Development, validation, and application of a new method for the quantitative determination of monohydrogen-substituted perfluoroalkyl carboxylic acids (H-PFCAs) in surface water

Awchi, M; Gebbink, WA; Berendsen, BJA; Benskin, JP; van Leeuwen, SPJ
2022 | Chemosphere | 287
h-pfcas , lc-ms , line , ms , pfas , pfcas , samples , substances , surface water , suspect
Per- and polyfluoroalkyl substances (PFASs) are a large and diverse class of chemicals. While some have been phased out internationally due to concerns over their human and environmental health risks, novel alternative PFASs continue to be manufactured and detected in environmental samples. The occurrence and fate of these alternatives remain poorly understood. The present study investigated the occurrence of an emerging class of PFAS alternative, the monohydrogen-substituted perfluoroalkyl carboxylic acids (H-PFCAs), in conjunction with the more well-known PFCAs. A weak anion exchange solid phase extraction-liquid chromatography tandem mass spectrometry method for quantitative determination of H-PFCAs in surface water was developed, validated, and applied on samples collected from the Netherlands. To improve chromatography, especially for short-chain (H-) PFCAs, an ion-pairing agent, tetrabutylammonium hydrogen sulphate, was used. The method was validated for linearity (R2 > 0.99), instrumental detection limits (0.01-0.09 ng/mL), method detection limits (0.03-0.75 ng/ mL), matrix effects (<20%), percent absolute- and relative recovery (57-121%), trueness (130-80%), repeatability (<20%), and within-lab reproducibility (<20%). Eleven out of fourteen PFASs showed acceptable results. Application of the newly validated method to surface water throughout the Netherlands revealed trace levels of H-PFCAs (including two new H-PFCAs) and high concentrations of PFCAs.

Editorial: ACS Environmental Au – Your Open Access Journal for Premier Environmental Research

Xiangdong, L.; Cousins, I.T.; Hornbuckle, K.
2021 | ACS Environ. Au | 1 (1) (1-3)

A New OECD Definition for Per- and Polyfluoroalkyl Substances

Wang, Z.; Buser, A.M.; Cousins, I.T.; Demattio, S.; Drost, W.; Johansson, O.; Ohno, K.; Patlewicz, G.; Richard, A.M; Walker, G.W.; White, G.S.; Leinala, E.
2021 | Environ. Sci. Technol. | 55 (23) (15575-15578)

Seasonal Variations in the Daily Mortality Associated with Exposure to Particles, Nitrogen Dioxide, and Ozone in Stockholm, Sweden, from 2000 to 2016

Olstrup, H.; Johansson, C.; Forsberg, B.; Åström, C.; Orru, H.
2021 | ATMOSPHERE | 12 (11)

Urban air pollutant emissions and concentrations vary throughout the year due to various factors, e.g., meteorological conditions and human activities. In this study, seasonal variations in daily mortality associated with increases in the concentrations of PM10 (particulate matter), PM2.5–10 (coarse particles), BC (black carbon), NO2 (nitrogen dioxide), and O3 (ozone) were calculated for Stockholm during the period from 2000 to 2016. The excess risks in daily mortality are presented in single and multi-pollutant models during the whole year and divided into four different seasons, i.e., winter (December–February), spring (March–May), summer (June–August), and autumn (September–November). The excess risks in the single-pollutant models associated with an interquartile range (IQR) increase for a lag 02 during the whole year were 0.8% (95% CI: 0.1–1.4) for PM10, 1.1% (95% CI: 0.4–1.8) for PM2.5–10, 0.5% (95% CI: −0.5–1.5) for BC, −1.5% (95% CI: −0.5–−2.5) for NO2, and 1.9% (95% CI: 1.0–2.9) for O3. When divided into different seasons, the excess risks for PM10 and PM2.5–10 showed a clear pattern, with the strongest associations during spring and autumn, but with weaker associations during summer and winter, indicating increased risks associated with road dust particles during these seasons. For BC, which represents combustion-generated particles, the pattern was not very clear, but the strongest positive excess risks were found during autumn. The excess risks for NO2 were negative during all seasons, and in several cases even statistically significantly negative, indicating that NO2 in itself was not harmful at the concentrations prevailing during the measurement period (mean values < 20 µg m−3). For O3, the excess risks were statistically significantly positive during “all year” in both the single and the multi-pollutant models. The excess risks for O3 in the single-pollutant models were also statistically significantly positive during all seasons.

