Posts Tagged 'metals'

A triple threat: ocean warming, acidification and rare earth elements exposure triggers a superior antioxidant response and pigment production in the adaptable Ulva rigida


  • La and Gd were accumulated in 24h;
  • Elimination of La and Gd did not occur in U. rigida;
  • La and Gd showed different accumulation and elimination patterns in future predicted scenarios;
  • La and Gd triggered an efficient antioxidant defence response in U. rigida;
  • REE and climate change exposure requested a superior antioxidant response.


Anthropogenic increased atmospheric CO2 concentrations will lead to a drop of 0.4 units of seawater pH and ocean warming up to 4.8°C by 2100. Contaminant’s toxicity is known to increase under a climate change scenario. Rare earth elements (REE) are emerging contaminants, that until now have no regulation regarding maximum concentration and discharge into the environment and have become vital to new technologies such as electric and hybrid-electric vehicle batteries, wind turbine generators and low-energy lighting. Studies of REE, namely Lanthanum (La) and Gadolinium (Gd), bioaccumulation, elimination, and toxicity in a multi-stressor environment (e.g., warming and acidification) are lacking. Hence, we investigated the algae phytoremediation capacity, the ecotoxicological responses and total chlorophyll and carotenoid contents in Ulva rigida during 7 days of co-exposure to La or Gd (15 µg L−1 or 10 µg L−1, respectively), and warming and acidification. Additionally, we assessed these metals elimination, after a 7-day phase. After one day of experiment La and Gd clearly showed accumulation/adsorption in different patterns, at future conditions. Unlikely for Gd, Warming and Acidification contributed to the lowest La accumulation, and increased elimination. Lanthanum and Gd triggered an adequate activation of the antioxidant defence system, by avoiding lipid damage. Nevertheless, REE exposure in a near-future scenario triggered an overproduction of ROS that requested an enhanced antioxidant response. Additionally, an increase in total chlorophyll and carotenoids could also indicate an unforeseen energy expense, as a response to a multi-stressor environment.

Continue reading ‘A triple threat: ocean warming, acidification and rare earth elements exposure triggers a superior antioxidant response and pigment production in the adaptable Ulva rigida’

Single and combined ecotoxicological effects of ocean warming, acidification and lanthanum exposure on the surf clam (Spisula solida)


  • Lanthanum was bioaccumulated after just one day of exposure.
  • Elimination did not occur during the 7-day depuration phase.
  • The biochemical response was triggered, however damage occurred.
  • The La toxic effects are more severe in a changing world.


Lanthanum (La) is one of the most abundant emergent rare earth elements. Its release into the environment is enhanced by its use in various industrial applications. In the aquatic environment, emerging contaminants are one of the stressors with the ability to compromise the fitness of its inhabitants. Warming and acidification can also affect their resilience and are another consequence of the growing human footprint on the planet. However, from information gathered in the literature, a study on the effects of ocean warming, acidification, and their interaction with La was never carried out. To diminish this gap of knowledge, we explored the effects, combined and as single stressors, of ocean warming, acidification, and La (15 μg L−1) accumulation and elimination on the surf clam (Spisula solida). Specimens were exposed for 7 days and depurated for an additional 7-day period. Furthermore, a robust set of membrane-associated, protein, and antioxidant enzymes and non-enzymatic biomarkers (LPO, HSP, Ub, SOD, CAT, GPx, GST, TAC) were quantified. Lanthanum was bioaccumulated after just one day of exposure, in both control and climate change scenarios. A 7-day depuration phase was insufficient to achieve control values and in a warming scenario, La elimination was more efficient. Biochemical response was triggered, as highlighted by enhanced SOD, CAT, GST, and TAC levels, however as lipoperoxidation was observed it was insufficient to detoxify La and avoid damage. The HSP was largely inhibited in La treatments combined with warming and acidification. Concomitantly, lipoperoxidation was highest in clams exposed to La, warming, and acidification combined. The results highlight the toxic effects of La on this bivalve species and its enhanced potential in a changing world.

