Why Mash?

• Transform a non-fermentable
Mashing Parameters: solid to a fermentable liquid,
Take Control of Your Mash a.k.a. Wort

• Wort is an “Aqueous fluid

containing
t i i a complex
l array off

Craft Brewers Conference soluble and suspended

April 8, 2010 Chicago, IL substances derived from the
Presented by Lars Larson, Trumer Brauerei
ingredient material”

[The Practical Brewer]

Propose new definition: Presentation Overview

• Mashing Objectives

• Water: Characteristics, Treatment and Minerals

• Mash Conditions
Nectar of the Gods

Mashing Objectives Mash Water Quality: Basic Assumptions

• Mix grist with water

• Dissolve substances which are immediately soluble (10-
15%)
• Conversion starch to sugar
• Change chemical structure, through enzymatic action,
of some of the other substances
• Retain malt husk as a filter aid (for mash and lauter
tuns)
• Must be potable and meet local drinking water
standards
• Regardless of source, must be “brewing water” and
not general service water
• Incoming water should be treated to get rid of
undesirables

• Treatment will depend on the source, quality

requirements and style intent

1
 Brewing Water Characteristics Key Water Characteristics

• Turbidity
• Vary considerably between the traditional global beer
• Color, Taste and Odor
style birth places • Dissolved Organics
• Water responsible in part for style differences • Dissolved Inorganics
• pH, Alkalinity and Hardness
• With full treatment and soft water
water, it is possible to • Mi bi l i l organisms
Microbiological i
recreate virtually any water • Disinfection residuals and byproducts
– TTHM’s, chloramine
• Water has impact with all product contact: mashing, • Dissolved gases
sparging, dilution etc.
– Therefore treat all water equally that does so

Water Treatment Analysis of Traditional Brewing Waters

• Clarification Ca++ Mg++ Na+ SO4-2 HCO3-2 Cl- NO3- Beer Type

• Activated carbon Burton-on-Trent 352 24 54 820 320 16 18 pale ales

• Microbiological control dry pale ales and

Dortmund 260 23 69 283 549 106 -
mild lagers
– UV,
UV heat
heat, sterile filtration
filtration, ClO2, O3
sweet dark
Munich 80 19 10 5 333 1 3
• Reverse osmosis lagers and stouts

• Nanofiltration Dublin 119 4 12 54 319 19 -

sweet dark
lagers and stouts

Pilsen 7 8 32 6 18 5 - pale lagers

Effect of Water Composition on Wort Effects of Ions on Wort and Beer

Water D
Composition (mg/l) Water A (Munich) Water B (Vienna) Water C (Dortmund)
• Calcium:
Ca++ 79 166 83 207
– Calcium Sulfate (CaSO4) and Calcium Chloride (CaCl2) precipitate
Mg++ 18 39 16 3 alkaline wort phosphates and thus reduces pH-values
Na+ 2 13 26 24
– Calcium Carbonate (CaCO3) and alkaline water precipitate acidic wort
phosphates and thus increase pH-values
SO4= 7 217 223 282
• May be needed in dark beers
HCO3- 319 396 51 136
– Protects, stabilizes and stimulates amylolytic and proteolytic enzymes
Cl- 3 38 40 127 during mash heating
EFFECT – Acidifying effect improves wort filtration and enhances protein
coagulation and complex formation which benefits trub formation. It
Saccharification time 75 60 15 10
limits the extraction of astringent substances and color.
Rel. Drainage rate 28 21 8 8 – Reduces the yield of isomerized alpha acids in wort
Wort Aroma strongly aromatic aromatic neutral neutral
– During fermentation it improves yeast flocculation and beer clarification
during storage (for flocculation need ~ 10-8moles of Ca+)
Wort Color dark brown/red less red pale yellow pale green – Precipitates oxalates as calcium-oxalate, thus decreasing gushing potential
and downstream beer stone production (>250mg/l CaSO4 prevents
% Extract 76.5 77.2 78.5 78.3 oxalate).
% Final Attenuation. 71.4 71.8 75.8 77.4 – Calcium content should be between 50-200 mg/l

