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Waters UniSpray Ionization Source

S. Bajic
Waters Corporation, Wilmslow, UK

INTRODUCTION
The first commercial electrospray ionization (ESI) sources for mass spectrometers became
available at the end of the 1980s. These early sources broadened the applications of mass
spectrometry (MS) to biological compounds such as peptides and proteins which would
typically be infused into the source at low flow rates of 1–5 µL/min. Under these low flow
conditions, atomisation was achieved via a classical Taylor cone which was formed at the
end of the liquid capillary following the application of a few kilovolts between the capillary
and the ion inlet cone. More recently, this type of infusion-based analysis for biological
applications has been superseded by nanospray ESI capillaries that operate at extremely
low flow rates (10–1000 nL/min) and offer high ionization efficiency for small sample
volumes. From a commercial viewpoint, the greatest leap in the utilisation of ESI sources
came from the marriage of mass spectrometry with liquid chromatography (LC-MS) which
enabled analytical chemists to benefit from the enhanced specificity offered by both
techniques. In order to adapt ESI sources to the high flow rates (0.1–1.0 mL/min) typically UniSpray Ionization Source.
used in LC, or its modern equivalent UPLC, it was necessary to aid the atomisation process
with the addition of a concentric flow of high velocity nitrogen gas at the ESI tip. However,
when conducting infusion experiments with a fixed analyte concentration from flow rates
of 10 nL/min to 1 mL/min, it is common to observe only a 20 times increase in analyte ion
signal at the higher flow rate whilst the analyte consumption has increased by a factor
of 100,000. This is known to be due to the poor ionization efficiency of high flow rate ESI
which is critically dependent on a number of factors such as droplet size distribution,
droplet charge per unit volume, droplet evaporation rates and additional factors such as
the inlet sampling efficiency. Additionally, ionization efficiency can become particularly
challenging when using highly aqueous mobile phases. In this white paper, we introduce a
new ionization technique called UniSpray™ which attempts to increase ionization efficiency
by interacting a high velocity spray with a high voltage, cylindrical target that is positioned
in an off-axis, cross-flow arrangement. A number of physical processes will be described
which are believed to be important mechanisms that lead to enhanced UniSpray sensitivity
when compared to ESI, viz. high Weber number droplet impacts, the Coanda effect, vortex
shedding, and counter-rotating surface microvortices.

