%0 conference lecture (invited) %@ %A Pröfrock, D., Hildebrandt, L., El Gareb, F., Nack, F., Zimmermann, T., Klein, O. %D 2022 %J Analytic Conference %T ICP-MS/MS and LDIR as complementary technique in small micro- and nanoplastic Research - From method optimization to the study of environmentally relevant polymers as vector for trace metals %U %X %0 journal article %@ 1618-3258 %A Hildebrandt, L., Nack, F., Zimmermann, T., El Gareb, F., Pröfrock, D. %D 2022 %J Mitteilungen der Fachgruppe Umweltchemie und Oekotoxikologie %N 1 %P 7-10 %T Mikroplastik als Trojanisches Pferd für Spurenmetalle %U 1 %X giert auch als Trojanisches Pferd für gelöste Metallkationen. %0 lecture %@ %A Hildebrandt, L., El Gareb, F., Nack, F., Zimmermann, T., Pröfrock, D. %D 2022 %J %T Nano-; microplastics and metals - how are they related? %U %X %0 conference lecture %@ %A Hildebrandt, L., Nack, F., Zimmermann, T., Pröfrock, D. %D 2022 %J Wasser 2022 - Jahrestagung der Wasserchemischen Gesellschaft %T Mikroplastikpartikel als Sorbens für Metall- und Halbmetallionen %U %X %0 conference lecture %@ %A Klein, O., Zimmermann, T., Ebeling, A., Kruse, M., Kirchgeorg, T., Pröfrock, D. %D 2022 %J Wasser 2022 - Jahrestagung der Wasserchemischen Gesellschaft %T Technologie-kritische Elemente - Entwicklung und Anwendung einer ICP-MS/MS basierten Methode zur Messung ihrer zeitlichen Variationen in Nordsee Sedimenten %U %X %0 conference lecture %@ %A El Gareb, F., Hildebrandt, L., Zimmermann, T., Klein, O., Kerstan, A., Emeis, K., Pröfrock, D. %D 2022 %J Wasser 2022 - Jahrestagung der Wasserchemischen Gesellschaft %T Analyse des Vorkommens und der Verteilung von Mikrokunststoffen im tropischen Indischen Ozean mittels Laser Direct Infrared (LDIR) Chemical Imaging und mikrowellenunterstützter Probenaufbereitung %U %X %0 conference poster %@ %A El Gareb, F., Hildebrandt, L., Kerstan, A., Zimmermann, T., Emeis, K., Pröfrock, D. %D 2022 %J SETAC Europe 2022 - annual meeting Copenhagen %T Investigation of microplastics in the tropical Indian Ocean using Laser Direct Infrared (LDIR) Chemical Imaging and microwave-assisted sample preparation %U %X %0 journal article %@ 1751-908X %A Ebeling, A., Zimmermann, T., Klein, O., Irrgeher, J., Pröfrock, D. %D 2022 %J Geostandards and Geoanalytical Research %N 2 %P 351-378 %R doi:10.1111/ggr.12422 %T Analysis of Seventeen Certified Water Reference Materials for Trace and Technology-Critical Elements %U https://doi.org/10.1111/ggr.12422 2 %X Concentrations of elements in the aquatic environment are a key parameter for various scientific fields such as biogeochemistry, biology and environmental science. Within this context, the scientific community asks for new analytical protocols to be able to quantify more and more elements of the periodic table. Therefore, the requirements for aqueous reference materials have increased drastically. Even though a wide variety of CRMs of different water matrices are available, certified values of many elements (e.g., rare earth elements, technology-critical elements, such as Ga and In, and generally those elements which are not part of current monitoring regulations) do not yet exist. Therefore, the scientific community relies on published elemental concentrations of many CRMs provided by other researchers. Some elements of interest, such as the rare earth elements, are well studied and plenty of literature values exist. However, less studied elements, such as Ga and In, are rarely studied. In this study, an 'externally' calibrated quantification method based on an optimised online pre-concentration method, coupled with ICP-MS/MS, is used for the quantification of thirty-four elements. The method is applied to seventeen water CRMs covering freshwater, brackish water and seawater. The measured data is combined with a comprehensive literature review on non-certified values in selected water CRMs and new consensus values are suggested for various non-certified elements. %0 journal article %@ 0269-7491 %A Logemann, A., Reininghaus, M., Schmidt, M., Ebeling, A., Zimmermann, T., Wolschke, H., Friedrich, J., Brockmeyer, B., Pröfrock, D., Witt, G. %D 2022 %J Environmental Pollution %P 119040 %R doi:10.1016/j.envpol.2022.119040 %T Assessing the chemical anthropocene – Development of the legacy pollution fingerprint in the North Sea during the last century %U https://doi.org/10.1016/j.envpol.2022.119040 %X The North Sea and its coastal zones are heavily impacted by anthropogenic activities, which has resulted in significant chemical pollution ever since the beginning of the industrialization in Europe during the 19th century. In order to assess the chemical Anthropocene, natural archives, such as sediment cores, can serve as a valuable data source to reconstruct historical emission trends and to verify the effectiveness of changing environmental legislation. In this study, we investigated 90 contaminants covering inorganic and organic pollutant groups analyzed in a set of sediment cores taken in the North Seas' main sedimentation area (Skagerrak). We thereby develop a chemical pollution fingerprint that records the constant input of pollutants over time and illustrates their continued great relevance for the present. Additionally, samples were radiometrically dated and PAH and PCB levels in porewater were determined using equilibrium passive sampling. Furthermore, we elucidated the origin of lead (Pb) contamination utilizing non-traditional stable isotopic analysis. Our results reveal three main findings: 1. for all organic contaminant groups covered (PAHs, OCPs, PCBs, PBDEs and PFASs) as well as the elements lead (Pb) and titanium (Ti), determined concentrations decreased towards more recent deposited sediment. These decreasing trends could be linked to the time of introductions of restrictions and bans and therefor our results confirm, amongst possible other factors, the effectiveness of environmental legislation by revealing a successive change in contamination levels over the decades. 2. concentration trends for ΣPAH and ΣPCB measured in porewater correspond well with the ones found in sediment which suggests that this method can be a useful expansion to traditional bulk sediment analysis to determine the biologically available pollutant fraction. 3. Arsenic (As) concentrations were higher in younger sediment layers, potentially caused by emissions of corroded warfare material disposed in the study area after WW II. %0 journal article %@ 0269-7491 %A Hildebrandt, L., El Gareb, F., Zimmermann, T., Klein, O., Kerstan, A., Emeis, K., Pröfrock, D. %D 2022 %J Environmental Pollution %P 119547 %R doi:10.1016/j.envpol.2022.119547 %T Spatial distribution of microplastics in the tropical Indian Ocean based on laser direct infrared imaging and microwave-assisted matrix digestion %U https://doi.org/10.1016/j.envpol.2022.119547 %X The mean microplastic concentration of the analyzed samples was 50 ± 30 particles/fibers m−3 (1 SD, n = 21). Number concentrations ranged from 8 to 132 particles/fibers m−3 (20–300 μm). The most abundant polymer clusters were acrylates/polyurethane/varnish (49%), polyethylene terephthalate (26%), polypropylene (8%), polyethylene (4%) and ethylene-vinyl acetate (4%). 96% of the microplastic particles had a diameter <100 μm. Though inter-study comparison is difficult, the investigated area exhibits a high contamination with particulate plastics compared to other open ocean regions. A distinct spatial trend was observed with an increasing share of the size class 20–50 μm from east to west. %0 thesis %@ %A Witthoff, C. %D 2022 %J %T Entwicklung einer HPLC-ICP-MS/MS-Methode zur Erfassung von ausgewählten Arsen-Spezies in marinen Sedimenten und deren Anwendung auf einen Sedimentkern aus dem Skagerrak %U %X %0 master thesis %@ %A Rohrweber, A. %D 2022 %J %T Optimized analysis of Pu-239 and Pu-240 in geological samples via ICP–MS/MS for use as a tracer for soil erosion rates %U %X %0 online contribution %@ %A Hildebrandt, L., El Gareb, F., Hansen, J., Takyar, H., Lange, M., Zimmermann, T., Jahnke, A., Bergmann, M., Peeken, I., Tekman, M., Gerdts, G., Bellou, N., Pohl, F., Baldewein, L., Pröfrock, D., Ebinghaus, R. %D 2022 %J Coastal Pollution Toolbox %T Microplastic Compendium %U %X URL: www.microplastic-compendium.eu %0 journal article %@ 0090-4341 %A Klein, O., Zimmermann, T., Ebeling, A., Kruse, M., Kirchgeorg, T., Pröfrock, D. %D 2022 %J Archives of Environmental Contamination and Toxicology %N 4 %P 481-492 %R doi:10.1007/s00244-022-00929-4 %T Occurrence and Temporal Variation of Technology-Critical Elements in North Sea Sediments - A Determination of Preliminary Reference Values %U https://doi.org/10.1007/s00244-022-00929-4 4 %X As interest in the investigation of possible sources and environmental sinks of technology-critical elements (TCEs) continues to grow, the demand for reliable background level information of these elements in environmental matrices increases. In this study, a time series of ten years of sediment samples from two different regions of the German North Sea were analyzed for their mass fractions of Ga, Ge, Nb, In, REEs, and Ta (grain size fraction < 20 µm). Possible regional differences were investigated in order to determine preliminary reference values for these regions. Throughout the investigated time period, only minor variations in the mass fractions were observed and both regions did not show significant differences. Calculated local enrichment factors ranging from 0.6 to 2.3 for all TCEs indicate no or little pollution in the investigated areas. Consequently, reference values were calculated using two different approaches (Median + 2 median absolute deviation (M2MAD) and Tukey inner fence (TIF)). Both approaches resulted in consistent threshold values for the respective regions ranging from 158 µg kg−1 for In to 114 mg kg−1 for Ce. As none of the threshold values exceed the observed natural variation of TCEs in marine and freshwater sediments, they may be considered baseline values of the German Bight for future studies. %0 journal article %@ 0033-4545 %A Prohaska, T., Irrgeher, J., Benefield, J., Böhlke, J., Chesson, L., Coplen, T., Ding, T., Dunn, P., Gröning, M., Holden, N., Meijer, H., Moossen, H., Possolo, A., Takahashi, Y., Vogl, J., Walczyk, T., Wang, J., Wieser, M., Yoneda, S., Zhu, X., Meija, J. %D 2022 %J Pure and Applied Chemistry %N 5 %P 573-600 %R doi:10.1515/pac-2019-0603 %T Standard atomic weights of the elements 2021 (IUPAC Technical Report) %U https://doi.org/10.1515/pac-2019-0603 5 %X Y (yttrium), 2021: from 88.905 84 +/- 0.000 01 to 88.905 838 +/- 0.000 002 %0 doctoral thesis %@ %A Hildebrandt, L. %D 2021 %J %T Development and application of analytical methods to sample; isolate and characterize nano- and microplastics in aquatic environments and associated trace metals %U %X %0 journal article %@ 0267-9477 %A Klein, O., Zimmermann, T., Pröfrock, D. %D 2021 %J Journal of Analytical Atomic Spectrometry %N 7 %P 1524-1532 %R doi:10.1039/D1JA00088H %T Improved determination of technologically critical elements in sediment digests by ICP-MS/MS using N2O as a reaction gas %U https://doi.org/10.1039/D1JA00088H 7 %X The investigation of technologically critical elements (TCEs) as emerging pollutants is a constantly growing field of environmental research and societal concern. Nevertheless, existing data for most TCEs are still unsatisfactory for an accurate assessment of their potential (eco)toxicological effects on humans and the environment. The limited availability of data mainly results from the technically challenging analysis of selected TCEs. Low concentrations of TCEs in environmental matrices (μg kg−1 or lower) and the associated complex and time-consuming sample preparation pose the greatest challenges. This work aims at developing a new ICP-MS/MS-based multi-elemental approach targeting the analysis of all major TCEs (Sc, Ga, Ge, Nb, In, Te, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Yb, Lu, and Ta) in sediment, which represents one of the most important matrices for environmental research. N2O is applied as a reaction gas to overcome possible spectral interferences during ICP-MS/MS analysis. The use of N2O as a reaction gas for ICP-MS/MS analysis enabled higher oxide-product ion yields for many TCEs in comparison to the frequently used O2 cell gas. Hence, the selectivity and sensitivity of the method were improved. The presented multi-element method using N2O as a reaction gas achieved LODs between 0.00023 μg L−1 (Eu) and 0.13 μg L−1 (Te) for all analyzed TCEs. Likewise, for all analyzed elements, except for Te, recoveries between 80% and 112% were obtained for at least one of the analyzed reference materials (GBW 07313, GBW 07311, and BCR-2). %0 journal article %@ 0304-3894 %A Hildebrandt, L., Zimmermann, T., Primpke, S., Fischer, D., Gerdts, G., Pröfrock, D. %D 2021 %J Journal of Hazardous Materials %P 125482 %R doi:10.1016/j.jhazmat.2021.125482 %T Comparison and uncertainty evaluation of two centrifugal separators for microplastic sampling %U https://doi.org/10.1016/j.jhazmat.2021.125482 %X For the first time in microplastic research, an expanded uncertainty was calculated according to the “Guide to the expression of Uncertainty in Measurement” (JCGM 100:2008). Bottom-up uncertainty evaluation revealed the different sampling methods (~ 44%), sample replicates (~ 26%) and the different detection techniques (~ 16%) as the major sources of uncertainty. Depending on the number of particles detected in the samples, the relative expanded uncertainty (Urel (k =2)) ranged from 24% up to > 200% underpinning tremendous importance of sound uncertainty evaluation. Our results indicate that scientist should rethink many “observed patterns” in the literature due to being insignificant and herewith not real. %0 conference lecture %@ %A Hildebrandt, L., El Gareb, F., Pröfrock, D. %D 2021 %J Agilent Analytik-Forum 2021 %T Nano- und Mikroplastik-Analytik mittels ICP-MS/MS und LDIR Imaging - Zwei Anwendungsbeispiele %U %X %0 conference lecture %@ %A Ebeling, A., Voigt, N., Obergfäll, D., Zimmermann, T., Erbsloeh, H., Kirchgeorg, T., Weinberg, I., Irrgeher, J., Proefrock, D. %D 2021 %J The 52nd International Liège colloquium on ocean dynamics %T Corrosion protection of offshore wind farms: An emerging contamination source for the marine environment? %U %X %0 lecture %@ %A Hildebrandt, L., Zimmermann, T., Nack, F., El Gareb, F., Mitrano, D., Pröfrock, D. %D 2021 %J %T Nano-; microplastics and metals - how are they related? %U %X %0 journal article %@ 0887-0624 %A Vetere, A., Pröfrock, D., Schrader, W. %D 2021 %J Energy & Fuels %N 10 %P 8723-8732 %R doi:10.1021/acs.energyfuels.1c00491 %T Qualitative and Quantitative Evaluation of Sulfur-Containing Compound Types in Heavy Crude Oil and Its Fractions %U https://doi.org/10.1021/acs.energyfuels.1c00491 10 %X Detailed molecular analysis of complex mixtures such as crude oil and its fractions has been successfully covered by a number of groups during the past two decades. On the other side, the most glaring need is some type of method that allows quantitative analysis of a single class, compound species, or even individual compounds. Here, the problem is being complicated by the complexity of the sample and the need for individual response factors necessary for the analysis of single compounds in almost all analytical methods. This can be circumvented by using a method with uniform response like inductively coupled plasma-mass spectrometry. Sulfur is one of the most important heteroelements present in crude oil and its products due to stringent regulations. Quantification of sulfur by means of mass spectrometry has always been a challenging task. Here, we present the combination of a sulfur-selective chromatographic separation of crude oil and its fractions on a Pd-coated stationary phase with two-dimensional detection. Qualitative analysis by ultrahigh-resolution Orbitrap mass spectrometry allows a detailed understanding of individual compositions after chromatographic separation, while the quantitative data from inductively coupled plasma tandem mass spectrometry details the quantities of each part of the chromatogram. The combination of the results from both methods allows assigning three different types of sulfur species and their quantitative determination in extremely complex heavy crude oil fractions. %0 master thesis %@ %A El Gareb, F. %D 2021 %J %T Optimization of a microplastic sample preparation protocol for Laser Direct Infrared Imaging (LDIR) measurements to analyze microplastic occurence and distribution along a transect in the Indian Ocean %U %X %0 conference lecture %@ %A Klein, O., Zimmermann, T., Pröfrock, D. %D 2021 %J 6. Doktorandenseminar des DAAS %T Enhanced detection of technologically critical elements in sediment digestions via ICP-MS/MS utilizing N2O as a reaction gas %U %X %0 journal article %@ 0048-9697 %A Deng, F., Hellmann, S., Zimmerman, T., Pröfrock, D. %D 2021 %J Science of the Total Environment %P 148127 %R doi:10.1016/j.scitotenv.2021.148127 %T Using Sr-Nd-Pb isotope systems to trace sources of sediment and trace metals to the Weser River system (Germany) and assessment of input to the North Sea %U https://doi.org/10.1016/j.scitotenv.2021.148127 %X In order to trace the sources of sediment materials and trace metals in the Weser River system (Germany), and the riverine input to the North Sea, Sr, Nd and Pb isotopes, together with multi-elemental compositions, were measured for sediments collected over the entire Weser River Basin, from headwaters to the estuary. Mass fractions of metals, including Ag, Cd, and Pb, and of one metalloid, Sb, higher than their crustal abundance, were observed within the entire Weser Basin. Isotope-amount ratio n(87Sr)/n(86Sr) and