Description: Our study followed the seasonal cycling of soluble (SFe), colloidal (CFe), dissolved (DFe), total dissolvable (TDFe), labile particulate (LPFe) and total particulate (TPFe) iron in the Celtic Sea (NE Atlantic Ocean). Preferential uptake of SFe occurred during the spring bloom, preceding the removal of CFe. Uptake and export of Fe during the spring bloom, coupled with a reduction in vertical exchange, led to Fe deplete surface waters (〈0.2 nM DFe; 0.11 nM LPFe, 0.45 nM TDFe, 1.84 nM TPFe) during summer stratification. Below the seasonal thermocline, DFe concentrations increased from spring to autumn, mirroring NO3- and consistent with supply from remineralised sinking organic material, and cycled independently of particulate Fe over seasonal timescales. These results demonstrate that summer Fe availability is comparable to the seasonally Fe limited Ross Sea shelf, and therefore is likely low enough to affect phytoplankton growth and species composition.

Description: We have assessed how varying CO2 (180, 380, and 720 μatm) and growth light intensity (40 and 400 μmol photons m−2 s−1) affected Trichodesmium erythraeum IMS101 growth and photophysiology over free iron (Fe′) concentrations between 20 and 9,600 pM. We found significant iron dependencies of growth rate and the initial slope and maximal relative PSII electron transport rates (rPm). Under iron-limiting concentrations, high-light increased growth rates and rPm; possibly indicating a lower allocation of resources to iron-containing photosynthetic proteins. Higher CO2 increased growth rates across all iron concentrations, enabled growth to occur at lower Fe′ concentrations, increased rPm and lowered the iron half saturation constants for growth (Km). We attribute these CO2 responses to the operation of the CCM and the ATP spent/saved for CO2 uptake and transport at low and high CO2, respectively. It seems reasonable to conclude that T. erythraeum IMS101 can exhibit a high degree of phenotypic plasticity in response to CO2, light intensity and iron-limitation. These results are important given predictions of increased dissolved CO2 and water column stratification (i.e., higher light exposures) over the coming decades.

Description: Coastal marine environments are contaminated globally with a vast quantity of unexploded ordnance and munitions from intentional disposal. These munitions contain organic explosive compounds as well as a variety of metals, and represent point sources of chemical pollution to marine waters. Most underwater munitions originate from World Wars at the beginning of the twentieth century, and metal munitions housings have been impacted by extensive corrosion over the course of the following decades. As a result, the risk of munitions-related contaminant release to the water column is increasing. The behavior of munitions compounds is well-characterized in terrestrial systems and groundwater, but is only poorly understood in marine systems. Organic explosive compounds, primarily nitroaromatics and nitramines, can be degraded or transformed by a variety of biotic and abiotic mechanisms. These reaction products exhibit a range in biogeochemical characteristics such as sorption by particles and sediments, and variable environmental behavior as a result. The reaction products often exhibit increased toxicity to biological receptors and geochemical controls like sorption can limit this exposure. Environmental samples typically show low concentrations of munitions compounds in water and sediments (on the order of ng/L and μg/kg, respectively), and ecological risk appears generally low. Nonetheless, recent work demonstrates the possibility of sub-lethal genetic and metabolic effects. This review evaluates the state of knowledge on the occurrence, fate, and effect of munition-related chemical contaminants in the marine environment. There remain a number of knowledge gaps that limit our understanding of munitions-related contaminant spread and effect, and the need for additional work is made all the more urgent by increasing risk of release to the environment.

