Molecular mass spectroscopy:

Introduction to mass spectrometry

Basics concepts and terminology
Instrumentation, ionization modes and types of
mass analyzers
Applications of mass spectrometry to the study
of biological molecules

History:
• In around 1940 MS is used for the routine analysis of hydrocarbon
mixtures (from petroleum products), instead of it, fractional
distillation and refractive index measurement are used before.
• Around in 1950 this method is used for the identification and
structure elucidation of organic compounds.
 General theory on mass spectroscopy:
• First step: production of charged particles from the analyte
molecule.
molecular ion/ parent ion.
• Accelerating these ions and separating them (m/z basis)
• Measuring mass of the separated fragments and also their
relative abundance
• Plotting the mass spectra
• Analyzing the mass spectra for

1. Molecular wt. determination

2. Structure elucidation.
MS: key tool for the chemical determination of compound.
First it determines molecular weight.
Second, we can smash out fragments that are intact structurally
Third, the fragments are linked back to the starting structure
 Fig: Electron impact ion source

Sample Different parts of mass spectrometer:

Inlet Ion Mass

system Detector
source analyzer

Vacuum Signal
system processor

Readout
Fig: Components of mass spectrometer

The inlet system:

The ion source:
Mass analyzer:
Mass detectors:
 Different terms:

• Molecular ion/ Parent ion: M+.

• Fragment ions: Ions formed by the decomposition of the M+.
• Radical Cation: Positively charged species with an odd number of
electrons
• Base peak : tallest peak with 100%
• Mass spectrum: Graph: Number of the fragments (relative amount ) vs.
m/z value.
• m/z: mass to charge ratio of an ion
• Molecular ion peak: Peak, due to the molecular ion
• Isotopic peak:
The intensity of isotopic peak w.r.t. the molecular ion peak
depends upon
The natural abundance of the isotope and
The number of atoms contributing to the isotopic mass in the molecule
Sample inlet systems:
(A) Batch inlet system:
– For gaseous sample, boiling point < 500oc .
– Small measured volume of gas is trapped in metering volume and is expanded.
– The tubing is maintained at vacuum pressure of about 10-4 to 10-5 torr.
– Temperature is controlled by the help of oven and heating tape.
– Small amount of gas sample is then leaked into the ionization area through fine
holes (0.005mm) of glass or metal diaphragm.

Liquid
introduction Oven
Gas
1 to 3 L
introduction
Reservoir
Septum
Pine hole

To ion source

Metering volume Heating tape

Other inlet systems Vacuum
Fig:4-external sample introduction system
(B) Direct probe inlet:
(C) Chromatographic inlet system:
 The ion source:
Based on the state of the analyte used.
(a) Gas phase source: For the gaseous sample BP<500oc and MW<103Da
[EI, CI, FI].
(b) Desorption sources: For non-volatile and thermally labile sample i.e.
sample with MW> 105 Da are directly introduced into the ionization
source (energy source), which directly converts the sample into
gaseous ions. [FD, ESI, MALDI, PD, FAB, SIMS and TS].
Based on the energy supplied for ionization.
(i) Hard sources: Leads to the formation of highly energetic molecular
ion, which under go maximum fragmentation. Produce large
numbers of fragmented ions with less mass. Hard ion source give
more information’s about types of groups and functional groups and
linkage presenting the analyte molecule. EI-source is a hard ion
source.
(ii)Soft ion source: Ion source has less energy, cause slight excitation of
the analyte at ionization, this ion under go less fragmentation. The
mass spectrum consist molecular ion and few other peaks. This gives
accurate information for the molecular weight of the compound. CI-
source is a soft ion source.
 Name of different ion sources:

1. Electron impact ion 6. Matrix assisted laser

source (EI) desorption or ionization
2. Chemical ionization ion source.(MALDI)
source (CI) 7. Plasma desorption ion
3. Field ionization ion source (PD)
source (FI) 8. Fast atom bombardment
4. Field desorption source (FAB)
(FD) 9. Secondary ion mass
5. Electro spray ionization spectroscopy (SIMS)
(ESI) 10. Thermo spray ionization
(TS)
 Base peak
100 41 +
CH3(CH2) 8CH2OH
C3H5
80 55 1-decanol
+
M
60 70
158
40 83
112 +
20 91 C8H16
Relative abundance

