ALBERT

Description: Interactions between dissolved trace elements and organic ligands in seawater play an important role in ocean biogeochemistry, ranging from regulating primary production in surface waters to element cycling on basin-wide scale, with strong feedbacks to climate variability. In this study, we review different aspects in the field of marine trace elements and their organic ligands: recent instrumental innovation, factors that affect the fate of trace element complexes at the molecular level, spatial distribution of organic matter – trace element complexes in the ocean, modeling approaches as well as prospect in the scenarios of climate variability. We also assess the critical issues of parameterization in the numerical simulation that incorporate the trace elements – organic ligands interactions. Given the predicted climate changes, we examine the potential of exchange between inorganic and organic complexes for trace elements in different oceanic provinces.

Description: The widespread diatom Pseudo-nitzschia can produce domoic acid (DA). DA is a compound with well described neurotoxic effects on vertebrates including humans known as amnesic shellfish poisoning (ASP) syndrome. It has also been suggested to serve as an organic ligand that binds to iron and copper. By binding these trace elements, DA may increase their solubility and bioavailability. In order to serve this function, DA has to be excreted and reabsorbed by the cells. Only few records of dissolved domoic acid (dDA) concentrations in the ocean exist. To accomplish quantification by ultra performance liquid chromatography (UPLC), samples have to be pre-concentrated and desalted using solid-phase extraction, a procedure commonly applied for dissolved organic matter. Our major goals were to quantify dDA in a basin-wide assessment in the East Atlantic Ocean, to determine extraction efficiencies for complexed and uncomplexed dDA, and to assess whether domoic acid is represented by its molecular formula in direct-infusion high resolution mass spectrometry. Our results showed that dDA was extracted almost quantitatively and occurred ubiquitously in the ocean surface but also in deeper (and older) water, indicating surprisingly high stability in seawater. The maximum concentration measured was 173 pmol L−1 and the average molar dDA carbon yield was 7.7 ppm. Both carbon yield and dDA concentration decreased with increasing water depth. Providing quantification of dDA in the water column, we seek to improve our understanding of toxic bloom dynamics and the mechanistic understanding of DA production.

Description: The overlay of cooler nutrient enriched Beagle–Magellan water with warmer nutrient depleted shelf water and a strong stratification of the water column in the San Jorge Gulf region, Argentina, coincided with relatively high dinoflagellate abundances in April 2012, up to 34,000 cells L− 1. This dinoflagellate proliferation was dominated by Ceratium spp., but environmental conditions also favored to a lesser amount the occurrence of toxigenic dinoflagellates, such as Alexandrium tamarense and Protoceratium reticulatum, whose toxins were hardly detected in any other areas along the expedition transect of the R/V Puerto Deseado between 38 and 56°S (Ushuaia–Mar del Plata) in March/April 2012. Generally vegetative cells of A. tamarense and P. reticulatum co-occurred with their respective phycotoxins in the water column and their cysts in the upper sediment layers. Two strains of A. tamarense were isolated from the bloom sample and morphologically characterized. Their PSP toxin profiles consisted of C1/2, gonyautoxins 1/4 and to a lesser amount of neosaxitoxin and confirmed earlier data from this region. The ratios between autotrophic picoplankton and heterotrophic bacteria were higher in shelf waters in the north than in Beagle–Magellan waters in the south of San Jorge Gulf.

Description: Fluorescence spectroscopy is commonly used to investigate the distribution and dynamics of dissolved organic matter (DOM) in marine systems. However, the direct comparison with chemical signatures is essential to substantiate the molecular composition of specific fluorescent components. Here we report the relation between optical and chemical signatures of DOM in waters of the Beagle Channel (BCW) (south-east of Tierra del Fuego, in the southern Argentine shelf) at the Pacific-Atlantic connection and neighboring coastal (CW) and oceanic (OW) waters (54.75–55.75°S, 64–68°W). The relationships among concentrations of total dissolved carbohydrates (TDCHO) and amino acids (TDAA), and fluorescent DOM (FDOM), including terrestrial “humic-like” (FDOMC) and “protein-like” compounds (FDOMT), and bioavailability of DOM components were assessed from field measurements acquired in the austral summer 2012. The maximal concentrations of TDCHO, dissolved organic carbon (DOC) and FDOMc intensities were found in BCW, while the minima in OW, displaying a negative correlation with salinity. This spatial distribution of biogeochemical signals suggests that humic compounds contributed by continental runoff contain refractory carbohydrates, and FDOMC resulted as a reliable tracer of carbon pathways in the Pacific-Atlantic connection. Conversely, TDAA and FDOMT showed the opposite distributional trend, with minimal concentrations in BCW and the maxima in CW and OW. The significant positive correlation of TDAA with salinity suggests open water sources of these components, however, phytoplankton biomass (Chla) in CW and OW was significantly lower than in BCW, ruling out the assumption of autochthonous source in open waters. TDAA were negatively correlated with the abundance of heterotrophic bacteria (HB), which displayed a consistent decrease from BCW towards OW, suggesting high bacterial uptake of TDAA in the BCW. This bacterial uptake is supported by the observed variation in carbon contribution of TDAA to DOC (amino acids carbon yield, in %), which is an indicator of DOM lability. The negative correlation found between amino acids carbon yield and HB abundance reflects intense bacterial activity in BCW, where phytoplankton biomass was maximum. Hence, higher DOM “freshness” occurs in the BCW, suggesting a tight coupling between microbial production and consumption.