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Increasing arsenic accumulation as an implication of climate change: a case study using red algae

Climate change due to an increasing concentration of carbon dioxide in the atmosphere is a global issue. It can impact aquatic environments by affecting water flow, pollutant transformation and migration, and other toxicant-related effects. We assessed the interactive effects of temperature warming and pH changes on variations in accumulation of total arsenic (AsT) in the red alga Sarcodia suae at different levels of arsenite (AsIII). Result showed that AsT variations in the alga were moderated by significant joint effects of warming temperature and/or increasing pH levels and their interactions with increasing AsIII concentrations. Our study suggests possible deleterious impacts on macroalgal populations due to toxicological effects associated with prevailing environmental conditions. Therefore, improved pollution management, climate change adaptation, and mitigation strategies are needed to deal with current environmental issues and As aggravation.

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The biological uptake of dissolved iron in the changing Daya Bay, South China Sea: effect of pH and DO


  • Fe bioavailability affected by pH and DO regulates phytoplanktonic Fe uptake.
  • Nano-phytoplankton is more sensitive to the variation of seawater pH and DO.
  • Phytoplankton community tend to be miniaturized in the changing DYB.
  • Fe requirement in DYB goes higher accompanied with the phytoplankton miniaturization.
  • DYB is not an Fe-rich environment derived from the relative low Fe:C ratio.


The oceanic acidification and coastal hypoxia have potential to enhance biological uptake of dissolved iron (Fe) by phytoplankton. In this study, the Fe uptake rate (FeUR) in Daya Bay was significantly negatively correlated with pH and dissolved oxygen (DO) (r = −0.81 and −0.73, respectively, p < 0.001). In addition, binary regression (FeUR = −1.45 × pH − 0.10 × DO + 13.64) also indicated that both pH and DO played key roles in FeUR variations. As pH and DO decreased, Fe uptake by phytoplankton was promoted, and the contribution of nano-phytoplankton to Fe uptake increased significantly, while that of pico-FeUR decreased. These will result in the phytoplankton community to be miniaturized and Fe requirement of phytoplankton goes higher, thereby leading changes of phytoplankton composition and coastal ecosystem. This study helps to understand how Fe could affect the coastal ecosystem under the increasing anthropogenic influences.

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Mangrove trace metal biogeochemistry response to global climate change

This review discusses observed impacts from different climate change-driven pressures on mangrove’s role in modulating trace metal transfer at the land-ocean interface. It contributes to the literature in a global context and shows mangroves as mitigators or providing positive feedback to metal mobilization. Most chalcophile metals2+ accumulate in mangrove soils associated with sulfides while high sedimentation rates avoid their oxidation. Exudation of oxygen by roots fixates Fe, which co-precipitates metals as oxyhydroxides in the rhizosphere. These two biogeochemical processes reduce trace metal availability to plants and their mobility within estuaries. However, climate change-driven pressures alter this geochemical equilibrium. Increasing atmospheric CO2 and temperature, and the intensity and frequency of extreme climatic events, have proved to affect mangrove functioning and cover, but no direct observation on the impact on metal biogeochemistry is presently available, whereas sea level rise and saline intrusion impacts on the fate of metals have already been observed. Sea level rise increases erosion, that dissociates deposited sulfides releasing metals to the water column. Released metals adsorb onto suspended particles and can re-deposit in the estuary or are exported to continental shelf sediments. Saline intrusion may oxidize deeper sediment layers releasing metals to porewaters. Part of the mobilized metals may remain in solution complexed with DOM and have their bioavailability increased, as shown by high bioaccumulation factors and biomagnification and high metal concentrations in the estuarine biota, which results in higher human exposure through fisheries consumption. Since erosion occurs preferentially at the sea border and higher sedimentation at the higher reaches of the estuary, triggering mangroves migration landward, spatial gradients are formed, and shall be taken into consideration when planning mitigation or adaptation strategies. These observations suggest disruption of traditional humans dwelling in mangrove dominated coastlines by increasing contamination of coastal fisheries, often the principal protein source for those groups and an important source of income. Further research into the environmental and socioeconomic impacts of climate change driven alterations to metal biogeochemical processes in mangroves as contaminant levels are expected to increase.

