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Chemometrics in Brewing—A Review

Karl J. Siebert

To cite this article: Karl J. Siebert (2001) Chemometrics in Brewing—A Review, Journal of the
American Society of Brewing Chemists, 59:4, 147-156

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Chemometrics in Brewing—A Review
Karl J. Siebert,1 Food Science and Technology Department, Cornell University, Geneva, NY 14456
ABSTRACT
J. Am. Soc. Brew. Chem. 59(4):147-156, 2001
Chemometrics is the application of principles of measurement science
and multivariate mathematics and statistics to efficiently extract maxi-
mum useful information from data. It can be applied to sensory, chemical,
and biological measurements and typically is applied when multiple
measurements are made on a set of samples. Exploratory data analysis
(EDA) is often used to simplify and gain better understanding of large,
complicated data sets. EDA can also be used to determine how many
fundamental properties are represented in a data set and the extent to
which measurements are redundant. Pattern recognition (PARC) can be
used to identify the cultivar or growing area of a raw material or the
brand or production plant in which a product was made from its pattern of
analytical results. Advanced PARC procedures can detect adulteration or
be used for multivariate quality assurance or quality control. Empirical
modeling has many applications, including development of analytical
methods, discerning the relationships between product composition and
sensory properties, developing knowledge of relationships between
molecular structure and biological properties, and developing control
algorithms for unit operations or processes.
Keywords: Empirical modeling, Exploratory data analysis, Pattern rec-
ognition, Statistical experiment design
RESUMEN
Quimiometría en cervecería: Una revisión.
La quimiometría es la aplicación de los principios de la ciencia de
medir y de las matemáticas y de la estadística multivariantes, para extraer
de manera eficaz el máximo de información útil a partir de los datos. Se
puede aplicar a medidas sensoriales, químicas y biológicas y,
normalmente, se emplea cuando se efectúan múltiples medidas sobre un
mismo conjunto de muestras. El análisis exploratorio de datos (EDA) se
utiliza a menudo para simplificar y alcanzar un mejor conocimiento sobre
grandes y complicados conjuntos de datos. El EDA también puede
emplease para determinar cuantas propiedades fundamentales están
representadas en un conjunto de datos y hasta que punto las medidas son
redundantes. El reconocimiento de pautas (PARC) se puede utilizar para
identificar la variedad o la zona de cultivo de una materia prima, o la
marca o la planta de producción en la que un determinado producto fue
fabricado, a partir de su patrón de resultados analíticos. Los
procedimientos avanzados de PARC pueden detectar adulteraciones o ser
empleados en el análisis multivariante de la calidad o en el control de la
misma. La creación de modelos empíricos tiene muchas aplicaciones, que
incluyen el desarrollo de métodos analíticos, el esclarecimiento de las
relaciones entre la composición de un producto y sus propiedades
sensoriales, el desarrollo del conocimiento sobre las correlaciones entre la
estructura molecular y las propiedades biológicas y el desarrollo de
algoritmos de control para determinadas operaciones o procesos.
Palabras clave: Creación de modelos empíricos, Análisis exploratorio
de datos, Reconocimiento de pautas, Diseño estadístico de experi-
mentos.
We increasingly appreciate that many phenomena of interest to
us in brewing are multivariate in nature. In other words, a single
factor is often not enough to completely account for a behavior.
Frequently, several factors in combination are responsible for a
1 Phone: 315/787-2299; Fax 315/787-2284, E-mail kjs3@cornell.edu
Publication no. J-2001-0912-01R.
© 2001 American Society of Brewing Chemists, Inc.
147
phenomenon or for our perception of it. For example, our overall
perception of beer quality involves flavor (olfaction and taste) as
well as several aspects of visual appearance (color, haze, and
foam), and tactile sensations (astringency and some other aspects
of mouthfeel). Perception of beer flavor clearly depends on multi-
ple beer constituents producing multiple stimuli among our taste
and olfactory receptors. The pattern of responses results in our
overall sensation. We can approach this analytically and focus on
individual flavor notes, but we know that, in most cases, each of
these in turn is caused by a number of similarly flavored com-
pounds that are perceived to some degree jointly. Most of the
other phenomena of greatest importance to consumers and brew-
ers also result from several beer constituents interacting. To
improve our understanding of these combined effects, it is neces-
sary to use multivariate thinking and multivariate methods.
