Changes In Seawater Chemistry Research Articles

Deccan volcanism induced high-stress environment during the Cretaceous–Paleogene transition at Zumaia, Spain: Evidence from magnetic, mineralogical and biostratigraphic records

We conducted detailed rock magnetic, mineralogical and geochemical (mercury) analyses spanning the Cretaceous–Paleogene boundary (KPB) at Zumaia, Spain, to unravel the signature of Deccan-induced climate and environmental changes in the marine sedimentary record. Our biostratigraphic results show that Zumaia is not complete, and lacks the typical boundary clay, zone P0 and the base of zone P1a(1) in the basal Danian. Presence of an unusual ∼1m-thick interval spanning the KPB is characterized by very low detrital magnetite and magnetosome (biogenic magnetite) contents and by the occurrence of akaganéite, a very rare mineral on Earth in oxidizing, acidic and hyper-chlorinated environments compatible with volcanic settings. These benchmarks correlate with higher abundance of the opportunist Guembelitria cretacea species. Detrital magnetite depletion is not linked to significant lithological changes, suggesting that iron oxide dissolution by acidification is the most probable explanation. The concomitant decrease in magnetosomes, produced by magnetotactic bacteria at the anoxic–oxic boundary, is interpreted as the result of changes in seawater chemistry induced by surficial ocean acidification. Mercury peaks up to 20–50 ppb are common during the last 100 kyr of the Maastrichtian (zone CF1) but only one significant anomaly is present in the early Danian, which is likely due to the missing interval. Absence of correlation between mercury content (R2 = 0.009) and total organic carbon (R2 = 0.006) suggest that the former originated from the Deccan Traps eruptions. No clear relation between the stratigraphic position of the mercury peaks and the magnetite-depleted interval is observed, although the frequency of the mercury peaks tends to increase close to the KPg boundary. In contrast to Bidart (France) and Gubbio (Italy), where magnetite depletion and akaganéite feature within a ∼50cm-thick interval located 5 cm below the KPg boundary, the same benchmarks are observed in a 1m-thick interval encompassing the KPg boundary at Zumaia. Results reinforce the synchronism of the major eruptions of the Deccan Traps Magmatic Province with the Cretaceous–Paleogene (KPg) mass extinction and provide new clues to better correlate the Deccan imprint of the global sedimentary record.

Controls over δ44/40Ca and Sr/Ca variations in coccoliths: New perspectives from laboratory cultures and cellular models

Coccoliths comprise a major fraction of the global carbonate sink. Therefore, changes in coccolithophores' Ca isotopic fractionation could affect seawater Ca isotopic composition, affecting interpretations of the global Ca cycle and related changes in seawater chemistry and climate. Despite this, a quantitative interpretation of coccolith Ca isotopic fractionation and a clear understanding of the mechanisms driving it are not yet available. Here, we address this gap in knowledge by developing a simple model (CaSri–Co) to track coccolith Ca isotopic fractionation during cellular Ca uptake and allocation to calcification. We then apply it to published and new δ44/40Ca and Sr/Ca data of cultured coccolithophores of the species Emiliania huxleyi and Gephyrocapsa oceanica. We identify changes in calcification rates, Ca retention efficiency and solvation–desolvation rates as major drivers of the Ca isotopic fractionation and Sr/Ca variations observed in cultures. Higher calcification rates, higher Ca retention efficiencies and lower solvation–desolvation rates increase both coccolith Ca isotopic fractionation and Sr/Ca. Coccolith Ca isotopic fractionation is most sensitive to changes in solvation–desolvation rates. Changes in Ca retention efficiency may be a major driver of coccolith Sr/Ca variations in cultures. We suggest that substantial changes in the water structure strength caused by past changes in temperature could have induced significant changes in coccolithophores' Ca isotopic fractionation, potentially having some influence on seawater Ca isotopic composition. We also suggest a potential effect on Ca isotopic fractionation via modification of the solvation environment through cellular exudates, a hypothesis that remains to be tested.