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The combined effects of ocean acidification and copper on the physiological responses of the tropical coral Stylophora pistillata


  • Exposure to increased Cu concentrations suppressed coral calcification.
  • Calcification was suppressed further when exposed to Cu under high pCO2.
  • Respiration decreased after two weeks when stressors were applied in combination.


A decrease in ocean pH of 0.3 units will likely double the proportion of dissolved copper (Cu) present as the free metal ion, Cu2+, the most bioavailable form of Cu, and one of the most common marine pollutants. We assess the impact of ocean acidification and Cu, separately and in combination, on calcification, photosynthesis and respiration of sub-colonies of a single tropical Stylophora pistillata colony. After 15 days of treatment, total calcification rates were significantly decreased in corals exposed to high seawater pCO2 (∼1000-μatm, 2100 scenario) and at both ambient (1.6–1.9 nmols) and high (2.5–3.6 nmols) dissolved Cu concentrations compared to controls. The effect was increased when both stressors were combined. Coral respiration rates were significantly reduced by the combined stressors after 2 weeks of exposure, indicating the importance of experiment duration. It is therefore likely rising atmospheric CO2 will exacerbate the negative effects of Cu pollution to S. pistillata.

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In contrast to diatoms, cryptophytes are susceptible to iron limitation, but not to ocean acidification

Previous field studies in the Southern Ocean (SO) indicated an increased occurrence and dominance of cryptophytes over diatoms due to climate change. To gain a better mechanistic understanding of how the two ecologically important SO phytoplankton groups cope with ocean acidification (OA) and iron (Fe) availability, we chose two common representatives of Antarctic waters, the cryptophyte Geminigera cryophila and the diatom Pseudo-nitzschia subcurvata. Both species were grown at 2°C under different pCO2 (400 vs. 900 μatm) and Fe (0.6 vs. 1.2 nM) conditions. For P. subcurvata, an additional high pCO2 level was applied (1400 μatm). At ambient pCO2 under low Fe supply, growth of G. cryophila almost stopped while it remained unaffected in P. subcurvata. Under high Fe conditions, OA was not beneficial for P. subcurvata, but stimulated growth and carbon production of G. cryophila. Under low Fe supply, P. subcurvata coped much better with OA than the cryptophyte, but invested more energy into photoacclimation. Our study reveals that Fe limitation was detrimental for the growth of G. cryophila and suppressed the positive OA effect. The diatom was efficient in coping with low Fe, but was stressed by OA while both factors together strongly impacted its growth. The distinct physiological response of both species to OA and Fe limitation explains their occurrence in the field. Based on our results, Fe availability is an important modulator of OA effects on SO phytoplankton, with different implications on the occurrence of cryptophytes and diatoms in the future.

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Interactive effects of acidification and copper exposure on the reproduction and metabolism of coral endosymbiont Cladocopium goreaui


  • Acidification raised growth by Fv/Fm, nutrient uptake and biomolecular biosynthesis.
  • Copper pollution alone decreased algal reproduction through toxic effects.
  • Combined stressor repressed reproduction through downregulated aromatic amino acid.
  • Abstract

Ocean acidification resulting from increased CO2 and pollution from land-sourced toxicants such as copper have been linked to coral cover declines in coastal reef ecosystems. The impacts of ocean acidification and copper pollution on corals have been intensively investigated, whereas research on their effects on coral endosymbiont Symbiodiniaceae is limited. In this study, reproduction, photosynthetic parameters, nutrient accumulation and metabolome of Symbiodiniaceae Cladocopium goreaui were investigated after a weeklong treatment with acute CO2-induced acidification and copper ion. Acidification promoted algal reproduction through increased nutrients assimilation, upregulated citrate cycle and biomolecular biosynthesis pathway, while copper exposure repressed algal reproduction through toxic effects. The combined acidification and copper exposure caused the same decline in algal reproduction as copper exposure alone, but the upregulation of pentose phosphate pathway and the downregulation of aromatic amino acid biosynthesis. These results suggest that copper pollution could override the positive effects of acidification on the symbiodiniacean reproduction.

