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Sensory and Monosaccharide Analysis of Drip Brew Coffee Fractions versus


Brewing Time

Article  in  Journal of the Science of Food and Agriculture · February 2020


DOI: 10.1002/jsfa.10323

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Research Article
Received: 29 June 2019 Revised: 3 December 2019 Accepted article published: 7 February 2020 Published online in Wiley Online Library:

(wileyonlinelibrary.com) DOI 10.1002/jsfa.10323

Sensory and monosaccharide analysis of drip


brew coffee fractions versus brewing time
Mackenzie E Batali,a Scott C Frost,a Carlito B Lebrilla,b
William D Ristenpartc* and Jean-Xavier Guinarda

Abstract
BACKGROUND: The composition of drip brew coffee versus brewing time has been chemically characterized in previous studies,
and it is known that the total dissolved solids (TDS) systematically decreases with each fraction during the brew. Little informa-
tion exists regarding the corresponding sensory attributes versus time, however, and it is unclear how TDS correlates with fla-
vor profile.
RESULTS: Standard drip brews were fractionated into distinct samples by switching in an empty carafe every 30 s during the
brew. Using a trained sensory descriptive panel, we found that most taste and flavor attributes decreased with brew time;
for example, the earlier fractions were systematically more bitter and more sour than later fractions. Surprisingly, however, sev-
eral flavor and taste attributes increased in time; for example, later fractions were systematically sweeter and more floral than
earlier fractions. Since later fractions had lower TDS, these results indicate that perceived sweetness in drip brew coffee is neg-
atively correlated with TDS. Mass spectrometry measurements of the monosaccharide content in the brews showed that none
of the fractions had perceptible concentrations of any monosaccharide.
CONCLUSION: The results of the sensory analysis and the monosaccharide analysis suggest that perceptible sweetness in coffee
is a consequence of masking effects and/or the presence of sweet-associated aromas and flavors. The results further suggest
that unique flavor profiles could be obtained from the same coffee grounds by judicious combinations of specific fractions.
© 2020 Society of Chemical Industry
Supporting information may be found in the online version of this article.

Keywords: Coffea arabica; descriptive analysis; mass spectrometry; monosaccharides

