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Bioenergetic model estimates of interannual and spatial patterns in consumption demand and growth potential of juvenile pink salmon (Oncorhynchus gorbuscha) in the Gulf of Alaska

A bioenergetic model of juvenile pink salmon (Oncorhynchus gorbuscha) was used to estimate daily prey consumption and growth potential of four ocean habitats in the Gulf of Alaska during 2001 and 2002. Growth potential was not significantly higher in 2002 than in 2001 at an alpha level of 0.05 (P=0.073). Average differences in growth potential across habitats were minimal (slope habitat=0.844 g d -1 , shelf habitat=0.806 g d -1 , offshore habitat=0.820 g d -1 , and nearshore habitat=0.703 g d -1 ) and not significantly different (P=0.630). Consumption demand differed significantly between hatchery and wild stocks (P=0.035) when examined within year due to the interaction between hatchery verses wild origin and year. However, the overall effect of origin across years was not significant (P=0.705) due to similar total amounts of prey consumed by all juvenile pink salmon in both study years. We anticipated that years in which ocean survival was high would have had high growth potential, but this relationship did not prove to be true. Therefore, modeled growth potential may not be useful as a tool for forecasting survival of Prince William Sound hatchery pink salmon stocks. Significant differences in consumption demand and a two-fold difference in nearshore abundance during 2001 of hatchery and wild pink salmon confirmed the existence of strong and variable interannual competition and the importance of the nearshore region as being a potential competitive bottleneck.

Deep-Sea Research Part II: Topical Studies in Ocea↗

Habitat suitability models for groundfish in the Gulf of Alaska

Identifying and quantifying the major ecosystem processes that regulate recruitment strength of commercially and ecologically important fish species is a central goal of fisheries management research. In the Gulf of Alaska (GOA) five groundfish species are of particular interest: sablefish ( Anoplopoma fimbria ), Pacific cod ( Gadus macrocephalus ), walleye pollock ( Gadus chalcogrammus ), arrowtooth flounder ( Atheresthes stomias ), and Pacific ocean perch ( Sebastes alutus ). Habitat suitability models (HSM) were developed for the demersal early juvenile stage to inform survival to recruitment for these species, using catch data and seafloor habitat metrics with presence-only models. Regional-scale maps were produced that predict the probability of suitable habitat available in the GOA from settlement through residency in nursery areas. For example, the HSM for sablefish (150–399 mm) described suitable habitat as bathymetrically low-lying areas with low rocky structure within 25–300 m depth. In contrast, the HSM for Pacific ocean perch (50–200 mm) described suitable habitat as bathymetry rises with rocky structure present on north-south facing slopes within 85–270 m depth. These habitat covariates are useful to refine population estimates for North Pacific groundfish species and to inform life stage-specific definitions of Essential Fish Habitat. This application of MaxEnt models should be applicable for species with low occurrence of spatial data in other marine ecosystems globally.

Alaska↗

Simulating the migration dynamics of juvenile salmonids through rivers and estuaries using a hydrodynamically driven enhanced particle tracking model

Juvenile salmonids migrate hundreds of kilometers from their natal streams to mature in the ocean. Throughout this migration, they respond to environmental cues such as local water velocities and other stimuli to direct and modulate their movements, often through heavily modified riverine and estuarine habitats. Management strategies in an uncertain future of climate change and altered land use regimes depend heavily on being able to reliably predict their ocean entry timings, route use, and survival rates through rivers and estuaries. We developed a spatially-explicit agent-based model of fish movement in response to hydrodynamic flows that uses movement dynamics gleaned from multi-dimensional tracking datasets of acoustically tagged juveniles moving through an urbanized, branched tidal estuary. We demonstrate how such models can be calibrated, and we apply it to the Sacramento-San Joaquin Delta in Central California. The quality of the out-of-sample validation of the model to predict juvenile salmon survival and route selection indicates that the model is versatile and flexible enough to be used in novel hydroclimatological conditions.

