Lignin Phenol Concentrations Research Articles

A rapid and sensitive method for the analysis of lignin phenols in environmental samples using ultra-high performance liquid chromatography-electrospray ionization-tandem mass spectrometry with multiple reaction monitoring

A novel ultra-high performance liquid chromatography-electrospray ionization-tandem mass spectrometry method was developed to enable the analysis of ultra-low levels of lignin phenols (<100 fmol) in environmental samples. The method included a sample clean-up with a polymer sorbent based solid-phase extraction and reversed-phase chromatography that allowed separation of all lignin phenols with minimal interference from co-eluting matrix components. The application of 13C-labeled surrogate standards effectively compensated for variability associated with sample preparation and ion suppression. The method was fully validated and compared to gas chromatography-electron impact ionization-tandem mass spectrometry for Suwannee River humic acid standard reference material and extracted riverine dissolved organic matter. The comparison demonstrated the robustness and suitability of the method for ultra-low lignin phenol concentrations and high matrix interference. The simple and fast sample preparation coupled to analysis without derivatization makes it feasible for routine and high-volume analyses.

Dissolved Organic Matter Compositional Change and Biolability During Two Storm Runoff Events in a Small Agricultural Watershed

AbstractAgricultural watersheds are globally pervasive, supporting fundamentally different organic matter source, composition, and concentration profiles in comparison to natural systems. Similar to natural systems, agricultural storm runoff exports large amounts of organic carbon from agricultural land into waterways. But intense management of upper soil layers, waterway channelization, wetland and riparian habitat removal, and postharvest vegetation removal promise to uniquely drive organic matter release to waterways. During a winter first flush and a subsequent storm event, this study investigated the influence of a small agricultural watershed on dissolved organic matter (DOM) source, composition, and biolability. Storm water discharge released strongly terrestrial yet biolabile (23 to 32%) dissolved organic carbon (DOC). Following a 21 day bioassay, a parallel factor analysis identified an 80% reduction in a protein‐like (phenylpropyl) component (C2) that was previously correlated to lignin phenol concentration, and a 10% reduction in a humic‐like, terrestrially sourced component (C4). Storm‐driven releases tripled DOC concentration (from 2.8 to 8.7 mg L−1) during the first flush event in comparison to base flow and were terrestrially sourced, with an eightfold increase in vascular plant derived lignin phenols (23.0 to 185 μg L−1). As inferred from system hydrology, lignin composition, and nitrate as a groundwater tracer, an initial pulse of dilute water from the upstream watershed caused a counterclockwise DOC hysteresis loop. DOC concentrations peaked after 3.5 days, with the delay between peak discharge and peak DOC attributed to storm water hydrology and a period of initial water repellency of agricultural soils, which delayed DOM leaching.

Patterns of Bacterial and Archaeal Gene Expression through the Lower Amazon River

Analysis of metatranscriptomic and metagenomic datasets from the lower reaches of the Amazon River between Obidos and the river mouth revealed microbial transcript and gene pools dominated by Actinobacteria, Thaumarchaeota, Bacteroidetes, Acidobacteria, Betaproteobacteria, and Planctomycetes. Three mainstem stations spanning a 625 km reach had similar gene expression patterns (transcripts gene copy-1) across a diverse suite of element cycling genes, but two tributary-influenced stations at the mouth of the Tapajos River and near the Tocantins River at Belem had distinct transcriptome composition and expression ratios, particularly for genes encoding light-related energy capture (higher) and iron acquisition and ammonia oxidation (lower). Environmental parameters that were useful predictors of gene expression ratios included concentrations of lignin phenols, suspended sediments, nitrate, phosphate, and particulate organic carbon and nitrogen. Similar to the gene expression data, these chemical properties reflected highly homogeneous mainstem stations punctuated by distinct tributary-influenced stations at Tapajos and Belem. Although heterotrophic processes were expected to dominate in the lower Amazon, transcripts from photosynthetic bacteria were abundant in tributary-influenced regions, and transcripts from Thaumarcheota taxa genetically capable of chemosynthetic ammonia oxidation accounted for up to 21% of the transcriptome at others. Based on regressions of transcript numbers against gene numbers, expression ratios of Thaumarchaeota populations were largely unchanged within the mainstem, suggesting a relatively minor role for gene regulation. These quantitative gene and transcript inventories detail a diverse array of energy acquisition strategies and metabolic capabilities for bacteria and archaea populations of the world’s largest river system.

