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Ice-nucleating particles (INPs) have a large impact on the climate-relevant properties of clouds over the oceans. Studies have shown that sea spray aerosols (SSAs), produced upon bursting of bubbles at the ocean surface, can be an important source of marine INPs, particularly during periods of enhanced biological productivity. Recent mesocosm experiments using natural seawater spiked with nutrients have revealed that marine INPs are derived from two separate classes of organic matter in SSAs. Despite this finding, existing parameterizations for marine INP abundance are based solely on single variables such as SSA organic carbon (OC) or SSA surface area, which may mask specific trends in the separate classes of INP. The goal of this paper is to improve the understanding of the connection between ocean biology and marine INP abundance by reporting results from a field study and proposing a new parameterization of marine INPs that accounts for the two associated classes of organic matter. The PEACETIME cruise took place from 10 May to 10 June 2017 in the Mediterranean Sea. Throughout the cruise, INP concentrations in the surface microlayer (INPSML) and in SSAs (INPSSA) produced using a plunging aquarium apparatus were continuously monitored while surface seawater (SSW) and SML biological properties were measured in parallel. The organic content of artificially generated SSAs was also evaluated. INPSML concentrations were found to be lower than those reported in the literature, presumably due to the oligotrophic nature of the Mediterranean Sea. A dust wet deposition event that occurred during the cruise increased the INP concentrations measured in the SML by an order of magnitude, in line with increases in iron in the SML and bacterial abundances. Increases in INPSSA were not observed until after a delay of 3 days compared to increases in the SML and are likely a result of a strong influence of bulk SSW INPs for the temperatures investigated (T=-18 ∘C for SSAs, T=-15 ∘C for SSW). Results confirmed that INPSSA are divided into two classes depending on their associated organic matter. Here we find that warm (T≥-22 ∘C) INPSSA concentrations are correlated with water-soluble organic matter (WSOC) in the SSAs, but also with SSW parameters (particulate organic carbon, POCSSW and INPSSW,-16C) while cold INPSSA (T<-22 ∘C) are correlated with SSA water-insoluble organic carbon (WIOC) and SML dissolved organic carbon (DOC) concentrations. A relationship was also found between cold INPSSA and SSW nano- and microphytoplankton cell abundances, indicating that these species might be a source of water-insoluble organic matter with surfactant properties and specific IN activities. Guided by these results, we formulated and tested multiple parameterizations for the abundance of INPs in marine SSAs, including a single-component model based on POCSSW and a two-component model based on SSA WIOC and OC. We also altered a previous model based on OCSSA content to account for oligotrophy of the Mediterranean Sea. We then compared this formulation with the previous models. This new parameterization should improve attempts to incorporate marine INP emissions into numerical models.

The deep chlorophyll maximum (DCM) is a ubiquitous feature of phytoplankton vertical distribution in stratified waters that is relevant to our understanding of the mechanisms that underpin the variability in photoautotroph ecophysiology across environmental gradients and has implications for remote sensing of aquatic productivity. During the PEACETIME (Process studies at the air-sea interface after dust deposition in the Mediterranean Sea) cruise, carried out from 10 May to 11 June 2017, we obtained 23 concurrent vertical profiles of phytoplankton chlorophyll a, carbon biomass and primary production, as well as heterotrophic prokaryotic production, in the western and central Mediterranean basins. Our main aims were to quantify the relative role of photoacclimation and enhanced growth as underlying mechanisms of the DCM and to assess the trophic coupling between phytoplankton and heterotrophic prokaryotic production. We found that the DCM coincided with a maximum in both the biomass and primary production but not in the growth rate of phytoplankton, which averaged 0.3 d−1 and was relatively constant across the euphotic layer. Photoacclimation explained most of the increased chlorophyll a at the DCM, as the ratio of carbon to chlorophyll a (C:Chl a) decreased from ca. 90–100 (g:g) at the surface to 20–30 at the base of the euphotic layer, while phytoplankton carbon biomass increased from ca. 6 mg C m−3 at the surface to 10–15 mg C m−3 at the DCM. As a result of photoacclimation, there was an uncoupling between chlorophyll a-specific and carbon-specific productivity across the euphotic layer. The ratio of fucoxanthin to total chlorophyll a increased markedly with depth, suggesting an increased contribution of diatoms at the DCM. The increased biomass and carbon fixation at the base of the euphotic zone was associated with enhanced rates of heterotrophic prokaryotic activity, which also showed a surface peak linked with warmer temperatures. Considering the phytoplankton biomass and turnover rates measured at the DCM, nutrient diffusive fluxes across the nutricline were able to supply only a minor fraction of the photoautotroph nitrogen and phosphorus requirements. Thus the deep maxima in biomass and primary production were not fuelled by new nutrients but likely resulted from cell sinking from the upper layers in combination with the high photosynthetic efficiency of a diatom-rich, low-light acclimated community largely sustained by regenerated nutrients. Further studies with increased temporal and spatial resolution will be required to ascertain if the peaks of deep primary production associated with the DCM persist across the western and central Mediterranean Sea throughout the stratification season.

