A.

ACIDS
1. Quinic Acid

Quinic acid along with citric and malic represent a significant portion of coffee's
total acid content. During roasting quinic acid progressively increases as the
levels of chlorogenic acid decrease, suggesting that its formation results from
the cleavage of the chlorogenic acid moiety.
Quinic acid concentrations reach a maximum at French roasts then progressively decrease as roasting
progresses. Actual temperature figures of when this occurs have yet to be published and vary depending on
environmental conditions within the roaster.
As seen from Table below - quinic acid is at the lower end in concentration when compared to the other acids
found in coffee. Upon roasting quinic acid approximately doubles in concentration due to the breakdown of
chlorogenic acid as mentioned before.
Organic Acid content in green and roasted coffee:

Further thermal degradation of quinic acid results in the formation of phenol, catechol, hydroquinone,
pyrogallol and several diphenols which are believed to be important coffee aroma precursors.

Quinic acid has also been associated with an increase in perceived acidity as coffee infusions are left standing
at elevated temperatures. This effect is best illustrated when coffee is left in carafes on heating plates (or
airpots) where temperatures can exceed 80C. The effect is also commonly seen during cupping when coffees
cool in temperature and there is a gradual rise in levels of perceived acidity.

2. Citric Acid

Like many living organisms, citric acid plays an important role as a key
intermediate compound in the plant's metabolic cycle. In green coffee citric
acid makes up a significant portion of coffee's total acid content and ultimately
in the development of perceived acidity.
During roasting, citric acid reaches a maximum at light to medium roasts then quickly diminishes as roasting
levels progress. A typical medium roast will lose about 50% of its initial citric acid concentration and with
progressive destruction in latter stages of roasting progresses.

From a taste perspective, citric exhibits strong sour characteristics similar to what we would taste in unripe
fruits. Although pure citric acid is commonly used as a food additive to impart sour/tart notes, excessive citric
acid is a sign of bad processing.
Since a high concentration of citric acid is found in unripe (green) cherries, it is important for producers to only
pick the ripest beans, especially for those bean destined to become specialty coffee.

However, as maturation continues citric acid levels continue to decrease with a parallel increase in sugar
production. Generally, Kenyan coffee tend to have lower levels of citric acid than those of Central America,
suggesting a less advanced form of plant metabolism.

3. Chlorogenic Acid

Discovered in 1932, chlorogenic acids (CGA) represent a large family of esterified

compounds present in green and roasted coffee. During roasting, CGA's slowly
decompose to form caffeic and quinic acid with about 50% of the original CGA
being destroyed in a medium roast.
Sensorially quinic and caffeic acid have been associated with the increased levels of astringency, bitterness
and body commonly seen in darker roasting styles.

Selected composition for raw coffee (%):

Coffee has by far the largest concentration of chlorogenic acid of any species in the plant kingdom, accounting
for 6-7% d.b. in Arabica and up to 10% d.b. in Robusta.
CGA production in the plant is initiated by several factors including changes in environmental conditions, plant
stress and pest infestation. It is no surprise then, that robusta, while grown in harsher conditions contains
almost twice the concentration of CGA than arabica.
CGA production also closely parallels with that of caffeine, such that, as CGA concentrations increase so does
the concentration of caffeine.

Although the term chlorogenic acid is used to identify a single compound, in reality, there are over a dozen
isomers each with different sensorial characteristics. Typically it is the 3-CGA isomer who predominates in
coffee with mono, di and feruloylquinic acid in varying concentrations.
Research has suggested that the "di-CGA" form of the acid may be responsible to the bitter/metallic taste
notes found in certain coffees. This may very well be true for coffees like robusta which contain a significant
higher concentrations of di-CGA and harsher taste profile.
Latest research has confirmed that coffee contains high concentrations of antioxidants in the range of 200 to
550mg per cup (6oz) - a level far exceeding that of green tea. But although both coffee and tea contain high
levels of antioxidants, coffee tends to contain higher levels of the simple phenolics whereas tea larger levels of
catechins.

Chlorogenic Acid

Catechin

4. Phosphoric Acid

In coffee there are over two dozen different types of organic acids such as
citric, malic, acetic, quinic, etc. But there is another branch of acids inorganic
acids that are also believed to play an important role. One inorganic acid that
has receive much attention is a phosphoric acid.
In coffee is makes up constitutes roughly less than 1% of coffee's dry matter and is believed to originate from
to hydrolysis of phytic acid from the soil. However, unlike some of the other acids - phosphoric is by far the

most potent and can easily be 100 times stronger than other acids. As such, many researchers believe that
phosphoric acid is significantly responsible for coffee's perceived acidity.

Although the argument is well backed, there is some debate over how much phosphoric acid actually
contributes to acidity. Those one side say that because phosphoric acids potency it has a much greater
potential at contributing hydrogens and affecting ultimately acidity.
While those on the other side state that phosphoric acid, though potent, is neutralized by an equal amount of
potassium in coffee. A 1999 study conducted by J. Rivera of the Coffee Quality Institute found an inverse
relationship between perceived acidity and phosphate concentration. Further studies are needed to further
establish a clear role between organic/inorganic acids and their role quality.