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WHAT IS UNISPRAY?
UniSpray shares some common features with high flow
rate ESI sources in that the liquid flow is nebulised by a
high velocity, concentric nitrogen gas flow. However, in
comparison to ESI, the high voltage is applied to a cylindrical
target electrode that is positioned in close proximity to
the grounded nebulizer such that the near-supersonic jet
impinges on the target surface. A schematic of the UniSpray
source is shown in Figure 1. The source is formed by directing
a high velocity nebulised jet from a grounded sprayer onto
a cylindrical metal target that is held at a high voltage and
is located between the sprayer and the ion inlet orifice of
the mass spectrometer. For singly charged analytes, it is
conventional to use a positive potential of typically 1 kV for
positive ion analysis and vice versa for negative ion analysis.
For multiply charged analytes, such as peptides and proteins,
it is generally found that higher potentials of 3–4 kV are
required for signal optimisation. The pneumatically-assisted
nebulizer is formed from a 130 µm I.D. by 220 µm o.d. liquid
delivery capillary (stainless steel) that is surrounded by a
330 µm I.D. nebulizer tube (stainless steel) with a restriction
length of 10 mm. Nitrogen gas is delivered to the nebulizer
tube at a gauge pressure of 7 bar. Under these conditions,
the nitrogen jet will be near supersonic at a distance of a few
millimetres from the nebulizer tip. The distance over which the
inner capillary protrudes from the nebulizer tube is adjustable
and is typically found to optimise at very small protrusions
(<0.2 mm) where the spray appears highly collimated. In a
conventional manner, the nebulizer is also surrounded by an
annular heater that delivers hot nitrogen gas at a flow rate of
typically 1200 L/hr.
Figure 1. A schematic of the UniSpray API source.
The 1.6 mm-diameter, 35 mm long, cylindrical HV target is
constructed from a cold-drawn, 316L stainless steel wire that
is polished to a near-mirror finish with 1 µm-grade lapping
paper. The target is connected to a 0–5 kV DC power supply
via a 47 MΩ current-limiting resistor. Since the target has a
low thermal conductance to the source housing, it rapidly
reaches an equilibrium temperature that is equal to the local
temperature of the heater gas (typically >250 °C for a heater
set-point temperature of 500 °C). In order to optimise source
sensitivity, it is critically important to adjust the point at which
the collimated spray impacts on the cylindrical target. As
shown in Figure 1, the maximum signal intensity is typically
obtained when the spray is asymmetrically positioned such
that it impacts on the upper right quadrant of the target.
Under these conditions, the gas flow becomes attached to a
portion of the curved surface and results in asymmetric gas
streamlines in the wake that are directed towards the ion
inlet orifice. This flow phenomenon is known as the Coanda
effect. Under the influence of the Coanda flow field, ions and
charged droplets are directed towards the ion inlet which is
surrounded by a cone gas nozzle that supports a drying gas
flow of nitrogen at 150 L/hr.
UniSpray sources are generally found to give enhanced
ionization efficiency when compared to high flow rate ESI
which, in turn, can lead to enhanced analytical sensitivity.
Some general characteristics of the UniSpray source have
been studied by Lubin et al1 . These authors compared the
signal intensity obtained by ESI and UniSpray for small
pharmaceutical compounds (16 analytes in positive ion
mode and 7 in negative ion mode) with acidic, basic and
neutral mobile phase types. Figure 2 shows the signal gains
(UniSpray ion intensity divided by ESI ion intensity) obtained
at various mobile phase compositions and for three different
flow rates. Here, each point is an average of the pooled data
for each compound and each mobile phase type. From these
plots it can be concluded that the signal intensity observed
with the UniSpray source is, on average, higher than the ESI
signal for all mobile phase compositions with relatively higher
gains observed under higher aqueous conditions. The full
data set exhibited a strong compound dependence where,
whilst UniSpray gains in excess of x20 were observed under
certain conditions, other analytes could occasionally give
greater responses with an ESI source.
In view of the performance enhancements outlined above,
the following sections will consider some underlying physical
mechanisms that are unique to the UniSpray source and may
contribute to the observed increase in ionization efficiency or
ion sampling efficiency.
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Figure 2. A comparison of the average signal intensity ratios for UniSpray and ESI versus mobile Figure 3. Typical droplet size distribution for a pneumatically
phase composition for 16 positive ion analytes and 7 negative ion analytes (from reference1). assisted ESI probe at a flow rate of 0.5 mL/min of water
(Malvern Instruments Spraytec system).

DROPLET SIZE DISTRIBUTION: THE LIMITATION OF HIGH experimental techniques where, in particular,
FLOW RATE ESI the ping-pong drift cell method4 more closely
In the traditional ESI model, charged droplets are formed by positive and resembles the dynamics of LC/MS sources.
negative charge separation in the high electric field region at the tip of the The diameter of a droplet, dp, after an evaporation
liquid capillary. At very low flow rates (<1 µL/min), this process proceeds time, t, an evaporation rate, s, and an initial
with extremely high efficiency to yield highly-charged, sub-micron droplets droplet diameter, d 0 , is given by
that almost instantaneously give rise to gas phase ions due to Rayleigh dp2 = d02 − st (i)
disintegration processes . However, at the high flow rates typically used in
2

