Personal care products (PCPs) are compounds entering into the environment through direct discharges or ineffective removal in wastewater treatment plants. Recreational activities in lakes and beaches are additional direct sources of PCPs, especially during widespread use of sunscreens in the summer. However, even if PCPs are largely emitted into the water compartment, the atmosphere is particularly prone to the contamination of these compounds, both from direct inputs during on purpose use (e.g., perfumes and fragrances), or through re-volatilization from various environmental media acting as secondary sources. Moreover, the atmosphere represents a key environmental matrix to understand the environmental fate of these compounds: recent research showed that fragrances and UV-Filters are significantly distributed in the snow both from the Arctic and Antarctica, likely deriving from the cold-condensation of long-range transported aerosols. Nevertheless, the direct analysis of the occurrence of these PCPs in polar and remote air samples is missing, and even in urban and anthropized areas the knowledge on their distribution in atmospheric samples is still limited, in comparison to the studies reported for the water compartment.

In this work we developed and validated an innovative analytical method using a low-temperature (°40 C) Accelerated Solvent Extraction (ASE) procedure for the analyses of fragrances and UV-Filters in aerosol samples, including the particulate (quartz filter) and gaseous (Polyurethane foam – PUF) phases, avoiding the large solvent volumes needed for classical extraction. The method was applied to exploratory air samples collected during summer 2023 in low and high impacted areas of the Veneto region, including urban, mountain and coastal environments. Highest levels were detected in the venetian coastline, reflecting the high local use of sunscreen lotions containing UV-filters, but PCPs were occurring with a different pattern also in background areas of the Dolomites (Alps). Urban samples resulted at intermediate concentrations. Confirming our previous hypotheses and findings, PCPs, in particular Salicylates, are mainly distributed in the gas phase, with the exception of octacrylene, which is generally associated with the particulate. The analytical improvements developed with this method will be fundamental for the future understanding of the behaviour of PCPs in the atmosphere, including studies in remote and polar areas to confirm the long-range transport hypothesis.

Acknowledgements: IRIDE funding received by the Department of Environmental Sciences, Informatics and Statistics (DAIS) of the Ca’ Foscari University of Venice.

How to cite: Vecchiato, M., Costa, D., Barbaro, E., Mazzi, G., and Gambaro, A.: A novel method for the determination of Personal Care Products (PCPs) in aerosol samples: occurrence in urban, mountain and coastal environments., EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2336, https://doi.org/10.5194/egusphere-egu24-2336, 2024.

Endocrine disruptors are widely present in the environment and are defined as a subset of endocrine disruptors due to the biological activity of environmental estrogens (xenoestrogens). These substances persist as trace environmental pollutants and contribute to the material cycle. Atmospheric transportation is regarded as the main source of xenoestrogens in inland lakes. However, previous research on the air-water exchange of ecological estrogens in freshwaters has been limited, and studies have indicated that sex differences may result in heterogeneity in the health effects of the same air pollutants. Consequently, this study aims to access the interface exchange process of selected xenoestrogens and the health risks associated with non-dietary exposure in adults.

The results showed significant differences in the direction of air-water exchange for various exogenous estrogens. The air-water exchange rate of dibutyl phthalate is closely correlated with temperature and humidity. Discrepancies in melting point and water solubility of other exogenous estrogens may contribute to differences in exchange rate. Moreover, the non-dietary intake of health hazards posed by six environmental estrogens in atmospheric fine particulate matter is within acceptable limits (Total Health Risk < 1). Among these, dioctyl phthalate, identified as a potential carcinogenic pollutant, also falls within an acceptable level of carcinogenic risk (<10^-6). In Suzhou, men are found to face higher health risks from inhalation and skin-to-skin contact compared to women when outdoors. This finding contributes to a comprehensive understanding of the pollution profile and hazards associated with environmental estrogens in the Taihu Lake Basin. It supports the refinement and implementation of policies for ecological estrogen management.

How to cite: Wang, M., Li, D., Tong, T., Wang, F., Chen, K., Zhang, H., and Han, L.: Air-Water Exchange of Xenoestrogen in Surface Water in Suzhou of China and the Health Assessment, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-2437, https://doi.org/10.5194/egusphere-egu24-2437, 2024.

Non-traditional VOC emissions, including emerging pollutants, air toxics, and volatile chemical products (VPCs) span a range of volatilities and molecular structures that impact their reactivity in the atmosphere and eventual fate. However, little is known their source apportionment, temporal behavior, and relative importance to health impacts along with ozone and SOA formation. With the need to characterize these emissions, comprehensive measurement techniques that capture the unexpected but are also highly specific to detail molecular structure and provide compound quantification are needed.

The work presented in this study uses chemical ionization (CI) techniques (H3O+, NH4+, NO+, O2+) for the direct detection and quantification of VOCs considered to be hazardous air pollutants (HAPs). With our work, we show that the ionization patterns for these classes of compounds within each ionization scheme can be used to expand these methods to interpret unknown signals in complex environments. This detailed characterization was conducted by coupling in-situ gas chromatography (GC) to the CI-TOF-MS for pre-separation of the complex mixture. Our results show how the speciated data can be used to deconvolve the complexities of chemical ionization detection (including the presence of fragmentation, cluster formation, and mixed ionization schemes e.g. proton transfer, charge transfer, dehydration).

