Biogeochemical Composition Research Articles

Molecular and isotopic biogeochemistry on recently-formed soils on King George Island (Maritime Antarctica) after glacier retreat upon warming climate

Maritime Antarctica is a climate-sensitive region that has experienced a continuous increase of temperature over the last 50 years. This phenomenon accelerates glacier retreat and promotes the exposure of ice-covered surfaces, triggering physico-chemical alteration of the ground and subsequent soil formation. Here, we studied the biogeochemical composition and evolution extent of soil on three recently exposed peninsulas (Fildes, Barton and Potter) on Southwest (SW) King George Island (KGI). Nine soil samples were analyzed for their lipid biomarkers, stable isotope composition, bulk geochemistry and mineralogy. Their biomarkers profiles were compared to those of local fresh biomass of microbial mats (n = 3) and vegetation (1 moss, 1 grass, and 3 lichens) to assess their contribution to the soil organic matter (SOM). The molecular and isotopic distribution of lipids in the soil samples revealed contributions to the SOM dominated by biogenic sources, mostly vegetal (i.e. odd HMW n-alkanes distributions and generally depleted δ13C ratios). Microbial sources were also present to a lesser extent (i.e. even LMW n-alkanes and n-alkanoic acids, heptadecane, 1-alkenes, 9-octadecenoic acid, or iso/anteiso 15: 0 and 17:0 alkanoic acids). Additional contribution from petrogenic sources (bedrock erosion-derived hydrocarbons) was also considered although found to be minor. Results from mineralogy (relative abundance of plagioclases and virtual absence of clay minerals) and bulk geochemistry (low chemical weathering indexes) suggested little chemical alteration of the original geology. This together with the low content of total nitrogen and organic carbon, as well as moderate microbial activity in the soils, confirmed little edaphological development on the recently-exposed KGI surfaces. This study provides molecular and isotopic fingerprints of SOM composition in young Antarctic soils, and contributes to the understanding of soil formation and biogeochemistry in this unexplored region which is currently being affected by thermal destabilization.

Biogeochemical and photobiological responses of subarctic lakes to UV radiation

Solar ultraviolet radiation (UV) induces photodegradation of optically and functionally important organic compounds in lakes and may negatively impact aquatic biota. We disentangled UV impacts on dissolved organic matter (DOM) transformation, and algal and zoobenthic micro-organisms in two shallow subarctic lakes in NW Finnish Lapland; in a high-UV + low-DOM (tundra, Iso-Jehkas) and a low-UV + high-DOM (mountain birch woodland, Mukkavaara) system. In addition to site and seasonal comparisons, in situ experiments with three treatments (DARK, photosynthetically active radiation [PAR], UV + PAR) were set up floating on the lakes for four weeks during midsummer. Lake water and experimental lake water were analyzed for basic limnology, optical properties (dissolved organic carbon [DOC], specific UV absorbance [SUVA], colored DOM [CDOM], and DOM compounds) as well as for photosynthetic and photoprotective pigments in algae and microzoobenthos. DOC concentrations remained largely unchanged after the exposure period in seasonal and experimental samples in both lakes yet the biochemical composition of the carbon pools was distinctly altered. CDOM and SUVA decreased seasonally and under UV exposure in the experiments, and terrestrial DOM compounds decreased in the experiments, suggesting UV induced photodegradation of large molecular size DOM of terrestrial origin. Higher seasonal and experimental (UV + PAR vs. PAR) proportional CDOM degradation occurred in Iso-Jehkas (32%, 29%) than in Mukkavaara (19%, 9%). Accordingly, the high-UV + low-DOM lake was more sensitive to photodegradation despite originally low CDOM relative to the low-UV + high-DOM system where DOM biodegradation likely prevailed. Experimental results showed elevated algal carotenoid/chlorophyll ratios and microzoobenthic melanin under UV exposure indicating photoinhibition and photoprotective pigmentation. UV has a significant impact on aquatic food webs of subarctic lakes altering the biogeochemical composition of organic matter and organisms through mechanisms of photodegradation, photoinhibition and photoprotection.