Measurements of free amino acids (FAAs) in the marine environment to elucidate their transfer from the ocean into the atmosphere, to marine aerosol particles and to clouds, were performed at the MarParCloud (marine biological production, organic aerosol particles and marine clouds: a process chain) campaign at the Cabo Verde islands in autumn 2017. According to physical and chemical specifications such as the behavior of air masses, particulate MSA concentrations and MSA∕sulfate ratios, as well as particulate mass concentrations of dust tracers, aerosol particles predominantly of marine origin with low to medium dust influences were observed. FAAs were investigated in different compartments: they were examined in two types of seawater underlying water (ULW) and in the sea surface microlayer (SML), as well as in ambient marine size-segregated aerosol particle samples at two heights (ground height based at the Cape Verde Atmospheric Observatory, CVAO, and at 744 m height on Mt. Verde) and in cloud water using concerted measurements. The ∑FAA concentration in the SML varied between 0.13 and 3.64 µmol L−1, whereas it was between 0.01 and 1.10 µmol L−1 in the ULW; also, a strong enrichment of ∑FAA (EFSML: 1.1–298.4, average of 57.2) was found in the SML. In the submicron (0.05–1.2 µm) aerosol particles at the CVAO, the composition of FAAs was more complex, and higher atmospheric concentrations of ∑FAA (up to 6.3 ng m−3) compared to the supermicron (1.2–10 µm) aerosol particles (maximum of 0.5 ng m−3) were observed. The total ∑FAA concentration (PM10) was between 1.8 and 6.8 ng m−3 and tended to increase during the campaign. Averaged ∑FAA concentrations in the aerosol particles on Mt. Verde were lower (submicron: 1.5 ng m−3; supermicron: 1.2 ng m−3) compared to the CVAO. A similar contribution percentage of ∑FAA to dissolved organic carbon (DOC) in the seawater (up to 7.6 %) and to water-soluble organic carbon (WSOC) in the submicron aerosol particles (up to 5.3 %) indicated a related transfer process of FAAs and DOC in the marine environment. Considering solely ocean–atmosphere transfer and neglecting atmospheric processing, high FAA enrichment factors were found in both aerosol particles in the submicron range (EFaer(∑FAA): 2×103–6×103) and medium enrichment factors in the supermicron range (EFaer(∑FAA): 1×101–3×101). In addition, indications for a biogenic FAA formation were observed. Furthermore, one striking finding was the high and varying FAA cloud water concentration (11.2–489.9 ng m−3), as well as enrichments (EFCW: 4×103 and 1×104 compared to the SML and ULW, respectively), which were reported here for the first time. The abundance of inorganic marine tracers (sodium, methanesulfonic acid) in cloud water suggests an influence of oceanic sources on marine clouds. Finally, the varying composition of the FAAs in the different matrices shows that their abundance and ocean–atmosphere transfer are influenced by additional biotic and abiotic formation and degradation processes. Simple physicochemical parameters (e.g., surface activity) are not sufficient to describe the concentration and enrichments of the FAAs in the marine environment. For a precise representation in organic matter (OM) transfer models, further studies are needed to unravel their drivers and understand their composition.