Distribution and Sources of Dissolved Black Carbon in Surface Waters of the Chukchi Sea, Bering Sea, and the North Pacific Ocean

Pyrogenic carbon, also called black carbon (BC), is an important component in the global carbon cycle. BC produced by biomass burning or fossil fuel combustion is transported to oceans by the atmosphere or rivers. However, environmental dynamics (i.e., major sources and sinks) of BC in marine environments have not been well documented. In this study, dissolved BC (DBC) collected from surface waters of the Chukchi Sea, the Bering Sea, and the subarctic and subtropical North Pacific were analyzed using the benzene polycarboxylic acid (BPCA) method. The DBC concentration and the ratio of B5CA and B6CA to all BPCAs (an index of the DBC condensation degree) ranged from 4.8 to 15.5 µg-C L-1 and from 0.20 to 0.43, respectively, in surface waters of the Chukchi/Bering Seas and the North Pacific Ocean. The concentration and condensation degree of DBC in the Chukchi/Bering Seas were higher and more variable than those in the subarctic and subtropical North Pacific, which implies that the major factors controlling DBC distribution were different in these marine provinces. In the Chukchi/Bering Seas, the DBC concentration was negatively correlated to salinity but positively correlated to chromophoric dissolved organic matter (CDOM) quantity and total dissolved lignin phenol concentration estimated by CDOM parameters. These correlations indicated that the possible major source of DBC in the Chukchi/Bering Seas was Arctic rivers. However, in the North Pacific, where riverine inputs are negligible for most sampling sites, DBC was possibly derived from the atmosphere. Although spectral slopes of CDOM at 275-295 nm (an index of the photodegradation degree of CDOM) differed widely between the subarctic and subtropical North Pacific, the concentration and condensation degrees of DBC were similar between the subarctic and subtropical North Pacific, which suggests that photodegradation was not the only major factor controlling DBC distribution. Therefore, DBC distributions of the North Pacific Ocean were considered to be mainly controlled by atmospheric deposition of BC and subsequent losses by photodegradation and adsorption onto sinking particles. This study implies that the main influence on DBC distribution in the open ocean and the coastal ocean are atmospheric deposition and fluvial inputs, respectively.

Photooxidation of pyrogenic organic matter reduces its reactive, labile C pool and the apparent soil oxidative microbial enzyme response

The surface chemistry of pyrogenic organic matter (PyOM) is altered by a variety of abiotic and biotic oxidative and sorption/desorption processes in the environment. Exposure of PyOM to high energy light prior to addition to soil or sediment, or while entrained in the atmosphere, may induce significant surface photooxidation, i.e., photochemical weathering, altering its environmental reactivity. We report on a 30-day soil incubation experiment testing the effects of the photochemical weathering of a 13C-enriched ponderosa pine PyOM, produced by pyrolysis at 450°C, on PyOM and soil organic carbon (SOC) mineralization. PyOM C mineralization was measured for both the photochemically weathered (i.e. UV treated PyOM or PyOMUV) and PyOM not exposed to high-energy light (i.e. PyOMW serving as a dark control). PyOMW exhibited a 3.7 times faster C mineralization rate across the 30-d study, which was driven by a large early mineralization of accessible/labile C during the first 6d. In contrast, PyOMUV had faster C mineralization rates in the later part of the experiment (days 11–30). Overall, PyOMUV had a 13% lower net C mineralization than the untreated PyOMW where the MRT of accessible PyOMUV-C and PyOMW-C was calculated at 25.7±6.8d and 1.7±0.2d, respectively. Both forms of PyOM promoted a similar net reduction in native SOC mineralization (i.e., negative priming) of approximately 50% relative to the unamended, control soil. Addition of either PyOM form resulted in an equivalent minor decrease in the concentration of extractable soil lignin phenols and substituted fatty acids chemistry with respect to the unamended soil. At 30d, soil phenol oxidase and peroxidase enzyme activities were higher with additions of either form of PyOM compared with the unamended control soils with PyOMUV exhibiting lower activities than PyOMW. Our results indicate that PyOM photochemical weathering can impart important changes to short-term PyOM reactivity and soil microbial activity, which could have important implications for soil systems by ultimately lowering turnover rates for both NSC and PyOM-C.