εNd ranged from 0.71182 ± 0.00005 to 0.72880 ± 0.00009 and −11.3 ± 0.3 to −21.0 ± 0.3, respectively. n(206Pb)/n(204Pb), n(207Pb)/n(204Pb), and n(208Pb)/n(204Pb) ranged from 18.226 ± 0.008 to 18.703 ± 0.012, 15.613 ± 0.007 to 15.653 ± 0.012 and 38.14 ± 0.02 to 38.84 ± 0.02, respectively. Sr and Nd isotope compositions reflected primarily a mixture of natural materials derived from the Weser Basin. Pb isotope signatures indicated strong anthropogenic influences in the middle-lower Weser region. Pb isotopic compositions in the sediments from the Aller (tributary of the Weser) and its tributary suggested influence from historical Pb-Zn ore mining in the Harz Mountains that might contribute to the observed elevated mass fractions of Ag, Cd, Sb and Pb in that region. K-means cluster and principal component analysis of the Sr, Nd, and Pb isotope data yielded results consistent with their isotope systematics, supporting statistical analysis as an unsupervised tool in isotope fingerprinting studies. Sr, Nd, and Pb isotopic signatures in the sediments of the Weser were distinctively different from those of another major river discharging into the North Sea, the Elbe. This suggested that this Sr, Nd, and Pb isotope dataset can be used to distinguish riverine input of sediment materials and metals between the two rivers, thereby assessing their individual contribution to materials transported into the North Sea. %0 journal article %@ 2666-9110 %A Hildebrandt, L., Nack, F., Zimmermann, T., Pröfrock, D. %D 2021 %J Journal of Hazardous Materials Letters %P 100035 %R doi:10.1016/j.hazl.2021.100035 %T Microplastics as a Trojan horse for trace metals %U https://doi.org/10.1016/j.hazl.2021.100035 %X Due to an assumed lack of anionic binding sites (most plastics are non-polar), scientists long considered virgin particulate plastics inert towards metal ions. However, we proved significant metal sorption to microplastics at neutral pH and release in a solution mimicking gastrointestinal chemistry serving as a proof-of-principle for environmental and human bioavailability. Competitive ion-exchange incubation experiments comprised 55 metals and metalloids. Fast kinetics were observed with 45 %–75 % of As, Be, Bi, Cr, Fe, In, Pb, Th, Sn and the rare-earth element ions being sorbed after 1 h. The investigated metal and metalloid cations showed significant differences in the extent of sorption, based upon which a distinct categorization was possible. Microplastics are not only a potential danger for aquatic and human life, but - as demonstrated in this paper - also serve as a Trojan Horse for dissolved metal cations. The corresponding effects on aquatic and human health will gain higher importance in the near future due to the predicted increases of marine plastic litter and microplastic sorbents. %0 conference lecture %@ %A Deng, F., Hellmann, S., Zimmerman, T., Pröfrock, D. %D 2021 %J EGU General Assembly 2020 %R doi:10.5194/egusphere-egu2020-13793 %T Sr-Nd-Pb isotope fingerprint analysis of sediment from the river Weser (Germany) and its implication to trace human and climate-induced impacts %U https://doi.org/10.5194/egusphere-egu2020-13793 %X Sediment samples were analysed for their elemental compositions to evaluate the load of each chemical composition in the river Weser. Isotopic ratios of Sr, Nd, and Pb were measured on MC-ICP-MS (Multi-collector-Inductively Coupled Plasma-Mass Spectrometry) with the newly-developed automated prepFAST sample purification method (Retzmann et al., 2017). The Sr, Nd and Pb isotope results reported here are the first such dataset obtained from the river Weser sediment. Combined with the statistical analysis, such as the principal component analysis, the dataset allows the evaluation of the contribution of various sources to the load of the river Weser, and enables the quantification of the flux of the river to the North Sea, and an estimate of the contribution of the river system to contaminants transported into the coastal zone. These estimates will also be of interest to stakeholders and governments for targeted management interventions of the socio-economically important Weser river system %0 conference lecture %@ %A Deng, F., Hellmann, S., Zimmermann, T., Pröfrock, D. %D 2021 %J Goldschmidt2020 %T Sr-Nd-Pb isotope systems as fingerprinting tools to trace anthropogenic controls on the Weser river system (Germany) %U %X to contaminants transported into the coastal zone. %0 journal article %@ 0039-9140 %A Clases, D., Ueland, M., Gonzalez de Vega, R., Doble, P., Pröfrock, D. %D 2021 %J Talanta %P 121424 %R doi:10.1016/j.talanta.2020.121424 %T Quantitative speciation of volatile sulphur compounds from human cadavers by GC-ICP-MS %U https://doi.org/10.1016/j.talanta.2020.121424 %X This work demonstrates the first forensic application of GC-ICP-MS for improved investigations of volatile organic compounds originating from a decomposing body. Volatile organic compounds were extracted from the headspace of human remains using sorbent tubes over a total time of 39 days. To account for naturally abundant species, control sites were prepared and sampled accordingly. All samples were spiked with an internal standard to minimise drift effects and errors during sample preparation and further analysis. Compound independent quantification was possible from a single chromatogram with a standard mix containing volatile pesticide compounds representing different mass fractions of target elements for calibration. Phosphorus, sulphur and chlorine were investigated as biologically relevant elements, which potentially form detectable volatile species during decomposition. The limits of detection of these elements in the headspace were 0.7, 5.4 and 1.6 ng/L, respectively. For sulphur, we identified abundant species which increased in concentrations of up to 1310 ng/L in the headspace above the remains. The concentrations were time dependent and show potential as forensic markers to determine post-mortem intervals or decomposition states. The universal quantification, standardisation and the high sensitivity of GC-ICP-MS augments traditional GC-MS analyses. %0 conference lecture %@ %A Hildebrandt, L., Zimmermann, T., El Gareb, F., Pröfrock, D. %D 2021 %J Agilent - Microplastics in the Environment Virtual Symposium %T Nano- and Microplastics Analysis via LDIR and ICP-MS %U %X %0 journal article %@ 2375-2548 %A Van Dam, B., Zeller, M., Lopes, C., Smyth, A., Böttcher, M., Osburn, C., Zimmerman, T., Pröfrock, D., Fourqurean, J., Thomas, H. %D 2021 %J Science Advances %N 51 %P eabj1372 %R doi:10.1126/sciadv.abj1372 %T Calcification-driven CO2 emissions exceed “Blue Carbon” sequestration in a carbonate seagrass meadow %U https://doi.org/10.1126/sciadv.abj1372 51 %X Long-term “Blue Carbon” burial in seagrass meadows is complicated by other carbon and alkalinity exchanges that shape net carbon sequestration. We measured a suite of such processes, including denitrification, sulfur, and inorganic carbon cycling, and assessed their impact on air-water CO2 exchange in a typical seagrass meadow underlain by carbonate sediments. Eddy covariance measurements reveal a consistent source of CO2 to the atmosphere at an average rate of 610 ± 990 μmol m−2 hour−1 during our study and 700 ± 660 μmol m−2 hour−1 (6.1 mol m−2 year−1) over an annual cycle. Net alkalinity consumption by ecosystem calcification explains >95% of the observed CO2 emissions, far exceeding organic carbon burial and anaerobic alkalinity generation. We argue that the net carbon sequestration potential of seagrass meadows may be overestimated if calcification-induced CO2 emissions are not accounted for, especially in regions where calcification rates exceed net primary production and burial. %0 journal article %@ 0048-9697 %A Zimmermann, T., Mohammed, F., Reese, A., Wieser, M., Kleeberg, U., Pröfrock, D., Irrgeher, J. %D 2020 %J Science of the Total Environment %P 135219 %R doi:10.1016/j.scitotenv.2019.135219 %T Zinc isotopic variation of water and surface sediments from the German Elbe River %U https://doi.org/10.1016/j.scitotenv.2019.135219 %X Recent studies suggested the use of the isotopic composition of Zn as a possible tracer for anthropogenic Zn emissions. Nevertheless, studies mainly focused on sampling areas of a few km2 with well-characterized anthropogenic Zn emissions. In contrast, this study focused on analyzing a large sample set of water and sediment samples taken throughout the course of the Elbe River, a large, anthropogenically impacted river system located in Central Europe. The primary objective was to evaluate the use of the isotopic composition of Zn to trace anthropogenic Zn emission on a large regional scale. In total 18 water and 26 surface sediment samples were investigated, covering the complete course of over 700 km of the German Elbe between the German/Czech border and the German North Sea, including six tributaries. Stable isotope abundance ratios of Zn were assessed by multi-collector inductively coupled plasma mass spectrometry (MC ICP-MS) in water filtrates (<0.45 µm) and total digests of the sieved surface sediment fraction (<63 µm) after analyte/matrix separation using Bio-Rad AG MP-1 resin via a micro-column approach and application of a 64Zn/67Zn double spike. Measured isotopic compositions of δ66Zn/64ZnIRMM-3702 ranged from −0.10 ‰ to 0.32 ‰ for sediment samples, and from −0.51 ‰ to 0.45 ‰ for water samples. In comparison to historical data some tributaries still feature high mass fractions of anthropogenic Zn (e.g. Mulde, Triebisch) combined with δ66Zn/64ZnIRMM-3702 values higher than the lithogenic background. The dissolved δ66Zn/64ZnIRMM-3702 values showed a potential correlation with pH. Our results indicate that biogeochemical processes like absorption may play a key role in natural Zn isotopic fractionation making it difficult to distinguish between natural and anthropogenic processes. %0 journal article %@ 2296-8016 %A Silva Campos, M.R., Blawert, C., Mendis, C.L., Mohedano, M., Zimmermann, T., Proefrock, D., Zheludkevich, M.L., Kainer, K.U. %D 2020 %J Frontiers in Materials %P 84 %R doi:10.3389/fmats.2020.00084 %T Effect of Heat Treatment on the Corrosion Behavior of Mg-10Gd Alloy in 0.5% NaCl Solution %U https://doi.org/10.3389/fmats.2020.00084 %X In 0.5 wt.% NaCl aqueous solution, Mg-10Gd alloy shows promising corrosion resistance. The microstructure of this alloy was modified via heat treatments to understand the effect of accompanying microstructural changes on the corrosion resistance. It was found that corrosion performance depends both on the amount and the distribution of the cathodic intermetallic phases. The T4 heat treatment (24 h at 540°C) caused the Gd to distribute uniformly in the matrix, which had positive effect on corrosion resistance showing a delay in the time required for the first observation of localized corrosion. The T4 heat treated specimens, specimens aged at 200°C and 300°C, showed relatively uniform degradation and thus these heat treatments are not detrimental in terms of corrosion resistance. In contrast, heat treatment at 400°C seems to increase the formation of small cuboidal particles rich in Gd, most likely to be GdH2 particles, in the matrix, resulting in a detrimental effect on the corrosion behavior. %0 journal article %@ 2296-665X %A Hildebrandt, L., Mitrano, D., Zimmermann, T., Pröfrock, D. %D 2020 %J Frontiers in Environmental Science %P 89 %R doi:10.3389/fenvs.2020.00089 %T A Nanoplastic Sampling and Enrichment Approach by Continuous Flow Centrifugation %U https://doi.org/10.3389/fenvs.2020.00089 %X Substantial efforts have been undertaken to isolate and characterize plastic contaminants in different sample matrices in the last years as the ubiquitous presence of particulate plastic in the environment has become evident. In comparison, plastic particles <1 µm (nanoplastic) in the environment remain mostly unexplored. Adequate techniques for the enrichment, as well as the detection of nanoplastic, are lacking but are urgently needed to assess the full scope of (potential) nanoplastic pollution. Use of Pd-doped nanoplastic particles constitutes a powerful tool to develop new analytical approaches, as they can be traced accurately and with ease in a variety of complex matrices by highly sensitive, time-efficient and robust ICP-MS(/MS) techniques. In this lab-scale study, for the first time, the capability of continuous flow centrifugation to retain nanoplastic particles (∼160 nm) from ultrapure water, as well as from filtered and unfiltered water from the German Elbe River was evaluated. Depending on the pump rate, the retention efficiency for the nanoplastic particles in ultrapure water ranged from 92% ± 8% (1 L h−1) to 53% ± 5% (5 L h−1) [uc (n = 3)] and from 75% ± 5% to 65% ± 6% (uc) (2.5 L h−1) in river water. Recirculating the water through the system two and three times at the highest tested flow rate led to retention efficiencies >90%. In a proof-of-principle setup, it was demonstrated that operating two continuous flow centrifuges sequentially at different rotational speeds bears the potential to enable size- and density-selective sampling of the colloidal fraction. A significant fraction of the spiked nanoplastic particles [76% ± 5% (uc)] could be separated from a model mixture of natural particles with a well-defined mean size of approximately 3 µm. While the certified reference plankton material used here was quantitatively retained in the first centrifuge rotor together with 23.0% ± 2.2% of the effective dose of the spiked nanoplastic, the remaining fraction of the nanoplastic could be recovered in the second rotor (53% ± 5%) and the effluent [24.4% ± 2.4% (uc)]. Based on the good retention efficiencies and the demonstrated separation potential, continuous flow centrifugation has proven to be a very promising technique for nanoplastic sampling and enrichment from natural water samples. %0 journal article %@ 0045-6535 %A Reese, A., Voigt, N., Zimmermann, T., Irrgeher, J., Proefrock, D. %D 2020 %J Chemosphere %P 127182 %R doi:10.1016/j.chemosphere.2020.127182 %T Characterization of alloying components in galvanic anodes as potential environmental tracers for heavy metal emissions from offshore wind structures %U https://doi.org/10.1016/j.chemosphere.2020.127182 %X The impact of offshore constructions on the marine environment is unknown in many aspects. The application of Al- and Zn-based galvanic anodes as corrosion protection results in the continuous emission of inorganic matter (e.g. >80 kg Al-anode material per monopile foundation and year) into the marine environment. To identify tracers for emissions from offshore wind structures, anode materials (Al-based and Zn-based) were characterized for their elemental and isotopic composition. An acid digestion and analysis method for Al and Zn alloys was adapted and validated using the alloy CRMs ERM®-EB317 (AlZn6CuMgZr) and ERM®-EB602 (ZnAl4Cu1). Digests were measured for their elemental composition by ICP-MS/MS and for their Pb isotope ratios by MC ICP-MS. Ga and In were identified as potential tracers. Moreover, a combined tracer approach of the elements Al, Zn, Ga, Cd, In and Pb together with Pb isotope ratios is suggested for a reliable identification of offshore-wind-farm-induced emissions. In the Al anodes, the mass fractions were found to be >94.4% of Al, >26200 mg kg−1 of Zn, >78.5 mg kg−1 of Ga, >0.255 mg kg−1 of Cd, >143 mg kg−1 of In and >6.7 mg kg−1 of Pb. The Zn anodes showed mass fractions of >2160 mg kg−1 of Al, >94.5% of Zn, >1.31 mg kg−1 of Ga, >254 mg kg−1 of Cd, >0.019 mg kg−1 of In and >14.1 mg kg−1 of Pb. The n(208Pb)/n(206Pb) isotope ratios in Al anodes range from 2.0619 to 2.0723, whereas Zn anodes feature n(208Pb)/n(206Pb) isotope ratios ranging from 2.0927 to 2.1263. %0 journal article %@ 1759-9660 %A Zimmermann, T., von der Au, M., Reese, A., Klein, O., Hildebrandt, L., Pröfrock, D. %D 2020 %J Analytical Methods %N 30 %P 3778-3787 %R doi:10.1039/D0AY01049A %T Substituting HF by HBF4 – an optimized digestion method for multi-elemental sediment analysis via ICP-MS/MS %U https://doi.org/10.1039/D0AY01049A 30 %X Determination of elemental mass fractions in sediments plays a major role in evaluating the environmental status of aquatic ecosystems. Herewith, the optimization of a new total digestion protocol and the subsequent analysis of 48 elements in different sediment reference materials (NIST SRM 2702, GBW 07313, GBW 07311 and JMC-2) based on ICP-MS/MS detection is presented. The developed method applies microwave acid digestion and utilizes HBF4 as fluoride source for silicate decomposition. Similar to established protocols based on HF, HBF4 ensures the dissolution of the silicate matrix, as well as other refractory oxides. As HBF4 is not acutely toxic; no special precautions have to be made and digests can be directly measured via ICP-MS without specific sample inlet systems, evaporation steps or the addition of e.g. H3BO3, in order to mask excess HF. Different acid mixtures with and without HBF4 were evaluated in terms of digestion efficiency based on the trace metal recovery. The optimized protocol (5 mL HNO3, 2 mL HCL, 1 mL HBF4) allows a complete dissolution of the analyzed reference materials, as well as quantitative recoveries for a wide variety of certified analytes. Low recoveries for e.g. Sr, Ba and rare earth elements due to fluoride precipitation of HF-based digestions protocols, can be avoided by the usage of HBF4 instead. Based on the usage of high purity HBF4 all relevant trace, as well as matrix elements can be analyzed with sufficiently low LOQs (0.002 μg L−1 for U up to 6.7 μg L−1 for Al). In total, 34 elements were within a recovery range of 80%–120% for all three analyzed reference materials GBW 07313, GBW 07311 and JMC-2. 