Short-term CO2 exposure and temperature rise effects on metazoan meiofauna and free-living nematodes in sandy and muddy sediments: Results from a flume experiment

Global concern over increasing CO2 emissions, and the resultant CO2 driven temperature rises and changes in seawater chemistry, necessitates the advancement of understanding into how these changes will affect marine life now and in the future. Here we report on an experimental investigation into the effects of increased CO2 concentration and elevated temperature on sedimentary meiofaunal communities. Cohesive (muddy) and non-cohesive (sandy) sediments were collected from the Eden Estuary in St. Andrews, Scotland, UK, placed within a flume setup and exposed to 2 levels of CO2 concentration (380 and 750ppmv, current at the time of the experiment, and predicted CO2 concentration by 2100, respectively) and 2 temperature levels (12°C and 16°C, current in-situ and predicted temperature by 2100, respectively). We investigated the metazoan meiofauna and nematode communities before and after 28days of exposure under these experimental conditions. The most determinative factor for abundance, diversity and community structure of meiofauna and nematodes was sediment type: on all levels, communities were significantly different between sand and mud sediments which agrees with what is generally known about the influence of sediment structure on meiofaunal organisms. Few CO2 and temperature effects were observed, suggesting that meiofauna and nematodes are generally much less responsive than, for instance, microbial communities and macrofauna to these environmental changes in estuarine environments, where organisms are naturally exposed to a fluctuating environment. This was corroborated by the observed effects related to the different seasons in which the samples were taken from the field to run the experiment. After 28days, meiofauna and nematode communities in muddy sediments showed a greater response to increased CO2 concentration and temperature rise than in sandy sediments. However, further study is needed to investigate the underlying mechanisms and meiofauna species-specific resilience and responses to ocean acidification and warming, and their interactions with other biota, to understand what such changes may mean for meiofauna communities and the ecosystem processes and functions they contribute to.

Ocean acidification impacts spine integrity but not regenerative capacity of spines and tube feet in adult sea urchins.

Increasing atmospheric carbon dioxide (CO2) has resulted in a change in seawater chemistry and lowering of pH, referred to as ocean acidification. Understanding how different organisms and processes respond to ocean acidification is vital to predict how marine ecosystems will be altered under future scenarios of continued environmental change. Regenerative processes involving biomineralization in marine calcifiers such as sea urchins are predicted to be especially vulnerable. In this study, the effect of ocean acidification on regeneration of external appendages (spines and tube feet) was investigated in the sea urchin Lytechinus variegatus exposed to ambient (546 µatm), intermediate (1027 µatm) and high (1841 µatm) partial pressure of CO2 (pCO2) for eight weeks. The rate of regeneration was maintained in spines and tube feet throughout two periods of amputation and regrowth under conditions of elevated pCO2. Increased expression of several biomineralization-related genes indicated molecular compensatory mechanisms; however, the structural integrity of both regenerating and homeostatic spines was compromised in high pCO2 conditions. Indicators of physiological fitness (righting response, growth rate, coelomocyte concentration and composition) were not affected by increasing pCO2, but compromised spine integrity is likely to have negative consequences for defence capabilities and therefore survival of these ecologically and economically important organisms.

Interactive Effects of Ocean Acidification and Warming on Growth, Fitness and Survival of the Cold-Water Coral Lophelia pertusa under Different Food Availabilities

Cold-water corals are important bioengineers that provide structural habitat for a diverse species community. About 70% of the presently known scleractinian cold-water corals are expected to be exposed to corrosive waters by the end of this century due to ocean acidification. At the same time, the corals will experience a steady warming of their environment. Studies on the sensitivity of cold-water corals to climate change mainly concentrated on single stressors in short-term incubation approaches, thus not accounting for possible long-term acclimatisation and the interactive effects of multiple stressors. Besides, preceding studies did not test for possible compensatory effects of a change in food availability. In this study a multifactorial long-term experiment (6 months) was conducted with end-of-the-century scenarios of elevated pCO2 and temperature levels in order to examine the acclimatisation potential of the cosmopolitan cold-water coral Lophelia pertusa to future climate change related threats. For the first time multiple ocean change impacts including the role of the nutritional status were tested on L. pertusa with regard to growth, “fitness,” and survival. Our results show that while L. pertusa is capable of calcifying under elevated CO2 and temperature, its condition (fitness) is more strongly influenced by food availability rather than changes in seawater chemistry. Whereas growth rates increased at elevated temperature (+4°C), they decreased under elevated CO2 concentrations (~800 μatm). No difference in net growth was detected when corals were exposed to the combination of increased CO2 and temperature compared to ambient conditions. A 10-fold higher food supply stimulated growth under elevated temperature, which was not observed in the combined treatment. This indicates that increased food supply does not compensate for adverse effects of ocean acidification and underlines the importance of considering the nutritional status in studies investigating organism responses under environmental changes.

