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Extraction // Steam Distillation

Chapter · December 2015

DOI: 10.1016/B978-0-12-409547-2.11557-4

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 Extraction // Steam Distillation☆
F Chemat, Avignon University, Avignon, France
C Boutekedjiret, Ecole Nationale Polytechnique, Alger, Algérie
ã 2015 Elsevier Inc. All rights reserved.

Conventional Steam Distillation 1

Microwave Steam Distillation 1
Steam Distillation coupled with Solvent Extraction 2
Application of SDE to the Analysis of Aqueous Samples 7
Application of SDE to the Analysis of Non-Fatty Environmental Samples 9
Application of the SDE to the Analysis of Fatty Biological Samples and Food 11
References 11

Conventional Steam Distillation

The traditional way of isolating volatile compounds as essential oils from plant material is distillation. During distillation, fragrant
plants exposed to boiling water or steam, release their essential oils through evaporation. Recovery of the essential oil is facilitated
by distillation of two immiscible liquids, namely, water and essential oil, based on the principle that, at the boiling temperature, the
combined vapour pressures equals the ambient pressure. Thus the essential oil ingredients, for which boiling points normally range
from 200 to 300
C, are evaporated at a temperature close to that of water. The essential oil laden steam rises and enters narrow
tubing that is cooled by an outside source. As steam and essential oil vapours are condensed, both are collected and separated in a
vessel traditionally called the ‘Florentine flask’. The essential oil, being lighter than water, floats at the top while water goes to the
bottbdom and can be easily separated. The amount of essential oil produced depends on four main criteria: the length of
distillation time, the temperature, the operating pressure and, most importantly, the type and quality of the plant material.
Typically, the yield of essential oils from plants is between 0.005 and 10%.
Historically, there have been three types of distillation: water distillation, water-steam distillation and steam distillation.
(Figure 1) Water distillation is sometimes referred to as ‘indirect’ steam distillation. In this method, plant material is soaked in
water and heated until it boils. The resulting steam from boiling water carries the volatile oils with it. Cooling and condensation
subsequently separate the oil from the water. Apart from its slowness, the disadvantage of this technique is that both materials and
scent deteriorate from constant heat exposure. In the water/steam method, the leafy plant material is placed on a grill above the hot
water, and the steam passes through the plant material. The leaves must be carefully distributed on the grill to allow for even
steaming and thorough extraction. ‘Direct’ steam distillation is the most common method for essential oil extraction. In this
process, no water is placed inside the distillation tank itself. Instead, steam is directed into the tank from an outside source. The
essential oils are released from the plant material when the steam bursts the sacs containing the oil molecules. From this stage, the
process of condensation and separation is standard.
In addition to those mentioned above, there are numerous other improved methods of producing natural fragrance materials
and essential oils including turbo-distillation, hydro-diffusion, vacuum-distillation, continuous-distillation, cold-expression,
dry-distillation and molecular-distillation.1
All these conventional extraction techniques have important drawbacks, such as low yields, formation of by-products and
limited stability. For steam distillation and hydro-distillation methods, the steam is percolated through the flask with plants from
the bottom and the oil evaporates. The emerging mixture of vaporised water and oil moves through a coil usually cooled with
running water, where the steam is condensed. The mixture of condensed water and essential oil is collected and separated by
decantation or in rare cases, by centrifugation. The elevated temperatures and prolonged extraction time can cause chemical
modifications of the essential oil components and often a loss of the most volatile molecules. Manufacturers use dry distillation to
extract high boiling point oils from wood. In this process, heat is applied usually as a direct flame to the vessel containing plant
material. The high temperatures release essential oils by evaporation. The vapor is piped away and condensed to give a mixture of
liquid oils. Some of the components in the plant material get degraded (pyrolyse) at the high temperatures used and add burnt,
smoky notes to the odor of the oil. Cade and birch tar oils are the two major oils produced by this method. When attempts are
made to extract essential oils by dry distillation, many organic compounds decompose.