Chemometrics is the application of statistical and mathematical
methods as well as the principles of good measurement science to
efficiently extract useful information from chemical data. The
sheer volume of large data sets with multiple measurements can
make them difficult to thoroughly explore and understand, but
that is the situation we are frequently faced with. The application
of good experiment design principles to collect data that is maxi-
mally useful for the intended purpose saves resources, including
time and money. Procedures that remove redundancy and noise
and extract the essential sense of a data set are extremely
valuable.
Chemometrics was developed beginning in the late 1960s (47).
One of the major spurs to its development was a change in the
nature of data sets and the recognition that this presented prob-
lems with many of the traditional statistical approaches. At the
time that many statistical methods were developed, samples were
cheap and measurements were expensive. For example, experi-
ments often produced many samples while measurements were
conducted rather laboriously using wet-chemical procedures. This
resulted in data sets with many samples on which relatively few
measurements had been made. Practically all statistical proce-
dures work well with this data set structure, provided that the
measurements are not highly correlated. Over time, however, the
nature of data sets changed. When a sample is a product produced
on the pilot-plant or production scale and measurements are made
by instruments that readily produce multiple results (for example,
absorbances at multiple wavelengths in spectroscopy or multiple
peaks in chromatography), the nature of the data sets is different.
Now samples are expensive, and measurements are cheap. In
other words, we tend to be confronted with data sets that have
relatively few samples and many measurements. This violates an
assumption of many statistical methods that there are significantly
more samples than measurements. Further, the assumption that
measurements are uncorrelated (have low collinearity) is never
true with spectroscopy (where absorbances at nearby wavelengths
are always highly correlated) or with chromatography of biologi-
cal systems (where many peaks move in parallel or opposition
because they are produced by common or competitive pathways).
These problems led to a need for robust procedures that will work
with problematic data. Fortunately, suitable procedures have been
developed.
Topics in chemometrics cover quite a broad range and include
exploratory data analysis, pattern recognition (PARC), statistical
experiment design, modeling and optimization, analytical method
148 / Seibert, K. J.
development and evaluation, multivariate calibration, and process
monitoring. To keep the length of this review reasonable, only a
few of these are discussed.
Applications of chemometrics in brewing have been reported in
the last 20 or so years. These have mostly been in the areas of
PARC and modeling, with a smaller number in exploratory data
analysis (EDA). In brewing we are particularly interested in
chemical measurements related to sensory perception. The most
important properties are those consumers can directly sense: fla-
vor (olfaction and taste), color, haze, foam, and possibly also
mouthfeel. Few of these are routinely measured by sensory panels
because people are expensive and rather imprecise instruments.
As a result, we tend to use instruments to control the process well
enough to keep the product’s sensory properties under control.
Some of the measurements, particularly the physical ones (color,
turbidity, and foam), give quite good indications of human
perceptions. Others, especially olfaction and taste, are much less
satisfactory because humans are so different from one another and
respond so differently than instruments do. Chemometrics can
help to elucidate the nature of the relationships between product
composition and sensory properties and between instrumental
measurements and sensory properties. A number of potential
brewing applications of chemometrics that could be beneficial
have yet to be reported.
EXPLORATORY DATA ANALYSIS
In modern chemical measurements we are often confronted
with so much data that the essential information may not be read-
ily evident. Certainly that can be the case with chromatographic
or spectral data for which many different observations (peaks or
wavelengths) have been made. Each different measurement can
be thought of as a different dimension. This makes it difficult to
visualize relationships, as many different two-way plots would be
needed. For example, if only 10 measurements were made on a
set of samples, 45 different two-way plots would be possible.
Clearly even this modest dimensionality is daunting. EDA meth-
ods enable us to greatly simplify complicated data sets by
reducing their dimensionality. The challenge is to do this by
Fig. 1. Principal component (PC) loading plot produced from visual
sensory data using descriptive analysis. (Reprinted, with permission,
from reference 4. Copyright 1999, Elsevier Science)
removing redundancy and noise while retaining the meaningful
information. A typical data set for EDA is organized with
samples as rows and measurements as columns. The major
brewing applications of EDA are analyses of sensory and chem-
ical measurements.