40 60 80 100 120 140 160

100 (a) 141

+
80 (M-OH)
+
Base peak ;CH 3(CH2) 8CH2
60
40 +
(M-1)
70 84 98
20 112 157

40 60 80 100 120 140 160

(b) m/z
Mass spectrum of 1-decanol ; Comparision between (a) a hard source (b) a soft source
 1. The Electron impact ion source (EI):-
Shield
Heater Electron slit

Filament First accel. Slit Second

Molecular Gas accel slit
leak beam Focus slit

To mass
5V analyzer
Repellers 3 5
10 -10 V
Ionizing region
Electron Ion accelerating region
beam
Anode

Fig:.Electron impact ion source

• Repelled to accelerating
slits.
• which are accelerated at
high speed.
 Look the mass
spectrum of
2-chloro propane,

35
Cl 37
Cl
ratio of peak height
+
CH3 CH CH3 at mass 78 and CH3 + CH CH3
78 80 is 3 : 1 80

Cl Cl
+
+ CH3 CH CH3 CH3 CH
CH3 CH CH3 CH3 CH +
+
43 63 43 65
(stable fragment)
 Collision product peak:

• After fragmentation the collision of ion/molecules can also produce

peaks at higher mass number than that of molecular ion.
If ABCD is the molecular ion, the collision reaction can be represented
as, ABCD+. +ABCD BCD + ABCDA +.
A is transferred in the collision
• The important and most common one is the collision transfer of
hydrogen atom. It gives (M+1)+ peak.
• This reaction is second order in kinetics w.r.t. to the reactant. Thus
collision product peak can be easily distinguish from other peaks like
isotopic peak, molecular ion peak etc..
i.e. With increasing the sample pressure the height of M +1 peak
increases sharply as compared to other peaks in the mass spectra.
 2. Chemical ionization source (CI)

Gas sample (either from batch inlet or heated probe) is ignited by

the collision with reagent ions.
• Reagent ions are ions produced by colliding low molecular weight
gases (CH4, C2H6, isobutene, ammonia) with energetic electron beam.
• Excess gaseous reagents(CH4, C2H4…) are introduced in ionization
region as compared to the sample, the concentration ratio between
two is about 103 to 104.
• Reagent ions are produced by colliding these gaseous reagents with
energetic electron beam. Because of large concentration difference
electron beam reacts exclusively with reagent gases.
• As compared to the EI source, it is a soft ion source. The vacuum
pressure of the ionization chamber is about 1 torr, and 105 torr in the
analyzer. The width of the slit to the mass analyzer is reduced.
 Mass Analyzers/Resolution:
Most analyzers should be able to discriminate even minute
mass difference between two or more mass fragments.
Also analyzers should pass sufficient numbers of ions to the
detector to have detectable signal.
• The efficiency of mass analyzer can be expressed in terms of
resolution, where resolution is defined by,
R m …. (1) Where m= mass of first (mean mass between two)
m and m= mass diff. of two successive peak
• The two peaks are considered to be separated if the height of
valley between them is less than 10% of their mean height.
• For example to discriminate following molecules should be.
Resolution of MS is calculated as
Sepcies Mass Choose two species with small mass difference, 0.0112
C2H4+ 28.0313 Average mass=28.0005
Resolution = 2500.045
CH2N+ 28.0187
[also try to calculate resolution for NH3+ (17) and CH4+(16)]
N2 + 28.0061
R= 16.5
CO+ 27.9949
 Different types of mass analyzers are:
Magnetic sector analyzer:
Quadrupole mass analyzer:
Time of flight mass analyzer:
Ion trap mass analyzer:
(a) Single focusing magnetic sector analyzer:
• Ions from ionization region are accelerated
first and passed into strong magnetic field.
• Light ions with less momentum will be
deflected more than heavier
• Ions are Deflected and Sorted at suitable
angle of deflection e.g., 90o, 60o, 100o, 180o
etc.
(b) Double focusing magnetic sector analyzer:
• In double focusing instrument ions are first
focused between electrostatic sector first and
then with the magnetic sector.
Magnetic
analyzer

Electrostatic ESA slit

Analyzer(ESA)
Point of
double focus
+ - Energy focal plane

Direction Exit slit here

focal plane

Ion
Source collector
exit slit

Ion source
2. Quadrupole mass analyzer:

More compact, less expensive more

rugged
High scan rate: Entire spectrum can be
obtained in less than 10ms.
Four parallel cylindrical rods serve as
electrode, + ve and - ve pair are
connected.
Variable DC potential and variable radio
frequency AC potential, which are at 180o
out of phase are applied in each pair of
rods.
Fig: Quadrupole mass analizer
At a given moment all the ions
except having a certain m/z Ions are accelerated between the
value strike the rod and rods by potential of 5-10V.
converts to molecules. Meanwhile AC and DC voltages
Variables that effect the ion to are increased simultaneously
penetrate completely are, its maintaining their ratio constant.
velocity, m/z value, frequency Maximum resolution is obtained
of ac potential etc. when the ratio ac/dc is slightly
The transmitted ion will go to less than six.
the transducer.
Positive rods which are in XZ plane:
Absence of dc potential ions will converge
towards the center during positive half of the x
ac-cycle and diverge away in the negative z
x
half cycle
During negative half ion may strike the rod B
z
and get collapsed. + A

If positive dc potential is superimposed. + y

From Newtonian physics, the momentum of
ion of equal Kinetic energy is proportional to
square root of its mass.

Transmission
Thus if ions are heavy or ac-frequency is high
the ions are less affected by alternating Transmitted zone
potential, and will be influenced largely by dc
potential.
Ion will remain in space between the rods. Mass

But if ions are light and/or ac frequency is

low, ions get collide with the rods during
negative excursion of ac potential. Thus pair
of positive rods along XZ plane acts as the
high pass mass filter for positive ions .
• Now if we focused on negative rods
(negative dc potential) which are in YZ
x
plane:

Transmission
• In absence of ac potential all positive z
Trans
ions get drawn to the rods and mitted
collapsed. In presence of ac potential, y zone
(b)
light ions do not readily move to the Mass
rods. Thus can pass in betn the
electrodes. These rods along YZ plane
acts as the low pass mass filter.

• Thus for an ion to travel through the

quadrupole it must have stable
trajectory in both XZ and YZ planes. i.e.
x
it must be sufficiently heavy, not to

Transmission
eliminated by high mass filter in xz z
plane and must sufficiently light , not to
be eliminated by low-mass filter in yz y (c)
plane. Mass
• Thus ions are transmitted as in the
band shown in fig (c). The center of this
band can be varied by adjusting ac and
dc potentials.
 Application of mass spectroscopy:
Determination of molecular weight from Determination of molecular formula from
mass spectra: isotopic ratio:
• From molecular ion peak • In case of low resolution MS the
• CI is good method to obtain M+ peak accurate molecular formula can be
for determination of exact M. Wt. determined by the comparing the
Determination of molecular formula from intensities of (M+1)+ ion and (M+2)+ ion
molecular mass: peak with the intensity of the (M)+ peak.
For the list of compounds, (M+1)+ and
• High resolution MS (M+2)+ ion peak intensity w.r.t. (M)+ ion peak
• From a list of compounds. is available.
compounds mass Some molecules with molecular mass of 83
Purine (C5H4N4) 120.044 is given in the table.
Benzamide (C7H8N2) 120.069
Abundance , % M peak height
Ethyl toluene(C9H12) 120.096 M Formula M+1 M+2 Mol. Wt.
Acetophenone(C8H8O) 120.058 C2HN3O 3.36 0.24 83.0120
83 C2H3N4 3.74 0.06 83.0359
• For example, If the measured mass is C3HNO2 3.72 0.45 83.0007
120.070 ± 0.005, from the compounds C3H3N3O 4.09 0.27 83.0246
in the table to be Benzamide (C7H8N2). C6H11 6.66 0.19 83.0861
• The precision of estimation of
molecular formula by high resolution
MS is few parts per million.
 Isotopic peak:
• The isotopic peaks are represented by (M+1)+, and (M+2)+ peaks.
• The isotopic peaks are most apparent when atoms like, chlorine, bromine,
sulphur etc are present in the molecule.
• For e.g.: For methylene chloride, can have peaks at, m= 84, 85, 86, 87
12C1H 35Cl [m=84], 13C1H 35Cl [m=85], 12C1H 35Cl37Cl [m=86],
2 2 2 2 2
13C1H 35Cl37Cl [m=87], 12C1H 37Cl [m=88]
2 2 2

Natural abundance of some common elements, in the organic compounds

Formula for calculation of relative intensity of M + 1 and M + 2 peak with M+ peak.

