Diagenesis of organic matter in a 400 m organic rich sediment core from offshore Namibia using solid state 13C NMR and FTIR

Although rates and mechanisms of early diagenesis have been well studied, the effects of microbial metabolism on the molecular composition of the sedimentary organic matter (SOM) over long periods of time need more investigation. In this study, we characterize the early diagenesis of marine SOM from organic rich sediments of the Ocean Drilling Program site 1082 located off Namibia, in the vicinity of the Benguela coastal upwelling system. We used both Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (¹³C NMR) to assess the quantitative partitioning of the organic carbon into major compound classes (aliphatic, aromatic, ester, carboxylic, amide and carbons from carbohydrates). Then, we calculate the SOM composition in the main biomolecules (proteins, carbohydrates, lipids and lignin) on the basis of previous ¹³C NMR based estimates of the molecular composition of the organic mixtures. Results show that the SOM is still labile at 7 m below the seafloor (mbsf) and composed of about 25% proteins and 15% carbohydrates. With increasing depth, the protein content exponentially decreases to 13% at 367 mbsf, whereas the carbohydrate content decreases linearly to 11%. The lignin and lipid content consistently represent around 10% and 40% of the SOM, respectively, and show an increase with depth, due mostly to selective enrichment as the more labile components are lost by degradation. Thus, these components of the SOM are considered refractory at the depth scale considered. The calculated remineralization rates are extremely slow ranging from 5.6 mol C m⁻³ ky⁻¹ at the top of the core to 0.2 mol C m⁻³ ky⁻¹ according to the organic carbon flux to the seafloor. Knowing the labile carbon losses, we propose a method to calculate the initial TOC before the diagenesis took place.     

Organic matter quality in reclaimed boreal forest soils following oil sands mining

Following surface mining of the Athabasca Oil Sands deposits in northeastern Alberta, Canada, land reclamation entails the reconstruction of soil-like profiles using salvaged soil materials such as peat and mining by-products. The overall objective of this research was to assess soil organic matter (SOM) quality in different reclamation practices as compared to undisturbed soils found in the region. Soil samples (0–10 cm) were taken from 45 plots selected to represent undisturbed reference ecosites and reclamation treatments. Soil OM pools were isolated using a combination of acid hydrolysis and physical separation techniques. Chemical composition of the low density fractions was characterized using ramped cross polarization (RAMP-CP) ¹³C nuclear magnetic resonance (NMR). Differences between disturbed and undisturbed sites reflected the influence of different botanical inputs (peat vs. forest litter) to SOM composition. Reconstructed soils were characterized by significantly lower alkyl over O-alkyl carbon (ALK/O-ALK) ratios (0.3) than undisturbed sites (0.5). For these reconstructed soils, a significantly higher proportion of soil carbon was present in the sand associated (Heavy sand) pool (49.2 vs. 37.3) and in the acid-unhydrolyzable residue (AUR) fraction (61.3 vs. 54.7). These SOM parameters were significantly related to time since reconstruction, with the AUR (p value = 0.012) and Heavy sand (p value = 0.05) fractions decreasing with time since reconstruction, while the ALK/O-ALK ratio increased (p value = 0.006). These findings suggest that the ALK/O-ALK, AUR, and Heavy sand parameters are suitable indicators for monitoring SOM quality in these reconstructed soils following oil sands mining.     

Methodological comparison for quantitative analysis of fossil and recently derived carbon in mine soils with high content of aliphatic kerogen