Experimental evidence that ooid size reflects a dynamic equilibrium between rapid precipitation and abrasion rates

Ooids are enigmatic concentrically coated carbonate sand grains that reflect a fundamental mode of carbonate sedimentation and inorganic product of the carbon cycle—trends in their composition and size are thought to record changes in seawater chemistry over Earth history. Substantial debate persists concerning the roles of physical, chemical, and microbial processes in their growth, including whether carbonate precipitation on ooid surfaces is driven by seawater chemistry or microbial activity, and what role—if any—sediment transport and abrasion play. To test these ideas, we developed an approach to study ooids in the laboratory employing sediment transport stages and seawater chemistry similar to natural environments. Ooid abrasion and precipitation rates in the experiments were four orders of magnitude faster than radiocarbon net growth rates of natural ooids, implying that ooids approach a stable size representing a dynamic equilibrium between precipitation and abrasion. Results demonstrate that the physical environment is as important as seawater chemistry in controlling ooid growth and, more generally, that sediment transport plays a significant role in chemical sedimentary systems.

Relationship between water and aragonite barium concentrations in aquaria reared juvenile corals

Coral barium to calcium (Ba/Ca) ratios have been used to reconstruct records of upwelling, river and groundwater discharge, and sediment and dust input to the coastal ocean. However, this proxy has not yet been explicitly tested to determine if Ba inclusion in the coral skeleton is directly proportional to seawater Ba concentration and to further determine how additional factors such as temperature and calcification rate control coral Ba/Ca ratios. We measured the inclusion of Ba within aquaria reared juvenile corals (Favia fragum) at three temperatures (∼27.7, 24.6 and 22.5°C) and three seawater Ba concentrations (73, 230 and 450nmolkg−1). Coral polyps were settled on tiles conditioned with encrusting coralline algae, which complicated chemical analysis of the coral skeletal material grown during the aquaria experiments. We utilized Sr/Ca ratios of encrusting coralline algae (as low as 3.4mmolmol−1) to correct coral Ba/Ca for this contamination, which was determined to be 26±11% using a two end member mixing model. Notably, there was a large range in Ba/Ca across all treatments, however, we found that Ba inclusion was linear across the full concentration range. The temperature sensitivity of the distribution coefficient is within the range of previously reported values. Finally, calcification rate, which displayed large variability, was not correlated to the distribution coefficient. The observed temperature dependence predicts a change in coral Ba/Ca ratios of 1.1μmolmol−1 from 20 to 28°C for typical coastal ocean Ba concentrations of 50nmolkg−1. Given the linear uptake of Ba by corals observed in this study, coral proxy records that demonstrate peaks of 10–25μmolmol−1 would require coastal seawater Ba of between 60 and 145nmolkg−1. Further validation of the coral Ba/Ca proxy requires evaluation of changes in seawater chemistry associated with the environmental perturbation recorded by the coral as well as verification of these results for Porites species, which are widely used in paleo reconstructions.

Demise of Ediacaran dolomitic seas marks widespread biomineralization on the Siberian Platform

Abstract The trigger for biomineralization of metazoans in the terminal Ediacaran, ca. 550 Ma, has been suggested to be the rise of oxygenation or an increase in seawater Ca concentration, but geochemical and fossil data have not been fully integrated to demonstrate cause and effect. Here we combine the record of macrofossils with early marine carbonate cement distribution within a relative depth framework for terminal Ediacaran to Cambrian successions on the eastern Siberian Platform, Russia, to interrogate the evolution of seawater chemistry and biotic response. Prior to ca. 545 Ma, the presence of early marine ferroan dolomite cement suggests dominantly ferruginous anoxic “aragonite-dolomite seas”, with a very shallow oxic chemocline that supported mainly soft-bodied macrobiota. After ca. 545 Ma, marine cements changed to aragonite and/or high-Mg calcite, and this coincides with the appearance of widespread aragonite and high-Mg calcite skeletal metazoans, suggesting a profound change in seawater chemistry to “aragonite seas” with a deeper chemocline. By early Cambrian Stage 3, the first marine low-Mg calcite cements appear, coincident with the first low-Mg calcite metazoan skeletons, suggesting a further shift to “calcite seas”. We suggest that this evolution of seawater chemistry was caused by enhanced continental denudation that increased the input of Ca into oceans so progressively lowering Mg/Ca, which, combined with more widespread oxic conditions, facilitated the rise of skeletal animals and in turn influenced the evolution of skeletal mineralogy.

