| 1. |
- Bey, Ergün, et al.
(författare)
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Ocean acidification reduces iodide production by the marine diatom Chaetoceros sp. (CCMP 1690)
- 2023
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Ingår i: Marine Chemistry. - : Elsevier. - 0304-4203 .- 1872-7581. ; 257
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Tidskriftsartikel (refereegranskat)abstract
- Phytoplankton in marine surface waters play a key role in the global iodine cycle. The biologically-mediated iodide production under future scenarios is limited. Here we compare growth, iodate to iodide conversion rate and membrane permeability in the diatom Chaetoceros sp. (CCMP 1690) grown under seawater carbonate chemistry conditions projected for 2100 (1000 ppm) and pre-industrial (280 ppm) conditions. We found no effect of CO2 on growth rates, but a significantly higher cell yield under high CO2, suggesting sustained growth from relief from carbon limitation. Cell normalised iodate uptake (16.73 +/- 0.92 amol IO3- cell-1) and iodide production (8.61 +/- 0.15 amol I-cell-1) was lower in cultures grown at high pCO2 than those exposed to preindustrial conditions (21.29 +/- 2.37 amol IO3- cell-1, 11.91 +/- 1.49 amol I-cell-1, respectively). Correlating these measurements with membrane permeability, we were able to ascertain that iodide conversion rates were not linked to cell permeability and that the processes of mediated iodate loss and diatom-iodide formation are decoupled. These findings are the first to implicate OA in driving a potential shift in diatom-mediated iodate reduction. If our results are indicative of diatom-mediated iodine cycling in 2100, future surface ocean conditions could experience reduced rates of iodide production by Chaetoceros spp., potentially lowering iodide concentrations in ocean regions dominated by this group. These changes have the potential to impact ozone cycling and new particle formation in the atmosphere.
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| 2. |
- Bridgestock, Luke, et al.
(författare)
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Assessing the utility of barium isotopes to trace Eurasian riverine freshwater inputs to the Arctic Ocean
- 2021
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Ingår i: Marine Chemistry. - : Elsevier. - 0304-4203 .- 1872-7581. ; 236, s. 104029-104029
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Tidskriftsartikel (refereegranskat)abstract
- Tracing riverine freshwater transport pathways within the Arctic Ocean is key to understanding changes in Arctic Ocean freshwater inventories. Dissolved Ba concentrations have been used in this capacity but are compromised by non-conservative processes. To assess the potential for Ba isotopes to provide insights into the impact of such processes on Arctic Ocean dissolved Ba inventories, Ba concentration and isotope data for surface seawater samples from the Siberian Shelf and Bering Sea/Strait are presented. These samples capture the mixing of riverine freshwater discharged by the rivers Yenisey, Lena and Ob, with Atlantic and Pacific derived seawater, which are traced by relationships between salinity, Ba concentration and δ138/134Ba. The δ138/134Ba of net river inputs, following modification by estuarine processes, are constrained to be 0.31 ± 0.04‰, 0.20 ± 0.06‰ and 0.23 ± 0.04‰, for the rivers Yenisey, Lena and Ob respectively. These values are used to estimate an average δ138/134Ba for Eurasian river freshwater input to the Arctic Ocean of 0.23 ± 0.04‰. The Ba concentration and δ138/134Ba of Lena River freshwater transported across the Laptev Sea are modified by non-conservative processes. These non-conservative processes do not result in distinctive modification of dissolved Ba concentration-δ138/134Ba mixing relationships between Eurasian riverine freshwater and Arctic seawater, which unfortunately limits the potential of Ba isotopes to improve tracing riverine freshwater sources in the central Arctic Ocean basins using dissolved Ba inventories. More generally the results of this study help advance understanding of Ba isotope cycling in the environment and their development as an emerging tracer of marine processes.
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| 3. |
- Cabral dos Santos, Alex, 1990, et al.
