Selecting a global optimization method to estimate the oceanic particle cycling rate constants

The objective is to select an inverse method to estimate the parameters of a dynamical model of the oceanic particle cycling from in situ data. Estimating the parameters of a dynamical model is a nonlinear inverse problem, even in the case of linear dynamics. Generally, biogeochemical models are characterized by complex nonlinear dynamics and by a high sensitivity to their parameters. This makes the parameter estimation problem strongly nonlinear. We show that an approach based on a linearization around an a priori solution and on a gradient descent method is not appropriate given the complexity of the related cost functions and our poor a priori knowledge of the parameters. Global Optimization Algorithms (GOAs) appear as better candidates. We present a comparison of a deterministic (TRUST), and two stochastic (simulated annealing and genetic algorithm) GOAs. From an exact model integration, a synthetic data set is generated which mimics the space-time sampling of a reference campaign. Simulated optimizations of two to the eight model parameters are performed. The parameter realistic ranges of values are the only available a priori information. The results and the behavior of the GOAs are analyzed in details. The three GOAs can recover at least two parameters. However, the gradient requirement of deterministic methods proves a serious drawback. Moreover, the complexity of the TRUST makes the estimation of more than two parameters hardly conceivable. The genetic algorithm quickly converges toward the eight parameter solution, whereas the simulated annealing is trapped by a local minimum. Generally, the genetic algorithm is less computationally expensive, swifter to converge, and has more robust procedural parameters than the simulated annealing

Tracers of physical and biogeochemical processes, past changes and ongoing anthropogenic impacts: the 43rd International Liege Colloquium on Ocean Dynamics, Liege, Belgium, May 2-6, 2011

The 43rd International Liege Colloquium on Ocean Dynamics (http://modb.oce.ulg.ac.be/colloquium/) gathered a hundred scientists from around the world to discuss new developments and insights related to tracers and proxies (from temperature and salinity to gases and isotopes) with a particular attention on the use of Trace Elements and Isotopes (TEI) as tracers. The colloquium was organized in connection with the Geotraces program (an ongoing international study of the global marine biogeochemical cycles of trace elements and their isotopes, http://www.geotraces.org/) and was the occasion to present the wealth of data collected during large oceanographic expeditions that occurred in connection with the International Polar year. In this framework, particular emphasis was given to the BONUS-GoodHope project, a multi-disciplinary oceanographic cruise that coupled full-depth ocean and atmosphere physical and biogeochemical observations, including trace metals and isotopes (Speich et al. 2013; Speich et al. 2008). The special issue presents a collection of papers dealing with these different thematics

Imprint of a dissolved cobalt basaltic source on the Kerguelen Plateau

International audienceProcesses of cobalt (Co) entrainment from shelf sediments over the Kerguelen Plateau were studied during the KEOPS (Kerguelen Ocean Plateau compared Study) in order to explain the exceptionally high dissolved cobalt concentrations that have been measured in the surface waters above the Kerguelen Plateau, and in intermediate and deep waters above its eastern slope. Lateral advection and dissolution of Co contained in basalt sediments around Heard Island, a main source of lithogenic Co in the study area, were shown to imprint the process of surface enrichment over the plateau. Dissolved Co enrichment was strongest at the intercept of the eastern slope with intermediate and deep waters, probably due to more efficient mobilisation of the sediments in the slope current, in addition to advection of Co-enriched and low-oxygenated ocean water masses. In surface waters, the strong sedimentary Co inputs were estimated to be much higher than biological Co uptake in phytoplankton blooms, underlining the potential use of dissolved cobalt as tracer of the natural iron fertilization above the Kerguelen Plateau. Based on a simple steady-state balance equation of the external input of dissolved iron over the plateau, the fertilization of iron inferred by using dissolved Co as a tracer of basalt sources is estimated to be 28 × 102 ± 21 × 102 t yr−1 in surface waters of the Kerguelen Plateau. This estimate is consistent with preceding ones (Zhang et al., 2008; Chever et al., 2010), and the calculated iron supply matches with the phytoplankton demand (Sarthou et al., 2008)

Methods for analyzing the concentration and speciation of major and trace elements in marine particles

Particles influence trace element and isotope (TEI) cycles through both their elemental composition and fate and their role on the partitioning of dissolved elements through scavenging and dissolution. Because of their complex compositions, a diverse suite of methods is required to analyze marine particles. Here we review some of the varied approaches used to study particle composition, speciation and fate. We focus on high throughput analytical methods that are useful for the international GEOTRACES program, and we also describe new spectroscopic techniques that are now being applied to study the spatial distribution and chemical speciation of TEIs in marine particles

Can nuclear weapons fallout mark the beginning of the Anthropocene Epoch?

