Reactivity of various types of iron(III) (hydr)oxides towards light-induced dissolution

Laboratory experiments were conducted on the light-induced dissolution of three well defined Fe(III) (hydr)oxide phases (γ-FeOOH, α-FeOOH, and α-Fe₂O₃) with oxalate as reductant/ligand. Upon irradiation of an aerated γ-FeOOH suspension of pH 3, photooxidation of oxalate and photochemical formation of dissolved Fe(II) occurred according to a 1:1 stoichiometry. This was not observed with aerated α-FeOOH and α-Fe₂O₃ suspensions of pH 3, where photooxidation of oxalate was not accompanied by formation of appreciable concentrations of dissolved Fe(II). We hypothesize that in aerated α-FeOOH and α-Fe₂O₃ suspensions, oxidation of surface Fe(II) outcompetes its detachment from the crystal lattice. Also in deaerated suspensions, α-FeOOH and α-Fe₂O₃ behaved differently from γ-FeOOH with regard to light-induced dissolution. We interpret our results by assuming that light-induced dissolution of α-FeOOH and α-Fe₂O₃ in deaerated suspensions of pH 3 occurred mainly through Fe(II)-catalyzed thermal dissolution of the solid phases, where Fe(II) was initially formed by photoreductive dissolution and then predominantly via photolysis of dissolved Fe(III) oxalate complexes. With γ-FeOOH, on the other hand, dissolved Fe(II) formation occurred probably mainly through photochemical reductive dissolution under photooxidation of adsorbed oxalate. From our results we conclude that the efficiency of detachment of reduced surface iron is a key parameter of the overall kinetics of photoreductive dissolution of Fe(III) (hydr)oxides in aquatic systems, and that thermodynamically stable phases such as α-FeOOH and α-Fe₂O₃ are not readily dissolved in the presence of O₂, even at low pH-values and in the presence of light and reductants like oxalate. We propose that redox cycling of iron at the surface of crystalline Fe(III) (hydr)oxide phases, i.e. reduction and oxidation of surface iron without transfer into solution, may be an important pathway of transformation of thermodynamically stable atmospheric Fe(III) (hydr)oxides into less stable and thus more soluble phases.     

Climate change and control of the southeastern Bering Sea pelagic ecosystem

We propose a new hypothesis, the Oscillating Control Hypothesis (OCH), which predicts that pelagic ecosystem function in the southeastern Bering Sea will alternate between primarily bottom-up control in cold regimes and primarily top-down control in warm regimes. The timing of spring primary production is determined predominately by the timing of ice retreat. Late ice retreat (late March or later) leads to an early, ice-associated bloom in cold water (e.g., 1995, 1997, 1999), whereas no ice, or early ice retreat before mid-March, leads to an open-water bloom in May or June in warm water (e.g., 1996, 1998, 2000). Zooplankton populations are not closely coupled to the spring bloom, but are sensitive to water temperature. In years when the spring bloom occurs in cold water, low temperatures limit the production of zooplankton, the survival of larval/juvenile fish, and their recruitment into the populations of species of large piscivorous fish, such as walleye pollock (Theragra chalcogramma), Pacific cod (Gadus macrocephalus) and arrowtooth flounder (Atheresthes stomias). When continued over decadal scales, this will lead to bottom-up limitation and a decreased biomass of piscivorous fish. Alternatively, in periods when the bloom occurs in warm water, zooplankton populations should grow rapidly, providing plentiful prey for larval and juvenile fish. Abundant zooplankton will support strong recruitment of fish and will lead to abundant predatory fish that control forage fish, including, in the case of pollock, their own juveniles. Piscivorous marine birds and pinnipeds may achieve higher production of young and survival in cold regimes, when there is less competition from large piscivorous fish for cold-water forage fish such as capelin (Mallotus villosus). Piscivorous seabirds and pinnipeds also may be expected to have high productivity in periods of transition from cold regimes to warm regimes, when young of large predatory species of fish are numerous enough to provide forage. The OCH predicts that the ability of large predatory fish populations to sustain fishing pressure will vary between warm and cold regimes.The OCH points to the importance of the timing of ice retreat and water temperatures during the spring bloom for the productivity of zooplankton, and the degree and direction of coupling between zooplankton and forage fish. Forage fish (e.g., juvenile pollock, capelin, Pacific herring [Clupea pallasii]) are key prey for adult pollock and other apex predators. In the southeastern Bering Sea, important changes in the biota since the mid-1970s include a marked increase in the biomass of large piscivorous fish and a concurrent decline in the biomass of forage fish, including age-1 walleye pollock, particularly over the southern portion of the shelf. Populations of northern fur seals (Callorhinus ursinus) and seabirds such as kittiwakes (Rissa spp.) at the Pribilof Islands have declined, most probably in response to a diminished prey base. The available evidence suggests that these changes are unlikely the result of a decrease in total annual new primary production, though the possibility of reduced post-bloom production during summer remains. An ecosystem approach to management of the Bering Sea and its fisheries is of great importance if all of the ecosystem components valued by society are to thrive. Cognizance of how climate regimes may alter relationships within this ecosystem will facilitate reaching that goal.     