Variations in lignin-derived phenols in sediments of Japanese lakes over the last century and their relation to watershed vegetation

Lignins have been used as a biomarker to explore changes in terrestrial organic matter input into lakes and to investigate past watershed vegetation. Burial of organic carbon (OC) in lake sediments, an important component of the global C cycle, is likely associated with the terrestrial OC input. However, few studies have explored changes in terrestrial C input into lakes in the last century. Furthermore, the relationship between lignin phenol compositions and watershed vegetation remains poorly examined. In this study, we examined changes in OC concentrations, OC mass accumulation rates (MAR), and lignin phenol compositions over the last century in sediments from six lakes in Japan that differ in watershed land-use and vegetation. The sediments were dated using 210Pb and 137Cs, and showed increased OC concentrations and MARs in three lowland lakes over the last century. This pattern was not found in three mountain lakes. In one of the lowland lakes, lignin phenol concentrations normalized to OC did not change during the periods with high OC concentrations and MARs. This indicates that not only eutrophication but also enhanced terrestrial OC input could lead to greater burial of OC. The lignin phenol compositions did not show clear trends over the last century in most of the lakes examined. The ratios of syringyl to vanillyl phenols and the lignin phenol vegetation index had significant relationships with proportions of angiosperms in watershed vegetation. These results demonstrate that lignin phenols are useful in inferring recent as well as past changes in lake watershed environments.

Macromolecular composition of terrestrial and marine organic matter in sediments across the East Siberian Arctic Shelf

Abstract. Mobilisation of terrestrial organic carbon (terrOC) from permafrost environments in eastern Siberia has the potential to deliver significant amounts of carbon to the Arctic Ocean, via both fluvial and coastal erosion. Eroded terrOC can be degraded during offshore transport or deposited across the wide East Siberian Arctic Shelf (ESAS). Most studies of terrOC on the ESAS have concentrated on solvent-extractable organic matter, but this represents only a small proportion of the total terrOC load. In this study we have used pyrolysis–gas chromatography–mass spectrometry (py-GCMS) to study all major groups of macromolecular components of the terrOC; this is the first time that this technique has been applied to the ESAS. This has shown that there is a strong offshore trend from terrestrial phenols, aromatics and cyclopentenones to marine pyridines. There is good agreement between proportion phenols measured using py-GCMS and independent quantification of lignin phenol concentrations (r2 = 0.67, p &lt; 0.01, n = 24). Furfurals, thought to represent carbohydrates, show no offshore trend and are likely found in both marine and terrestrial organic matter. We have also collected new radiocarbon data for bulk OC (14COC) which, when coupled with previous measurements, allows us to produce the most comprehensive 14COC map of the ESAS to date. Combining the 14COC and py-GCMS data suggests that the aromatics group of compounds is likely sourced from old, aged terrOC, in contrast to the phenols group, which is likely sourced from modern woody material. We propose that an index of the relative proportions of phenols and pyridines can be used as a novel terrestrial vs. marine proxy measurement for macromolecular organic matter. Principal component analysis found that various terrestrial vs. marine proxies show different patterns across the ESAS, and it shows that multiple river–ocean transects of surface sediments transition from river-dominated to coastal-erosion-dominated to marine-dominated signatures.

Sources, Distributions, and Dynamics of Dissolved Organic Matter in the Canada and Makarov Basins

