Study of acrylamide in coffee using an improved liquid chromatography mass spectrometry method Investigation of colour changes and acrylamide

Food Additives and Contaminants
ISSN: 0265-203X (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/tfac19
Study of acrylamide in coffee using an improved
liquid chromatography mass spectrometry
method: Investigation of colour changes and
acrylamide formation in coffee during roasting
Hamide Z. Şenyuva & Vural Gökmen
To cite this article: Hamide Z. Şenyuva & Vural Gökmen (2005) Study of acrylamide in coffee
using an improved liquid chromatography mass spectrometry method: Investigation of
colour changes and acrylamide formation in coffee during roasting, Food Additives and
Contaminants, 22:3, 214-220, DOI: 10.1080/02652030500109834
To link to this article: https://doi.org/10.1080/02652030500109834
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Food Additives and Contaminants, March 2005; 22(3): 214–220
Study of acrylamide in coffee using an improved liquid chromatography
mass spectrometry method: Investigation of colour changes and
acrylamide formation in coffee during roasting
HAMIDE Z. ŞENYUVA1, & VURAL GÖKMEN2
1
Ankara Test and Analysis Laboratory, Scientific and Technical Research Council of Turkey, Ankara 06330, Turkey,
and 2Food Engineering Department, Hacettepe University, Ankara, Turkey
(Received 16 January 2005; revised 25 February 2005; accepted 28 February 2005)
Abstract
An improved analytical method for the determination of acrylamide in coffee is described using liquid chromatography
coupled to mass spectrometric detection (LC-MS). A variety of instant, ground and laboratory roasted coffee samples were
analysed using this method. The sample preparation entails extraction of acrylamide with methanol, purification with Carrez
I and II solutions, evaporation and solvent change to water, and clean-up with an Oasis HLB solid-phase extraction (SPE)
cartridge. The chromatographic conditions allowed separation of acrylamide and the remaining matrix co-extractives with
accurate and precise quantification of acrylamide during MS detection in SIM mode. Recoveries for the spiking levels of
50, 100, 250 and 500 mg/kg ranged between 99 and 100% with relative standard deviations of less than 2%. The effects of
roasting on the formation of acrylamide and colour development were also investigated at 150, 200 and 225 C. Change in
the CIE (Commission Internationale de l’Eclairage) a* colour value was found to show a good correlation with the change in
acrylamide. CIE a* and acrylamide data was fitted to a non-linear logarithmic function for the estimation of acrylamide level
in coffee. Measured acrylamide levels in commercial roasted coffees compared well with the predicted acrylamide levels from
the CIE a* values.
Keywords: Acrylamide, coffee, colour, roasting
Introduction
Since the discovery of acrylamide in foods was made
public in April 2002 (Tareke et al. 2002), several
research groups have been involved in developing
methods to reliably quantify acrylamide at relatively
low levels in a large variety of different foodstuffs.
The general findings are that acrylamide will
invariably be found in heated carbohydrate foods.
One possible pathway to the formation of acrylamide
in some foods is probably via the Maillard reaction,
which involves the reaction of an amino acid with a
carbonyl compound during heating (Mottram et al.
2002; Stadler et al. 2002).
The high consumption of coffee in many countries
makes it a potentially significant source of daily
exposure to acrylamide. Due to the use of roasted
coffee beans in making coffee, the probability of
significant levels of acrylamide being present was
considered to be high. The chemistry of coffee
roasting is complex and still not completely
understood. Aromatics, acids, and other flavor
components are either created, balanced, or altered
in a way that should augment the flavor, acidity, after
taste and body of the coffee during roasting. The
roasting temperature determines the specific types of
chemical reactions that occur in coffee. In addition
to desired characteristics, undesirable changes such
as the formation of acrylamide should also be
considered in this process.
Coffee, as a source of acrylamide, needs to be
investigated in depth to determine the effects of
roasting conditions on acrylamide levels. Analysis
of acrylamide in coffee is challenging because of
co-extractives and the inherent difficulties in confirming a low molecular mass (MW 71) compound
in a complex matrix. Most of the methods published
so far are based on either GC-MS (Castle et al. 1991,
Biedermann et al. 2002, Ono et al. 2003, Nemoto
et al. 2002) or LC-MS (Rosén and Hellenäs 2002;
Ahn et al. 2002; Zyzak et al. 2003; Becalski et al.
