Identification of possible sources for potentially toxic elements and polycyclic aromatic hydrocarbons and their spatially varying relationships in urban soils of Dublin, Ireland.

Potentially toxic elements (PTEs) and polycyclic aromatic hydrocarbons (PAHs) harm the ecosystem and human health, especially in urban areas. Identifying and understanding their potential sources and underlying interactions in urban soils are critical for informed management and risk assessment. This study investigated the potential sources and the spatially varying relationships between 9 PTEs and PAHs in the topsoil of Dublin by combining positive matrix factorisation (PMF) and geographically weighted regression (GWR). The PMF model allocated four possible sources based on species concentrations and uncertainties. The factor profiles indicated the associations with high-temperature combustion (PAHs), natural lithologic factors (As, Cd, Co, Cr, Ni), mineralisation and mining (Zn), as well as anthropogenic inputs (Cu, Hg, Pb), respectively. In addition, selected representative elements Cr, Zn, and Pb showed distinct spatial interactions with PAHs in the GWR model. Negative relationships between PAHs and Cr were observed in all samples, suggesting the control of Cr concentrations by natural factors. Negative relationships between PAHs and Zn in the eastern and north-eastern regions were related to mineralisation and anthropogenic Zn-Pb mining. In contrast, the surrounding regions exhibited a natural relationship between these two variables with positive coefficients. Increasing positive coefficients from west to east were observed between PAHs and Pb in the study area. This special pattern was consistent with prevailing south-westerly wind direction in Dublin, highlighting the predominant influences on PAHs and Pb concentrations from vehicle and coal combustion through atmospheric deposition. Our results provided a better understanding of geochemical features for PTEs and PAHs in the topsoil of Dublin, demonstrating the efficiency of combined approaches of receptor models and spatial analysis in environmental studies.

In-Silico Approaches for the Screening and Discovery of Broad-Spectrum Marine Natural Product Antiviral Agents Against Coronaviruses.

The urgent need for SARS-CoV-2 controls has led to a reassessment of approaches to identify and develop natural product inhibitors of zoonotic, highly virulent, and rapidly emerging viruses. There are yet no clinically approved broad-spectrum antivirals available for beta-coronaviruses. Discovery pipelines for pan-virus medications against a broad range of betacoronaviruses are therefore a priority. A variety of marine natural product (MNP) small molecules have shown inhibitory activity against viral species. Access to large data caches of small molecule structural information is vital to finding new pharmaceuticals. Increasingly, molecular docking simulations are being used to narrow the space of possibilities and generate drug leads. Combining in-silico methods, augmented by metaheuristic optimization and machine learning (ML) allows the generation of hits from within a virtual MNP library to narrow screens for novel targets against coronaviruses. In this review article, we explore current insights and techniques that can be leveraged to generate broad-spectrum antivirals against betacoronaviruses using in-silico optimization and ML. ML approaches are capable of simultaneously evaluating different features for predicting inhibitory activity. Many also provide a semi-quantitative measure of feature relevance and can guide in selecting a subset of features relevant for inhibition of SARS-CoV-2.

Niche partitioning by photosynthetic plankton as a driver of CO2-fixation across the oligotrophic South Pacific Subtropical Ocean.

Oligotrophic ocean gyre ecosystems may be expanding due to rising global temperatures [1-5]. Models predicting carbon flow through these changing ecosystems require accurate descriptions of phytoplankton communities and their metabolic activities [6]. We therefore measured distributions and activities of cyanobacteria and small photosynthetic eukaryotes throughout the euphotic zone on a zonal transect through the South Pacific Ocean, focusing on the ultraoligotrophic waters of the South Pacific Gyre (SPG). Bulk rates of CO2 fixation were low (0.1 µmol C l-1 d-1) but pervasive throughout both the surface mixed-layer (upper 150 m), as well as the deep chlorophyll a maximum of the core SPG. Chloroplast 16S rRNA metabarcoding, and single-cell 13CO2 uptake experiments demonstrated niche differentiation among the small eukaryotes and picocyanobacteria. Prochlorococcus abundances, activity, and growth were more closely associated with the rims of the gyre. Small, fast-growing, photosynthetic eukaryotes, likely related to the Pelagophyceae, characterized the deep chlorophyll a maximum. In contrast, a slower growing population of photosynthetic eukaryotes, likely comprised of Dictyochophyceae and Chrysophyceae, dominated the mixed layer that contributed 65-88% of the areal CO2 fixation within the core SPG. Small photosynthetic eukaryotes may thus play an underappreciated role in CO2 fixation in the surface mixed-layer waters of ultraoligotrophic ecosystems.

