ALBERT

Description: Perfluorocarbons (PFCs) are potent greenhouse gases with global warming potentials up to several thousand times greater than CO2 on a 100-year time horizon. The lack of any significant sinks for PFCs means that they have long atmospheric lifetimes of the order of thousands of years. Anthropogenic production is thought to be the only source for most PFCs. Here we report an update on the global atmospheric abundances of the following PFCs, most of which have for the first time been analytically separated according to their isomers: c-octafluorobutane (c-C4F8), n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14), and n-hexadecafluoroheptane (n-C7F16). Additionally, we report the first data set on the atmospheric mixing ratios of perfluoro-2-methylpentane (i-C6F14). The existence and significance of PFC isomers have not been reported before, due to the analytical challenges of separating them. The time series spans a period from 1978 to the present. Several data sets are used to investigate temporal and spatial trends of these PFCs: time series of air samples collected at Cape Grim, Australia, from 1978 to the start of 2018; a time series of air samples collected between July 2015 and April 2017 at Tacolneston, UK; and intensive campaign-based sampling collections from Taiwan. Although the remote “background” Southern Hemispheric Cape Grim time series indicates that recent growth rates of most of these PFCs are lower than in the 1990s, we continue to see significantly increasing mixing ratios that are between 6 % and 27 % higher by the end of 2017 compared to abundances measured in 2010. Air samples from Tacolneston show a positive offset in PFC mixing ratios compared to the Southern Hemisphere baseline. The highest mixing ratios and variability are seen in air samples from Taiwan, which is therefore likely situated much closer to PFC sources, confirming predominantly Northern Hemispheric emissions for most PFCs. Even though these PFCs occur in the atmosphere at levels of parts per trillion molar or less, their total cumulative global emissions translate into 833 million metric tonnes of CO2 equivalent by the end of 2017, 23 % of which has been emitted since 2010. Almost two-thirds of the CO2 equivalent emissions within the last decade are attributable to c-C4F8, which currently also has the highest emission rates that continue to grow. Sources of all PFCs covered in this work remain poorly constrained and reported emissions in global databases do not account for the abundances found in the atmosphere.

Description: We present new observations of trace gases in the stratosphere based on a cost-effective sampling technique that can access much higher altitudes than aircraft. The further development of this method now provides detection of species with abundances in the parts per trillion (ppt) range and below. We obtain mixing ratios for six gases (CFC-11, CFC-12, HCFC-22, H-1211, H-1301, and SF6), all of which are important for understanding stratospheric ozone depletion and circulation. After demonstrating the quality of the data through comparisons with ground-based records and aircraft-based observations, we combine them with the latter to demonstrate its potential. We first compare the data with results from a global model driven by three widely used meteorological reanalyses. Secondly, we focus on CFC-11 as recent evidence has indicated renewed atmospheric emissions of that species relevant on a global scale. Because the stratosphere represents the main sink region for CFC-11, potential changes in stratospheric circulation and troposphere–stratosphere exchange fluxes have been identified as the largest source of uncertainty for the accurate quantification of such emissions. Our observations span over a decade (up until 2018) and therefore cover the period of the slowdown of CFC-11 global mixing ratio decreases measured at the Earth's surface. The spatial and temporal coverage of the observations is insufficient for a global quantitative analysis, but we do find some trends that are in contrast with expectations, indicating that the stratosphere may have contributed to the slower concentration decline in recent years. Further investigating the reanalysis-driven model data, we find that the dynamical changes in the stratosphere required to explain the apparent change in tropospheric CFC-11 emissions after 2013 are possible but with a very high uncertainty range. This is partly caused by the high variability of mass flux from the stratosphere to the troposphere, especially at timescales of a few years, and partly by large differences between runs driven by different reanalysis products, none of which agree with our observations well enough for such a quantitative analysis.

Description: Leads play an important role in the exchange of heat, gases, vapour, and particles between seawater and the atmosphere in ice-covered polar oceans. In summer, these processes can be modified significantly by the formation of a meltwater layer at the surface, yet we know little about the dynamics of meltwater layer formation and persistence. During the drift campaign of the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC), we examined how variation in lead width, re-freezing, and mixing events affected the vertical structure of lead waters during late summer in the central Arctic. At the beginning of the 4-week survey period, a meltwater layer occupied the surface 0.8 m of the lead, and temperature and salinity showed strong vertical gradients. Stable oxygen isotopes indicate that the meltwater consisted mainly of sea ice meltwater rather than snow meltwater. During the first half of the survey period (before freezing), the meltwater layer thickness decreased rapidly as lead width increased and stretched the layer horizontally. During the latter half of the survey period (after freezing of the lead surface), stratification weakened and the meltwater layer became thinner before disappearing completely due to surface ice formation and mixing processes. Removal of meltwater during surface ice formation explained about 43% of the reduction in thickness of the meltwater layer. The remaining approximate 57% could be explained by mixing within the water column initiated by disturbance of the lower boundary of the meltwater layer through wind-induced ice floe drift. These results indicate that rapid, dynamic changes to lead water structure can have potentially significant effects on the exchange of physical and biogeochemical components throughout the atmosphere–lead–underlying seawater system.