The cold/wet anomaly of the 1310s (“Dantean Anomaly”) has attracted a lot of attention from scholars, as it is commonly interpreted as a signal of the transition between the Medieval Climate Anomaly (MCA) and the Little Ice Age (LIA). The huge variability that can be observed during this decade, like the high interannual variability observed in the 1340s, has been highlighted as a side effect of this rapid climatic transition. In this paper, we demonstrate that a multi-seasonal drought of almost 2 years occurred in the Mediterranean between 1302 and 1304, followed by a series of hot, dry summers north of the Alps from 1304 to 1306. We suggest that this outstanding dry anomaly, unique in the 13th and 14th centuries, together with cold anomalies of the 1310s and the 1340s, is part of the climatic shift from the MCA to the LIA. Our reconstruction of the predominant weather patterns of the first decade of the 14th century – based on both documentary and proxy data – identifies multiple European precipitation seesaw events between 1302 and 1307, with similarities to the seesaw conditions which prevailed over continental Europe in 2018. It can be debated to what extent the 1302–1307 period can be compared to what is currently discussed regarding the influence of the phenomenon of Arctic amplification on the increasing frequency of persistent stable weather patterns that have occurred since the late 1980s. Additionally, this paper deals with socioeconomic and cultural responses to drought risks in the Middle Ages as outlined in contemporary sources and provides evidence that there is a significant correlation between pronounced dry seasons and fires that devastated cities.

The eastern tropical South Pacific (ETSP) represents one of the most productive areas in the ocean that is characterised by a pronounced oxygen minimum zone (OMZ). Particulate organic matter (POM) that sinks out of the euphotic zone is supplied to the anoxic sediments and utilised by microbial communities, and the degradation of POM is associated with the production and reworking of dissolved organic matter (DOM). The release of DOM to the overlying waters may, therefore, represent an important organic matter escape mechanism from remineralisation within sediments but has received little attention in OMZ regions so far. Here, we combine measurements of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) with DOM optical properties in the form of chromophoric (CDOM) and fluorescent (FDOM) DOM from pore waters and near-bottom waters of the ETSP off Peru. We evaluate diffusion-driven fluxes and net in situ fluxes of DOC and DON to investigate processes affecting DOM cycling at the sediment–water interface along a transect at 12∘ S. To our knowledge, these are the first data for sediment release of DON and pore water CDOM and FDOM for the ETSP off Peru. Pore water DOC accumulated with increasing sediment depth, suggesting an imbalance between DOM production and remineralisation within sediments. High DON accumulation resulted in very low pore water DOC ∕ DON ratios (≤1) which could be caused by an “uncoupling” in DOC and DON remineralisation. Diffusion-driven fluxes of DOC and DON exhibited high spatial variability and ranged from 0.2±0.1 to 2.5±1.3 mmolm-2d-1 and from -0.04±0.02 to 3.3±1.7 mmolm-2d-1, respectively. Generally low net in situ DOC and DON fluxes, as well as a steepening of spectral inclination (S) of CDOM and an increase in humic-like DOM at the sediment–water interface over time, indicated active microbial DOM utilisation. The latter may potentially be stimulated by the presence of nitrate (NO3-) and nitrite (NO2-) in the water column. The microbial DOC utilisation rates, estimated in our study, are potentially sufficient to support denitrification rates of 0.2–1.4 mmolm-2d-1, suggesting that the sediment release of DOM may on occasion contribute to nitrogen loss processes in the ETSP off Peru.