LC and UPLC-MS (100–800 µL/min), it is necessary to use a high velocity where s has been experimentally determined as
nebulizer gas to atomize the liquid flow, a process which is known to 1250 and 6500 µm2s-1 for water and acetonitrile,
produce larger droplets with a lower charge per unit volume and hence respectively4 . According to equation (i), Figure
lower ionization efficiency3 . 4 shows a plot of initial droplet diameter versus
droplet diameter after an evaporation period
Whilst the use of a high velocity gas is advantageous from an atomisation
of 100µs for water and acetonitrile. From these
viewpoint, it has the disadvantage of reducing the residence time of
data, it becomes apparent that (i) droplets above
droplets between the ESI capillary and the ion inlet orifice of the mass
2 µm in diameter do not undergo significant
spectrometer, which, in turn, reduces the time available for droplet
evaporation in this time frame and (ii) rapid
evaporation which is critical to the Rayleigh disintegration process.
evaporation only occurs for diameters below
In-house measurements, using Phase Doppler Anemometry (PDA) and
the “knee” of the curve, which corresponds
Laser Diffraction Particle Sizing (LDPS) reveal that the ESI and UniSpray
to approximately 0.4 and 1.0 µm for water
nebulizers typically produce initial droplet size distributions that peak at
and acetonitrile, respectively. Initial droplets
typical diameters of d 0 =10 µm in the volume domain and d 0 =1 µm in the
diameters below the value d0 (crit.) in Figure 4
number domain. Figure 3 shows typical LDPS droplet distributions obtained
will completely evaporate in this time period
by nebulising a flow of 0.5 mL/min of water under ambient conditions
(approximately 0.35 and 0.8 µm for water and
using a nebulizer as described above (no target). These distributions reveal
acetonitrile, respectively). In essence, this would
that although the greatest numbers of droplets are produced at micron
suggest that a 100 µs residence time is totally
and submicron diameters, the overwhelming volume of the spray, and
inadequate for efficient evaporation of the larger
hence analyte, is contained within droplets that are significantly greater
droplets that dominate the volume distribution
than a micron in diameter. PDA measurements also reveal that droplets
in high flow rate ESI. While this laminar-flow
on the spray axis can have average velocities in excess of 100 ms -1 which
evaporation model may be oversimplified, it
corresponds to a residence time of <100 µs for the sources used in this
would suggest that only sub-micron droplets
study (ignoring recirculation effects). This source residence time represents
would participate in the production of gas phase
the time period during which significant droplet evaporation must occur in
ions by the ESI process. Since the sub-micron
order to promote the Rayleigh disintegration process. Droplet evaporation
population represents <1% of the total sprayed
rates have been determined for a number of common solvents and

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Figure 4. Evaporation rates for water and acetonitrile droplets for a 100 µs
evaporation time.
volume at high flow rates (Figure 3), this would contribute
to the low ionization efficiency typically observed with high
flow rate ESI when compared to nanospray ESI (<1 µL/min),
where submicron-sized droplets contribute significantly to
the volume distribution.
HIGH WEBER NUMBER DROPLET IMPACTS
The above inefficiency argument was the original inspiration
for the UniSpray ionization source that compels high velocity
droplets to impact onto a hot metallic surface which results
in their break-up into smaller secondary droplets that can
be evaporated more efficiently at low source residence
times. A number of groups have studied the break-up of
water droplets on heated stainless steel surfaces 5 . These
workers experimentally determined that the number of visible
secondary droplets (Nvis) produced per impact was directly
proportional to the droplet Weber number (We), which, in turn,
is directly proportional to the droplet diameter (d) and the
square of its velocity (v):
Nvis = 0.0427 We + 10.465 (ii)
We = ρv2 d⁄σ (iii)
where is ρ the droplet density and σ is the liquid surface
tension. The Weber number can be regarded as the ratio
of droplet kinetic energy to droplet surface energy. Thus, it
stands to reason that the collision of a droplet with kinetic
energy that far exceeds the droplet surface energy will result
in instability and droplet break-up.
To illustrate the break-up mechanism, Figure 5 shows a time
lapse sequence of a water droplet (We=630) as it impacts on
a planar, polished stainless steel surface which is held at a
temperature of 260 °C. In the case of a UniSpray source, it can
Figure 5. High speed photographs of the break-up of a water droplet on a hot
stainless steel plate (from reference5).
be shown from equations (ii) and (iii) that a water droplet with a
diameter of 4 µm and a velocity of 100 m/s would have a Weber
number of 571 and would give rise to 35 visible secondary
droplets on impact with the hot target. If we consider a
simple, linear break-up model, this would result in secondary
droplets with diameters of the order 1.2 µm. More realistically,
a skewed Gaussian distribution for the secondary population
would contain sub-micron droplets (equivalent to the invisible
droplets that could not be detected by the experimental
method used in the above work). As described in the previous
section, an increase in the sub-micron droplet population could
be expected to significantly increase the droplet desolvation
process and aid ionization efficiency.
In addition to shifting the droplet size distribution to smaller
diameters, the impact process may play an additional role
that may be important for ionising certain analytes that may
be weakly ionised by ESI due to their low surface affinity. In
ESI, droplets with a high surface affinity (such as detergents)
tend to preferentially ionise at the droplet surface and are
ejected from the parent droplet as Rayleigh fission processes
occur. Less surface active analytes which may previously
have been paired with negative counterions in the core of the
parent droplet may now populate the surface. However, the
surface charge of the parent droplet has become reduced as
a result of the fissions which greatly reduces the probability of
further fissions and hence ionization of the less surface active
analytes. A prompt and violent breakup of initial droplets
that have already partitioned due to their relative surface
affinity may increase the probability of secondary droplets
being formed from the core of the initial droplet provided that
adequate charging occurs during this process.
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When a droplet in a flow of gas approaches a target, the