Contemporary Approaches to the Discovery and Development of Broad-Spectrum Natural Product Prototypes for the Control of Coronaviruses.

The pressing need for SARS-CoV-2 controls has led to a reassessment of strategies to identify and develop natural product inhibitors of zoonotic, highly virulent, and rapidly emerging viruses. This review article addresses how contemporary approaches involving computational chemistry, natural product (NP) and protein databases, and mass spectrometry (MS) derived target-ligand interaction analysis can be utilized to expedite the interrogation of NP structures while minimizing the time and expense of extraction, purification, and screening in BioSafety Laboratories (BSL)3 laboratories. The unparalleled structural diversity and complexity of NPs is an extraordinary resource for the discovery and development of broad-spectrum inhibitors of viral genera, including Betacoronavirus, which contains MERS, SARS, SARS-CoV-2, and the common cold. There are two key technological advances that have created unique opportunities for the identification of NP prototypes with greater efficiency: (1) the application of structural databases for NPs and target proteins and (2) the application of modern MS techniques to assess protein-ligand interactions directly from NP extracts. These approaches, developed over years, now allow for the identification and isolation of unique antiviral ligands without the immediate need for BSL3 facilities. Overall, the goal is to improve the success rate of NP-based screening by focusing resources on source materials with a higher likelihood of success, while simultaneously providing opportunities for the discovery of novel ligands to selectively target proteins involved in viral infection.

Changing atmospheric acidity as a modulator of nutrient deposition and ocean biogeochemistry.

Anthropogenic emissions to the atmosphere have increased the flux of nutrients, especially nitrogen, to the ocean, but they have also altered the acidity of aerosol, cloud water, and precipitation over much of the marine atmosphere. For nitrogen, acidity-driven changes in chemical speciation result in altered partitioning between the gas and particulate phases that subsequently affect long-range transport. Other important nutrients, notably iron and phosphorus, are affected, because their soluble fractions increase upon exposure to acidic environments during atmospheric transport. These changes affect the magnitude, distribution, and deposition mode of individual nutrients supplied to the ocean, the extent to which nutrient deposition interacts with the sea surface microlayer during its passage into bulk seawater, and the relative abundances of soluble nutrients in atmospheric deposition. Atmospheric acidity change therefore affects ecosystem composition, in addition to overall marine productivity, and these effects will continue to evolve with changing anthropogenic emissions in the future.

Discovering hidden spatial patterns and their associations with controlling factors for potentially toxic elements in topsoil using hot spot analysis and K-means clustering analysis.

The understanding of sources and controlling factors of potentially toxic elements (PTEs) in soils plays an important role in the improvement of environmental management. With the rapid growth of data volume, effective methods are required for data analytics for the large geochemical data sets. In recent years, spatial machine learning technologies have been proven to have the potential to reveal hidden spatial patterns in order to extract geochemical information. In this study, two spatial clustering techniques of Getis-Ord Gi* statistic and K-means clustering analysis were performed on 15 PTEs in 6,862 topsoil samples from the Tellus datasets of Northern Ireland to investigate the hidden spatial patterns and association with their controlling factors. The spatial clustering patterns of hot spots (high values) and cold spots (low values) for the 15 PTEs were revealed, showing clear association with geological features, especially peat and basalt. Peat was associated with high concentrations of Bi, Pb, Sb and Sn, while basalt was associated with high concentrations of Co, Cr, Cu, Mn, Ni, V and Zn. The high concentrations of As, Ba, Mo and U were associated with mixture of various lithologies, indicating the complicated influences on them. In addition, three hidden patterns in the 6,862 soil samples were revealed by K-means clustering analysis. The soil samples in the first and second clusters were overlaid on the peatland and basalt formation, respectively, while the samples in the third cluster were overlaid on the mixture of the other lithologies. These hidden patterns of soil samples were consistent with the spatial clustering patterns for PTEs, highlighting the dominant control of peat and basalt in the topsoil of Northern Ireland. This study demonstrates the power of spatial machine learning techniques in identifying hidden spatial patterns, providing evidences to extract geochemical knowledge in environmental studies.

A survey of arsenic, mercury, cadmium, and lead residues in seafood (fish, crustaceans, and cephalopods) from the south-eastern Mediterranean Sea.

