Nature and dynamics of phosphorus-containing components of marine dissolved and particulate organic matter

The molecular sources, dynamics and analytical characterizations of the phosphorus (P) containing components of marine dissolved and particulate organic matter (OM) are reviewed. Using a combination of ¹³C and ³¹P nuclear magnetic resonance spectroscopy on samples collected from a depth profile (20-4000 m) at Station Aloha in the North Pacific subtropical gyre, the biomolecular associations of P functional groups in marine OM are identified. Compositional differences between ultrafiltered dissolved organic matter (UDOM; 1-100 nm size fraction) and ultrafiltered particulate organic matter (UPOM; 0.1-60 μm size fraction) as reflected by NMR and elemental analyses indicate that UDOM does not originate from simple solubilization of UPOM, and the aggregation of UDOM is not the primary source of UPOM. Regression analyses indicated a large fraction of the P in UDOM is associated with carbohydrates and amino acids, but not with lipids. Similar analyses for UPOM indicated that P is associated with carbohydrates, amino acids and lipids. The P functional groups also appear to be balanced in their distribution among molecular classes, because they remain in relatively constant proportion throughout the ocean.     

Influence of organic-mineral aggregates on microbial degradation of the dinoflagellate Scrippsiella trochoidea

Aggregation of particulate organic matter (POM) and mineral grains may result in physical protection of organic matter (OM). To test this, phytoplankton cells of the dinoflagellate Scrippsiella trochoidea were inoculated with a natural bacterial assemblage and incubated with or without the clay montmorillonite. Within 5 h, aggregation of phytoplankton OM and clay resulted in transfer of the majority (∼80%) of OM into the >1.6 g cm⁻³ density fraction. Degradation of particulate organic carbon (POC), particulate nitrogen (PN), dissolved organic carbon (DOC), and dissolved and particulate total hydrolyzable amino acids (THAA), were modeled with a multi-G approach. Quantity of resistant OM was between two and four times larger during clay incubation relative to clay-free incubation. The two incubations did not exhibit significant differences in degradation state of particulate amino acids nor were there indications of preferential sorption of basic amino acids. The results suggest that a considerable fraction of phytoplankton OM can become resistant, at least on a timescale of weeks, mostly due to aggregation of POM and clay mineral grains.     

Amino acid nitrogen isotopic fractionation patterns as indicators of heterotrophy in plankton, particulate, and dissolved organic matter

Bulk nitrogen (N) isotope signatures have long been used to investigate organic N source and food web structure in aquatic ecosystems. This paper explores the use of compound-specific δ¹⁵N patterns of amino acids (δ¹⁵N-AA) as a new tool to examine source and processing history in non-living marine organic matter. We measured δ¹⁵N-AA distributions in plankton tows, sinking particulate organic matter (POM), and ultrafiltered dissolved organic matter (UDOM) in the central Pacific Ocean. δ¹⁵N-AA patterns in eukaryotic algae and mixed plankton tows closely resemble those previously reported in culture. δ¹⁵N differences between individual amino acids (AA) strongly suggest that the sharply divergent δ¹⁵N enrichment for different AA with trophic transfer, as first reported by [McClelland, J.W. and Montoya, J.P. (2002) Trophic relationships and the nitrogen isotopic composition of amino acids. Ecology83, 2173-2180], is a general phenomenon. In addition, differences in δ¹⁵N of individual AA indicative of trophic transfers are clearly preserved in sinking POM, along with additional changes that may indicate subsequent microbial reworking after incorporation into particles.We propose two internally normalized δ¹⁵N proxies that track heterotrophic processes in detrital organic matter. Both are based on isotopic signatures in multiple AA, chosen to minimize potential problems associated with any single compound in degraded materials. A trophic level indicator (ΔTr) is derived from the δ¹⁵N difference between selected groups of AA based on their relative enrichment with trophic transfer. We propose that a corresponding measure of the variance within a sub-group of AA (designated ΣV) may indicate total AA resynthesis, and be strongly tied to heterotrophic microbial reworking in detrital materials. Together, we hypothesize that ΔTr and ΣV define a two dimensional trophic “space”, which may simultaneously express relative extent of eukaryotic and bacterial heterotrophic processing.In the equatorial Pacific, ΔTr indicates an average of 1.5-2 trophic transfers between phytoplankton and sinking POM at all depths and locations. The ΣV parameter suggests that substantial variation may exist in bacterial heterotrophic processing between differing regions and time periods. In dissolved material δ¹⁵N-AA patterns appear unrelated to those in POM. In contrast to POM, δ¹⁵N-AA signatures in UDOM show no clear changes with depth, and suggest that dissolved AA preserved throughout the oceanic water column have undergone few, if any, trophic transfers. Together these data suggest a sharp divide between processing histories, and possibly sources, of particulate vs. dissolved AA.     

