Photochemical alkene formation in sea water from dissolved organic carbon:results from laboratory experiments

The production mechanism of light alkenes, alkanes, and isoprene was investigated in laboratory experiments by measuring their concentrations in natural seawater as a function of spectral range, exposure time and origin, and concentration of dissolved organic carbon (DOC). The production mechanism of alkanes and of isoprene could not be clarified. Ethene and propene are produced photochemically from DOC. The relevant spectral range is UV and short‐wavelength visible light. Initial production rates (up to day 10 of exposure) were in the range of several pmol L−1 h−1 (mg DOC)−1; the corresponding mean quantum yields for the spectral range of 300–420 nm were about 10−8. Generally, the production rates and the quantum yields for ethene were about 2 times that of propene. The key factors in the total column integrated oceanic alkene production are the solar photon flux at sea surface, the penetration depth of the light into the ocean (especially the relation between different light absorbers, i.e., the extinction due to absorption of DOC), and the wavelength‐ and DOC‐dependent quantum yields. As a result of the high variability of these parameters, actual local alkene production rates for a specific oceanic region may differ considerably from the globally averaged oceanic alkene production rates. The latter were estimated to be at most 5 Mt yr−1

Bestimmung der Bindung von Trijodthyronin an Serumproteine mittels Dextran-Gel-Filtration

1. Es wird eine Methode zur gleichzeitigen Bestimmung des sog. freien und des proteingebundenen Anteils von in vitro zugesetztem L-Trijodthyronin-131Jod im Serum mittels Dextran-Gel-Filtration angegeben. In der beschriebenen Form ist diese Technik für die routinemäßige Anwendung in der Klinik zur Bestimmung der Bindungs- und Transportverhältnisse von Trijodthyronin geeignet. 2. In sog. Verdrängungsversuchen wurde nichtmarkiertes Trijodthyronin dem Inkubationsgemisch von Serum und L-Trijodthyronin-131Jod zugesetzt. Die zugesetzten Trijodthyroninmengen erschöpfen die Gesamtbindungskapazität der Serumproteine in dem gewählten Konzentrationsbereich keineswegs. Im Gegensatz zum Verhalten der prozentualen Anteile des sog. freien und des proteingebundenen Trijodthyronins steigt die absolute Menge des proteingebundenen Trijodthyronins dabei steil an. Man findet eine Kurve, die nicht einer einfachen Sättigunskurve entspricht, sondern eine Resultante aus Sättigungskurven verschiedener Trijodthyronin-bindender Proteine und Verdrängungskurven kompetitiv gebundener Substanzen (z.B. Thyroxin) darstellt. 3. Dextran-Gel wirkt nicht als einfaches Molekülsieb für Trijodthyronin. Es greift vielmehr durch Adsorptionsvorgänge kompetitiv in die Serumproteinbindungsverhältnisse des Trijodthyronins ein. Die physiologische Bedeutung des sog. freien Anteils an Trijodthyronin wird diskutiert. 4. Die Methode zur Bestimmung des proteingebundenen Jods (PB127I) mittels alkalischer offener Veraschung (Barker) wurde technisch vereinfacht und bezüglich ihrer Reproduzierbarkeit untersucht. Die131Jodausbeute aus zugesetztem L-Thyroxin-131Jod lag bei diesem Verfahren bei ca. 80%

Interdisciplinarity to reconstruct historical introductions: solving the status of cryptogenic crayfish