necessary conditions for a collision with the target will be
determined by the Stokes number, Stk, and the turbulence
of the flow where

Stk = ρvd2 ⁄18µD (iv)

Here, µ is the dynamic viscosity of the gas, D is the diameter

of the target and the other terms are as defined in equation
(iii). Flow turbulence is governed by the Reynolds number,
R e , which will be described in more detail in the following
sections of this paper. Droplets that have Stk≤1 (termed
Stokesian particles) tend to follow the gas streamlines
whilst those with Stk>1 tend to deviate from the streamlines
and strike the target owing to momentum dominance over
the drag forces. Figure 6 shows a plot of Stk versus droplet
diameter for water droplets with a velocity of 100 m/s and
a UniSpray target diameter of D = 1.6 mm. This shows that
small droplets with diameters below dlim.= 2.5 µm would be
expected to avoid collisions with the target and would follow
the gas streamlines. Conversely, larger droplets (d>2.5 µm),
which account for the majority of the spray volume in a
UniSpray source (Figure 3), would be expected to strike
the target, thus creating smaller secondary droplets. As
previously mentioned, the impact efficiency will decrease
with increasing flow turbulence. Importantly, it should also
be noted that the smaller droplets that avoid collisions
with the target will still benefit from other unique flow
characteristics of the UniSpray source which will be
described in the following sections.
Although the impact of high Weber number droplets
is believed to be an important feature of the enhanced
sensitivity observed with the UniSpray source, it can be
experimentally demonstrated that wide area, flat-plate
stainless steel targets do not give rise to significant and
stable signal enhancements over ESI. In this respect, it is
believed that the geometrical form of the UniSpray source,
shown schematically in Figure 1, plays an additional role
in the enhancement of ionization efficiency. In particular,
it is believed that the curved profile of the target and the
off-axis, perpendicular cross-flow arrangement between
the sprayer and the target give rise to two important gas
flow phenomena that may aid the break-up and desolvation
of liquid droplets in the source, viz. the Coanda effect and
6 desolvation process by enhanced mixing and hence dilution
surface microvortices 7.
Figure 6. A plot of Stokes Number versus droplet diameter for 100m/s water
droplets in a UniSpray source.
THE COANDA EFFECT
The Coanda effect is a phenomenon whereby a fluid flow
attaches itself to a nearby surface and remains attached even
as the surface bends away from the initial fluid direction.
Figure 7(a) shows a schematic illustration of this effect
and an actual photographic image of flow attachment to
the high-voltage cylindrical target in a UniSpray ionization
source. This image shows that the gas and droplets from
the off-axis, nebulizer jet are deflected towards the ion inlet
orifice as shown schematically in Figure 1. As a water droplet
evaporates, the gas surrounding the droplet can rapidly
become saturated with water vapour, which ultimately
reduces the rate of evaporation due to re-condensation on
the droplet surface. In API sources, this effect is minimised by
supplying a flow of heated dry nitrogen gas to the nebulised
spray where the nitrogen becomes “entrained” into the
nebulizer flow due to the low pressure created by the high
velocity nebulising jet. In the case of Coanda flow attachment
to a curved surface, as occurs at the UniSpray high-voltage
target, it is the imbalance of the entrainment flow where flow
cannot penetrate from one side that ultimately leads to a
deflection of the gas streamlines towards the target surface.
This effect is known to create a stronger total entrainment
when compared to a free jet which could aid the droplet
of the water vapor.