14 elements were outside a recovery range of 80%–120% for at least one of the analyzed reference materials. %0 conference lecture %@ %A Hildebrandt, L., Proefrock, D., Kerstan, A. %D 2020 %J 37. Agilent Forum Analytik Wien 2020 %T First steps in applying Quantum-Cascade-Laser Imaging for microplastic analysis in environmental samples %U %X Nevertheless, first results show that there are still some challenges to master. Especially, when it comes to the analysis of environmental samples bearing a highly complex matrix. To demonstrate the capabilities of the new QCL system it has been applied for the analysis of suspended particlulate matter sample from the German Elbe River estuary, which have been obtained during the testing of two new water-sampling approaches for microplastic. After an iterative optimization process of the spectral library, first results agree with the results obtained by the FPA-based FTIR approach. %0 conference lecture %@ %A Hildebrandt, L., Zimmermann, T., Mitrano, D., Proefrock, D. %D 2020 %J SETAC Europe Meeting %T First lab-scale feasibility study on the enrichment of nanoplastic particles from water samples by continuous flow centrifugation using metal-doped nanoplastics and ICP-MS/MS detection %U %X %0 conference lecture %@ %A Zimmermann, T., Klein, O., Reese, A., Irrgeher, J., Pröfrock, D. %D 2020 %J 53rd Annual Conference of the German Society for Mass Spectrometry DGMS including 27th ICP-MS User´s Meeting %T Boron and strontium isotope ratio analysis of the Rhine river – tracer for anthropogenic boron emissions? %U %X The combination of Sr and B isotopic compositions can be used to distinguish different inputs into a complex river system, and can therefore provide a better insight into possible sources and distribution of anthropogenic B inputs. %0 journal article %@ 1932-6203 %A Hildebrandt, L., von der Au, M., Zimmermann, T., Reese, A., Ludwig, J., Pröfrock, D. %D 2020 %J PLoS One %N 7 %P e0236120 %R doi:10.1371/journal.pone.0236120 %T A metrologically traceable protocol for the quantification of trace metals in different types of microplastic %U https://doi.org/10.1371/journal.pone.0236120 7 %X The presence of microplastic (MP) particles in aquatic environments raised concern about possible enrichment of organic and inorganic pollutants due to their specific surface and chemical properties. In particular the role of metals within this context is still poorly understood. Therefore, the aim of this work was to develop a fully validated acid digestion protocol for metal analysis in different polymers, which is a prerequisite to study such interactions. The proposed digestion protocol was validated using six different certified reference materials in the microplastic size range consisting of polyethylene, polypropylene, acrylonitrile butadiene styrene and polyvinyl chloride. As ICP-MS/MS enabled time-efficient, sensitive and robust analysis of 56 metals in one measurement, the method was suitable to provide mass fractions for a multitude of other elements beside the certified ones (As, Cd, Cr, Hg, Pb, Sb, Sn and Zn). Three different microwaves, different acid mixtures as well as different temperatures in combination with different hold times were tested for optimization purposes. With the exception of Cr in acrylonitrile butadiene styrene, recovery rates obtained using the optimized protocol for all six certified reference materials fell within a range from 95.9% ± 2.7% to 112% ± 7%. Subsequent optimization further enhanced both precision and recoveries ranging from 103% ± 5% to 107 ± 4% (U; k = 2 (n = 3)) for all certified metals (incl. Cr) in acrylonitrile butadiene styrene. The results clearly show the analytical challenges that come along with metal analysis in chemically resistant plastics. Addressing specific analysis tools for different sorption scenarios and processes as well as the underlying kinetics was beyond this study’s scope. However, the future application of the two recommended thoroughly validated total acid digestion protocols as a first step in the direction of harmonization of metal analysis in/on MP will enhance the significance and comparability of the generated data. It will contribute to a better understanding of the role of MP as vector for trace metals in the environment. %0 journal article %@ 1759-9660 %A Lechthaler, S., Hildebrandt, L., Stauch, G., Schüttrumpf, H. %D 2020 %J Analytical Methods %N 42 %P 5128-5139 %R doi:10.1039/D0AY01574A %T Canola Oil Extraction in Conjunction with a Plastic Free Separation Unit Optimises Microplastics Monitoring in Water and Sediment %U https://doi.org/10.1039/D0AY01574A 42 %X Microplastics are widely distributed in the environment and to define contamination hot spots, environmental samples have to be analysed by means of cost- as well as time-efficient and reliable standardised protocols. Due to the lipophilic characteristics of plastic, oil extraction as a fast and density-independent separation is beneficial for the crucial extraction step. It was extensively validated (480 experiments) in two test setups by using canola oil and a cost-effective, plastic-free separation unit with spiked microplastic (19 different polymer types) in the density range from ρ = 11 - 1,760 kg/m³ and in the size range from 0.02 mm - 4.4 mm. Thus, an innovative, new method combination was developed and profoundly validated for water and sediment samples using only a short settling time of 15 minutes. Some experiments were also carried out with zinc chloride to obtain additional reference data (particles ≤ 359 µm). The total mean recovery rate was 89.3%, 91.7% within the larger microplastic fraction and 85.7% for the small fraction. Compared to zinc chloride (87.6%), recovery rates differed not significantly with oil (87.1%). Furthermore, size limits were set, since the method works best with particles 0.02 mm ≥ d ≤ 3 mm. The proposed method exhibits higher efficiency (84.8% for 20 - 63 µm) for the potentially most harmful microplastic size fraction than the classic setup using brine solution. As a result, oil is a comparably effective separation medium and offers further advantages for separating water and sediment samples due to its density independence, simple and fast application and environmental friendliness. Based on this, a new extraction protocol is presented here that confirms oil separation as a sound and effective separation in microplastic analysis and identifies previously missing information. %0 conference lecture %@ %A El Gareb, F., Hildebrandt, L., Kerstan, A., Zimmermann, T., Emeis, K., Pröfrock, D. %D 2020 %J YOUMARES 11 %T Microplastics in the Indian Ocean - Analyzed by Quantum Cascade laser- based infrared imaging %U %X %0 conference lecture %@ %A Zimmermann, T., Klein, O., Reese, A., Wieser, M., Mohamed, F., Irrgeher, J., Pröfrock, D. %D 2020 %J Goldschmidt 2020 %R doi:10.46427/gold2020.3228 %T “Non-Traditional” Stable Isotope Analysis as Tracer so Identify Sources and Sinks of Inorganic Contaminants in Riverine Environments %U https://doi.org/10.46427/gold2020.3228 %X Our results clearly indicate that the exclusive focus on the quantitative analysis of metal contamination within the context of environmental research provides only limited information. The progress achieved in isotope ratio analysis over the last decade therefore opens valuable additional information for environmental scientists. %0 other %@ %A Hildebrandt, L., El Gareb, F., Zimmermann, T., Klein, O., Emeis, K., Pröfrock, D., Kerstan, A. %D 2020 %J %T Fast, Automated Microplastics Analysis Using Laser Direct Chemical Imaging : Characterizing and quantifying microplastics in water samples from marine environments %U %X It is estimated that more than 75% of the 8.3 billion metric tons of plastic produced over the last 65 years have turned into waste (1). Up to 13 million metric tons of this waste ends up in the ocean every year (2) and recent calculations estimate that more than 5.25 trillion plastic particles float in the world’s oceans (3). Scientists have demonstrated the alarming environmental ubiquity and persistence of particulate plastic in aquatic ecosystems (4). Models predict that approximately 14% of the plastic debris in the ocean surface layer can be classified as so-called microplastics (often referred to as particles between 1 μm and 5 mm in size) (5). These ingestible and potentially harmful particles have been formed by UV-induced, mechanical, or biological degradation of larger debris items (6). To verify the estimates and to meet upcoming regulatory measures (e.g., California Senate Bill 1422) and directives (MSFD, 2008/56/EC), accurate, time-efficient, and robust analytical workflows and techniques are required. %0 conference lecture %@ %A Hildebrandt, L., Voigt, N., Proefrock, D. %D 2019 %J Goldschmidt 2019 %T First evaluation of continuous flow centrifugation as a novel straightforward and non-size-disriminating sampling technique for microplastic in waters %U %X %0 journal article %@ 1618-2642 %A Retzmann, A., Blanz, M., Zitek, A., Irrgeher, J., Feldmann, J., Teschler-Nicola, M., Prohaska, T. %D 2019 %J Analytical and Bioanalytical Chemistry %N 3 %P 565-580 %R doi:10.1007/s00216-018-1489-5 %T A combined chemical imaging approach using (MC) LA-ICP-MS and NIR-HSI to evaluate the diagenetic status of bone material for Sr isotope analysis %U https://doi.org/10.1007/s00216-018-1489-5 3 %X This paper presents a combination of elemental and isotopic spatial distribution imaging with near-infrared hyperspectral imaging (NIR-HSI) to evaluate the diagenetic status of skeletal remains. The aim is to assess how areas with biogenic n(87Sr)/n(86Sr) isotope-amount ratios may be identified in bone material, an important recorder complementary to teeth. Elemental (C, P, Ca, Sr) and isotopic (n(87Sr)/n(86Sr)) imaging were accomplished via laser ablation (LA) coupled in a split stream to a quadrupole inductively coupled plasma mass spectrometer (ICP-QMS) and a multicollector inductively coupled plasma mass spectrometer (MC ICP-MS) (abbreviation for the combined method LASS ICP-QMS/MC ICP-MS). Biogenic areas on the bone cross section, which remained unaltered by diagenetic processes, were localized using chemical indicators (I(C)/I(Ca) and I(C) × 10/I(P) intensity ratios) and NIR-HSI at a wavelength of 1410 nm to identify preserved collagen. The n(87Sr)/n(86Sr) isotope signature analyzed in these areas was in agreement with the biogenic bulk signal revealed by solubility profiling used as an independent method for validation. Elevated C intensities in the outer rim of the bone, caused by either precipitated secondary minerals or adsorbed humic materials, could be identified as indication for diagenetic alteration. These areas also show a different n(87Sr)/n(86Sr) isotopic composition. Therefore, the combination of NIR-HSI and LASS ICP-QMS/MC ICP-MS allows for the determination of preserved biogenic n(87Sr)/n(86Sr) isotope-amount ratios, if the original biogenic material has not been entirely replaced by diagenetic material. %0 journal article %@ 0048-9697 %A Reese, A., Zimmermann, T., Proefrock, D., Irrgeher, J. %D 2019 %J Science of the Total Environment %P 512-523 %R doi:10.1016/j.scitotenv.2019.02.401 %T Extreme spatial variation of Sr, Nd and Pb isotopic signatures and 48 element mass fractions in surface sediment of the Elbe River Estuary - Suitable tracers for processes in dynamic environments? %U https://doi.org/10.1016/j.scitotenv.2019.02.401 %X This study indicates the general potential of combined element fingerprinting and isotope tracer approaches to elucidate processes in complex river systems. Furthermore, it represents an initial characterization of the catchment area of the Elbe River as basis for future studies on river and harbor management. %0 journal article %@ 0584-8547 %A Zimmermann, T., Retzmann, A., Schober, M., Proefrock, D., Prohaska, T., Irrgeher, J. %D 2019 %J Spectrochimica Acta B %P 54-64 %R doi:10.1016/j.sab.2018.11.009 %T Matrix separation of Sr and Pb for isotopic ratio analysis of Ca-rich samples via an automated simultaneous separation procedure %U https://doi.org/10.1016/j.sab.2018.11.009 %X This paper presents a systematic investigation of the effects of Ca on the matrix separation of Sr and Pb and subsequent isotope-amount ratio measurements using a variety of synthetic solutions and reference materials with varying Ca content during the application of an automated analyte/matrix separation approach. The separation method based on the DGA resin was optimized by using increased column bed volumes, comparing two different column sizes (1-mL and 3-mL-bed volume). Certified reference materials (synthetic calcium carbonate – MACS-3, basalt – BCR-2, saggital otolith – FEBS-1, bone meal – NIST SRM 1486, bone ash – NIST SRM 1400, and skim milk powder – BCR-063R) with varying Ca content, Ca/Sr and Ca/Pb mass fraction ratios were separated using the optimized method and analyzed for the Sr and Pb isotopic composition by multi collector inductively coupled plasma mass spectrometry (MC ICP-MS). The developed separation method based on the 3-mL-bed volume column provides quantitative recoveries (84% to 105% for Sr, 77 % to 96% for Pb), while maintaining a quantitative separation of Sr and Pb. Procedural blank levels were <0.04 ng g−1 for Sr and <0.05 ng g−1 for Pb, respectively. The method allows for the automated extraction of Sr in Ca-rich matrices with Ca/Sr mass fraction ratios of up to 4051 corresponding to an absolute Ca load of 965 µg ± 86 µg (BCR-063R, milk powder). Furthermore, the method allows for the simultaneous extraction of Pb from these matrices showing Ca/Pb mass fraction ratios of up to 42095 corresponding to an absolute Ca load of 761 µg ± 122 µg on column (NIST SRM 1400, bone tissue), respectively. %0 conference poster %@ %A Zimmermann, T., Reese, A., Voigt, N., Irrgeher, J., Proefrock, D. %D 2019 %J ANAKON 2019 %T Online matrix separation coupled to inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) for the ultra-trace analysis of seawater %U %X %0 conference poster %@ %A Zimmermann, T., Klein, O., Orth, T., Oppermann, B., Retzmann, A., Irrgeher, J., Proefrock, D. %D 2019 %J European Winter Conference on Plasma Spectrochemistry 2019 %T Analysis of anthropogenic Gd emissions into the German North Sea and potential new insights by the analysis of Gd isotope ratios in MRI contrast agents %U %X %0 conference poster %@ %A Reese, A., Voigt, N., Zimmermann, T., Irrgeher, J., Proefrock, D. %D 2019 %J ANAKON 2019 %T Characterization of galvanic anode material for corrosion protection of offshore wind farms by (laser ablation) inductively coupled plasma mass spectrometry %U %X %0 conference lecture %@ %A Reese, A., Voigt, N., Zimmermann, T., Kirchgeorg, T., Weinberg, I., Irrgeher, J., Proefrock, D. %D 2019 %J Goldschmidt 2019 %T Corrosion protection of offshore wind farms: An emerging inorganic contamination source for the marine environment? %U %X %0 conference lecture %@ %A Zimmermann, T., Reese, A., Retzmann, A., Orth, T., Klein, O., Irrgeher, J., Prohaska, T., Proefrock, D. %D 2019 %J Vortrag im Rahmen eines Arbeitskreisseminars %T Element- und Isotopenanalytik in der marinen Umweltanalytik – Anwendungsgebiete und neue Entwicklungen zur Probenvorbereitung %U %X %0 conference lecture %@ %A Hildebrandt, L., Voigt, N., Proefrock, D. %D 2019 %J International Conference on Microplastic Pollution in the Mediterranean Sea %T First evaluation of continuous flow centrifugation as a novel straightforward and non-size-discriminating sampling technique for microplastic in waters %U %X %0 conference poster %@ %A Hildebrandt, L., Voigt, N., Proefrock, D. %D 2019 %J SETAC Europe 29th Annual Meeting %T First evaluation of continuous flow centrifugation as a novel straightforward and non-size-discriminating sampling technique for microplastic in waters %U %X %0 conference poster %@ %A Reese, A., Voigt, N., Zimmermann, T., Kirchgeorg, T., Weinberg, I., Irrgeher, J., Proefrock, D. %D 2019 %J Symposium Marine resources and offshore wind farms %T Corrosion protection of offshore wind farms: An emerging contamination source for the marine environment? %U %X In this study, Al and Zn anodes from several manufacturers were analyzed using inductively coupled plasma mass spectrometry (ICP-MS) based techniques to identify suitable tracers for anode specific emissions as wells as the content of elements of environmental concern. High mass fractions of rare and/or technology- and environmentally-critical elements such as In (≤ 230 mg/kg), Ga (≤ 130 mg/kg), Cd (≤ 700 mg/kg), and Pb (≤ 20 mg/kg) were found. ICP-MS-based techniques were developed for the quantification of new tracer analytes, such as In and Ga, and applied to water, sediment and biota (Mytilidae) samples from inside and around offshore wind farms located in the German North Sea. First results of elemental concentrations in biota (Mytilidae) and spatial trends in seawater and sediment samples will be presented and discussed. %0 conference poster %@ %A Nack, F., Hildebrandt, L., Zimmermann, T., Reese, A., Proefrock, D. %D 2019 %J SETAC Europe 29th Annual Meeting %T Studying the sorption of 60 different metals to virgin and UV exposed small PE and PET microplastic using ICP-MS/MS %U %X %0 master thesis %@ %A Klein, O. %D 2019 %J %T Untersuchung von Borisotopenfraktionierung in verschiedenen Flusssystemen als potenzieller neuer Tracer fuer anthropogene Kontaminationsquellen (Masterarbeit) %U %X %0 journal article %@ 0269-7491 %A Lorenz, C., Roscher, L., Meyer, M.S., Hildebrandt, L., Prume, J., Loeder, M.G.J., Primpke, S., Gerdts, G. %D 2019 %J Environmental Pollution %P 1719-1729 %R doi:10.1016/j.envpol.2019.06.093 %T