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Tropospheric ozone (O3) concentrations depend on a combination of hemispheric, regional, and local-scale processes. Estimates of how much O3 is produced locally vs. transported from further afield are essential in air quality management and regulatory policies. Here, a tagged-ozone mechanism within the Weather Research and Forecasting model coupled with chemistry (WRF-Chem) is used to quantify the contributions to surface O3 in the UK from anthropogenic nitrogen oxide (NOx) emissions from inside and outside the UK during May–August 2015. The contribution of the different source regions to three regulatory O3 metrics is also examined. It is shown that model simulations predict the concentration and spatial distribution of surface O3 with a domain-wide mean bias of −3.7 ppbv. Anthropogenic NOx emissions from the UK and Europe account for 13 % and 16 %, respectively, of the monthly mean surface O3 in the UK, as the majority (71 %) of O3 originates from the hemispheric background. Hemispheric O3 contributes the most to concentrations in the north and the west of the UK with peaks in May, whereas European and UK contributions are most significant in the east, south-east, and London, i.e. the UK's most populated areas, intensifying towards June and July. Moreover, O3 from European sources is generally transported to the UK rather than produced in situ. It is demonstrated that more stringent emission controls over continental Europe, particularly in western Europe, would be necessary to improve the health-related metric MDA8 O3 above 50 and 60 ppbv. Emission controls over larger areas, such as the Northern Hemisphere, are instead required to lessen the impacts on ecosystems as quantified by the AOT40 metric.

A global compilation of in situ data is vital to evaluate the quality of ocean-colour satellite data records. Here, we describe data compiled for the validation of ocean-colour products from the ESA Ocean Colour Climate Change Initiative (OC-CCI). The data were acquired from several sources (including, inter alia, MOBY, BOUSSOLE, AERONET-OC, SeaBASS, NOMAD, MERMAID, AMT, ICES, HOT, GeP&CO) and span the period from 1997 to 2021. Observations of the following variables were compiled: spectral remote-sensing reflectance, concentration of chlorophyll-a, spectral inherent optical properties, spectral diffuse attenuation coefficient and total suspended matter. The data were obtained from multi-project archives acquired via open internet services, or from individual projects, acquired directly from data providers. Methodologies were implemented for homogenisation, quality control and merging of all data. No changes were made to the original data, other than averaging of observations that were close in time and space, elimination of some points after quality control and conversion to a standard format. The result is a merged table available in text format. Metadata of each in situ measurement (original source, cruise or experiment, principal investigator) were propagated throughout the work and made available in the final table. By making the metadata available, provenance is better documented, and it is also possible to analyse each set of data separately. This paper also describes the changes that were made to the compilation in relation to the previous version.

Coccolithophores are globally important marine calcifying phytoplankton that utilize a haplo-diplontic life cycle. The haplo-diplontic life cycle allows coccolithophores to divide in both life cycle phases and potentially expands coccolithophore niche volume. Research has, however, to date largely overlooked the life cycle of coccolithophores and has instead focused on the diploid life cycle phase of coccolithophores. Through the synthesis and analysis of global scanning electron microscopy (SEM) coccolithophore abundance data (n=2534), we find that calcified haploid coccolithophores generally constitute a minor component of the total coccolithophore abundance (≈ 2 %–15 % depending on season). However, using case studies in the Atlantic Ocean and Mediterranean Sea, we show that, depending on environmental conditions, calcifying haploid coccolithophores can be significant contributors to the coccolithophore standing stock (up to ≈30 %). Furthermore, using hypervolumes to quantify the niche of coccolithophores, we illustrate that the haploid and diploid life cycle phases inhabit contrasting niches and that on average this allows coccolithophores to expand their niche by ≈18.8 %, with a range of 3 %–76 % for individual species. Our results highlight that future coccolithophore research should consider both life cycle stages, as omission of the haploid life cycle phase in current research limits our understanding of coccolithophore ecology. Our results furthermore suggest a different response to nutrient limitation and stratification, which may be of relevance for further climate scenarios. Our compilation highlights the spatial and temporal sparsity of SEM measurements and the need for new molecular techniques to identify uncalcified haploid coccolithophores. Our work also emphasizes the need for further work on the carbonate chemistry niche of the coccolithophore life cycle.