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Figure 7(b) illustrates the effect of “droplet beam steering” that occurs due
to the Coanda effect in UniSpray sources. As the nebulizer jet impact point
is adjusted from a central to an off-axis position on the upper right hand
quadrant of the Ø1.6 mm target, the ion signal intensity rapidly increases
until an optimum is reached. This characteristic is found to be compound
dependent but is generally a subtle, as opposed to a critical, tuning
parameter that allows an acceptable compromise tuning position to be
found for multi-polarity analyte mixtures. Conversely, Figure 7(b) shows that
impacting on the upper left hand quadrant of the target results in a severe
loss of ion signal as the deflected wake is directed away from the ion inlet
cone and ion sampling efficiency is adversely affected. It should be noted
that the term beam steering is used as opposed to focussing since the gas
streamlines will not cross to form a focal point. It is also anticipated that this
flow geometry will give rise to a momentum separation effect where smaller
droplets will tend to follow the Coanda flow towards the MS ion inlet whilst
the larger non-Stoksian droplets will continue in a forward direction and
become separated from the Coanda flow.

Effects that occur in the “wake” of the deflected gas flow could also be
beneficial in terms of droplet break up and enhanced droplet desolvation as
charged droplets are directed towards the ion inlet cone. One such effect is
periodic vortex shedding that occurs behind a cylindrical object where the Figure 8. A typical illustration of van Karmen vortex flow
frequency of shedding increases as the velocity of the gas flow increases. behind a cylinder for moderate Reynolds numbers.

Figure 8 shows an example of classic vortex shedding that occurs behind

a cylinder as the gas flow moves from the top to the bottom of the image. parallel plane in front of, or behind, the plane
The transition between laminar (uniform) flow and turbulent flow in these of Figure 8. However, as R e progressively
systems is determined by the Reynolds number (R e) where increases above a value of 2300, the flow
becomes turbulent, or three-dimensional. It can
Re = ρvD⁄µ (v)
be shown that the near-supersonic gas flow at
where ρ and µ are the density and viscosity of the gas. At low R e (<10), the the UniSpray target will have a highly turbulent
gas will flow uniformly around the cylinder which results in a uniform wake flow wake with a R e of typically 30,000. Under
that contains no vortices. As R e is increased to a value of, for example 400, these conditions, it is proposed that primary
the flow wake will include a number of vortices as shown in Figure 8. This or secondary droplets will be subjected to
flow regime is not considered to be turbulent since the “vortex street” is enhanced desolvation due to increased shear
relatively two-dimensional, such that the same vortex pattern exists in a forces, increased entrainment (mixing) and an
increased residence time in the turbulent flow.

To understand the importance of turbulence in

aiding droplet break-up, we should reconsider
the expression for the Weber number (equation
(iii) above). In pneumatic nebulisers, liquid
droplets are created with low initial velocities,
vl , and are surrounded by a high speed gas
jet with a velocity, vg . It is the difference in
these two velocities that gives rise to initial
droplet shearing where v2 in equation (iii) is
now substituted by (vg−vl)2. In a pneumatically-
assisted ESI probe, where the gas flow is
significantly less turbulent than the gas flow at
Figure 7. (a) A schematic and photographic evidence of Coanda gas flow in a UniSpray source; a UniSpray target, the initial droplets reach a
(b) The dependence of UniSpray ion signal versus the position of the spray impact point.

