Role of macroalgal forests within Mediterranean shallow bays in blue carbon storage.

Although seaweeds rank among the most productive vegetated habitats globally, their inclusion within Blue Carbon frameworks is at its onset, partially because they usually grow in rocky substrates and their organic carbon (Corg) is mostly exported and stored beyond their habitat and thus, demonstrating its long-term storage is challenging. Here, we studied the sedimentary Corg storage in macroalgal forests dominated by Gongolaria barbata and in adjacent seagrass Cymodocea nodosa mixed with Caulerpa prolifera algae meadows, and bare sand habitats in Mediterranean shallow coastal embayments. We characterized the biogeochemistry of top 30 cm sedimentary deposits, including sediment grain-size, organic matter and Corg contents, Corg burial rates and the provenance of sedimentary Corg throughout stable carbon isotopes (δ13Corg) and pyrolysis analyses. Sediment Corg stocks and burial rates (since 1950) in G. barbata forests (mean ± SE, 3.5 ± 0.2 kg Corg m-2 accumulated at 15.5 ± 1.6 g Corg m-2 y-1) fall within the range of those reported for traditional Blue Carbon Ecosystems. Although the main species contributing to sedimentary Corg stocks in all vegetated habitats examined was C. nodosa (36 ± 2 %), macroalgae contributed 49 % (19 ± 2 % by G. barbata and 30 ± 3 % by C. prolifera) based on isotope mixing model results. Analytical pyrolysis confirmed the presence of macroalgae-derived compounds in the sediments, including N-compounds and α-tocopherol linked to G. barbata and C. prolifera, respectively. The sedimentary Corg burial rate linked to macroalgae within the macroalgal forests examined ranged from 5.4 to 9.5 g Corg m-2 y-1 (7.4 ± 2 g Corg m-2 y-1). This study provides empirical evidence for the long-term (∼70 years) sequestration of macroalgae-derived Corg within and beyond seaweed forests in Mediterranean shallow coastal embayments and thereby, supports the inclusion of macroalgae in Blue Carbon frameworks.

Impact of wildfire ash on bacterioplankton abundance and community composition in a coastal embayment (Ría de Vigo, NW Spain).

Wildfire ash can have an impact on coastal prokaryotic plankton. To understand the extent to which community composition and abundance of coastal prokaryotes are affected by ash, two ash addition experiments were performed. Ash from a massive wildfire that took place in the Ría de Vigo watershed in October 2017 was added to natural surface water samples collected in the middle sector of the ría during the summer of 2019 and winter of 2020, and incubated for 72 h, under natural water temperature and irradiance conditions. Plankton responses were assessed through chlorophyll a and bacterial abundance measurements. Prokaryotic DNA was analyzed using 16S rRNA gene partial sequencing. In summer, when nutrient concentrations were low in the ría, the addition of ash led to an increase in phytoplankton and bacterial abundance, increasing the proportions of Alteromonadales, Flavobacteriales, and the potentially pathogenic Vibrio, among other taxa. After the winter runoff events, nutrient concentrations in the Ría de Vigo were high, and only minor changes in bacterial abundance were detected. Our findings suggest that the compounds associated with wildfire ash can alter the composition of bacterioplanktonic communities, which is relevant information for the management of coastal ecosystems in fire-prone areas.

Variation of wood color and chemical composition in the stem cross-section of oak (Quercus spp.) trees, with special attention to the sapwood-heartwood transition zone.

The transformation of sapwood (SW) into heartwood (HW) during ageing of wood tissues is the result of physiological and biochemical changes initiated in the transition zone (TZ). These changes contribute to the evolution of active (living) wood cells in SW into less/non-active (dead) wood cells in HW. Previous studies established that the biosynthesis of extractive contents is the most prominent process that occurs in the TZ. To improve our understanding of the extent and characteristics of the TZ in oak wood, the present study reports the results of color parameters (using CIELab color space) and molecular structure and composition of polysaccharide and lignin compounds (using FTIR-ATR and Py-GC-MS). For that purpose, six wood cores from individual living oak (Quercus spp.) trees were collected from two forests with similar environmental conditions, located in the Basque Country (Northern Spain). The color data indicated significant differences between SW, TZ and HW by showing that SW samples were characterized by higher hue (h°) and lower redness (a*) values than the HW, and intermediate values for the TZ. They also suggested that the variations of wood color from SW to HW occur gradually, along a wide TZ counting 4-10 measurement points in a row, depending on the tree. Furthermore, FTIR and Py-GC-MS data gave evidence of the variation trends of polysaccharide and lignin contents in the radial direction, through various FTIR ratios (1735/1325, 1590/1735, 1590/1230, and 1230/1325 cm-1) and one pyrolysis ratio (acetic acid/total polysaccharide: Ps01/Tot_Ps). The observed variations in this present study suggest that the cross-sectional transition patterns can be related to the continuous lignification process of xylem parenchyma cells, as well as the storage of polysaccharide compounds. These results contribute to our fundamental knowledge on the TZ, which may be valuable in research and industrial applications where a clear delimitation of sapwood and/or heartwood is required.

Fingerprinting macrophyte Blue Carbon by pyrolysis-GC-compound specific isotope analysis (Py-CSIA).

There is a need for tools to determine the origin of organic matter (OM) in Blue Carbon Ecosystems (BCE) and marine sediments to (1) facilitate the implementation of Blue Carbon strategies into carbon accounting and crediting schemes and (2) decipher changes in ecosystem condition over decadal to millennial time scales and thus to understand and predict the stability of BCE in a changing world. Pyrolysis-GC-compound specific isotope analysis (Py-CSIA) is applied for the first time in marine environments and BCE research. We studied Australian mangrove, tidal marsh and seagrass sediments, in addition to potential sources of OM (Avicennia, Posidonia, Zostera, Sarcocornia, Ecklonia and Ulva species and seagrass epiphytes), to identify precursors of different biomacromolecule constituents (lignin, polysaccharides and aliphatic structures). Firstly, the link between bulk δ13C and δ13C reconstructed from compound-specific δ13C showed that the pyrolysis approach allows for the isotopic screening of a representative portion of the OM. Secondly, for all samples, the C isotope fingerprint of the carbohydrate products (plant polysaccharides) was the heaviest (13C enriched), followed by lignin and aliphatic products. The differences in δ13C among macromolecules and the overlap in δ13C among putative sources reflect the limitations of bulk δ13C analyses for deciphering OM provenance. Thirdly, phanerogams specimen had the heaviest carbohydrate and lignin, confirming that seagrass-derived lignocellulose can be traced based on δ13C. Consistent differences for individual compounds were identified between seagrasses and between Avicennia and Sarcocornia using Py-CSIA. Fourth, ecosystem shifts (colonization of seagrass habitats by mangrove) on millenary time scales, hypothesized in previous studies on the basis of bulk δ13C and Py-GC-MS, were confirmed by Py-CSIA. We conclude that Py-CSIA is useful in Blue Carbon research to decipher OM sources in marine sediments, identify ecosystem transitions in palaeoenvironmental records, and to understand the role of different OM compounds in Blue Carbon storage.

Molecular Probing of DOM Indicates a Key Role of Spruce-Derived Lignin in the DOM and Metal Cycles of a Headwater Catchment: Can Spruce Forest Dieback Exacerbate Future Trends in the Browning of Central European Surface Waters?

Peatlands of the Northern Hemisphere and Central European coniferous forests experience significant environmental change. The resultant browning of surface waters, that is, elevated concentrations of dissolved organic matter (DOM) and metals, is of interest in the context of the global C cycle, peatland and forest management, and water treatment. In an attempt to identify the causes of this process in the Harz Mountains (Central Germany), we studied the spatiotemporal variations in DOM molecular composition (thermally assisted hydrolysis and methylation combined with GC-MS) and metal concentrations in headwater stream samples. We found strong relationships between DOM and metals and seasonal variations in the DOM quality and tentatively DOM-metal binding mode: during summer base flow, DOM and metal concentrations are low, and all elements other than the alkali and alkaline earth metals (Ca, Mg, Sr, K, and Na) are positively correlated to DOM, whereas during spring and autumn (high discharge), only metals with strong affinity for DOM (Fe, As, Cu, Cr, Pb, and Ti), but not weakly binding ones (Al, Cd, La, Mn, Ni, Zn, and Zr), are correlated to DOM, indicative of selectivity in DOM-metal interactions. The products of polyphenols are the key ingredients of the DOM-metal complexes. We argue the importance of spruce lignin-derived vanillic acid moieties, which are involved in weak (all seasons) and strong, multidentate and/or colloidal, binding (spring and autumn) of metals. Considering the ongoing spruce forest dieback and climate change acceleration, it is tempting to conclude that spruce necromass and forest soils may release vast amounts of lignin-derived DOM and associated metals to headwater streams. This would have significant implications for forest soil C stocks and the management of connected drinking water reservoirs.

Faeces of marine birds and mammals as substrates for microbial plankton communities.

The chemical composition of the seawater soluble fraction (WSF) of yellow-legged gulls and harbour seal faeces and their impact on microbial plankton communities from an eutrophic coastal area have been tested. After characterisation of the C:N:P stoichiometry, trace metals content and organic molecular composition of the faeces, significant differences between species have been observed in all parameters. Seagull faeces present about three times larger N content than seal faeces and are also richer in trace elements except for Cu and Zn. Organic nitrogen in seagull faeces is dominated by uric acid, while the proteins are the main N source in seal faeces. It is remarkable that seagull faeces are five times more soluble in seawater than seal faeces and present a much higher N content (48.0 versus 3.5 mg N in the WSF per gram of dry faeces), >85% of which as dissolved organic nitrogen, with C:N molar ratios of 2.4 and 13 for seagull and seal faeces, respectively. Based on this contrasting N content, large differences were expected in their impact on microbial populations. To test this hypothesis, a 3-day microcosm incubation experiment was performed, in which coastal seawater was amended with realistic concentrations of the WSF of seagull or seal faeces. A significant and similar increase in bacterial biomass occurred in response to both treatments. In the case of phytoplankton, the impact of the treatment with seagull faeces was significantly larger that the effect of the treatment with seal faeces. Our data suggest that the distinct competitive abilities of phytoplankton and bacteria largely influence the potential impact of distinct animal faeces on primary productivity in coastal ecosystems. Impacts on the microbial plankton communities do not affect only this trophic level, but the whole trophic chain, contributing to nutrient recycling in coastal areas where large populations of these species are settled.

Short-Term Soil Flushing with Tannic Acid and Its Effect on Metal Mobilization and Selected Properties of Calcareous Soil.

Cadmium, Cu, Ni, Pb, and Zn removal via soil flushing with tannic acid (TA) as a plant biosurfactant was studied. The soil was treated for 30 h in a column reactor at a constant TA concentration and pH (3%, pH 4) and at variable TA flow rates (0.5 mL/min or 1 mL/min). In the soil leachates, pH, electrical conductivity (EC), total dissolved organic carbon, and metal concentrations were monitored. Before and after flushing, soil pH, EC, organic matter content, and cation exchange capacity (CEC) were determined. To analyze the organic matter composition, pyrolysis as well as thermally assisted hydrolysis and methylation coupled with gas chromatography-mass spectrometry were used. Metal fractionation in unflushed and flushed soil was analyzed using a modified sequential extraction method. The data on cumulative metal removal were analyzed using OriginPro 8.0 software (OriginLab Corporation, Northampton, MA, USA) and were fitted to 4-parameter logistic sigmoidal model. It was found that flushing time had a stronger influence on metal removal than flow rate. The overall efficiency of metal removal (expressed as the ratio between flushed metal concentration and total metal concentration in soil) at the higher flow rate decreased in this order: Cd (86%) > Ni (44%) > Cu (29%) ≈ Zn (26%) > Pb (15%). Metals were removed from the exchangeable fraction and redistributed into the reducible fraction. After flushing, the soil had a lower pH, EC, and CEC; a higher organic matter content; the composition of the organic matter had changed (incorporation of TA structures). Our results prove that soil flushing with TA is a promising approach to decrease metal concentration in soil and to facilitate carbon sequestration in soil.

Deciphering organic matter sources and ecological shifts in blue carbon ecosystems based on molecular fingerprinting.

Blue carbon ecosystems (BCE) play an essential role in the global carbon cycle by removing atmospheric carbon dioxide and storing it as organic carbon (OC) in biomass and sediments. However, organic matter (OM) deposition and degradation/preservation processes are poorly understood, especially on the long-term and at molecular scales. We analysed sediment samples from six cores collected in tidal marshes, mangroves and seagrasses (up to 150 cm long cores spanning up to 10,000 yrs of OC accumulation) from Spencer Gulf (South Australia), by pyrolysis (Py-GC-MS and THM-GC-MS), and we compared the results with elemental and stable isotope data, to decipher OM provenance and to assess degradation/preservation dynamics. The results showed that: (1) the major biopolymers preserved were polysaccharides, polyphenolic moieties (lignin and tannin) and polymethylenic moieties (e.g. cutin, suberin, chlorophyll) with smaller apportions of proteins and resins; (2) the OM originates predominantly from vascular plant materials (in particular lignocellulose) that have been well-preserved, even in some of the oldest sediments; (3) mangroves were found to be the most efficient OC sinks, partially explained by syringyl lignin preservation; (4) seagrasses were shown to store polysaccharide-enriched OM; (5) large proportions of polycyclic aromatic hydrocarbons (PAHs) in surficial tidal marsh and mangrove sediments probably reflect pyrogenic OM from industrial combustion, and; (6) "ecosystem shifts", i.e. mangrove encroachment in tidal marsh and transition from seagrass to mangrove, were detected. Deposition environment and source vegetation control OC sequestration and there is no specific recalcitrant form of OM that is selectively preserved. For the first time, we demonstrate how analytical pyrolysis in combination with stable isotope analysis can be used to reconstruct (palaeo-)ecological shifts between different BCE. This study improves our knowledge on OC accumulation dynamics and the response of BCE to environmental change, which can inform the implementation of strategies for climate change mitigation.

Linking the electron donation capacity to the molecular composition of soil dissolved organic matter from the Three Gorges Reservoir areas, China.

Soil dissolved organic matter (DOM) plays an essential role in the Three Gorges Reservoir (TGR) as a linkage between terrestrial and aquatic systems. In particular, the reducing capacities of soil DOM influence the geochemistry of contaminants such as mercury (Hg). However, few studies have investigated the molecular information of soil DOM and its relationship with relevant geochemical reactivities, including redox properties. We collected samples from eight sites in the TGR areas and studied the link between the molecular characteristics of DOM and their electron donation capacities (EDCs) toward Hg(II). The average kinetic rate and EDC of soil DOM in TGR areas were (0.004 ± 0.001) hr-1 and (2.88 ± 1.39) nmol e-/mg DOMbulk, respectively. Results suggest that higher EDCs and relatively rapid kinetics were related to the greater electron donating components of lignin-derived and perhaps pyrogenic DOM, which are the aromatic constituents that influenced the reducing capacities of DOM in the present study. Molecular details revealed that even the typical autochthonous markers are important for the EDCs of DOM as well, in contrast to what is generally assumed. More studies identifying specific DOM molecular components involved in the abiotic reduction of Hg(II) are required to further understand the relations between DOM sources and their redox roles in the environmental fate of contaminants.

FTIR and Py-GC-MS data of wood from various living oak species and Iberian shipwrecks.

Data in this article are related to the chemical characterization of various oak wood samples. Data have been obtained by the application of Fourier Transform Infrared (FTIR) spectroscopy and pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) to living tree species and shipwreck wood fragments. Measurements were performed on individual rings in order to facilitate the understanding of the variability in wood chemical composition along the radial cores, i.e. the same kind of material traditionally used for dendrochronological analysis. The data in this article is labelled according to the anatomical sections of the wood (sapwood, transition wood and heartwood) where the samples were taken. The experimental background and the results can be found in the related research article, "Chemometric tools for identification of wood from different oak species and their potential for provenancing of Iberian shipwrecks (16th-18th centuries CE)" (Traoré et al., 2018).

Mineral dust as a driver of carbon accumulation in northern latitudes.

Peatlands in northern latitudes sequester one third of the world's soil organic carbon. Mineral dusts can affect the primary productivity of terrestrial systems through nutrient transport but this process has not yet been documented in these peat-rich regions. Here we analysed organic and inorganic fractions of an 8900-year-old sequence from Store Mosse (the "Great Bog") in southern Sweden. Between 5420 and 4550 cal yr BP, we observe a seven-fold increase in net peat-accumulation rates corresponding to a maximum carbon-burial rate of 150 g C m-2 yr-1 - more than six times the global average. This high peat accumulation event occurs in parallel with a distinct change in the character of the dust deposited on the bog, which moves from being dominated by clay minerals to less weathered, phosphate and feldspar minerals. We hypothesize that this shift boosted nutrient input to the bog and stimulated ecosystem productivity. This study shows that diffuse sources and dust dynamics in northern temperate latitudes, often overlooked by the dust community in favour of arid and semi-arid regions, can be important drivers of peatland carbon accumulation and by extension, global climate, warranting further consideration in predictions of future climate variability.

Differentiation between pine woods according to species and growing location using FTIR-ATR.

Attenuated total reflectance-Fourier transform infrared (FTIR-ATR) spectroscopy was applied to 120 samples of heartwood rings from eight individual pine trees from different locations in Spain. Pinus sylvestris cores were collected at the Artikutza natural park (Ps-ART). Pinus nigra cores were collected in Sierra de Cazorla (Pn-LIN) and in La Sagra Mountain (Pn-LSA). Three discriminant analysis tests were performed using all bands (DFT), lignin bands only (DFL) and polysaccharides bands only (DFP), to explore the ability of FTIR-ATR to separate between species and growing location. The DFL model enabled a good separation between pine species, whereas the DFP model enabled differentiation for both species and growing location. The DFT model enabled virtually perfect separation, based on two functions involving twelve FTIR bands. Discrimination between species was related to bands at 860 and 1655 cm-1, which were more intense in P. sylvestris samples, and bands at 1425 and 1635 cm-1, more intense in P. nigra samples. These vibrations were related to differences in lignin structure and polysaccharide linear chains. Discrimination between growing locations was mainly related to polysaccharide absorptions: at 900, 1085 and 1335 cm-1 more representative of Pn-LIN samples, and at 1105 and 1315 cm-1 mostly associated to Pn-LSA samples. These absorptions are related to ß-glycosidic linkages (900 cm-1), cellulose and hemicellulose (C-O bonds, 1085 and 1105 cm-1) and content in amorphous/crystalline cellulose (1315 and 1335 cm-1). These results show that FTIR-ATR in combination with multivariate statistics can be a useful tool for species identification and provenancing for pine wood samples of unknown origin.

Composition of dissolved organic matter (DOM) from periodically submerged soils in the Three Gorges Reservoir areas as determined by elemental and optical analysis, infrared spectroscopy, pyrolysis-GC-MS and thermally assisted hydrolysis and methylation.

Soil-derived dissolved organic matter (DOM) has a major influence in biogeochemical processes related to contaminant dynamics and greenhouse gas emissions, due to its reactivity and its bridging role between the soil and aquatic systems. Within the Three Gorges Reservoir (TGR, China) area, an extensive water-fluctuation zone periodically submerges the surrounding soils. Here we report a characterization study of soil-derived DOM across the TGR areas, using elemental and optical analysis, infrared spectroscopy (FTIR), pyrolysis-GC-MS (Py-GC-MS) and thermally assisted hydrolysis and methylation (THM-GC-MS). The results showed that the soil DOM from the TGR area is a mixture of "allochthonous" (i.e., plant-derived/terrigenous) and "autochthonous" (i.e., microbial) origins. The terrigenous DOM is composed primarily of phenolic and aliphatic structures from lignin and aliphatic biopolymers (i.e. cutin, suberin), respectively. Multivariate statistics differentiated between two fractions of the microbial DOM, i.e. chitin-derived, perhaps from fungi and arthropods in soil, and protein-derived, partially sourced from algal or aquatic organisms. Molecular proxies of source and degradation state were in good agreement with optical parameters such as SUVA254, the fluorescence index (FI) and the humification index (HIX). The combined use of elemental analysis, fluorescence spectroscopy, and Py-GC-MS provides rigorous and detailed DOM characterization, whereas THM-GC-MS is useful for more precise but qualitative identification of the different phenolic (cinnamyl, p-hydroxyphenyl, guaiacyl, syringyl and tannin-derived) and aliphatic materials. With the multi-methodological approach used in this study, FTIR was the least informative, in part, because of the interference of inorganic matter in the soil DOM samples. The soil DOM from the TGR's water fluctuation zone exhibited considerable compositional diversity, mainly related to the balance between DOM source (microbial- or plant-derived), local vegetation and anthropogenic activities (e.g., agriculture). Finally, the relationship between DOM composition and its potential reactivity with substances of environmental concerns in the TGR area are also discussed.

Application of FTIR spectroscopy to the characterization of archeological wood.

Two archeological wood samples were studied by attenuated total reflectance Fourier transform infrared (FTIR-ATR) spectroscopy. They originate from a shipwreck in Ribadeo Bay in the northwest of Spain and from a beam wood of an old nave of the Cathedral of Segovia in the central Spain. Principal component analysis was applied to the transposed data matrix (samples as columns and spectral bands as rows) of 43 recorded spectra (18 in the shipwreck and 25 in the beam wood). The results showed differences between the two samples, with a larger proportion of carbohydrates and smaller proportion of lignin in the beam than in the shipwreck wood. Within the beam wood, lignin content was significantly lower in the recent than the old tree rings (P=0.005). These variations can be attributed to species differences between the two woods (oak and pine respectively), with a mixture of guaiacyl and syringyl in hardwood lignin, whereas softwood lignin consists almost exclusively of guaiacyl moieties. The influence of environmental conditions on the FTIR fingerprint was probably reflected by enhanced oxidation of lignin in aerated conditions (beam wood) and hydrolysis of carbohydrates in submerged-anoxic conditions (shipwreck wood). Molecular characterization by analytical pyrolysis of selected samples from each wood type confirmed the interpretation of the mechanisms behind the variability in wood composition obtained by the FTIR-ATR.

Thermally assisted hydrolysis and methylation of purified tannins from plants.

A collection of tannins extracted from various plant species was subjected to thermally assisted hydrolysis and methylation (THM) using tetramethylammonium hydroxide. The products obtained included 1,3,5-trimethoxybenzenes, derived from A rings of condensed tannins (CTs), and 1,2-dimethoxybenzene, 1,2,3-trimethoxybenzene, and derivatives as major products from the B ring. 1,2,4-Tri- and two tetramethoxybenzenes were also detected in most analyses. Correlation analyses revealed that they were derived from the B ring, with 1,2,4-trimethoxybenzene being derived from a procyanidin (PC) B ring and 1,2,3,5-tetramethoxybenzene from a prodelphinidin (PD) ring. Tannins from species that contained both CT and hydrolyzable tannin (HT) produced mainly permethylated gallic acid moieties upon THM, and the products derived from CTs were less abundant. Most likely, the ester-bound HTs are more easily transmethylated than the cleavage and methylation of the C-C and C-O linked CTs. Statistical analyses of the THM products and 13C NMR data of the tannins showed good correlations between the B ring hydroxylation and the di- and trimethoxybenzenes observed. Using the ratio of the methyl esters of 3,4-dimethoxybenzoic acid and 3,4,5-trimethoxybenzoic acid only provided good correlations of the percent PC as well. Furthermore, the 1,3,5-trimethoxybenzenes may serve as good markers of tannins in plant, soil, sediment or other samples as analyzed by THM.