In mine soil, quantification of soil organic carbon (OC) derived recently from biomass decomposition is complicated by the presence of fossil (geogenic) C derived from coal, oil shale, or similar material in the overburden. The only reliable method for such measurement is ¹⁴C analysis (i.e. radiocarbon dating) using instrumentation such as accelerator mass spectrometry, which is too expensive for routine laboratory analysis. We tested two previously used and two new methods for recent C quantification and compared them with ¹⁴C AMS radiocarbon dating as a reference using a set of soil samples (n = 14) from Sokolov, Czech Republic: (i) ¹³C isotope ratio composition, (ii) cross polarization magic angle spinning ¹³C nuclear magnetic resonance (CPMAS ¹³C NMR) spectroscopy, (iii) near infrared spectroscopy (NIRS) coupled with partial least squares regression and (iv) Rock–Eval pyrolysis. Conventional methods for OC determination (dry combustion, wet dichromate oxidation, loss-on-ignition) were also compared to quantify any bias connected with their use. All the methods provided acceptable recent carbon estimates in the presence of mostly aliphatic fossil C from kerogen. However, the most accurate predictions were obtained with two approaches using Rock–Eval pyrolysis parameters as predictors, namely (i) S₂ curve components and (ii) oxygen index (OI). The S₂ curve approach is based on the lower thermal stability of recent vs. fossil organic matter. The OI approach corresponded well with ¹³C NMR spectra, which showed that samples rich in recent C were richer in carboxyl C and O-alkyl C. These two methods showed the greatest potential as routine methods for recent C quantification.     

Mineralisation and structural changes during the initial phase of microbial degradation of pyrogenic plant residues in soil

The microbial recalcitrance of char accumulated after vegetation fires was studied using pyrogenic organic material (PyOM) with increasing degrees of charring, produced from rye grass (Lolium perenne) and pine wood (Pinus sylvestris) at 350 °C under oxic conditions. Solid state ¹³C and ¹⁵N nuclear magnetic resonance (NMR) spectroscopy confirmed increasing aromaticity and the formation of heterocyclic N with prolonged charring. After mixing with a mineral soil, the PyOM was aerobically incubated for 48 days at 30 °C. To account for the input of fresh litter after a fire event, unburnt rye grass residue was added as a co-substrate. The grass-derived PyOM showed the greatest extent of C mineralisation. After 48 days incubation, up to 3.2% of the organic C (OC) was converted to CO₂. More severe thermal alteration resulted in a decrease in the total C mineralisation to 2.5% of OC. In the pine-derived PyOM, only 0.7% and 0.5% of the initial C were mineralised. The co-substrate additions did not enhance PyOM mineralisation during initial degradation. ¹³C NMR spectroscopic analysis indicated structural changes during microbial degradation of the PyOM. Concomitant with a decrease in O-alkyl/alkyl-C, carboxyl/carbonyl C content increased, pointing to oxidation. Only the strongly thermally altered pine PyOM showed a reduction in aromaticity. The small C losses during the experiment indicated conversion of aryl C into other C groups. As revealed by the increase in carboxyl/carbonyl C, this conversion must have included the opening and partial oxidation of aromatic ring structures. Our study demonstrates that plant PyOM can be microbially attacked and mineralised at rates comparable to those for soil organic matter (SOM), so its role as a highly refractory SOM constituent may need re-evaluation.     

Total and pyrogenic carbon stocks in black spruce forest floors from eastern Canada

Pyrogenic carbon (PyC), a by-product of recurrent boreal wildfires, is an important component of the global soil C pool, although precise assessment of boreal PyC stock is scarce. The overall objective of this study was to estimate total C stock and PyC stock in forest floors of Eastern Canada boreal forests. We also investigated the environmental conditions controlling the stocks and characterized the composition of the forest floor layers. Forest floor samples were collected from mesic black spruce sites recently affected by fire (3–5 yr) and analyzed using elemental analysis and solid state ¹³C nuclear magnetic resonance (NMR) spectroscopy. PyC content was further estimated using a molecular mixing model. Total C stock in forest floors averaged 5.7 ± 2.9 kg C/m² and PyC stock 0.6 ± 0.3 kg C/m². Total stock varied with position in the landscape, with a greater accumulation of organic material on northern aspects and lower slope positions. In addition, total stock was significantly higher in spruce-dominated forest floors than stands where jack pine was present. The PyC stock was significantly related to the atomic H/C ratio (R² 0.84) of the different organic layers. ¹³C NMR spectroscopy revealed a large increase in aromatic carbon in the deepest forest floor layer (humified H horizon) at the organic-mineral soil interface. The majority of the PyC stock was located in this horizon and had been formed during past high severity fires rather than during the most recent fire event.     

