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The offshore Gulf of Alaska—in the north-eastern subarctic Pacific—is a high nitrate, low chlorophyll (HNLC) oceanic region where concentrations of dissolved iron (DFe) and zinc (DZn) are of the order ~0.1 nmol kg-1 in surface waters. At the average winter mixed layer depth of ~120 m, concentrations of DFe and DZn are of the orders ~0.1–0.2 nmol kg-1 and ~1–2 nmol kg-1 respectively. Vertical supply of Fe to surface waters is therefore limited, with phytoplankton blooms driven by episodic inputs of Fe. In contrast, DZn is presumably replenished through seasonal vertical mixing, though maintained at low levels in surface waters, even in winter, implying that removal processes are in operation.Previous supplementation experiments have demonstrated that phytoplankton biomass (chl-a) and growth, and drawdown of nitrate (NO3-), are stimulated strongly by Fe but only minimally, if at all, by Zn alone. Using on-deck bioassay incubations of surface waters, we confirm that addition of Fe stimulates significant increases in chl-a and large diatoms, and drawdown of NO3-and silicic acid (Si(OH)4). Associated drawdown of DZn and dissolved cadmium (DCd) indicated Zn stress in control and +Fe treatments. Supplementation with Zn alone had no significant impact on dissolved NO3- and commonly monitored pigments such as chl-a and fucoxanthin. However, in +Zn treatments, DFe and coccolithophore abundance were significantly lower, and the concentration of particulate organic carbon (POC) and the pigments alloxanthin and chlorophyll c1+2 were significantly higher than in control incubations. Our experiment corroborates previously observed relationships between DZn and alloxanthin and chlorophyll c across the subarctic north Pacific and Bering Sea and could help to explain the low or undetectable concentrations of alloxanthin frequently observed in this region. Alloxanthin is a pigment specific to the cryptophytes, either within free-living cells, or within functional plastids retained by mixotrophic protists. Both cryptophytes and mixotrophic ciliates, such as Laboea sp. and Stombidium spp., make a variable but significant contribution to phytoplankton biomass in this area. In the absence of Fe supply to surface waters, Zn could play a hitherto unsuspected role in shaping plankton communities in the HNLC Gulf of Alaska.

Este artículo contiene 18 páginas, 6 figuras, 1 tabla., Our knowledge of the factors that can influence the stock of organic carbon (OC) that is stored in the soil of seagrass meadows is evolving, and several causal effects have been used to explain the variation of stocks observed at local to national scales. To gain a global-scale appreciation of the drivers that cause variation in soil OC stocks, we compiled data on published species-specific traits and OC stocks from monospecific and mixed meadows at multiple geomorphological settings. Species identity was recognized as an influential driver of soil OC stocks, despite their large intraspecific variation. The most important seagrass species traits associated with OC stocks were the number of leaves per seagrass shoot, belowground biomass, leaf lifespan, aboveground biomass, leaf lignin, leaf breaking force and leaf OC plus the coastal geomorphology of the area, particularly for lagoon environments. A revised estimate of the global average soil OC stock to 20 cm depth of 15.4 Mg C ha −1 is lower than previously reported. The largest stocks were still recorded in Mediterranean seagrass meadows. Our results specifically identify Posidonia oceanica from the Mediterranean and, more generally, large and persistent species as key in providing climate regulation services, and as priority species for conservation for this specific ecosystem service., HK was supported by the Ecosystem Services for Poverty Alleviation program Coastal Ecosystem Services in East Africa (NE/L001535/1). JFP acknowledges financial support from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie Grant 795315. JWF and JLH were supported by the Florida Coastal Everglades Long-Term Ecological Research program under the U.S. National Science Foundation Grant DEB-2025954, and this paper is contribution #1494 from the Institute of Environment at Florida International University. TK was supported in part by Grants-in-Aid for Scientific Research (KAKENHI) Grant 18H04156 from the Japan Society for the Promotion of Science. DKJ was funded by European Union H2020 (FutureMARES, contract #869300). OS was supported by I+D+i projects RYC2019-027073-I and PIE HOLOCENO 20213AT014 funded by MCIN/AEI/10.13039/501100011033 and FEDER. PIM was supported by an Australian Research Council Discovery Grant (DP200100575). PM This work is contributing to the ICTA ‘‘Unit of Excellence’’ (MinECo, MDM2015-0552). The IAEA is grateful for the support provided to its Environment Laboratories by the Government of the Principality of Monaco. NM was supported by the project RTI2018-095441-B-C21 funded by MCIN/AEI/10.13039/501100011033 and by FEDER. IM was supported by a Juan de la Cierva Incorporación postdoctoral fellowship (IJC2020-045917-I I) from the Ministry of Science and Innovation (Spanish Government).

