ALBERT

Description: We present the development of a multiphase adjoint for the Community Multiscale Air Quality (CMAQ) model, a widely used chemical transport model. The adjoint model provides location- and time-specific gradients that can be used in various applications such as backward sensitivity analysis, source attribution, optimal pollution control, data assimilation, and inverse modeling. The science processes of the CMAQ model include gas-phase chemistry, aerosol dynamics and thermodynamics, cloud chemistry and dynamics, diffusion, and advection. Discrete adjoints are implemented for all the science processes, with an additional continuous adjoint for advection. The development of discrete adjoints is assisted with algorithmic differentiation (AD) tools. Particularly, the Kinetic PreProcessor (KPP) is implemented for gas-phase and aqueous chemistry, and two different automatic differentiation tools are used for other processes such as clouds, aerosols, diffusion, and advection. The continuous adjoint of advection is developed manually. For adjoint validation, the brute-force or finite-difference method (FDM) is implemented process by process with box- or column-model simulations. Due to the inherent limitations of the FDM caused by numerical round-off errors, the complex variable method (CVM) is adopted where necessary. The adjoint model often shows better agreement with the CVM than with the FDM. The adjoints of all science processes compare favorably with the FDM and CVM. In an example application of the full multiphase adjoint model, we provide the first estimates of how emissions of particulate matter (PM2.5) affect public health across the US.

Description: The role that climate and environmental history may have played in influencing human evolution has been the focus of considerable interest and controversy among paleoanthropologists for decades. Prior attempts to understand the environmental history side of this equation have centered around the study of outcrop sediments and fossils adjacent to where fossil hominins (ancestors or close relatives of modern humans) are found, or from the study of deep sea drill cores. However, outcrop sediments are often highly weathered and thus are unsuitable for some types of paleoclimatic records, and deep sea core records come from long distances away from the actual fossil and stone tool remains. The Hominin Sites and Paleolakes Drilling Project (HSPDP) was developed to address these issues. The project has focused its efforts on the eastern African Rift Valley, where much of the evidence for early hominins has been recovered. We have collected about 2 km of sediment drill core from six basins in Kenya and Ethiopia, in lake deposits immediately adjacent to important fossil hominin and archaeological sites. Collectively these cores cover in time many of the key transitions and critical intervals in human evolutionary history over the last 4 Ma, such as the earliest stone tools, the origin of our own genus Homo, and the earliest anatomically modern Homo sapiens. Here we document the initial field, physical property, and core description results of the 2012–2014 HSPDP coring campaign.

Description: The aerosol-driven radiative effects on marine low-level cloud represent a large uncertainty in climate simulations, in particular over the Southern Ocean, which is also an important region for sea spray aerosol production. Observations of sea spray aerosol organic enrichment and the resulting impact on water uptake over the remote Southern Hemisphere are scarce, and therefore the region is under-represented in existing parameterisations. The Surface Ocean Aerosol Production (SOAP) voyage was a 23 d voyage which sampled three phytoplankton blooms in the highly productive water of the Chatham Rise, east of New Zealand. In this study we examined the enrichment of organics to nascent sea spray aerosol and the modifications to sea spray aerosol water uptake using in situ chamber measurements of seawater samples taken during the SOAP voyage. Primary marine organics contributed up to 23 % of the sea spray mass for particles with diameter less than approximately 1 µm and up to 79 % of the particle volume for 50 nm diameter sea spray. The composition of the submicron organic fraction was consistent throughout the voyage and was largely composed of a polysaccharide-like component, characterised by very low alkane-to-hydroxyl-concentration ratios of approximately 0.1–0.2. The enrichment of organics was compared to the output from the chlorophyll-a-based sea spray aerosol parameterisation suggested by Gantt et al. (2011) and the OCEANFILMS (Organic Compounds from Ecosystems to Aerosols: Natural Films and Interfaces via Langmuir Molecular Surfactants) models. OCEANFILMS improved on the representation of the organic fraction predicted using chlorophyll a, in particular when the co-adsorption of polysaccharides was included; however, the model still under-predicted the proportion of polysaccharides by an average of 33 %. Nascent 50 nm diameter sea spray aerosol hygroscopic growth factors measured at 90 % relative humidity averaged 1.93±0.08 and did not decrease with increasing sea spray aerosol organic fractions. The observed hygroscopicity was greater than expected from the assumption of full solubility, particularly during the most productive phytoplankton bloom (B1), during which organic fractions were greater than approximately 0.4. The water uptake behaviour observed in this study is consistent with that observed for other measurements of phytoplankton blooms and can be partially attributed to the presence of sea salt hydrates, which lowers the sea spray aerosol hygroscopicity when the organic enrichment is low. The inclusion of surface tension effects only marginally improved the modelled hygroscopicity, and a significant discrepancy between the observed and modelled hygroscopicity at high organic volume fractions remained. The findings from the SOAP voyage highlight the influence of biologically sourced organics on sea spray aerosol composition; these data improve the capacity to parameterise sea spray aerosol organic enrichment and water uptake.