Structural changes of humic acids from sinking organic matter and surface sediments investigated by advanced solid-state NMR: Insights into sources, preservation and molecularly uncharacterized components

Knowledge of the structural changes that particulate organic matter (POM) undergoes in natural systems is essential for determining its reactivity and fate. In the present study, we used advanced solid-state NMR techniques to investigate the chemical structures of sinking particulate matter collected at different depths as well as humic acids (HAs) extracted from these samples and underlying sediments from the Saguenay Fjord and the St. Lawrence Lower Estuary (Canada). Compared to bulk POM, HAs contain more non-polar alkyls, aromatics, and aromatic C-O, but less carbohydrates (or carbohydrate-like structures). In the two locations studied, the C and N contents of the samples (POM and HAs) decreased with depth and after deposition onto sediments, leaving N-poor but O-enriched HAs and suggesting the involvement of partial oxidation reactions during POM microbial degradation. Advanced NMR techniques revealed that, compared to the water-column HAs, sedimentary HAs contained more protonated aromatics, non-protonated aromatics, aromatic C-O, carbohydrates (excluding anomerics), anomerics, OC_q, O-C_q-O, OCH, and OCH₃ groups, but less non-polar alkyls, NCH, and mobile CH₂ groups. These results are consistent with the relatively high reactivity of lipids and proteins or peptides. In contrast, carbohydrate-like structures were selectively preserved and appeared to be involved in substitution and copolymerization reactions. Some of these trends support the selective degradation (or selective preservation) theory. The results provide insights into mechanisms that likely contribute to the preservation of POM and the formation of molecules that escape characterization by traditional methods. Despite the depletion of non-polar alkyls with depth in HAs, a significant portion of their general structure survived and can be assigned to a model phospholipid. In addition, little changes in the connectivities of different functional groups were observed. Substituted and copolymerized carbohydrates and fused-ring aromatics detected in the present study likely represented an important part of molecularly uncharacterized components (MUC).     

Amino acid and amino sugar yields and compositions as indicators of dissolved organic matter diagenesis

Microbial decomposition experiments were used to characterize changes in the amino acid and amino sugar yields and compositions of natural marine substrates during early diagenesis in seawater. On average, 63% of added carbon and 68% of added nitrogen were removed within the first 30 days of decomposition. In all cases, amino acid utilization accounted for a substantial fraction of the removed C and N. Carbon-normalized amino acid yields decreased to less than 50% of their starting values and most of this change occurred within the first 10 days of decomposition. Increases in the concentrations of amino sugars and decreases in the GlcN:GalN ratio in particulate organic matter (POM) illustrated the significance of microbial production during the decomposition of added substrates. Changes in the mol % composition of amino acids during early diagenesis were substantial but highly variable with substrate. Previous survey data collected from the same region were used in conjunction with the experimental data to investigate the utility of several established amino acid-based indices of organic matter diagenesis. This comparison showed that a combination of these degradation indexes is most effective for describing the diagenetic state of dissolved organic matter (DOM). Carbon-normalized amino acid yields were found to be the most effective indicator for early diagenesis. Relative abundances of amino acids were effective indicators of intermediate stages of diagenesis and the mol % composition of the non-protein amino acid γ-Aba (γ-aminobutyric acid) was an effective indicator of advanced DOM diagenesis.     