As part of the Model Intercomparison Project on the climatic response to Volcanic forcing (VolMIP), several climate modeling centers performed a coordinated pre-study experiment with interactive stratospheric aerosol models simulating the volcanic aerosol cloud from an eruption resembling the 1815 Mt. Tambora eruption (VolMIP-Tambora ISA ensemble). The pre-study provided the ancillary ability to assess intermodel diversity in the radiative forcing for a large stratospheric-injecting equatorial eruption when the volcanic aerosol cloud is simulated interactively. An initial analysis of the VolMIP-Tambora ISA ensemble showed large disparities between models in the stratospheric global mean aerosol optical depth (AOD). In this study, we now show that stratospheric global mean AOD differences among the participating models are primarily due to differences in aerosol size, which we track here by effective radius. We identify specific physical and chemical processes that are missing in some models and/or parameterized differently between models, which are together causing the differences in effective radius. In particular, our analysis indicates that interactively tracking hydroxyl radical (OH) chemistry following a large volcanic injection of sulfur dioxide (SO2) is an important factor in allowing for the timescale for sulfate formation to be properly simulated. In addition, depending on the timescale of sulfate formation, there can be a large difference in effective radius and subsequently AOD that results from whether the SO2 is injected in a single model grid cell near the location of the volcanic eruption, or whether it is injected as a longitudinally averaged band around the Earth.

Much of our understanding of Earth's past climate states comes from the measurement of oxygen and carbon isotope variations in deep-sea benthic foraminifera. Yet, major intervals in those records that lack the temporal resolution and/or age control required to identify climate forcing and feedback mechanisms. Here we document 66 million years of global climate by a new high-fidelity Cenozoic global reference benthic carbon and oxygen isotope dataset (CENOGRID). Using recurrence analysis, we find that on timescales of millions of years Earth's climate can be grouped into Hothouse, Warmhouse, Coolhouse and Icehouse states separated by transitions related to changing greenhouse gas levels and the growth of polar ice sheets. Each Cenozoic climate state is paced by orbital cycles, but the response to radiative forcing is state dependent.

High-resolution atmospheric carbon dioxide (CO2) and methane (CH4) records derived from the European Project for Ice Coring in Antarctica (EPICA) Dome C ice core covering Marine Isotope Stage (MIS) 9e - 12a (~330 - 450 ka BP). The majority of the CO2 data were measured at an average temporal resolution of ~300 years using a novel dry-extraction device called the Centrifugal Ice Microtome (CIM) employed at Climate and Environmental Physics (CEP), Physics Institute, University of Bern, Switzerland. Additional 33 data points were measured at the Institut des Géosciences de l'Environnement (IGE), Univ. Grenoble Alpes, France using the Ball Mill dry-extraction system. The CH4 data were measured at both CEP and IGE, improving the temporal resolution of existing data previously published by the same laboratories to ~350 years on average. These ice core records are complemented by high-resolution planktic and benthic stable isotope (δ18O and δ13C) records from the International Ocean Discovery Program (IODP) Site U1385 located on the Iberian Margin off the coast of Portugal (Shackleton Site) covering MIS 9e - 11c (~330 - 410 ka BP). All marine sediment data were measured at an average temporal resolution of ~150 years at the Godwin Laboratory of Palaeoclimate Research, University of Cambridge, UK.

The geologic time scale for the Cenozoic Era has been notably improved over the last decades by virtue of integrated stratigraphy, combining high-resolution astrochronologies, biostratigraphy and magnetostratigraphy with high-precision radioisotopic dates. However, the middle Eocene remains a weak link. The so-called "Eocene time scale gap" reflects the scarcity of suitable study sections with clear astronomically-forced variations in carbonate content, primarily because large parts of the oceans were starved of carbonate during the Eocene greenhouse. International Ocean Discovery Program (IODP) Expedition 369 cored a carbonate-rich sedimentary sequence of Eocene age in the Mentelle Basin (Site U1514, offshore southwest Australia). The sequence consists of nannofossil chalk and exhibits rhythmic clay content variability. Here, we show that IODP Site U1514 allows for the extraction of an astronomical signal and the construction of an Eocene astrochronology, using 3-cm resolution X-Ray fluorescence (XRF) core scans. The XRF-derived ratio between calcium and iron content (Ca/Fe) tracks the lithologic variability and serves as the basis for our U1514 astrochronology. We present a 16 million-year-long (40-56 Ma) nearly continuous history of Eocene sedimentation with variations paced by eccentricity and obliquity. We supplement the high-resolution XRF data with low-resolution bulk carbon and oxygen isotopes, recording the long-term cooling trend from the Paleocene-Eocene Thermal Maximum (PETM - ca. 56 Ma) into the middle Eocene (ca. 40 Ma). Our early Eocene astrochronology corroborates existing chronologies based on deep-sea sites and Italian land sections. For the middle Eocene, the sedimentological record at U1514 provides a single-site geochemical backbone and thus offers a further step towards a fully integrated Cenozoic geologic time scale at orbital resolution.