2003; Roach et al. 2003; Jezussek and Schieberle
2003; Riediker and Stadler 2003) techniques, with
comparable performance of two approaches. The
Correspondence: Hamide Şenyuva, Email: hamide.senyuva@tubitak.gov.tr
ISSN 0265–203X print/ISSN 1464–5122 online ß 2005 Taylor & Francis Group Ltd
DOI: 10.1080/02652030500109834
Study of acrylamide in coffee
results of an inter-laboratory study of the determination of acrylamide in crispbread and butter cookies
have shown that only 50% of the participating
laboratories reported satisfactory analytical values
(Wenzl et al. 2004). Many of these methods do not
perform well in difficult matrixes such as cocoa and
coffee.
As previously highlighted by some researchers, the
selected mass transitions reveal difficulty of obtaining
baseline separation in certain profiles during LCMS-MS analysis. The significant loss of the analyte
throughout the sample preparation steps and ion
suppression effect leading to a low response of
acrylamide are common problems encountered
after a two-step extract clean-up (Andrzejewski et al.
2004; Delatour et al. 2004).
We previously described a sample preparation
method for the determination of acrylamide in
processed potato products using LC with diode
array detection (Gökmen et al. 2005). Here, we also
successfully applied same method for the determination of acrylamide in a variety of instant, ground and
laboratory roasted coffees using LC-MS. The effects
of temperature and time were also studied on
the formation of acrylamide and colour in order to
understand the changes and any relation in these
variables during roasting process.
Experimental procedures
Chemicals and consumables
Acrylamide (99þ%) and 13C3-labelled acrylamide
(99% isotopic purity) were obtained from Sigma
(Diesenhofen, Germany) and Cambridge Isotope
Laboratories (Andover, MA, USA), respectively.
Methanol, potassium hexacyanoferrate and zinc
sulfate were analytical grade and obtained from
Merck (Darmstadt, Germany). Bidistilled, deionized
and 0.20 mm filtered water was used throughout the
experiments. Oasis HLB (1 ml, 30 mg) SPE cartridges were supplied by Waters (Milford, MA,
USA). Glass vials with septum screw caps and
headspace vials seal caps were supplied by Agilent
Technologies (Wilmington, DE, USA). Reference
test material (FAPAS T3008 coffee) was obtained
from CSL (Central Science Laboratory, UK) to
verify the accuracy of method. Stock solution of
acrylamide (1 mg/ml) and 13C3-labelled acrylamide
(0.1 mg/ml) by dissolving in distilled water. Working
standards were prepared daily by diluting the stock
solution to concentrations of 0.01, 0.02, 0.05,
0.1, 0.2, 0.3, 0.5 and 1.0 mg/ml with distilled water.
Carrez I solution was prepared by dissolving 15 g of
potassium hexacyanoferrate in 100 ml of water, and
Carrez II solution by dissolving 30 g of zinc sulfate
in 100 ml of water.
215
Heat treatment (roasting) of green coffee
A total of 3 g of ground green coffee was put in a
headspace vial and sealed. Samples were roasted in a
temperature-controlled oven (Heraeus Instruments
model T 60) set to 150, 200 and 225 C for the
determination of time-dependent changes in acrylamide and colour with sampling at 5, 10, 15, 20 and
30 min. Green coffee was spiked with 200 ng/g of
deuterium labelled acrylamide in order to determine
the rate of degradation at 225 C. Immediately after
roasting for each selected time, the headspace vials
were allowed to cool to room temperature prior to
analyses.
