Synthetic and practical reconstructions of SST and seawater pH using the novel multiproxy SMITE method.

Geochemical proxies of sea surface temperature (SST) and seawater pH (pHsw) in scleractinian coral skeletons are valuable tools for reconstructing tropical climate variability. However, most coral skeletal SST and pHsw proxies are univariate methods that are limited in their capacity to circumvent non-climate-related variability. Here we present a novel multivariate method for reconstructing SST and pHsw from the geochemistry of coral skeletons. Our Scleractinian Multivariate Isotope and Trace Element (SMITE) method optimizes reconstruction skill by leveraging the covariance across an array of coral elemental and isotopic data with SST and pHsw. First, using a synthetic proxy experiment, we find that SMITE SST reconstruction statistics (correlation, accuracy, and precision) are insensitive to noise and variable calibration period lengths relative to Sr/Ca. While SMITE pHsw reconstruction statistics remain relative to δ11B throughout the same synthetic experiment, the magnitude of the long-term trend in pHsw is progressively lost under conditions of moderate-to-high analytical uncertainty. Next, we apply the SMITE method to an array of seven coral-based geochemical variables (B/Ca, δ11B, Li/Ca, Mg/Ca, Sr/Ca, U/Ca & Li/Mg) measured from two Bermudan Porites astreoides corals. Despite a <3.5 year calibration period, SMITE SST and pHsw estimates exhibit significantly better accuracy, precision, and correlation with their respective climate targets than the best single- and dual-proxy estimators. Furthermore, SMITE model parameters are highly reproducible between the two coral cores, indicating great potential for fossil applications (when preservation is high). The results shown here indicate that the SMITE method can outperform the most common coral-based SST and pHsw reconstructions methods to date, particularly in datasets with a large variety of geochemical variables. We therefore provide a list of recommendations and procedures for users to begin implementing the SMITE method as well as an open-source software package to facilitate dissemination of the SMITE method.

Three-dimensional reconstruction of high latitude bamboo coral via X-ray microfocus Computed Tomography.

The skeletons of long-lived bamboo coral (Family Keratoisididae) are promising archives for deep-water palaeoceanographic reconstructions as they can record environmental variation at sub-decadal resolution in locations where in-situ measurements lack temporal coverage. Yet, detailed three dimensional (3D) characterisations of bamboo coral skeletal architecture are not routinely available and non-destructive investigations into microscale variations in calcification are rare. Here, we provide high-resolution micro-focus computed tomography (µCT) data of skeletal density for two species of bamboo coral (Acanella arbuscula: 5 specimens, voxel size, 15 µm (central branch scans) and 50 µm (complete structure scan); Keratoisis sp.: 4 specimens, voxel size, 15 µm) collected from the Labrador Sea and Baffin Bay deep-water basins, Eastern Canadian Arctic. These data provide reference models useful for developing methods to assess structural integrity and other fine-scale complexities in many biological, geological, and industrial systems. This will be of wider value to those investigating structural composition, arrangement and/or composition of complex architecture within the fields and subdisciplines of biology, ecology, medicine, environmental geology, and structural engineering.

Correlative geochemical imaging of Desmophyllum dianthus reveals biomineralisation strategy as a key coral vital effect.

The chemical and isotopic composition of stony coral skeletons form an important archive of past climate. However, these reconstructions are largely based on empirical relationships often complicated by "vital effects" arising from uncertain physiological processes of the coral holobiont. The skeletons of deep-sea corals, such as Desmophyllum dianthus, are characterised by micron-scale or larger geochemical heterogeneity associated with: (1) centres of calcification (COCs) where nucleation of new skeleton begins, and (2) fibres that thicken the skeleton. These features are difficult to sample cleanly using traditional techniques, resulting in uncertainty surrounding both the causes of geochemical differences and their influence on environmental signals. Here we combine optical, and in-situ chemical and isotopic, imaging tools across a range of spatial resolutions (~ 100 nm to 10 s of µm) in a correlative multimodal imaging (CMI) approach to isolate the microstructural geochemistry of each component. This reveals COCs are characterised by higher organic content, Mg, Li and Sr and lower U, B and δ11B compared to fibres, reflecting the contrasting biomineralisation mechanisms employed to construct each feature. CMI is rarely applied in Environmental/Earth Sciences, but here we illustrate the power of this approach to unpick the "vital effects" in D. dianthus, and by extension, other scleractinian corals.

Including environmental and climatic considerations for sustainable coral reef restoration.