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terminal velocity at a distance of approximately 5 mm from
the tip. At this point, vg−vl becomes zero and the shearing
process stops. In comparison, the UniSpray source creates
chaotic, turbulent flow over a greater proportion of the droplet
in-source trajectory which reduces the probability that
vg−vl=0, particularly for the larger, non-Stokesian droplets.
In the case of the UniSpray source geometry, it can be shown
that the frequency of shedding (fs) is given by
fs = v S r ⁄D (vi)
where v is the freestream gas velocity, D is the cylinder
diameter and S r is the dimensionless Strouhal number. S r is
related to the Reynolds number (R e) by
S r = 0.198(1−19.7/Re) (vii)
For a near-supersonic nitrogen gas flow (v=300 ms -1) and a
Ø1.6 mm cylinder, it can be shown that the vortex shedding
frequency in the wake of the UniSpray target may be as
high as 37 kHz (ultrasonic). As an experimental observation,
it is found that the point of signal optimisation shown in
Figure 7(b) is accompanied by both a visual increase in
“wake disturbance” and an audible increase in sound from
the UniSpray source. On this latter point, it is not clear
whether significant energy is mechanically imparted into
the cantilevered target, but experiments in this laboratory
with ultrasonic nebulisation via a similar 40 kHz agitation
of a target (no gas) reveal enhanced ionization of non-polar
analytes that are difficult to ionise by ESI; relatively large
sensitivity enhancements over ESI for certain non-polar
compounds is also a characteristic of UniSpray under
certain conditions.
CROSS-FLOW SURFACE MICROVORTICES
As described in the section above, a gas flow will become
attached to the surface of a cylinder at the stagnation point
and will detach from the surface at a downstream point
known as the separation point. This is shown schematically
in Figure 9 where the region bounded by the stagnation
and separation points is known as the stagnation zone.
For the near supersonic nebulizer conditions encountered
with UniSpray, the stagnation zone can be shown to have a
radial thickness of the order 10 µm over which a flow velocity
gradient exists from zero at the surface to the freestream
velocity. Primary or secondary droplets that enter this
reduced velocity region would be expected to experience
enhanced desolvation due to (i) an increased residence time,
(ii) greater thermal transfer from the hot target surface and
(iii) increased agitation/entrainment with the hot nitrogen flow
due to surface vortex effects.
Figure 9. A schematic representation of the stagnation zone that is formed
as gas flows over a cylinder.
This latter point is a further feature that is unique to the cross-
flow geometry of the UniSpray source and will be considered
in more detail in this section.
For a cylinder in cross-flow, a uniform gas flow will become
inherently unstable (three dimensional) in the stagnation
region where the flow becomes attached to the curved
surface. These instabilities take the form of a linear series
of counter-rotating vortices whose axes of rotation are
aligned with the streamlines of the gas flow. A single vortex
pair is shown schematically in Figure 10(a). The disturbance
wavelength, λ, between adjacent counter-rotating pairs is
known to be directly proportional to the cylinder diameter
(D) and inversely proportional to the square root of the local
Reynolds number (R e) so that
λ = κD⁄√R e (viii)
where κ is a constant and Re is defined in equation (v) above.
Kestin and Wood7 have used wind tunnel tests with oil coated
cylinders to experimentally verify the relationship between λ
and Re and their results are reproduced in Figure 10(b). Using
the Tu=4% (tubulence intensity) plot and assuming a nebulizer
velocity of Mach-1 and D=1.6 mm, Figure 10(b) would predict
a disturbance wavelength (λ) of approximately 37 µm for the
surface microvortices on a UniSpray target electrode. Firstly,
this disturbance dimension is significant in that it is of the
same order as the size of the larger droplets and thus could
be expected to efficiently impart energy into the droplets to
aid break-up. This efficiency dependence on the size of the
perturbation is analogous to, for example, microwave heating
where the microwave frequency is chosen to match the natural
rotational frequencies of water molecules. Secondly, the highly
mobile smaller droplets that enter the vortex region would be
highly agitated compared to those in the freestream and would
benefit from enhanced mixing and enhanced heat transfer.
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Therefore, in a similar manner to the vortex shedding region described in the

previous section, this surface boundary layer region represents an additional
desolvation enhancement zone that subjects droplets to an increase in
residence time, shearing and entrainment.

