Food Chemistry 172 (2015) 486–496

Contents lists available at ScienceDirect

Food Chemistry
journal homepage: www.elsevier.com/locate/foodchem

The combined impact of vineyard origin and processing winery

on the elemental profile of red wines
Helene Hopfer a,b,⇑, Jenny Nelson a,c, Thomas S. Collins a,b, Hildegarde Heymann a, Susan E. Ebeler a,b
a
Department of Viticulture and Enology, University of California-Davis, One Shields Avenue, Davis, CA 95616, USA
b
Food Safety and Measurement Facility, University of California-Davis, One Shields Avenue, Davis, CA 95616, USA
c
Agilent Technologies, Inc., 5301 Stevens Creek Blvd., Santa Clara, CA 95051, USA

a r t i c l e i n f o a b s t r a c t

Article history: The combined effects of vineyard origin and winery processing have been studied in 65 red wines sam-
Received 23 May 2014 ples. Grapes originating from five different vineyards within 40 miles of each other were processed in at
Received in revised form 8 September 2014 least two different wineries. Sixty-three different elements were determined with inductively coupled-
Accepted 19 September 2014
plasma mass spectrometry (ICP-MS), and wines were classified according to vineyard origin, processing
Available online 26 September 2014
winery, and the combination of both factors. Vineyard origin as well as winery processing have an impact
on the elemental composition of wine, but each winery and each vineyard change the composition to a
Keywords:
different degree. For some vineyards, wines showed a characteristic elemental pattern, independent of
Wine
Elemental composition
the processing winery, but the same was found for some wineries, with similar elemental pattern for
Inductively-coupled plasma-mass all grapes processed in these wineries, independent of the vineyard origin. Studying the combined effects
spectrometry (ICP-MS) of grapegrowing and winemaking provides insight into the determination of geographical origin of red
Vineyard wines.
Winery Ó 2014 Elsevier Ltd. All rights reserved.
Determination of geographical origin

1. Introduction From an analytical standpoint, the presence and/or absence of

Determining the geographical origin of food products has
gained increased research interest over the last decade, mostly
due to growing concern and interest of consumers to know the ori-
gin of the food they eat (Drivelos & Georgiou, 2012; Kelly, Heaton,
& Hoogewerff, 2005). The European Union (EU) established various
food quality schemes based on geographical regions, thus, success-
fully classifying food products according to the geographical origin
has also an economic component, as food products tend to sell for
higher prices if associated with a certain geographical origin
(Drivelos & Georgiou, 2012).
Especially for specialty food products, with a strong reputation
of and association to specific geographical areas (e.g. ham, cheese
or wine), fraud with regards to geographical origin is expected,
and various analytical strategies have been proposed. Besides
untargeted profiling methods, such as nuclear magnetic, infrared
and fluorescence spectroscopy, the use of stable isotope ratios, as
well as multi-element profiles have been proposed for food
authenticity (Drivelos & Georgiou, 2012; Kelly et al., 2005).
⇑ Corresponding author at: HM.Clause, 9241 Mace Blvd., Davis, CA 95616, USA.
Tel.: +1 530 220 2116.
E-mail address: hhopfer@ucdavis.edu (H. Hopfer).
certain elements in a food product as well as ratios of certain ele-
ment to each other could be used for elemental fingerprinting.
However, before a successful determination of geographical origin
of wines is possible, one needs to understand (i) how controlled
studies correlate to real life grapegrowing and winemaking, (ii)
which changes are possibly introduced during the whole produc-
tion chain, (iii) how different varieties and/or wine styles vary,
and finally (iv) how variable the impact of winery processes within
and between different regions and countries is.
The major elements in wine, present at levels between 10 and
1000 mg/L, are Ca, K, Na, and Mg, followed by minor elements,
such as Al, Fe, Cu, Mn, Rb, Sr, and Zn, present in the range of
0.1–10 mg/L. Trace elements are present in the ppt range
(0.1–1000 lg/L), and include Ba, Cd, Co, Cr, Li, Ni, Pb, and V among
others (Pohl, 2007).
The elemental composition of wine is the result of many fac-
tors, including the elemental composition of the soil the vine is
growing on, the viticultural practices (application of fertilizers,
pesticides, herbicides, and insecticides; irrigation), as well as
winemaking processes, including storage and ageing (Aceto,
2003; Almeida & Vasconcelos, 2003a,b; Castiñeira Gómez,
Brandt, Jakubowski, & Andersson, 2004; Cheng & Liang, 2012;
Galani-Nikolakaki & Kallithrakas-Kontos, 2006; Hopfer, Nelson,
Mitchell, Heymann, & Ebeler, 2013; Jakubowski, Brandt,

http://dx.doi.org/10.1016/j.foodchem.2014.09.113
0308-8146/Ó 2014 Elsevier Ltd. All rights reserved.
 H. Hopfer et al. / Food Chemistry 172 (2015) 486–496 487

Stuewer, Eschnauer, & Görtges, 1999; Kristl, Veber, & Slekovec,
2002; Nicolini, Larcher, Pangrazzi, & Bontempo, 2004; Pereira,
1988; Pohl, 2007; Rossano, Szilágyi, Malorni, & Pocsfalvi, 2007;
Tariba, 2011; Volpe et al., 2009).
Volpe et al. (2009) categorise elements into so called (i) ‘‘natu-
ral’’ elements which are the result of their presence in the vineyard
soil and their uptake by the vine plant (Al, B, Ba, Li, Mg, Mo, Si, Sr,
Ti, rare earth elements (REEs), transition elements of the second
and third period), (ii) ‘‘artificial’’ elements which result from
human intervention (viticultural practices, winemaking proce-
dures, environmental pollution; e.g. Pb, Co, Cr, Ni, V, Cd, Hg), and
(iii) elements that are both ‘‘natural’’ and ‘‘artificial’’, and result
from either endogenous or exogenous processes (e.g. Ca, Mg, Co,
Zn, Fe, P, Na, K) (Pohl, 2007) (see also Fig. 1a).
1.1. Viticultural changes in elemental composition
From a plant perspective, elements like K, P, and N are essential
for a plant’s health, thus, the presence of these elements in wine is
expected. Elements, such as K, Ca, Cu, Cd, Mn, Zn, and Pb, are used
in fertilizers, pesticides, and fungicides (Pohl, 2007), in some cases
(e.g. Cd, Pb) due to anthropogenic pollution (Kment et al., 2005).
Some elements have beneficial effects on the plant, higher yield,
sugar accumulation, polyphenols and amino acids in wine grapes
have been reported after the application of B, Cr, Mn, Mo, W, and
Zn onto the vine or vineyard soil (Aceto, 2003; Pereira, 1988), thus,
are most likely also found in the resulting wine. The proximity to
an ocean has been reported to increased Na levels in the grapes
resulting from marine sprays, while wines from vineyards closely