INTRODUCTION extraction over time, showing that a brew time of 10–11 min will
Coffee flavor and taste are the result of a complex relationship of extract 90% of the material in coffee,8 and that the majority of
volatile aroma compounds and nonvolatile carbohydrates, acids, antioxidants (which can contribute to sourness and bitterness)
melanoidins, antioxidants, and lipids.1–3 These components are are extracted in the first 75–150 s of drip brew.9 Other studies
influenced by factors ranging from the genetics of the plant all have characterized how aroma compounds are extracted relating
the way to brewing,4 with over 100 important sensory attributes to polarity and volatility, and have demonstrated that more polar
identified in the official Coffee Taster's Flavor Wheel.5 (and therefore more water-soluble) compounds are extracted
The coffee industry has generally conducted drip brewing fol- early.10 Furthermore, sweetness is a desirable sensory property
lowing the guidelines of the Coffee Brewing Control Chart and for coffee consumers,11,12 and coffee is known to have sucrose,
associated Coffee Brewing Handbook, which relates total dissolved oligosaccharides, and polysaccharides in green, roasted, and
solids (TDS) to percentage extraction (PE) as an index of the sen- brewed coffee in varying quantities.13–15
sory quality of coffee.6,7 This approach, which was originally Despite the prominence of TDS as a key metric for brewed cof-
developed by Lockhart in the 1960s, has not been rigorously fee, few published studies have looked directly at the relationship
updated as understanding of coffee composition and flavor has
expanded. A detailed picture into the sensory and chemical pro-
files of coffee based on extraction parameters will give brewers * Correspondence to: WD Ristenpart, Department of Chemical Engineering,
a clearer understanding of how to extract exactly the flavors they University of California, Davis, One Shields Avenue, Davis, CA 95616, USA,
E-mail: wdristenpart@ucdavis.edu
want. For example, anyone who has watched a drip brew in pro-
gress will agree that the extraction and resulting sensory and a Department of Food Science and Technology, University of California, Davis,
chemical profiles change as a function of time; it is readily Davis, CA, USA
observed that the first brewed coffee that comes out is stronger
b Department of Chemistry, University of California, Davis, CA, USA
than the coffee that comes out later. Quantitative measures of this
behavior and corresponding impact on the sensory qualities, c Department of Chemical Engineering, University of California, Davis, Davis,
however, are lacking. Past studies have looked at chemical CA, USA
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between TDS and sensory properties. Although the TDS of the feedback on their performance (i.e. ability to discriminate, repro-
coffee exiting the brew basket clearly decreases over the course ducibility, and concept alignment).
of the brew, it is unclear how the sensory properties of the brew,
such as sweetness, sourness, and bitterness, and the correspond- Descriptive analysis testing procedure
ing TDS vary with time. To compare samples, a generic descriptive analysis that com-
The objective of this study was to measure the sensory and bined elements of the quantitative descriptive analysis and spec-
physical properties of a drip brew from a commercial coffee trum methods16 was performed using RedJade sensory science
machine, where the carafe was changed every 30 s to collect ‘frac- software (RedJade Sensory Solutions LLC, Redwood City, CA,
tions’ of the brewed coffee. The individual fractions were evalu- USA). Sixteen flavors, one mouthfeel, and the five basic tastes
ated by trained descriptive sensory panelists16 for intensities of were retained for evaluation (Table 1). The individual fractions
22 attributes. The TDS was measured for each fraction; likewise, were served in a blind randomized Williams Latin square block
to investigate the chemical basis of sweetness, the total and free design, randomized across panelists and replicates to minimize
monosaccharide compositions of each fraction were measured the effects of sensory fatigue on the results, with codes generated
by mass spectrometry. The experiments were designed to yield from RedJade to prevent sample recognition. Participants were
insight into the correlations between the sensory and physical seated in isolated, temperature-controlled, and red-lit sensory
attributes of brewed coffee. booths. Three to five participants were served per session, each
receiving 20–30 g of each coffee served between 60 and 65 °C,
in white ceramic mugs. Panelists recorded attributes via an iPad
MATERIALS AND METHODS logged in to RedJade, with a 15 cm unstructured line scale for
Coffee preparation each specific sensory attribute from ‘low’ to ‘high’. Participants
were served one sample at a time and evaluated all nine samples
Excelso European Prep grade Coffea arabica from the Huila region
(eight fractions and one ‘whole brew’) in a 1 h session, with a
of Colombia, donated by Java City Coffee Roasters in Sacramento,
1–2 min break to rinse their mouths with water and unsalted sal-
CA, was roasted to an Agtron score of 54. Whole beans were
tine crackers between samples. Three trial replicates were tasted
stored in 450 g quantities, vacuum sealed in a −20 °C freezer until
on three separate tasting days.
the day of evaluation, when they were brought to room tempera-
ture. Thawed coffee beans were ground to setting 5 (‘percolator’) Physical measurements of coffee samples
on a Mahlkönig Guatemala grinder, yielding a particle size of
Small aliquots of coffee from each fraction were cooled to room
1200 ± 44 μm.17 Commercial drip brewers (Wilbur Curtis Co. G4
temperature in sealed containers, and the TDS was measured with
Gold Cup) were used to brew the samples. Each set of fractions
a VST LAB coffee refractometer (Cambridge, MA, USA) using one
was brewed with 210 g of ground coffee and a 3.8 L dose of water
drop of the cooled coffee. Independent calibration tests of the
at 91 °C dispensed continuously for 3 min 20 s, followed by a
mass of dissolved solids remaining after drying indicated the
2 min ‘drip out’ where the brewed coffee continued to drain by
refractometer yielded excellent measurements of the TDS (see
gravity. Stainless steel 1 L thermal carafes were used to collect
Supporting Information Fig. S1). Measurements of the TDS were
the respective fractions (1 through 8) in 30 s time increments,
taken for every fraction and whole brew during every replicate.
with the timer starting upon observation of the first drip. The mass
of coffee collected in each fraction was measured to determine
Monosaccharide analysis
the average flow rate for that fraction; note that earlier fractions
Preparation for monosaccharide analysis
had lower masses because of water absorption into the initially
Samples of the brewed coffee were saved in 10 mL cryovials in a
dry grounds.18 A second full brew under equivalent conditions
−20 °C freezer prior to chemical analysis. Methods presented here
was also performed without fractionating to yield a ‘whole brew’
for workup were based on work by Xu et al. then refined for mono-
sample. One full set of nine samples (eight fractions and one full
saccharide composition of polysaccharides by Amicucci et al.19,20
brew) was brewed per day, with panelists returning three times
For total monosaccharide analysis, frozen brewed coffee samples
on different days to complete three tasting replicates. Serving
(fractions 1–9 from Table 2, along with the whole brew sample)
began 30 min after brewing.
were vortexed and aliquoted in a 96-well plate for hydrolysis.
Dry and spent grounds were put into a 10 mg mL−1 solution with
Panel recruitment and training water and blended in a Storm 24 Bullet Blender made by Next
Panelists were recruited from the UC Davis community, giving Advance (Averill Park, NY, USA) with 1.4 mm stainless steel beads,
preference to those who had previously served on descriptive heated at 100 °C for 1 h, and then blended again and aliquoted
analysis panels and who were regular coffee drinkers. Twelve pan- into a 96-well plate for hydrolysis. All of these samples were
elists between 20 and 35 years old were selected and underwent performed in triplicate. Standard-curve solutions containing
5 weeks of training twice per week. 14 monosaccharides (fructose, allose, mannose, glucose, galac-
Panelists used the Coffee Taster's Flavor Wheel for reference tose, xylose, arabinose, ribose, fucose, rhamnose, glucuronic
and were given the opportunity for term generation across the acid, galacturonic acid, N-acetylglucosamine, and N-acetyl-galac-
training set of coffees.5 The most commonly generated terms tosamine, purchased from Sigma Aldrich, St. Louis, MO, USA or
were put on an unlabeled line scale, and panelists ranked four dif- Fisher Scientific, Waltham, MA, USA) were prepared at concentra-
ferent coffee samples on each attribute. Further training was per- tions ranging from 1 ng mL−1 to 100 μg mL−1. The food and poly-
formed using flavor/taste references spiked directly into the saccharide standard solutions underwent acid hydrolysis with
evaluation sample coffee, as well as Folgers instant coffee, to com- trifluoroacetic acid (TFA). Upon completion of hydrolysis, samples
pare attribute intensity (Table 1). Panelists also underwent an were quenched with cold water.
assessment session in the booths, with identical serving condi- Aliquots of TFA-hydrolyzed coffee samples (for total monosaccha-
tions as the final evaluation, after which all judges received ride analysis), untreated coffee samples (for free monosaccharide
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Table 1. Consensus attribute descriptions and preparation method for descriptive analysis standards

Attribute Description Aroma reference in training Flavor/taste reference in training