Soil discrimination using diffuse reflectance Vis–NIR spectroscopy in a local toposequence

Vis–NIR spectroscopy is nowadays presented as a possible routine method for soil sample analysis. However, there is still no consensus on which is the best multivariate statistical method to use. We propose to use principal component analysis to complete the spectral data treatment. The soil samples came from a pedological cover made up of red–yellow Latosols: 88 samples of 11 soil profiles on four toposequences were collected; clay, organic matter, silica, iron, aluminum and titanium total contents were determined; the contents of goethite, hematite, gibbsite, and kaolinite were calculated. Diffuse reflectance Vis–NIR spectroscopy at wavelengths from 400 to 2400 nm combined with principal component analysis (PCA) was sufficiently sensitive to discriminate different Latosols. Wavelengths of 700 nm and 2200 to 2300 nm were influenced by content ratios of organic matter and iron oxides (700 nm), and kaolinite and gibbsite absorption (2200 and 2300 nm). The spectral responses were affected not only by the content of these constituents, but also by the composition of the minerals, so that the same class of Latosol may have different or similar spectral responses. The role of microaggregation is discussed.     

A demonstration of the high variability of chars produced from wood in bushfires

Vegetation fires play a major role in global C cycling through the addition of inert carbon (char) to the environment. The objective of this study was to compare and contrast the chemical composition of 53 natural chars collected from the soil surface 6–32 years after a natural fire. In order to achieve this, we applied a recently developed nuclear magnetic resonance (NMR) technique that gauges the degree of condensation of aromatic structures within chars. Our results show that the degree of condensation varied considerably among char samples (n = 4–5), collected from burnt-out tree stumps at each of the 11 fire sites. This demonstrates that there is a great degree of variability in the composition of the char produced in natural fires, which is likely to be reflected in widely varying rates of char decomposition. This highlights a major difficulty in quantifying the effects of vegetation fires on global C cycling. Importantly, no differences could be discerned between chars of different ages, indicating that ageing of this type of char in this environment is slow on the decadal timescale. Finally, this study demonstrates that although char samples appear to preserve a record of fire conditions, great care must be taken when interpreting this record to account for the high degree of heterogeneity in char composition. Bulking of char samples would alleviate this problem to some extent; however, bulking would mask the inter-particle heterogeneity clearly evident in this study.     

Variability of Indian monsoonal rainfall over the past 100 ka and its implication for C3–C4 vegetational change

Oxygen and carbon isotope ratios of soil carbonate and carbon isotope ratios of soil organic matter (SOM) separated from three cores, Kalpi, IITK and Firozpur, of the Ganga Plain, India are used to reconstruct past rainfall variations and their effect on ambient vegetation. The δ¹⁸O values of soil carbonate (δ¹⁸O_SC) analyzed from the cores range from ? 8.2 to ? 4.1‰. Using these variations in δ¹⁸O_SC values we are able, for the first time, to show periodic change in rainfall amount between 100 and 18 ka with three peaks of higher monsoon at about 100, 40 and 25 ka. The estimation of rainfall variations using δ¹⁸O value of rainwater-amount effect suggests maximum decrease in rainfall intensity (~ 20%) during the last glacial maximum. The δ¹³C values of soil carbonate (δ¹³C_SC) and SOM (δ¹³C_SOM) range from ? 6.3 to + 1.6‰ and ? 28.9 to ? 19.4‰, respectively, implying varying proportions of C₃ and C₄ vegetations over the Ganga Plain during the last 100 ka. The comparison between monsoonal rainfall and atmospheric CO₂ with vegetation for the time period 84 to 18 ka indicate that relative abundances of C₃ and C₄ vegetations were mainly driven by variations in monsoonal rainfall.     

Organic phosphorus fractionation in wetland soil profiles by chemical extraction and phosphorus-31 nuclear magnetic resonance spectroscopy

Organic P (OP) plays an important role in soil P cycling and is a potential P source for wetland plants. In this study, a modified chemical sequential fractionation method and ³¹P nuclear magnetic resonance spectroscopy (³¹P NMR) of NaOH–EDTA extracts were used to examine the distribution of organic P fractions and compounds in soil profiles of the Beijing Yeyahu Wetland, China. The influence of acid treatment prior to NaOH–EDTA extraction on ³¹P NMR spectra was also investigated. Results show that highly resistant OP was the major class of organic P. The rank order of organic P fractions was highly resistant OP (on average accounting for 68.5% of total OP) > moderately resistant OP (15.8%m of total OP) > moderately labile OP (11.4% of total OP) > labile OP (4.3% of total OP). Most of the organic P fractions decreased with soil depth due to the accumulation of plant residues in surface soils and the deposition and diagenesis of soils. Moderately (r = 0.586, p < 0.01) and highly (r = 0.741, p < 0.01) resistant OP fractions were positively correlated with soil organic matter. Phosphorus compounds including orthophosphate (23–74.6% of total P in spectra), monoester phosphate (18.6–76%), diester phosphate (nil-7.8%) and pyrophosphate (nil-6.7%) were characterized using ³¹P NMR. Monoester-P was the dominant soil organic P compound identified. The proportion of monoester-P increased significantly in NaOH–EDTA extracts with HCl pretreatment and it was confirmed by chemical analysis. Therefore, it can be concluded that HCl pretreatment can remove more than half of the inorganic P and increase the overall recovery rate of organic P during subsequent NaOH–EDTA extraction, which might be a new approach for organic P detection. Furthermore, the OP chemical sequential fractionation method presented in this study is an integrated and comprehensive approach which can be used for further verification.     

Accumulation of terrestrial organic carbon on an active continental margin offshore southwestern Taiwan: Source-to-sink pathways of river-borne organic particles

Sediment samples (213 sites) collected from the tectonic-active continental margin, offshore southwestern Taiwan were analyzed for grain sizes, organic carbon, nitrogen and carbon isotopic composition to obtain mass accumulation rate of terrestrial organic carbon and carbon budget to evaluate fate of terrestrial organic carbon from small mountainous rivers on the continental margin offshore southwestern Taiwan. Terrestrial organic carbon accumulation rates range from 0.29 to 45.6 g C m⁻² yr⁻¹ with a total accumulation budget of 0.063 Mt yr⁻¹, which accounts for less than 13% of total river particulate organic carbon loads exported from the adjacent rivers, the Gaoping (a.k.a., Kaoping), Erhjen and Tsengwen rivers. This low burial efficiency of terrestrial organic carbon demonstrated that a majority of river-borne particles together with organic materials was moved away from the study area.For the river-borne particles from the Gaoping river, a pair of depocenters in the upper slope flanking the Gaoping submarine canyon are the locations where the maximum TC_org accumulation rate were observed which hold up to 45% (0.016 Mt yr⁻¹) of the calculated accumulation found in the study region. On the other hand, the occurrence of higher-fraction terrestrial organic carbon in the upper and middle Gaoping submarine canyon suggests that a majority of particulate organic carbon of the Gaoping river was transported directly into the deep-sea basin through the Gaoping submarine canyon. Our results demonstrated that active margin with narrow shelf and slope is not an efficient sink for the large amount of terrigenous organic carbon supplied by the small rivers, but, a transient environment for these river derived particles.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.     

Scytonemin-imine,a mahogany-colored UV/Vis sunscreen of cyanobacteria exposed to intense solar radiation

We report the structure of a novel sunscreen based on the scytoneman skeleton. This pigment, scytonemin-3a-imine, was isolated from cultures of the cyanobacterium, Scytonema hoffmani, only when grown under high to intense (300–1500+ μmol quanta m⁻² s⁻¹) light conditions, with or without added UVR (ultraviolet radiation). It was also isolated from samples of natural cyanobacterial mats growing in shallow/short hydroperiod fresh water (Florida Everglades), soils (Loxahatchee, Florida) and saline cyanobacterial mats (Eleuthera, The Bahamas). These natural samples were all growing under intense (e.g. > 1500 μmol quanta m⁻² s⁻¹) light conditions. Scytonemin-3a-imine may eventually become a biomarker for such biota.Characterization included UV/Vis spectrophotometry, Fourier transform infrared (FTIR) spectroscopy, matrix assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) mass spectrometry (MS and MSⁿ), and both 1- and 2-D ¹H nuclear magnetic resonance (NMR) spectrometry. Derivatization (NaBH₄ reduction, acetylation, deuterium exchange) were utilized to confirm structural features. The UV/Vis spectrum had maxima at 237, 366, 437 and 564 nm. The absorption of UVR is in line with other scytoneman-based pigments. The strong visible absorption bands (437 and 564 nm) indicate an alternate or additional physiological role for the pigment. We propose that it may protect both the chlorophyll reaction centers and the cytochromes from excess radiation. We speculate that excitation of the cytochromes, potentially leading to excess electron transport, or photo-oxidative destruction of the cytochromes, may enhance reactive oxygen species (ROS) generation.     

Impact of recent lake eutrophication on microbial community changes as revealed by high resolution lipid biomarkers in Rotsee (Switzerland)

The effects of eutrophication on short term changes in the microbial community were investigated using high resolution lipid biomarker and trace metal data for sediments from the eutrophic Lake Rotsee (Switzerland). The lake has been strongly influenced by sewage input since the 1850s and is an ideal site for studying an anthropogenically altered ecosystem. Historical remediation measures have had direct implications for productivity and microbial biota, leading to community composition changes and abundance shifts. The higher sewage and nutrient input resulted in a productivity increase, which led predominantly to a radiation in diatoms, primary producers and methanogens between about 1918 and 1921, but also affected all microorganism groups and macrophytes between about 1958 and 1972. Bacterial biomass increased in 1933, which may have been related to the construction of a mechanical sewage treatment plant. Biomarkers also allowed tracing of fossil organic matter/biodegraded oil contamination in the lake. Stephanodiscus parvus, Cyclotella radiosa and Asterionella formosa were the dominant sources of specific diatom biomarkers. Since the 1850s, the cell density of methanogenic Archaea (Methanosaeta spp.) ranged within ca. 0.5–1.8 × 10⁹ cells g⁻¹ dry sediment and the average lipid content of Rotsee Archaea was ca. 2.2 fg iGDGTs cell⁻¹. An altered BIT index (BIT_CH), indicating changes in terrestrial organic matter supply to the lake, is proposed.     

Elucidating the chemical structure of pyrogenic organic matter by combining magnetic resonance,mid-infrared spectroscopy and mass spectrometry

Fire-derived organic matter (pyrogenic organic matter, or PyOM), despite its apparent long term stability in the environment, has recently been reported to degrade faster than previously thought. Current studies have suggested that the composition and structure of PyOM can provide new insights on the mechanisms by which C and N from pyrolyzed biomaterials are stabilized in soils. To better understand the chemical structure of PyOM produced under typical fire conditions in temperate forests, samples of dual-enriched (¹³C/¹⁵N) Pinus ponderosa wood and the charred material produced at 450 °C were analyzed by solid state nuclear magnetic resonance (ssNMR), electron paramagnetic resonance (EPR), diffuse reflectance Fourier transform infrared (DRIFT) spectroscopy, and both isotopic and elemental composition (C, H, O, and N). Notably, the use of high magnetic field strengths in combination with isotopic enrichment augmented the NMR detection sensitivity, and thus improved the quality of molecular information as compared with previously reported studies of pyrogenic materials. The key molecular groups of pine wood and the corresponding PyOM materials were determined using magic-angle spinning (MAS) ¹³C, ¹⁵N, and ¹H NMR. Together with DRIFT and EPR measurements, ssNMR revealed the formation of a free radical-containing disordered blend of nitrogenous aromatics and heat resistant aliphatics in the PyOM due to incomplete combustion of the precursor wood. ¹³C ssNMR and DRIFT analyses showed the removal of oxygenated aliphatics due to pyrolysis of the precursor wood and the dominant contribution of multiply-bonded and oxygenated aromatic structures in the resulting PyOM. However, the ¹⁸O isotopic analyses indicated selective retention of ligneous moieties during charring at 450 °C. ¹⁵N ssNMR studies implied that the nitrogenous species in PyOM corresponded to thermally altered rather than heat resistant domains of the pine wood precursor. Our molecular characterization suggests that biomaterials pyrolyzed near 450 °C may degrade in soils faster than those pyrolyzed at higher temperatures and may not represent a stable C sink in terrigenous ecosystems.     

The geographic distribution of Sr isotopes from surface waters and soil extracts over the island of Bornholm (Denmark) – A base for provenance studies in archaeology and agriculture

In this paper we report the Sr isotope signatures, and Sr, Al and Na concentrations of 30 surface waters (lakes/ponds and rivers/creeks) and 19 soil sample extracts from the island of Bornholm (Denmark) and present a categorized ⁸⁷Sr/⁸⁶Sr value distribution map that may serve as a base for provenance studies, including archaeological migration and authenticity proof for particular food products. The Sr isotopic compositions of surface waters range from ⁸⁷Sr/⁸⁶Sr = 0.7097–0.7281 (average 0.7175 ± 0.0049; 1σ), whereas 0.1 M HNO₃, 0.05 M HNO₃, and 0.01 M CaCl₂ soil extracts range from ⁸⁷Sr/⁸⁶Sr = 0.7095–0.7197 and define somewhat lower but statistically indistinguishable averages of 0.7125 ± 0.003 (1s). These compositions are lower than the values expected from the Precambrian granitoid basement (⁸⁷Sr/⁸⁶Sr = 0.758–0.944), and from the overlying, mainly clastic Paleozoic sediments. Combined Sr isotope composition vs. Sr, Na and Al concentration relationships of soil extracts imply that lowering of the isotopic composition of leachable Sr on Bornholm results as a consequence of significant admixture to this fraction of Sr deposited as marine salts (aerosols), and that rainwater only has a minor influence on the Sr budget of the surface waters. Positively correlated Al/Na and [1/Sr] vs. ⁸⁷Sr/⁸⁶Sr relationships in soil extracts and surface waters indicate that the surface run-off on Bornholm is characterized by two predominant sources, namely marine aerosols (sea salts) with high Sr and low ⁸⁷Sr/⁸⁶Sr values, and a source with lower [Sr] delivering radiogenic Sr to the surface waters, which we equate with Sr leached from the products of mineral weathering (soils).A feasibility study for using Sr isotopic compositions of surface waters and soil extracts as a proxy for bioavailable Sr signatures was performed with a few samples collected in the vicinity of the eleventh century AD Ndr. Grødbygård cemetery site in SW Bornholm, from where Sr isotope compositions of modern fauna samples and tooth enamel of humans buried in the cemetery have been reported. Waters and soil extracts studied herein from around this site range from ⁸⁷Sr/⁸⁶Sr = 0.7104–0.7166 and correspond to Sr compositions extracted from snail shells in this area which span a range of ⁸⁷Sr/⁸⁶Sr = 0.7095–0.7160. Some human tooth enamel is characterized by more radiogenic values (⁸⁷Sr/⁸⁶Sr up to 0.718) which points to a possible provenance of these humans from the granite–gneiss terrain in the north of the island and/or to immigration of these humans in their childhood from other places (for example from mainland Sweden) to Bornholm. If the total compositional range of ⁸⁷Sr/⁸⁶Sr = 0.709–0.718 (n = 44) recorded in human enamel from the Ndr. Grødbygård site is considered representative for the variation of bioavailable Sr on Bornholm, then our soil leachate and surface water data entirely covers this range. We therefore propose that the combination of Sr isotope analyses of surface waters and soil leachates are an easy, fast and relatively cost efficient way to characterize a local bioavailable ⁸⁷Sr/⁸⁶Sr signature, and consequently propose that the overall average of ⁸⁷Sr/⁸⁶Sr = 0.7153 ± 0.0048 (1σ; n = 50) can be taken as a band for bioavailable Sr fractions suitable to discriminate between local and non-local signatures in provenance studies in the field of archaeology and for food and plant authenticity control in agricultural applications.     

Fate of bacterial biomass derived fatty acids in soil and their contribution to soil organic matter

Soil organic matter (SOM) is a major pool of the global C cycle and determines soil fertility. The stability of SOM strongly depends on the molecular precursors and structures. Plant residues have been regarded as the dominant precursors, but recent results showed a major contribution of microbial biomass. The fate of microbial biomass constituents has not yet been explored; therefore, we investigated the fate of fatty acids (FA) from ¹³C labeled Gram-negative bacteria (Escherichia coli) in a model soil study [Kindler, R., Miltner, A., Richnow, H.H., Kästner, M., 2006. Fate of gram negative bacterial biomass in soil—mineralization and contribution to SOM. Soil Biology & Biochemistry 38, 2860–2870]. After 224 days of incubation, the label in the total fatty acids (t-FA) in the soil decreased to 24% and in the phospholipid fatty acids (PLFA) of living microbes to 11% of the initially added amount. Since the bulk C decreased only to 44% in this period, the turnover of FA is clearly higher indicating that other compounds must have a lower turnover. The ¹³C label in the t-FA reached a stable level after 50 days but the label of the PLFA of the living microbial biomass declined until the end of the experiment. The isotopic enrichment of individual PLFA shows that the biomass derived C was spread across the microbial food web. Modelling of the C fluxes in this experiment indicated that microbial biomass is continuously mineralized after cell death and recycled by other organisms down to the 10% level, whereas the majority of biomass derived residual bulk C (～33%) was stabilized in the non-living SOM pool.     

Comparison of dissolved inorganic and organic carbon yields and fluxes in the watersheds of tropical volcanic islands,examples from Guadeloupe (French West Indies)

Organic matter is an important factor that cannot be neglected when considering global carbon cycle. New data including organic matter geochemistry at the small watershed scale are needed to elaborate more constrained carbon cycle and climatic models. The objectives are to estimate the DOC and DIC yields exported from small tropical watersheds and to give strong constraints on the carbon hydrodynamic of these systems. To answer these questions, we have studied the geochemistry of eleven small watersheds around Basse-Terre volcanic Island in the French West Indies during different hydrological regimes from 2006 to 2008 (i.e. low water level versus floods). We propose a complete set of carbon measurements, including DOC and DIC concentrations, δ¹³C data, and less commonly, some spectroscopic indicators of the nature of organic matter. The DOC/DIC ratio varies between 0.07 and 0.30 in low water level and between 0.25 and 1.97 during floods, indicating that organic matter is mainly exported during flood events. On the light of the isotopic composition of DOC, ranging from ? 32.8 to ? 26.2‰ during low water level and from ? 30.1 to ? 27.2‰ during floods, we demonstrate that export of organic carbon is mainly controlled by perennial saprolite groundwaters, except for flood events during which rivers are also strongly influenced by soil erosion. The mean annual yields ranged from 2.5 to 5.7 t km^? 2 year^? 1 for the DOC and from 4.8 to 19.6 t km^? 2 year^? 1 for the DIC and exhibit a non-linear relationship with slopes of watersheds. The flash floods explain around 60% of the annual DOC flux and between 25 and 45% of the DIC flux, highlighting the important role of these extreme meteorological events on global carbon export in small tropical volcanic islands. From a carbon mass balance point of view the exports of dissolved carbon from small volcanic islands are important and should be included in global organic carbon budgets.     

Quantitative C NMR of whole and fractionated Iowa Mollisols for assessment of organic matter composition

Both the concentrations and the stocks of soil organic carbon vary across the landscape. Do the amounts of recalcitrant components of soil organic matter (SOM) vary with landscape position? To address this question, we studied four Mollisols in central Iowa, two developed in till and two developed in loess. Two of the soils were well drained and two were poorly drained. We collected surface-horizon samples and studied organic matter in the particulate organic matter (POM) fraction, the clay fractions, and the whole, unfractionated samples. We treated the soil samples with 5 M HF at ambient temperature or at 60 °C for 30 min to concentrate the SOM. To assess the composition of the SOM, we used solid-state nuclear magnetic resonance (NMR) spectroscopy, in particular, quantitative ¹³C DP/MAS (direct-polarization/magic-angle spinning), with and without recoupled dipolar dephasing. Spin counting by correlation of the integral NMR intensity with the C concentration by elemental analysis showed that NMR was ?85% quantitative for the majority of the samples studied. For untreated whole-soil samples with <2.5 wt.% C, which is considerably less than in most previous quantitative NMR analyses of SOM, useful spectra that reflected ?65% of all C were obtained. The NMR analyses allowed us to conclude (1) that the HF treatment (with or without heat) had low impact on the organic C composition in the samples, except for protonating carboxylate anions to carboxylic acids, (2) that most organic C was observable by NMR even in untreated soil materials, (3) that esters were likely to compose only a minor fraction of SOM in these Mollisols, and (4) that the aromatic components of SOM were enriched to ∼53% in the poorly drained soils, compared with ∼48% in the well drained soils; in plant tissue and particulate organic matter (POM) the aromaticities were ∼18% and ∼32%, respectively. Nonpolar, nonprotonated aromatic C, interpreted as a proxy for charcoal C, dominated the aromatic C in all soil samples, composing 69-78% of aromatic C and 27-36% of total organic C in the whole-soil and clay-fraction samples.     

Mercury in European agricultural and grazing land soils

Agricultural (Ap, A_p-horizon, 0–20 cm) and grazing land soil samples (Gr, 0–10 cm) were collected from a large part of Europe (33 countries, 5.6 million km²) at an average density of 1 sample site/2500 km². The resulting more than 2 × 2000 soil samples were air dried, sieved to <2 mm and analysed for their Hg concentrations following an aqua regia extraction. Median concentrations for Hg are 0.030 mg/kg (range: <0.003–1.56 mg/kg) for the Ap samples and 0.035 mg/kg (range: <0.003–3.12 mg/kg) for the Gr samples. Only 5 Ap and 10 Gr samples returned Hg concentrations above 1 mg/kg. In the geochemical maps the continental-scale distribution of the element is clearly dominated by geology. Climate exerts an important influence. Mercury accumulates in those areas of northern Europe where a wet and cold climate favours the build-up of soil organic material. Typical anthropogenic sources like coal-fired power plants, waste incinerators, chlor-alkali plants, metal smelters and urban agglomerations are hardly visible at continental scales but can have a major impact at the local-scale.     

Altitudinal shift in stable hydrogen isotopes and microbial tetraether distribution in soils from the Southern Alps,NZ: Implications for paleoclimatology and paleoaltimetry

The Southern Alps are an ideal locality for studying patterns of isotopic fractionation associated with orographic precipitation. We have evaluated whether altitudinal change is reflected in the stable hydrogen isotopic composition (δ²H) of stream water, plant stem water and leaf wax lipids (n-alkanes) from living plants and soils, as well as in soil temperature. Samples were collected along an altitudinal transect from the windward side of the Southern Alps to Lake Hawea in the rain shadow. The results indicate that δ²H values of stem water overlap with stream water, demonstrating a gradual decrease with elevation that complied with modeled Rayleigh distillation, reflecting an isotopic lapse rate of −18.0 (± 1.1, 1σ)‰/km. Leaf and soil n-alkanes shared similar δ²H values and were ²H depleted relative to stem/stream waters. The values for soil n-alkanes indicated an isotopic lapse rate of −21.8 (± 2.0, 1σ)‰/km, consistent with precipitation data and long term observations. MBT/CBT derived soil temperature values based on the relative distribution of microbial tetraether lipids were similar to midsummer temperature observations, displaying an elevational decrease rate of −5.6 (± 1.5, 1σ) °C/km, consistent with regional and global observations.The results indicate that sedimentary lipid δ²H and microbial tetraether temperature estimates captured altitudinal trends in the isotopic composition of precipitation and mean temperature and further support their application in the reconstruction of past climate and surface uplift histories. However, notable differences in isotopic composition and temperature estimates between in situ soils and those with downslope transport of material emphasize the importance of facies analysis when interpreting past systems.