Description: The Neogene and Quaternary are characterized by enormous changes in global climate and environments, including global cooling and the establishment of northern high-latitude glaciers. These changes reshaped global ecosystems, including the emergence of tropical dry forests and savannahs that are found in Africa today, which in turn may have influenced the evolution of humans and their ancestors. However, despite decades of research we lack long, continuous, well-resolved records of tropical climate, ecosystem changes, and surface processes necessary to understand their interactions and influences on evolutionary processes. Lake Tanganyika, Africa, contains the most continuous, long continental climate record from the mid-Miocene (∼10 Ma) to the present anywhere in the tropics and has long been recognized as a top-priority site for scientific drilling. The lake is surrounded by the Miombo woodlands, part of the largest dry tropical biome on Earth. Lake Tanganyika also harbors incredibly diverse endemic biota and an entirely unexplored deep microbial biosphere, and it provides textbook examples of rift segmentation, fault behavior, and associated surface processes. To evaluate the interdisciplinary scientific opportunities that an ICDP drilling program at Lake Tanganyika could offer, more than 70 scientists representing 12 countries and a variety of scientific disciplines met in Dar es Salaam, Tanzania, in June 2019. The team developed key research objectives in basin evolution, source-to-sink sedimentology, organismal evolution, geomicrobiology, paleoclimatology, paleolimnology, terrestrial paleoecology, paleoanthropology, and geochronology to be addressed through scientific drilling on Lake Tanganyika. They also identified drilling targets and strategies, logistical challenges, and education and capacity building programs to be carried out through the project. Participants concluded that a drilling program at Lake Tanganyika would produce the first continuous Miocene–present record from the tropics, transforming our understanding of global environmental change, the environmental context of human origins in Africa, and providing a detailed window into the dynamics, tempo and mode of biological diversification and adaptive radiations.

Description: Ferruginous lacustrine systems, such as Lake Towuti, Indonesia, are characterized by a specific type of phosphorus cycling in which hydrous ferric iron (oxyhydr)oxides trap and precipitate phosphorus to the sediment, which reduces its bioavailability in the water column and thereby restricts primary production. The oceans were also ferruginous during the Archean, thus understanding the dynamics of phosphorus in modern-day ferruginous analogues may shed light on the marine biogeochemical cycling that dominated much of Earth's history. Here we report the presence of large crystals (〉5 mm) and nodules (〉5 cm) of vivianite – a ferrous iron phosphate – in sediment cores from Lake Towuti and address the processes of vivianite formation, phosphorus retention by iron and the related mineral transformations during early diagenesis in ferruginous sediments. Core scan imaging, together with analyses of bulk sediment and pore water geochemistry, document a 30 m long interval consisting of sideritic and non-sideritic clayey beds and diatomaceous oozes containing vivianites. High-resolution imaging of vivianite revealed continuous growth of crystals from tabular to rosette habits that eventually form large (up to 7 cm) vivianite nodules in the sediment. Mineral inclusions like millerite and siderite reflect diagenetic mineral formation antecedent to the one of vivianite that is related to microbial reduction of iron and sulfate. Together with the pore water profiles, these data suggest that the precipitation of millerite, siderite and vivianite in soft ferruginous sediments stems from the progressive consumption of dissolved terminal electron acceptors and the typical evolution of pore water geochemistry during diagenesis. Based on solute concentrations and modeled mineral saturation indices, we inferred vivianite formation to initiate around 20 m depth in the sediment. Negative δ56Fe values of vivianite indicated incorporation of kinetically fractionated light Fe2+ into the crystals, likely derived from active reduction and dissolution of ferric oxides and transient ferrous phases during early diagenesis. The size and growth history of the nodules indicate that, after formation, continued growth of vivianite crystals constitutes a sink for P during burial, resulting in long-term P sequestration in ferruginous sediment.