(författare)
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Fresh and saline submarine groundwater discharge as sources of carbon and nutrients to the Japan Sea
- 2023
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Ingår i: Marine Chemistry. - : Elsevier BV. - 0304-4203. ; 249
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Tidskriftsartikel (refereegranskat)abstract
- Submarine groundwater discharge (SGD) is an important pathway for carbon and nutrients to the coastal ocean, sometimes exceeding river inputs. SGD fluxes can have implications for long-term carbon storage, ocean acidification and nutrient dynamics. Here, we used radium (223Ra and 226Ra) isotopes to quantify SGD-derived fluxes of dissolved inorganic (DIC) and organic (DOC) carbon, nitrate (NO3−), nitrite (NO2−), ammonium (NH4+) and phosphate (PO43−) in a spring-fed coastal bay in the Japan Sea. The average coastal water residence times using 223Ra/226Ra ratios was 32.5 ± 17.9 days. Fresh and saline SGD were estimated using a radium mixing model with short- and long-lived isotopes. The volume of fresh SGD entering the bay (4.6 ± 4.6 cm day−1) was more than twice that of the volume of saline SGD (1.9 ± 2.1 cm day−1). Fresh SGD (mmol m2 day−1) was the main source of DOC (2.7 ± 2.6), DIC (13.9 ± 13.7), PO43− (0.3 ± 0.3) and NO3− (6.6 ± 6.5) to the coastal ocean, whereas saline SGD was the main source of NH4+ (0.2 ± 0.2). Total SGD-derived carbon and nutrient fluxes were 4 – 7 and 2–16 times greater than local river inputs. Positive correlations between chlorophyll-a, 226Ra and δ13C-DIC indicate that SGD significantly (p < 0.05) enhances primary productivity nearshore. Overall, fresh SGD of nitrogen and carbon to seawater drove chlorophyll-a, decreased DIC/Alkalinity ratios, and modified the carbonate biogeochemistry of the coastal ocean.
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| 4. |
- Clegg, Simon L., et al.
(författare)
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Chemical speciation models based upon the Pitzer activity coefficient equations, including the propagation of uncertainties. II. Tris buffers in artificial seawater at 25 °C, and an assessment of the seawater ‘Total’ pH scale
- 2022
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Ingår i: Marine Chemistry. - : Elsevier BV. - 0304-4203. ; 244
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Tidskriftsartikel (refereegranskat)abstract
- The substance Tris (or THAM, 2-amino-2-hydroxymethyl-1,3-propanediol, CAS 77–86-1), and its protonated form TrisH+, is used in the preparation of pH buffer solutions for applications in seawater chemistry. The development of an acid-base chemical speciation model of buffer solutions containing Tris, TrisH+, and the major ions of seawater is desirable so that: (i) the effects of changes in the composition of the medium on pH can be calculated; (ii) pH on the free (a measure of [H+]) and total (a measure of ([H+] + [HSO4−])) scales can be interconverted; (iii) approximations inherent in the definition of the total pH scale can be quantified; (iv) electrode pairs such as H+/Cl− and H+/Na+ can more easily be calibrated for the measurement of pH. As a first step towards these goals we have extended the Pitzer-based speciation model of Waters and Millero (Mar. Chem. 149, 8–22, 2013) for artificial seawater to include Tris and TrisH+, at 25 °C. Estimates of the variances and covariances of the additional interaction parameters were obtained by Monte Carlo simulation. This enables the total uncertainty of any model-calculated quantity (e.g., pH, speciation) to be estimated, as well as the individual contributions of all interaction parameters and equilibrium constants. This is important for model development, because it allows the key interactions to be identified. The model was tested against measured EMFs of cells containing Tris buffer in artificial seawater at 25 °C, and the mean deviation was found to be 0.13 ± 0.070 mV for salinities 20 to 40. Total variances for calculated electromotive forces of the buffer solutions are dominated by contributions from just a few interaction parameters, making it likely that the model can readily be improved. The model was used to quantify the difference between various definitions of total pH and –log10([H+] + [HSO4−]) in Tris buffer solutions at 25 °C, for the first time (item (iii) above). The results suggest that the total pH scale can readily be extended to low salinities using the established approach for substituting TrisH+ for Na+ in the buffer solutions, especially if the speciation model is used to quantify the effect on pH of the substitution. The relationships between electromotive force (EMF), and pH on the total scale, with buffer molality in artificial seawater at constant salinity are shown to be linear above about 0.01 to 0.02 mol kg−1 buffer molality. The pH of Tris buffers containing ratios of TrisH+ to Tris that vary from unity can be calculated very simply. Technical aspects of the total pH scale, such as the extrapolation of pH to zero buffer (at constant salinity), are clarified. Recommendations are made for further work to extend the model to the temperature range 0–45 °C, and improve accuracy, so that requirements (i) to (iv) above can be fully met.