RI% =  Number of atoms contributing to (M  1) X its natural abundance

=  Number of atoms responsible to (M  2) X its natural abundance
Q: Calculate the ratios of (M + 1) + and (M + 2)+
to M+ For the following two compounds:
Dinitrobenzene, C6H4N2O4(m=168) and an olefin
C12H24(m=168).

Dinitrobenzene, C6H4N2O4 An olefin C12H24

13C 6 X 1.08 = 6.48% 13C 12 X 1.08 = 12.96%
2H 4 X 0.015 = 0.060% 2H 24 X 0.015 = 0.36%
15N 2 X 0.37 = 0.74% (M+1)+/M+ = 13.32%
17O 4 X 0.04 = 0.16%
(M+1)+/M+ =  7.44%
14C 6X~0=~0% 14C 12 X ? = ?%
3H 4X~0=~0% 3H 24 X ? = ?%
16N 2X?=~0% (M+1)+/M+ = negligible
18O 4 X 0.20 = 0.80%
(M+1)+/M+ 0.80%
Structure information from fragmentation pattern: The fragmentation of odd electron
molecular ion M.+ may occur through,

Hemolytic cleavage of bond But in some cases odd electron

.+ . + cation/radical cation can give
H3C CH2 O R CH3 + H2C O R again odd electron cation after
even electron cation the fragmentation. But even
Heterolytically (by movement of electron pairs): electron cations always give even
electron ion.
.. .+ + .
H3C CH2 CH 2Br H3C CH2 CH2 + Br
even electron cation

If an ion m1 fragments after acceleration but before entering into the magnetic field it is
deflected as m2. The resulting ion current will be of low intensity, it gives a broad peaks at
apparent mass (m*), where,
m2  2
m 
m1
This peak is called Metastable ion peak. If we are able to identify this peak, it informs that m2
is directly formed from m1, by the loss of neutral fragment.
 Nitrogen rule: The masses of molecular ion also reflect the electron count depending
upon the number of N-atoms in the species. The compound containing an even number
of N-atom (or zero) will give a molecular ion with even mass number, CH4(16),
CH3OH(32), CClF3(104), C6H5OH(44), C5H5N2(72). But the compound containing odd
number of N-atom gives the molecular ion of odd mass number, NH3(17), C2H5NH2(45)
etc.
That is an odd electron ion will be at even mass number if it contains an even number
of nitrogen and has odd mass if it contains odd no of Nitrogen atoms.
Ions with no or Odd electron ion Even electron ion
even N-atoms even mass number odd mass number
Ions with odd Odd electron ion Even electron ion
no of N-atoms odd mass number Even mass number

The index of hydrogen deficiency / Degree of unsaturation (DU):

The number of pairs of H-atoms that must be removed from the original saturated
compound is called DU. Presence of DU represents either cyclic or multiple bonded
structure.
For the compound containing C, N, X, O and S,
Index of hydrogen deficiency / Degree of unsaturation (DU): = C –H/2 –X/2 + N/2 + 1.
or DU = IV – I/2 + III/2 + 1
(IV,I,III = no of 4th,1st,3rd valency elements respectively).
For example, In C7H7NO, DU = …4……..?
 Fragmentation patterns:
• The process of fragmentation follows simple and predictable chemical pathway and the ions
which are formed will reflect the most stable cations and free radicals formed from that
molecule.
• The most stable molecular ions are those from aromatic rings, other conjugated pi-electron
systems and cyclo-alkanes. Alcohols, ethers and highly branched alkanes generally show the
greatest tendency toward fragmentation.
Straight chain hydrocarbon give cluster of peaks
General mode that differs by mass unit of 14 (-CH2-).
i. Hydrocarbons The stable cation is with 3-4 carbon atoms (EI).
(Alkanes): Simple alkanes tend to undergo fragmentation
by the initial loss of a methyl group (-CH3) or
acetylene (CH2=CH2), to form species with
masses of M-15 and M-28 respectively.
Branched hydrocarbons form more stable
secondary and tertiary carbocations, and these
peaks will tend to dominate other peaks in the
mass spectrum.
 ii. Aromatic Hydrocarbons:
The fragmentation of the aromatic nucleus is somewhat complex,
CH 2+
generating a series of peaks having m/e = 77, 65, 63, etc. While
these peaks are difficult to describe in simple terms, they do Benzylic
cation
form a pattern (the "aromatic cluster") that becomes (stabilized C+ CH 2
recognizable with experience. including H
If the molecule contains a benzyl unit, the major cleavage will be “tropylium” +
HC
ion m/z=91
to generate the benzyl carbocation, which rearranges to form the
tropylium ion (gives major peak at m/z = 91). Expulsion of CH 2
acetylene (ethyne) from this generates a characteristic m/e = 65
peak(minor peak). CH+