Spatial distribution of microplastics in sediments and surface waters of the southern North Sea %U https://doi.org/10.1016/j.envpol.2019.06.093 %X Microplastic pollution within the marine environment is of pressing concern globally. Accordingly, spatial monitoring of microplastic concentrations, composition and size distribution may help to identify sources and entry pathways, and hence allow initiating focused mitigation. Spatial distribution patterns of microplastics were investigated in two compartments of the southern North Sea by collecting sublittoral sediment and surface water samples from 24 stations. Large microplastics (500−5000 μm) were detected visually and identified using attenuated total reflection (ATR) Fourier transform infrared (FTIR) spectroscopy. The remaining sample was digested enzymatically, concentrated onto filters and analyzed for small microplastics (11−500 μm) using Focal Plane Array (FPA) FTIR imaging. Microplastics were detected in all samples with concentrations ranging between 2.8 and 1188.8 particles kg−1 for sediments and 0.1–245.4 particles m−3 for surface waters. On average 98% of microplastics were <100 μm in sediments and 86% in surface waters. The most prevalent polymer types in both compartments were polypropylene, acrylates/polyurethane/varnish, and polyamide. However, polymer composition differed significantly between sediment and surface water samples as well as between the Frisian Islands and the English Channel sites. These results show that microplastics are not evenly distributed, in neither location nor size, which is illuminating regarding the development of monitoring protocols. %0 journal article %@ 0141-1136 %A Hildebrandt, L., Voigt, N., Zimmermann, T., Reese, A., Proefrock, D. %D 2019 %J Marine Environmental Research %P 104768 %R doi:10.1016/j.marenvres.2019.104768 %T Evaluation of continuous flow centrifugation as an alternative technique to sample microplastic from water bodies %U https://doi.org/10.1016/j.marenvres.2019.104768 %X The scientific and public interest regarding environmental pollution with microplastic has considerably increased within the last 15 years. Nevertheless, up to now there is no widely applied standard operation procedure for microplastic sampling, resulting in a lack of inter-study comparability. In addition, many studies on microplastic occurrences do not indicate a sound methodological validation of the applied methods and procedures. This study presents an alternative volume-reduced sampling technique to sample the entire load of suspended particulate matter including microplastic particles in natural waters, based on continuous flow centrifugation. For the lab-scale validation of the proposed instrumental setup, six different microplastic types (PE, PET, PS, PVDC, EPS and PP) were used. The particles covered a size range from 1 μm to 1 mm and a density range from 0.94 g mL−1 to 1.63 g mL−1. Recoveries ranged from 95.0% ± 2.3%–99.1% ± 0.3% for virgin powders and from 96.1% ± 0.6%–99.4% ± 0.2% (1 SD, n = 2–3) for microplastic suspended in river water for 40 days. Gravimetric and microscopic analysis of the effluent indicates efficient removal of microplastic from the suspensions. Static light scattering analysis of the microplastic suspensions prior to and after centrifugation confirmed that no change of the particle size distribution has occurred – neither through aggregation nor through size-discrimination during centrifugation. Moreover, the system was tested in the field and used twice to sample suspended particulate matter from the Elbe estuary directly on site. Based on these first lab-scale experiments, continuous flow centrifugation proves a promising technique bearing potential to alleviate drawbacks such as contamination, filter clogging and particle size-discrimination of commonly used volume-reduced microplastic sampling approaches. %0 doctoral thesis %@ %A Zimmermann, T. %D 2019 %J %T Development and application of new analytical methods to describe transport processes within the German Bight using selected non-traditional isotopic systems (Dissertation) %U %X %0 journal article %@ 1438-2377 %A Tchaikovsky, A., Zitek, A., Irrgeher, J., Opper, C., Scheiber, R., Moder, K., Congiu, L., Prohaska, T. %D 2019 %J European Food Research & Technology %N 11 %P 2515-2528 %R doi:10.1007/s00217-019-03363-4 %T Chemometric tools for determining site-specific elemental and strontium isotopic fingerprints in raw and salted sturgeon caviar %U https://doi.org/10.1007/s00217-019-03363-4 11 %X This study presents a chemometric protocol for the determination of site-specific elemental and strontium isotopic fingerprints in sturgeon caviar. The elemental and strontium isotopic composition of water, fish feed, salt, raw (i.e., unsalted) and salted sturgeon caviar samples from six fish farms in Europe and Iran was determined by (multi-collector) inductively coupled plasma mass spectrometry ((MC) ICP–MS). Multiple linear regression revealed six site-specific markers absorbed from water into sturgeon caviar (n(87Sr)/n(86Sr) isotope ratio and content of Na, Mn, Cu, Mo, Fe/Ca). Salting changed the chemical composition of four (n(87Sr)/n(86Sr), Na, Mn, Fe/Ca) of the six site-specific markers significantly. Washing of salted caviar could not fully remove the influence of salt on the affected site-specific markers. Therefore, a novel mathematical procedure based on mass balance calculations was developed for determining the n(87Sr)/n(86Sr) isotope ratio absorbed from water into sturgeon caviar. The resulting variable is an estimate for the environmental strontium isotopic signal and independent of the production process. Hierarchical cluster analysis showed that the combination of the mathematically determined n(87Sr)/n(86Sr) isotope ratio of water in sturgeon caviar and two site-specific markers, which were not affected by salting (Cu, Mo), allowed differentiating salted caviar samples from six fish farms into five distinct clusters. The proposed combination of statistical and mathematical tools provides the basis for origin determination of salted sturgeon caviar using site-specific elemental and strontium isotopic fingerprints, even in cases where the initial environmental signature was altered by the production process. %0 lecture %@ %A Hildebrandt, L. %D 2019 %J %T Mikro-, Nanoplastik und Metalle – Wie hängt das zusammen? : Ringvorlesung "Ausgewählte Kapitel der Toxikologie und Umweltmedizin %U %X %0 journal article %@ 1025-6016 %A Tchaikovsky, A., Häusler, H., Kralik, M., Zitek, A., Irrgeher, J., Prohaska, T. %D 2019 %J Isotopes in Environmental and Health Studies %N 2 %P 179-198 %R doi:10.1080/10256016.2019.1577832 %T Analysis of n(87Sr)/n(86Sr), δ88Sr/86SrSRM987 and elemental pattern to characterise groundwater and recharge of saline ponds in a clastic aquifer in East Austria %U https://doi.org/10.1080/10256016.2019.1577832 2 %X Elemental and isotopic pattern of n(87Sr)/n(86Sr) and δ88Sr/86SrSRM987 were used to characterise groundwater and recharge of saline ponds in a clastic aquifer in East Austria. Therefore, shallow, artesian and thermal groundwaters of the investigated aquifer along with rainfall and rivers were analysed using (MC) ICP-MS. The n(87Sr)/n(86Sr) ratio and elemental pattern changed with aquifer depth as a result of progressing bedrock leaching and dissolution with increasing groundwater residence time. The n(87Sr)/n(86Sr) ratio of shallow groundwater below saline ponds of 0.71019 ± 0.00044 was significantly different from thermal groundwater of 0.71205 ± 0.00035 (U, k = 2). In contrast to previous theories, this result suggested no recharge of saline ponds by upwelling paleo-seawater. Isotope pattern deconvolution revealed that rainfall accounted to about 60% of the n(87Sr)/n(86Sr) ratio of shallow groundwater below saline ponds. The δ88Sr/86SrSRM987 values of groundwater decreased from about 0.25 ‰ in most shallow, to predominantly negative values of about –0.24 ‰ in artesian groundwater. This result indicated leaching and dissolution of weathered minerals. In turn, the δ88Sr/86SrSRM987 of deep thermal groundwater showed positive values of about 0.12 ‰, which suggested removal of 86Sr from solution by carbonate precipitation. These results highlight the potential of δ88Sr/86SrSRM987 signature as an additional geochemical tracer. %0 conference poster %@ %A Hildebrandt, L., Zimmermann, T., Reese, A., Proefrock, D. %D 2019 %J European Winter Conference on Plasma Spectrochemistry 2019 %T Development of a microwave-assisted digestion protocol for trace metal analysis in different types of polymers using ICP-MS/MS %U %X %0 conference lecture %@ %A Reese, A., Voigt, N., Zimmermann, T., Irrgeher, J., Proefrock, D. %D 2019 %J European Winter Conference on Plasma Spectrochemistry 2019 %T Corrosion protection of offshore wind farms: A new potential source of inorganic contaminants for the marine environment? %U %X %0 conference poster %@ %A Reese, A., Voigt, N., Zimmermann, T., Irrgeher, J., Proefrock, D. %D 2018 %J 9th Nordic Conference on Plasma Spectrochemistry %T Offshore Wind Constructions: Corrosion Protection as a New Potential Source of Inorganic Contaminants into the Marine Environment? %U %X %0 conference poster %@ %A Reese, A., Voigt, N., Zimmermann, T., Irrgeher, J., Proefrock, D. %D 2018 %J 26. ICPMS-Anwendertreffen und 13. Symposium Massenspektrometrische Verfahren der Elementspurenanalyse %T Charakterisierung galvanischer Anodenmaterialien zur Identifizierung potentieller Tracer für anorganische Kontaminanten aus Offshore-Windparks %U %X %0 conference lecture %@ %A Hildebrandt, L., Lorenz, C., Primpke, S., Gerdts, G. %D 2018 %J Conference for Young Marine Researchers, Youmares 9 Conference %T Microplastics in coastal North Sea sediments – Analyzed using Fourier Transform Infrared Spectroscopy %U %X %0 conference lecture (invited) %@ %A Irrgeher, J., Reese, A., Zimmermann, T., Proefrock, D. %D 2018 %J 9th Nordic Conference on Plasma Spectrochemistry %T Extreme natural abundance variation of multiple isotopes in the estuaries of large rivers to the North Sea %U %X %0 conference poster %@ %A Hildebrandt, L., Lorenz, C., Primpke, S., Gerdts, G. %D 2018 %J Nano and Microplastics in Technical and Freshwater Systems, Microplastics 2018 %T Microplastics in Coastal North Sea Sediments – Analyzed using Fourier Transform Infrared Spectroscopy %U %X %0 lecture %@ %A Hildebrandt, L., Gerdts, G., Proefrock, D., Primpke, S., Lorenz, C. %D 2018 %J %T Ausgewaehlte Kapitel der Toxikologie und Umweltmedizin %U %X %0 conference poster %@ %A Zimmermann, T., Wieser, M., Mohammed, F., Proefrock, D., Irrgeher, J. %D 2018 %J 9th Nordic Conference on Plasma Spectrochemistry 2018 %T A first comprehensive study in zinc isotopic variation of water and sediment surface sediment samples from the Elbe River %U %X %0 journal article %@ 1759-9660 %A Bookhagen, B., Obermaier, W., Opper, C., Koeberl, C., Hofmann, T., Prohaska, T., Irrgeher, J. %D 2018 %J Analytical Methods %N 31 %P 3864-3871 %R doi:10.1039/c8ay01192c %T Development of a versatile analytical protocol for the comprehensive determination of the elemental composition of smartphone compartments on the example of printed circuit boards %U https://doi.org/10.1039/c8ay01192c 31 %X A versatile approach to determining the elemental content of more than 50 elements in different components of electronic devices on the example of smartphones was developed. The analytical protocol is based on accurate disassembly of smartphones, a single processing microwave-assisted acid digestion followed by ICP-OES and ICP-MS measurements. Method optimization and validation were performed using the certified reference material ERM®-EZ505 electronic scrap. Combined uncertainties revealed measurement uncertainty and sample heterogeneity as main contributors. The contents of up to 57 elements could be quantified in the certified reference material ERM®-EZ505 electronic scrap. The results of the certified elements Au, Be, Cu, In, Ni, Pd, and Pt overlapped within their uncertainties with the certified range and revealed recoveries of 100% ± 16%. Only Ag shows incomplete recoveries (75% ± 35%). The validated method was applied to all metal-containing components of selected smartphones, excluding batteries. The contents of up to 57 elements could be quantified and are presented exemplarily for printed circuit boards, which represent the most complex components in the investigated smartphones and thus limit the capability of the method. The ten most abundant elements in decreasing order are Cu, Fe, Si, Ni, Sn, Zn, Ba, Al, Cr, Ti, which comprise approx. 80% of the weight of the printed circuit boards. The method allows for the determination of metal content in various parts of modern smartphones, providing the basis for the estimation and prediction of future metal usage and thus the comprehensive investigation of recycling and circular economy aspects. %0 conference lecture %@ %A Zimmermann, T., Wieser, M., Mohammed, F., Proefrock, D., Irrgeher, J. %D 2018 %J Massenspektrometrische Verfahren der Elementspurenanalyse, 13. Symposium und 26. ICPMS-Anwendertreffen %T Erste Ergebnisse zur Untersuchung von Zinkisotopenverhaeltnissen in Wasser- und Oberflaechensedimentproben der Elbe %U %X %0 conference lecture %@ %A Zimmermann, T., Retzmann, A., Irrgeher, J., Prohaska, T., Proefrock, D. %D 2018 %J DAAS-Doktorandenseminar 2018 %T New, automated sample preparation techniques for the analysis of non-traditional stable isotopes in environmental samples %U %X %0 conference poster %@ %A Reese, A., Irrgeher, J., Zimmermann, T., Proefrock, D. %D 2017 %J European Winter Conference on Plasma Spectrochemistry 2017 %T Investigation of elemental and isotopic fingerprints in riverine sediments from the German Elbe catchment %U %X %0 conference lecture (invited) %@ %A Irrgeher, J., Dutschke, F., Reese, A., Retzmann, A., Zimmermann, T., Prohaska, T., Wieser, M.E., Proefrock, D. %D 2017 %J European Winter Conference of Plasma Spektroskopie 2017, EWCPS 2017 %T Multi-isotope tracers to investigate processes in river catchment systems: Selected application examples using B, Mo, Sr, Pb, and Ti isotope ratios assessed by MC ICP-MS %U %X %0 conference poster %@ %A Voigt, N., Zimmermann, T., Irrgeher, J., Proefrock, D. %D 2017 %J European Winter Conference on Plasma Spectrochemistry 2017 %T Multi-elemental characterization of anode materials used for cathodic corrosion protection of offshore structures using ICP-MS/MS %U %X %0 bachelor thesis %@ %A Klein, O. %D 2017 %J %T Vergleichende Untersuchung von Multi-Elementfingerprints zweier Flusssysteme (Weser und Ems) unter besondererBeruecksichtigung der Metalle der Seltenen Erden (Bachelorarbeit) %U %X %0 journal article %@ 1742-7061 %A Draxler, J., Martinelli, E., Weinberg, A.M., Zitek, A., Irrgeher, J., Meischel, M., Stanzl-Tschegg, S.E., Mingler, B., Prohaska, T. %D 2017 %J Acta Biomaterialia %P 526-536 %R doi:10.1016/j.actbio.2017.01.054 %T The potential of isotopically enriched magnesium to study bone implant degradation in vivo %U https://doi.org/10.1016/j.actbio.2017.01.054 %X This pilot study highlights the substantial potential of using isotopically enriched (non-radioactive) metals to study the fate of biodegradable metal implants. It was possible to show that magnesium (Mg) release can be observed by combining isotopic mass spectrometry and isotopic pattern deconvolution for data reduction, even at low amounts of Mg released a from slowly degrading 26Mg enriched (>99%) Mg metal. Following implantation into rats, structural in vivo changes were monitored by μCT. Results showed that the applied Mg had an average degradation rate of 16 ± 5 μm year−1, which corresponds with the degradation rate of pure Mg. Bone and tissue extraction was performed 4, 24, and 52 weeks after implantation. Bone cross sections were analyzed by laser ablation inductively coupled plasma mass spectrometry (ICP-MS) to determine the lateral 26Mg distribution. The 26Mg/24Mg ratios in digested tissue and excretion samples were analyzed by multi collector ICP-MS. Isotope pattern deconvolution in combination with ICP-MS enabled detection of Mg pin material in amounts as low as 200 ppm in bone tissues and 20 ppm in tissues up to two fold increased Mg levels with a contribution of pin-derived Mg of up to 75% (4 weeks) and 30% (24 weeks) were found adjacent to the implant. After complete degradation, no visual bone disturbance or residual pin-Mg could be detected in cortical bone. In organs, increased Δ26Mg/24Mg values up to 16‰ were determined compared to control samples. Increased Δ26Mg/24Mg values were detected in serum samples at a constant total Mg level. In contrast to urine, feces did not show a shift in the 26Mg/24Mg ratios. This investigation showed that the organism is capable of handling excess Mg well and that bones fully recover after degradation. %0 journal article %@ 0267-9477 %A Tchaikovsky, A., Irrgeher, J., Zitek, A., Prohaska, T. %D 2017 %J Journal of Analytical Atomic Spectrometry %N 11 %P 2300-2307 %R doi:10.1039/C7JA00251C %T Isotope pattern deconvolution of different sources of stable strontium isotopes in natural systems %U https://doi.org/10.1039/C7JA00251C 11 %X Isotope pattern deconvolution (IPD) was used to determine the contribution of different Sr sources to the Sr isotopic composition of natural samples on the example of sturgeon caviar and otoliths. For this purpose, the Sr isotopic composition of raw and salted sturgeon caviar, otoliths as well as water, fish feed and salt (representing the assumed main contributors to the final isotopic composition of strontium in caviar) were analyzed using MC ICP-MS. The molar fractions and their uncertainties were determined using multiple-linear