Seagrass meadows deliver multiple ecosystem services that are of particular importance to resource-poor coastal communities, yet they are rapidly declining globally. The Payments for Ecosystem Services (PES) approach has been used to fund the protection of other ‘Blue Carbon’ Ecosystems (BCE), yet seagrass has been incorporated in just one PES project worldwide. Some of the ecosystem services delivered by seagrass have the potential for inclusion under a PES framework but multiple challenges currently make this difficult, particularly under community-based management. PES programmes typically focus on carbon as the tradable service, but scientific uncertainties regarding seagrass carbon are likely to remain significant barriers to using carbon as the sole commodity under current carbon trading standards and market conditions. It is recommended here that project developers demonstrate the multiple ecosystem services delivered by seagrass meadows, along with their importance to coastal communities, in the planning and marketing of seagrass PES projects. Moreover, they should consider approaches that incorporate seagrass meadows into other blue carbon certified projects. The capacities of the communities that rely most heavily on seagrass are generally very limited. Consequently, demanding high levels of scientific certainty over carbon stocks and flows will exclude most of these communities. Standards, buyers and policy makers should consider building community capacity in the technical and marketing requirements of voluntary carbon standards. The voluntary carbon market has the flexibility to pioneer certified seagrass carbon, potentially leading to the inclusion of seagrass carbon in formal policy instruments, such as Nationally Determined Contributions (NDCs).

Global inventories that show mangrove forests have rich carbon stores currently lack data from arid areas where carbon stocks may be functionally impoverished relative to humid regions. We quantified total carbon stocks (C) of three arid Avicennia marina stands in Qatar and report an aboveground biomass allometric equation and the first below ground biomass allometric equation in the region. The allometric relationships indicate that below ground mangrove C stocks in arid locations are more important than previously reported. Comparison of previously published and our locally developed allometric equations show that A. marina in Qatar allocate comparatively more biomass to below ground components than the same species in tropical humid settings, which is consistent with plant adaptations to living in stressed conditions. Total C stocks were 45.70 ± 3.70 Mg C ha−1, of which tree and soil C stocks to 50 cm depth represented 10.18 ± 0.82 Mg C ha−1 and 35.52 ± 2.88 Mg ha−1 respectively. Soil C stocks to 1 m depth were 50.17 ± 6.27 Mg C ha−1. Overall, mangroves sustain relatively small C stocks in the arid, hypersaline environment of Qatar, which may be due to both relatively low tree productivity and growth, as well as limited rainfall-driven transport of terrigenous sediment inputs. By providing further estimates of mangrove carbon at their climatic extremes, these results can contribute to a better quantification of global mangrove carbon, reduce uncertainty in below ground tree C estimates from arid mangroves and have implications for mangrove carbon stocks in the face of climate change. Qatar National Research Fund, National Priorities Research Program (NPRP) [grant number 7–1302 – 1–242

Seagrass ecosystems provide a wide variety of services that support human well-being around the world (Barbier et al. 2011). It is estimated that more than 1 billion people live within 100 km of a coast with seagrass meadows, thus potentially benefiting from their provisioning, regulating and cultural services. Seagrasses play a significant global role in supporting food security, mitigating climate change, enriching biodiversity, purifying water, protecting the coastline and controlling diseases (Figure 2). The integrity and provision of services by seagrass meadows are enhanced by their proximity and connectivity to other coastal ecosystems such as tidal marshes, coral reefs, mangrove and kelp forests, and oyster and mussel beds. The maintenance and regulation of these services is therefore essential to support human well-being and promote development in the future. info:eu-repo/semantics/publishedVersion

Highlights • pH of Tris buffers determined in synthetic seawater and brines with the Harned cell. • pH determination of Tris buffers to the freezing point of synthetic solutions. • pH determination of the equimolal and non-equimolal Tris buffer variants. • pH measurement is facilitated at below-zero temperatures, such as in sea ice brines. The pH on the total proton scale of the Tris-HCl buffer system (pH(Tris)) was characterized rigorously with the electrochemical Flamed cell in salinity (S) 35 synthetic seawater and S = 45-100 synthetic seawater-derived brines at 25 and 0 degrees C, as well as at the freezing point of the synthetic solutions (-1.93 degrees C at S = 35 to -6 degrees C at S = 100). The electrochemical characterization of the common equimolal Tris buffer [R-Tris = m(Tris)/m(Tris-H+) = 1.0, with m(Tris) = m(Tris-H+) = 0.04 mol kg(H2O)(-1) = molality of the conjugate acid-base pair of 2-amino-2-hydroxymethyl-1,3-propanediol (Tris)] yielded pH(Tris) values which increased with increasing salinity and decreasing temperature. The electrochemical characterization of a non-equimolal Tris buffer variant (R-Tris = 0.5, with m(Tris) = 0.02 mol kg(H2O)(-1) and MTris-H+ = 0.04 mol kg(H2O)(-1)) yielded pH(Tris) values that were consistently less alkaline by 03 pH unit than those of the equimolal Tris buffer. This is in agreement with the values derived from the stoichiometric equilibrium of the Tris-H+ dissociation reaction, described by the Henderson - Hasselbalch equation, pH(Tris) = pK(Tris)* + logR(Tris), with pK(Tris)* = stoichiometric equilibrium dissociation constant of Tris-H+, equivalent to equimolal pH(Tris). This consistency allows reliable use of other R-Tris variants of the Tris-HCl buffer system within the experimental conditions reported here. The results of this study will facilitate the pH measurement in saline and hypersaline systems at below-zero temperatures, such as sea ice brines.

The sea ice microstructure is permeated by brine channels and pockets that contain concentrated seawater-derived brine. Cooling the sea ice results in further formation of pure ice within these pockets as thermal equilibrium is attained, resulting in a smaller volume of increasingly concentrated residual brine. The coupled changes in temperature and ionic composition result in supersaturation of the brine with respect to mirabilite (Na2SO4·10H2O) at temperatures below −6.38 °C, which consequently precipitates within the sea ice microstructure. Here, mirabilite solubility in natural and synthetic seawater derived brines, representative of sea ice at thermal equilibrium, has been measured in laboratory experiments between 0.2 and −20.6 °C, and hence we present a detailed examination of mirabilite dynamics within the sea ice system. Below −6.38 °C mirabilite displays particularly large changes in solubility as the temperature decreases, and by −20.6 °C its precipitation results in 12.90% and 91.97% reductions in the total dissolved Na+ and SO42− concentrations respectively, compared to that of conservative seawater concentration. Such large non-conservative changes in brine composition could potentially impact upon the measurement of sea ice brine salinity and pH, whilst the altered osmotic conditions may create additional challenges for the sympagic organisms that inhabit the sea ice system. At temperatures above −6.38 °C, mirabilite again displays large changes in solubility that likely aid in impeding its identification in field samples of sea ice. Our solubility measurements display excellent agreement with that of the FREZCHEM model, which was therefore used to supplement our measurements to colder temperatures. Measured and modelled solubility data were incorporated into a 1D model for the growth of first-year Arctic sea ice. Model results ultimately suggest that mirabilite has a near ubiquitous presence in much of the sea ice on Earth, and illustrate the spatial and temporal evolution of mirabilite within sea ice as it grows throughout an Arctic winter, reaching maximum concentrations of 2.3 g kg−1.

Although salt rejection from sea ice is a key process in deep-water formation in ice-covered seas, the concurrent rejection of CO(2) and the subsequent effect on air-sea CO(2) exchange have received little attention. We review the mechanisms by which sea ice directly and indirectly controls the air-sea CO(2) exchange and use recent measurements of inorganic carbon compounds in bulk sea ice to estimate that oceanic CO(2) uptake during the seasonal cycle of sea-ice growth and decay in ice-covered oceanic regions equals almost half of the net atmospheric CO(2) uptake in ice-free polar seas. This sea-ice driven CO(2) uptake has not been considered so far in estimates of global oceanic CO(2) uptake. Net CO(2) uptake in sea-ice-covered oceans can be driven by; (1) rejection during sea-ice formation and sinking of CO(2)-rich brine into intermediate and abyssal oceanic water masses, (2) blocking of air-sea CO(2) exchange during winter, and (3) release of CO(2)-depleted melt water with excess total alkalinity during sea-ice decay and (4) biological CO(2) drawdown during primary production in sea ice and surface oceanic waters.

8 páginas, 4 figuras, 1 tabla., Seagrass meadows are highly productive habitats found along many of the world's coastline, providing important services that support the overall functioning of the coastal zone. The organic carbon that accumulates in seagrass meadows is derived not only from seagrass production but from the trapping of other particles, as the seagrass canopies facilitate sedimentation and reduce resuspension. Here we provide a comprehensive synthesis of the available data to obtain a better understanding of the relative contribution of seagrass and other possible sources of organic matter that accumulate in the sediments of seagrass meadows. The data set includes 219 paired analyses of the carbon isotopic composition of seagrass leaves and sediments from 207 seagrass sites at 88 locations worldwide. Using a three source mixing model and literature values for putative sources, we calculate that the average proportional contribution of seagrass to the surface sediment organic carbon pool is ∼50%. When using the best available estimates of carbon burial rates in seagrass meadows, our data indicate that between 41 and 66 gC m−2 yr−1 originates from seagrass production. Using our global average for allochthonous carbon trapped in seagrass sediments together with a recent estimate of global average net community production, we estimate that carbon burial in seagrass meadows is between 48 and 112 Tg yr−1, showing that seagrass meadows are natural hot spots for carbon sequestration., Finaciación proveniente de Florida Keys National Marine Sanctuary Water Quality Protection Program, de U.S. Environmental Protection Agency (contract X97468102-0), la National Science Foundation a través del programa Florida Coastal Everglades Long-Term Ecological Research en virtud de las concesiones DBI-0620409 y DEB-9910514, y Seagrass Recovery, Inc.

The carbon, nitrogen and the stable carbon isotopic composition, δ13C, of organic matter has been used to elucidate the source(s) of this material to coastal sediments. Sediments were collected at 15 coastal locations in the Philippines and Vietnam, which broadly represented different depositional environments ranging from seagrass meadows, through seagrass meadows located near mangroves and to mangrove stands. In addition, short-term sediment traps were deployed at 12 of the sites where seagrass was present. Mean sediment organic carbon concentration and C/N increased and δ13C of organic matter decreased from seagrass to mangrove dominated settings. The organic carbon flux measured by the sediment trap deployments was very variable (32 ± 3 to ∼ 700 mmol m-2 d-1) and represented only a small fraction of the total particle flux. The importance of seagrass as a source of organic matter to the sediments was assessed by using a simple mixing model and the average δ 13C values for seagrass, their epiphytic community and surface water particulate matter (seston). A positive correlation between seagrass leaf biomass and sediment δ13C in seagrass dominated settings suggests that these macrophytes do significantly influence the composition of sedimentary organic matter. Seagrass was however rarely found to be the dominant source of organic matter to the underlying sediments. Both sediment trap and sediment data suggest that material of planktonic origin was the dominant source of sedimentary organic matter in these settings. At the sites dominated by mangroves the concentration of organic matter (∼ 1-13 × 103 mmol g-1) in the sediment is generally higher than at seagrass dominated sites due to the outwelling of organic matter from the mangrove stands. Mangrove organic matter often dominates the sedimentary input but other sources of organic matter must contribute to cause the observed range in sediment δ13C. © 2004 Elsevier Ltd. All rights reserved.