New Insights Into the Composition and Origins of Ultrafine Aerosol in the Summertime High Arctic

Lawler, M. J.; Saltzman, E. S.; Karlsson, L.; Zieger, P.; Salter, M.; Baccarini, A.; Schmale, J.; Leck, C.
2021 | Geophys Res Lett | 48 (21)

The summertime high Arctic atmosphere is characterized by extremely low aerosol abundance, such that small natural aerosol inputs have a strong influence on cloud formation and surface temperature. The physical sources and the mechanisms responsible for aerosol formation and development in this climate-critical and changing region are still uncertain. We report time-resolved measurements of high Arctic Aitken mode (∼20–60 nm diameter) aerosol composition during August–September 2018. During a significant Aitken mode formation event, the particles were composed of a combination of primary and secondary materials. These results highlight the importance of primary aerosol sources for high Arctic cloud formation, and they imply the action of a poorly understood atmospheric mechanism separating larger particles into multiple sub-particles.

Estimates of mass absorption cross sections of black carbon for filter-based absorption photometers in the Arctic

Sho Ohata; Tatsuhiro Mori; Yutaka Kondo; Sangeeta Sharma; Antti Hyvärinen; Elisabeth Andrews; Peter Tunved; Eija Asmi; John Backman; Henri Servomaa; Daniel Veber; Konstantinos Eleftheriadis; Stergios Vratolis; Radovan Krejci; Paul Zieger; Makoto Koike; Yugo Kanaya; Atsushi Yoshida; Nobuhiro Moteki; Yongjing Zhao; Yutaka Tobo; Junji Matsushita; Naga Oshima
2021 | Atmos. Meas. Tech. | 14 (6723-6748)

Long-term measurements of atmospheric mass concentrations of black carbon (BC) are needed to investigate changes in its emission, transport, and deposition. However, depending on instrumentation, parameters related to BC such as aerosol absorption coefficient (babs) have been measured instead. Most ground-based measurements of babs in the Arctic have been made by filter-based absorption photometers, including particle soot absorption photometers (PSAPs), continuous light absorption photometers (CLAPs), Aethalometers, and multi-angle absorption photometers (MAAPs). The measured babs can be converted to mass concentrations of BC (MBC) by assuming the value of the mass absorption cross section (MAC; MBC= babs/ MAC). However, the accuracy of conversion of babs to MBC has not been adequately assessed. Here, we introduce a systematic method for deriving MAC values from babs measured by these instruments and independently measured MBC. In this method, MBC was measured with a filter-based absorption photometer with a heated inlet (COSMOS). COSMOS-derived MBC (MBC (COSMOS)) is traceable to a rigorously calibrated single particle soot photometer (SP2), and the absolute accuracy of MBC (COSMOS) has been demonstrated previously to be about 15 % in Asia and the Arctic. The necessary conditions for application of this method are a high correlation of the measured babs with independently measured MBC and long-term stability of the regression slope, which is denoted as MACcor (MAC derived from the correlation). In general, babs–MBC (COSMOS) correlations were high (r2= 0.76–0.95 for hourly data) at Alert in Canada, Ny-Ålesund in Svalbard, Barrow (NOAA Barrow Observatory) in Alaska, Pallastunturi in Finland, and Fukue in Japan and stable for up to 10 years. We successfully estimated MACcor values (10.8–15.1 m2 g−1 at a wavelength of 550 nm for hourly data) for these instruments, and these MACcor values can be used to obtain error-constrained estimates of MBC from babs measured at these sites even in the past, when COSMOS measurements were not made. Because the absolute values of MBC at these Arctic sites estimated by this method are consistent with each other, they are applicable to the study of spatial and temporal variation in MBC in the Arctic and to evaluation of the performance of numerical model calculations.