regression modeling and linear algebra calculations. The optimized approach was applied to caviar and otolith samples of different origin. The Sr isotopic composition of raw caviar and otoliths was formed to 79.8 ± 4.3 % by water and 20.2 ± 4.3 % by fish feed (1 SD, n=5, between sites variation). Deconvolution was possible even when the isotopic difference of the n(87Sr)/n(86Sr) between sources was less than 0.1 %. The influence of salting to the isotopic compostion of processed caviar accounted up to almost 80 % for samples treated with salt containing high concentrations of Sr. The developed methodology provides the basis for the accurate origin determination of samples by n(87Sr)/n(86Sr) isotopic-amount ratios, in cases, where the initial natural signature is modified by known additives. %0 journal article %@ 1618-2642 %A Retzmann, A., Zimmermann, T., Proefrock, D., Prohaska, T., Irrgeher, J. %D 2017 %J Analytical and Bioanalytical Chemistry %N 23 %P 5463-5480 %R doi:10.1007/s00216-017-0468-6 %T A fully automated simultaneous single-stage separation of Sr, Pb, and Nd using DGA Resin for the isotopic analysis of marine sediments %U https://doi.org/10.1007/s00216-017-0468-6 23 %X A novel, fast and reliable sample preparation procedure for the simultaneous separation of Sr, Pb, and Nd has been developed for subsequent isotope ratio analysis of sediment digests. The method applying a fully automated, low-pressure chromatographic system separates all three analytes in a single-stage extraction step using self-packed columns filled with DGA Resin. The fully automated set-up allows the unattended processing of three isotopic systems from one sediment digest every 2 h, offering high sample throughput of up to 12 samples per day and reducing substantially laboratory manpower as compared to conventional manual methods. The developed separation method was validated using the marine sediment GBW-07313 as matrix-matched certified reference material and combines quantitative recoveries (>90% for Sr, >93% for Pb, and >91% for Nd) with low procedural blank levels following the sample separation (0.07 μg L-1 Sr, 0.03 μg L-1 Pb, and 0.57 μg L-1 Nd). The average δ values for Sr, Pb, and Nd of the separated reference standards were within the certified ranges (δ (87Sr/86Sr)NIST SRM 987 of -0.05(28) ‰, δ(208Pb/206Pb)NIST SRM 981 of -0.21(14) ‰, and δ(143Nd/144Nd)JNdi-1 of 0.00(7) ‰). The DGA Resin proved to be reusable for the separation of >10 sediment digests with no significant carry-over or memory effects, as well as no significant on-column fractionation of Sr, Pb, and Nd isotope ratios. Additional spike experiments of NIST SRM 987 with Pb, NIST SRM 981 with Sr, and JNdi-1 with Ce revealed no significant impact on the measured isotopic ratios, caused by potential small analyte peak overlaps during the separation of Sr and Pb, as well as Ce and Nd. %0 journal article %@ 1759-9660 %A Dutschke, F., Irrgeher, J., Proefrock, D. %D 2017 %J Analytical Methods %N 24 %P 3626-3635 %R doi:10.1039/c7ay00635g %T Optimisation of an extraction/leaching procedure for the characterisation and quantification of titanium dioxide (TiO2) nanoparticles in aquatic environments using SdFFF-ICP-MS and SEM-EDX analyses %U https://doi.org/10.1039/c7ay00635g 24 %X The quantitative recovery of nanoparticles from environmental samples represents a critical step during the implementation of routine analytical monitoring methods for the reliable quantitative determination of nanomaterials released into aquatic environments at the expected low concentration levels. In this work, several approaches based on different extraction agents have been evaluated with respect to their suitability for the recovery of TiO2 nanomaterials from fresh sediment samples. Centrifugal-field-flow-fractionation (SdFFF) hyphenated to inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) has been applied to separate the extracted nanoparticles as well as to overcome the known interference problem related to their Ti-specific detection when using ICP-based techniques. SdFFF-ICP-MS/MS method validation included in particular parameters such as particle recovery or stability of the particle size-distribution. Spike recoveries from the optimized colloidal extraction procedure of up to 95 ± 11% have been achieved. In a case study conducted from 2015 to 2016, the developed method was applied to monitor the release of nano-sized TiO2 materials into a lake environment that is frequently used for recreational activities such as swimming and surfing. The investigated sediment samples show a significant increase of the Ti concentration from 26.2 ± 2.7 mg kg−1 in June 2015 to 40.2 ± 4.6 mg kg−1 in December 2016 originating from TiO2 particles. %0 conference poster %@ %A Zimmermann, T., Retzmann, A., Irrgeher, J., Prohaska, T., Proefrock, D. %D 2017 %J International Conference Goldschmidt 2017 %T A new fully automated sample preparation system for the isotopic analysis of Sr, P band Nd via MC ICP-MS and its application to sediment digests %U %X %0 conference poster %@ %A Proefrock, D., Irrgeher, J., Zimmermann, T., Retzmann, A., Dutschke, F., Erbsloeh, H.-B., Ruhnau, C. %D 2016 %J 49. Jahrestagung der Deutschen Gesellschaft fuer Massenspektrometrie %T Overview about the potential of collision cell ICP-MS and ICP-MS/MS for sensitive and interference free element and elemental speciation analysis of environmental samples %U %X %0 journal article %@ 0033-4545 %A Meija, J., Coplen, T.B., Berglund, M., Brand, W.A., De Bieve, P., Gröning, M., Holden, N.E., Irrgeher, J., Loss, R.D., Walczyk, T., Prohaska, T. %D 2016 %J Pure and Applied Chemistry %N 3 %P 293-306 %R doi:10.1515/pac-2015-0503 %T Isotopic compositions of the elements 2013 (IUPAC Technical Report) %U https://doi.org/10.1515/pac-2015-0503 3 %X The Commission on Isotopic Abundances and Atomic Weights (ciaaw.org) of the International Union of Pure and Applied Chemistry (iupac.org) has revised the Table of Isotopic Compositions of the Elements (TICE). The update involved a critical evaluation of the recent published literature. The new TICE 2013 includes evaluated data from the “best measurement” of the isotopic abundances in a single sample, along with a set of representative isotopic abundances and uncertainties that accommodate known variations in normal terrestrial materials. %0 journal article %@ 0267-9477 %A Prohaska, T., Irrgeher, J., Zitek, A. %D 2016 %J Journal of Analytical Atomic Spectrometry %N 8 %P 1612-1621 %R doi:10.1039/C6JA00087H %T Simultaneous multi-element and isotope ratio imaging of fish otoliths by laser ablation split stream ICP-MS/MC ICP-MS %U https://doi.org/10.1039/C6JA00087H 8 %X The simultaneous retrieval of spatially resolved information on the elemental content and isotope ratios from the same sampling spot (e.g. in incrementally grown biological material) still represents an analytical challenge. In order to assess multi-elemental (Sr/Ca; Mg/Ca; Ba/Ca; Na/Ca) and isotopic (87Sr/86Sr) data simultaneously on a fish otolith surface, a laser ablation (LA) system was coupled simultaneously to a multicollector inductively coupled plasma mass spectrometer (MC ICP-MS) and a quadrupole (single collector) ICP-MS via an aerosol split. In addition, a membrane desolvation nebulizer was used for introducing liquid standards in-line to the MC ICP-MS system. The recorded time resolved data of different data density (number of data points/time unit were by a factor of 4 higher using MC ICP-MS) were spatially referenced to the picture using ArcGIS® software. This allowed for the creation of elemental and isotopic images and the combination of data of different spatial resolution. Finally, regions of similar chemical composition were retrieved by cluster analysis. The method was applied to analyze an otolith of a lenok (Brachymystax lenok) caught in the river Eg (northern Mongolia) to assess habitat use and migration in a river system, where only little is known about the migrations of native fish. The combined statistical evaluations of the data showed that the Sr/Ca elemental and 87Sr/86Sr isotope ratios assessed in the otolith were the main discriminators of three clearly different zones on the otolith, indicating habitat shifts. Split-stream LA-ICP-MS/MC ICP-MS proved to be a compelling approach to gain elemental and isotopic data simultaneously from the same sampling spots on solid samples with a minimum loss of information. %0 journal article %@ 0033-4545 %A Meija, J., Coplen, T.B., Berglund, M., Brand, W.A., De Bieve, P., Gröning, M., Holden, N.E., Irrgeher, J., Loss, R.D., Walczyk, T., Prohaska, T. %D 2016 %J Pure and Applied Chemistry %N 3 %P 265-291 %R doi:10.1515/pac-2015-0305 %T Atomic weights of the elements 2013 (IUPAC Technical Report) %U https://doi.org/10.1515/pac-2015-0305 3 %X thorium to 232.0377(4) from 232.038 06(2). %0 conference lecture %@ %A Irrgeher, J., Prohaska, T., Zitek, A., Kleeberg, U., Erbsloeh, H.-B., Karcher, D.B., Zimmermann, T., Von der Au, M., Proefrock, D. %D 2016 %J 49. Jahrestagung der Deutschen Gesellschaft für Massenspektrometrie, DGMS 2016 %T Tracing of Nutrients and Pollutants in the German Wadden Sea Catchment via the Establishment of Aquatic Isoscapes %U %X %0 conference lecture %@ %A Dutschke, F., Soto-Alvaredo, J., Proefrock, D., Prange, A., Bettmer, J. %D 2016 %J 18th International Symposium on Field- and Flow-Based Separations %T Development of an analytical approach using centrifugal field-flow-fractionation hyphenated to ICP-MS/MS for the detection and characterization of titanium dioxide nanoparticles in the environment %U %X %0 journal article %@ 0267-9477 %A Soto-Alvaredo, J., Dutschke, F., Bettmer, J., Montes-Bayon, M., Proefrock, D., Prange, A. %D 2016 %J Journal of Analytical Atomic Spectrometry %N 7 %P 1549-1555 %R doi:10.1039/C6JA00079G %T Initial results on the coupling of sedimentation field-flow fractionation (SdFFF) to inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS) for the detection and characterization of TiO2 nanoparticles %U https://doi.org/10.1039/C6JA00079G 7 %X Manufactured TiO2 nanoparticles (TiO2 NPs) are nowadays widely present in products accessible to the mass market like paints, cosmetics or sunscreens. Despite the great increase in the use of these nanoparticles, up to now their potential effects to the environment and biological systems have not been sufficiently studied. Reliable analytical methods are therefore required for a better characterization of these emerging materials. We suggest the hyphenation of inductively coupled plasma-mass spectrometry (ICP-MS), with a separation technique like sedimentation field-flow fractionation (SdFFF) to obtain information related to size and state of agglomeration of the investigated nanoparticles. In this work, initial experiments related to the on-line coupling of SdFFF with inductively coupled plasma-tandem mass spectrometry (ICP-MS/MS) have been conducted allowing the detection and separation of TiO2 NPs. The application of the ICP-MS/MS technology using the NH3 mass shift mode allowed the removal of the different molecular and isobaric interferences that complicate the reliable detection and quantification of Ti. Under optimised conditions, the achievable instrumental detection limits in matrix solutions were below 10 ng·L-1of Ti. The separation parameters of the SdFFF system were optimized using two commercially available model TiO2 NPs (nominal sizes: 21 and 50 nm). These materials were characterised concerning hydrodynamic sizes and state of aggregation using also a multiangle light scattering analysis detector (MALS). Transmission electron microscopy technique (TEM) was also applied to confirm the sizes and the shapes of the TiO2 NPs as well as the presence of aggregates. To demonstrate the applicability of the combination of SdFFF and ICP-MS/MS for the detection of TiO2 NPs at trace levels as well as to gain information about their hydrodynamic size and agglomeration state, the optimized method has been applied to the analysis of real water samples from a local lake in Germany. %0 journal article %@ 0013-936X %A Booij, K., Robinson, C.D., Burgess, R.M., Mayer, P., Roberts, C.A., Ahrens, L., Allan, I.J., Brant, J., Jones, L., Kraus, U.R., Larsen, M.M., Lepom, P., Petersen, J., Proefrock, D., Roose, P., Schaefer, S., Smedes, F., Tixier, C., Vorkamp, K., Whitehouse, P. %D 2016 %J Environmental Science and Technology %N 1 %P 3-17 %R doi:10.1021/acs.est.5b04050 %T Passive Sampling in Regulatory Chemical Monitoring of Nonpolar Organic Compounds in the Aquatic Environment %U https://doi.org/10.1021/acs.est.5b04050 1 %X We reviewed compliance monitoring requirements in the European Union, the United States, and the Oslo-Paris Convention for the protection of the marine environment of the North-East Atlantic, and evaluated if these are met by passive sampling methods for nonpolar compounds. The strengths and shortcomings of passive sampling are assessed for water, sediments, and biota. Passive water sampling is a suitable technique for measuring concentrations of freely dissolved compounds. This method yields results that are incompatible with the EU’s quality standard definition in terms of total concentrations in water, but this definition has little scientific basis. Insufficient quality control is a present weakness of passive sampling in water. Laboratory performance studies and the development of standardized methods are needed to improve data quality and to encourage the use of passive sampling by commercial laboratories and monitoring agencies. Successful prediction of bioaccumulation based on passive sampling is well documented for organisms at the lower trophic levels, but requires more research for higher levels. Despite the existence of several knowledge gaps, passive sampling presently is the best available technology for chemical monitoring of nonpolar organic compounds. Key issues to be addressed by scientists and environmental managers are outlined. %0 conference lecture %@ %A Irrgeher, J., Prohaska, T., Zitek, A., Proefrock, D. %D 2016 %J An interdisciplinary view on climate change issues - Phase II, Joint Seminar TW-AT %T Development of a Multi-Isotope Tracer Tool for Aquatic Ecosystems on the Example of the German Wadden Sea %U %X %0 conference lecture %@ %A Zimmermann, T., Irrgeher, J., Proefrock, D. %D 2016 %J 49. Jahrestagung der Deutschen Gesellschaft für Massenspektrometrie, DGMS 2016 %T Application and optimization of inductively coupled plasma tandem mass spectrometry (ICP-MS/MS) for ultra-trace element analysis of undiluted seawater %U %X %0 journal article %@ 1618-2642 %A Zitek, A., Irrgeher, J., Prohaska, T. %D 2016 %J Analytical and Bioanalytical Chemistry %N 2 %P 341-343 %R doi:10.1007/s00216-015-9037-z %T Applications of isotopes in analytical ecogeochemistry %U https://doi.org/10.1007/s00216-015-9037-z 2 %X Analytical ecogeochemistry is an emerging transdisciplinary field of science dealing with the development and application of analytical methods for the advanced and reliable measurement of compounds, elements and isotopes at trace levels in abiotic and biological media. The aim is to answer fundamental questions in different research fields, such as ecology, biology, ecosystem research and environmental science as well as climatology and geology. Evidently, a link to other disciplines can be established as well. Therefore, analytical ecogeochemistry conceptually ties analytical chemistry to the holistic view of the The Total Human Ecosystem according to Naveh [1] (Fig. 1). That is why its research objects also include the human sphere with its technologies and products, environmental effects created and the environmental services needed. %0 conference lecture %@ %A Irrgeher, J., Dutschke, F., Proefrock, D. %D 2016 %J 12. Symposium Massenspektrometrische Verfahren der Elementspurenanalyse und 25. ICP-MS Anwendertreffen %T Precise titanium isotope ratio measurements using MC ICP-MS: Method validation and characterization of TiO2 nanoparticles %U %X %0 conference poster %@ %A Zimmermann, T., Retzmann, A., Irrgeher, J., Prohaska, T., Proefrock, D. %D 2016 %J 39th International Symposium on Environmental Analytical Chemistry, ISEAC 39 %T Optimization of novel automated sample preparation systems for elemental and isotopic analysis of environmental samples via (MC) ICP-MS %U %X %0 conference lecture %@ %A Irrgeher, J., Prohaska, T., Zitek, A., Kleeberg, U., Erbsloeh, H.