In‐lake transformations of dissolved organic matter composition in a subalpine lake do not change its biodegradability

AbstractIn freshwater ecosystems, dissolved organic matter (DOM) originates from terrestrial and aquatic primary production, and its microbial biodegradability is expected to vary due to differences in its biogeochemical composition. However, the interaction of various DOM sources with the aquatic microbial population remains widely debated. Here, we performed laboratory bioassays, conducted in the dark for 20 d, to examine how changes in DOM composition influence its microbial biodegradability along a hydrological continuum (i.e., lake inlet, lake layers, and lake outlet) of a subalpine lake over four seasons. Despite a predominance of terrestrial DOM and lowest initial abundance of microorganisms, the highest microbial growth rates were observed at the lake inlet (0.0076 ± 0.0011 cells mL−1 h−1) across all seasons. DOM reactivity differed more with time (seasons) than with space (sampling sites) and DOM compositional differences showed higher degradability in upper lake layers, but not at the lake outlet. Additionally, gradual humification over incubation time was observed in almost all seasons and sites. Overall, an enhanced biodegradability of DOM was not detected even though lake sites were characterized by an autochthonous, presumably labile DOM signature. However, our results highlight the potential of thriving bacteria in terrestrial‐dominated DOM environments. This observation challenges a previous hypothesis that DOM of terrestrial origin is less accessible and more recalcitrant, while emphasizing the flexible response of aquatic systems to seasonal fluctuations.

Assessment of the state of the urboecosystem by integral indicators of pine and soil cover

Soil contamination due to the accumulation of heavy metals directly affects the biogeochemical composition, development stability (fluctuating asymmetry) of urban vegetation. To assess the condition of urbanized territories, monitoring is required, especially biological. This work shows an assessment of the stability of the development of populations of Scots pine growing in the urban environment, depending on the content of heavy metals in the soil cover, needles. The representativeness of the data obtained is confirmed by appropriate statistical processing. Higher values of integral indicators were found for all the territories examined, especially for the Central Park, which is characterized by maximum traffic load. The values of the fluctuating asymmetry index of pine needles reflect the elemental composition of the soil cover (Pb, Cd, Zn, Cu, Ni, Co Cr, Mn).

Mercury Content in Central and Southern Adriatic Sea Sediments in Relation to Seafloor Geochemistry and Sedimentology.

Mercury contents were determined in surface sediments from the Central and Southern Adriatic Sea to gain insight into the processes, factors, and variables affecting its distribution. Mercury concentration was measured by thermal decomposition amalgamation atomic absorption spectrometry in samples collected by box-corer from Ancona to Santa Maria di Leuca during the CNR-PERTRE cruise (16/9-4/10/2016). Sediments were also evaluated for chemical-physical parameters (pH, Eh), biogeochemical composition (total carbon, inorganic carbon, total organic carbon, organic matter) and grain size. The average mercury concentration in the Adriatic Sea sediment was 0.053 mg/Kg (d.w.), range 0.011–0.12 mg/Kg (d.w.). Mercury content was mainly affected by grain size and organic matter (OM) distribution, whereas anthropic factors exerted a limited influence. Concentrations followed the distribution of sediment types (clay > silt > sand) due to Adriatic Sea hydrodynamics and were well below the regulatory limits in all samples.

Impact of Hydrological Conditions on the Biogeochemical Dynamics of Suspended Particulate Organic Matter in the Upper Mixed Layer of the Southern East China Sea