Description: Advancing our understanding of the behaviour of dissolved organic matter (DOM) in aquatic environments necessitates efforts to combine complementary analytical data sets. However, some analytical measurements require sample pre-treatment, while others are carried out on bulk water samples, and it remains unclear if the resulting data sets can be compared. Here, we investigated the impact of solid-phase extraction with PPL resins on DOM optical properties. In samples from contrasting Arctic fjords, extraction efficiencies based on optical properties varied spectrally with averages between 31 ± 13% at 411 nm and 40 ± 12% at 363 nm for chromophoric DOM. Similarly, the extraction efficiency for specific fluorescence components varied between 37 ± 16% and 58 ± 18%. Solid-phase extraction also decreased S275–295, fluorescence index, and the freshness index, but increased S350–400, and apparent fluorescence quantum yields, indicating that the extraction process was qualitatively selective. Six fluorescence components identified independently in bulk water samples and extracted DOM using parallel factor analysis exhibited different behaviours. Three had identical spectral properties before and after extraction, although their extraction efficiencies varied with water mass characteristics and DOM composition, whereas three other components appeared to change after extraction. With the exception of one fluorescence component, the dynamics of optical properties in bulk water samples were not accurately reflected by DOM extracts. These results indicate that solid-phase extraction imparts a qualitative selectivity that leads to the homogenization of DOM extracts relative to their original samples. Efforts to integrate chemical information from different analytical methods should prioritize comparisons of measurements obtained on the same samples.

Description: The present work reports the first data set on particulate organic carbon (POC) and nitrogen (PON), and the highresolution modelling of their stable isotope variability in the Patagonian Cold Estuarine System (PCES), with focus on particulate organic matter (POM) origin and distribution in dependence on physical, chemical and biological parameters. POC, PON, stable carbon (δ13C) and nitrogen isotopes (δ15N), dissolved organic nitrogen, phaeopigments, diatom, dinoflagellate and heterotrophic bacteria (HB) abundance are reported for 17 stations in different waters masses in the southern end of the Argentine shelf in late summer 2012. Most parameters denote clear differences between Beagle-Magellan Water (BMW), Subantarctic ShelfWater (SSW) and Subantarctic Water (SAW). POC and PON decreased frommaxima in BMWto intermediate values in SSWandminima in SAW. There was a highly significant correlation among POC, PON and fluorescence indicators of diagenetic maturity of dissolved humic matter. This, together with the inverse correlations of salinity with POC and PON, and the wide range of C:N ratios indicate that POM in the study area is partly derived from terrestrial runoff, superimposed by autochthonous components from plankton of different life stages. HB abundance was significantly correlated with POC and dissolved organic matter (DOM), likely reflecting a resource control of HB and a significant contribution of bacterial biomass to POM in the nanoparticle fraction. The direct relationship between HB and dissolved humics suggests bacterial uptake of DOM fractions otherwise considered refractory. POM complexity was reflected in a wide variation of δ13C, despite the narrowtemperature range of this region. The variability of stable isotopes of POC could be accounted for by a modelwith a degree of detail hitherto not reported in the literature. Amultiple regression including C:N ratio, ammonium and the quotient between log abundance of diatoms, dinoflagellates and HB explained 92% of δ13C variance, mostly produced by ammonium. Despite the strong effect of ammonium on δ13C, δ15N variability was largely explained by a strong inverse relationship with the fraction of unutilized nitrate, suggesting dominance of nitrate uptake. However, the proportion of presumably isotopically heavier ammoniumderived fromcontinental runoff in the marine δ15N-POM pool is unknown and requires investigation of the isotopic composition of dissolved inorganic nitrogen in the PCES. The presented newinformation and its comparison with data fromother sectors of the Argentine shelf constitute a contribution to an approach for the understanding of the organicmatter dynamics that can be potentially expanded to the entire Southwest Atlantic.