These are the supplementary datasets for the manuscript: Drury, A.J., Liebrand, D., Westerhold, T., Beddow, H., Hodell, D., Rohlfs, N., Wilkens, R.H., Lourens, L., 'History of South Atlantic carbonate deposition since the Oligocene (30-0 Ma)', in final preparation for submission Climate of the Past

The marine silicon cycle is intrinsically linked with carbon cycling in the oceans via biological production of silica by a wide range of organisms. The stable silicon isotopic composition (denoted by δ30Si) of siliceous microfossils extracted from sediment cores can be used as an archive of past oceanic silicon cycling. However, the silicon isotopic composition of biogenic silica has only been measured in diatoms, sponges and radiolarians, and isotopic fractionation relative to seawater is entirely unknown for many other silicifiers. Furthermore, the biochemical pathways and mechanisms that determine isotopic fractionation during biosilicification remain poorly understood. Here, we present the first measurements of the silicon isotopic fractionation during biosilicification by loricate choanoflagellates, a group of protists closely related to animals. We cultured two species of choanoflagellates, Diaphanoeca grandis and Stephanoeca diplocostata, which showed consistently greater isotopic fractionation (approximately −5 ‰ to −7 ‰) than cultured diatoms (−0.5 ‰ to −2.1 ‰). Instead, choanoflagellate silicon isotopic fractionation appears to be more similar to sponges grown under similar dissolved silica concentrations. Our results highlight that there is a taxonomic component to silicon isotope fractionation during biosilicification, possibly via a shared or related biochemical transport pathway. These findings have implications for the use of biogenic silica δ30Si produced by different silicifiers as proxies for past oceanic change.

Bottom trawling in the deep sea is one of the main drivers of sediment resuspension, eroding the seafloor and altering the content and composition of sedimentary organic matter (OM). The physical and biogeochemical impacts of bottom trawling were studied on the continental slope of the Gulf of Castellammare, Sicily (southwestern Mediterranean), through the analysis of two triplicate sediment cores collected at trawled and untrawled sites (∼550 m water depth) during the summer of 2016. Geochemical and sedimentological parameters (excess 210Pb, excess 234Th, 137Cs, dry bulk density, and grain size), elemental (organic carbon and nitrogen) and biochemical composition of sedimentary OM (proteins, carbohydrates, lipids), as well as its freshness (phytopigments) and degradation rates were determined in both coring locations. The untrawled site had a sedimentation rate of 0.15 cm yr−1 and presented a 6 cm thick surface mixed layer that contained siltier sediment with low excess 210Pb concentrations, possibly resulting from the resuspension, posterior advection, and eventual deposition of coarser and older sediment from adjacent trawling grounds. In contrast, the trawled site was eroded and presented compacted century-old sediment highly depleted in OM components, which were between 20 % and 60 % lower than those in the untrawled site. However, the upper 2 cm of the trawled site consisted of recently accumulated sediments enriched in excess 234Th, excess 210Pb, and phytopigments, while OM contents were similar to those from the untrawled core. This fresh sediment supported protein turnover rates of 0.025 d−1, which doubled those quantified in surface sediments of the untrawled site. The enhancement of remineralization rates in surface sediment of the trawled site was associated with the arrival of fresh particles on a chronically trawled deep-sea region that is generally deprived of OM. We conclude that the detrimental effects of bottom trawling can be temporarily and partially abated by the arrival of fresh and nutritionally rich OM, which stimulate the response of benthic communities. However, these ephemeral deposits are likely to be swiftly eroded due to the high trawling frequency over fishing grounds, highlighting the importance of establishing science-based management strategies to mitigate the impacts of bottom trawling.