Figure 11 shows a scanning electron microscope (SEM) image of a 1.6 mm

diameter, stainless steel UniSpray target which was used for the analysis
of analytes contained in protein-precipitated human plasma. The granular,
circular “halo” is due to the deposition of involatile components of the
plasma and is not relevant to the present discussion. The SEM image was
taken in the same direction as the impinging droplet stream and nebulizer
gas jet. The cross (+) in Figure 11 is an approximation of the point of impact,
and hence stagnation point, of the incoming nebulizer jet and was located
from an optical micrograph of the same target. A close examination of the
circled region of the image reveals a linear series of striation marks which
are aligned with the direction of the flow streamlines. These striation marks,
which are not visible at optical wavelengths, are evidence of the existence
of counter-rotating surface vortices as described above. From this image,
we can estimate a disturbance wavelength (λ) of 23 µm which assumes that
three striation marks represent the outer extent and centre of one counter-
rotating vortex pair. Thus, there would appear to be some correlation
Figure 11. An electron micrograph of an UniSpray target
between the observed experimental data and the theory of surface vorticity showing evidence for the existence of a linear series of
for cylinders in cross-flow. surface microvortices at the flow separation point.

Figure 10. (a) A schematic of a counter-rotating vortex pair on the surface of a cylinder with a cross flow of gas; (b) The relationship between disturbance wavelength
(λ) and the inverse of the square root of the Reynolds number for a cylinder in cross flow (from reference7).

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Figure 12. The effect of a large surface defect on the sensitivity of a
UniSpray source.
THE ROLE OF THE TARGET SURFACE
In this paper, we have sought to provide an explanation of
how the unique geometry of the UniSpray source gives rise
to a number of hydrodynamic and aerodynamic phenomena
that may aid in the nebulisation and desolvation of primary
droplets from the liquid capillary. Whilst these hypotheses
may be supported by the observation of a greater increase
in sensitivity over ESI for high flow rates and highly aqueous
mobile phases, where nebulisation and desolvation are
particularly difficult, it is clear that a full understanding of
these effects is far from complete. The processes described
thus far are highly interdependent and highly complex from
a modelling perspective. In particular, the exact role of the
metallic surface in the flow stagnation region is not
fully understood.
It is known that any significant damage (gouging) to the
target surface in the stagnation region will severely affect
the UniSpray source performance. Referring to Figure 11, if
we assume that the cross represents the location of the flow
stagnation point and the end of the striation marks represent
the flow separation point, we can determine from a simple
geometric projection that the UniSpray target stagnation
zone subtends a radial angle of approximately 46 degrees.
For a 1.6 mm diameter target, this equates to a stagnation
zone that has a 0.65 mm circumferential length. Since the
effects of Coanda steering, surface microvorticity and vortex
shedding are all associated with the formation of a stagnation
zone, one would assume that any gross interference
with this region would have detrimental effects on the
performance of the UniSpray source. To test this hypothesis,
an experiment was conducted where a surface groove, with
an equivalent width to the stagnation length (0.65 mm), was
cut longitudinally into the 1.6 mm diameter stainless steel
Figure 13. A schematic representation of the formation of surface liquid
filaments and secondary droplets at the flow separation point on a
UniSpray target.
target. It can be shown that by rotating the position of the
groove with respect to the stagnation region, significant
sensitivity decreases are observed when the groove overlaps
the stagnation zone. Figure 12 shows the effect of target
groove position on the relative signal intensity for a UniSpray-
MS analysis of busiprone and reserpine which were infused
into the source at a concentration of 0.125 pg/µL and a flow
rate of 0.8 mL/min. Referring to Figure 12, the highest signal
intensity is observed when the groove is positioned well away
from the stagnation zone (upper right hand quadrant). The
lowest sensitivity is observed when the groove completely
overlaps the upper right hand quadrant, where presumably,
the stagnation region is overwhelmed by turbulence such that
a clear definition between a stagnation zone and freestream
flow no longer exists. The two additional reference points
for busiprone and reserpine were obtained from a different
1.6 mm-diameter target which contained no groove. Whilst
this experiment does not distinguish between the relative
importance of the dominant processes described in this
paper, it further reinforces the hypothesis that the curved
surface is central to the enhanced signal and ionization
efficiency observed with the UniSpray source.
Throughout this paper, we have considered the dominant
ionization mechanism to be based on an electrospray-type
process where gas phase ions are created by evaporating
charged liquid droplets. Whilst some droplet charging may
originate at the point of nebulisation, it is likely that charging
will occur at the point of impact on the high voltage target via
a process that resembles (i) electrospray charge separation,
(ii) spray electrification 8 or (iii) statistical charging such as
observed in sonic spray9 or thermospray ionization10 . It is
plausible that an explanation of all experimental data obtained
over a wide range of analyte classes, mobile phases and flow
Waters UniSpray Ionization Source 9
[ WHITE PAPER ]

