Analytica Chimica Acta 677 (2010) 3–18

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Review

Fundamentals and applications of needle trap devices

A critical review
Heather L. Lord, Weiqiang Zhan, Janusz Pawliszyn ∗
Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, ON, Canada, N2L 3G1

a r t i c l e i n f o a b s t r a c t

Article history: The needle trap device (NTD) is an extraction trap that contains a sorbent inside a small needle, through
Received 30 March 2010 which fluid can be actively drawn into and out of by a gas-tight syringe or pump, or analytes can be
Received in revised form 16 June 2010 introduced passively to the trap by diffusion. The needle trap (NT) is a potentially solventless sampling
Accepted 16 June 2010
technique/sample preparation and introduction device. Both fluid-borne analytes and particles can be
Available online 25 June 2010
trapped inside the needle and then adsorbed analytes are desorbed in an inlet of analytical instrument
and introduced for identification and quantification. The fluid may be either gaseous or liquid. The objec-
Keywords:
tives of this critical review are to summarize the theory of the sampling process for both active and
Needle trap device
Sample preparation
passive time-average extraction modes in addition to outlining the evolution of the technology and main
Solid phase extraction applications.
Solid phase microextraction © 2010 Elsevier B.V. All rights reserved.
Liquid chromatography
Gas chromatography

Heather Lord is a Research Associate in the group
of Professor Pawliszyn with experience in analyti-
cal device and method development, sorbent design,
and solid phase sample preparation. She has authored
over 40 scientific papers in biochemical toxicology
and bioanalytical method development. Her primary
research interests are in the areas of in vivo sample
preparation and new bioanalytical methods develop-
ment.
application of imaging detection combined with microseparation approaches.
The primary focus of Professor Pawliszyn’s research
program is the design of highly automated and inte-
grated instrumentation for the isolation of analytes
from complex matrices and the subsequent sep-
aration, identification and determination of these
species. Currently his research is focusing on elimina-
tion of organic solvents from the sample preparation
step to facilitate on-site monitoring and in-vivo
analysis. Professor Pawliszyn is also exploring appli-
cation of computational and modeling techniques to
enhance performance of sample preparation, chro-
matographic separations and detection. An additional
area of his interest involves the development and

Weiqiang Zhan is currently a Master’s student in Pro-

fessor Pawliszyn’s group. He primarily works on the
development and application of needle trap. 1. Introduction

There are five types of needle-based extraction methods (Fig. 1).

∗ Corresponding author. Tel.: +1 519 888 4641; fax: +1 519 746 0435.
E-mail addresses: hlord@uwaterloo.ca (H.L. Lord), w2zhan@uwaterloo.ca
(W. Zhan), janusz@uwaterloo.ca (J. Pawliszyn).
A number of reviews summarize the evolution and progress of
these relatively new technologies [1–10]. In the current review we
aim to provide a broader treatment of the subject as well as bring
the material covered as up to date as possible. The most commer-
cially successful of the needle-based extraction methods to date is
solid phase microextraction (SPME) in the coated micro fiber for-
mat [11–14] (Fig. 1A). This technology introduced the concept of an
extraction phase within a small 22–23 gauge needle and demon-
strated high sensitivity of the microextraction approach. Sensitivity
is comparable to traditional large volume extraction methods due
to high enrichment onto the small volume of extraction phase and
introduction of all extracted analytes to instrumental analysis. A

0003-2670/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.aca.2010.06.020
4 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18
Fig. 1. Schematics of: A: SPME fiber located in a needle; B: in-tube SPME or INCAT;
C: SPDE; D: SDME; and E: scheme of a sorbent-packed NTD.
very important feature of this technique has been the solvent-
free nature of this extraction format and convenient instrument
introduction resulting in high level automation using autosampler
robots. Following the success of SPME other small needle extrac-
tion methods were proposed [15] and developed [15–17] which
used a piece of gas chromatography (GC) capillary column inside
the needle (in-tube SPME or in-needle capillary adsorption trap
(INCAT), Fig. 1B). Also described were the internally coated needles
(Fig. 1C) named solid phase dynamic extraction (SPDE) [18,19], a
needle microliter volume liquid phase microextraction (Fig. 1D)
named a single drop microextraction (SDME) [20–22] and finally
a packed needle format (Fig. 1E) named needle trap device (NTD),
which is the subject of this review. The strength of the NTD tech-
nique, similar to other needle-based techniques, is its potential
for laboratory automation and on-site sampling compatibility with
convenient coupling to analytical instrumentation. The main dif-
ference between NTD and the first four is its exhaustive extraction
nature, which simplifies the calibration and allows particle trap-
ping, resulting in total concentration information as compared to
a free concentration information provided by the other techniques
illustrated in Fig. 1. In that regard it is similar to the much larger
sorbent traps commonly used in numerous analytical applications
[23].
As NT it is an exhaustive technique rather than a microex-
traction, for air analysis it may be compared to other exhaustive
methods where pumps, filters and sorbents are employed to inter-
rogate the total sample. Such methods require back extraction from
the sorbent or filter followed by subsequent analysis. For liquid
samples SPE methods are comparable. These techniques are typ-
ically applied to large sample volumes, and consequently require
lengthy and large volume clean-up and desorption steps, with only
a small proportion of the final purified analyte being applied to the
analytical instrument. By miniaturizing all components the method
is perhaps more comparable to micro-SPE, although the NTD design
permits the sampling, sample preparation, and sample introduction
to be combined, with quantitative transfer of analyte to the instru-
mental analysis. The goal is to simplify the sample preparation
by eliminating the time and expense associated with processing
unnecessarily large volumes, while retaining the required method
sensitivity.
In NTD quantification is performed by simply determining the
amount of compound exhaustively extracted by reference to instru-
ment detector response calibration, and expressing this per volume
of original sample. The first four techniques are microextraction
techniques and so extraction depends on the kinetic and thermo-
dynamic properties of the extraction phase and sample. In this case
calibration by either internal or external standard is used to account
for both the kinetics/thermodynamics of the extraction as well as
the instrument detector response. Below we summarize the fun-
damental principles behind the NTD technique that could be useful
in optimization of the needle trap design, and summarize progress
and applications investigated to date.
2. Theory
2.1. Exhaustive active sampling
In NT sampling, since the sample is introduced continuously into
the needle, the process of extraction in the needle can be described
as frontal (gas–solid) chromatography. In frontal chromatography,
the capacity of column – the packed needle in our case – is an impor-
tant parameter since it determines when the needle is saturated by
the analytes and consequently unable to adsorb any more analytes.
The capacity, described by the breakthrough volume in needle trap,
is affected by gas pressure, temperature, humidity, flow rate and
sorbent bed geometry [24], and is closely related to the shape of the
eluting front which can be described as the integral of a Gaussian
peak.
Based on the frontal chromatography assumption, many
attempts have been made to find a mathematical relationship
between sampling capacity and chromatographic parameters such
as the retention volume and number of theoretical plates. With
such attempts, several models have been developed [25–27],
among which the model of Lovkvist et al. [27] is the most appro-
priate for needle trap. In this model, the theoretical plate number
(n) was expressed as:
uL
n= (1)
2D
where L is the length of the packed sorbent bed, D is the apparent
diffusion constant which is intended to include all mechanisms of
dispersion, and u is the linear gas velocity.
Ignoring the gas compressibility and assuming that the flow rate
is constant, the linear flow rate (u) of the gas sample through the
needle can be calculated by considering the packing density and the
pressure drop using typical equation applicable for porous media:
Q
u= (2)
A
where Q is the volume flow rate in the needle, A is the cross-
sectional area of the needle,  is the porosity of the sorbent bed.
The volumetric flow rate can be defined by [28]:
  
kp A p
Q = (3)
 L
where p is the hydrostatic pressure drop, and  is the viscosity
of the fluid, kp is permeability of the sorbent bed defined as:
d̄22 5.5
p
kp = (4)
5.6K
d̄p2 is surface average sphere diameter which equals to the parti-
cle diameter, dp , when the particles are assumed spherical, K is a
constant and K = 1 for a narrow particle distribution.
Eq. (3) shows that the sampling rate is determined by the par-
ticle size and packing density for constant pressure drop along
the bed. Considering that sampling is typically done by a pump
with which the pumping pressure is controlled, then at one end of
the sorbent bed the pressure is equal to environmental pressure
(1 atm), while the other end of sorbent bed is the inner pressure
produced by the pump. Both the linear and volume flow rates for
air sampling may be calculated by Eqs. (2) and (3), respectively. The
 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18 5

time of sampling a given volume Q0 of the air sample then can be mass flow through the beginning of the sorbent bed (when x = 0 in
calculated to be: Eq. (6)):

ts =
Q0
(5)
 t
Q n(t) = Au C(0, t)dt = Aucs t (10)
In the frontal chromatography arrangement, the concentration pro- 0

file along the axis x, of the tubing containing the extracting phase,
The breakthrough level can then be defined as the percentage of
as a function of time t, can be described by adopting and deriving
mass exiting the end of the sorbent bed compared with the initial
the expression for dispersion of a concentration front [27]:
mass passing through the beginning of the sorbent bed:
 
1 x − (ut/(L(1 + k))) 1  
C(x, t) = cs 1 − erf √ − cs × exp(2n) Au
t
C(L, t)dt
t
C(L, t)dt
2 L 2 2 0 0
b= = (11)
Aucs t cs t
x − (ut/(L(1 + k))) + 2
× (1 − erf √ ) (6)
L 2 The approximated solution of b may be found in Lovkvist et al.’s
where cs is the concentration of analyte in the sample, k is the work [27], from which the breakthrough time may be obtained by
retention factor defined as: derivation:

Ve L(1 + k)

a1 a2

−1/2
k = Kes (7) tb =
2
(1 − b) + + 2 (12)
Vv u n n
and Kes is the extraction phase/sample matrix distribution constant,
Ve is the volume of the extracting phase, and Vv is the void volume a1 , a2 are complicated functions of b, and their values correspond-
of the tubing containing the extracting phase.  is the root mean ing to b were provided in the work of Lovkvist et al. [27] as well.
square dispersion of the front defined as: We assume breakthrough happens when b ≥ 5%. When b = 5%,
   a1 = 5.360, a2 = 4.603. As a result, Eq. (11) could be rewritten as:
u L ut 2Dt
−1/2
= Ht = = (8) L(1 + k) 5.360 4.603
1+k n 1+k 1+k tb = 0.903 + + (13)
u n n2
The difference between Eq. (6) and other frontal equations is that it
is more applicable when n is very small. n is usually small in needle By converting the breakthrough from the time scale to volume
trap, due to the short sorbent bed [27]. scale, we obtain the breakthrough volume:
Fig. 2 illustrates the normalized concentration profiles produced
in the bed during extraction [29] based on an equation similar
5.360 4.603

−1/2
Vb = AL(1 + k) 0.903 + + (14)
to Eq. (6). Full breakthrough is obtained for the right-most curve, n n2
which corresponds to the appropriate volume of the sample matrix
for extraction. The time required to pass this volume through the Comparing Eqs. (9) and (13), we find that te is very close to tb at high
extraction system corresponds to the equilibration time of the com- plate numbers (n > 10). Therefore, at a high plate numbers we can
pound with the bed and the equilibration time can be assumed to use Eq. (9) to calculate the breakthrough time as an approximation.
be the time required for the center of the front to reach the end of The above gives clear guidance on how to construct the nee-
the sorbent: dles for chemical trapping (i.e. exhaustive sampling). In order to
get a higher sampling rate and reduce the sampling time, the linear
L(1 + k)
te = (9) flow rate should not be too low; while for obtaining larger capac-
u
ity the linear flow rate should not exceed certain value. Therefore,
During sampling, before breakthrough, the sorbent bed may be the porosity should be kept in a defined range. Large particle size
treated as “perfect sink” for analyte. In this case, the mass of a cer- would be helpful to decrease the resistance but disadvantageous for
tain analyte loaded in the sorbent bed can be described as the total increasing the capacity since large particle size would decrease the
surface area as well. For obtaining higher capacity, a longer sorbent
bed can be used, however, this would result in an increase in resis-
tance. As a result, a larger diameter of needle can be used to increase
the capacity without suffering lower sampling rate. Moreover, a
higher retention adsorbent can be used when desorption efficiency
is not greatly affected. However, due to limited surface area, the
adsorbent is easily saturated at high concentrations long before
an equilibrium condition has been achieved, and since the above
model was based on a linear distribution isotherm assumption, it
is more applicable at sufficiently low concentrations. Nevertheless,
it could be quite useful to predict the maximum sampling time or
breakthrough volume in on-site sampling since in such places, the
concentrations are usually low and a much longer sampling time is
required.
Calibration. So long as the needle trap is designed to perform
exhaustive sampling, calibration is conducted identically to other
exhaustive sampling techniques such as SPE or sorbent trapping.
Sample volume must be controlled and known. Amount extracted is
determined from a pre-determined instrument detector response
Fig. 2. (A) Schematic representation of a packed needle; (B) theoretical concentra-
tion profiles in the sorbent bed assuming, Cs is the concentration of the analyte in
calibration, and then sample concentration is calculated directly
the sample, L is the length of the sorbent bed, x is the relative position along L. from the ratio of amount extracted and sample volume.
6 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18
Fig. 3. Scheme of a TWA sampling. A: Scheme of a packed needle with a distance Z
between the needle opening and the position of the sorbent bed; B: concentration
profile along the distance Z as a function of time t.
2.2. Passive sampling
A NTD packed with a strong sorbent at a defined distance from
the needle opening is a very simple arrangement for use in passive
time-weighted average (TWA) sampling. The sampling device as
shown in Fig. 3A is able to generate a response proportional to the
integral of the analyte concentration over time and space (when
the needle is moved through space) [30]. Under these conditions
the only mechanism of analyte transport to the extracting phase is
diffusion through the matrix contained in the tip of the needle. Dur-
ing this process a linear concentration profile (shown in Fig. 3B) is
established in the tubing between the small needle opening, char-
acterized by a surface area A and the distance, Z, between the needle
opening and the position of the extracting phase. The amount of
analyte extracted, dn, during time interval, dt, can be calculated by
considering Fick’s first law of diffusion [31]:
dc C(t)
dn = ADm dt = ADm dt (15)
dz Z
where C(t)/Z is an expression of the gradient established in the
needle between the needle opening and the position of the extract-
ing phase; C(t) = C(t) − CZ , where C(t) is the time-dependent
concentration of analyte in the sample in the vicinity of the nee-
dle opening, and CZ is the concentration of the analyte in the
vicinity of the sorbent bed. CZ is close to zero for a high extrac-
tion phase/matrix distribution constant (“zero” sink). In this case
C(t) = C(t). The concentration of analyte, CZ , at the beginning of
sorbent position in the needle will increase with integration time,
but it will remain low compared with the sample concentration
outside the needle, because of the presence of the extraction phase.
The amount of analyte accumulated over time can therefore be
calculated as:
 Its efficiency is governed by the value of Stokes number and related
A
n = Dm Cs (t)dx (16)
Z
As expected, the amount of analyte extracted is proportional to
the integral of sample concentration over time, the diffusion coeffi-
cient of analyte in the matrix filling the needle, Dm , and the area of
the needle opening, A, and inversely proportional to the distance,
Z, of the sorbent from the needle opening. It should be emphasized
that Eqs. (15) and (16) are valid only when the amount of ana-
lyte extracted onto the sorbent is a small fraction (typically about
10%) of the equilibrium amount for a given analyte in the sample,
in order to meet the “zero” sink requirement. To extend integra-
tion times the sorbent bed can be placed further into the needle
(larger Z), the opening of the needle can be reduced by placing an
additional orifice over the needle (smaller A), or a higher capac-
ity sorbent can be used. The first two solutions will result in low
measurement sensitivity. Increasing the sorbent capacity is a more
attractive proposition. It can be achieved either by increasing sor-
bent volume or by changing its affinity for the analyte. Because
increasing the sorbent volume would require an increase in the size
of the device, the optimum approach to increasing the integration
time is to use sorbents characterized by large sorbent/gas distri-
bution constants, like Carboxen. If the matrix filling the needle is
something other than the sample matrix an appropriate diffusion
coefficient should be used in Eq. (16).
In the system described the length of the diffusion channel can
be adjusted to ensure that mass transfer in the narrow channel of
the needle controls overall mass transfer to the extraction phase,
irrespective of convection conditions outside the needle [32]. This
is a very desirable feature of TWA sampling, because the perfor-
mance of this device is independent of the flow conditions in the
system investigated. This is difficult to ensure for high surface
area membrane permeation-based TWA devices, for example pas-
sive diffusive badges [33] and semipermeable membrane devices
(SPMD) [34]. For analytes characterized by moderate to high distri-
bution constants, mass transport is controlled by diffusive transport
in the boundary layer. The performance of these devices therefore
depends on the convection conditions in the investigated system
[35].
Calibration: In the case of passive sampling, so long as the
appropriate conditions are met, calibration is conducted similarly
for other passive samplers. This involves determining the total
amount adsorbed over the sampling time and converting this to
the time-weighted average sample concentration from a previously
determined response factor. The conditions that must be met for
the device to perform properly include that the sorbent responds
as a zero-sink with a fast response to variable ambient analyte con-
centrations throughout the sampling time, and that the tip of the
sampler is always exposed to a sample that is representative of the
bulk analyte concentration in the sample. This process is described
in more detail in a recent publication [36].
2.3. Particle trapping
The NTD is able to act as a filter to trap particulate matter in a
sample. There are four mechanical collection mechanisms by which
aerosol particles can be trapped by a NTD: interception, inertial
impaction, diffusion and gravitational settling [37]. Interception
(see Fig. 4A) happens when a particle follows a gas stream that hap-
pens to come within one particle radius of the surface of a sorbent
particle [37]. The single sorbent efficiency for interception is closely
related to the ratio of particle diameter to sorbent diameter, and the
packing density [37]. Inertial impaction (see Fig. 4B) occurs when a
particle, because of its inertia, is unable to adjust quickly enough to
the abruptly changing streamlines in the vicinity of a sorbent par-
ticle and crosses those streamlines to hit the sorbent particle [37].
to the ratio of particle diameter to sorbent diameter as well as the
packing density [37]. Diffusion (see Fig. 4C) is caused by the Brown-
ian motion of small particles, which is sufficient to greatly enhance
the probability of their hitting a sorbent particle while traveling
past it on a nonintercepting streamline [37]. The efficiency of diffu-
sion is related to the particle size of the sorbent, the linear flow rate,
and the diffusion coefficient of the particle [37]. The gravitational
settling is negligible compared with the other three mechanisms
[37].
Mathematical equations for the efficiencies of the above
mechanisms for the traditional fibrous filters have already been
investigated and it was found that the total collection efficiency
might not reach 100% for some range of particle sizes under a cer-
tain sorbent size, porosity, and linear flow rate for a fibrous filter.
 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18
Fig. 4. Schematic explanation of interception, impaction, and diffusion [from William C. Hinds, Aerosol Technology: Properties, Behavior, and Measurement of Airborne
Particles, 1st ed., John Wiley & Sons, Inc., New York, 1982, reprinted with permission].
When the same equations are applied to NTDs packed with dif-
ferent sorbents, penetrations might also happen for the sample
particles with particle size at certain ranges, as indicated in Fig. 5.
As seen from Fig. 5, the conventional NTDs (NTD 1) packed with
particles with sizes of about 150 ␮m are only able to completely col-
lect the particles with a diameter larger than 0.5 ␮m. Even when
the needle trap devices are packed with a sorbent with smaller par-
ticle sizes, the penetrations of the sample particles might decrease
Fig. 5. Extraction efficiencies for the fibrous filter and the needle trap devices
(fibrous filter: thickness = 1 mm, solidity = 0.05, sorbent diameter = 2 ␮m, and the
linear flow rate of sampling is 10 cm s−1 ; NTD 1: packed with sorbent particles, the
length of sorbent bed = 10 mm, solidity = 0.35, sorbent particle diameter = 150 ␮m,
and the linear flow rate of sampling is 100 cm s−1 ; NTD 2: packed with sorbent
particles, the length of sorbent bed = 10 mm, solidity = 0.35, sorbent particle diame-
ter = 50 ␮m, and the linear flow rate of sampling is 100 cm s−1 ; NTD 3: packed with
glass wool, the length of sorbent bed = 10 mm, solidity = 0.10, sorbent particle diam-
eter = 10 ␮m, and the linear flow rate of sampling is 100 cm s−1 ; NTD 4: packed with
thinner glass wool, the length of sorbent bed = 10 mm, solidity = 0.10, sorbent par-
ticle diameter = 5 ␮m, and the linear flow rate of sampling is 50 cm s−1 ) [adapted
from William C. Hinds, Aerosol Technology: Properties, Behavior, and Measurement
of Airborne Particles, 1st ed., John Wiley & Sons, Inc., New York, 1982].
7
but still be significant (see NTD 2). One solution to this penetra-
tion problem might be packing the needles with glass wools which
have a much smaller sorbent diameter but also a large porosity (see
NTD 3 and 4). During the sampling process, smaller sorbent diame-
ter would help to decrease the penetration significantly, while the
large porosity would help to reduce the resistance. By packing the
glass wool, especially the silanized glass wool, in the front of a nee-
dle, to trap the particles, while packing another sorbent afterwards
to extract free molecules, the NTD would be able to extract the free
molecules and particles simultaneously.
3. Evolution of needle trap technologies
3.1. Devices
The first reported use of a syringe needle packed with a sor-
bent bed for trapping organic compounds in air was described in
the 1970s when a large Tenax-filled needle was used for fragrance
collection [38]. More recently in 1996 a similar approach was devel-
oped for preconcentration of gaseous trace organic compounds on
solid sorbents including charcoal and silica gel for determination of
the analytes in natural and industrial atmospheres and their moni-
toring in human breath [39]. The sampling procedure was found to
be rapid and sensitive with detection limits approaching a few ppb,
standard deviation of 10% and linear range over five orders of mag-
nitude, similar in performance to typical sorbent traps. The major
limitation of these earlier applications was the large size of the
needle, requiring modification of the standard inlet systems, which
eliminated their advantages over well-accepted sorbent traps. Typ-
ically a dedicated carrier gas purge line or an additional volume of
clean air was needed to aid the introduction of desorbed analytes
to the column. It was primarily used as a fast screening tool for
qualitative purposes.
The needle trap approach became more practical for automa-
tion and on-site application when smaller diameter needles of 22
or 23 gauge were used, which fit conveniently into common GC
inlets. In 2001 a needle trap device for trapping large particles was
described that consisted of a 40 mm long 23 gauge stainless steel
8 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18