-B., Karcher, D.B., Zimmermann, T., Von der Au, M., Proefrock, D. %D 2016 %J 2016 Winter Conference on Plasma Spectrochemistry %T Isotopic Tracer Tools for nutrients and pollutants in the Marine Ecosystem of the German Wadden Sea %U %X %0 conference poster %@ %A Dutschke, F., Irrgeher, J., Proefrock, D. %D 2016 %J 4th Workshop on Field Flow Fractionation (FFF) and Mass Spectro-metric techniques (MS) %T Optimized strategies for the characterization of TiO2-nanoparticles in complex environmental matrices like sediments and water samples using centrifugal-FFF hyphenated to ICP-MS/MS %U %X %0 journal article %@ 1618-2642 %A Irrgeher, J., Prohaska, T. %D 2016 %J Analytical and Bioanalytical Chemistry %N 2 %P 369-385 %R doi:10.1007/s00216-015-9025-3 %T Application of non-traditional stable isotopes in analytical ecogeochemistry assessed by MC ICP-MS - A critical review %U https://doi.org/10.1007/s00216-015-9025-3 2 %X Analytical ecogeochemistry is an evolving scientific field dedicated to the development of analytical methods and tools and their application to ecological questions. Traditional stable isotopic systems have been widely explored and have undergone continuous development during the last century. The variations of the isotopic composition of light elements (H, O, N, C, and S) have provided the foundation of stable isotope analysis followed by the analysis of traditional geochemical isotope tracers (e.g., Pb, Sr, Nd, Hf). Questions in a considerable diversity of scientific fields have been addressed, many of which can be assigned to the field of ecogeochemistry. Over the past 15 years, other stable isotopes (e.g., Li, Zn, Cu, Cl) have emerged gradually as novel tools for the investigation of scientific topics that arise in ecosystem research and have enabled novel discoveries and explorations. These systems are often referred to as non-traditional isotopes. The small isotopic differences of interest that are increasingly being addressed for a growing number of isotopic systems represent a challenge to the analytical scientist and push the limits of today’s instruments constantly. This underlines the importance of a metrologically sound concept of analytical protocols and procedures and a solid foundation of data processing strategies and uncertainty considerations before these small isotopic variations can be interpreted in the context of applied ecosystem research. This review focuses on the development of isotope research in ecogeochemistry, the requirements for successful detection of small isotopic shifts, and highlights the most recent and innovative applications in the field. %0 conference lecture %@ %A Proefrock, D., Irrgeher, J., Zimmermann, T., Dutschke, F. %D 2016 %J Agilent ICP-QQQ European User Group Meeting %T Application and Possibilities of ICP-QQQ for Marine Environmental Research %U %X %0 journal article %@ 0048-9697 %A Helmholz, H., Ruhnau, C., Proefrock, D., Erbsloeh, H.-B., Prange, A. %D 2016 %J Science of the Total Environment %P 626-636 %R doi:10.1016/j.scitotenv.2016.04.202 %T Seasonal and annual variations in physiological and biochemical responses from transplanted marine bioindicator species Mytilus spp. during a long term field exposure experiment %U https://doi.org/10.1016/j.scitotenv.2016.04.202 %X In a pilot field study the long term response of transplanted bioindicator organisms Mytilus spp. was analyzed on the basis of physiological indices and biochemical measurements related to the energy budget. Three different time series with deployment times of eight to twelve months were compared according to seasonality and repeatability of the responses. Test organisms were incubated at a coastal station in the anthropogenically impacted estuary of the river Elbe and at a North Sea station located in vicinity to the Island of Helgoland in the German Bight. The stations differ in their hydrological as well as chemical characteristics. They can be discriminated by statistical factor analysis based on the measured biochemical parameter. Levels of all energy budget biomarker varied between seasons; however, the degree of variation of the specific response was differently expressed. The mussels deployed at Helgoland showed a reproducible high Condition Index in each sampling series and an oscillating Gonadosomatic Index representing the reproduction cycle. The lowest available energy was recorded in mussels at the estuarine sampling station compared to the off-shore station. This may be caused by the energetically costly maintenance of osmotic balance and consequently result in a lower amount of energy available for defense again chemical stress, growth and reproduction. %0 journal article %@ 1618-2642 %A Horsky, M., Irrgeher, J., Prohaska, T. %D 2016 %J Analytical and Bioanalytical Chemistry %N 2 %P 351-367 %R doi:10.1007/s00216-015-9003-9 %T Evaluation strategies and uncertainty calculation of isotope amount ratios measured by MC ICP-MS on the example of Sr %U https://doi.org/10.1007/s00216-015-9003-9 2 %X This paper critically reviews the state-of-the-art of isotope amount ratio measurements by solution-based multi-collector inductively coupled plasma mass spectrometry (MC ICP-MS) and presents guidelines for corresponding data reduction strategies and uncertainty assessments based on the example of n(87Sr)/n(86Sr) isotope ratios. This ratio shows variation attributable to natural radiogenic processes and mass-dependent fractionation. The applied calibration strategies can display these differences. In addition, a proper statement of uncertainty of measurement, including all relevant influence quantities, is a metrological prerequisite. A detailed instructive procedure for the calculation of combined uncertainties is presented for Sr isotope amount ratios using three different strategies of correction for instrumental isotopic fractionation (IIF): traditional internal correction, standard-sample bracketing, and a combination of both, using Zr as internal standard. Uncertainties are quantified by means of a Kragten spreadsheet approach, including the consideration of correlations between individual input parameters to the model equation. The resulting uncertainties are compared with uncertainties obtained from the partial derivatives approach and Monte Carlo propagation of distributions. We obtain relative expanded uncertainties (U rel; k = 2) of n(87Sr)/n(86Sr) of < 0.03 %, when normalization values are not propagated. A comprehensive propagation, including certified values and the internal normalization ratio in nature, increases relative expanded uncertainties by about factor two and the correction for IIF becomes the major contributor. %0 journal article %@ 2053-1400 %A Petersen, J., Proefrock, D., Paschke, A., Broekaert, J.A.C., Prange, A. %D 2016 %J Environmental Science: Water Research & Technology %N 1 %P 146-153 %R doi:10.1039/c5ew00126a %T Development and field test of a mobile continuous flow system utilizing Chemcatcher for monitoring of rare earth elements in marine environments %U https://doi.org/10.1039/c5ew00126a 1 %X An important limiting factor that hampers accurate determination of the time-weighted average (TWA) concentrations of aqueous micropollutants by passive sampling is unsteady water turbulence, which can cause high variations of the uptake rates of target substances by the samplers during their field exposure. A mobile continuous flow system (MCFS) was developed for the improved utilization of the Chemcatcher passive sampler for time-integrated field monitoring of metals under controlled and reproducible hydrodynamic conditions. The mobile system is based on a specifically designed stirring system integrated in a flow-through cell. This design enables the adjustment of hydrodynamic conditions around the samplers as used in the laboratory calibration experiments. By using this system, the reliability of monitoring data can be improved. A prototype of this mobile continuous flow system was tested during a research cruise in May 2014 (HE422) to collect TWA concentrations for rare earth elements (REEs). The field test covered two areas in the German Bight of the North Sea. The Chemcatcher® results yield TWA concentration levels of REEs between 3.9 ng L−1 and 19.4 ng L−1 for the off-shore (low anthropogenic influence) and between 7.0 ng L−1 and 38.6 ng L−1 for the near-shore (high anthropogenic impact) areas, while the direct measurements of the ultra-trace levels of the REEs in the seawater spot samples were nearly impossible. The successful application of the developed MCFS demonstrated that monitoring with passive samplers on ships is possible with high accuracy under controlled hydrodynamic conditions even at the ultra-trace element concentration levels as typical for off-shore areas. %0 journal article %@ 1759-9660 %A Hanousek, O., Brunner, M., Proefrock, D., Irrgeher, J., Prohaska, T. %D 2016 %J Analytical Methods %N 42 %P 7661-7672 %R doi:10.1039/C6AY02177H %T The performance of single and multi-collector ICP-MS instruments for fast and reliable 34S/32S isotope ratio measurements %U https://doi.org/10.1039/C6AY02177H 42 %X The performance and validation characteristics of different single collector inductively coupled plasma mass spectrometers based on different technical principles (ICP-SFMS, ICP-QMS in reaction and collision modes, and ICP-MS/MS) were evaluated in comparison to the performance of MC ICP-MS for fast and reliable S isotope ratio measurements. The validation included the determination of LOD, BEC, measurement repeatability, within-lab reproducibility and deviation from certified values as well as a study on instrumental isotopic fractionation (IIF) and the calculation of the combined standard measurement uncertainty. Different approaches of correction for IIF applying external intra-elemental IIF correction (aka standard-sample bracketing) using certified S reference materials and internal inter-elemental IIF (aka internal standardization) correction using Si isotope ratios in MC ICP-MS are explained and compared. The resulting combined standard uncertainties of examined ICP-QMS systems were not better than 0.3–0.5% (uc,rel), which is in general insufficient to differentiate natural S isotope variations. Although the performance of the single collector ICP-SFMS is better (single measurement uc,rel = 0.08%), the measurement reproducibility (>0.2%) is the major limit of this system and leaves room for improvement. MC ICP-MS operated in the edge mass resolution mode, applying bracketing for correction of IIF, provided isotope ratio values with the highest quality (relative combined measurement uncertainty: 0.02%; deviation from the certified value: <0.002%). %0 conference poster %@ %A Zimmermann, T., Retzmann, A., Irrgeher, J., Prohaska, T., Proefrock, D. %D 2016 %J 12. Symposium Massenspektrometrische Verfahren der Elementspurenanalyse und 25. ICP-MS Anwendertreffen %T Optimization of a new fully-automated sample preparation system for isotopic analysis of sediment digests via MC ICP-MS %U %X %0 journal article %@ 0584-8547 %A Irrgeher, J., Galler, P., Prohaska, T. %D 2016 %J Spectrochimica Acta B %P 31-42 %R doi:10.1016/j.sab.2016.09.008 %T 87Sr/86Sr isotope ratio measurements by laser ablation multicollector inductively coupled plasma mass spectrometry: Reconsidering matrix interferences in bioapatites and biogenic carbonates %U https://doi.org/10.1016/j.sab.2016.09.008 %X The major focus was set on analysing human tooth samples, fish hard parts and geological carbonates. Potential sources of interferences were identified and corrected for. The combined corrections of interferences and adequate instrumental isotopic fractionation correction procedures lead to accurate data even though increased uncertainties have to be taken into account. The results are discussed along with approaches presented in literature for data correction in laser ablation analysis. %0 conference lecture %@ %A Proefrock, D., Zimmermann, T., Retzmann, A. %D 2016 %J 2016 Winter Conference on Plasma Spectrochemistry %T Optimization and Application of ICP-MS/MS for the Analysis of Elements and Element Species of Growing Concern %U %X %0 conference lecture %@ %A Proefrock, D., Irrgeher, J., Zimmermann, T., Kleeberg, U. %D 2016 %J Sino-German Workshop Biogeochemical Pressures and their Effects on Marine Ecosystems in China and Europe %T Linking Catchments and Coastal Seas –New Possibilities Through the Application of Non-Traditional Stable Isotopes and Elemental Fingerprints to Trace Sources and Sinks of Inorganic Contaminants in the Wadden Sea %U %X %0 conference lecture %@ %A Proefrock, D., Irrgeher, J., Zimmermann, T., Dutschke, F., Retzmann, A. %D 2016 %J 12. Symposium Massenspektrometrische Verfahren der Elementspurenanalyse und 25. ICP-MS Anwendertreffen %T Element and Element Speciation Analysis of Environmental Samples: Current Challenges and Solutions %U %X %0 conference lecture (invited) %@ %A Proefrock, D., Irrgeher, J., Zimmermann, T., Dutschke, F., Erbsloeh, H.-B., Ruhnau, C. %D 2016 %J International Symposium on Environmental Analytical Chemistry, ISEAC 39 - Environmental and Food Monitoring %T Developments in element and element speciation analysis of environmental samples - Recent trends and future perspectives %U %X %0 journal article %@ 0141-1136 %A Helmholz, H., Lassen, S., Ruhnau, C., Proefrock, D., Erbsloeh, H.-B., Prange, A. %D 2015 %J Marine Environmental Research %P 69-80 %R doi:10.1016/j.marenvres.2015.07.021 %T Investigation on the proteome response of transplanted blue mussel (Mytilus sp.) during a long term exposure experiment at differently impacted field stations in the German Bight (North Sea) %U https://doi.org/10.1016/j.marenvres.2015.07.021 %X In a pilot field study the proteome response of Mytilus sp. was analyzed in relation to the concentration of different trace metal contaminants. Over a period of eight month test organisms have been exposed at a near-shore station in the anthropogenic impacted estuary of the river Elbe and at an off-shore station in the vicinity of the Island of Helgoland in the German Bight (North Sea). The stations differ in their hydrological as well as chemical characteristics. The physiological biomarkers, such as condition index which have been continuously monitored during the experiment clearly indicate the effects of the different environmental conditions. Multiple protein abundance changes were detected utilizing the techniques of two dimensional gel electrophoresis (2dGE) and consequently proteins arising as potential candidates for ecotoxicological monitoring have been identified by MALDI-ToF and ToF/ToF mass spectrometry. Different cytoskeletal proteins, enzymes of energy metabolism, stress proteins and one protein relevant for metal detoxification have been pointed out. %0 journal article %@ 0267-9477 %A Gonzalez-Gago, A., Proefrock, D., Prange, A. %D 2015 %J Journal of Analytical Atomic Spectrometry %P 180-190 %R doi:10.1039/c4ja00112e %T Optimizing GC-ICP-MS for ultra-trace quantification of PBDEs in natural water samples using species-specific isotope dilution %U https://doi.org/10.1039/c4ja00112e %X Due to the increased interest regarding the fate, transport and toxic effects of polybrominated diphenyl ethers (PBDEs) within the aquatic environment a variety of different methods have been reported, trying to fulfil the requirements of the European Water Framework Directive (WFD, Directive 2000/60/EC). For PBDEs the WFD specifies Environmental Quality Standards (EQS) at very low trace levels, which correspond to 0.5 ng L−1 for 6 priority brominated flame retardants. The reliable quantification of such low concentration levels in environmental sample matrices requires the development of new analytical approaches. Current standard GC-MS methods, which are frequently used for PBDE analysis, often do not provide sufficient sensitivity for their reliable analysis at ultra-trace levels. Within this context a new GC-ICP-MS method has been developed and optimized allowing the ultra-trace determination of the selected priority congeners at sub ng L−1 levels. The quantification approach is based on the application of 81Br labelled PBDEs as internal standards for species-specific isotope dilution analysis. Natural water samples were analysed to demonstrate the potential of this new detection and quantification approach. %0 conference poster %@ %A Zimmermann, T., Proefrock, D., Prange, A. %D 2015 %J European Winter Conference on Plasma Spectrochemistry 2015 %T On-line matrix removal and preconcentration using the ESI seaFAST system coupled to ICP-MS/MS for the ultra-trace analysis of undiluted seawater %U %X %0 journal article %@ 1618-2642 %A Gonzalez-Gago, A., Proefrock, D., Prange, A. %D 2015 %J Analytical and Bioanalytical Chemistry %N 26 %P 8009-8018 %R doi:10.1007/s00216-015-8973-y %T Comparison of GC–NCI MS, GC–ICP-MS, and GC–EI MS–MS for the determination of PBDEs in water samples according to the Water Framework Directive %U https://doi.org/10.1007/s00216-015-8973-y 26 %X The Water Framework Directive (WFD) includes some polybrominated diphenyl ethers (PBDEs) in the list of priority substances that must be measured in surface waters at very low concentrations. The typical approaches applied to the determination of PBDEs in environmental samples might not meet the demanding requirements of the WFD. In this work, the instrumental capabilities of the mass-spectrometry (MS) techniques most frequently used in the determination of PBDEs, namely gas chromatography–negative-chemical-ionisation MS (GC–NCI MS) and GC–electrospray-ionisation tandem MS (EI MS–MS), are evaluated in comparison with highly sensitive GC–inductively-coupled-plasma MS (ICP-MS) for the reliable determination of PBDEs according to the WFD. Three analytical methods based on the liquid–liquid extraction of water samples and measurement of the extracts by GC–NCI MS, GC–EI MS–MS, or GC–ICP-MS are described. The priority PBDEs were quantified in different types of water sample by means of isotope-dilution mass spectrometry (IDMS) using 81Br-labelled or 13C-labelled PBDEs spikes, depending on the selected ionisation source. The three proposed methods met the requirements of the European legislation in terms of LOQs and expanded uncertainties. The determination method using 81Br-labelled PBDEs and GC–ICP-MS had the highest sensitivity and the lowest instrumental limits of detection and expanded uncertainties. %0 conference poster %@ %A Irrheher, J., Proefrock, D., Prohaska, T., Zitek, A., Kleeberg, U., Erbsloeh, B., Prange, A. %D 2015 %J 2015 Goldschmidt Conference %T Development of a Multi-Isotope Tracer Tool for Aquatic Ecosystems on the Example of the German Wadden Sea %U %X %0 conference lecture %@ %A Proefrock, D., Gonzalez-Gago, A., Zimmermann, T., Retzmann, A., Prange, A. %D 2015 %J European Winter Conference on Plasma Spectrochemistry 2015 %T ICP-MS and hyphenated techniques for trace analysis of emerging contaminants in marine environmental samples %U %X %0 conference lecture %@ %A Dutschke, F., Soto-Alvaredo, J., Proefrock, D., Prange, A., Bettmer, J. %D 