Phytic Acid
Interestingly higher levels of phosphate have been documented in both dry processed robustas and arabicas
but their role in perceived acidity still remains a mystery. Though wet processed arabicas do tend to contain
the lowest phosphate concentrations this is partly see due to leeching of minerals during fermentation.

It has also been documented that residual amounts of phosphoric acid survive the roasting process with an
estimated figures listed in the Table below. The increase in phosphoric acid at higher roasting levels is still not
understood and may be due to artifacts produced during the analytical process as such further studies are
needed.
Acids as function of roast weight loss (%):

5. Acetic Acid

Acetic acid, or more commonly known as vinegar, is one of the many organic
acids that play an important role in coffee quality. Although, there are varying
levels found in both dry and wet processed coffees, its formation during post
harvest processing comes primarily from fermentation.
During the wet process microbes within mucilage consume sugars to produce acetic acids as well as a number
of other compounds. Since the reaction is dependent on time and temperature, final concentrations of acetic
acid in will vary depending on environmental factors as well as the nature of the bean. It's estimated that
after fermentation only a small portion (0.01%db) of acetic acid produced during fermentation will remain
within the bean.

Coffee Fermentation Tank - photo courtesy of Edwin Martinez

However, it is during the roasting process where the formation of acetic acid significantly increases. During
this stage small to medium chained carbohydrates like sucrose begin to breakdown, resulting in the formation
of aliphatic acids such as acetic, formic and others.
Depending on actual roasting conditions, acetic acid concentrations can increase up to 25 times its initial
green bean concentration. Overall acetic acid concentrations reach a maximum at light to medium roasts,
then quickly dissipate as roasting progresses due to its volatile nature.
The following table summarizes acetic acid concentrations in green and roasted coffee:

Chemically, acetic acid is a weak volatile organic acid, but plays a significant role in both perceived acidity and
aroma formation. According to Sivetz, a noticeable increase in acidity can be gained by the use of a pressureroaster, which is believed to retain volatile acids and improve quality.
Sensorially in low concentrations acetic acid imparts a pleasant clean, sweet-like characteristic, but can quickly
become ferment-like at higher concentrations.

B. ALKALOIDS
1. Trigonelline

Trigonelline is a bitter alkaloid in coffee which serves to produce important

aroma compounds. In terms of concentration trigonelline is higher for arabica
than robusta and ranges from about 0.6-1.3% and 0.3-0.9%, respectively.
During roasting trigonelline partially degrades to produce two important compounds - pyridines and nicotinic
acid - such that a very dark roast will only a fraction of its original trigonelline content.

Nicotinic acid or also known was vitamin B3 (niacin) is produced by the demethylation of trigonelline at
temperatures above 160C-230C where approximately 85% is decomposed. But when compared to green
coffee - there is an overall net increase of about 10x from green to roasted.
According to lab experiments formation of nicotinic acid depends more on the roasting temperature than on
the actual duration of the roast.
Interestingly, coffee has been found to contain a significant amount of niacin - providing 10-40mg of
niacin/100g of coffee and far exceeding the daily recommended dosage.

Decaffeinated coffees typically contain about 35% less nicotinic acid due to the elimination of trigonelline by
chlorinated solvents. Recently, trigonelline has been found to reduce the incidence of dental caries due to its
ability to prevent Stretococcal mutans from adhering to teeth enamel.

2. Caffeine

In its pure state - caffeine, or 1,3,7-trimethylxanthine, exists as a white

powdered alkaloid with an intensely bitter taste. Caffeine acts as a stimulant
for the central nervous system (CNS) having the temporary effect of warding off
sleep and restoring alertness in both humans and animals.
It is commonly found in the leaves and beans of over sixty plants worldwide and is believed to have evolved as
a protection mechanism for plants. In Arabica coffee, caffeine content averages at 1.2% while Robusta at 2.2%.
It is believed that this larger level of caffeine allows for robusta plants to thrive in more hostile environments
as caffeine acts as a chemosterilant for insects.

In addition to difference seen between species, researchers have found slight differences across varietals - see
Table 1 below.
Table 1: Caffeine content by species and variety:

Illy, A. Espresso coffee, 1st ed.

In the beverage, actual concentrations of caffeine depending primarily on the method of brewing and type of
coffee used. As seen from Table 1, caffeine levels can vary significantly but its been estimated that 90% of the
caffeine is extracted within the first minute of brewing. The variance in caffeine levels is attributed to several
factors including extraction time, temperature, grind level and type of coffee used - making true calculations
difficult to publish.
Table 2: Caffeine content of common beverages:

NCA, Aug 1999. www.coffeescience.org

Contrary to popular belief, caffeine levels remain virtually unchanged after roasting - its high sublimation
temperature and retention within the beans cells make it a very stable compound even at +400F
temperatures.