Many scientists are making the case that humanity is living in a new geological epoch, the Anthropocene, but there is no agreement yet as to when this epoch began. The start might be defined by a historical event, such as the beginning of the fossil-fueled Industrial Revolution or the first nuclear explosion in 1945. Standard stratigraphic practice, however, requires a more significant, globally widespread, and abrupt signature, and the fallout from nuclear weapons testing appears most suitable. The appearance of plutonium 239 (used in post- 1945 above-ground nuclear weapons tests) makes a good marker: This isotope is rare in nature but a significant component of fallout. It has other features to recommend it as a stable marker in layers of sedimentary rock and soil, including: long half-life, low solubility, and high particle reactivity. It may be used in conjunction with other radioactive isotopes, such as americium 241 and carbon 14, to categorize distinct fallout signatures in sediments and ice caps. On a global scale, the first appearance of plutonium 239 in sedimentary sequences corresponds to the early 1950s. While plutonium is easily detectable over the entire Earth using modern measurement techniques, a site to define the Anthropocene (known as a Ògolden spikeÓ) would ideally be located between 30 and 60 degrees north of the equator, where fallout is maximal, within undisturbed marine or lake environments

Sources and input mechanisms of hafnium and neodymium in surface waters of the Atlantic sector of the Southern Ocean

Radiogenic isotopes of hafnium (Hf) and neodymium (Nd) are powerful tracers for water mass transport and trace metal cycling in the present and past oceans. However, due to the scarcity of available data the processes governing their distribution are not well understood. Here we present the first combined dissolved Hf and Nd isotope and concentration data from surface waters of the Atlantic sector of the Southern Ocean. The samples were collected along the Zero Meridian, in the Weddell Sea and in the Drake Passage during RV Polarstern expeditions ANTXXIV/3 and ANTXXIII/3 in the frame of the International Polar Year (IPY) and the GEOTRACES program. The general distribution of Hf and Nd concentrations in the region is similar. However, at the northernmost station located 200 km southwest of Cape Town a pronounced increase of the Nd concentration is observed, whereas the Hf concentration is minimal, suggesting much less Hf than Nd is released by the weathering of the South African Archean cratonic rocks. From the southern part of the Subtropical Front (STF) to the Polar Front (PF) Hf and Nd show the lowest concentrations (<0.12 pmol/kg and 10 pmol/kg, respectively), most probably due to the low terrigenous flux in this area and efficient scavenging of Hf and Nd by biogenic opal. In the vicinity of landmasses the dissolved Hf and Nd isotope compositions are clearly labeled by terrigenous inputs. Near South Africa Nd isotope values as low as ε[subscript Nd] = −18.9 indicate unradiogenic inputs supplied via the Agulhas Current. Further south the isotopic data show significant increases to ε[subscript Hf] = 6.1 and ε[subscript Nd] = −4.0 documenting exchange of seawater Nd and Hf with the Antarctic Peninsula. In the open Southern Ocean the Nd isotope compositions are relatively homogeneous (ε[subscript Nd] ∼ −8 to −8.5) towards the STF, within the Antarctic Circumpolar Current, in the Weddell Gyre, and the Drake Passage. The Hf isotope compositions in the entire study area only show a small range between ε[subscript Hf] = + 6.1 and +2.8 support Hf to be more readily released from young mafic rocks compared to old continental ones. The Nd isotope composition ranges from ε[subscript Nd] = −18.9 to −4.0 showing Nd isotopes to be a sensitive tracer for the provenance of weathering inputs into surface waters of the Southern Ocean.This is the publisher’s final pdf. The article is sponsored by the Geochemical Society and the Meteoritical Society and published by Elsevier. It can be found at: http://www.journals.elsevier.com/geochimica-et-cosmochimica-acta