Seasonal and annual variations in the organic matter contributed by the St Lawrence River to the Gulf of St. Lawrence

The St. Lawrence River discharges a substantial volume of water (405 km³/a) containing suspended (SPM; 3.42 × 10⁶t) and dissolved (68.0 × 10⁶t) materials to the Gulf of St. Lawrence. The total load contains organic carbon in paniculate (POC; 3–14% of SPM), and dissolved (DOC; 3.76 ± 0.63 mg/l) form. The concentration of POC (and particulate organic nitrogen) is positively correlated with discharge (increased during the spring flood and the fall enhancement of flow), but concentration of DOC is not so simply related to discharge. In consequence, the total organic carbon (POC + DOC) load is relatively invariant, and increased annually by only 2–3% despite a progressive increase of 8% in discharge over the years of this study. Seasonal differences in the composition of the particulate organic matter (POM) are interpreted as reflecting dominant contributions from within-river production in summer and from terrestrial sources in spring and fall. In years when the annual discharge was greater than average, a higher proportion of the POM was terrigenous. The organic matter in surface sediments of the estuary to which the river discharges is predominantly of terrestrial provenance.     

Humic acids from particulate organic matter in the Saguenay Fjord and the St. Lawrence Estuary investigated by advanced solid-state NMR

Detailed structural information on two humic acids extracted from two sinking particulate matter samples at a water depth of 20 m in the Saguenay Fjord (F-20-HA) and the St. Lawrence Estuary (E-20-HA) (Canada), was obtained by advanced solid-state NMR. Spectral-editing analyses provided numerous structural details rarely reported in geochemical studies. The NMR data account almost quantitatively for the elemental compositions. The two humic acids were found to be quite similar, consisting of four main structural components: peptides (ca. 39 ± 3% vs. 34 ± 3% of all C for E-20-HA and F-20-HA, respectively); aliphatic chains, 14-20 carbons long (ca. 25 ± 5% vs. 17 ± 5% of all C); aromatic structures (ca. 17 ± 2% vs. 26 ± 2% of all C); and sugar rings (14 ± 2% vs. 15 ± 2% of all C). Peptides were identified by ¹³C{¹⁴N} SPIDER NMR, which selects signals of carbons bonded to nitrogen, and by dipolar DEPT, which selects CH-group signals, in particular the NCH band of peptides. The SPIDER spectra also indicate that heterocycles constitute a significant fraction of the aromatic structures. The aliphatic (CH₂)_n chains, which are highly mobile, contain at least one double bond per two chains and end in methyl groups. ¹H spin diffusion NMR experiments showed that these mobile aliphatic chains are in close (<10 nm) proximity to the other structural components. A major bacterial contribution to these two samples could explain why the samples, which have different dominant organic matter sources (terrestrial vs. marine), are similar to each other as well as to degraded algae and particles from other waters. The NMR data suggest structures containing mobile lipids in close proximity to peptides and carbohydrates (e.g., peptidoglycan) as found in bacterial cell walls. Measured yields of muramic acid and d-amino acids confirmed the presence of bacterial cell wall components in the studied samples.     

珠江中下游颗粒有机质的碳氮℃稳定同位素、氨基酸和木质素组成及其地球化学意义

从东江到珠江口采集了悬浮颗粒物,通过测定总有机质的元素（TOC、TN）、同位素（δ13C、δ15N）组成以及生物标志物（氨基酸、木质素）等地球化学性质,来揭示颗粒有机质的来源和组成。结果表明,浮游生物（13%-52%）和土壤（45%-77%）是珠江颗粒有机质的主要来源,植物（0%-11%）对颗粒物的贡献较小。颗粒有机质含有高比例的氨基酸碳（TAAC）,说明浮游生物对颗粒物的重要性。氨基酸的降解指数（DI）在-0.51到0.79之间,说明这些水生来源有机质的降解程度比较小。木质素的降解参数（Ad/Al、3,5-BD/V）较大,表明珠江颗粒有机碳的陆源来源主要是土壤。在颗粒物中检测到了少量的二氨基庚二酸（Dapa）,说明细菌对颗粒有机碳也有所贡献。不同环境中颗粒物的木质素组成主要与颗粒物丰度和粒径有关：（1）相对于河流,水库颗粒物中的木质素含量显著偏低,降解程度更高;（2）相对于中游,下游颗粒物丰度较高,木质素含量较高。     

Sources and distribution of terrigenous organic matter delivered by the Atchafalaya River to sediments in the northern Gulf of Mexico