Onset, development, and cessation of basal Early Triassic microbialites (BETM) in the Nanpanjiang pull-apart Basin, South China Block

New investigations in the Nanpanjiang Basin indicate that the onset of the iconic microbialites associated with the Paleozoic-Mesozoic boundary was Early Triassic in age. Bathymetry (water agitation, oxygenation, light penetration) and clastic load are shown to have exerted a direct control on the growth of microbialites. Carbonate supersaturation is also required for the deposition of the microbialites. Bathymetric control is further corroborated by the inheritance of the topography of a latest Permian pull-apart basin into Early Triassic times, with a distribution of basal Early Triassic microbialites (BETM) restricted to uplifted blocks and the accumulation of carbonaceous black shales in adjacent troughs. The geographically most extensive Nanpanjiang BETM bloomed on a large NW–SE trending uplifted block exceeding 12,000km2 (Luolou Platform) centered on northwestern Guangxi. Post-Triassic displacements along the Youjiang Fault obscure the paleogeographic relation of BETM exposed west of this fault.Triassic foraminifers occur in the basal most BETM episode, which is locally bracketed by high-energy grainstones made of reworked Permian foraminifers. Therefore, the Permian-Triassic boundary (PTB) is within the unconformity that separates the Late Permian Heshan Fm. from the basal most BETM. Where accommodation space was sufficient, up to five event surfaces are associated with the unconformity. Microfacies analysis supports chemical dissolution but did not reveal evidence for subaerial erosion, although intercalated grainstone made of Permian foraminifers indicate reworking. Chemical dissolution and mechanical erosion both conceivably contributed to the genesis of the unconformity. The upward shift from tabulated to domical microbial build-ups is accompanied by accumulation of coquinoid lenses between domes, which indicates deepening of the Luolou Platform BETM. The main drowning resulting from both regional tectonic subsidence and a global sea-level rise led to the cessation of the BETM that were buried under predominant fine siliciclastics. Any concomitant change in sea water chemistry appears unlikely.

Effect of ocean acidification on the structure and fatty acid composition of a natural plankton community in the Baltic Sea

Abstract. Increasing atmospheric carbon dioxide (CO2) is changing seawater chemistry towards reduced pH, which affects various properties of marine organisms. Coastal and brackish water communities are expected to be less affected by ocean acidification (OA) as these communities are typically adapted to high fluctuations in CO2 and pH. Here we investigate the response of a coastal brackish water plankton community to increasing CO2 levels as projected for the coming decades and the end of this century in terms of community and biochemical fatty acid (FA) composition. A Baltic Sea plankton community was enclosed in a set of offshore mesocosms and subjected to a CO2 gradient ranging from natural concentrations ( ∼ 347 µatm fCO2) up to values projected for the year 2100 ( ∼ 1333 µatm fCO2). We show that the phytoplankton community composition was resilient to CO2 and did not diverge between the treatments. Seston FA composition was influenced by community composition, which in turn was driven by silicate and phosphate limitation in the mesocosms and showed no difference between the CO2 treatments. These results suggest that CO2 effects are dampened in coastal communities that already experience high natural fluctuations in pCO2. Although this coastal plankton community was tolerant of high pCO2 levels, hypoxia and CO2 uptake by the sea can aggravate acidification and may lead to pH changes outside the currently experienced range for coastal organisms.

Seawater residence times of some elements of geochemical interest and the salinity of the oceans

Residence times of several dissolved chemical elements in seawater are revisited on the basis of updated river and groundwater chemical fluxes. A classification of the considered elements of geochemical interest (B, C, N, Na, Mg, Si, P, S, Cl, Ca, K, Li and Sr) is proposed accordingly to the solubility products of their main host minerals as well as their biological reactivity in the seawater column. The origin of seawater salinity is also discussed through both processes of early mantle degassing and continental growth. Finally, changes in seawater chemistry as well as in the total concentration of dissolved elements are investigated in the light of geological and biological processes such as continental erosion, hydrothermal activity, closure and opening of marine basins, climate forcing, marine productivity, and the Devonian rising of vascular plants. Taking into account groundwater fluxes and chemistry, and a revised lower mass of the oceans, residence times of chemical elements in the ocean have been calculated lower than commonly accepted in the literature for several decades. Both changes in salinity and chemistry of seawater took place throughout the Earth’s history at the m.y. timescale. Continents did not emerge before 3 Gy ago, thus excluding the weathering of their surfaces and the transport of alkali and calc-alkali elements by the rivers to the oceans. The only available sources, albeit to a limited extent, were possibly volcanic islands. As sodium is the main cation responsible for seawater salinity, calcium could have contributed to the charge balance of seawater to preclude the development of highly acidic waters. Indeed, the high-temperature hydrothermal alteration of oceanic crust is an important source of calcium that could have accumulated in seawater in the absence of its removal by calcifying organisms. It means that the earliest oceans could have been ‘CaCl2 dominated oceans’ instead of the ‘NaCl dominated oceans’ that prevailed during the Proterozoic and Phanerozoic.

