Peter L. Morton

Determination of Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in seawater using high resolution magnetic sector inductively coupled mass spectrometry (HR-ICP-MS)

A novel method, combining isotope dilution with standard additions, was developed for the analysis of eight elements (Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb) in seawater. The method requires just 12 mL of sample and employs an off-line pre-concentration step using the commercially available chelating resin Toyopearl AF-Chelate-650M prior to determination by high resolution inductively coupled plasma magnetic sector mass spectrometry (ICP-MS). Acidified samples were spiked with a multi-element standard of six isotopes ((57)Fe, (62)Ni, (65)Cu, (68)Zn, (111)Cd and (207)Pb) enriched over natural abundance. In addition, standard additions of a mixed Co and Mn standard were performed on sub-sets of the same sample. All samples were irradiated using a low power (119 mW cm(-2); 254 nm) UV system, to destroy organic ligands, before pre-concentration and extraction from the seawater matrix. Ammonium acetate was used to raise the pH of the 12 mL sub-samples (off-line) to pH 6.4+/-0.2 prior to loading onto the chelating resin. The extracted metals were eluted using 1.0 M Q-HNO(3) and determined using ICP-MS. The method was verified through the analysis of certified reference material (NASS-5) and the SAFe inter-comparison samples (S1 and D2), the results of which are in good agreement with the certified and reported consensus values. We also present vertical profiles of the eight metals taken from the Bermuda Atlantic Time Series (BATS) station collected during the GEOTRACES inter-comparison cruise in June 2008.

Asian Industrial Lead Inputs to the North Pacific Evidenced by Lead Concentrations and Isotopic Compositions in Surface Waters and Aerosols

Recent trends of atmospheric lead deposition to the North Pacific were investigated with analyses of lead in aerosols and surface waters collected on the fourth Intergovernmental Oceanographic Commission Contaminant Baseline Survey from May to June, 2002. Lead concentrations of the aerosols varied by 2 orders of magnitude (0.1-26.4 pmol/m(3)) due in part to variations in dust deposition during the cruise. The ranges in lead aerosol enrichment factors relative to iron (1-119) and aluminum (3-168) were similar, evidencing the transport of Asian industrial lead aerosols across the North Pacific. The oceanic deposition of some of those aerosols was substantiated by the gradient of lead concentrations of North Pacific waters, which varied 3-fold (32.7-103.5 pmol/kg), were highest along with the Asian margin of the basin, and decreased eastward. The hypothesized predominance of Asian industrial lead inputs to the North Pacific was further corroborated by the lead isotopic composition of ocean surface waters ((206)Pb/(207)Pb = 1.157-1.169; (208)Pb/(206)Pb = 2.093-2.118), which fell within the range of isotopic ratios reported in Asian aerosols that are primarily attributed to Chinese industrial lead emissions.

How well can we quantify dust deposition to the ocean

Deposition of continental mineral aerosols (dust) in the Eastern Tropical North Atlantic Ocean, between the coast of Africa and the Mid-Atlantic Ridge, was estimated using several strategies based on the measurement of aerosols, trace metals dissolved in seawater, particulate material filtered from the water column, particles collected by sediment traps and sediments. Most of the data used in this synthesis involve samples collected during US GEOTRACES expeditions in 2010 and 2011, although some results from the literature are also used. Dust deposition generated by a global model serves as a reference against which the results from each observational strategy are compared. Observation-based dust fluxes disagree with one another by as much as two orders of magnitude, although most of the methods produce results that are consistent with the reference model to within a factor of 5. The large range of estimates indicates that further work is needed to reduce uncertainties associated with each method before it can be applied routinely to map dust deposition to the ocean. Calculated dust deposition using observational strategies thought to have the smallest uncertainties is lower than the reference model by a factor of 2–5, suggesting that the model may overestimate dust deposition in our study area. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’.