Description: Melt ponds water sampling for biogeochemical parameters such as dissolved inorganic carbon (DIC), total alkalinity (TA), oxygen isotopes were examined from August to September 2020. To obtain discrete water samples from the melt ponds and leads, we checked the vertical structure and depth of the meltwater layer from the same hole used for the RINKO Profiler by attaching a conductivity sensor (Cond 315i, WTW GmbH, Germany) to a 2-m-long ruler and inserting the ruler into the lead water until the salinity measured with the Cond 315i increased at the meltwater–seawater interface (Nomura et al., 2024) . Water was pumped up with a peristaltic pump through a 2-m-long PTFE tube (L/S Pump Tubing, Masterflex, USA) at depths corresponding to meltwater (surface), the interface between meltwater and seawater (interface), and seawater (bottom). Salinity was measured at each depth by attaching a Cond 315i conductivity sensor to the bottom of the ruler. The tube intake was likewise attached to the bottom of the ruler. Seawater was subsampled into a 250-mL glass vial (Duran Co., Ltd., Germany) for measurement of dissolved inorganic carbon (DIC) and total alkalinity (TA) and a 50-mL glass, screw-cap, narrow-neck vial (VWR international LLC, Germany) for measurement of the oxygen isotopic ratio (δ18O) of the water. Immediately after subsampling for measurement of DIC and TA, a 6.0% (wt.) mercuric chloride (HgCl2) solution (100 µL) was added to stop biological activity. Samples for DIC and TA were stored at +4°C on the R/V Polarstern. Samples for δ18O were stored at room temperature (20°C). During the discrete water sampling, the CO2 concentration in the water column was measured directly on site by passing the water through an equilibrator Liqui-Cel® (G542, S/N: 132462, 3M Company, USA) connected to an infrared gas analyzer (LI-8100A, LI-COR Inc., USA). The analyzer was calibrated with standard gases containing 0.0, 299.3, and 501.3 ppm CO2 before MOSAiC Leg 5. RMS (root means square) noise at 370 ppm with 1 sec signal averaging is 〈1 ppm (https://www.licor.com/env/products/soil-flux/LI-8100a). The equilibrator was connected in the loop for water sampling (vide supra), and a 2-m-long ruler was inserted into the water and kept at that depth until the CO2 was equilibrated with air (about 1 minute) by monitoring the CO2 values. The CO2 concentration was measured at each depth (i.e., surface, interface, and bottom). At the ROV lead sites, vertical CO2 measurements were made every 0.05 m for detailed profiles. The DIC of water was determined by coulometry (Johnson et al., 1985; Johnson, 1992) using a home-made CO2 extraction system (Ono et al., 1998) and a coulometer (CM5012, UIC, Inc., Binghamton, NY, USA). The TA of water was determined by titration (Dickson et al., 2007) using a TA analyzer (ATT-05, Kimoto Electric Co., Ltd., Japan). Both DIC and TA measurements were calibrated with reference seawater materials (Batch AR, AU, and AV; KANSO Technos Co., Ltd., Osaka, Japan) traceable to the Certified Reference Material distributed by Prof. A. G. Dickson (Scripps Institution of Oceanography, La Jolla, CA, USA). Oxygen isotope analyses were carried out at the ISOLAB Facility at AWI Potsdam (hdl:10013/sensor.ddc92f54-4c63-492d-81c7-696260694001) with mass spectrometers (DELTA-S Finnigan MAT, USA): hdl:10013/sensor.af148dea-fe65-4c87-9744-50dc4c81f7c9 and hdl:10013/sensor.62e86761-9fae-4f12-9c10-9b245028ea4c employing the equilibration method (details in Meyer et al., 2000). δ18O values were given in per mil (‰) vs. Vienna standard mean ocean water (V-SMOW) as the standard.

Description: Discrete seawater samples in a Weddell Sea coastal polynya along the Ekström Ice Shelf were collected from two sets of repeat CTD casts, capturing tidal variability in the water column. One set was collected during RV POLARSTERN expedition PS89, between 8 and 11 January 2015. The second set was collected during RV POLARSTERN expedition PS117, between 11 and 12 January 2019. Dissolved inorganic carbon (DIC) and total alkalinity (TA) were measured using coulometric titration and potentiometric titration, respectively, on a VINDTA 3C system. DIC and TA have been normalised to salinity: nDIC and nTA. Nutrients were measured with UV-Vis spectrophotometry and a continuous gas-segmented flow auto-analyser.