California↗

Nutrient contributions to the Santa Barbara Channel, California, from the ephemeral Santa Clara River

The Santa Clara River delivers nutrient rich runoff to the eastern Santa Barbara Channel during brief (???1-3 day) episodic events. Using both river and oceanographic measurements, we evaluate river loading and dispersal of dissolved macronutrients (silicate, inorganic N and P) and comment on the biological implications of these nutrient contributions. Both river and ocean observations suggest that river nutrient concentrations are inversely related to river flow rates. Land use is suggested to influence these concentrations, since runoff from a subwatershed with substantial agriculture and urban areas had much higher nitrate than runoff from a wooded subwatershed. During runoff events, river nutrients were observed to conservatively mix into the buoyant, surface plume immediately seaward of the Santa Clara River mouth. Dispersal of these river nutrients extended 10s of km into the channel. Growth of phytoplankton and nutrient uptake was low during our observations (1-3 days following runoff), presumably due to the very low light levels resulting from high turbidity. However, nutrient quality of runoff (Si:N:P = 16:5:1) was found to be significantly different than upwelling inputs (13:10:1), which may influence different algal responses once sediments settle. Evaluation of total river nitrate loads suggests that most of the annual river nutrient fluxes to the ocean occur during the brief winter flooding events. Wet winters (such as El Nin??o) contribute nutrients at rates approximately an order-of-magnitude greater than "average" winters. Although total river nitrate delivery is considerably less than that supplied by upwelling, the timing and location of these types of events are very different, with river discharge (upwelling) occurring predominantly in the winter (summer) and in the eastern (western) channel. ?? 2004 Elsevier Ltd. All rights reserved.

Estuarine, Coastal and Shelf Science↗

Anthropogenic influences on shoreline and nearshore evolution in the San Francisco Bay coastal system

Analysis of four historical bathymetric surveys over a 132-year period has revealed significant changes to the morphology of the San Francisco Bar, an ebb-tidal delta at the mouth of San Francisco Bay estuary. From 1873 to 2005 the San Francisco Bar vertically-eroded an average of 80 cm over a 125 km 2 area, which equates to a total volume loss of 100 ± 52 million m 3 of fine- to coarse-grained sand. Comparison of the surveys indicates the entire ebb-tidal delta contracted radially, with the crest moving landward an average of 1 km. Long-term erosion of the ebb-tidal delta is hypothesized to be due to a reduction in the tidal prism of San Francisco Bay and a decrease in coastal sediment supply, both as a result of anthropogenic activities. Prior research indicates that the tidal prism of the estuary was reduced by 9% from filling, diking, and sedimentation. Compilation of historical records dating back to 1900 reveals that a minimum of 200 million m3 of sediment has been permanently removed from the San Francisco Bay coastal system through dredging, aggregate mining, and borrow pit mining. Of this total, ~54 million m 3 of sand-sized or coarser sediment was removed from central San Francisco Bay. With grain sizes comparable to the ebb-tidal delta, and its direct connection to the bay mouth, removal of sediments from central San Francisco Bay may limit the sand supply to the delta and open coast beaches. SWAN wave modeling illustrates that changes to the morphology of the San Francisco Bar have altered the alongshore wave energy distribution at adjacent Ocean Beach, and thus may be a significant factor in a persistent beach erosion ‘hot spot’ occurring in the area. Shoreline change analyses show that the sandy shoreline in the shadow of the ebb-tidal delta experienced long-term (1850s/1890s to 2002) and short-term (1960s/1980s to 2002) accretion while the adjacent sandy shoreline exposed to open-ocean waves experienced long-term and short-term erosion. Therefore, the recently observed accelerating rates of bay sediment removal, ebb-tidal delta erosion, and open coast beach erosion are all correlated temporally.