Two main procedures are used for EDA, principal components
analysis (PCA) and cluster analysis (CA). In PCA, an axis is pro-
jected through a multidimensional data set that captures most of
the variance (47). This typically looks much like a regression line
through a swarm of points. Each sample is then projected perpen-
dicularly down onto this axis. This captures much of the sense of
the data on the single new one-dimensional axis, or principal
component (PC), where the location of each sample along the
new axis (its PC score) is known. A second axis is then con-
structed that accounts for maximum remaining variance; this axis
is orthogonal (perpendicular in the multidimensional space) to the
first PC axis. This constraint has the effect of assuring that the
PCs are completely uncorrelated and thus represent entirely
different properties of the samples. Additional PCs are then
extracted, each orthogonal to all previously extracted, until there
are as many PCs as original measurements. Typically, most of the
information content of the system is extracted in the first few PCs
and by retaining just these, the dimensionality of the data set is
considerably reduced. It is then more readily possible to examine
a smaller number of two-way plots to detect “structure” in the
data. The plot may show the presence of outliers or the natural
tendencies of some of the samples to group together. Since the
PCs are uncorrelated, they are thought to represent different
fundamental properties of the samples, and the number judged
significant is considered to indicate how many fundamental (dis-
tinctly different) properties were contained in the original data set.
An example of the application of PCA to a sensory analysis
data set was shown in a study of human visual perception of
turbidity using descriptive analysis (4). A sensory panel was
asked to develop a list of terms describing the appearance of sam-
ples in which colloidal particles of several sizes were suspended
at different concentrations in liquids of three colors. The panel
agreed to use six terms (dark, turbid, opaque, glowing,
homogeneous, and particulate) and rated a set of samples on each
of these. The results were subjected to PCA, which indicated that
only two components were needed to account for 98% of the vari-
ance in the data set. This means that although six terms were used
by the panelists, they were responding only to two fundamentally
Fig. 2. Hierarchical cluster analysis of beers produced in different plants
(designated by numbers) of four brewing companies (designated by
letters). (Reprinted from reference 49)

different phenomena. The PC loading plot (Fig. 1) shows that
several of the terms were highly redundant. Turbid, opaque, and
glowing almost completely overlapped and were opposite to dark
on the first PC axis, while particulate and homogeneous were in
opposite directions along the second PC.
Factor analysis (47) is a variation of PCA in which PCs are
extracted, the number to retain is decided, and these are then
rotated in multidimensional space to maximize their alignment
with particular original measurements. This makes it easier to
conceptualize the meaning and interpretation of the factors.
CA reduces dimensionality by representing the “similarity” of
samples (92). Similarity between samples can be judged by
correlation between measurement results or, more frequently, by
any of a number of distance measures. The metric most often
applied is simple Euclidean distance (the vector length between
samples using the measurement values as coordinates in multidi-
mensional space). The samples with the shortest-length vector
joining them are judged to be the most similar, while those that
are furthest apart are judged to be most dissimilar. Variations of
cluster analysis include hierarchical, nonhierarchical, and fuzzy
clustering, each of which has advantages in some situations. In
hierarchical clustering, the results are usually presented as a den-
drogram indicating the degree of similarity. Samples that join
together close to the bottom are considered to be quite similar,
while those that combine near the top are quite dissimilar. This
effectively reduces the dimensionality to one. CA can be used to
represent either the similarity between samples or the similarity
between measurements. Hierarchical CA was applied to flavor
analysis data of beers produced in different breweries by four
Japanese companies (49). Some of the results are shown in Figure
2. Beers produced in different plants of three of the companies
were similar to each another, but there was overlap between beers
produced by company B and two of the other companies.
EDA has frequently been applied to brewing sensory data
(39,49,52,53). Meilgaard reviewed methods of sensory analysis
and described the application of a number of multivariate tech-
niques (52). Powers gave examples of the use of multivariate
analysis of sensory data for product formulation and quality
assurance (68). In one study, PCA was applied to sensory data
from 16 brands of beer including ales and lagers of two different
strengths each (7); plots on the first two PC axes showed separa-
tion of the samples into four classes. In another study, descriptive
analysis results for nine attributes that contributed to the mouth-
feel of 30 beers were analyzed by PCA (45); two PCs accounted
for most of the variance, and a two-way plot of the samples on
these axes separated several beer types. Factor analysis was
applied to data from a consumer sensory panel in which 40 Bel-
gian beers were rated with 119 descriptors (9); six factors were
found to be sufficient to explain 82% of the variance in the
responses and to group the beers in a meaningful way. General-
ized Procrustes Analysis, a method of multivariate transformation
of results to improve agreement between individual panelists (11),
was applied to aroma profile data of raw hops (81); three PCs
separated the samples into five groups.
EDA has also been applied to brewing chemical analysis data.
Factor analysis of chemical data (trace elements, tannins, and
protein degradation) from micromalted barleys showed differ-
ences between malting facility, barley growing region, and crop
year (33). Factor analysis of volatile compounds in Norwegian
beers brewed in several locations with several yeasts at different
fermentation temperatures resulted in three significant factors
that separated the samples according to the yeast strain,
fermentation temperature, and brewery (38). Combined beer
volatile analysis and flavor profile data were analyzed by PCA;
beers produced with two different yeast strains could be
distinguished (44).