Bitter Basic taste of bitter 0.0085 g/0.017 g/0.029 g Prolab


caffeine pills crushed per 1 g Folgers
instant coffeea
Sour Basic taste of sour 0.013 g/0.025 g/0.043 g citric acid per
1 g Folgers instant coffee
Salty Basic taste of salty 0.5 tbsp table salt in sample coffee
Sweet Basic taste of sweet 0.5 tbsp baking sugar in sample coffee,
0.85 g/1 g/1.15 g baking sugar per
1 g Folgers instant coffee
Umami Basic taste of savory 1% monosodium glutamate solution in
water
Smoky/Burnt Liquid smoke, charcoal, ash 5 drops liquid smoke dried under a
vent in a mug
Tea/Floral Black tea/tannic, chamomile, 1 pack each Lipton black tea and
dried floral Celestial Seasonings chamomile
tea dry
Caramelized Brown sugar, maple syrup, 1 tbsp brown sugar drizzled with 0.5 tbsp brown sugar in sample coffee
molasses maple syrup
Cereal Dried cereal, grain, oat, 50/50 grape nuts and Chex
woody, musty
Fruity Apple, peach, pear (fruit and 2 tbsp unsweetened applesauce 1 tbsp pear syrup from fruit cups in
juice) sample coffee
Meaty/Brothy Beef broth 2 tbsp Campbell's beef broth
Rubber Rubber band Rubber band
Citrus Lemon juice, fresh lemon 2 tbsp of lemon juice 1 tbsp lemon juice in sample coffee
Nutty Almond, hazelnut, peanut Equal parts crushed almond, 5 drops almond extract in sample coffee
hazelnut, and peanut
Berry Blackberry, blueberry, Smucker's blackberry jam and 1 tbsp Smucker's blackberry jam in
cranberry frozen cranberries, microwaved sample coffee
30 s
Dried fruit Prune/prune juice Dried prunes with 1 tbsp prune 1 tbsp prune juice in sample coffee
juice, microwaved 30 s
Green/Vegetative Cooked spinach, olive oil, 2 tbsp canned spinach, drizzled with 1 tbsp olive oil in sample coffee
herbs olive oil
Alcoholic/Winey Sour, fermented, winey, 2 tbsp red wine
ethanol
Vinegar White vinegar, pungent, 2 tbsp white vinegar 1 tbsp white vinegar in sample coffee
acidic
Honey Honey, floral sweetness 1 tbsp honey 1 tbsp honey in sample coffee
Cocoa Cocoa powder, dark 1 tbsp Hershey's cocoa powder 1 tbsp Hershey's cocoa powder in
chocolate sample coffee
Astringent Mouth drying, puckering 0.07% solution of alum in water, or
0.026 g/0.043 g/0.06 g alum per 1 g
Folgers instant coffee
a
Coffee in training was brewed with 85 g water per 1 g Folgers instant coffee.

analysis), and monosaccharide standard curves were added directly 6495 triple quadrupole mass spectrometer coupled to an Agilent
to polypropylene 96-well plates containing ammonium hydroxide 1290 Infinity II ultrahigh-performance liquid chromatograph. Sepa-
(NH4OH) and 1-phenyl-3-methyl-pyrazolone (PMP) in methanol ration was performed on an Agilent Zorbax C18 column
and incubated at 70 °C. Samples were then dried to completion (2.1 mm × 100 mm i.d., 1.8 μm particle size, Santa Clara, CA, USA).
by vacuum centrifugation and reconstituted in water. Two Chromatographic solvents consisted of 25 mmol L−1 ammonium
chloroform–water extractions were performed to remove excess acetate adjusted to pH 8.2 using NH4OH in 5% acetonitrile in water
PMP. The aqueous layer was collected and stored at −20 °C until (v/v; solvent A) and 95% acetonitrile in water (v/v; solvent B). The
the time of analysis. mass spectrometer was operated in positive ion mode, and
Analysis was performed using the following procedures pro- dynamic multiple reaction monitoring mode was used for data
vided by Amicucci et al.19 Samples were analyzed on an Agilent acquisition. Separation of PMP-labeled monosaccharides was
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Table 2. Mean attribute intensities for each factor, with Fischer's LSD groups indicated by letters

Attribute Fraction 1 Fraction 2 Fraction 3 Fraction 4 Fraction 5 Fraction 6 Fraction 7 Fraction 8 Whole brew LSD