Anciently introduced species can be confounded with native species because introduction pre-dates the first species inventories or because of the loss of the collective memory of the introductions. The term ‘cryptogenic species’ denotes species of unknown or unclear status (native versus non-native) in a given territory, and disciplinary approaches are often insufficient for solving their true status. Here, we follow an integrative, multidisciplinary approach to solve the status of a cryptogenic species, proposing that building on evidence from multiple disciplines can produce robust and clarifying insights. We undertook an exhaustive review of information on a putatively native crayfish (Austropotamobius italicus) in Spain. The reviewed information included taxonomy, genetics and phylogeography, history, archaeology, linguistics, biogeography, ecology, symbiotic organisms and even gastronomy and pharmacy. The knowledge produced by different scientific disciplines converges to indicate that A. italicus is a non-native species in Spain. Historical documents even identify the first introduction event: crayfish were shipped from Italy to Spain in 1588 as a diplomatic gift from Francesco I de' Medici to King Philip II of Spain. Previous discussions on the status of A. italicus focussed on inconclusive and often confusing genetic results and excluded the rich and clarifying evidence available from other approaches and disciplines. Interdisciplinarity is an often-invoked but rarely implemented practice in an academic environment that increasingly promotes narrow-focussed specialization. Our review shows that the integration of disciplines can surpass disciplinary approaches in solving scientific controversies. Our results have straightforward implications for strategies to conserve biological diversity in Spain and Europe, urging a debate on the appropriateness of devoting conservation efforts to non-native species.Peer Reviewe

Effects of suspended solids and dissolved organic carbon on nickel toxicity

Nickel (Ni) is a common and potentially toxic heavy metal in many fluvial ecosystems. We examined the potentially competitive and complementary roles of suspended sediment and a dissolved organic ligand, humate, in affecting the partitioning and toxicity of Ni to a model organism, Daphnia magna , in both batch and stream-recirculating flume (SRF) tests. Sediments included a fine-grained deposit, montmorillonite, and kaolinite. Survival of D. magna was unaffected by the range of suspended solids used in the present study (8–249 mg/L). However, exposure to suspended solids that were amended with Ni had a deleterious effect on test organism survival, which is attributed to partitioning of Ni into the aqueous phase. At comparable levels of dissolved Ni, survival of D. magna was reduced in tests with Ni-amended suspended solids compared to Ni-only aqueous exposures, suggesting potentiation between these two aquatic contaminants. Addition of humate attenuated toxicity to D. magna in both Ni-only and Ni-amended suspended sediment exposures. These results indicate that organic ligands and suspended solids have important functions in affecting the bioavailability and toxicity of Ni to aquatic organisms and should be incorporated into predictive models to protect ecosystem quality. Environ. Toxicol. Chem. 2010; 29:1781–1787. © 2010 SETACPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/77536/1/226_ftp.pd

Copper and nickel partitioning with nanoscale goethite under variable aquatic conditions

Metal contaminated sediments can be toxic to aquatic organisms and are common in human‐dominated ecosystems, which results in metals being a leading cause of ecosystem impairment. Bioavailability of metals is influenced by their affinity for dissolved and solid‐phase ligands, including iron (Fe) oxyhydroxides, which have been hypothesized to reduce metal toxicity in sediments. The authors examined the adsorption kinetics of copper (Cu) and nickel (Ni) with goethite (α‐FeOOH) and characterized the influences of solute metal concentration, pH, ionic strength, and humate concentration on steady‐state partitioning of the metals with goethite under conditions representative of natural aquatic environments. Copper and Ni readily adsorbed to goethite, and steady‐state partitioning was achieved within 2 h. Although ionic strength had no effect on metal partitioning, adsorption of Cu and Ni to goethite was enhanced by alkaline pH and reduced by competition with humate. Because distribution coefficient (KD) values for Cu and Ni from the present study are comparable to values measured in natural systems, the authors hypothesize that goethite may contribute significantly to the adsorption of both Ni and Cu to particles in the environment. The authors suggest that incorporating binding by Fe oxides in metal bioavailability models should be a priority for improving risk assessment of metal‐contaminated oxic sediments. Environ Toxicol Chem 2015;34:1705–1710. © 2015 SETACPeer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/112217/1/etc2977.pd

Sources and cycling of dissolved and particulate organic radiocarbon in the northwest Atlantic continental margin

