Fresenius J Anal Chem (1999) 363 : 347–352
O R I G I N A L PA P E R
R. Grümping · A. V. Hirner
HPLC/ICP-OES determination
of water-soluble silicone (PDMS) degradation products in leachates
Received: 10 July 1998 / Revised: 2 November 1998 / Accepted: 5 November 1998
Abstract Inductively coupled plasma optical emission
spectrometry (ICP-OES) was used for the element-spe-
cific determination of water-soluble organosilicon species
separated by high-performance liquid chromatography
(HPLC). Leachates from different waste deposit sites
were investigated. The polydimethylsiloxane (PDMS)
degradation product dimethylsilanediol (DMSD) could be
detected in almost all samples in the low mg L–1 range,
and it was furthermore possible to determine trimethylsi-
lanol (TMSOL) in some leachate samples in the µg L–1
range. TMSOL was additionally analyzed by a method es-
tablished before (LT-GC/ICP-OES). This study proved the
occurrence of silanol compounds in leachates from loca-
tions were silicone material is deposited.
Introduction
PDMS degradation products in the environment
Silicone (polydimethylsiloxane, or PDMS) fluids are widely
used in industrial and consumer products and the potential
for environmental dispersion is greatest for PDMS mater-
ial used in down-the-drain applications [1]. The environ-
mental degradation of PDMS is believed to be abiotic hy-
drolysis of the polymers, since studies showed that all of
the clays tested were catalysts for PDMS degradation [2]
and PDMS hydrolysis increased with decreased soil mois-
ture [3]. PDMS hydrolysis is the main source of low-mol-
ecular methylsilanols in the environment [4]. Silanols are
monomeric organosilicon compounds containing at least
one Si-OH group:
RxSi(OH)4-x; x = 1–3, R = CH3, C6H5 or other groups
Dimethylsilandiol (DMSD) has been identified as main
PDMS degradation product, and the generation of small
R. Grümping · A. V. Hirner (쾷)
Institute of Environmental Analytical Chemistry,
University of Essen, D-45177 Essen, Germany
© Springer-Verlag 1999
amounts of trimethylsilanol (from end-groups) has been
observed [5].
Low-molecular silanol species usually occur as tran-
sient intermediates only, because silanols are generally
unstable and tend to condense in acidic or alkaline envi-
ronments to produce organosiloxanes [6]. Therefore, plas-
tic vials and containers should be used for work with
silanols and samples should be stored at low temperatures
[7]. DMSD is quite unstable in pure solid form, but aque-
ous solutions (100 ppm DMSD) are stable for over a year
[8].
Volatilization and sorption could be identified as im-
portant factors affecting the fate of DMSD in soils and
laboratory tests with different soil matrices showed that
only traces of DMSD could be detected in percolating wa-
ters [9]. Several degradation processes for methylsilanols
in air, water and soil have been demonstrated. Methylsi-
lanols are expected to degrade photolytically in the atmo-
sphere [10] and in water [11] to silica and carbon dioxide.
Microbial degradation of DMSD in soils has been shown
recently [12].
The water solubility of the methylsilanols, combined
with their partly low vapor pressures, indicate that they
will appear as well in aqueous as in atmospheric compart-
ments. TMSOL has been determined by us in gaseous and
aqueous samples from waste sites [13].
Analytical methods for silanol determination
Organosilicon extraction techniques have found wide ap-
plication to water and soil samples. The efficiency of most
organic solvents for the extraction of hydrophilic organo-
silicon compounds (OSC) like silanols is poor [14].
Therefore, Lehmann et al. [8] used sequential extraction
procedures with aqueous CaCl2, methanol and tetrahydro-
furan (THF) for the extraction of hydrophobic silicones
and polar degradation products like DMSD from soils;
subsequently the extracts were investigated by GC-MS
[7]. The use of a mixed solvent of (1:1) 1-pentanol and
methyl isobutyl ketone (MIBK) for the effective extrac-
348
tion of hydrophobic and hydrophilic OSC in water sam-
ples is described by Parker [15]; the extracted material is
analyzed by AAS. A method including the derivatization
of waterborne OSC by hexamethyldisiloxane and GC-MS
investigation of the derivatives has been developed by
Mahone et al. [16]. Porous polymers have been used by
Cassidy et al. [17] to collect polar and non-polar OSC
from water samples. Liquid chromatography techniques
and AAS detection were applied to identify the collected
OSC.
The most powerful tools that satisfy the needs of sensi-
tivity as well as speciation are various combinations of
chromatographical techniques, coupled on-line with ele-
ment-specific detectors. Varaprath et al. [18] analyzed
low-molecular siloxanes and silanols in different matrices
by HPLC on reverse C-18 column using a water/ acetoni-
trile (ACN) mobile phase and Watanabe et al. [19] used
ICP-OES for silicone detection in organic extracts in the
µg L–1 range. Thus, the combination of high-performance
liquid chromatography (HPLC) for separation and induc-
tively coupled plasma atomic emission spectrometry
(ICP-OES) for detection should be ideal for the sensitive
determination of organosilicon species in water samples.
When organic solvents are aspirated for long periods, it
can be difficult to achieve a stable argon plasma because
of carbon deposition on the injector and other parts of the
torch system. In a study by Boorn and Browner [20] the
tolerance of Ar ICP to 30 organic solvents is discussed
and the established solvent vapor loading is the major ef-
fect influencing plasma stability. Therefore, the use of or-
ganic solvents has often required redesign of the ICP in-
terface or other parts of the ICP. Pneumatic [21], direct in-
jection [22], crossflow [23], ultrasonic [24] or thermo-
spray [25] nebulizers have been applied as ICP interface
in HPLC/ICP systems. Some applications include spray
chamber modifications for the use of volatile organic sol-
vents [26]. The plasma operating conditions which were
employed for studies with organic solvents are differing
from normal conditions. An increase in forward rf power
produced a corresponding increase in tolerance for or-
ganic solvents; additionally an auxiliary gas flow is used
for most ICP applications with organic matrices [20].
Biggs et al. [27] realized the determination of siloxanes
by RP-HPLC separation with DCP-AES detection. The
coupling of RP-HPLC and ICP-OES for speciation and
quantification of silanol compounds has been realized by
Dorn and Skelly Frame [28].
Experimental
Materials
Silicate standard used was Si4+ (Merck, Germany, Si in 5% HNO3
and traces of HF, 1000 mg L–1). The following silanol compounds
were provided by Wacker Chemie (Burghausen, Germany): TMSOL
(about 97%), DMSD (about 79%) and tetramethyldisiloxane-1,3-
diol (TMSD) (about 99%). The silanol standards were weighed into
polypropylene vials and diluted with water. Stock standard solutions
of approximately 1000 mg L–1 were prepared and the silanol com-
pounds and standard solutions were stored frozen at –30 °C.
The mobile phase consisted of ACN for HPLC (Acros, New
Yersey, USA) diluted in deionized water (Seral, Ransbach, Ger-
many).
Locations of leachate sampling and sampling procedure
At four landfill sites leachate samples were taken by pumping
them from wells. Furthermore, percolating water was taken from
two kinds of waste composting tanks.
Location 1: domestic waste deposit with sewage sludge disposal,
Location 2: domestic waste deposit (sewage sludge disposal has
stopped 3 years ago),
Location 3: waste deposit without sewage sludge disposal,
Location 4: abandoned waste deposit site,
Location 5: waste composting tank (volume: 1 m3) filled with me-
chanical pretreated waste material including about 5%
sewage sludge,
Location 6: waste composting tank (volume:1 m3) filled with me-
chanical and biological pretreated waste material in-
cluding about 5% sewage sludge.
The aqueous samples were stored in polypropylene (PP) bottles at
3 °C in the dark. Before measurement the samples were filtered by
means of 0.2 µm syringe filters (Nalgene, Rochester, USA).
HPLC/ICP-OES technique
Analysis of methylsilanols requires strict avoidance of glass mate-
rial and for this reason, polypropylene vials with a volume of 1 mL
(neoLab, Heidelberg, Germany) were used for HPLC investiga-
tions of silanol standards and samples.