☆
Change History: March 2015. F Chemat and C Boutekedjiret updated Abstract, Extended synopsis, definition of steam distillation, detailed description of
microwave steam distillation, the reference section, Added Figures 1 and 2 and 5, and added Table 1.

Reference Module in Chemistry, Molecular Sciences and Chemical Engineering http://dx.doi.org/10.1016/B978-0-12-409547-2.11557-4 1

2 Extraction // Steam Distillation

Figure 1 Schematic representation of the individual steps in the extraction process of steam distillation of volatile compounds.

Microwave Steam Distillation

According to ISO and AFNOR standards, the technics used for the extraction of essential oils is steam distillation, water distillation,
water-steam distillation or cold pressing for citrus peel oils. Although these processes are simple to implement, it does not remain
about it that they present several disadvantages, such as a very long extraction time, high energy consumption; moreover recovered
products can undergo chemical conversions caused by long durations of treatment with high temperature. Due these negative
effects, it became imperative to find new technologies more effective in term of duration of treatment, energy consumption, and
respectful of the environment. In this context, several technologies were developed; among them microwaves technology was
object of several applications.
Ganzler et al.2 was the first to have applied in 1986 the microwaves technology in the field of the extraction; whereas,
microwaves assisted extraction of essential oils was carried out for the first time by Craveiro et al.3 Since, several processes were
developed among which we can quote Microwave Hydrodistillation (MWHD) developed by,Stashenko et al.4 and improved by
Flamini et al., 2007; Solvent Free Microwave Extraction (SFME) developed by Chemat et al. in 2004, and improved by,Wang et al.5
Microwave Accelerated Steam Distillation (MASD), Microwave Steam Distillation (MSD), Microwave Hydrodiffusion and Gravity
(MHG), and Microwave Steam Diffusion (MSDF) developed by.6–8 (Figure 2) give a schematic description of these processes.
Nowadays, microwave extraction of essential oil is well known as a technique for green extraction and several studies highlighted
the effectiveness of the microwaves in the extraction of essential oils. Indeed, all these microwave methods shows advantages of
increased quality of the produced essential oil, time and energy saving having for consequence a reduction of the costs of essential
oil extraction.
Some examples of plants that have been treated by different microwave processes are given in Table 1.

Steam Distillation coupled with Solvent Extraction

The monitoring of toxic organic chemicals in environmental and biological samples is a major concern in many different fields.
However, the large variety of compounds of interest, the differences existing in their environmental levels and physico-chemical
properties, and the complexity of the matrices typically investigated make the development of universal analytical methods for such
an analysis a very difficult goal. This is especially true for the most toxic organic pollutants as their high toxicity makes their reliable
detection and accurate quantification at the trace level more relevant.
Most of the procedures described in the literature for the analysis of less volatile organic pollutants are time-consuming,
laborious and specific for the determination of an analyte (or family of compounds) in a selected matrix. Examples of selective
extraction of the target compounds, allowing their determination without any additional clean-up, can be found in the literature.
Extraction // Steam Distillation 3

Figure 2 (Continued)
4 Extraction // Steam Distillation

Figure 2 (Continued)
 Extraction // Steam Distillation
Figure 2, Cont’d Microwave steam distillation processes.