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Particulate iron bioavailability to phytoplankton in Antarctic and Arctic waters: effects of ocean acidification and the organic ligand EDTA

Particulate iron (PFe) usually is not considered as a bioavailable iron fraction to phytoplankton. In this study we tested the bioavailability of one PFe species, goethite (α-FeO(OH)), to phytoplankton community in Southern Ocean under the effect of ocean acidification (OA) (pHT ca. 7.5) and representative concentration pathways (RCP) 8.5 condition (pCO2 ca. 1300 µatm), and to an Arctic diatom species, Nitzschia frigida, under the effect of the organic ligand, EDTA (using the commercially available salt disodium ethylenediaminetetraacetate dihydrate), as a chelator, respectively.

In March 2019, a natural phytoplankton community was sampled and used for the deck incubation experiment in the Southern Ocean. The sampling site was 68.10°S, 6.00° W, which was in the region of Queen Maud Land (Norwegian: Dronning Maud Land, DML). We observed marine biogeochemical performance of the phytoplankton community under OA. Different chemical and biological parameters during the incubation were determined, including dissolved iron (DFe), total acid leachable iron (TaLFe), macronutrients including nitrate (NO3-), phosphate (PO43-) and silicate, total pH (pHT), dissolved inorganic carbon (DIC), the concentration & fugacity of carbon dioxide (fCO2), chlorophyll a (Chla) concentration & in vivo fluorescence. The results show that the tested phytoplankton assemblage was more severely influenced by OA than iron bioavailability, especially under severe OA. Goethite, as one type of PFe, is insoluble under the tested OA scenarios. There could be PO43- remineralization in all treatments but species shift to diatoms only in ambient pH treatments (mild OA), which coincides with the judgement that OA impact is predominant in comparison to iron enrichment in this experiment. We should analyze phytoplankton species to test this hypothesis. OA can result in that phytoplankton launches Hv channel-mediated H+ efflux mechanism, carbon concentration mechanism (CCM) down-regulation of phytoplankton and the thriving of more tolerant species with more efficient CCM.

In April 2021, using an Arctic diatom species, Nitzschia frigida, we investigated the possibility of EDTA increasing goethite bioavailability to phytoplankton and photosynthetic performance by measuring relative electron transport rate (rETR) in the experiment performed at Trondheim Biological Station (Norwegian: Trondheim Biologiske Stasjon, TBS). The results show that elevating EDTA concentration can increase the bioavailability of goethite while decrease that of ferric chloride (FeCl3). This is inconclusive according to possibly negatively biased α (the slope of a typical P/E (photosynthesis/irradiance) curve), because it results in underestimation of goethite bioavailability under the influence of EDTA.

Further research regarding the combined effect of OA and EDTA on PFe bioavailability to phytoplankton is recommended.

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Aluminium in aquatic environments: abundance and ecotoxicological impacts

Aluminium (Al) is a common chemical element released into the aquatic environment from the Earth’s crust and many anthropogenic activities. It may be present in various dissolved and precipitated forms [Al3+, AlOH2+, Al(OH)2+, Al(OH)03, Al(OH)4, etc.], which are potentially toxic for organisms. This review summarizes information about the concentrations of Al detected in aquatic ecosystems and its effects on both freshwater and marine organisms (such as growth disturbance, reproduction, and respiration alterations). As the chemistry of Al is different in freshwater and marine systems, we discuss the behaviour of aluminium and its effects on marine or freshwater fauna. Therefore, the solubility of Al, as other metals, is highly pH dependent, which increases when pH decreases. We are assuming that ocean acidification, linked to climate change, would affect the Al bioavailability in the aquatic environment, which may increase its ecotoxicological effects on semi-closed (Bays, Mediterranean Sea, etc.) or closed (lakes, etc.) aquatic ecosystems.