Suspended sediments (SS) from the Atchafalaya River (AR) and the Mississippi River and surficial sediment samples from seven shallow cross-shelf transects west of the AR in the northern Gulf of Mexico were examined using elemental (%OC, C/N), isotopic (δ¹³C, Δ¹⁴C), and terrigenous biomarker analyses. The organic matter (OM) delivered by the AR is isotopically enriched (∼−24.5‰) and relatively degraded, suggesting that soil-derived OM with a C4 signature is the predominant OM source for these SS. The shelf sediments display OC values that generally decrease seaward within each transect and westward, parallel to the coastline. A strong terrigenous C/N (29) signal is observed in sediments deposited close to the mouth of the river, but values along the remainder of the shelf fall within a narrow range (8-13), with no apparent offshore trends. Depleted stable carbon isotope (δ¹³C) values typical of C3 plant debris (−27‰) are found near the river mouth and become more enriched (−22 to −21‰) offshore. The spatial distribution of lignin in shelf sediments mirrors that of OC, with high lignin yields found inshore relative to that found offshore (water depth > 10 m).The isotopic and biomarker data indicate that at least two types of terrigenous OM are deposited within the study area. Relatively undegraded, C3 plant debris is deposited close to the mouth of the AR, whereas more degraded, isotopically enriched, soil-derived OM appears to be deposited along the remainder of the shelf. An important input from marine carbon is found at the stations offshore from the 10-m isobath. Quantification of the terrigenous component of sedimentary OM is complicated by the heterogeneous composition of the terrigenous end-member. A three-end-member mixing model is therefore required to more accurately evaluate the sources of OM deposited in the study area. The results of the mixing calculation indicate that terrigenous OM (soil-derived OM and vascular plant debris) accounts for ∼79% of the OM deposited as inshore sediments and 66% of OM deposited as offshore sediments. Importantly, the abundance of terrigenous OM is 40% higher in inshore sediments and nearly 85% higher in offshore sediments than indicated by a two-end-member mixing model. Such a result highlights the need to reevaluate the inputs and cycling of soil-derived OM in the coastal ocean.     

Abundance and structural diversity of bacteriohopanepolyols in suspended particulate matter along a river to ocean transect

The concentration and structural diversity of a suite of bacteriohopanepolyols (BHPs) was measured in suspended particulate matter (SPM) from six stations along a river-ocean transect off the Pacific coast of Panama. Riverine SPM contained BHPs diagnostic of soil input consistent with a terrigenous source. The concentration of BHPs was 10 times greater in riverine SPM than marine SPM demonstrating that terrigenous OM exported to marine sediments could provide a significant contribution to the marine sedimentary hopanoid inventory. Given the rich structural diversity of BHPs in terrigenous SPM, interpretations of the sedimentary record of hopanoids in coastal marine settings must resolve inputs from marine pelagic and terrigenous sources.     

Sources and composition of organic matter for bacterial growth in a large European river floodplain system (Danube, Austria)

Dissolved and particulate organic matter (DOM and POM) distribution, lignin phenol signatures, bulk elemental compositions, fluorescence indices and microbial plankton (algae, bacteria, viruses) in a temperate river floodplain system were monitored from January to November 2003. We aimed to elucidate the sources and compositions of allochthonous and autochthonous organic matter (OM) in the main channel and a representative backwater in relation to the hydrological regime. Additionally, bacterial secondary production was measured to evaluate the impact of organic carbon source on heterotrophic prokaryotic productivity. OM properties in the backwater tended to diverge from those in the main channel during phases without surface water connectivity; this was likely enhanced due to the exceptionally low river discharge in 2003. The terrestrial OM in this river floodplain system was largely derived from angiosperm leaves and grasses, as indicated by the lignin phenol composition. The lignin signatures exhibited significant seasonal changes, comparable to the seasonality of plankton-derived material. Microbially-derived material contributed significantly to POM and DOM, especially during periods of low discharge. High rates of bacterial secondary production (up to 135 μg C L(-1) d(-1)) followed algal blooms and suggested that autochthonous OM significantly supported heterotrophic microbial productivity.     