The RP-HPLC/ICP-OES technique realized by Dorn and
Skelly Frame [28] is partly implemented in our developments, but
several modifications were necessary to establish a reliable method
with the available analytical equipment. The liquid chromatograph
interfaced to the spectrometer consisted of a Waters (Eschborn,
Germany) HPLC pump (Model 510), a Waters 717 Autosampler
and a control device (Model 600 E). Chromatographic separation
of silanol compounds in the reversed-phase HPLC mode was car-
ried out on a YMC-Pack polymer C18 column, 250 × 2 mm i.d.
(YMC, Wilmington, USA) with a cartridge precolumn. Samples
were eluted by mobile phases consisting of ACN diluted in deion-
ized water (5% ACN/95% water or 20% ACN/80% water) with a
flow rate of 0.3 mL min–1. Between 25 and 100 µL injections of
standards and samples were used. After the elution of the analytes
a mixture of 60% ACN/40% water was used for flushing the col-
umn. This composition was held for approximately 15 min, fol-
lowed by an immediate return to the initial conditions after a 15 min
equilibration period.
The Unicam (Offenbach, Germany) ICP-OES PU 7000 used
for this technique was identical with the system described before
[13]. The HPLC effluent was introduced into the ICP by pneu-
matic nebulization (Grid nebulizer in a Teflon spray chamber at
20 °C). The configuration of the interface is shown in detail in Fig. 1.
Two parts of polyether ketone (PEEK) tubing with 0.125 mm i.d.
(Dionex, Idstein, Germany) connected by an adaptor were used for
coupling of the column outlet and the pneumatic nebulizer.
Fig. 1 Schematic illustration of HPLC/ICP-OES interface

Optimization of ICP parameters (Table 1) and a maximum
loading of 20% ACN in the mobile phase with a flow rate of
0.3 mL min–1 guaranteed stable plasma conditions. When the col-
umn was flushed with 60% ACN, the transfer line between HPLC
and ICP was interrupted and the effluent was fed to a waste con-
tainer. During these periods another tubing was connected to the
transfer line adaptor and by means of a peristaltic pump aqueous
solutions were introduced to optimize the ICP parameters and de-
termine over-all instrument performance.
Results and discussion
Silanol standards
After optimization of the chromatographic parameters, the
YMC-Pack polymer column resolved the three low-mole-
Table 1 HPLC/ICP-OES op- ICP parameter
erating conditions
R.f./MHz
Forward power/W
Plasma gas flow rate/L min–1
Auxiliary gas flow rate/L min–1
Nebulizer gas pressure/hPa
Nebulizer
Spray chamber
Torch
OES parameter
Monochromator
Resolution/nm
Linear dispersion/nm mm–1
Primary (entrance) slit/µm
Secondary (exit) slit/µm
Wavelength of Si spectral line
HPLC parameter
HPLC column
Mobile phase
Solvent flow rate/mL min–1
Fig. 2 Determination of silanol
standards (eluant: 20%
ACN/80% H2O). 1 (DMSD),
2 (TMSD), 3 (TMSOL)
349
cular silanol compounds of interest. The species DMSD,
TMSD and TMSOL could be separated by an isocratic
operation using an eluent with 20% ACN and 80% water
and a typical chromatogram is presented in Fig. 2. This
isocratic operation did not permit the separation of soluble
inorganic silicon species (silicate) and DMSD (Fig. 3 b).
Therefore, for the determination of DMSD in samples
with higher silicate concentrations, a second isocratic op-
eration with 5% ACN and 95% water was necessary. This
more polar eluant permitted the separation of silicate and
DMSD (Fig. 3 a).
For quantitative analysis an external calibration was
realized and calibration graphs were linear over the range
of 1 to 100 mg Si L–1 for DMSD and 0.3 to 30 mg Si L–1
for TMSOL. The long-term precision, calculated from
40.68
1300–1500
15–18
0–0.2
1930–2206
Grid type, no cooling
Teflon material
Semi-demountable
Fixed echelle grating with quartz prism
0.0075–0.024
0.083–0.270
60
30
288.158 (molecular line)
YMC-Pack polymer C18 column, 250 × 2 mm i.d.