Delayed euxinia in Paleoproterozoic intracontinental seas: Vital havens for the evolution of eukaryotes?

Increased flux of sulfate to the oceans in the aftermath of the Great Oxidation Event (GOE) ∼2.4billionyears ago (Ga) caused major changes in seawater chemistry, which eventually contributed to the cessation of iron formation deposition ∼1.8Ga. It is generally accepted that this engendered heterogeneous stratified redox conditions, with anoxic and sulfidic (euxinic) conditions in shallow open-marine environments and anoxic ferruginous conditions in deeper environments. However, the redox evolution of intracontinental marine basins following the cessation of iron formation deposition remains poorly understood.Here, we report contrasting paleoredox conditions in two shale units of the lower McArthur Basin, northern Australia, soon after the cessation of iron formation deposition ∼1.84Ga. Our data shows that the ∼1.78Ga McDermott Formation was deposited in a sulfur-limited, anoxic shallow-marine environment, whereas the younger ∼1.73Ga Wollogorang Formation was deposited in a euxinic shallow-marine environment. This implies a delay in the development of euxinia in a shallow intracontinental basin following the onset of euxinia in the open marine realm. Since bioessential metals are sequestered by pyrite deposition under euxinic conditions, protracted low-sulfidic conditions in 1.78Ga intracontinental shallow environments could have provided vital niches for nitrogen-fixing prokaryotes and eukaryotes. Thus the ability for localized Paleoproterozoic intracontinental basins to remain non-euxinic after the onset of euxinia in shallow open-marine shelves highlights the importance of intracontinental environments to the evolution and diversification of microbial life, perhaps throughout the wider Proterozoic.

Revisiting ocean carbon sequestration by direct injection: a global carbon budget perspective

Abstract. In this study we look beyond the previously studied effects of oceanic CO2 injections on atmospheric and oceanic reservoirs and also account for carbon cycle and climate feedbacks between the atmosphere and the terrestrial biosphere. Considering these additional feedbacks is important since backfluxes from the terrestrial biosphere to the atmosphere in response to reducing atmospheric CO2 can further offset the targeted reduction. To quantify these dynamics we use an Earth system model of intermediate complexity to simulate direct injection of CO2 into the deep ocean as a means of emissions mitigation during a high CO2 emission scenario. In three sets of experiments with different injection depths, we simulate a 100-year injection period of a total of 70 GtC and follow global carbon cycle dynamics over another 900 years. In additional parameter perturbation runs, we varied the default terrestrial photosynthesis CO2 fertilization parameterization by ±50 % in order to test the sensitivity of this uncertain carbon cycle feedback to the targeted atmospheric carbon reduction through direct CO2 injections. Simulated seawater chemistry changes and marine carbon storage effectiveness are similar to previous studies. As expected, by the end of the injection period avoided emissions fall short of the targeted 70 GtC by 16–30 % as a result of carbon cycle feedbacks and backfluxes in both land and ocean reservoirs. The target emissions reduction in the parameter perturbation simulations is about 0.2 and 2 % more at the end of the injection period and about 9 % less to 1 % more at the end of the simulations when compared to the unperturbed injection runs. An unexpected feature is the effect of the model's internal variability of deep-water formation in the Southern Ocean, which, in some model runs, causes additional oceanic carbon uptake after injection termination relative to a control run without injection and therefore with slightly different atmospheric CO2 and climate. These results of a model that has very low internal climate variability illustrate that the attribution of carbon fluxes and accounting for injected CO2 may be very challenging in the real climate system with its much larger internal variability.

Diagenesis of echinoderm skeletons: Constraints on paleoseawater Mg/Ca reconstructions