Meta-omic signatures of microbial metal and nitrogen cycling in marine oxygen minimum zones

Iron (Fe) and copper (Cu) are essential cofactors for microbial metalloenzymes, but little is known about the metalloenyzme inventory of anaerobic marine microbial communities despite their importance to the nitrogen cycle. We compared dissolved O2, NO3−, NO2−, Fe and Cu concentrations with nucleic acid sequences encoding Fe and Cu-binding proteins in 21 metagenomes and 9 metatranscriptomes from Eastern Tropical North and South Pacific oxygen minimum zones and 7 metagenomes from the Bermuda Atlantic Time-series Station. Dissolved Fe concentrations increased sharply at upper oxic-anoxic transition zones, with the highest Fe:Cu molar ratio (1.8) occurring at the anoxic core of the Eastern Tropical North Pacific oxygen minimum zone and matching the predicted maximum ratio based on data from diverse ocean sites. The relative abundance of genes encoding Fe-binding proteins was negatively correlated with O2, driven by significant increases in genes encoding Fe-proteins involved in dissimilatory nitrogen metabolisms under anoxia. Transcripts encoding cytochrome c oxidase, the Fe- and Cu-containing terminal reductase in aerobic respiration, were positively correlated with O2 content. A comparison of the taxonomy of genes encoding Fe- and Cu-binding vs. bulk proteins in OMZs revealed that Planctomycetes represented a higher percentage of Fe genes while Thaumarchaeota represented a higher percentage of Cu genes, particularly at oxyclines. These results are broadly consistent with higher relative abundance of genes encoding Fe-proteins in the genome of a marine planctomycete vs. higher relative abundance of genes encoding Cu-proteins in the genome of a marine thaumarchaeote. These findings highlight the importance of metalloenzymes for microbial processes in oxygen minimum zones and suggest preferential Cu use in oxic habitats with Cu > Fe vs. preferential Fe use in anoxic niches with Fe > Cu.

Processes controlling the distributions of Cd and PO4 in the ocean

Depth profiles of dissolved Cd and PO4 from a global data compilation were used to derive the Cd/P of particles exported from the surface layer, and the results indicate lowest values in the North Atlantic (0.17 ± 0.05), highest in the Southern (0.56 ± 0.24), and intermediate in the South Indian (0.31 ± 0.14) and North Pacific (0.36 ± 0.08) Ocean basins. The Cd/P of exported particles in high nutrient-low chlorophyll (HNLC) regions is twice that for particles exported in non-HNLC regions as is the fractionation effect during biological uptake of Cd and PO4, and these trends primarily determine the spatial trends of dissolved Cd/PO4 observed in the surface ocean. In deep waters the lowest dissolved Cd/PO4 of 0.23 ± 0.07 is found in the North Atlantic Ocean and the result primarily of low Cd/PO4 of North Atlantic Deep Water (0.23). In contrast, deep waters in the Southern Ocean have significantly higher dissolved Cd/PO4 (0.30 ± 0.06), which is a result of the Cd/PO4 of upwelled deep water from the South Pacific and South Indian (0.28) and the high Cd/P of degrading particles. A multibox model that accounts for the impacts of particle degradation and thermohaline circulation in the deep sea yields dissolved Cd and PO4 interbasin trends close to observations. Model experiments illustrate the dependence of the dissolved Cd/PO4 of the deep sea on the extent of HNLC conditions in the Southern Ocean and the impact on reconstructing paleo PO4 concentrations from a Cd proxy.

Trace element and isotope deposition across the air-sea interface: progress and research needs

The importance of the atmospheric deposition of biologically essential trace elements, especially iron, is widely recognized, as are the difficulties of accurately quantifying the rates of trace element wet and dry deposition and their fractional solubility. This paper summarizes some of the recent progress in this field, particularly that driven by the GEOTRACES, and other, international research programmes. The utility and limitations of models used to estimate atmospheric deposition flux, for example, from the surface ocean distribution of tracers such as dissolved aluminium, are discussed and a relatively new technique for quantifying atmospheric deposition using the short-lived radionuclide beryllium-7 is highlighted. It is proposed that this field will advance more rapidly by using a multi-tracer approach, and that aerosol deposition models should be ground-truthed against observed aerosol concentration data. It is also important to improve our understanding of the mechanisms and rates that control the fractional solubility of these tracers. Aerosol provenance and chemistry (humidity, acidity and organic ligand characteristics) play important roles in governing tracer solubility. Many of these factors are likely to be influenced by changes in atmospheric composition in the future. Intercalibration exercises for aerosol chemistry and fractional solubility are an essential component of the GEOTRACES programme. This article is part of the themed issue ‘Biological and climatic impacts of ocean trace element chemistry’.

