A TASTE OF WINE CHEMISTRY
Nina Notman talks to the wine detectives uncovering the flavour molecules in our
favourite tipples
‘Wine is a rare example of a consumer packaged good where variation is not just
tolerated, it is celebrated,’ explains Gavin Sacks, wine chemist at Cornell University
in New York state, US. Over 400,000 different wines are currently available for sale
in the US and drinkers expect each of these to have a distinct smell, look and
taste. While they may not all realise it, they therefore expect the chemistry in each
of these bottles to be different too.
Wine is a surprisingly complex chemical mixture. It is 97% water and ethanol, but
each bottle also contains thousands, if not tens of thousands, of different
molecules, ranging from acids and sugars to phenolic compounds and vanishingly
low concentration aroma compounds.
The job of wine chemists such as Sacks is to identify which of these compounds,
or even classes of compounds, is the most dominant in each wine variety and then
direct winemakers towards practices that increase or decrease their concentrations
as desired for the wines they are making. This could mean changes to vineyard
management, how and when grapes are picked, the wine making process or even
how the wine is stored.
Identifying the important flavour and aroma molecules in a wine is challenging. This
is partly due to the vast number of different molecules it contains, but also because
these volatile compounds tend to be present at very low levels. Some can be
detected by discerning drinkers at parts per trillion (ppt) concentrations.
Once identified, determining where a molecule came from can be equally difficult.
It’s rare for wine flavour molecules to be found in the grapes themselves, and
instead they form during fermentation and wine storage. ‘It is like someone went to
a chemical store, knocked all the bottles over and then pointed to the mess and
asked what reactions have happened,’ says Sacks. ‘They’re not hard reactions to
figure out but there are so many possibilities.’
The reactions are also pretty obscure, at least to the eyes of a traditional chemist.
‘Wine is so different to a typical organic chemistry matrix,’ he explains. He
describes wine making as a one-pot synthesis taking place under mildly acidic
aqueous conditions, at room temperature and in the presence of a mild reducing
agent. ‘If you look at textbooks nothing interesting happens under these conditions,
but what’s unique in wine is that it’s happening for long periods of time,’ Sacks
says. And these reactions don’t stop when the winemaking process does – the
molecules in wine continue to evolve once bottled. This is why wine is often
described as a living, breathing thing.
The secrets of Sauvignon
Despite these challenges, there are a growing number of examples of flavour
molecules being identified and winemakers then using this knowledge to improve
their product. The combination of the related thiols 3-mercaptohexanol and 3-
mercaptohexyl acetate that give New Zealand Sauvignon blanc its distinctive
passionfruit aroma is one such example. These molecules are straight chains of six
carbon atoms with either an alcohol or an acetate group on one end and a thiol
three carbons along the chain, explains Andrew Waterhouse, a US wine chemist at
the University of California, Davis. ‘Almost anything that has a thiol on it that is also
volatile will have a potent aroma because our olfactory detectors just love SH
groups,’ he says. Analysing the finished product is important as these compounds
can develop during fermentation and even after bottling
These molecules are typically found in Sauvignon blanc from New Zealand at
several-fold higher concentrations that in the same variety produced elsewhere,
and when scientists went looking for the reason they found an unexpectedly
complicated story. It is due to a series of happy accidents in New Zealand’s unique
environment for growing and processing Sauvignon blanc grapes, explains
Waterhouse.
Firstly, their precursor – a linolenic acid – is more prevalent in Sauvignon blanc
grapes grown in New Zealand than those in warmer climates. ‘Under cool climate
conditions, cell membranes tend to have more unsaturated lipids in order to
maintain the integrity of their lipid bilayer,’ Waterhouse says. Secondly, a lack of
manual labour in New Zealand means grapes are normally harvested by machine.
The grape berries are bashed off the vine with a plastic beater bar and drop down
onto a moving conveyer belt below. ‘It’s a rather violent process,’ says
Waterhouse, which tends to break open the grapes. Once open to the air, the lipid
precursor very rapidly oxidises (within a minute or so) to form the six-carbon α,β-
unsaturated aldehyde.