5
6 Extraction // Steam Distillation

Table 1 Examples of plant treated by different microwave processes

Process Plant Operating conditions References

Microwave Rosmarinus 400 g, 500 ml H2O, 460 W, t ¼ 80 min, YEO ¼ 1.47% 9

Hydrodistillation eriocalyx
(MWHD) Tetraclinis articulata 250 g, 500 ml deionized H2O, 500 W, 10
(Vahl) Masters t ¼ 90 min, YEO ¼ 0.54%
Mentha piperita 30 g, 500 ml salted water (1% W/V), 500 W, t ¼ 2 h, YEO ¼ 2.17% 10
Origanum majorana 100 g, 500 ml deionized H2O, 700 W, 12
L. t ¼ 30 min, YEO ¼ 5.0 ml/ 100 g dm
Mentha pulegium L. 100 g, 500 ml deionized H2O, 700 W, 12
t ¼ 30 min, YEO ¼ 2.2 ml/ 100 g dm
Solvent Free Microwave Pigeon pea [Cajanus 200 g soaked in water during 1 h, P(atm), 660 W, t ¼ 44 min, YEO ¼ 0.33% (w/w) 13
Extraction cajan (L.) Millsp.]
(SMFE) Schisandra chinensis 100 g soaked in water during 1 h (proportion of water pre-treatment ¼ 30%), 8
P(atm), 800 W, diameter particles ¼ 0.25 mm, t ¼ 45 min, YEO ¼ 1.75%
Dryopteris fragrans 200 g soaked in water during 1 h Humidity ¼ 51%, P(atm), 520 W, 14
t ¼ 34 min, YEO ¼ 0.33%
Rosmarinus 150 g, P(atm), 150 W, t ¼ 30 min, 15
officinalis YEO ¼ 0.54%
Microwave Steam Lavandula 20 g, P(atm), 200 W, Steam flow rate ¼ 8 g. min1, t ¼ 6 min, YEO ¼ 2.7% 16
Distillation angustifolia Mil.
(MSD) Citrus sinensis L. 100 g, P(atm), 500 W, Steam flow rate ¼ 14 g. min1, t ¼ 6 min, YEO ¼ 5.43% 17
Lavandula intermedia 125 g soaked in water during 10 min, 18
var. Grosso 500 W, t ¼ 40 min, YEO ¼ 5.4%
Microwave Lavandula intermedia 125 g soaked in water during 10 min, 18
Hydrodiffusion and var. Grosso 500 W, t ¼ 15 min, YEO ¼ 5.4%
Gravity (MHG) Citrus sinensis L. 400 g, 500 W, t ¼ 15 min, YEO ¼ 4.22% 19
Microwave Steam Lavandula 30 g, Steam flow rate ¼25 g.min1, 20
Diffusion (MSDF) angustifolia Mil. 200 W, t ¼ 3 min, YEO ¼ 4.42%
Lavandula intermedia 125 g soaked in water during 10 min, 500 W, t ¼ 15 min, YEO ¼ 5.4% 18
var. Grosso
Citrus sinensis L. 250 g, Steam flow rate ¼ 25 g. min1, 20
200 W, t ¼ 12 min, YEO ¼ 1.54%

However, most of these procedures involve sophisticated and expensive analytical techniques, such as supercritical fluid extraction
or gel permeation chromatography. On the other hand, the efficiency of these methods has been recognized to be highly matrix-
dependent. Because of these unresolved shortcomings, classical exhaustive extraction techniques, that is liquid–liquid extraction,
LLE, solid–liquid extraction or Soxhlet extraction, are still widely used in official methods and routine applications. Due to the low
selectivity of these methods, subsequent elimination of the co-extracted material is recommended. Such a clean-up step is
mandatory for reliable trace level determination of lipophilic and bio-accumulative pollutants in biological and complex
environmental samples.
Steam distillation-solvent extraction (SDE) has been used mainly for the extraction and concentration of fragrance and flavor
compounds. However, a variety of SDE methods reporting sample preparation for the analysis of pollutants in environmental
samples can be found in the literature. Most of these methods allow the simultaneous extraction, clean up and concentration of the
target compounds. The investigated compounds range from volatile polar and non-polar pollutants to non-ionic surfactants. This
article reviews the suitability and the limitations of SDE for the determination of less volatile trace organic pollutants, such as
pesticides, polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), or surfactants, in envi-
ronmental and biological matrices. The most relevant variables affecting the efficiency of the SDE of these compounds are discussed
and the results of some selected applications reviewed.
According to the theoretical model developed by,Rijks et al.21 the efficiency of the SDE process increased with the extraction
time and with the liquid and vapor flows. The process also depends on analyte-specific parameters related to the activity coefficient
(calculated from the water solubility of the analyte at 100
C) and the gas–liquid distribution coefficient of the compound in water
at the process temperature (i.e., 100
C for water steam). Not unexpectedly, the recoveries increased with the affinity of the target
compounds for the extracting solvent. This theoretical model is applicable only under ideal conditions, which are achieved when
all volumes and flow rates remain constant and there is ideal mixing and equilibrium at every stage. In spite of these limitations, the
model reflects the effect of several experimental factors on the SDE process. In fact, the different modifications carried out on the
SDE devices originally described by Likens and Nickerson in 1964 and by Flath and Forrey in 1977 reveal the influence of several
parameters on the recoveries of the target compounds. The modifications were mainly focused on increasing the size of the vapor
chamber and/or the condensing surface to allow a more complete mixing of the solvent and steam vapors, as well as on the
miniaturization of the system. As a consequence of the changes in design, (Figure 3) the efficiency of the extraction was increased,
 Extraction // Steam Distillation 7