A comprehensive survey of dissolved organic carbon (DOC) and chromophoric dissolved organic matter (CDOM) was conducted in the Canada and Makarov Basins and adjacent seas during 2010-2012 to investigate the dynamics of dissolved organic matter (DOM) in the Arctic Ocean. Sources and distributions of DOM in polar surface waters were very heterogeneous and closely linked to hydrological conditions. Canada Basin surface waters had relatively low DOC concentrations (69±6 µmol L-1), CDOM absorption (a325: 0.32±0.07 m-1) and CDOM-derived lignin phenols (3±0.4 nmol L-1) and high spectral slope values (S275-295: 31.7±2.3 µm-1), indicating minor terrigenous inputs and evidence of photochemical alteration in the Beaufort Gyre. By contrast, surface waters of the Makarov Basin had elevated DOC (108±9 µmol L-1) and lignin phenol concentrations (15±3 nmol L-1), high a325 values (1.36±0.18 m-1) and low S275-295 values (22.8±0.8 µm-1), indicating pronounced Siberian river inputs associated with the Transpolar Drift and minor photochemical alteration. Observations near the Mendeleev Plain suggested limited interactions of the Transpolar Drift with Canada Basin waters, a scenario favoring export of Arctic DOM to the North Atlantic. The influence of sea-ice melt on DOM was region-dependent, resulting in an increase (Beaufort Sea), a decrease (Bering-Chukchi Seas), and negligible change (deep basins) in surface DOC concentrations and a325 values. Halocline structures differed between basins, and the Canada Basin upper halocline and Makarov Basin halocline were comparable in their average DOC (65-70 µmol L-1) and lignin phenol concentrations (3-4 nmol L-1) and S275-295 values (22.9-23.7 µm-1). Deep-water DOC concentrations decreased by 6-8 µmol L-1 with increasing depth, water mass age, nutrient concentrations, and apparent oxygen utilization. Maximal estimates of DOC degradation rates (0.036-0.039 µmol L-1 yr-1) in the deep Arctic were lower than those in other ocean basins, possibly due to low water temperatures. DOC concentrations in bottom waters (>2500 m; 46±2 µmol L-1) of the Canada and Makarov Basins were slightly lower than those reported for deep waters of the Eurasian Basin and Nordic Seas. Elevated a325 values (by 10-20%) were observed near the seafloor, indicating biological activity in Arctic basin sediments.

Fate of terrigenous organic matter across the Laptev Sea from the mouth of the Lena River to the deep sea of the Arctic interior

Abstract. Ongoing global warming in high latitudes may cause an increasing supply of permafrost-derived organic carbon through both river discharge and coastal erosion to the Arctic shelves. Mobilized permafrost carbon can be either buried in sediments, transported to the deep sea or degraded to CO2 and outgassed, potentially constituting a positive feedback to climate change. This study aims to assess the fate of terrigenous organic carbon (TerrOC) in the Arctic marine environment by exploring how it changes in concentration, composition and degradation status across the wide Laptev Sea shelf. We analyzed a suite of terrestrial biomarkers as well as source-diagnostic bulk carbon isotopes (δ13C, Δ14C) in surface sediments from a Laptev Sea transect spanning more than 800 km from the Lena River mouth (&lt; 10 m water depth) across the shelf to the slope and rise (2000–3000 m water depth). These data provide a broad view on different TerrOC pools and their behavior during cross-shelf transport. The concentrations of lignin phenols, cutin acids and high-molecular-weight (HMW) wax lipids (tracers of vascular plants) decrease by 89–99 % along the transect. Molecular-based degradation proxies for TerrOC (e.g., the carbon preference index of HMW lipids, the HMW acids ∕ alkanes ratio and the acid ∕ aldehyde ratio of lignin phenols) display a trend to more degraded TerrOC with increasing distance from the coast. We infer that the degree of degradation of permafrost-derived TerrOC is a function of the time spent under oxic conditions during protracted cross-shelf transport. Future work should therefore seek to constrain cross-shelf transport times in order to compute a TerrOC degradation rate and thereby help to quantify potential carbon–climate feedbacks.

Sources and Transformations of Dissolved Lignin Phenols and Chromophoric Dissolved Organic Matter in Otsuchi Bay, Japan

Dissolved lignin phenols and optical properties of dissolved organic matter (DOM) were measured to investigate the sources and transformations of terrigenous DOM (tDOM) in Otsuchi Bay, Japan. Three rivers discharge into the bay, and relatively high values of syringyl:vanillyl phenols (0.73 ± 0.07) and cinnamyl:vanillyl phenols (0.33 ± 0.10) indicated large contributions of non-woody angiosperm tissues to lignin and tDOM. The physical mixing of river and seawater played an important role in controlling the concentrations and distributions of lignin phenols and chromophoric DOM (CDOM) optical properties in the bay. Lignin phenol concentrations and the CDOM absorption coefficient at 350 nm, a(350), were strongly correlated in river and bay waters. Measurements of lignin phenols and CDOM in bay waters indicated a variety of photochemical and biological transformations of tDOM, including oxidation reactions, photobleaching and a decrease in molecular weight. Photodegradation and biodegradation of lignin and CDOM were investigated in decomposition experiments with river water and native microbial assemblages exposed to natural sunlight or kept in the dark. There was a rapid and substantial removal of lignin phenols and CDOM during the first few days in the light treatment, indicating transformations of tDOM and CDOM can occur soon after discharge of buoyant river water into the bay. The removal of lignin phenols was slightly greater in the dark (34%) than in the light (30%) during the remaining 59 days of the incubation. Comparison of the light and dark treatments indicated biodegradation was responsible for 67% of total lignin phenol removal during the 62-day incubation exposed to natural sunlight, indicating biodegradation is a dominant removal process in Otsuchi Bay.

Pan-Arctic Trends in Terrestrial Dissolved Organic Matter from Optical Measurements

Climate change is causing extensive warming across arctic regions resulting in permafrost degradation, alterations to regional hydrology, and shifting amounts and composition of dissolved organic matter (DOM) transported by streams and rivers. Here, we characterize the DOM composition and optical properties of the six largest arctic rivers draining into the Arctic Ocean to examine the ability of optical measurements to provide meaningful insights into terrigenous carbon export patterns and biogeochemical cycling. The chemical composition of aquatic DOM varied with season, spring months were typified by highest lignin phenol and dissolved organic carbon (DOC) concentrations with greater hydrophobic acid content, and lower proportions of hydrophilic compounds, relative to summer and winter months. Chromophoric DOM (CDOM) spectral slope (S275-295) tracked seasonal shifts in DOM composition across river basins. Fluorescence and parallel factor analysis identified seven components across the six Arctic rivers. The ratios of ‘terrestrial humic-like’ versus ‘marine humic-like’ fluorescent components co-varied with lignin monomer ratios over summer and winter months, suggesting fluorescence may provide information on the age and degradation state of riverine DOM. CDOM absorbance (a350) proved a sensitive proxy for lignin phenol concentrations across all six river basins and over the hydrograph, enabling for the first time the development of a single pan-arctic relationship between a350 and terrigenous DOC (R2 = 0.93). Combining this lignin proxy with high-resolution monitoring of a350, pan-arctic estimates of annual lignin flux were calculated to range from 156 to 185 Gg, resulting in shorter and more constrained estimates of terrigenous DOM residence times in the Arctic Ocean (spanning 7 months to 2½ years). Furthermore, multiple linear regression models incorporating both absorbance and fluorescence variables proved capable of explaining much of the variability in lignin composition across rivers and seasons. Our findings suggest that synoptic, high-resolution optical measurements can provide improved understanding of northern high-latitude organic matter cycling and flux, and prove an important technique for capturing future climate-driven changes.

Predicting Dissolved Lignin Phenol Concentrations in the Coastal Ocean from Chromophoric Dissolved Organic Matter (CDOM) Absorption Coefficients

Dissolved lignin is a well-established biomarker of terrigenous dissolved organic matter (DOM) in the ocean, and a chromophoric component of DOM. Although evidence suggests there is a strong linkage between lignin concentrations and chromophoric DOM (CDOM) absorption coefficients in coastal waters, the characteristics of this linkage and the existence of a relationship that is applicable across coastal oceans remain unclear. Here, 421 paired measurements of dissolved lignin concentrations (sum of 9 lignin phenols) and CDOM absorption coefficients (ag(λ)) were used to examine their relationship along the river-ocean continuum (0-37 salinity) and across contrasting coastal oceans (sub-tropical, temperate, high-latitude). Overall, lignin concentrations spanned four orders of magnitude and revealed a strong, non-linear relationship with ag(λ). The characteristics of the relationship (shape, wavelength dependency, lignin-composition dependency) and evidence from degradation indicators were all consistent with lignin being an important driver of CDOM variability in coastal oceans, and suggested physical mixing and long-term photodegradation were important in shaping the relationship. These observations were used to develop two simple empirical models for estimating lignin concentrations from ag(λ) with a +/- 20% error relative to measured values. The models are expected to be applicable in most coastal oceans influenced by terrigenous inputs.

Optical Proxies for Terrestrial Dissolved Organic Matter in Estuaries and Coastal Waters

