CEAC Bericht 2007 Report_2007.pdf · 3 Table of Contents 1. Preface 5 2. Joint CEAC Activities 7 3....

Annual Report

CEAC

Center of Excellence in Analytical Chemistry

2007

2

Impressum © 2007 Eidgenössische Technische Hochschule Zürich Switzerland Edited by: Prof. Dr. Renato Zenobi and Brigitte Bräm, ETH Zürich Copies of this report are available from: Ms Brigitte Bräm Laboratory of Organic Chemistry HCI E 325 / ETH Zürich CH-8093 Zürich Telephone: +41 44 632 4377 Fax: +41 44 632 1292 e-mail: [email protected] CEAC on World Wide Web: http://www.ceac.ethz.ch Cover, Layout, Printing: Adag Copy AG, 8033 Zürich

3

Table of Contents

1. Preface 5

2. Joint CEAC Activities 7

3. Active Research at CEAC Member Laboratories 13

4. Publications 57

5. Contact addresses 79

5

1

Preface

6

Preface

by Renato Zenobi

This will be the last annual report of the Center of Excellence in Analytical Chemistry that you will hold in your hands: the board of directors has decided to not seek continuation of the funding from the institutions that have supported the CEAC over the years. We are by no means fed up with our joint activities in the field of Analytical Chemistry. Quite on the contrary, the main reason that led to this decision is that most if not all of the goals of the CEAC have been reached by now: there are numerous scientific interactions within CEAC and with neighboring institutes that have been built over the years, many of them triggered by joint events. The teaching and education in Analytical Chemistry at ETH Zurich is thriving and can take advantage of competences outside of ETH. Analytical Chemistry is one of the most popular electives in the B.Sc. and in the M.Sc. curricula. The number of Analytical faculty members is up: starting with only one assistant professor in 1995 when the CEAC was founded, ETH has now two tenured professors and just hired a third, on the assistant professor level, in Analytical Chemistry. The new faculty member, Dr. Petra Dittrich, currently at ISAS (Dortmund, Germany), has expertise in miniaturized analytical systems, microfluidics and cell manipulation and analysis on microchips, and will thus ideally complement the existing analytical research at ETH Zurich. She will join ETH in June, 2008. During the past year, the CEAC organized numerous seminars that were well attended. A highlight was the summer workshop, co-sponsored by the Swiss Chemical Society (Division of Analytical Chemistry) on “Development and Application of Chemical Sensors”. This conference, which took place in June 2007 at ETH Zurich, was held in honor of Prof. Ernö Pretsch, one of the founders of the CEAC, and serving as its director in 2004. The conference was a great success, drew a good size audience, and featured many excellent lectures. There is one “crown jewel” of the CEAC activities that we would like to see continue in the future, the Wilhelm Simon postdoctoral fellowship program. In the fall of 2007, we have therefore submitted a proposal to the ETH council for financial support of such a program, because the ETH domain has become the key player in analytical sciences in Switzerland. The goal of the planned fellowship program is to attract top level postdoctoral researchers in analytical sciences to the ETH domain/Switzerland and to provide them with the opportunity to carry out a collaborative, interdisciplinary project. The proposal application is still pending at the time this annual report went to press. On behalf of the board of the CEAC, I would like to thank all contributors to this annual report, and the ETH Zürich, EAWAG, EMPA, and PSI for the long term financial support.

Zürich, March 2008

7

2

Joint CEAC Activities

8

Summer Workshop on Development and Application of Chemical Sensors,

June 28 – 29, 2007 at ETH Zürich, Switzerland

Ernö Pretsch – Symposium

co-sponsored by The Swiss Chemical Society (Division of Analytical Chemistry)

Organisation: B. Wehrli. (EAWAG), B. Müller (EAWAG), W. Giger (ex EAWAG)

Thursday, 28 June 07

Bernhard Wehrli 10:00 - 10:30 Welcome and introduction

Róbert E. Gyurcsányi 10:30 - 11:00 Hybridization-modulated ion fluxes through peptide-nucleic-acid-

functionalized gold nanotubes. A new approach to quantitative

label-free DNA analysis

Philippe Bühlmann 11:00 - 11:30 Ion-selective electrodes with three-dimensionally ordered

macroporous (3DOM) carbon as solid contact

Ernö Pretsch

Climbing the gate 11:30 - 12:30

lunch break 12:30 - 14:00 Milena Koudelka-Hep 14:00 - 14:30 Microelectrode arrays: technology and applications

Marylou Tercier-Waeber 14:30 - 15:00 Voltammetric microsensors and submersible probes for reliable

efficient environmental trace metal analysis and speciation

George W. Luther III 15:00 - 15:30 Voltammetric solid state (micro)electrodes as chemical sensors to

understand redox processes: from sediments and microbial mats to

hydrothermal vents

coffee break, Posters 15:30 - 16:30 Mark E. Meyerhoff 16:30 - 17:30 Electrochemical sensors for nitrosothiol species based on immobilized

chemical/biochemical catalysts: design and biomedical applications

Ernö Lindner 17:30 - 18:00 Mathematical model of current polarized ionophore-based ion-selective

membranes

9

Friday, 29 June 07

Magdalena Maj-Zurawska 9:00 - 9:30 Screen printed electrochemical DNA biosensors in dsDNA testing.

Interactions with various chemical compounds

Joseph Wang 9:30 - 10:00 Nanomaterials for monitoring and controlling biomolecular

interactions

coffee break, Posters 10:00 - 11:00 Peter C. Hauser 11:00 - 11:30 Contactless conductivity detection for microseparation techniques

Niels Peter Revsbech 11:30 - 12:00 In situ analysis of marine environments by amperometric gas

microsensors and microscale biosensors

lunch break 12:00 - 13:30 William Davison 13:30 - 14:00 New developments in aquatic and sediment chemistry stimulated by

the use of in situ dynamic measurements using DGT

Eric Bakker 14:00 - 15:00 Good times with ions and membranes: a friendship and a legacy

end of conference 15:00

10

CEAC Seminars – Summer & Winter Semsters 2007

22.03.2007 Prof. Kevin C. Jones, Lancaster Environment Centre Lancaster University, UK

Field Studies on the Global Cycling of Persistent Organic Pollutants 26.04.2007 Prof. Jean-Claude Tabet, Université Pierre et Marie Curie,

Laboratoire de Chimie Biologique Organique et Structurale, Paris, France Salt Bridge interaction in DNA/peptide complexes 24.05.2007 Prof. Thomas Bürgi, Institut de Microtechnique, Université de

Neuchâtel, Neuchâtel, Switzerland In situ infrared spectroscopy of catalytic solid-liquid interfaces, chiral surfaces and nanoparticles 21.06.2007 Prof. Luke Lee, Professur für System Nanobiologie, ETH Zürich Cellular BASICs & PRET for Quantitative Cell Biology

27.09.2007 Prof. Dr. Janos Vörös, Institut für Biomedizinische Technik, ETH

Zürich Nanobiotechnology Based Analytical Approaches: Self-Assembling Micro-arrays, Nanowires and Nanoparticles as Biosensors 18.10.2007 Prof. Yury O. Tsybin, Biomolecular Mass Spectrometry Laboratory,

Ecole Polytechnique Fédérale Lausanne Electron Capture/Transfer Dissociation Mass Spectrometry: a Swiss Army Knife for Peptide and Protein Structure Analysis 15.11.2007 Prof. Dr. Thorsten Hoffmann, Institut für Anorganische und

Analytische Chemie, Johannes Gutenberg Universität Mainz Online Aerosol Mass Spectrometry: Contributions to Understand Composition and Chemistry of Tropospheric Aerosols 13.12.2007 Prof. Ewa Bulska, Faculty of Chemistry, Warsaw University, Poland

Modern analytical techniques supporting the examination of works of art and cultural heritage

11

WWW

The CEAC WWW address is: www.ceac.ethz.ch Currently the following information and links can be found on the CEAC web page: ! Who is Who: Who belongs to the Center of Excellence in Analytical Chemistry. A

list of the CEAC board of directors, with links to their WWW home pages.

! Seminars: a list of the special analytical seminars organized by the CEAC. ! Workshops: Information on the CEAC summer workshop, including registration

information ! Links: long list of interesting analytical and chemistry links ! CEAC Research Projects ! Annual Report: The Annual Report 2007 will be made available online.

13

3

Active Research at CEAC Member Laboratories

14

Title: Terrestrial derived organic material in marine sediments

Researchers: Carsten J. Schubert, Oliver Scheidegger, Anna Nele Meckler

Institute/Group: Department of Surface Waters - Research and Management, Eawag

Project Description:

One of the big questions in paleoceanography is the origin of organic material in sediments of

the world ocean. In this study we investigated the relation between marine and terrigenous

organic material (OM) in a sediment core from the Orca Basin (Gulf of Mexico). The normal

parameters used for the distinction between allochthonous (terrestrial derived material) and

autochthonous (material produced in the water column) like for instance carbon isotopic

composition of the OM or the concentration of n-alkanes derived from leaves and grasses

gave no conclusive results. Another parameter that we measured was the nitrogen isotopic

composition of the OM to reveal information about the origin and production process of the

nitrogen containing OM (mainly amino acids, amino sugars, and pigments). However, we

were mainly interested in the nitrogen isotopic composition of the pigments namely the

degradation products of chlorophyll. Since our lab is only equipped with a gaschromatograph

linked to an isotope mass spectrometer we needed to produce maleimide derivatives which

are volatile and thus amenable for the GC analysis. Total pigments were extracted by various

solvents in an ultrasonic ice bath under low light conditions.

Subsequently, phaeophytin was separated from the collected extracts by high performance

liquid chromatography. Afterwards it was degraded to maleimides by HCl treatment and

chromic acid oxidation [1, 2]. The oxidation products were analysed as trimethylsilyl (TMS)

derivatives (Fig. 1).

The nitrogen isotopic

measurements on these single

maleimides enabled us to

decipher the terrestrial vs.

marine contribution of the

organic material in the

sediment core from the Orca

Basin.

References:

[1] Baker, E.W et al., 1968. Deoxophyllerythroetioporphyrin. The journal of Organic

Chemistry 33, 3144-3148.

[2] Nomoto et al., 2001. A new maturity indicator of sedimentary organic matter based on

thermal fission of allylic bond in porphyrins. Chemical Letters 2001, 1174-1175.

N OO

Si

N OO

Si

N OO

Si

O

O

N OO

Si

O

O

N OO

Si

O

O

Figure 1: Maleimide derivatives (oxidation

products of phaeophytin)

15

Title: Endocrine Disrupting Compounds in the Aquatic Environment

Researchers: Marc J-F Suter, Rik IL Eggen, Anja Liedtke, René Schönenberger,

A Christiane Vögeli Institute/Group: Department of Environmental Toxicology, Eawag Project Description: After more than a decade of research, the actual exposure to endocrine disrupting compounds in the aquatic environment is well documented. Very often, direct chemical target analysis is combined with modeling based on information available for a given catchment. However, less information is available on the effect side, and it is rarely possible to link chemical data to biological effects. This is clearly illustrated by the fact that despite of all the efforts that went into identifying the source(s) of gonadal malformations in whitefish (Coregonus lavaretus) of Lake Thun, no clear link between chemical exposure and the observed effect could be found.

Sediment and plankton extracts were analyzed for their estrogenic activity, using the yeast estrogen screen (YES). Active samples were further fractionated and reanalyzed in the YES. Identification of estrogenic unknowns is possible with the accurate mass and fragment ion information available on the high resolution Orbitrap. Both Lakes Thun and Brienz plankton extracts showed estrogenic activity (Fig. 1), possibly caused by degradation products of natural substances [1].

Figure 1: Estrogenic effects in estradiol equivalents (EEQ) of the plankton samples measured with the YES. Five of twelve plankton extracts contained unknown estrogen receptor agonists. (THU: Lake Thun, BRI: Lake Brienz, GS: Lake Greifen, VWS: Lake Lucerne; month/year sampled; TOC: total organic carbon).

References: [1] AC Vögeli, PhD Thesis, ETHZ, submitted. Collaborations:

Swiss National Research Programme 50 H Segner (Uni Bern)

16

Title: High-throughput Proteomics for the Analysis of Environmental

Stress Response in the green algae Chlamydomonas reinhardtii

Researchers: Marc J-F Suter, Holger Nestler, Victor J Nesatyy Institute/Group: Department of Environmental Toxicology, Eawag Project Description:

Proteomics allows the identification of protein markers for (multiple) stress that can provide insights into the underlying modes of action and can be used to assess exposure. We are using the multidimensional protein identification technology (mudPIT) [1] to analyze stress response of the green algae Chlamydomonas reinhardtii on the proteome level. Extracts from exposure experiments with herbicides (diuron or paraquat) and UV radiation were acquired in triplicates, analyzed using X!Tandem and The Open Mass Spectrometry Search Algorithm (OMSSA), and further validated by the target-decoy database strategy and Peptide / Protein Prophet from CPAS and TPP pipelines. Quantitation of the results will be done using normalized spectral counts as described by Zybailov et al [2] and validated using generalized G-test [3]. MudPIT experiments on the protein extracts derived from the control samples showed significant variance in protein identification depending on the number of charge states acquired. Acquisition of charge states from +1 to +3 resulted in a significant improvement in both the number of protein IDs and reproducibility of protein ID in comparison to acquisitions based on +2 and +3 charge states only. The same phenomenon was observed by artificial removal of the + 1 charge state from the analysis of the data with 3 charge states. Analysis of the results produced by X!Tandem and OMSSA searches revealed significant overlap which allows implementing consensus scoring, thus significantly improving confidence of the protein ID. Case / control studies with combined exposure to various herbicides and UV radiation are underway. Significant changes in protein levels have been observed. As expected, paraquat exposure resulted in a significant upregulation of both chloroplastic (Fe) and mitochondrial (Mn) superoxide dismutases, thus validating our approach. Also, exposure with photosensitizer Rose Bengal, known to induce oxidative stress in Chlamydomonas

reinhardtii [4], led to increased levels of a glutathion peroxidase homolog (GPXH), confirming gene expression results previously published. Other changes on the proteome level have been observed, but more careful investigation using pathway and cluster analysis is required in order to understand the underlying mechanisms of stress response.

References: [1] MB Washburn et al, Nat Biotechnol 2001, 19, 242-247. [2] B Zybailov et al, Proteome Res 2006, 5, 2339-2347. [3] B Zhang et al, J Proteome Res 2006, 5, 2909-2918. [4] BB Fischer et al, Plant Science 2005, 168, 747-759. Collaborations: Functional Genomics Center Zurich

17

Title: Transformation products of micropollutants in aquatic

environments - Identification by high-resolution LC-MSMS

Researchers: Susanne Kern1,2, Heinz Singer1, Juliane Hollender1, Kathrin Fenner1,2

Institute/Group: 1 Swiss Federal Institute for Aquatic Science and Technology (Eawag), Department of Environmental Chemistry

2 Institute of Biogeochemistry and Pollutant Dynamics, Swiss Federal

Institute of Technology (ETH)


Today, chemical risk assessment and the evaluation of water quality mainly focus on parent

micropollutants. However, there is evidence that transformation products of the structurally

complex contaminants of current concern for aquatic resources might also contribute to the

overall chemical burden in the environment [1]. The aim of this study is to elucidate the

presence and identity of transformation products of pesticides, biocides and pharmaceuticals

in surface and waste water based on computational predictions and screening measurements.

A biodegradation pathway prediction system [2] and thorough literature studies were used to

generate a list of possible transformation products, which serve as target list for analytical

screening. To achieve accurate and reliable target compound monitoring, also in cases where

no reference standards are available, an analytical screening strategy using solid-phase

extraction and liquid chromatography high resolution tandem mass spectrometry (LTQ-

Orbitrap) has been developed and successfully applied to detect transformation products of

about 50 parent compounds in a set of water samples. High-resolution (HR) MSMS spectra

were mainly used to identify and confirm the target compounds as shown in Figure 1.

Extracting HR -MS

Chromatogram for

target analytes

Positive findings

Peak intensity 10 ^5

Extracting HR -MSMS

Comparison with

reference standard

Target analysis with standards

Target analysis without standards

Extracting HR -MSMS

Interpretation of MSMS

fragments

Confirmation of identity

• Exact mass of fragments leading

to a reasonable molecular formula

• Fragment pattern similar to that of

parent compound

• Match with fragment prediction by

Mass Frontier

Confirmation of identity

• Comparing exact mass of fragments

• Peak matching by retention time

• Similar ion ratios and intensities

Figure 1: Procedure for the confirmation of target compounds using high mass resolution and MSMS fragments

24 pesticides, 6 biocides and 18 personal care products were screened for a set of 324 known

and predicted transformation products and metabolites. For all parent compounds and for 27

transformation products reference standards were available to optimize the analytical

procedure. Besides the regularly detected pesticide transformation products, we found less

frequently reported ones, such as metamitron-desamino and azoxystrobin-demethyl. We also

succeeded in identifying transformation products of personal care products, including the

biodegradation products atenolol acid and a cleavage product of verapamil (D 617).

References:

[1] Boxall, A.B.A.; Sinclair, C.J.; Fenner, K.; Kolpin, D.; Maud, S.J. Environ. Sci. Technol.

2004. 38, 368A-375A.

[2] University of Minnesota Pathway Prediction System. http://umbbd.msi.umn.edu/predict/

Collaborations:

Funding by the Swiss Federal Office for the Environment (FOEN) within the project KoMet

18

Title: Analysis of cytostatics in hospital wastewater by LC-MS/MS

Researchers: Lubomira Kovalova1,2, Christa S. McArdell1, Juliane Hollender1

Institute/Group: 1Swiss Federal Institute of Aquatic Science and Technology (Eawag),

Department of Environmental Chemistry 2Institute of Hygiene and Environmental Health, RWTH Aachen

University, Germany


Cytostatics, drugs used in cancer chemotherapy, do not belong to pharmaceuticals widely

used in high amounts. Nevertheless, they were intentionally synthesized for killing fast

growing cells, which arises an environmental concern that still needs to be proved. Hospitals

are considered to be a point source of many pharmaceutical classes in the environment, and

this is also the case of cytostatics despite increasing popularity of oncology out-patient

treatment.

To determine the hospital wastewater concentrations of selected cytostatics and their

metabolites, an analytical method was established. It employs preconcentration on two SPE

materials (ENV+ and SA-DVB), separation on hydrophilic interaction chromatography

column ZIC-HILIC and detection by triple-quadrupole MS. The challenge of the method

development was high polarity of the analytes, low environmental concentrations and

presence of interfering substances. Median concentrations detected in wastewater of a Swiss

hospital during a nine days flow-proportional sampling campaign were between the limit of

detection and limit of quantification for 5-fluorouracil (LOQ 5 ng/L), 0.9 ng/L for

gemcitabine (LOQ 0.9 ng/L) and 105 ng/L for 2',2'-difluorodeoxyuridine, the major human

metabolite of gemcitabine (LOQ 9 ng/L). In average, the measured concentrations accounted

for less than 4% of predicted wastewater concentrations calculated from known data on

human pharmacokinetics and the actual consumption at the investigated hospital at each given

day. In a future study the results will be confirmed in another hospital and the elimination of

cytostatics will be investigated by a combination of a biological and physical-chemical

treatment at the hospital.

Collaborations:

Funding by AQUAbase - Marie Curie Host Fellowship for Early Stage Research Training,

RWTH Aachen University, Germany. Incorporated in a project funded by the Swiss State

Secretariat for Education and Research (SER)/COST in the framework of COST Action 636

(SBF Nr. C05.0135), the EU project NEPTUNE (Contract No. 036845). the Swiss Federal

Office for the Environment (FOEN) and several Swiss cantons.

19

Title: Emissions of additives from polymer and bitumen materials for

waterproofing of roofs

Researchers: Michael Burkhardt1), Andrea Ulrich2), Peter Schmid2), Sivotha Hean3), Cornelia Seiler2), Adrian Wichser2), Regula Haag2), Markus Boller1), Heinz Vonmont2)

Institute/Group:

1)Eawag, Department of Urban Water Management 2)Empa, Laboratory of Analytical Chemistry 3)Empa, Road Engineering and Sealing Components

Project Description: Modern polymer materials for waterproofing of flat roofs contain biocides and other additives such as plasticizers or flame retardants which can be released to the environment under the influence of the atmospheric conditions. In this project, commercial products are investigated under controlled elution conditions. The goal of the project is the identification and quantification of additives and their transformation products in eluates. The quantification of the emission rates allows the assessment of the fluxes to the environment.

