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Environmental Measurements Methods

Two birds with one stone – fast and simultaneous analysis of microplastics: microparticles derived from thermoplastics and tire wear Paul Eisentraut, Erik Duemichen, Aki Sebastian Ruhl, Martin Jekel, Mirko Albrecht, Michael Gehde, and Ulrike Braun Environ. Sci. Technol. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.estlett.8b00446 • Publication Date (Web): 13 Sep 2018 Downloaded from http://pubs.acs.org on September 14, 2018

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Environmental Science & Technology Letters

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Two birds with one stone – fast and simultaneous analysis of microplastics: microparticles derived from thermoplastics and tire wear

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Paul Eisentraut1, Erik Dümichen1, Aki Sebastian Ruhl2, Martin Jekel2, Mirko Albrecht3, Michael Gehde3 and Ulrike Braun1*

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Bundesanstalt für Materialforschung und -prüfung, Unter den Eichen 87, 12205 Berlin, Germany 2 Technische Universität Berlin, Straße des 17, Juni 135, 10623 Berlin, Germany 3 Technische Universität Chemnitz, Reichenhainer Straße 70, 09126 Chemnitz, Germany

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Abstract

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Analysis of microplastic particles (MP) in environmental samples needs sophisticated techniques and is time intensive due to sample preparation and detection. An alternative to the most common (micro-) spectroscopic techniques, FTIR or Raman spectroscopy, are the thermoanalytical methods, where specific decomposition products can be analyzed as marker compounds for different kind of plastics types and mass contents. Thermal extraction desorption gas chromatography mass spectrometry (TED-GC-MS) allows the fast identification and quantification of MP in environmental samples without sample preparation. Whereas up to now only the analysis of thermoplastic polymers was realized, this is the first time that even the analysis of tire wear (TW) content in environmental samples is possible. Various marker compounds for TW were identified. They include characteristic decomposition products of elastomers, antioxidants and vulcanization agents. Advantages and drawbacks of these marker substances were evaluated. Environmental samples from street run off were exemplarily investigated and presented.

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Introduction

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Due to many advantageous properties, synthetic polymers are well established as important materials. Annual production rates have been rising since the 1950s and have reached 335 million tons in 2017 [1]. It is estimated that up to 12 million tons per year are released to the environment uncontrolled [2]. Plastic fragments degrade and break down into smaller particles over time. When the particles reach sizes smaller than 5 mm, they are called microplastics (MP) [3]. MP have been found in seas, rivers and sediments worldwide [4-7]. The risks posed by MP for humans and the environment are currently discussed intensively. A recent study shows that MP are expected to play only a minor role as a sorbent for other pollutants such as marine persistent organic pollutants (POPs). On the other hand, MP have been proposed to be considered as POPs themselves [8-9]. As POPs, MP would fall under the Stockholm Convention treaty, simplifying worldwide legal restrictions or even bans on MP, reducing their environmental impact.

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Besides thermoplastics, such as polyethylene (PE), polypropylene (PP) or polystyrene (PS), elastomer materials (colloquially: rubbers) are included in the MP discussion. By definition, only thermoplastics and duroplastics are defined as plastics or microplastics. But elastomers made from synthetic polymers (e.g. styrene butadiene rubber), chemically modified natural polymers (e.g. natural rubber, viscose, cellophane), and products based on synthetic polymers (e.g. fibers, coatings, tires) are also discussed in current MP activities. They also produce microparticles that can be identified as synthetic polymers. To simplify matters, all these materials are colloquially referred to as MP in this article.

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With regional differences, the contribution of rubber particles to the MP emissions into the environment can reach up to 60 % [10-13]. The main sources for rubber contamination are wear and tear of tire treads used in road traffic [14-15]. Tire wear (TW) as environmental contaminant has received attention since the 1960s [16] because of its contribution to the overall atmospheric pollution with airborne particles. Beside the risks of TW caused by its particulate nature, leachates from TW pose additional risks to organisms because of teratogenic, mutagenic and estrogenic activities [17].