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Ocean acidification effect on the iron-gallic acid redox interaction in seawater

Ocean acidification impacts the iron (Fe) biogeochemistry both by its redox and its complexation reactions. This has a direct effect on the ecosystems due to Fe being an essential micronutrient. Polyphenols exudated by marine microorganisms can complex Fe(III), modifying the Fe(II) oxidation rates as well as promoting the reduction of Fe(III) to Fe(II) in seawater. The effect of the polyphenol gallic acid (GA; 3,4,5-trihydroxy benzoic acid) on the oxidation and reduction of Fe was studied. The Fe(II) oxidation rate constant decreased, increasing the permanence of Fe(II) in solutions at nM levels. At pH = 8.0 and in the absence of gallic acid, 69.3% of the initial Fe(II) was oxidized after 10 min. With 100 nM of gallic acid (ratio 4:1 GA:Fe), and after 30 min, 37.5% of the initial Fe(II) was oxidized. Fe(III) is reduced to Fe(II) by gallic acid in a process that depends on the pH and composition of solution, being faster as pH decreases. At pH > 7.00, the Fe(III) reduction rate constant in seawater was lower than in NaCl solutions, being the difference at pH 8.0 of 1.577 × 10–5 s–1. Moreover, the change of the Fe(III) rate constant with pH, within the studied range, was higher in seawater (slope = 0.91) than in NaCl solutions (slope = 0.46). The Fe(III) reduction rate constant increased with increasing ligand concentration, being the effect higher at pH 7.0 [k′ = 1.078 × 10–4 s–1; (GA) = 250 nM] compared with that at pH 8.0 [k′ = 3.407 × 10–5 s–1; (GA) = 250 nM]. Accordingly, gallic acid reduces Fe(III) to Fe(II) in seawater, making possible the presence of Fe(II) for longer periods and favoring its bioavailability.

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Responses of a natural phytoplankton community from the Drake Passage to two predicted climate change scenarios

Contrasting models predict two different climate change scenarios for the Southern Ocean (SO), forecasting either less or stronger vertical mixing of the water column. To investigate the responses of SO phytoplankton to these future conditions, we sampled a natural diatom dominated (63%) community from today’s relatively moderately mixed Drake Passage waters with both low availabilities of iron (Fe) and light. The phytoplankton community was then incubated at these ambient open ocean conditions (low Fe and low light, moderate mixing treatment), representing a control treatment. In addition, the phytoplankton was grown under two future mixing scenarios based on current climate model predictions. Mixing was simulated by changes in light and Fe availabilities. The two future scenarios consisted of a low mixing scenario (low Fe and higher light) and a strong mixing scenario (high Fe and low light). In addition, communities of each mixing scenario were exposed to ambient and low pH, the latter simulating ocean acidification (OA). The effects of the scenarios on particulate organic carbon (POC) production, trace metal to carbon ratios, photophysiology and the relative numerical contribution of diatoms and nanoflagellates were assessed. During the first growth phase, at ambient pH both future mixing scenarios promoted the numerical abundance of diatoms (∼75%) relative to nanoflagellates. This positive effect, however, vanished in response to OA in the communities of both future mixing scenarios (∼65%), with different effects for their productivity. At the end of the experiment, diatoms remained numerically the most abundant phytoplankton group across all treatments (∼80%). In addition, POC production was increased in the two future mixing scenarios under OA. Overall, this study suggests a continued numerical dominance of diatoms as well as higher carbon fixation in response to both future mixing scenarios under OA, irrespective of different changes in light and Fe availability.