2015 %J 10th International Conference on the Environmental Effects of Nanoparticles and Nanomaterials %T Evaluation of the fate and the behavior of anthropogenic Titanium dioxide nanoparticles in seawater and marine sediments using Centrifugal Field-Flow-Fractionation hyphenated to ICP-MS/MS (CFFF-ICP-MS/MS) %U %X %0 conference poster %@ %A Dutschke, F., Soto-Alvaredo, J., Proefrock, D., Prange, A. %D 2015 %J European Winter Conference on Plasma Spectrochemistry 2015 %T Separation and detection of titanium dioxide nanoparticles from marine sediments samples using centrifugal-Field-Flow-Fractionation hyphenated to ICP-MS-MS %U %X %0 conference lecture %@ %A Dutschke, F., Soto-Alvaredo, J., Proefrock, D., Prange, A. %D 2015 %J ANAKON 2015 %T Detection and separation of titanium dioxide nanoparticles from marine sediments samples using centrifugal-Field-Flow-Fractionation hyphenated to ICP-MS-MS %U %X %0 journal article %@ 1759-9660 %A Somoano-Blanco, L., Rodriquez-Gaozalez, P., Proefrock, D., Prange, A., Garcia Alonso, J.I. %D 2015 %J Analytical Methods %N 21 %P 9068-9075 %R doi:10.1039/c5ay01752a %T Comparison of different mass spectrometric techniques for the determination of polychlorinated biphenyls by isotope dilution using 37Cl-labelled analogues %U https://doi.org/10.1039/c5ay01752a 21 %X This work presents the comparison of four different mass spectrometric techniques coupled to gas chromatography (single quadrupole ICP-MS, triple quadrupole ICP-MS/MS, single quadrupole NCI-MS and triple quadrupole EI-MS/MS) for the detection of polychlorinated biphenyls (PCBs) in environmental samples and their determination by a new isotope dilution mass spectrometry (IDMS) approach. A mixture of twelve priority PCBs labelled with 37Cl was employed as the species-specific isotopically labelled internal standard. The 37Cl-labelled PCBs enable the use of both molecular and elemental ionization sources, such as ICP or NCI, as the isotopic label is in the heteroatom. First, the comparison was carried out by assessing the capabilities of all instruments to measure chlorine isotope ratios and calculating the isotopic enrichment of the labelled analogues. Finally, the analysis of the Certified Reference Material SRM 1941b (organics in marine sediment) containing PCBs in the low ng g−1 range was carried out for method comparison. Elemental ionization sources such as ICP and NCI combined with quadrupole mass spectrometry provided chlorine specific detection and high sensitivity for higher chlorinated compounds but suffered from high background signals from other chlorine containing, co-eluting compounds in the sample which prevented the accurate measurement of PCB-specific chlorine isotope ratios. On the other hand, the use of GC-MS/MS in the selected reaction monitoring mode (SRM) provided selective and accurate measurements but suffered from lower sensitivity for higher chlorinated compounds. %0 conference lecture %@ %A Dutschke, F., Soto-Alvaredo, J., Proefrock, D., Prange, A. %D 2014 %J 24. ICP-MS Anwendertreffen und 11. Symposium Massenspektrometrische Verfahren Elementspurenanalyse 2014 %T Optimization of Centrifugal-FFF coupled to ICP-MS-MS for the detection of nanoparticles in marine samples %U %X %0 conference poster %@ %A Zimmermann, T., Dutschke, F., Soto-Alvaredo, J., Krystek, P., Proefrock, D., Prange, A. %D 2014 %J 24. ICP-MS Anwendertreffen und 11. Symposium Massenspektrometrische Verfahren Elementspurenanalyse 2014 %T Goldrausch oder die Frage was schmiere ich mir da ins Gesicht? Charakterisierung von anorganischen partikulaeren Bestandteilen in einem Kosmetikprodukt %U %X %0 conference lecture %@ %A Dutschke, F., Soto-Alvaredo, J., Proefrock, D., Prange, A. %D 2014 %J 3. Doktorandenseminar des DAAS, Spektroskopie und Spurenanalytik %T Optimization of Centrifugal-FFF coupled to ICP-MS-MS for the detection of nanoparticles in marine samples %U %X %0 journal article %@ 0048-9697 %A Strizak, Z., Ivankovic, D., Proefrock, D., Helmholz, H., Cindric, A.-M., Erk, M., Prange, A. %D 2014 %J Science of the Total Environment %P 159-170 %R doi:10.1016/j.scitotenv.2013.09.051 %T Characterization of the cytosolic distribution of priority pollutant metals and metalloids in the digestive gland cytosol of marine mussels: Seasonal and spatial variability %U https://doi.org/10.1016/j.scitotenv.2013.09.051 %X Cytosolic profiles of several priority pollutant metals (Cu, Cd, Zn, Pb) and metalloid As were analyzed in the digestive gland of the mussel (Mytilus galloprovincialis) sampled at locations with different environmental pollution levels along the Croatian coast in the spring and summer season. Size-exclusion chromatography (SEC) connected to inductively coupled plasma mass spectrometry (ICP-MS) was used to determine selected elements bound to cytosolic biomolecules separated based on their molecular size. Copper, cadmium and zinc eluted mostly associated with high molecular weight (HMW) and medium molecular weight (MMW) biomolecules, but with a more prominent elution in the MMW peak at polluted locations which were probably associated with the 20 kDa metallothionein (MT). Elution of all three metals within this peak was also strongly correlated with cytosolic Cd as strong inducer of MT. Lead mostly eluted in HMW biomolecule range, but in elevated cytosolic Pb concentrations, significant amount eluted in low molecular weight (LMW) biomolecules. Arsenic, on the other hand eluted almost completely in LMW range, but we could not distinguish specific molecular weight biomolecules which would be predominant in detoxification mechanism. Seasonal variability in element abundance within specific peaks was present, although not in the same extent, for all elements and locations, especially for As. The results confirm the suitability of the distribution of selected metals/metalloids among different cytosolic ligands as potential indicator for metal exposure. Obtained findings can also serve as guidelines for further separation and characterization of specific cytosolic metal-binding biomolecules. %0 journal article %@ 1748-7692 %A Kakuschke, A., Pröfrock, D., Prange, A. %D 2013 %J Marine Mammal Science %N 2 %P E183-E192 %R doi:10.1111/j.1748-7692.2012.00603.x %T C-reactive protein in blood plasma and serum samples of harbor seals (Phoca vitulina) %U https://doi.org/10.1111/j.1748-7692.2012.00603.x 2 %X C-reactive protein (CRP) belongs to the acute phase proteins. Increased levels are present in inflammatory conditions, trauma, or intoxications. In veterinary medicine CRP is used as powerful diagnostic parameter in health studies, whereas little is known about the role of CRP in Pinnipedia. Therefore, samples were collected from 131 harbor seals from the North Sea between November 2002 and November 2007. CRP blood values were measured and the physiological range was calculated. Furthermore, the influence of age and sex of the animal, geographical location and season was investigated. The CRP concentrations in plasma/serum showed a median of 33 μg/mL, a 5th percentile of 18 μg/mL, and a 95th percentile of 80 μg/mL. No significant influences of sex, season, or geographical location on CRP concentration were detected. Juveniles showed significantly higher CRP levels than adult animals, whereas CRP values in newborns appear to be lower than in juveniles and adults. Our report describes for the first time CRP plasma/serum concentrations in a large group of harbor seals. It suggests that CRP is useful to detect inflammatory conditions and may help to improve health studies of this species. %0 conference poster %@ %A Petersen, J., Proefrock, D., Broekaert, J., Prange, A. %D 2013 %J 6th International Passive Sampling Workshop and Symposium, IPSW 2013 %T Passive sampling as a tool for time-integrated analysis of metals in marine waters using ICP-MS-MS %U %X %0 conference poster %@ %A Helmholz, H., Erk, M., Proefrock, D., Strizak, Z., Ivankovic, D., Prange, A. %D 2012 %J 6th World Congress, SETAC Europe 22nd Annual Meeting, SETAC 2012 %T Metal exposure and associated effects in mussels: An integrated approach – hyphenated analytical techniques and biomarkers %U %X %0 conference poster %@ %A Helmholz, H., Rieker, E., Proefrock, Lassen, S., Prange, A. %D 2012 %J 6th World Congress, SETAC Europe 22nd Annual Meeting, SETAC 2012 %T Proteom analysis of Blue Mussel tissue by two dimensional gel electrophoresis and MALDI – MS %U %X %0 journal article %@ 0267-9477 %A Grebe, M., Proefrock, D., Kakuschke, A., del Castillo Busto, M.E., Montes Bayon, M., Sanz-Medel, A., Broekaert, J.A.C., Prange, A. %D 2012 %J Journal of Analytical Atomic Spectrometry %N 3 %P 440-448 %R doi:10.1039/c2ja10287k %T Comparison of different methods for the absolute quantification of harbour seal transferrin glycoforms using HPLC-ICP-MS %U https://doi.org/10.1039/c2ja10287k 3 %X Marine mammals such as harbour seals (Phoca vitulina) represent a valuable indicator for the state of their habitat or environmental changes in particular due to their key role as top predators within the marine food web. Therefore, the characterization (qualitative and quantitative) of target proteins of such organisms can be of potential use for environmental monitoring processes. In this regard, serum transferrin (Tf) is a key protein related to iron transport and its metabolism. Thus, the present work illustrates the development and comparison of different approaches for the accurate, absolute quantification of Tf isolated from blood samples of North Sea harbour seals with the aim to use possible changes in Tf glycoform patterns as an additional parameter in extended studies, focusing on the assessment of their immune status. For this purpose, different HPLC-ICP-MS approaches have been developed, which allow the highly resolved separation and detection of up to nine different Tf glycoforms in seal blood samples in less than 30 minutes, as well as their sensitive and specific absolute quantification on the basis of their characteristic iron content. One method is based on the application of a reversed gradient sheath flow to compensate gradient related effects during the iron specific detection of Tf. Here a simple flow injection with a certified element standard was used for calibration. The second developed methodology utilizes isotope dilution analysis, which was applied for the quantification of the separated Tf glycoforms. Such accurate protein quantification methods are urgently needed in particular when aiming on comparable long term health related investigations. However, since both methods can be applied independently of the availability of specific protein standards or antibodies they can be seen as universal quantification methods for the targeted biomarker. %0 journal article %@ 0041-0101 %A Lassen, S., Wiebring, A., Helmholz, H., Ruhnau, C., Prange, A. %D 2012 %J Toxicon %N 6 %P 610-616 %R doi:10.1016/j.toxicon.2012.02.004 %T Isolation of a Na-v channel blocking polypeptide from Cyanea capillata medusae - A neurotoxin contained in fishing tentacle isorhizas %U https://doi.org/10.1016/j.toxicon.2012.02.004 6 %X Jellyfish are efficient predators which prey on crabs, fish larvae, and small fish. Their venoms consist of various toxins including neurotoxins that paralyse prey organisms immediately. One possible mode of action of neurotoxins is the blockage of voltage-gated sodium (Na) channels. A novel polypeptide with Na channel blocking activity was isolated from the northern Scyphozoa Cyanea capillata (L., 1758). For that purpose, a bioactivity-guided multidimensional liquid chromatographic purification method has been developed. A neurotoxic activity of resulting chromatographic fractions was demonstrated by a bioassay, which based on the mouse neuroblastoma cell line Neuro2A. The purification process yielded one fraction containing a single polypeptide with proven activity. The molecular weight of 8.22 kDa was determined by matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-ToF MS). Utilising Laser Microdissection and Pressure Catapulting (LMPC) for the separation of different nematocyst types in combination with direct MALDI-ToF MS analysis of the intact capsules, the neurotoxin was found to be present in all types of fishing tentacle isorhizas (A-isorhizas, a-isorhizas, O-isorhizas) of C. capillata medusae. %0 journal article %@ 0214-8358 %A Helmholz, H., Wiebring, A., Lassen, S., Ruhnau, C., Schuett, C., Prange, A. %D 2012 %J Scientia Marina %N 2 %P 339-348 %R doi:10.3989/scimar.03381.16E %T Cnidom analysis combined with an in vitro evaluation of the lytic, cyto- and neurotoxic potential of Cyanea capillata (Cnidaria: Scyphozoa) %U https://doi.org/10.3989/scimar.03381.16E 2 %X The cnidocysts and the lytic, cyto- and neurotoxic potency of a large specimen of Cyanea capillata (L.) with 55 cm umbrella diameter were compared with those of a pooled C. capillata sample (average ø 14 cm) in order to investigate organismal developments at a cellular and biochemical level. Nematocysts of the type A-isorhiza in both fishing tentacles and oral arms and the O-isorhizas of oral arms were enlarged in the 55 cm specimen. Additionally, the number of nematocysts per battery in the fishing tentacles was increased. Increased gill cell toxicity and neurotoxic activity were demonstrated for the fishing tentacle venom of the 55 cm C. capillata in comparison with the smaller medusae. A two-fold higher haemolytic activity was detected for the venom of oral arms obtained from the large C. capillata compared with the oral arm venom prepared from the smaller medusae. %0 conference lecture %@ %A Wolschke, H., Sturm, R., Proefrock, D., Prange, A., Ebinghaus, R. %D 2012 %J Mikroplastik! Quo Vadis? Workshop Alfred-Wegener-Institut %T Persistente Schadstoffe in der marinen Umwelt: Welche Rolle hat Microplastik bei Eintrag, Transport und Verbleib %U %X %0 journal article %@ 0003-7028 %A Pröfrock, D., Prange, A. %D 2012 %J Applied Spectroscopy %N 8 %P 844-868 %R doi:10.1366/12-06681 %T Inductively Coupled Plasma–Mass Spectrometry (ICP-MS) for Quantitative Analysis in Environmental and Life Sciences: A Review of Challenges, Solutions, and Trends %U https://doi.org/10.1366/12-06681 8 %X This focal point review provides an overview of recent developments and capabilities of inductively coupled plasma mass spectrometry (ICPMS) coupled with different separation techniques for applications in the fields of quantitative environmental and bio-analysis. Over the past years numerous technical improvements, which are highlighted in this review, have helped to promote the evolution of ICP-MS to one of the most versatile tools for elemental quantification. In particular, the benefits and possibilities of using state-of-the-art hyphenated ICP-MS approaches for quantitative analysis are demonstrated with a focus on environmental and bio-analytical applications. %0 journal article %@ 0972-8228 %A Helmholz, H., Dong, Z., Ruhnau, C., Liu, D. %D 2011 %J Current Topics in Toxicology %P 79-87 %T Investigation on fish gill cell toxicity and haemolytic activity of Nemopilema nomurai (Scyphozoa: Rhizostoma) from the northern Yellow Sea of China %U %X Incidences of increasing jellyfish mass occurrences necessitate fundamental investigation on their distribution, development and impacts. The potential toxic activity of the giant jellyfish Nemopilema nomurai has been determined by means of in vitro assays using fish gill cells and erythrocytes as responsive elements. Fishing tentacle and oral arm tissues were used for venom analysis. The whole tissue was lyophilized in order to ensure an efficient handling and storage. For testing the toxic activity, the dried material was resuspended and the intact nematocysts were discharged by ultrasound. Four different types of nematocysts have been described using light microscopy by means of their length, width and length to width ratio. The fish gill cells showed a remarkable high susceptibility to N. nomurai venom. A five times increased toxic activity has been measured compared to the boreal Scyphozoa Cyanea capillata corresponding to an EC50 value of 1.5 µg total venom protein per mL cell culture medium. The haemolytic activity of N. nomurai venom was also potentiated compared to C. capillata venom and was determined as HE50 80.2 µg mL-1. %0 book part %@ %A Helmholz, H. %D 2011 %J Persistent Pollution Past, Present and Future %P 319-335 %R doi:10.1007/978-3-642-17419-3_17 %T Natural Substances of Marine Origin with Toxic Properties %U https://doi.org/10.1007/978-3-642-17419-3_17 %X The marine environment covers more than 70% of the earth surface and is one of the richest biospheres of the world. Biological and chemical investigations of marine ecosystems have provided insights into a fascinating and complex world underwater. The biological and chemical diversity is very high due to the array of natural conditions. It encompasses a high thermal range from −1.5°C to 350°C and a pressure range of 1–1,000 atm. The food conditions vary between nutrient rich and nutritionally sparse regions and photic and non-photic zones. Marine organisms have to adapt to these wide variety of living conditions. The adaptation capabilities are different from those of land-based organisms (Lindequist and Schweder 2001). Marine organisms live in close associations and therefore in nutrition and substrate competition (Ianora et al. 2006). In order to ensure survival and fitness it is necessary to produce secondary metabolites. The variety of secondary metabolites provides a biochemical reflection of the biotic interactions. The function of secondary metabolites is manifold. Allelochemicals are used for intra- and interspecies signaling and communication, for the deterrence of predators and