Highly dealkylated copper and nickel etioporpyfrins in marine sediments

Copper porphyrins have been recognized as natural constituents of marine sediments only within the past 5 years (Palmer and Baker, 1978, Science201, 49-51). In that report it was suggested that these pigments may derive from and be markers for oxidized terrestrial organic matter redeposited in the marine environment. In the present study we describe the distribution of copper porphyrins in sediments from several north Pacific and Gulf of California DSDP/IPQD sites (Legs 56,63,64). These allochthonous pigments have now been found to be accompanied by identical arrays of highly dealkylated nickel etioporphyrins. Evaluation of data from this and past studies clearly reveals that there is a strong carbon-number distribution similarity betweeen coincident Cu and Ni etioporphyrins. This homology match is taken as reflecting a common source for the tetrapyrrole ligands of this population of Cu and Ni chelates. Predepositional generation of these highly dealkylated etioporphyrins is concluded from the occurrence of these pigments in sediments continuing essentially all stages of in situ chlorophyll diagenesis (cf. Baker and Louda, 1983). That is, their presence is not regulated by the in situ diagenetic continuum. Thus, the highly dealkylated Cu and Ni etioporphyrins represent an 'allochthonous' background over which 'autochthonous' (viz. marine produced) chlorophyll derivatives are deposited and are undergoing in situ diagenesis.

Water chemistry and heat budget of the Churchill River estuary region

A conceptual scheme for the transition from winter to spring is developed for a small Arctic estuary (Churchill River, Hudson Bay) using hydrological, meteorological and oceanographic data together with models of the landfast ice. Observations within the Churchill River estuary and away from the direct influence of the river plume (Button Bay), between March and May 2005, show that both sea ice (production and melt) and river water influence the region's freshwater budget. In Button Bay, ice production in the flaw lead or polynya of NW Hudson Bay result in salinization through winter until the end of March, followed by a gradual freshening of the water column through April-May. In the Churchill Estuary, conditions varied abruptly throughout winter-spring depending on the physical interaction among river discharge, the seasonal landfast ice, and the rubble zone along the seaward margin of the landfast ice. Until late May, the rubble zone partially impounded river discharge, influencing the surface salinity, stratification, flushing time, and distribution and abundance of nutrients in the estuary. The river discharge, in turn, advanced and enhanced sea ice ablation in the estuary by delivering sensible heat. Weak stratification, the supply of riverine nitrogen and silicate, and a relatively long flushing time (~6 days) in the period preceding melt may have briefly favoured phytoplankton production in the estuary when conditions were still poor in the surrounding coastal environment. However, in late May, the peak flow and breakdown of the ice-rubble zone around the estuary brought abrupt changes, including increased stratification and turbidity, reduced marine and freshwater nutrient supply, a shorter flushing time, and the release of the freshwater pool into the interior ocean. These conditions suppressed phytoplankton productivity while enhancing the inventory of particulate organic matter delivered by the river. The physical and biological changes observed in this study highlight the variability and instability of small frozen estuaries during winter-spring transition, which implies sensitivity to climate change.

Area-averaged mean seasonal cycles of chlorophyll-a concentration, sea surface temperature, alongshore wind stress, westward wind speed and dust component of the aerosol optical depth at 550 nm

Nutrient supply in the area off Northwest Africa is mainly regulated by two processes, coastal upwelling and deposition of Saharan dust. In the present study, both processes were analyzed and evaluated by different methods, including cross-correlation, multiple correlation, and event statistics, using remotely sensed proxies of the period from 2000 to 2008 to investigate their influence on the marine environment. The remotely sensed chlorophyll-a concentration was used as a proxy for the phytoplankton biomass stimulated by nutrient supply into the euphotic zone from deeper water layers and from the atmosphere. Satellite-derived alongshore wind stress and sea-surface temperature were applied as proxies for the strength and reflection of coastal upwelling processes. The westward wind and the dust component of the aerosol optical depth describe the transport direction of atmospheric dust and the atmospheric dust column load. Alongshore wind stress and induced upwelling processes were most significantly responsible for the surface chlorophyll-a variability, accounting for about 24% of the total variance, mainly in the winter and spring due to the strong north-easterly trade winds. The remotely sensed proxies allowed determination of time lags between biological response and its forcing processes. A delay of up to 16 days in the surface chlorophyll-a concentration due to the alongshore wind stress was determined in the northern winter and spring. Although input of atmospheric iron by dust storms can stimulate new phytoplankton production in the study area, only 5% of the surface chlorophyll-a variability could be ascribed to the dust component in the aerosol optical depth. All strong desert storms were identified by an event statistics in the time period from 2000 to 2008. The 57 strong storms were studied in relation to their biological response. Six events were clearly detected in which an increase of chlorophyll-a was caused by Saharan dust input and not by coastal upwelling processes. Time lags of <8 days, 8 days, and 16 days were determined. An increase in surface chlorophyll-a concentration of up to 2.4 mg m**3 after dust storms in which the dust component of the aerosol optical depth was up to 0.9 was observed.