Figure 3 A typical SDE modern design.

the analysis time reduced and the field of SDE expanded through the analysis of residue levels of less volatile pollutants in
environmental samples.
Due to the characteristics of the technique, the feasibility of SDE for the analysis of less volatile compounds depends on their
(i) potential for forming azeotropes with water and (ii) relative solubility in water and in the extraction solvent. However, the SDE
of the target compounds from complex samples can be expected to occur only after destruction or degradation of the main matrix
components, which usually entrap the analytes (see below). Therefore, as stated by,22 the applicability of the SDE technique to the
analysis of this kind of environmental matrices would be limited by the resistance of the investigated compounds to the selected
degradation procedure. Alternatively, in some cases, co-distillation solvents have been used to improve the SDE efficiency by
reducing the surface tension of the water and by increasing the extraction power (polarity) of the organic solvent. Finally, rather
different results have been published about the suitability of adding anti-foam agents in applications involving fatty samples
(Table 2).

Application of SDE to the Analysis of Aqueous Samples

Water was one of the first environmental samples selected to evaluate the feasibility of the SDE technique for the determination of
less volatile organic contaminants levels. Table 3 summarizes relevant data concerning some reported methods for the analysis of
this matrix.
Quantitative recoveries of spiked organochlorinated pesticides, OCPs (globally, in the range 90–106 ppb), and PCBs (globally,
in the range 70–104 ppb) in aqueous samples have been reported using the SDE technique. The reported methods allowed the
simultaneous extraction and concentration of the analytes in 1–1.3 h in a relatively small amount of a non-polar solvent
(1–15 ml). Usually, no additional treatment of the sample or the organic extract was required. The SDE technique was favourably
compared with other widely used extraction procedures, such as LLE or solid-phase extraction (SPE), by 30 for example similar
recoveries have been published for the analysis of PCBs in water at the ppb (ng ml1) level by using SDE, LLE or SPE. However, the
higher repeatability of the SDE procedure (relative standard deviations, RSD, lower than 10%) and the small amount of organic
solvent involved, as well as the short sample preparation times, makes SDE a valuable alternative technique for such an extraction,
especially when a large number of analyses have to be carried out.
Nevertheless, some limitations of SDE have also been reported for less volatile pollutants in water samples.22 studied different
parameters affecting the efficiency of the steam distillation process. They concluded that this technique is probably limited to
compounds with a vapour pressure of about 1kPa at 100
C. Their results also showed that the performance of SDE depends on the
concentration investigated and that recoveries tend to increase with the spiking level.
8 Extraction // Steam Distillation

Table 2 SDE methods for the analysis of less volatile organic pollutants in fatty environmental samples

Matrix Compound Spiking Pre-treatment Solvent Extraction Post- Recovery RSD Ref.
level time (h) treatment (%) (%)
(ng g1)