Chemometrics in Brewing—A Review / 149
Over time, brewing companies developed and began applying
as routine procedures methods that were found to contribute some
useful information, often to solve a particular problem. In most
cases, however, the methods were never examined collectively to
see which were more or less redundant and to consider the
possibility that a well-chosen subset of procedures might provide
as much information as all of them collectively. This could be
discovered by applying PCA to results of all current analytical
methods on the same set of beers to determine how many funda-
mental properties are represented.
PATTERN RECOGNITION
Identification of samples according to some category has long
been of interest in many situations in brewing. For example, hop
cultivars are known to impart different aroma characteristics to
beer and command different prices largely based upon this, so
cultivar identification is of interest. Certain barley cultivars are
known to be suitable or unsuitable for malting, and brewers spec-
ify the proportions of the barley cultivars they find suitable in
their malts. Identification of these, as a result, has economic
value. Discrimination of culture yeasts (for example ale vs. lager)
and contaminants such as wild yeast and bacteria (especially
spoilage organisms) is often desired to monitor strain purity and
consistency. Methods of identification can be based on physical
characteristics (e.g., barley seed appearance or the morphology of
microbial cells or colonies), chemical analysis results, responses
in biochemical tests (e.g., microbial patterns of carbohydrate utili-
zation), protein or DNA fragment patterns on electrophoresis gels,
or any combination of these. All of these cases, however, are
applications of PARC.
The same techniques used for EDA can be used for unsuper-
vised PARC. This approach simply seeks to determine whether
samples tend to group according to their supposed class identity.
It is also useful in detecting outliers, which in many cases result
from errors of some sort (analytical, data transcription, etc.). Out-
liers should be investigated and, if appropriate, corrected or
removed from the data set.
Supervised PARC procedures use information about the class to
which samples are assigned to develop rules that can assign class
identity to an unknown sample from its pattern of measurement
results (92). This has many different applications in brewing,
including identification of unknown microorganisms (yeasts or
Fig. 3. Concept of soft independent modeling of class analogies pattern
recognition. Each sample class is separately modeled and completely
bounded. The class model shape depends on the number of significant
principal components.
150 / Seibert, K. J.
contaminating organisms) from their patterns of behavior,
identification of cultivars of raw materials (most notably, hops or
barley), identification of beer brands or production plants, and
detection of adulteration. The typical data set for PARC is organ-
ized with samples as rows, measurements as columns, and one
additional column containing the class assignment of each sample
(usually represented as an integer).
Techniques frequently used for supervised PARC include near-
est neighbor analysis, discriminant analysis, and soft independent
modeling of class analogies (SIMCA). In K-nearest neighbor
analysis, some integer (K) is specified, and distance (as in cluster
analysis) is used to find the K samples nearest to the one under
consideration (92). The estimated class identity of the sample
under consideration is assigned based on the class identities of a
majority of the K nearest samples. For example, if K = 3 is used
and, of the three samples closest to the one under consideration,
two belong to class B and one to class D, the sample would be
assigned to class B (majority wins).
With discriminant analysis (92), a boundary is constructed
between each pair of classes present. In two dimensions, the
boundary is a line, in three a plane, and in more a hyperplane.
Depending on which side of the boundary a sample to be classi-
fied falls, it is assigned to that class. This can have the disadvan-
tage that a sample that bears little relationship to any sample class
used to build the rules is nevertheless assigned to one of them.
SIMCA (92) operates by making a PC model of each class that
completely bounds it. After each PC is extracted, it is tested for
significance by cross-validation. If that PC is found to be signifi-
cant, another PC is extracted and tested, and so on. The dispersion
of the samples about each significant PC is used to set the
boundaries (Fig. 3). It is possible to have no significant compo-
nents for a class; this indicates that the samples represented as
belonging to a class are not homogeneous. Even in this case, it is
possible to use the sample dispersion to produce a class boundary
(in this case, a sphere about the class centroid). Classes with one,
two, or three significant PCs are represented as cylinders, boxes,
or hyperboxes, respectively. A sample being considered may fall
within a class model (in which case it is identified as belonging to
that class), outside any class envelope (in which case it is consid-
ered to not belong to any class previously defined), or into a
region of overlap of two classes (in which case it could belong to
either). Since SIMCA completely bounds the samples comprising
Fig. 4. Soft independent modeling of class analogies is useful even when
one class is surrounded by another. This occurs in adulteration problems
and in multivariate quality assurance or quality control.
a class, it has utility in situations where outliers could occur in
any direction (in a multivariate sense) from the “good” samples
(Fig. 4). That is the situation in detection of adulteration or in
multivariate quality assurance or quality control (QA/QC).