Chemical characteristics of dissolved organic nitrogen in an oligotrophic subtropical coastal ecosystem

Water samples were collected from rivers and estuarine environments within the Florida Coastal Everglades (FCE) ecosystem, USA, and ultrafiltered dissolved organic matter (UDOM; <0.7 μm, >1 kDa) was isolated for characterization of its source, bioavailability and diagenetic state. A combination of techniques, including ¹⁵N cross-polarization magic angle spinning nuclear magnetic resonance (¹⁵N CPMAS NMR) and X-ray photoelectron spectroscopy (XPS), were used to analyze the N components of UDOM. The concentrations and compositions of total hydrolysable amino acids (HAAs) were analyzed to estimate UDOM bioavailability and diagenetic state. Optical properties (UV-visible and fluorescence) and the stable isotope ratios of C and N were measured to assess the source and dynamics of UDOM. Spectroscopic analyses consistently showed that the major N species of UDOM are in amide form, but significant contributions of aromatic-N were also observed. XPS showed a very high pyridinic-N concentration in the FCE-UDOM (21.7 ± 2.7%) compared with those in other environments. The sources of this aromatic-N are unclear, but could include soot and charred materials from wild fires. Relatively high total HAA concentrations (4 ± 2% UDOC or 27 ± 4% UDON) are indicative of bioavailable components, and HAA compositions suggest FCE-UDOM has not undergone extensive diagenetic processing. These observations can be attributed to the low microbial activity and a continuous supply of fresh UDOM in this oligotrophic ecosystem. Marsh plants appear to be the dominant source of UDOM in freshwater regions of the FCE, whereas seagrasses and algae are the dominant sources of UDOM in Florida Bay. This study demonstrates the utility of a multi-technique and multi-proxy approach to advance our understanding of DON biogeochemistry.     

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.     

Suspended sediments and organic matter in mountain headwaters of the Amazon River: Results from a 1-year time series study in the central Peruvian Andes

Few studies have examined the dynamics of sediments and suspended organic matter and their export from headwater basins in the Andes Mountains to the Amazon River, despite the fact that the Andes are the primary source of sediments to the lower Amazon basin. We measured river discharge as well as the concentration, δ¹⁵N, δ¹³C, %N, and %OC of coarse and fine suspended sediments (CSS and FSS) in the Chorobamba River, located in the central Andean Amazon of Peru. Samples were taken at least weekly over an entire year (July 2004-July 2005), with additional sampling during storms. Concentrations of particulate organic matter (POM) were generally low in the study river, with concentrations increasing by up to several orders of magnitude during episodic rain events. Because both overall flow volumes and POM concentrations increased under stormflow conditions, the export of POM was enhanced multiplicatively during these events. We estimated that a minimum of 80% of annual suspended sediment transfer occurred during only about 10 days of the year, also accounting for 74% of particulate organic carbon and 64% of particulate organic nitrogen transport. Significant differences occurred between seasons (wet and dry) for δ¹³C of coarse and fine POM in the Chorobamba River, reflecting seasonal changes in organic matter sources. The time series data indicate that this Andean river exports approximately equal amounts of fine and coarse POM to the lower Amazon. The observation that the vast majority of sediments and associated OM exported from Andean rivers is mobilized during short, infrequent storm events and landslides has important implications for our understanding of Amazon geochemistry, especially in the face of incipient global change.     

Soil organic matter as an important contributor to Late Quaternary sediments of the tropical West African continental margin