needle (0.53 mm O.D.) containing 5 mm of quartz wool packing

[40,41]. The analytes in an air sample were collected by drawing air
across the NTD with a luer-lock gas-tight syringe. The mass loading
of particulate matter was performed by adjusting the volume of air
pulled through the NTD and the particulates were then trapped by
the filter plug inside the needle. The device was introduced via a
conventional inlet to a gas chromatograph with FID or mass spec-
trometer detector by delivering 10 ␮L of clean air or a carrier gas
with a help of gas-tight syringe to aid the transfer of the desorbed
analytes from the hot needle. The results showed that the NTD
can be used for airborne aerosols and solid particulates sampling
and determination of the volatiles and semi-volatiles collected on
adsorbed components. No carryover was observed. The NTD per-
formed well in extracting diesel exhaust particulates containing
polycyclic aromatic hydrocarbons (PAHs), triamcinolone acetonide
in an aerosol dose of asthma drug and DEET in an insect repellent
spray.
Since the early 2000s several groups worked in parallel on
development of sorbent-packed needles or related devices. In 2003
Berezkin et al. [42] described two approaches: Tenax packed hypo-
dermic needles (0.5 mm I.D. and 0.8 mm O.D.) (Fig. 6A) and a
tubular cylindrical microconcentrator approach, using a 1 mm I.D.
and 100–150 mm tube stem with integrated needle at its end to
effectively puncture the septum for introduction to an analyti-
cal instrument (e.g. GC) (Fig. 6B). A dedicated external desorption
system was used to facilitate desorption from the large cartridge.
The second approach has similar construction to two high capac-
ity commercial systems: a CTC ITEX [43] developed by Shilling
(BGB Analytik AG, Switzerland) for gaseous and aqueous headspace
samples and the SGE microextraction in packed syringe (MEPS)
developed by Blomberg and Abdel-Rehim [44] for liquid samples
with analysis by either LC or GC applications.
The devices described by Berezkin were applied to the determi-
nation of volatile aromatic hydrocarbons in cigarette smoke. The
obtained results correlated well with previously published data.
Berezkin and his co-workers subsequently developed a needle-
based direct water extraction system [45,46]. In this approach
they used Porapak Q as a sorbent material and wet alumina as
a water reservoir for desorptive water vapor flow in a closed
analytical system. The analytical characteristics of the devel-
Fig. 6. (A) Needle microconcentrator: 1-needle stem (0.5 mm I.D. x0.8 mm O.D.); 2-
oped device and of a compared purge-and-trap device for BTEX plugs, limiting the sorbent layer; 3-sorbent layer (Tenax); 4-holder; and 5-capillary
compounds are similar. The same authors also developed a purge- line for carrier gas. (B) Cylindrical microconcentrator: 1-needle stem; 2-tube stem
and-trap system using Carbopack X as a sorbent material which (1 mm I.D. x2 mm O.D.); 3-plugs, limiting the sorbent layer; 4-sorbent layer; 5-
facilitated preconcentration and desorption of volatile benzene, holder; and 6-capillary line for carrier gas [from V.G. Berezkin, E.D. Makarov, B.V.
Stolyarov, J. Chromatogr. A 985 (2003) 63–65, reprinted with permission].
toluene, ethylbenzene and xylenes (BTEX) into a gas chromato-
graph [47]. A closed system of stripping the analytes from water
samples was used. An injection port with a modified metal liner the limitation that it extracts less selectively than does a microex-
was used to desorb analytes trapped in the NTD. An alterna- traction.
tive purge-and-trap approach using a bidirectional syringe pump The various devices and techniques introduced over the years by
has been published recently [48]. This approach has proven very various groups are presented and compared in Table 1 along with
versatile for developing a sequential purge-and-trap sampling their typical applications and most appropriate references.
technique for needle trap devices. The sequential sampling/purging
method with recycled headspace gas offered higher efficiency 3.2. Sorbent immobilization
of extraction, resulting in effective extraction in less time and
with minimized dilution effect compared with the continuous The immobilization of sorbents has been accomplished with the
(simultaneous) purge-and-trap technique with clean nitrogen use of side-hole needles [49], glue combined with inert wire [48]
gas. or frits [45]. To retain sorbent with frits, Kubinec et al. employed
The main advantage of the NTD lies in the simple methodol- a 1.1 mm I.D. stainless steel tube and fashioned two stainless steel
ogy and speed of the analysis [47]. Although needle-based sample o-rings from 1.1 mm O.D. tubing to retain the frits at each end of
preparation strategies relying on microextraction have a limita- a multi-layered sorbent bed [45]. Three stainless steel frits with
tion in the additional method optimization required for appropriate 20 ␮m porosity and 0.16 mm depth were fitted inside the tubing to
calibration, the exhaustive NTD does not. The main limitations of separate and retain aluminium oxide and Porapaq Q sorbents. For
the NTD are the additional care that must go into device design the side-hole needle approach, Wang et al. explored two possibil-
to ensure it is capable of exhaustive extraction with simplified ities [49]. First, they described a 21 gauge needle (Hamilton) with
methodology, and for the user to ensure that breakthrough does a sealed pointed tip and side-hole near the point. Quartz wool was
not occur during sampling. As an exhaustive technique it also has packed into the tip of the needle up to the level of the side-hole. Sep-
 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18
Table 1
Overview of needle trap and related techniques.
Technique name Description
Microextraction techniques
INCAT Section of GC capillary inside needle
SPDE Sorbent coating inside wall of needle
Exhaustive techniques
MEPS Sorbent-packed syringe
Needle trap Packed particulate sorbent in needle
Fiber in needle Fiber bundle sorbent in needle
ITEX Headspace syringe, needle body packed with sorbent
arate layers of PDMS, DVB and Carboxen were subsequently added.
No additional mechanism to retain the sorbent at the distal end
of the needle was employed. NTDs based on this construction are
presently available from Shinwa as NeedlEx. In the second option,
a 22 gauge open needle with an open blunt tip was packed with
Carboxen 1000. A side-hole was incorporated 3 cm back from the
tip. The sorbent was packed either right to the tip for exhaustive
grab sampling, or a set distance back to act as a diffusion barrier
for TWA sampling. To immobilize the sorbent, a mixture of rapid
curing (5 min) epoxy glue and the sorbent was packed into the nee-
dle. Before the glue cured a syringe was connected to the needle.
Air was moved in and out of the sorbent bed to prevent the epoxy
from curing as a solid block and plugging the needle trap. After full
cure of the epoxy the needle trap was conditioned in a GC injec-
tor at 300 ◦ C for 5 h to remove impurities. In the inert wire method
[48,50,51], a spring was first fashioned by wrapping a 0.002 diam-
eter stainless steel wire in six revolutions around a 0.006 diameter
support wire. The ends of the thin wire were trimmed and set flush
with the support wire. The spring was then positioned into a 22
gauge needle at the distal (luer-lock) end of the desired packing
length, by temporarily inserting a support wire into the distal end
of the needle, after which the support wire is removed. Sufficient
packing is added with the aid of a water aspirator attached to the
distal end of the needle and finally a small drop of fast cure (5 min)
epoxy is aspirated into the packing through the tip of the needle.
After an initial cure at room temperature while attached to the aspi-
rator, the needle was moved to a stand-alone heater or GC injector
(300 ◦ C) and nitrogen was passed through the sorbent bed for 2 h.
The choice of incorporating a side-hole with the latter means of
retaining sorbent was optional, and dependent on the operator’s
choice of desorption method.
3.3. Device configurations
In 2003 Pawliszyn and Bloomberg reported the designs and
applications of sorbent-packed needles (Needle Trap) and syringes
(MEPS) respectively at ExTech 2003 in Tampa and they discussed
initial results corresponding to spot and TWA gas and auto-
mated liquid sampling/enrichment, which were later published
[44,49,52,53].
In MEPS, a small amount of a sorbent is packed in the barrel of
a gas-tight syringe, or in a special container positioned between
the barrel and the needle. The goal was to provide an automated
high-throughput solution for conventional SPE, where sample
preparation is fully integrated with other components in the analyt-
ical system. An additional goal was to miniaturize the process such
that a minimum volume of solvent was required for elution, with
quantitative introduction of eluent into the instrumental analysis
system, typically LC, GC, or directly to mass spectrometry (MS). Full
automation was enabled by the use of a CTC CombiPAL autosam-
pler.
The MEPS method has a lot in common with typical syringe
cartridge SPE as the same sorbents are used in both techniques
therefore transferring a method from traditional SPE to MEPS is
9
Application Reference
VOCs, BTEX, gas or liquid samples [15–17]
Pesticides and hydrocarbons in water [18,19]
Liquid analysis, drugs in plasma [44]
Gaseous sample analysis [49]
Phthalates in wastewater, drugs in urine [4]
Hydrocarbons from aqueous headspace [43]
relatively straightforward. A number of automated pharmaceuti-
cal and clinical applications have been developed based on this
technique [6]. The system is now available commercially from SGE.
Two types of needle trap devices were proposed to address
convenience in packing and desorption, in order to improve man-
ufacture and performance of the NT technology, particularly in
desorption modes [49]. One type of NTD, shown in Fig. 7, was
designed with a sealed tip in which particles of PDMS, DVB, and
Carboxen were packed in sequential discrete layers. The lengths of
the layers were 3, 2, and 2 mm, respectively, and quartz wool was
packed between the tip of the needle and the side port. Packing in
this way was easier as the sorbent does not fall out. In this approach
simple desorption is accomplished by considering the fact that the
flow of the gas is naturally reversible. Thermal desorption can be
simplified if the structure of the sorbent in the micro cartridge con-
sists of layers of with different sorbing characteristics divided into
segments (as shown in Fig. 7) by locating the weakest sorbent close
to the entrance passage (left end) and the strongest sorbent deepest
into the cartridge near the closure (right end). In this arrangement,
the middle sorbent is preferably of medium effectiveness. This will
result in the analytes that are the most difficult to adsorb being
adsorbed on the third sorbent from the entrance, the analytes of
medium difficulty will be adsorbed on the second sorbent from
the entrance and the easiest analytes to adsorb will be adsorbed
on the first sorbent from the entrance. Desorption may be accom-
plished by applying inert gas to the luer-lock end. Also water vapor
as mentioned above [45] and expanded gas in a needle [48] can
facilitate desorption, as is described in detail below (Section 3.3). If
the strongest adsorbing sorbent is located nearest the entrance or
if only one strong sorbent is used, the sorbent will adsorb strongly
binding analytes so well that it would be difficult to desorb analytes
from the sorbent bed.
The second type of NTD in which Carboxen 1000 was packed
near the blunt tip of the needle was designed with a side-hole (I.D.
0.016 in.) positioned 3 cm from the tip of the needle, as illustrated
in Fig. 8A [49]. The carrier gas enters the needle through side-hole,
passes through the sorbent, and aids the delivery of desorbed ana-
lytes into the GC column. This desorption method was convenient
and no carryover was observed. This type of NTD, used to quanti-
tatively detect BTEX, was simpler and more convenient than the
Fig. 7. Schematic of the NTD packed with PDMS, DVB and Carboxen particles [from
A. Wang, F. Fang, J. Pawliszyn, J. Chromatogr. A 1072 (2005) 127–135, reprinted with
permission].
10 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18