Fish tissue PCBs 1700 Blended with Isooct/tol.(15) 7–14 NR 82–85 ? 23

2.5 l water
Muscle, PCBs, PCNs, 5000 Blended with n-heptane (10) 2 Concentration 67–100 1.0–20 24
liver, SDDTa 0.1 l water
kidney
Muscle, PCBs, PCNs, 1000 Blended with n-heptane (10) 2 Concentration 65–85 ?
liver, SDDTa 0.1 l water
kidney
Dairy Endogenous – 10 g sample Petrobenzine (?) 1 NR – ? 25
products, OCPs +water
Human +ethanol
milk
Pumpkin OCPs 100 10 g sample Petrobenzine (?) 1 NR 65–89 6–12
seed +water
+ethanol
+surfactant
Certif. dairy OCPs 1.5–6.6 5 g sample Petrobenzine 1.5 Concentration 73–111 ? 23
product +80 ml 2 M (20)
H2SO4
+ultrasonic,
1 min+1 ml
ethanol
+surfactant
Powdered OCPs 20.0–51.3 5 g sample Petrobenzine 1.5 Concentration 83–126 ?
milk, +80 ml 2 M (20)
Human H2SO4
milk +ultrasonic,
1 min+1 ml
ethanol
+surfactant
Powdered Endogenous – 15 g sample Dichlorometane 60–90 SiO2-HSO4 <26 ? 26
milk PCBs +60 ml 1 M (2)
H2SO4
+ultrasonic,
1 min
Dairy PCBs 0.5 15 g sample Dichlorometane 60 SiO2-HSO4 <10 ?
products +60 ml 1 M (2)
H2SO4
+ultrasonic,
1 min
Herbal OCPs 500–10,000 Blended with ? ? LLE (hexane: 83–105 2.4–10 27
essential 0.05 L water ethyl ether)
oils +H2SO4
OPPs 500–10,000 Blended with ? ? LLE (hexane: 72–116 0.5–10
0.05 L water ethyl ether)
+H2SO4

Similar tendencies have been observed by30 when using the SDE technique for the extraction of water spiked with the 2,3,7,
8-substituted-CDD/Fs at different levels of concentration (0.25–2 ng ml 1, 0.025–0.2 ng ml 1 and 0.0025–0.02 ng ml 1). The
recoveries obtained for the lower and higher boiling point congeners (tetra- and octa-CDD/Fs, respectively) are consistently lower
than those found for the rest of the investigated congeners: respectively 40–76% and 73–137% at the highest level of concentration
investigated, 39–60% and 62–92% at the intermediate, and 37–55% and 25–72% at the lowest spiking level. These results also
show that the SDE recoveries for a given compound decrease with the concentration level when using n-pentane as the extraction
solvent. The simple substitution of n-pentane for a solvent more selective for the PCDD/Fs (dichloromethane) increases recoveries
from 25–73% to 71–139% for tetra- to hepta-CDD/Fs at the 0.0025–0.02 ng ml 1 level. However, no additional improvement is
obtained for the octa-CDD/F recoveries (38–56%). In spite of the low recoveries obtained for OCDD/F, the proposed SDE
procedure compares favourably with results previously published by using LLE or SPE in terms of repeatability, analysis time
and solvent consumption.
 Extraction // Steam Distillation 9

Table 3 SDE methods for the analysis of less volatile organic pollutants in aqueous samples

Spiking level Extraction Cc. factoa (water: Post- Recovery RSD

Compound (ng ml1) Solvent (ml) time (h) solvent, v/v) treatmentb (%) (%) Ref.