Description: Dissolved Fe(II) in seawater is deemed an important micronutrient for microbial organisms, but its analysis is challenging due to its transient nature. We conducted a series of Fe(II) method comparison experiments, where spikes of 5 to 31 nM Fe(II) were added to manipulated seawaters with varying dissolved oxygen (37 to 156 μM) concentrations. The observed Fe(II) concentrations from four analytical methods were compared: spectrophotometry with ferrozine, stripping voltammetry, and flow injection analysis using luminol (with, and without, a pre-concentration column). Direct comparisons between the different methods were undertaken from the derived apparent Fe(II) oxidation rate constant (k1). Whilst the two luminol based methods produced the most similar concentrations throughout the experiments, k1 was still subject to a 20–30% discrepancy between them. Contributing factors may have included uncertainty in the calibration curves, and different responses to interferences from Co(II) and humic/fulvic organic material. The difference in measured Fe(II) concentrations between the luminol and ferrozine methods, from 10 min–2 h after the Fe(II) spikes were added, was always relatively large in absolute terms (〉4 nM) and relative to the spike added (〉20% of the initial Fe(II) concentration). k1 derived from ferrozine observed Fe(II) concentrations was 3–80%, and 4–16%, of that derived from luminol observed Fe(II) with, and without, pre-concentration respectively. The poorest comparability of k1 was found after humic/fulvic material was added to raise dissolved organic carbon to 120 μM. A luminol method without pre-concentration then observed Fe(II) to fall below the detection limit (〈0.49 nM) within 10 min of a 17 nM Fe(II) spike addition, yet other methods still observed Fe(II) concentrations of 2.7 to 3.7 nM 30 min later. k1 also diverged accordingly with the ferrozine derived value 4% of that derived from luminol without pre-concentration. These apparent inconsistencies suggest that some inter-dataset differences in measured Fe(II) oxidation rates in natural waters may be attributable to differences in the analytical methods used rather than arising solely from substantial shifts in Fe(II) speciation.

Description: Iron (Fe), cobalt (Co), and vitamin B12 addition experiments were performed in the eastern Equatorial Pacific/Peruvian upwelling zone during the 2015 El Niño event. Near the Peruvian coastline, apparent photosystem II photochemical efficiencies (Fv/Fm) were unchanged by nutrient addition and chlorophyll‐a tripled in untreated controls over two days, indicating nutrient replete conditions. Conversely, Fe amendment further away from the coastline in the high nitrate, low Fe zone significantly increased Fv/Fm and chlorophyll‐a concentrations. Mean chlorophyll‐a was further enhanced following supply of Fe+Co and Fe+B12 relative to Fe alone, but this was not statistically significant; further offshore, reported Co depletion relative to Fe could enhance responses. The persistence of Fe limitation in this system under a developing El Niño, as previously demonstrated under non‐El Niño conditions, suggests that diminished upwelled Fe is likely an important factor driving reductions in offshore phytoplankton productivity during these events.

Description: Anthropogenic activities have resulted in enhanced lead (Pb) emissions to the environment over the past century, mainly through the combustion of leaded gasoline. Here, we present the first combined dissolved (DPb), labile (LpPb) and particulate (PPb) Pb dataset from the Northeast Atlantic (Celtic Sea) since the phasing out of leaded gasoline in Europe. Concentrations of DPb in surface waters have decreased by 4-fold over the last four decades. We demonstrate that anthropogenic Pb is transported from the Mediterranean Sea over long distances (〉2500 km). Benthic DPb fluxes exceeded the atmospheric Pb flux in the region, indicating the importance of sediments as a contemporary Pb source. A strong positive correlation between DPb, PPb and LpPb indicates a dynamic equilibrium between the phases and the potential for particles to ‘buffer’ the DPb pool. This study provides insights into Pb biogeochemical cycling and demonstrates the potential of Pb in constraining ocean circulation patterns.

Description: Phytoplankton deal with metal toxicity using a variety of biochemical strategies. One of the strategies involves glutathione (GSH) and phytochelatins (PCs), which are metal-binding thiol peptides produced by eukaryotes and these compounds have been related to several intracellular functions, including metal detoxification, homeostasis, metal resistance and protection against oxidative stress. This paper assesses our state of knowledge on the production of PCs and GSH by marine phytoplankton in laboratory and field conditions and the possible applications of PCs for environmental purposes. Good relationships have been observed between metal exposure and PC production in phytoplankton in the laboratory with Cd, Pb, and Zn showing the greatest efficacy, thereby indicating that PCs have a potential for application as a biomarker. Fewer studies on PC distributions in particulate material have been undertaken in the field. These studies show that free Cu has a strong relationship with the levels of PC in the particulate material. The reason for this could be because Cu is a common contaminant in coastal waters. However it could also be due to the lack of measurements of other metals and their speciation. GSH shows a more complex relationship to metal levels both in the laboratory and in the field. This is most likely due to its multifunctionality. However, there is evidence that phytoplankton act as an important source of dissolved GSH in marine waters, which may form part of the strong organic ligands that control metal speciation, and hence metal toxicity. © 2006 by the Phycological Society of America.