Fig. 8. (A) Side-hole needle with inert spring to retain sorbent; (B) preferred desorption approach which does not require a valve, but rather uses a liner containing a
restriction to divert the carrier gas flow through the cartridge when the needle is introduced through the septum (not shown) into the liner [from Gong et al., Anal. Chem.
80 (2008) 7275–7282, reprinted with permission]; (C) schematic side view of the cartridge located in the liner [from Wang et al., J. Chromatogr. A 1072 (2005) 127–135,
reprinted with permission].

design associated with the modification of the carrier gas line or an
additional volume of clean air injection. In this case desorption was
carried out by flow created as the carrier gas was diverted through
the needle. Fig. 8B illustrates the preferred desorption approach,
which does not require a valve, but rather uses a liner containing
a restriction to divert the carrier gas flow through the sorbent bed
when the needle is introduced through the septum (not shown) into
the liner. Fig. 8C shows a schematic side view of the NTD located in
the liner. The restriction of the liner seals the needle, which facil-
itates the diversion of flow of gas through the sorbent by closure
of the gas path to a column during the introduction of the nee-
dle into the injection port. The carrier gas is forced to enter the
needle through the hole and pass through the sorbent and effec-
tively transfers the analytes into column which is also sealed by the
restriction producing very low dead volume. The side-hole needle
desorption approach has been demonstrated recently as effective
in larger size needles [54].
3.4. Sorbents
The bulk of the efforts to date in developing NTD have
employed conventional sorbents for extraction. For internally
coated needles (INCAT and SPDE), sorbents conventionally used
for wall-coating have been applied, such as PDMS, carbowax or
carbon particles [2,15,55]. For packed needles and syringes, bare
silica particles, silica particles coated with PDMS or alkylsilanes,
cation-exchange particles, divinylbenzene copolymers, Tenax and
Carboxen have been employed, in either continuous or segmented
beds [6,47,49,56]. The performance characteristics of the sorbents
generally mirrored the experience with their use in SPE, so method
transfer from SPE to needle trap was straightforward.
In addition to conventional sorbents, more polar ones have
been proposed and introduced by Saito et al. [57]. They pro-
posed use of a newly synthesized polymeric extraction medium
consisting of a copolymer of methacrylic acid and ethylene gly-
col dimethacrylate. The results clearly demonstrated the excellent
extraction performance for typical organic solvents and also sug-
gested future possibilities such as in the applications for the
analysis of work environments. These materials have been com-
mercialized by Shinwa as a NeedlEx and the needles have been used
for extraction of very polar compounds including formic acid [58].
A combined method of dynamic headspace-needle trap sample
preparation and GC for the determination of formic and acetic acids
in aqueous solution was developed. A needle extraction device cou-
pled with a gas aspirating pump was used to perform sampling and
preconcentration of target compounds from aqueous sample before
GC analysis. The needle trap extraction technique also allows for the
successful sampling of short chain fatty acids under dynamic condi-
tions while keeping the headspace (HS) volume constant [58]. Two
important parameters, including extraction temperature and effect
of acidification, have been optimized and evaluated using the NTD.
The method detection limits for the compounds estimated were
87.2 g L−1 for acetic acid and 234.8 g L−1 for formic acid in spite of
the low flame ionization detection response for formic acid and its
low Henry’s law constant in aqueous solution. Precision was deter-
mined based on two real samples and ranged between 4.7% and
10.7%. The validated headspace-needle trap extraction method was
also successfully applied to several environmental samples [58].
Around the same time the group of Jinno also introduced the
fiber in needle concept and subsequently developed devices with
a range of polarity characteristics for their application in GC and
SPE [4,59–61]. The technology was based on advances made previ-
 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18
ously in the use of a fiber-packed capillary as the extraction phase
for sample preparation for liquid phase separations, and as the
stationary phase in GC. Polymeric fiber filaments were used as
the extraction medium for microscale liquid phase and gas phase
separations and a miniaturized sample preparation technique con-
sisting of a fine fiber-packed needle as the extraction medium was
described. The primary application was to the analysis of volatile
organic compounds by GC. When the needle was packed longitudi-
nally with a bundle of fine filaments (12 ␮m O.D.) which were also
surface-coated with polymeric materials, successful sample pre-
concentration was obtained. The storage performance of the needle
clearly demonstrated the potential of the technique for typical
on-site sampling during environmental analysis. A comprehensive
review on the subject appeared recently [7].
The authors’ previous work with extraction devices constructed
from fiber-packed needles for on-line coupling of miniaturized
sample preparation and chromatographic separation and for
hyphenation of LC–GC also bears mention [62]. A fiber-packed nee-
dle was developed on the basis of several successful studies on
the use of a fiber-packed capillary as a miniaturized extraction and
separation medium [4].
The same group also enhanced sensitivity by introduction of a
derivatization reagent in the needle, similar to the way this was
accomplished previously in SPE and SPME. The resulting simulta-
neous extraction and derivatization enhanced the sensitivity and
selectivity of the detection and determination of target analyte(s)
[60]. The authors described a needle device designed for GC analysis
of aldehydes and ketones found in typical in-house environments.
A bundle of polymer-coated filaments was packed longitudinally
into a specially designed needle. Derivatization reactions were
facilitated by 2,4-dinitrophenylhydrazine (NDPH) pre-loaded in
the needle, to convert the aldehydes and ketones to their corre-
sponding hydrazones during extraction. Although some additional
studies targeting a more systematic optimization of the extrac-
tion and determination procedures might be necessary along with
additional investigations into the derivatization reaction and iso-
merization, the results suggest the practical applicability of the
method to the analysis of other volatile compounds in typical in-
house air. The results highlighted potential future benefit in the
further development of the technology, particularly in relation to
the development of other fibrous materials and the design and
synthesis of additional novel polymeric extraction media utilizing
surface derivatization reactions [63], and its application to biolog-
ical gas or liquid analysis with high selectivity.
A needle trap (NT) technique for simultaneous sampling and
analysis of vapor and particle mercury in ambient air using gold
wire filled in a syringe needle has been developed [64]. This
NT technique relies on gold amalgamation rather than adsorp-
tion/absorption to achieve traditional solid phase microextraction.
Hg trapped by Au-amalgamation in the NT device is thermally des-
orbed in a hot injection port of a gas chromatograph. Desorbed Hg is
then determined by the coupled mass spectrometer. This simulta-
neous sampling and analysis technique was optimized, tested, and
used for the collection and accurate determination of elemental Hg
in ambient air. Linear calibration curves spanning over 4 orders of
magnitude were obtained for Hg sampling by NT when MS was
used for detection. MS offered excellent sensitivity and selectivity.
Selected ion monitor (SIM) mode was used for the linear calibration
curves. The selected quantification ion was m/z 202, as this was the
strongest isotope of the mercury mass spectrum. The method was
verified with HgCl2 spiked solution samples. An excellent agree-
ment was found between the results obtained for the Hg-saturated
air samples and HgCl2 spiked solution samples.
Molecularly imprinted polymers have seen extensive use in
extractions for selective sample preparation, and these so-called
plastic antibodies have also been employed in needle trap format
11
[65]. The authors described a MEPS application where approxi-
mately 1 mg of a solid MIP sorbent was inserted into a syringe
(100–250 ␮L) as a plug inside the syringe, or between the barrel and
the needle. An autosampler was used to draw 20–250 ␮L of plasma
through the sorbent, which was subsequently washed with 50 ␮L of
water and the analytes eluted with 20–50 ␮L of solvent directly into
the injector of an LC. A bupivacaine imprinted polymer was used
for the analysis of ropivacaine in plasma in the range of 2–2000 nM
with high correlation coefficients (R2 0.999). The assembly could
be used more than 100 times with extraction recovery of 60%. The
accuracy, given as a percentage deviation from the nominal con-
centration values, ranged from 26% to 3%. The precision at three
different concentrations in QC samples was 3–10% and the limit of
quantification was 2 nM.
Monolithic materials were first described for use in separations
[66] but have also seen application to sample preparation [67]. In
2006 Zhang et al. described a monolith prepared in fused silica cap-
illary, incorporated in a needle trap device [68]. A 2 cm section of
the monolith-filled capillary was used in place of the steel barrel in
a hypodermic needle assembly. The device was assembled with a
disposable plastic syringe and used to extract angiotensin II recep-
tor agonists from 2 mL of human urine, with the extracted analytes
subsequently desorbed in 50 ␮L of acetonitrile and analyzed by
CZE. Recoveries of 80% were achieved with precisions of 1–3% for
analysis of samples at concentrations between 0.08 and 3 ␮g mL−1 .
More recently Blomberg has described a monolithic acrylamide
plug as sorbent in polypropylene tips primarily intended for use
with 96-well plate systems [6]. The devices were used for quanti-
tative analysis of local anaesthetics in human plasma with an LOQ
of 2 nmol L−1 . Accuracy for quality-control samples was between
101% and 118% and precision ranged from 4% to 17%.
Sae-Khow and Mitra recently reported the implementation
of micro-solid phase extraction (␮-SPE) employing nanomateri-
als in the needle of a syringe for integrating sampling, analyte
enrichment, and sample introduction into a single device [69].
Both single- and multi-walled carbon nanotubes (CNTs) were
explored as high performance sorbents for ␮-SPE in packed and
self-assembled formats. The need for such a sorbent was criti-
cal because the needle probe could hold only a small amount of
material (around 300 ␮g). Conventional C-18 and self-assembled
CNTs were found to be ineffective with enrichment factors less
than one. However, packed beds of CNTs were found to be excel-
lent sorbent phases, where high extraction efficiencies (as high
as 27%) as well as enrichment factors close to seven could be
achieved. The overall method showed excellent linearity, repro-
ducibility, and low method detection limit (0.1–3 ng mL−1 for
MWNTs). The sorption on CNTs followed Freundlich isotherms and
functionalized CNTs were more effective for enriching the polar
compounds.
3.5. Desorption
3.5.1. Desorption schemes
Achieving efficient desorption with needle trap devices has been
a focus of attention for many authors. Several approaches have been
investigated to date, including filling the syringe with air or inert
gas to aid desorption in a heated injector, diverting carrier gas flow
at the injector to the inlet of the needle, incorporating a side-hole
in the needle and employing a narrow-neck liner to seal the tip of
the syringe to enable desorption in an unmodified injector, simply
heating the sealed needle in a GC injector and relying on thermal
expansion of the contained gasses to sweep analytes to the column,
the addition of a small amount of water inside the needle to facil-
itate desorption with heated water vapor, or the application of an
external heater to the sorbent outside of an instrument injector to
effect external thermal desorption.
12 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18
3.5.2. Air-assisted desorption
In this simplest and first implemented desorption technique
[40], clean air is drawn into the syringe barrel and expelled to aid
desorption when the needle is inserted into the GC injector. Koziel
et al. used just 10 ␮L of air to desorb diesel exhaust compounds from
the needle trap consisting of a 5 mm long bed of quart wool packed
into a 23 gauge needle. Later Lipinski used 2.5 mL of air to desorb
analytes from the SPDE device packed with PDMS for the analy-
sis of pesticides in water [18]. The authors compared desorption
aided air injection with carrier gas aided injection and found that
carryover was higher with the air injection. Subsequently Wang et
al. also compared air injection with carrier gas for desorption [49].
These authors observed split injection peaks for analysis of VOCs
(alkanes and BTEX). The first peak was found to be due to desorp-
tion aided by thermal expansion of gasses within the needle and
the second due to analytes desorbed when the air plug was pushed
through.
3.5.3. Thermal expansion desorption
Several authors have conducted needle trap or related des-
orptions by thermal expansion only. In one of the earliest
demonstrations of the technology [15], McComb et al. describe the
preparation of needles with internal diameters of 0.25 or 0.4 mm,
either coated internally with carbon or containing a section of GC
capillary coated with DB-5 (INCAT). After either active or passive
sampling of gas, liquid or headspace samples containing VOCs, the
distal end of the needle was plugged with septum and the needle
desorbed at 175 ◦ C in a GC injector. While a DB-5 extraction phase
resulted in extensive peak tailing, analytes desorbed efficiently