Fig. 1. (a) Elements that can be changed by grapegrowing and/or winemaking practices (Aceto, 2003; Almeida & Vasconcelos, 2003a,b; Castiñeira Gómez, Brandt et al., 2004;
Cheng & Liang, 2012; Eschnauer et al., 1989; Jakubowski et al., 1999; Kristl et al., 2002; Nicolini et al., 2004; Pereira, 1988; Rossano et al., 2007; Tariba, 2011; Volpe et al.,
2009). (b) Elements that have been used for the determination of geographical origin of wines from different regions within Australia (Martin et al., 2012), Canada (Greenough
et al., 1997; Taylor et al., 2003), Czech Republic (Sperkova & Suchanek, 2005), Germany (Castiñeira Gómez, Feldmann et al., 2004; Thiel et al., 2004), Italy (Marengo & Aceto,
2003), New Zealand (Angus et al., 2006), South Africa (Coetzee et al., 2005), Spain (Baxter et al., 1997; Iglesias et al., 2007; Pérez Trujillo et al., 2011), Great Britain (Baxter
et al., 1997), Turkey (Sen & Tokatli, 2013).
488 H. Hopfer et al. / Food Chemistry 172 (2015) 486–496

located to roads or industrial areas tend to have higher levels of Cd Clarification with bentonites, added either to grape must or fin-
and Pb (Pohl, 2007). ished wine, was identified as a source for Al, Cd, Hf, REEs, Pb, U, and
The presence of elements in the soil is not necessarily directly Zr (Castiñeira Gómez, Brandt et al., 2004; Jakubowski et al., 1999;
correlated to the presence of these elements in the grapes or wine Kristl et al., 2002; Nicolini et al., 2004; Rossano et al., 2007), while
(Almeida & Vasconcelos, 2003a; Taylor, Longerich, & Greenough, different filtration practices (silica filters, cellulose filters, bed fil-
2003), as elements differ in their bioaccumulation behaviour tration) have been shown to increase the REE content (Rossano
(Kabata-Pendias, 2004). Elements like B, Cd, Cs, Ni, Rb, Sn, and Zn et al., 2007), as well as Co, Cr, Fe, and Ni levels (Eschnauer et al.,
are more mobile than others, and thus, accumulate in the plant 1989). On the other hand, during clarification and filtration some
more easily. Elements are transported as ions to the plant roots, elements also decrease due to settling of protein, sulphate and
where their absorption rate is dependent on the ion concentration amino acid metal complexes (Nicolini et al., 2004; Pohl, 2007).
as well as the soil pH (Bañuelos & Ajwa, 1999; Kabata-Pendias, Lastly, also during ageing and storage various studies showed
2004). The accumulation of elements from the soil is also depen- that the elemental composition of wine can be changed by the
dent on how strong they are chelated; B, Cd, Mn, Mo, Se, and Zn materials used (e.g. increasing Sn levels in screw-capped bottles
are weakly chelated, thus, are more easily absorbed by the plant. (Hopfer et al., 2013), Cr from use of Cr oxides to colour glass bottles
Other elements are strongly bound to the soil or are retained in (Tariba, 2011), higher REEs when stored in glass bottles (Rossano
the roots and not translocated into the other parts of the plant even et al., 2007)).
if present in high concentrations in the soil (e.g., Ag, Al, Cu, Cr, Fe,
Hg, Pb, Si, Sn, Zr) (Bañuelos & Ajwa, 1999). The absorption of ele-
1.2. Determination of geographical origin of wines with multi-element
ments into a plant is also dependent on the chemical properties,
fingerprints
e.g. non-nutrient elements share similar chemical properties with
nutritional elements (e.g. Cu and Ni, S and Se, Cd and Zn), thus
Several studies have evaluated the use of multi-element
these elements may also be assimilated by the plant (Bañuelos &
fingerprints for the determination of geographical origin of wines
Ajwa, 1999). Finally, the plant species itself may impact absorp-
(Angus, O’Keeffe, Stuart, & Miskelly, 2006; Baxter, Crews, Dennis,
tion. For example, it has been shown that different grape pheno-
Goodall, & Anderson, 1997; Castiñeira Gómez, Feldmann,
types exist for amino acid accumulation (Oungoulian, 2012); as
Jakubowski, & Andersson, 2004; Coetzee et al., 2005; Greenough,
the nitrogen source for these amino acids is taken up by the plant
Longerich, & Jackson, 1997; Iglesias, Besalú, & Anticó, 2007;
through its roots, similar phenotypic differences could exist for
Marengo & Aceto, 2003; Martin, Watling, & Lee, 2012; Pérez
other elements as well, especially for elements that are either
Trujillo, Conde, Pérez Pont, Câmara, & Marques, 2011; Sen &
essential for the health of the plant and/or that share chemical