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Lead in the marine environment: concentrations and effects on invertebrates

Lead (Pb) is a non-essential metal naturally present in the environment and often complexed with other elements (e.g., copper, selenium, zinc). This metal has been used since ancient Egypt and its extraction has grown in the last centuries. It has been used until recently as a fuel additive and is currently used in the production of vehicle batteries, paint, and plumbing. Marine ecosystems are sinks of terrestrial contaminations; consequently, lead is detected in oceans and seas. Furthermore, lead is not biodegradable. It remains in soil, atmosphere, and water inducing multiple negative impacts on marine invertebrates (key species in trophic chain) disturbing ecological ecosystems. This review established our knowledge on lead accumulation and its effects on marine invertebrates (Annelida, Cnidaria, Crustacea, Echinodermata, and Mollusca). Lead may affect different stages of development from fertilization to larval development and can also lead to disturbance in reproduction and mortality. Furthermore, we discussed changes in the seawater chemistry due to Ocean Acidification, which can affect the solubility, speciation, and distribution of the lead, increasing potentially its toxicity to marine invertebrates.

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The combined effects of ocean acidification and heavy metals on marine organisms: a meta-analysis

Ocean acidification (OA) may interact with anthropogenic pollutants, such as heavy metals (HM), to represent a threat to marine organisms and ecosystems. Here, we perform a quantitative meta-analysis to examine the combined effects of OA and heavy metals on marine organisms. The results reveal predominantly additive interactions (67%), with a considerable proportion of synergistic interactions (25%) and a few antagonistic interactions (8%). The overall adverse effects of heavy metals on marine organisms were alleviated by OA, leading to a neutral impact of heavy metals in combination with OA. However, different taxonomic groups showed large variabilities in their responses, with microalgae being the most sensitive when exposed to heavy metals and OA, and having the highest proportion of antagonistic interactions. Furthermore, the variations in interaction type frequencies are related to climate regions and heavy metal properties, with antagonistic interactions accounting for the highest proportion in temperate regions (28%) and when exposed to Zn (52%). Our study provides a comprehensive insight into the interactive effects of OA and HM on marine organisms, and highlights the importance of further investigating the responses of different marine taxonomic groups from various geographic locations to the combined stress of OA and HM.

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The Southern Ocean diatom Pseudo-nitzschia subcurvata flourished better under simulated glacial than interglacial ocean conditions: combined effects of CO2 and iron

The ‘Iron Hypothesis’ suggests a fertilization of the Southern Ocean by increased dust deposition in glacial times. This promoted high primary productivity and contributed to lower atmospheric pCO2. In this study, the diatom Pseudo-nitzschia subcurvata, known to form prominent blooms in the Southern Ocean, was grown under simulated glacial and interglacial climatic conditions to understand how iron (Fe) availability (no Fe or Fe addition) in conjunction with different pCO2 levels (190 and 290 μatm) influences growth, particulate organic carbon (POC) production and photophysiology. Under both glacial and interglacial conditions, the diatom grew with similar rates. In comparison, glacial conditions (190 μatm pCO2 and Fe input) favored POC production by Psubcurvata while under interglacial conditions (290 μatm pCO2 and Fe deficiency) POC production was reduced, indicating a negative effect caused by higher pCO2 and low Fe availability. Under interglacial conditions, the diatom had, however, thicker silica shells. Overall, our results show that the combination of higher Fe availability with low pCO2, present during the glacial ocean, was beneficial for the diatom Psubcurvata, thus contributing more to primary production during glacial compared to interglacial times. Under the interglacial ocean conditions, on the other hand, the diatom could have contributed to higher carbon export due to its higher degree of silicification.

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Variability of trace metals in coastal and estuary: distribution, profile, and drivers


  • Trace-metal distributions in ocean systems have been classified into conservative-, nutrient-, and scavenged-type profiles.
  • Several variability drivers of trace metals may be involved in differences of metal distribution in particular ocean systems.
  • The availability of dissolved trace metals is likely to increase in the future due to increasing SST, decreasing pH or decreasing DO.
  • Suspended matter which generally derives from terrestrial input plays a role in determining the fate of trace metals
  • The study findings improve our understanding of trace-metal characteristics in the marine environment.