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Analysis of MP is most commonly performed with (micro-)spectroscopic methods such as Fourier transformed infrared spectroscopy (FTIR) techniques and Raman scattering. These methods use polymer specific absorption patterns of irradiated IR or laser light and are suited for the unambiguous detection of MP [18-20]. Such spectroscopic methods are particularly qualified for imaging of particles (providing number, size and shape) and when only a few particles with low contribution to the overall mass content in the sample are present. Extensive sample preparation, usually including digestion of matrix compounds and density separation, is a necessity. This represents the main disadvantage of spectroscopic methods: the overall time required for analysis. Using spectroscopic methods, it is also difficult to derive metrological parameters for MP contents, e.g. on a mg/kg scale, as preferred by regulators. Additional challenges arise when investigating TW with spectroscopic methods: filler components in TW, especially carbon black, cause strong fluorescence phenomena when using laser light and near-complete absorption of IR light [15]. Thermoanalytical methods present an alternative approach to analyze MP in environmental samples. Pyrolysis-gas chromatography coupled with mass spectrometry (Py-GC-MS) and thermal extraction desorption-gas chromatography-mass spectrometry (TED-GC-MS) use polymer-specific decomposition products (marker compounds) to identify polymers [21-22]. Quantification of polymer contents, e.g. on a mg/kg scale, is possible. Py-GC-MS requires a thorough sample pretreatment and so far, published Py-GC-MS methods rely on somewhat unspecific decomposition products regarding TW [23-27]. The use of TED-GC-MS for detection of MP in environmental samples is already published [21, 29], as well as a comparison to other MP detection methods [28].

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The aim of the present investigation was the simultaneous analysis of MP and TW with minimal sample preparation using the novel fully automated TED-GC-MS system. Shortly, samples are heated in a thermogravimetric analyzer (TGA) in a nitrogen atmosphere. Decomposition products are purged from the TGA and transferred through a heated coupling device to a solid-phase adsorber bar, which is coupled to the decomposition product gas flow only in selected temperature ranges. After the solid-phase is loaded with an excerpt of the decomposition products, an auto sampling robot transports the adsorber to a thermal desorption unit (TDU) of the GC-MS. Here the decomposition products are thermally desorbed and mobilized, cryo-focused in a cooled injection system, separated through a chromatographic column and detected in the mass spectrometer.

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Material and Methods

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Chromatograms of MP marker compounds were obtained using the automated TED-GC-MS system as described in the literature [21, 28-29]. Thermal extractions were performed with a thermogravimetric analyzer equipped with an autosampler (TGA2, Mettler/Toledo, Gießen, Germany). Samples in 150 µL alumina crucibles were heated from 25 – 600 °C with a heating rate of 10 K/min. Sample masses of ca. 0.2 - 0.4 mg were used for pure polymers and tire materials and ca. 10 - 50 mg for matrices and environmental samples. Decomposition products were purged with a constant nitrogen flow of 50 mL/min from the TGA and transferred through a coupling device (Gerstel, Mülheim, Germany and BAM, Germany) heated to 240 °C. The decomposition products ACS Paragon Plus Environment

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were trapped using a solid-phase adsorber bar heated to 40 °C (SorbStar, Innovative Messtechnik, Vohenstrauß, Germany) that consisted of polydimethylsiloxane. The adsorber was coupled to the decomposition product gas flow only in selected temperature ranges of 25 – 600 °C for tire materials and matrices and 350 – 600 °C for pure polymers and environmental samples. The loaded absorber was transported by the robot (MultiPurposeSampler MPS, Gerstel) to the thermal desorption gas chromatograph mass spectrometer (TDU-GC-MS). Here the decomposition products were thermally mobilized (50 – 200 °C, heating rate 40 K/min, 5 min 200 °C isotherm, helium atmosphere, splitless mode) from the adsorber with a thermodesorption unit (TDU, Gerstel). The mobilized decomposition products were cryo-focused at -100 °C and re-released (-100 – 270 °C, heating rate 12 K/s) with a cooled injection system (CIS4, Gerstel). Separation of compounds was achieved in the gas chromatograph (7890, Agilent, Palo Alto, CA, USA) equipped with a chromatographic column (HP5ms, 40 – 300 °C, heating rate 5 K/min, 4 min 300 °C isotherm, 1 mL/min He flow, Agilent) and detected (temperatures: GC/MS-Interface 300 °C, ion source 230 °C, quadrupole 150 °C, electron ionization at 70 eV) in the mass spectrometer (5973N, Agilent). Scan mode was used in a range of 35 - 350 m/z. Using the present parameters, we observed for the common thermoplastic MP limits of detection (LOD) between 0,2 µg for PS (2,4-Diphenyl-1-butene) and 0,44 µg for PP (2,4,6Trimethylnon-1-ene) up to 1,6 µg for PE respectively (1,12-Tridecadiene). The LOD of TW will be discussed in the text in detail.