Seafood is capable of bioaccumulating heavy metals (HM), making it a potentially major dietary source of HM for humans. Presently, little data exists on seafood from the eastern-most boundary of the Mediterranean Sea. This study aims to provide exposure insight of the Israeli population to HM through the consumption of locally caught seafood by assessing the levels of arsenic, mercury, cadmium, and lead in raw tissues of seafood. A wide survey of local fisheries was conducted providing 296 samples from 11 different species, including seven fish, two crustacean, and two cephalopod species. Total arsenic, cadmium, and lead were analyzed by graphite-furnace atomic absorption. Total mercury was measured by cold-vapor mercury analyzer. Arsenic speciation was performed by anion chromatography-inductively coupled plasma sector field mass spectrometry. Results suggested that the total arsenic concentrations were significantly higher in crustaceans and cephalopods than fish. Arsenic speciation revealed two samples that exceed 1 mg/kg of inorganic arsenic, whereas methylated arsenic was below the detection limit. Elevated mercury levels were detected in the commercial benthic species Mullus barbatus (red mullet), cadmium was detected in one-third of the samples, and lead detected in eight samples. Comparing the results to health guidelines, 99.4% of seafood tested in this study abide with acceptable levels of heavy metals in seafood, as defined by both Israeli and European Union guidelines.

Elucidating Biodiversity Shifts in Ballast Water Tanks during a Cross-Latitudinal Transfer: Complementary Insights from Molecular Analyses.

In this study, the evolution of ballast water (BW) assemblages across different trophic levels was characterized over a 21 day cross-latitudinal vessel transit using a combination of molecular methods. Triplicate BW samples were collected every second day and size-fractionated (<2.7, 10, >50 µm). Measurements of adenosine triphosphate (ATP) and metabarcoding of environmental nucleic acid (DNA and RNA) analyses, complemented by microscopy and flow cytometry, were performed on each sample. Measured ATP concentrations exhibited high variance between replicates and a strong negative trend in the large (≥50 µm) fraction over the voyage. In concert with microscopy, the metabarcoding data indicated a die-off of larger metazoans during the first week of study and gradual reductions in dinoflagellates and ochrophytes. The ATP and metabarcoding data signaled persistent or increased cellular activity of heterotrophic bacteria and protists in the BW, which was supported by flow cytometry. The metabarcoding showed the presence of active bacteria in all size fractions, suggesting that the sequential filtration approach does not ensure taxonomical differentiation, which has implications for BW quality assessment. Although our data show that ATP and metabarcoding have potential for indicative BW screening for BW compliance monitoring, further research and technological development is needed to improve representativeness of sampling and deliver the unequivocal response criteria required by the international Ballast Water Management Convention.

Tracing sources of natural organic matter, trihalomethanes and metals in groundwater from a karst region.

Groundwater offers an important source for drinking water around the world; however, groundwater quality is under increasing pressure and is particularly vulnerable in karst areas. Total organic carbon (TOC) is significantly related to groundwater quality and when not removed by water treatment processes can give rise to the formation of disinfection by-products trihalomethanes (THMs) above the level of compliance. This study investigated the source of organic matter giving rise to the THM exceedances in a groundwater supply in a karst area. Results highlighted that source water for this groundwater supply was prone to surface water infiltration linked to rainfall events; was not accurately captured in the zone of contribution (ZoC); had inadequate treatment of natural organic matter (NOM) and suffered THM exceedances in 45% of sampling events. THMs were mostly represented by chloroform and caused by terrestrial delivered reprocessed organic matter. This work will support water managers tasked with decision-making.

Global sea-surface iodide observations, 1967-2018.

The marine iodine cycle has significant impacts on air quality and atmospheric chemistry. Specifically, the reaction of iodide with ozone in the top few micrometres of the surface ocean is an important sink for tropospheric ozone (a pollutant gas) and the dominant source of reactive iodine to the atmosphere. Sea surface iodide parameterisations are now being implemented in air quality models, but these are currently a major source of uncertainty. Relatively little observational data is available to estimate the global surface iodide concentrations, and this data has not hitherto been openly available in a collated, digital form. Here we present all available sea surface (<20 m depth) iodide observations. The dataset includes values digitised from published manuscripts, published and unpublished data supplied directly by the originators, and data obtained from repositories. It contains 1342 data points, and spans latitudes from 70°S to 68°N, representing all major basins. The data may be used to model sea surface iodide concentrations or as a reference for future observations.

Microplastic Ingestion by Gelatinous Zooplankton May Lower Efficiency of the Biological Pump.