Derivation of mean age of air (AoA) and age spectra from atmospheric measurements remains a challenge and often requires output from atmospheric models. This study tries to minimize the direct influence of model output and presents an extension and application of a previously established inversion method to derive age spectra from mixing ratios of long- and short-lived trace gases. For a precise description of cross-tropopause transport processes, the inverse method is extended to incorporate air entrainment into the stratosphere across the tropical and extratropical tropopause. We first use simulations with the Chemical Lagrangian Model of the Stratosphere (CLaMS) to provide a general proof of concept of the extended principle in a controllable and consistent environment, where the method is applied to an idealized set of 10 trace gases with predefined constant lifetimes and compared to reference model age spectra. In the second part of the study we apply the extended inverse method to atmospheric measurements of multiple long- and short-lived trace gases measured aboard the High Altitude and Long Range (HALO) research aircraft during the two research campaigns POLSTRACC–GW-LCYCLE–SALSA (PGS) and Wave-driven Isentropic Exchange (WISE). As some of the observed species undergo significant loss processes in the stratosphere, a Monte Carlo simulation is introduced to retrieve age spectra and chemical lifetimes in stepwise fashion and to account for the large uncertainties. Results show that in the idealized model scenario the inverse method retrieves age spectra robustly on annual and seasonal scales. The extension to multiple entry regions proves reasonable as our CLaMS simulations reveal that in the model between 50 % and 70 % of air in the lowermost stratosphere has entered through the extratropical tropopause (30–90∘ N and S) on annual average. When applied to observational data of PGS and WISE, the method derives age spectra and mean AoA with meaningful spatial distributions and quantitative range, yet large uncertainties. Results indicate that entrainment of fresh tropospheric air across both the extratropical and tropical tropopause peaked prior to both campaigns, but with lower mean AoA for WISE than PGS data. The ratio of moments for all retrieved age spectra for PGS and WISE is found to range between 0.52 and 2.81 years. We conclude that the method derives reasonable and consistent age spectra using observations of chemically active trace gases. Our findings might contribute to an improved assessment of transport with age spectra in future studies.

An optimized method is presented to determine dissolved free (DFCHO) and dissolved combined carbohydrates (DCCHO) in saline matrices, such as oceanic seawater, Arctic ice core samples or brine using a combination of a desalination with electro-dialysis (ED) and high-performance anion exchange chromatography coupled to pulsed amperometric detection (HPAEC-PAD). Free neutral sugars, such as glucose and galactose, were found with 95 %–98 % recovery rates. Free amino sugars and free uronic acids were strongly depleted during ED at pH=8, but an adjustment of the pH could result in higher recoveries (58 %–59 % for amino sugars at pH=11; 45 %–49 % for uronic acids at pH=1.5). The applicability of this method for the analysis of DCCHO was evaluated with standard solutions and seawater samples compared with another established desalination method using membrane dialysis. DFCHO in field samples from different regions on Earth ranged between 11 and 118 nM and DCCHO between 260 and 1410 nM. This novel method has the potential to contribute to a better understanding of biogeochemical processes in the oceans and sea–air transfer processes of organic matter into the atmosphere in future studies.

Mean age of air (AoA) is a diagnostic of transport along the stratospheric Brewer–Dobson circulation. While models consistently show negative trends, long-term time series (1975–2016) of AoA derived from observations show non-significant positive trends in mean AoA in the Northern Hemisphere. This discrepancy between observed and modelled mean AoA trends is still not resolved. There are uncertainties and assumptions required when deriving AoA from trace gas observations. At the same time, AoA from climate models is subject to uncertainties, too. In this paper, we focus on the uncertainties due to the parameter selection in the method that is used to derive mean AoA from SF6 measurements in Engel et al. (2009, 2017). To correct for the non-linear increase in SF6 concentrations, a quadratic fit to the time series at the reference location, i.e. the tropical surface, is used. For this derivation, the width of the AoA distribution (age spectrum) has to be assumed. In addition, to choose the number of years the quadratic fit is performed for, the fraction of the age spectrum to be considered has to be assumed. Even though the uncertainty range due to all different aspects has already been taken into account for the total errors in the AoA values, the systematic influence of the parameter selection on AoA trends is described for the first time in the present study. For this, we use the EMAC (ECHAM MESSy Atmospheric Chemistry) climate model as a test bed, where AoA derived from a linear tracer is available as a reference and modelled age spectra exist to diagnose the actual spatial age spectra widths. The comparison of mean AoA from the linear tracer with mean AoA from a SF6 tracer shows systematic deviations specifically in the trends due to the selection of the parameters. However, for an appropriate parameter selection, good agreement for both mean AoA and its trend can be found, with deviations of about 1 % in mean AoA and 12 % in AoA trend. In addition, a method to derive mean AoA is evaluated that applies a convolution to the reference time series. The resulting mean AoA and its trend only depend on an assumption about the ratio of moments. Also in that case, it is found that the larger the ratio of moments, the more the AoA trend gravitates towards the negative. The linear tracer and SF6 AoA are found to agree within 0.3 % in the mean and 6 % in the trend. The different methods and parameter selections were then applied to the balloon-borne SF6 and CO2 observations. We found the same systematic changes in mean AoA trend dependent on the specific selection. When applying a parameter choice that is suggested by the model results, the AoA trend is reduced from 0.15 to 0.07 years per decade. It illustrates that correctly constraining those parameters is crucial for correct mean AoA and trend estimates and still remains a challenge in the real atmosphere.