References: [1] M. Burkhardt, T. Kupper, S. Hean, P. Schmid, R. Haag, L. Rossi, M. Boller, Release of

biocides from urban areas into aquatic systems. Novatech, 6th International Conference

on Sustainable Techniques and Strategies in Urban Water Management, Lyon/F, June 25-28, 2007

Collaborations: Industries

Financial support: Novatlantis, Awel, Empa, Eawag

20

Title: Chromium(VI) in old corrosion protective coatings – a new

analytical method

Researchers: Renato Figi, Oliver Nagel

Institute/Group: Laboratory for Analytical Chemistry, Empa Dübendorf


The development of a robust analytical method for the quantitative determination of chromium species with oxidation numbers +III and +VI as well as the total chromium content in anticorrosive coats of paint is presented. Difficultly soluble chromium(VI) compounds such as lead chromate, lead-oxochromate, strontium chromate, alkaline zinc-chromate and zinc-potassiumchromate were mainly used as pigments in corrosion protective coatings. For the top coating, the green pigment chromium(III) oxide was frequently used. In high-performance corrosion control of railway bridges, roofs of railway platforms, fuel depots as well as in hall constructions mainly lead-siliconchromate (chromium(VI) was used. With regard to occupational health and safety as well as to water and soil pollution control data on the levels of chromium(IV) are indispensable in the remediation of constructions protected with anticorrosive chromium containing coatings. This information is required to meet the targets of Swiss Federal Office for the Environment concerning chromium(VI) („Stand der Technik, Umweltschutzmassnahmen bei der Instandhaltung des

Korrosionsschutzes von Stahltragwerken der Elektrizitätsübertragung BAFU 2006“: …

Bestmögliche Schutzmassnahmen sind erforderlich, wenn die Chrom(VI)-Konzentration in

der Beschichtung über 0.1% liegt). Up to now, an analytical method for the quantification of chromium species in corrosion protective coatings is lacking in the scientific literature as well as in practice. Difficultly soluble chromium(VI) pigments in old paint coatings the are often accompanied by other pigments containing chromium(III), lead and zinc. Furthermore, these pigments are chemically incorporated into other additives such as binding and bulking agents. The selective extraction and quantification of chromium(VI) is impeded by the risk of a reduction to chromium(III) and thus an inaccurate quantification of chromium(VI). A method was developed based on specific hot alkaline extraction of chromium(VI) from old paint coatings. In a second step, total chromium was determined after oxidative high pressure ashing using concentrated nitric acid. Under the assumption that no other chromium species except chromium(III) and chromium(VI) are present, the concentration of chromium(III) is the difference between the chromium(VI) level and total chromium.

Collaborations:

Agency for Environment of the Canton of Glarus, Glarus, Switzerland Swiss Federal Office for the Environment (FOEN), Bern, Switzerland

21

Title: Secondary effects of catalytic diesel particulate filters: Copper-

induced formation of PCDD/Fs

Researchers: Norbert V. Heeb1), Markus Zennegg1), Erika Guyer1), Regula Haag1), Peter Honegger1), Kerstin Zeyer1), Daniela Wenger1), Urs Gfeller1), Adrian Wichser1), Martin Kohler1), Cornelia Seiler1), Peter Schmid1), Lukas Emmenegger1), Andrea Ulrich1), Jean-Luc Petermann2), Jan Czerwinski2), Thomas Mosimann3), Markus Kasper3), Andreas Mayer4)

Institutes/Groups:

1) Empa, Laboratory for Analytical Chemistry, Laboratory for Air Pollution/Environmental Technology, Laboratory for Solid State Chemistry and Catalysis, 8600-Dübendorf

2) UASB, Laboratory for Exhaust Emission Control, 2560-Nidau 3) Matter Engineering AG, 5610-Wohlen 4) Technik Thermischer Maschinen, 5443-Niederrohrdorf Project Description: Potential risks of a secondary formation of polychlorinated dibenzodioxins/furans (PCDD/Fs)

were assessed for two cordierite-based, wall-flow diesel particulate filters (DPFs) for which

soot combustion was either catalyzed with an iron- or a copper-based fuel additive [1]. A

heavy duty diesel engine was used as test platform, applying the ISO 8178/4 C1 cycle valid

for construction machinery. DPF applications neither affected the engine performance, nor

did they increase NO, NO2, CO, and CO2 emissions. The latter is a metric for fuel

consumption. THC emissions decreased by about 40% when deploying DPFs. PCDD/F

emissions, with a focus on the toxic tetra- to octachloro congeners, were compared under

standard and worst case conditions (enhanced chlorine uptake). The iron-catalyzed DPF

neither increased PCDD/F emissions, nor did it change the congener pattern, even when traces

of chlorine became available. In case of copper, PCDD/F emissions increased by up to three

orders of magnitude from 22 to 200 to 12700 pg I-TEQ/L with fuels of <2, 14, and 110 µg/g

chlorine, respectively. Mainly lower chlorinated DD/Fs were formed. Based on these

substantial effects on PCDD/F emissions, the copper-catalyzed DPF system was not approved

for workplace applications, whereas the iron system fulfilled all the specifications of the

Swiss procedures for DPF approval (VERT).

References: [1] N.V. Heeb, M. Zennegg, E. Guyer, P. Honegger, K. Zeyer, U. Gfeller, A.Wichser, M.

Kohler, P. Schmid, L. Emmenegger, A. Ulrich, D. Wenger, J.-L. Petermann, J. Czerwinski, T. Mosimann, M. Kasper, A. Mayer, Secondary Effects of Catalytic Diesel Particulate Filters: Copper-induced formation of PCDD/Fs, Environ. Sci. Technol. , 2007, 41, 5789-5794

22

Title: Endocrine Disruptors in Ambient Air Particulate Matter from an

Urban and Rural Site in Switzerland

Researchers: Daniela Wenger1) 4), Andreas C. Gerecke1), Norbert V. Heeb1), Peter

Schmid1), Cornelia Seiler1), Christoph Hüglin2), Hanspeter Nägeli3),

Renato Zenobi4)

Institute/Group: 1) Laboratory for Analytical Chemistry, 2) Laboratory for Air Pollution

and Environmental Technology, Swiss Federal Laboratories for

Materials Testing and Research (Empa); 3) Institute of Pharmacology

and Toxicology, University of Zurich-Vetsuisse; 4) Laboratory of

Organic Chemistry, ETH Zurich


Endocrine disruptors are naturally occurring or man-made exogenous compounds that

interfere with the normal functioning of the endocrine systems in humans and animals. By

mimicking or antagonizing hormones and/or by modulating hormonal responses, these

compounds may induce adverse health effects (reviewed in [1]). To assess the endocrine-

disrupting potential of environmental samples, reporter gene assays have proven to be a

suitable tool [2]. Chemically activated luciferase expression assays (CALUX) use the

luciferase gene of the firefly as reporter gene to detect (hormone) receptor-mediated

alterations of gene expression in mammalian cells.

In preceding studies, we used CALUX assays to investigate endocrine disruptors in diesel

exhaust. We have shown that diesel engines are an emission source of compounds with an

estrogen-receptor (ER)-mediated or with an aryl hydrocarbon receptor (AhR)-mediated mode

of action (i.e., ER ligands, AhR ligands) [3, 4]. In our present project, we use the same two

reporter gene assays to measure ambient air concentrations of endocrine disruptors associated

with particulate matter (PM). Sampling of PM1 (aerodynamic diameter <1 !m) was

performed at two measuring sites of the Swiss National Air Pollution Monitoring Network

(NABEL) during a long-lasting winter smog period in 2006. The sampling sites in Berne and

Payerne were selected to represent an urban and a rural air quality situation of the Swiss

plateau, respectively.

Our latest results show that ER and AhR ligands are present in ambient air particulate matter

collected in Berne and Payerne. For both groups of endocrine disruptors, we have found 3–5

orders of magnitude lower amounts per m3 of sampled air than per m3 of diesel exhaust. In

future work, the contribution of polycyclic aromatic hydrocarbons (PAHs) to the ER- and

AhR-mediated activity will be estimated by combination of quantitative analysis by

GC/HRMS with known or measured relative potency values of the compounds in the CALUX

assays.

References:

[1] Damstra, T., Barlow, S., Bergman, A., Kavlock, R., van der Kraak, G., International

Programme on Chemical Safety (ICPS) 2002

[2] Wenger, D.; Gerecke, A. C.; Heeb, N. V.; Naegeli, H.; Zenobi, R., CEAC Annual Report

2006, 14-20

[3] Wenger, D.; Gerecke, A. C.; Heeb, N. V.; Zennegg, M.; Kohler, M.; Naegeli, H.; Zenobi,

R. Environ. Sci. Technol. 2008, doi: 10.1021/es071827x

[4] Wenger, D.; Gerecke, A. C.; Heeb, N. V.; Naegeli, H.; Zenobi, R. Anal. Bioanal. Chem.

2008, doi: 10.1007/s00216-008-1872-8

23

Title: Polychlorinated Biphenyls (PCBs) in Capacitors from Electrical

and Electronic Waste

Researchers: Martin Eugster1, Cornelia Seiler2, Markus Zennegg2, Ueli Kasser3

Institute/Group: 1Technology and Society, Empa St. Gallen

2Laboratory for Analytical Chemistry, Empa Dübendorf

3Büro für Umweltchemie, Zürich

Project Description: Due to their outstanding physical and chemical properties for technical applications polychlorinated biphenyls (PCBs) have often been used in paper film capacitors in electrical and electronic equipment. Increasing concern on the toxicity and persistence of PCBs in the environment led to a general ban of production and use of these chemicals in the mid eighties in Switzerland. PCB levels have been determined in capacitors of different product categories collected from various recycling facilities and sampled over several months in large sample quantities. The shredded capacitors were homogenized, extracted and analyzed using gas chromato-graphy/electron capture detection and gas chromatography/mass spectrometry. Furthermore, PCB-substitutes and electrolytes used in capacitors were identified by gas chromatography/ mass spectrometry full scan analysis. The study revealed that the analysis of PCBs in heterogeneous matrices such as shredded capacitors is highly critical and may contain significant uncertainties. Nevertheless, the results of the study clearly show still increased PCB concentrations in capacitors from diverse household applications, particularly in starters for fluorescent tubes. Surprisingly, also increased PCB levels were observed in recent information and communications technology products as well as in consumer electronics. The results can be considered as representative in terms of the current PCB content in Swiss end-of-life applications.

24

Title: Absolute configurations of (+) and (-) !-, "-, and #-

hexabromocyclo-dodecanes (HBCDs)

Researchers: Norbert V. Heeb1), W. Bernd Schweizer2), Peter Mattrel1), Regula

Haag1), Andreas C. Gerecke1), Martin Kohler1), Peter Schmid1), Markus Zennegg1), Max Wolfensberger1)

Institutes/Groups:

1) Empa, Laboratory for Analytical Chemistry 2) ETH Zurich, Laboratory of Organic Chemistry

Project Description: Hexabromocyclododecanes (HBCDs) are high production volume chemicals widely used as

flame retardants for plastics and textiles. They are currently produced in quantities exceeding

20'000 t/y. More and more findings indicate that certain HBCDs are persistent,

bioaccumulative, toxic and have become ubiquitous in the environment.

Despite these facts, the correct stereochemistry of most HBCDs is still not known. Six

stereocenters are formed during bromination of cyclododecatrienes, resulting in mixtures of

different stereoisomers. Considering all elements of symmetry, 16 stereoisomers including 6

pairs of enantiomers as well as 4 meso forms are possible. Recently, we isolated 8 of the 16

possible stereoisomers from a technical HBCD mixture and assigned their relative

configurations [1]. We have now reported on the isolation of 6 enantiomerically pure !-, "-,

and #-HBCDs, obtained from preparative chiral-phase liquid chromatography, and we

presented their absolute configurations, which were determined from X-ray diffraction

analysis [2,3].

The absolute configuration of (-) !-HBCD was found to be (1R,2R,5S,6R,9R,10S), while the

one of (+) "-HBCD is assigned to (1S,2S,5S,6R,9S,10R), whereas the one of (-) #-HBCD

corresponds to (1S,2S,5S,6R,9R,10S). The given structural information allows, for the first

time, the unambiguous identification of the six most important HBCD stereoisomers, which

typically account for more than 95% of technical HBCDs. In addition, we compared the solid-

state conformations of racemic and enantiomerically pure !-, "-, and #-HBCDs. In all cases,

the vicinal dibromides adopted synclinal (sc) conformations with torsion angles of 69 ± 6 °. A

unique structural motive was common to all examined HBCD solid-state conformations. This

conserved structure was described as an extended triple turn consisting of an arrangement of

three pairs of synclinal and two antiperiplanar torsion angles.

References: [1] N.V. Heeb, W.B. Schweizer, M. Kohler, A.C. Gerecke, Structure elucidation of

hexabromocyclododecanes - a class of compounds with a complex stereochemistry.

Chemosphere 2005, 61, 65-73.

[2] N.V. Heeb, W.B. Schweizer, P. Mattrel, R. Haag, M. Kohler, Crystal structure analysis of

enantiomerically pure (+) and (-) "-hexabromocyclododecanes. Chemosphere 2007, 66,

1590-1594.

[3] N.V. Heeb, W.B. Schweizer, P. Mattrel, R. Haag, A.C. Gerecke, M. Kohler, P. Schmid, M. Zennegg, M. Wolfensberger: Solid-state conformations and absolute configurations of (+) and (-) !-, "-, and #-hexabromocyclododecanes (HBCDs). Chemosphere 2007, 68, 940-950.

.

25

Title: Spatially, time resolved and element-specific in-situ corrosion

investigations using a novel online microflow-capillary FI-ICP-MS set-up

Researchers: N. Homazava 1), A. Ulrich

1), P. Schmutz 2), U. Krähenbühl 3)

Institute/Group:

1) Empa, Laboratory for Analytical Chemistry, 2) Empa, Laboratory for Corrosion and Materials Integrity

3) University of Bern, Department for Chemistry and Biochemistry

Project Description: Corrosion processes often initiate on weakest microstructural features such as inclusions or

grain boundaries. Thus, spatially resolved methods are required for the characterization of the

local chemistry controlling the corrosion mechanisms. Hence a novel micro-analytical

technique is developed, which allows an element-specific, spatially and time resolved in-situ

investigation of dissolution processes.

The technique is based on an adjustable online microflow-capillary set-up especially designed

for local in-situ experiments. The capillary is connected via flow injection analysis system

FIAS to an inductively coupled plasma mass spectrometry ICP-MS. FIAS allows a transient

sample introduction, whereas ICP-MS is designed for highly sensitive multi-element

quantification.

The coupling to FI-ICP-MS requires an evaluation of alternative micro-flow sample

introduction systems and a careful optimization of the ICP-MS method. High salt matrix of

the corrosion solution probes, spectral and non-spectral interferences and limited sample

volumes represent particular challenges in the method development.

The technique was applied to investigate local corrosions phenomena of aluminum alloys

used in automotive and aerospace applications.

References: [1] Homazava N.; Ulrich, A.; Trottmann, M.; Krähenbühl, U. J. Anal. Atom. Spectrom. 2007,

22, 1122-1130.

Collaborations: University of Bern

Finance:

SNF Swiss National Science Foundation, Empa

26

Title: Emissions of biocides and nanoparticles from facades

Researchers: Michael Burkhardt1), Andrea Ulrich2), Steffen Zuleeg1), Roger

Vonbank3), Adrian Wichser2), Peter Schmid2), Cornelia Seiler2), Regula Haag2), Hans Simmler3), Ralf Kaegi

1), Brian Sinnet

1), Samuel

Brunner3), Markus Boller1), Heinz Vonmont2) Institute/Group:

1)Eawag, Department of Urban Water Management, 2)Empa, Laboratory of Analytical Chemistry, 3)Empa, Building Technologies

Project Description: Modern building materials provide improved energy efficiency and water-repellent properties. The hydrodynamic properties of such materials may result in increasing microbial colonization and biogenic growth of algae, fungi or lichen on facades. An increase of biocides and recently also nanoparticles such as nano-Ag (algicide) or nano-TiO2 (self-cleaning) as alternative biocides should reduce the hazard of biogenic growth. However, the increasing use of biocides and nanoparticles leads to unknown risks with respect to emissions of additives from building materials and possible adverse effects on humans and ecosystems. Starting from commercial products and tailor-made formulations, laboratory and field scale experiments are carried out to quantify the release of nanoparticles, biocides and transformation products from typical plasters and coatings. Effect studies under controlled conditions and in field tests allow a ranking of biocides with respect to release behaviour. Moreover, nanoparticles as a new technology can directly be compared to conventional biocides. New analytical methods will be developed for the characterization of components which are difficult to characterize such as zinc pyrithione. The data are used to investigate the processes and to model the impact to the environment. Modeling enables an assessment of fluxes from urban settlements to the environment. The general objective of the project is an improvement of the sustainability of materials used in advanced building envelopes.

References: [1] M. Burkhardt, R. Kägi, B. Sinnet, S. Zuleeg, A. Ulrich, H. Simmler, R. Vonbank and M.

Boller, What happens with Nano-Silver in Exterior Paints? Contribution to NanoEco – Nanoparticles in the Environment – Implications and Applications, March 2-7, 2008, Monte Verità, Switzerland.

[2] M. Burkhardt, R. Kägi, H. Simmler, A. Ulrich and M. Boller, Nanopartikel auf Fassaden erforschen; Push Thema Umwelt 2/2007, 12-13.

Collaborations: BAM Federal Institute for Materials Research and Testing, Berlin, Germany University of Duisburg-Essen, Germany Fraunhofer Institute for Building Physics (IBP) Holzkirchen Industries Financial support: BAFU, Empa, Eawag

27

Title: Size fractionated analysis of nanoparticulates and colloidal

fractions

Researchers: Andrea Ulrich1), Ralf Kägi2)

Institute/Group: 1)Empa, Laboratory of Analytical Chemistry, 2)Eawag, Department of Urban Water Management


The characterization of nanoparticles requires new methods to achieve both size- and element-specific information. This requires the development of alternative analyzing strategies which allows size fractionation before chemical and morphological characterization. An asymmetric flow field flow fractionation system (AsFFF) will be online-coupled to a plasma mass spectrometer (ICP-MS) and a self-designed LASER induced breakdown detection system (LIBD). The instrumentation enables investigations of size distribution, elemental composition and morphology of nanoparticles.

References: [1] A. Ulrich, Charakterisierung und Quantifizierung von Nanopartikeln in Aerosolen und

Flüssigkeiten, NanoSafety Workshop 2007, Empa Dübendorf.

[2] C. Latkoczy, R. Kägi, M. Boller, D. Günther, Development of a portable Laser Induced

Breakdown Detection (LIBD) - system for the analysis of nanometer colloids in aqueous

media, Contribution to NanoEco – Nanoparticles in the Environment – Implications and

Applications, March 2-7, 2008, Monte Verità, Switzerland.

Collaborations: ETHZ, Group of Prof. D. Günther

Finance:

SNF Swiss National Science Foundation, Empa, Eawag

28

Title: Environmental Emissions and Occurrences of Perfluoroalkyl

Substances in Switzerland

Researchers: Andreas C. Gerecke1, Hong-wen Sun2, Alfredo C. Alder3,

Claudia E. Müller1, Walter Giger4

Institute/Group: 1 Laboratory for Analytical Chemistry, Empa

2 College of Environmental Science and Engineering,

Nankai University, Tianjin, China

3 Department of Environmental Chemistry, Eawag

4 GRC, Giger Research Consulting and ETH, Swiss Federal Institute of

Technology, Zurich


Perfluoroalkyl substances (PFAS) are an important class of chemicals, used in numerous

industrial and consumer products as well as in high-tech materials [1]. PFAS exhibit unique

chemical properties, e.g. they are able to repel both water and oil. Recently, PFAS have been

found globally in air, water, and soil samples. Special concern has been raised by the

detection of elevated PFAS concentrations in biota (e.g., polar bear), which indicates that

these PFAS are persistent and bioaccumulative chemicals [2,3].

Triggered by their frequent detection in the environment and their toxicological properties,

international research efforts are focusing on open questions on the sources, fate, and

transport behaviour of perfluoroalkyl sulfonic acids (PFSA) and their potential precursors, the

perfluoralkyl sulfonamides, as well as on perfluoroalkyl carboxylic acids (PFCA) and their

potential precursors, the fluorotelomer alcohols (FtOH).

Within two projects that start in early 2008, we intend to shed some light on these unanswered

issues. Four topics will be in the focus of our research: (1) emission of PFAS from materials,

(2) long-range transport of PFAS into the Alpine region, (3) the PFAS occurrence in ambient

surface waters. In an initial project phase PFAS and their precursors will be investigated in

municipal wastewaters and sewage sludges (4).

References:

[1] Fluorinated Surfactants and Repellents. Editor: Kissa, E. New York, Marcel Dekker,

Inc.,2001.

[2] Giesy, J. P. and Kannan, K. Perfluorochemical surfactants in the environment. Environ.

Sci. Technol. 2002, 36, 146A-152A.

[3] Lau, C., Anitole, K., Hodes, C., Lai, D., Pfahles-Hutchens, A. and Seed, J. Tox. Sci. 2007,

99, 366-394.

Collaborations:

These two projects are funded by the Federal Office for the Environment (FOEN) and by the

Sino-Swiss Science and Technology Cooperation (SSSTC) of ETH Zurich, respectively.