from the thinner carbon sorbent, resulting in good chromato-
graphic peak shape. The authors suggested this was due to both the
difference in sorbent thickness as well as the difference in thermal
conductivity between the DB-5 coated fused silica and the car-
bon. These authors subsequently published advances in the INCAT
technique and application to a broader range of analytes [16]. Opti-
mization of the thermal expansion desorption technique resulted
in a reduction of carryover. The method compared favourably to
Purge and Trap.
Eom and Pawliszyn subsequently made a study of desorp-
tion characteristics for thermal desorption of an alkane mixture
(C6–C15) from a packed DVB sorbent bed [50]. Desorption time
and temperature, along with the optimal dead space volume in
the needle above the sorbent were investigated. Thirty seconds of
desorption at 250 ◦ C was determined to be optimal. Peak shape
deteriorated noticeably with increasing dead space volume. Zero
dead space was determined as optimal. Wang et al. also investi-
gated the effect of the GC injector temperature profile for thermal
expansion desorption [49]. These authors determined that the
length and profile of the temperature variation within the injec-
tor was a critical parameter in determining the optimal sorbent
bed length. Carryover was significantly worse if part of the sorbent
bed was located outside of the optimal heated zone in the injector
during desorption.
Although very simple in design and use, direct thermal expan-
sion desorption has not been widely applied for needle trap
technologies, likely due to the limitations of desorption carryover
and high dependence on analyte type, device configuration and GC
injector set-up for desorption efficiency. Where these variables can
be adequately controlled the method proves simple and effective.
3.5.4. Water vapor assisted desorption
Several authors have noted improved desorption efficiency and
broader application when water vapor expansion is incorporated
in thermal expansion desorption. Prikryl et al. demonstrated the
use of water vapor to aid thermal expansion desorption, to desorb
VOCs from a DVB sorbent bed [46]. The ‘needle concentrator’ was
packed with separate layers of DVB (divinylbenzene) and alumina:
DVB was used for enriching VOCs and alumina was used to adsorb
water. After enrichment of BTEX from water by dynamic headspace
sampling, the alumina layer of the concentrator was soaked with
water and then the device was inserted into a GC injector for ther-
mal desorption. The water on the alumina layer was vaporized
quickly due to the hot injector temperature which desorbed and
flushed the BTEX compounds into the separation column. A clean
and sharp BTEX chromatogram was achieved but the use of water
for aiding desorption was problematic. The massive water injec-
tion produced a long tailing water peak with high noise and which
co-eluted with the early eluting benzene and toluene. As a result,
poorer LODs for benzene and toluene were reported compared to
those of ethylbenzene and xylenes. Also slightly worse detection
and quantification limits were observed for all compounds in com-
parison with the purge-and-trap method. In addition bulk injection
of water can shorten column life time and cause possible interfer-
ences with detectors.
3.5.5. Inert gas-assisted desorption
Numerous authors have recognized that superior desorption
performance may be obtained by using inert mobile phase gas
passed through the sorbent bed during thermal desorption. The
major disadvantages of using a syringe during desorption (filled
with either air or inert gas) include the introduction of oxygen to the
sorbent and a potentially insufficient amount of desorption gas to
quantitatively move all analytes from the sorbent to the analytical
device.
Soon after the appearance of the INCAT and SPDE techniques,
authors described the use of inert carrier gasses to aid desorp-
tion. Jochmann et al. described a popular desorption technique
whereby a volume of inert gas (nitrogen in this case) is with-
drawn through the needle trap into the syringe, after extraction
and just prior to desorption [55]. In this work, commercially avail-
able SPDE needles (Chromtech, Germany), coated with carbowax,
cyanopropylphenyl/PDMS, PDMS, and PDMS with 10% embedded
activated carbon were compared for the extraction of polar VOCs.
The target compounds included 3 ethers and 12 alcohols. Efficient
desorption for a range of the target compounds was achieved by
withdrawing 1 mL of nitrogen and desorbing over 20 s at 200 ◦ C in
splitless mode. The lowest method detection limits were obtained
with the carbowax and the PDMS/AC phase. Following desorption
the needle was removed from the injector and flushed with nitro-
gen for 5 min at 200 ◦ C to eliminate carryover.
Joachmann et al. have also described desorption processes for
their work on ITEX (see Fig. 6B, Section 3.1) where the larger
diameter of the needle body is packed with Tenax TA [43]. In
this configuration the packed sorbent bed is located external to
the GC injector during desorption with an external heater to
control desorption temperature. VOCs are extracted from sample
headspace by dynamic extraction. After extraction, 700 ␮L helium
was withdrawn from the injector into the syringe. Subsequently,
the desorber around the needle body was heated in a few seconds
to 170 ◦ C and the sorbed analytes were transferred with a desorp-
tion flow rate of 10 ␮L s−1 into the hot injector. After desorption,
the device was flushed with nitrogen gas at 210 ◦ C for 20 min to
prevent carryover and to condition the sorbent for the next sam-
ple. Slower desorption flow rates were found to be more effective,
with 4× to 26× higher peak areas observed for desorption flows of
10 ␮L s−1 relative to 100 ␮L s−1 . The effect of desorption volume in
the range of 500–1000 ␮L was less important.
Ueta et al. have described a needle packed with a particulate
sorbent consisting of copolymer of methacrylic acid and ethyleneg-
lycol dimethacrylate, applied to breath acetone analysis [70]. The
sorbent was packed into a sealed tip needle with a side-hole adja-
cent to the tip. On the completion of the sampling, the needle was
 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18
removed from the vacuum sampler and attached to an injection
syringe. 0.5 mL of N2 gas was withdrawn, the needle was inserted
to a heated GC injection port and the extracted analyte was injected
by the N2 gas in the syringe after a preheating time of 10 s in the
injector. The desorption was efficient and quantitative recovery of
acetone was maintained over all the concentration range between
10 ppmv and the limit of quantification (0.001–0.01 ppmv).
Several authors have investigated means of directing carrier
gas through the sorbent bed during desorption as an alternative
to withdrawing inert gas into the needle and injecting this to aid
thermal desorption. Two general means of achieving this have been
described [49]. Where a standard needle is employed, a secondary
carrier gas split valve is used. In separation mode the carrier gas
flows to the injector and through the column as normal. For des-
orption a line from the split valve is connected to the back of the
needle trap and carrier gas is directed to flow through the needle
during desorption. The other option described utilizes a needle with
a side-hole positioned about 3 cm back from the tip of the needle,
with sorbent packing located between the side-hole and the tip.
When a narrow-neck liner is used the needle trap can be injected
to the resistance point where it is sealed against the narrow neck
(Fig. 8C). Carrier gas is then automatically directed to flow through
the side-hole and sorbent before entering the column. In the carrier
gas bypass mode any standard GC injector liner can be employed
but the system is a bit more cumbersome and difficult to automate.
In the side-hole approach the needles are somewhat more cum-
bersome to prepare and the injector liner must be changed, but the
technique is the simplest to automate.
Wang et al. compared desorption efficiencies either by applying
the desorption gas to the distal end of the needle trap through a
divert valve, when the needle was in a conventional GC injector
liner, or by employing a side-hole in the needle with a narrow-neck
GC liner and diverting the injector carrier gas through the sorbent
during desorption [49]. The latter method, where injector carrier
gas was automatically diverted through the needle side-hole during
desorption was convenient and no memory effect was observed.
To summarize all of the various gas-assisted desorption regimes
evaluated to date, it appears a consensus is developing that desorp-
tions assisted by inert gas flushing of the sorbent bed generally
produces the most efficient desorptions with the least amounts
of carryover, although the techniques are generally more cumber-
some and difficult to automate than thermal expansion desorption
options. The approach with the side-hole above the sorbent bed
(Fig. 8) forces the desorption gas through the sorbent bed on
injection to facilitate diversion of the existing carrier gas path for
desorption. Further efforts to simplify these processes would aid
considerably in the general acceptance of the technology.
3.5.6. Solvent desorption
Solvent desorption has also been frequently applied, particularly
where the aim is to inject desorbed analytes to LC (or possibly GC)
for analysis. Saito et al. have reported a sample preparation strategy
termed “fiber-in-tube” for the direct coupling of aqueous extraction
to LC for the analysis of n-butylphthalate in wastewater [71]. To
prepare the extraction tube a heterocyclic polymer (Zylon® ) multi-
filament fiber was cut to 10 cm and packed longitudinally into the
same length of PEEK tubing (0.25 mm I.D.). The diameter of each
filament in the fiber was about 11.5 ␮m with about 280 total fila-
ments packed in the PEEK tubing. The observed preconcentration
factor for phthalate was about 160× with a 20 min extraction at
16 ␮L min−1 . Solvent desorption involved pumping pure methanol
through the tube at 2 ␮L min−1 for 3.5 min. The extracted analytes
were desorbed and directly transferred into the loop of the LC injec-
tion valve. The volume of the desorption solvent and the flow rate
were optimized to ensure that the analytes were quantitatively
transferred to the injection loop during the desorption and to elim-
13
inate carryover. Limits of quantification were estimated at sub-ppb
levels for various organic analytes in aqueous sample matrix.
MEPS has been coupled to GC with solvent desorption [52]. In
this report, 1 mg of sorbent (C2 silica) was packed into a syringe for
the extraction of local anaesthetics from plasma. Plasma (50 ␮L)
was drawn through the sorbent bed followed by a wash with
50 ␮L of water. The analytes were then eluted with 30 ␮L of
methanol directly into the GC injector. The authors reported that
it was sometimes necessary to dilute the plasma with water 1:1 to
avoid clogging the sorbent bed. Extraction recoveries of 60% were
reported with LOQ of 10 nM. To obtain carryover between samples
in the range of 0.2% the sorbent bed was washed four times with
methanol and four times with water after every injection.
Altun et al. followed up on this work with a comparison of MEPS
sample preparation for LC [44]. The sorbent was switched to 1 mg
of silica-based benzenesulphonic acid cation exchanger packed in
a 250 ␮L syringe. Again the application was the analysis of local
anaesthetics and their metabolites from plasma. The goals of the
effort were a simplified sample preparation with a low quantifica-
tion limit, high recovery and the possibility to automate. Plasma
(25 ␮L) was extracted at 20 ␮L s−1 . After a water wash (100 ␮L),
desorption was accomplished with 50 ␮L of methanol/water 95:5
with 50% recovery reported. The sorbent was cleaned and recondi-
tioned between analyses with 5 × 50 ␮L elution solution followed
by 5 × 50 ␮L of the washing solution, which resulted in 0.5% car-
ryover. The LOQ for the method was 2 nmol L−1 with accuracy 97%
and 105% with precision ranging between 8.2% and 10.6%.
To date, numerous sorbents have been investigated with the
MEPS technology based on the nature of the target analyte, in
order to achieve acceptable clean-up and recovery [6]. Relatively
large particles are used to avoid high backpressures, with gener-
ally 1 mg packed into a 100–250 ␮L syringe. 50 ␮L of desorption
solvent is typically employed, with the advantage that the entire
elution volume may be injected into the chromatograph. Heat-
ing of the syringe during elution improves desorption efficiency.
An advantage is that the technique may be fully automated with
carryover being the primary limitation. More recently, the tech-
nology has been applied to polypropylene pipet tips packed with
monolithic sorbent. A significant advantage with this approach
is that the price per unit is reduced and so the sorbent may be
replaced for each extraction, effectively eliminating any possibil-
ity of carryover while maintaining a high degree of automation.
Sorbent amount was increased to about 3 mg and sample vol-
ume increased to 100–150 ␮L. Elution was with 100–150 ␮L of 60%
methanol/water. Limits of quantification for local anaesthetics in
plasma were reported as 2 nmol L−1 with accuracy between 101%
and 118% and precision between 4% and 17%.
4. Applications
Numerous applications have been introduced in the preceding
text describing the development and evolution of the various nee-
dle trap based techniques. These have been summarized in Table 2
according to the device and method used to provide the reader with
a convenient comparison of the types of samples, sorbents, tech-
niques and method parameters described by the various authors.
From these some broad categories of applications warrant more
detailed discussion, which is presented below.
4.1. Breath
To facilitate their use in trace gas analysis, the adsorption capac-
ity of needle trap devices (NTDs) was increased by combining three
adsorbent materials and increasing total adsorbent amount [56].
The use of 22 gauge needles, application of thermal expansion
desorptive flow without cryofocusing and a new on-site alveolar
Table 2