Dissolved Fe and Al in the upper 1000 m of the eastern Indian Ocean: A high‐resolution transect along 95°E from the Antarctic margin to the Bay of Bengal

A high-resolution section of dissolved iron (dFe) and aluminum (dAl) was obtained along ~95°E in the upper 1000?m of the eastern Indian Ocean from the Antarctic margin (66°S) to the Bay of Bengal (18°N) during the U.S. Climate Variability and Predictability (CLIVAR) CO2 Repeat Hydrography I08S and I09N sections (February–April 2007). In the Southern Ocean, low concentrations of dAl (

Molybdenum-based diazotrophy in a Sphagnum peatland in northern Minnesota

ABSTRACT Microbial N2 fixation (diazotrophy) represents an important nitrogen source to oligotrophic peatland ecosystems, which are important sinks for atmospheric CO2 and are susceptible to the changing climate. The objectives of this study were (i) to determine the active microbial group and type of nitrogenase mediating diazotrophy in an ombrotrophic Sphagnum-dominated peat bog (the S1 peat bog, Marcell Experimental Forest, Minnesota, USA); and (ii) to determine the effect of environmental parameters (light, O2, CO2, and CH4) on potential rates of diazotrophy measured by acetylene (C2H2) reduction and 15N2 incorporation. A molecular analysis of metabolically active microbial communities suggested that diazotrophy in surface peat was primarily mediated by Alphaproteobacteria (Bradyrhizobiaceae and Beijerinckiaceae). Despite higher concentrations of dissolved vanadium ([V] 11 nM) than molybdenum ([Mo] 3 nM) in surface peat, a combination of metagenomic, amplicon sequencing, and activity measurements indicated that Mo-containing nitrogenases dominate over the V-containing form. Acetylene reduction was only detected in surface peat exposed to light, with the highest rates observed in peat collected from hollows with the highest water contents. Incorporation of 15N2 was suppressed 90% by O2 and 55% by C2H2 and was unaffected by CH4 and CO2 amendments. These results suggest that peatland diazotrophy is mediated by a combination of C2H2-sensitive and C2H2-insensitive microbes that are more active at low concentrations of O2 and show similar activity at high and low concentrations of CH4. IMPORTANCE Previous studies indicate that diazotrophy provides an important nitrogen source and is linked to methanotrophy in Sphagnum-dominated peatlands. However, the environmental controls and enzymatic pathways of peatland diazotrophy, as well as the metabolically active microbial populations that catalyze this process, remain in question. Our findings indicate that oxygen levels and photosynthetic activity override low nutrient availability in limiting diazotrophy and that members of the Alphaproteobacteria (Rhizobiales) catalyze this process at the bog surface using the molybdenum-based form of the nitrogenase enzyme.

The role of external inputs and internal cycling in shaping the global ocean cobalt distribution : insights from the first cobalt biogeochemical model

Abstract Cobalt is an important micronutrient for ocean microbes as it is present in vitamin B12 and is a co‐factor in various metalloenzymes that catalyze cellular processes. Moreover, when seawater availability of cobalt is compared to biological demands, cobalt emerges as being depleted in seawater, pointing to a potentially important limiting role. To properly account for the potential biological role for cobalt, there is therefore a need to understand the processes driving the biogeochemical cycling of cobalt and, in particular, the balance between external inputs and internal cycling. To do so, we developed the first cobalt model within a state‐of‐the‐art three‐dimensional global ocean biogeochemical model. Overall, our model does a good job in reproducing measurements with a correlation coefficient of >0.7 in the surface and >0.5 at depth. We find that continental margins are the dominant source of cobalt, with a crucial role played by supply under low bottom‐water oxygen conditions. The basin‐scale distribution of cobalt supplied from margins is facilitated by the activity of manganese‐oxidizing bacteria being suppressed under low oxygen and low temperatures, which extends the residence time of cobalt. Overall, we find a residence time of 7 and 250 years in the upper 250 m and global ocean, respectively. Importantly, we find that the dominant internal resupply process switches from regeneration and recycling of particulate cobalt to dissolution of scavenged cobalt between the upper ocean and the ocean interior. Our model highlights key regions of the ocean where biological activity may be most sensitive to cobalt availability.