29

Title: Long-term aging effects of catalytic diesel particle filters

Researchers: Andrea Ulrich1), Norbert V. Heeb1), Jan Czerwinski2)

Adrian Wichser1), Renato Figi1), Cornelia Seiler1) Institute/Group:

1) Empa, Laboratory of Analytical Chemistry, 2) Emission Laboratory of the University of Applied Sciences Biel

Project Description: Appropriate diesel particle filters (DPFs) efficiently eliminate soot, fuel-, and oil-ash emissions of diesel engines, but data on long-term aging or deterioration effects of DPFs under real world operating conditions are still scarce. Aging of wash-coat- and catalyst-materials, catalyst poisoning, ash sintering, reversible adsorption, and long lasting storage of semi- or non-volatile substances can take place, which over time may influence filtration and conversion properties of DPFs or support secondary processes resulting in the formation of new pollutants. The VERT procedures for DPF approval includes an assessment of secondary emissions as well as an inspection of filter efficiency of new and aged DPFs after field application for 2000 hours. To assess the effect of DPF aging on particle filtration characteristics, the particle number concentrations (PN), and particle mass (PM) emissions are determined after a 2000 hours endurance test. Some DPF systems in particular those with noble metal-based catalytic coatings, showed negative particle mass filtration efficiencies after long term use, whereas the particle number filtration efficiencies were still 99 – 99.9%. Negative particle mass filtration efficiencies were mainly observed during the first tests under full load conditions. The effect decreased during the test. A release of sulphates was clearly identified as the main cause. Contributions due to condensation were determined by drying differentiation method, followed by an extraction of the sampled filters using a water-ethanol mixture prior ionic chromatography (IC) analysis to identify sulphate originating from stored sulphur dioxide or sulphuric acid from the emissions. About a third of the mass could be explained by condensation and about a quarter by sulphate. In a next step, the occurrence of potential organic sulphur species was determined by high performance liquid chromatography (HPLC) and gas chromatography mass spectrometry (GC-MS) after extraction using methanol or hexane. However, no organic species could be detected. Hence, the total sulphur content was determined using plasma optical emission spectrometry after acid digestion. The formation of sulphur artefacts was found to be catalysed by strongly oxidizing exhaust gas after-treatment systems. Such converters oxidize sulphur containing compounds present at trace levels in diesel exhaust to sulphur oxide (SOx) nanoparticles, which have to be considered as a secondary pollutant of the DPF as well. Depending on volatility of the obtained sulphur oxidation products, such compounds can accumulate in surface-rich systems like particulate traps or oxidation catalysts at lower operating temperatures. A later release at higher temperatures leads to the emission of semi-volatile secondary SOx aerosols. Such events can even be detected, when low sulphur fuels were applied.

References: [1] A. Ulrich, A. Wichser, R. Figi, N.V. Heeb, T. Neubert, J. Czerwinski, A. Mayer:

Identification of storage and release effects of SOx artefacts on DPF systems after long-

term use, Conference Proceedings of 11th Conference on Combustion Generated

Nanoparticles 2007, P67-1 - P67-13.

[2] A. Mayer, A. Ulrich, N.V, Heeb, J. Czerwinski, T. Neubert: Particle Filter Properties after

2000 hrs Real World Operation, SAE 2008-01-0332.

Collaborations: University of Applied Sciences Biel, TTM Mayer, Matter Engineering

30

Title: Brominated flame retardants in Lake Thun:

A multimedia mass balance model predicts impact of new chemicals and effectiveness of regulatory measures

Researchers: Christian Bogdal1, Peter Schmid1, Martin Kohler1, Heinz Vonmont1,

Markus Bläuenstein2, Martin Scheringer2, Konrad Hungerbühler2

Institute/Group: 1Laboratory for Analytical Chemistry, Empa Dübendorf

2Institute for Chemical and Bioengineering, ETH Zürich


Every year more than 70’000t of polybrominated diphenyl ethers (PBDE) are used as additives to protect electric equipment, textiles, and construction materials from fire. However, PBDE are slowly released from flame-retarded products. As a result, humans, wildlife and the environment are exposed to harmful pollutants. This is of concern, since PBDE are able to interfere with the hormone system and may cause developmental disorders. While direct measurements of the occurrence of these persistent chemicals in the environment are essential to assess the current situation, computer models can substantially enhance the identification of processes that are responsible for the transfer of these chemicals to the environment. In close collaboration with ETHZ, a tailor-made multimedia mass balance model was designed for Lake Thun serving as the study ecosystem. Mass balance equations were set up, and relevant transformation processes were considered. Specifically designed analytical methods allowed measuring PBDE at ultra-trace levels in various environmental compartments of Lake Thun. Measured concentrations in the atmosphere and in tributary rivers served to define the input of PBDE into the Lake Thun ecosystem. Calculations assuming constant PBDE input revealed that the atmosphere is the main input pathway for PBDE into the lake. Water and sediment contain the largest inventory of PBDE, and finally, PBDE are buried in the sediment. In a second step, dynamic calculations enabled us to test various hypothetical scenarios of future PBDE usage. The model can also be extended to other existing or newly developed chemicals. Thus, it is an effective complementary tool to the complex and demanding direct measurements of chemicals in the environment providing a significant contribution to a comprehensive risk assessment. References:

[1] Bogdal, C.; Kohler, M.; Schmid, P.; Scheringer, M.; Hungerbühler K. Organohal.

Comp.2007, 69, 441-444

[2] Bläuenstein, M. Master thesis, Empa, ETHZ, Switzerland, Dübendorf, 2007 Collaborations:

Rik Eggen, Erwin Grieder, Anja Liedtke, Michael Sturm, (Eawag); Daniel Bernet, Helmut Segner, Thomas Wahli, (University Bern); Ueli Ochsenbein, Daniel Scheidegger, Markus Zeh (Canton Bern); Franziska Blum, Thomas Bucheli, Anna Sobek (Agroscope ART).

31

Title: Visualization of aerosol particles generated by laser ablation -

expansion and transport phenomena

Researchers: Joachim Koch, Markus Wälle, Detlef Günther Institute/Group: ETHZ, D-CHAB, Laboratory of Inorganic Chemistry, Trace Element

and Micro Analysis Project Description: To provide insight into mechanisms that control the formation of laser-produced aerosol particles, in recent years, a series of studies dealing with plasma plume propagation and material ejection have been carried out. For instance, Geohegan et al. [1] investigated the expansion of the particulate phase for delay times up to several milliseconds, i.e. far beyond the point where the condensational growth of particles is already finished. Within the scope of their studies, the authors were using laser-induced scattering for visualization allowing them to monitor even strongly dispersed aerosols. However, measurements were restricted to nanosecond laser ablation (ns-LA) and low background pressures. In contrast, less attention has been paid to the expansion of aerosols formed under atmospheric conditions even though data about the dynamics of particles interacting with higher background pressures would well complement the “patchwork”-like knowledge about LA and provide an adequate basis for (i) examining the consistency of models used to describe the aerosol formation and (ii) design optimization of conventional ablation cells which are being used for LA inductively coupled plasma mass spectrometry (ICP-MS) [2]. In this project, specific expansion and transport phenomena of aerosols generated by NIR-ns- and femtosecond (fs)-LA at atmospheric pressures were explored by laser-induced scattering [3 - 5]. It could be shown that NIR-ns-LA under quiescent argon atmosphere provokes the formation of a dense and spatially confined aerosol. In contrast, NIR-fs-LA generally resulted in extremely dynamic but somewhat chaotic expansion patterns which often consisted of multiple branches propagating into different directions. Initial aerosol velocities varied from 10 m/s up to 30 m/s for fs-LA using argon and helium, respectively. In addition, particles were found to be captured in symmetric vortices when striking a solid boundary during their kinetic stage of expansion. Our data indicate that aerosols released under those conditions experience only minor losses of around 1 % if they get in contact with the inner walls of ablation cells. These findings imply that severe deposition only happens if miniaturized

ablation cells whose dimensions fall below the stopping distance of laser-induced plasmas are

used, as demonstrated by Leach et al. [6]. In such cases, reactive matter consisting of non-

condensed vapour, molecular species, and small clusters reach the boundaries which gives

rise to a higher adsorption rate.

Furthermore, the structure of laser-produced aerosols prior to analysis by ICP-MS was examined. For this purpose, aerosol particles were visualized over the cross-section of a transport tube attached to the outlet of a conventional ablation cell. Experiments were carried out under laminar or turbulent in-cell flow conditions applying throughputs of up to 2.0 L/min and reveal the nature of aerosol transportation to strongly depend on both flow rate and carrier gas chosen. For instance, LA using laminar in-cell flow and helium as aerosol carrier resulted in stationary but inhomogeneous dispersion patterns. Moreover, aerosols appear to be separated into two coexisting phases consisting of (i) dispersed particles which accumulate at the boundary layer of several vortex channel flows randomly arranged along the tube axis and (ii) larger fragments moving inside. The occurrence of these fragments was found to affect the accuracy of Si-, Zn-, and Cd-specific ICP-MS analyses of aerosols released by LA of silicate glass (SRM NIST610). Accuracy drifts of more than 10 % were observed for helium flow

32

rates > 1 L/min, most probably, due to preferential evaporation and diffusion losses of volatile constituents inside the ICP. References: [1] D. B. Geohegan, A. A. Puretzky, G. Duscher, S. J. Pennycook, Appl. Phys. Lett. 72

(1998), 2987 - 2989 [2] D. Bleiner, A. Bogaerts, J. Anal. At. Spectrom. 21 (2006), 1161 - 1174 [3] J. Koch, S. Schlamp, T. Rösgen, D. Fliegel, D. Günther, Spectrochim. Acta B 62 (2007),

20 - 29 [4] J. Koch, M. Wälle, S. Schlamp, T. Rösgen, D. Günther, Spectrochim. Acta B 63 (2008),

37 - 41 [5] J. Koch, M. Wälle, R. Dietiker, D. Günther, Anal. Chem. 80 (2008), 915 - 921 [6] A. M. Leach, G. M. Hieftje, Appl. Spectrosc. 56 (2002), 62 - 69

33

Title: The Influence of the Operating Conditions on Mass Bias in Multi

Collector-Inductively Coupled Plasma Mass Spectrometry

Researchers: Gisela Fontaine, Bodo Hattendorf, Detlef Günther

Institute/Group: ETHZ, D-CHAB, Laboratory of Inorganic Chemistry, Trace Element

and Micro Analysis

Project Description: Today’s interest in precise isotope ratios is constantly increasing and spreading from its traditional

geochemistry and archaeology applications (e.g. dating) to general provenance studies and to isotope

tracing in clinical trials. The sensitivity, acquisition speed, simultaneous measurement and high

resolution capability of multi-collector-inductively coupled plasma-mass spectrometry (MC-ICPMS)

has led to a large number of publications 1. However, the isotope ratios measured always differ from

the true isotopic composition of the sample and need to be corrected by internal and/or external

standardization procedures even for interference-free samples2. The deviation between the measured

and true isotope ratios depends on many factors, starting with the aerosol formation and transport,

diffusion in the ICP and the interface up to space charge and collisions in the ion optics and the mass

spectrometer. Due to the complex interaction of individual operating parameters of an ICPMS, a

general description of the underlying processes is difficult. In 2004, Andrén et al.3 reported a

dependence of the mass bias on sampling position and the nebulizer flow rate under wet plasma

conditions.

This project attempts to identify instrumental sources of mass bias and describe their respective

influence for sample aerosols from different sources. Variations of the measured isotope ratios for

single element standards were recorded using a Nu Plasma HR MC-ICPMS in dependence on carrier

gas flow rate, sampling depth and the acceleration voltage for wet as well as dry plasma conditions.

The dependence of the isotopic ratios on each of these parameters was shown. Changes of both

parameters show similar trends in the measured isotope ratios when increasing the carrier gas flow rate

or decreasing the sampling depth, respectively. The deviation from the true isotope ratios in the

samples was always found to minimize for either lower gas flow rates or higher sampling depths than

those conditions that lead to highest signal intensities, i.e. highest overall transmission for the isotopes.

The extent to which the ratios change can furthermore be reduced by adjusting the ion optics settings

specifically to the ICP-operating conditions.

These observations indicate that the plasma temperature and residence time of the sample inside the

ICP affect the radial distribution and kinetic energies of the isotopes. Those properties of the ion beam

in turn influence the mass bias observed. Based on these findings, it appears that tuning the MC-

ICPMS for isotope ratio measurements solely to highest signal intensities is not the optimal strategy

for minimizing the mass bias and its variability in high precision isotope ratio measurements.

References: [1] Douthitt, C.B. Anal. Bioanal. Chem. 2008, 390, 437-440.

[2] Albarede, F.; Telouk, P.; Blichert-Toft, J.; Boyet, M.; Agranier, A.; Nelson, B.

Geochim.Cosmochim.Acta 2004, 68, 2725-44.

[3] Andren,H.; Rodushkin,I.; Stenberg,A.; Malinovsky,D; Baxter,D.C. J. Anal. At. Spectrom.

2004, 19, 1217-1224.

Collaborations: B. Bourdon (ETH Zürich, Zürich/CH).

34

Title: CeO2 Nanoparticle Uptake into Maize Plants

Researchers: Karin Birbaum, Robert Brogioli, Detlef Günther


and Micro Analysis


Nanoparticles (NPs) are widely used new materials. Due to their properties they are applied in

many fields. Up to now, the effects of NPs to the environment are barely understood. So far,

studies have already shown that CeO2 NPs are taken up by human lung cells [1], whereas in

this project, the possibility for an uptake into plants was investigated. Furthermore, we were

interested to see whether transport of the NPs into newer leaves (un-grown at time of

exposure) occurs. In this study, maize plants, playing an important role in the food chain,

were exposed to NPs at an age of 3-5 weeks.

Two different approaches of exposure were carried out (air exposure and soil exposure).

During air exposure, the plants were placed in a closed box, where the NPs were produced for

1 minute. After an exposure time of 20 minutes maize plants were removed. To see any

effects of the opening of the stomata for uptake, half of the plants were exposed in light and

others during a dark period. In the soil exposure, suspensions of CeO2 NPs were given to the

soil over a period of 14 days. After each exposure, the plants were either cut or left for some

weeks to grow and then later cut. After digestion with HNO3/H2O2 in a microwave assisted

autoclave at 230° C and 90 bar, the samples were measured with liquid nebulisation

inductively coupled plasma sector field mass spectrometry (ICP-SF-MS).

The results show that the exposure at light leads to twice the concentration of Ce compared to

the dark. However, a washing before the digestion reduces the Ce concentration by a factor of

3-6 and the resulting concentrations of the dark and light exposures do not show a significant

difference in the Ce concentrations. Therefore, an uptake through the stomata can be excluded

and the most likely effect of Np influence is based on surface desorption. Furthermore, plants

were grown for 9 weeks after the air exposure. The newly grown leaves (not directly exposed)

were collected for analysis. The Ce concentration in those leaves is below the limit of

determination.

Soil exposure experiment showed that the concentration in the stem and the leaves of the

plants was below the limit of determination.

References:

[1] Limbach, L.K.; Li, Y.; Grass R.N.; Brunner, T.J.; Hintermann, M.A.; Muller, M.;

Günther, D.; Stark, W.J. Env. Sci. Technol.2005, 29 (23), 9370-9376

Collaborations:

L. Limbach, W. Stark (Institute for chemical and bioengineering, ETH Zurich)

E. Martinoia (Institute of Plant Biology, Uni Zurich

35

Title: LA-ICPMS analysis of fluid inclusions entrapped within colossal

crystals from the Naica caves (Mexico) by LA-ICPMS

Researchers: Mattias Fricker1, Paolo Garofalo2, Detlef Günther1

Institute/Group: 1Laboratory of Inorganic Chemistry, D-CHAB, ETH Zurich

2Dipartimento di Scienze della Terra, Universita' di Bologna


Fluid Inclusions (FIs) are tiny compartments of natural solutions made of liquid, gas and solid

phases trapped within minerals during various stages of their growth. Often times, these FIs

represent the only remnants of the pristine natural solutions from which crystals grow over

geologic time. The chemical analyses of these solutions provide therefore fundamental

insights into the large variety of processes that generate crystals (and associated rocks) in

nature.

Here, we present the analyses of FIs (ca. 60-100 µm in diameter) found within enormous (up

to 14 m long) crystals of gypsum from several karst caves of Northern Mexico. These caves

are located at Naica, one of the largest Ag-Pb-Zn mines of the area, and have been discovered

in the year 2002 during deep mining activity. A multi-disciplinary research project lead by the

Italian Exploration Team La Venta is under way to unveil the process that controlled such a

peculiar crystal growth.

As part of this larger project, we analyzed the FIs using LA-ICPMS. Elemental concentrations

were calculated by internal standardization, for which the NaCleq concentration, i.e. the

salinity was employed. The salinity had been determined prior to laser ablation by

microthermometry, a non-destructive method. The acquired MS signals must be deconvolved,

i.e. separating the small FI signal from the signal of the matrix [1] preliminary to the

quantification procedure.

References:

[1] Heinrich, C. A, et al. Geochimica et Cosmochimica Acta 2003, 67, 3473-3496.

Collaborations:

Paolo S. Garofalo, Universita' di Bologna, Italy

36

Title: High spatial resolution analysis of major and minor trace elements

in speleothem (India) by LA-ICPMS: implications to climate

reconstruction

Researchers: Mattias Fricker1, Sebastian Breitenbach2, Beat Aeschlimann1, Gerald

Haug2, Detlef Günther1

Institute/Group: 1Laboratory of Inorganic Chemistry, D-CHAB, ETH Zurich

2Climate Geology, D-ERDW, ETH Zürich


Speleothems are recently understood as important terrestrial archive of past climate. The main

reasons are the highly accurate and precise dating routines applicable to these cave

carbonates, and the wealth of proxy information (including trace elements) incorporated into

stalagmites unaltered over thousands of years. Although understanding of past monsoonal

variability is pending, only few high-resolution records are available from the Indian summer

monsoon region. Knowledge of past rainfall variability and drought frequency is of great

importance for predicting future monsoon changes. Prediction of inter-annual precipitation

variability is vital for adaptation strategies by government and economy of agriculture-based

countries such as India.

Stalagmite records from the heart region of the summer monsoon (i.e. our study site

Meghalaya) are extremely valuable to not only reconstruct changes in precipitation, soil, and

vegetation conditions, but also to understand the teleconnection between monsoon and other

atmospheric circulation patterns, such as El Niño/Southern Oscillation.

The analyzed sample (KRUM-3) covers the last ~11,000 years in ~65 cm total length. For

transportation out of the cave the sample was broken into three pieces, each of which can fit

the new ablation cell.

For the analysis, one track (~5.5 cm) after another was scanned from the top to the base of the

stalagmite. Data treatment included common data reduction but quantification was performed

not for the signal average but for every single datapoint acquired. Thereafter the sum of the

oxides of all measured elements for each datapoint was normalized to 99.5% wt total,

assuming all elements contained in the sample were analyzed. The last step comprised

reassembling of all these transient signals to give one curve from top to bottom of the

stalagmite for each analyzed element to the interpretation by climate geologists.

Collaborations:

Sebastian Breitenbach, Gerald Haug

37

Title: Aerosol transport efficiency and total ion yield in femtosecond laser

ablation inductively coupled plasma mass spectrometry

Researchers: Markus Wälle, Luca Flamigni, Joachim Koch, Detlef Günther

Institute/Group: ETHZ, D-CHAB, Laboratory of Inorganic Chemistry, Trace Element and Micro Analysis


In the late 1980s Arrowsmith and Hughes [1] presented the first data about transport efficiencies in laser ablation ICP-MS showing theoretical considerations on transportable particle sizes and specifying a transport efficiency of ~40%. Afterwards, Huang et al. [2] reported on transport efficiencies of 10% to 60% depending on the matrix studied. Recently Garcia et al [3, 4] published transport efficiencies for NIR- and UV-femtosecond laser ablation (fs-LA) of 75% to 95% for brass. However, some inconsistencies exist in these results since the authors did do not take into account the material loss on the sample surface. In Ref. [4] a new approach was already proposed which makes use of determining the ablated volume from the thickness of a layer and the crater diameter. Using this approach, in Ref. [4] the transport efficiency could be adjusted to 60% using Argon as carrier gas. A Chromium coated Nickel sample and a Copper coated glass sample with a layer thickness of 5 um and 0.2 um, respectively, were used. In this way, transport efficiencies of 65% +/- 10% and 78% +/- 10% were achieved using Argon and Helium as carrier gas, respectively. In further epxeriments, the total ion yield, i.e. counts in the ICP-MS divided by the amount of ablated atoms, for laser ablation Q-ICP-MS was determined applying UV-nanosecond and NIR-femtosecond LA. Depending on the conditions chosen, the total ion yield varied from 5E-5 to 1E-7 for the high and low mass range, respectively. Furthermore, LA of silicate glasses (NIST SRM 610, 612, 614) showed no significant differences in Helium and only a small difference for NIST 614 using Argon as carrier gas. The utilization of Argon was also found to reduce the total ion yield by factor of 5 or 2 for nanosecond laser ablation (ns-LA) and fs-La, respectively. In addition, the total ion yield for NIR-fs-LA and UV-ns-LA in Helium provide similar results. References: [1] Arrowsmith, P.; Hughes, S. K. Appl. Spetrosc., 1988, 42, 1231 - 1239 [2] Huang, Y.; Shibata, Y.; Morita, M. Anal. Chem., 1993, 65, 2999 - 3003 [3] Garcia, C. C.; Lindner, H.; Niemax, K. Spectrochim. Acta Part B, 2007, 62, 13 - 19 [4] Garcia, C.C.; Wälle, M.; Lindner, H.; Koch, J.; Niemax, K.; Günther, D. Spectrochim.