California↗

Barrier islands influence the assimilation of terrestrial energy in nearshore fishes

We examined the relative importance of landscape features on estuarine fish trophic structure and dependence on terrestrial organic matter (OM terr ) in four barrier island lagoon systems along the Alaskan Beaufort Sea coast. Our study compared two relatively large lagoon systems characterized by high river discharge and relatively free ocean water exchanges (central region near Prudhoe Bay, Alaska) with two highly protected lagoons characterized by low river discharge and limited exchange with ocean waters (eastern region near Kaktovik, Alaska). We hypothesized that freshwater discharge would be a strong determinant of food web structure for both resident marine and diadromous fishes if more discharge increases availability of OM terr relative to lagoons with limited or no river inputs. To consider differences in trophic characteristics in fishes between study regions, we estimated community-wide measures of trophic structure (hereafter, community metrics) and the relative use of OM terr from mixing models using stable isotope composition (δ 13 C and δ 15 N; muscle tissue) among 12 species and identified the influences of region and body size. Fish captured in lagoons well protected by barrier islands had more distinct and diverse isotopic niches relative to those in more exposed lagoons based on community metrics. The use of OM terr by nearshore fishes in both regions was substantial and was >50% for diadromous species. Between regions, OM terr use differed in 6 of the 8 species considered but was not consistently higher in one region. The relative importance of OM terr varied with fish size in 7 of 10 species considered, with more OM terr used by smaller individuals. This work highlights the importance of OM terr to Arctic fishes and fisheries, some of which are of subsistence importance, even when feeding grounds are primarily marine. We propose that landscape features, particularly barrier islands, play an important role in structuring nearshore food webs. Barrier islands may provide a previously undocumented ecosystem service of increasing food web complexity, which may promote system resilience.

Alaska↗

Flushing time variability in a short, low-inflow estuary

Flushing time, the time scale for exchange and mixing between embayed and oceanic waters in an estuary, plays an integral role in determining water quality and aquatic ecosystem health. Here, we investigated the spatiotemporal variability of flushing times throughout Morro Bay, a short, low-inflow estuary (LIE) on the California coast, using a calibrated and validated hydrodynamic model (Delft3D). Morro Bay has historically supported an extensive eelgrass ( Zostera marina ) habitat, which declined substantially from 139 to 5.4 ha during 2007–2017. Eelgrass decline motivated the current research into the role of changing bed roughness and oceanic drivers (i.e., tide and sea-level rise) on estuarine hydrodynamics and flushing times. We found that tidal variability exerts the strongest control on flushing times compared to other effects, i.e., bed roughness or sea-level rise. Additionally, we found that increasing sea level and decreasing bed roughness (associated with declining seagrass coverage) yielded higher rates of mixing (lower flushing times). We detected a strong correspondence between areas having shorter flushing times (e.g., near the estuary mouth) and areas occupied by resilient eelgrass populations in Morro Bay. Our findings further indicated that flushing times in short LIEs are particularly sensitive to several factors (e.g., bed roughness, sea level) that are susceptible to anthropogenic disturbance and future climate change.

California↗

The challenges and opportunities in cumulative effects assessment

The cumulative effects of increasing human use of the ocean and coastal zone have contributed to a rapid decline in ocean and coastal resources. As a result, scientists are investigating how multiple, overlapping stressors accumulate in the environment and impact ecosystems. These investigations are the foundation for the development of new tools that account for and predict cumulative effects in order to more adequately prevent or mitigate negative effects. Despite scientific advances, legal requirements, and management guidance, those who conduct assessments—including resource managers, agency staff, and consultants—continue to struggle to thoroughly evaluate cumulative effects, particularly as part of the environmental assessment process. Even though 45 years have passed since the United States National Environmental Policy Act was enacted, which set a precedent for environmental assessment around the world, defining impacts, baseline, scale, and significance are still major challenges associated with assessing cumulative effects. In addition, we know little about how practitioners tackle these challenges or how assessment aligns with current scientific recommendations. To shed more light on these challenges and gaps, we undertook a comparative study on how cumulative effects assessment (CEA) is conducted by practitioners operating under some of the most well-developed environmental laws around the globe: California, USA; British Columbia, Canada; Queensland, Australia; and New Zealand. We found that practitioners used a broad and varied definition of impact for CEA, which led to differences in how baseline, scale, and significance were determined. We also found that practice and science are not closely aligned and, as such, we highlight opportunities for managers, policy makers, practitioners, and scientists to improve environmental assessment.