rates cannot be attributed to a single ionization mechanism. Referring to References

Figure 2, it is known that the general behaviour of the UniSpray source 1. A. Lubin, S. Bajic, D. Cabooter, P. Augustijns, and F.
undergoes a transition at flow rates between 100 and 200 µL/min, which Cuyckens, J. Am. Soc. Mass Spectrom., 28, 286-293
(2017).
results in distinct differences in the gain versus mobile phase composition
2. P. Kebarle, J. Mass Spectrom., 35, 804-817 (2000).
plots for the low flow rate data. In view of this observation, an alternative
3. R. Juraschek, T. Dulcks, and M. Karas, J. Am. Soc.
model could be considered where the actual generation of charged droplets
Mass Spectrom., 10, 300-308 (1999).
occurs due to wetting of the target surface and the subsequent effects of
4. R.L. Grimm and J.L. Beauchamp, Anal. Chem., 74,
the high velocity gas flow on the wetted zones. A schematic of this process 6291-6297 (2002).
is shown in Figure 13 where the size of the wetted region is massively 5. S.W. Akhtar, G.G. Nasr, and A.J. Yule, Atomization
exaggerated. Wetting is known to occur on the underside of the cylindrical and Sprays, 17, 659-681 (2007).

target and is particularly prevalent at high flow rates and with highly 6. A. Dumitrache, F. Frunzulica, and T.C. Ionescu,
Mathematical Modelling and Numerical
aqueous mobile phases. The surface liquid could exist just below the Investigations on the Coanda Effect, Chapter 5 of
flow separation point shown in Figures 9 and 13 where the local surface Nonlinearity, Bifurcation and Chaos - Theory and
gas flow is stagnant but the flow velocity is high at a small distance (>10 µm) Applications, ISBN 978-953-51-0816-0 (2012).

from the surface. This gas flow could create secondary droplets from the 7. J. Kestin and R.T. Wood, J. Fluid Mech., 44,
461-479 (1970).
resulting liquid filaments shown in Figure 13. In fact, it is conceivable
8. L.B. Loeb, Static Electrification, ISBN 978-3-
that the surface liquid at this junction could be “squeezed” between the 642-88243-2 (1958).
counter-rotating microvortices (Figure 10(a)) to form a linear series of 9. A. Hirabayashi, M. Sakairi, and H. Koizumi, Anal.
secondary droplet emitters which may be responsible for the striation Chem., 66, 4557-4559 (1994).
marks shown in Figure 11. Although this model differs from one based on 10. V. Katta, A.L. Rockwood, and M.L. Vestal, Int. J.
Mass Spectrom. Ion Processes, 103, 129-148 (1991).
high We -number droplet impacts, it does however depend on the same
aerodynamic principles outlined in the previous sections.

Although not covered in any detail here, it is also believed that the
nebulizer/target gap current and its effect on the charging of both the target
surface and gas phase molecules is another important parameter that will
influence the performance of a UniSpray source. In fact, experiments with
an ambient UniSpray source in this laboratory have shown that gas phase
ion/molecule reactions are highly likely to occur under these operating
conditions. Furthermore, such reactions can be expected to benefit from
the enhanced desolvation processes that occur with the UniSpray
geometry, as highlighted in the previous sections.

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