Stable oxygen isotope analyses of U-shaped spines removed at intervals along profiles of the outer shell surface of Pinna nobilis (L) were used to reconstruct sea surface temperature (SST) and validate the periodicity of adductor-muscle scar rings on the inner shell surface. Elemental ratios (Mg:Ca and Sr:Ca) of spines, determined using Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES), were compared with the SST estimated from the stable oxygen isotopic composition of the shell deposited at the same time. The elemental ratios and the stable oxygen isotopic composition recorded in the shell were significantly correlated: Mg:Ca ratio = 0.0002 (seawater temperature) + 0.0095 (r2 = 0.445), Sr:Ca ratio=0.00005 (seawater temperature) + 0.0014 (r2 = 0.887). The ratios in the spines were highest when the seawater temperature was warmest during July and August and were lowest between January and February when seawater temperatures were minimal. The positions of the first and second adductor muscle scar rings, unlike the later rings, are often difficult to discern, and in large shells they are obscured by nacre. Seasonal patterns in the elemental ratios were used to characterise the age in regions of the outer shell surface corresponding to the first two years of shell growth. A combination of both elemental ratios and muscle scar rings were used to estimate the age and hence the growth rate of P. nobilis from 3 locations in the Croatian Adriatic. Annual cycles of shell growth, inferred from the seasonal pattern in the element ratios, were used to determine the season of recruitment of fan mussels at several localities along the Croatian coastline. Pinnids generally settled during late autumn and winter although one shell from Mali Ston Bay settled during the summer. Pinna nobilis from Mali Ston Bay exhibited the fastest growth reaching a length of ~60cm and an age of 9 years, whereas those from Malo jezero grew the slowest attaining a length of ~50cm at 12 years of age.

The fan shell Pinna nobilis L. is the largest Mediterranean bivalve and has been protected in the Croatian Adriatic since 1977. However, little is still known about its population structure at different locations. Richardson et al. (1999) used inner shell adductor-muscle scar rings to estimate the age of fan mussels from the Spanish Mediterranean and using stable oxygen isotopes (d18O) demonstrated that the rings were deposited annually during a period of increasing sea water temperatures. In this study we examine potential use of Mg/Ca and Sr/Ca ratios for estimating age of P. nobilis collected at three sites in the Croatian Adriatic; Mali Ston Bay, and Veliko jezero and Malo jezero on island of Mljet. Our results show that variations in Mg/Ca and Sr/Ca ratios are closely correlated with d18O variations. Recorded variations reflect seasonal differences in shell growth rate and can therefore be used to estimate the number of winter-summer growth cycles. Growth rings on adductor-muscle scar form in the winter and early spring as a result of slow shell growth, first clearly visible ring forms when fan mussels reach 20-30 cm length and probably represents the second winter of growth. The oldest Pinna nobilis collected was 9 years old.

The kinetics of calcium carbonate hexahydrate (ikaite) precipitation and dissolution were investigated in seawater and seawater-derived brines at sub-zero temperatures using the constant addition experimental technique. The steady state rate of these two processes was found to be a function of the deviation of the solution from equilibrium with respect to ikaite and conformed to the same empirical rate law as the anhydrous CaCO3 polymorphs, calcite and aragonite. In addition to the saturation state of the brine with respect to ikaite, the salinity of the brine and the temperature of the reaction evidently exerted some control on the ikaite precipitation kinetics, while the dissolution kinetics of the polymorph were not noticeably influenced by these two parameters. The experimental salinity and temperature conditions were equivalent to those at thermal equilibrium between brine and ice in the sea ice cover of polar seas. Simple modelling of the CO2 system by extrapolation of the oceanic equivalent to sea ice brines showed that the physical concentration of seawater ions and the changes in ikaite solubility as a function of salinity and temperature, both inherent in the sea ice system, would be insufficient to drive the emergent brines to ikaite supersaturation and precipitation in sea ice down to −8°C. The loss of dissolved inorganic carbon to the gas phase of sea ice and to sympagic autotrophs are two independent mechanisms which, in nature, could prompt the brine CO2 system towards ikaite supersaturation and precipitation. Under these conditions, the steady state precipitation rate of ikaite was found to be fast enough for rapid formation within short time scales (days to weeks) in sea ice. The observed ikaite dissolution kinetics were also found conducive to short turn-over time scales of a few hours to a few days in corrosive solutions, such as surface seawater.