Tokatli, 2013; Sperkova & Suchanek, 2005; Taylor et al., 2003;
properties with these nutrients.
Thiel, Geisler, Blechschmidt, & Danzer, 2004). The elements that
Besides the impact of viticulture and the environment the
were found to discriminate among different wine regions are
winemaking process has been shown to also affect the elemental
summarised in Fig. 1b. The most discriminating elements in these
composition of wine. Generally, the elemental content in wine
studies include Sr, Mn, Mg, Li, Co, Rb, B, Cs, Zn, Al, Ba, Si, Pb, and Ca,
decreases after fermentation is completed (Almeida &
which are reported in at least 4 different studies (Angus, O’Keeffe,
Vasconcelos, 2003a; Castiñeira Gómez, Brandt et al., 2004), due
Stuart, & Miskelly, 2006; Baxter et al., 1997; Castiñeira Gómez,
to precipitation of element complexes with tartrates, polyphenols,
Brandt et al., 2004; Coetzee et al., 2005; Greenough et al., 1997;
proteins and sugars (Eschnauer, Jakob, Meierer, & Neeb, 1989;
Iglesias et al., 2007; Marengo & Aceto, 2003; Martin et al., 2012;
Tariba, 2011), lower elemental solubility in the ethanolic solution
Pérez Trujillo et al., 2011; Sen & Tokatli, 2013; Sperkova &
compared to the grape juice, yeasts consuming elements during
Suchanek, 2005; Taylor et al., 2003; Thiel et al., 2004).
fermentation (Ca, Cu, Fe, K, Mg, Zn), and/or racking of sediments
There is quite some overlap in elements that have been used in
and precipitates at the end of fermentation (Pohl, 2007).
the past for the determination of geographical origin (Fig. 1b) and
However, the use of different materials in wineries, including
elements that have been shown to change during various viticul-
stainless steel, brass, wood, and plastics, have been shown to intro-
tural and/or enological processes (Fig. 1a). It seems that depending
duce elements into the wine as well (Aceto, 2003; Almeida &
on the samples used, different elemental patterns emerge. The
Vasconcelos, 2003a; Castiñeira Gómez, Brandt et al., 2004; Kristl
question is which elements could be useful in discriminating
et al., 2002; Tariba, 2011). These elements include Al, Cr, Cd, Co,
between different vineyards, despite the impact of the processing
Fe, Mo, Mn, Ni, Pb, Sr, Ti, V, Zn from stainless steel and brass con-
winery? This is the central question in this study, where we look
tainers, oak barrels, tubes, fittings, and traps (Aceto, 2003; Almeida
at the combined effects of vineyard and winery on the elemental
& Vasconcelos, 2003a; Almeida & Vasconcelos, 2003b; Castiñeira
composition of red wines. By including wines that originated from
Gómez, Brandt et al., 2004; Kristl et al., 2002; Rossano et al.,
the same vineyard but were processed in different wineries, and
2007; Tariba, 2011). Ageing in oak barrels was reported to increase
vice versa, we are able to separate the vineyard from the winery
the Al, Fe, and V content (Almeida & Vasconcelos, 2003a), while Cr
effect, and add to our understanding of how the elemental profile
and Ni levels remained constant once the wine was racked for solid
changes during the winemaking process.
removal, indicating contamination by the fermentation container
(Almeida & Vasconcelos, 2003a).
Besides winery equipment, also various winemaking practices 2. Materials and methods
have been identified as sources for elemental ‘‘contamination’’ of
wine. During pressing and fermentation Pb was freed from grape 2.1. Samples and materials
skins and seeds and led to higher Pb levels in the resulting wine
(Almeida & Vasconcelos, 2003b); monitoring Pb along the wine- Sixty-five commercial red wine samples were included in this
making process Almeida and Vasconcelos (2003b) were able to study. All samples came from five different vineyards (vineyard
divide the final content in the wine into 1/3 coming from contam- 1–5, Fig. 2) in Northern California (vineyard 1 near Cloverdale, vine-
inated soil and atmospheric deposition, and 2/3 coming from wine- yard 2 and 3 between Geyserville and Calistoga, vineyard 4 outside
making. The separation of grape berries from the rachises during of St. Helena, and vineyard 5 outside of Sonoma), and were pro-
destemming increased the Al, Cu, Fe, Zn, Mn and Sr levels, while cessed in five different commercial wineries (winery A–D, Fig. 2).
crushing increased Cu and Zn levels (Cheng & Liang, 2012). Based on soil maps, each vineyard shows a range of different soils,
 H. Hopfer et al. / Food Chemistry 172 (2015) 486–496 489