Acta Part B, 2007, doi:10.1016/j.sab.2007.11.017

38

Title: Accuracy and Reproducibility in Elemental Analysis

using LA-ICPMS

Researchers: Bodo Hattendorf, Zhongke Wang and Detlef Günther

Institute/Group: ETHZ, D-CHAB, Laboratory of Inorganic Chemistry, Trace Element and Micro Analysis


We investigate the effect of optimization criteria of laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) instrumentation on the accuracy and reproducibility of element analyses. In this study a specific sample (GSE1 G from the United States Geological survey) was analyzed by different combinations of laser ablation (266 nm ns, 213 nm ns, 193 nm ns, 266 nm fs) and ICPMS instruments. The operating conditions were adjusted either to maximize ion signal intensities or with a specific focus on the relative response of different elements. In the latter case the ICPMS was adjusted to ensure that sensitivity for U and Th in the calibration standard matches the concentration ratio in the sample. The results were evaluated with respect to the accuracy obtained for the analysis of GSE 1G and detection efficiency for the operating conditions used. Further the long term reproducibility of the techniques was compared for different LA-ICPMS instrument combinations. References: [1] Wang. Z., Hattendorf B., Günther D.; Analyte Response in Laser Ablation Inductivel

y Coupled Plasma Mass Spectrometry, J. Am. Soc. Mass Spectrom., 2006, 17, 641-651 [2] Wang, Z., Hattendorf, B., Günther, D., Vaporization and ionization of laser ablation

generated aerosols in an inductively coupled plasma mass spectrometer—implications

from ion distribution maps, J. Anal. At. Spectrom., 2006, 21, 1143 - 1151

39

Title: Investigation of the influence of the transport system on signal

response in LA-ICP-MS

Researchers: Robert Kovacs and Detlef Günther


and Micro Analysis


Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) has become one

of the most attractive methods for spatially resolved analysis of solid materials [1]. Due to its

complexity, the fundamental processes are still of major interest for better understanding of

the ablation, transport and plasma related processes. Beside the aerosol generation and

decomposition of the ablated material in the high temperature Ar plasma, the transport of the

laser generated particles is of importance for quantitative analysis. The transport tube is

responsible for the aerosol dispersion [2, 3] and can contribute to material losses, which can

lead to inaccurate analysis [4]. Luo et. al. [5] reported recently that the uncertainty of the

concentration of the standard reference materials and drift are the major components

contributing the most significantly to the total uncertainty budget in LA-ICP-MS. However,

source and magnitude of drift remain partially unknown.

This study was focused on the purity of the carrier gas and the importance of the transport

tube material used in LA-ICP-MS. The results demonstrate that the tube material influences

the plasma when using dry plasma conditions. Four types of tube materials (PVC, nylon,

Teflon, copper) were investigated. The wash-out of air components such as H2, O2, CO2, H2O

from the PVC and nylon tubings were found to be a long-term process. Especially the

presence of hydrogen and oxygen changed the plasma most significantly. The results indicate

that the tube degassing process (desorption of the gas molecules from the wall of the tubings

into the gas stream) has a larger influence on the plasma conditions than the gas or water

diffusion through the tubes. This degassing process using PVC and nylon is time and tube

length dependent. In the presence of low amount impurities of hydrogen, carbon and oxygen,

signal enhancements in dependence on tube length upstream or downstream of the sample cell

were measured. It was found that the PVC and nylon tube materials contribute significantly to

a long term drift, while the use of Teflon and copper transport tubes provided the most stable

intensity ratios. Therefore, these tube materials are highly recommended for LA-ICP-MS.

References:

[1] Durrant, S. F. J. Anal. At. Spectrom., 1999, 14, 1385-1403.

[2] Bleiner, D.; Günther, D. J. Anal. At. Spectrom., 2001, 16, 449-456.

[3] Blankenburg, L. M.; Gäckle, M.; Günther, D.; Kammel, J.

Plasma Source Mass Spectrometry, Royal Soc. of Chem., Cambridge, UK, 1989, 1-17.

[4] Koch, J.; Feldmann, I.; Jakubowski, N.; Niemax, K. Spectrochim. Acta Part B, 2002, 57,

975-985.

[5] Luo, Y.; Gao, S.; Longerich, H. P.; Günther, D.; Wunderli, S.; Yuan, H. L.; Liu, X. M.

J. Anal. At. Spectrom., 2007, 22, 122-130.

40

Title: Monolithic CMOS multi-transducer gas sensor microsystem for

organic and inorganic analytes

Researchers: Yue Li, Cyril Vancura, Diego Barrettino, Markus Graf, Christoph Hagleitner, Adrian Kummer, Martin Zimmermann, Kai-Uwe Kirstein, Andreas Hierlemann

Institute/Group: Laboratorium für Physikalische Elektronik, Dept. Physik, ETH Zürich, Hönggerberg

Project Description: A monolithically integrated multi-transducer microsystem to detect organic and inorganic gases has

been developed. The system comprises two polymer-based sensor arrays based on capacitive and

gravimetric transducers, a metal-oxide-based sensor array, the respective driving and signal processing

electronics and a digital communication interface (Figure 1). The chip has been fabricated in industrial

0.8-µm, complementary-metal-oxide-semiconductor (CMOS)-technology with subsequent post-

CMOS micromachining. The simultaneous detection of organic and inorganic target analytes with the

single chip multi-transducer system has been demonstrated. The system is very flexible and can

provide different information of interest: The capacitive sensors can, e.g., act as humidity sensors to

deal with the cross-sensitivity of the metal-oxide-based sensors to water, or they can be coated with

differently thick polymer layers to detect organic volatiles even in a background of water. The multi-

transducer approach provides a wealth of information that can be used to improve the system

discrimination capability and performance in gas detection.

0.8 µm CMOS; Chip size : 7 mm x 7 mm

Capacitive

sensors

Resonant

cantilevers

Microhot-

plates

Sigma-delta

converter

Temperature

sensor and

circuitry

Cantilever

feedback circuitry

Digital circuitry

Biasing

Temperature

controller and

readout circuitry

Fig 1. Micrograph of the monolithic multi-transducer chip hosting three different transducers:

polymer-coated microcapacitors and resonant cantilevers sensitive to organic volatiles, and metal-

oxide coated microhotplates for gases like carbon monoxide, nitrogen dioxide, methane.

References: 1] Y. Li, C. Vancura, D. Barrettino, M. Graf, C. Hagleitner, A. Kummer, M. Zimmermann, K.-U.

Kirstein, A. Hierlemann, “Monolithic CMOS multi-transducer gas sensor microsystem for

organic and inorganic analytes”, Sensor and Actuators B, Chemical, 2007, 126, 431-440.

[2] A. Hierlemann, Integrated Chemical Microsensors in CMOS Technology, Springer Verlag,

Berlin, Heidelberg, 2005, IX, 229 p. 125 illus., ISBN: 3-540-23782-8.

41

Title: Potentiometric Biosensors

Researchers: Tamás Vigassy

Ernö Pretsch

Institute/Group: Inst. Biogeochem. & Pollutant Dynam., ETH Zürich


Miniaturized ion-selective electrodes with very low detection limits (down to 100 picomolar) can be used in small samples down to 3 µL. By using the recently established labeling of biomolecules with nanoparticle-based metal (Ag) or semiconductor (CdSe) tags and dissolving these metals in small sample volumes, highly sensitive potentiometric immunoassays have been introduced.

References:

[1] Potentiometric immunoassay with quantum dot labels

R. Thürer, T. Vigassy, M. Hirayama, J. Wang, E. Bakker, E. Pretsch

Anal. Chem. 2007, 79, 5107-5110. [2] Potentiometric detection of DNA hybridization

A. Numnuam, K.Y. Chumbimuni-Torres, Y. Xiang, R. Bash, P. Thavarungkul, P. Kanatharana, E. Pretsch, J. Wang, E. Bakker J. Am. Chem. Soc. 2008, 130, 410-411.

[3] Aptamer-based potentiometric measurements of proteins using ion-selective microelectrodes

A. Numnuam, K.Y. Chumbimuni-Torres, Y. Xiang, R. Bash, P. Thavarungkul, P. Kanatharana, E. Pretsch, J. Wang, E. Bakker Anal. Chem. 2008, 80, 707-712.

Collaborations: Prof. E. Bakker, Curtin University, Perth, Australia, Prof. R.E. Gyurcsányi, Budapest University of Technology and Economics, Prof. M. Hirayama, Zürcher Hochschule Winterthur, CH-8400 Winterthur, Prof. J Wang, Arizona State University, Tempe, AZ, USA

42

Title: Backside Calibration Potentiometry

Researchers: Károly Tompa

Adam Malon

Tamás Vigassy

Ernö Pretsch

Institute/Group: Inst. Biogeochem. & Pollutant Dynam., ETH Zürich


Ion fluxes through supported liquid membranes are so fast that steady-state concentration profiles across ion-selective membranes are established rapidly and reproducibly. At concentrations below ca. 10–4 M, the potentiometric response depends on the compositions of the solutions on both sides of the sensing membrane. Chemical asymmetries across the membranes are assessed by determining the direction of potential drift upon changing the stirring rate on either side of the membrane. Disappearance of this drift indicates the disappearance of concentration gradients across the membrane and is used to determine the sample composition if the solution composition at the backside of the membrane is known. The practical applicability of the method has been demonstrated with different environmental water samples, for which the results obtained with the novel method have been compared with those got by traditional calibration using standard additions [1, 2].

References:

[1] Ion activity measurements with selective supported liquid membranes by calibrating from the back side of the membrane

A. Malon, E. Bakker, E. Pretsch

Anal. Chem. 2007, 79, 632–638. [2] Sensitivity and working range of backside calibration potentiometry

W. Ngeontae, Y. Xu, Ch. Xu, W.Aeungmaitrepirom, T. Tuntulani, E. Pretsch, E. Bakker

Anal. Chem. 2007, 79, 8705-8711.

Collaborations: Prof. E. Bakker, Curtin University, Perth, Australia.

43

Title: Development of Computational Algorithms for High-throughput

Detection and Discovery of Protein Modifications in Mass Spectrometry Data

Researchers: D. Rutishauser, C. Panse, B. Gerrits, and R. Schlapbach Institute/Group: Functional Genomics Center Zurich, UZH/ETH Zurich Project Description:

Despite the great importance of PTMs for biological function, their study on a large scale has been hampered by a lack of suitable methods and many key modifications have only been discovered late in the elucidation of various biological processes. In general, PTMs can be studied by applying tandem mass spectrometry. High mass accuracy is beneficial for finding related peaks, corresponding to peptides that cover the same amino acid sequence but have different mass due to modifications.

Illustration of a mass shift in the MS/MS spectra due to a chemical modification. The MS/MS spectrum of the cICAT-light labelled peptide DQYELLCLDNTR (black) is overlaid by the MS/MS of the same peptide carrying the cICAT-heavy label (red). The y-ion series are marked with dashed lines. The cysteine residues of the two peptides are specifically labelled resulting in a delta mass of m/z 9:0301. The precursor masses of m/z 1708:8090 Da and m/z 1717:8392 Da respectively, were determined using an FTICR mass spectrometer. The project aims to develop an automated posttranslational modification discovery and identification tool for known and hitherto unknown PTMs. Using highest achievable mass accuracy data provides the basis for PTM discovery. Technically, we mine high accuracy mass spectrometry data generated on FT–ICR or LTQ–Orbitrap systems by using modification specific algorithms that are newly developed. The key improvement of the tool over existing approaches is a novel grouping model of the calculated delta masses. The group size is specified according to the mass accuracy of the measurement – the higher the accuracy the more precise the grouping. In order to verify the identity of the peptides of each delta mass, the MS/MS pairs are searched against a preprocessed protein database. With this information it is possible to assign a discovery ratio to each group defined as the ratio of the verified delta masses per total number of elements in this group. References: [1] Potthast,F., Gerrits,B. et al.;The Mass Distance Fingerprint: A statistical framework for

de novo detection of predominant modifications using highaccuracy mass spectrometry, J

Chromatogr B, 2007, 854(1-2),173-182. [2] Craig, R., Beavis, R. C.;TANDEM: matching proteins with tandem mass spectra,

Bioinformatics, 2004, 9, 1466-7.

44

Title: Next Generation Proteomics Data Analysis Strategies – Using the

Power of Multiple Search Strategies

Researchers: J. Grossmann, S. Barkow-Oesterreicher, C. Panse, and R. Schlapbach Institute/Group: Functional Genomics Center Zurich, UZH/ETH Zurich

Project Description: Development of new strategies and algorithms for the combination of database search results with the goal of achieving confident protein identification based on mass spectrometry data. One of the most popular approaches to protein identification considers a database search against the protein database of an organism. It was shown before that the overlap of different search algorithms is surprisingly small. Furthermore, in a complex biological sample up to 30% of the proteins are only identified by a single peptide. Especially these assignments are critical in proteomics studies. A comprehensive analysis of several model organism proteomics datasets reveals that the false discovery rate can be decreased dramatically as well as the number of proteins can be increased if peptide identifications only are accepted if more than one search engine confirms the identification. In this study five search engines were used (Sequest (Eng, Mccormack et al. 1994), Mascot (Perkins, Pappin et al. 1999), X!Tandem (Craig and Beavis 2004), omssa (Geer, Markey et al. 2004) and PepSplice (Roos, Jacob et al. 2007) – the latter three are open source) and a list of most confidently identified MS/MS scans were generated for each search engine. At the FGCZ we envision new strategies and algorithms for the combination of database search results with the goal to have more confident protein identification.

Illustration of protein identifications using a fixed FDR (Fals Discovery Rate) cutoff on the MS/MS level. References: [1] Craig, R. and R. C. Beavis; "TANDEM: matching proteins with tandem mass

spectra."Bioinformatics, 2004, 20(9), 1466-7. [2] Geer, L. Y., S. P. Markey, et al.; "Open mass spectrometry search algorithm." J Proteome

Res, 2004, 3(5), 958-64. [3] Perkins, D. N., D. J. Pappin, et al.; "Probability-based protein identification by searching

sequence databases using mass spectrometry data." Electrophoresis, 1999, 20(18), 3551-67.

[4] Roos, F. F., R. Jacob, et al.; "PepSplice: Cache-Efficient Search Algorithms for Comprehensive Identificationof Tandem Mass Spectra." Bioinformatics, 2007, 23(22):3016-23.

Collaborations: C. Ahrens, E. Brunner (University of Zurich) R. Aebersold (ETH Zurich) W. Gruissem (ETH Zurich)

45

Title: Development of PET radiopharmaceuticals

Researchers: S M Ametamey, M Honer, C Lucatelli, T. Ross, PA Schubiger Institute/Group: Institut für Pharmazeutische Wissenschaften, ETH Hönggerberg Project Description:

The main focus of research in our group is the development of PET (Positron emission tomography) radiopharmaceuticals for diagnostic application in neurology and oncology. Last year, we reported on the evaluation of a new CNS compound which showed promising in vivo properties in rodents [1] and humans [2]. We were successful in evaluating the new mGluR5 (metabotropic glutamate receptor subtype 5) PET ligand, 11C-ABP688, in healthy volunteers in collaboration with clinical partners and industry. To avoid the practical drawbacks arising from the short physical half-life of 20.3 min for carbon-11, we are currently working on developing new fluorine-18 labelled ABP688 analogs, as mGluR5 PET ligands. A new ligand, FPECMO, has been successfully developed and radiolabelled with fluorine-18 [3]. In vitro evaluation of this new ligand, revealed a high affinity for mGluR5 and high specific binding. However, the in vivo evaluation of 18F-FPECMO in rodents showed a rapid metabolism of the radioligand making 18F-FPECMO unsuitable for further in vivo evaluation. However, the easy radiosynthesis and the excellent in vitro characteristics make this ligand a very promising probe for in vitro work. With regard to folic receptor imaging, we have now radiolabelled two new compounds which are currently being evaluated for their potential as imaging agents. References:

[1] S. M. Ametamey, L. J. Kessler, M. Honer, M. T. Wyss, A. Buck, S. Hintermann, Y. P. Auberson, F. Gasparini, P. A. Schubiger “Radiosynthesis and preclinical evaluation of [11C]-ABP688 as a probe for imaging the metabotropic glutamate receptor subtype5 (mGluR5)“ J. Nucl Med. 2006;47:698-705

[2] S. M. Ametamey ”Human PET studies of metabotropic glutamate receptor subtype5 with [11C]-ABP688” J. Nucl Med. 2007;48:1-6

[3] C. Lucatelli, M. Honer, J.-F. Salazar, P. A. Schubiger, S. M. Ametamey “Synthesis and evaluation of [18F]-FPEMO as a PET ligand for imaging the metabotropic glutamate receptors subtype 5 (mGluR5)” J. Label. Compounds Radiopharm. 2007;50:S134

46

Title: Nanoscale Chemical Analysis and Spectroscopy

Researchers: Johannes Stadler, Gerardo Gamez, Thomas Schmid, Thomas Schmitz,

Jason Yeo, Weihua Zhang, Liang Zhu, Renato Zenobi

Institute/Group: Laboratorium für Organische Chemie, ETH Hönggerberg Project Description: For developments in nanoscience and nanotechnology, powerful nanodiagnostic tools capable of recording chemical/molecular information with high spatial resolution are becoming increasingly important. Scanning near-field optical microscopy (SNOM), the "optical member" of the family of scanning probe microscopies, is particularly well suited as a tool for nanoscale molecular analysis [1]. In 2007, a new set-up combining upright illumination confocal microscopy, atomic force microscopy (AFM), Raman spectroscopy including detection with one of the best CCD cameras available on the market, and software optimized for chmical imaging was installed in our laboratories. Our research uses two different embodiments of SNOM: (i) Aperture SNOM with tips designed for high optical transmission and for sustaining pulsed laser radiation, for nanoscale laser ablation mass spectrometry, and (ii) apertureless SNOM, employing an external CW laser field and a metallic tip to greatly enhance the local field for “tip-enhanced” Raman spectroscopy (TERS) [1]. The latter method has a resolution that exceeds that of aperture SNOM. Much progress has been achieved in the area of TERS during the past year. In particular, new ways for the production of robust and highly enhancing TERS tips were described [2]. Using “gap mode” TERS, we even achieved single molecule sensitivity [3,4]. We have also combined experiments with simulations [5,6] that yielded a greatly improved understanding of the enhancement mechanisms. The combination of chemical identification (via the Raman spectral signature), spatial resolution of ! 20 nm, and a detection limit at the single molecule level has never before been possible. Applications that are currently being pursued include the analysis of biological nanostructures, of artificial membranes, of polymers blends, and of inorganic nanomaterials. References: [1] T. Schmid, B.-S. Yeo, W. Zhang, and R. Zenobi, in Advances in Nano-Optics and Nano-

Photonics, Eds. S. Kawata and V. M. Shalaev (Elsevier, Amsterdam 2007). [2] B.-S. Yeo, T. Schmid, W. Zhang, and R. Zenobi, Anal. Bioanal. Chem. 2007, 387, 2655-

2662. [3] W. Zhang, B.-S. Yeo, T. Schmid, and R. Zenobi, J. Phys. Chem. C 2007, 111, 1733-1738. [4] W. Zhang, T. Schmid, B.-S. Yeo, and R. Zenobi, Israel J. Chem. 2007, 47, 111 – 118. [5] X. Cui, W. Zhang, B.-S. Yeo, R. Zenobi, C. Hafner, and D. Erni, Opt. Exp. 2007, 15,

8309-8316. [6] W. Zhang, X. D. Cui, B.-S. Yeo, T. Schmid, C. Hafner, and R. Zenobi, Nano Lett. 2007,

7, 1401-1405. Collaborations: C. Hafner (ETH Zurich), V. Deckert (ISAS, Dortmund/D), NT-MDT (Zelenograd/Russia), Goodyear (Luxembourg).

47

Title: Direct Analysis of Biological Matter by

Extractive Electrospray Ionization Mass Spectrometry

Researchers: Huanwen Chen, Gerardo Gamez, Liang Zhu, Arno Wortmann, Renato Zenobi

Institute/Group: Laboratorium für Organische Chemie, ETH Hönggerberg Project Description:

50 tons of spoiled meat discovered in Bavaria – authorities need to screen hundreds of warehourses! Spinach contaminated with E. coli leaves 200 people sick in the USA – rapid screening needed for suspected epidemic! What do these and similar headlines have in common? They all challenge modern analytical science in terms of sensitivity, specificity, speed, and especially throughput. It appears that Extractive Electrospray Mass Spectrometry (EESI) provides a viable solution to these and other challenges. EESI is a variant of electrospray ionization (ESI). In ESI, the sample is present in solution, and is nebulized and ionized under the influence of a high electric field and with the aid of an additional desolvation gas. Mass analysis is performed with a mass spectrometer having an atmospheric pressure ionization inlet; many different instruments for this purpose are available commercially. In EESI, the ion formation is turned “upside down”: a pure solution – usually diluted acetic acid – is sprayed, and the samples enters the charged mist through the desolvation gas line. The sample molecules get efficiently ionized by charge transfer processes, and can be analyzed in a standard fashion. The power of EESI has been demonstrated in a number of practical applications [1]: (i) The rapid in vivo fingerprinting of breath without sample pre-treatment; metabolic dynamics was promptly reflected in the EESI data [2]. (ii) Investigation of the maturity of fruit with high sensitivity, specificity, high throughput, and non-invasively [3]. EESI fingerprinting of compounds released from various fruits yielded information on the ripening stages of bananas, grapes and strawberries, which were then successfully differentiated by performing principal component analysis (PCA). (iii) Direct, on-line analysis of biological matter such as skin, meat (even in the frozen state), and vegetables, by directing a jet of N2 gas onto the sample (Figure 3), followed by EESI-MS of the compounds liberated [4,5]. Finally, it has also been shown that the charge states of biopolymer ions can be manipulated by atmospheric pressure ion/molecule reactions in an EESI source [5].

References: [1] H. Chen and R. Zenobi, Chimia 2007, 61, 834. [2] H. Chen, A. Wortmann, W. Zhang, and R. Zenobi, Angew. Chem. Internat. Ed. 2007, 119, 580-583. [3] H. Chen, Y. Sun, A. Wortmann, H. Gu, and R. Zenobi, Anal. Chem. 2007, 79, 1447-1455. [4] H. Chen, A. Wortmann, and R. Zenobi, J. Mass Spectrom. 2007, 42, 1123-1132. [5] H. Chen, S. Yang, A. Wortmann, and R. Zenobi, Angew. Chem. Int. Ed. 2007, 119, 7735- 7738. [6] H. Chen, D. Touboul, M. J. Jecklin, J. Zheng, M. Luo, and R. Zenobi, Eur. J. Mass

Spectrom. 2007, 13, 273-279. Collaborations:

University Hospital, Zurich (Prof. E. Russi, Pneumology, PD Dr. Katharina Rentsch, Clinical Chemistry); Excercizse Physiology Institute ETH/UniZ (Dr. M. Toigo, Prof. U. Boutellier), East China Institute of Technology.

48

Title: Environmental Trace Analysis and Aerosol Chemistry Researchers: Markus Kalberer, Vera Samburova, Renato Zenobi Institute/Group: Laboratorium für Organische Chemie, ETH Hönggerberg

Project Description: Organic aerosols are of importance in such different fields as global climate change, regional air quality and human health. Of particular interest to us are to study the formation, composition, and chemical fate of secondary organic aerosol in detail, to better define the high-molecular weight fraction (so called humic acid like substances, HULIS) in ambient urban aerosols, and to push the limits for trace detection of organics in environmental samples. The tools we are using are mass spectrometric [1], chromatographic [2], optical spectroscopy and NMR [3] methods that are applied to controlled laboratory experiments in a flow tube reactor as well as in a smog chamber, built in collaboration with the PSI. These are complemented with field experiments from urban and rural areas. An important recent advance is based on the application of ultra-high"FTICR-MS [1]. Studying the ozonolysis of � -pinene in the smog chamber, about several 100 compounds were detected, their elemental composition determined, and their chmical relationshiip established. The results give new insight into oligomer formation processes taking place in the aerosol phase. A second recent study focused on quantification of carboxylic, arylic, phenolic and aliphatic functional groups of HULIS, performed by a specially adapted and optimized H-NMR method [3]. A good correlation between the H-NMR results and potentiometric titration of carboxylic groups was observed. A third focus is to quantify organic peroxides in laboratory-generated, atmospherically relevant aerosols and to investigate the biological responses of lung cells to these oxidized particles. This research is carried out in collaboration with the University of Bern. The main hypothesis is that the oxidation capacity of organic particles containing peroxides is mainly responsible for biological effects because of their high reactivity and oxidation potential. Well-characterized particles generated in the smog chamber were analysed for their peroxide content and then deposited onto lung cell cultures in first test experiments. Increased expression of inflammation markers (IL-6, IL-8) was observed for lung cells exposed to these oxidized smog chamber organic aerosols. References: [1] A. Reinhardt, C. Emmenegger, B. Gerrits, C. Panse, J. Dommen, U. Baltensperger, R.

Zenobi, and M. Kalberer, Anal. Chem. 2007, 79, 4079-4082. [2] C. Emmenegger, A. Reinhardt, C. Hueglin, R. Zenobi, and M. Kalberer, Envir. Sci.

Technol. 2007, 41, 2473-2478. [3] V. Samburova, T. Didenko, E. Kunenkov, C. Emmenegger, R. Zenobi, and M. Kalberer,

J. Atmos. Chem. 2007, 41, 4703-4710. Collaborations: U. Baltensperger (PSI), H. Gaeggeler (Univ. Bern / PSI), C. Hüglin (EMPA), P. Gehr, M. Geiser (Univ. Bern), Functional Genomics Center Zurich.

49

Title: Electrospray Ionization Mass Spectrometry for Studying

Noncovalent Interactions

Researchers: Cédric Bovet, Matthias Jecklin, Sonal Mathur, Tatiana Pimenova, David Touboul, Arno Wortmann, Renato Zenobi Institute/Group: Laboratorium für Organische Chemie, ETH Hönggerberg Project Description:

Electrospray ionization (ESI), and variations thereof such as electrosonic spray ionization (ESSI) or chip-based nanoelectrospray (nanoESI) ionization allow, under carefully chosen conditions, the preservation of noncovalently bound complexes and supramolecular assemblies in the gas phase. We are working on a better understanding of the fundamentals for the detection of noncovalent complexes with ESI-MS based methods. This knowledge is also used to further develop mass spectrometry based methods to for quantitative measurment of dissociation constants (KDs) of noncovalent interactions [1]. In this context, we also conducted a detailed investigation of the influence of the ESI spray on chemical equilibria in solution and its dependence on the time scale of droplet evolution relative to the time scale of the equilibrium kinetics [2]. Currently, we pursue the following sub-projects: (i) Comparison of EIS titration based KD determinations with standard methods such as surface plasmon resonance (SPR), circular dichroism (CD) and H/D exchange followed by MALDI readout (a method called SUPREX) [1]. We found that due to the detection limit of native ESI has KDs in the high nM range are possible to measure, but not below. For high affinity ligands, a new method has been developed that allows KDs down to the femtomolar range to be deterimed [3]. (ii) Study of complex, real-world noncovalent interactions such as the inhibition or activation of the endocrine receptor by small molecules that occur in the environment, so-called endocrine disruptors [4], and the fast classification of inhibitors of human kinases [3], important drug targets, by automated nanoESI-MS. (iv) An interesting side line is the discovery of ESSI-MS based method for measuring the apparent gas-phase basicity GBapp of peptides and proteins at atmospheric pressure with good sensitivity (for concentrations less than 10 #M in denaturing or non-denaturing buffer), very good precision (less than 2%) and in a short time (less than 30 minutes to screen up to 23 volatile reference bases) [5]. References: [1] S. Mathur, M. Badertscher, M. Scott, and R. Zenobi, Phys. Chem. Chem. Phys. 2007, 9,

6187-6198. [2] A. Wortmann, M. C. Heine, O. Wilhelm, A. Kistler-Momotova, S. E. Pratsinis, and R.

Zenobi, J. Am. Soc. Mass Spectrom. 18, 385 - 393(2007). [3] A. Wortmann, M. C. Jecklin, D. Touboul, M. Badertscher, and R. Zenobi, J. Mass

Spectrom. (available online, http://dx.doi.org/10.1002/jms.1355, Dec. 2007). [4] C. Bovet, A. Wortmann, S. Eiler, F. Granger, M. Ruff, B. Gerrits, D. Moras, and R.

Zenobi, Protein Sci. 2007, 16, 938-946. [5] D. Touboul, M. C. Jecklin, and R. Zenobi, Rapid and Accurate Measurements of Gas-

Phase Basicity of Peptides and Proteins at Atmospheric Pressure by Electrosonic Spray

Ionization-Mass Spectometry (Letter), J. Phys. Chem. B 2007, 111, 11629-11631. Collaborations: S. E. Pratsinis (ETHZ), D. Moras (IGBMC / CNRS, Strasbourg, France), Functional Genomics Center Zurich, Novartis Institutes for BioMedical Research (Cambridge).

50

Title: MALDI Mass Spectrometry - Applications and Fundamentals

Researchers: Claudia Bich, Stefanie Mädler, Tatiana Pimenova, Renato Zenobi

Institute/Group: Laboratorium für Organische Chemie, ETH Hönggerberg

Project Description: MALDI Mass Spectrometry has emerged as an effective analytical tool for soft ionization of complex (bio-) molecules up to several 100 000 Da. In MALDI, the sample is embedded in an excess of a solid matrix, which, upon laser irradiation, assists in the volatilization and ionization of the analyte. We are contributing to both the fundamental understanding of the MALDI process [1,2] as well as to application of MALDI to study high-mass biomolecules and their complexes. In 2007, a novel high-mass detector was installed on one of our MALDI mass spectrometers This new technology circumvents the familiar drop-off of the detection efficiency with increasing mass and allows detection up to 1 MDa and beyond. We are using high-mass MALDI for the following projects: (i) Detection of high-mass protein complexes by direct mass analysis of unfragmented, undigested, intact protein complexes by MALDI [3-5]. The method consists of a chemical stabilization of the non-covalent interaction partners prior to high-mass MALDI-MS analysis. (ii) In this context, the cross-linking chemistry (reactivity, amino acid specificity, kinetics,…) is also investigated in detail. (iii) Detection of extremely high mass assemblies of solvophobically-driven 3-D self-assemblies of "exploded"-type polyphenylene dendrimers [4,5]. Interestingly, these dendrimers assemble to tetramers that are stable even in the absence of any chemical cross-linking. (iv) Epitope mapping, using the intensity fading approach [6]. Here, the high-mass MALDI is employed to ensure efficient cross-linking of the epitope to an antibody. This is then followed up with high-resolution FT-ICR measurements of the digested, cross-linked complex. References: [1] A. Wortmann, T. Pimenova, S. Alves, and R. Zenobi, The Analyst 2007, 132, 199-207. [2] M. Dashtiev, E. Wäfler, M. Gorshkov, F. Hillenkamp, and R. Zenobi, Int. J. Mass

Spectrom. 2007, 268, 122-130 (2007) (Roepstorff special issue). [3] O. Yanes, F. X. Aviles, R. Wenzel, A. Nazabal, R. Zenobi, and J. J. Calvete, J. Am. Soc.

Mass Spectrom. 2007, 18, 600-606. [4] C. G. Clark, Jr., R. J. Wenzel, E. V. Andreitchenko, W. Steffen, R. Zenobi, and K.

Müllen, J. Am. Chem. Soc. 2007, 129, 3292-3301. [5] C. G. Clark, R. J. Wenzel, E. V. Andreitchenko, W. Steffen, R. Zenobi, and K. Müllen,

New J. Chem. 2007, 31, 1300-1305. [6] T. Pimenova, A. Nazabal, B. Roschitzki, J. Seebacher, O. Rinner and R. Zenobi, J. Mass

Spectrom. 43, 185 – 195 (2008). Collaborations: Franz Hillenkamp (University of Münster/D), K. Müllen (MPI for Polymer Research, Mainz/D), S. Hornemann (ETHZ), A. Trkola (University Hospital, Zurich), Institute for Systems Biology (ETHZ), Functional Genomics Center Zurich, CovalX GmbH (Zürich).

51

Title: Fourier-Transform Ion Cyclotron Resonance (FT-ICR) Researchers: Konstantin Chingin, Huanwen Chen, Renato Zenobi Institute/Group: Laboratorium für Organische Chemie, ETH Hönggerberg Project Description:

Fourier-transform ion cyclotron resonance (FT-ICR) is a very powerful mass spectrometric method, celebrated for its extremely high mass accuracy and resolting power. For many applications, high-resolution measurements are very important to correctly assign peaks in the spectrum, for example to unambiguously determine a molecule's elemental composition. Since the FT-ICR instrument is an ion trap, it is very well suited for obtaining complementary optical spectroscopic information of gas-phase ions. In a project closely related to our investigations of noncovalent complexes, we are studying the conformation of biomolecules in the gas phase, by combining FT-ICR with fluorescence spectroscopy of trapped ions. For example, there are many current debates about whether biomolecules ionized by MALDI or ESI retain their native conformation. We plan to utilize the fluorescence emission of green fluorescent protein (GFP) and fluorescence resonant energy transfer (FRET) in doubly labeled proteins and in molecular beacons based on self-complementary DNA strands. The fluorescence properties of such biomolecular ions brought into the gas phase by MALDI or ESI should give important new insights about conformation of gas-phase-ions. Using single photon counting, we have already demonstrated the capability to observe fluorescence resonance energy transfer in doubly labeled trapped gas-phase ions [1]. In 2007, an ESI source was installed on our FT-ICR instrument, and we are now in a position to study much higher molecular weight compounds than previously possible (with MALDI), and to investigate questions such as how the charge state of a biomolecular ion influences its conformation. References: [1] M. Dashtiev, V. Azov, V. Frankevich, L. Scharfenberg, and R. Zenobi, Observation of

Fluorescence Resonance Energy Transfer in Gas-Phase Ions, J. Am. Soc. Mass Spectrom. 16, 1481 - 1487 (2005).

Collaborations: B. Schuler (University of Zurich), E. Nikolaev and M. Gorshkov (Moscow State Univ.)

52

Title: Single Cell Metabolomics Researchers: Andrea Amantonico, Nils Goedecke, Matthias Heinemann, Andreas

Hierlemann, Ralf Streichan, Oliver Kotte, Joo-Yeon Oh, Sven Panke, Renato Zenobi

Institute/Group: Bioprocess Laboratory, Institut für Verfahrenstechnik, ETH Zentrum

Laboratorium für Organische Chemie, ETH Hönggerberg Physical Electronics Laboratory, ETH Hönggerberg Institute for Systems Biology, ETH Hönggerberg

Project Description: Almost all currently employed analytical ‘-omics’ methods provide data that are averaged over an entire cell population, while even genetically identical cells exposed to the same environmental conditions can display strong variations in molecular content and even in phenotypes. Such heterogeneity has been shown to be involved in many cellular and also disease related processes such as antibiotic resistance, competence for DNA uptake, and in viral life-cycle decisions. The increasing number of such findings suggests that cellular heterogeneity is underestimated, which in turn calls for development of novel single cell-based analytical methodologies. For the purpose of detecting metabolites in single cells, we are developing highly sensitive methods that can detect on the order of 105 molecules in the volume of a single cell, which is in the femtoliter range. Furthermore, the technology should be amenable to high-throughput operation. The approach consists of a microfluidic cell processing and sample preparation platform interfaced (off-line) to an extremely sensitive version of MALDI mass spectrometry. It has been shown that metabolites - even in cellular extracts - can be detected by MALDI with sufficient sensitivity, using nanoliter spotting of the samples onto a specially prepared matrix layer, in negative ion mode [1]. The deposition from a microfluidic chip onto the MALDI sample target has also been demonstrated. The next and final step will be to bring together the microfluidic platform and the MALDI detection, and to work on heterogeneous cell populations. References: [1] A. Amantonico, J.-Y. Oh, J. Sobek, M. Heinemann, and R. Zenobi, Mass Spectrometric

Method for Analyzing Metabolites in Yeast with Single Cell Sensitivity, Angew. Chem (submitted, Dec. 2007).

Collaborations: Functional Genomics Center Zurich.

53

Title: Two-dimensional chemical imaging on the micrometer scale

Researchers: Enzo Curti, Daniel Grolimund, Camelia Borca, Dominik Kunz

Institute/Group: Swiss Light Source (SLS) and Waste Management Laboratory (LES),

Paul Scherrer Institute (PSI), Villigen


Identifying and recording variations in the chemical speciation in physically or chemically heterogeneous materials is of fundamental importance in many areas of science. The fine structure of an X-ray absorption edge reveals manifold and detailed information on the chemical speciation of the absorber atom. An illustrative as an example is the observation of a distinct shift in the edge position depending on the oxidation state of a multivalent absorber. Other disparities in the absorption spectrum can arise from differences in the local chemical environment (within a distance of ~5 Å). As a result, pronounced absolute differences in the normalized absorption can be observed at characteristic energies. These differences represent chemical contrast which can be used to record two-dimensional distribution maps of oxidation states, mineral phases, or different molecular species. This is achieved by tuning the excitation energy sequentially to these selected energies (a capability unique to synchrotron-based x-ray microprobe facilities) and subsequent logical filtering allows one to make two-dimensional chemical speciation maps [1]. Within the present project we have applied the described analytical strategy to investigate

redox reactions occurring during the corrosion

of vitrified nuclear waste materials. Figure 1

shows the spatial distribution of the oxidation

states III and IV of Cerium (a chemical analog

of Plutonium and Uranium). The different glass

beads, as cross sections, are clearly visible.

Within the unaffected interior part of the beads

cerium is present as Ce(IV). In contrast, the

Ce(III) is the predominant oxidation state

within the corrosion layer, mainly composed by

clay minerals. Accordingly, Cerium released

during the weathering of the glass material is

reduced and is immobilized as Ce(III) by

precipitation of secondary phases in the

corrosion layer. Such fundamental

understanding of corrosion – re-precipitation

phenomena is of crucial important in the

context of safety assessment of nuclear waste

disposal concepts.

References:

[1] D. Grolimund, M. Senn, M. Trottmann, M. Janousch, I. Bonhoure, A.M. Scheidegger, M.

Marcus, Shedding new Light on Historical Metal Samples using Micro-focused Synchrotron X-

Ray Fluorescence and Spectroscopy, Spectrochimica Acta Part B: Atomic Spectroscopy, 59,

1627-1635, (2004).

[2] E. Curti, D. Grolimund, C. Borca, D. Kunz, Corrosion of vitrified nuclear waste: New

microscopic insights, in preparation, (2008).

100 µm100 µm100 µm

Figure 1: Oxidation state map of cerium

observed in corroded vitrified nuclear waste

materials. Black represents void areas, grey

corresponds to Cerium(IV) mainly found in

the pristine part of the glass, while

Cerium(III) is enriched within the corrosion

layer (white areas).

54

Title: In situ characterization of poly(vinyl alcohol) based microbubbles

using soft x-ray microscopy

Researchers: G. Tzvetkov, R.H. Fink

Institute/Group: Swiss Light Source (SLS), Paul Scherrer Institute (PSI), PolLux beamline


In this work, we report on the first in situ scanning-transmission x-ray microspectroscopy

(STXM) investigation of gas-filled PVA-based microbubbles in aqueous environment. Gas-

encapsulated microballoons are of big interest for ultrasound imaging and drug delivery

applications [1]. From the oxygen K-edge x-ray absorption fine structure (NEXAFS) spectra

taken from the microballoon interiors we unambiguously distinguished between water- and

air-filled particles.We also demonstrate that STXM imaging below and above the oxygen K

threshold (520 eV and 550 eV) can provide unique information on the composition of the

microbubbles in water [2]. Detailed characterization of the polymeric shell structures has also

been performed. 2D profiling gives direct access to the shell properties-to a much better

accuracy compared to confocal optical microscopy. We could monitor in situ changes due to

the release of gases upon extended illumination with x-rays. The temperature-dependence in

the regime relevant for medical applications has been studied in detail. This study is financed

by the BMBF within the PolLux project (05 KS7WE1).

Fig. 1. STXM images of microbubbles recorded below and above the O K-edge.

References:

[1] Cavalieri, F.; El Hamassi, A.; Chiessi, E.; Paradossi, G. Langmuir 2005, 21, 8758-8764.

[2] Tzvetkov, G.; Graf, B.; Fernandes, P.; Fery, A.; Cavalieri, F.; Paradossi, G.; Fink, R.H.

Soft Matter 2008, 4, 510-514.

Collaborations:

A. Fery, P. Fernandes (University of Bayreuth) and F. Cavalieri, G. Paradossi (Università di

Roma).

55

Title: Lipidomics in Clinical Diagnostics

Researchers: Ratna Karuna, Carine Steiner, Patrick Setz,Arnold von Eckardstein, Katharina Rentsch

Institute/Group: Institut für Klinische Chemie, Universitätsspital Zürich

Project Description: Lipids comprise a family of biomolecules that play prominent roles in many critical metabolic

and biochemical processes such as energy production and storage, the formation and

functioning of cellular membranes, signal transduction, and steroidgenesis. The critical point

in studying the in-vivo metabolism and the clinical impact of the different lipids is the need of

one or several analytical methods which enable the sensitive, specific determination of the

different lipid classes in their unaltered state. The title which has recently been given to the

theme of studying lipids in their natural environment is lipidomics. As yet only cholesterol

and its distribution in different lipoproteins as well as triglycerides have been used as

diagnostic and prognostic markers. We are interested in the diagnostic and prognostic value of

various lipids including oxysterols, bile acids, phospholipids and sphingolipids in human

disease. Liquid chromatography mass spectrometry (LC-MS/(MS)) methods are beeing

developed and used as analytical tools for the determination of the various lipid classes in

serum and lipoprotein subfractions using either a targeted or profiling approach, respectively.

Healthy individuals will be analyzed to establish reference values of the different markers and

to unravel associations and correlations with demographic and anthropometric measures as

well as clinical biochemical markers. Well defined patient cohorts will be evaluated to

unravel the association of candidate lipids with diseases, for example cardiovascular or

metabolic diseases.

References: [1] I. Burkard, K. M. Rentsch and A. von Eckardstein, Determination of 24S- and 27-

hydroxycholesterol in plasma by high-performance liquid chromatography-mass

spectrometry, J Lipid Res, 45, 776-781 (2004). [2] I. Burkard, A. von Eckardstein and K. M. Rentsch, Differentiated quantification of

human bile acids in serum by high-performance liquid chromatography-tandem mass

spectrometry, J Chromatogr B Analyt Technol Biomed Life Sci, 826, 147-159 (2005).

