Application Note · PlasmaQuant 9100 Elite

Direct Analysis of Beer by HR ICP-OES

Introduction
Beer is traditionally brewed from water, malted barley and hop. Often yeast is
added during the fermentation process. Other base ingredients such as rice, wheat
or corn are also used to brew beers of a huge variety with a wide range of different
tastes. Since the brewing ingredients affect the taste and quality of the final beer,
their quality is of highest importance. Metal contamination originating from the
raw materials or the brewing process itself can adversely affect the final quality of
the beer.
Copper contamination originating from the brewing kettle and increased iron
Challenge contents may result in an unwanted metallic taste. Iron significantly contributes
Direct analysis of beer exhibiting to the characteristics of the froth, which is important especially in regions where
a high amount of total dissolved beer is traditionally served in a glass. Other elements to be monitored in beer and
solids as well as volatile alcoholic its precursors are sodium, zinc, manganese and calcium. Similar to iron, calcium
components affects the froth of the beer. Since calcium or zinc salts (CaSO4, ZnSO4) are added
intentionally as a pH buffer, their final concentration needs to be adjusted.

Solution Monitoring metallic contents in final beer products as well as in precursors of

the brewing process by the use of inductively coupled plasma optical emission
HR ICP-OES with exceptional spectroscopy (ICP-OES) demonstrates a routine task of quality control laboratories
matrix tolerance towards in the brewing industry. The main focus is on highly precise and accurate
complex matrices, high sensitivity measurements with minimum sample preparation and data evaluation efforts.
and industry leading high-
Major challenges in the analysis of beer are the varying contents of alcohol
resolution optical system for
(typically 4–6% (v/v)), the high amount of total dissolved solids (TDS) and the
interference-free detection of
carbon dioxide (CO2) contents. CO2 causes unsteady sample introduction and thus
metals with high precision and
poor precision of the obtained results. Therefore it must be removed before the
accuracy
analysis.
2 Direct Analysis of Beer by HR ICP-OES

Running high TDS samples in combination with moderate amounts of alcoholic components additionally requires a highly
robust sample introduction and plasma system to avoid poor precision due to plasma-based signal fluctuation. To account for
these effects, many ICP-OES systems require dilution of the samples. The resulting dilution factors eventually compromise
limits of detection (LOD), which is a limitation for trace elemental analysis.

The presented methodology describes a direct analysis of beer for calcium, sodium, copper, zinc, manganese and iron
contents by the use of a high-resolution ICP-OES, the PlasmaQuant 9100 Elite. The exceptionally high resolution allows for
interference-free analysis of all investigated analytes in the demanding matrix of undiluted beer samples. The dedicated
introduction kit for high matrix samples combined with the robust plasma of the high-frequency generator enables precise
and accurate measurements of demanding matrices with LODs in the sub-ppb range.

Materials and Methods

Samples and reagents

Sample preparation
Beer samples were divided into two aliquots in order to investigate different sample degassing methodologies:
■ sonication (20 min)
■ pass-through of argon stream (60 min)

The obtained samples were acidified with nitric acid (65%, p.a.)

Calibration
Ethanol (GC grade) was added to the standards in order to perform a matrix-matched calibration. The standards were
prepared from single element standard solutions (1000 mg/L). Yttrium and gallium were used as internal standards. Table 1
summarizes the used calibration levels.

Table 1: Concentration of calibration standards

Element Unit Cal.0 Cal.1 Cal.2 Cal.3

Ca mg/L 0 10 25 50

Cu mg/L 0 0.05 0.10 0.25

Fe mg/L 0 0.01 0.025 0.05

Na mg/L 0 5.0 10 25

Mn mg/L 0 0.025 0.05 0.10

Zn mg/L 0 0.01 0.025 0.05

Instrumentation
Instrument settings
For the analysis a PlasmaQuant 9100 Elite equipped with a sample introduction kit tailored to high matrix samples and an
ASPQ 3300 autosampler was used. The detailed system configuration is shown in Table 2.

Table 2: Configuration of the PlasmaQuant 9100 Elite equipped with Salt kit

Parameter Settings Parameter Settings

Power 1300 W Injector 2 mm, Quartz

Plasma gas flow 14 L/min Outer tube/Inner tube Quartz/Quartz

Auxillary gas flow 0.5 L/min Pump tubing PVC (0.76 mm ID) black/black

Nebulizer gas flow 0.6 L/min Sample pump rate 1.0 mL/min

Nebulizer Concentric nebulizer seaspray Rinse/Read delay 45 s

(2.0 mL/min)

Spray chamber Cyclonic spray chamber with dip tube, Auto sampler Yes
50 mL
 Direct Analysis of Beer by HR ICP-OES 3

Evaluation parameters

Table 3: Overview of method-specific evaluation parameters

Line Integration Read time Evaluation

Element Plasma view
[nm] mode [s] No. of Pixel Baseline fit Polynomial degree Correction

Ca 315.887 radial peak 3.0 3 ABC1 auto Y2 (radial)

Ca 317.933 radial peak 3.0 3 ABC auto Y (radial)

Cu 324.933 axial peak 3.0 3 ABC auto Ga3 (axial)