The contribution of soil organic matter (SOM) to continental margins is largely ignored in studies on the carbon budget of marine sediments. Detailed geochemical investigations of late Quaternary sediments (245-0 ka) from the Niger and Congo deep-sea fans, however, reveal that C_org/N_tot ratios and isotopic signatures of bulk organic matter (δ¹³C_org) in both fans are essentially determined by the supply of various types of SOM from the river catchments thus providing a fundamentally different interpretation of established proxies in marine sciences. On the Niger fan, increased C_org/N_tot and δ¹³C_org (up to −17‰) were driven by generally nitrogen-poor but ¹³C-enriched terrigenous plant debris and SOM from C₄/C₃ vegetation/Entisol domains (grass- and tree-savannah on young, sandy soils) supplied during arid climate conditions. Opposite, humid climates supported drainage of C₃/C₄ vegetation/Alfisol/Ultisol domains (forest and tree-savannah on older/developed, clay-bearing soils) that resulted in lower C_org/N_tot and δ¹³C_org (< −20‰) in the Niger fan record. Sediments from the Congo fan contain a thermally stable organic fraction that is absent on the Niger fan. This distinct organic fraction relates to strongly degraded SOM of old and highly developed, kaolinite-rich ferallitic soils (Oxisols) that cover large areas of the Congo River basin. Reduced supply of this nitrogen-rich and ¹²C-depleted SOM during arid climates is compensated by an elevated input of marine OM from the high-productive Congo up-welling area. This climate-driven interplay of marine productivity and fluvial SOM supply explains the significantly smaller variability and generally lower values of C_org/N_tot and δ¹³C_org for the Congo fan records. This study emphasizes that ignoring the presence of SOM results in a severe underestimation of the terrigenous organic fraction leading to erroneous paleoenvironmental interpretations at least for continental margin records. Furthermore, burial of SOM in marine sediments needs more systematic investigation combining marine and continental sciences to assess its global relevance for long-term sequestration of atmospheric CO₂.     

Biogeochemical characteristics of settling particulate organic matter in Lake Superior: A seasonal comparison

To assess settling particulate organic matter (POM) seasonality and its availability to the benthic community, settling particulate matter was studied in terms of mass fluxes and main biogeochemical characteristics (including organic carbon (OC), nitrogen, and stable carbon and nitrogen isotopic values) at two Lake Superior offshore sites over the course of a year. Fourier transform infrared spectroscopy (FTIR) and hydrolysis, extraction, and derivatization were used to provide further compositional information. Carbon and nitrogen content, isotopic and wet chemical data, and FTIR spectra show that summer particulate material is mainly autochthonous, with higher proportions of amide and carbohydrate. FTIR shows that spring particulate material contains relatively high proportions of clay minerals, indicating major sources from sediment resuspension and/or spring runoff. Distinct amino acid distributions at the two sites, revealed by principal component analysis (PCA) based on amino acid mol% composition, possibly result from differences in OM sources and the degree of degradation occurring at the two sites. Carbohydrate (PCHO), total hydrolyzable amino acid (THAA) and FTIR data suggest that the nutritional value of bulk POM to benthic heterotrophs should be lower in spring than summer-fall, although both periods exhibited high sinking fluxes of total mass and OC. Due to sediment resuspension events and an oxic water column, organic matter eventually buried in Lake Superior’s sediments has probably experienced extensive alteration due to several cycles through the water column and the bacterially-active sediment-water interface.     

The role of biodegradation and photo-oxidation in the transformation of terrigenous organic matter

Microbial and photochemical decomposition are two major processes regulating organic matter (OM) transformation in the global carbon cycle. However, photo-oxidation is not as well understood as biodegradation in terms of its impact on OM alteration in terrigenous environments. We examined microbial and photochemical transformation of OM and lignin derived phenols in two plant litters (corn leaves and pine needles). Plant litter was incubated in the laboratory over 3 months and compositional changes to OM were measured using nuclear magnetic resonance (NMR) and gas chromatography-mass spectrometry. We also examined the susceptibility of soil organic matter (SOM) to ultraviolet (UV) radiation. Solid-state ¹³C NMR spectra showed that O-alkyl type structures (mainly from carbohydrates) decreased during biodegradation and the loss of small carbohydrates and aliphatic molecules was observed by solution-state ¹H NMR spectra of water extractable OM from biodegraded litters. Photochemical products were detected in the aliphatic regions of NaOH extracts from both litter samples by solution-state ¹H NMR. Photo-oxidation also increased the solubility of SOM, which was attributed to the enhanced oxidation of lignin derived phenols and photochemical degradation of macromolecular SOM species (as observed by diffusion edited ¹H NMR). Overall, our data collectively suggests that while biodegradation predominates in litter decomposition, photo-oxidation alters litter OM chemistry and plays a role in destabilizing SOM in soils exposed to UV radiation.     