Smoky/Burnt 47.58a 40.94ab 37.97b 27.36c 21.89cde 19.94de 17.03ef 10.92f 24.83cd 6.91
Tea/Floral 9.36e 7.83e 13.5e 20.92d 29.69bc 34.39b 41.83a 41.97a 23.42cd 7.34
Caramelized 21.03b 21.75ab 27.81a 17.61b 19.69b 17.22b 18.92b 20.19b 19.61b 6.28
Cocoa 24.47a 24.75a 22.44ab 15.25c 13.92cd 16.56bc 8.42d 11.47cd 16.47bc 6.14
Cereal 11.42d 13.5bcd 13.39cd 17.94abc 17.86abc 17.5abcd 19.83ab 22.03a 12.14cd 6.42
Fruity 9.81d 12.22cd 14.47bcd 15.17bcd 18.22abc 18.92ab 23.39a 12.08cd 20.19ab 6.58
Meaty/Brothy 22.11a 17.89ab 13.92bc 9.78cd 7.92d 6.81d 5.53d 6.17d 9.22cd 5.15
Rubber 24.42a 17.31b 15.36bc 10.03de 6.08e 8.39de 5.75e 7.08e 11.81cd 4.52
Citrus 19.31a 20.78a 19.58a 12.97bc 15.31ab 15.44ab 8.61c 9.75bc 20.19ab 5.71
Nutty 15.89ab 18.61ab 21.56a 19.83a 12.89b 16.44ab 17.67ab 16.92ab 17.75ab 6.16
Berry 14.11abc 13.56abc 19.03a 17.72a 15.53ab 8.36c 9.25bc 15.22ab 18a 6.78
Dried/Fruit 27.69a 23.61ab 26.67a 19.42bc 14.14cd 9.78d 13.61cd 16.08cd 23.42ab 6.67
Green/Vegetative 19.36a 18.14ab 18.31ab 16.97ab 13.72ab 16.03ab 13.03b 18.17ab 16.14ab 5.82
Alcoholic/Winey 43.47a 36.28b 25.36c 13.06d 10.64de 6.78e 5.14e 6.56e 15.25d 6.27
Vinegar 26.33a 22.19a 10.94b 8.25bcd 7.83bcd 3.69d 4.5d 5.58cd 10.25bc 5.14
Honey 6.97b 9.89b 8.89b 11.31b 18.31a 19.89a 18.64a 22.25a 9.08b 4.88
Astringent 42.67a 41.19ab 35.08bc 28.19d 29.28cd 28.39cd 20.61e 24.89de 31.03cd 6.88
Bitter 56.56a 47.89b 41.03c 31.53de 26.19ef 20.81fg 19.75g 21.06fg 35.53d 5.41
Sour 55.89a 52.03a 38.69b 27.64c 23.53cd 18.89de 15.92ef 11.47f 37.44b 5.38
Sweet 9.92e 13.64de 17.53cd 19.31c 24.86b 27.39b 34.11a 29.97ab 18cd 5.38
Salty 12.14a 10.97ab 6.42bc 6.39c 6.22c 5.25c 4.36c 5.92c 7.53bc 3.50
Umami 20.69a 18.06a 10.42bc 8.81bcd 7cd 6.92cd 5.33d 4.67d 11.5b 4.31

performed using the parameters developed by Xu et al., with an of judge effect.21 One attribute (Cereal) was dropped. All factors
optimized 10 min binary gradient of 12–15% B at 0–7 min, 99% B determined to be significant by ANOVA were then analyzed using
at 7.1–8.5 min, and 12% B at 8.6–10 min.20 All measurements used Fisher's least significant difference (LSD) through the Agricolae
a flow rate of 0.5 mL min−1 and a column temperature of 35 °C. package. Total and free monosaccharide concentrations were
Data analysis was performed on the Agilent Mass Hunter B.08 quan- analyzed by a two-way ANOVA, with Fisher's LSD run through
titative analysis software and peaks were automatically integrated. the Agricolae package to determine significant differences
To account for the addition of water during hydrolysis, the concen- among samples. Principal component analysis22 biplots were pro-
tration of each monosaccharide was multiplied by a correction fac- duced in R using the FactoMineR package, the factoextra package,
tor derived from the ratio of the monosaccharide residue molar and the ggplot2 package to select for significant attributes and
mass to the monosaccharide molar mass. visually represent the outcomes. Pearson's correlations were cal-


Free monosaccharide concentration×Monosaccharide molar mass g mol−1 −18 g mol−1
Bound monosaccharide concentration = 
Monosaccharide molar mass g mol−1

Free monosaccharides were analyzed without hydrolysis; so, for culated in R using the ‘cor.test’ function both between attribute
those, the correction factor was not used. and TDS with significance determined at ⊍ = 0.05. The attribute
correlation table was plotted with the Corrplot package with sig-
nificance determined at ⊍ = 0.05.
DATA ANALYSIS
Descriptive analysis results were exported from RedJade, convert-
ing positions on the 15-point line scale into scores on a scale from RESULTS
0-100 for each attribute. R version 3.5.3 ‘Great Truth’ (R Core Team, Physical measures of coffee
2019) was used to perform a three-factor analysis of variance The measured TDS and dispensed coffee mass for each individual
(ANOVA) with two-way interactions across panelists, samples, fraction, as well as the full brew, are shown in Fig. 1. The TDS of the
and replicates to determine which attributes were significant, cal- first fraction was highest, at about 3%, and then decreased sys-
culated at ⊍ = 0.05. F values were adjusted from the original tematically to about 0.3% by fraction 8 (Fig. 1(A)). The standard
ANOVA by performing a pseudomixed ANOVA to calculate new deviation for the TDS in the early fractions was larger, approxi-
F ratios and determine which attributes were significant in spite mately ±0.5%, compared with the more consistent later fractions
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Figure 1. Boxplots of (A) total dissolved solids (TDS) percentage by fraction and (B) coffee mass by fraction (n = 9). Fraction 1: 0–30 s; fraction 2: 31–60 s;
fraction 3: 61–90 s; fraction 4: 91–120 s; fraction 5: 121–150 s; fraction 6: 151–180 s; fraction 7: 181–210 s; fraction 8: 211 –240 s; fraction 9 (only for phys-
ical and chemical evaluations, 241–300 s); and whole brew (WB): 0–300 s.