The impacts of microplastics on some individual organisms have been well studied but what is less clear is what impacts microplastics have on wider ecosystem processes. Using salps as model organisms, we studied the effect of microplastic ingestion on the downward flux of high-density particulate organic matter in the form of salp faecal pellets. While to date most microplastic studies used virgin microplastics at unrealistic environmental concentrations here we exposed Salpa fusiformis to fractured and UV exposed polyethylene and polystyrene microplastics possessing a biofilm. It was found that when exposed to environmentally relevant concentrations, reported for the Mediterranean and the South Pacific Gyre, only few faecal pellets had microplastics incorporated within them. Under potential future scenarios, however, up to 46% of faecal pellets contained microplastics. Incorporated microplastics significantly altered the size, density and sinking rates of salp faecal pellets ( p-value < 0.05 in each instance). Sinking rates decreased by 1.35-fold (95% CI = 1.18, 1.56) for faecal pellets with polyethylene microplastics and 1.47-fold (95% CI = 1.34, 1.61) for polystyrene. These results suggest that today, microplastic ingestion by salps has minimal impact on the biological pump. However, under future microplastic concentrations (or in areas such as convergent zones), microplastics may have the potential to lower the efficiency of the biological pump.

H2S events in the Peruvian oxygen minimum zone facilitate enhanced dissolved Fe concentrations.

Dissolved iron (DFe) concentrations in oxygen minimum zones (OMZs) of Eastern Boundary Upwelling Systems are enhanced as a result of high supply rates from anoxic sediments. However, pronounced variations in DFe concentrations in anoxic coastal waters of the Peruvian OMZ indicate that there are factors in addition to dissolved oxygen concentrations (O2) that control Fe cycling. Our study demonstrates that sediment-derived reduced Fe (Fe(II)) forms the main DFe fraction in the anoxic/euxinic water column off Peru, which is responsible for DFe accumulations of up to 200 nmol L-1. Lowest DFe values were observed in anoxic shelf waters in the presence of nitrate and nitrite. This reflects oxidation of sediment-sourced Fe(II) associated with nitrate/nitrite reduction and subsequent removal as particulate Fe(III) oxyhydroxides. Unexpectedly, the highest DFe levels were observed in waters with elevated concentrations of hydrogen sulfide (up to 4 µmol L-1) and correspondingly depleted nitrate/nitrite concentrations (<0.18 µmol L-1). Under these conditions, Fe removal was reduced through stabilization of Fe(II) as aqueous iron sulfide (FeSaqu) which comprises complexes (e.g., FeSH+) and clusters (e.g., Fe2S2|4H2O). Sulfidic events on the Peruvian shelf consequently enhance Fe availability, and may increase in frequency in future due to projected expansion and intensification of OMZs.

National scale assessment of total trihalomethanes in Irish drinking water.

Ireland reported the highest non-compliance with respect to total trihalomethanes (TTHMs) in drinking water across the 27 European Union Member States for the year 2010. We carried out a GIS-based investigation of the links between geographical parameters and catchment land-uses with TTHMs concentrations in Irish drinking water. A high risk catchment map was created using peat presence, rainfall (>1400 mm) and slope (<5%) and overlain with a map comprising the national dataset of routinely monitored TTHM concentrations. It appeared evident from the map that the presence of peat, rainfall and slope could be used to identify catchments at high risk to TTHM exceedances. Furthermore, statistical analyses highlighted that the presence of peat soil with agricultural land was a significant driver of TTHM exceedances for all treatment types. PARAFAC analysis from three case studies identified a fluorophore indicative of reprocessed humic natural organic matter as the dominant component following treatment at the three sites. Case studies also indicated that (1) chloroform contributed to the majority of the TTHMs in the drinking water supplies and (2) the supply networks contributed to about 30 µg L-1 of TTHMs.

Differences in the sensitivity to Cu and ligand production of coastal vs offshore strains of Emiliania huxleyi.

Copper is an essential trace metal for different physiological processes in phytoplankton, being either a limiting or toxic element depending on its bioavailability, which may induce local physiological adaptations. Atmospheric Cu deposition to the oceans can negatively impact phytoplankton growth, with the most Cu-sensitive phytoplankton exhibiting differences based on coastal vs oceanic origin. The goal of this work was to analyze sensitivity to Cu toxicity of the cosmopolitan marine calcifying phytoplankton, Emiliania huxleyi, exploring what factors determine intraspecific variability in sensitivity. We compared 17 strains isolated from coastal and open ocean waters of the Eastern South Pacific (ESP), the Mediterranean Sea, and the Tasman Sea. Offshore strains were as sensitive to Cu than coastal strains. Sensitivity to Cu was explained well by predicted depositional inputs of atmospheric Cu in the ESP both for coastal and offshore strains, but not when considered globally. The variability in Cu-sensitivity was also due to the production of organic Cu-ligands (CL), being the most productive strains the most tolerant to Cu at constitutive levels. When exposed to 100nM Cu, E. huxleyi produced significantly higher amounts of CL, especially coastal strains, but CL production did not correlate to observed EC50s.