Mixtures of ACN in water (isocratic operation)
0.3
350
Fig. 3 a Determination of sili-
con species in leachate sample
(eluant: 5% ACN / 95% H2O). a
1 (silicate), 2 (DMSD); b De-
termination of silicon species
in leachate sample (eluant:
20 ACN/80% H2O). 1 (sili-
cate), 2 (DMSD), 3 (TMSOL)

14 sets of standards analyzed over a 72 h period, ex-
pressed as the relative standard deviation of peak areas, is
about 6.6% for DMSD and 8.9% for TMSOL within the
concentration ranges listed above.
Standards of TMSOL showed a significantly higher re-
sponse than DMSD or silicate standards. This is mainly
due to the high volatility of this species that leads to an al-
most quantitatively transfer into the ICP. A large part of
the other compounds is separated during the pneumatic
nebulization process and only about 5% of the non-
volatile analytes is transferred into the plasma. The detec-
tion limits are about 50 ng of Si for DMSD and about 3 ng
of Si for TMSOL.
Further modifications of the HPLC equipment could
minimize the dead volume of the system and would en-
able lower flow rates and the use of mobile phase gradi-
ents. By the implementation of another ICP interface the
argon plasma could be stabilized when higher organic
loadings are aspirated. Some of these modifications are
realized by Dorn and Skelly Frame [28]; they used a mi-
cro HPLC system with a flow rate of 0.2 mL min–1, mo-
bile phase gradients consisting of 10 to 40% ACN in wa-
ter, a special ICP interface and they achieved a detection
limit of 3.75 ng of Si for DMSD.
Leachate samples
The pH value of the leachates varied between 7.1 and
7.8 and a solid phase was recognizable in every sample.

Table 2 Determination of wa-
ter-soluble silicone degradation Sampling Number of
products in leachates location measurements
HPLC/LT-GC
1 12/6
2 10/8
3 6/6
a Samples stored for about one
4 5/4
year at 3 °C in the dark 5 7/7
b Rather fresh samples
n.d. not detected 6 6/7
In particular in the leachates from waste composting
sites (location 5 and 6) a rather high concentration of
ferric hydroxide can be observed. The leachate from lo-
cation 2 showed a higher amount of organic material
and a negative redox potential (anaerobic conditions).
Due to the storage in PP bottles for several months, aer-
obic conditions appeared in the other leachate samples
with the redox potential varying between + 270 and
+ 425 mV.
Between five and twelve HPLC runs were carried out
for every leachate sample and additional investigations by
stripping of volatile compounds and LT-GC/ICP-OES
analysis were realized [13].
The results presented in Table 2 demonstrate the pres-
ence of DMSD in almost all of the investigated leachate
samples. Only in leachate samples from location 4, where
the deposition of waste material has stopped, no methylsi-
lanol compounds can be determined. The DMSD concen-
trations in leachates from the other locations varied be-
tween 0.7 and 10.7 mg Si L–1 with a standard deviation of
22%. TMSOL could be detected by HPLC/ICP-OES in
leachate samples from three locations. Medium concen-
trations between 51 and 654 µg Si L–1 with a standard de-
viation of 26% have been found.
Because of a higher sensitivity of detection, LT-GC/
ICP-OES measurements enabled the determination of
TMSOL in every leachate sample in the µg Si L–1 range.
TMSOL concentrations found by LT-GC measurements
were significantly lower than the concentrations estab-
lished by HPLC analysis. Almost quantitative stripping of
volatile compounds from aqueous samples has been veri-
fied for hydrophobic compounds like volatile methyl-
siloxanes [13]. TMSOL is a volatile and water-soluble
species, which is not quantitatively stripped from water
samples by the applied method and finally resulted in
lower TMSOL concentrations. Thus, HPLC/ICP-OES in-
vestigations proved to be more suitable for the determina-
tion of water-soluble compounds.