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| 5. |
- Clegg, S. L., et al.
(författare)
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Chemical speciation models based upon the Pitzer activity coefficient equations, including the propagation of uncertainties. III. Seawater from the freezing point to 45 & DEG;C, including acid-base equilibria
- 2023
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Ingår i: Marine Chemistry. - : Elsevier BV. - 0304-4203. ; 250
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Tidskriftsartikel (refereegranskat)abstract
- A quantitative understanding of pH, acid-base equilibria, and chemical speciation in natural waters including seawater is needed in applications ranging from global change to environmental and water quality management. In a previous study (Humphreys et al., 2022) we implemented a model of solutions containing the ions of artificial seawater, based upon the use of the Pitzer equations for the calculation of activity coefficients and including, for the first time, the propagation of uncertainties. This was extended (Clegg et al., 2022) to include the Tris buffer solutions that are used to calibrate the seawater total pH scale. Here we apply the same methods to develop a model of solutions containing the ions of standard reference seawater, based upon studies by Millero and co-workers. We compare the predictions of the model to literature data for: the dissociation of dissolved CO2 and bicarbonate ion; boric acid dissociation; saturation with respect to calcite, the ion product of water, and osmotic coefficients of seawater. Estimates of the uncertainty contributions of all thermodynamic equilibrium constants and Pitzer parameters to the variance of the calculated quantity are used to determine which elements of the model need improvement, with the aim of agreeing with properties noted above to within their experimental uncertainty. Further studies are recommended. Comparisons made with several datasets for carbonate system dissociation in seawater suggest which are the most reliable, and identify low salinity waters (S < 10) as a region for which dissociation constants of bicarbonate are not yet accurately known. At present, the model is likely to be most useful for the direct calculation of equilibria in natural waters of arbitrary composition, or for adjusting dissociation constants known for seawater media to values for natural waters in which the relative compositions of the major ions are different.
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| 6. |
- Davis, K. L., et al.
(författare)
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Calcification and organic productivity at the world's southernmost coral reef
- 2020
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Ingår i: Marine Chemistry. - : Elsevier BV. - 0304-4203. ; 227
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Tidskriftsartikel (refereegranskat)abstract
- Estimates of coral reef calcification and organic productivity provide valuable insight to community functionality and the response of an ecosystem to stress events. High-latitude coral reefs are expected to experience rapid changes in calcification rates and become refugia for tropical species following climate change and increasing bleaching events. Here, we estimate ecosystem-scale calcification and organic productivity at the world's southernmost coral reef using seawater carbon chemistry observations (Lord Howe Island, Australia). We reduce uncertainties in metabolic calculations by producing a detailed bathymetric model and deploying two current meters to refine residence time and volume estimates. Bathymetry-modelled transect depths ranged from 74% shallower to 20% deeper than depths averaged from reef crest/flat current meters, indicating that higher-resolution depth observations help to reduce uncertainties in reef metabolic calculations. Rates of ecosystem calcification were 56.6 +/- 14.8 mmol m(-2) d(-1) in the winter and 125.3 +/- 39.4 mmol m(-2) d(-1) in the summer. These rates are lower than most other high-latitude reefs according to our compilation of high-latitude coral ecosystem metabolism estimates. Coral cover ranged from 14.7 +/- 2.3% in winter to 19.8 +/- 2.1% in the summer. A concurrent bleaching event and cyclone occurred during summer sampling (February - March 2019), resulting in 47% of corals bleached at the study site and 2% mortality due to cyclonal damage. Therefore, it is likely that the summertime G(net) rates underestimate baseline calcification. Our results enable future assessments of long-term change, but do not resolve the impact of bleaching at Lord Howe Island.