AbstractWe investigate suspended particles collected from the upper mixed layer in the inner shelf of the southern East China Sea during autumn 2013 for carbon and nitrogen (POC and PN) contents and their isotope compositions (δ13C and δ15N) along with hydrographic parameters to understand the sources and dynamics of particulate organic matter (POM) in the study area. Results indicated that the extensive hydrological processes affect the biogeochemical composition of suspended POM, as revealed by the horizontally mixing POM and the spatial variation of δ15N and molar C/N ratio. Low C/N (2.4–6.5) and a weak correlation between POC and in situ chlorophyll fluorescence suggested that POM is dominated by the recently formed and well‐preserved planktonic OM. By fitting the linear correlation between δ13C and POC data with a photosynthetic fractionation model, we further disentangled dynamic controls of phytoplankton production and species diversity on δ13C variability (−24.3 to −21.3‰), emphasizing the constant effect of productivity‐derived POC on δ13C (0.02‰ per μg/L). The δ15N variability (2.3–7.4‰) is largely controlled by the mixing of isotopically different nitrogen sources, in which the importance of biological nitrogen fixation is unfolded based on the small δ15N and the negative correlation between δ15N of POM and seawater temperature. This implies that Kuroshio‐induced biological N fixation plays an important role in supporting the marine production in the East China Sea. These hydrologically driven δ13C and δ15N changes of marine productivity‐derived POM suggest that internal biophysical dynamics rather than terrestrial versus marine OM mixing largely control the C and N compositional variability in the shelf seas.

Millennial-scale carbon accumulation and molecular transformation in a permafrost core from Interior Alaska

Abstract Organic carbon stored in high-latitude permafrost represents a potential positive feedback to climate warming as well as a valuable store of paleoenvironmental information. The below-freezing conditions have effectively removed permafrost organic material from the modern carbon cycle and preserved its pre-freezing bulk and molecular states. The conditions that lead to efficient burial of organic carbon (OC) within permafrost were investigated by measuring OC stocks, past accumulation rates, and biogeochemical composition of a permafrost core taken from Interior Alaska dating back to 40 ka. The post-glacial Marine Isotope Stage 1 is represented by the top 1.2 m of the core and contains 64.7 kg OC/m2 with an accumulation rate of 4.3 g OC/m2/yr. The sediments that accumulated around the Last Glacial Maximum contain 9.9 kg OC/m2 with an accumulation rate of 0.5 g OC/m2/yr. Carbon storage (144.7 kg OC/m2) and accumulation (26.1 g OC/m2/yr) are both observed to be greatest between 35 and 40 ka, late during the Marine Isotope Stage 3 global interstadial. The extent of OC degradation was assessed using lignin and amino acid biomarkers with both approaches indicating well-preserved contemporary active layer and interstadial OC, whereas stadial OC was highly degraded. Lignin compositional indices throughout the core appear altered by sorptive processes that confounded some expected trends in the overall organic matter composition, while amino acids provided a more integrated pattern of change. Significant correlations between carbon-normalized hydroxyproline and total lignin concentrations further support the usefulness of hydroxyproline as an indicator for the abundance of plant organic matter. A novel amino acid plant-microbial index of the ratio of microbial-specific muramic acid and diaminopimelic acid biomarkers to the plant-specific hydroxyproline biomarker, indicate a transition from plant-dominated organic matter in fresh organic soils (index values of 0.01–0.20) to more microbial-dominated organic matter in degraded mineral soils (index values of 0.50–2.50). The branched glycerol dialkyl glycerol tetraether composition is complex and is not immediately compatible with existing temperature transfer functions. Residence time within the active layer is interpreted to integrate key factors such as primary productivity, inorganic sediment delivery, and other climate factors that control soil organic matter degradation. The Marine Isotope Stage 3, mid-Wisconsin interstadial period at this locality was forest-dominated and suggests the currently prevailing tundra ecotone is sensitive to environmental change. The majority of buried permafrost OC is high in degradability and if thawed, would be expected to be highly vulnerable to microbial decomposition.

The Large Jellyfish Rhizostoma luteum as Sustainable a Resource for Antioxidant Properties, Nutraceutical Value and Biomedical Applications.