Palynology, source vegetation, environment and age of ODP Site 188-1166 sediments

Twenty-three core catcher samples from Site 1166 (Hole 1166A) in Prydz Bay were analyzed for their palynomorph content, with the aims of determining the ages of the sequence penetrated, providing information on the vegetation of the Antarctic continent at this time, and determining the environments under which deposition occurred. Dinocysts, pollen and spores, and foraminiferal test linings were recovered from most samples in the interval from 142.5 to 362.03 meters below seafloor (mbsf). The interval from 142.5 to 258.72 mbsf yielded palynomorphs indicative of a middle-late Eocene age, equivalent to the lower-middle Nothofagidites asperus Zone of the Gippsland Basin of southeastern Australia. The Prydz Bay sequence represents the first well-dated section of this age from East Antarctica. Dinocysts belonging to the widespread "Transantarctic Flora" give a more confident late Eocene age for the interval 142.5-220.5 mbsf. The uppermost two cores within this interval, namely, those from 142.5 and 148.36 mbsf, show significantly higher frequencies of dinocysts than the cores below and suggest that an open marine environment prevailed at the time of deposition. The spore and pollen component may reflect a vegetation akin to the modern rainforest scrubs of Tasmania and New Zealand. Below 267 mbsf, sparse microfloras, mainly of spores and pollen, are equated with the Phyllocladidites mawsonii Zone of southeastern Australia, which is of Turonian to possibly Santonian age. Fluvial to marginal marine environments of deposition are suggested. The parent vegetation from this interval is here described as "Austral Conifer Woodland." The same Late Cretaceous microflora occurs in two of the cores above the postulated unconformity at 267 mbsf. In the core at 249.42 mbsf, the Late Cretaceous spores and pollen are uncontaminated by any Tertiary forms, suggesting that a clast of this older material has been sampled; such a clast may reflect transport by ice during the Eocene. At 258.72 mbsf, Late Cretaceous spores and pollen appear to have been recycled into the Eocene sediments.

Major, trace element and XRF data for sediments and fish tooth samples, from a shallow marine setting with varying redox conditions (Site U1356, Wilkes Land Margin, E.Antarctica)

Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources. This article is protected by copyright. All rights reserved.

Crustaceans and fish abundances and species at and around artificially introduced tetrapod fields in the southern North Sea, 2009

The micro-scale spatial distribution patterns of a demersal fish and decapod crustacean assemblage were assessed in a hard-bottom kelp environment in the southern North Sea. Using quadrats along line transects, we assessed the in situ fish and crustacean abundance in relation to substratum types (rock, cobbles and large pebbles) and the density of algae. Six fish and four crustacean species were abundant, with Ctenolabrus rupestris clearly dominating the fish community and Galathea squamifera dominating the crustacean community. Differences in the substratum types had an even stronger effect on the micro-scale distribution than the density of the dominating algae species. Kelp had a negative effect on the fish abundances, with significantly lower average densities in kelp beds compared with adjacent open areas. Averaged over all of the substrata, the most attractive substratum for the fish was large pebbles. In contrast, crustaceans did not show a specific substratum affinity. The results clearly indicate that, similar to other complex systems, significant micro-scale species-habitat associations occur in northern hard-bottom environments. However, because of the frequently harsh environmental conditions, these habitats are mainly sampled from ships with sampling gear, and the resulting data cannot be used to resolve small-scale species-habitat associations. A detailed substratum classification and community assessment, often only possible using SCUBA diving, is therefore important to reach a better understanding of the functional relationships between species and their environment in northern temperate waters, knowledge that is very important with respect to the increasing environmental pressure caused by global climate change.

Response of three krill species to hypoxia and warming: An experimental approach to oxygen minimum zones expansion in coastal ecosystems