[3] I. Burkard, A. von Eckardstein, G. Waeber, P. Vollenweider, K.M. Rentsch, Lipoprotein distribution and biological variation of 24S- and 27-hydroxycholesterol in

healthy volunteers, Atherosclerosis, in press (2007) [4] I. Burkard, Oxysterols and bile acids – biochemical characterization of the cholesterol

catabolism pathway, Dissertation ETHZ, Februar 2006 Collaborations: HDLomics, Functional genomics of inborn errors and therapeutic interventions in high density lipoprotein (HDL) metabolism (EU, 6th framework programme)

57

4

Publications

58

Swiss Federal Institute of Aquatic Science and Technology (Eawag)

W. Aeschbach-Hertig, C. P. Holzner, M. Hofer, M. Simona, A. Barbieri, and R. Kipfer, A

time series of environmental tracer data from deep, meromictic Lake Lugano, Switzerland, Limnology and Oceanography 52(1), 257-273 (2007). A. A. Ammann, Inductively coupled plasma mass spectrometry (ICP MS): a versatile tool, J. Mass Spectrom. 42(4), 419-427 (2007). M. Berg, J. Bolotin, and T. B. Hofstetter, Compound-specific nitrogen and carbon isotope

analysis of nitroaromatic compounds in aqueous samples using solid-phase microextraction

coupled to GC/IRMS, Anal. Chem. 79(6), 2386-2393 (2007). M. Berg, C. Stengel, P. T. K. Trang, P. H. Viet, M. L. Sampson, M. Leng, S. Samreth, and D. Fredericks, Magnitude of arsenic pollution in the Mekong and Red River Deltas - Cambodia

and Vietnam, Sci. Total Environ. 372(2-3), 413-425 (2007). A. Birkenmaier, J. Holert, H. Erdbrink, H. M. Moeller, A. Friemel, R. Schoenenberger, M. J. F. Suter, J. Klebensberger, and B. Philipp, Biochemical and genetic investigation of initial

reactions in aerobic degradation of the bile acid cholate in Pseudomonas sp strain Chol1, J. Bacteriol. 189(20), 7165-7173 (2007). P. M. Borer, S. J. Hug, B. Sulzberger, S. M. Kraemer, and R. Kretzschmar, Photolysis of

citrate on the surface of lepidocrocite: An in situ attenuated total reflection infrared

spectroscopy study, J. Phys. Chem. C 111(28), 10560-10569 (2007). M. Burkhardt, T. Kupper, S. Hean, R. Haag, P. Schmid, M. Kohler, and M. Boller, Biocides

used in building materials and their leaching behavior to sewer systems, Water Sci. Technol. 56(12), 63-67 (2007). M. Burkhardt, and C. Stamm, Depth distribution of sulfonamide antibiotics in pore water of

an undisturbed loamy grassland soil, J. Environ. Qual. 36(2), 588-596 (2007). O. A. Cirpka, M. N. Fienen, M. Hofer, E. Hoehn, A. Tessarini, R. Kipfer, and P. K. Kitanidis, Analyzing bank filtration by deconvoluting time series of electric conductivity, Ground Water 45(3), 318-328 (2007). P. F. X. Corvini, R. Meesters, M. Mundt, A. Schäffer, B. Schmidt, H. F. Schröder, W. Verstraete, R. Vinken, and J. Hollender, Contribution to the detection and identification of

oxidation metabolites of nonylphenol in Sphingomonas sp Strain TTNP3, Biodeg. 18(2), 233-245 (2007). J. Dittmar, A. Voegelin, L. C. Roberts, S. J. Hug, G. C. Saha, M. A. Ali, A. B. M. Badruzzaman, and R. Kretzschmar, Spatial distribution and temporal variability of arsenic in

irrigated rice fields in Bangladesh. 2. Paddy soil, Environ. Sci. Technol. 41(17), 5967-5972 (2007).

59

A. E. Efimov, A. G. Tonevitsky, M. Dittrich, and N. B. Matsko, Atomic force microscope

(AFM) combined with the ultramicrotome: a novel device for the serial section tomography

and AFM/TEM complementary structural analysis of biological and polymer samples, J. Microscopy 226(3), 207-217 (2007). D. A. Gilichinsky, E. Nolte, A. E. Basilyan, J. Beer, A. V. Blinov, V. E. Lazarev, A. L. Kholodov, H. Meyer, P. A. Nikolskiy, L. Schirrmeister, and V. E. Tumskoy, Dating of

syngenetic ice wedges in permafrost with 36Cl, Quat. Sci. Rev. 26(11-12), 1547-1556 (2007). A. Göbel, C. S. McArdell, A. Joss, H. Siegrist, and W. Giger, Fate of sulfonamides,

macrolides, and trimethoprim in different wastewater treatment technologies, Sci. Total Environ. 372(2-3), 361-371 (2007). T. B. Hofstetter, C. M. Reddy, L. J. Heraty, M. Berg, and N. C. Sturchio, Carbon and

chlorine isotope effects during abiotic reductive dechlorination of polychlorinated ethanes, Environ. Sci. Technol. 41(13), 4662-4668 (2007). M. Kahle and C. Stamm, Sorption of the veterinary antimicrobial sulfathiazole to organic

materials of different origin, Environ. Sci. Technol. 41(1), 132-138 (2007). I. A. Katsoyiannis, S. J. Hug, A. Ammann, A. Zikoudi, and C. Hatziliontos, Arsenic

speciation and uranium concentrations in drinking water supply wells in Northern Greece:

Correlations with redox indicative parameters and implications for groundwater treatment, Sci. Total Environ. 383(1-3), 128-140 (2007). S. Klump, Y. Tomonaga, P. Kienzler, W. Kinzelbach, T. Baumann, D. M. Imboden, and R. Kipfer, Field experiments yield new insights into gas exchange and excess air formation in

natural porous media, Geochim. Cosmochim. Acta 71(6), 1385-1397 (2007). J. Knies, S. Brookes, and C. J. Schubert, Re-assessing the nitrogen signal in continental

margin sediments: New insights from the high northern latitudes, Earth Planetary Sci. Let. 253(3-4), 471-484 (2007). O. Kracht, M. Gresch, and W. Gujer, A stable isotope approach for the quantification of

sewer infiltration, Environ. Sci. Technol. 41(16), 5839-5845 (2007). J.-H. Kwon, H. M. Liljestran, L. E. Katz, and H. Yamamoto, Partitioning thermodynamics of

selected endocrine disruptors between water and synthetic membrane vesicles: Effects of

membrane compositions, Environ. Sci. Technol. 41(11), 4011-4018 (2007). C. Lee, C. Schmidt, J. Yoon, and U. von Gunten, Oxidation of N-nitrosodimethylamine

(NDMA) precursors with ozone and chlorine dioxide: Kinetics and effect on NDMA formation

potential, Environ. Sci. Technol. 41(6), 2056-2063 (2007). C. Lee, J. Yoon, and U. von Gunten, Oxidative degradation of N-nitrosodimethylamine by

conventional ozonation and the advanced oxidation process ozone/hydrogen peroxide, Wat. Res. 41(3), 581-590 (2007).

60

K. Ljung, S. Björck, R. Muscheler, J. Beer, and P. W. Kubik, Variable 10

Be fluxes in

lacustrine sediments from Tristan da Cunha, South Atlantic: a solar record?, Quat. Sci. Rev. 26(7-8), 829-835 (2007). S. Meylan, F. Hammes, J. Traber, E. Salhi, U. von Gunten, and W. Pronk, Permeability of low

molecular weight organics through nanofiltration membranes, Wat. Res. 41(17), 3968-3976 (2007). R. Muscheler, F. Joos, J. Beer, S. A. Müller, M. Vonmoos, and I. Snowball, Solar activity

during the last 1000 yr inferred from radionuclide records, Quat. Sci. Rev. 26(1-2), 82-97 (2007). V. J. Nesatyy and M. J. F. Suter, Proteomics for the analysis of environmental stress

responses in organisms, Environ. Sci. Technol. 41(20), 6891-6900 (2007). A. Peter and U. von Gunten, Oxidation kinetics of selected taste and odor compounds during

ozonation of drinking water, Environ. Sci. Technol. 41(2), 626-631 (2007). V. Raina, A. Hauser, H. R. Buser, D. Rentsch, P. Sharma, R. Lal, C. Holliger, T. Poiger, M. D. Müller, and H. P. E. Kohler, Hydroxylated metabolites of !- and "-hexachlorocyclohexane:

Bacterial formation, stereochemical configuration, and occurrence in groundwater at a

former production site, Environ. Sci. Technol. 41(12), 4291-4298 (2007). A. K. Reineke, T. Göen, A. Preiss, and J. Hollender, Quinoline and derivatives at a tar oil

contaminated site: Hydroxylated products as indicator for natural attenuation? Environ. Sci. Technol. 41(15), 5314-5322 (2007). L. C. Roberts, S. J. Hug, J. Dittmar, A. Voegelin, G. C. Saha, M. A. Ali, A. B. M. Badruzzaman, and R. Kretzschmar, Spatial distribution and temporal variability of arsenic in

irrigated rice fields in Bangladesh. 1. Irrigation water, Environ. Sci. Technol. 41(17), 5960-5966 (2007). E. Rodriguez, G. D. Onstad, T. P. J. Kull, J. S. Metcalf, J. L. Acero, and U. von Gunten, Oxidative elimination of cyanotoxins: Comparison of ozone, chlorine, chlorine dioxide and

permanganate, Wat. Res. 41(15), 3381-3393 (2007). M. Ronteltap, M. Maurer, and W. Gujer, The behaviour of pharmaceuticals and heavy metals

during struvite precipitation in urine, Wat. Res. 41(9), 1859-1868 (2007). 35. M. Sánchez-Polo, J. Rivera-Utrilla, J. D. Méndez-Diaz, S. Canonica, and U. von Gunten, Photooxidation of naphthalenesulfonic acids: Comparison between processes based

on O3, O3/activated carbon and UV/H2O2, Chemosphere 68(10), 1814-1820 (2007). S. Suarez, M. C. Dodd, F. Omil, and U. von Gunten, Kinetics of triclosan oxidation by

aqueous ozone and consequent loss of antibacterial activity: Relevance to municipal

wastewater ozonation, Wat. Res. 41(12), 2481-2490 (2007). S. Töpperwien, R. Behra, and L. Sigg, Competition among zinc, manganese, and cadmium

uptake in the freshwater alga Scenedesmus vacuolatus, Environ. Toxicol. Chem. 26(3), 483-490 (2007).

61

S. Töpperwien, H. Xue, R. Behra, and L. Sigg, Cadmium accumulation in Scenedesmus

vacuolatus under freshwater conditions, Environ. Sci. Technol. 41(15), 5383-5388 (2007). M. Zennegg, M. Kohler, P. C. Hartmann, M. Sturm, E. Gujer, P. Schmid, A. C. Gerecke, N. V. Heeb, H. P. E. Kohler, and W. Giger, The historical record of PCB and PCDD/F

deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999, Chemosphere 67(9), 1754-1761 (2007).

62

Laboratory for Analytical Chemistry, Empa Dübendorf

Brändli, R. C., Kupper, T., Bucheli, T. D., et al., Organic pollutants in compost and digestate: Part 2. Polychlorinated dibenzo-p-dioxins, and -furans, dioxin-like polychlorinated biphenyls, brominated flame retardants, perfluorinated alkyl substances, pesticides, and other compounds, J. of Environm. Monitoring, 2007, 9, 465-472. Bruehlmann, S., Novak, P., Lienemann, P., et al. Three-way-catalyst induced benzene formation: A precursor study, Appl. Catalysis B: Environm., 2007, 70, 276-283. Heeb, N. V., Bernd Schweizer, W., Mattrel, P., Haag, R. and Kohler, M., Crystal structure analysis of enantiomerically pure (+) and (-) $-hexabromocyclododecanes, Chemosphere, 2007, 66, 1590-1594. Heeb, N. V., Schweizer, W. B., Mattrel, P., et al., Solid-state conformations and absolute configurations of (+) and (-) %-, $-, and &-hexabromocyclododecanes (HBCDs), Chemosphere, 2007, 68, 940-950. Heeb, N. V., Zennegg, M., Gujer, E., et al., Secondary effects of catalytic diesel particulate filters: Copper-induced formation of PCDD/Fs, Environm. Science and Technology, 2007, 41, 5789-5794. Homazava, N., Ulrich, A., Trottmann, M. and Krähenbühl, U., Micro-capillary system coupled to ICP-MS as a novel technique for investigation of micro-corrosion processes, J. of

Analytical Atomic Spectrometry, 2007, 22, 1122-1130. Hugener, M., Emmenegger, L. and Mattrel, P., Emissions of tar-containing binders: A laboratory study, J. of Environm. Science and Health - Part A Toxic/Hazardous Substances

and Environm. Engineering, 2007, 42, 241-247. Schmid, P., Kohler, M., Gujer, E., Zennegg, M. and Lanfranchi, M., Persistent organic pollutants, brominated flame retardants and synthetic musks in fish from remote alpine lakes in Switzerland, Chemosphere, 2007, 67, S16-S21. Ulrich, A., Barrelet, T. and Krähenbühl, U., Spatially resolved plant physiological analysis using LA-HR-ICP-MS, Chimia, 2007, 61, 111. Vikan, H., Justnes, H., Winnefeld, F. and Figi, R., Correlating cement characteristics with rheology of paste, Cement and Concrete Research, 2007, 37, 1502-1511. Vital, A., Richter, J., Figi, R., et al., One-step flame synthesis of ultrafine SiO2-C nanocomposite particles with high carbon loading and their carbothermal conversion, Industr.

& Engineering Chemistry Research, 2007, 46, 4273-4281. Zennegg, M., Kohler, M., Hartmann, P. C., et al., The historical record of PCB and PCDD/F deposition at Greifensee, a lake of the Swiss plateau, between 1848 and 1999, Chemosphere, 2007, 67, 1754-1761.

63

Mayer, A., Kasper, M., Mosimann, Th, Nanoparticle-Emission of EURO 4 and EURO 5 HDV Compared to EURO 3 With and Without DPF, SAE International, 2007-01-1112, 2089, 335-343

Burkhardt, M., Kupper, T., Hean, S., Haag, R., Schmid, P., Kohler, M., Boller, M., Biocides used in Building Materials and their Leaching Behavior to Sewer Systems, Water Science

Technology 2007, 56, 63-67.

Burkhardt, M., Kägi, R., Simmler, H., Ulrich, A., Boller, B, Nanopartikel auf Fassaden erforschen, Push Thema Umwelt 2/2007, 12-13.

Book Eschenlohr, L., Friedli, V., Robert-Charrue Linder, C., Senn, M., in Develier-Courtetélle, un habitat rural mérowingien. 2. Métallurgie du fer et mobilier métallique, Cahier d’archéologie

jurassienne caj 14, Office de la culture Société jurasienne d’Emulation Porrenruy 2007, 1-356

Theses

Müller, C. E., Master thesis, Empa, ETHZ, Dübendorf, Switzerland, 2007. Bläuenstein, M., Master thesis, Empa, ETHZ, Switzerland, Dübendorf, 2007. Naef, M., Master thesis, Empa, ETHZ, Switzerland, Dübendorf, 2007.

64

Group of Prof. D. Günter, Laboratory of Inorganic Chemistry, ETH Hönggerberg

Koch, J., Schlamp, S., Rösgen, T., Fliegel, D., Günther, D. Visualization of aerosol particles generated by near infrared nano- and femtosecond laser ablation. Spectrochimica Acta Part B,

2007, 62, 20–29

Pisonero J., Koch J., Wälle M., Hartung W., Spencer N.D., Günther D. Capabilities of Femtosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry for Depth Profiling of Thin Metal Coatings. Anal. Chem., 2007, 79, 2325-2333

Koch, J., Günther, D. Femtosecond laser ablation inductively coupled plasma mass spectrometry: achievements and remaining problems. Analytical and Bioanalytical Chemistry, 2007, 387/1, 149-153

Tanner, M., Günther, D. Signal acquisition in #s time resolution for in-torch LA-ICP-MS. J.

Anal. At. Spectrom., 2007, 22, 1189–1192

Hochstrasser-Kurz, S., Mueller, Y., Latkoczy, C., Virtanen, S., Schmutz, P., Analytical characterization of the corrosion mechanisms of WC-Co by electrochemical methods and inductively coupled plasma mass spectroscopy. Corrosion Science, 2007, 49 (4), 2002-2020

Vasconcelos, RP., Reis-Santos, P., Tanner, S., Fonseca, V., Latkoczy, C., Günther, D., Costa, MJ., Cabral, H. Discriminating estuarine nurseries for five fish species through otolith elemental fingerprints. Marine Ecology Progress Series, 2007, 350, 117-126

Hannemann, St, Grunwaldt, J-D., Lienemann, P., Guenther,D., Krumeich, F., Pratsinis, S. E., Baiker, A. Combination of flame synthesis and high-throughput experimentation: The preparation of alumina-supported noble metal particles and their application in the partial oxidation of methane. Applied Catalysis A-General, 2007, 316 (2), 226-239

Schmidt,V., Hirt,A., Hametner, K., Günther, D. Magnetic anisotropy of carbonate minerals at room temperature and 77 K. American Mineralogist, 2007, 92, 1673-1684

Schweizer S. , Hattendorf B. , Schneider P., Aeschlimann B., Gauckler L., Müller R., Günther D. Preparation and characterization of calibration standards for bone density determination by micro-computed tomography. Analyst, 2007, 132, 1040 - 1045

Quitte, G., Halliday, Alex N., Meyer, Bradley S., Markowski, A., Latkoczy, Ch., Günther, D. Correlated iron 60, nickel 62, and zirconium 96 in refractory inclusions and the origin of the solar system. Astrophysical Journal, 2007, 655(1), 678-684

Vermeesch, P.,Seward, D., Latkoczy, Ch., Wipf, M., Günther, D., Baur, H. alpha-Emitting mineral inclusions in apatite, their effect on (U-Th)/He ages, and how to reduce it. Geochimica et Cosmochimica Acta, 2007, 71(7), 1737-1746

Guillong, M., Heimgartner, P., Kopajtic, Z., Günther, D., Günther-Leopold, I. A laser ablation system for the analysis of radioactive samples using inductively coupled plasma mass spectrometry. J. Anal. At. Spectrom., 2007, 22, 399 - 402

Horvath, M., Guillong, M., Izmer, A., Kivel, N., Restani, R., Günther-Leopold, I., Opitz

65

Coutureau, J., Hellwig, Ch., Günther, D. Analysis of xenon gas inclusions in nuclear fuel using laser ablation ICP-MS. J. Anal. At. Spectrom. 2007, 22, 1266 - 1274

Luo, Y., Gao, S., Longerich, Henry P., Günther, D., Wunderli, S., Yuan, Hong-Lin Liu, Xiao-Ming. The uncertainty budget of the multi-element analysis of glasses using LA-ICP-MS. J.

Anal. At. Spectrom., 2007, 22, 122-130

Wanner H., Gu H., Hattendorf B., Günther D., Dorn S. Tracking parasitoids with the stable isotope 44Ca in agroecosystems, Agriculture. Ecosystems & Environment, 2007, 118, 143-148

66

Group Prof. A. Hierlemann, Laboratorium für Physikalische Elektronik, Dept. Physik,

ETH Hönggerberg

Frauke Greve, Livia Seemann, Andreas Hierlemann, Jan Lichtenberg, “Hybrid microsystem for parallel perfusion experiments on living cells”, Journal of Micromechanical Systems, 2007, 17, 1721-1730. Antonio Tricoli, Markus Graf, Felix Mayer, Stéphane Kühne, Andreas Hierlemann and Sotiris E. Pratsinis, "Micropatterning Layers by Flame Aerosol Deposition - Annealing", Advanced Materials, 2007, in press. Y. Li, C. Vancura, D. Barrettino, M. Graf, C. Hagleitner, A. Kummer, M. Zimmermann, K.-U. Kirstein, A. Hierlemann, “Monolithic CMOS multi-transducer gas sensor microsystem for organic and inorganic analytes”, Sensor and Actuators B, Chemical, 2007, 126, 431-440. C. Vancura, Yue Li, J. Lichtenberg, K.-U. Kirstein, A. Hierlemann, “Liquid-phase chemical and biochemical detection using fully integrated magnetically actuated complementary metal oxide semiconductor resonant cantilever sensor systems”, Anal. Chem. 2007, 79 (19), 1646-1654. U. Frey, M. Graf, S. Taschini, K.U. Kirstein, A. Hierlemann, “A digital CMOS architectures for a microhotplate array”, IEEE Journal of Solid-State Circuits, 2007, 42 (2), 441-450. D. Barrettino, P. Malcovati, M. Graf M, A. Hierlemann, “CMOS-based monolithic controllers for smart sensors comprising micromembranes and microcantilevers”, IEEE Transactions on Circuits and Systems I, 2007, 54 (1), 141-152.

67

Group of E. Pretsch, Inst. Biogeochem. & Pollutant Dynam., ETH Zürich

L. Bodis, A. Ross, E. Pretsch, „A novel spectral similarity measure“, Chemom. Intell. Lab. Syst. 2007, 85, 1-8. E. Pretsch, „The new wave of ion-selective electrodes“, Trends. Anal. Chem. 2007, 26, 46-51. A. Malon, E. Bakker, E. Pretsch, „Backside Calibration Potentiometry: Ion activity measurements with selective supported liquid membranes by calibrating from the back side of the membrane“, Anal. Chem. 2007, 79, 632-638. W. E. Morf, E. Pretsch, N. F. de Rooij, „Computer simulation of ion-selective membrane electrodes and related systems by finite-difference procedures“, J. Electroanal. Chem. 2007, 602, 43-54. G. Jágerszki, R.E. Gyurcsányi, L. Höfler, E. Pretsch, „Hybridization-modulated ion fluxes through peptide-nucleic-acid-functionalized gold nanotubes. A new approach to quantitative label-free DNA analysis“, Nano Lett. 2007, 7, 1609-1612. R. Thürer, T. Vigassy, M. Hirayama, J. Wang, E. Bakker, E. Pretsch, „Potentiometric immunoassay with quantum dot labels“, Anal. Chem. 2007, 79, 5107-5110. E. Bakker, E. Pretsch, „Modern potentiometry“, Angew. Chem., Int. Ed. 2007, 46, 5660-5668; Angew. Chem. 2007, 119, 5758-5767. W. Ngeontae, Y. Xu, Ch. Xu, W.Aeungmaitrepirom, T. Tuntulani, E. Pretsch, E. Bakker, „Sensitivity and working range of backside calibration potentiometry“, Anal. Chem. 2007, 79, 8705-8711.

