Open Access

Shipping plays a significant role in the global trade. However, it is negatively impacted by the unwanted accumulation of marine organisms on the ship hulls. To prevent the so-called bio-fouling, antifoulant paints containing the organometallic compound tributyltin (TBT) have been used on ship hulls since the 1960s. Compared to the generally considered non-toxic inorganic tin, the endocrine disruptor TBT leads to the endangerment of non-target organisms. The most prominent effects are imposex in snails and shell deformation in oysters. This resulted in a global ban by the International Maritime Organization in 2008. Nevertheless, recent studies have found alarmingly high concentrations in sediment. Organotin compounds (OTCs) are known to persist and accumulate in marine sediments, posing a long-term threat to the environment. Once released from the ship hull, TBT gets effectively absorbed into the sediment. Under anaerobic conditions and the absence of light, the half-life is extended up to several decades. The resuspension and transport of sediment remobilizes butyltin compounds, making them bioavailable even in distant regions. The monitoring of OTCs in sediment is inevitable to conduct a comprehensive risk assessment and a thorough monitoring of pollution. Conventionally, species-specific analysis of OTCs involves (gas-)chromatographic separation after extraction and pre-concentration of the analytes. However, the sample preparation is time-consuming, chemical-intensive, and prone to species-transformation, respectively incomplete extraction. In this context, electrothermal vaporization coupled with inductively coupled plasma-mass spectrometry (ETV/ICP-MS) shows high potential as a rapid and chemical-saving screening tool for OTCs in environmental samples. The main challenge for obtaining correct, quantitative data with direct solid sampling techniques like ETV/ICP-MS is the application of a suitable calibration strategy. In this context, a new quantification method based on on-line isotope dilution analysis has been developed and validated by a reference material with certified OTC content. Our approach overcomes matrix effects while being compatible with commercially available ETV systems. Using an optimized multi-step ETV temperature program, the full separation of OTCs, inorganic tin, and major matrix components could be achieved. Since its use as a screening tool, analyzing OTCs as a sum parameter is beneficial and can complement chromatographic approaches.

We report a quantification approach for directly determining total tin and tin-based pollutants/species in sediments via electrothermal vaporization/inductively coupled plasma-mass spectrometry (ETV/ICP-MS) utilizing an on-line isotope dilution mass spectrometry (IDMS) approach. The method was developed and validated using an estuarine sediment reference material (BCR-277R), yielding a recovery of 106%. A relative standard deviation (RSD) of 14%, comparable to published data using a similar method, was obtained. A limit of quantification (LOQ) was estimated at 0.008 mg Sn kg−1 and sufficient for quantifying the total tin mass fraction of surface sediments along the tidal River Elbe course. Hereby, a decrease towards the river mouth, presumably due to dilution effects by less polluted marine sediment, was observed. Besides total tin, monitoring of organotin compounds (OTCs)/species is of interest in sediments due to their toxic effects on aquatic life. The method’s capability was extended by separating an OTC fraction in a sediment certified reference material (CRM) through the ETV temperature program. While spiking experiments with OTC standards confirmed the assignment, only a small fraction of the total certified OTC amount (3%), likely due to matrix effects, was recovered. However, applying the method to real-world samples, OTCs were detectable along the River Elbe course. By this, we demonstrated the potential of our method as a complementary fast-screening approach to species-specific analysis procedures.

Organic fluorine sum parameters are used to detect F-containing pollutants, e.g., per- and polyfluoroalkyl substances (PFASs), in the environment, within materials, or for monitoring technical processess, e.g., thermal decomposition of PFAS during municipal waste incineration. However, established approaches determining the extractable organic and adsorbable organic fluorine content (EOC and AOC) require laborious and error-prone sample preparation. We report a solid sampling-electrothermal vaporization (ETV) method for direct fluorine measurement based on the formation of [138Ba19F]+ with an inductively coupled plasma-triple quadrupole-mass spectrometer (ICP-QQQ-MS). Method development involved the instrumental setup for Ba introduction and fluorine-specific tuning of lens and collision-reaction cell (CRC) parameters. An inorganic fluorine fraction was detected in a cyclonic dust sample from a municipal waste incineration plant as a peak above a broad background signal. The content was estimated through standard addition using a NaF solution to 2300 mgg−1. With a limit of detection (LOD) of 130 mg g−1, which was below the reported value for an electrothermal vaporization/inductively coupled plasma-mass spectrometry (ETV/ICP-MS) approach, acquiring [19F]+. The method's potential for fractionation analysis was demonstrated by analyzing polytetrafluoroethylene (PTFE) powder.

Electrothermal vaporization coupled with inductively coupled plasma-mass spectrometry (ETV/ICP-MS) shows potential as a fast and convenient screening tool for the monitoring of emerging metal-based pollutants in environmental samples. Organo tin compounds (OTCs) have been widely applied as biocidal ingredients in ship paints in the last century, but are still present in the environment. Conventionally, the analysis of OTCs in sediment samples involves (gas-) chromatographic separation after extraction and pre-concentration of the analytes. With ETV/ICP-MS, it is possible to skip time-consuming and chemical-intensive sample preparation steps, which are prone to errors.

Plastics are indispensable in our daily lives. Due to their easy processability, durability, and lightweight properties, they are the base material of many consumer and industry products. However, with reported amounts of millions of tons per year, plastic pollution has become a globally emerging problem. In the environment, plastic waste undergoes degradation, leading to the formation of persistent, synthetic particles smaller than 5 mm, known as microplastics (MPs). Toxicological concerns mainly arise from MP uptake by various organisms, including humans. MPs act as transport vectors for hazardous chemicals, e.g., polymer additives, bacteria, and other environmental pollutants. Existing approaches for MP analysis focus on particle size, number, and information on the polymer types. However, there is a lack of analytical tools for a fast and comprehensive assessment of the pollution situation based on the MP mass without limitations to size and polymer types. In this context, a new mass balance approach for the MPs analysis in environmental samples via electrothermal vaporization coupled with inductively coupled plasma-mass spectrometry (ETV/ICP-MS) has been developed as a complementary screening tool to existing methods. With ETV/ICP-MS, the bulk detection of MPs via the 13C isotope as a sum parameter of common polymer types was achievable relatively unaffected by the respective size across the nano-to-micrometer scale. A new mass-based approach through an external gas calibration with carbon dioxide enabled the fast quantification of the MP content in MP-soil mixtures of different portions. By this, the analysis was achievable within a few minutes of analysis time per sample. Furthermore, the potential of polymer heteroatoms and contaminants for the sensitive detection in carbon-rich matrices was investigated.