Linking lithology and land use to sources of dissolved and particulate organic matter in headwaters of a temperate, passive-margin river system

A number of rivers have been found to transport highly aged organic matter [OM]; however, the sources of this aged material remain a matter of debate. One potential source may be erosion and weathering of headwater lithologies rich in ancient sedimentary OM. In this study, waters, suspended particulates, streambed sediments, rocks and soils from fourteen small headwater watersheds of a mid-size, temperate, passive margin river were sampled and characterized by Δ¹⁴C, δ¹³C, and POC/TPN ratios to identify sources of particulate and dissolved OM delivered to the river mainstem. These headwater sites encompass a range in lithology (OM-rich shales, OM-lean carbonate/mudstone facies, and OM-free crystalline rocks) and land use types (forested and agricultural), and allow investigation of the influence of agriculture and bedrock types on stream OM characteristics. Streams draining large areas of both agricultural land use and OM-rich lithology contain particulate OM [POM] that is more ¹⁴C-depleted than streams draining forested, shale-free watersheds. However, this is not sufficient to account for the significantly lower Δ¹⁴C-POC measured in the river mainstem. Dissolved OM [DOM] Δ¹⁴C are in all cases enriched compared to POM from the same stream, but are otherwise highly variable and unrelated to either land use or lithology. POC/TPN ratios were likewise highly variable. POC and DOC δ¹³C signatures were similar across all watersheds. Based on isotope mass balance, ¹⁴C-free fossil OM sources contribute 0-12% of total stream POM. Although these results do not unequivocally separate the influences of land use and lithology, watershed coverage by shale and agriculture are both important controls on stream Δ¹⁴C-POC. Thus export of aged, particle-associated OM may be a feature of river systems along both passive and active continental margins.     

Large variations of δ13C values in stalagmites from southeastern China during historical times: implications for anthropogenic deforestation

Variations in speleothem δ¹³C values can reflect changes in overlying surface vegetation, which, over historical time scales, may represent the influence of human activities. Here, we examined δ¹³C variations in two stalagmites growing for the last 2200 years in Shennong Cave, Jiangxi Province, SE China. The two δ¹³C records corroborate well one another and show a prominent 6‰ enrichment of the δ¹³C values from AD 700 to 1100. The isotopic equilibrium for modern calcite and negative correlation between δ¹⁸O and δ¹³C values along the growth axis suggest that the influences of kinetic fractionation are negligible. Varied correlations between Mg/Ca and Sr/Ca ratios and divergent changes between δ¹³C values and Mg/Ca and Sr/Ca ratios from AD 700 to 1100 reveal that the prior calcite precipitation (PCP) and water–rock interaction did not dominate the increase of δ¹³C values. It is plausible that the obvious δ¹³C variation was largely influenced by the changes in vegetation cover overlying the cave. Our δ¹³C results, together with the records of climate and human activity from historical documentary records, suggest that: (i) prior to AD 700, small fluctuations in relatively light δ¹³C values reflect the presence of lush forest coverage above the cave, which was minimally disturbed by human activities; (ii) during AD 700–1100, the drastic increase in δ¹³C values indicates persistent and massive deforestation associated with large‐scale immigration into northern Jiangxi after the Rebellion of An & Shi (AD 755–763) in the Tang Dynasty and the subsequent development of agriculture and economic activity; and (iii) since AD 1100, fluctuations in relatively high δ¹³C values suggest that local vegetation during the last millennium has been sparse. Since the Rebellion of An & Shi, southeastern China was progressively developed, coincident with deforestation and vegetation deterioration caused by human disturbance in the form of deforestation and cultivation.     

Influence of production variables and starting material on charcoal stable isotopic and molecular characteristics

We present a systematic study on the effect of starting species, gas composition, temperature, particle size and duration of heating upon the molecular and stable isotope composition of high density (mangrove) and low density (pine) wood. In both pine and mangrove, charcoal was depleted in δ¹³C relative to the starting wood by up to 1.6‰ and 0.8‰, respectively. This is attributed predominantly to the progressive loss of isotopically heavier polysaccharides, and kinetic effects of aromatization during heating. However, the pattern of δ¹³C change was dependant upon both starting species and atmosphere, with different structural changes associated with charcoal production from each wood type elucidated by Solid-State ¹³C Nuclear Magnetic Resonance Spectroscopy. These are particularly evident at lower temperatures, where variation in the oxygen content of the production atmosphere results in differences in the thermal degradation of cellulose and lignin. It is concluded that production of charcoal from separate species in identical conditions, or from a single sample exposed to different production variables, can result in significantly different δ¹³C of the resulting material, relative to the initial wood. These results have implications for the use of charcoal isotope composition to infer past environmental change.     

Iron Isotope Compositions of Natural River and Lake Samples in the Karst Area, Guizhou Province, Southwest China

To better understand the Fe isotope characteristics of natural samples in the Karst area, the Fe isotope compositions of riverine suspended particulates, lake suspended particulates, lake sediments, porewaters, phytoplanktons, and aerosols in the watersheds of Lake Aha (a mineralized water system) and Lake Hongfeng (a mesotrophic water system), which are located in the Karst area, southwest China, were investigated. The studied samples displayed a variable range between δ56Fe=?2.03‰ and 0.36‰. Aerosols and phytoplanktons have similar or slightly heavier Fe isotope compositions relative to the average of igneous rocks. Fe isotope compositions of riverine Suspended Particulate Matter (SPM) were mainly affected by the types of tributaries. Suspended particulates collected from tributaries seriously contaminated with coal mine drainages displayed negative δ56Fe values (?0.89‰ to ?0.31‰) during summer, and there were significant increases of δ56Fe values in winter, except AR2, which was polluted with both coal mine drainage and sewage effluent. Characteristics of lakes have important influences on Fe isotope compositions of suspended particulates, lake sediments, and porewaters. The epilimnetic particulate Fe of Lake Hongfeng had δ56Fe=?0.04‰ to 0.13‰, while lighter Fe isotope compositions were measured for particulate Fe from Lake Aha, ranging from ?0.42‰ to ?0.09‰. Sediments collected from Hou Wu (HW) station of Lake Hongfeng have an average δ56Fe value of 0.09‰ and their corresponding porewaters have lighter Fe isotope compositions, ranging from ?0.57‰ to ?0.31‰; no significant variations have been observed. For the Liang Jiang Kou (LJK) station of Lake Aha, the content of reactive Fe and the concentration of sulfate were all high. Due to the reactive Fe recycling, including dissimilatory Fe reduction, adsorption, and Fe–sulfide formation, porewaters sampled near the sediment surface have been found to have a δ56Fe value as low as ?2.03‰ and an increase up to 0.12‰, with a burial depth of 10?cm. In contrast, an opposite variation trend was found for LJK sediments. Sediments sampled at 1-cm depth had a value of δ56Fe=?0.59‰ and decrease as low as ?1.75‰ with burial depth. This investigation demonstrated that significant Fe isotope fractionations occur in surface environments. Fe isotope compositions of particulate Fe were seriously affected by Fe sources, and Fe biogeochemical recycling has an important influence on Fe isotope fractionations in lake sediments, especially when there are significant amounts of reactive Fe and sulfate.     

Water and Organic Carbon Cycles in Monsoon-driven Humid Tropics of the Western Ghats Mountain Belt,India: Insights from Stable Isotope Approach