with a standard deviation of approximately ±0.03%. The TDS increased in intensity over the course of the brew: Sweet taste,
increased slightly in the final ‘drip out’ phase collected in Tea/Floral, Honey, and Fruity flavor. These four attributes
fraction 9, the last minute of the brew. The whole brew (unfractio- increased and then plateaued in intensity at the end of the brew
nated) sample had a TDS of 0.84 ± 0.05%. except in the case of Fruity flavor, which exhibited a slight
The corresponding mass flow rates steadily increased from decrease between fraction 7 and fraction 8.
fraction 1, with an average of 141 g per 30 s, to a peak at A principal component analysis of all statistically significant
fraction 6, with an average of 543 g per 30 s. The slight increase attributes gives an overall view of how the samples trend across
in TDS observed after fraction 8 corresponded with the end of the attributes. The first two components, plotted in Fig. 3, account
water dispensation after 3 min, as the 2:20 drip out had a gradual for 95.8% of the variance in the products, with the coffees separat-
decrease in flow rate down to 100 g per 70 s in the last fraction of ing primarily across the first principal component, which
the brew. accounted for 93.1% of the variance. In dimension 1 we see Frac-
tion 1 on the positive side associated with all the attributes with all
Descriptive analysis attributes seen to decrease as the brew progresses. The fractions
The ANOVA showed significant sensory differences among coffee move sequentially toward the negative side, to Fraction 8 charac-
fractions for 19 of the 22 attributes (bold F values in Supporting Infor- terized most by the attributes shown to increase as the brew pro-
mation Table S1). Eighteen of those attributes also showed a signifi- gresses, particularly Sweet, Tea/Floral, and Honey. Importantly,
cant judge × sample interaction (bold F values in Supporting dimension 2 only accounts for 2.7% of the variance, indicating
Information Table S1), and therefore a pseudomixed ANOVA was that the linear spread in order of fractions on Dimension 1 is the
performed to determine which attributes were significant in spite only relevant information to describe these products.
of the judge effect. This process yielded 17 attributes significantly dif- Since the different fractions have highly different TDS values,
ferent across all samples. These attributes were Sweet, Sour, Bitter, with the TDS decreasing steadily from the first to the last fractions
Salty, and Umami taste, Astringent mouthfeel, Tea/Floral, Honey, Fru- (see Fig. 1), a natural question is how the flavor intensities corre-
ity, Citrus, Smoky/Burnt, Rubber, Alcoholic/Winey, Meaty/Brothy, Vin- late with TDS. To our knowledge, this relationship has not been
egar, Cocoa, and Dried Fruit flavors. Of these attributes, 13 were explored in existing coffee literature. Figure 4 shows the attribute
highest in fraction 1, and then systematically decreased as the brew intensity correlations to TDS for three representative sample attri-
progressed. In contrast, four attributes (Sweet, Tea/Floral, Honey, and butes. Bitter, positively correlated in Fig. 4(A), decreases as TDS
Fruity) were lowest in fraction 1 and increased significantly as the decreases. Sweet, negatively correlated in Fig. 4(B), increases as
brew progressed. The mean intensities, LSD values, and groupings TDS decreases. Berry, not correlated in Fig. 4(C), is present at rela-
for all attributes and all samples are shown in Table 2. tively consistent levels in all samples. Figure 4(D) shows the corre-
A representative subset of attributes versus fraction number is lation coefficients of all samples. As shown in Fig. 4(D), in order of
shown in Fig. 2. We highlight these attributes here because they decreasing correlation coefficient, Vinegar, Meaty/Brothy, Alco-
had large changes in intensity during the brew; data for all mea- holic/Winey, Umami, Salty, Rubber, Bitter, Sour, Astringent,
sured attributes is available in Table 2, with additional statistical Smoky/Burnt, Cocoa, Dried Fruit, and Citrus attributes were all
information in the supplementary material. Four attributes that positively correlated to TDS. In order of increasing correlation
decreased in intensity over the course of the brew were Bitter coefficient, Sweet, Tea/Floral, Honey and Fruity attributes were
and Sour taste, Astringent mouthfeel, and Smoky/Burnt flavor all negatively correlated to TDS. In total, 13 attributes were posi-
(Fig. 2(A)–(D) respectively). These four sensory attributes tively correlated to TDS, four attributes were negatively corre-
decreased significantly and systematically versus fraction number. lated, and the remaining five attributes showed no statistically
Figure 2(E)–(H) respectively show the four attributes that significant relationship with TDS.
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Figure 2. Attribute intensity by fraction for eight of the 22 attributes, with error bars and letter codes indicating significant difference based on LSD
values (Supporting Information Table S1): (A) Bitter taste; (B) Sour taste; (C) Astringent mouthfeel; (D) Smoky/Burnt flavor; (E) Sweet taste; (F) Tea/Floral
flavor; (G) Honey flavor; (H) Fruity flavor.

Figure 3. Principal component biplot showing evaluated samples (fractions 1–8 and the ‘whole brew’) and significant descriptive attributes as deter-
mined by the pseudomixed ANOVA.

Monosaccharide analysis differences between samples for all free monosaccharides (bold
After an increase in Sweet taste was measured by the descriptive values shown in F table of Supporting Information Table S2). Mean
panel, the chemical analysis on total monosaccharide and free intensities, LSD values, and groups for all measured monosaccha-
monosaccharide content was carried out to investigate the rides and all samples are shown in Table 3.
hypothesis that sugar would be responsible for the increase in Figure 5 shows the change in total and free monosaccharides
sweetness. over the course of the brew, omitting those that were measured
ANOVA of all samples showed significant differences between in less than 1.5% abundance for all samples, color coded by chem-
total monosaccharide composition of samples for all monosaccha- ical component showing relative composition. The graphs indi-
rides, aside from allose and N-acetyl-galactosamine, and significant cate the highest concentration of monosaccharides always
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Figure 4. Correlations for (A) Sweet/TDS, (B) Bitter/TDS, and (C) Berry/TDS. (D) R values for all sensory attributes to TDS showing which attributes are pos-
itively and negatively correlated with percentage TDS.