Jellyfish is a compartment in the marine food web that often achieves high increases of biomass and that it is starting to be explored for several human potential uses. In this paper, a recently rediscovered large jellyfish, Rhizostoma luteum, is studied for the first time to describe its organic compounds for the isolation and production of bioactive compounds in several fields of food, cosmetics, or biomedical industries. The biogeochemical composition (Carbon, Nitrogen and Sulfur content), protein and phenols content, together with their antioxidant activity, and the analysis of lipid content (identifying each of the fatty acids presented) was analyzed. The results presented here suggested this jellyfish has the highest antioxidant activity ever measured in a jellyfish, but also with high content in polyunsaturated fatty acids (PUFAs), including the essential fatty acid linoleic. The large natural biomass of Rhizostoma luteum in nature, the wide geographical spread, the fact that already its life cycle has been completed in captivity, establishes a promising positive association of this giant jellyfish species and the isolation of bioactive compounds for future use in marine biotechnology.

Benthic meltwater fjord habitats formed by rapid glacier recession on King George Island, Antarctica.

The coasts of the West Antarctic Peninsula are strongly influenced by glacier meltwater discharge. The spatial structure and biogeochemical composition of inshore habitats are shaped by large quantities of terrigenous particulate material deposited in the vicinity of the coast, which impacts the pelagic and benthic ecosystems. We used a multitude of geochemical and environmental variables to identify the radius extension of the meltwater impact from the Fourcade Glacier into the fjord system of Potter Cove, King George Island. The k-means cluster algorithm, canonical correspondence analysis, variance analysis and Tukey's post hoc multiple comparison tests were applied to define and cluster coastal meltwater habitats. A minimum of 10 clusters were needed to classify the 8 km2 study area into meltwater fjord habitats (MFHs), fjord habitats and marine habitats. Strontium content in surface sediments is the main geochemical indicator for lithogenic creek discharge in Potter Cove. Furthermore, bathymetry, glacier distance and geomorphic positioning are the essential habitats explaining variables. The mean and maximum MFH extent amounted to 1 km and 2 km, respectively. Extrapolation of the identified meltwater impact ranges to King George Island coastlines, which are presently ice-covered bays and fjord areas, indicated an overall coverage of 200-400 km2 MFH, underpinning the importance of better understanding the biology and biogeochemistry in terrestrial marine transition zones.This article is part of the theme issue 'The marine system of the West Antarctic Peninsula: status and strategy for progress in a region of rapid change'.

Modeling the Impact of Stream Discharge Events on Riparian Solute Dynamics.

The biogeochemical composition of stream water and the surrounding riparian water is mainly defined by the exchange of water and solutes between the stream and the riparian zone. Short-term fluctuations in near stream hydraulic head gradients (e.g., during stream flow events) can significantly influence the extent and rate of exchange processes. In this study, we simulate exchanges between streams and their riparian zone driven by stream stage fluctuations during single stream discharge events of varying peak height and duration. Simulated results show that strong stream flow events can trigger solute mobilization in riparian soils and subsequent export to the stream. The timing and amount of solute export is linked to the shape of the discharge event. Higher peaks and increased durations significantly enhance solute export, however, peak height is found to be the dominant control for overall mass export. Mobilized solutes are transported to the stream in two stages (1) by return flow of stream water that was stored in the riparian zone during the event and (2) by vertical movement to the groundwater under gravity drainage from the unsaturated parts of the riparian zone, which lasts for significantly longer time (> 400 days) resulting in long tailing of bank outflows and solute mass outfluxes. We conclude that strong stream discharge events can mobilize and transport solutes from near stream riparian soils into the stream. The impact of short-term stream discharge variations on solute exchange may last for long times after the flow event.