We present novel measurements of five short-lived brominated source gases (CH2Br2, CHBr3, CH2ClBr, CHCl2Br and CHClBr2). These rather short-lived gases are an important source of bromine to the stratosphere, where they can lead to depletion of ozone. The measurements have been obtained using an in situ gas chromatography and mass spectrometry (GC–MS) system on board the High Altitude and Long Range Research Aircraft (HALO). The instrument is extremely sensitive due to the use of chemical ionization, allowing detection limits in the lower parts per quadrillion (ppq, 10−15) range. Data from three campaigns using HALO are presented, where the upper troposphere and lower stratosphere (UTLS) of the northern hemispheric mid-to-high latitudes were sampled during winter and during late summer to early fall. We show that an observed decrease with altitude in the stratosphere is consistent with the relative lifetimes of the different compounds. Distributions of the five source gases and total organic bromine just below the tropopause show an increase in mixing ratio with latitude, in particular during polar winter. This increase in mixing ratio is explained by increasing lifetimes at higher latitudes during winter. As the mixing ratios at the extratropical tropopause are generally higher than those derived for the tropical tropopause, extratropical troposphere-to-stratosphere transport will result in elevated levels of organic bromine in comparison to air transported over the tropical tropopause. The observations are compared to model estimates using different emission scenarios. A scenario with emissions mainly confined to low latitudes cannot reproduce the observed latitudinal distributions and will tend to overestimate organic bromine input through the tropical tropopause from CH2Br2 and CHBr3. Consequently, the scenario also overestimates the amount of brominated organic gases in the stratosphere. The two scenarios with the highest overall emissions of CH2Br2 tend to overestimate mixing ratios at the tropical tropopause, but they are in much better agreement with extratropical tropopause mixing ratios. This shows that not only total emissions but also latitudinal distributions in the emissions are of importance. While an increase in tropopause mixing ratios with latitude is reproduced with all emission scenarios during winter, the simulated extratropical tropopause mixing ratios are on average lower than the observations during late summer to fall. We show that a good knowledge of the latitudinal distribution of tropopause mixing ratios and of the fractional contributions of tropical and extratropical air is needed to derive stratospheric inorganic bromine in the lowermost stratosphere from observations. In a sensitivity study we find maximum differences of a factor 2 in inorganic bromine in the lowermost stratosphere from source gas injection derived from observations and model outputs. The discrepancies depend on the emission scenarios and the assumed contributions from different source regions. Using better emission scenarios and reasonable assumptions on fractional contribution from the different source regions, the differences in inorganic bromine from source gas injection between model and observations is usually on the order of 1 ppt or less. We conclude that a good representation of the contributions of different source regions is required in models for a robust assessment of the role of short-lived halogen source gases on ozone depletion in the UTLS.