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A detailed overview about all investigated materials are given in Table 1 of SI. The sources of the pure rubber materials of four styrene butadiene rubbers (SBR), three natural rubbers (NR) and one butadiene rubber (BR, 91 % 1-4-polymerized, 9 % 1-2-polymerized), the tires, matrices and environmental samples can be found in the SI. Seven samples were cut from different passenger car tires, two samples from truck tire and three samples were tire recyclates. Matrix materials, expected to be free from plastic, included suspended particulate matter from a river, one lake sediment, three soils, three fish samples and one plant matter sample.

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Environmental samples were taken from a treatment system for highway street runoff (BerlinHalensee) (see schematic graphic in SI, Figure S1). Three liters of street runoff were withdrawn from the influent channel (GPS 52.497, 13.282) after a rain event, sieved into five size fractions (1000, 500, 100, 50 and 10 µm), re-suspended from the stainless steel micro-sieves in ultrapure water, separated on glass fiber filters and dried. A sludge grab sample was manually taken from the sediment of the drained sedimentation basin (GPS 52.496, 13.280) and dried. The samples were homogenized when necessary using a ball mill (Cryo Mill, Retsch, Haan, Germany) cooled with liquid nitrogen. All samples are spiked with internal standard of deuterated polystyrene (Polymer Source, Dorval, Canada) to keep the single measurements better compatible. Blank measurements were performed at least on a daily basis. Peak areas were normalized for sample mass and for the peak area of a selected decomposition product of the internal standard. For quantification of MP in the present work we spiked the environmental samples with known amounts of identified polymers. This is more time and measurement expensive, than determination of calibration curves. However according to the few environmental samples and for achieving a good, matrix-independent results we preferred this quantification method.

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Results and Discussion

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Identification of elastomer or tire specific marker compounds. At first, pure elastomer materials were analyzed and various potentially exclusive marker compounds for TW were identified. These are exclusively decomposition products of the respective elastomers. No products related to



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additives, vulcanization steps etc. were found. A selection of decomposition products with high abundance is presented in Table 1, chromatograms are illustrated in SI (Figure S2-S5). The compounds are well covered in the literature regarding Py-GC-MS of elastomeric materials [30]. But, because the new TED-GC-MS method includes ad- and desorption steps, renewed analysis of polymer decomposition was necessary.

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Second, tire samples were analyzed. Further tire related compounds were detected, namely benzothiazole-based vulcanization agents, their decomposition products and amine-based antioxidants. These substances were not considered as marker compounds for TW because of their high leachability reported in the literature [31].

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Table 1: Summery of identified decomposition products for elastomer and tire materials using TED-GC-MS

Characteristic fragment ions

Retention time in min

S

Styrene

104, 78, 51

7.2

MeS

Methylstyrene

118, 103, 78

9.6

Cyclopentylbenzene

117, 104, 146, 91

16.6

Cyclopentenylbenzene

144, 129, 115

17.8

SB

Cyclohexenylbenzene

104, 158, 129, 115

19.6

SBB

Phenyl[4.4.0]bicyclodecene

104, 91, 156, 212

26.8

B2

Vinylcyclohexene

79, 54, 93, 108

5.6-6.4

B3

Trimers of Butadiene & Homologues

91, 148, 162, 176

13.1-21.7

BR

I2

Dipentene

68, 93, 121, 136

11.0

I3

Trimers of Isoprene

119, 162, 189, 204

21.5-23.3

I4

Tetramers of Isoprene

121, 93, 134, 272

31.0-36.0

Structure

Parental Elastomer

SBR

Substance

SBR , BR

Peak Assignment

NR

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SBR is acknowledged as the major compound of passenger car tires [32] and it has received some attention as marker compound [27, 33-34]. It has severe advantages over other marker compounds used so far: high abundance granting high sensitivity, constant abundance without leaching phenomena and related problems and little to no sources of non-tire origin. Using a sufficient ACS Paragon Plus Environment