Optical proxies, especially DOM fluorescence, were used to track terrestrial DOM fluxes through estuaries and coastal waters by comparing models developed for several coastal ecosystems. Key to using optical properties is validating and calibrating them with chemical measurements, such as lignin-derived phenols - a proxy to quantify terrestrial DOM. Utilizing parallel factor analysis (PARAFAC), and comparing models statistically using the OpenFluor database (http://www.openfluor.org) we have found common, ubiquitous fluorescing components which correlate most strongly with lignin phenol concentrations in several estuarine and coastal environments. Optical proxies for lignin were computed for the following regions: Mackenzie River Estuary, Atchafalaya River Estuary, Charleston Harbor, Chesapeake Bay, and Neuse River Estuary. The slope of linear regression models relating CDOM absorption at 350 nm (a350) to DOC and to lignin, varied 5 to 10 fold among systems. Where seasonal observations were available from a region, there were distinct seasonal differences in equation parameters for these optical proxies. Despite variability, overall models using single linear regression were developed that related dissolved organic carbon (DOC) concentration to CDOM (DOC = 40×a350+138; R2 = 0.77; N = 130) and lignin (Σ8) to CDOM (Σ8 = 2.03×a350-0.5; R2 = 0.87; N = 130). This wide variability suggested that local or regional optical models should be developed for predicting terrestrial DOM flux into coastal oceans and taken into account when upscaling to remote sensing observations and calibrations.

Phenolic profile within the fine-root branching orders of an evergreen species highlights a disconnect in root tissue quality predicted by elemental- and molecular-level carbon composition.

Fine roots constitute a significant source of plant productivity and litter turnover across terrestrial ecosystems, but less is known about the quantitative and qualitative profile of phenolic compounds within the fine-root architecture, which could regulate the potential contribution of plant roots to the soil organic matter pool. To understand the linkage between traditional macro-elemental and morphological traits of roots and their molecular-level carbon chemistry, we analyzed seasonal variations in monomeric yields of the free, bound, and lignin phenols in fine roots (distal five orders) and leaves of Ardisia quinquegona. Fine roots contained two-fold higher concentrations of bound phenols and three-fold higher concentrations of lignin phenols than leaves. Within fine roots, the concentrations of free and bound phenols decreased with increasing root order, and seasonal variation in the phenolic profile was more evident in lower order than in higher order roots. The morphological and macro-elemental root traits were decoupled from the quantity, composition and tissue association of phenolic compounds, revealing the potential inability of these traditional parameters to capture the molecular identity of phenolic carbon within the fine-root architecture and between fine roots and leaves. Our results highlight the molecular-level heterogeneity in phenolic carbon composition within the fine-root architecture, and imply that traits that capture the molecular identity of the root construct might better predict the decomposition dynamics within fine-root orders.

Incipient changes of lignin and substituted fatty acids under N addition in a Chinese forest soil

Elevated nitrogen (N) deposition has the potential to increase litter and soil carbon (C) storage by suppressing lignolytic activity, but reports of the response of forest floor and soil have shown inconsistent responses. We investigated organic carbon and nitrogen as well as lignin phenols and substituted fatty acids (SFA) in forest floor litter and organic horizons, and mineral soil profiles from a mixed broad-leaf Korean pine (Pinus koraiensis) forest, China after 6years of N addition treatment at double the current N deposition rate. Total C and N were not influenced by experimental N deposition. However, incipient changes in extractable lignin phenol concentration were seen for degraded litter (P=0.100) exhibiting increases of about 5% while mineral soil, surface litter and O-horizon showed no change. The degree of lignin oxidation was not substantially influenced in any layer although a significant decrease in vanillyl lignin phenol oxidation was measured in the degraded litter under elevated N. Extractable substituted fatty acids in the forest floor and mineral soil horizons were also, essentially, insensitive to N addition with the minor exception of the O-horizon showing a small but significant (∼16%, P=0.041) increase. Our results are consistent with one group of literature showing little change in overall soil and litter character under short term, 5–10years, of N addition. Minor changes in molecular C dynamics, such as those observed for lignin phenols and substituted fatty acids could possibly be attributed to the suppression of microbial decay under N addition.

Multi-proxy evidence for compositional change of organic matter in the largest tropical (peninsular) river basin of India

