TY - JOUR A1 - Faßbender, Sebastian A1 - von der Au, Marcus A1 - Koenig, Maren A1 - Pelzer, J. A1 - Piechotta, Christian A1 - Vogl, Jochen A1 - Meermann, Björn T1 - Species-specific isotope dilution analysis of monomethylmercury in sediment using GC/ICP-ToF-MS and comparison with ICP-Q-MS and ICP-SF-MS N2 - A recently introduced inductively coupled plasma-time-of-flight-mass spectrometer (ICP-ToF-MS) shows enhanced sensitivity compared to previous developments and superior isotope ratio precision compared to other ToF and commonly used single-collector ICP-MS instruments. Following this fact, an improvement for isotope dilution ICP-MS using the new instrumentation has been reported. This study aimed at investigating whether this improvement also meets the requirements of species-specific isotope dilution using GC/ICP-MS, where short transient signals are recorded. The results of the analysis of monomethylmercury (MMHg) of a sediment reference material show that isotope ratio precision of ICP-MS instruments equipped with quadrupole, sector-field, and time-of-flight mass analyzers is similar within a broad range of peak signal-to-noise ratio when analyzing one isotopic system. The procedural limit of quantification (LOQ) for MMHg, expressed as mass fraction of Hg being present as MMHg, w(Hg)MMHg, was similar as well for all investigated instruments and ranged between 0.003 and 0.016 μg/kg. Due to the simultaneous detection capability, the ICP-ToF-MS might, however, be more favorable when several isotopic systems are analyzed within one measurement. In a case study, the GC/ICP-ToF-MS coupling was applied for analysis of MMHg in sediments of Finow Canal, a historic German canal heavily polluted with mercury. Mass fractions between 0.180 and 41 μg/kg (w(Hg)MMHg) for MMHg, and 0.056 and 126 mg/kg (w(Hg)total) for total mercury were found in sediment samples taken from the canal upstream and downstream of a former chemical plant. KW - Methylmercury KW - Legacy pollution KW - Finow Canal KW - Isotope dilution KW - Mercury speciation PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-529967 DO - https://doi.org/10.1007/s00216-021-03497-z SN - 1618-2642 VL - 413 IS - 21 SP - 5279 EP - 5289 PB - Springer CY - Berlin AN - OPUS4-52996 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Faßbender, Sebastian T1 - Mercury speciation in sediments of a historic industrially used canal in Northern Germany using SSID GC-ICP-ToF-MS N2 - Sediments and soils can act as sinks of species of inorganic mercury (Hg2+), while they are simultaneously sources of volatile (Hg0) and organic species, such as monomethylmercury (MMHg). Although the fraction of MMHg in total Hg of sediments is suggested to be as low as 0.1 1%, MMHg is a serious threat for humans and wildlife due to its high potential for bioaccumulation and biomagnification and the ability to pass the blood-brain barrier. This is highlighted by exceptionally high MMHg concentrations found in fish and fish predators, as well as aquatic insects and birds living in close vicinity to Hg contaminated waterbodies. Humans are exposed to MMHg mainly by ingestion of (predatory) fish and rice. One example of a highly Hg contaminated waterbody is Finow Canal, the oldest artificial waterway still in operation in Germany, with Hg mass fractions of up to or even more than 100 µg/g found in the sediment, which are suggested to be attributable to a chemical plant producing (among other things) mercury-based seed dressings. Despite this high mass fraction of Hg, anaerobic conditions, high amounts of organic matter and iron, which are all favorable for Hg methylation, no investigations of Hg speciation have been conducted there up to now. We investigated Hg speciation in sediments of Finow Canal on length from before the known polluted sited into the confluence with another waterway using species-specific isotope dilution (SSID) GC-ICP-ToF-MS. Mass fraction of up to 41 ng/g MMHg were determined in samples taken from Finow Canal and elevated concentrations could also be found around 14 km downstream of the confluence of Finow Canal with another waterway. In addition to this, highly toxic monoethylmercury (EtHg) could be detected in most of the sediment samples. These results are the first evidence of the occurrence of MMHg in this region and show the need for further investigation of the whole regional ecosystem, as well as the consideration of possible measures of remediation. T2 - Virtual Goldschmidt 2021 CY - Online meeting DA - 04.07.2021 KW - Methylmercury KW - Finow Canal KW - Legacy pollution KW - Isotope dilution PY - 2021 AN - OPUS4-52945 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -