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The valorization of tuna bones from industrial waste as a source of halal collagen presents a promising alternative to land-based collagen sources, such as bovine and porcine collagen. This study aims to evaluate the effect of extraction duration on the quality of collagen produced, focusing on yield, proximate composition (moisture, ash, fat, and protein content), functional group analysis, and collagen morphology. Collagen was extracted using the acid-soluble collagen (ASC) method, which involved pretreatment with NaOH to remove non-collagenous proteins, isopropyl alcohol to remove fat, and hydrolysis using acetic acid (CH3 COOH). The extraction durations tested were 24, 48, 72, and 96 hours, with a solution-to-sample ratio of 1:10 using 0.75 M CH3 COOH. Results showed that extraction for 96 hours yielded the highest collagen at 4.70%. FTIR analysis confirmed the presence of functional groups Amide I, II, III, A, and B, while SEM analysis revealed collagen morphology as small, rounded particles with fine pores and clearly visible collagen fibers. The moisture content decreased with longer extraction times, from 12.8% at 24 hours to 4.2% at 96 hours, while protein content increased, reaching 85.2% at 96 hours. The fat content was reduced to 0.2%, and ash content minimized to 0.8%. The proximate composition met the Indonesian National Standard (SNI 8076:2014), indicating that tuna bone collagen is a viable and good-quality source of halal collagen derived from industrial waste. [ABSTRACT FROM AUTHOR]

This study investigates the biogeochemical drivers of aragonite saturation state (ΩAr) in Baffin Bay, with a focus on the relatively undersampled west Greenland shelf. Our findings reveal two main depth‐dependant processes controlling the spatial distribution of ΩAr in Baffin Bay; within the upper 200 m, lower ΩAr coincides with increasing fractions of Arctic‐outflow waters, while below 200 m organic matter respiration decreases ΩAr. A temporal analysis comparing historical measurements from 1997 and 2004 with our 2019 data set reveals a significant decrease in the ΩAr of Arctic‐outflow waters, coinciding with reduced total alkalinity (TA). However, no discernible anthropogenic ocean acidification signal is identified. Significant Arctic water fractions (20%–40%) are found to be present on the west Greenland shelf, associated with reduced TA and ΩAr. A numerical modeling simulation incorporating a passive tracer demonstrates that periodic changes in wind direction lead to a switch from onshore to offshore Ekman transport along the Baffin Island current, transporting Arctic waters toward the west Greenland shelf. This challenges the conventional understanding of Baffin Bay's circulation and underscores the need for further research on the region's physical oceanography. Based on salinity‐TA relationships, surface waters on the west Greenland shelf have a significantly lower meteoric TA end‐member compared to waters of the Baffin Island Current in western Baffin Bay. The low eastern TA freshwater end‐member agrees well with recent glacial meltwater TA measurements, suggesting that glacial meltwater is the main freshwater source to surface waters on the west Greenland shelf. Plain Language Summary: Baffin Bay, with its complex interplay of Atlantic and Arctic water masses, is particularly susceptible to ongoing ocean acidification, mainly due to the presence of relatively fresh and low‐alkalinity Arctic waters. To date measurements of the inorganic carbon system in Baffin Bay have primarily been captured at key entrance and exit gateways, and on the Canadian side of the bay, leaving the west Greenland shelf relatively undersampled. This study provides a bay‐wide perspective of the main factors influencing aragonite saturation state (ΩAr; an indicator of ocean acidification impacts on marine calcifying organisms) across Baffin Bay, including the west Greenland shelf. We found that within the upper 200 m, low ΩAr coincides with increased presence of Arctic waters, while below 200 m the breakdown of organic matter decreases ΩAr. Historical data from 1997 and 2004 compared to our 2019 measurements show a significant drop in ΩAr of Arctic waters, but no clear signal of anthropogenic ocean acidification was observed. Surprisingly, the west Greenland shelf has significant fractions (20%–40%) of Arctic water. A numerical modeling simulation suggests that periodic changes in wind direction can transport Arctic waters from across Baffin Bay, challenging our traditional understanding of the bay's circulation. Key Points: Increased fractions of Arctic waters decrease aragonite saturation state (ΩAr) in the upper 200 m, while respiration does so below 200 mDecreased ΩAr of Arctic waters over the last two decades is associated with decreased alkalinity, not additional CO2Significant fractions of Arctic‐outflow waters on the west Greenland shelf challenges current knowledge of circulation in Baffin Bay [ABSTRACT FROM AUTHOR]

Grazing dynamics are one of the most poorly constrained components of the marine carbon cycle. We use inverse modeling to infer the distribution of community‐integrated zooplankton grazing dynamics based on the ability of different grazing formulations to recreate the satellite‐observed seasonal cycle in phytoplankton biomass after controlling for physical and bottom‐up controls. We find large spatial variability in the optimal community‐integrated half saturation concentration for grazing (K1/2), with lower (higher) values required in more oligotrophic (eutrophic) biomes. This leads to a strong sigmoidal relationship between observed mean‐annual phytoplankton biomass and the optimally inferred grazing parameterization. This relationship can be used to help constrain, validate and/or parameterize next‐generation biogeochemical models. Plain Language Summary: To improve predictions of the ocean's ability to feed a growing human population and buffer a changing climate, we need to improve our understanding of what happens to carbon once it is absorbed into the surface ocean. One of the largest knowledge gaps in marine carbon cycling is the role of zooplankton grazing. The rate at which zooplankton graze phytoplankton modifies the size and seasonal evolution of phytoplankton populations and in turn, the associated rates of net primary production at the base of the food‐web, secondary production of grazers (an indicator of fisheries potential) and export production (the biological sequestration of carbon). However, regional differences in grazing, which are difficult to measure outside of the laboratory, remain poorly constrained by observations and thus difficult to model. Here, we run a suite of model simulations, which each simulate grazing differently, then compare the results to infer which grazing dynamics best match observations. We find that there is dramatic spatial variability in how zooplankton, as a community, appear to be grazing and that this variability maps well onto observed phytoplankton abundance, suggesting that the type of zooplankton present may be determined by the amount of prey available. Key Points: Oligotrophic (eutrophic) biomes exhibit more (less) efficient community‐integrated grazing, characteristic of micro‐ (meso‐) zooplanktonWe find a strong link between observed mean‐annual phytoplankton biomass and the grazing dynamics required to recreate its seasonal cycleA type III functional response typically does a better job recreating observed phytoplankton seasonal cycles than a type II response [ABSTRACT FROM AUTHOR]

The ocean carbon reservoir controls atmospheric carbon dioxide (CO2) on millennial timescales. Radiocarbon (14C) anomalies in eastern North Pacific sediments suggest a significant release of geologic 14C‐free carbon at the end of the last ice age but without evidence of ocean acidification. Using inverse carbon cycle modeling optimized with reconstructed atmospheric CO2 and 14C/C, we develop first‐order constraints on geologic carbon and alkalinity release over the last 17.5 thousand years. We construct scenarios allowing the release of 850–2,400 Pg C, with a maximum release rate of 1.3 Pg C yr−1, all of which require an approximate equimolar alkalinity release. These neutralized carbon addition scenarios have minimal impacts on the simulated marine carbon cycle and atmospheric CO2, thereby demonstrating safe and effective ocean carbon storage. This deglacial phenomenon could serve as a natural analog to the successful implementation of gigaton‐scale ocean alkalinity enhancement, a promising marine carbon dioxide removal method. Plain Language Summary: The ocean is the largest carbon reservoir on Earth's surface and, as such, it controls the concentration of the greenhouse gas carbon dioxide (CO2) in the atmosphere over long time periods. When CO2 was rising at the end of the last ice age, marine sediment evidence indicates a regional carbon release into the ocean, due to a distinct carbon isotope fingerprint left behind. Using a carbon cycle model and atmospheric data, we simulated different geologic carbon addition scenarios since the last ice age. We find that substantial carbon addition to the ocean could have occurred (up to 1.3 billion tons per year) without causing significant changes to the carbon cycle, but only if the carbon is neutralized by alkalinity in an approximate 1:1 ratio. This neutralized release is similar to an approach of carbon removal called ocean alkalinity enhancement (OAE), which aims to reduce atmospheric CO2 as a potential solution for climate change. These findings suggest that neutralized carbon addition—in the form of "neutralized" bicarbonate ion HCO3− $\left({\text{HCO}}_{3}^{-}\right)$ instead of "acidic" CO2—could explain the low levels of radiocarbon during the last deglaciation and shows that large‐scale OAE is feasible without causing major changes to the marine carbon cycle. Key Points: Observed deglacial changes in atmospheric CO2 and 14C/C allow for up to 2,396 Pg of neutralized geologic carbon (i.e., bicarbonate) releaseThe global carbon cycle is essentially "blind" to neutralized carbon release, only constrained by 14C budgetThis gigaton‐scale neutralized carbon release may be a natural analog to the marine CO2 removal method of ocean alkalinity enhancement [ABSTRACT FROM AUTHOR]

This paper is based on a comparison of the carbon parameters at the western and eastern borders of the tropical Atlantic using data collected from 55 cruises. Oceanic and coastal data, mainly total alkalinity (TA), total dissolved inorganic carbon (CT), sea surface salinity (SSS) and sea surface temperature (SST), were compiled from different sources. These data were subdivided into three subsets: oceanic data, coastal data and adjacent to the Brazilian (western) and African coastal areas (eastern) data. Significant differences between the TA data (2099.4 ± 286.4 µmol kg−1) at the western and eastern edges (2198 ± 141.9 µmol kg−1) were observed. Differences in the CT values between the western edge (1779.6 ± 236.4 µmol kg−1) and eastern edge (1892.2 ± 94.2 µmol kg−1) were also noted. This pattern was due to the different variabilities in the carbon parameters between the eastern and western border coastal areas and to the biogeochemistry that drives these parameters. In the western coastal area, the physical features of the continental carbon and oceanic waters mixing with the freshwater that flows from the Amazon and Orinoco Rivers to the South American coast are different than the physical features of the water that flows from the Congo, Volta and Niger Rivers in the eastern region. Applying the TA empirical relationship to TA with values of SSS < 35 in the western and eastern regions leads to a higher root mean square error (rmse) in the eastern and western regions. Therefore, most of the existing TA empirical relationships are most useful at the regional scale due to the difference in the water properties of each region. The relationships of TA and CT determined in the western and eastern regions do not reproduce in situ data well, especially at the adjacent edges. This difference is explained by the difference between the African and Brazilian coasts in terms of their carbon parameter characteristics and processes responsible for their variation. Based on the mixing model, it has been shown that the primary productivity in the eastern region is higher than that in the western region. This is one of the reasons why the carbon parameters are higher in the eastern region. For each region studied, an equation for TA is introduced in this study. [ABSTRACT FROM AUTHOR]

Recent studies, including many from the GEOTRACES program, have expanded our knowledge of trace metals in the Arctic Ocean, an isolated ocean dominated by continental shelf and riverine inputs. Here, we report a unique, pan‐Arctic linear relationship between dissolved copper (Cu) and nickel (Ni) present north of 60°N that is absent in other oceans. The correlation is driven primarily by high Cu and Ni concentrations in the low salinity, river‐influenced surface Arctic and low, homogeneous concentrations in Arctic deep waters, opposing their typical global distributions. Rivers are a major source of both metals, which is most evident within the central Arctic's Transpolar Drift. Local decoupling of the linear Cu‐Ni relationship along the Chukchi Shelf and within the Canada Basin upper halocline reveals that Ni is additionally modified by biological cycling and shelf sediment processes, while Cu is mostly sourced from riverine inputs and influenced by mixing. This observation highlights differences in their chemistries: Cu is more prone to complexation with organic ligands, stabilizing its riverine source fluxes into the Arctic, while Ni is more labile and is dominated by biological processes. Within the Canadian Arctic Archipelago, an important source of Arctic water to the Atlantic Ocean, contributions of Cu and Ni from meteoric waters and the halocline are attenuated during transit to the Atlantic. Additionally, Cu and Ni in deep waters diminish with age due to isolation from surface sources, with higher concentrations in the younger Eastern Arctic basins and lower concentrations in the older Western Arctic basins. Plain Language Summary: The trace metals copper and nickel are key elements involved in the biological and chemical cycles present in the ocean that help fuel the algae forming the base of the marine food web. The Arctic Ocean is heavily influenced by inputs from land including river discharge and continental sediments, and it has limited exchange with other oceans. We found that dissolved copper and nickel have Arctic distributions unique from the rest of the global ocean and are also surprisingly linearly correlated in the Arctic. We carefully compared them to each other and to other chemical tracers in order to identify the processes that control their distributions. We found that copper and nickel concentrations are highest in Western Arctic surface waters, due to riverine discharge for both metals, and also continental shelf sources of nickel. In deeper waters, copper and nickel concentrations are low and constant, unlike in other ocean basins. Also, unique to the Arctic, biological cycling was not a controlling factor for copper and nickel behavior, and interactions of these metals with particles were also less than observed elsewhere. Overall, the Arctic was an ideal case study for the importance of different ocean processes on controlling marine copper and nickel. Key Points: Dissolved Cu and Ni share a unique linear correlation in the Arctic Ocean, with high surface water and low deep water concentrationsCu is sourced primarily from rivers, while Ni is also sourced from sediments on the Chukchi ShelfConcentrations of both are lower in Western than in Eastern Arctic deep waters, and both are attenuated in the Canadian Arctic Archipelago [ABSTRACT FROM AUTHOR]

Vargas and collaborators (Vargas et al., 2018), therein V2018, reported measurements of pH, total alkalinity (AT), dissolved inorganic carbon (CT), dissolved oxygen (DO) and other hydrographic variables along a portion of the Strait of Magellan and associated fjords during the spring of 2010. Using the measured values of AT and pH to calculate the partial pressure of CO2 (pCO2), they showed that DO supersaturated waters in the upper 50 m depth were often associated with pCO2 higher than atmospheric CO2 levels. Here we show that this anomalous pattern arises because V2018′s carbonate system parameters were apparently incorrectly calculated, resulting in positively biased pCO2 values. AT measurements in this layer were often higher than the marine end‐member, which could indicate an additional source of bias. Biased carbonate system parameters used by V2018 imply a sub‐estimation of the capacity of CO2 uptake, with important consequences for local capacity to modulate the potential deleterious effects of freshening and ocean acidification on fjord biota. The critical analysis of the global sources of uncertainty in carbonate‐system parameters, and evaluation of internal and external consistency (i.e., with complementary hydrographic information or with previous reports), are necessary to detect bias, and generate data with sufficient quality to study the effect of ocean acidification on marine ecosystems (GOA‐ON, 2019). Key Points: Partial pressure of CO2 (pCO2) in Southern Patagonia inner waters overestimated in Vargas et al., 2018Omega Aragonite in Southern Patagonia inner waters sub estimated in Vargas et al., 2018The analysis of carbonate system internal and external consistency help to detect bias in calculated carbonate system parameters [ABSTRACT FROM AUTHOR]

The decrease in δ13C of dissolved inorganic carbon (δ13CDIC) owing to uptake of anthropogenic CO2 (the oceanic 13C Suess effect) in the Southeastern Indian Ocean over the last decade was calculated using an extended multiparameter linear regression technique. Samples collected on the CROCCA‐2S (Coring to Reconstruct Ocean Circulation and Carbon Dioxide Across 2 Seas) cruise in November–December 2018 were compared to samples from the CLIVAR (Climate and Ocean: Variability, Predictability, and Change) and OISO (Océan Indien Service d'Observation) programs from 2007 to 2009. Surface ocean δ13CDIC decreased by an average of −0.53 ± 0.04‰ across this period, at an average rate of −0.053 ± 0.004‰ per year. This rate of δ13CDIC change is an increase from −0.021 ± 0.024‰ per year between 1994 and 2008. We find that the interior water mass most impacted by the oceanic 13C Suess effect between 2008 and 2018 was Subantarctic Mode Water (SAMW), within which δ13CDIC decreased by −0.044 ± 0.002‰ per year. Using previously published relationships between the oceanic 13C Suess effect and anthropogenic carbon, we estimate the annual storage of anthropogenic carbon within SAMW in the southeastern Indian Ocean has increased from ∼2.0 ± 0.2 μmol/kg per year between 1994 and 2008 to 5.5 ± 0.6 μmol/kg per year between 2008 and 2018. Plain Language Summary: We measured the ratio of carbon isotopes within seawater to identify the amount of atmospheric carbon sourced from the burning of biomass and fossil fuels which has been absorbed into the southeastern Indian Ocean over the last decade. We find that the rate at which this human‐sourced carbon is being absorbed by the ocean has increased up to 3‐fold over this time period, when compared with the period between 1994 and 2008. Key Points: The oceanic Suess effect disproportionately affects Subantarctic Mode Water (SAMW), within which δ13C has decreased by c. −0.44‰ from 2008 to 2018The observed δ13C change of −0.044‰/year represents roughly a 3‐fold increase in the rate of δ13C change compared to 1994–2008Between 2008 and 2018 SAMW in the SE Indian Ocean absorbed 5.5 ± 0.6 μmol/kg−1 of anthropogenic carbon per year [ABSTRACT FROM AUTHOR]

Deep-water renewal (DWR) events are characterized in the Strait of Georgia, Canada using 11 years of real-time physical and chemical oceanographic data and seafloor videos. At least 6 DWRs occur per year at 300 m water depth and each event continues for over 3 days. They initiate during neap tides and are associated with increased turbidity. In the spring, DWRs introduce cold, oxygenated and nutrient-poor waters, and in the fall they introduce warm, oxygen-depleted, nutrient-rich and saline waters. Although the timing and magnitude of DWRs differ from year to year, we demonstrate that they are not restricted to two seasons, but continue throughout the year. High-resolution videos of DWRs show that these events comprise a plume of high suspended sediment concentration that flows parallel to the basin axis and deposits approximately 1.5 cm per event. [ABSTRACT FROM AUTHOR]

An overview of chemical and biological oceanographic conditions in the Gulf of St. Lawrence (GSL) in 2017 is presented as part of the Atlantic Zone Monitoring Program (AZMP). AZMP data as well as data from regional monitoring programs are analyzed and presented in relation to long-term means in the context of a strong warming event that began in 2010. Oxygen levels at 300 m reached their lowest concentration measured so far in several GSL regions during 2017. Negative anomalies in deep O2 concentration were especially strong in central GSL and the Cabot Strait region. Nitrate inventories in the surface layer (0-50 m) were generally near normal everywhere in the GSL all year round. However, they were above normal in deep waters of eastern GSL (eGSL), which has been observed since 2012 and is associated with intrusions of warm and salty waters. Vertically integrated chlorophyll a (chl a; 0-100 m) was below normal in western GSL (wGSL) and above normal in southern GSL (sGSL) during summer and fall. In sGSL, the positive chl a anomaly measured in situ was actually the strongest recorded since 2002. However, according to satellite imagery, the spring bloom amplitude was generally below normal everywhere in the GSL, including sGSL. Satellite estimates show a near-normal surface chl a annual mean throughout the GSL despite low spring biomass. Dinoflagellate abundance reached a record low at Rimouski station, while it was above normal at Shediac Valley as were flagellates and ciliates at this station. In 2017, zooplankton biomass was below average everywhere in the GSL, but the main zooplankton functional groups and species abundances were all above normal in eGSL with the exception of Calanus hyperboreus. In wGSL and sGSL, C. finmarchicus, Pseudocalanus spp., and total copepod abundances showed negative anomalies. It is the first time since 2012-2013 that negative anomalies have been recorded for Pseudocalanus spp. Moreover, the widespread positive anomalies of small calanoid abundance that have been observed since 2008 were restricted to Rimouski station and eGSL in 2017. Higher-than-normal abundances of copepod species associated with warm water were again observed in 2017, continuing a trend observed since 2011. Development of C. finmarchicus was delayed at Rimouski station in 2017, unlike observations in recent years. Some of these phytoplankton and zooplankton dynamics could reflect the influence of a St. Lawrence freshwater runoff well above the normal in May and June 2017 and of year-round warmer-thannormal deep waters. [ABSTRACT FROM AUTHOR]

Past occurrences of widespread and severe anoxia in the ocean have frequently been associated with abundant geological evidence for free hydrogen sulfide (H2S) in the water column, so‐called euxinic conditions. Free H2S may react with, and modify, the chemical structure of organic matter settling through the water column and in marine sediments, with hypothesized implications for carbon sequestration. Here, taking the example of Ocean Anoxic Event 2, we explore the potential impact of organic matter sulfurization on marine carbon and oxygen cycling by means of Earth system modeling. Our model experiments demonstrate that rapid sulfurization (ksulf≥ = 105 M−1 year−1) of organic matter in the water column can drive a more than 30% enhancement of organic carbon preservation and burial in marine sediments and hence help accelerate climate cooling and Ocean Anoxic Event 2 recovery. As a consequence of organic matter sulfurization, we also find that H2S can be rapidly scavenged and the euxinic ocean volume reduced by up to 80%—helping reoxygenate the ocean as well as reducing toxic H2S emissions to the atmosphere, with potential implications for the kill mechanism at the end‐Permian. Finally, we find that the addition of organic matter sulfurization induces a series of additional feedbacks, including further atmospheric CO2 drawdown and ocean reoxygenation by the creation of a previously unrecognized net source of alkalinity to the ocean as H2S is scavenged and buried. Key Points: The impact of organic matter sulfurization on C and O2 cycling during Ocean Anoxic Events is quantified by means of 3‐D Earth system modelingOrganic matter sulfurization reduces the extent and intensity of toxic euxinic conditions as well as H2S emissions to the atmosphereOrganic matter sulfurization drives enhanced OM burial, draws down atmospheric CO2, and accelerates climate cooling and OAE recovery [ABSTRACT FROM AUTHOR]

Ocean chemistry has been almost exclusively based upon retrieving samples from the ocean for laboratory or shipboard analysis, or deploying sensors to recover natural signals. The ability to execute complex experiments in the deep ocean akin to the manipulations carried out in laboratories has largely been absent. In this paper, we review the progress made in manipulating and sensing complex gases, liquids, and solids in real time in the deep sea to advance understanding of natural processes. These experiments were made possible by access to the remarkable capabilities of Monterey Bay Aquarium Research Institute's (MBARI's) remotely operated vehicle and the skills of the operational teams. Here, we report on advances made in methane hydrate research and deep-ocean Raman spectroscopy, and on proposals for fossil fuel CO2 sequestration and on controlled ocean acidification studies. The skills necessary to advance this work have been made possible only by the joint efforts of engineers and scientists as envisaged by MBARI's founder. We note with some concern that in reporting progress here there were few antecedents to draw upon, so that the citations listed have a distinctly unbalanced look. Nonetheless, the impacts of the institute's work have been far-reaching. [ABSTRACT FROM AUTHOR]

Nitrate persists in eastern equatorial Pacific surface waters because phytoplankton growth fueled by nitrate (new production) is limited by iron. Nitrate isotope measurements provide a new constraint on the controls of surface nitrate concentration in this region and allow us to quantify the degree and temporal variability of nitrate consumption. Here we show that nitrate consumption in these waters cannot be fueled solely by the external supply of iron to these waters, which occurs by upwelling and dust deposition. Rather, a substantial fraction of nitrate consumption must be supported by the recycling of iron within surface waters. Given plausible iron recycling rates, seasonal variability in nitrate concentration on and off the equator can be explained by upwelling rate, with slower upwelling allowing for more cycles of iron regeneration and uptake. The efficiency of iron recycling in the equatorial Pacific implies the evolution of ecosystem-level mechanisms for retaining iron in surface ocean settings where it limits productivity. [ABSTRACT FROM AUTHOR]

The kinetics of particulate organic carbon (POC) mineralization in marine surface sediments is not well constrained. This creates considerable uncertainties when benthic processes are considered in global biogeochemical or Earth system circulation models to simulate climate-ocean interactions and biogeochemical tracers in the ocean. In an attempt to improve our understanding of the rate and depth distribution of organic carbon mineralization in bioturbated (0-10 cm) sediments, we parameterized a 1-D diagenetic model that simulates the reactivity of three discrete POC pools at global scale (a multi-G model). The rate constants of the three reactive classes (highly reactive, reactive, refractory) are fixed and determined to be 70 yr-1, 0.5 yr-1, and ~0.001 yr-1, respectively, based on the Martin curve model for pelagic POC degradation. In contrast to previous approaches, the reactivity of the organic material degraded in the seafloor is continuous with, and set by, the apparent reactivity of material sinking through the water column. The model is able to simulate a global database (185 stations) of benthic oxygen and nitrate fluxes across the sediment-water interface in addition to porewater oxygen and nitrate distributions and organic carbon burial efficiencies. It is further consistent with degradation experiments of fresh phytoplankton. We propose that an important yet mostly overlooked consideration in previous upscaling approaches is the proportion of the relative reactive POC classes reaching the seafloor in addition to their reactivity. The approach presented is applicable to both steady-state and non-steady state scenarios, and links POC degradation kinetics in sedimentary environments to water depth and the POC rain rate to the seafloor. [ABSTRACT FROM AUTHOR]

Numerous studies have been conducted on the effect of ocean acidification on calcifiers inhabiting nearshore benthic habitats, such as the blue mussel Mytilus edulis. The majority of these experiments was performed under stable CO2 partial pressure (pCO2), carbonate chemistry and oxygen (O2) levels, reflecting present or expected future open ocean conditions. Consequently, levels and variations occurring in coastal habitats, due to biotic and abiotic processes, were mostly neglected, even though these variations largely override global long-term trends. To highlight this hiatus and guide future research, state-of-the-art technologies were deployed to obtain high-resolution time series of pCO2 and [O2] on a mussel patch within a Zostera marina seagrass bed, in Kiel Bay (western Baltic Sea) in August and September 2013. Combining the in situ data with results of discrete sample measurements, a full seawater carbonate chemistry was derived using statistical models. An average pCO2 more than 50 % (~ 640 μatm) higher than current atmospheric levels was found right above the mussel patch. Diel amplitudes of pCO2 were large: 765 ± 310 (mean ± SD). Corrosive conditions for calcium carbonates (Ωarag and Ωcalc < 1) centered on sunrise were found, but the investigated habitat never experienced hypoxia throughout the study period. It is estimated that mussels experience conditions limiting calcification for 12-15 h per day, based on a regional calcium carbonate concentration physiological threshold. Our findings call for more extensive experiments on the impact of fluctuating corrosive conditions on mussels. We also stress the complexity of the interpretation of carbonate chemistry time series data in such dynamic coastal environments. [ABSTRACT FROM AUTHOR]

In estuarine coastal systems such as the Baltic Sea, mussels suffer from low salinity which limits their distribution. Anthropogenic climate change is expected to cause further desalination which will lead to local extinctions of mussels in the low saline areas. It is commonly accepted that mussel distribution is limited by osmotic stress. However, along the salinity gradient environmental conditions for biomineralization are successively becoming more adverse as a result of reduced [Ca2+] and dissolved inorganic carbon (CT) availability. In larvae, calcification is an essential process starting during early development with formation of the prodissoconch I (PD I) shell which is completed under optimal conditions within 2 days. Experimental manipulations of seawater [Ca2+] start to impair PD I formation in Mytilus larvae at concentrations below 3 mM, which corresponds to conditions present in the Baltic at salinities below 8 g kg-1. In addition, lowering dissolved inorganic carbon to critical concentrations (< 1 mM) similarly affected PD I size which was well correlated with calculated ΩAragonite and [Ca2+][HCO3-]/[H+] in all treatments. Comparing results for larvae from the western Baltic with a population from the central Baltic revealed significantly higher tolerance of PD I formation to lowered [Ca2+] and [Ca2+][HCO3-]/[H+] in the low saline adapted population. This may result from genetic adaptation to the more adverse environmental conditions prevailing in the low saline areas of the Baltic. The combined effects of lowered [Ca2+] and adverse carbonate chemistry represent major limiting factors for bivalve calcification and can thereby contribute to distribution limits of mussels in the Baltic Sea. [ABSTRACT FROM AUTHOR]

Ocean dissolved inorganic carbon (DIC) storage can be conceptualized as the sum of four components: saturation (DICsat), disequilibrium (DICdis), carbonate (DICcarb) and soft tissue (DICsoft). Among these, DICdis and DICsoft have the potential for large changes that are relatively difficult to predict. Here we explore changes in DICsoft and DICdis in a large suite of simulations with a complex coupled climate-biogeochemical model, driven by changes in orbital forcing, ice sheets and the radiative effect of CO2. Both DICdis and DICsoft vary over a range of 40 μmol kg-1 in response to the climate forcing, equivalent to changes in atmospheric CO2 on the order of 50 ppm for each. We find that, despite the broad range of climate states represented, changes in global DICsoft can be well-approximated by the product of deep ocean ideal age and the global export production flux, while global DICdis is dominantly controlled by the fraction of the ocean filled by Antarctic Bottom Water (AABW). Because the AABW fraction and ideal age are inversely correlated between the simulations, DICdis and DICsoft are also inversely correlated. This inverse correlation could be decoupled if changes in deep ocean mixing were to alter ideal age independently of AABW fraction, or if independent ecosystem changes were to alter export and remineralization, thereby modifying DICsoft. As an example of the latter, iron fertilization causes DICsoft to increase, and causes DICdis to also increase by a similar or greater amount, to a degree that depends on climate state. We propose a simple framework to consider the global contribution of DICsoft + DICdis to ocean carbon storage as a function of the surface preformed nitrate and DICdis of dense water formation regions, the global volume fractions ventilated by these regions, and the global nitrate inventory. More extensive sea ice increases DICdis, and when sea ice becomes very extensive it also causes significant O2 disequilibrium, which may have contributed to reconstructions of low O2 in the Southern Ocean during the glacial. Global DICdis reaches a minimum near modern CO2 because the AABW fraction reaches a minimum, which may have contributed to preventing further CO2 rise during interglacial periods. [ABSTRACT FROM AUTHOR]

Tidewater glaciers are glaciers that terminate in, and calve icebergs into, the ocean. In addition to the influence that tidewater glaciers have on physical and chemical oceanography, floating icebergs serve as habitat for marine animals such as harbor seals (Phoca vitulina richardii). The availability and spatial distribution of glacier ice in the fjords is likely a key environmental variable that influences the abundance and distribution of selected marine mammals; however, the amount of ice and the fine-scale characteristics of ice in fjords have not been systematically quantified. Given the predicted changes in glacier habitat, there is a need for the development of methods that could be broadly applied to quantify changes in available ice habitat in tidewater glacier fjords. We present a case study to describe a novel method that uses object-based image analysis (OBIA) to classify floating glacier ice in a tidewater glacier fjord from high-resolution aerial digital imagery. Our objectives were to (i) develop workflows and rule sets to classify high spatial resolution airborne imagery of floating glacier ice; (ii) quantify the amount and fine-scale characteristics of floating glacier ice; (iii) and develop processes for automating the object-based analysis of floating glacier ice for large number of images from a representative survey day during June 2007 in Johns Hopkins Inlet (JHI), a tidewater glacier fjord in Glacier Bay National Park, southeastern Alaska. On 18 June 2007, JHI was comprised of brash ice ( = 45.2%, SD = 41.5%), water ( = 52.7%, SD = 42.3%), and icebergs ( = 2.1%, SD = 1.4%). Average iceberg size per scene was 5.7 m2 (SD = 2.6 m2). We estimate the total area (± uncertainty) of iceberg habitat in the fjord to be 455,400 ± 123,000 m2. The method works well for classifying icebergs across scenes (classification accuracy of 75.6%); the largest classification errors occur in areas with densely-packed ice, low contrast between neighboring ice cover, or dark or sediment-covered ice, where icebergs may be misclassified as brash ice about 20% of the time. OBIA is a powerful image classification tool, and the method we present could be adapted and applied to other ice habitats, such as sea ice, to assess changes in ice characteristics and availability. [ABSTRACT FROM AUTHOR]

Crude oil is a complex mixture of many thousands of mostly hydrocarbon and nitrogen-, sulfur-, and oxygen-containing compounds with molecular weights ranging from below 70 Da to well over 2,000 Da. When this complex mixture enters the environment from spills, ruptures, blowouts, or seeps, it undergoes a continuous series of compositional changes that result from a process known as weathering. Spills of petroleum involving human activity generally result in more rapid input of crude oil or refined products (diesel, gasoline, heavy fuel oil, and diluted bitumens) to the marine system than do natural processes and urban runoffs. The primary physicochemical processes involved in weathering include evaporation, dissolution, emulsification, dispersion, sedimentation/flocculation, microbial degradation, and photooxidation. [ABSTRACT FROM AUTHOR]

Covering: up to 2016 Dictazoles and sceptrins are singular metabolites of marine origin. The present dichotomic case study provides a comprehensive perspective on these cyclobutane-centered alkaloids and their respective families. Indeed, their upstream and downstream chemistry are both treated herein. Relevant isolation reports and bio-inspired total syntheses are used to decipher the currently admitted biosynthetic hypotheses as well as the emergence of diversity in the two series. This review proposes a transversal vision of the topic, where most aspects of natural product chemistry have a critical importance. [ABSTRACT FROM AUTHOR]

We develop an optical classification of marine particle assemblages from an extensive dataset of particle optical properties collected in the Chukchi and Beaufort Seas. Hierarchical cluster analysis of the spectral particulate backscattering-to-absorption ratio partitioned the dataset into seven optically-distinct clusters of particle assemblages, each associated with different characteristics of particle concentration, composition, and phytoplankton taxonomic composition and size. Three phytoplankton-dominated clusters were identified. One was characterized by small-sized phytoplankton that are typically associated with regenerated production, and comprised samples from the subsurface chlorophyll- a maximum in oligotrophic waters of the Beaufort Sea. The other two clusters represented diatom-dominated particle assemblages in turbid shelf waters with differing contributions of photoprotective pigments. Such situations are generally associated with significant new production. Two clusters were dominated by organic nonalgal material, one representing clear waters off the shelf, the other representative of post-diatom bloom conditions in the Chukchi Sea. Another distinct cluster represented mineral-dominated particle assemblages that were observed in the Colville and Mackenzie River plumes and near the seafloor. Finally, samples in a cluster of mixed particle composition were scattered throughout all locations. Optical classification improved performance of predictive bio-optical relationships. These results demonstrate a capability to discriminate distinct assemblages of suspended particles associated with specific ecological conditions from hyperspectral measurements of optical properties, and the potential for identification of ecological provinces at synoptic time and space scales from optical sensors. Analogous analysis of multispectral optical data strongly reduced this capability. [ABSTRACT FROM AUTHOR]

A box model incorporating a state-of-the-art chemical mechanism for atmospheric mercury (Hg) cycling was developed to investigate the oxidation of gaseous elemental mercury (GEM) at three locations in the northeastern United States: Appledore Island (AI; marine), Thompson Farm (TF; coastal, rural), and Pack Monadnock (PM; inland, rural, elevated). The chemical mechanism in this box model included the most up-to-date Hg and halogen chemistry. As a result, the box model was able to simulate reasonably the observed diurnal cycles of gaseous oxidized mercury (GOM) and chemical speciation bearing distinct differences between the three sites. In agreement with observations, simulated GOM diurnal cycles at AI and TF showed significant daytime peaks in the afternoon and nighttime minimums compared to flat GOM diurnal cycles at PM. Moreover, significant differences in the magnitude of GOM diurnal amplitude (AI > TF > PM) were captured in modeled results. At the coastal and inland sites, GEM oxidation was predominated by O3 and OH, contributing 80-99% of total GOM production during daytime. H2O2-initiated GEM oxidation was significant (~33% of the total GOM) at the inland site during nighttime. In the marine boundary layer (MBL) atmosphere, Br and BrO became dominant GEM oxidants, with mixing ratios reaching 0.1 and 1 pptv, respectively, and contributing 70% of the total GOM production during midday, while O3 dominated GEM oxidation (50-90% of GOM production) over the remaining day when Br and BrO mixing ratios were diminished. The majority of HgBr produced from GEMCBr was oxidized by NO2 and HO2 to form brominated GOM species. Relative humidity and products of the CH3O2CBrO reaction possibly significantly affected the mixing ratios of Br or BrO radicals and subsequently GOM formation. Gas-particle partitioning could potentially be important in the production of GOM as well as Br and BrO at the marine site. [ABSTRACT FROM AUTHOR]

Repeated hydrographic sections provide critically needed data on and understanding of changes in basin-wide ocean CO2 chemistry over multi-decadal timescales. Here, high-quality measurements collected at twelve cruises carried out along the same track between 1991 and 2015 have been used to determine long-term changes in ocean CO2 chemistry and ocean acidification in the Irminger and Iceland basins of the North Atlantic Ocean. Trends were determined for each of the main water masses present and are discussed in the context of the basin-wide circulation. The pH has decreased in all water masses of the Irminger and Iceland basins over the past 25 years with the greatest changes in surface and intermediate waters (between 0.0010 0.0001 and 0.0018 0.0001 pH units yr-1). In order to disentangle the drivers of the pH changes, we decomposed the trends into their principal drivers: changes in temperature, salinity, total alkalinity (AT) and total dissolved inorganic carbon (both its natural and anthropogenic components). The increase in anthropogenic CO2 (Cant) was identified as the main agent of the pH decline, partially offset by AT increases. The acidification of intermediate waters caused by Cant uptake has been reinforced by the aging of the water masses over the period of our analysis. The pH decrease of the deep overflow waters in the Irminger basin was similar to that observed in the upper ocean and was mainly linked to the Cant increase, thus reflecting the recent contact of these deep waters with the atmosphere. [ABSTRACT FROM AUTHOR]

Although molybdenum (Mo) isotopic compositions of carbonatites, phosphorites and siliceous rocks can be used as proxies to reconstruct conditions of marine chemistry throughout geological time, only a few studies have, so far, analysed these low-Mo (ng g−1) geological samples because of analytical limitations. In this study, a low blank, high yield two-column Mo purification procedure was developed for various low-Mo geological samples. The sample-standard bracketing (SSB) and double-spike (DS) methods for mass fractionation correction were used to compare the accuracy of Mo isotope ratio measurements. Six Mo reference materials, NIST SRM 3134 Mo, JMC Mo, SC+1 and SC−1 (eluted fractions of Sigma-Aldrich Mo), CRM GSR-6 limestone and USGS BCR-2 basalt, were used as quality controls. The results showed that the Mo delta values of reference materials and geological samples corrected by the SSB and DS methods were, within error, consistent with each other and the DS method was the method of choice for samples with ＜0.5 μg g−1 Mo. The average instrument long-term (over 1 year) external reproducibility of NIST SRM 3134 Mo was better than ±0.03‰ amu−1 (2SD, n = 288) and the analytical precision of low-Mo (101 to 103 ng g−1) geological samples was better than ±0.04‰ amu−1. This method can facilitate Mo isotope ratio measurements in geological samples with a low Mo content, offering a possibility to study a wider range of Mo reservoirs in geological processes. [ABSTRACT FROM AUTHOR]

The net export of organic matter from the surface ocean and its respiration at depth create vertical gradients in nutrient and oxygen availability that play a primary role in structuring marine ecosystems. Changes in the properties of this 'biological pump' have been hypothesized to account for important shifts in marine ecosystem structure, including the Cambrian explosion. However, the influence of variation in the behavior of the biological pump on ocean biogeochemistry remains poorly quantified, preventing any detailed exploration of how changes in the biological pump over geological time may have shaped long-term shifts in ocean chemistry, biogeochemical cycling, and ecosystem structure. Here, we use a 3-dimensional Earth system model of intermediate complexity to quantitatively explore the effects of the biological pump on marine chemistry. We find that when respiration of sinking organic matter is efficient, due to slower sinking or higher respiration rates, anoxia tends to be more prevalent and to occur in shallower waters. Consequently, the Phanerozoic trend toward less bottom-water anoxia in continental shelf settings can potentially be explained by a change in the spatial dynamics of nutrient cycling rather than by any change in the ocean phosphate inventory. The model results further suggest that the Phanerozoic decline in the prevalence ocean anoxia is, in part, a consequence of the evolution of larger phytoplankton, many of which produce mineralized tests. We hypothesize that the Phanerozoic trend toward greater animal abundance and metabolic demand was driven more by increased oxygen concentrations in shelf environments than by greater food (nutrient) availability. In fact, a lower-than-modern ocean phosphate inventory in our closed system model is unable to account for the Paleozoic prevalence of bottom-water anoxia. Overall, these model simulations suggest that the changing spatial distribution of photosynthesis and respiration in the oceans has exerted a first-order control on Earth system evolution across Phanerozoic time. [ABSTRACT FROM AUTHOR]

Using a global ocean biogeochemical model, we investigate the suitability of the N2/Ar supersaturation ratio (ΔN2/Ar) as a tracer of marine nitrogen fixation and denitrification, i.e., the main biological processes that add or remove fixed nitrogen to or from the ocean. In a series of factorial simulations, we demonstrate that, in regions away from the oxygen minimum zones (OMZs), the ΔN2/Ar characteristics are mostly determined by benthic denitrification occurring in the deep ocean with minor contributions from benthic and water column denitrification at shallower depths. In the OMZs, the subsurface maxima of ΔN2/Ar are mainly determined by water column denitrification. In contrast, nitrogen fixation has little impact on ΔN2/Ar owing to the rapid loss of the N2 supersaturation signal through air-sea exchange. We thus conclude that ΔN2/Ar can act as a powerful constraint on water column and benthic denitrification occurring in intermediate to deep waters, but it cannot be used to estimate nitrogen fixation. A comparison between the currently very limited observations of the ΔN2/Ar with our model results shows an acceptable level of agreement, suggesting that the model's prescribed rates and distributions of benthic and water column denitrification (i.e., 140 and 52 Tg N yr−1, respectively) are reasonable and confirm the results derived from other constraints. [ABSTRACT FROM AUTHOR]

Climate change is affecting marine ecosystems, but different investigative approaches in physical, chemical, and biological disciplines may influence interpretations of climate-driven changes in the ocean. Here, we review the ocean change literature from 2007 to 2012 based on 461 of the most highly cited studies in physical and chemical oceanography and three biological subdisciplines. Using highly cited studies, we focus on research that has shaped recent discourse on climate-driven ocean change. Our review identified significant differences in spatial and temporal scales of investigation among disciplines. Physical/chemical studies had a median duration of 29 years (n = 150) and covered the greatest study areas (median 1.41 × 107 km², n = 148). Few biological studies were conducted over similar spatial and temporal scales (median 8 years, n = 215; median 302 km², n = 196), suggesting a more limited ability to separate climate-related responses from natural variability. We linked physical/chemical and biological disciplines by tracking studies examining biological responses to changing ocean conditions. Of the 545 biological responses recorded, a single physical or chemical stressor was usually implicated as the cause (59%), with temperature as the most common primary stressor (44%). The most frequently studied biological responses were changes in physiology (31%) and population abundance (30%). Differences in disciplinary studies, as identified in this review, can ultimately influence how researchers interpret climate-related impacts in marine systems. We identified research gaps and the need for more discourse in (1) the Indian and other Southern Hemisphere ocean basins; (2) research themes such as archaea, bacteria, viruses, mangroves, turtles, and ocean acidification; (3) physical and chemical stressors such as dissolved oxygen, salinity, and upwelling; and (4) adaptive responses of marine organisms to climate-driven ocean change. Our findings reveal that highly cited biological studies are rarely conducted on scales that match those of physical and chemical studies. Rather, we suggest a need for measuring responses at biologically relevant scales. [ABSTRACT FROM AUTHOR]

The term oceanic salts concerns the salts, which can be formed from solutions containing the major ions of seawater, that is the hexary system Na+, K+, Mg++, Ca++, Cl-, SO4--H2O. Besides in geochemistry of evaporites and the potash extraction the solubility equilibria and properties of aqueous solutions containing these ions are of importance in many fields of science and technology in a wide range of temperature and composition. After a short introduction into the types of subsystems and the main features of their solubility diagrams the known salt phases, their properties and stability are listed and discussed with a focus on recent work and discoveries. The status of solubility data evaluation of the multi-component system is discussed from the view point of the data itself and the possibilities and limitations of applying thermodynamic modelling. This is demonstrated with the data compilation of Usdowski and Dietzel, the Pitzer models of Harvie, Möller and Weare as well as the model developed in the THEREDA project. Future work should be directed to improve accuracy of solubility data in multi-component solutions combined with modelling and to consider kinetics and mechanistic aspects in crystallization of phases like anhydrite or polyhalite. [ABSTRACT FROM AUTHOR]

Organic macromolecules constitute a high percentage of remote sea spray. They enter the atmosphere through adsorption onto bubbles followed by bursting at the ocean surface, and go on to influence the chemistry of the fine mode aerosol. We present a global estimate of mixed-layer macromolecular distributions, driven by offline marine systems model output. The approach permits estimation of oceanic concentrations and bubble film surface coverages for several classes of organic compound. Mixed layer levels are computed from the output of a global ocean ecodynamics model by relating the macromolecules to standard biogeochemical tracers. Steady state is assumed for labile forms, and for longer-lived components we rely on ratios to existing transported variables. Adsorption is then represented through conventional Langmuir isotherms, with equilibria deduced from laboratory analogs. Open water concentrations locally exceed one micromolar carbon for the total of proteins, polysaccharides and refractory heteropolycondensates. The shorter-lived lipids remain confined to regions of strong biological activity. Results are evaluated against available measurements for all compound types, and agreement is generally well within an order of magnitude. Global distributions are further estimated for both fractional coverage of bubble films at the air-water interface and the two-dimensional concentration excess. Overall, we show that macromolecular mapping provides a novel tool for the comprehension of oceanic surfactant patterns. These results may prove useful in planning field experiments and assessing the potential response of surface chemical behaviors to global change. [ABSTRACT FROM AUTHOR]

Depth profiles of nitrous oxide (N2O) were measured during six cruises to the upwelling area and oxygen minimum zone (OMZ) off Peru in 2009 and 2012/13, covering both the coastal shelf region and the adjacent open ocean. N2O profiles displayed a strong sensitivity towards oxygen concentrations. Open ocean profiles showed a transition from a broad maximum to a double-peak structure towards the centre of the OMZ where the oxygen minimum was more pronounced. Maximum N2O concentrations in the open ocean were about 80 nM. A linear relationship between AN2O and apparent oxygen utilization (AOU) could be found for all measurements within the upper oxy- cline, with a slope similar to studies in other oceanic regions. N2O profiles close to the shelf revealed a much higher variability, with N2O concentrations in the upper oxycline reaching up to several hundred nanomoles per liter at selected stations. Due to the extremely sharp oxygen gradients at the shelf, these maxima occurred in very shallow water depths of less than 50 m. In this area, a linear relationship between AN2O and AOU could not be observed. N2O concentrations above 100 nM were observed at oxygen concentrations ranging from close to saturation to suboxic conditions. Our results indicate that the coastal upwelling off Peru at the shelf causes conditions that lead to extreme N2O accumulation. [ABSTRACT FROM AUTHOR]

Hydrochemical study in the Kara Sea was part of the program of the integrated expedition of the 59th cruise of the RV Akademik Mstislav Keldysh. Primary hydrochemical surveys were performed on the sections in the Yenisei Gulf, along the eastern and western branches of the St. Anna Trough, and across the Novozemel'skii Trough. Moreover, a flow-through system throughout, in which pH values of the surface waters were measured and samples for hydrochemical analyses were collected, was operated during vessel movement. A wide set of hydrochemical analyses was carried out, including tests for key nutrients (silicon and different forms of nitrogen and phosphorus), dissolved oxygen, and values of pH and total alkalinity. The report describes the hydrochemical conditions in the southwestern part of the Kara Sea. The basic results are presented and compared to those of the preceding integrated expeditions (49th cruise of the RV Dmitrii Mendeleev in 1993 and 54th cruise of the RV Akademik Mstislav Keldysh in 2007). [ABSTRACT FROM AUTHOR]

Convenient reading out and/or determination of ionic strength (IS) is of great significance for both scientific research and real life applications. We presented here a novel method for the rapid and sensitive IS assay based on the electrolyte-induced sensitive wavelength blueshifts of the reflection spectra of polyacrylate capped Fe3O4 magnetic photonic crystals (PA–Fe3O4-MPCs). For HCl, MgSO4 and the common electrolytes corresponding to the salinity of seawater (including NaCl, KCl, MgCl2, CaCl2, Na2SO4 and their mixtures), the PA–Fe3O4-MPCs displayed wavelength blueshifts identical to the total IS of the aqueous solutions, regardless of the kind of above-mentioned electrolytes in the solutions. Besides, the PA–Fe3O4-MPCs exhibited relatively high sensitivity (an average of 294 nm L mmol−1 in the range of 0.05–0.30 mmol L−1, and an even higher value of 386 nm L mmol−1 at 0.05–0.15 mmol L−1) and fast response (within 8 s) to the IS of aqueous solutions. The relative standard deviation (RSD) for IS (NaCl, 0.1 mmol L−1) was 4.4% (n = 5). The developed method was applied to determine the salinity of seawater samples, and the determined results were validated by the traditional standard chlorinity titration and electric conductimetry method. The recoveries were in the range of 92–104%. The proposed PA–Fe3O4-MPCs based reflectometry method would have great potential for IS and salinity assays. [ABSTRACT FROM AUTHOR]

Retrievals of aerosol optical depth (AOD) from the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) satellite sensor require the assumption of the extinction-to-backscatter ratio, also known as the lidar ratio. This paper evaluates a new method to calculate the lidar ratio of marine aerosols using two independent sources: the AOD from the Synergized Optical Depth of Aerosols (SODA) project and the integrated attenuated backscatter from CALIOP. With this method, the particulate lidar ratio can be derived for individual CALIOP retrievals in single aerosol layer, cloud-free columns over the ocean. Global analyses are carried out using CALIOP level 2, 5 km marine aerosol layer products and the collocated SODA nighttime data from December 2007 to November 2010. The global mean lidar ratio for marine aerosols was found to be 26 sr, roughly 30% higher than the current value prescribed by the CALIOP standard retrieval algorithm. Data analysis also showed considerable spatiotemporal variability in the calculated lidar ratio over the remote oceans. The calculated marine aerosol lidar ratio is found to vary with the mean ocean surface wind speed (U10). An increase in U10 reduces the mean lidar ratio for marine regions from 32 ± 17 sr (for 0 < U10 < 4 m s-1) to 22 ± 7sr (for U10 > 15 m s-1). Such changes in the lidar ratio are expected to have a corresponding effect on the marine AOD from CALIOP. The outcomes of this study are relevant for future improvements of the SODA and CALIOP operational product and could lead to more accurate retrievals of marine AOD. [ABSTRACT FROM AUTHOR]

A number of studies have shown that the boron isotopic composition (δ11B) and the B/ Ca ratio of biogenic carbonates (mostly foraminifers) can serve as proxies for two parameters of the ocean's carbonate chemistry, rendering it possible to calculate the entire carbonate system. However, the B incorporation mechanism into marine carbonates is still not fully understood and analyses of field samples show species-specific and hydrographic effects on the B proxies complicating their application. Identifying the carbonate system parameter influencing boron incorporation is difficult due to the co-variation of pH, CO32- and B(OH)4- To shed light on the question which parameter of the carbonate system is related to the boron incorporation, we performed culture experiments with the benthic symbiont-bearing foraminifer Amphistegina lessonii using a decoupled pH-CO32- chemistry. The determination of the δ11 B and B/ Ca ratios was performed simultaneously by means of a new in situ technique combining optical emission spectroscopy and laser ablation MC-ICP-MS. The boron isotopic composition in the tests gets heavier with increasing pH and B/ Ca increases with increasing B(OH)4-/HCO3- of the culture media. The latter indicates that boron uptake of A. lessonii features a competition between B(OH)4- and HCO3- Furthermore, the simultaneous determination of B / Ca and δ11B on single specimens allows for assessing the relative variability of these parameters. Among different treatments the B / Ca shows an increasing variability with increasing boron concentration in the test whereas the variability in the isotope distribution is constant. [ABSTRACT FROM AUTHOR]

The ocean acidification (OA) literature is replete with laboratory studies that report species sensitivity to seawater carbonate chemistry in experimental treatments as an "effect of OA". I argue that this is unintentionally misleading, since these studies do not actually demonstrate an effect of OA but rather show sensitivity to CO2. Documenting an effect of OA involves showing a change in a species (e.g. population abundance or distribution) as a consequence of anthropogenic changes in marine carbonate chemistry. To date, there have been no unambiguous demonstrations of a population level effect of anthropogenic OA, as that term is defined by the IPCC. [ABSTRACT FROM AUTHOR]

This review covers the isolation and chemistry of diterpenoids from terrestrial as opposed to marine sources and includes labdanes, clerodanes, abietanes, pimaranes, kauranes, cembranes and their cyclization products. There are 179 references. [ABSTRACT FROM AUTHOR]

Dissolved cobalt (DCo; <0.2 µm; 14 to 93 pM) and the apparent particulate cobalt (PCo; >0.2 µm; <1 to 15 pM) were determined in the upper water column (<1000 m) of the western Atlantic Ocean along the GEOTRACES-A02 section (64°N to 50°S). The lowest DCo concentrations, typical of a nutrient-type distribution were observed in surface waters of the subtropical domains. Strong linear relationships between DCo and phosphate (P) as well as meridional gradients of decreasing DCo from high latitudes were characterized and both linked to the Co biological requirement. External sources such as the Amazon and the atmospheric deposition were found to contribute significantly (>10%) to the DCo stock of the mixed layer in the equatorial and north subtropical domains. Biotic and abiotic processes as well as the physical terms involved in the biogeochemical cycle of Co were defined and estimated. This allowed establishing the first global budget of DCo for the upper 100 m in the western Atlantic. The biological DCo uptake flux was the dominant sink along the section, as reflected by the overall nutrient-type behavior of DCo. The regeneration varied widely within the different biogeochemical domains, accounting for 10% of the DCo-uptake rate in the subarctic gyre and for up to 85% in southern subtropical domain. These findings demonstrated that the regeneration is likely the prevailing source of DCo in the surface waters of the western Atlantic, except in the subpolar domains where physically driven sources can sustain the DCo biological requirement. [ABSTRACT FROM AUTHOR]

Biological N2 fixation is the dominant supply of new nitrogen (N) to the oceans, but is often inhibited in the presence of fixed N sources such as nitrate (NO3−). Anthropogenic fixed N inputs to the ocean are increasing, but their effect on marine N2 fixation is uncertain. Thus, global estimates of new oceanic N depend on a fundamental understanding of factors that modulate N source preferences by N2-fixing cyanobacteria. We examined the unicellular diazotroph Crocosphaera watsonii (strain WH0003) to determine how the light-limited growth rate influences the inhibitory effects of fixed N on N2 fixation. When growth (µ) was limited by low light (µ = 0.23 d−1), short-term experiments indicated that 0.4 µM NH4+ reduced N2-fixation by ∼90% relative to controls without added NH4+. In fast-growing, high-light-acclimated cultures (µ = 0.68 d−1), 2.0 µM NH4+ was needed to achieve the same effect. In long-term exposures to NO3−, inhibition of N2 fixation also varied with growth rate. In high-light-acclimated, fast-growing cultures, NO3− did not inhibit N2-fixation rates in comparison with cultures growing on N2 alone. Instead NO3− supported even faster growth, indicating that the cellular assimilation rate of N2 alone (i.e. dinitrogen reduction) could not support the light-specific maximum growth rate of Crocosphaera. When growth was severely light-limited, NO3− did not support faster growth rates but instead inhibited N2-fixation rates by 55% relative to controls. These data rest on the basic tenet that light energy is the driver of photoautotrophic growth while various nutrient substrates serve as supports. Our findings provide a novel conceptual framework to examine interactions between N source preferences and predict degrees of inhibition of N2 fixation by fixed N sources based on the growth rate as controlled by light. [ABSTRACT FROM AUTHOR]

Increasing Transparent Exopolymer Particle (TEP) formation during diatom blooms as a result of elevated temperature and pCO2 have been suggested to result in enhanced aggregation and carbon flux, therewith potentially increasing the sequestration of carbon by the ocean. We present experimental results on TEP and aggregate formation by Thalassiosira weissflogii (diatom) in the presence or absence of bacteria under two temperature and three pCO2 scenarios. During the aggregation phase of the experiment TEP formation was elevated at the higher temperature (20°C vs. 15°C), as predicted. However, in contrast to expectations based on the established relationship between TEP and aggregation, aggregation rates and sinking velocity of aggregates were depressed in warmer treatments, especially under ocean acidification conditions. If our experimental findings can be extrapolated to natural conditions, they would imply a reduction in carbon flux and potentially reduced carbon sequestration after diatom blooms in the future ocean. [ABSTRACT FROM AUTHOR]

Coral reef calcification is predicted to decline as a result of ocean acidification and other anthropogenic stressors. The majority of studies predicting declines based on in situ relationships between environmental parameters and net community calcification rate have been location-specific, preventing accurate predictions for coral reefs globally. In this study, net community calcification and production were measured on a coral reef flat at One Tree Island, Great Barrier Reef, using Lagrangian flow respirometry and slack water methods. Net community calcification, daytime net photosynthesis and nighttime respiration were higher under the flow respirometry method, likely due to increased water flow relative to the slack water method. The two methods also varied in the degrees to which they were influenced by potential measurement uncertainties. The difference in the results from these two commonly used methods implies that some of the location-specific differences in coral reef community metabolism may be due to differences in measurement methods. [ABSTRACT FROM AUTHOR]

A three dimensional biophysical model was employed to illustrate the biological impacts of a meandering frontal jet, in terms of efficiency and persistency of the autotrophic frontal production, in marginal and semi-enclosed seas. We used the Alboran Sea of the Western Mediterranean as a case study. Here, a frontal jet with a width of 15–20 km, characterized by the relatively low density Atlantic water mass, flows eastward within the upper 100 m as a marked meandering current around the western and the eastern anticyclonic gyres prior to its attachment to the North African shelf/slope topography of the Algerian basin. Its inherent nonlinearity leads to the development of a strong ageostrophic cross-frontal circulation that supplies nutrients into the nutrient-starved euphotic layer and stimulates phytoplankton growth along the jet. Biological production is larger in the western part of the basin and decreases eastwards with the gradual weakening of the jet. The higher production at the subsurface levels suggests that the Alboran Sea is likely more productive than predicted by the satellite chlorophyll data. The Mediterranean water mass away from the jet and the interiors of the western and eastern anticyclonic gyres remain unproductive. [ABSTRACT FROM AUTHOR]

Changes in ocean chemistry and climate induced by anthropogenic CO2 affect a broad range of ocean biological and biogeochemical processes; these changes are already well underway. Direct effects of CO2 (e.g. on pH) are prominent among these, but climate model simulations with historical greenhouse gas forcing suggest that physical and biological processes only indirectly forced by CO2 (via the effect of atmospheric CO2 on climate) begin to show anthropogenically-induced trends as early as the 1920s. Dates of emergence of a number of representative ocean fields from the envelope of natural variability are calculated for global means and for spatial ‘fingerprints’ over a number of geographic regions. Emergence dates are consistent among these methods and insensitive to the exact choice of regions, but are generally earlier with more spatial information included. Emergence dates calculated for individual sampling stations are more variable and generally later, but means across stations are generally consistent with global emergence dates. The last sign reversal of linear trends calculated for periods of 20 or 30 years also functions as a diagnostic of emergence, and is generally consistent with other measures. The last sign reversal among 20 year trends is found to be a conservative measure (biased towards later emergence), while for 30 year trends it is found to have an early emergence bias, relative to emergence dates calculated by departure from the preindustrial mean. These results are largely independent of emission scenario, but the latest-emerging fields show a response to mitigation. A significant anthropogenic component of ocean variability has been present throughout the modern era of ocean observation. [ABSTRACT FROM AUTHOR]

This study investigates the regional distribution of marine aerosol originated species (Na, Cl, nss-SO and MSA) in the snow pits (or firn cores) collected along a transect between Zhongshan Station and the Grove Mountain area (450 km inland) on the eastern side of the Lambert Glacier Basin. Concentrations of Na and Cl decrease exponentially with distance from the coast to 100 km inland (i.e., 1500 m a.s.l.). Statistical results demonstrate that distance from the coast inland and elevation affect the concentration of sea-salt originated ions in inland areas significantly. Increase of Cl-/Na ratio and higher variability in its standard deviation suggest that there are other sources of ions in addition to sea-salt in inland areas of the Antarctic continent. The concentrations of Na and Cl from nine sampling sites in the Grove Mountain area are relatively higher than those from sites along CHINARE transect, although all sites are at similar distance inland. This phenomenon indicates that the barrier effect of the mountain may be the most important factor influencing ion deposition. In addition, nss-SO and MSA vary differently, with nss-SO decreasing with distance more significantly. This implies that sources and transporting pathways influence the deposition of the two sulfur compounds considerably, being supported by the spatial pattern of correlation coefficients between the nss-SO and MSA. [ABSTRACT FROM AUTHOR]

Anionic fucose-containing polysaccharides (fucoidans of brown seaweeds, sulfated fucans and fucosylated chondroitin sulfates of invertebrates) are attracting a rapidly growing research interest due to different types of their biological activity discovered in recent years. In particular, algal fucoidans are characterized by large structural variations depending on the species used for their isolation and by the lack of structural regularity due to random distribution of both carbohydrate and non-carbohydrate substituents along the polymer chains. These features make it difficult to find distinct correlations between structural elements and biological properties of polysaccharides. Nevertheless, there is expectation that systematic structural and biochemical studies of fucoidans will form a basis for the development of new drugs. Herewith we summarize our recent results on the influence of fucoidan structure on blood coagulation. [ABSTRACT FROM AUTHOR]

Nitrification, the microbial oxidation of ammonium to nitrate, is a central part of the nitrogen cycle. In the ocean’s surface layer, the process alters the distribution of inorganic nitrogen species available to phytoplankton and produces nitrous oxide. A widely held idea among oceanographers is that nitrification is inhibited by light in the ocean. However, recent evidence that the primary organisms involved in nitrification, the ammonia-oxidizing archaea (AOA), are present and active throughout the surface ocean has challenged this idea. Here we show, through field experiments coupling molecular genetic and biogeochemical approaches, that competition for ammonium with phytoplankton is the strongest regulator of nitrification in the photic zone. During multiday experiments at high irradiance a single ecotype of AOA remained active in the presence of rapidly growing phytoplankton. Over the course of this three day experiment, variability in the intensity of competition with phytoplankton caused nitrification rates to decline from those typical of the lower photic zone (60 nmol L−1 d−1) to those in well-lit layers (<1 nmol L−1 d−1). During another set of experiments, nitrification rates exhibited a diel periodicity throughout much of the photic zone, with the highest rates occurring at night when competition with phytoplankton is lowest. Together, the results of our experiments indicate that nitrification rates in the photic zone are more strongly regulated by competition with phytoplankton for ammonium than they are by light itself. This finding advances our ability to model the impact of nitrification on estimates of new primary production, and emphasizes the need to more strongly consider the effects of organismal interactions on nutrient standing stocks and biogeochemical cycling in the surface of the ocean. [ABSTRACT FROM AUTHOR]

Ocean acidification is expected to have a major effect on the marine carbonate system over the next century, particularly in high latitude seas. Less appreciated is natural environmental variation within these systems, particularly in terms of pH, and how this natural variation may inform laboratory experiments. In this study, we deployed sensor-equipped moorings at 20 m depths at three locations in McMurdo Sound, comprising deep (bottom depth>200 m: Hut Point Peninsula) and shallow environments (bottom depth ∼25 m: Cape Evans and New Harbor). Our sensors recorded high-frequency variation in pH (Hut Point and Cape Evans only), tide (Cape Evans and New Harbor), and water mass properties (temperature and salinity) during spring and early summer 2011. These collective observations showed that (1) pH differed spatially both in terms of mean pH (Cape Evans: 8.009±0.015; Hut Point: 8.020±0.007) and range of pH (Cape Evans: 0.090; Hut Point: 0.036), and (2) pH was not related to the mixing of two water masses, suggesting that the observed pH variation is likely not driven by this abiotic process. Given the large daily fluctuation in pH at Cape Evans, we developed a simple mechanistic model to explore the potential for biotic processes – in this case algal photosynthesis – to increase pH by fixing carbon from the water column. For this model, we incorporated published photosynthetic parameters for the three dominant algal functional groups found at Cape Evans (benthic fleshy red macroalgae, crustose coralline algae, and sea ice algal communities) to estimate oxygen produced/carbon fixed from the water column underneath fast sea ice and the resulting pH change. These results suggest that biotic processes may be a primary driver of pH variation observed under fast sea ice at Cape Evans and potentially at other shallow sites in McMurdo Sound. [ABSTRACT FROM AUTHOR]

This paper reports on the synthesis of spherical silver nanoparticles and the consequent formation of self-assembled humic-silver supramolecules. The method described in this article is eco-friendly and the supramolecules formed were stable for several months. The silver nanoparticles themselves were synthesised from humic acid extracted from mudbank sediments (from Aleppey, south west coast of India) and characterised by UV-Vis spectra and HRTEM. Tuning of dipole and quadrouple oscillation of spherical nanoparticles was achieved. Variable self-assembled distribution mechanism of humic-silver nanoparticles in the solution responsible for quadrouple intensification was investigated. [ABSTRACT FROM AUTHOR]