Environmental Impact Assessment Review↗

Observations of nearshore groundwater discharge: Kahekili Beach Park submarine springs, Maui, Hawaii

Study region The study region encompasses the nearshore, coastal waters off west Maui, Hawaii. Here abundant groundwater—that carries with it a strong land-based fingerprint—discharges into the coastal waters and over a coral reef. Study focus Coastal groundwater discharge is a ubiquitous hydrologic feature that has been shown to impact nearshore ecosystems and material budgets. A unique combined geochemical tracer and oceanographic time-series study addressed rates and oceanic forcings of submarine groundwater discharge at a submarine spring site off west Maui, Hawaii. New hydrological insights for the region Estimates of submarine groundwater discharge were derived for a primary vent site and surrounding coastal waters off west Maui, Hawaii using an excess 222 Rn ( t 1/2 = 3.8 d) mass balance model. Such estimates were complemented with a novel thoron ( 220 Rn, t 1/2 = 56 s) groundwater discharge tracer application, as well as oceanographic time series and thermal infrared imagery analyses. In combination, this suite of techniques provides new insight into the connectivity of the coastal aquifer with the near-shore ocean and examines the physical drivers of submarine groundwater discharge. Lastly, submarine groundwater discharge derived constituent concentrations were tabulated and compared to surrounding seawater concentrations. Such work has implications for the management of coastal aquifers and downstream nearshore ecosystems that respond to sustained constituent loadings via this submarine route.

Hawaii↗

Reducing energy-related CO 2 emissions using accelerated weathering of limestone

The use and impacts of accelerated weathering of limestone (AWL; reaction: CO 2 +H 2 O+CaCO 3 →Ca 2+ +2(HCO 3 - ) is explored as a CO 2 capture and sequestration method. It is shown that significant limestone resources are relatively close to a majority of CO 2 -emitting power plants along the coastal US, a favored siting location for AWL. Waste fines, representing more than 20% of current US crushed limestone production (>10 9 tonnes/yr), could provide an inexpensive or free source of AWL carbonate. With limestone transportation then as the dominant cost variable, CO 2 mitigation costs of $3-$4/tonne appear to be possible in certain locations. Perhaps 10–20% of US point–source CO 2 emissions could be mitigated in this fashion. It is experimentally shown that CO 2 sequestration rates of 10 -6 to 10 -5 moles/sec per m 2 of limestone surface area are achievable, with reaction densities on the order of 10 -2 tonnes CO 2 m -3 day -1 , highly dependent on limestone particle size, solution turbulence and flow, and CO 2 concentration. Modeling shows that AWL would allow carbon storage in the ocean with significantly reduced impacts to seawater pH relative to direct CO 2 disposal into the atmosphere or sea. The addition of AWL-derived alkalinity to the ocean may itself be beneficial for marine biota.

Energy↗

The airborne lava-seawater interaction plume at Kilauea Volcano, Hawai'i

Lava flows into the sea at Kīlauea Volcano, Hawaiʻi, and generates an airborne gas and aerosol plume. Water (H 2 O), hydrogen chloride (HCl), carbon dioxide (CO 2 ), nitrogen dioxide (NO 2 ) and sulphur dioxide (SO 2 ) gases were quantified in the plume in 2004–2005, using Open Path Fourier Transform infra-red Spectroscopy. The molar abundances of these species and thermodynamic modelling are used to discuss their generation. The range in molar HCl / H 2 O confirms that HCl is generated when seawater is boiled dry and magnesium salts are hydrolysed (as proposed by [T.M. Gerlach, J.L. Krumhansl, R.O. Fournier, J. Kjargaard, Acid rain from the heating and evaporation of seawater by molten lava: a new volcanic hazard, EOS (Trans. Am. Geophys. Un.) 70 (1989) 1421–1422]), in contrast to models of Na-metasomatism. Airborne droplets of boiled seawater brine form nucleii for subsequent H 2 O and HCl condensation, which acidifies the droplets and liberates CO 2 gas from bicarbonate and carbonate. NO 2 is derived from the thermal decomposition of nitrates in coastal seawater, which takes place as the lava heats droplets of boiled seawater brine to 350–400 °C. SO 2 is derived from the degassing of subaerial lava flows on the coastal plain. The calculated mass flux of HCl from a moderate-sized ocean entry significantly increases the total HCl emission at Kīlauea (including magmatic sources) and is comparable to industrial HCl emitters in the United States. For larger lava ocean entries, the flux of HCl will cause intense local environmental hazards, such as high localised HCl concentrations and acid rain.