Facets of diazotrophy in the oxygen minimum zone waters off Peru.

Nitrogen fixation, the biological reduction of dinitrogen gas (N2) to ammonium (NH4(+)), is quantitatively the most important external source of new nitrogen (N) to the open ocean. Classically, the ecological niche of oceanic N2 fixers (diazotrophs) is ascribed to tropical oligotrophic surface waters, often depleted in fixed N, with a diazotrophic community dominated by cyanobacteria. Although this applies for large areas of the ocean, biogeochemical models and phylogenetic studies suggest that the oceanic diazotrophic niche may be much broader than previously considered, resulting in major implications for the global N-budget. Here, we report on the composition, distribution and abundance of nifH, the functional gene marker for N2 fixation. Our results show the presence of eight clades of diazotrophs in the oxygen minimum zone (OMZ) off Peru. Although proteobacterial clades dominated overall, two clusters affiliated to spirochaeta and archaea were identified. N2 fixation was detected within OMZ waters and was stimulated by the addition of organic carbon sources supporting the view that non-phototrophic diazotrophs were actively fixing dinitrogen. The observed co-occurrence of key functional genes for N2 fixation, nitrification, anammox and denitrification suggests that a close spatial coupling of N-input and N-loss processes exists in the OMZ off Peru. The wide distribution of diazotrophs throughout the water column adds to the emerging view that the habitat of marine diazotrophs can be extended to low oxygen/high nitrate areas. Furthermore, our statistical analysis suggests that NO2(-) and PO4(3-) are the major factors affecting diazotrophic distribution throughout the OMZ. In view of the predicted increase in ocean deoxygenation resulting from global warming, our findings indicate that the importance of OMZs as niches for N2 fixation may increase in the future.

Pathways of superoxide (O2(-)) decay in the Eastern Tropical North Atlantic.

Superoxide (O2(-): IUPAC name dioxide (•1-)) is an important transient reactive oxygen species (ROS) in the ocean formed as an intermediate in the redox transformation of oxygen (O2) into hydrogen peroxide (H2O2) and vice versa. This highly reactive and very short-lived radical anion can be produced both via photochemical and biological processes in the ocean. In this paper we examine the decomposition rate of O2(-) throughout the water column, using new data collected in the Eastern Tropical North Atlantic (ETNA) Ocean. For this approach we applied a semi factorial experimental design to identify and quantify the pathways of the major identified sinks in the ocean. In this work we occupied six stations, two on the West African continental shelf and four open ocean stations, including the CVOO time series site adjacent to Cape Verde. Our results indicate that, in the surface ocean impacted by Saharan aerosols and coastal sediment resuspension, the main decay pathways for superoxide are via reactions with Mn(II) and organic matter.

Reactivity of inorganic Mn and Mn desferrioxamine B with O2, O2(-), and H2O2 in seawater.

Manganese (Mn) is a required element for oceanic phytoplankton as it plays a critical role in photosynthesis, through its unique redox chemistry, as the active site in photosystem II, and in enzymes that act as defenses against reactive oxygen species (ROS), most notably for protection against superoxide (O2(-)), through the action of superoxide dismutase (SOD), and against hydrogen peroxide (H2O2) via peroxidases and catalases. The distribution and redox speciation of Mn in the ocean is also apparently controlled by reactions with ROS. Here we examine the connections between ROS and dissolved Mn species in the upper ocean using field and laboratory experimental data. Our results suggest it is unlikely that significant concentrations of Mn(III) are produced in the euphotic zone, as in the absence of evidence for the existence of strong Mn(III) ligands, Mn(II) reacts with O2(-) to form the short-lived transient manganous superoxide, MnO2(+), which may react rapidly with other redox species in a manner similar to O2(-). Experiments with the strong Mn(III) chelator, desferrioxamine B (DFB), in seawater indicated that the Mn(III) species are unlikely to form, as formation of the precursor Mn(II) complex is hindered due to the stability of the Ca complex with DFB.

Deep carbon export from a Southern Ocean iron-fertilized diatom bloom.