In a study made some years ago, the essential oils of many
samples of hops, including eight European and domestic varieties
that were well represented, were steam distilled and then analyzed
by capillary gas chromatography (GC) (80). The peaks were
matched up between chromatograms, and the data was subjected
to multivariate analysis with a variety of PARC procedures
including SIMCA. SIMCA classified the data more successfully
than the other techniques. However, it was interesting to note that
this technique did not find any significant PCs for one of the
cultivars, Hallertau Hallertau (HHA). While samples from all the
other cultivars were well separated (Fig. 5), those of the HHA
class overlapped two or three other classes (Fig. 6). This finding
of nonhomogeneity for HHA indicates that the samples of this
cultivar were inconsistent. Discussions with hop suppliers pro-
vided a possible explanation. HHA hops are quite disease prone,
and occasionally when a hill of these dies, the farmer may replace
it with another cultivar. As a result, the hops collected and identi-
fied as HHA may have contained some portion of a different
cultivar. Different farmers substituting to different extents or with
different cultivars would lead to dissimilarity between individual
lots of nominally HHA hops. SIMCA was able to perceive this,
and it is likely that the cultivars that were poorly separated from
HHA were those that had been partially substituted for it.
Many brewing applications of PARC have been reported. A
number of these are in the raw material area. As mentioned above,
PARC was applied to results of gas chromatographic analyses of
hop essential oil components to classify cultivars (43,80).
Polyphenol patterns of 40 barley cultivars were analyzed by PCA
but showed little difference; most feed barleys were not separated
from malting cultivars (94). PCA of analytical measurements was
used to select promising samples (quality groups) in a malting
barley development program (59). Fuzzy CA was applied to nine
chemical or physical malt analytical parameters and was able to
distinguish three groups of samples differing in steeping condi-
tions (which affected fine/coarse difference and friability) and
kilning temperature (which influenced the dimethyl sulfide
precursor) (34).
Fig. 5. Example of SIMCA. Results of analysis of hop essential oil patterns
in Saaz (¤) and Spalt (î) cultivars. (Reprinted from reference 80)

A number of studies involving classification of yeast have been
carried out. Multivariate analysis of pyrolysis GC and Fourier
transform infrared spectroscopy data was used for whole-organ-
ism fingerprinting of 22 brewing yeast strains including ale and
lager yeasts (83); results of hierarchical CA were in good agree-
ment with genotypic studies. In another study, a battery of tests
was applied to 124 wild yeast isolates from brewing culture yeast
samples (90); CA of carbohydrate assimilation patterns resulted in
11 clusters. The fatty acid composition patterns of brewing and
wild yeasts were examined by PCA and found to exhibit three
groups (60). One of the groups contained culture and nonbrewing
Saccharomyces strains. The other two were mainly Candida and
Rhodotorula species.
The various brands of beer produced in a plant could be identi-
fied on-line by applying discriminant analysis to the outputs of
two instruments (original gravity and electrical conductivity); this
was used to ensure that each beer was placed in the correct pack-
age (98).
Pattern recognition has fairly often been applied to finished
beers and often to data on the aroma volatiles of beer. The beer
brand and brewery within a multiplant company could be deter-
mined by PARC applied to beer volatile compounds determined by
GC (76). Multivariate analysis was much more successful than
univariate techniques in distinguishing between patterns of aroma
volatile compounds in beers made with different yeasts and fer-
mented at different temperatures (85). A total of 27 beer samples
from three breweries were grouped into three clusters by fuzzy
clustering of 12 volatile compounds (35); the yeast strain had
greater influence than did the brewery. Iso-α-acids in beers pro-
duced in 14 breweries were analyzed by CA (37); three groups of
samples were found, which mainly differed in iso-/co- ratio and
were not related to hop utilization. PCA of polyphenol patterns in
beers had some ability to distinguish beer types (94). PCA and
discriminant analysis of the results of beer volatile analysis enabled
classification of beer samples with 85% agreement with the results
from an expert sensory panel (63). Results from eight of 51
laboratory analyses could be used to predict taste panel rating as
“good” or “passable” with 80.5% success (58).