Cu 327.396 axial peak 3.0 3 ABC auto Ga (axial)

Fe 238.204 axial peak 3.0 3 ABC auto Y (axial)

Fe 259.940 radial peak 3.0 3 ABC auto Y (axial)

Na 588.995 radial peak 3.0 3 ABC auto Ga (radial)

Na 589.592 radial peak 3.0 3 ABC auto Ga (radial)

Mn 257.610 axial peak 3.0 3 ABC auto Y (axial)

Mn 260.568 axial peak 3.0 3 ABC auto Y (axial)

Zn 202.548 axial peak 3.0 3 static auto Y (axial)

Zn 213.856 axial peak 3.0 3 ABC auto Ga (axial)

1 Automatic Baseline Correction

2 Y 371.030
3 Ga 294.364

Results and Discussion

Prior to the analysis, the samples were degassed using the approaches of degassing by a an argon stream (60 min) and
sonication (20 min). Since the differences of the obtained concentrations and precision values (RSD) are negligible,
sonication demonstrates the more practical sample preparation technique due to the shorter processing times and its
straightforward approach to process multiple samples at the same time.

Table 4 displays the as-recorded spectra of a beer sample for copper at 327.396 nm and zinc at 202.548 nm including
their spectral surrounding. It can be seen that lines which are amongst the most sensitive ones for the respective
element are base-line separated from their spectral vicinity and hence interference-free.

Verification of the obtained results was performed via multi-line evaluation of each analyte. The evaluation of two lines
for each element shows excellent accuracy with deviations of less than 3% for each line pair. Furthermore, excellent
precision of RSD values far below 1% and QC recoveries within ±5% were achieved. All results are summarized in
Table 5.

Table 4: Collection of high-resolution spectral data and applicability of the CSI tool

Cu327.396 Zn202.548
4 Direct Analysis of Beer by HR ICP-OES

Table 5: Overview of the results for a representative beer sample

Ar gas stream Sonication

Line LOD1 Recovery
Element Concentration RSD Concentration RSD
[nm] [µg/L] [%]
[mg L-1] [%] [mg L-1] [%]

Ca 315.887 38.8 0.3 38.3 0.8 0.80 99

Ca 317.933 38.7 0.7 38.4 0.7 1.01 99

Cu 324.933 0.110 0.8 0.108 0.9 0.25 105

Cu 327.396 0.110 0.6 0.111 0.6 0.84 103

Fe 238.204 0.021 2.1 0.024 5.8 0.07 96

Fe 259.940 0.021 0.4 0.023 0.3 0.05 95

Na 588.995 19.9 0.5 20.6 0.3 4.51 103

Na 589.592 19.8 0.6 20.5 0.9 4.80 103

Mn 257.610 0.064 0.3 0.065 0.4 0.02 98

Mn 260.568 0.064 0.6 0.065 0.4 0.03 99

Zn 202.548 0.018 0.2 0.018 0.1 0.06 95

Zn 213.856 0.018 4.9 0.019 1.8 0.14 105

1 Matrix-specific detection limit obtained from 3σ of SD for QC matrix blank

Conclusion
The analysis of beer for trace and major levels of metals represents a routine task in quality control laboratories. The focus
is on achieving highly accurate and precise results with a robust and reliable methodology. This application note describes a
straightforward approach starting at the sample preparation routine of degassing the samples. Within this study, degassing
via sonication proofed to be the most convenient approach due to a rather short processing time and the ability to process
many samples in parallel.

Sample dilution is an often required approach to reduce the matrix load within the plasma and hence to obtain sufficient
accuracy and precision of the results. The PlasmaQuant 9100 Elite allows for a direct measurement of undiluted beer
samples, which minimizes sample preparation efforts, reduces the risk of contamination and enables lowest limits of
detection. The analysis of high TDS samples such as neat beer greatly benefits from a vertical torch concept in combination
with a powerful RF generator to ensure long term stability of the measurements as well as reliable excitation of the samples.
Here the PlasmaQuant 9100 Elite offers the unique V-shuttle torch, which ensures easy handling and maintenance and
exceptionally long-term stability for the analysis of demanding samples. Excellent method robustness with RSD values well
below 1% was achieved by the instruments High-Frequency Generator and the use of a sample introduction kit specific to the
analysis of matrix-rich samples.

Due to the high spectral resolution (2 pm @ 200 nm) of the PlasmaQuant 9100 Elite, an interference-free analysis of
all investigated elements is possible. Thus time-consuming data analysis of multi-line evaluation becomes obsolete.
The PlasmaQuant 9100 Elite delivers results of highest confidence by single line evaluation in a routine task such as the
analysis of beer. The PlasmaQuant 9100 Elite executes this analytical task with high matrix samples including varying
concentrations of ethanol in a precise and robust manner and achieves low limits of detection in the sub-ppb range. At the
same time major levels can be quantified from one measurement by exploiting the wide working range of the DualView Plus
plasma observation modes. Single-line evaluation and the absence of sample dilution reduce analysis time significantly. The
PlasmaQuant 9100 Elite therefore is the ideal instrument for the analysis of metals in beer samples.

This document is true and correct at the time of publication; the information within is subject to change. Other documents may supersede this document, including technical modifications and
corrections.

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