Continental shelves and slopes are productive and dynamic ocean margin systems that also regulate the fluxes of terrestrial, riverine, and estuarine materials between the continents and oceans. In order to evaluate the ages, potential sources, and transformations of organic matter in an ocean margin system, we measured the radiocarbon (A14C) and 613C distributions of total dissolved organic carbon (DOC), suspended particulate organic carbon (POC), and dissolved inorganic carbon (DIC) in waters of the Middle Atlantic Bight (MAB) continental shelf and slope in April-May 1994. The A•4C of DOC was greatest (as high as -39%0) in surface waters of the shelf, decreasing rapidly offshore and with depth, even in relatively shallow (25-50 m depth) shelf waters. The lowest A14C-DOC values were observed in deep slope waters, where they were significantly lower than values measured previously for the deep Sargasso Sea. There was a strong inverse relationship between A14C-DOC and 613C-DOC in all shelf and surface slope waters of the MAB, which is likely attributable to varying contributions of young, 14C-enriched organic matter of terrestrial and/or riverine origin. The more highly •4C-depleted DOC in deep slope waters (as low as -442%0) generally had a correspondingly lower bl3C (as low as -22.3%0) component. However, this must originate from relic terrestrial material either in the MAB itself or be discharged to the MAB from rivers and estuaries. The isotopic signatures of POC were clearly differentiable from DOC and indicate that this pool also contained a broad range of both old and young material of terrestrial (•3C as low as -24.9%0) and marine (•3C as high as -19.9%o) origin throughout the MAB shelf and slope. The highest A14C-POC values (up to 78%0) were observed in shallow shelf waters of the southern MAB. Conversely, the lowest A14C-POC values as low as -394%0) were found in MAB deep slope waters and were also significantly more depleted in 14C than POC from the central north Atlantic (Sargasso Sea). A multiple-source isotopic mass balance model employing both 14C and 13C was used to evaluate the relative contributions of both young and old terrigenous versus marine organic matter to DOC and POC in the MAB. The results indicate that shelf and slope DOC is comprised of an old "marine" fraction (represented by offshore Sargasso Sea material) and either a young "terrestrial/riverine/ estuarine" (TRE) component (in shelf and shallow slope waters) or a relic TRE component (in deep and some shallow slope waters). In contrast, suspended POC from the MAB appears to originate predominantly from a mixture of recent MAB primary production and an old, TRE component, similar to that observed in one of the major subestuaries of the Chesapeake Bay. These results suggest that both young and old sources of terrestrial and rivefine organic matter can comprise a significant fraction of the DOC and POC in ocean margins. Preliminary calculations indicate that the export of this compositionally unique DOC and suspended POC may be significant terms in the organic carbon budgets of the MAB and other margin system

Sulfate deprivation triggers high methane production in a disturbed and rewetted coastal peatland

In natural coastal wetlands, high supplies of marine sulfate suppress methanogenesis. Coastal wetlands are, however, often subject to disturbance by diking and drainage for agricultural use and can turn to potent methane sources when rewetted for remediation. This suggests that preceding land use measures can suspend the sulfate-related methane suppressing mechanisms. Here, we unravel the hydrological relocation and biogeochemical S and C transformation processes that induced high methane emissions in a disturbed and rewetted peatland despite former brackish impact. The underlying processes were investigated along a transect of increasing distance to the coastline using a combination of concentration patterns, stable isotope partitioning, and analysis of the microbial community structure. We found that diking and freshwater rewetting caused a distinct freshening and an efficient depletion of the brackish sulfate reservoir by dissimilatory sulfate reduction (DSR). Despite some legacy effects of brackish impact expressed as high amounts of sedimentary S and elevated electrical conductivities, contemporary metabolic processes operated mainly under sulfate-limited conditions. This opened up favorable conditions for the establishment of a prospering methanogenic community in the top 30–40&thinsp;cm of peat, the structure and physiology of which resemble those of terrestrial organic-rich environments. Locally, high amounts of sulfate persisted in deeper peat layers through the inhibition of DSR, probably by competitive electron acceptors of terrestrial origin, for example Fe(III). However, as sulfate occurred only in peat layers below 30–40&thinsp;cm, it did not interfere with high methane emissions on an ecosystem scale. Our results indicate that the climate effect of disturbed and remediated coastal wetlands cannot simply be derived by analogy with their natural counterparts. From a greenhouse gas perspective, the re-exposure of diked wetlands to natural coastal dynamics would literally open up the floodgates for a replenishment of the marine sulfate pool and therefore constitute an efficient measure to reduce methane emissions.</p