+ +
CH2Br CH2 -C2H2
- Br + +
Benzyl bromide Benzyl cation
+ + Tropylium ion m/z = 65
M (M-Br)
m/z = 91

may under go resonance stabilization

iii. Carbonyl group (Aldehydes and Ketones):
The predominate cleavage in aldehydes and ketones is loss of one of
the side-chains to generate the substituted oxonium ion. This is an
extremely favorable cleavage and this ion often represents the base
peak in the spectrum.

Commonly two peaks differ by mass of 28 ,–CO- group.

Another common fragmentation observed in carbonyl compounds (and in nitriles, etc.)
involves the expulsion of neutral ethene via a process known as the McLafferty
rearrangement, following the general mechanism shown below. For this the compound
must contain a γ-hydrogen.
General mechanism of Mclafferty rearrangement is,

Esters, Acids and Amides also gives the similar fragmentations as the aldehydes and ketones.
.+ H .+ H .+ .+
O H H
O O N

OH NH2
RO
acid amide nitrile
ester

.+ .+
.+ .+ H
H H OH NH H
OH
OH

CH 2 NH2 CH2 H H CH2 H H

CH 2 H H OH H H
RO
iv. Alcohols: Looses water molecule and gives a intense peak. In addition to losing
water (a proton and hydroxy radical), alcohols tend to lose one of the
 -alkyl groups (or hydrogens) to form the oxonium ions shown below. For primary
alcohols, this generates a peak at m/e = 31; secondary alcohols generate peaks with
m/e = 45, 59, 73, etc., according to substitution.

v. Halides: Organic halides fragment with simple expulsion of the halogen, as shown
below. The molecular ions of chlorine and bromine-containing compounds will show
multiple peaks due to the fact that each of these exists as two isotopes in relatively high
abundance. Thus for chlorine, the 35Cl/37Cl ratio is roughly 3.08:1 and for bromine, the
79Br/81Br ratio is 1.02:1. The molecular ion of a chlorine-containing compound will have

two peaks, separated by two mass units, in the ratio 3:1, and a bromine-containing
compound will have two peaks, again separated by two mass units, having approximately
equal intensities.
 Compound identification from comparison of spectra: From the analysis of mass
spectra; mass-spectroscopist can be able to narrow the possible structure of the
sample. The final identification of the sample is based on the comparison of mass
spectrum of the unknown with spectra for authentic sample of suspected compound or
to library search system.
The assumption behind this are, the fragmentation pattern for unknown and standard
must be unique (same ion source). For this the experimental conditions must be
sufficiently controlled, to have reproducible spectra.

The lists given are by no

means exhaustive and
represents only the
simplest and most
common fragments seen
in the mass spectrum.
Reading a Mass Spec from the M+• Down
(EI)
Fragment Due to loss of… Interpretation
M+• -1 -H• Aldehydes, tert. Alcohols, cyclic amines
M+• -2 Multiple -H• Secondary alcohols
M+• -3 Multiple -H• Primary alcohols
M+• -4 to -13 (doubtful) Consider contaminants
M+• -14 (doubtful) CH2• , N• not good losses
M+• -15 CH3• Available methyl groups, methylesters
M+• -16 O• Peroxides
M+• -17 OH• Alcohols, phenols, RCO2H
M+• -18 H2O alcohols
M+• -19 -F•
M+• -20 -HF
M+• -21 to -25 No peaks expected
M+• -26 HCCH
M+• -27 •HC=CH2 or HCN HCN from pyridine, anilines
M+• -28 CO or CH2=CH2 Check for McLafferty R&R
1. Predict the peak which gives the following cluster of its isotopic mass?
m/e 94 95 96 97