From some locations also rather fresh leachate samples
stored for about one year at 3 °C in the dark were investi-
gated by LT-GC/ICP-OES. A significant decrease of TM-
SOL concentrations in samples from the locations 1, 2
and 3 was noticeable. Transformation, volatilization and
degradation processes discussed before could be impor-
tant reasons for the loss of low-molecular silanols from
the water phase. In contrast, an increase of TMSOL con-
351
HPLC/ICP-OES LT-GC/ICP-OES
DMSDa TMSOLa TMSOLa TMSOLb
[mg L–1] (µg L–1] [µg L–1] [µg L–1]
10.7 ± 3.6 654 ± 124 369 ± 125 688 ± 94
1.8 ± 1.0 n.d. 8± 3 15 ± 4
0.7 ± 0.4 n.d. 9± 2 24 ± 8
n.d. n.d. 3± 1 –
2.5 ± 0.4 395 ± 128 202 ± 54 70 ± 24
5.2 ± 0.8 51 ± 14 45 ± 15 9± 2
centrations could be observed in leachate samples from
the waste composting sites (location 5 and 6). It can be
supposed that a loss of silanols in these samples is pre-
dominated by PDMS degradation processes, which pro-
duce silanol compounds. High PDMS concentrations (de-
position of sewage sludge) and a high amount of ferric hy-
droxide (catalytic surfaces) in these samples could enable
the degradation of PDMS material in the aqueous me-
dium. In a study by D.C. van der Post [29] it was con-
cluded that silicone oil, when present as a water pollutant,
does not remain chemically stable, but is subject to hy-
drolysis, producing silanols as hydrolysis products. And
the hydrolysis from 4–9% of PDMS in freshwater sedi-
ments following a year of incubation under aerobic condi-
tions has also been proved [30]. For future analysis of
organosilanols it would be useful to store samples frozen
as recommended in literature [28].
Obviously the DMSD concentration in leachates from
waste composting tanks with mechanically and biologi-
cally pretreated waste (location 6) is significantly higher
than in leachates from composting tanks with only me-
chanical pretreated waste (location 5). This may indicate
that the aerobic microbial pretreatment of the waste mate-
rial might support the degradation of PDMS material. Mi-
crobial effects on PDMS degradation are controversely
discussed in literature [31–33]. It is somewhat striking
that the TMSOL contents in leachates are lowered by bio-
logical pretreatment. This may be due to the volatility of
this compound so that most of the formed TMSOL enters
the atmosphere during the aerobic biological pretreatment
processes. Thus, TMSOL concentrations in the gas [13]
and aqueous phase could be reduced during the subse-
quent anaerobic composting.
Conclusion
Coupling of HPLC and ICP-OES permits the separation
and element-specific detection of silanol compounds in
aqueous samples from contaminated sites.
According to literature data [4, 5] most organosilanols
generated in the environment will consist of DMSD and
its low oligomer diols, and to a much lesser extent TM-
SOL will be formed by the cleavage of end-groups in
PDMS molecules. DMSD could be determined in almost
all of the investigated leachates from waste sites in the
352
low mg L–1 range, but no further diol compounds were de-
tectable. The species TMSOL could be determined in
some leachate samples by HPLC/ICP-OES and LT-
GC/ICP-OES investigations in the µg L–1 range.
Comparing the TMSOL concentrations in leachates
with the TMSOL concentrations in the corresponding gas
phases [13], it can be concluded that most of the volatile
and water-soluble species can be found in the aqueous
phase.
At locations where sewage sludge is deposited, higher
amounts of PDMS degradation products can be observed.
Thus, literature data [1] and our preceding results [13] are
confirmed. The deposition of sewage sludge, including most
of the environmental silicone material used in down-the-
drain applications, has a great influence on the concentra-
tions of PDMS and their degradation products at waste sites.
Therefore, it is not surprising that at an abandoned waste
dump no PDMS degradation products can be determined.