68

Group Dr. Ralph Schlapbach, Functional Genomics Center Zurich, ETH&UZH

Ahrens, C. H.; Wagner, U.; Rehrauer, H. K.; Türker, C.; Schlapbach, R., Current challenges and approaches for the synergistic use of systems biology data in the scientific community. In Plant

Systems Biology 1st ed.; Baginsky, S.; Alisdair, F. R., Eds. Springer Verlag (Birkhäuser): Berlin, 2007; Vol. 97, p 357. Bodenmiller, B.; Malmstrom, J.; Gerrits, B.; Campbell, D.; Lam, H.; Schmidt, A.; Rinner, O.; Mueller, L. N.; Shannon, P. T.; Pedrioli, P. G.; Panse, C.; Lee, H. K.; Schlapbach, R.; Aebersold, R., PhosphoPep--a phosphoproteome resource for systems biology research in Drosophila Kc167 cells. Mol Syst Biol 2007, 3, ( ), 139. Brunner, E.; Gerrits, B.; Scott, M.; Roschitzki, B.; Baginsky, S., Differential display and protein quantification. In Plant Systems Biology 1st ed.; Baginsky, S.; Alisdair, F. R., Eds. Springer Verlag (Birkhäuser): Berlin, 2007; Vol. 97, p 357. Cannavo, E.; Gerrits, B.; Marra, G.; Schlapbach, R.; Jiricny, J., Characterization of the interactome of the human MutL homologues MLH1, PMS1, and PMS2. J Biol Chem 2007, 282, (5 ), 2976-86. Gyenesei, A.; Wagner, U.; Barkow-Oesterreicher, S.; Stolte, E.; Schlapbach, R., Mining co-regulated gene profiles for the detection of functional associations in gene expression data. Bioinformatics 2007, 23, (15 ), 1927-35. Munton, R. P.; Tweedie-Cullen, R.; Livingstone-Zatchej, M.; Weinandy, F.; Waidelich, M.; Longo, D.; Gehrig, P.; Potthast, F.; Rutishauser, D.; Gerrits, B.; Panse, C.; Schlapbach, R.; Mansuy, I. M., Qualitative and Quantitative Analyses of Protein Phosphorylation in Naive and Stimulated Mouse Synaptosomal Preparations. Mol Cell Proteomics 2007, 6, (2 ), 283-293. Potthast, F.; Gerrits, B.; Hakkinen, J.; Rutishauser, D.; Ahrens, C. H.; Roschitzki, B.; Baerenfaller, K.; Munton, R. P.; Walther, P.; Gehrig, P.; Seif, P.; Seeberger, P. H.; Schlapbach, R., The Mass Distance Fingerprint: a statistical framework for de novo detection of predominant modifications using high-accuracy mass spectrometry. J Chromatogr B 2007, 854, (1-2 ), 173-82. Rehrauer, H.; Zoller, S.; Schlapbach, R., MAGMA: analysis of two-channel microarrays made easy. Nucleic Acids Res 2007, 35, (Web Server issue ), W86-90. Sobek, J.; Aquino, C.; Schlapbach, R., Optimization workflow for the processing of high quality glass-based microarrays. Application in DNA, peptide, antibody, and carbohydrate microarraying. In Microarrays, 2nd ed.; Rampal, J. B., Ed. Humana: Totowa, N.J., 2007; Vol. 2. Sobek, J.; Aquino, C.; Schlapbach, R., Processing protocols for high qualiity glass.based microarrays. Application in DNA, peptide, antibody, and carbohydrate microarraying. In Microarrays, 2nd ed.; Rampal, J. B., Ed. Humana: Totowa, N.J., 2007; Vol. 2. Sobek, J.; Aquino, C.; Schlapbach, R., Quality considerations and selection of surface chemistry for glass-based DNA, peptide, antibody, carbohydrate, and small molecule microarrays. In Microarrays, 2nd ed.; Rampal, J. B., Ed. Humana: Totowa, N.J., 2007; Vol. 2.

69

Group Prof. P. A. Schubiger, Institut für Pharmazeutische Wissenschaften, ETH

Hönggerberg

K. Knogel, J. Grünberg, K. Zimmermann, S. Cohrs, M. Honer, S. M. Ametamey, P. Altevogt, M. Fogel, P. A. Schubiger, I. Novak-Hofer, ”Copper-67 radioimmunotherapy and growth inhibition by anti-L1 cell adhesion molecule monoclonal antibodies in a therapy model of ovarian cancer metastasis” Clin. Cancer Res 13(2), 603-611, (2007) S. M. Ametamey, V. Treyer, J. Streffer, M. T. Wyss, M. Schmidt, M. Blagoev, S. Hintermann, Y. P. Auberson, F. Gasparini, U. Fischer, A.. Buck „Human PET studies of metabotropic glutamate receptor subtype5 with [11C]-ABP688“ J. Nucl Med. 48, 247-252, (2007). M. T. Wyss, S. M. Ametamey, V. Treyer, A. Bettio, M. Blagoev, L. J. Kessler, C. Burger, B. Weber, M. Schmidt, F. Gasparini, A. Buck “Quantitative evaluation of 11C-ABP688 as PET ligand for the measurement of the metabotropic glutamate receptor subtype 5 using autoradiographic studies and a beta-scintillator” NeuroImage, 35, 1086-1092 (2007) M. Honer, A. Stoffel, L.J. Kessler, P. A. Schubiger, S. M. Ametamey „Radiolabeling, in vitro and in vivo evaluation of [18F]-FE-DABP688 as a PET ligand for the metabotropic glutamate receptor subtype 5” Nucl. Med. Biology, 34, 973-980 (2007). V. Treyer, J. Streffer, M. T. Wyss, A. Bettio, S. M. Ametamey, U. Fischer, M. Schmidt, F. Gasparini, C. Hock, A. Buck „Evaluation of the metabotropic glutamate receptor subtype5 using PET and [11C]-ABP688, assessment of methods“ J. Nucl Med. 48, 1207-1215, (2007).

70

Group Prof. R. Zenobi, Laboratorium für Organische Chemie, ETH Hönggerberg

A. Wortmann, M. C. Heine, O. Wilhelm, A. Kistler-Momotova, S. E. Pratsinis, and R. Zenobi, Shrinking Dtoplets in Electrospray Ionization and their Influence on Chemical

Equilibria, J. Am. Soc. Mass Spectrom. 2007, 18, 385-393. O. Yanes, F. X. Aviles, R. Wenzel, A. Nazabal, R. Zenobi, and J. J. Calvete, Proteomic

Profiling of a Snake Venom using Cryodetection MALDI-TOF Mass Spectrometry, J. Am. Soc. Mass Spectrom. 2007, 18, 600-606. C. G. Clark, Jr., R. J. Wenzel, E. V. Andreitchenko, W. Steffen, R. Zenobi, and K. Müllen, Controlled MegaDalton Assembly with Locally Stiff but Globally Flexible Polyphenylene

Dendrimers, J. Am. Chem. Soc. 2007, 129, 3292-3301. C. Emmenegger, A. Reinhardt, C. Hueglin, R. Zenobi, and M. Kalberer, Evaporative Light

Scattering: a Novel Detection Method for the Quantitative Analysis of Humic-like Substances

in Aerosols, Envir. Sci. Technol. 2007, 41, 2473-2478. A. Wortmann, T. Pimenova, S. Alves, and R. Zenobi, Investigation of the First Shot

Pheonmenon in MALDI, The Analyst 2007, 132, 199-207. H. Chen, A. Wortmann, W. Zhang, and R. Zenobi, Rapid in-vivo Finterprinting of Non-

volatile Compounds in Breath by Extractive Electrospray Ionization Quadrupole Time-of-

Flight Mass Spectrometry, Angew. Chem. Internat. Ed. 2007, 119, 580-583. W. Zhang, B.-S. Yeo, T. Schmid, and R. Zenobi, Single Molecule Tip-enhanced Raman

Spectroscopy with Ag tips, J. Phys. Chem. C 2007, 111, 1733-1738. H. Chen, Y. Sun, A. Wortmann, H. Gu, and R. Zenobi, Differentiation of Maturity And

Quality of Fruit Using Non-Invasive Extractive Electrospray Ionization Quadrupole Time-of-

Flight Mass Spectrometry, Anal. Chem. 2007, 79, 1447-1455. C. Bovet, A. Wortmann, S. Eiler, F. Granger, M. Ruff, B. Gerrits, D. Moras, and R. Zenobi, Estrogen receptor – ligand complexes measured by nanoelectrospray mass spectrometry: an

approach for the screening of endocrine disruptors, Protein Sci. 2007, 16, 938-946. H. Chen, A. Wortmann, and R. Zenobi, Neutral Desorption Sampling Coupled to Extractive

Electrospray Ionization Mass Spectrometry for Rapid Differentiation of Biosamples by

Metabolic Fingerprinting (Special Feature: Tutorial), J. Mass Spectrom. 2007, 42, 1123-1132. B.-S. Yeo, T. Schmid, W. Zhang, and R. Zenobi, Towards Rapid Nanoscale Chemical

Analysis using Tip-enhanced Raman Spectroscopy with Ag-Coated Dielectric Tips, Anal. Bioanal. Chem. 2007, 387, 2655-2662. V. Samburova, T. Didenko, E. Kunenkov, C. Emmenegger, R. Zenobi, and M. Kalberer, Functional Group Analysis of High Molecular Weight Comounds in the Water-soluble

Fraction of Organic Aerosols, J. Atmos. Chem. 2007, 41, 4703-4710. A. Reinhardt, C. Emmenegger, B. Gerrits, C. Panse, J. Dommen, U. Baltensperger, R. Zenobi, and M. Kalberer, Ultra-high Mass Resolution and Accurate Mass Measurements as a New

Tool to Characterize Oligomers in Secondary Organic Aerosol, Anal. Chem. 2007, 79, 4079-4082.

71

M. Dashtiev, E. Wäfler, M. Gorshkov, F. Hillenkamp, and R. Zenobi, Positive and Negative

Analyte Ion Yields in Matrix-assisted Laser Desorption/Ionization, Int. J. Mass Spectrom. 2007, 268, 122-130 (2007) (Roepstorff special issue). S. Mathur, M. Badertscher, M. Scott, and R. Zenobi, Critical Evaluation of Mass

Spectrometric Measurement of Dissociation Constants: Accuracy and Cross-Validation

against Surface Plasmon Resonance and Circular Dichroism for the Calmodulin-Melittin

System, Phys. Chem. Chem. Phys. 2007, 9, 6187-6198. W. Zhang, X. D. Cui, B.-S. Yeo, T. Schmid, C. Hafner, and R. Zenobi, Nanoscale Roughness

on Metal Surfaces Can Increase Tip-Enhanced Raman Scattering by an Order of Magnitude, Nano Lett. 2007, 7, 1401-1405. D. Touboul, M. C. Jecklin, and R. Zenobi, Rapid and Accurate Measurements of Gas-Phase

Basicity of Peptides and Proteins at Atmospheric Pressure by Electrosonic Spray Ionization-

Mass Spectometry (Letter), J. Phys. Chem. B 2007, 111, 11629-11631. C. G. Clark, R. J. Wenzel, E. V. Andreitchenko, W. Steffen, R. Zenobi, and K. Müllen,

Solvophobically-driven 3-D self-assembly of "exploded"-type polyphenylene dendrimers, New J. Chem. 2007, 31, 1300-1305. H. Chen, D. Touboul, M. J. Jecklin, J. Zheng, M. Luo, and R. Zenobi, Manipulation of Charge

States of Biopolymer Ions by Atmospheric Pressure Ion/Molecule Reactions Implemented in

an EESI Source, Eur. J. Mass Spectrom. 2007, 13, 273-279. X. Cui, W. Zhang, B.-S. Yeo, R. Zenobi, C. Hafner, and D. Erni, Tuning the Resonance

Frequency of Ag-coated Dielectric Tips, Opt. Exp. 2007, 15, 8309-8316. H. Chen, S. Yang, A. Wortmann, and R. Zenobi, Neutral Desorption Sampling of Living

Objects for Rapid Analysis by Extractive Electrospray Ionization Mass Spectrometry, Angew. Chem. Int. Ed. 2007, 119, 7735-7738. W. Zhang, T. Schmid, B.-S. Yeo, and R. Zenobi, Tip-enhanced Raman Spectroscopy Reveals

Rich Nanoscale Adsorption Chemistry of 2-Mercaptopyridine on Ag, Israel J. Chem. (R. N. Zare special issue) 2007, 47, 111 – 118. T. Schmid, B.-S. Yeo, W. Zhang, and R. Zenobi, Use of Tip-Enhanced Vibrational

Spectroscopy for Analytical Applications in Chemistry, Biology, and Materials Science, in Advances in Nano-Optics and Nano-Photonics, Eds. S. Kawata and V. M. Shalaev (Elsevier, Amsterdam 2007). H. Chen and R. Zenobi, Direct Analysis of Living Objects by Extractive Electrospray

Ionization Mass Spectrometry, (Highlights of Analytical Chemistry in Switzerland), Chimia 2007, 61, 834.

72

Group Prof. Dr. U. Baltensperger, Laboratory of Atmospheric Chemistry,

Paul Scherrer Institut Alfarra, M.R.; Prevot, A.S.H.; Szidat, S.; Sandradewi, J.; Weimer, S.; Lanz, V.A.; Schreiber, D.; Mohr, M. , Baltensperger, U., Identification of the mass spectral signature of organic aerosols from wood burning emissions, Environ. Sci.Technol., 2007, 41, 16, 5770-5777. Aymoz, G.; Jaffrezo, J.L.; Chapuis, D.; Cozic, J. , Maenhaut, W., Seasonal variation of PM10 main constituents in two valleys of the French Alps. I: EC/OC fractions, Atmos. Chem. Phys., 2007, 7, 3, 661-675. Bae, M.S.; Demerjian, K.L.; Schwab, J.J.; Weimer, S.; Hou, J.; Zhou, X.L.; Rhoads, K. , Orsini, D., Intercomparison of real time ammonium measurements at urban and rural locations in New York, Aerosol Sci. Technol., 2007, 41, 3, 329-341. Bae, M.-S.; Schwab, J.J.; Zhang, Q.; Hogrefe, O.; Demerjian, K.L.; Weimer, S.; Rhoads, K.; Orsini, D.; Venkatachari, P., Hopke, P.K., Interference of organic signals in highly time resolved nitrate measurements by low mass resolution aerosol mass spectrometry, J. Gephy.

Res., 2007, 112, D22305, doi:10.1029/2007JD008614. Battipaglia, G.; Cherubini, P.; Saurer, M.; Siegwolf, R.T.W.; Strumia, S. , Cotrufo, M.F., Volcanic explosive eruptions of the Vesuvio decrease tree-ring growth but not photosynthetic rates in the surrounding forests, Global Change Biology, 2007, 13, 6, 1122-1137. Boettger, T.; Haupt, M.; Knoller, K.; Weise, S.M.; Waterhouse, J.S.; Rinne, K.T.; Loader, N.J.; Sonninen, E.; Jungner, H.; Masson-Delmotte, V.; Stievenard, M.; Guillemin, M.T.; Pierre, M.; Pazdur, A.; Leuenberger, M.; Filot, M.; Saurer, M.; Reynolds, C.E.; Helle, G. , Schleser, G.H., Wood cellulose preparation methods and mass spectrometric analyses of d13C, d18O, and nonexchangeable d2H values in cellulose, sugar, and starch: An interlaboratory comparison, Anal. Chem., 2007, 79, 12, 4603-4612. Bukowiecki, N.; Gehrig, R.; Hill, M.; Lienemann, P.; Zwicky, C.N.; Buchmann, B.; Weingartner, E. , Baltensperger, U., Iron, manganese and copper emitted by cargo and passenger trains in Zurich (Switzerland): Size-segregated mass concentrations in ambient air, Atmos. Environ., 2007, 41, 4, 878-889. Canagaratna, M.R.; Jayne, J.T.; Jimenez, J.L.; Allan, J.D.; Alfarra, M.R.; Zhang, Q.; Onasch, T.B.; Drewnick, F.; Coe, H.; Middlebrook, A.; Delia, A.; Williams, L.R.; Trimborn, A.M.; Northway, M.J.; DeCarlo, P.F.; Kolb, C.E.; Davidovits, P. , Worsnop, D.R., Chemical and microphysical characterization of ambient aerosols with the aerodyne aerosol mass spectrometer, Mass Spectrometry Reviews, 2007, 26, 2, 185-222. Chirico, R.; Spezzano, P. , Cataldi, D., Gas-particle partitioning of polycyclic aromatic hydrocarbons during the spring and summer in a suburban site near major traffic arteries, Polycyclic Aromatic Compounds, 2007, 27, 5, 401-423. Collaud Coen, M.; Weingartner, E.; Nyeki, S.; Cozic, J.; Henning, S.; Verheggen, B.; Gehrig, R., Baltensperger, U., Long-term trend analysis of aerosol variables at the high alpine site Jungfraujoch, Geophys. Res., 2007, 112, D13213, doi: 10.1029/2006JD007995.

73

Cozic, J.; Verheggen, B.; Mertes, S.; Connolly, P.; Bower, K.; Petzold, A.; Baltensperger, U. , Weingartner, E., Scavenging of black carbon in mixed phase clouds at the high alpine site Jungfraujoch, Atmos. Chem. Phys., 2007, 7, 7, 1797-1807. Crosier, J.; Jimenez, J.L.; Allan, J.D.; Bower, K.N.; Williams, P.I.; Alfarra, M.R.; Canagaratna, M.R.; Jayne, J.T.; Worsnop, D.R. , Coe, H., Technical note: Description and use of the new jump mass spectrum mode of operation for the aerodyne quadrupole aerosol mass spectrometers (Q-AMS), Aerosol Sci.Technol., 2007, 41, 9, 865-872. David, T.S.; Henriques, M.O.; Kurz-Besson, C.; Nunes, J.; Valente, F.; Vaz, M.; Pereira, J.S.; Siegwolf, R.; Chaves, M.M.; Gazarini, L.C. , David, J.S., Water-use strategies in two co-occurring Mediterranean evergreen oaks: surviving the summer drought, Tree Physiology, 2007, 27, 6, 793-803. De Micco, V.; Saurer, M.; Aronne, G.; Tognetti, R. , Cherubini, P., Variations of wood anatomy and $13C within-tree rings of coastal Pinus pinaster showing intra-annual density fluctuations, Iawa Journal, 2007, 28, 1, 61-74. Drewnick, F.; Schneider, J.; Hings, S.S.; Hock, N.; Noone, K.; Targino, A.; Weimer, S. , Borrmann, S., Measurement of ambient, interstitial, and residual aerosol particles on a mountaintop site in Central Sweden using an aerosol mass spectrometer and a CVI, Atmos.

Chem., 2007, 56, 1-20. Drobinski, P.; Steinacker, R.; Richner, H.; Baumann-Stanzer, K.; Beffrey, G.; Benech, B.; Berger, H.; Chimani, B.; Dabas, A.; Dürr, B.; Flamant, C.; Frioud, M.; Furger, M.; Gröhn, I.; Gubser, S.; Gutermann, T.; Häberli, C.; Häller-Scharnhorst, E.; Jaubert, G.; Lothon, M.; Mitev, V.; Pechinger, U.; Piringer, M.; Ratheiser, M.; Ruffieux, D.; Seiz, G.; Spatzierer, M.; Tschannett, S.; Vogt, S.; Werner, R. , Zängl, G., Föhn in the Rhine Valley during MAP: A review of its multiscale dynamics in complex valley geometry, Quarterly Journal of the Royal

Meteorological Society, 2007, 133, 897-916. Furger, M., Book review: Symon et al. (Eds)., Arctic Climate Impact Assessment, Meteorologische Zeitschrift, 2007, 16, 3, 317-318 doi:10.1127/0941-2948/2007/0211. Gehrig, R.; Hill, M.; Lienemann, P.; Zwicky, C.N.; Bukowiecki, N.; Weingartner, E.; Baltensperger, U. , Buchmann, B., Contribution of railway traffic to local PM10 concentrations in Switzerland, Atmos. Environ., 2007, 41, 5, 923-933. Gilmanov, T.G.; Soussana, J.F.; Aires, L.; Allard, V.; Ammann, C.; Balzarolo, M.; Barcza, Z.; Bernhofer, C.; Campbell, C.L.; Cernusca, A.; Cescatti, A.; Clifton-Brown, J.; Dirks, B.O.M.; Dore, S.; Eugster, W.; Fuhrer, J.; Gimeno, C.; Gruenwald, T.; Haszpra, L.; Hensen, A.; Ibrom, A.; Jacobs, A.F.G.; Jones, M.B.; Lanigan, G.; Laurila, T.; Lohila, A.; Manca, G.; Marcolla, B.; Nagy, Z.; Pilegaard, K.; Pinter, K.; Pio, C.; Raschi, A.; Rogiers, N.; Sanz, M.J.; Stefani, P.; Sutton, M.; Tuba, Z.; Valentini, R.; Williams, M.L. , Wohlfahrt, G., Partitioning European grassland net ecosystem CO2 exchange into gross primary productivitiy and ecosystem respiration using light response function analysis, Agriculture, Ecosystems and

Environment, 2007, 121, 93-120.