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| 7. |
- Humphreys, Matthew P., et al.
(författare)
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Chemical speciation models based upon the Pitzer activity coefficient equations, including the propagation of uncertainties: Artificial seawater from 0 to 45 °C
- 2022
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Ingår i: Marine Chemistry. - : Elsevier BV. - 0304-4203. ; 244
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Tidskriftsartikel (refereegranskat)abstract
- Accurate chemical speciation models of solutions containing the ions of seawater have applications in the calculation of carbonate system equilibria and trace metal speciation in natural waters, and the determination of pH. Existing models, based on the Pitzer formalism for the calculation of activity coefficients, do not yet agree with key experimental data (potentiometric determinations of H+ and Cl− activity products in acidified artificial seawaters) and, critically, do not include uncertainty estimates. This hampers applications of the models, and also their further development (for which the uncertainty contributions of individual ion interactions and equilibrium constants need to be known). We have therefore implemented the models of Waters and Millero (Mar. Chem. 149, 8-22, 2013) and Clegg and Whitfield (Geochim. et Cosmochim. Acta 59, 2403-2421, 1995) for artificial seawater, within a generalised treatment of uncertainties, as a first step towards a more complete model of standard seawater and pH buffers. This addition to the models enables both the total uncertainty of any model-calculated quantity (e.g., pH, speciation) to be estimated, and also the contributions of all interaction parameters and equilibrium constants. Both models have been fully documented (and some corrections made). Estimates of the variances and covariances of the interaction parameters were obtained by Monte Carlo simulation, with simplifying assumptions. The models were tested against measured electromotive forces (EMFs) of cells containing acidified artificial seawaters. The mean offsets (measured – calculated) at 25 °C for the model of Waters and Millero are: 0.046 ± 0.11 mV (artificial seawater without sulphate, 0.280 mol kg−1 to 0.879 mol kg−1 ionic strength); and −0.199 ± 0.070 mV (artificial seawater, salinities 5 to 45). Results are similar at other temperatures. These differences compare with an overall uncertainty in the measured EMFs of about 0.04 mV. Total uncertainties for calculated EMFs of the solutions were dominated by just a few contributions: mainly H+-Cl−, Na+-Cl−, and H+-Na+-Cl− ionic interactions, and the thermodynamic dissociation constant of HSO4−. This makes it likely that the accuracy of the models can readily be improved, and recommendations for further work are made. It is shown that standard EMFs used in the calibration of the marine ‘total’ pH scale can be accurately predicted with only slight modification to the original models, suggesting that they can contribute to the extension of the scale to lower salinities.
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| 8. |
- Jonsson, Sofi, et al.
(författare)
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Distribution of total mercury and methylated mercury species in Central Arctic Ocean water and ice
- 2022
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Ingår i: Marine Chemistry. - : Elsevier BV. - 0304-4203 .- 1872-7581. ; 242
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Tidskriftsartikel (refereegranskat)abstract
- The central Arctic Ocean remains largely unexplored when it comes to the presence and cycling of mercury and its methylated forms including mono- and dimethylmercury (MMeHg and DMeHg, respectively). In this study, we quantified total Hg (HgT) and methylated Hg species in seawater, ice cores, snow, brine, and water from melt ponds collected during the SWEDARCTIC 2016 expedition to the Amerasian and Eurasian side of the Lomonosov Ridge. In the water column, concentrations of HgT, MMeHg and DMeHg ranged from 0.089 to 1.5 pM, <25 to 520 fM and from <1.6 to 160 fM, respectively. HgT was enriched in surface waters while MMeHg and DMeHg were low at the surface (i.e. in the polar mixed layer) and enriched at a water depth of around 200–400 m. A 1:2 ratio of DMeHg to MMeHg was observed in the water column suggesting a lower ratio in the central parts of the Arctic Ocean than what has previously been reported from other parts of the Arctic Ocean. At the ice stations, average HgT ranged from 0.97 ± 1.2 pM in the ice cores to 27 ± 17 pM in melt pond waters and average MeHgT (total MeHg) from 28 ± 15 fM in brine to 130 ± 18 fM in melt pond water. The HgT observed in melt ponds and brine was an order of magnitude greater than HgT observed in surface waters and HgT in the upper part of the ice-cores was ~4–8 times higher HgT in comparison to lower layers. Our study suggests that ice may act as a source of HgT to surface waters but not to be a likely source of the methylated Hg forms. Unlike elemental Hg, DMeHg did not enrich in surface waters covered by ice. Concentrations of DMeHg observed in the ice cores and other samples collected from the ice stations were low, suggesting ice to not act as a source of DMeHg to the atmosphere nor to surface waters.