2
 Effects of Ions on Wort and Beer Effects of Ions on Wort and Beer

• Magnesium:
– More soluble than calcium and less influence on pH
– Secondary magnesium-phosphates are soluble but tertiary phosphates are
precipitated during boiling.
– Often Malt provides sufficient Mg in wort
• Calcium precipitates Magnesium (avoid excess Ca+)
• Magnesium is diluted by adjuncts
– It enhances the activity of some enzymes (e.g. peptidases, and is an
important co-factor for other enzymes
– At low concentrations does not affect beer flavor, at higher levels can
impart sour and bitter taste and laxative effect. Bitterness is more
astringent in presence of magnesium carbonate than calcium carbonate
• Sodium:
– Sodium mineral salts soluble at all temperatures
– Sodium carbonates and bicarbonates are strongly alkalizing in increase pH
of both mash and wort
– Imparts a sour and salty taste to beer
– When associated with chlorides, sodium gives a salty taste at
concentrations above 150 mg/l. Occasionally it is added to pale beers at
low concentrations to improve mouthfeel and fullness
– Flavor of ales is less affected than lagers by sodium chloride
– Acts on yeast metabolism to maintain the potassium transport system

Effects of Ions on Wort and Beer Effects of Ions on Wort and Beer

• Iron: • Zinc:
– Brewing liquor should contain less than 0.2 mg/l – Concentrations of 0.1-0.2 mg/l improve fermentation and flocculation by
– Is present in the reduced Fe2+ form, but if oxidized precipitates as Fe3+ stimulating yeast activity
– Iron salts have negative impact on the brewing process – Higher concentrations may be toxic to yeast and will inhibit action of
– Inhibits the action of some enzymes and interferes with saccharification some enzymes
– It is removed with spent grain after mashing and wort separation • Manganese:
– In fermentation, higher levels will enfeeble yeast – Should not exceed 0.2 mg/l in the mash
– Iron ions form complexes which catalyze auto-oxidation reaction – Exerts
e ts a positive
pos t ve action
act o on
o hydrolysis
yd o ys s of
o proteinaceous
p ote aceous material
ate a
(oxidation without oxygen) and gives rise to irreversible hazes – Is essential co-factor for some yeast enzymes
• Copper: – Favors yeast growth (multiplication)
– Disadvantages similar to iron. It is scavenged by yeast and levels higher – At very high concentrations has similar properties to iron, particularly in
than 0.6 mg/l inhibits yeast and >10 mg/l in wort are toxic relation to chemical stability of beer
– Can react with sulfides to reduce sulfidic flavors (therefore sometimes • Ammonium:
sacrificial copper in all stainless systems) – Presence of ammonium ion in water indicates that organic mater has
– Its level can be increased through insecticide residues from hops decomposed, thus indicating serious contamination

Effects of Ions on Wort and Beer
• Bicarbonate:
– Alkalinizing ions which decompose on heating and simultaneously react
with hydrogen ions to produce free carbon-dioxide
– Recommended that concentrations are less than 50 mg/l particularly for
lager and pale beers
– Has an alkalinizing effect and so increases the pH value of mash. At
concentrations of 100 mg/l it can reduce extract yield by 0.2-0.3 %
• Sulphate
p :
– Calcium and magnesium sulfates have an acidifying effect and reduce the
pH of mash
– Sulfate ions react with Magnesium carbonate to form magnesium sulfate
which gives beer a dry, bitter and harsh taste
– Small amounts of sulfur dioxide and hydrogen sulfide are produced from
sulphates during fermentation
Effects of Ions on Wort and Beer
• Chloride:
– Enhances alpha-amylase activity though peptidases are unaffected
– Chloride inhibits yeast flocculation
– Fermentation rate is reduced and beer clarification in lager-tank is
adversely affected by concentrations higher than 500 mg/l. Beer
clarification, body and colloidal stability are improved when
concentrations are less than 300 mg/l
– Chloride levels above 400 mg/l have adverse effect on beer taste
– At concentrations higher than 100 mg/l chloride ions are corrosive and
attackk materials
i l off construction
i including
i l di chrome/nickel
h / i k l stainless
i l steell
• Nitrate:
– Occurs in ground water as a consequence of fertilizer use. Nitrates are the
last link in the processes of organic oxidation and degradation
– Nitrate concentration should not exceed 10 mg/l in mashing water
– Concentrations 50-100 mg/l are toxic to yeast: yeast growth, fermentation
rate and wort final attenuation are adversely affected
– When concentrations of other salts are high, effects of nitrate less
pronounced
– Nitrates are reduced to Nitrites by several yeasts and by contaminant
bacteria