The Western Ghats form a major mountain belt, next to the Himalayas, in controlling the flux of water and carbon to the northern Indian Ocean. This study attempts to understand the water and carbon cycles in two humid tropical river basins with its streams originating at higher altitudes of the Western Ghats, India. Water and suspended particulate matter (SPM) were collected on a monthly scale during summer monsoon season (June-September) from Swarna and Nethravati rivers draining into the Arabian Sea. For the source apportionment, samples have been measured for stable isotopes of oxygen (δ¹⁸O) and hydrogen (δ²H) in water and stable isotopes of carbon (δ¹³C_POC) in particulate organic matter (POM) at spatial scale from tributaries and main channel of rivers, and runoff water from agricultural land (dominant paddy field) and forest in the downstream region. The association between δ¹⁸O and deuterium-excess in river water and rain water shows that water in these tropical basins depicts rainout effect of marine source moisture during the onset of summer monsoon. As the monsoon intensifies, the fresher rain water replenishes older water stored previously in sub surface soil layer leading to its flushing into the river during summer monsoon season. Stable carbon isotope ratio and elemental ratio of POM (δ¹³C_POC = -27.1 ± 0.4 ‰ and C/N = 8.1 ± 1.7) in two humid tropical river water during summer monsoon season is an admixture of suspended particulates from runoff water of forest (δ¹³C_POC = - 27.82 ± 0.4 ‰) and agricultural land (δ¹³C_POC = -26.29 ± 0.4 ‰). It is found that δ¹³C_POC shows minimal variability with SPM content and C/N ratio within the same organic carbon pool. The study emphasizes the need to consider the agricultural runoff contribution to the rivers while establishing the global elemental budget and observing the global climate change.     

Remotely sensed observations of the turbidity maximum in the highly turbid Humber Estuary, UK

The Humber Estuary, UK, divides into the Ouse and Trent estuaries at the so-called Apex within its upper reaches. Remotely sensed Compact Airborne Spectrographic Imager (CASI) images and boat measurements were used to observe a strong turbidity maximum in the upper Humber and Ouse during a spring tide in November 1995. Surface suspended particulate matter (SPM) concentrations during the late ebb, as estimated from the CASI data, increased from approximately 6 to 13 g I⁻¹ moving up-estuary into the Ouse. Greater SPM concentrations (∼10 g I⁻¹) were evident in the deeper channels of the Ouse, compared with shallower areas, possibly due to faster ebb currents there and differential down-estuary advection of the turbidity maximum. Ribbons, or streaks, of lower SPM and slightly cooler waters were observed. It appears that slightly cooler and lower turbidity waters from the confluent Trent estuary remained fairly distinct for distances of approximately 2 km down-stream of its confluence with the upper Humber and Ouse. These waters eventually broke into ribbon-like or streak-like structures within the higher SPM-laden and slightly warmer waters of the Humber. They were discernible for more than 5 km down-estuary of the confluence of the Humber, Ouse, and Trent. Boat measurements showed that the turbidity maximum occurred over a fairly restricted region of the upper Humber, between about 20 to 50 km from the tidal limit at high water. The turbidity maximum’s sediment load was largely suspended in the water column during stronger currents. SPM rapidly settled close to the bed during high water and low water slack periods. At these times, SPM concentrations in a thin, near-bed layer were >60 g I⁻¹ in the turbidity maximum region of the Ouse and >30 g 1⁻¹ in the upper Humber (where channel volumes were much greater). SPM within the turbidity maximum comprised very fine-grained material and its low organic content demonstrated that the SPM was essentially mineral, clastic sediment derived originally from erosion and decay of crustal rocks.     

Using Stable Isotopes to Assess the Contribution of Terrestrial and Riverine Organic Matter to Diets of Nearshore Marine Consumers in a Glacially Influenced Estuary

Terrestrial and marine ecosystems in Southeast Alaska are linked by the flow of freshwater from precipitation and glacial runoff, which transports nutrients and organic matter (OM) downstream to estuaries. We examined the contribution of terrestrial-riverine and marine OM to diets of fishes (N = 257, four species) and invertebrates (N = 90, six species) collected from glacially influenced estuaries in Southeast Alaska using multiple stable isotopes (δ¹³C, δ¹⁵N, and δ³⁴S). Multivariate analysis of similarity (ANOSIM) was used to quantify variation in stable isotope composition of consumers across 6 months and three sites with watersheds that differed in their glacier and forest composition. Fishes showed weak differences (ANOSIM R = 0.141) in stable isotope composition among sampling months, moderate differences (ANOSIM R = 0.375) among sites, and strong differences (ANOSIM R = 0.583) among species. Invertebrates showed moderate differences (ANOSIM R = 0.352) in stable isotope composition among sampling months and strong differences among sites (ANOSIM R = 0.710) and species (ANOSIM R = 0.858). We found the greatest differences in stable isotope composition between the two estuary sites with watersheds containing the highest and lowest glacial coverage, indicating that the contribution of allochthonous OM to consumer diets varies across watershed types. Invertebrates collected from the site with the lowest glacial coverage in the watershed were more depleted in δ¹³C and δ³⁴S, indicating higher use of terrestrial-riverine OM, than those at sites with higher watershed glacial coverage. High variation in stable isotope composition among species, months, and sites underscores the complexity of estuary food web responses to future glacier loss.     