• We report OM source variability in largest monsoonal river of India. • We examine the impact of natural and man made impact on OM distribution. • Effect of land use changes on the OM source have been highlighted. • Effect of reduced monsoon and dams on the OM source change is described. The distribution and compositional changes of organic matter (OM) within the Godavari river system is increasingly influenced by reduced monsoon rainfall and an increased number of damming. To track these changes stable isotopes of organic carbon and concentrations of lignin phenols were analyzed in total suspended matter (TSM), sediments, agriculture soils and plants from Godavari basin. The results indicated that the upper tributaries drained heavier carbon (δ 13 C org = −20.4 ± 2.2‰) than the lower tributaries (δ 13 C org = −25.4 ± 1.5‰) owing to the regional vegetation in the upper to lower basins. OM originating from algae near dam impoundments was incorporated into TSM and sediment due to extreme drought condition. The organic carbon (OC) content was higher in TSM and in the sediment of the region after the middle reach dam (Sriram Sagar) than before (2.2 ± 1.6 vs. 1.0 ± 0.1% OC and 2.1 ± 2.3 vs. 0.6 ± 0.2% OC, respectively). The lignin yield (Λ8) was lower in TSM and in the sediment after the dam impoundment than before (0.37 vs. 1.94 mg/100 mg OC and 2.9 ± 1.1 vs. 5.4 ± 2.3 mg/100 mg OC, respectively) due to an increased contribution of lignin free OC from algae and degraded soil. Less rainfall and dam impoundments enhanced the fraction of labile OM from freshwater algae and an estuarine phytoplankton bloom in the study year. Our study is the first to document lignin fluxes from an Indian monsoonal river (Godavari). The flux of lignin phenols of 7.26 × 10 9 g yr −1 is much lower than those of most world rivers except the rivers from polar arctic.

Organic matter compositions and loadings in soils and sediments along the Fly River, Papua New Guinea

The compositions and loadings of organic matter in soils and sediments from a diverse range of environments along the Fly River system were determined to investigate carbon transport and sequestration in this region. Soil horizons from highland sites representative of upland sources have organic carbon contents (%OC) that range from 0.3 to 25wt%, carbon:nitrogen ratios (OC/N) that range from 7 to 25mol/mol, highly negative stable carbon isotopic compositions (δ13Corg<−26‰) and variable concentrations of lignin phenols (1<LP<5mg/100mgOC). These compositions reflect inputs from local vegetation, with contributions from bedrock carbon in the deeper mineral horizons. Soils developed on the levees of active floodplains receive inputs of allochthonous materials by overbank deposition as well as autochthonous inputs from local vegetation. In the forested upper floodplain reaches, %OC contents are lower than upland soils (0.8–1.5wt%) as are OC/N ratios (9–15mol/mol) while δ13Corg (−25 to −28‰) and LP (2–6mg/100mgOC) values are comparable to upland soils. These results indicate that organic matter present in these active floodplain soils reflect local (primarily C3) vegetation inputs mixed with allochthonous organic matter derived from eroded bedrock. In the lower reaches of the floodplain, which are dominated by swamp grass vegetation, isotopic compositions were less negative (δ13Corg>−25‰) and non-woody vegetation biomarkers (cinnamyl phenols and cutin acids) more abundant relative to upper floodplain sites. Soils developed on relict Pleistocene floodplain terraces, which are typically not flooded and receive little sediment from the river, were characterized by low %OC contents (<0.6wt%), low OC/N ratios (<9mol/mol), more positive δ13Corg signatures (>−21‰) and low LP concentrations (∼3mg/100mgOC). These relict floodplain soils contain modern carbon that reflects primarily local (C3 or C4) vegetation sources. Total suspended solids collected along the river varied widely in overall concentrations (1<TSS<9000mg/L), %OC contents (0.1–60wt%), OC/N ratios (7–17mol/mol) and δ13Corg signatures (−26 to −32‰). These compositions reflect a mixture of C3 vascular plants and freshwater algae. However, little of this algal production appears to be preserved in floodplain soils. A comparison of organic carbon loadings of active floodplain soils (0.2 and 0.5mgC/m2) with previous studies of actively depositing sediments in the adjacent delta–clinoform system (0.4–0.7mgC/m2) indicates that Fly River floodplain sediments are less effective at sequestering organic carbon than deltaic sediments. Furthermore, relict Pleistocene floodplain sites with low or negligible modern sediment accumulation rates display significantly lower loadings (0.1–0.2mgC/m2). This deficit in organic carbon likely reflects mineralization of sedimentary organic carbon during long term oxidative weathering, further reducing floodplain carbon storage.