Ongoing global changes such as increasing sea-surface temperatures, decreasing acidity levels, and expanding oxygen-minimum zone may impact on the biogeochemical cycles of trace metals in ocean systems. Each trace metal has unique characteristics and a distinctive distribution pattern controlled by chemical, biological, and physical processes that occur in ocean systems. The correlations of variability drivers in trace metals are interesting topics for investigation. Following up on ocean research in the coastal and estuary area, we specifically review the distribution of trace metals in seawater and suspended and surface sediment. The marginal seas usually feature significant terrestrial inputs accompanied by several active water-mass currents. The purpose of this review is to provide an overview of variability related to trace-metal distribution in coastal and estuary systems and to specifically describe the distribution, profile and drivers that affect trace metals variability.

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Integrative assessment of sediments affected by CO2 enrichment: a case study in the Bay of Santos—SP, Brazil

CO2 enrichment in the marine environment caused by leakages from carbon capture and storage technologies may occur over operational procedures. An integrated approach using weight-of-evidence was applied to assess the environmental risk associated with the acidification caused by CO2 enrichment in coastal sediments from Santos (Brazil). Chemical analyses (metal(loid)s and organic contaminant (e.g., hydrocarbons), toxicity tests (amphipods mortality, sea-urchin embryo-larval development) and macro-benthic community structure alteration assessment were performed with different acidified scenarios (pH 8.0–6.0) for two stations with different contamination degrees. These lines of evidence were statistically analyzed and integrated (multivariate analysis and ANOVA). Results of toxicity showed significant chronic effects starting at pH 7.0 while acute effects were observed starting at pH 6.5. The macro-benthic community integrity showed significant differences for all treatments at the Piaçaguera channel station, considered to be moderately contaminated. Results from the multivariate analysis correlated toxic effects and increase in the mobility of some elements with acidification. Also, the biological indexes were correlated with concentrations of dissolved Zn in seawater. The pH of 6.0 was extremely toxic for marine life due to its high acidification and metal bioavailability. The approach herein identified and discriminated the origin of the degradation caused by the acidification related to the enrichment of CO2.

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Equilibrium calculations of iron speciation and apparent iron solubility in the Celtic Sea at ambient seawater pH using the NICA-Donnan model

We used a combined ion pairing – organic matter speciation model (NICA-Donnan) to predict the organic complexation of iron (Fe) at ambient pH and temperature in the Celtic Sea. We optimized our model by direct comparison with Fe speciation determined by Adsorptive Cathodic Stripping Voltammetry using the added Fe-binding ligand 1-nitroso-2-naphthol (HNN) in the presence and absence of natural organic matter. We compared determined Fe speciation with simulated titrations obtained via application of the NICA-Donnan model with four different NICA parameter sets representing a range of binding site strengths and heterogeneities. We tested the assumption that binding sites scale to dissolved organic carbon (DOC) concentrations in marine waters. We found that a constant low DOC concentration resulted in an improved fit of our titration data to the simulated titrations, suggesting that inputs of autochthonous marine DOM may not increase the heterogeneity or concentrations of Fe binding sites. Using the optimal parameter set, we calculated pFe(III)´ (−log(∑Fe(OH)i3−i)) and apparent Fe(III) solubility (SFe(III)app) at ambient pH and temperature in the water column of the Celtic Sea. SFe(III)app was defined as the sum of aqueous inorganic Fe(III) species and Fe(III) bound to DOM formed at a free Fe (Fe3+) concentration equal to the limiting solubility of Fe hydroxide (Fe(OH)3(s)). SFe(III)app was within range of the determined dissolved Fe concentrations observed after winter mixing on the shelf and in waters >1500 m depth at our most offshore stations. Our study supports the hypothesis that the ocean dissolved Fe inventory is controlled by the interplay between Fe solubility and Fe binding by organic matter, although the overall number of metal binding sites in the marine environment may not be directly scalable to DOC concentrations.