Information requirements under the essential-use concept: PFAS case studies

Glüge, J.; London, R.; Cousins, I.T.; DeWitt, J.C.; Goldenman, G.; Herzke, D.; Lohmann, R.; Miller, M.; Ng, C.A.; Patton, S.; Trier, X.; Vierke, L.; Wang, Z.; Scheringer, M.
2021 | Environ. Sci. Technol. | XX (XX) (XXX-XXX)

Addressing Urgent Questions for PFAS in the 21st Century

Ng, C.; Cousins, I.T.; DeWitt, J.C.; Glüge, J.; Goldenman, G.; Herzke, D.; Lohmann, R.; Miller, M.; Patton, S.; Scheringer, M.; Trier, X.; Wang, Z.
2021 | Environ. Sci. Technol. | 55 (19) (12755-12765)

Effects of organic carbon origin on hydrophobic organic contaminant fate in the Baltic Sea

Nybom, I.; Horlitz, G.; Gilbert, D.; Berrojalbiz, N.; Martens, J.; Arp, H-P., H.; Sobek, A.
2021 | Environ. Sci. Technol.

The transport and fate of hydrophobic organic contaminants (HOCs) in the marine environment are closely linked to organic carbon (OC) cycling processes. We investigated the influence of marine versus terrestrial OC origin on HOC fluxes
at two Baltic Sea coastal sites with different relative contributions of terrestrial and marine OC. Stronger sorption of the more than four-ring polycyclic aromatic hydrocarbons and penta-heptachlorinated polychlorinated biphenyls (PCBs) was observed at the marine OC-dominated site. The site-specific partition coefficients
between sediment OC and water were 0.2−1.0 log units higher at the marine OC site, with the freely dissolved concentrations in the sediment pore-water 2−10 times lower, when compared with the terrestrial OC site. The stronger sorption at the site characterized with marine OC was most evident for the most hydrophobic PCBs, leading to reduced fluxes of these compounds from sediment to water. According to these results, future changes in OC cycling because of climate change, leading to increased input of terrestrial OC to the marine system, can have consequences for the availability and mobility of HOCs in aquatic systems and thereby also for the capacity of sediments to store HOCs.

Long-term trends in nitrogen oxides concentrations and on-road vehicle emission factors in Copenhagen, London and Stockholm.

Krecl, P.; Harrison, R.M.; Johansson, C.; Targino, A.C.: Beddows, D.C.: Ellermann, T.; Lara, C.; Ketzel, M.
2021 | Environ. Pollut.

Road transport is the main anthropogenic source of NOx in Europe, affecting human health and ecosystems. Thus, mitigation policies have been implemented to reduce on-road vehicle emissions, particularly through the Euro standard limits. To evaluate the effectiveness of these policies, we calculated NO2 and NOx concentration trends using air quality and meteorological measurements conducted in three European cities over 26 years. These data were also employed to estimate the trends in NOx emission factors (EFNOx, based on inverse dispersion modeling) and NO2:NOx emission ratios for the vehicle fleets under real-world driving conditions. In the period 1998–2017, Copenhagen and Stockholm showed large reductions in both the urban background NOx concentrations (−2.1 and −2.6% yr−1, respectively) and EFNOx at curbside sites (68 and 43%, respectively), proving the success of the Euro standards in diminishing NOx emissions. London presented a modest decrease in urban background NOx concentrations (−1.3% yr−1), while EFNOx remained rather constant at the curbside site (Marylebone Road) due to the increase in public bus traffic. NO2 primary emissions –that are not regulated– increased until 2008–2010, which also reflected in the ambient concentrations. This increase was associated with a strong dieselization process and the introduction of new after-treatment technologies that targeted the emission reduction of other species (e.g., greenhouse gases or particulate matter). Thus, while regulations on ambient concentrations of specific species have positive effects on human health, the overall outcomes should be considered before widely adopting them. Emission inventories for the on-road transportation sector should include EFNOx derived from real-world measurements, particularly in urban settings.

