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Organic macromolecules constitute a high percentage of remote sea spray. They enter the atmosphere through adsorption onto bubbles followed by bursting at the ocean surface, and go on to influence the chemistry of the fine mode aerosol. We present a global estimate of mixed-layer macromolecular distributions, driven by offline marine systems model output. The approach permits estimation of oceanic concentrations and bubble film surface coverages for several classes of organic compound. Mixed layer levels are computed from the output of a global ocean ecodynamics model by relating the macromolecules to standard biogeochemical tracers. Steady state is assumed for labile forms, and for longer-lived components we rely on ratios to existing transported variables. Adsorption is then represented through conventional Langmuir isotherms, with equilibria deduced from laboratory analogs. Open water concentrations locally exceed one micromolar carbon for the total of proteins, polysaccharides and refractory heteropolycondensates. The shorter-lived lipids remain confined to regions of strong biological activity. Results are evaluated against available measurements for all compound types, and agreement is generally well within an order of magnitude. Global distributions are further estimated for both fractional coverage of bubble films at the air–water interface and the two-dimensional concentration excess. Overall, we show that macromolecular mapping provides a novel tool for the comprehension of oceanic surfactant patterns. These results may prove useful in planning field experiments and assessing the potential response of surface chemical behaviors to global change.

We have recently argued that marine interfacial surface tension must have a distinctive biogeography because it is mediated by fresh surfactant macromolecules released locally through the food web. Here we begin the process of quantification for associated climate flux implications. A low dimensionality (planar) equation of state is invoked at the global scale as our main analysis tool. For the reader’s convenience, fundamental surfactant physical chemistry principles are reviewed first, as they pertain to tangential forces that may alter oceanic eddy, ripple, and bubble fields. A model Prandtl (neutral) wind stress regime is defined for demonstration purposes. It is given the usual dependence on roughness, but then in turn on the tension reduction quantity known as surface pressure. This captures the main net influences of biology and detrital organics on global microlayer physics. Based on well-established surrogate species, tangent pressures are related to distributed ecodynamics as reflected by the current marine systems science knowledge base. Reductions to momentum and related heat-vapor exchange plus gas and salt transfer are estimated and placed on a coarse biogeographic grid. High primary production situations appear to strongly control all types of transfer, whether seasonally or regionally. Classic chemical oceanographic data on boundary state composition and behaviors are well reproduced, and there is a high degree of consistency with conventional micrometeorological wisdom. But although our initial best guesses are quite revealing, coordinated laboratory and field experiments will be required to confirm the broad hypotheses even partially. We note that if the concepts have large scale validity, they are super-Gaian. Biological control over key planetary climate-transfer modes may be accomplished through just a single rapidly renewed organic monolayer.

The effort to accurately estimate global radiative forcing has long been hampered by a degree of uncertainty in the tropospheric aerosol contribution. Reducing uncertainty in natural aerosol processes, the baseline of the aerosol budget, thus becomes a fundamental task. The appropriate representation of aerosols in the marine boundary layer (MBL) is essential to reduce uncertainty and provide reliable information on offsets to global warming. We developed an International Ocean Model Benchmarking package to assess marine biogeochemical process representations in Earth System Models (ESMs), and the package was employed to evaluate surface ocean concentrations and the sea–air fluxes of dimethylsulfide (DMS). Model performances were scored based on how well they captured the distribution and variability contained in high-quality observational datasets. Results show that model-data biases increased as DMS enters the MBL, but unfortunately over three-quarters of the models participating in the fifth Coupled Model Intercomparison Project (CMIP5) did not have a dynamic representation of DMS. When it is present, models tend to over-predict sea surface concentrations in the productive region of the eastern tropical Pacific by almost a factor of two, and the sea–air fluxes by a factor of three. Systematic model-data benchmarking as described here will help to identify such deficiencies and subsequently lead to improved subgrid-scale parameterizations and ESM development.