clarification, racking, blending, etc.). Metal-free 50 mL plastic tubes

(VWR, Radnor, PA, USA) were used for collecting the samples, and
all samples were stored at 4 °C until analysis took place. All sampled
wines were made for commercial use, and none of the samples
were specifically made for this study (i.e. no specific research
samples).
Multi-element calibration standards (1, 2A, 3 and 4) were pur-
chased from SPEX CertiPrep (Metuchen, NJ, USA), ultrapure con-
centrated nitric acid was obtained from Fisher Scientific (Optima
grade, Pittsburgh, PA, USA), and an environmental spike mix was
purchased from Agilent Technologies (Santa Clara, CA, USA). Ultra-
pure water (18 MXcm, EMD Millipore Bellerica, MA, USA) and 200
proof ethanol (GoldShield, Hayward, CA, USA) were used for the
calibration solutions and dilutions. An internal standard (IS) mix
(10 mg/L in 1% HNO3, SPEX CertiPrep) was diluted 1:10 in 1%
HNO3 prior to use.

2.2. Instrumentation

An inductively coupled plasma-mass spectrometry (ICP-MS)

Fig. 2. Sixty-five red wine samples originated from five different vineyards (1–5),
and were processed in five different wineries, labeled A through E.
thus, we expect differences in soil metal composition between the 5
different vineyards, and probably, although this was not the scope
of this study, also within each vineyard site. Vineyards showed a
wide range of various gravelly and clay loams, as well as sandy
alluvial land, clay and rock land. Grapes from one vineyard were
processed in at least two different wineries (Suppl. Table 1). All
wines were made from monovarietal grapes, and included Vitis
vinifera cv. Cabernet Sauvignon, cv. Merlot, and cv. Pinot Noir. All
wineries fermented all grapes from the individual vineyards in
separate fermentation tanks. Similar to Coetzee et al. (2005),
sampling took place in each winery directly from stainless steel fer-
mentation vessels after fermentation was finished, but before any
additional post-fermentation treatments took place (e.g. filtration,
instrument from Agilent (7700x, Santa Clara, CA, USA) was used
for the elemental profiling of 63 trace elements in a mass range
between 7 and 238 m/z. The IS mix was constantly fed into and
mixed with the sample stream immediately before entering the
spray chamber (quartz double wall, cooled to 2 °C), using a mixing
tee (sample tubing inner diameter 1.02 mm, IS tubing inner diam-
eter 0.25 mm). The peristaltic pump was operated at 0.1 rps. A con-
centric nebulizer (Micromist, Agilent) was used for sample
transport into the plasma (RF power of 1550 W, RF matching
1.8 V, sampling depth 10 mm, carrier gas flow 1.05 mL/min). The
instrument was calibrated and tuned daily, using a tuning mix
(Li, Y, Ce, Tl, Co; Agilent) and the Pulse/Analog solutions (Zn, Be,
Cd, As, Ni, Pb, Mg, Th, Ca, Co, Sr, V, Cr, Mn, 6Li, Sc, In, Lu, Bi, Y,
Yb, Mo, Sb, Sn, Ge, Ru, Pd, Ti, Ir; Agilent).
All wine were analysed in duplicate, and they were 1:3 dilutions
in 5% HNO3. Elements were monitored in no gas, helium (He flow
4.3 mL/min) and/or high energy helium (He flow 10 mL/min) gas
mode using the ORS3 system. A 6-point calibration between 0
and 500 lg/L was carried out for the elements listed in Table 1 in

Table 1
Monitored elements together with detection mode and limits of detection (LOD).