Testing for polluting agents in wine
The carbon–carbon double bond in this molecule then reacts with a sulfur-
containing nucleophile, inserting a sulfur-containing group in the C3 position.
According to Waterhouse the identity of this nucleophile is still being determined
but it is probably glutathione, a natural antioxidant in grapes, or sulfite, which is
routinely sprayed onto machine-harvested grapes before they leave vineyards to
prevent oxidation (see box Oxidation fundamentals below). When Waterhouse
started exploring this passionfruit flavour in New Zealand Sauvignon blanc he had
no idea that some oxidation was needed.
The grapes are then taken into the winery where they undergo the standard white
wine-making process – crushing, decanting and then fermenting with yeast. The
yeast transforms the aldehyde to an alcohol and the sulfur-containing group into a
thiol, Waterhouse explains. ‘The yeast also converts some of the alcohol to the
acetate ester, so you end up with 3-mercaptohexanol and the 3-mercaptohexyl
acetate that give the wine its distinctive flavour.’
Uncovering the science behind their wine has allowed New Zealand producers
tight control over the flavour of the Sauvignon blanc they produce. Hand-harvesting
can be avoided, the length of skin to juice contact during pressing boosted and
yeast strains that are particularly good at putting on acetate groups selected, for
example. The storage of the finished wine has also changed. During ageing the
acetate group tends to hydrolyse, upsetting the perfect balance of flavour
molecules present in the wine at bottling, says Waterhouse. ‘Once that was
understood, New Zealand winemakers started to keep their wines very cold until
they were sold, because you can slow the process of hydrolysis by lowering the
temperature.’
Oxidation fundamentals
Winemakers have a complicated relationship with oxygen, explains US wine
chemist Andrew Waterhouse from the University of California, Davis. ‘Traditionally,
oxygen was viewed as the enemy of winemaking because the technology available
until around hundred years ago couldn’t keep oxygen out.’ Wine that was more
than a year old at that time would taste like vinegar.
Today, it is possible to almost completely exclude oxygen from the wine making
and storage process. But this isn’t always wanted as oxygen can drive the
formation of some desirable flavour molecules. ‘Winemakers have had to learn
how to control the use of oxygen in winemaking,’ says Waterhouse. Since the mid-
1990s, for example, the controlled addition of oxygen – known as
microoxygenation – has been widely practiced. ‘In Cabernet sauvignon, for
example, it diminishes the vegetable, bell pepper aroma and you ended up with
fruitier tasting wines,’ Waterhouse says. ‘There’s been a lot of interest in
understanding the reactions that are occurring. It’s very complicated because there
are so many components in wine and they can all react in different ways.’
Another chemist looking into this is UK-based John Danilewicz. Prior to his
‘retirement’ 20 years ago, Danilewicz was a drug discovery chemist for the
pharmaceutical giant Pfizer at their Sandwich site in Kent. When he left Pfizer,
Danilewicz planted a small commercial vineyard nearby and built a winery, which
he recently sold. He also set up a still-operational wine chemistry research lab in
his garden at home. Here, he studies the mechanism of wine oxidation. ‘I am very
interested in the mechanism of oxidation because oxygen doesn’t react directly
with any wine components; its reactions are catalysed by iron, which is always
present in small amounts in wine,’ Danilewicz explains. ‘Iron(II) is first oxidised by
oxygen in single electron transfer steps to produce iron(III). This is the oxidant that
oxidises various things in wine, the polyphenols and so on.’
He is also working to improve fundamental understanding of how sulfite works. It is
routinely added to wines to prevent oxidation at various stages in the production
process and finally to finished wine. Danilewicz’s ultimate goal is seeing sulfite
used more scientifically to improve wine quality.
Cracking the pepper mystery
Another distinctive wine flavour that has been under the microscope is the cracked
black pepper character in Shiraz grown in cool climates. ‘Until recently we didn’t
know what the chemical was that causes the black pepper flavour in cool climate
Shiraz,’ explains Leigh Francis, a wine chemist at the Australian Wine Research
Institute in Adelaide. The quest was made harder by the molecule’s high bioactivity
in the wine – some people can detect it at just 16ppt.