OCP 0.004–0.016 Isooctane/ 1 167:1 NRc 90–104 ? 28

toluene (15)
Arochlor1016, 1242, 0.016 Isooctane/ 1 167:1 NR 98–100 ?
1248, 1254 toluene (15)
OCP 0.4–4.0 n-pentane (1) 1.3 50:1 NR 97–106 ? 29
Arochlor 1260 10 n-pentane (1) 1.3 50:1 NR 81–104d ?
Toxic PCBs 0.01–1.0 n-pentane (2) 1 50:1 Concentration 70–115 <10 30
PCDD/Fs 0.025–2.0 n-pentane (2) 1 50:1 Concentration 49–139 <10
PCDD/Fs 0.0025–0.02 Dichloromethane 1 50:1 Change of 49–139 <10
(2) solvent
Fatty alcohol 500 nM Ethyl acetate (2) 3e 100:1 Derivatization 87–100 5.6–7.0 31
sulfates
Alkyl polyglycosides 2 mM Ethyl acetate (2) 4e 25:2 Derivatization 84 ?
a
Concentration factor
b
Post-SDE treatment required.
c
NR, not required
d
Recoveries for some selected peaks.
e
The SDE was conducted after hydrolysis with 4 M H2SO4 plus liquid–liquid extraction with diethyl ether of the hydrolysate and concentration.

Good recoveries (in the range 84–100%) have been reported by Meissner et al. for the analysis of surfactants such as fatty
alcohol sulfates and alkyl polyglycosides in water (Table 1). SDE of the fatty alcohols yielded by hydrolysis and subsequent LLE of
the original compounds is an attractive technique for the effective clean-up and concentration of these complex mixtures of
compounds at the trace level. On the other hand, the application of SDE to the extraction of fatty alcohol ethoxylates with more
than three ethoxy units in the molecule cannot be accomplished due to their high solubility in water.

Application of SDE to the Analysis of Non-Fatty Environmental Samples

Table 4 summarizes relevant data related to some reported SDE methods for the analysis of less volatile organic pollutants in
non-fatty environmental samples. Most of the reported SDE applications referred to the analysis of OCPs and toxic aromatic
compounds, for example PCBs, polychlorinated naphthalenes (PCNs), or polynuclear aromatic hydrocarbons (PNAs), in soils and
sediments. Contrary to what might be expected from the high complexity of these samples, most of the methods did not include
any further pre-treatment of the matrix but blending with the selected volume of water. Only a few procedures involving drastic
treatments (e.g., blending of the sample with H2SO4 and K2Cr2O7) during the SDE to guarantee the destruction of the soil or
sediment components in which the target compounds could be entrapped, can be found in the literature.
The efficiency (or need) of such a drastic treatment is difficult to evaluate from the data published. In general, high
(quantitative) recoveries have been reported for freshly spiked analytes (globally in the range 78–102% for PCBs and OCPs at
the 20–90 mg g1 level) with all the procedures (Table 4). However, the efficiency of the proposed SDE methods for the extraction
of endogenous pollutants from weathered samples has been scarcely evaluated. In these studies, Seidel and Lindner 25 and Cooke
et al.38 found concentrations very close or below the limit of detection have usually been reported for the endogenous contam-
inants, but the lack of comparison of the SDE results with those obtained by standard or more exhaustive methods, that is Soxhlet
extraction, do not allow any discussion about the methods used.
Dunnivant and Elzerman 24 reported recoveries ranging from 47 to 99% for SDE of certified sediments with PCBs at the
2.34–24.6 mg g1. However, as quoted above, this SDE method involved a digestion of the sample under drastic conditions.
In a closely related study, Nash et al. compared the efficiency of steam distillation with subsequent organic solvent extraction to
that of Soxhlet extraction for the analysis of pesticides in soil, plant tissues and air (polyurethane foam filters). Both procedures
provided similar recoveries for the spiked samples (in the ranges 80–90%, 80–90% and 90–100%, respectively). However, the SDE
levels determined for weathered soils blended with water were 40–50% lower than the concentrations found by the Soxhlet
procedure. The study also showed that the efficiency of the SDE depends on the soil type and, in agreement with that mentioned for
aqueous samples, on the volatility of the selected compounds. The less volatile the compound, the lower the recovery: SDE
recoveries for DDT were only 21–60% of those found by Soxhlet extraction.
Onuska and Terry observed a similar trend when comparing the SDE and the Soxhlet efficiencies for the extraction of spiked
chlorinated benzenes from a sediment. The concentrations found using SDE were 14–36% lower than those using the Soxhlet
method, except for pentachlorobenzene and 1,3-dichlorobenzene, which were not determined by the latter procedure. The authors
also reported a decrease in the SDE recoveries of the target compounds as the investigated concentration level decreased (Table 4).
 10
Extraction // Steam Distillation
Table 4 SDE methods for the analysis of less volatile organic pollutants in non-fatty environmental samples

Spiking level Extraction Recovery RSD

Matrix Compound (mg g1) Pre-treatment Solvent time (h) Post-treatment (%) (%) Ref.