The Comparison of δ<Superscript>13</Superscript>C Values of a Deposit- and a Suspension-Feeder Bio-Indicates Benthic vs. Pelagic Couplings and Trophic Status in Contrasted Coastal Ecosystems

δ¹³C and δ¹⁵N values of two generalists primary consumers, a strict deposit-feeder polychaete (Arenicola marina), and a strict suspension-feeder bivalve (Crassostrea gigas), were investigated to typify the trophic functioning of two contrasted marine coastal ecosystems (eutrophic and mesotrophic, east and west Cotentin peninsula, respectively, English Channel, Normandy, France). On average, δ¹³C and δ¹⁵N values of lugworms mirrored those of sediment organic matter (SOM), whereas δ¹³C and δ¹⁵N of oysters mirrored those of suspended particulate organic matter (SPOM). δ¹³C values of the two species displayed significant differences on the west coast (mesotrophic) contrary to the east coast (eutrophic; significant interactions). δ¹⁵N values differed only between sites and not between species. Diet of A. marina relied exclusively on microphytobenthos (MPB) and detritus of macroalgae (ULV) on the mesotrophic coast, whereas diet of C. gigas relied mainly on SPOM. Conversely, on the eutrophic ecosystem (the east coast), both species displayed the same diet, which was a mixture of pelagic sources (SPOM), benthic sources (MPB and ULV) and to a lesser extent riverine particulate organic matter (rPOM). These results were explained by the intensity of benthic vs. pelagic couplings (i.e. benthic-pelagic and pelagic-benthic) which differed in the two ecosystems. Low trophic coupling occurred on the mesotrophic (west) coast, whereas benthic-pelagic (SOM resuspension) and pelagic-benthic (settling of SPOM such as phytoplankton blooms) couplings were typified on the eutrophic (east) coast. This higher particulate organic matter (POM) pelagic-benthic coupling on the east coast was probably enhanced by nutrient enrichment caused by eutrophication. Comparison of δ¹³C ratios of both the strict deposit-feeder (e.g. A. marina) and the strict suspension-feeder (e.g. C. gigas) was then proposed as a bio-indicator of the trophic status and of POM benthic vs. pelagic couplings of soft-bottom coastal ecosystems.     

Composition and genesis of the organic matter in the bottom sediments of the East Siberian Sea

The chemical composition of organic matter (C_org, N_org, δ¹³C, δ¹⁵N, and n-alkanes) was studied in the top layer of bottom sediments of the East Siberian Sea. Possible ways were proposed to estimate the amount of the terrigenous component in their organic matter (OM). The fraction of terrigenous OM estimated by the combined use of genetic indicators varied from 15% in the eastern part of the sea, near the Long Strait, to 95% in the estuaries of the Indigirka and Kolyma rivers, averaging 62% over the sea area.     

Sources and Exchange of Particulate Organic Matter in an Estuarine Mangrove Ecosystem of Xuan Thuy National Park, Vietnam

The spatio-temporal variations in stable isotope signatures (??¹³C and ??¹⁵N) and C/N ratios of particulate organic matter (POM), and physicochemical parameters in a creek water column were examined in an estuarine mangrove ecosystem of Xuan Thuy National Park, Vietnam. The objective was to examine the factors influencing creek water properties, and the sources and exchange of POM in this important mangrove ecosystem. The diel and seasonal variations in water temperature, flow velocity, pH, dissolved oxygen, and salinity demonstrated that tidal level, season, and biological factors affected the creek water properties. Mangroves had relatively low ??¹⁵N and very low ??¹³C values, with respective average values of 1.5?±?0.9?? and ?28.1?±?1.4??. The low mangrove leaf ??¹⁵N indicated minor anthropogenic nitrogen loading to the mangrove forests. A significant positive correlation between POM?C??¹³C and salinity along the axis of Ba Lat Estuary, Red River, indicated that marine phytoplankton (??¹³C value, ?21.4?±?0.5??) was the predominant source of POM at the estuary mouth. Based on the co-variation of ??¹³C and C/N ratios, marine phytoplankton and mangrove detritus were predominant in POM of major creeks and small creeks, respectively. During the diurnal tidal cycle, the dynamics of POM were affected by sources of organic matter, tidal energy, and seasonal factors. The contribution of mangrove detritus to POM reached a maximum at the low tide and was enhanced during the rainy season, whereas marine phytoplankton contribution was highest at high tide.