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amount of sample material enables a straightforward quantification of TW, although data on the SBR content for the worldwide tire mass in use is difficult to find. Taking data from the literature [35-37] into account grants worldwide production tonnages of the major elastomer tire compounds and their individual fractions used for tire production for all types of tire including truck and passenger car tires. Based on these numbers, including all types of tires, we estimate the average content of SBR in whole tire material to be roughly 11.3 %. With this approach, the content of TW in a sample can be calculated using the SBR content although heavy duty vehicle tires usually contain little to no SBR. It is, however, worth noting that there are uncertainties. Effects of different stages of ageing, varying degrees of vulcanization of the elastomers and local differences in vehicle usage are not included. The content of TW in mixtures of tire and road wear particles, was estimated by Unice et al. to be 50 % [38].

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All four SBR pure polymer materials investigated originate from different manufacturers and are expected to have different chemical compositions regarding the sequence of the different monomers within the polymer chain based on the individual production parameters. The materials have different appearances (white-brown, no odor to intense odor). Surprisingly, the normalized peak areas of the marker molecules SB and SBB were comparable in all materials (SD = 15 %; SD = 27 %, respectively). Other decomposition products of SBR were found in low abundances or were suspected to be too unspecific (e.g. styrene, vinyl cyclohexene) and therefore not considered as TW marker compounds. The limit of detection of 0.23 µg for SBR using the decomposition product SB was calculated on basis of quintuple signal to noise ratio [39].

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BR is another elastomeric compound of tires used in high abundances [32]. Decomposition products that are detectable with TED-GC-MS include the butadiene dimer vinyl cyclohexene, trimers and a plethora of homologues of the trimers. The dimer is not exclusive to BR as it is also a decomposition product of SBR. The homologues of butadiene trimers either have an additional methylene group or one less methylene group in comparison with the trimers. All of these substances have plenty of isomers and are chemically quite similar which results in complex overlapping peaks in the chromatograms. Unfortunately, no outstanding decomposition product with high abundance or clear assignment to BR was found.

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NR is the main elastomeric compound of truck tires [27]. NR decomposition products were numerous isomers of dimers (I2), trimers (I3) and tetramers (I4) of isoprene and were highly comparable in the pure polymer materials. The limit of detection for NR using the I2 decomposition product is 0.22 µg.

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To evaluate the chosen marker compounds, twelve tire samples were analyzed in the next step. SB and SBB markers were detected in all tires except for the truck tire sample of which the only rubber component is NR. Tire recyclate has the lowest abundance of SBR marker compounds and is probably mixed from passenger and truck tire materials. Marker substances for SBR were found in varying abundances (SD = 55 %) linked to the individual composition.

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NR marker compounds were found in all tire materials. In four samples, only dimers and trimers of isoprene were found whereas one sample exhibited only dimers of isoprene. These findings are probably directly linked to the NR content in the samples. Only small amounts of BR decomposition products were found in the chromatograms of tire materials. The partially low abundance of the marker compounds in the tire samples compared to the pure polymers may be caused by the vulcanization process, where unsaturated, aliphatic double bonds are crosslinked.

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Environmental matrix compounds might develop decomposition products interfering with the chosen marker compound for elastomers. To address this possibility, matrix samples, considered to be free from MP, were analyzed. They include suspended particular matter from the Danube river, lake sediments, soils, fishes and plant material. One of the matrix samples, plant matter, ACS Paragon Plus Environment


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decomposed into dimers and higher oligomers of isoprene suggesting 0.7 µg NR per 1 mg of plant matter. This result leads to the assumption that analysis of NR in environmental samples is impossible as soon as plant matter cannot be excluded from the sample. For all other marker compounds no interfering substances were detected in the chromatograms of any matrix sample.

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Environmental samples from street run off. In general, peak areas were normalized for peak areas of a decomposition product of the internal standard before calculation. All values refer to total dry masses of samples or sample fractions. Figure 1 summarizes the results from the Berlin street run-off samples.