Element m/z Modea LODb [lg/L] Element m/z Modea LODb [lg/L]
Li 7 ng 2.25E 01 Rh 103 He 1.00E 03
Be 9 ng 1.40E 02 Cd 111 He 9.00E 03
B 11 ng 1.12E 01 Sn 118 He 2.10E 02
Na 23 ng 1.79E+00 Sb 121 He 4.00E 03
Mg 24 ng 4.03E 01 Cs 133 ng 5.00E 04
Al 27 ng 4.68E 01 Ba 137 He 1.30E 02
Si 28 ng 4.23E 01 La 139 He 6.00E 04
P 31 ng 6.92E 01 Ce 140 He 2.00E 03
K 39 He 1.16E+00 Pr 141 He 3.00E 04
Ca 43 He 8.79E 01 Nd 142 He 7.00E 04
Ti 47 He 5.43E 01 Sm 147 He 2.00E 03
V 51 He 2.40E 02 Eu 153 He 4.60E 06
Cr 52 He 7.70E 02 Gd 157 He 1.00E 03
Mn 55 He 2.30E 02 Dy 163 ng 4.00E 04
Co 59 He 9.00E 03 Ho 165 He 6.00E 04
Ni 60 He 3.47E 01 Er 166 ng 8.00E 04
Cu 63 He 2.30E 02 Tm 169 ng 3.00E 04
Zn 66 He 1.50E 02 Yb 172 ng 1.00E 03
Ga 69 He 5.00E 03 W 182 He 1.90E 02
As 75 He 7.00E 03 Re 185 He 5.00E 04
Se 78 HEHe 5.20E 02 Tl 205 ng 2.00E 03
Rb 85 ng 2.00E 03 Pb 208 He 5.00E 03
Sr 88 He 1.00E 02 U 238 He 6.60E 06
Mo 95 ng 3.10E 02
a
ng . . . no gas; He . . . helium; HEHe . . . high energy helium.
b
Limit of detection (LOD); n = 10 calibration blank measurements; 99% confidence interval.
490 H. Hopfer et al. / Food Chemistry 172 (2015) 486–496
matrix-matched calibration solutions (5% HNO3 and 4% Ethanol) to
account for matrix interferences of the ethanolic wine solutions.
Elements were detected using a 3-point peak pattern in triplicate
with 100 sweeps per replicate. Previous studies have shown that
a reduction of the ethanol content to around 5% is a good compro-
mise between a stable plasma and sufficient sensitivity (Boorn &
Browner, 1982; Dams, Goossens, & Moens, 1995; Goossens,
Moens, & Dams, 1994; Rossano et al., 2007). Higher concentration
elements (>500 lg/L; B, Na, Mg, Si, P, K, Ca, Mn, Cu, Rb, Sr, Ba) were
measured after a 1:1000 dilution in 5% HNO3. Spiked samples were
analysed throughout the analysis run to ensure validity of the ana-
lytical method. Continuous calibration blank verification (CCB)
runs were performed every 10th sample.
2.3. Data analysis
All monitored isotopes were calibrated using the MassHunter
ICP-MS software (G7201B, version B.01.03, Agilent). Based on limits
of detection (LOD), determined with 10 calibration blank measure-
ments (Thomsen, Schatzlein, & Mercuro, 2003), detection limits
(DL) and background equivalent concentrations (BEC), reported
by the software, isotopes and gas modes were selected for each ele-
ment, and used for further data analysis. For statistical significance
testing as well as multivariate classification, elements that were
detected below LOD were assigned a concentration of LOD/10. Mul-
tivariate and univariate analyses of variance (MANOVA and
ANOVA) were carried out for the main effects winery, and vineyard,
as well as for the winery-by-vineyard interaction, using log-
transformed concentration data. Statistical significance was set at
5%. Canonical Variate Analysis (CVA) was chosen as a classification
technique to study how individual wineries, vineyards as well as
the winery–vineyard combinations differed from each other, using
the respective one-way MANOVA models. Canonical variates (CVs)
were tested for significance using the Bartlett’s test (homogeneity
of variances) (Bartlett, 1937). All analyses were carried out in R (R
Core Team, 2013), using RStudio (version 0.98.953, Boston, MA,
USA) with the additional candisc package (Friendly & Fox, 2010).
3. Results and discussion
3.1. Elemental profiling
Of the 63 monitored elements, 47 were detected in the 65 dif-
ferent wine samples at concentrations above their LODs, and thus,
were included in the data analysis. For none of the elements was a
significant replicate effect was found, indicating that the ICP-MS
analysis method was repeatable (P 6 0.05). Recoveries for the
spiked samples, measured throughout the analysis sequence, were
between 93% (for Ba) and 103% (for Ca).
Similar to Martin and coworkers (Martin et al., 2012) we found
no significant elemental differences between different cultivars
from one region.
Significant differences for the winery, vineyard and the interac-
tion effect were detected in the MANOVA (P 6 0.05). Individual
ANOVAs revealed that all detected elements but 14 differed signif-
icantly among the wineries (33 significantly different elements,
Suppl. Table 2a), while 26 out of the 47 detected elements differed
significantly among the five different vineyards (P 6 0.05) (Suppl.
Table 2b).
Significant winery-by-vineyard interactions (i.e. the combination
of both winery and vineyard impact) were found for 17 elements
(Be, Na, P, Ti, Zn, As, Rb, Cd, Sb, Cs, La, Pr, Dy, Er, Tm, Yb, Tl)
(P 6 0.05).
In Suppl. Table 2a–b the detected elements are summarised for
the five vineyards and five wineries. These results show that both
grapegrowing and winemaking have an effect on the elemental