14
Summary of applications for needle trap and related techniques.

Method Sorbents Instrumentation Application Parameters LOD Publication Year Reference

Sampling Desorption
mode
Microextraction methods
DB-5TM or coating of carbon in GC-FID BTEX in both air and water Active and Thermal expansion N/A 1997 [15]
needle passive
Carbon blacks GC-FID BTEX in aqueous solution Active Thermal expansion 65 ppb–2 ppm 1999 [16]
INCAT
Carbon coating GC-FID BTEX in air Active and Thermal expansion N/A 1999 [17]
passive
Porapak Q and alumina GC-FID BTEX in aqueous sample Active Water vapor flow enabled TD 0.23–0.36 ppb 2004 [45]
Porapak Q and alumina GC-FID BTEX in aqueous sample Active Water vapor flow enabled TD 0.059–0.125 ppb 2006 [46]
Tenax TA GC-FID Both liquid and gaseous BTEX sample Active Carrier gas-assisted TD N/A 2009 [54]

PDMS GC-ECD/NPD Pesticides in water Active External air-assisted TD 1–100 ppt 2001 [18]
Multi-layer (PDMS/DVB/Carboxen) GC-MS Volatiles in honey Active Carrier gas-assisted TD N/A 2004 [76]
SPDE
WAX, 1701, PDMS, PDMS/AC GC–MS Polar VOCs in water Active External N2 assisted TD 0.004–4.9 ppb 2006 [55]
PDMS with embedded activated GC–MS Volatile organic hydrocarbons in water Active External N2 assisted TD 12–870 ppt 2007 [19]
carbon