The Sea Surface Microlayer (SML) is known to be enriched by trace metals relative to the underlying water and harbor diverse microbial communities (i.e., neuston). However, the processes linking metals and biota in the SML are not yet fully understood. The metal (Cd, Co, Cu, Fe, Ni, Mo, V, Zn and Pb) concentrations in aerosol samples in the SML (dissolved and total fractions) and in subsurface waters (SSWs; dissolved fraction at ∼1 m depth) from the western Mediterranean Sea were analyzed in this study during a cruise in May–June 2017. The composition and abundance of the bacterial community in the SML and SSW, the primary production, and Chl a in the SSW were measured simultaneously at all stations during the cruise. Residence times in the SML of metals derived from aerosol depositions were highly variable and ranged from minutes for Fe (3.6±6.0 min) to a few hours for Cu (5.8±6.2 h). Concentrations of most of the dissolved metals in both the SML and SSW were positively correlated with the salinity gradient and showed the characteristic eastward increase in the surface waters of the Mediterranean Sea (MS). In contrast, the total fraction of some reactive metals in the SML (i.e., Cu, Fe, Pb and Zn) showed a negative correlation with salinity and a positive correlation with microbial abundance, which might be associated with microbial uptake. Our results show a strong negative correlation between the dissolved and total Ni concentration and heterotrophic bacterial abundance in the SML and SSW, but we cannot ascertain whether this correlation reflects a toxicity effect or is the result of some other process.

Preschool through third grade (P-3) alignment is regularly named as a key aspect of early childhood education and the transition to formal schooling. However, little is known about P-3 alignment in practice. Using data from 265 observations of math instruction in preschool, kindergarten, first-, and third-grade classrooms in New York City public schools, we explore P-3 instructional alignment as it would be experienced sequentially, over time and across grades, by students. We examine the continuity of developmentally appropriate instructional environments and high-quality pedagogical practices, as well as the progression of P-3 mathematics content coverage. We find notable discontinuities in instructional environments and some pedagogical practices, particularly across preschool and kindergarten. We also find both progression and repetition in math content coverage. Results suggest that, on some dimensions, kindergarten may be poorly aligned with both preschool and the early elementary grades.

Extension Professionals have varying expectations of academic publication depending on tenure and promotion. And, the field of Extension needs the contributions of professionals across the system to support the translation and dissemination of the impacts of and findings from their Extension programming for academic and practitioner audiences. A writing retreat was held to support 4-H Youth Development professionals in academic writing. Because of this writing retreat five teams started working on an academic writing project which resulted in three journal articles being published. Teams also published conference presentations and Extension publications as a result of the initial academic writing project. Intentionally providing writing retreats that prepare professionals to write can support effective capacity building for academic publishing.

We present the Young Supernova Experiment Data Release 1 (YSE DR1), comprised of processed multicolor PanSTARRS1 griz and Zwicky Transient Facility (ZTF) gr photometry of 1975 transients with host–galaxy associations, redshifts, spectroscopic and/or photometric classifications, and additional data products from 2019 November 24 to 2021 December 20. YSE DR1 spans discoveries and observations from young and fast-rising supernovae (SNe) to transients that persist for over a year, with a redshift distribution reaching z ≈ 0.5. We present relative SN rates from YSE’s magnitude- and volume-limited surveys, which are consistent with previously published values within estimated uncertainties for untargeted surveys. We combine YSE and ZTF data, and create multisurvey SN simulations to train the ParSNIP and SuperRAENN photometric classification algorithms; when validating our ParSNIP classifier on 472 spectroscopically classified YSE DR1 SNe, we achieve 82% accuracy across three SN classes (SNe Ia, II, Ib/Ic) and 90% accuracy across two SN classes (SNe Ia, core-collapse SNe). Our classifier performs particularly well on SNe Ia, with high (>90%) individual completeness and purity, which will help build an anchor photometric SNe Ia sample for cosmology. We then use our photometric classifier to characterize our photometric sample of 1483 SNe, labeling 1048 (∼71%) SNe Ia, 339 (∼23%) SNe II, and 96 (∼6%) SNe Ib/Ic. YSE DR1 provides a training ground for building discovery, anomaly detection, and classification algorithms, performing cosmological analyses, understanding the nature of red and rare transients, exploring tidal disruption events and nuclear variability, and preparing for the forthcoming Vera C. Rubin Observatory Legacy Survey of Space and Time.