Biological disturbance and camouflage of sedimentary features on the Northeast United States slope and rise

Evidence from over 200 sediment cores, numerous submersible dives, and bottom photographs prove that bioturbation and bioerosion are ongoing processes affecting northeastern U.S. continental slope and rise sedimentation. Evidence of biological activity was found in greater than 95% of the cores examined. Submersible dive observations reveal that the results of biological activity often dominate sea-floor microtopography. Bioturbation can disturb sediments several centimeters deep in a matter of seconds and is in some areas the primary sediment transport mechanism. Many cores with sandy intervals were profoundly disturbed by bioturbation. Biologically camouflaged sand-rich intervals can easily be missed by visual observation.     

Relationships between primary productivity and bottom‐water oxygenation off northwest Africa during the last deglaciation

The upwelling region off northwest Africa is one of the most productive regions in the world ocean. This study details the response of surface‐ and deep‐water environments off Mauritania, northwest Africa, to the rapid climate events of the last deglaciation, especially the Bølling–Allerød (15.5–13.5 ka BP) and Younger Dryas (13.5–11.5 ka BP). A high accumulation rate gravity core GeoB7926‐2, recovered at ～20° N, 18° W, was analysed for the grain size distribution of the terrigenous sediment fraction, the organic carbon content, diatom and benthic foraminifera communities. Humid conditions were observed during the Bølling–Allerød with a high contribution of fluvial sediment input. During the Younger Dryas intensified trade winds caused a larger sediment input of aeolian dust from the Sahara and more intense upwelling with higher primary productivity, as indicated by high diatom concentrations. The abrupt and large increase of organic matter caused low oxygen conditions at the sea floor, reflected by the poor benthic foraminiferal fauna and the dominance of the low‐oxygen‐tolerant foraminiferal species Bulimina exilis. This is surprising since low‐oxygen conditions have not been recorded during modern times at the sea floor in this region, despite present‐day intensive upwelling and high primary productivity. After the Younger Dryas, more humid conditions returned, diatom abundance decreased and B. exilis was replaced by typical deep‐sea species as found in the region today, indicating the return of more oxygenated conditions at the sea floor. Copyright © 2011 John Wiley & Sons, Ltd.     

How soil moisture mediates the influence of transpiration on streamflow at hourly to interannual scales in a forested catchment

The water balance equation dictates that streamflow may be reduced by transpiration. Yet temporal disequilibrium weakens the relationship between transpiration and streamflow in many cases where inputs and outputs are unbalanced. We address two critical knowledge barriers in ecohydrology with respect to time, scale dependence and lags. Study objectives were to correlate components of the water balance equation at hourly to annual scales, quantify time lags, and simplify critical components of the water budget during wet and dry conditions. We tested interrelationships among precipitation, vapour pressure deficit, transpiration, soil moisture, and streamflow within the confines of a 60‐hectare forested watershed in the western Cascades of Oregon. The Pacific Northwest is an ideal location to compare wet and dry seasons because of its Mediterranean climate. Soil moisture explained more than 80% of the variation in streamflow at all temporal scales investigated. Streamflow was most strongly coupled to soil moisture in the wet season because of gravitational drainage patterns; strong coupling of transpiration to vapour pressure deficit was dominant in the dry season and driven by low humidity. We observed progressively longer hourly time lags between soil moisture and streamflow in the dry season, which relates to an increasing soil moisture deficit that took an average of 48 days to refill after the onset of winter rains. We propose that transpiration drives seasonal patterns in soil moisture that relate to patterns in streamflow only after long time lags. In other words, soil moisture mediates the influence of transpiration on streamflow. Copyright © 2011 John Wiley & Sons, Ltd.     

Skin toxins in coral‐associated Gobiodon species (Teleostei: Gobiidae) affect predator preference and prey survival