occurred in the early fractions. Specifically, the total concentra- average recognition threshold of 6.4 mg mL−1 and 3.5 mg mL−1
tions were 2.6 mg mL−1 for total monosaccharide and respectively.23 The aforementioned literature does report an
0.016 mg mL−1 for free monosaccharide in fraction 1. Both the incredibly wide range of detection and recognition thresholds
total and free monosaccharides then exhibited an overall but based on the method used and the population detected, but even
non-monotonic decrease, with the lowest concentration of mono- assuming trained sensory panelists are better than average for
saccharides in fraction 6 (0.23 mg mL−1 for total monosaccha- sweet detection, the minimum reported detection threshold
rides and 0.0018 mg mL−1 for free monosaccharides). A (0.18 mg mL−1 for glucose and 0.108 mg mL−1 for fructose) found
subsequent statistically significant but relatively slight uptick in for the most sensitive tasters is still significantly higher (by about
overall monosaccharide concentration occurred in fractions 7, 8, one order of magnitude) than the highest free monosaccharide
and 9 near the end of the brew. A statistically significant but slight concentration measured here at 0.015 mg mL−1 (see Fig. 5(A), first
increase also occurred between fractions 3 and 4, followed by a column). Additionally, monosaccharides aside from fructose and
decreased from fractions 4 to 5. Table 3 shows the concentrations glucose (making up the majority of both the total and free mono-
of all measured total and free monosaccharides, with LSD group- saccharides) are even less sweet.24 Nor do all polysaccharides
ings by letter and standard deviation based on three analytical measured in the total monosaccharide composition contribute
replicates. to perceptible sweetness. There may be some degree of enhance-
ment of sweet taste compared with literature detection and rec-
ognition thresholds based on temperature, since some studies
DISCUSSION have found that higher temperature increases perceived sweet-
The most surprising result presented here is that sweetness and ness intensity.25 Even so, the combination of decreasing concen-
several other sensory attributes increased in later fractions; that trations in later fractions and their overall low magnitudes
is, these attributes were negatively correlated with TDS. A simple indicate that the physiological perception of sugar is not the pri-
explanation would be that the later fractions actually had higher mary contribution to the perceived sweetness in any of these cof-
sugar content. However, our chemical measurements of mono- fee samples.
saccharide content do not support this hypothesis, with the If the monosaccharides are not responsible for the perceived
monosaccharide concentrations following the same general pat- sweetness, the natural question is what does drive the perceived
tern as TDS, decreasing as the coffee dilutes in the later fractions. sweetness? There are several potential hypotheses that can be
Additionally, when comparing monosaccharide concentrations put forth to explain the trends observed in the sensory analysis.
with recognition and detection thresholds found in literature, glu- It is possible that there is some degree of masking of attributes
cose and fructose have an average sensory detection threshold in from the sour‑ and bitter-tasting compounds that overpower
the range of 3.1 mg mL−1 and 1.7 mg mL−1 respectively, and an some of the other more delicate flavors, which then appear to
7

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8

Table 3. Mean and standard deviation of all measured monosaccharide concentrations with Fisher's LSD value and letter groups indicating significant differences (n = 3). All quantities reported in

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mg L−1

Monosaccharide Fraction 1 Fraction 2 Fraction 3 Fraction 4 Fraction 5 Fraction 6 Fraction 7 Fraction 8 Fraction 9 Whole brew LSD