Hawaii↗

Poroelastic stress-triggering of the 2005 M8.7 Nias earthquake by the 2004 M9.2 Sumatra-Andaman earthquake

The M9.2 Sumatra-Andaman earthquake (SAE) occurred three months prior to the M8.7 Nias earthquake (NE). We propose that the NE was mechanically triggered by the SAE, and that poroelastic effects were a major component of this triggering. This study uses 3D finite element models (FEMs) of the Sumatra-Andaman subduction zone (SASZ) to predict the deformation, stress, and pore pressure fields of the SAE. The coseismic slip distribution for the SAE is calibrated to near-field GPS data using FEM-generated Green's Functions and linear inverse methods. The calibrated FEM is then used to predict the postseismic poroelastic contribution to stress-triggering along the rupture surface of the NE, which is adjacent to the southern margin of the SAE. The coseismic deformation of the SAE, combined with the rheologic configuration of the SASZ produces two transient fluid flow regimes having separate time constants. SAE coseismic pore pressures in the relatively shallow forearc and volcanic arc regions (within a few km depth) dissipate within one month after the SAE. However, pore pressures in the oceanic crust of the down-going slab persist several months after the SAE. Predictions suggest that the SAE initially induced MPa-scale negative pore pressure near the hypocenter of the NE. This pore pressure slowly recovered (increased) during the three-month interval separating the SAE and NE due to lateral migration of pore fluids, driven by coseismic pressure gradients, within the subducting oceanic crust. Because pore pressure is a fundamental component of Coulomb stress, the MPa-scale increase in pore pressure significantly decreased stability of the NE fault during the three-month interval after the SAE and prior to rupture of the NE. A complete analysis of stress-triggering due to the SAE must include a poroelastic component. Failure to include poroelastic mechanics will lead to an incomplete model that cannot account for the time interval between the SAE and NE. Our transient poroelastic model explains both the spatial and temporal characteristics of triggering of the NE by the SAE.

Earth and Planetary Science Letters↗

Does calving matter? Evidence for significant submarine melt

During the summer in the northeast Pacific Ocean, the Alaska Coastal Current sweeps water with temperatures in excess of 12 °C past the mouths of glacierized fjords and bays. The extent to which these warm waters affect the mass balance of Alaskan tidewater glaciers is uncertain. Here we report hydrographic measurements made within Icy Bay, Alaska, and calculate rates of submarine melt at Yahtse Glacier, a tidewater glacier terminating in Icy Bay. We find strongly stratified water properties consistent with estuarine circulation and evidence that warm Gulf of Alaska water reaches the head of 40 km-long Icy Bay, largely unaltered. A 10–20 m layer of cold, fresh, glacially-modified water overlies warm, saline water. The saline water is observed to reach up to 10.4 °C within 1.5 km of the terminus of Yahtse Glacier. By quantifying the heat and salt deficit within the glacially-modified water, we place bounds on the rate of submarine melt. The submarine melt rate is estimated at >9 m d −1 , at least half the rate at which ice flows into the terminus region, and can plausibly account for all of the submarine terminus mass loss. Our measurements suggest that summer and fall subaerial calving is a direct response to thermal undercutting of the terminus, further demonstrating the critical role of the ocean in modulating tidewater glacier dynamics.

Alaska↗

The role of preexisting upper plate strike-slip faults during long-lived (ca. 30 Myr) oblique flat slab subduction, southern Alaska

Upper plates of subduction zones commonly respond to flat slab subduction by structural reactivation, magmatic arc disruption, and foreland basin inversion. However, the role of active strike-slip faults in focusing convergent deformation and magmatism in response to oblique flat slab subduction remains less clear. Here, we present new detrital apatite fission-track (dAFT) ages from 12 modern catchments in the eastern Alaska Range, Alaska, USA, to reveal how the dextral Denali fault system has facilitated bedrock exhumation and topographic growth during ca. 30 Ma-to-present oblique flat slab subduction of the Yakutat oceanic plateau. Additionally, a 940 ka ( 40 Ar/ 39 Ar whole rock) basalt flow is spatially associated with Cenozoic structures, locally reset AFT ages and provides the first evidence for Quaternary volcanism along the southern flank of the eastern Alaska Range. We integrate our new data with other thermochronologic, geochronologic, and regional geologic datasets to show that (1) most high topography regions in southern Alaska have undergone rapid bedrock cooling and exhumation since ca. 30 Ma; (2) elevated terrain and young cooling are spatially associated with long-lived active strike-slip fault systems; (3) topographic growth associated with strike-slip fault deformation led to local inversion of basin systems and drainage reorganization; (4) the onset of oblique oceanic plateau subduction is coeval with a southward shift in arc magmatism from one region of active strike-slip faulting to another above the northeastern edge of the flat slab; and (5) Quaternary volcanism marks the revival of magmatism in the eastern Alaska Range above the geophysically imaged northeastern edge of the flat slab. Our analysis of the post-30 Ma geologic evolution of southern Alaska demonstrates that strike-slip fault systems that were active at the time of slab flattening evolved into transpression zones that focused bedrock cooling, rock exhumation, and topographic growth.

Alaska↗

A life cycle model for evaluating estuary residency and restoration potential in Chinook salmon

Understanding the spatial and temporal habitat use of a population is a necessary step for recovery planning. For Chinook salmon ( Oncorhynchus tshawytscha ), variation in their migration and habitat use complicate predicting how restoring habitats could impact total recruitment. To evaluate how juvenile life history variation affects a population’s response to potential restoration, we developed a stage-structured model for a Chinook salmon population in a northern California river with a seasonally closed estuary. We modeled the timing of juvenile migration and estuarine use as a function of freshwater conditions and fish abundance. We used the model to evaluate the sensitivity of the population to different estuary and freshwater restoration scenarios that could affect population parameters at different life stages. The population’s run size increased most in response to freshwater restoration that enhanced spawning productivity (egg and fry survival), followed by spawner capacity. In contrast, estuary restoration scenarios affected only a subset of Chinook salmon (average 15%), and as a result, did not have a large impact on the total recruitment of a cohort. Under current condition, estuary rearing fish were over six times less likely to survive than fish that migrate to the ocean in the spring or early summer before estuary closure. Because estuary residents experienced low survival in the estuary and in the ocean, improvements to both estuary survival and growth would be needed to increase their total survival. When life cycle monitoring data is available, life cycle models such as ours generate predictions at scales relevant to conservation and are an advantageous approach to managing and conserving anadromous salmon that use multiple habitats throughout their life cycle.

California↗

The stable carbon isotope biogeochemistry of acetate and other dissolved carbon species in deep subseafloor sediments at the northern Cascadia Margin

Ocean drilling has revealed the existence of vast microbial populations in the deep subseafloor, but to date little is known about their metabolic activities. To better understand the biogeochemical processes in the deep biosphere, we investigate the stable carbon isotope chemistry of acetate and other carbon-bearing metabolites in sediment pore-waters. Acetate is a key metabolite in the cycling of carbon in anoxic sediments. Its stable carbon isotopic composition provides information on the metabolic processes dominating acetate turnover in situ. This study reports our findings for a methane-rich site at the northern Cascadia Margin (NE Pacific) where Expedition 311 of the Integrated Ocean Drilling Program (IODP) sampled the upper 190 m of sediment. At Site U1329, δ 13 C values of acetate span a wide range from −46.0‰ to −11.0‰ vs. VPDB and change systematically with sediment depth. In contrast, δ 13 C values of both the bulk dissolved organic carbon (DOC) (−21.6 ± 1.3‰ vs. VPDB) and the low-molecular-weight compound lactate (−20.9 ± 1.8‰ vs. VPDB) show little variability. These species are interpreted to represent the carbon isotopic composition of fermentation products. Relative to DOC, acetate is up to 23.1‰ depleted and up to 9.1‰ enriched in 13 C. Broadly, 13 C-depletions of acetate relative to DOC indicate flux of carbon from acetogenesis into the acetate pool while 13 C-enrichments of pore-water acetate relative to DOC suggest consumption of acetate by acetoclastic methanogenesis. Isotopic relationships between acetate and lactate or DOC provide new information on the carbon flow and the presence and activity of specific functional microbial communities in distinct biogeochemical horizons of the sediment. In particular, they suggest that acetogenic CO 2 -reduction can coexist with methanogenic CO 2 -reduction, a notion contrary to the hypothesis that hydrogen levels are controlled by the thermodynamically most favorable electron-accepting process. Further, the isotopic relationship suggests a relative increase in acetate flow to acetoclastic methanogenesis with depth although its contribution to total methanogenesis is probably small. Our study demonstrates how the stable carbon isotope biogeochemistry of acetate can be used to identify pathways of microbial carbon turnover in subsurface environments. Our observations also raise new questions regarding the factors controlling acetate turnover in marine sediments.