Alphaproteobacteria fix nitrogen in a Sphagnum -dominated peat bog using molybdenum-dependent nitrogenase

Microbial N2 fixation (diazotrophy) represents an important nitrogen source to oligotrophic peatland ecosystems, which are important sinks for atmospheric CO2 and susceptible to changing climate. The objective of this study was to investigate the pathways and controls of diazotrophy, as well as the active microbial groups that mediate the process in Sphagnum-dominated peat bogs. In an ombrotrophic peat bog (S1) in the Marcell Experimental Forest (Minnesota, USA), low (μM) levels of inorganic nitrogen were observed, suggesting that diazotrophy could have a significant influence on ecosystem properties. Despite higher dissolved vanadium (V) (11 nM) than molybdenum (Mo) (3 nM) in surface peat, a combination of metagenomic, amplicon sequencing and activity measurements indicated that Mo-containing nitrogenases dominate over the V-containing form. Diazotrophy was only detected in surface peat exposed to light, with the highest rates observed in peat collected from hollows with the highest water content. Rates were suppressed by O2, and unaffected by CH4 and CO2 amendments. Acetylene fully inhibited CH4 consumption under oxic conditions, but only partially inhibited 15N2 incorporation in degassed incubations, and had a minimal effect on oxic 15N2 incorporation. Through a close coupling of process rate measurements with molecular analysis of the metabolically active microbial communities, our findings suggest that diazotrophy in surface layers of the S1 bog is mediated by Alphaproteobacteria (Bradyrhizobiaceae and Beijerinckiaceae) supported by photosynthate, rather than methane, for carbon and/or energy. Importance Previous studies indicate that diazotrophy provides an important nitrogen source and is linked to methanotrophy in Sphagnum-dominated peatlands. However, the environmental controls and enzymatic pathways of diazotrophy, as well as the metabolically active microbial populations that catalyze this process in peatlands, remain in question. Our findings indicate that oxygen levels and photosynthetic activity override low nutrient availability in limiting diazotrophy, and that primarily non-methanotrophic members of the Alphaproteobacteria (Bradyrhizobiaceae and Beijerinckiaceae) catalyze this process primarily at the bog surface.Microbial N2 fixation (diazotrophy) represents an important nitrogen source to oligotrophic peatland ecosystems, which are important sinks for atmospheric CO2 and susceptible to changing climate. The objectives of this study were: (i) to determine the active microbial group and type of nitrogenase mediating diazotrophy in a ombrotrophic Sphagnum-dominated peat bog (the S1 peat bog, Marcell Experimental Forest, Minnesota, USA); and (ii) to determine the effect of environmental parameters (light, O2, CO2, CH4) on potential rates of diazotrophy measured by acetylene (C2H2) reduction and 15N2 incorporation. Molecular analysis of metabolically-active microbial communities suggested that diazotrophy in surface peat was primarily mediated by Alphaproteobacteria (Bradyrhizobiaceae and Beijerinckiaceae). Despite higher dissolved vanadium (V) (11 nM) than molybdenum (Mo) (3 nM) in surface peat, a combination of metagenomic, amplicon sequencing and activity measurements indicated that Mo-containing nitrogenases dominate over the V-containing form. Acetylene reduction was only detected in surface peat exposed to light, with the highest rates observed in peat collected from hollows with the highest water content. Incorporation of 15N2 was suppressed 90% by O2 and 55% by C2H2, and was unaffected by CH4 and CO2 amendments. These results suggest that peatland diazotrophy is mediated by a combination of C2H2-sensitive and C2H2-insensitive microbes that are more active at low O2 and show similar activity at high and low CH4.