Description: The capability of ambient particles to generate in vivo reactive oxygen species (ROS), called oxidative potential (OP), is a potential metric for evaluating the health effects of particulate matter (PM) and is supported by several recent epidemiological investigations. Studies using various types of OP assays differ in their sensitivities to varying PM chemical components. In this study, we systematically compared two health-relevant acellular OP assays that track the depletion of antioxidants or reductant surrogates: (i) the synthetic respiratory-tract lining fluid (RTLF) assay that tracks the depletion of ascorbic acid (AA) and glutathione (GSH) and (ii) the dithiothreitol (DTT) assay that tracks the depletion of DTT. Yearlong daily samples were collected at an urban site in Atlanta, GA (Jefferson Street), during 2017, and both DTT and RTLF assays were performed to measure the OP of water-soluble PM2.5 components. PM2.5 mass and major chemical components, including metals, ions, and organic and elemental carbon were also analyzed. Correlation analysis found that OP as measured by the DTT and AA depletion (OPDTT and OPAA, respectively) were correlated with both organics and some water-soluble metal species, whereas that from the GSH depletion (OPGSH) was exclusively sensitive to water-soluble Cu. These OP assays were moderately correlated with each other due to the common contribution from metal ions. OPDTT and OPAA were moderately correlated with PM2.5 mass with Pearson's r=0.55 and 0.56, respectively, whereas OPGSH exhibited a lower correlation (r=0.24). There was little seasonal variation in the OP levels for all assays due to the weak seasonality of OP-associated species. Multivariate linear regression models were developed to predict OP measures from the particle composition data. Variability in OPDTT and OPAA were not only attributed to the concentrations of metal ions (mainly Fe and Cu) and organic compounds but also to antagonistic metal–organic and metal–metal interactions. OPGSH was sensitive to the change in water-soluble Cu and brown carbon (BrC), a proxy for ambient humic-like substances.

Description: The Earth System Model Evaluation Tool (ESMValTool) is a community diagnostics and performance metrics tool designed to improve comprehensive and routine evaluation of Earth system models (ESMs) participating in the Coupled Model Intercomparison Project (CMIP). It has undergone rapid development since the first release in 2016 and is now a well-tested tool that provides end-to-end provenance tracking to ensure reproducibility. It consists of (1) an easy-to-install, well-documented Python package providing the core functionalities (ESMValCore) that performs common preprocessing operations and (2) a diagnostic part that includes tailored diagnostics and performance metrics for specific scientific applications. Here we describe large-scale diagnostics of the second major release of the tool that supports the evaluation of ESMs participating in CMIP Phase 6 (CMIP6). ESMValTool v2.0 includes a large collection of diagnostics and performance metrics for atmospheric, oceanic, and terrestrial variables for the mean state, trends, and variability. ESMValTool v2.0 also successfully reproduces figures from the evaluation and projections chapters of the Intergovernmental Panel on Climate Change (IPCC) Fifth Assessment Report (AR5) and incorporates updates from targeted analysis packages, such as the NCAR Climate Variability Diagnostics Package for the evaluation of modes of variability, the Thermodynamic Diagnostic Tool (TheDiaTo) to evaluate the energetics of the climate system, as well as parts of AutoAssess that contains a mix of top–down performance metrics. The tool has been fully integrated into the Earth System Grid Federation (ESGF) infrastructure at the Deutsches Klimarechenzentrum (DKRZ) to provide evaluation results from CMIP6 model simulations shortly after the output is published to the CMIP archive. A result browser has been implemented that enables advanced monitoring of the evaluation results by a broad user community at much faster timescales than what was possible in CMIP5.