One of the most profound environmental changes thought to be reflected in chemical composition of numerous geological archives is Mg/Ca ratio of the seawater, which has varied dramatically throughout the Phanerozoic. Echinoderms that today typically form high magnesium calcite skeletons are increasingly being utilized as a proxy for interpreting secular changes in seawater chemistry. However, accurate characterization of the diagenetic changes of their metastable high magnesium calcite skeletons is a prerequisite for assessing their original, major-element geochemical composition. Here we expand the existing models of diagenesis of echinoderm skeleton by integration of various analytical methods that up to now rarely have been used to assess the diagenetic changes of fossil echinoderms. We validated the preservation of a suite of differently preserved echinoderm ossicles, mostly crinoids, ranging in age from the Cambrian through Recent. In 13 of 99 fossil echinoderm ossicles we found well-preserved porous microstructure (stereom), non-luminescent behaviour or blotchy dark color in cathodoluminescence, and distinct nanostructural features (layered and nanocomposite structure). Moreover, in representatives of such preserved samples, distribution of sulphates associated with organic matter is identical to those in Recent echinoderms. Only such ossicles, despite of local micrometer-scale diagenetic changes, were herein considered well-preserved, retaining their original major-element skeletal composition. By contrast, majority of samples show transformation to the stable low magnesium calcite that leads to obliteration of the primary geochemical and micro/nanostructural features and is accompanied with increase in cathodoluminescence emission intensity. Using only well-preserved fossil echinoderm samples, we found purely random variation in Mg/Ca in echinoderm skeletons through the observed time series; any periodicities in echinoderm skeletal Mg/Ca ratio which might be related to the secular transitions in calcite and aragonite seas were not confirmed. These findings suggest that, in contrast to some groups of organisms with relatively weak control over their biomineralization (such as algae, sponges, and bryozoans), in which polymorph mineralogies consistently changed according to the seawater type, application of fossil echinoderms, in particular crinoids, to seawater Mg/Ca reconstructions is unreliable. These data emphasize a key-role of physiological factors (the so-called vital effects) in echinoderm biomineralization.

Evaluating chemical signatures in a coastal upwelling region to reconstruct water mass associations of settlement-stage rockfishes

Vol. 550: 191–206, 2016 doi: 10.3354/meps11704 MARINE ECOLOGY PROGRESS SERIES Mar Ecol Prog Ser Published May 25 O PEN A CCESS Evaluating chemical signatures in a coastal upwelling region to reconstruct water mass associations of settlement-stage rockfishes Sarah G. Wheeler 1, *, Ann D. Russell 2 , Jennifer S. Fehrenbacher 2 , Steven G. Morgan 3 Graduate Group in Ecology at the University of California at Davis and San Diego State University, 5500 Campanile Dr, San Diego, California 92184-4614, USA University of California, Davis, One Shields Ave, Davis, California 95616, USA Bodega Marine Laboratory, University of California, Davis, 2099 Westside Dr, Bodega Bay, California 94923-0247, USA ABSTRACT: Characterizing the behavior of larvae prior to settlement is integral to understanding population dynamics because coastal oceanography may facilitate or limit settlement. Otolith microchemistry can be used to determine patterns of fish movement, although there is a limited understanding of how this tool can be applied in coastal marine systems. Our goal in this study was to evaluate the application of otolith microchemistry to characterize water mass associations of settlement-stage marine fish in a coastal upwelling region using a 3-step approach. First, we characterized seawater chemistry of coastal water mass types across multiple years, finding differ- ences in the chemical signatures of strong upwelling, weak upwelling, and relaxation events. Sec- ond, we experimentally determined the effect of temperature on the partitioning of trace elements in otoliths for 2 rockfishes (Sebastes spp.) to find that the effect of temperature on otolith partition coefficients was element- and species-specific. Finally, we compared coeval changes in seawater and otolith chemistry of settlement-stage rockfishes that were exposed to naturally variable con- ditions over an upwelling-relaxation cycle. We subsequently evaluate whether laser ablation inductively coupled plasma mass spectrometry effectively measures otolith chemistry over eco- logically relevant time scales. We discovered that elemental concentrations in otoliths respond rapidly to changes in seawater chemistry and reflect equivalent proportional changes. This study provides evidence that elemental signatures are valuable tools for reconstructing larval histories of marine fish in coastal upwelling regions. KEY WORDS: Barium · Laser ablation · Inductively coupled plasma mass spectrometry · ICP-MS · Otolith · Seawater INTRODUCTION The elemental compositions of seawater and fish otoliths have numerous applications to ecological research and fisheries management (Campana 1999, Campana & Thorrold 2001, Thorrold et al. 2007, Els- don et al. 2008). Otolith chemistry research capital- izes on differences in the chemical composition of environments to reconstruct fish movements, and heterogeneity in trace elements in freshwater and *Corresponding author: sarahgracewheeler@gmail.com estuarine environments has led to a substantial body of research in these systems (Campana & Thorrold 2001, Gillanders 2005, Elsdon & Gillanders 2006). The validation and application of chemical tags in marine fishes is relatively understudied (Sturrock et al. 2012). However, chemical gradients between near shore and offshore environments and water masses have revealed fish cross-shelf movements (Kingsford et al. 2009), larval dispersal or migrations (Swearer et al. 1999, Hamilton et al. 2008), and settle- © The authors 2016. Open Access under Creative Commons by Attribution Licence. Use, distribution and reproduction are un - restricted. Authors and original publication must be credited. Publisher: Inter-Research · www.int-res.com