Coral reefs provide ecosystem benefits to millions of people but are threatened by rapid environmental change and ever-increasing human pressures. Restoration is becoming a priority strategy for coral reef conservation, yet implementation remains challenging and it is becoming increasingly apparent that indirect conservation and restoration approaches will not ensure the long-term sustainability of coral reefs. The important role of environmental conditions in restoration practice are currently undervalued, carrying substantial implications for restoration success. Giving paramount importance to environmental conditions, particularly during the pre-restoration planning phase, has the potential to bring about considerable improvements in coral reef restoration and innovation. This Essay argues that restoration risk may be reduced by adopting an environmentally aware perspective that gives historical, contemporary, and future context to restoration decisions. Such an approach will open up new restoration opportunities with improved sustainability that have the capacity to dynamically respond to environmental trajectories.

Large-scale culturing of Neogloboquadrina pachyderma, its growth in, and tolerance of, variable environmental conditions.

The planktic foraminifera Neogloboquadrina pachyderma is a calcifying marine protist and the dominant planktic foraminifera species in the polar oceans, making it a key species in marine polar ecosystems. The calcium carbonate shells of foraminifera are widely used in palaeoclimate studies because their chemical composition reflects the seawater conditions in which they grow. This species provides unique proxy data for past surface ocean hydrography, which can provide valuable insight to future climate scenarios. However, little is known about the response of N. pachyderma to variable and changing environmental conditions. Here, we present observations from large-scale culturing experiments where temperature, salinity and carbonate chemistry were altered independently. We observed overall low mortality, calcification of new chambers and addition of secondary calcite crust in all our treatments. In-culture asexual reproduction events also allowed us to monitor the variable growth of N. pachyderma's offspring. Several specimens had extended periods of dormancy or inactivity after which they recovered. These observations suggest that N. pachyderma can tolerate, adapt to and calcify within a wide range of environmental conditions. This has implications for the species-level response to ocean warming and acidification, for future studies aiming to culture N. pachyderma and use in palaeoenvironmental reconstruction.

Laser ablation mass spectrometry blast through detection in R.

RATIONALE: Organisms that grow a hard carbonate shell or skeleton, such as foraminifera, corals or molluscs, incorporate trace elements into their shell during growth that reflect the environmental change and biological activity they experienced during life. These geochemical signals locked within the carbonate are archives used in proxy reconstructions to study past environments and climates, to decipher taxonomy of cryptic species and to resolve evolutionary responses to climatic changes. METHODS: Here, we use laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) as a time-resolved acquisition to quantify the elemental composition of carbonate shells and skeletons. We present the LABLASTER (Laser Ablation BLASt Through Endpoint in R) package, which imports a single time-resolved LA-ICP-MS analysis, then detects when the laser has ablated through the carbonate as a function of change in signal over time and outputs key summary statistics. We provide two examples within the package: a fossil planktic foraminifer and a tropical coral skeleton. RESULTS: We present the first R package that automates the selection of desired data during data reduction workflows. This is achieved by automating the detection of when the laser has ablated through a sample using a smoothed time series, followed by removal of off-target data points. The functions are flexible and adjust dynamically to maximise the duration of the desired geochemical target signal, making this package applicable to a wide range of heterogenous bioarchives. Visualisation tools for manual validation are also included. CONCLUSIONS: LABLASTER increases transparency and repeatability by algorithmically identifying when the laser has either ablated fully through a sample or across a mineral boundary and is thus no longer documenting a geochemical signal associated with the desired sample. LABLASTER's focus on better data targeting means more accurate extraction of biological and geochemical signals.

Characterisation and calibration of low-cost PM sensors at high temporal resolution to reference-grade performance.

Particulate Matter (PM) low-cost sensors (LCS) present a cost-effective opportunity to improve the spatiotemporal resolution of airborne PM data. Previous studies focused on PM-LCS-reported hourly data and identified, without fully addressing, their limitations. However, PM-LCS provide measurements at finer temporal resolutions. Furthermore, government bodies have developed certifications to accompany new uses of these sensors, but these certifications have shortcomings. To address these knowledge gaps, PM-LCS of two models, 8 Sensirion SPS30 and 8 Plantower PMS5003, were collocated for one year with a Fidas 200S, MCERTS-certified PM monitor and were characterised at 2 min resolution, enabling replication of certification processes, and highlighting their limitations and improvements. Robust linear models using sensor-reported particle number concentrations and relative humidity, coupled with 2-week biannual calibration campaigns, achieved reference-grade performance, at median PM2.5 background concentration of 5.5 µg/m3, demonstrating that, with careful calibration, PM-LCS may cost-effectively supplement reference equipment in multi-nodes networks with fine spatiotemporality.