Instruments based on arrays of detectors, each with a somewhat
different response characteristic, are popularly called “electronic
Fig. 6. Example of SIMCA. Results of analysis of hop essential oil
patterns in Hallertau Hallertau (¤) and Hallertau Northern Brewer (î)
samples. (Reprinted from reference 80)
Chemometrics in Brewing—A Review / 151
noses.” Almost invariably, the data produced with these instru-
ments is subjected to multivariate analysis. PARC of electronic
nose patterns has been shown to be capable of making discrimina-
tions between many beer, hop, and malt samples representing
different brands, cultivars, or storage treatments (3,82,86,93).
Multivariate methods have been used to assess sensory data,
adjust quality, and design new products. PCA of 12 flavor
descriptors was able to classify beers into three flavor qualities
(good, medium, or poor) (58). Pattern recognition was applied to
beer sensory data to match product quality and ensure uniformity
between plants (89). Factor analysis, together with perceptual
mapping, was used to evaluate consumer perceptions in position-
ing a beer brand in the market (62). Multivariate methods have
also been used to design a light beer to fit a particular product
property niche in the market (39).
Possible brewing applications of PARC include detecting adul-
teration or misrepresentation of raw materials and performing
multivariate QA/QC, where it is desirable to ensure that a number
of different properties of a product are simultaneously acceptable.
Peppard described the use of PCA for multivariate QC (66).
EMPIRICAL MODELING
Modeling has played an important role in the long history of
brewing. Generally, knowledge of system behavior has proceeded
from a qualitative association, through a semiquantitative concept
to a mathematical equation describing behavior. This does not
always happen, and many relationships are still only partially
understood. However, in those cases where an equation has been
developed, it is possible to use it to make predictions and to con-
trol and optimize performance. In some cases, it has been possible
to apply first principles to a system so that the mathematical form
of the equation is well known and accepted. This deterministic
approach is more common with systems that are firmly grounded
in physics and engineering. In such cases, all that is needed is to
fit experimental data to the accepted form to determine the coeffi-
cients in the particular system. In many other cases, the precise
form of the equation is unknown or unclear, and in many cases,
not all the relevant factors have been identified. Those are the
situations in which empirical modeling is useful.
Empirical modeling makes no prior judgment about the
theoretical form or behavior of a system (47). It has broad
applicability to develop relationships that explain behavior and
that have utility for optimization. It has been applied to processes
and unit operations, development and optimization of laboratory
methods, and the identification of relationships between product
composition and physical or sensory properties.
Quite often, the principles of statistical experiment design (47)
are used to efficiently collect data of maximal utility for model-
ing. This is the case both at the screening stage and at the
response surface model stage. A frequently used experiment
design called the one-variable-at-a-time (OVAT) approach holds
all factors but one constant and sets that one at several different
levels. The results obtained are used to determine an optimum
condition. The tested variable is then set at the optimum level
and another factor is varied to find its optimum and so on. The
problem with the OVAT approach is that it is incapable of
detecting interactions between factors and is best suited to
situations of complicated curvature. Further, it will fail to find
the true optimum in a number of common situations (47). Since
most systems, at least within regions of practical interest,
demonstrate gentle curvature and interaction, the OVAT
approach is ill-suited to the real world. The principles of
statistical experiment design are to use few levels of each
independent variable but to include these levels in combinations
that span all parts of the region of interest. This has great
152 / Seibert, K. J.
leverage (high signal-to-noise ratio) for modeling and is readily
capable of detecting and modeling interactions.
Empirical modeling is typically initiated by making a list of
factors of possible relevance (47). The first stage is screening to
determine which are indeed relevant and which are not. Once the
relevant factors have been identified, their combined effects are
studied by response surface modeling. It is valid to interpolate
with empirical models but not to extrapolate beyond the condi-
tions explored in model development.
The typical data set for empirical modeling is organized with
samples as rows, independent variables as columns, and one or
more additional columns containing dependent or response vari-
ables. Any of a number of regression techniques can be used to
develop a formula relating the dependent variable to some combi-
nation of the independent variables. The regression procedures
generally used include multiple linear regression (MLR), princi-
pal components regression (PCR), and partial least squares
regression (PLS). PCR and PLS are more robust and successful
with problematic data sets (47).
An example follows in which a response surface model relating
product composition to a physical property was developed. A
model system in buffer was used to study formation of haze with
the haze-active protein gliadin and the haze-active polyphenol
tannic acid at different pH levels and alcohol contents (74). A
statistical experiment design was used to choose combinations of
conditions with considerable statistical leverage for modeling.