3
 Effects of Ions on Wort and Beer Effects of Ions on Wort and Beer

• Nitrite:
– Also a product of organic decay. Its presence indicates sewage or effluent
pollution
– Toxic to yeast
– Reacts with polyphenols to give a reddish color in beer
– The presence is a major problem since they can be formed from nitrate
through the activity of gram negative bacteria present in water or wort
– Nitrite can react with nitrogenous mater to form toxic substances. The
main concern is the possibility of reactions with amines to give
nitrosamines; these are possible carcinogens and harmful to human health
• Silicate:
– Concentrations do not usually exceed 15-30 mg/l
– At concentrations higher than 30 mg/l complexes with Ca+ and Mg+ can
be formed
– Concentrations higher than 40-100 mg/l, fermentation rate reduced and
beer turbidity increased: this causes difficulty in beer clarification and
chemical stabilization after pasteurization
– Silicates can cause scale formation in steam boilers.
• Fluoride:
– Some tap water supplies are actively fluorinated
– Does not have an adverse affect at <10 mg/l
• Phosphates:
– Can indicate organic contamination of water
– Malt contains 7-13 g/kg and is the major source of phosphates in mash
– Phosphates react with calcium and magnesium ions to form complexes
which stabilize the presence of alkaline earth ions
– Up to 70% of calcium- and magnesium-carbonates are precipitated by
phosphates. The levels of calcium and magnesium remain stable through
the formation of undissociated complexes which may remain in solution
– Phosphates precipitate up to 28% of non-carbonates

Mash pH overview
Mash Conditions and Influence on Enzymatic Activity
pH affects the following:
• pH • Ideal mash pH is a compromise: 5.2 to 5.7
• Time and Temperature • Enzyme activity: each enzyme has it’s own pH
optimum
• Grind • Yield
• Consistency;
Consistenc ; Thick v. Thin • Malt flavors in final beer
• Starch Conversion • Extraction of astringent flavors in sparging
• Extraction of polyphenols; affects shelf life
• B-glucans
• Speed of LT runoff; grain bed permeability
• Protein Degradation • Extraction of hop bitterness in boil
• LOX • Final beer pH

Mash pH Mash Buffering

• Natural buffering action of the malt phosphates,

• Relationship between mash pH and yield
mainly dibasic potassium phosphate (K2HPO4) and
monobasic potassium phosphate (KH2PO4).
• Presence of calcium and magnesium causes reaction to
take place, removes now insoluble Ca-phosphate salts
from the equation, and potassium phosphates adjust
the pH downwards to the desired range
• If a strong acid is present, the phosphates will buffer
back up to a more alkaline range
• Carbonate ions (CO32-) and bicarbonate ions (HCO32-)
from water also act as strong buffers
• These can be removed by direct acidification, or also
Taken from Fix, George; The Role of pH in Brewing
deionization or microfiltration

4
 Influencing Mash pH Mash pH: Salt treatment

• Salt treatment of brewing liquor • Calcium chloride (CaCl2)

• Acidification • Gypsum (CaSO4) (aka “burtonization”)

• Grain bill • Calcium carbonate (CaCO3) (dark malt brewing)

• Treatment
T off mashing
hi water, sparge water and
d wort iin
kettle

• Time of addition (in particular in kettle)

Mash pH: Acidification Mash pH: Grain bill

• Weak organic acids typically used • Dark malts are more acidic than pale malts
– Lactic acid • Use of portion of dark malts will bring overall mash pH
– Phosphoric down
– Sulfuric has been used,, not typical
yp
– Biological (either through acid malt, sour wort, or
purchased drum (the horror, the horror))
• What the bacteria can do on the side: lactic
fermentation and aldehyde removal

Time and Temperature Time and Enzyme activity

• Maximum activity reached after 10-20 minutes

• Selected to optimize enzymatic activity and desired end
• After 40-60 minutes activity decreases rapidly
wort profile • So, with increasing time the extract concentration
increases, but the rate of increase slows
• Time: just long enough to allow the enzymes to do their
• With increased time, the attenuation limit increases
work.

• Temperatures: Different goals depending on type of

mash chosen: single step infusion, step up infusion,
decoction, use of adjuncts.