Description: The Southern Ocean (south of 30∘ S) is a key global-scale sink of carbon dioxide (CO2). However, the isolated and inhospitable nature of this environment has restricted the number of oceanic and atmospheric CO2 measurements in this region. This has limited the scientific community's ability to investigate trends and seasonal variability of the sink. Compared to regions further north, the near-absence of terrestrial CO2 exchange and strong large-scale zonal mixing demands unusual inter-site measurement precision to help distinguish the presence of midlatitude to high latitude ocean exchange from large CO2 fluxes transported southwards in the atmosphere. Here we describe a continuous, in situ, ultra-high-precision Southern Ocean region CO2 record, which ran at Macquarie Island (54∘37′ S, 158∘52′ E) from 2005 to 2016 using a LoFlo2 instrument, along with its calibration strategy, uncertainty analysis and baseline filtering procedures. Uncertainty estimates calculated for minute and hourly frequency data range from 0.01 to 0.05 µmol mol−1 depending on the averaging period and application. Higher precisions are applicable when comparing Macquarie Island LoFlo measurements to those of similar instruments on the same internal laboratory calibration scale and more uncertain values are applicable when comparing to other networks. Baseline selection is designed to remove measurements that are influenced by local Macquarie Island CO2 sources, with effective removal achieved using a within-minute CO2 standard deviation metric. Additionally, measurements that are influenced by CO2 fluxes from Australia or other Southern Hemisphere land masses are effectively removed using model-simulated radon concentration. A comparison with flask records of atmospheric CO2 at Macquarie Island highlights the limitation of the flask record (due to corrections for storage time and limited temporal coverage) when compared to the new high-precision, continuous record: the new record shows much less noisy seasonal variations than the flask record. As such, this new record is ideal for improving our understanding of the spatial and temporal variability of the Southern Ocean CO2 flux, particularly when combined with data from similar instruments at other Southern Hemispheric locations.

Description: The balance between denitrification and nitrogen fixation is the key control of the availability of nitrogen in coastal ecosystems and thus the primary productivity of these environments. However, evaluating the importance of denitrification and nitrogen fixation over large spatial and temporal scales is problematic. In this study, a combined mass and stable isotope balance of nitrogen was used to constrain the cycling of nitrogen in Western Port, Victoria – a temperate, intertidal embayment in south-eastern Australia. This method is a more effective approach compared to the extrapolation of discrete measurements and geochemical approaches. The validity of the isotope and mass balance model has been tested by comparing the output of the model with the average measured isotopic signature of the sediment in Western Port. Using previously measured rates of nitrogen fixation and denitrification in combination with the isotopic signature of nitrogen inputs from the catchment, atmosphere and the marine environment, the model returned an isotopic signature of 4.1 ± 2.5 ‰. This compares favorably with the average measured isotopic signature of the sediment of 3.9 ± 1.2 ‰. Sensitivity analysis confirmed that it was the isotopic values of the end-members, fractionation factors of assimilation and denitrification that exerted the greatest control over the isotopic signature of the sediment and not the loadings of the source and sink terms. Analysis of the relative importance of the various nitrogen inputs into the bay suggests that nitrogen fixation contributes 36 % of the total nitrogen inputs to Western Port.

Description: We validate the Ozone Monitoring Instrument (OMI) Ozone Profile (PROFOZ) product from October 2004 through December 2014 retrieved by the Smithsonian Astrophysical Observatory (SAO) algorithm against ozonesonde observations. We also evaluate the effects of OMI row anomaly (RA) on the retrieval by dividing the dataset into before and after the occurrence of serious OMI RA, i.e., pre-RA (2004–2008) and post-RA (2009–2014). The retrieval shows good agreement with ozonesondes in the tropics and midlatitudes and for pressure