The combinations were prepared in buffer, and the samples were
incubated. The haze was measured in each case, and the results
were modeled by MLR. This resulted in the following equation:
log(haze) = –10.097 – 0.017 Al + 4.879 pH + 7.804 × 10–4 Gl +
0.057 TA + 3.202 × 10–3 (Al)2 – 0.548 (pH)2 – 2.816
× 10–6 (Gl)2 – 1.431 × 10–4 (TA)2 – 0.006 (Al)(pH) +
4.711 × 10–4 (pH)(Gl) – 0.008 (pH)(TA)
in which haze = haze in nephelos turbidity units, Al = percent
ethanol (v/v), Gl = gliadin (mg/L), and TA = tannic acid (mg/L).
Note that three interaction terms (Al*pH, pH*Gl, and pH*TA)
were found to be significant. Although this is a five-dimensional
model (the four independent variables plus the response variable),
it is possible to fix the levels of two of the independent variables
Fig. 7. Example of a composition-to-property model: response surface
model showing the effects of alcohol and pH on haze intensity in a buffer
model system predicted at 275 mg of gliadin and 55 mg of tannic acid per
liter. (Reprinted, with permission, from reference 74. Copyright 1996,
American Chemical Society)
at a time and graph the effect of the other two independent
variables on the response (Figs. 7 and 8).
Modeling has been more widely used in brewing than most of
the other chemometric methods. Many applications to laboratory
method development have been reported, and the use of statistical
experiment design to evaluate and improve analyses through rug-
gedness testing is an official ASBC method (1). Modeling has
also been applied to relate physical, chemical, or sensory proper-
ties to beer composition. Many examples of the use of modeling
for control of processes and unit operations have been developed.
Some of the most basic beer measurements are multivariate in
nature. Both alcohol and dissolved solids influence density and
both also affect refractive index. For many years, this principle
has been used to calculate real extract, original gravity, alcohol,
and calories from refractive index and density measurements
according to official ASBC methods. However, these properties
can be calculated more simply using multivariate equations (71).
Experiment design and response surface modeling have been
used in development of several analytical methods. Knudson and
Siebert used them to model and optimize HPLC mobile-phase
composition for analysis of hop resins (40) and for ion
chromatography (41). Siebert and Wisk used response surface
modeling to adjust Coulter Counter operating conditions to obtain
results that were numerically similar to those of microscopic
counting (77). A model of the partial molal volume of CO2 as a
function of real extract and ethanol was developed, which permit-
ted more precise measurement of the density of packaged beer
(64).
Malt diastatic power was modeled as a function of a number of
malt parameters (α- and β-amylase, limit dextrinase, protein, and
β-glucan); these accounted for 79% of the variation (26). The
object was to provide a selection tool for use in barley breeding
programs.
The ability to model multiple analytes as a function of multiple
measurements, or multivariate calibration, has been widely used
with spectral data, particularly in the-near infrared region. In the
laboratory, it has been used to measure malt moisture and protein
content (56); α-acid, β-acid, and hop storage index in hops (24);
and wort extract and fermentability (78). It has been used to
Fig. 8. Example of a composition-to-property model: response surface
model showing the effects of protein (gliadin) and polyphenol (tannic
acid) concentrations on haze intensity in a buffer model system predicted
for 6% (v/v) alcohol and pH 3.7. (Reprinted, with permission, from
reference 74. Copyright 1996, American Chemical Society)

measure alcohol, original gravity, and calories in beer for on-line
blending control (50).
Empirical models that predict product properties as a function
of composition have been constructed. Both human and
instrumental perception of haze as a function of particle size and
concentration and solution color were modeled (4). The approach
was used to predict haze intensity as a function of protein and
polyphenol concentrations, pH level, and alcohol content in the
example described above (74). Similar approaches were used to
model the rate of haze development in beer as a function of sensi-
tive protein and dimeric proanthocyanidin concentrations (51) or
beer haze as a function of package air content, MgSO4 precipi-
table nitrogen, iron, and pH (42). CA of results of colloidal stabil-
ity prediction techniques was used to separate 22 beers into two
groups according to brewery process details; it was then possible
to use PLS to develop colloidal stability predictions for each
group that were far better than predictions based on the data for
the two groups combined (36).
Foam behavior in beer has been modeled in a number of stud-
ies. Some of the behavior could be accounted for as a function of
Coomassie Brilliant Blue responsive protein (75). The effect of
individual malt proteins and nonstarch carbohydrates on beer
foam was studied in more detail, and an equation accounting for
82% of the variation in foam stability was obtained by stepwise
MLR (17). Another study showed excellent prediction of foam
collapse times from a response surface model based on bitterness
units, pH, real extract, and high molecular weight protein (54).