H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18

Exhaustive extraction methods
Cation-exchange sorbent HPLC–MS Anaesthetics in human plasma Active Solvent desorption N/A 2004 [44]
Silica C2 particle and other materials GC–MS Anaesthetics in plasma samples Active Solvent desorption N/A 2004 [52]
MEPS
Molecularly imprinted polymer LC–MS-MS Ropivacaine in plasma Active Solvent desorption 2 nmol L−1 2006 [65]
Polymer monolith CZE-UV/VIS Angiotensin II receptor antagonists in human Active Solvent desorption 15–20 ppb 2006 [68]
urine

Charcoal and silica gel GC-FID Gaseous trace organic compounds in human Active Carrier gas-assisted TD A few ppb 1997 [39]
breath and air
Quartz wool GC–MS Airborne particulate matter and aerosol Active Air-assisted TD N/A 2001 [40]
Tenax N/A Tobacco smoke Active Carrier gas-assisted TD N/A 2003 [42]
Multi-layer (PDMS/DVB/Carboxen) GC-FID VOCs in air Active and External air or carrier 0.23–2.1 ppt 2005 [49]
and Carboxen passive gas-assisted TD
Copolymer of methacrylic acid and GC-FID VOCs in air Active External N2 assisted TD N/A 2006 [57]
ethylene glycol dimethacrylate
Needle Trap
Polymer based beads and GC–MS Smoking-related compounds in hair and air Active External N2 assisted TD 1.0–3.6 ppt 2007 [59]
polymer-coated fiber samples
Carboxen 1000 GC–MS VOCs in air Passive Carrier gas-assisted TD N/A 2008 [36]
Carbopack X GC-FID BTEX in aqueous samples Active Carrier gas-assisted TD 0.05–0.07 ppb 2008 [47]
Divinylbenzene GC-FID BTEX in aqueous samples Active Thermal expansion 1 ppb 2008 [48]
Divinylbenzene particle GC–MS VOCs in air Active Thermal expansion N/A 2008 [50]
Divinylbenzene particle GC-FID Formic and acetic acids in aqueous solution Active External N2 assisted TD 87.2 ppb and 2008 [58]
234.8 ppb
Gold wire GC–MS Vapor mercury in ambient air Active Carrier gas-assisted TD 0.23 ppt 2008 [64]
Multi-bed (Carboxen 1000, GC–MS Volatile breath biomarkers Active Thermal expansion 0.4–8.3 ppt 2009 [56]
Carbopack X, Tenax)
Carbon nanotubes LC-UV 2-Nitrophenol, 2,6-dichloroaniline, and Active Solvent desorption 0.1–3 ppb 2009 [69]
naphthalene in water
Copolymer of methacrylic acid and GC–MS Breath acetone Active External N2 assisted TD N/A 2009 [70]
ethylene glycol dimethacrylate
Divinylbenzene particle GC–MS Free and particle-bound compounds in Active Carrier gas-assisted TD N/A 2009 [73]
mosquito-coil smoke

Polymer-coated fiber LC–UV/VIS n-Butylphthalate in wastewater Active Solvent desorption Sub-ppb level 2000 [71]
Fiber in Polymer-coated fiber GC–MS Volatile aldehydes in air sample Active External N2 assisted TD 1.2–11.7 ppt 2006 [60]
needle Polymer-coated fiber GC–MS Aromatic compounds in aqueous samples Active Solvent desorption 0.2–2 ppb 2007 [61]
Novel polymer-coated fibrous phase 2D LC-UV/VIS-GC-FID Aliphatic and aromatic hydrocarbons in Active Solvent desorption N/A 2009 [62]
aqueous sample