Although wine is often sold alongside an image of age-old tradition, the industry
uses modern techniques and analysis
In 2008, Francis’s colleagues used gas chromatography–mass spectrometry (GC–
MS) paired with a panel of expert human sniffers to identify the molecule as the
sesquiterpene rotundone. ‘We discovered that it had been reported previously in
the nut grass Cyperus rotundus but it hadn’t previously been recognised as a
flavour compound,’ he says. Later research found that rotundone is prevalent in
black peppercorns and many other herbs and spices. It is also – unusually for a
wine flavour compound – also present in grapes.
Further work by Francis’s team found that rotundone concentrations increase as
grapes mature. Shiraz producers are therefore starting to consider how peppery
they want their wine when deciding when to start harvesting grapes.
Stainless steel wine tanks
The scientists have also been looking at how rotundone levels can vary across
individual vineyards. ‘It’s well known that vineyards are not necessarily uniform,’
explains Francis. ‘Even if it looks visually identical, is planted with the same
material and grown in the same way, certain areas can produce a darker-coloured
or different-flavoured wine.’ This flavour variation means that some winemakers
harvest their vineyards in parcels; grouping together rows of vines that ripen at
similar times.
Francis’s team have been working with some wineries to better inform this so-
called batching process, by mapping the concentration of rotundone in Shiraz
grape berries across their vineyards. The Mount Langi Ghiran vineyard in
neighbouring Australian state Victoria has very high levels of rotundone, and they
found a 50-fold variation in concentrations in a six hectare area. The team found
that the level variations strongly correlated with light levels. ‘Vines with more
shading had high levels of this pepper compound,’ explains Francis.
Find the perfect blend
Damien Sheehan, viticulturist and general manager at Mount Langi Ghiran,
explains that before working with Francis they picked the six hectares used to
produce their flagship wine in just two or three separate batches. ‘We would start at
one end of the row and go all the way to the other end of the row and then keep
working along. It was fairly crude. Now we pick as many as 13 separate parcels of
fruit out of that block and do separate ferments with each of those parcels.’ The
result, he explains, is a higher quality wine. His team are now picking fruit that
contains the concentration of rotundone that best suits their buyer’s tastes. Some
wineries have also started to change canopy management strategies to manipulate
rotundone levels.
Bench scale fermentation.
The compounds we associate with different types of wine are often not actually
present in the original grapes
Cool climate Shiraz and Sauvignon blanc may have one or two dominant flavour
compounds, but this is unusual. It’s normally combinations of compounds that give
wine varieties their unique flavours, Francis explains. His team is currently
exploring the origin of the apricot and peach flavours in Chardonnay and some
other white wines. Earlier gas chromatography paired with human sniffing work
didn’t find a single common aroma compound responsible for this so-called stone-
fruit character – a mixture was suspected instead. In 2018, Francis’s team reported
that using a sensory reconstitution study they had determined that it is a mixture of
monoterpenes and lactones that gives rise to this stone-fruit flavour. ‘Once you
think you’ve identified what the compounds are, they are added to a neutral
medium to see if the character can be reproduced,’ explains Francis. ‘This
reconstitution step hasn’t been done very much in wine research so far.’
Another approach being taken to unpick mixtures of flavour compounds in wine is
to ‘delete’ individual molecules from an artificial wine matrix and see how the
flavour changes. ‘The method involves removing an individual component from a
known mixture of aroma chemicals and see how it contributes to the mix,’ explains
Waterhouse. ‘Understanding the interaction of all these aroma components and
how they affect each other in a mixture has become a major area of study in wine,
and more broadly in sensory science.’
The wine chemists interviewed for this article all agreed that theirs was a dream
job, allowing them to combine a love of chemical research with their favourite
tipple. ‘This job has enhanced my enjoyment of wine because when I taste different
wines I can understand what I taste on a different level,’ explains Waterhouse. ‘If
there are other chemists around, we’ll talk about a wine’s flavour in terms of
chemical components. But if I’m not with chemists, I’m not going to do that,
because I want to be polite!