composition of the wine samples. Based on the ANOVA results it
seems that more elements are affected by the winemaking, as
more elements differ significantly in the wines across the different
processing wineries compared to the different vineyard origins.
Using the one-way MANOVA models for winery, vineyard and
winery-by-vineyard effects, Canonical Variate Analysis (CVA) was
conducted to establish a classification for each of these factors.
3.2. Vineyard effect
Canonical Variate Analysis (CVA) was used to classify the sam-
ples according to their vineyard origin, using the log-transformed
concentrations of the 26 elements that differed significantly among
the vineyards (P 6 0.05). All four CVs were highly significant in the
Bartlett’s test (P 6 0.05), and the first two CVs explain over 81% of
the total variance ratio, as shown in Fig. 3.
Along the first CV, capturing 55% of the total variance ratio,
vineyards were separated based on the elemental differences
between vineyard 1, and vineyards 2 and 5, with the remaining
two vineyards located in between.
Along the first CV vineyards line up according to their geo-
graphic north–south location (see also Fig. 1), except for vineyard
2 which showed more similarities to the most southern vineyard
5, while being the second most northern vineyard. Also, along
the first CV the two neighbouring vineyards (2 and 3) were not
close to each other (Fig. 3a).
Wines from vineyard 1 showed higher levels in B, Mg, P, Ca, Ti,
Cr, Ni, As, Mo, and to a lesser extent, Al, Co, Zn, and Sr, while wines
from the more southern vineyards showed higher concentrations
in Li, Be, Si, Mn, Rb, Cs, Er, Yb, Tl, and to a smaller extent, Ga, Se,
Ba, and Eu (Fig. 3b-c).
Boron, Mg, P, and Ti levels in wines from vineyard 1 were 1.5
times higher than in the wines from all other vineyards. Boron is
an essential element for plants, but its precise role in the plant
metabolism is not fully understood. Boron levels need to be man-
aged in a very narrow range, to avoid either deficiency or toxicity,
due to its easy mobilisation from the soil into the plant. Boron-rich
soils are the result of either marine sediments or boron rich miner-
als, which enhances the danger of boron toxicity if combined with
low rainfall and high salinity (Soilquality Pty Ltd., 2013;
Yermiyahu, Ben-Gal, & Sarig, 2006).
Potassium, N and P are essential plant elements, and are often
added to the soil with fertilizers (Aceto, 2003), while Mg, Ti, Mo,
Mn, and Si are mainly influenced by the mineral content of the soil
and mineral grape uptake as reported by Marengo and Aceto
(Marengo & Aceto, 2003) who successfully discriminated among
Nebbiolo wines from different sub-regions within the Piemonte
region in Italy.
The second CV separates wines from the vineyards 1, 4, and 5
from those from the two neighbouring vineyards 2 and 3
(Fig. 3d). The former three vineyards are positively correlated to
B, Si, Tl, Cs, and Se, while the levels in Cr, Mn, Co, Ni, Zn, As, and
Mo were very similar in the wines from the two neighbouring
vineyards 2 and 3, leading to a clear separation of these two vine-
yards from the others along CV 2 (Fig. 3e). All other elements (Li,
Be, Mg, Al, P, Ca, Ti, Ga, Rb, Sr, Ba, Eu, Er, and Yb) contributed to
a smaller degree to the separation of the different classes along
CV 2.
According to Pereira (Pereira, 1988) the application of B, Cr, Mo,
Mn, Co, and Zn as grapevine, soil or foliage treatments or as fertil-
izers impact both grape yield and grape composition, especially the
polyphenol, sugar, ester and amino acid levels. Any viticultural
practices, such as fertilizer application, would most likely also
affect the elemental composition of wine produced from such
treated grapes, depending on how easily the element would be
 H. Hopfer et al. / Food Chemistry 172 (2015) 486–496 491

(a)

6
2
3

2 2 3

33 3
3 3 33
2 2 3 3
2 3
33
3
3 3 3
2 3 33 33
33 3
3
2 3
3 3
CV 2, 26%

3
3
0

5 4

5
5
5
5 55
5 1
5 5
1

4 1 11
1 1

1 1
1
−6

−8 0 8
CV 1, 55%

(b) (d)
5

1 2 3 4 5

(c) (e)
0.6

Tl
Yb Cr Zn
Er As
Eu
Ba Ni
Cs Co Mo
Mn
Mo
Sr
Rb
BaEu
Se
As Ga
Mg P Ti
Ga
CV 2, 26%

Zn
0.0

Ni
Co
Mn Rb
Cr Li Al Ca Sr
Ti Be
Ca Er Yb
P Se
Si
Al Si
Mg Cs
B
Be Tl
Li
−0.7

B
−1.0 0.0 0.8
CV 1, 55%

Fig. 3. Canonical Variate Analysis (CVA) plots for the vineyard effect. (a) Product plot showing the individual wine samples, coded according to their vineyard origin with
different numbers (vineyard 1 (1), vineyard 2 (2), vineyard 3 (3), vineyard 4 (4), vineyard 5 (5)). Boxplots and total structures coefficients for the first (b-c) and second (d-e)
dimension showing the contribution of each element to the separation along CV 1 and CV 2.
492 H. Hopfer et al. / Food Chemistry 172 (2015) 486–496