To understand the adaptation of euphausiid (krill) species to oxygen minimum zones (OMZ), respiratory response and stress experiments combining hypoxia/reoxygenation exposure with warming were conducted. Experimental krill species were obtained from the Antarctic (South Georgia area), the Humboldt Current system (HCS, Chilean coast), and the Northern California Current system (NCCS, Oregon). Euphausia mucronata from the HCS shows oxyconforming or oxygen partial pressure (pO2)-dependent respiration below 80% air saturation (18 kPa). Normoxic subsurface oxygenation in winter posed a "high oxygen stress" for this species. The NCCS krill, Euphausia pacifica, and the Antarctic krill, Euphausia superba maintain respiration rates constant down to low critical pO2 values of 6 kPa (30% air saturation) and 11 kPa (55% air saturation), respectively. Antarctic krill had the lowest antioxidant enzyme activities, but the highest concentrations of the molecular antioxidant glutathione (GSH) and was not affected by 6 h exposure to moderate hypoxia. Temperate krill species had higher SOD (superoxide dismutase) values in winter than in summer, which relate to higher winter metabolic rate (E. pacifica). In all species, antioxidant enzyme activities remained constant during hypoxic exposure at habitat temperature. Warming by 7°C above habitat temperature in summer increased SOD activities and GSH levels in E. mucronata (HCS), but no oxidative damage occurred. In winter, when the NCCS is well mixed and the OMZ is deeper, +4°C of warming combined with hypoxia represents a lethal condition for E. pacifica. In summer, when the OMZ expands upwards (100 m subsurface), antioxidant defences counteracted hypoxia and reoxygenation effects in E. pacifica, but only at mildly elevated temperature (+2°C). In this season, experimental warming by +4°C reduced antioxidant activities and the hypoxia combination again caused mortality of exposed specimens. We conclude that a climate change scenario combining warming and hypoxia represents a serious threat to E. pacifica and, as a consequence, NCCS food webs.

Distribution of biological, anthropogenic, and volcanic constituents in the San Francisco Bay Coastal System

Although conventional sediment parameters (mean grain size, sorting, and skewness) and provenance have typically been used to infer sediment transport pathways, most freshwater, brackish, and marine environments are also characterized by abundant sediment constituents of biological, and possibly anthropogenic and volcanic, origin that can provide additional insight into local sedimentary processes. The biota will be spatially distributed according to its response to environmental parameters such as water temperature, salinity, dissolved oxygen, organic carbon content, grain size, and intensity of currents and tidal flow, whereas the presence of anthropogenic and volcanic constituents will reflect proximity to source areas and whether they are fluvially- or aerially-transported. Because each of these constituents have a unique environmental signature, they are a more precise proxy for that source area than the conventional sedimentary process indicators. This San Francisco Bay Coastal System study demonstrates that by applying a multi-proxy approach, the primary sites of sediment transport can be identified. Many of these sites are far from where the constituents originated, showing that sediment transport is widespread in the region. Although not often used, identifying and interpreting the distribution of naturally-occurring and allochthonous biologic, anthropogenic, and volcanic sediment constituents is a powerful tool to aid in the investigation of sediment transport pathways in other coastal systems.

Dinoflagellate cysts and pollen distribution of marine surface sediments off West Africa

An organic-walled dinoflagellate cyst analysis was carried out on 53 surface sediment samples from West Africa (17-6°N) to obtain insight in the relationship between their spatial distribution and hydrological conditions in the upper water column as well as marine productivity in the study area. Multivariate analysis of the dinoflagellate cyst relative abundances and environmental parameters of the water column shows that sea-surface temperature, salinity, marine productivity and bottom water oxygen are the factors that relate significantly to the distribution patterns of individual species in the region. The composition of cyst assemblages and dinoflagellate cyst concentrations allows the identification of four hydrographic regimes; 1) the northern regime between 17 and 14°N characterized by high productivity associated with seasonal coastal upwelling, 2) the southern regime between 12 and 6°N associated with high-nutrient waters influenced by river discharge 3) the intermediate regime between 14 and 12°N influenced mainly by seasonal coastal upwelling additionally associated with fluvial input of terrestrial nutrients and 4) the offshore regime characterized by low chlorophyll-a concentrations in upper waters and high bottom water oxygen concentrations. Our data show that cysts of Polykrikos kofoidii, Selenopemphix quanta, Dubridinium spp., Echinidinium species, cysts of Protoperidinium monospinum and Spiniferites pachydermus are the best proxies to reconstruct the boundary between the NE trade winds and the monsoon winds in the subtropical eastern Atlantic Ocean. The association of Bitectatodinium spongium, Lejeunecysta oliva, Quinquecuspis concreta, Selenopemphix nephroides, Trinovantedinium applanatum can be used to reconstruct past river outflow variations within this region.

Effect of simulated ocean acidification on the acute toxicity of Cu and Cd to Tigriopus japonicus