ITEX Tenax TA GC/MS Volatile organic hydrocarbons in aqueous Active External He assisted TD 28–799 ppt 2008 [43]
sample
Note: TD is abbreviated for thermal desorption; N/A stands for the information is not provided or investigated; part per billion (ppb) and part per trillion (ppt) are based on weight/volume scale.
 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18
sampling method for NTDs provided sensitivity in the parts per
trillion range of VOC concentrations without losing precision or
linearity. LODs were 0.4 ng L−1 for isoprene, 0.5 ng L−1 for dimethyl
sulphide, 0.9 ng L−1 for 2-butenal, 1.0 ng L−1 for hexane, 1.2 ng L−1
for pentane, 2.3 ng L−1 for hexanal, 5.3 ng L−1 for pentanal, and
8.3 ng L−1 for acetone. Calibration curve linear correlation coeffi-
cients (r2 ) were consistently >0.98. Loss of volatile aldehydes during
storage for 7 days was less than 10%. NTDs packed with more than
one adsorbent material represent a promising alternative to SPE
and SPME for analysis of volatile organic compounds in the low
parts per billion/parts per trillion range. Crucial problems of clin-
ical breath analysis concerning sensitivity of analytical methods,
limited stability, and decomposition of breath compounds during
sampling and storage could be solved.
The authors recently extended this work to GC × GC charac-
terization of breath samples extracted by a multi-bed sorbent
NTD [72]. NTDs used with high-throughput automatic desorp-
tion and separation systems were tested in a study with patients
undergoing cardiac surgery for analysis of blood-based biomarkers,
intravenous drugs and clinical contaminants. The use of heart-cut
GC/MS allowed the linearity of analyte response to be conserved
even in the presence of high concentrations of contaminants such
as anaesthetic gasses.
Another approach to the determination of human breath
acetone with particle-packed sample preparation needle was
developed by the group of Jinno [70]. The extraction needle was
packed with a copolymer of methacrylic acid and ethylene gly-
col dimethacrylate as the extraction medium. For the analysis of
breath sample, exhaled breath was collected in a sampling bag,
and 50 mL of the breath sample was extracted with the needle-
type sample preparation device followed by analysis using GC/MS.
After the optimization of several basic extraction conditions for
standard acetone samples, breath acetone concentration taken
from controlled type-2 diabetic patients was determined. Fur-
thermore, time variations of breath and urine acetone of four
healthy individuals under fasting conditions were measured. Urine
samples were collected in glass vials and urine acetone concen-
tration was determined with the extraction needle by analyzing
the corresponding headspace gas. The results demonstrated that
the particle-packed extraction needle showed an excellent extrac-
tion performance for acetone in both breath and urine headspace
samples, and that there is a clear correlation between the con-
centration of breath acetone and HbA1c level of controlled type-2
diabetic patients. The breath acetone levels in controlled dia-
betic patients were in a range between 0.19 and 0.66 ppmv,
where its concentration in medically untreated type-2 patients
was between 0.92 and 1.20 ppmv. The breath acetone concen-
tration in healthy males was increased to 5.66 ppmv under the
24 h of fasting test and a high correlation between the breath
and urine acetone concentration was also observed. On the basis
of the above results, the potential applications of the proposed
method to the diagnosis of diabetes and/or ketoacidosis were sug-
gested.
4.2. Distinguishing free/total
For many matrixes, a significant portion of the analyte of interest
is found closely associated with one or more discontinuous phases,
with an equilibrium condition determining the proportion of free
vs. bound analyte. Depending on the configuration of the extraction
device and the nature of the sample preparation, either the free,
bound, or total analyte concentration may be determined. Whereas
a filter will physically retain particulate matter, sorbents extract
only free analyte. However, where sample is percolated through a
packed sorbent bed, the bed may act as both a filter and a sorbent,
thereby retaining total analyte.
15
Koziel et al. described the use of filter media (quartz wool)
inside a NTD, to determine analyte bound to particulate matter after
trapping of the particulate and thermal desorption of the bound
analyte [40]. Simultaneous extraction of the gas sample by SPME
provided free analyte concentration. The utility of the technique
was demonstrated through the analysis of PAHs in diesel exhaust,
triamcinolone acetonide in a dose of aerosolized asthma drug
and DEET in an application of insect repellent spray. The authors
pointed out that it should be possible to combine the two samplers
into one device for simplified combined sample preparation, with
the option of performing thermal desorption either separately or
together, depending on whether free, total, or particle-bound con-
centrations were desired. The authors also pointed out the potential
utility of NTD with packed sorbent.
The simultaneous determination of total (particle-bound plus
free) concentrations of analytes with packed sorbent bed NTD
and free concentrations with SPME was later described for the
analysis of smoke generated by a mosquito coil [73]. Allethrin as
the active ingredient in mosquito coils was chosen as the tar-
get analyte. Under the same sampling conditions, the amount
of allethrin extracted from the mosquito-coil smoke was higher
for the NTD compared to the SPME fiber, while the extracted
amounts were almost the same for both devices when sampling
gaseous samples of allethrin. Semi-volatiles were extracted more
efficiently by the PDMS-coated SPME fiber, likely due to their
higher partition coefficients, whereas highly volatile compounds
such as benzene, which have lower partition coefficients for PDMS,
and particle-bound analytes were better extracted by the NTD.
Breakthrough for NTD and carryover for both NTD and SPME
were negligible under the given sampling and desorption condi-
tions.
The discrimination of free and bound analyte concentrations
is beneficial in several areas including assessments of human and
environmental health impacts as well as for product development
and quality control. Simpler, quantitative tools will be beneficial in
expanding applications in this area, as will be the development of
similar tools for liquid samples analysis.
4.3. VOCs
A simple, cost-effective NT analysis combining solventless
extraction, thermal desorption, and determination of volatile
organic compounds (VOCs) was recently developed and validated
for TWA analysis [36]. In the method, a NTD packed with the sor-
bent Carboxen 1000 was used as a TWA diffusive sampler to collect
target compounds by molecular diffusion and adsorption to the
packed sorbent. This process can be described with derivations
of Fick’s first law of diffusion (see Section 2), which expresses
the relation between the TWA concentrations to which the pas-
sive sampler is exposed and the mass of analytes adsorbed to the
packed sorbent in the sampler. The effects of experimental factors
such as temperature, pressure, humidity, and face velocity were
taken into account in applying diffusive sampling under non-ideal
conditions. This study demonstrated that this NTD configuration
is effective for air analysis of benzene, toluene, ethylbenzene, and
o-xylene (BTEX), due to the good adsorption/desorption quality of
Carboxen 1000 and to the special geometric shape of the needle
with a small cross-section avoiding the need for calibration. Stor-
age tests showed good storage stability for BTEX. Verification of
the theoretical model showed good agreement between theoretical
and experimental sampling rates. Method validation done against
NIOSH method 1501, SPME, and NTD active sampling revealed good
agreement between those methods. Automated NTD sample intro-
duction to a GC facilitates the use of this technology for industrial
hygiene applications.
16 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18
4.4. Automation
The simplicity of needle trap designs and their ready incor-
poration with standard injectors and autosampler equipment has
permitted a wide variety of options for automating the entire sam-
ple preparation and instrument injection processes for many of
the techniques. Although INCAT was the first needle trap device
to be reported, to the best of our knowledge no automated ver-
sions of this technology have been reported. However SPDE, which
was introduced soon after and is a closely related technology, has
been automated for numerous applications. The reported appli-
cations all make use of the CTC Analytics (Zwingen, Switzerland)
CombiPAL autosampler that was also first used for SPME analyses
at about the same time. One of the first examples was the auto-
mated SPDE extraction and GC analysis of pesticides and organics
from water using needles coated internally with 7 ␮m of PDMS [18].
The extraction and desorption steps were automated using a CTC
CombiPAL supplied by Chromtech. All movements of the syringe,
the sample vials, and the plunger of the syringe were controlled
by macros written with the CTC Cycle Composer software. Soon
after, Musshoff et al. described the automated SPDE analysis of
both amphetamines [74] and cannabinoids [75] from hydrolysed
hair samples for clinical and forensic toxicology. The SPDE needles
for these analyses were coated with PDMS containing 10% activated
carbon. In both of these analyses an on-fiber derivatization was con-
ducted from a separate vial containing derivatization agent after
extraction and before injection. Again all of the SPDE method steps
were fully automated, controlled by a CTC CombiPAL autosampler
and software with custom-made macros. The authors identified the
strengths of the technology as robustness, capacity, reproducibility,
low detection limits, and simple automation.
In 2004 Ampuero et al. described a technique related to SPDE
termed inside-needle dynamic extraction (INDEx) for the auto-
mated analysis of honey volatiles [76]. This was also automated
with a CTC CombiPAL. Although it is not clear whether the sorbent
was packed or wall coated in the needle, the authors’ character-
ization of the technique as dynamic and the statement that the
sorbent amount was smaller than for SPME points to this being a
microextraction technique. It was used for chemometric character-
ization of honey floral origin. Good correlation with conventional
methods was shown.
Ridgway et al. later described the use of PDMS-coated SPDE
devices and a CombiPAL autosampler for the automated GC analy-
sis of aromatic VOCs from water [2]. The technique was evaluated
for the determination of furan, benzene and toluene. The system
was used successfully for both liquid and headspace extraction and
results were compared to static headspace extraction at the same
temperature. The sensitivity for toluene was greatly improved on
using SPDE compared to static headspace. A slight increase in sen-
sitivity was observed for benzene but none for determination of
furan. Estimated limits of detection ranged from 0.2 to 2 ␮g L−1 .
Jochmann et al. used SPDE needles coated with various phases
for the extraction of polar VOCs from water [55]. The desorption
process used was described in detail in Section 3.5.5. For this work
the autosampler was supplied with a heatable CTC agitator for
incubation and agitation, an additional gas station to withdraw
desorption gas prior to injection, and a heated flushing station for
conditioning of the SPDE needles and reconditioning after each
analysis to prevent carryover.
The same group reported in 2008 on the automation of ITEX for
analysis of VOCs from water [43]. Again the details of the desorp-
tion process used was described in Section 3.5.5. In this technique
the analytes were extracted from sample headspace by dynamic
extraction (multiple draw and eject cycles with a 2.5 mL headspace
syringe plunger) into a Tenax packed cartridge located between
the syringe and the needle. The Tenax cartridge was surrounded
by a separate heater for efficient thermal desorption of analytes
into the GC injection port. For the automation, a modified Combi-
PAL autosampler head was used that was able to hold the 2.5 mL
headspace syringe with a longer interchangeable ITEX needle to
accommodate the cartridge. The entire ITEX extraction and desorp-
tion procedure was fully automated by the autosampler, controlled
by the PAL Cycle Composer software and homemade macros. The
control of the thermal desorber around the needle body was inte-
grated in the CombiPal software and allowed reproducible heating
to desorption temperature within a few seconds. The autosampler
was equipped with a single magnet mixer and a temperature con-
trolled (45 ◦ C) sample holder tray. Before extraction the sample
was stirred for 15 min in the single magnet mixer at an incuba-
tion temperature of 50 ◦ C to establish equilibrium distribution of
the analytes between aqueous and gas phase in the vial before
extraction.
Another example of packed syringe NTD automation is the MEPS
technology introduced by Abdel-Rehim in 2004 for the analysis
of local anaesthetics in plasma and commercialized by SGE [52].
The authors employed solvent desorption as was described in Sec-
tion 3.5.6. Again, automated sample preparation was accomplished
with a CTC Analytics CombiPAL and a PTV injector was used to
allow GC injection of 30 ␮L of methanol containing the desorbed
analytes. More recently Blomberg has reported a related tech-
nique involving sorbent-packed pipet tips [6]. Here automation
was achieved by means of commercially available systems using
96-well extraction plates and a robot. The utility of the method was
demonstrated again by extraction of local anaesthetics from plasma
and desorption, this time for LC–MS/MS analysis, in 100–150 ␮L
of 60% methanol. The observed method limit of quantification
was 2 nmol L−1 . Accuracy for quality-control samples was between
101% and 118% and precision ranged from 4% to 17%.
The concept of automation employed in the packed pipet tip
approach is a significant departure from the other automation
strategies described to this point. A set of replaceable extraction
devices offers both the option of conducting multiple extractions
off-line with automated desorption and analysis, as well as the
important feature of eliminating the most significant source of car-
ryover from one analysis to the next. The concept was also explored
by Gong et al. in 2008 with the introduction of the PAS Tech-
nology Concept autosampler capable of sequential desorption and
analysis of a set of NTD previously used for off-line extractions,
stored in a rack on the autosampler [36]. In the Gong paper the
NTD were designed for off-line TWA analysis of BTEX in gaseous
samples. After extraction the NTDs were assembled manually with
luer-lock adapters on a NTD sampler tray. The NTDs were trans-
ferred one by one to the GC injector by the magnetic arm, and
then the closure (pneumatic arm) closed the NTD to supply car-
rier gas through a lure-lock needle head. After a ready signal was
received from the GC, the control software (CONCEPT 1.1) started
the GC and data acquisition simultaneously. The GC was equipped
with a programmable GC injector (OPTIC 3, ATAS GL) which kept
the carrier gas flow at 3.5 mL min−1 and controlled the injector
temperature as programmed. A similar automation system was
later evaluated for automated sampling with NTD designed for
clinical breath analysis [56], and subsequently employed for auto-
mated desorption and GC analysis of NTD used for clinical breath
analysis [72]. Clinical studies usually require large numbers of anal-
yses in a short time. The NTD autosampler was a critical too to
allow needle traps to be employed for such high-throughput pur-
poses. It is encouraging that such a high number of publications
have appeared describing various options for automating NTD sam-
pling and analysis. The potential for automated high through put
analysis will be a critical feature of the technology going forward
to enable broader acceptance in a variety of analytical applica-
tions.
 H.L. Lord et al. / Analytica Chimica Acta 677 (2010) 3–18
5. Future directions
Interesting future avenues of investigation for this rapidly pro-
gressing technology are envisioned in the areas of additional
sorbent technologies, the incorporation of focusing technologies,
automation to enable high-throughput analysis, and on-site appli-
cation.
In the area of sorbent advances, incorporation of monolithic
sorbents in a rugged needle would appear particularly interesting
due to their high porosity and good flow characteristics (low back-
pressure) with high extraction efficiencies. Although monolithic
sorbents for sample preparation have been successfully incorpo-
rated in wide bore (4–5 mm I.D.) stainless steel tubes [77–79],
silica-based capillaries [68,80], pipet tips [6], and microfluidic
devices [68,81], technical challenges to date have prevented their
deposition in narrow stainless steel capillaries. The coating of the
interior surface of a stainless steel capillary with a thin silica layer
may provide a solution here. Sorbent modification to better tai-
lor the selectivity of NTD extraction to the target analyte(s) is also
of interest. This can be envisioned through either developing a
non-selective general sorbent (or mixed bed sorbent) where the
distribution of a broad range of extracted target analytes closely
matches their distribution in the sample matrix, which could be
beneficial in proteomics and metabolomics applications, or through
the broader use of selective derivatizations to stabilize unstable or
short-lived species in the NTD, provide better extraction efficiency
of analytes with low partitioning or affinity, or to provide better
sensitivity for compounds that do not generate strong signals in
current detectors.
New options for applying focusing to the sample preparation
step could also be considered. For instance, van der Vlis et al. have
described the application of electrofocusing to liquid–liquid extrac-
tion in a needle preconcentration device, for sample preparation
prior to HPLC [82]. The method was applied for the analysis of a
variety of compounds in the ␮mol L−1 range. Although the authors
pointed out that the technique could be applied in conjunction with
SPE prior to HPLC, it appears this has not yet been reported.
To date needle trap technologies have not been broadly accepted
as main stream analytical techniques. We see the primary imped-
iment to this as the current limited supply of commercial devices
and lack of convenient technical solutions to many of the somewhat
cumbersome handling requirements. In particular, more efficient
and simplified desorption regimes would be beneficial. Finally we
envision the potential for broad application of the technology to
on-site analysis. The NTD technology is applicable to a broad range
of analytical strategies. It is simple and can be used in both active
and TWA sampling, as well as for the analysis of both total and free
concentrations in combination with SPME devices, in air and water
matrixes. To date field application has focused on field sampling
with laboratory analysis of the extracted samples [49], but the capa-
bilities of on-site instrumentation are progressing rapidly. Future
application of needle trap technology to conducting the entire ana-
lytical method in the field is a distinct possibility.
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