On the Habitability of Desert Varnish: A Combined Study by Micro-Raman Spectroscopy, X-ray Diffraction, and Methylated Pyrolysis–Gas Chromatography–Mass Spectrometry

In 2020, the ESA ExoMars and NASA Mars 2020 missions will be launched to Mars to search for evidence of past and present life. In preparation for these missions, terrestrial analog samples of rock formations on Mars are studied in detail in order to optimize the scientific information that the analytical instrumentation will return. Desert varnishes are thin mineral coatings found on rocks in arid and semi-arid environments on Earth that are recognized as analog samples. During the formation of desert varnishes (which takes many hundreds of years), organic matter is incorporated, and microorganisms may also play an active role in the formation process. During this study, four complementary analytical techniques proposed for Mars missions (X-ray diffraction [XRD], Raman spectroscopy, elemental analysis, and pyrolysis-gas chromatography-mass spectrometry [Py-GC-MS]) were used to interrogate samples of desert varnish and describe their capacity to sustain life under extreme scenarios. For the first time, both the geochemistry and the organic compounds associated with desert varnish are described with the use of identical sets of samples. XRD and Raman spectroscopy measurements were used to nondestructively interrogate the mineralogy of the samples. In addition, the use of Raman spectroscopy instruments enabled the detection of β-carotene, a highly Raman-active biomarker. The content and the nature of the organic material in the samples were further investigated with elemental analysis and methylated Py-GC-MS, and a bacterial origin was determined to be likely. In the context of planetary exploration, we describe the habitable nature of desert varnish based on the biogeochemical composition of the samples. Possible interference of the geological substrate on the detectability of pyrolysis products is also suggested. Key Words: Desert varnish-Habitability-Raman spectroscopy-Py-GC-MS-XRD-ExoMars-Planetary science. Astrobiology 17, 1123-1137.

Environmental dynamics and carbon accumulation rate of a tropical peatland in Central Sumatra, Indonesia

Tropical peatlands are important for the global carbon cycle as they store 18% of the total global peat carbon. As they are vulnerable to changes in temperature and precipitation, a rapidly changing environment endangers peatlands and their carbon storage potential. Understanding the mechanisms of peatland carbon accumulation from studying past developments may, therefore, help to assess the future role of tropical peatlands. Using a multi-proxy palaeoecological approach, a peat core taken from the Sungai Buluh peatland in Central Sumatra has been analyzed for its pollen and spore, macro charcoal and biogeochemical composition. The result suggests that peat and C accumulation rates were driven mainly by sea level change, river water level, climatic variability and anthropogenic activities. It is also suggested that peat C accumulation in Sungai Buluh is correlated to the abundance of Freycinetia, Myrtaceae, Calophyllum, Stemonuraceae, Ficus and Euphorbiaceae. Sungai Buluh has reasonable potential for being a future global tropical peat C sinks. However, considering the impact of rapid global climate change in addition to land-use change following rapid economic growth in Indonesia, such potential may be lost. Taking advantage of available palaeoecological records and advances made in Quaternary studies, some considerations for management practice such as identification of priority taxa and conservation sites are suggested.

Ancient DNA analysis identifies marine mollusc shells as new metagenomic archives of the past

Marine mollusc shells enclose a wealth of information on coastal organisms and their environment. Their life history traits as well as (palaeo-) environmental conditions, including temperature, food availability, salinity and pollution, can be traced through the analysis of their shell (micro-) structure and biogeochemical composition. Adding to this list, the DNA entrapped in shell carbonate biominerals potentially offers a novel and complementary proxy both for reconstructing palaeoenvironments and tracking mollusc evolutionary trajectories. Here, we assess this potential by applying DNA extraction, high-throughput shotgun DNA sequencing and metagenomic analyses to marine mollusc shells spanning the last ~7,000years. We report successful DNA extraction from shells, including a variety of ancient specimens, and find that DNA recovery is highly dependent on their biomineral structure, carbonate layer preservation and disease state. We demonstrate positive taxonomic identification of mollusc species using a combination of mitochondrial DNA genomes, barcodes, genome-scale data and metagenomic approaches. We also find shell biominerals to contain a diversity of microbial DNA from the marine environment. Finally, we reconstruct genomic sequences of organisms closely related to the Vibrio tapetis bacteria from Manila clam shells previously diagnosed with Brown Ring Disease. Our results reveal marine mollusc shells as novel genetic archives of the past, which opens new perspectives in ancient DNA research, with the potential to reconstruct the evolutionary history of molluscs, microbial communities and pathogens in the face of environmental changes. Other future applications include conservation of endangered mollusc species and aquaculture management.