Sediment Arochlor 1016 50 Blended with 2.5 l water Isooct/tola 1 Elimination S 78 ? 32

(15)
Weathered PCBs, PCNs, PNAs – Blended with 0.8–1.1 l water n-hexane (10) 2.2 Concentration – 1.1–23 33
sediment
Sediment Chlorinated 100–1000 Blended with 0.25 l water n-hexane (10) 3 Elimination S 76–91 0.5–21 34
benzenes
Sediment Chlorinated 10–100 Blended with 0.25 l water n-hexane (10) 3 Elimination S 71–88 1.4–33
benzenes
Sediment Chlorinated 1–10 Blended with 0.25 l water n-hexane (10) 3 Elimination S 66–89 1.4–17
benzenes
Certif. PCBs 2.34–24.6 200 ml H2SO4 + K2Cr2O7 n-hexane 8 Alumina 47–99 0.3–5.4 24
Sediment (15) b
Sediment PCBs 33.6–90.0 200 ml H2SO4 + K2Cr2O7 n-hexane 8 Alumina 102 4.7–9.3
(15) b
Soil HCB 20.0 100 g soil + 20 ml water + 10 ml ethanol + ultrasonic, Petrolbenzine 1 NR 100 2.7 25
1 min (?)
Weathered soil Endogenous OCP – 100 g soil + 20 ml water + 10 ml ethanol + ultrasonic, Petrolbenzine 1 NR – –
1 min (?)
Particulate PCDD (homologues) 0.045–8.56c 150 g (sample + water) + HCl + sonication n-hexane (10) 3 Basic alumina 85–116d ? 35
Fruits, OCCs, OCPs 0.01–1.0 5–10 g sample blended with 0.25 l water n-hexane (5) 1.5 NR 66–108 ? 28
vegetables
Fruits, PCBs 0.1 5–10 g sample blended with 0.25 l water n-hexane (5) 1.5 NR 68–89 ?
vegetables
Sediments Chiral PCBs – 5 g sample blended with 4 g Cu + 50 ml water n-pentane (2) 1 NR – – 36
Sewage sludge Nonylphenol 100e 1 g sample blended with 0.1 L water Cyclohexane 3 NR (HPLC) <30a ? 37
polyethoxylates (1–2) Alumina (GC)
Toothpaste Fatty alcohol sulfates – 30 g sample + 50 ml 4 M H2SO4 + LLE (diethyl ether, Ethyl acetate 3 Derivatization – – 31
10 ml) + concentrat. (2)
a
Isooctane/toluene.
b
Replace hexane layer after 1, 2, 4 and 8 h intervals.
c
Range for different homologues.
d
Mass balance calculations for the whole SDE system by comparison with the initial amount.
e
Total concentration for all NPnEO (n ¼ 1–17).
 Extraction // Steam Distillation 11

The recoveries of the studied chlorinated benzenes decreased from 76–91% to 66–89% as the spiking level decreases from
100–1000 mg g1 to 1–10 mg g1.
In a recent study, Meissner et al. used SDE for the determination of fatty alcohol sulfates in cosmetics (toothpaste) by combining
this technique with a hydrolysis treatment. However, the application of SDE to the analysis of nonylphenol polyethoxylates in
sewage sludge by Lee et al. failed when compared with the more efficient supercritical fluid extraction technique.
In general, the published SDE methods for the analysis of non-fatty environmental samples involve longer extraction times
(1–8 h) than those reported for aqueous samples (1–1.3 h). In addition, and contrary to that proposed by the theoretical model of
Rijks et al., the recoveries of less volatile compounds from non-fatty complex samples have been found to be independent of the
vapour flow rates. However, it is important to note that in this study by Seidel ethanol was added to the water flask to improve the
OCP recoveries, and that the possible effect of a co-distillation solvent was not included in the theoretical model.