Persistent high latitude amplification of the Pacific Ocean over the past 10 million years.

While high latitude amplification is seen in modern observations, paleoclimate records, and climate modeling, better constraints on the magnitude and pattern of amplification would provide insights into the mechanisms that drive it, which remain actively debated. Here we present multi-proxy multi-site paleotemperature records over the last 10 million years from the Western Pacific Warm Pool (WPWP) - the warmest endmember of the global ocean that is uniquely important in the global radiative feedback change. These sea surface temperature records, based on lipid biomarkers and seawater Mg/Ca-adjusted foraminiferal Mg/Ca, unequivocally show warmer WPWP in the past, and a secular cooling over the last 10 million years. Compiling these data with existing records reveals a persistent, nearly stationary, extratropical response pattern in the Pacific in which high latitude (~50°N) temperatures increase by ~2.4° for each degree of WPWP warming. This relative warming pattern is also evident in model outputs of millennium-long climate simulations with quadrupling atmospheric CO2, therefore providing a strong constraint on the future equilibrium response of the Earth System.

Abrupt upwelling and CO2 outgassing episodes in the north-eastern Arabian Sea since mid-Holocene.

Identifying the causes and consequences of natural variations in ocean acidification and atmospheric CO2 due to complex earth processes has been a major challenge for climate scientists in the past few decades. Recent developments in the boron isotope (δ11B) based seawater pH and pCO2 (or pCO2sw) proxy have been pivotal in understanding the various oceanic processes involved in air-sea CO2 exchange. Here we present the first foraminifera-based δ11B record from the north-eastern Arabian Sea (NEAS) covering the mid-late Holocene (~ 8-1 ka). Our record suggests that the region was overall a moderate to strong CO2 sink during the last 7.7 kyr. The region behaved as a significant CO2 source during two short intervals around 5.5-4 ka and 2.8-2.5 ka. The decreased pH and increased CO2 outgassing during those abrupt episodes are associated with the increased upwelling in the area. The upwelled waters may have increased the nutrient content of the surface water through either increased supply or weaker export production. This new dataset from the coastal NEAS suggests that, as a potential result of changes in the strength of the El-Nino Southern Oscillation, the region experienced short episodes of high CO2 outgassing and pre-industrial ocean acidification comparable to or even greater than that experienced during the last ~ 200 years.

Surface ocean warming and acidification driven by rapid carbon release precedes Paleocene-Eocene Thermal Maximum.

The Paleocene-Eocene Thermal Maximum (PETM) is recognized by a major negative carbon isotope (δ13C) excursion (CIE) signifying an injection of isotopically light carbon into exogenic reservoirs, the mass, source, and tempo of which continue to be debated. Evidence of a transient precursor carbon release(s) has been identified in a few localities, although it remains equivocal whether there is a global signal. Here, we present foraminiferal δ13C records from a marine continental margin section, which reveal a 1.0 to 1.5‰ negative pre-onset excursion (POE), and concomitant rise in sea surface temperature of at least 2°C and a decline in ocean pH. The recovery of both δ13C and pH before the CIE onset and apparent absence of a POE in deep-sea records suggests a rapid (< ocean mixing time scales) carbon release, followed by recovery driven by deep-sea mixing. Carbon released during the POE is therefore likely more similar to ongoing anthropogenic emissions in mass and rate than the main CIE.

Sea level and deep-sea temperature reconstructions suggest quasi-stable states and critical transitions over the past 40 million years.

Sea level and deep-sea temperature variations are key indicators of global climate changes. For continuous records over millions of years, deep-sea carbonate microfossil-based δ18O (δc) records are indispensable because they reflect changes in both deep-sea temperature and seawater δ18O (δw); the latter are related to ice volume and, thus, to sea level changes. Deep-sea temperature is usually resolved using elemental ratios in the same benthic microfossil shells used for δc, with linear scaling of residual δw to sea level changes. Uncertainties are large and the linear-scaling assumption remains untested. Here, we present a new process-based approach to assess relationships between changes in sea level, mean ice sheet δ18O, and both deep-sea δw and temperature and find distinct nonlinearity between sea level and δw changes. Application to δc records over the past 40 million years suggests that Earth's climate system has complex dynamical behavior, with threshold-like adjustments (critical transitions) that separate quasi-stable deep-sea temperature and ice-volume states.