Measurement of acrylamide
Sample preparation. A sample preparation procedure
previously described by us elsewhere was used
(Gökmen et al. 2005). A total of 1 g of coffee was
weighed into a 10 ml centrifuge tube. The sample
was spiked with acrylamide (50, 100, 250 and 500 ng/
g of acrylamide, and 50 and 100 n/g of 13C3-labelled
acrylamide) to determine the percentage recovery of
the method at this stage. The sample was suspended
in 5 ml of methanol and extracted for 2 min in a
vortex mixer. The suspension was centrifuged at
5000 rpm for 10 min (Sigma model 2–16 K). The
clear supernatant was transferred into a centrifuge
tube and treated with Carrez I and II solutions (25 ml
each) to precipitate the co-extractives. Following
centrifugation at 5000 rpm for 5 min, 1.0 ml of clear
supernatant (0.2 g sample) was quantitatively transferred into a conical bottom glass test tube placed in
a water bath at 40 C (Zymark Turbo VapÕ LV
Evaporator) and evaporated to dryness under nitrogen at 3 psig. The remaining residue was immediately redissolved in 1 ml of water by mixing in a
vortex mixer for 1 min. For the SPE clean-up, Oasis
HLB cartridge was preconditioned consequently
with 1 ml of methanol and 1 ml of water at a rate of
two drops per second using a syringe. Then, 1 ml of
the extract was passed through the cartridge at a rate
of one drop per second using a syringe. The first ten
drops of the effluent were discarded to prevent any
dilution of sample by replacing water held in the
sorbent void fraction with the sample effluent. The
forthcoming drops were collected and filtered
through a 0.45 mm syringe filter. 20 ml of the final
test solution was injected onto LC column for
quantitation by LC-APCI-MS.
LC-APCI-MS analysis. LC-APCI-MS analyses were
performed by an Agilent 1100 HPLC system
(Waldbronn, Germany) consisting of a binary
pump, an autosampler and a temperature-controlled
column oven, coupled to an Agilent 1100 MS
216
H. Z. Şenyuva & V. Go¨kmen
detector equipped with atmospheric pressure
chemical ionization (APCI) interface. The analytical
separation was performed on an Inertsil ODS-3
column (250 4.6 mm, 5 mm) using the isocratic
mixture of 0.01 mM acetic acid in 0.2% aqueous
solution of formic acid at a flow rate of 0.6 ml/min at
25 C. The LC eluent was directed to the MS system
after a delay time of 6.5 min using MSD software.
Data acquisition was performed in selected ion
monitoring (SIM) mode using the interface parameters: Drying gas (N2, 100 psig) flow of 4 l/min,
nebulizer pressure of 60 psig, drying gas temperatures 325 C, vaporizer temperature of 425 C,
capillary voltage of 4 kV, corona current of 4 mA,
fragmentor voltage of 55 eV. Ions monitored were
m/z 72 and 55 for acrylamide and m/z 75 and 58
for 13C3-labelled acrylamide for the quantification of
acrylamide in the samples.
Measurement of CIE L*a*b* colour values
Colour measurements (CIE L*a*b* values) were
performed using a Minolta CM-3600d model
spectrophotometer. According to CIE colour
space, L* indicates lightness and a* and b* indicate
color directions. þa* and a* are the red and the
green directions, þb* and b* are the yellow and
the blue directions, respectively. The sample was
transferred into a disposable cuvette to measure the
reflectance at least twice from both front and rear
sides of the specimen.
Results and discussion
Performance of method for acrylamide
Sample preparation. Since acrylamide is highly soluble in water (215.5 g/100 ml), the sample preparation
was usually started by extracting the food samples
with water enough for a proper swelling in most
of the methods based on LC coupled to tandem
MS detection system (Tareke et al. 2002; Rosén and
Hellenäs 2002; Becalski et al. 2003; Roach et al.
2003; Riediker and Stadler 2003). Our initial
attempts of analysing coffee samples for acrylamide
which started with extraction with water resulted in
undesirable results during LC-MS analyses due
to interfering co-extractives. These interfering
co-extractives could not be eliminated completely
after a single SPE clean-up in different modes
including hydrophilic-lipophilic balanced copolymer
sorbent packed cartridge (Oasis HLB) and cationanion exchanger based sorbent packed cartridges
(Oasis MCX or MAX), and satisfactory chromatograms could not be obtained.
In fact, peaks of acrylamide and interferences
completely overlapped each other and co-detected
during MS detection in SIM mode. Co-detection of
acrylamide and interferences in coffee extract was
confirmed by analysing the purity of co-eluted peaks
in scan mode. The ion having m/z of 71 appeared as
the major interference during the MS detection of
acrylamide in SIM mode. Some researchers, therefore, used sequential SPE cartridge clean-up using
Oasis HLB cartridge and then a Bond Elut-Accucat
(cation and anion exchange sorbent) cartridge.