Fertilization of the ocean by adding iron compounds has induced diatom-dominated phytoplankton blooms accompanied by considerable carbon dioxide drawdown in the ocean surface layer. However, because the fate of bloom biomass could not be adequately resolved in these experiments, the timescales of carbon sequestration from the atmosphere are uncertain. Here we report the results of a five-week experiment carried out in the closed core of a vertically coherent, mesoscale eddy of the Antarctic Circumpolar Current, during which we tracked sinking particles from the surface to the deep-sea floor. A large diatom bloom peaked in the fourth week after fertilization. This was followed by mass mortality of several diatom species that formed rapidly sinking, mucilaginous aggregates of entangled cells and chains. Taken together, multiple lines of evidence-although each with important uncertainties-lead us to conclude that at least half the bloom biomass sank far below a depth of 1,000 metres and that a substantial portion is likely to have reached the sea floor. Thus, iron-fertilized diatom blooms may sequester carbon for timescales of centuries in ocean bottom water and for longer in the sediments.

Iron organic speciation determination in rainwater using cathodic stripping voltammetry.

A sensitive method using Competitive Ligand Exchange-Adsorptive Cathodic Stripping Voltammetry (CLE-ACSV) has been developed to determine for the first time iron (Fe) organic speciation in rainwater over the typical natural range of pH. We have adapted techniques previously developed in other natural waters to rainwater samples, using the competing ligand 1-nitroso-2-naphthol (NN). The blank was equal to 0.17±0.05 nM (n=14) and the detection limit (DL) for labile Fe was 0.15 nM which is 10-70 times lower than that of previously published methods. The conditional stability constant for NN under rainwater conditions was calibrated over the pH range 5.52-6.20 through competition with ethylenediaminetetraacetic acid (EDTA). The calculated value of the logarithm of ß'(Fe(3+)(NN)(3)) increased linearly with increasing pH according to log ß'(Fe(3+)(NN)(3)) (salinity=2.9, T=20 °C). The validation of the method was carried out using desferrioxamine mesylate B (DFOB) as a natural model ligand for Fe. Adequate detection windows were defined to detect this class of ligands in rainwater with 40 µM of NN from pH 5.52 to 6.20. The concentration of Fe-complexing natural ligands was determined for the first time in three unfiltered and one filtered rainwater samples. Organic Fe-complexing ligand concentrations varied from 104.2±4.1 nM equivalent of Fe(III) to 336.2±19.0 nM equivalent of Fe(III) and the logarithm of the conditional stability constants, with respect to Fe(3+), varied from 21.1±0.2 to 22.8±0.3. This method will provide important data for improving our understanding of the role of wet deposition in the biogeochemical cycling of iron.

The importance of kinetics and redox in the biogeochemical cycling of iron in the surface ocean.

It is now well established that Iron (Fe) is a limiting element in many regions of the open ocean. Our current understanding of the key processes which control iron distribution in the open ocean have been largely based on thermodynamic measurements performed under the assumption of equilibrium conditions. Using this equilibrium approach, researchers have been able to detect and quantify organic complexing ligands in seawater and examine their role in increasing the overall solubility of iron. Our current knowledge about iron bioavailability to phytoplankton and bacteria is also based heavily on carefully controlled laboratory studies where it is assumed the chemical species are in equilibrium in line with the free ion association model and/or its successor the biotic ligand model. Similarly most field work on iron biogeochemistry generally consists of a single profile which is in essence a "snap-shot" in time of the system under investigation. However it is well known that the surface ocean is an extremely dynamic environment and it is unlikely if thermodynamic equilibrium between all the iron species present is ever truly achieved. In sunlit waters this is mostly due to the daily passage of the sun across the sky leading to photoredox processes which alter Fe speciation by cycling between redox states and between inorganic and organic species. Episodic deposition events, dry and wet, are also important perturbations to iron cycling as they bring in new iron to the system and alter the equilibrium between iron species and phases. Here we utilize new field data collected in the open ocean on the complexation kinetics of iron in the surface ocean to identify the important role of weak iron binding ligands (i.e., those that cannot maintain iron in solution indefinitely at seawater pH: α(FeL) < α(Fe)') in allowing transient increases in iron solubility in response to iron deposition events. Experiments with the thermal [Formula: see text] source SOTS-1 also indicate the short term impact of this species on iron solubility also with relevance to the euphotic zone. This data highlights the roles of kinetics, redox, and weaker iron binding ligands in the biogeochemical cycling of iron in the ocean.