Past climates inform our future.

As the world warms, there is a profound need to improve projections of climate change. Although the latest Earth system models offer an unprecedented number of features, fundamental uncertainties continue to cloud our view of the future. Past climates provide the only opportunity to observe how the Earth system responds to high carbon dioxide, underlining a fundamental role for paleoclimatology in constraining future climate change. Here, we review the relevancy of paleoclimate information for climate prediction and discuss the prospects for emerging methodologies to further insights gained from past climates. Advances in proxy methods and interpretations pave the way for the use of past climates for model evaluation-a practice that we argue should be widely adopted.

Author Correction: Long-term field comparison of multiple low-cost particulate matter sensors in an outdoor urban environment.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Atmospheric CO2 during the Mid-Piacenzian Warm Period and the M2 glaciation.

The Piacenzian stage of the Pliocene (2.6 to 3.6 Ma) is the most recent past interval of sustained global warmth with mean global temperatures markedly higher (by ~2-3 °C) than today. Quantifying CO2 levels during the mid-Piacenzian Warm Period (mPWP) provides a means, therefore, to deepen our understanding of Earth System behaviour in a warm climate state. Here we present a new high-resolution record of atmospheric CO2 using the δ11B-pH proxy from 3.35 to 3.15 million years ago (Ma) at a temporal resolution of 1 sample per 3-6 thousand years (kyrs). Our study interval covers both the coolest marine isotope stage of the mPWP, M2 (~3.3 Ma) and the transition into its warmest phase including interglacial KM5c (centered on ~3.205 Ma) which has a similar orbital configuration to present. We find that CO2 ranged from [Formula: see text]ppm to [Formula: see text]ppm, with CO2 during the KM5c interglacial being [Formula: see text]ppm (at 95% confidence). Our findings corroborate the idea that changes in atmospheric CO2 levels played a distinct role in climate variability during the mPWP. They also facilitate ongoing data-model comparisons and suggest that, at present rates of human emissions, there will be more CO2 in Earth's atmosphere by 2025 than at any time in at least the last 3.3 million years.

Automation of boron chromatographic purification for δ11 B analysis of coral aragonite.

RATIONALE: To detect the small changes in past pH, the boron isotope ratio of coral carbonates, expressed as the δ11 B value, needs to be both precise and accurate (2sd <<1‰). Boron measurements by Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS) require the boron to be carefully purified before analysis, which is time consuming, and requires specialist training. Here, we use the prepFAST-MC method that enables the automatic extraction of B (up to 25 ng load) from a CaCO3 matrix. METHODS: Samples were purified using the prepFAST-MC automated system with a ~25-µL column of Amberlite IRA743 resin. Boron isotope measurements were performed by MC-ICPMS. The effects of matrix load, speed of sample loading onto the column, and blank contamination were tested to evaluate the effects on the purification process. The optimised protocol was tested on various standards and samples of aragonite corals. RESULTS: The blank contribution for the approach is ~60 pg and is negligible given our sample size (<0.2% sample size). Efficiency of matrix removal is demonstrated with the addition of up to 1.6 mg of dissolved low-B calcium carbonate to NIST SRM 951 with no impact on the accuracy of δ11 B values. The Japanese Geological Survey Porites reference material JCp-1, boric acid standard NIST SRM 951, and seawater, all processed on the prepFAST-MC system, give δ11 B values within error of literature values (δ11 BJCp-1 = 24.31 ± 0.20‰ (2sd, n = 20); δ11 BNIST 951 = -0.02 ± 0.15‰ (2sd, n = 13) and δ11 BSeawater = 39.50 ± 0.06‰ (2sd, n = 2)). Results obtained from the coral Siderastrea siderea purified with the prepFAST-MC system show an average offset from the manual ion-exchange protocols of Δδ11 B = 0.01 ± 0.28‰ (2sd, n = 12). CONCLUSIONS: Our study demonstrates the capacity of the prepFAST-MC method to generate accurate and reproducible δ11 B values for a range of materials, without fractionation, with efficient matrix removal and with negligible blank contribution.

Long-term field comparison of multiple low-cost particulate matter sensors in an outdoor urban environment.