Direct and indirect effects of near-future pCO2 levels on zooplankton dynamics

Ocean acidification has direct physiological effects on organisms, for example by dissolving the calcium carbonate structures of calcifying species. However, non-calcifiers may also be affected by changes in seawater chemistry. To disentangle the direct and indirect effects of ocean acidification on zooplankton growth, we undertook a study with two model organisms. Specifically, we investigated the individual effects of short-term exposure to high and low seawater pCO2, and different phytoplankton qualities as a result of different CO2 incubations on the growth of a heterotrophic dinoflagellate (Oxyrrhis marina) and a copepod species (Acartia tonsa). It was observed previously that higher CO2 concentrations can decrease phytoplankton food quality in terms of carbon:nutrient ratios. We therefore expected both seawater pCO2 (pH) and phytoplankton quality to result in decreased zooplankton growth. Although we expected lowest growth rates for all zooplankton under high seawater pCO2 and low algal quality, we found that direct pH effects on consumers seem to be of lesser importance than the associated decrease in algal quality. The decrease in the quality of primary producers under high pCO2 conditions negatively affected zooplankton growth, which may lead to lower availability of food for the next trophic level and thus potentially affect the recruitment of higher trophic levels.

Applying organized scepticism to ocean acidification research

Abstract “Ocean acidification” (OA), a change in seawater chemistry driven by increased uptake of atmospheric CO2 by the oceans, has probably been the most-studied single topic in marine science in recent times. The majority of the literature on OA report negative effects of CO2 on organisms and conclude that OA will be detrimental to marine ecosystems. As is true across all of science, studies that report no effect of OA are typically more difficult to publish. Further, the mechanisms underlying the biological and ecological effects of OA have received little attention in most organismal groups, and some of the key mechanisms (e.g. calcification) are still incompletely understood. For these reasons, the ICES Journal of Marine Science solicited contributions to this special issue. In this introduction, I present a brief overview of the history of research on OA, call for a heightened level of organized (academic) scepticism to be applied to the body of work on OA, and briefly present the 44 contributions that appear in this theme issue. OA research has clearly matured, and is continuing to do so. We hope that our readership will find that, when taken together, the articles that appear herein do indeed move us “Towards a broader perspective on ocean acidification research”.

Community-Level Actions that Can Address Ocean Acidification

Ocean acidification has led to detectable changes in seawater chemistry around the world, which are associated with reduced growth and survival of many species. Acute ocean acidification “events” in the Pacific Northwest United States have jeopardized the $270 million, 3,200 jobs/year shellfish aquaculture industry in Washington State, and this has contributed to the state’s broad-based, legislatively driven response to ocean acidification. Even though impacts from ocean acidification have yet to be felt in many locations, states and regions are beginning to take action on the issue. In this paper, we present an array of actions that can be undertaken by communities or regions to address ocean acidification. The actions can be coupled, completed one at a time, or aligned with other environmental initiatives, and they can be tailored to the prevailing political or economic environment. We review which have been used by different U.S. states and identify common themes and popular choices. We close by suggesting combinations of conditions and clusters of activities that seem to promote rapid and sustained action. Cutting atmospheric carbon dioxide levels internationally is still the most comprehensive way to address ocean acidification, but this analysis shows that productive actions can still be taken at smaller scales to help marine resource-dependent communities adapt to existing ocean acidification and prepare for possible future impacts.

Mollusc and brachiopod skeletal hard parts: Intricate archives of their marine environment