Land use, water quality, and the history of coral assemblages at Bocas del Toro, Panamá

As human activities have intensified along tropical coastlines, the anthropic influ- ence on adjacent coral reefs has become increasingly deleterious. Changes in land use generally degrade water quality, but controversy persists over the degree to which reduced water quality affects the ecology of reef communities. We cored reef frameworks at 4 sites in Bahia Almirante, a semi-enclosed, coastal lagoon in northwestern Panama, to explore the historical relationship between turnover in coral-species dominance and terrigenous input. The coral constituents of the cores were analyzed in tandem with lignin-phenol concentrations. Chronologies and sedimenta- tion rates were determined from 210 Pb profiles in the cores. Increased terrigenous input from agri- cultural development and expansion of the human population degraded water quality in Bahia Almirante over the last century. Documented episodes of heavy rainfall after 1970 accelerated a phase shift from dominance by branching corals of the genus Porites to dominance by the lettuce coral Agaricia tenuifolia at water depths of 5 to 10 m by increasing runoff, increasing sediment and nutrient loads, and lowering light levels. The phase shift in coral dominance was unprece- dented on a millennial time scale and the degree to which it occurred varied along a gradient of terrigenous input to the Bahia.

Lignin phenols and BIT index distributions in the Amur River and the Sea of Okhotsk: Implications for the source and transport of particulate terrestrial organic matter to the ocean

Delta and coastal regions play a key role in the global carbon cycle as the main repository of inputs of terrestrial organic matter, delivered by rivers to marine sediments. The Amur River system is one of the largest in Asia and supplies organic matter to the Sea of Okhotsk and the North Pacific Ocean. We measured lignin phenols (a proxy for terrestrial plant derived organic matter) and the branched and isoprenoidal tetraether (BIT) index (a proxy for riverborne soil organic matter), in soils and river bed sediments from the Amur River basin and surface sediments from the Sea of Okhotsk, to study the source, transport, and deposition of fluvial particulate organic matter to the ocean. Concentrations of lignin phenols are relatively high in sediments from the shallow continental shelf compared to that of the deep offshore basin. For the first time we report a spatial distribution of the BIT index which shows a similar pattern to that of lignin phenol concentrations, with relatively high values in the coastal sites. The highest values of both lignin concentrations and BIT values are observed in a site proximal to mouth of Amur River. These results indicate that terrestrial organic matter deposited in the Sea of Okhotsk mostly originates from soil organic matter supplied from Amur River. Spatial distributions of lignin phenols/TOC (LP/TOC) and the BIT index in the Sea of Okhotsk and comparison with S/V (a contribution index of angiosperm vs. gymnosperms) and C/V ratios (indicative of the relative contribution of non-woody tissue vs. woody tissue), between the Amur River basin and Okhotsk Sea samples, suggest that Amur River fluvial organic matter is supplied and deposited to the northwestern continental shelf. Furthermore, S/V values from our Amur River and Okhotsk Sea continental shelf sediment samples are consistent with the reported S/V ratio (0.32) of particulate organic matter in the North Pacific Intermediate Water (NPIW) layer (750m depth). Hence, our study supports previous studies from the NW Pacific Ocean, which suggest inputs of terrestrial organic matter from the Amur River via the Sea of Okhotsk, as a major source of particulate organic matter to the North Pacific Ocean.

The biogeochemistry of carbon across a gradient of streams and rivers within the Congo Basin

Dissolved organic carbon (DOC) and inorganic carbon (DIC, pCO2), lignin biomarkers, and theoptical properties of dissolved organic matter (DOM) were measured in a gradient of streams and rivers within the Congo Basin, with the aim of examining how vegetation cover and hydrology influences the composition and concentration of fluvial carbon (C). Three sampling campaigns (February 2010, November 2010, and August 2011) spanning 56 sites are compared by subbasin watershed land cover type (savannah, tropical forest, and swamp) and hydrologic regime (high, intermediate, and low). Land cover properties predominately controlled the amount and quality of DOC, chromophoric DOM (CDOM) and lignin phenol concentrations (∑8) exported in streams and rivers throughout the Congo Basin. Higher DIC concentrations and changing DOM composition (lower molecular weight, less aromatic C) during periods of low hydrologic flow indicated shifting rapid overland supply pathways in wet conditions to deeper groundwater inputs during drier periods. Lower DOC concentrations in forest and swamp subbasins were apparent with increasing catchment area, indicating enhanced DOC loss with extended water residence time. Surface water pCO2 in savannah and tropical forest catchments ranged between 2,600 and 11,922 µatm, with swamp regions exhibiting extremely high pCO2 (10,598–15,802 µatm), highlighting their potential as significant pathways for water-air efflux. Our data suggest that the quantity and quality of DOM exported to streams and rivers are largely driven by terrestrial ecosystem structure and that anthropogenic land use or climate change may impact fluvial C composition and reactivity, with ramifications for regional C budgets and future climate scenarios.