestion HGAAS 28
Al, Ca, Cu, Metals in real Ultrafiltration through 0.2 and 0.45 μm membrane
Fe, K, Na, solutions, colloids or filters FAAS, ETAAS 130
Pb suspensions
Cu, Pb Total Cu and RP-HPLC, C18218TP54 column, gradient elution Total Pb: ETAAS;
Pb;bioavailable Cu 0–30% ethanol in 20 mmol L-1 KH2PO4, off line. Total Cu: FAAS;
and Pb, complexed Bioavailable fractions: gastrointestinal digestion Pb and Cu in dialysates: ETAAS
Cu and Pb Complexed Pb: SWCV 81,
Complexed Cu: potentiometry, ISE 82
Cu, Fe, Zn Fractionation Fractions of Cu, Fe and Zn bound to polyphelons, FAAS 121
proteins and polysaccharides. Labile species of Cu, ETAAS
Fe(II), Fe(III) and Zn.
Fe Fe species IC FAAS 131
Fe Total and Fe(III) Fe(III):extraction of thiocyanate complex into MIBK, Sequential injection analysis by
total Fe: FAAS FAAS 122
Fe Free and bounded Fe Sequential cloud point extraction FAAS 123
Fe Fe(II), Fe(III), Liquid/liquid extractuion (thiocyanate,
Organically bounded o-phenantroline)
Fe Column solid phase extraction FAAS 124
Fe Labile Fe(II) and Solid phase extraction by using 1,10-phenantroline
Fe(III) and 8-hydroxy-7-iodoquinoline-5-sulphonic acid FAAS 125
Fe Fe(III), total Fe HPLC, Spherisorb S5 ODS 2 column, mobile phases: Electrochemical Fe(II)
50 mM CH3COONH4+CH3OH (70+30 v/v) pH 4; FAAS 128
CH3COOSO4/H2SO4 pH 2.5
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