Description: In this study we show that metals, and in particular copper (Cu), can disrupt the lytic cycle in the Emiliania huxleyi-EhV86 host-virus system. E. huxleyi lysis rates were reduced at high total Cu concentrations (〉 approximately 500 nM) in the presence and absence of EDTA (ethylenediaminetetraacetic acid) in acute short term exposure experiments. Zinc (Zn), cadmium (Cd), and cobalt (Co) were not observed to affect the lysis rate of EhV86 in these experiments. The cellular glutathione (GSH) content increased in virus infected cells, but not as a result of metal exposure. In contrast, the cellular content of phytochelatins (PCs) increased only in response to metal exposure. The increase in glutathione content is consistent with increases in the production of reactive oxygen species (ROS) on viral lysis, while increases in PC content are likely linked to metal homeostasis and indicate that metal toxicity to the host was not affected by viral infection. We propose that Cu prevents lytic production of EhV86 by interfering with virus DNA (deoxyribonucleic acid) synthesis through a transcriptional block, which ultimately suppresses the formation of ROS. © 2012 Gledhill, Devez, Highfield, Singleton, Achterberg and Schroeder.

Description: The behaviour of a series of hydroxamate siderophores - microbially produced iron complexes - was investigated using electrospray ionisation mass spectrometry (ESI-MS). Three groups of iron hydroxamate siderophores, namely the ferrioxamines, ferrichromes and coprogens/ fusigens, were separated by high-performance liquid chromatography (HPLC) prior to ESI and MS2 fragmentation. For the majority of the siderophores, both protonated molecules and sodium adducts were observed. The most abundant ion was selected for collision-induced fragmentation. Potential fragmentation mechanisms are postulated and discussed. Fragmentation patterns differed between siderophore groups; however, common fragmentation patterns were observed for siderophore ions within the groups examined. Cleavage frequently occurred at carbon-nitrogen or carbon-oxygen bonds. Fragmentation of the ions also involved cleavage of iron-oxygen bonds and transfer of the charge to iron.

Description: Concentrations of heme b, the iron-containing component of b-type hemoproteins, ranged from 〈 0.4 to 5.3 pM with an average of 1.18 ± 0.8 pM (± 1σ; n = 86) in the Iceland Basin (IB), from 〈 0.4 to 19.1 pM with an average of 2.24 ± 1.67 pM (n = 269) in the tropical northeast Atlantic (TNA) and from 0.6 to 21 pM with an average of 5.1 ± 4.8 pM (n = 34) in the Scotia Sea (SS). Heme b concentrations were enhanced in the photic zone and decreased with depth. Heme b concentrations correlated positively with chlorophyll a (chl a) in the TNA (r = 0.41, p 〈 0.01, n = 269). Heme b did not correlate with chl a in the IB or SS. In the IB and SS, stations with high-chlorophyll and low-nutrient (Fe and/or Si) concentrations exhibited low heme b concentrations relative to particulate organic carbon (〈 0.1 μmol mol−1), and high chl a:heme b ratios (〉 500). High chl a:heme b ratios resulted from relative decreases in heme b, suggesting proteins such as cytochrome b6f, the core complex of photosystem II, and eukaryotic nitrate reductase were depleted relative to proteins containing chlorophyll such as the eukaryotic light-harvesting antenna. Relative variations in heme b, particulate organic carbon, and chl a can thus be indicative of a physiological response of the phytoplankton community to the prevailing growth conditions, within the context of large-scale changes in phytoplankton community composition.