Description: Samples for the analysis of dissolved nutrients were collected during the Multidisciplinary drifting Observatory for the Study of Arctic Climate (MOSAiC) from the water column, sea ice cores and from special events/locations (e.g., leads, melt ponds, brine, incubation experiments). Samples for dissolved inorganic nutrients (NO3 +NO2 , NO2 , PO4 , Si(OH)4, NH4 ) were analysed onboard during PS122 legs 1 to 3, with duplicate samples collected from CTD casts for later analysis of total dissolved nitrogen (TDN) and total dissolved phosphorus (TDP). From leg 4, all samples collected were stored frozen at -20°C for later analysis. Analyses of stored samples were carried out at the AWI Nutrient Facility between January and March 2021. Nutrient analyses onboard and on land were carried out using a Seal Analytical AA3 continuous flow autoanalyser, controlled by the AACE software version 7.09. Best practice procedures for the measurement of nutrients were adopted following GO-SHIP recommendations (Hydes et al., 2010; Becker et al., 2019). Descriptions of sample collection and handling can be found in the various cruise reports (Haas & Rabe, 2023; Kanzow & Damm, 2023; Rex & Metfies, 2023; Rex & Nicolaus, 2023; Rex & Shupe, 2023). Here we provide data from the water column, obtained from the analysis of discrete samples collected from CTD-Rosette casts from Polarstern (https://sensor.awi.de/?site=search&q=vessel:polarstern:ctd_sbe9plus_321) and Ocean City (https://sensor.awi.de/?site=search&q=vessel:polarstern:ctd_sbe9plus_935). Data from sea ice cores and special events are presented elsewhere. Data from sea ice cores and special events are presented elsewhere. For reference, here we included data from CTD-BTL files associated with nutrient samples. These data are presented by Tippenhauer et al. (2023) Polarstern CTD and Tippenhauer et al. (2023) Ocean City CTD.

Description: Discrete seawater samples for the determination of dissolved inorganic carbon (DIC) and total alkalinity (TA) were collected from CTD stations during RV POLARSTERN expedition PS117, between 15 December 2018 and 7 February 2019. Seawater samples were collected from stations that used the AWI-operated CTD, as well as the Ultra-Clean-CTD, operated by NIOZ. DIC and TA were measured using coulometric titration and potentiometric titration, respectively, on a VINDTA 3C system. Nutrients were measured with UV-Vis spectrophotometry and a continuous gas-segmented flow auto-analyser. Data for station 41 have previously been published on Pangaea and are excluded from this dataset (https://doi.org/10.1594/PANGAEA.946363). Bottle data (including nutrients) from the AWI CTD and Ultra-Clean-CTD stations have already been published and are stored on Pangaea under https://doi.org/10.1594/PANGAEA.910673 and https://doi.org/10.1594/PANGAEA.940209, respectively. Data quality flags follow the WOCE quality code definitions for water sample measurements. Details on sample collection and analysis methods for DIC and TA can be found in Droste et al. (2022).

Description: Algal pigment concentrations were retrieved from meltponds and leads, during Leg 4 and 5 of the MOSAiC expedition (Multidisciplinary drifting Observatory for the Study of Arctic Climate) in 2020. The summer increase in meltpond area and open lead water in the Arctic associated with increased light availability is of specific significance for biological production within the Arctic system (Smith et al. 2023). Over a period of 3.5 months, 46 samples have been collected and analysed. After extraction in 90 % acetone, samples were analysed using high-performance liquid chromatography (HPLC) on a Waters system. Algal pigments contain a multiple set of information. Firstly, pigment concentrations can show the presence of algal biomass in the various water masses sampled. Secondly, marker pigments can reveal seasonal and temporal dynamics in algal community structure, by discerning specific algal classes like diatoms, cryptophytes, haptophytes and chlorophytes that have specific roles in biogeochemical cycles. Thirdly, certain pigments are indicative of the (photo)-physiological state of micro-algae and fourth, degradation products of the main chlorophyll a pigment further give an indication about senescence and grazing in the various habitats.

Description: Size segregated aerosol samples were collected during the OASIS (“Organic very short lived substances and their Air Sea Exchange from the Indian Ocean to the Stratosphere”) cruises (FS Sonne, SO234-2 & SO235) during 8 - 20 July & 23 July – 7 August 2014 in the southern Indian Ocean (~30 E - 75 E, 30 S – 5 N). The samples were collected by Birgit Quack of GEOMAR, Kiel, Germany. The aerosol sampler was situated on the roof of the ship's wheelhouse and was connected to an automatic wind sector controller to prevent contamination of the samples from the ship's stack. Most samples were collected using a Sierra-type cascade impactor to separate the aerosol particles at an aerodynamic diameter cutoff of 1 µm. Collection time for these samples varied between 27.7 and 46.9 hours. For one sample, 6 impactor stages and a backup filter were used to give more detailed information aerosol size distribution. This sample was collected over 91.7 hours. Samples were extracted with ultrapure water and the major ions Na+, NH4+, Mg2+, K+, Ca2+, Cl-, NO3-, SO42-, oxalate, Br- and methanesulfonate were determined by ion chromatography (IC). Total soluble iodine (TSI) was determined by inductively coupled plasma - mass spectrometry (ICP-MS) and iodide (I-) and iodate (IO3-) were determined by IC-ICP-MS. The dataset contains the atmospheric concentrations of all measured soluble major ions (in nmol/m³) and iodine species (in pmol/ m³).