For some time, it has been of interest to associate particular
aspects of beer flavor with individual compounds. Models of beer
flavor as a function of beer volatile compounds and other chemi-
cal analysis data were described by Clapperton in 1979 (6) and by
Moll and coworkers in 1981 (57). A model of beer fruitiness as a
function of volatile compounds was published by Winell and
coworkers in 1979 (96). Peppard et al associated some com-
pounds derived from hop oil with particular hop aromas using
PLS (67). An even more ambitious goal was prediction of beer
flavor quality from analyses of the barley and malt from which
the beer would be made (57).
Flavor staling has also been investigated by empirical model-
ing. Models of stale flavor development in beer as a function of a
large number of volatile compounds (28,29) or electronic nose
response (88) have been developed. A response surface model of
the rate of loss of SO2 as a function of beer composition was
developed using PLS (32). A model expressing the decline of
headspace O2 as a function of ascorbic acid levels, time, and tem-
perature was developed (2).
The susceptibility of beer to spoilage by lactic acid bacteria as a
function of its composition was modeled using PLS (18).
Some models of biological or physical properties as a function
of molecular properties have been developed. A very successful
model expressing the flavor thresholds of organic acids in beer as
a function of molecular properties has been developed (72,73).
Hughes and coworkers studied the bitterness of hop resin conge-
ners as a function of the structure of iso-α-acid isomers (31).
Multivariate techniques have been widely used in investiga-
tions of human health in connection with alcohol consumption.
Among many others, these have involved the French Paradox (8),
and relationships of alcohol consumption with breast cancer (79),
high density lipoprotein (46), and waist girth (10). The incidence
of myocardial infarctions in relation to alcoholic beverage type
was also studied (25).
Many models of portions of the malting and brewing processes
have been developed. Malting studies include a model of barley
dormancy (97), models of steeping water uptake by barley
(30,55), and optimization of steeping, germination, and kilning
(48).
Chemometrics in Brewing—A Review / 153
Mashing is an area in which there has been considerable activ-
ity in model development. Models that predict amylolysis
(14,15,87) in normal mashes and fermentable sugar production in
high-temperature mashes (61) have been described. Models of
cytolysis (15) and proteolysis (13) during mashing have also been
reported, as has a model that predicts the extent of starch hydroly-
sis and levels of β-glucans and proteins (27).
A model of hop utilization in the kettle as a function of carbon-
ate hardness, Mg2+ and Ca2+ concentrations, wort pH, boiling and
holding times, fermentation temperature, and yeast recycling was
developed (95).
A number of models of different aspects of fermentation have
been developed. A response surface model that predicts alcohol
production as a function of metal ions in a defined medium was
described (20). Models of production of alcohols (21,84), esters
(23,84), volatile compounds (70), and ethanol (16) in terms of
beer fermentation conditions have been developed. A model of
vicinal diketone level as a function of wort amino acid composi-
tion (5) and a model of diacetyl level in terms of fermentation
conditions (22) were reported. A model of yeast flocculation as a
function of cells in suspension, power input, and flocculating
strength was developed (91).
Filtration models have been developed to choose appropriate
grades of filter media (69) and to adjust dosing of diatomaceous
earth as a function of beer solids loading (19).
Response surface modeling has been used to relate can filling
parameters to the fill level and O2 content achieved (65). Model-
ing of the heat penetration of bottles as a function of their physi-
cal parameters was accomplished with MLR (12).
Obviously, there is a tremendous range of possible applications
of modeling to develop better understanding and control of many
aspects of the malting and brewing processes. One of the
possibilities in the laboratory and on-line sensor arena is to put to
greater use multivariate calibration for determination of multiple
analytes. Yet another possibility, as yet unreported in brewing, is
the use of multivariate calibration to determine analytes in diffi-
cult matrices without prior separation.
CONCLUSIONS
Chemometrics offers great potential for efficiently extracting
useful information from large and complicated brewing data sets.
It has been applied over the last 20 years and has great promise
for the future. One possibility is the use of exploratory data analy-
sis to reduce the number of routine measurements in the QC lab.
Pattern recognition can be used to detect adulteration of raw
materials and to carry out multivariate QA/QC. Statistical experi-
ment design and empirical modeling can lead to predictions and
optimization of product properties as a function of composition,
better models for predicting product shelf life, and better models
for process control.
ACKNOWLEDGMENT
This material is based upon work supported by the Cooperative State
Research, Education and Extension Service, United States Department of
Agriculture, under Project NYG-623-496.
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[Received March 1, 2001. Accepted April 13, 2001.]