We apply principles of Gibbs phase plane chemistry across the entire ocean-atmosphere interface to investigate aerosol generation and geophysical transfer issues. Marine surface tension differences comprise a tangential pressure field controlling trace gas fluxes, primary organic inputs, and sea spray salt injections, in addition to heat and momentum fluxes. Mapping follows from the organic microlayer composition, now represented in ocean system models. Organic functional variations drive the microforcing, leading to (1) reduced turbulence and (by extension) laminar gas-energy diffusion; plus (2) altered bubble film mass emission into the boundary layer. Interfacial chemical behaviors are, therefore, closely reviewed as the background. We focus on phase transitions among two dimensional “solid, liquid, and gaseous” states serving as elasticity indicators. From the pool of dissolved organic carbon (DOC) only proteins and lipids appear to occupy significant atmospheric interfacial areas. The literature suggests albumin and stearic acid as the best proxies, and we distribute them through ecodynamic simulation. Consensus bulk distributions are obtained to control their adsorptive equilibria. We devise parameterizations for both the planar free energy and equation of state, relating excess coverage to the surface pressure and its modulus. Constant settings for the molecular surrogates are drawn from laboratory study and successfully reproduce surfactant solid-to-gas occurrence in compression experiments. Since DOC functionality measurements are rare, we group them into super-ecological province tables to verify aqueous concentration estimates. Outputs are then fed into a coverage, tension, elasticity code. The resulting two dimensional pressure contours cross a critical range for the regulation of precursor piston velocity, bubble breakage, and primary aerosol sources plus ripple damping. Concepts extend the water-air adsorption theory currently embodied in our OCEANFILMS aerosol emissions package, and the two approaches could be inserted into Earth System Models together. Uncertainties in the logic include kinetic and thermochemical factors operating at multiple scales.

High uncertainties associated with some of the underlying studies of the Earth system have undermined Earth System Model predictions of impending climate changes. Disparity between model results and field observations in studies involving parameters such as Arctic sea ice extent and sea-air flux of marine aerosol precursors tends to show the necessity for an improved climate model with more detailed and appropriate processes. The tremendous effort of the climate science community to improve the understanding of inter-connected processes has led to the initiation of the biogeochemistry field. Three different environments associated with marine/ice biogeochemistry and sea-air transfer of marine aerosol precursors were presented in this dissertation, with the ultimate goal of improving the representation of the processes in Earth System Models. Speciation of marine dissolved organic carbon into various classes of organic macromolecules is now achievable. This will aid in effectively identifying and quantifying organic fractions of sea spray aerosols. Influence of the changing El niño pattern on biological marker such as dimethyl sulfide and the possible effect on tropical cloud reflectivity can now be considered a substantial piece in the analysis of the Earth’s albedo in a changing climate. Another crucial result presented in this dissertation is that chlorophyll light absorption in the Arctic sea ice is considerably significant compared to light absorption by black carbon deposited on the ice/snow. These results will surely play major roles in developing next generation simulations to adequately represent changes in the Earth system as the science community improves the capabilities to match observations and give more accurate predictions of climate.

The International Ocean Model Benchmarking (IOMB) software package is a new community resource used here to evaluate surface and upper ocean variables from CMIP5 and CMIP6 Earth System Models (ESMs) Our analysis reveals general improvement in the multi-model mean of CMIP6 compared to CMIP5 for most of the variables we examined including surface nutrients, temperature, and salinity. We find that both CMIP5 and CMIP6 ocean models underestimate anthropogenic carbon dioxide uptake after the 1970s. For the period of 1994 to 2007, the multi-model mean from CMIP6 yields a mean cumulative carbon uptake of 27.2 +-2.2 Pg C, which is about 15% lower than the 32.0+-5.7 Pg C estimate derived from two sets of observations. Negative biases in the change in anthropogenic carbon inventory exist in the northern North Atlantic and at mid-latitudes in the southern hemisphere (30-60S). For the few models that provided simulations of chlorofluorocarbon (CFC), we demonstrate that regions with negative anthropogenic DIC biases coincide with regions that have a negative bias in CFC concentrations. This relationship suggests that underestimates of anthropogenic carbon storage in some models originates, in part, from weak transport between the surface and interior ocean. To examine the robustness of this attribution across the full suite of CMIP5 and CMIP6 models, we examined the vertical temperature gradient between 200 and 1000m as a metric for stratification and exchange between the surface and deeper waters. On a global scale across different models and different MIPs we find a linear relationship between the bias of vertical temperature gradients and the bias in anthropogenic carbon uptake, consistent with the hypothesis that model biases in the ocean carbon sink are related to biases in surface-to-interior transport.