Loadings of dissolved organic matter and nutrients from the Neva River into the Gulf of Finland – Biogeochemical composition and spatial distribution within the salinity gradient

We studied the loadings of dissolved organic matter (DOM) and nutrients from the Neva River into the Eastern Gulf of Finland, as well as their distribution within the salinity gradient. Concentrations of dissolved organic carbon (DOC) ranged from 390 to 840μM, and were related to absorption of colored DOM (CDOM) at 350nm, aCDOM(350), ranging from 2.70 to 17.8m−1. With increasing salinity both DOC and aCDOM decreased, whereas the slope of aCDOM spectra, SCDOM(300–700), ranging from 14.3 to 21.2μm−1, increased with salinity.Deviations of these properties from conservative mixing models were occasionally observed within the salinity range of approximately 1–4, corresponding to the region between 27 and 29°E. These patterns are suggested to mostly reflect seasonal changes in properties of river end-member and hydrodynamics of the estuary, rather than non-conservative processes. On the other hand, observed nonlinear relationships observed between aCDOM*(350) and SCDOM(275–295) emphasized the importance of photochemistry among various transformation processes of DOM.Dissolved inorganic nitrogen was effectively transformed in the estuary into particulate organic nitrogen (PON) and dissolved organic nitrogen (DON), of which DON was mostly exported from the estuary, enhancing productivity in nitrogen limited parts of the Gulf of Finland. DON concentrations ranged from 12.4 to 23.5μM and its estuarine dynamics were clearly uncoupled from DOC. In contrast to DOC, estuarine DON dynamics suggest that its production exceeds losses in the estuary.Total nitrogen (TN) and phosphorus (TP) loadings from the Neva River and St. Petersburg were estimated as 73.5GgNyr−1 and 4.2GgPyr−1, respectively. Approximately 59% of TN and 53% of TP loads were in organic forms. DOC and DON loadings were estimated as 741.4GgCyr−1 and 19.0GgNyr−1, respectively. Our estimate for DOC loading was evaluated against a previously published carbon budget of the Baltic Sea. According to the updated model, the Baltic Sea could be identified as a weak source of carbon into the atmosphere.

The variability of particle backscattering coefficient in an oligo-to-hypertrophic cascading reservoir system: implications to TSM bio-optical model development

The particle backscattering coefficient (b bp ) has been obtained either by equipment or semi-analytically based on relations between b bp and the remote sensing reflectance (R rs ). Correlation between b bp and R rs can be significantly high allowing the development of bio-optical model to estimate the total suspended matter concentration [TSM] on water surface from satellite images. The development of such model to monitor cascading reservoir systems can be challenging since this type of water resources changes their biogeochemical composition from upstream to downstream; the water in such system can range from hypertrophic to oligotrophic state. The scientific question raised in this letter is that: in an oligo-to-hypertrophic water system the models based on b bp will keep their good agreement or the influence of organic matter (e.g. chlorophyll-a) can affect this relationship? The aim of this letter was to analyze the b bp variability in a cascading reservoir system and search for empirical models that can capture the relationship between the b bp and [TSM]. The results showed that there are not only differences in the biogeochemical concentrations but also in the b bp from upstream to downstream. In addition there is an influence of chlorophyll-a concentration [Chl-a] on the relationship between b bp and [TSM] which prevents the bio-optical model development.