Although we did not present data on soil systems, this
study indicates that a great degree of PDMS degradation
products should be transferred from soil compartments to
the corresponding water phase. Results of a work by
Lehmann et al. [9] are partly contradicted, because in
these laboratory experiments with PDMS added to soil
microcosms only traces of water-soluble silanols were
found in leachates. Further research work is necessary.
References
1. Fendinger NJ, Lehmann RG, Mihaich EM (1997) In: Chandra
G (ed) Organosilicon Materials. Springer, Berlin Heidelberg
New York, p 181
2. Xu S, Lehmann RG, Miller J, Chandra G (1998) Environ Sci
Technol 32 : 1199
3. Lehmann RG, Miller JR, Xu S, Singh UB, Reece CF (1998)
Environ Sci Technol 32 : 1260
4. Spivack JL, Pohl ER, Kochs P EM (1997) In: Chandra G (ed)
Organosilicon Materials. Springer, Berlin Heidelberg New
York, p 106
5. Carpenter JC, Cella JA, Dorn SB (1995) Environ Sci Technol
29 : 864
6. Cella JA, Carpenter JC (1994) J Organomet Chem 480 : 23
7. Smith AL (ed) (1991) In: The analytical chemistry of silicones.
Wiley, New York, p 23
8. Varaprath S, Lehmann RG (1997) J Environ Poly Degrad 5 : 17
9. Lehmann RG, Miller JR (1996) Environ Toxicol Chem 15 :
1455
10. Sommerlaide R, Parlar H, Wrobel D, Kochs P (1993) Environ
Sci Technol 27 : 2435
11. Anderson C, Hochgeschwendner K, Weidemann H, Wilmes R
(1987) Chemosphere 16 : 2567
12. Sabourin CL, Carpenter JC, Leib TK, Spivack JL (1996) Appl
Environ Microbiol 62 : 4352
13. Grümping R, Mikolajczak D, Hirner AV (1998) Fresenius
J Anal Chem 361 : 133
14. Smith AL (ed) Parker RD (1991) In: The analytical chemistry
of silicones. Wiley, New York, p 71
15. Parker RD (1978) Fresenius Z Anal Chem 292 : 362
16. Mahone LG, Garner PJ, Buch RR, Lane TH, Tatera JF, Smith
RC, Frye CL (1983) Environ Toxicol Chem 2 : 307
17. Cassidy RM, Hurteau MT, Mislan JP, Ashley RW (1976)
J Chromatogr Sci 14 : 444
18. Varaprath S, Salyers KL, Plotzke KP, Nanavati S (1998) Anal
Biochem 256 : 14
19. Watanabe N, Nagase H, Ose Y (1988) Sci Tot Environ 73 : 1
20. Boorn AW, Browner RF (1982) Anal Chem 54 : 1402
21. Al-Rashdan A, Heitkemper D, Caruso JA (1991) J Chromatogr
Sci 29 : 98
22. Gjerde DT, Wiederin DR, Smith FG, Mattson BM (1993)
J Chromatogr 640 : 73
23. Heine DR, Denton MB, Schlabach TD (1985) J Chromatogr
Sci 23 : 454
24. Tarr MA, Zhu G, Browner RF (1993) Anal Chem 65 : 1689
25. Roychowdhury SB, Koropchak JA (1990) Anal Chem 62 : 484
26. Hausler DW, Taylor LT (1981) Anal Chem 53 : 1223
27. Biggs WR, Fetzer JC, Brown RJ (1987) Anal Chem 59 : 2798
28. Dorn SB, Skelly Frame EM (1994) Analyst 119 : 1687
29. van der Post DC (1978) Wat Pollut Control 77 : 520
30. Carpenter JC, Leib TK, Sabourin CL, Spivack JL (1996)
SETAC 17th Annual Meeting, Washington DC, Abs. no. PO 578
31. Hobbs EJ, Keplinger ML, Calandra JC (1975) Environ Res 10 :
397
32. Wasserbauer R, Zadak (1990) Folia Microbiol 35 : 384
33. Heinen W (1978) In: Bendz G, Lindquist I (eds) Biochemistry
of Silicon and Related Problems. Proc. 40th Nobel Symp., New
York, p 129