Total monosaccharides
Fructose 150 ± 6.4ab 70 ± 28bc 70 ± 49bc 190 ± 120a 54 ± 32bc 39 ± 12c 150 ± 89ab 59 ± 31bc 120 ± 77abc 46 ± 2.6c 100
Mannose 700 ± 87a 340 ± 12b 150 ± 31c 150 ± 20c 75 ± 19de 34 ± 5.3e 29 ± 06.8e 46 ± 16de 99 ± 28cd 76 ± 6.3de 57
Glucuronic acid 6.6 ± 1.5a 4.1 ± 0.47b 2.3 ± 0.1c 1.6 ± 0.37cd 1.3 ± 0.8cd 0.58 ± 0.15d 2.2 ± 1.6c 0.78 ± 0.39d 1.6 ± 0.56cd 1.4 ± 0.18cd 1.3
Ribose 8.9 ± 0.83a 6.3 ± 0.52b 3.3 ± 0.09 c 2.9 ± 0.28cd 1.7 ± 0.32efg 1.2 ± 0.18g 1.9 ± 0.6defg 1.7 ± 0.73fg 2.8 ± 1.2cde 2.3 ± 0.16cdef 1.1
Allose 0.026 ± 0.24ab 0.75 ± 0.92a 0.38 ± 0.18ab 0.25 ± 0.21ab 0.2 ± 0.18ab 0.35 ± 0.3ab 0.25 ± 0.36ab 0.2 ± 0.17ab 0.37 ± 0.49ab 0b 0.6
Rhannose 170 ± 24a 96 ± 6b 34 ± 5.9c 21 ± 0.32cd 11 ± 1.6de 6.5 ± 0.9e 5.2 ± 0.95e 5.2 ± 0.97e 13 ± 1.5de 22 ± 1.6cd 14
Galacturonic acid 5.0 ± 0.52a 2.3 ± 0.23b 1.0 ± 0.024cd 1.4 ± 0.75c 0.64 ± 0.43de 0.33 ± 0.086e 0.68 ± 0.23de 0.45 ± 0.27de 0.87 ± 0.46cde 0.68 ± 0.17de 0.67
Glucose 170 ± 22a 100 ± 32bc 70 ± 24abc 150 ± 88bc 70 ± 63bc 27 ± 4.8c 97 ± 42abc 46 ± 22c 140 ± 67ab 40 ± 7c 0.56
N-Acetylglucosamine 1.6 ± 0.32a 1.4 ± 0.44ab 1.1 ± 0.25abcd 1.0 ± 0.26bcd 0.90 ± 0.31bcd 0.74 ± 0.41cd 0.58 ± 0.12d 0.74 ± 0.066cd 1.2 ± 0.52abc 0.91 ± 0.15bcd 0.56
N-Acetylgalactosamine 0.16 ± 0.071ab 0.12 ± 0.053ab 0.055 ± 0.071b 0.17 ± 0.061ab 0.25 ± 0.15a 0.18 ± 0.033ab 0.23 ± 0.068a 0.15 ± 0.088ab 0.19 ± 0.12a 0.18 ± 0.074ab 0.14
Galactose 700 ± 87a 390 ± 12b 170 ± 32de 240 ± 19cd 95 ± 19e 56 ± 3.3e 160 ± 62de 350 ± 210bc 140 ± 26de 120 ± 8.2de 130
Xylose 17 ± 3.5a 11 ± 1.4ab 4.1 ± 1.6bcd 110 ± 12abc 4.0 ± 1.2cd 1.8 ± 0.14d 3.0 ± 1.4d 3.4 ± 02.6d 4.2 ± 2.2bcd 3.4 ± 0.48d 67.9
Arabinose 710 ± 110a 480 ± 41b 190 ± 24c 150 ± 21cd 84 ± 6.9de 59 ± 7.8e 62 ± 9.2e 53 ± 13e 140 ± 32cd 140 ± 11cd 71.5
Fucose 1.9
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5.7 ± 1.1a 4.2 ± 0.81ab 2.3 ± 0.43bcd 3.0 ± 1.9bcd 1.9 ± 0.28cd 1.5 ± 0.31d 2.6 ± 0.93bcd 1.9 ± 0.5cd 3.7 ± 2bc 2.1 ± 0.14cd
Free monosaccharides
Fructose 3.8 ± 0.28a 3.3 ± 1.2ab 0.93 ± 0.37def 1.8 ± 0.61cde 0.93 ± 0.45def 0.36 ± 0.14f 0.91 ± 0.035ef 0.99 ± 0.09def 1.9 ± 0.93cd 2.3 ± 0.029bc 1.0
Mannose 0.43 ± 0.015a 0.34 ± 0.063b 0.099 ± 0.0048e 0.18 ± 0.012d 0.071 ± 0.0014ef 0.049 ± 0.0027f 0.1 ± 0.014e 0.09 ± 0.017e 0.16 ± 0.0063d 2.6 ± 0.0032c 0.04
Glucuronic acid 0.78 ± 0.046a 0.63 ± 0.12b 0.18 ± 0.013e 0.33 ± 0.014d 0.13 ± 0.015ef 0.087 ± 0.003f 0.2 ± 0.029e 0.2 ± 0.022e 0.6 ± 0.0028d 0.46 ± 0.032c 0.079

© 2020 Society of Chemical Industry


Ribose 0.43 ± 0.01a 0.33 ± 0.043b 0.094 ± 0.0029e 0.16 ± 0.0064d 0.065 ± 0.0021fg 0.046 ± 0.0036g 0.094 ± 0.0084ef 0.09 ± 0.012e 0.14 ± 0.015d 0.25 ± 0.00093c 0.028
Allose 0.057 ± 0.0056a 0.041 ± 0.004b 0.015 ± 0.0023e 0.022 ± 0.0025d 0.012 ± 0.0018ef 0.01 ± 0.0015f 0.015 ± 0.0034e 0.013 ± 0.0022ef 0.02 ± 0.0031d 0.035 ± 0.0043c 0.0045
Rhannose 0.61 ± 0.029a 0.44 ± 0.1b 0.11 ± 0.012de 0.13 ± 0.0078d 0.044 ± 0.0025f 0.032 ± 0.0013f 0.059 ± 0.0067ef 0.051 ± 0.0083f 0.087 ± 0.0076def 2.4 ± 0.0045c 0.057
Galacturonic acid 0.19 ± 0.0043a 0.13 ± 0.023b 0.027 ± 0.0014ef 0.042 ± 0.0025d 0.016 ± 0.0031fg 0.0098 ± 0.0012g 0.02 ± 0.000044fg 0.018 ± 0.0017fg 0.036 ± 0.0027de 0.095 ± 0.0068c 0.014
Glucose 0.87 ± 0.012a 0.93 ± 0.49a 0.32 ± 0.14b 0.59 ± 0.21ab 0.39 ± 0.28b 0.2 ± 0.023b 0.4 ± 0.12b 0.29 ± 0.047b 0.61 ± 0.39ab 0.57 ± 0.039ab 0.43
N-Acetylglucosamine 0.03 ± 0.00014a 0.03 ± 0.0096a 0.012 ± 0.0015de 0.02 ± 0.0016b 0.0087 ± 0.00075de 0.0068 ± 0.00099cd 0.014 ± 0.0023cd 0.014 ± 0.0025cd 0.019 ± 0.0018bc 0.024 ± 0.0025ab 0.0062
N-Acetylgalactosamine 0.0047 ± 0.0029ab 0.0025 ± 0.0012cd 0.0014 ± 0.00049d 0.002 ± 0.00048cd 0.0015 ± 0.0013d 0.0017 ± 0.00047d 0.003 ± 0.0011bcd 0.0035 ± 0.00045abc 0.0028 ± 0.00064cd 0.0051 ± 0.00094a 0.0018
Galactose 4.5 ± 0.21a 3.6 ± 0.66b 1.1 ± 0.047ef 2.0 ± 0.14d 0.75 ± 0.03fg 0.55 ± 0.011g 1.2 ± 0.19ef 1.2 ± 0.28e 1.9 ± 0.14de 2.7 ± 0.11c 0.45
Xylose 0.25 ± 0.027a 0.18 ± 0.041b 0.05 ± 0.0022def 0.074 ± 0.018d 0.035 ± 0.0034d 0.021 ± 0.0033f 0.04 ± 0.0035ef 0.04 ± 0.0033ef 0.054 ± 0.012d 0.12 ± 0.0057c 0.031
Arabinose 4.0 ± 0.16a 3.1 ± 0.51b 0.91 ± 0.064ef 1.6 ± 0.11d 0.65 ± 0.015fg 0.42 ± 0.023g 1.0 ± 0.11e 0.97 ± 0.17ef 1.6 ± 0.18d 2.4 ± 0.08c 0.35
Fucose 0.26 ± 0.004a 0.18 ± 0.022b 0.044 ± 0.0043ef 0.063 ± 0.0039d 0.026 ± 0.0018gh 0.016 ± 0.0024h 0.028 ± 0.0016gh 0.031 ± 0.0027fg 0.048 ± 0.0025e 0.11 ± 0.0047c 0.014