5
 Mash Off Temperature
• Classic mash off temp range is 75 - 78 ºC (167 – 173 ºF)
• Render enzymes inert and decrease viscosity for easy
filtration
– At temperatures under 75 C alpha-amylase is still active
to break down any starch that is freed which can lead
to:
– Starch haze from released starch from sparging and
kettle heating
Grist/Water Ratio
• Thin mashes (ex. 4 hl water/100 kg grist or 25kg/hl; or
2.1 lbs/gal):
– More extract into solution. Hydrolytic reactions proceed
at a greater rate, because products of the reaction are less
concentrated and so inhibit enzyme activity less
– Dilutes the enzymes
y – More soluble hexose sugars
– Dilutes the substrate upon which the enzymes act
– Dilutes the product of the enzyme action
– Reduces the viscosity of the wort
– Enzymes not suppressed by increasing sugar
concentrations
– Thin mashes used for light beers to reduce carbs
Starch Conversion
1. Gelatinization
– Absorption of water into starch molecules, resulting in swelling
and bursting. Begins at 60 ºC (140 ºF)
2. Liquefaction
– Reduction of viscosity of gelatinized starch by α-amylase
3. Saccharification
– Combined activity of α- and β-amylases to form maltose,
maltotriose and glucose, as well as leaving limit dextrins in
solution
Mash Parameters: Grind
• Depends on the mill capabilities (number of rollers),
type of mash vessel (mash/lauter combined; stand alone
with heating capabilities), and type of separation
utilized ((mash/lauter tun,, lauter tun or mash filter))
• The finer the grind, the higher the enzyme activity
– This due to easier access to substrate
• Balance needs to be found between good access and too
fine a grind that plugs up the lauter run-off
Grist/Water Ratio
• Thick mashes (ex. 2.5 hl water/100 kg grist or 40kg/hl
or 3.3 lbs/gal):
– Protects enzymes from too rapid thermal degradation
– Consequently greater amount of fermentable sugars
– More soluble nitrogen
– Higher wort viscosity
– Reactions become inhibited by increasing
concentrations of sugar in the solution
• However, ratio has a smaller effect on mash effectivity
than other factors such as temperature and pH
Starch Conversion
• α-amylases: break down long starch chains to smaller
dextrins of 7 to 12 glucose residuals.
– Optimums: pH 5.6 to 5.8; 72 - 75 ºC (162 – 167 ºF)
• β-amylases: splits off maltose from non-reducing end of
chains, but also produces glucose and maltotriose.
– Optimums: pH 5.45 4 to 5.5;
5 5; 60 - 65 ºC (140 – 149 ºF) … and
rapidly inactive at 70 ºC (158 ºF)
• Don’t forget, enzymes still work across a range! However
don’t work once you cross the inactivation temperature
upper limit
• Rule of thumb: above 60 ºC, 1 ºC decrease equals 5 min
increase for α-amylase activity OR
• To increase RDF by 1 deg, adjust mash temp down by 2 ºC
or add 10 minutes
6
 Starch Conversion Typical Carbohydrate Profile

• Why test? Standard Brew Brew with Exo.

Enzymes
– Residues of degraded starch and larger dextrins cause
Maltose 47.5 % 1.4 %
haze
– Loss of fermentable extract Glucose 10.3 % 78.9 %

• Iodine test Sucrose 4.5 % 6.2 %

– Helix temperature dependent Maltotriose 14.7 % 1.5 %

– Light sensitive
DP4/Dextrins 23.0 % 12.0 %

% Fermentables 77.0 % 88.0 %

β-Glucans β-glucan structure

• Unbranched and extended molecules, bound together

• β-glucans can cause:
by hydrogen bonds
– lautering difficulties due to high viscosity • Called fringed micelles, soluble
– filtration problems due to gel formation • Bound to protein in cell walls, in particular in poorly
modified malt and especially in tips
– Conflict in the literature:
• No effect on head retention or body
• Positive effect on head retention
• Cytolysis is provenance of Maltster and can only partly
be compensated for in the brewhouse

β-glucanases β-glucan structural changes

• Endo-β-glucanases are very temperature sensitive: • Thermal breakdown of hydrogen bonds

– Wort boiling, wort cooling
40 ºC- 45 ºC (104 – 113 ºF) optimum
• Once degraded, with slow cooling, calm sedimentation,
• β-glucan-solubilase; optimum 62 ºC (144 ºF) no shear forces
– Releases high molecular weight β-glucan but does not – Little risk of gels
d
degrade
d it
i further
f h • High velocities,
velocities vigorous swirling (pumps or
whirlpools), narrow pipe work, shear forces
• During gelatinization the interlinked micelles set free –
beyond range of endo-β-glucanases – High risk of gels