To apply these methods to ambient atmospheric measurements we need to reconcile the need for both continuous isomer specific quantification and high time resolution data. To accomplish this, we simultaneously coupled the in-situ GC with both CI and electron ionization (EI) TOF-MS. Resulting in the generation of three data sets (GC-EI, GC-CI, and direct-CI data) that offer continuous GC quantification, universal detection of speciated organics (EI), speciated CI data to constrain interferences, and direct-CI data for high time resolution data. This instrument combination was deployed in Spring 2023 for a 4-week mobile laboratory campaign in a region of southeast Louisiana, US that is dense with petrochemical production and industrial activity, to quantify hazardous air pollutants to gauge exposure for the local population. The combination of the in-situ GC, EI-TOF-MS, PTR-TOF-MS was used to provide highly specific, quantitative data on VOCs considered to be air toxics in the area, while also acquiring high time resolution PTR-TOF data that allowed the characterization of different point sources and their variability over time-of-day and day-of-week.

How to cite: Claflin, M., Lerner, B., Stark, H., Krechmer, J., and DeCarlo, P.: ­­Non-targeted VOC Quantification through the Simultaneous Coupling of an in-situ Gas Chromatograph to Electron and Chemical Ionization Time-of-Flight Mass Spectrometers, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-4171, https://doi.org/10.5194/egusphere-egu24-4171, 2024.

Hydrofluoroolefins (HFOs) are being used as substitutes for potent greenhouse gases hydrofluorocarbons (HFCs). However, the use and environmental impacts of HFOs are of great concern due to the rapid degradation of HFOs to produce persistent and phytotoxic trifluoroacetic acid (TFA), one of the per- and polyfluoroalkyl substances (PFAS). HFO-1234yf is the most widely used HFO and has the greatest formation potential of TFA. Here, we provided a comprehensive projection of HFO-1234yf emission in China during 2025-2060. GEOS-Chem was applied to simulate the atmospheric processes of HFO-1234yf and to characterize the distribution of the degradation product TFA. A water quality model was further adopted to assess the impact of HFO-1234yf emissions on surface terminal water body TFA concentrations in China. Under the Kigali Amendment to the Montreal Protocol, HFO-1234yf emission in China was estimated to increase from 1.5 to 79.0 kt in 2025-2060 with cumulative emission of 1.7 Mt. The annual deposition flux (dry plus wet) of TFA due to HFO-1234yf emission was expected to grow from 0.02 kg/km²/year in 2025 to 0.9 kg/km²/year in 2060, dominated by wet deposition. After continuous emission of HFO-1234yf from 2025 to 2060, the average concentration of TFA in terminal waters in China was projected to increase by 7.4 μg/L. The results of this study can provide scientific support for evaluating the environmental risks of HFOs uses and help in developing HFCs phase-out pathways for addressing climate change.

How to cite: Wang, Y., Liu, L., and Zhang, J.: Projections of emission, fate and impact of HFO-1234yf in China, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-6239, https://doi.org/10.5194/egusphere-egu24-6239, 2024.

Endosulfan is a persistent organochlorine pesticide that was globally distributed before it was banned in 2013, and it continues to cycle in the Earth system. The chemical kinetics of the gas-phase reaction of α-endosulfan with the hydroxyl radical (OH) was studied by means of pulsed vacuum UV flash photolysis and time resolved resonance fluorescence (FP-RF) as k_OH = 5.8×10^-11 e^{(-1960 K/T)} cm³ s^-1 with an uncertainty range of 7×10^-12 e^{(-1210 K/T)} to 4×10^-10 e^{(-2710 K/T)} cm³ s^-1. This corresponds to an estimated photochemical atmospheric half-life in the range of 3-12 months, which is much longer than previously assumed (days to weeks).

Comparing the atmospheric concentrations observed after the global ban of endosulfan with environmental multimedia model predictions, we find that photochemical degradation in the atmosphere is slower than biodegradation in soil or water, and that the latter limits the total environmental lifetime of endosulfan. We conclude that the lifetimes typically assumed for soil and aquatic systems are likely underestimated and should be revisited, in particular for temperate and warm climates. Moreover, the pollutant may persist in soil and sediment burdens disconnected from compartmental interfaces.

How to cite: Lammel, G., Alarcon, P. C., Padervand, M., Pöschl, U., and Zetzsch, C.: Why is the pesticide endosulfan not disappearing from the global environment after ban?, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-20039, https://doi.org/10.5194/egusphere-egu24-20039, 2024.

Emerging particulate pollutants, ranging from nanoparticles to microplastics, present multifaceted challenges in their detection and characterisation within the atmosphere. Particle immobilisation techniques, which we originally developed for the analysis of microplastics (MP), have demonstrated great versatility for experimental and methodological development, allowing per-particle manipulative investigations and sample persistence over extended periods under various treatments. These techniques may prove useful for wider applicability to other particulate pollutants.

We have been immobilising particles below 100 µm to for the evaluation of purification methods and for conducting interlaboratory analytical comparisons (ILCs). In purification method evaluation, our immobilisation approaches withstand chemical treatments, enabling pre-post comparisons while preserving particle integrity and aiding in method validation. By immobilising MP on suitable substrates, we have established a framework for serial ILCs where the same sample is measured by all ILC participants, reducing inter-participant analytical variation by up to 77% compared to a conventional parallel ILC design using suspended samples.

Beyond MP, these techniques have potential applications for atmospheric particulate pollutants such as soot or fly ash. The immobilisation concept, using filtration with inorganic adhesives, allows reproducibility in analytical assessments across different types of particulate matter. In addition, we discuss the opportunities and obstacles of particle immobilisations as routine procedures, which can help to build up persistent sample archives or to establish robust re-measureable QA/QC reference samples. Multi-method analyses such as correlative microscopy and microspectroscopy can benefit from the application of particle immobilisation techniques.

How to cite: Lenz, R., Enders, K., Schumacher, M., Lötsch, J., Labrenz, M., and Fischer, D.: Particle immobilisation techniques: Applications for microplastics and beyond, EGU General Assembly 2024, Vienna, Austria, 14–19 Apr 2024, EGU24-20085, https://doi.org/10.5194/egusphere-egu24-20085, 2024.