(a)

6
B
B B B
B
B B
B B
B B B
B
B B

B
A A
A
A A
AA A
A AA
A AA
AA A AA
0

A
A A
CV 2, 37%

A A
A
A
A
A

C
DD
E C C

C
C C
C C
E C
C C

E E
−8

−7 0 6
CV 1, 50%

(b) (d)
E

(c) (e)
A B C D E

Pb
0.9

Tl
Re
Yb Zn
Er
Ho As
Dy
Gd
Pr Cr
Ce
La K
Ba
Cs
Sb P Mo CdSb
Co
Cd Mg Ni Ba
Rh Pb
CV 2, 37%

Mo
Sr
Rb Gd
Se Ti
As Sr Dy
Zn Mn Pr
Ni Ca Rh HoEr
Co La
0.0

Mn
Cr
Ti Al Yb
Ca Ce
K Rb
P
Al
Mg B
B
Re
Se
−0.5

Tl
−0.8 0.0 0.7 Cs
CV 1, 50%

Fig. 4. Canonical Variate Analysis (CVA) plots for the winery effect. (a) Product plot showing the individual wine samples, coded according to their processing winery with
different letters (winery A (A), winery B (B), winery C (C), winery D (D), winery E (E)). Boxplots and total structures coefficients for the first (b-c) and second (d-e) dimension
showing the contribution of each element to the separation along CV 1 and CV 2.
 H. Hopfer et al. / Food Chemistry 172 (2015) 486–496
mobilised in the soil. Elemental mobilisation is heavily dependent
on the soil constitution, mainly pH and aeration status, the soil
microbiota, as well as the element itself. While so called lithophile
elements (e.g. geochemically stable Al, Rb, Sc, Ti, and Zr (Boës,
Rydberg, Martinez-Cortizas, Bindler, & Renberg, 2011)) are bound
to various minerals, and are thus, less mobile, the anthropogenic
elements (e.g. B, Si) are typically present as ions, resulting in higher
soil mobility and thus, bioavailability (Bañuelos & Ajwa, 1999;
Kabata-Pendias, 2004). Based on these results, we hypothesise that
the discrimination among the different geographic origins (i.e.
vineyards) of the wines is the result of both soil elemental content
and viticultural practices. Further studies are needed to directly
relate the elemental composition of these vineyard soils to the
composition in the wines. Additional studies relating the effects
of viticultural practices on elemental composition of grapes are
also needed.
3.3. Winery effect
Similarly to the vineyard effect, the CVA on the winery effect as a
classifier, using the 33 elements that differed significantly among
the wineries in the ANOVA (P 6 0.05), led to a clear separation of
all wines according to their processing winery. All four canonical
variates (CVs) were significantly different from each other as deter-
mined by the Bartlett’s test (Bartlett, 1938; Friendly & Fox, 2010).
Eighty-seven percent of the total variance ratio was explained
within the first two CVs, thus only the first two dimensions are
shown. Wine samples were grouped according to the winery they
were processed as shown in Fig. 4a, where all wineries were well
separated from each other. Wines from winery B are more different
from the wines processed in all other wineries, as the remaining
wineries (A, C–E) are closer to or overlap with each other. Along
the first CV, 50% of the total variance ratio was explained, mainly
driven by the elemental differences of wines processed in winery
A, compared to wines processed in winery B or E, with the wines
from winery C and D in between (Fig. 4b). Wines from winery A
are separated from the other wineries based on the higher concen-
trations in Mg, P, Ca, Ti, Ni, Se, Sr, Rh, Re, while B, Cr, and Mo con-
tribute to a smaller degree to the separation (Fig. 4c). The most
likely source for Cr, Ti, Ni, and Mo are winery equipment and wine
containers as reported previously (Almeida & Vasconcelos, 2003a;
Galani-Nikolakaki, Kallithrakas-Kontos, & Katsanos, 2002; Galani-
Nikolakaki & Kallithrakas-Kontos, 2006; Pohl, 2007; Tariba, 2011;
Volpe et al., 2009). Molybdenum and Ti are stainless steel alloy ele-
ments (http://www.ssina.com), but are also present in the soil, so
their presence in the wines could be the result of both grapegrow-
ing and winemaking practices. Magnesium, P, Ca, B, Sr, and Rh have
been reported to come from vineyard soil by some authors (Pohl,
2007; Taylor et al., 2003), while others argue that P, Mg and Ca
can also be influenced by winemaking processes (Volpe et al.,
2009). Iglesias et al. (2007) report that Sr levels are not influenced
by production, however, this is neither confirmed by our results
nor by the results of Taylor et al. (2003) who found larger variation
in Sr levels in wines than in the soil.
Higher levels of Al, Mn, Zn, Rb, Cd, Sb, Cs, Tl, Pb, and the signif-
icantly different concentrations of REEs are contributing the most
to the separation of the wines from wineries B and E from the other
wineries, while K, Co, As, and Ba contribute to a lesser extent to this
separation (Fig. 4c). Selenium, Rb and Cs are commonly reported
elements used to differentiate the geographical origin of wines
(Angus, O’Keeffe, Stuart, & Miskelly, 2006; Castiñeira Gómez,
Feldmann et al., 2004; Coetzee et al., 2005; Martin et al., 2012;
Pohl, 2007; Taylor et al., 2003), but in most of these previous stud-
ies, only finished wines have been analysed. Almeida and
Vasconcelos (2003a) reported that the Rb levels remained constant
throughout red wine making.
493
The contents of Al, Mn, Cd, Co, and Pb in wines were reported
previously to result from winery equipment and containers
(Almeida & Vasconcelos, 2003a; Galani-Nikolakaki et al., 2002;
Galani-Nikolakaki & Kallithrakas-Kontos, 2006; Pohl, 2007;
Tariba, 2011; Volpe et al., 2009), and Almeida and Vasconcelos
(2003a) were only able to find a significant correlation between
vineyard soil and finished wine if they excluded Al and Ca from
their model, indicating that these latter two elements were heavily
influenced by the winemaking process.
The presence of Zn in wines could be the result of various fac-
tors, such as industrial activity (Marengo & Aceto, 2003), the use
of pesticides and fertilizers (Pohl, 2007; Tariba, 2011), as well as
winery containers (Pohl, 2007; Tariba, 2011). Both Al and Zn have
an impact on wine stability, and excess levels (<10 mg/L for Al) can
lead to haze formation and/or colour changes (Aceto, 2003; Tariba,
2011), but Zn and Mn are also favourable for yeasts during fermen-
tation as they are involved in enzyme activation (Pohl, 2007).
The higher levels in the REEs in the wines from winery B and E
are most likely the result of both vineyard and winery effects. As
reported in the materials and method section, none of the wines
have been clarified nor filtered, both reported causes for increases
in REE levels (Jakubowski et al., 1999; Rossano et al., 2007), there-
fore the high contribution of the REEs to the separation of the dif-
ferent wineries is unclear.
The second CV explains an additional 37% of the total variance
ratio, and is driven by the separation of wines from winery B and
winery E (Fig. 4d), with all other wineries located in between those
two. Wines from winery B showed higher levels of all elements
except for 9 (B, Al, Se, Rb, Cs, Ce, Yb, Re, and Tl) which were more
correlated to the wines from winery E (Fig. 4e). Chromium, Ti, Mn,
Co, Ni, Zn, As, Mo, Cd, and Pb again could result from various win-
ery equipment (Aceto, 2003; Galani-Nikolakaki & Kallithrakas-
Kontos, 2006; Pohl, 2007; Tariba, 2011).
Overall, the all wineries had an impact on the elemental compo-
sition of the wine, and this impact was different among the five
wineries. Especially winery B affected the wines to a different
extent than the other wineries. Also, elements that differed signif-
icantly among the wineries were mostly related to winery equip-
ment (e.g. Fe, Cd, Cr, Pb) and had been previously reported in red
wines.
3.4. Winery and vineyard interaction
In a last step, samples were classified using the winery-by-
vineyard interaction in the CVA model. In the ANOVA model, out
of the 47 detected elements, 17 showed significant differences
(P 6 0.05) between the 15 winery–vineyard combinations (Suppl.
Table 1), and were subsequently used in the classification. The first
seven CVs were found to differ significantly using the Bartlett’s test
(P 6 0.05), and using the first two canonical variates, 78% of the
total variance ratio was explained. Adding the third and fourth
CV to the model increased the ratio to over 90%, but when plotting
the eigenvalues over the dimensions, a ‘‘knee’’ was observed after
the first 2 CVs, thus, only the first two dimensions are shown in
Fig. 5a–e. The classification using the interaction effect separated
the wine samples due to both factors, but also allows identification
of those elements that are most useful in discriminating different
vineyards or different wineries, thus, separating the winery from
the vineyard effect.
In the score plot (Fig. 5a), wines from the wineries A and B clus-
ter together, independent of the vineyard source, except for wines
that were processed in winery A from grapes grown in vineyard 1.
These wines (A1) group together at the top of the score plot
together with all other wines made from vineyard 1 grapes (C1,
D1). Similar to vineyard 1, but with a larger scatter, wines made
from grapes from vineyard 5 are grouped together on the right
494 H. Hopfer et al. / Food Chemistry 172 (2015) 486–496

(a)

6
C1
A1
A1
D1 C1
C1
A1 C1

D1
A3 A2
C1
C5 C5
A3 A3 E4
A2
CV 2, 12%

A3 A2 A2
A3 C5
A3 A5
A3A3A3 A2 C5
A3 A3 E5 E5
0

A3 C3A3 C5 E5
B3A3 A2
A3
A3
A3
A3
B3
B3
A3
E5
B3 B3
B3 E5
C2
B3
B3 B3 B3
B3
B3
B3 B4
B5
B2
−5

−7 0 14
CV 1, 66%

(b) (d)
E5
E4
D1
C5
C3
C2
C1
B5
B4
B3
B2
A5
A3
A2
A1

(c) (e) A1 A2 A3 A5 B2 B3 B4 B5 C1 C2 C3 C5 D1 E4 E5

Tl
1

Yb
Tm
Er
Dy
Pr Ti

La P
Cs
CV 2, 12%

Sb
Cd
0

Rb
As Na
La Tl
Zn Cs Pr
Be Tm
Ti As Sb
Cd
P Dy Er Yb
Na
Rb
Be Zn
−1

−1 0 1

Fig. 5. Canonical Variate Analysis (CVA) for the first two dimensions using the winery-by-vineyard interaction term as classifier. (a) Shown are the individual scores, labeled
as in Suppl. Table 1, and additionally colour-coded by winery (winery A (in blue), winery B (in red), winery C (in green), winery D (in black), winery E (in orange)). Boxplots
and total structure coefficients for the first (b-c) and second (d-e) canonical variate. Elements that are represented by a long line in the structure coefficient plot have a larger
contribution to the observed separation in the CVA. Samples in the boxplots (b, d) are colour coded according to winery. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
 H. Hopfer et al. / Food Chemistry 172 (2015) 486–496
hand side of the score plot, independent of the processing wineries
(A, B, C, E). Within the wines from winery A and B, vineyard 2
wines are located towards the right, while wines from vineyard 3
are positioned to the left. Those two vineyards are located next
to each other geographically, thus, most likely sharing a similar
elemental soil composition. For the last vineyard, 4, only two sam-
ples were available, so one of them, processed in winery B, clusters
together with the other B wines, while the other one (E4), is posi-
tioned together with the wines coming out of vineyard 5. It seems
that for this vineyard, the winery is able to ‘‘overwrite’’ any vine-
yard effect on elemental composition, and/or could be the result
of the limited number of samples from this vineyard.
Looking at the score boxplots and the total structure coeffi-
cients in Fig. 5b-c the separation along CV 1 between the samples
is a driven by either a strong vineyard effect in case of vineyard 1
and 5 or a combined winery-vineyard effect as shown for both
winery A and B and the vineyards 2 and 4. Samples on the right
hand side of the score plot show higher levels in Be, Rb, Cs, Tl,
and some rare earth elements, while samples on the left hand side
are correlated to Na, P, Ti, Zn, As, and to a smaller degree Cd and
Sb (Fig. 5c).
Along the second dimension, samples processed in winery B
group together at the bottom of the plot, showing higher levels
of nearly all elements, except P, and Ti, which were positively cor-
related along CV 2, together with wines originating in vineyard 1
(Fig. 5e).
Many of these elements have been reported in the past to be
useful for wine classification, including Be (Greenough et al.,
1997; Thiel et al., 2004), Na (Marengo & Aceto, 2003; Martin
et al., 2012; Pohl, 2007), P (Marengo & Aceto, 2003; Martin et al.,
2012), Ti (Marengo & Aceto, 2003; Volpe et al., 2009), Zn (Martin
et al., 2012; Volpe et al., 2009), Rb (Angus, O’Keeffe, Stuart, &
Miskelly, 2006; Coetzee et al., 2005; Greenough et al., 1997;
Martin et al., 2012; Pohl, 2007; Taylor et al., 2003), Cd (Angus
et al., 2006; Baxter et al., 1997; Volpe et al., 2009), (Angus et al.,
2006; Baxter et al., 1997; Greenough et al., 1997; Martin et al.,
2012), Tl (Coetzee et al., 2005; Greenough et al., 1997), and the lan-
thanides (Marengo & Aceto, 2003; Volpe et al., 2009), so it is not
too surprising that also in this study these elements were found
discriminatory. However, for at least some of these reported ele-
ments (e.g. lanthanides and other REEs, Cd, and Ti) other studies
(Jakubowski et al., 1999; Pohl, 2007; Rossano et al., 2007; Tariba,
2011) have shown that winemaking processes (filtration, clarifica-
tion, storage, etc.) can change the concentrations. Due to the study
design, where we sampled all wines immediately out of the fer-
mentation container, before any further winemaking steps were
made (e.g. racking, settling, additions, filtration, blending, barrel
storage, bottling) our results capture only the very first step in
the winemaking process. Nevertheless, at least for two wineries
(A and B) the impact of the winery is already visible in the elemen-
tal profiles.
4. Conclusions
The combined effects of vineyard origin and winery processing
have been studied with 65 different red wines samples, originating
from five different Northern Californian vineyards within 40 miles
(65 km) to each other. All wines were processed in at least two of
the five different wineries. Based on the multi-elemental pattern,
measured with 63 elements by inductively coupled-plasma mass
spectrometry (ICP-MS), we were able to classify the wines accord-
ing to their vineyard origin, their processing winery, as well as the
combined effects of both origin and processing.
Each classification successfully separated the wines according
to their vineyard or winery, indicating that both grapegrowing
and winemaking impact the elemental composition of red wine.
495
Significant differences among the five vineyards were found for
26 elements, and most of these elements have been reported
previously to be present in soil and/or are being used by different
viticultural practices (e.g. herbicides, fertilizers, pesticides, fungi-
cides). Five elements showed only a significant vineyard effect
(Be, Eu, Ga, Li, Si), indicating that these elements were either not
changed at all or changed to the same extent during winemaking
in the different wineries.
Based on these results, we hypothesise that the discrimination
among the different geographic origins (i.e. vineyards) is the result
of both soil elemental content and viticultural practices. Further
studies are needed to directly relate the elemental composition
of these vineyard soils to the composition in the wines. Additional
studies relating the effects of viticultural practices on elemental
composition of grapes are also needed.
A total of 33 elements differed significantly among the five dif-
ferent wineries, with Cd, Ce, Dy, Gd, Ho, K, La, Pb, Pr, Re, Rh, and Sb
differing significantly only among the wineries, indicating that
they were either not present at all or present at the same levels
when they arrived at the processing winery, and were changed
during winemaking in the five wineries to a different extent. Over-
all, all wineries had an impact on the elemental composition of the
wine, and this impact was different among the five wineries. Espe-
cially winery B affected the wines to a different extent than the
other wineries. Also, elements that differed significantly among
the wineries were mostly related to winery equipment (e.g. Fe,
Cd, Cr, Pb) and had been previously reported in red wines.
Seventeen elements showed a significant winery-by-vineyard
interaction, i.e. were affected by both grapegrowing and winemak-
ing to a different degree among the 15 winery-vineyard combina-
tions. Many of these elements have been used in the past for wine
classification according to the geographical origin, so it is not too
surprising that they were important for the discrimination in this
study.
However, while for some vineyards wines were found to show
a characteristic elemental pattern, independent of the processing
winery, the same was found for some wineries, with similar ele-
mental pattern for all grapes processed in these wineries, indepen-
dent of the vineyard origin. This is consistent with previous
reports that some of the discriminating elements (e.g. REEs, Cd,
and Ti) were shown to be influenced by various winemaking pro-
cesses (filtration, clarification, storage, etc.). Due to our study
design, where wines were sampled immediately out of the fer-
mentation container, before any further winemaking steps were
conducted, the presented results capture only the very first step
in the winemaking process. Nevertheless, the impact of the winery
is already visible in the elemental profiles, thus raising the ques-
tion whether wines could ever be traced back to their vineyard
or if the traceability ends when the grapes enter the processing
winery.
Further studies are needed to study this question, including a
close monitoring of grapes from the same vineyard processed in
different wineries.
In summary, this work provides further insight into the deter-
mination of geographical origin of red wines, but in contrast to ear-
lier studies, the combined effects of both grapegrowing and
winemaking were studied, and found to both impact the elemental
profile of red wine.
Acknowledgements
The Food Safety and Measurement Facility is supported by
generous loans and donations from Agilent Technologies, Gerstel
US, and Constellation Brands. We thank Jerry Lohr for financial
postdoctoral support, as well as the donating wineries for their
collaboration.
496 H. Hopfer et al. / Food Chemistry 172 (2015) 486–496
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.foodchem.2014.
09.113.
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