Application of the SDE to the Analysis of Fatty Biological Samples and Food

Due to the high lipophility of some of the most toxic pollutants, such as OCPs, PCBs and PCDD/Fs, the classical procedures for the
analysis of these pollutants in fatty samples were based on an exhaustive extraction of the lipids from the matrix. Subsequent
removal of the co-extracted lipids has been widely recognized as the main problem with these kinds of methods, especially when
analyzing samples with high fat contents such as dairy products. Because of the characteristics of the SDE technique, the disruption
of the strongly bound pollutant-matrix in these samples can be accomplished before SDE by degradation of the matrix components
entrapping the target compounds. Treatment with 1–2 M sulfuric acid followed by ultrasonication in a bath and heating of the
sample during the SDE process has been found to be one of the most efficient procedures for breaking down the matrix structure
allowing steam distillation of the analytes. Furthermore, this acid treatment allowed a simultaneous clean up of the final extract as
the matrix components form more polar products, which can then be easily separated from the non-polar analytes. According to
the published results, most samples submitted to this kind of treatment did not require any additional clean up. Filek et al. report
good recoveries for the SDE of OCPs from dairy products when using this type of acid pre-treatment: in the range 83–126% for
powdered milk and human milk spiked at the 20.0–51.3 ng g1 level, and in the range of 73–111% for a certified dairy product
(OCP levels ranging from 1.5 to 6.6 ng g1). However, the SDE method failed when it was used for the extraction of the
endogenous PCBs from dairy products with different fat contents. According to the reference method, the PCBs detected by
Ramos et al.26 ranged from 2 to 0.01 ng g1 in the investigated matrices. Nevertheless, most of the PCB congeners were found to be
non-detectable with the SDE procedure and, when found at quantifiable levels, the reported concentrations were less than 26% of
those determined by the reference method.
Rather similar results were reported by Seidel and Lindner 25 for the analysis of the OCPs in dairy products and human milk as
none of the investigated compounds were found to be at a quantifiable level. However, no additional comparison with a reference
method was included in this study, in which 10 g of sample was blended with water and ethanol. In this case, the alcohol, added as
a co-distillation solvent, would also be able to disrupt the fat globule thereby allowing the SDE of the analytes. An important
shortcoming of this kind of approach is the formation of large oil drops during the extraction, which increase the diffusion layer
and hinder the SDE process. Filek et al. proposed blending of the sample with surfactants has been proposed as a possible solution
for the case of fatty matrices without natural emulsifiers.
When no pre-treatment of the fatty sample was carried out, a co-distillation (total, according to Yoon et al., or partial, according
to Ramos et al.) of the lipids with the less volatile compounds occurred. Then, a post-treatment for isolation of the target
compounds from the co-extracted matrix components was required. Following the implication of these results, it is rather
surprising that neither pre- nor post-treatment of the sample was included in some of the first reported applications of SDE for
the analysis of toxic aromatic compounds in biological matrices. The investigated samples included fish tissues, muscle, liver and
kidney and, although satisfactory recoveries (67–100%) were reported for the spiked PCBs, PCNs and SDDT (i.e., DDT + DDE
+ TDE), it is important to note that the spiking level in these experiments ranged from 1000–5000 ng g1 (Table 3). Even at such a
high level of concentration. In fact, Cooke et al. found that the authors reported an evident dependence of SDE recoveries on the
analyte concentration the PCB, PCN and SDDT recoveries from animal tissues decreased from 67–100% to 65–85% when
the spiking level decreased from 5000 to 1000 ng g1. According to this trend, it can be concluded that the very low levels of the
endogenous pollutants in environmental samples together with the typical complexity of the matrix would be the main reasons for
the disappointing results reported for some SDE applications involving non-spiked fatty samples.

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