Coastal Ocean and Shelf-Sea Biogeochemical Cycling of Trace Elements and Isotopes: Lessons Learned from GEOTRACES

Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES programme as well as a proof of concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T1/2 = 5.75 yr), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf 228Ra fluxes are combined with TEI/ 228Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric deposition by factors of approximately 3-23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean.This article is part of the themed issue \u27Biological and climatic impacts of ocean trace element chemistry\u27

Continental bedrock and riverine fluxes of strontium and neodymium isotopes to the oceans

Author Posting. © American Geophysical Union, 2010. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 11 (2010): Q03016, doi:10.1029/2009GC002869.Realistic models of past climate and ocean chemistry depend on reconstructions of the Earth's surface environments in the geologic past. Among the critical parameters is the geologic makeup of continental drainage. Here we show, for the present, that the isotope composition of dissolved strontium in rivers increases linearly with the age of bedrock in drainage basins, with the notable exception of the drainage area of Arabia, India, and Southeast Asia that is affected by unusually radiogenic dissolved Sr from the Himalaya. We also demonstrate that the neodymium isotope compositions of suspended matter in rivers as well as clastic sediments deposited along the ocean margins decrease linearly with the bedrock ages of river drainage basins and large-scale continental drainage regions, as determined from digital geologic maps. These correlations are used to calculate the present-day input of dissolved Sr (4.7 × 1010 mol yr−1, 87Sr/86Sr of ∼0.7111) and particulate Nd isotopes (ɛNd of approximately −7.3 ± 2.2) to the oceans. The fact that the regionally averaged ɛNd of the global detrital input to the global coastal ocean is identical to globally averaged seawater (ɛNd of −7.2 ± 0.5) lends credence to the importance of “boundary exchange” for the Nd isotope composition of water masses. Regional biases in source areas of detrital matter and runoff are reflected by the observation that the average age of global bedrock, weighted according to the riverine suspended sediment flux, is significantly younger (∼336 Myr) than the age of global bedrock weighted according to water discharge (394 Myr), which is younger than the average bedrock age of the nonglaciated, exorheic portions of the continents (453 Myr). The observation that the bedrock age weighted according to Sr flux is younger (339 Myr) than that weighted according to water flux reflects the disproportionate contribution from young sedimentary and volcanic rocks to the dissolved Sr load. Neither the isotope composition of the dissolved nor the particulate continental inputs to the ocean provide unbiased perspectives of the lithologic makeup of the Earth's surface. Temporal changes in bedrock geology as well as the shifting focal points of physical erosion and water discharge will undoubtedly have exerted strong controls on temporal and spatial changes in the isotope chemistry of past global runoff and thus seawater.NSF grants EAR‐ 0125873, EAR‐0519387, and OCE‐0851015 to B.P.‐E. and a CNRS‐funded “poste rouge” position for B.P.‐E. at the Observatoire Midi‐Pyrénées in Toulouse supported this work

The geological cycle of plastics and their use as a stratigraphic indicator of the Anthropocene

The rise of plastics since the mid-20th century, both as a material element of modern life and as a growing environmental pollutant, has been widely described. Their distribution in both the terrestrial and marine realms suggests that they are a key geological indicator of the Anthropocene, as a distinctive stratal component. Most immediately evident in terrestrial deposits, they are clearly becoming widespread in marine sedimentary deposits in both shallow- and deep-water settings. They are abundant and widespread as macroscopic fragments and virtually ubiquitous as microplastic particles; these are dispersed by both physical and biological processes, not least via the food chain and the ‘faecal express’ route from surface to sea floor. Plastics are already widely dispersed in sedimentary deposits, and their amount seems likely to grow several-fold over the next few decades. They will continue to be input into the sedimentary cycle over coming millennia as temporary stores – landfill sites – are eroded. Plastics already enable fine time resolution within Anthropocene deposits via the development of their different types and via the artefacts (‘technofossils’) they are moulded into, and many of these may have long-term preservation potential when buried in strata