Arctic sea ice extent has declined continuously for the past decade, owing partially to light absorption by black carbon (BC) and other impurities deposited on snow and the underlying pack. We present simulations for the contemporary period showing that the optical depth contributed by Arctic ice algal chlorophyll may be comparable during Boreal Spring to the corresponding values attributable to BC. The largest chlorophyll attenuation is obtained in the bottom layer, which supports pigment concentrations of about 300 to 1000 mg/m3 in the Bering Sea and Sea of Okhotsk. However, chlorophyll concentrations for the ice interior in regions north of 75 N and across the Canadian Archipelago are less than 0.1 micro g/m3. Freeboard and infiltration communities lead to intermediate levels of light removal. Since BC works its way downward from the atmospheric interface, there will be regions where it appropriates photosynthetic capability. Where ice thicknesses permit significant penetration through the pack column the ice algae may be crucial absorbers. We propose a continuous increase in relative chlorophyll activity and attenuation in the future, as biological activity becomes stronger in thin ice toward the center of the Arctic basin. A shift in relative importance of the two absorber types could occur as total BC mixing ratios are reduced because of environmental advocacy.

Mycotoxins pose a major problem to poultry production as a result of feed contamination which has deleterious consequences such as production losses and human health risks. A total of 158 chicken feed samples were randomly collected from 46 consenting poultry farms in Oyo State throughout the wet season (April–October; 91 samples) and the dry season (November–March; 67 samples), including compounded feed ( n  = 129) and feed ingredients ( n  = 29). Samples were promptly transported to the laboratory in sterile plastic vials for lateral flow assay for mycotoxins using six different commercial mycotoxin test kits each for aflatoxin B1, zearalenone, deoxynivalenol, ochratoxin A, fumonisin, and T-2 toxin/HT-2 toxin. Summary values of mycotoxin levels (µg/kg) in the feedstuffs were represented as frequency or median (and range). Fisher exact or Mann-Whitney U tests were carried out where appropriate at α  = 0.05. Every sample contained at least four mycotoxins. Aflatoxins and fumonisin co-occurred in 80% of the samples. Aflatoxin and fumonisin concentrations were above the permissible limits in 32.9% and 18.4% respectively in feedstuff sampled in the dry season while the values were 17.1% and 6.3% respectively during the wet season. Among feed ingredients, peanut cake and maize had the highest median concentration of aflatoxin and fumonisin, respectively. Median aflatoxin concentration in the feedstuff was significantly higher than the permissible limit irrespective of season. There is a need to frequently monitor mycotoxin levels of feed and feed ingredients and improve storage system for feed ingredients in order to reduce the risk associated with high mycotoxin intake in poultry.

Avian influenza (AI) is a severe respiratory disease affecting wild and domestic birds globally. There is currently no approved vaccine for AI control in Nigeria. Therefore, biosecurity measures remain the primary preventive strategy. However, there is limited information on the AI carrier status of captive wild birds and the implementation of biosecurity programs (BPs) in zoological gardens across the country. This study aimed to screen captive wild birds for AI and evaluate the BPs in selected zoological gardens in southwestern Nigeria. Using a cross‐sectional approach, cloacal swabs and freshly deposited faecal samples ( n = 149) were collected from captive wild birds in seven zoological gardens in southwestern Nigeria following an AI outbreak in 2022. The samples were screened for AI viruses using RT‐qPCR, and BPs in 13 consenting zoological gardens were assessed using a structured questionnaire. The responses were scored, and the BPs were categorised as ‘Poor’, ‘Fair’, or ‘Good’. Descriptive and inferential statistical methods were used to analyse the data. All samples tested negative for AI viruses. Documented institutional biosecurity and disease outbreak contingency plans were available in 84.6% of the zoos. Most of the zoos demonstrated good BPs across key categories, including vehicle and animal movement control (100%), food and water supply management (92.3%), enclosure hygiene, ground maintenance and waste disposal (84.6%), pest control (76.9%), and quarantine and sick animal management (69.2%). These findings suggest that the captive wild birds in zoological gardens in southwestern Nigeria are unlikely to serve as AI reservoirs, and most of the zoos have robust BPs that contribute to preventing AI and other avian diseases.