Exposure to ambient particulate matter (PM) air pollution is a leading risk factor for morbidity and mortality, associated with up to 8.9 million deaths/year worldwide. Measurement of personal exposure to PM is hindered by poor spatial resolution of monitoring networks. Low-cost PM sensors may improve monitoring resolution in a cost-effective manner but there are doubts regarding data reliability. PM sensor boxes were constructed using four low-cost PM micro-sensor models. Three boxes were deployed at each of two schools in Southampton, UK, for around one year and sensor performance was analysed. Comparison of sensor readings with a nearby background station showed moderate to good correlation (0.61 < r < 0.88, p < 0.0001), but indicated that low-cost sensor performance varies with different PM sources and background concentrations, and to a lesser extent relative humidity and temperature. This may have implications for their potential use in different locations. Data also indicates that these sensors can track short-lived events of pollution, especially in conjunction with wind data. We conclude that, with appropriate consideration of potential confounding factors, low-cost PM sensors may be suitable for PM monitoring where reference-standard equipment is not available or feasible, and that they may be useful in studying spatially localised airborne PM concentrations.

The effect of matrix interferences on in situ boron isotope analysis by laser ablation multi-collector inductively coupled plasma mass spectrometry.

RATIONALE: Boron isotope analysis of marine carbonates by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) offers the potential for rapid sample throughput, and the means to examine micron-scale variations in the δ11 B signatures of fossil skeletons and shells/tests of marine organisms. Existing studies demonstrate an acceptable level of reproducibility is achievable, but also typically show a level of accuracy outside the limits required by most applications. Here we investigate matrix interference effects as a cause of inaccuracy and imprecision. METHODS: Analyses were performed on a standard format Thermo Scientific Neptune Plus MC-ICP mass spectrometer coupled to a New Wave Research 193 nm ArF laser ablation system. The effects of matrix interference on δ11 B analysis were investigated through analyses of a set of reference materials with differing B/Ca ratios. Three approaches to correct for matrix-induced effects were trialled: (1) use of matrix-matched standards, (2) utilisation of the relationship between δ11 B inaccuracy and11 B/43 Ca, 11 B/40 ArCa4+ or 11 B/Cainterference from three reference materials with known δ11 B values and varying B/Ca ratios, and (3) direct characterisation of the (sloping) interference itself. RESULTS: Matrix interference from scattered Ca ions on 10 B can impede both the accuracy and the reproducibility of δ11 B analysis by LA-MC-ICP-MS. Based on analyses of two in-house reference materials, deep sea coral PS69/3181 and inorganic calcite UWC-1, we find approach 2, following the 11 B/Cainterference relationship, gives the best mean accuracies (within 0.4‰ of solution values) and external reproducibilities (± 0.5‰ 2 SD for PS69/3181). This approach has been applied to analyses of an annual growth cycle of a Siderastrea siderea coral and eight Cibicidoides wuellerstorfi benthic foraminifera. Both coral and foraminifera data match solution MC-ICP-MS analyses within reported uncertainties. CONCLUSIONS: LA-MC-ICP-MS can produce accurate and precise δ11 B data to a 0.5‰ (2σ) level on <0.3 ng B after correction for Ca interference effects.

City Scale Particulate Matter Monitoring Using LoRaWAN Based Air Quality IoT Devices.

Air Quality (AQ) is a very topical issue for many cities and has a direct impact on citizen health. The AQ of a large UK city is being investigated using low-cost Particulate Matter (PM) sensors, and the results obtained by these sensors have been compared with government operated AQ stations. In the first pilot deployment, six AQ Internet of Things (IoT) devices have been designed and built, each with four different low-cost PM sensors, and they have been deployed at two locations within the city. These devices are equipped with LoRaWAN wireless network transceivers to test city scale Low-Power Wide Area Network (LPWAN) coverage. The study concludes that (i) the physical device developed can operate at a city scale; (ii) some low-cost PM sensors are viable for monitoring AQ and for detecting PM trends; (iii) LoRaWAN is suitable for city scale sensor coverage where connectivity is an issue. Based on the findings from this first pilot project, a larger LoRaWAN enabled AQ sensor network is being deployed across the city of Southampton in the UK.

Placing our current 'hyperthermal' in the context of rapid climate change in our geological past.

'…there are known knowns. These are things we know that we know. There are known unknowns. That is to say, there are things that we know we don't know. But there are also unknown unknowns. There are things we don't know we don't know.' Donald Rumsfeld 12th February 2002.This article is part of a discussion meeting issue 'Hyperthermals: rapid and extreme global warming in our geological past'.