Measurements of halogenated trace gases in ambient air frequently rely on canister sampling followed by offline laboratory analysis. This allows for a large number of compounds to be analysed under stable conditions, maximizing measurement precision. However, individual compounds might be affected during the sampling and storage of canister samples. In order to assess halocarbon stability in whole-air samples from the upper troposphere and lowermost stratosphere, we performed stability tests using the high-resolution sampler (HIRES) air sampling unit, which is part of the Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container (CARIBIC) instrument package. The HIRES unit holds 88 lightweight stainless-steel cylinders that are pressurized in flight to 4.5 bar using metal bellows pumps. The HIRES unit was first deployed in 2010 but has up to now not been used for regular halocarbon analysis with the exception of chloromethane analysis. The sample collection unit was tested for the sampling and storage effects of 28 halogenated compounds. The focus was on compound stability in the stainless-steel canisters during storage of up to 5 weeks and on the influence of ozone, since flights take place in the upper troposphere and lowermost stratosphere with ozone mixing ratios of up to several hundred parts per billion by volume (ppbv). Most of the investigated (hydro)chlorofluorocarbons and long-lived hydrofluorocarbons were found to be stable over a storage time of up to 5 weeks and were unaltered by ozone being present during pressurization. Some compounds such as dichloromethane, trichloromethane, and tetrachloroethene started to decrease in the canisters after a storage time of more than 2 weeks or exhibited lowered mixing ratios in samples pressurized with ozone present. A few compounds such as tetrachloromethane and tribromomethane were found to be unstable in the HIRES stainless-steel canisters independent of ozone levels. Furthermore, growth was observed during storage for some species, namely for HFC-152a, HFC-23, and Halon 1301.

Oxygen minimum zones (OMZs) show distinct biogeochemical processes that relate to microorganisms being able to thrive under low or even absent oxygen. Microbial degradation of organic matter is expected to be reduced in OMZs, although quantitative evidence is low. Here, we present heterotrophic bacterial production (3H leucine incorporation), extracellular enzyme rates (leucine aminopeptidase/β-glucosidase) and bacterial cell abundance for various in situ oxygen concentrations in the water column, including the upper and lower oxycline, of the eastern tropical South Pacific off Peru. Bacterial heterotrophic activity in the suboxic core of the OMZ (at in situ ≤ 5 µmol O2 kg−1) ranged from 0.3 to 281 µmol C m−3 d−1 and was not significantly lower than in waters of 5–60 µmol O2 kg−1. Moreover, bacterial abundance in the OMZ and leucine aminopeptidase activity were significantly higher in suboxic waters compared to waters of 5–60 µmol O2 kg−1, suggesting no impairment of bacterial organic-matter degradation in the core of the OMZ. Nevertheless, high cell-specific bacterial production was observed in samples from oxyclines, and cell-specific extracellular enzyme rates were especially high at the lower oxycline, corroborating earlier findings of highly active and distinct micro-aerobic bacterial communities. To assess the impact of bacterial degradation of dissolved organic matter (DOM) for oxygen loss in the Peruvian OMZ, we compared diapycnal fluxes of oxygen and dissolved organic carbon (DOC) and their microbial uptake within the upper 60 m of the water column. Our data indicate low bacterial growth efficiencies of 1 %–21 % at the upper oxycline, resulting in a high bacterial oxygen demand that can explain up to 33 % of the observed average oxygen loss over depth. Our study therewith shows that microbial degradation of DOM has a considerable share in sustaining the OMZ off Peru.

Activated chlorine compounds in the polar winter stratosphere drive catalytic cycles that deplete ozone and methane, whose abundances are highly relevant to the evolution of global climate. The present work introduces a novel dataset of in situ measurements of relevant chlorine species in the lowermost Arctic stratosphere from the aircraft mission POLSTRACC–GW-LCYCLE–SALSA during winter 2015/2016. The major stages of chemical evolution of the lower polar vortex are presented in a consistent series of high-resolution mass spectrometric observations of HCl and ClONO2. Simultaneous measurements of CFC-12 are used to derive total inorganic chlorine (Cly) and active chlorine (ClOx). The new data highlight an altitude dependence of the pathway for chlorine deactivation in the lowermost vortex with HCl dominating below the 380 K isentropic surface and ClONO2 prevailing above. Further, we show that the Chemical Lagrangian Model of the Stratosphere (CLaMS) is generally able to reproduce the chemical evolution of the lower polar vortex chlorine budget, except for a bias in HCl concentrations. The model is used to relate local measurements to the vortex-wide evolution. The results are aimed at fostering our understanding of the climate impact of chlorine chemistry, providing new observational data to complement satellite data and assess model performance in the climate-sensitive upper troposphere and lower stratosphere region.