However, it is possible that coffee brewed from darker roasts may contain higher levels of caffeine, since more
coffee is required to achieve the desired throw weight.
Recent studies have shown that drinking coffee coffee increases levels of dopamine and glutumate in the
brain, thereby having a "pleasurable" effect on the drinker.

C. Carbohydrates
1. Sugars
Although we are all familiar with sugars sweet taste, in coffee, it serves an entirely different purpose all
together.
Of the two species of coffee produced globally, Arabica coffee contains roughly twice the concentration of
sugars than Robusta. As such, these compounds play an important role during roasting to create a vast array
of aromatic flavor compounds.
But where do these compounds come from?

Through a series of complex reactions, most of these flavor compounds result from the decomposition of
sugars during roasting producing. But sugar's role in coffee is far more than just producing a sweet cup, just
consider the following:

Aromas - during roasting the decomposition of sugar results in a special class of aromatic compounds
called furans to provide caramel-like aromas in our cup; while like compounds such as hydroxymethylfurfural
(HMF) provide a sweeter aroma to coffee.

Furan

HMF

Antioxidants - sugars also serves as an important precursor in the development of numerous

antioxidants present in roasted coffee. Its even been said that a cup of coffee may have even more antioxidant
capacity than green tea.

Color - sugars also play an important role in the formation its characteristic brown color. Due to sugars
uncanny ability to react with other compounds, it able to form long chains of polymers that ultimately give rise
to its brown color.

Long polymer chains create coffee's brown color

So, how do we produce the best coffee at origin?
Sugars not only play an important role in the flavor of coffee, but also in the formation of a number of acids
found within the bean.
We still have a long way to go to fully understanding the complex nature of coffee, but for now, sugars seem
like a sweet place to start.

2. Carbohydrates

Carbohydrates are perhaps one of the largest family of compounds in organic

chemistry. As the name implies, carbohydrates are simply hydrated carbon
molecules with complex structure. Of course, the most common carbohydrate
is that of sucrose, or table sugar, but there are literally thousands of molecules
in this branch of chemistry.

In green coffee, carbohydrates represent a significant portion of its structural matter making up
approximately 50% of coffee's total dry basis. The composition is made up of a complex mixture of both
soluble and insoluble matter including mono, oligo and polysaccharides.
In the case of Arabica, there is almost double the concentration of sugars than that of Robusta. Table 1 below
outlines the basic differences in carbohydrates within each species.
Table 1: Carbohydrate content in Green coffee (% dry base):

As expected, the sucrose concentration varies with degree of ripening and should always be considered when
making analytic comparisons. This is particularly true for defective beans where differences between sucrose
concentration can vary significantly. See Table 2 below.

Carbohydrate
Table 2: Monosaccharide content in Green Coffee:

During roasting, sugars play a critical role with many of them participating in the Maillard reaction a reaction,
that is of prime importance to cooking/roasting. During coffee roasting a vast portion of these molecules
decompose to form water, carbon dioxide (CO2), aroma, brown color, as well as smaller organic acids.

D. Lipids

Of the two commercially important species of coffee - arabica generally

contains more lipids than robusta averaging 15-17% and 10-11.5%, respectively.
With the actual coffee bean only a small percentage of the lipid oil is actually
contained in the waxy portion covering the bean, while the majority being
distributed in the endosperm.
The following table summarizes the lipid fraction composition generally found in green coffee.
Lipids in Green Coffee:

In terms of quality, arabica contains almost 60% more lipids than robusta which may play an important role in
aroma retention. In one study of Central American coffees it showed a direct correlation between lipid content
and beverage quality by a panel of cupping experts.
Studies on coffee storage have also shown that fatty acid concentrations increase when coffee is stored for an
extended period of time at subtropical temperatures. As a result, it is believed that decomposition of lipids
during elevated temperate storage may lead to the formation of flavors in the coffee.
But interestingly during roasting lipids (as well as caffeine) remain virtually unchanged owing to their relatively
high melting points.

E. Protein

In both arabica and robusta coffee, free and bound proteins account for roughly
10 to 13% of coffees dry matter. Since proteins are made of smaller
components called amino acids - these can vary significantly within each coffee
based on a number of factors.
For example allowing the cherry to ripen further typically increases the levels of tryptophan, threonine,
glycine, tyronine, serine, alanine, lysine and arginine. Likewise, storage of green coffee at elevated
temperatures increase the concentration of several amino acids due to proteolysis and non-enzymatic
reactions. The following table illustrates amino acid concentration for both arabica and robusta coffee.
Amino Acid composition of coffee (%):

During roasting amino acids play a critical role in the development of color, aroma, and flavor compound via
the Maillard reaction. Coincidentally it is these very same reactions that are responsible for the aroma
produced when grilling a steak or baking a loaf of bread.