A global study of hygroscopicity-driven light-scattering enhancement in the context of other in situ aerosol optical properties

Gloria Titos; Maria Burgos; Paul Zieger; Lucas Alados-Arboledas; Urs Baltensperger; Anne Jefferson; James Sherman; Ernest Weingartner; Bas Henzing; Krista Luoma; Colin O'Dowd; Alfred Wiedensohler; Elisabeth Andrews
2021 | Atmos. Chem. Phys. | 21 (13031-13050)

The scattering and backscattering enhancement factors (f(RH) and fb(RH)) describe how aerosol particle light scattering and backscattering, respectively, change with relative humidity (RH). They are important parameters in estimating direct aerosol radiative forcing (DARF). In this study we use the dataset presented in Burgos et al. (2019) that compiles f(RH) and fb(RH) measurements at three wavelengths (i.e., 450, 550 and 700 nm) performed with tandem nephelometer systems at multiple sites around the world. We present an overview of f(RH) and fb(RH) based on both long-term and campaign observations from 23 sites representing a range of aerosol types. The scattering enhancement shows a strong variability from site to site, with no clear pattern with respect to the total scattering coefficient. In general, higher f(RH) is observed at Arctic and marine sites, while lower values are found at urban and desert sites, although a consistent pattern as a function of site type is not observed. The backscattering enhancement fb(RH) is consistently lower than f(RH) at all sites, with the difference between f(RH) and fb(RH) increasing for aerosol with higher f(RH). This is consistent with Mie theory, which predicts higher enhancement of the light scattering in the forward than in the backward direction as the particle takes up water. Our results show that the scattering enhancement is higher for PM1 than PM10 at most sites, which is also supported by theory due to the change in scattering efficiency with the size parameter that relates particle size and the wavelength of incident light. At marine-influenced sites this difference is enhanced when coarse particles (likely sea salt) predominate. For most sites, f(RH) is observed to increase with increasing wavelength, except at sites with a known dust influence where the spectral dependence of f(RH) is found to be low or even exhibit the opposite pattern. The impact of RH on aerosol properties used to calculate radiative forcing (e.g., single-scattering albedo, ω0, and backscattered fraction, b) is evaluated. The single-scattering albedo generally increases with RH, while b decreases. The net effect of aerosol hygroscopicity on radiative forcing efficiency (RFE) is an increase in the absolute forcing effect (negative sign) by a factor of up to 4 at RH = 90 % compared to dry conditions (RH < 40 %). Because of the scarcity of scattering enhancement measurements, an attempt was made to use other more commonly available aerosol parameters (i.e., ω0 and scattering Ångström exponent, αsp) to parameterize f(RH). The majority of sites (75 %) showed a consistent trend with ω0 (higher f(RH = 85 %) for higher ω0), while no clear pattern was observed between f(RH = 85 %) and αsp. This suggests that aerosol ω0 is more promising than αsp as a surrogate for the scattering enhancement factor, although neither parameter is ideal. Nonetheless, the qualitative relationship observed between ω0 and f(RH) could serve as a constraint on global model simulations.

Insights into the factors influencing mercury concentrations in tropical reservoir sediments

Baptista-Salazar, C.; Quadra, G.R.; Sobek, A.; Jonsson, S.
2021 | Environ. Sci.-Process Impacts

Thousands of dams are currently under construction or planned worldwide to meet the growing need for electricity. The creation of reservoirs could, however, lead to conditions that promote the accumulation of mercury (Hg) in surface sediments and the subsequent production of methylmercury (MeHg). Once produced, MeHg can bioaccumulate to harmful levels in organisms. It is unclear to what extent variations
in physical features and biogeochemical factors of the reservoir impact Hg accumulation. The objective of this study was to identify key drivers of the accumulation of total Hg (THg) in tropical reservoir sediments. The concentration of THg in all analyzed depth intervals of 22 sediment cores from the five contrasting reservoirs investigated ranged from 16 to 310 ng g1 (n ¼ 212, in the different sediment cores, the maximum depth varied from 18 to 96 cm). Our study suggests reservoir size to be an important parameter determining the concentration of THg accumulating in tropical reservoir
sediments, with THg ranging up to 50 ng g1 in reservoirs with an area exceeding 400 km2 and from 100 to 200 ng g1 in reservoirs with an area less than 80 km2. In addition to the reservoir size, the role of land use, nutrient loading, biome and sediment properties (e.g., organic carbon content) was tested as potential drivers of THg levels. The principal component analysis conducted suggested THg to be related to the properties of the watershed (high degree of forest cover and low degree of agricultural land use), size and age of the reservoir, water residence time and the levels of nutrients in the reservoir. A direct correlation between THg and tested variables was, however, only observed with the area of the reservoir.

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Stockholm University
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