However, a number of peaks were observed both
before and after the acrylamide peak in the ion
profiles monitored for coffee extracts during LCMS-MS analysis, despite two SPE cartridge clean-up
steps (Andrzejewski et al. 2004). The significant loss
of the analyte and ion suppression effect leading to a
low response of acrylamide were also encountered
after a two-step extract clean-up approach with
Isolute Multimode and cation-exchange cartridges
for coffee (Delatour et al. 2004). Recently, a singlestep clean-up procedure using Isolute multimode
solid phase cartridge was described for the analysis of
acrylamide in ready-to-drink coffee. However, it was
noted that the loading of the SPE cartridge with the
sample exceeding 0.5 ml resulted in an increased
suppression of the MS response (Granby and Fagt
2004).
Acrylamide is also highly soluble in methanol
(155.0 g/100 ml) which can be used as an alternative
extracting solvent. It was previously shown by us
elsewhere that methanol as the extraction solvent was
successfully applied for the analysis of acrylamide
in potato chips and crisps with subsequent Carrez
clarification and SPE cleanup (Gökmen et al. 2005).
Here, the same approach was applied for the analysis
of acrylamide in coffee. After acrylamide was
extracted from coffee with methanol, the colloids
(mainly proteins) which were soluble in methanol
were precipitated by Carrez reagents. Carrez clarification not only purified the extract by precipitation of
dissolved colloids, but also prevented the loss
of acrylamide during the evaporation of methanol
under a gentle stream of nitrogen. The addition of
50 ml of water added into approximately 5 ml of
methanolic extract in the form of aqueous Carrez I
and II solutions had a significant contribution to
retain acrylamide residue on the wall of glass tube
during evaporation. Following evaporation to complete dryness, the residue on the wall of glass tube
was redissolved by water in a vortex mixer.
By changing solvent from methanol to water,
lipophilic co-extractives present in the methanolic
extract of coffee were excluded leaving them as a
residue on the wall of glass tube, but acrylamide was
completely transferred into water. The extract was
further cleaned up by using Oasis HLB cartridge.
Since acrylamide does not interact with the sorbent
material, the pass through strategy during the SPE
Study of acrylamide in coffee
Table I. Percentage recoveries of acrylamide from ground filter
coffee for different spiking levels.
abundance
interference
1200
Spiking level,
ng/g
50
100
250
500
Recovery, %
217
RSD, % (n ¼ 4)
AA
d3-AA
AA
d3-AA
98.8
100.0
100.0
101.5
100.5
101.2
–
–
0.5
1.0
0.6
1.0
1.1
0.9
1.0
1.5
1100
1000
acrylamide
900
800
clean-up was applied to retain only the matrix
interferences. It was determined that first ten drops
(0.4 ml) should be discarded, then collecting the
remaining effluents (0.6 ml) during SPE clean-up
to prevent any dilution with water left in the cartridge
after conditioning. Doing so, a colourless final
extract could be obtained prior to LC-MS analyses
for coffee samples, excepting instant coffees.
The recovery of acrylamide was determined by
analysing each of the spiked sample four times
for levels ranging from 50–500 ng/g. Recovery
samples were prepared by spiking ground filter
coffee containing an acrylamide level of
49.0 1.0 ng/g. The mean percentage recoveries
exceeded 99% for all spiking levels for coffee
(see Table I). The accuracy of the method was
further tested analysing reference material (FAPAS
T3008 coffee) supplied by the CSL. The mean value
of acrylamide was found to be in the satisfactory
range.
700
600
6.5
6
7
7.5
min
Figure 1. Chromatogram of coffee showing the co-elution
of acrylamide and interfering co-extractive in the presence
of acetonitrile in the mobile phase mixture.
abundance
spiked coffee (+50 ng/g acrylamide)
800
750
blank coffee (~50 ng/g acrylamide)
700
10 ng/ml acrylamide standard
650
600
Chromatographic separation
The chromatographic separation of acrylamide was
performed on an Inertsil ODS-3 analytical column.
Initially, the isocratic mixture of 0.01 mM acetic acid
in 0.2% aqueous solution of formic acid and 0.2%
acetic acid in acetonitrile (98:2, v/v) as the mobile
phase at a flow rate of 0.6 ml/min was used to
separate acrylamide from the matrix co-extractives
of coffee samples. As reported by us elsewhere,
acrylamide could be successfully resolved from the
matrix co-extractives using these chromatographic
conditions during the analysis of acrylamide in
potato and cereal based foods using LC-MS with
APCI (Şenyuva and Gökmen 2005). However,
co-eluting compounds from the coffee extract interfered with acrylamide during MS detection in
SIM mode as illustrated in Figure 1. In order to
improve chromatographic separation, acetonitrile
was excluded from the mobile phase mixture.
Doing so, acrylamide and interfering co-extractive
was completely resolved using the isocratic mixture
of 0.01 mM acetic acid in 0.2% aqueous solution of
formic acid at a flow rate of 0.6 ml/min (Figure 2).
550
8.5
9.0
min
Figure 2. Chromatograms of coffee blank, coffee spiked with
50 ng/g of acrylamide, and acrylamide standard 10 ng/ml.
Detection sensitivity and linearity
LC-MS with APCI allowed us to determine acrylamide sensitively and precisely. Under the positive
APCI conditions applied here, scan MS analysis
of acrylamide and 13C3-labelled acrylamide
showed both [MþH]þ ions with compoundspecific product ions due to loss of NH3 from the
protonated molecule. The acrylamide response was
linear over a concentration range of 1–1000 ng/ml
with correlation coefficients of higher than 0.999.
Based on a signal to noise ratio of 3, limit of
detection (LOD) and limit of quantitation (LOQ)
was found to be ca. 2.0 ng/g and 10.0 ng/g acrylamide
in coffee.
H. Z. Şenyuva & V. Go¨kmen
350
Table II. Acrylamide level of commercial coffee samples.
300
29–75
50
42–338
250
150
100
0
0
5
10
15
20
25
30
time, min
Figure 3. Acrylamide formation during roasting of green coffee at
different temperatures.
350
7
(a)
acrylamide, ng/g
300
250
6
5
Acrylamide
Color
200
4
150
3
100
2
50
1
0
0
0
5
10
15
20
25
30
time, min
350
7
(b)
acrylamide, ng/g
300
6
Acrylamide
250
5
Color
200
4
150
3
100
2
50
1
0
Effect of heat treatment (roasting) on acrylamide
and colour
0
0
5
10
15
20
25
30
time, min
7
350
(c)
300
acrylamide, ng/g
In order to determine the effects of heating on the
amounts of acrylamide in relation to colour, green
coffee was roasted at three temperatures of 150,
200 and 225 C for up to 30 min. The amount of
acrylamide measured increased rapidly at the onset
of roasting, reaching an apparent maximum, and
then decreasing exponentially as the rate of degradation exceeded the rate of formation at 200 and
225 C. However, the amount of acrylamide measured continued to increase during roasting at
150 C. As illustrated in Figure 3, experiments with
deuterium labelled acrylamide spiked to green coffee
prior to roasting confirmed the exponential degradation during heating at 225 C. The acrylamide level
200
50
Survey of acrylamide in commercial coffee samples
In this study, a total of 20 coffee samples from four
groups were analysed for their acrylamide contents.
Samples were randomly selected from coffee shops
and supermarkets in Ankara in December 2004,
therefore, may not representative of coffee supply.
We would like to stress that results cannot provide
guidance in consumers’ choice between different
products and brands within certain Turkish coffee
types. However, the results are a general guide to
acrylamide concentrations in a selected segment of
coffee supply. According to our results, acrylamide
levels averaged as 19 ng/g in roasted ground coffees
from different origins. The acrylamide levels of
Turkish type coffee was slightly higher and averaged
as 46 ng/g. Gold type instant coffees were found to
contain significantly higher amounts of acrylamide
(see Table II). Andrzejewski et al (2004) have
reported the average acrylamide levels ranging from
45 ng/g to 374 ng/g in 31 ground coffees.
225 deg C
225 deg C (d3-acrylamide)
CIE a* value
14
18
29
15
22
15
18
12
28
21
18
200 deg C
CIE a* value
Turkish coffees (n ¼ 5)
Filter coffee (n ¼ 1)
Instant coffees (n ¼ 3)
Roasted ground coffees (n ¼ 11)
Irish coffee
Mexico
Costa Rica S.H.B.