Composition and sources of sedimentary organic matter in the deep eastern Mediterranean Sea

Abstract. Surface sediments collected from deep slopes and basins (1018–4087 m depth) of the oligotrophic eastern Mediterranean Sea have been analysed for bulk elemental and isotopic composition of organic carbon, total nitrogen and selected lipid biomarkers, jointly with grain size distribution and other geochemical proxies. The distribution and sources of sedimentary organic matter (OM) have been subsequently assessed and general environmental variables, such as water column depth and physical circulation patterns, have been examined as causative factors of deep-sea sediment characteristics. Lithogenic and biogenic carbonates are the dominant sedimentary fractions, accounting for up to 85.4 and 66.5 % of the total weight respectively. The low OC and TN contents in the surface sediments of the study area, which ranged from 0.15 to 1.15 % and 0.06 to 0.11 % respectively, reflect the oligotrophic character of the eastern Mediterranean Sea. Both bulk and molecular organic tracers reflect a mixed contribution from autochthonous and allochthonous sources for the sedimentary OM, as indicated by relatively degraded marine OM, terrestrial plant waxes and anthropogenic OM (e.g. degraded petroleum by-products) respectively. Wide regional variations have been observed amongst the studied proxies, which reflect the multiple factors controlling sedimentation in the deep eastern Mediterranean Sea. Our findings highlight the role of deep eastern Mediterranean basins as depocentres of organic-rich fine-grained sediments (mean 5.4 ± 2.4 μm), with OM accumulation and burial being attributed to aggregation mechanisms and hydrodynamic sorting. A multi-proxy approach is applied aiming to investigate the biogeochemical composition of sediment samples, which sheds new light on the sources and transport mechanisms along with the impact of preservation vs. diagenetic processes on the composition of sedimentary OM in the deep basins of the oligotrophic eastern Mediterranean Sea.

Recent decadal trends in global phytoplankton composition

AbstractIdentifying major trends in biogeochemical composition of the oceans is essential to improve our understanding of biological responses to climate forcing. Using the NASA Ocean Biogeochemical Model combined with ocean color remote sensing data assimilation, we assessed the trends in phytoplankton composition (diatoms, cyanobacteria, coccolithophores, and chlorophytes) at a global scale for the period 1998–2012. We related these trends in phytoplankton to physical conditions (surface temperature, surface photosynthetically available radiation (PAR), and mixed layer depth (MLD)) and nutrients (iron, silicate, and nitrate). We found a significant global decline in diatoms (−1.22% yr−1, p < 0.05). This trend was associated with a significant (p < 0.05) shallowing of the MLD (−0.20% yr−1), a significant increase in PAR (0.09% yr−1), and a significant decline in nitrate (−0.38% yr−1). The global decline in diatoms was mostly attributed to their decline in the North Pacific (−1.00% yr−1, p < 0.05), where the MLD shallowed significantly and resulted in a decline in all three nutrients (p < 0.05). None of the other phytoplankton groups exhibited a significant change globally, but regionally there were considerable significant trends. A decline in nutrients in the northernmost latitudes coincided with a significant decline in diatoms (North Pacific, −1.00% yr−1) and chlorophytes (North Atlantic, −9.70% yr−1). In the northern midlatitudes (North Central Pacific and Atlantic) where nutrients were more scarce, a decline in nutrients was associated with a decline in smaller phytoplankton: cyanobacteria declined significantly in the North Central Pacific (−0.72% yr−1) and Atlantic (−1.56% yr−1), and coccolithophores declined significantly in the North Central Atlantic (−2.06% yr−1). These trends represent the diversity and complexity of mechanisms that drives phytoplankton communities to adapt to variable conditions of nutrients, light, and mixed layer depth. These results provide a first insight into the existence of trends in phytoplankton composition over the maturing satellite ocean color era and illustrate how changes in the conditions of the oceans in the last ~15 years may have affected them.

Assessment of bioavailability and potential toxicity of Cu, Zn and Pb, a case study in Jurujuba Sound, Rio de Janeiro, Brazil

Potential toxicity of sedimentary Cu, Zn and Pb were evaluated based on their fractionation at the inner part of Jurujuba, a small sound at the eastern margin of Guanabara Bay, Rio de Janeiro. Biogeochemical composition revealed an environment extremely enriched with anthropic organic matter and characterized as a detrital heterotrophic system. The fractionation analysis showed that Pb exhibited more affinity with the residual fraction followed by the amorphous Fe/Mn fraction. Cu and Zn were more expressive in the amorphous Fe/Mn fraction followed by the organic one and crystalline Fe/Mn fraction, respectively. According to Igeo index, sediments proved to be highly polluted by Zn and Cu and moderated polluted by Pb. Despite the actual contamination of Jurujuba sediments, the mobility of these elements seems to be limited since the most excessive concentrations were found in the less available fractions, depending on extreme physico-chemical variations to be released.