7
 Relevant Malt Analysis Indicators
• High correlation of high β-glucan levels to high
viscosity and low friability
• Friability value of 85% or greater are desirable
Lipids
• Unsaturated fatty acids in the mash are converted to
intermediate products by the lipoxygenases (LOX) and
oxygen
• The resulting aging carbonyls are partly responsible
for oxidation flavor
• Very small amounts available in the wort, but they
convert very quickly
• LOX formed in germination and destroyed in kilning,
but about a third remain active; susceptible to high
temperatures
– Paler malt can have higher LOX activity
Polyphenols
• Polyphenols present in malt are leached into wort, and
can contribute astringency and color.
• Quantities extracted increase with pH and sparge
temperature
Protein Degradation
• FAN – essential for yeast nutrition and rapid
fermentation
• High molecular weight degradation products are foam
positive; help with palate fullness
• Medium weight degradation products are haze
producers
• 45-50 ºC (113 – 122 ºF) more low molecular weight
protein
t i degradation
d d ti products
d t are fformed,
d particularly
ti l l
peptides and amino acids
• 60-70 ºC (140 – 158 ºF) : more high molecular weight
degradation products are formed, which are
responsible for foam stability
• Generally well modified malt will provide sufficient
amino acids (in all malt brewing). Some sources
indicate a long rest at 45-50 ºC always causes bad foam.
Influences on LOX
• Barley variety and location
• Inert gassing the grist case
• Malt conditioning with hot water 80 ºC
• Grist fineness: increases proportionally
• Short mashing time and low mash pH of 5.1 to 5.2 reduce
LOX activity
• Mashing in above 60 ºC recommended
• Cloudy lautering and poor trub removal downstream
increase other saturated fatty acids
Oxygen
• Oxygen pick up begins in milling, as air is mixed with the grist and
in the hopper
• Mashing in should include thorough mixing to eliminate clumps
and entrained oxygen
• Mash water can be deaerated to prevent additional reactions with
dissolved oxygen (however hot water has little DO)
• Also possible to enclose and flush all vessels with inert gas
8
 Final Mash Profile Fishbone Diagram
Diagram VIIa

• Attenuation limits
– Established during mash by manipulation of the
mashing parameters
p Fermentation testing
• Rapid g
– Fermentation tubes
– Shaker table

Fishbone Diagram Downstream Treatments

(zoom in view of same)

• PVPP
– Bind polyphenols
• Silica Gels
– Bind haze forming polypeptides
• Enzymes
– Papain
P i as proteolytic
l i enzyme: must be b pasteurized
i d to
destroy
• Tannic acid:
– Forces completion of haze formation in storage by
binding with proteins, which is then filtered out

Recent developments in Mashing Literature

• BRIGGS, D.E., HOUGH, J.S, STEVENS, R. and YOUNG T.W. (1981). Malting
• Focus on the brewing process as whole, not as isolated and Brewing Science; Volume 1 Malt and Sweet Wort. 2nd Edition, Kluwer
Academic/Plenum Publishers
incident • FIX, G.J. (1995); The Role of pH in Brewing; The New Brewer
• FIX, G.J. (1989); Principles of Brewing Science. Brewers Publications
• GALES, P. W. (Ed.) (2007); Brewing Chemistry and Technology in the Americas.
– Improve wort filtration American Society of Brewing Chemists
• HAMMOND, J., van WAESBERGHE, J., WHEELER, R. (Ed.) (2007). EBC
• Minimize shear stress Manual of Good Practice - Mashing and Mash Separation
Separation. Fachverlag Hans Carl
Carl.
• Improve heat transfer • KUNZE, W. (2004). Technology Brewing and Malting. 3rd Edition. Versuchs- und
Lehranstalt für Brauerei in Berlin.
– Increase beer shelf life • McCABE, J.T. (Ed.) (1999). The Practical Brewer. 3rd Edition. Master Brewers
Association of the Americas
• Minimize O2 pickup • OCKERT, K. (2006). MBAA Practical Handbook for the Specialty Brewer;
Volume 1: Raw Materials and Brewhouse Operations. Master Brewers Association
of the Americas
– Improve hop utilization

9
 THANK YOU

• Brewers Association for the invitation to come present

• Carlos Alvarez of The Gambrinus Company for giving me the

opportunity
pp y to do so

10