Heavy metals pollution in marine environments has caused great damage to marine biological and ecological systems. Heavy metals accumulate in marine creatures, after which they are delivered to higher trophic levels of marine organisms through the marine food chain, which causes serious harm to marine biological systems and human health. Additionally, excess carbon dioxide in the atmosphere has caused ocean acidification. Indeed, about one third of the CO2 released into the atmosphere by anthropogenic activities since the beginning of the industrial revolution has been absorbed by the world's oceans, which play a key role in moderating climate change. Modeling has shown that, if current trends in CO2 emissions continue, the average pH of the ocean will reach 7.8 by the end of this century, corresponding to 0.5 units below the pre-industrial level, or a three-fold increase in H+ concentration. The ocean pH has not been at this level for several millions of years. Additionally, these changes are occurring at speeds 100 times greater than ever previously observed. As a result, several marine species, communities and ecosystems might not have time to acclimate or adapt to these fast changes in ocean chemistry. In addition, decreasing ocean pH has the potential to seriously affect the growth, development and reproduction reproductive processes of marine organisms, as well as threaten normal development of the marine ecosystem. Copepods are an important part of the meiofauna that play an important role in the marine ecosystem. Pollution of the marine environment can influence their growth and development, as well as the ecological processes they are involved in. Accordingly, there is important scientific value to investigation of the response of copepods to ocean acidification and heavy metals pollution. In the present study, we evaluated the effects of simulated future ocean acidification and the toxicological interaction between ocean acidity and heavy metals of Cu and Cd on T. japonicus. To accomplish this, harpacticoids were exposed to Cu and Cd concentration gradient seawater that had been equilibrated with CO2 and air to reach pH 8.0, 7.7, 7.3 and 6.5 for 96 h. Survival was not significantly suppressed under single sea water acidification, and the final survival rates were greater than 93% in both the experimental groups and the controls. The toxicity of Cu to T. japonicus was significantly affected by sea water acidification, with the 96h LC50 decreasing by nearly threefold from 1.98 to 0.64 mg/L with decreasing pH. The 96 h LC50 of Cd decreased with decreasing pH, but there was no significant difference in mortality among pH treatments. The results of the present study demonstrated that the predicted future ocean acidification has the potential to negatively affect survival of T. japonicus by exacerbating the toxicity of Cu. The calculated safe concentrations of Cu were 11.9 (pH 7.7) and 10.5 (pH 7.3) µg/L, which were below the class I value and very close to the class II level of the China National Quality Standard for Sea Water. Overall, these results indicate that the Chinese coastal sea will face a

Sea-suface microlayer (SML) and underlying water (ULW) samples focusing on CDOM spectral characteristics during METEOR cruise M91

The coastal upwelling system off the coast of Peru is characterized by high biological activity and a pronounced subsurface oxygen minimum zone, as well as associated emissions of atmospheric trace gases such as N2O, CH4 and CO2. From 3 to 23 December 2012, R/V Meteor (M91) cruise took place in the Peruvian upwelling system between 4.59 and 15.4°S, and 82.0 to 77.5°W. During M91 we investigated the composition of the sea-surface microlayer (SML), the oceanic uppermost boundary directly subject to high solar radiation, often enriched in specific organic compounds of biological origin like chromophoric dissolved organic matter (CDOM) and marine gels. In the SML, the continuous photochemical and microbial recycling of organic matter may strongly influence gas exchange between marine systems and the atmosphere. We analyzed SML and underlying water (ULW) samples at 38 stations focusing on CDOM spectral characteristics as indicator of photochemical and microbial alteration processes. CDOM composition was characterized by spectral slope (S) values and excitation-emission matrix fluorescence (EEMs), which allow us to track changes in molecular weight (MW) of DOM, and to determine potential DOM sources and sinks. Spectral slope S varied between 0.012 to 0.043 1 nm-1 and was quite similar between SML and ULW, with no significant differences between the two compartments. Higher S values were observed in the ULW of the southern stations below 15°S. By EEMs, we identified five fluorescent components (F1-5) of the CDOM pool, of which two had excitation/emission characteristics of amino-acid-like fluorophores (F1, F4) and were highly enriched in the SML, with a median ratio SML : ULW of 1.5 for both fluorophores. In the study region, values for CDOM absorption ranged from 0.07 to 1.47 m-1. CDOM was generally highly concentrated in the SML, with a median enrichment with respect to the ULW of 1.2. CDOM composition and changes in spectral slope properties suggested a local microbial release of DOM directly in the SML as a response to light exposure in this extreme environment. In a conceptual model of the sources and modifications of optically active DOM in the SML and underlying seawater (ULW), we describe processes we think may take place (Fig. 1); the production of CDOM of higher MW by microbial release through growth, exudation and lysis in the euphotic zone, includes the identified fluorophores (F1, F2, F3, F4, F5). Specific amino-acid-like fluorophores (F1, F4) accumulate in the SML with respect to the ULW, as photochemistry may enhance microbial CDOM release by (a) photoprotection mechanisms and (b) cell-lysis processes. Microbial and photochemical degradation are potential sinks of the amino-acid-like fluorophores (F1, F4), and potential sources of reworked and more refractory humic-like components (F2, F3, F5). In the highly productive upwelling region along the Peruvian coast, the interplay of microbial and photochemical processes controls the enrichment of amino-acid-like CDOM in the SML. We discuss potential implications for air-sea gas exchange in this area.