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Prospective life cycle assessment of metal commodities obtained from deep-sea polymetallic nodules


  • A Life Cycle Assessment of commodities from polymetallic nodules was performed.
  • Climate change, photochemical oxidant formation and acidification were considered.
  • The main hotspots are at onshore processes (e.g., hydrometallurgical processing).
  • 38% reduction in carbon footprint can be observed, when comparing to terrestrial.
  • Deep-sea operations may contribute significantly to the growing demand of metals.


Sustainable metal supply will be essential to achieve climate and sustainability goals (e.g., Paris agreement), for instance by providing the necessary raw materials for renewable energy infrastructure systems. The potential exploitation of mineral resources from the deep sea (e.g., polymetallic nodules) can play a major role in this supply. A holistic environmental analysis is needed, in order to consider the entire value chain of the products obtained out of deep-sea exploitation. Therefore, the objective of this study was to perform a prospective life cycle assessment (LCA) of deep-sea-sourced commodities and compare it to equivalent products obtained from terrestrial mining. It considered as reference flow one tonne of (dry) nodules, using a cradle-to-gate approach up to the final metal commodities, analyzing the delivery to the market of 10.5 kg of copper, 12.8 kg of nickel, 2.3 kg of cobalt and 311.3 kg of ferromanganese. Three environmental impact categories were analyzed, i.e., climate change, acidification and photochemical oxidant formation. Overall, onshore activities (e.g., hydrometallurgical processing) are the main hotspots for environmental impacts of metals sourced from the deep sea; offshore activities play a minor role in the value chain. While photochemical oxidant formation impacts would be similar to terrestrial alternatives, the deep-sea-sourced commodities can bring environmental gains in the order of 38% for climate change and up to 72% for acidification. As this study shows, a strategic selection of the location for onshore processing of the polymetallic nodules is key to target cleaner production, not only because of the distance from the nodules site, but especially because of the available energy mix. The results should be interpreted with care, though, due to intrinsic limitations of the LCA study, e.g., the prospective nature of this study, the limited access to terrestrial mining data, amongst others. Nonetheless, regardless the limitations a prospective LCA imposes, this study highlights some important potential benefits that commodities from deep-sea polymetallic nodules can bring to society with respect to three important environmental impacts.

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Effect of increased CO2 on iron-light-CO2 co-limitation of growth in a marine diatom

Light affects iron (Fe) growth requirements in marine phytoplankton while CO2 can influence energy allocation and light sensitivity. Therefore, ongoing increases in seawater CO2 concentrations could impact the growth of Fe- and light-limited phytoplankton. In this study, Phaeodactylum tricornutum was used as a model diatom to examine the interactive effects of Fe, light, and CO2 on photosynthesis, growth, and protein expression in marine phytoplankton. Low concentration of biologically available inorganic iron (Fe′) and low-light intensity decreased specific rates of carbon (C)-fixation and growth, and the two together had an even greater effect, indicating a co-limitation. Increased partial pressure of CO2 from its current value (400 μatm) to 750 μatm had no effect at growth sufficient levels of Fe and light, but increased C-fixation and growth rate under Fe or light limitation, and had an even greater effect in Fe and light co-limited cells. The results suggest that ongoing increases in CO2 may increase C-fixation rates in Fe- and light-limited and co-limited regions, which cover at least 30% of the ocean. Measurements of photosynthetic proteins in photosystems II and I, and transcripts of proteins involved in CO2 concentrating mechanisms (CCMs), photorespiration, and antioxidant protection, suggest that the benefit of increased CO2 in the Fe- and light-limited cells was from a downregulation of CCMs and resultant decreased demands for energy supplied from photosynthesis, and from decreased rates of photorespiration, which consumes photosynthetically produced ATP and NADPH. A decrease in oxidative stress with increased CO2 also contributed.

Continue reading ‘Effect of increased CO2 on iron-light-CO2 co-limitation of growth in a marine diatom’

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