The eastern tropical South Pacific (ETSP) hosts the Peruvian upwelling system, which represents one of the most productive areas in the world ocean. High primary production followed by rapid heterotrophic utilization of organic matter supports the formation of one of the most intense oxygen minimum zones (OMZs) in the world ocean, where dissolved oxygen (O2) concentrations reach less than 1 µmol kg−1. The high productivity leads to an accumulation of dissolved organic matter (DOM) in the surface layers that may serve as a substrate for heterotrophic respiration. However, the importance of DOM utilization for O2 respiration in the Peruvian upwelling system in general and for shaping the upper oxycline in particular remains unclear so far. This study reports the first estimates of diapycnal fluxes and supply of O2, dissolved organic carbon (DOC), dissolved organic nitrogen, dissolved hydrolysable amino acids (DHAA) and dissolved combined carbohydrates (DCCHO) for the ETSP off Peru. Diapycnal flux and supply estimates were obtained by combining measured vertical diffusivities and solute concentration gradients. They were analysed together with the molecular composition of DCCHO and DHAA to infer the transport of labile DOM into the upper OMZ and the potential role of DOM utilization for the attenuation of the diapycnal O2 flux that ventilates the OMZ. The observed diapycnal O2 flux (50 mmol O2 m−2 d−1 at maximum) was limited to the upper 80 m of the water column; the O2 supply of ∼1 µmol kg−1 d−1 was comparable to previously published O2 consumption rates for the North and South Pacific OMZs. The diapycnal DOM flux (31 mmol C m−2 d−1 at maximum) was limited to ∼30 m water depth, suggesting that the labile DOM is extensively consumed within the upper part of the shallow oxycline off Peru. The analyses of DCCHO and DHAA composition support this finding, suggesting that DOM undergoes comprehensive remineralization within the upper part of the oxycline, as the DOM within the core of the OMZ was found to be largely altered. Estimated by a simple equation for carbon combustion, aerobic respiration of DCCHO and DHAA, supplied by diapycnal mixing (0.46 µmol kg−1 d−1 at maximum), could account for up to 38 % of the diapycnal O2 supply in the upper oxycline, which suggests that DOM utilization plays a significant role for shaping the upper oxycline in the ETSP.

An accelerating Brewer–Dobson circulation (BDC) is a robust signal of climate change in model predictions but has been questioned by trace gas observations. We analyse the stratospheric mean age of air and the full age spectrum as measures for the BDC and its trend. Age of air is calculated using the Chemical Lagrangian Model of the Stratosphere (CLaMS) driven by ERA-Interim, JRA-55 and MERRA-2 reanalysis data to assess the robustness of the representation of the BDC in current generation meteorological reanalyses. We find that the climatological mean age significantly depends on the reanalysis, with JRA-55 showing the youngest and MERRA-2 the oldest mean age. Consideration of the age spectrum indicates that the older air for MERRA-2 is related to a stronger spectrum tail, which is likely associated with weaker tropical upwelling and stronger recirculation. Seasonality of stratospheric transport is robustly represented in reanalyses, with similar mean age variations and age spectrum peaks. Long-term changes from 1989 to 2015 turn out to be similar for the reanalyses with mainly decreasing mean age accompanied by a shift of the age spectrum peak towards shorter transit times, resembling the forced response in climate model simulations to increasing greenhouse gas concentrations. For the shorter periods, 1989–2001 and 2002–2015, the age of air changes are less robust. Only ERA-Interim shows the hemispheric dipole pattern in age changes from 2002 to 2015 as viewed by recent satellite observations. Consequently, the representation of decadal variability of the BDC in current generation reanalyses appears less robust and is a major uncertainty of modelling the BDC.