herbivores or the suppression of competing neighbors. Bacterial and fungal invasion can be inhibited. Secondary metabolites can also be used for protection against UV radiation. %0 journal article %@ 0041-0101 %A Lassen, S., Helmholz, H., Ruhnau, C., Prange, A. %D 2011 %J Toxicon %N 5 %P 721-729 %R doi:10.1016/j.toxicon.2011.02.004 %T A novel proteinaceous cytotoxin from the northern Scyphozoa Cyanea capillata (L.) with structural homology to cubozoan haemolysins %U https://doi.org/10.1016/j.toxicon.2011.02.004 5 %X It is well known that jellyfish are producers of complex mixtures of proteinaceous toxins for prey capture and defence. Nevertheless, studies on boreal scyphozoans concerning venom composition and toxic effects are rare. Here the isolation of a novel cytotoxic protein from the fishing tentacle venom of Cyanea capillata (L. 1758) using bioactivity-guided, multidimensional liquid chromatography is described. The crude venom was purified utilising preparative size-exclusion, ion-exchange, and reversed-phase chromatography. The cytotoxicity of resulting chromatographic fractions has been proven by a dye-uptake assay with the human hepatocyte cell line HepG2. The final purification step yielded, among other fractions, a fraction containing a single protein (named CcTX-1) with a molecular weight of its main isoform of 31.17 kDa The purification process leads to an increased cytotoxic activity per protein equivalents and the finally isolated CcTX-1 caused a nearly total loss of cell viability at a protein concentration of 1.3 μg mL−1 corresponding to 0.4 μg/105 cells. De novo sequencing of CcTX-1 was conducted after enzymatic digestion and subsequent matrix-assisted laser desorption ionisation time-of-flight/time-of-flight mass spectrometry (MALDI-ToF/ToF MS/MS). The obtained sequence data provide an approximate 85% description of the amino acid sequence. This sequence information partially matched that of two known haemolytic proteins of two cubozoan species: CaTX-1 from Carybdea alata Reynaud, 1830 and CrTX-1 from Carybdea rastonii Haacke, 1886. %0 journal article %@ 1756-5901 %A Grebe, M., Pröfrock, D., Kakuschke, A., Broekaert, J.A.C., Prange, A. %D 2011 %J Metallomics %N 2 %P 176-185 %R doi:10.1039/c0mt00076k %T Absolute quantification of transferrin in blood samples of harbour seals using HPLC-ICP-MS %U https://doi.org/10.1039/c0mt00076k 2 %X Currently, most assay based quantification methods for Tf are limited since they often provide only information of the total Tf concentration rather than its different isoforms or deliver only relative concentrations of the Tf isoforms. Due to the lack of suitable antibodies for seal Tf also the application of more specific antibody based approaches is not possible. Within this background a new approach for the absolute quantification of the iron-transport protein Tf in the blood of harbour seals using its characteristic iron content and HPLC-ICP-MS detection is described. Method validation was performed using a certified human serum reference material (ERM-DA470K/IFCC). A Tf concentration of 2.33 ± 0.03 g L-1 (sum of all quantified isoforms) has been calculated, which is in good agreement with the certified total Tf concentration of 2.35 ± 0.08 g L-1, confirming the accuracy of the proposed analytical method. Finally, different seal samples were analysed to demonstrate the suitability of the method for the quantification of Tf in real samples as well as to observe modified glycoform patterns. A baseline reference range of 1.50 – 2.44 g L-1 Tf in serum and 0.00 – 0.18 g L-1 CDT in serum of harbour seals of the German North Sea was estimated. %0 book part %@ %A Prange, A., Proefrock, D. %D 2010 %J The Encyclopedia of Mass Spectrometry - Elemental, Isotopic & Inorganic Analysis by Mass Spectrometry %P 46-58 %T Sample Introduction in ICP-MS: Capillary Electrophoresis %U %X Requirements and challenges for the hyphenation of capillary electrophoresis (CE) with inductively coupled plasma mass spectrometry (ICP-MS) as an alternative sample introduction technique in chemical- and biochemical speciation analysis are reviewed in this chapter. Beneficial aspects and limitations of different concepts for the hyphenation of CE and ICP-MS are discussed. Recent applications of CE-ICP-MS are reviewed to demonstrate its potential and limitation in modern biochemical speciation analysis. %0 journal article %@ 0025-326X %A Kakuschke, A., Valentine-Thon, E., Griesel, S., Gandreass, J., Perez Luzardo, O., Dominguez Boada, L., Zumbado Pena, M., Almeida Gonzalez, M., Grebe, M., Pröfrock, D., Erbsloeh, H.-B., Kramer, K., Fonfara, S., Prange, A. %D 2010 %J Marine Pollution Bulletin %N 11 %P 2079-2086 %R doi:10.1016/j.marpolbul.2010.07.011 %T First health and pollution study on harbor seals (Phoca vitulina) living in the German Elbe estuary %U https://doi.org/10.1016/j.marpolbul.2010.07.011 11 %X The Elbe is one of the major rivers releasing pollutants into the coastal areas of the German North Sea. Its estuary represents the habitat of a small population of harbor seals (Phoca vitulina). Only little is known about the health status and contamination levels of these seals. Therefore, a first-ever seal catch was organized next to the islands of Neuwerk and Scharhörn in the region of the Hamburg Wadden Sea National Park. The investigations included a broad set of health parameters and the analysis of metals and organic pollutants in blood samples. Compared to animals of other Wadden Sea areas, the seals showed higher γ-globulin levels, suggesting higher concentrations of pathogens in this near-urban area, elevated concentrations for several metals in particular for V, Sn, Pb, and Sr, and comparable ranges for chlorinated organic contaminants, except for elevated levels of hexachlorobenzene, which indicates characteristic inputs from the Elbe. %0 journal article %@ 1756-5901 %A Grebe, M., Proefrock, D., Kakuschke, A., Broekaert, J.A.C., Prange, A. %D 2010 %J Metallomics %N 10 %P 683-693 %R doi:10.1039/C0MT00009D %T Metallomics approach for the identification of the iron transport protein transferrin in the blood of harbour seals (Phoca vitulina) %U https://doi.org/10.1039/C0MT00009D 10 %X The health status of marine mammals such as harbour seals (Phoca vitulina) represents an indirect but powerful way for the assessment of environmental changes. The present work illustrates the first investigation and characterisation of Tf isolated from blood samples of North Sea harbour seals with a view to using changes in Tf isoform patterns as an additional parameter in extended studies of their health status. Therefore, an HPLC-ICP-MS approach has been developed which allows the highly resolved separation and fractionation of up to eight different Tf isoforms, as well as their sensitive and specific detection on the basis of their characteristic iron content. Molecule-specific detection techniques such as nanoLC-ESI-QTRAP-MS or MALDI-TOF-MS were used as complementary techniques to unambiguously identify the isolated proteins as Tf via cross species protein identification and to further characterise the molecular weight as well as the sialic acid content, which is responsible for the elution behaviour of the different isoforms during their ion exchange separation. A molecular mass above 80 kDa has been measured for the different seal Tf isoforms, which is in good agreement with the known molecular mass in other mammalian species, while the estimated pI of the different isoforms indicates some differences in comparison to other species. A number of homologies to known Tf sequences have been observed, which finally allows the cross species protein identification. The combined metallomics orientated analytical approach, which includes the complementary application of element and molecule-specific detection techniques, opens up interesting possibilities for the fast and targeted isolation and identification of a diagnostically relevant metal containing protein from an un-sequenced mammalian species prior to its utilisation in extended studies. %0 journal article %@ 0005-2736 %A Helmholz, H. %D 2010 %J Biochimica et Biophysica Acta: Biomembranes %N 10 %P 1944-1952 %R doi:10.1016/j.bbamem.2010.06.014 %T Selective toxin–lipid membrane interactions of natural, haemolytic Scyphozoan toxins analyzed by surface plasmon resonance %U https://doi.org/10.1016/j.bbamem.2010.06.014 10 %X A comparison of the molecular interaction of natural Scyphozoan lysins with their bioactivity in a haemolytic assay was performed by establishing an efficient, automatable and reproducible procedure for the measurement of protein-membrane interactions. The toxin–membrane interactions were analyzed utilising a chip-based technology with immobilized liposomes as artificial cell membranes. The technique was established with streptolysin O as a cholesterol-selective model toxin and its cholesterol-selectivity has been proven. The haemolytic potency of protein fractions derived from the venom of the jellyfish Aurelia aurita and Cyanea capillata was tested and EC50 values of 35.3 μg/mL and 43.1 μg/mL against sheep and 13.5 μg/mL and 8.8 μg/mL against rabbit erythrocytes were measured. Cell membrane binding as a first step in the haemolytic process was analyzed using the Biacore® technology. Major cell membrane lipids (cholesterol, sphingomyelin and phosphatidylcholine) were immobilized as pure liposomes and in binary mixtures. A preference for cholesterol and sphingomyelin of both jellyfish species was demonstrated. The specificity of the method was proven with a non-haemolytic A. aurita protein fraction that did not express a lipid binding. Additionally, an inactivated C. capillata lysine with negligible haemolytic activity showed a remaining but reduced adsorption onto lipid layers. The binding level of the lytic venom fraction of these dominant boreal jellyfish species increased as a function of protein concentration. The binding strength was expressed in RU50 values ranging from 12.4 μg/mL to 35.4 μg/mL, which were in the same order of magnitude as the EC50 values in the haemolytic assay. %0 journal article %@ 1436-2228 %A Wiebring, A., Helmholz, H., Soetje, I., Lassen, S., Prange, A., Tiemann, H. %D 2010 %J Marine Biotechnology %N 3 %P 308-317 %R doi:10.1007/s10126-010-9261-7 %T A New Method for the Separation of Different Types of Nematocysts from Scyphozoa and Investigation of Proteinaceous Toxins Utilizing Laser Catapulting and Subsequent Mass Spectrometry %U https://doi.org/10.1007/s10126-010-9261-7 3 %X Jellyfish have an increasing impact on marine ecology. Cnidocysts bearing stinging cells afford, amongst others, prey capture and defence. Several different types of stinging capsules are found in one species and they are supposed to have specific functions, e.g. paralysing prey or adhering to it. Due to these assumed different roles of the capsules, it is suggested that toxins, which are contained in the capsules, differ in composition. Analysis of distinct types of nematocysts requires an appropriate method for the separation of the different types. Mixtures of types of nematocysts were obtained of two species of jellyfish, Aurelia aurita and Cyanea lamarckii, by maceration of the tissue. These mixtures were treated with a method called laser microdissection and pressure catapulting (LMPC). Optimized maceration methods, which were firstly introduced as a method for this purpose, in conjunction with optimized LMPC parameters lead to sufficient amounts of separated capsules of individual types for subsequent mass-spectrometric analyses. In case of A. aurita, the resulting mass spectra had some constituents in common, whereas in the overall pattern, the two distinct nematocyst types differed. %0 journal article %@ 0018-8158 %A Helmholz, H., Johnston, B.D., Ruhnau, C., Prange, A. %D 2010 %J Hydrobiologia %N 1 %P 223-234 %R doi:10.1007/s10750-010-0216-9 %T Gill cell toxicity of northern boreal scyphomedusae Cyanea capillata and Aurelia aurita measured by an in vitro cell assay %U https://doi.org/10.1007/s10750-010-0216-9 1 %X Scyphozoan medusae are very successful foragers which occasionally occur in high abundances in boreal waters and may impact many different groups in the marine ecosystem by means of a variety of toxins. A rainbow trout gill cell line, RTgill-W1, was tested for its suitability as quantitative indicator of the cytotoxicity of Cyanea capillata and Aurelia aurita; the major scyphozoan species in the North and Baltic seas. Cultures of rainbow trout gill cells were exposed to whole venoms extracted from fishing tentacles and oral arms at increasing protein concentrations. The venom caused detachment, clumping and lysis of cells, as well as a drop in vitality, in a dose-dependent manner. Morphological changes in the cells were evident within 1 h after venom addition. The damage to gill cells was quantified by measuring the metabolic activity of the cells by means of the fluorescence of resorufin derived from the nonfluorescent substrate, resazurin. In general, a decrease in the metabolic activity of the cells was detected at a venom (protein) concentration above 2.0 μg ml−1 (corresponding to 0.2 μg 104 cells−1), and a total loss of activity was observed above 40.0 μg ml−1 (corresponding to 4.0 μg 104 cells−1). C. capillata venoms had increased cytotoxic activity as compared to A. aurita venoms at the same concentration. Cnidocyst extracts from oral arms of A. aurita induced an 85% loss of gill cell viability at concentrations of 0.2 μg 104 cells−1, whereas crude venoms from fishing tentacles reduced cell viability by 18% at the same concentration. Gel electrophoresis of the venoms indicated that these consist of a large number of proteins in a fairly wide size range, from 6 to 200 kDa, including some that are the same size as those found in cubomedusae. It also appears that larger (i.e., older) medusae have more complex venoms and, in some cases, more potent venoms than smaller animals. %0 journal article %@ 0018-8158 %A Wiebring, A., Helmholz, H., Lassen, S., Prange, A., Jarms, G. %D 2010 %J Hydrobiologia %N 1 %P 203-212 %R doi:10.1007/s10750-010-0227-6 %T Separation and analysis of different types of nematocysts from Cyanea capillata (L.) medusae %U https://doi.org/10.1007/s10750-010-0227-6 1 %X Medusae play an important role in marine ecosystems, as competitors of many invertebrate and fish species. Additionally, jellyfish stings can cause severe pain, inflammation of the affected skin, and allergic reactions in human. Climate and environmental changes are likely to affect the medusae, but it is not yet clear whether these will affect their distribution, physiology, and their toxicity. Very little is known about the effect of biotic and abiotic factors on the proliferation and the distribution of medusan nematocysts. In this study, we compared three types of nematocysts (euryteles and A- and O-isorhizas) and venoms of Cyanea capillata medusae (Scyphozoa) obtained from the North Sea and the Baltic Sea, which have different salinity and temperature ranges. Different types of nematocysts were separated by laser microdissection and pressure catapulting (LMPC), and the proteinaceous contents of the nematocysts were analyzed by matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS). Medusae from the brackish Baltic Sea possessed more euryteles than those from the North Sea. The O-isorhizas and A-isorhizas were smaller in the Baltic Sea sample compared to the North Sea samples and the length-to-width ratios were larger in the Baltic Sea sample. Moreover, the pattern of proteins (potential toxins) obtained from the separated nematocysts showed differences among samples and nematocyst types, but no clear pattern was observable. This study displays the novel LMPC/MALDI-TOF MS approach as a useful tool to investigate the function and venom of cnidarian nematocysts types. %0 journal article %@ 0018-8158 %A Lassen, S., Helmholz, H., Ruhnau, C., Prange, A. %D 2010 %J Hydrobiologia %N 1 %P 213-221 %R doi:10.1007/s10750-010-0215-x %T Characterisation of neurotoxic polypeptides from Cyanea capillata medusae (Scyphozoa) %U https://doi.org/10.1007/s10750-010-0215-x 1 %X Cnidarian venoms include neurotoxins, which are able to paralyse prey organisms immediately. Important targets for neurotoxins are voltage-gated ion channels in membranes of excitable cells. By blocking specific receptor sites, neurotoxic components disturb the physiological ion channel functions. Here, we describe the isolation and characterisation of potential neurotoxic polypeptides from the crude tentacle venom of the boreal scyphomedusan Cyanea capillata. Partially purified venom fractions were obtained by size-exclusion and subsequent reversed-phase chromatography. To assess the blocking activity of the venom on voltage-gated sodium channels, we modified a mouse neuroblastoma (MNB) cell assay. Venom fractions containing channel-blocking activity were analysed by matrix-assisted laser desorption ionisation time-of-flight mass spectrometry (MALDI-TOF MS). The resulting mass spectra revealed a cluster of singly charged peptides within a mass range from 3,900 to 7,000 Da. A group of three potentially neurotoxic peptides with molecular masses of 3983.4, 5795.4 and 6962.1 Da could be tracked throughout the purification process. This investigation of the crude venom is part of a multidimensional assay-guided approach for the isolation and structural characterisation of toxic polypeptides in northern Scyphozoa. %0 journal article %@ 0169-7439 %A Aulinger, A., Einax, J.W., Prange, A. %D 2004 %J Chemometrics and Intelligent Laboratory Systems %N 1 %P 35-41 %T Setup and optimization of a PLS regression model for predicting element contents in river sediments %U 1