Predation risk is high for the many small coral reef fishes, requiring successful sheltering or other predator defence mechanisms. Coral‐dwelling gobies of the genus Gobiodon live in close association with scleractinian corals of the genus Acropora. Earlier studies indicated that the low movement frequency of adult fishes and the development of skin toxins (crinotoxicity) are predation avoidance mechanisms. Although past experiments showed that predators refuse food prepared with goby skin mucus, direct predator–prey interactions have not been studied. The present study compares the toxicity levels of two crinotoxic coral gobies – Gobiodon histrio, representative of a conspicuously coloured species, and Gobiodon sp.3 with cryptic coloration – using a standard bioassay method. The results show that toxin levels of both species differ significantly shortly after mucus release but become similar over time. Predator preferences were tested experimentally in an aquarium in which the two gobies and a juvenile damselfish Chromis viridis were exposed to the small grouper Epinephelus fasciatus. Video‐analysis revealed that although coral gobies are potential prey, E. fasciatus clearly preferred the non‐toxic control fish (C. viridis) over Gobiodon. When targeting a goby, the predator did not prefer one species over the other. Contrary to our expectations that toxic gobies are generally avoided, gobies were often captured, but they were expelled quickly, repeatedly and alive. This unusual post‐capture avoidance confirms that these gobies have a very good chance of surviving attacks in the field due to their skin toxins. Nonetheless, some gobies were consumed: the coral shelter may therefore also provide additional protection, with toxins protecting them mainly during movement between corals. In summary, chemical deterrence by crinotoxic fishes seems to be far more efficient in predation avoidance than in physical deterrence involving body squamation and/or strong fin spines.     

A revisitation of TRIX for trophic status assessment in the light of the European Water Framework Directive: application to Italian coastal waters

The trophic status classification of coastal waters at the European scale requires the availability of harmonised indicators and procedures. The composite trophic status index (TRIX) provides useful metrics for the assessment of the trophic status of coastal waters. It was originally developed for Italian coastal waters and then applied in many European seas (Adriatic, Tyrrhenian, Baltic, Black and Northern seas). The TRIX index does not fulfil the classification procedure suggested by the WFD for two reasons: (a) it is based on an absolute trophic scale without any normalization to type-specific reference conditions; (b) it makes an ex ante aggregation of biological (Chl-a) and physico-chemical (oxygen, nutrients) quality elements, instead of an ex post integration of separate evaluations of biological and subsequent chemical quality elements. A revisitation of the TRIX index in the light of the European Water Framework Directive (WFD, 2000/60/EC) and new TRIX derived tools are presented in this paper. A number of Italian coastal sites were grouped into different types based on a thorough analysis of their hydro-morphological conditions, and type-specific reference sites were selected. Unscaled TRIX values (UNTRIX) for reference and impacted sites have been calculated and two alternative UNTRIX-based classification procedures are discussed. The proposed procedures, to be validated on a broader scale, provide users with simple tools that give an integrated view of nutrient enrichment and its effects on algal biomass (Chl-a) and on oxygen levels. This trophic evaluation along with phytoplankton indicator species and algal blooms contribute to the comprehensive assessment of phytoplankton, one of the biological quality elements in coastal waters.     

Sub-bottom profiling and coring of sub-basins along the lower French River, Ontario: insights into depositional environments within the North Bay outlet

Sub-bottom profiling was conducted at eight sub-basins within the lower French River area, Ontario, to investigate deposits preserved within the ancient North Bay outlet. Ten cores were collected that targeted the four depositional acoustic facies identified in the sub-bottom profiling records. The rhythmically laminated/bedded glaciolacustrine deposits of facies I are interpreted to have aggraded within glacial Lake Algonquin and its associated recessional lakes that persisted between 13,000 and 11,300 cal BP (~11,100 and 9,900 BP). The majority of the facies II, III and IV lacustrine deposits accumulated between about 9,500 cal BP (~8,500 BP) and the mid-Holocene, based on radiocarbon-dated organic materials. These deposits represent sedimentation within a ‘large’ lake during the late portion of the Mattawa-Stanley phase, and the Nipissing transgression, Nipissing Great Lakes and post-Nipissing recession phases of lake levels. Two sets of organic-rich sand beds are preserved within facies II deposits and reveal that the large lake lacustrine depositional environment was interrupted during the late Mattawa-Stanley phase between 9,500–9,300 and 9,000–8,400 cal BP (~8,500–8,300 and ~8,000–7,600 BP), when the water surface of Lake Hough fell below the outlet threshold and the lake basin became hydrologically closed. Pre-9,500 cal BP (~8,500 BP), the early and middle portions of the Mattawa-Stanley phase were dominated by erosion, as reflected by an unconformity at the base of facies II that occurs widely in the sub-basins and the general lack of preserved deposits for these intervals in the cores. This erosion is attributed to wave action and fluvial scouring within the outlet mouth during the early and mid-Stanley-Hough low stages and relates specifically to the period when the flowing portion of the North Bay outlet was situated over the lower French River area. This study reveals that the majority of the post-glacial deposits accumulated after the outlet threshold had shifted permanently eastwards and the lower French River area was inundated under the multiple phases of the large lake occupying the Nipissing Lowlands and Georgian-Huron basins, extending well into the mid-Holocene. The occurrence of deposits marking two closed-basin intervals during the late Stanley-Hough stage are well preserved locally within the lacustrine depositional sequence, but identifying earlier closed-basin intervals from the French River stratigraphy is hindered by the lack of preserved pre-9,500 cal BP (~8,500 BP) post-glacial deposits.