Relative 100 6.1 96 1.1

abundance
Solution:
•Since the abundance of M+ and M2+ is approximately 1:1 , which indicates the
presence of Br(79).
•The rest mass is 15 (94 – 79) so -CH3 must be present.
•Thus the molecular formula should be CH3 – Br .
2. Suggest the structure of a compound with molecular formula C10H12O,
which gives peaks at m/e 15, 43, 91, 105, 148
Solution:
•m/e of 15 suggest the presence of CH3. O
•m/e of 43(15+28) indicates the presence of carbonyl group C (m = 28) as acetyl
•highest m/e 148 gives the molecular weight .
•The peak at m/e of 148 – 43 = 105 can also be explained.
•The peak at m/e = 91 (105-14) sugest presence of CH2 group. So CH3-CO-CH2-
(m=57) must be one part of the molecule.
•To explain 148-57 = 91, this peak corresponds the tropylium ion, whose precursor
is stable benzyl cation C6H5-CH2+.
•Thus the molecular formula must be C6H5-CH2-CH2-CO-CH3.
 5. If neopentane give spectrum at m/e = 72, 57, 41, 29, 27, write its
fragmentation pattern.

.+ CH3
CH3 - CH3 .
-e - CH3 +
CH3 C. CH3 H3C C CH3 C CH3
CH3 CH3 CH3
m/z=72 m/z=57
.
. H CH 2
H2C
. . CH
+C CH + CH4
3
..
CH2 +CH2
H m/z=41
in the similar rearrangement mechanism

CH3 -H2
+ - CH 2 CH 2 + CH CH 2
C CH3 CH 2 CH 3
m/z=27
gives m/z=29
CH3
 6. If compound with empirical weight C9H10O M= 134.18 has mass spectrum
try to analyze its structure. Mass Spectrum

C9H10O MW = 134.18
From M - formula, DU = C – H/2 –X/2 +
N/2 + 1= 9-5+1=5
"5 degrees of unsaturation" (five double
bonds, carbonyls, rings or any combination there
of).
Large degrees of un saturation strongly suggests an aromatic molecule (DU = 4).
A peak at m-15, strongly suggesting the presence of a labile methyl group.
The base peak occurs at m/e = 91, which is highly suggestive of a benzyl fragment.
The presence of an intense peak at m/e = 43 (28 +15)is also suggestive of the presence
of a methyl ketone, which can fragment to form the acylium ion.

Structure:

IUPAC Name: 1- phenyl propane-2-one

MS Fragments:
7. If compound with empirical weight C7H12Br MW = 171.04 has mass
spectrum try to analyze its structure.

C7H12Br MW = 171.04
From the molecular formula, the compound
has "4 DU " (four double bonds, rings or
any combination there of).
The large number of (=4) strongly suggests
an aromatic molecule.
The spectrum shows two small peaks of equal intensity in the molecular ion region,
strongly suggesting that the molecule contains bromine (equal concentrations of the 79Br
and 81Br isotopes).
The base peak represents loss of this bromine to give the peak at m/e = 91, which is
highly suggestive of a benzyl fragment, which rearranges to form the tropylium cation..
Structure:
IUPAC Name: bromomethyl
benzene (benzyl bromide)
MSFragments:
Commonly encountered Electron-
Impact fragments

O
+
29
H
CH3 C=O+
CH2 + m/z=43
43

H 77

+
CH2 +
H H
N 92
+ +
H 91
 The GC-MS
A mixture of compounds is separated
by gas chromatography, then identified
by mass spectrometry.

=>
 Molecules with
Heteroatoms
• Isotopes: present in their usual abundance.
• Hydrocarbons contain 1.1% C-13, so there will
be a small M+1 peak.
• If Br is present, M+2 is equal to M+.
• If Cl is present, M+2 is one-third of M+.
• If iodine is present, peak at 127, large gap.
• If N is present, M+ will be an odd number.
• If S is present, M+2 will be 4% of M+.
 The Mass Spectrum
Masses are graphed or tabulated according to their
relative abundance.

=>
Mass Spectrum
with Sulfur

=>
Mass Spectrum
with Chlorine

=>
Mass Spectrum
with Bromine

=>
 Mass Spectra
of Alkanes
More stable carbocations will be more
abundant.

=>
• End