Geochimica et Cosmochimica Acta↗

An initial investigation into the organic matter biogeochemistry of the Congo River

The Congo River, which drains pristine tropical forest and savannah and is the second largest exporter of terrestrial carbon to the ocean, was sampled in early 2008 to investigate organic matter (OM) dynamics in this historically understudied river basin. We examined the elemental (%OC, %N, C:N), isotopic (&delta; 13 C, &Delta; 14 C, &delta; 15 N) and biochemical composition (lignin phenols) of coarse particulate (>63 &mu;m; CPOM) and fine particulate (0.7&ndash;63 &mu;m; FPOM) OM and DOC, &delta; 13 C, &Delta; 14 C and lignin phenol composition with respect to dissolved OM (<0.7 &mu;m; DOM) from five sites in the Congo River Basin. At all sample locations the organic carbon load was dominated by the dissolved phase (~82&ndash;89% of total organic carbon) and the total suspended sediment load was principally fine particulate material (~81&ndash;91% fine suspended sediment). Distinct compositional and isotopic differences were observed between all fractions. Congo CPOM, FPOM and DOM all originated from vegetation and soil inputs as evidenced by elemental, isotopic and lignin phenol data, however FPOM was derived from much older carbon pools (mean &Delta; 14 C = -62.2 &plusmn; -13.2&permil;, n = 5) compared to CPOM and DOM (mean &Delta; 14 C = 55.7 &plusmn; 30.6&permil;, n = 4 and 73.4 &plusmn; 16.1&permil;, n = 5 respectively). The modern radiocarbon ages for DOM belie a degraded lignin compositional signature (i.e. elevated acid:aldehyde ratios (Ad:Al) relative to CPOM and FPOM), and indicate that the application of OM degradation patterns derived from particulate phase studies to dissolved samples needs to be reassessed: these elevated ratios are likely attributable to fractionation processes during solubilization of plant material. The relatively low DOM carbon-normalized lignin yields (&Lambda;8; 0.67&ndash;1.12 (mg(100 mg OC) -1 )) could also reflect fractionation processes, however, they have also been interpreted as an indication of significant microbial or algal sources of DOM. CPOM appears to be well preserved higher vascular plant material as evidenced by its modern radiocarbon age, elevated C:N (17.2&ndash;27.1) and &Lambda;8 values (4.56&ndash;7.59 (mg(100 mg OC) -1 )). In relation to CPOM, the aged FPOM fraction (320&ndash;580 ybp 14 C ages) was comparatively degraded, as demonstrated by its nitrogen enrichment (C:N 11.4&ndash;14.3), lower &Lambda;8 (2.80&ndash;4.31 (mg(100 mg OC) -1 )) and elevated lignin Ad:Al values similar to soil derived OM. In this study we observed little modification of the OM signature from sample sites near the cities of Brazzaville and Kinshasa to the head of the estuary (~350 km) highlighting the potential for future studies to assess seasonal and long-term OM dynamics from this logistically feasible location and derive relevant information with respect to OM exported to the Atlantic Ocean. The relative lack of OM data for the Congo River Basin highlights the importance of studies such as this for establishing baselines upon which to gauge future change.

Congo River↗

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

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

Geochimica et Cosmochimica Acta↗