Tanzanian peaberry
Colombian supremo
Colombian decaffeinated
Guatemala
Yemen mocha
Indonesian sumatra
Ethiopian mocha
Kenya
150 deg C
Acrylamide, ng/g
acrylamide,ng/g
Coffee sample
6
Acrylamide
250
5
Color
200
4
150
3
100
2
50
1
CIE a* value
218
0
0
0
5
10
15
time, min
20
25
30
Figure 4. Changes in the amount of acrylamide and CIE a* value
in coffee during heating at (a) 150 C, (b) 200 C, (c) 225 C.
Study of acrylamide in coffee
was reduced by a factor of approximately 20 at
the end of 30 min of roasting at 200 and
225 C, compared to the highest level recorded.
As noted by other researchers (Taeymans et al.
2004), the results obtained in this study also revealed
that the darker coloured coffee may contain much
lower amounts of acrylamide than light coloured
coffee.
Changes in the CIE L*a*b* colour values of coffee
were also monitored during roasting. Although CIE
L* and b* values decreased exponentially with time,
CIE a* values measured increased rapidly at the
onset of roasting, reaching an apparent maximum,
and then decreasing exponentially at 200 and 225 C,
but reached to a maximum with continuous increase
at 150 C. It was interesting to see that changes in the
amounts of acrylamide and CIE a* values followed
almost the same pattern, as shown in Figure 4.
These results recommend that there is a significant
correlation between the amount of acrylamide and
the CIE a* value of roasted coffee. Since similar
correlations were obtained between the amount of
acrylamide and CIE a* value during roasting at all
temperatures studied, it was concluded that the
7
6
CIE a* value
5
4
y = 1.4364Ln(x) - 2.3366
3
2
r = 0.9286
2
1
0
0
50
100
150
200
250
300
350
acrylamide, ng/g
Figure 5. Non-linear function for the correlation between
acrylamide concentration and CIE a* value for roasted coffee.
correlation between acrylamide and CIE a* value is
independent of temperature. Therefore, the acrylamide level of coffee can be estimated roughly from
the measured CIE a* value by knowing a reasonable
regression equation. Here, randomly selected data
points (measured acrylamide concentrations versus
CIE a* values) for roasted green coffee were used to
perform non-linear regression analysis. A logarithmic
function was fitted well to the experimental data as
shown in Figure 5.
Acrylamide concentrations of a variety of roasted
coffee samples were determined roughly using this
function. As seen in Table III, the difference
between the predicted and measured acrylamide
concentrations was ranged from 1–59% for roasted
coffees of different origin, as well as for a commercial
gold type instant coffee.
Conclusions
Coffee was studied in a time-dependent manner to
determine the effects of roasting temperature in the
amounts of acrylamide in relation with colour.
A significant correlation was found between the
acrylamide level and colour measured as CIE a*
value. This correlation was fitted to a non-linear
logarithmic function and successfully used to predict
acrylamide concentration from the measured CIE a*
value in a variety of commercial coffee samples.
The preliminary results show that the acrylamide
level in roasted coffee may be estimated approximately from the CIE a* value. However, further
investigation is required to establish a more useful
relation based on a statistical database for roasted
coffees taking the variations in raw material origin
into account for an accurate prediction of acrylamide
levels in roasted coffee.
The method used to analyse acrylamide in coffee
was rapid, rugged and accurate, utilizing methanol
extraction and clean-up steps prior to LC-MS
analysis. Since the sample preparation method
presented here can be applied to basically all foods
Table III. Measured and predicted AA levels of ground roasted coffee samples using the logarithmic correlation model.
Measured
Roasted coffee
Mexico
Irish coffee
Tanzanian peaberry
Colombian supremo
Guatemala
Colombian decaf
Indonesian sumatra
Ethiopian mocha
Jacobs monarch
219
Predicted
Acrylamide, ng/g
CIE a* colour
Acrylamide, ng/g
Difference, %
18
14
15
22
18
15
28
21
338
2.22
2.20
2.17
2.11
2.30
2.14
2.59
2.48
5.94
24
22
23
22
25
22
31
29
318
33
59
54
1
40
50
10
36
6
220
H. Z. Şenyuva & V. Go¨kmen
known to contain traces of acrylamide, it can be
considered as a generic one prior to LC-MS
analyses.
Acknowledgements
We thank the Turkish Academy of Sciences (GEBIP
Study Grant) for financial support, TUBITAK
Ankara Test and Analysis Laboratory (ATAL)
for LC-MS analyses, and Waters Corporation
and Agilent Technologies for supplying some
consumables.
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