AbstractThe biogenic carbonate hard parts of fossil bivalves, cephalopods and brachiopods are among the most widely exploited marine archives of Phanerozoic environmental and climate dynamics research. The advent of novel analytical tools has led many workers to explore non‐traditional geochemical and petrographic proxies, and work performed in neighbouring disciplines sheds light on the complex biomineralization strategies applied by these organisms. These considerations form a strong motivation to review the potential and problems related to the compilation and interpretation of proxy data from bivalve, cephalopod and brachiopod hard parts from the viewpoint of the sedimentologist and palaeoceanographer. Specific focus is on the complex biomineralization pathways of a given dissolved ion or food particle from its aquatic environment via the digestion and biomineralization apparatus in molluscs and brachiopods and its incorporation into a biomineral. Given that molluscs and brachiopods do not secrete their hard parts from seawater but rather from their mantle and periostracum, this paper evaluates differences and similarities of seawater versus that of body fluids. Cephalopods, bivalves and brachiopods exert a strong biological control on biomineralization that, to some degree, may buffer their shell geochemistry against secular changes in seawater chemistry. Disordered (amorphous) calcium carbonate precursor phases, later transformed to crystalline biominerals, may be significant in carbonate archive research due to expected geochemical offset relative to the direct precipitation of stable phases. A reasonable level of understanding of the related mechanisms is thus crucial for those who use these skeletal hard parts as archives of the palaeo‐environment. The impact of what is commonly referred to as ‘biological factors’ on the geochemistry of mollusc and brachiopod hard parts is explored for conventional isotope systems such as carbon, oxygen, strontium and traditionally used element to calcium ratios. In particular, the often used δ13Ccarbor the Mg/Ca and Sr/Ca elemental proxies are fraught with problems. An interesting new research field represents the analysis, calibration and application of non‐traditional proxies to mollusc and brachiopod hard parts. Examples include the carbonate clumped isotope (Δ47) approach and the analysis of the isotopes of Ca, Mg, N, Li, S or element to Ca ratios such as Li/Ca or B/Ca and rare earth elements. Based on considerations discussed here, a series of “do's and don'ts” in mollusc and brachiopod archive research are proposed and suggestions for future work are presented. In essence, the suggestions proposed here include experimental work (also field experiments) making use of recent archive organisms or, where possible, a reasonable recent analogue in the case of extinct groups. Moreover, the detailed understanding of the architecture of mollusc and brachiopod hard parts and their ultra‐structures must guide sampling strategies for geochemical analyses. Where feasible, a detailed understanding of the diagenetic pathways and the application of multi‐proxy and multi‐archive approaches should form the foundation of fossil carbonate archive research. The uncritical compilation of large data sets from various carbonate‐shelled organisms collected at different locations is not encouraged.

Secular changes of water chemistry in shallow-water Ediacaran ocean: Evidence from carbonates at Xiaofenghe, Three Gorges area, Yangtze Platform, South China

Ediacaran carbonates from the shallow-water section near Xiaofenghe (Three Gorges area, Hubei Province) on the Yangtze Platform, South China have been studied to understand post Marinoan changes in seawater chemistry. Major and trace element abundances and Sr–Nd isotopic compositions were obtained on acetic acid leachates of carbonate sediments from both the Doushantuo Formation (Members D1–D4) and the overlying Dengying Formation. C and O isotopic compositions of these samples were analysed using the phosphoric acid method. With the exception of the D1 cap carbonates (87Sr/86Sr=0.7088–0.713), most samples show low Mn/Sr and 87Sr/86Sr (0.7078 in D2–D4 and 0.709 in the Dengying Formation) similar to seawater values inferred from Ediacaran carbonates elsewhere. These data, together with the absence of a correlation between 87Sr/86Sr and δ18Ocarb, indicate minor diagenetic fluid overprinting. The initial ɛNd values of the carbonate leachates show a limited variation range from −4.3 to −7.5 with the highest values in D1. These data overlap with published data for Doushantuo sediments in South China, and possibly indicate an isotopically homogenous Nd source in the source area during most of the Ediacaran. D1 samples of cap carbonates display negative δ13Ccarb values of −2.0 to −3.6 (VPDB) and δ18Ocarb values ranging from −6.5 to −7.3 (VPDB), whereas the overlying D2 strata show positive δ13Ccarb values around 6. Carbonate rocks from D3 and D4 show a large variation of δ13Ccarb from −1.4 to 9.4, with some samples having unusually high δ13Ccarb values coupled to low TOC contents. Most carbonate leachates at the base of the Doushantuo display superchondritic Y/Ho and variable HREE enrichment (Pr/Yb<1), similar to modern seawater. This suggests a similar seawater chemistry as under modern open ocean conditions at the beginning of the Ediacaran, whereas lower Y/Ho in D3 correlate with flat REE+Y patterns, indicating a change to variable freshwater–seawater mixing and suppression of HREE/LREE fractionation as in modern estuaries. Carbonate rock samples from D4 are rich in clay minerals (up to 15%), of possible authigenic origin, such as nontronite and saponite. Formation of these clay minerals may only be possibly under extreme alkaline and saline conditions. The D4 carbonate leachates show the highest Y/Ho and lowest Ce/Ce* values and have unusually high δ13Ccarb values, which may also support the conditions of extreme shallowing and perhaps temporarily restricted basins that led to a rise in salinity due to high evaporation rates. Ce anomalies in carbonate leachates show strong variation throughout the profile. A secular increase of seawater oxygenation through the Ediacaran is not obvious. However the most pronounced Ce anomalies can be found in the upper Doushantuo (Ce/Ce* as low as 0.64).