74

Gysel, M.; Crosier, J.; Topping, D.O.; Whitehead, J.D.; Bower, K.N.; Cubison, M.J.; Williams, P.I.; Flynn, M.J.; McFiggans, G.B. , Coe, H., Closure study between chemical composition and hygroscopic growth of aerosol particles during TORCH2, Atmospheric

Chemistry and Physics, 2007, 7, 23, 6131-6144. Jäggi, M. , Fuhrer, J., Oxygen and carbon isotopic signatures reveal a long-term effect of free-air ozone enrichment on leaf conductance in semi-natural grassland Atmos. Environ., 2007, doi:10.1016/j.atmosenv.2007.07.044. Jenk, T.M.; Szidat, S.; Schwikowski, M.; Gaggeler, H.W.; Wacker, L.; Synal, H.A. , Saurer, M., Microgram level radiocarbon (C-14) determination on carbonaceous particles in ice, Nuclear Instruments & Methods in Physics Research Section B-Beam Interactions with

Materials and Atoms, 2007, 259, 1, 518-525. Keel, S.G.; Siegwolf, R.T.W.; Jaggi, M. , Körner, C., Rapid mixing between old and new C pools in the canopy of mature forest trees, Plant Cell and Environment, 2007, 30, 8, 963-972. Keller, J.; Bojinski, S. , Prevot, A.S.H., Simultaneous retrieval of aerosol and surface optical properties using data of the Multi-angle Imaging SpectroRadiometer (MISR), Remote Sensing

of Environment, 2007, 107, 1-2, 120-137. Lanz, V.A.; Alfarra, M.R.; Baltensperger, U.; Buchmann, B.; Hueglin, C. , Prevot, A.S.H., Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra, Atmos. Chem. Phys., 2007, 7, 6, 1503-1522. Liu, L.; Andreani-Aksoyoglu, S.; Keller, J.; Ordóñez, C.; Junkermann, W.; Hak, C.; Braathen, G.O.; Reimann, S.; Astorga-Llorens, C.; Schultz, M.; Prevot, A.S.H. , Isaksen, I.S.A., A photochemical modeling study of ozone and formaldehyde generation and budget in the Po basin, Geophys. Res. , 2007, 112, D22303, doi:10.1029/2006JD008172. Liu, L.; F. Flatøy; C. Ordoñez; G.O. Braathen; C. Hak; W. Junkermann; S. Andreani-Aksoyoglu; J. Mellqvist; B. Galle; A.S.H. Prévôt , Isaksen, I.S.A., Photochemical modelling in the Po basin with focus on formaldehyde and ozone, Atmos. Chem. Phys., 2007, 7, 121-137. Mertes, S.; Verheggen, B.; Walter, S.; Connolly, P.; Ebert, M.; Schneider, J.; Bower, K.N.; Cozic, J.; Weinbruch, S.; Baltensperger, U. , Weingartner, E., Counterflow virtual impact or based collection of small ice particles in mixed-phase clouds for the physico-chemical characterization of tropospheric ice nuclei : Sampler description and first case study, Aerosol

Sci. Technol., 2007, 41, 9, 848-864. Novak, K.; Cherubini, P.; Saurer, M.; Fuhrer, J.; Skelly, J.M.; Kräuchi, N. , Schaub, M., Ozone air pollution effects on tree-ring growth, $13C, visible foliar injury and leaf gas exchange in three ozone-sensitive woody plant species, Tree Physiology, 2007, 27, 7, 941-949. Ólafsson, H.; Furger, M. , Brümmer, B., The weather and climate of Iceland, Meteorologische

Zeitschrift, 2007, 16, 1, 5-8.

75

Ordóñez, C.; Brunner, D.; Staehelin, J.; Hadjinicolaou, P.; Pyle, J.A.; Jonas, M.; Wernli, H. , Prevot, A.S.H., Strong influence of lowermost stratospheric ozone on lower tropospheric background ozone changes over Europe, Geophys. Res. Lett., 2007, 34, L07805, doi:10.1029/2006GL029113. Petzold, A.; Weinzierl, B.; Huntrieser, H.; Stohl, A.; Real, E.; Cozic, J.; Fiebig, M.; Hendricks, J.; Lauer, A.; Law, K.; Roiger, A.; Schlager, H. , Weingartner, E., Perturbation of the European free troposphere aerosol by North American forest fire plumes during the ICARTT-ITOP Experiment in summer 2004, Atmos. Chem. Phys., 2007, 7, 5105-5127. Reinhardt, A.; Emmenegger, C.; Gerrits, B.; Panse, C.; Dommen, J.; Baltensperger, U.; Zenobi, R. , Kalberer, M., Ultrahigh mass resolution and accurate mass measurements as a tool to characterize oligomers in secondary organic aerosols, Anal. Chem., 2007, 79, 4074-4082. Reynolds-Henne, C.E.; Siegwolf, R.T.W.; Henne, S.; Treydte, K.; Esper, J. , Saurer, M., Temporal stability of climate-isotope relationships in tree rings of oak and pine (Ticino, Switzerland), Global Biogeochemical Cycles, 2007, 21, GB4009, doi:10.1029/2007GB002945. Ruff, M.; Wacker, L.; Gäggeler, H.W.; Suter, M.; Synal, H.-A. , Szidat, S., A gas ion source for radiocarbon measurements at 200 kV, Radiocarbon, 2007, 49, 2, 307-314. Salcedo, D.; Onasch, T.B.; Canagaratna, M.R.; Dzepina, K.; Huffmann, J.A.; Jayne, J.T.; Worsnop, D.R.; Kolb, C.E.; Weimer, S.; Drewnick, F.; Allan, J.D.; Delia, A.E. , Jimenez, J.L., Technical note: Use of a beam width probe in an aerosol mass spectrometer to monitor particle collection efficiency in the field, Atmos. Chem. Phys., 2007, 7, 549-556. Schaub, D.; Brunner, D.; Boersma, K.F.; Keller, J.; Folini, D.; Buchmann, B.; Berresheim, H.; Staehelin, J., SCIAMACHY tropospheric NO2 over Switzerland: Estimates of NOx lifetimes and impact of inaccurate representation of the complex Alpine topography on the retrieval Atmos. Chem. Phys., 2007, 7, 23, 5971-5987. Sjogren, S.; Gysel, M.; Weingartner, E.; Baltensperger, U.; Cubison, M.J.; Coe, H.; Zardini, A.A.; Marcolli, C.; Krieger, U.K. , Peter, T., Hygroscopic growth and water uptake kinetics of two-phase aerosol particles consisting of ammonium sulfate, adipic and humic acid mixtures, J. Aerosol Sci., 2007, 38, 2, 157-171. Steinbacher, M.; Zellweger, C.; Schwarzenbach, B.; Bugmann, S.; Buchmann, B.; Ordóñez, C.; Prevot, A.S.H. , Hueglin, C., Nitrogen oxide measurements at rural sites in Switzerland: Bias of conventional measurement techniques, J. Geophys. Res., 2007, 112, D11307, doi:10.1029/2006JD007971. Szidat, S.; Prevot, A.S.H.; Sandradewi, J.; Alfarra, M.R.; Synal, H.A.; Wacker, L. , Baltensperger, U., Dominant impact of residential wood burning on particulate matter in Alpine valleys during winter, Geophys. Res. Lett., 2007, 34, 5, L05820, doi:10.1029/2006GL028325.

76

Theis, D.E.; Jäggi, M.; Äschlimann, D.; Blum, H.; Frossard, E. , Siegwolf, R.T.W., Dynamics of soil organic matter turnover and soil respired CO2 in a temperate grassland labeled with 13C European Journal of Soil Science, 2007, doi: 10.1111/j.1365-2389.2007.00941.x. Verheggen, B.; Cozic, J.; Weingartner, E.; Bower, B.K.N.; Mertes, S.; Connolly, P.; Gallagher, M.W.; Flynn, M.; Choularton, T. , Baltensperger, U., Aerosol activation in liquid and mixed phase clouds at the high alpine site Jungfraujoch, Geophys. Res., 2007, 112, D23202, doi:10.1029/2007JD008714R. Verheggen, B.; Mozurkewich, M.; Caffrey, P.; Frick, G.; Hoppel, W., Sullivan, W., alpha-Pinene oxidation in the presence of seed aerosol: Estimates of nucleation rates, growth rates, and yield, Environ. Sci. Technol., 2007, 41, 17, 6046-6051. von Felten, S.; Hättenschwiler, S.; Saurer, M. , Siegwolf, R., Carbon allocation in shoots of alpine treeline conifers in a CO2 enriched environment, Trees-Structure and Function, 2007, 21, 3, 283-294. Wagner, T.; Burrows, J.; Deutschmann, T.; Dix, B.; Hendrick, F.; von Friedeburg, C.; Frieß, U.; Heue, K.-P.; Irie, H.; Iwabuchi, H.; Keller, J.; McLinden, C.; Oetjen, H.; Palazzi, E.; Petrotoli, A.; Platt, U.; Postylyakov, O.; Pukite, J.; Richter, A.; van Roozendael, M.; Rozanov, A.; Rozanov, V.; Sinreich, R.; Sanghavi, S. , Wittrock, F., Comparison of box-air-mass-factors and radiances for MAX-DOAS-geometries calculated from different UV/visible radiative transfer models, Atmos. Chem. Phys., 2007, 7, 1809-1833. Zhang, Q.; Jimenez, J.L.; Canagaratna, M.R.; Allan, J.D.; Coe, H.; Ulbrich, I.; Alfarra, M.R.; Takami, A.; Middlebrook, A.M.; Sun, Y.L.; Dzepina, K.; Dunlea, E.; Docherty, K.; DeCarlo, P.F.; Salcedo, D.; Onasch, T.B.; Jayne, J.T.; Miyoshi, T.; Shimono, A.; Hatakeyama, S.; Takegawa, N.; Kondo, Y.; Schneider, J.; Drewnick, F.; Borrmann, S.; Weimer, S.; Demerjian, K.; Williams, P.; Bower, K.N.; Bahreini, R., Cottrell, L.; Griffin, R.J.; Rautiainen, J.; Sun, J.Y.; Zhang, Y.M. , Worsnop, D.R., Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes, Geophys. Res. Lett., 2007, 34, 13, L13801, doi:10.1029/2007GL029979. Zieger, P.; Ruhtz, T.; Preusker, R. , Fischer, J., Dual-aureole and sun spectrometer system for airborne measurements of aerosol optical properties, Appl. Opt., 2007, 46, 35, 8542-8552.

77

Laboratory for Materials Behaviour, Paul Scherrer Institut, Villigen

Horvath, M.; Guillong, M.; Izmer, A.; Kivel, N.; Restani, R.; Günther-Leopold, I.; Opitz Coutureau, J.; Hellwig, Ch.; Günther, D. J. Anal. At. Spectrom. 2007, 22, 1266-1274. Guillong, M.; Heimgartner, P.; Kopajtic, Z.; Günther, D.; Günther-Leopold, I. J. Anal. At.

Spectrom. 2007, 22, 399-402. Romano, A.; Horvath, M.I.; Restani R. J. Nucl. Mat. 2007, 361, 62-68.

Group PD Dr. K. Rentsch, Institute for Clinical Chemistry, University Hospital Zurich

W. Bernauer, M.A. Thiel, K.M.Rentsch, Phosphate concentrations in antiglaucoma

medication, Klin Monatsbl Augenheilkund. 224, 249-251 (2007)

I. Burkard, A. von Eckardstein, K.M. Rentsch, Lipoprotein distribution and biological

variation of 24S- and 27-hydroxycholesterol in healthy volunteers, Atherosclerosis 194, 71-78 (2007)

S. Zgraggen, R. Bonafini, U. Gutteck-Amsler, K.M. Rentsch, Toxicological screening after

the REMEDI™ – comparison of a GC-MS screening with the REMEDI™, Ther Drug Monit 29, 492 (2007)

U. Gutteck-Amsler, K.M. Rentsch, Therapeutic drug monitoring of antiretroviral drugs using

LC-MS, Ther Drug Monit 29, 468 (2007)

P.H. Kook, S. Schellenberg, K.M. Rentsch, T.M. Glausch, C.E. Reusch, Evaluation of bile

acid commposition in dogs with iatrogenic hypercortisolism, J Vet Int Med 21, 596-597 (2007)

N. Corti, A. Heck, K. Rentsch, W. Zingg, C. Pauli-Magnus, Interaction study of oral

albendazole and mebendazole with short and long term oral ritonavir in healthy volunteers, Clin Pharmacol Ther 81, 108-109 (2007)

U. Gutteck-Amsler, K.M. Rentsch, Does A.M. have a tumour in the pancreas? Chimia 61, 199 (2007)

79

5

Contact Addresses

80

Contact addresses

Laboratory of Organic Chemistry, ETHZ:

! Prof. Dr. Renato Zenobi, Organic Chemistry, ETH Zürich, HCI E329, CH-8093 Zürich, Tel.: 044 / 632 4376, Fax: 044 / 632 1292, e-mail: [email protected] Research activities: Mass Spectrometry, nanoscale chemical analysis. ! Prof. Dr. Ernö Pretsch, current address Inst. für Biogeochemie und Schadstoff-dynamik, ETH Zürich, CHN F 16, CH-8092 Zürich, Tel.: 044 / 632 2926, Fax: 044 / 632 1164, e-mail: [email protected] Research activities: Computer-assisted analytical chemistry, chemical sensors. Laboratory of Inorganic Chemistry, ETHZ: ! Prof. Dr. Detlef Günther, Inorganic Chemistry, ETH Zürich, HCI G113, CH-8093 Zürich, Tel.: 044 / 632 4687, Fax: 044 / 632 1090, e-mail: [email protected] Research activities: Trace element and isotope analysis, ICP-MS, laser ablation ICP-MS, glow discharge-TOFMS, Aerosol formation and transport. Laboratory of Physical Chemistry, ETHZ:

! Prof. Beat H. Meier, Laboratory of Physical Chemistry, ETH Zürich, HCI D225,

CH-8093 Zürich, Tel.: 044 / 632 4401, Fax: 044 / 632 1621,

e-mail: [email protected]

Research activities: Solid state nuclear magnetic resonance spectroscopy. ! Prof. Vahid Sandoghdar, Nano-Optics, ETH Zürich, HCI F205, CH-8093 Zürich, Tel.: 044 / 633 4621, Fax: 044 / 633 1316, e-mail: [email protected] Research activities: Nano-optics with applications to quantum optics, photonics, ultrahigh-resolution optical microscopy and biophotonics. Institute of Pharmaceutical Sciences, ETHZ:

! Dr. Irmgard Werner Kaeslin, Pharmaceutical Analytics, ETH Zürich, HCI H411, CH-8093 Zürich, Tel.: 044 / 633 7419, Fax: 044 / 633 1366, e-mail: [email protected] Research activities: Pharmaceutical analytics.

81

Institute of Mineralogy and Petrography, ETHZ:

! Dr. Eric Reusser, Mineralogy and Petrography, ETH Zürich, NO E53.2, CH-8092 Zürich, Tel.: 044 / 632 3780, Fax: 044 / 632 1088, e-mail: [email protected] Research activities: Electron microprobe, raman-spectroscopy Institute of Quantum Electronics, ETHZ:

! Prof. Andreas Hierlemann, Physical Electronics Laboratory, ETH Zürich, HPT-H4.2, CH-8093 Zürich, Tel.: 044 / 633 3494, Fax: 044 / 633 1054, e-mail: [email protected] Research activities: Bioelectronics and molecular diagnostics. Institute of Plant Sciences, ETHZ:

! Prof. Wilhelm Gruissem, Plant Biotechnology, ETH Zürich, LFW E 56.1, CH-8092 Zürich, Tel.: 044 / 632 0857, Fax: 044 / 632 1079, e-mail: [email protected] Research activities: Chloroplast systems biology, functional genomics and modeling of plant isoprenoid biosynthesis, coordination of cell cycle control and differentiation, biotechnology of cassava, rice and wheat. Institute of Molecular Systems Biology, ETHZ: ! Prof. Rudolf Aebersold, Molecular Systems Biology, ETH Zürich, HPT E 78, CH-8093 Zürich, Tel.: 044 / 633 3170, Fax: 044 / 633 1051, e-mail: [email protected]

Research activities: Quantitative proteomics, Signal transduction, Biomarkers.

Institute for Nanometallurgy, ETHZ:

! Prof. Ralph Spolenak, Nanometallurgy, ETH Zürich, HCI F529, CH-8093 Zürich, Tel.: 044 / 632 2590, Fax: 044 / 632 1101, e-mail: [email protected] Research activities: Microdiffraction, In-situ diffraction, electron microscopy, plasticity in thin films, Ion-induced grain growth. Functional Genomics Center Zürich: ! Dr. Ralph Schlapbach, Functional Genomics Center Zürich, Y32 H 52a, Winterthurerstrasse 190, CH-8057 Zürich, Tel.: 044 / 635 3920 e-mail: [email protected]

82

Research activities: Proteomics methods, mass spectrometry, surface plasmon resonance.

Department for Environmental Sciences, Eawag:

! Dr. Marc Suter, Environmental Toxicology, Ueberlandstrasse 133, CH-8600 Dübendorf, Tel.: 044 / 823 5479, Fax: 044 / 823 5028, e-mail: [email protected] Research activities: Environmental analytical chemistry, environmental fate of organic pollutants. ! Dr. Juliane Hollender, Environmental Chemistry, Ueberlandstrasse 133, CH-8600 Dübendorf, Tel.: 044 / 823 5493, Fax: 044 / 823 5028, e-mail: [email protected] Research activities: Environmental analytical chemistry, environmental fate of organic pollutants. EAWAG Kastanienbaum:

! Prof. Dr. Bernhard Wehrli, Limnological Research Centre, Seestrasse 79, CH-6047 Kastanienbaum, Tel.: 041 / 349 2117, Fax: 041 / 349 2168, e-mail: [email protected]

Research activities: Biogeochemical processes in surface waters (rivers, lakes, wetlands). Swiss Federal Laboratories for Materials Testing and Research (Empa):

! Dr. Max Wolfensberger, Organic chemistry department, Ueberlandstrasse 129, CH-8600 Dübendorf, Tel.: 044 / 823 4132, Fax: 044 / 821 6244, e-mail: [email protected] Research activities: Inorganic chemical analysis, atomic spectroscopy, organic analysis, surface chemical analysis, chemical characterization of solids. ! Dr. Peter Hofer, Mobility and Environment, Ueberlandstrasse 129, CH-8600 Dübendorf, Tel.: 044 / 823 4110, Fax: 044 / 821 6244, e-mail: [email protected] Research activities: Mobility and environment. ! Prof. Hans-Josef Hug, Nanoscale Materials Science, Ueberlandstrasse 129, CH-8600 Dübendorf, Tel.: 044 / 823 4125, e-mail: [email protected] Research activities: Forces, surfaces & magnetism. ! Dr. Heinz Vonmont, Solid State Chemistry and Analysis, Ueberlandstrasse 129, CH-8600 Dübendorf, Tel.: 044 / 823 4131, Fax: 044 / 821 6244, e-mail: [email protected] Research activities: Inorganic analytical chemistry / Characterization of solids.

83

! Dr. Martin Mohr, Combustion Engines Internal, Ueberlandstrasse 129, CH-8600 Dübendorf, Tel.: 044 / 823 4190, e-mail: [email protected] Research activities: Internal combustion engines. Paul Scherrer Institut (PSI):

! PD Dr. Urs Baltensperger, Paul Scherrer Institut, CH-5232 Villigen, Tel.: 056 / 310 2184, Fax: 056 / 310 4435, e-mail: [email protected] Research activities: Aerosols, inorganic chemical analysis, radiochemical methods. ! Dr. Thomas A. Jung, Paul Scherrer Institut, CH-5232 Villigen, Tel.: 056 / 310 4518, Fax: 056 / 310 2646, e-mail: [email protected] Research activities: Micro- and nanotechnology. ! Dr. Ines Günther-Leopold, Paul Scherrer Institut, CH-5232 Villigen, Tel.: 056 / 310 2286, Fax: 056 / 310 2203, e-mail: [email protected] Research activities: Nuclear fuels. ! Prof. Friso Van der Veen, Paul Scherrer Institut, CH-5232 Villigen, Tel.: 056 / 310 5118, Fax: 056 / 310 3151, e-mail: [email protected] Research activities: Synchrotron radiation and nanotechnology. ! PD Dr. Thomas Lippert, Paul Scherrer Institut, CH-5232 Villigen, Tel.: 056 / 310 4076, Fax: 056 / 310 2688, e-mail: [email protected] Research activities: Electrochemistry. ! Prof. August Schubiger, Paul Scherrer Institut, CH-5232 Villigen, Tel.: 056 / 310 2813, Fax: 056 / 310 2849, e-mail: [email protected] or @pharma.ethz.ch Research activities: Radiopharmaceutical chemistry, biochemistry, molecular biology, pharmacy and pharmacology.

Institute for Clinical Chemistry, University Hospital Zürich:

! Dr. Katharina Rentsch, Clinical Chemistry, University Hospital Zürich, Rämistrasse 100, CH-8091 Zürich, Tel.: 044 / 255 4590, Fax: 044 / 255 2290, e-mail: [email protected] Research activities: Development of mass spectrometric methods for the determination of small molecules and clinical validation of new markers for the monitoring of drug treatment or diagnosis of disease.

CEAC Bericht 2007 Report_2007.pdf · 3 Table of Contents 1. Preface 5 2. Joint CEAC Activities 7 3....

Documents

Transcript of CEAC Bericht 2007 Report_2007.pdf · 3 Table of Contents 1. Preface 5 2. Joint CEAC Activities 7 3....