J Sci Food Agric 2020


ME Batali et al.
Analysis of drip brew coffee fractions versus time www.soci.org

Figure 5. (A) Total and (B) free monosaccharide concentrations, with monosaccharides in less than 1.5% abundance in all samples omitted. With omitted
measurements, figure shows at least 98% of all total or free monosaccharides in each sample. All mean concentrations can be seen in Table 3.

increase once those masking compounds are flushed out of the picture of the extraction profile of nonvolatile and volatile com-
grounds. Caffeine26 and bitter, astringent chlorogenic acids27 pounds to make claims as to what exactly is causing the increase
are highly soluble and would be in high concentrations in early in Sweet, Honey, Tea/Floral, and Fruity attributes at the end of the
fractions. Organic acids contributing to sour taste would be solu- brew in spite of the overall decrease in TDS. The change in extrac-
ble early extractors as well.28 The masking effect might explain the tion with flow rate is also an interesting result that opens many
perceived increase in flavor attributes; however, this observation paths for further exploration as to how flow rate impacts what
is at odds with the observation that sweet-active molecules, specific components are extracted from coffee based on differing
particularly in the later fractions, were below the reported recog- amounts of contact time, from physical, chemical, and sensory
nition thresholds for sweetness even when sourness and bitter- perspectives.
ness receded. Regardless of the precise chemical mechanisms for the
Potentially related to the masking effects, another likely factor is increased sweetness in later fractions, there are immediate practi-
the role of aroma compounds in the differences seen between cof- cal implications for the coffee industry. Our results clearly show
fee taste attributes. Prior work has shown that the perception of pronounced and systematic sensory differences among fractions,
sweetness increases in the presence of sweet-associated aromas, suggesting that very different sensory profiles could be generated
even if no sweet taste stimulation is being perceived.29 Previous from the same coffee grounds by judicious combination of differ-
chemical studies have been conducted on the rates of extraction ent fractions. For example, the same batch of coffee grounds
of various aroma compounds from coffee, with Sánchez López could be used to make a batch of bitter and smoky coffee for con-
et al.30 performing online proton transfer reaction time-of-flight sumers who prefer to use cream and sugar, and also to make a
mass spectrometry showing different groupings of when aroma batch of more sweet and floral coffee for consumers who prefer
compounds extracted during the brewing process. The aforemen- that style.
tioned results showed some flavors like guaiacol (sweet, floral,
vanilla), 4-allylguaiacol (spicy carnation floral), ethyl acetoacetate
(fruity), and 2-oxopropylacetate (fruity), extracting in the later CONCLUSION
group.30 Further chemical studies have shown that, among other Our results provide the first quantitative indication that some sen-
things, floral/honey flavored ⊎-damascenone is a less-polar, later- sory attributes in brewed coffee (Sweet taste, Tea/Floral, Fruity,
extracting compound.10 Thus, there is some chemical literature and Honey flavors) are negatively correlated with TDS. Chemical
that corroborates the sensory results of increase in Honey, Tea/- analyses demonstrated that the perceived sweetness is not due
Floral, and Fruity flavors, and these may be sufficiently sweet- to any monosaccharides extracted during the brew, since both
associated aromas. Coupled nosespace analysis with temporal the total and free monosaccharide concentrations were well
dominance of sensation in coffee has indicated that an increase below the detection threshold of any sugars. In other words, our
in sweetness by added sugars also increased the dominance of data indicate the perceptible sweet taste is not related to the
certain aromas, such as roasted, caramel, and nutty.31 This behav- physiological perception of coffee carbohydrates. This finding
ior suggests that the inverse effect might also be operative, where helps motivate multiple new hypotheses for the driving factors
an increase in those aromas may result in increased perceived of perceived sweetness in black coffee, and further analysis
sweetness, as has been reported in non-coffee products. should investigate the relationship between TDS and perceived
The ambiguity left by the monosaccharide analysis indicates the sweetness, or aroma intensity and perceived sweetness. Nonethe-
need for further chemical analysis; there is not a complete enough less, understanding the timing of attribute extraction allows
9

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www.soci.org ME Batali et al.

coffee brewers to customize their process in order to extract the 9 Ludwig IA, Sanchez L, Caemmerer B, Kroh LW, De Peña MP and Cid C,
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method. Food Res Int 48:57–64 (2012).
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11 Cines BM and Rozin P, Some aspects of the liking for hot coffee and
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