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In street runoff from Halensee, MP and especially TW marker compounds were detected (See also chromatogram in SI, Figure S6). To assess the content of TW, the amount of SBR was quantified first. Sample aliquots were spiked with a certain amount (m1) of pure SBR, measured again and the peak areas (A1) of decomposition product SB compared to those of the unspiked sample aliquots (A0). The mass m0 of SBR in the original sample aliquot was then calculated according to equation 1:

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஺బ భ ି஺బ

. (eq. 1)

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Figure 1: MP contents in different particles size fractions of a street runoff grab sample and in a sediment sample taken from the bottom of the clarification tank


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To verify the presence of SBR from TW, the samples were screened for decomposition products of NR and BR. Decomposition products of NR were detected in all samples but, again, these could also be decomposition products of plant matter. No decomposition products of BR were found.

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Identification of other MP types was performed according to marker compounds published earlier [21]. Quantification of PS was realized using the signals of the internal standard of deuterated PS. This was done under the assumption that the deuterated PS behaves like normal PS throughout the whole analytical process and no further spiked experiments were done. Surprisingly, we found PS decomposition products in all samples, even on the blank glass fiber filters which hampered the straightforward calculation. A possible source of contamination could be an applied sizing on the fibers, a more detailed analysis is not possible, because the sizing of a technical product is a well-kept secret of all glass fiber producers. More details about the relevance and the possibility of reduction are given in the SI. Assuming constant styrene related sizing content for all filters used, the marker compound peak areas of the environmental samples were corrected accordingly. However, for future studies, the choice or pretreatment of sampling tools and materials will be reconsidered. Further complications arise from the high content of SBR in the samples. A minor decomposition product of SBR, the styrene dimer, is used as marker compound for PS and gives false positive results for PS. Because of this interference between SBR and PS, results for PS should be regarded as estimates when SBR is present in excessive amounts. But, according to the different contents of PS and SBR content and their trends in the samples with varying particle size fraction, SBR was clearly not the only source of the marker compound and PS was present as well.

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Quantification of PE and PP was performed in an approach similar to that of TW. Because of the limited sample masses available, only a few selected aliquots were spiked with defined polymer masses and measured again. The resulting differences in peak areas were used to derive matrix dependent response factors. These factors were applied to the other samples if they were not spiked themselves. Additionally, all samples were screened for decomposition products of polyethyleneterephthalate, polyamide and polymethylmethacrylate; with negative results.

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Since the street runoff sample was taken shortly after a rain event while the settled sediment accumulated over longer periods (as time integral), a direct comparison of the results is difficult. SBR was found in ranges of 3.9 – 9.3 mg/g in the samples. Only two particle size fractions, 50 - 100 µm and > 1000 µm, contained PE with 3.09 and 4.75 mg/g, respectively. PP was found in all but one samples in the range of 0.15 – 1.16 mg/g. PS contents ranged from 0.25 – 0.95 mg/g, but should be considered as estimates as mentioned before.

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With the approximately determined averaged SBR content of 11.3 % in tire materials from literature data, the content of TW was estimated. The TW content of dry weight samples can be calculated from the determined SBR mass, using a factor of 8.9. The resulting value of 3.4 – 8.2 % (± 15 % for the deviation of the SB signal in SBR materials) TW is the relative mass content of TW in the filtered particular matter of the present samples, which is a factor of 13 - 49 higher than the sum of thermoplastic MP contents of 0.07 – 0.62 %. It should be noticed once again, that the calculation includes a high degree of uncertainty, because different car and tire types, different stage of ageing, varying degrees of elastomers and additive composition in tires and local differences in vehicle usage are not considered.

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However, performing TED-GC-MS measurements, it was possible for the first time to simultaneously measure MP originating from thermoplastics and tire wear abrasion in real environmental samples.

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Author Information ACS Paragon Plus Environment


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Corresponding Author

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*E-Mail: [email protected], Phone +49 30 8104 4317, Fax +49 30 8104 1617

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Notes

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The authors declare no conflict of interest.

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Acknowledgement

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The authors acknowledge financial support by the German Federal Ministry of Education and Research (BMBF) within the project MiWa (funding number 02WRS1378A) and like to thank various partners for helpful discussions, especially S. Wagner und P. Klöckner (UFZ, Leipzig) and C. G. Bannick (UBA, Berlin).

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