The influence of ocean acidification on nitrogen regeneration and nitrous oxide production in the northwest European shelf sea

Abstract. The assimilation and regeneration of dissolved inorganic nitrogen, and the concentration of N2O, was investigated at stations located in the NW European shelf sea during June/July 2011. These observational measurements within the photic zone demonstrated the simultaneous regeneration and assimilation of NH4+, NO2− and NO3−. NH4+ was assimilated at 1.82–49.12 nmol N L−1 h−1 and regenerated at 3.46–14.60 nmol N L−1 h−1; NO2- was assimilated at 0–2.08 nmol N L−1 h−1 and regenerated at 0.01–1.85 nmol N L−1 h−1; NO3− was assimilated at 0.67–18.75 nmol N L−1 h−1 and regenerated at 0.05–28.97 nmol N L−1 h−1. Observations implied that these processes were closely coupled at the regional scale and that nitrogen recycling played an important role in sustaining phytoplankton growth during the summer. The [N2O], measured in water column profiles, was 10.13 ± 1.11 nmol L−1 and did not strongly diverge from atmospheric equilibrium indicating that sampled marine regions were neither a strong source nor sink of N2O to the atmosphere. Multivariate analysis of data describing water column biogeochemistry and its links to N-cycling activity failed to explain the observed variance in rates of N-regeneration and N-assimilation, possibly due to the limited number of process rate observations. In the surface waters of five further stations, ocean acidification (OA) bioassay experiments were conducted to investigate the response of NH4+ oxidising and regenerating organisms to simulated OA conditions, including the implications for [N2O]. Multivariate analysis was undertaken which considered the complete bioassay data set of measured variables describing changes in N-regeneration rate, [N2O] and the biogeochemical composition of seawater. While anticipating biogeochemical differences between locations, we aimed to test the hypothesis that the underlying mechanism through which pelagic N-regeneration responded to simulated OA conditions was independent of location. Our objective was to develop a mechanistic understanding of how NH4+ regeneration, NH4+ oxidation and N2O production responded to OA. Results indicated that N-regeneration process responses to OA treatments were location specific; no mechanistic understanding of how N-regeneration processes respond to OA in the surface ocean of the NW European shelf sea could be developed.

Can Rock-Eval pyrolysis assess the biogeochemical composition of organic matter during peatification?

Understanding the responses of soil organic carbon to an increase in global temperature is crucial to estimate potential feedbacks on global warming. In such a context, Rock-Eval pyrolysis has been recently proposed as a screening tool to investigate soil organic matter (SOM) chemistry and vulnerability. In order to test the validity of Rock-Eval as an indicator of SOM chemistry and of OM transformations, we compared classical Rock-Eval derived parameters (total organic carbon [TOC], Hydrogen Index [HI] and Oxygen Index [OI]) to Fourier infrared (FTIR) spectroscopy measured on peat sampled in two contrasting moisture conditions. The increase of TOC in the peat record depicted OM enrichment in aromatic moieties and lipids, whereas HI and OI, respectively, depicted the decomposition of carbohydrates and decarboxylation during early decay processes. Thought to be complementary to the classical parameters, other indicators based on the pyrolysis curve (S2) gave redundant or contradictory results. As an example, SOM cracking around 450°C (namely the F3 component) was linked with carboxylic acids only in the dryer site. In the wetter one, no correlation was found between the F3 component and any FTIR absorption bands. This study underlined the current limitations of deconvolution derived parameters for the characterization of the biochemistry of OM. Finally, our work suggested that the routine use of Rock-Eval pyrolysis must be always associated with another characterization tool of OM, such as FTIR, to avoid misunderstanding.