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| 9. |
- Kubeneck, L. Joëlle, et al.
(författare)
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Phosphorus burial in vivianite-type minerals in methane-rich coastal sediments
- 2021
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Ingår i: Marine Chemistry. - : Elsevier BV. - 0304-4203. ; 231
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Tidskriftsartikel (refereegranskat)abstract
- Sediments are a key sink for phosphorus (P) in coastal systems. This allows coastal areas to act as a filter for P that is transported from land to sea. Recent work suggests that vivianite-type ferrous iron (Fe(II))-P minerals may be more important as a sink for P in coastal sediments than previously thought. Here, we investigate the occurrence of such vivianite-type minerals in sediments of three eutrophic coastal sites with contrasting dynamics with respect to iron (Fe) and sulfur (S), covering a salinity range of 0 to 7. We only find authigenic vivianite-type minerals at the low and intermediate salinity sites, where Fe is available in excess over sulfide production. Sequential extractions combined with SEM-EDS and μXRF analysis point towards substitution of Fe in vivianite-type minerals by other transition metal cations such as magnesium and manganese, suggesting potentially different formation pathways modulated by metal cation availability. Our results suggest that vivianite-type minerals may act as a key sink for P in sediments of many other brackish coastal systems. Climate change-driven modulations of coastal bottom water salinity, and hence, Fe versus S availability in the sediment, may alter the role of vivianite-type minerals as a P burial sink over the coming decades. Model projections for the Baltic Sea point towards increased river input and freshening of coastal waters, which could enhance P burial. In contrast, sea level rise in the Chesapeake Bay area is expected to lead to an increase in bottom water salinity and this could lower rates of P burial or even liberate currently buried P, thereby enhancing eutrophication.
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| 10. |
- Liem-Nguyen, Van, et al.
(författare)
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Spatial patterns and distributional controls of total and methylated mercury off the Lena River in the Laptev Sea sediments
- 2022
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Ingår i: Marine Chemistry. - : Elsevier BV. - 0304-4203 .- 1872-7581. ; 238
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Tidskriftsartikel (refereegranskat)abstract
- A warmer climate is predicted to accelerate the export of mercury (Hg) from Siberian rivers to the Arctic Ocean, yet there is a dearth of process-oriented studies on the speciation and fate of Hg in the shelf sea system. Here, we present data on total Hg (HgT) and methylmercury (MeHg) in Laptev Sea surface sediments along a cross-shelf transect starting at the mouth of the Lena River. Concentrations of HgT along the 330 km cross-shelf transect ranged within a fairly narrow span from 480 to 150 pmol g(-1) d.w., while concentrations of MeHg decreased one hundredfold from 13 pmol g(-1) d.w. near the Lena river to 0.095 pmol g(-1) d.w. in the more distall stations. The highest concentrations of HgT and MeHg were observed close to the river delta and were associated with a high supply of organic carbon (OC). Enrichment of the OC normalized HgT concentration (HgTOC) and depletion of the OC normalized MeHg concentration (MeHgOC) across the shelf suggests bulk OC content to not be the only driver of the HgT and MeHg spatial distributions. Based on correlations observed between HgTOC and MeHgOC and proxies for sediment physics and organic matter pools we suggest the spatial distribution of Hg and MeHg to also be influenced by hydrodynamic sorting of riverine-derived material. For MeHg, depletion of the MeHgOC across the shelf is likely driven by the trapping of terrestrial MeHg in sediments close to the river delta before it is degraded in the water column.
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