Stable carbon and nitrogen isotopic compositions of high molecular weight dissolved organic matter from four U.S. estuaries

High molecular weight dissolved organic matter (HMW-DOM) represents an important component of dissolved organic carbon (DOC) in seawater and fresh-waters. In this paper, we report measurements of stable carbon (δ¹³C) isotopic compositions in total lipid, total hydrolyzable amino acid (THAA), total carbohydrate (TCHO) and acid-insoluble “uncharacterized” organic fractions separated from fourteen HMW-DOM samples collected from four U.S. estuaries. In addition, C/N ratio, δ¹³C and stable nitrogen (δ¹⁵N) isotopic compositions were also measured for the bulk HMW-DOM samples. Our results indicate that TCHO and THAA are the dominant organic compound classes, contributing 33-46% and 13-20% of the organic carbon in HMW-DOM while total lipid accounts for only <2% of the organic carbon in the samples. In all samples, a significant fraction (35-49%) of HMW-DOM was included in the acid-insoluble fraction. Distinct differences in isotopic compositions exist among bulk samples, the compound classes and the acid-insoluble fractions. Values of δ¹³C and δ¹⁵N measured for bulk HMW-DOM varied from −22.1 to −30.1‰ and 2.8 to 8.9‰, respectively and varied among the four estuaries studied as well. Among the compound classes, TCHO was more enriched in ¹³C (δ¹³C = −18.5 to −22.8‰) compared with THAA (δ¹³C = −20.0 to −29.6‰) and total lipid (δ¹³C = −25.7 to −30.7‰). The acid-insoluble organic fractions, in general, had depleted ¹³C values (δ¹³C = −23.0 to −34.4‰). Our results indicate that the observed differences in both δ¹³C and δ¹⁵N were mainly due to the differences in sources of organic matter and nitrogen inputs to these estuaries in addition to the microbial processes responsible for isotopic fractionation among the compound classes. Both terrestrial sources and local sewage inputs contribute significantly to the HMW-DOM pool in the estuaries studied and thus had a strong influence on its isotopic signatures.     

Carbon and Oxygen Isotopic Compositions: How Lacustrine Environmental Factors Respond in Northwestern and Northeastern China

Surface lake sediments,28 from Hoh Xil,24 from northeastern China,99 from Lake Bosten,31 from Ulungur and 26 from Heihai were collected to determine δ13C and δ18O values.Considering the impact factors,conductivity,alkalinity,pH,TOC,C/N and carbonate-content in the sediments,Cl,P,S,and metal element ratios of Mg/Ca,Sr/Ca,Fe/Mn of bulk sediments as environmental variables enable evaluation of their influences on δ13C and δ18O using principal component analysis(PCA) method.The closure and residence time of lakes can influence the correlation between δ13C and δ18O.Lake water will change from fresh to brackish with increasing reduction and eutrophication effects.Mg/Ca in the bulk sediment indicates the characteristic of residence time,Sr/Ca and Fe/Mn infer the salinity of lakes.Carbonate formation processes and types can influence the δ13C–δ18O correlation.δ18O will be heavier from Mg-calcite and aragonite formed in a high-salinity water body than calcite formed in freshwater conditions.When carbonate content is less than 30%,there is no relationship with either δ13C or δ18O,and also none between δ13C and δ18O.More than 30%,carbonate content,however,co-varies highly to δ13C and δ18O,and there is also a high correlation between δ13C and δ18O.Vegetation conditions and primary productivity of lakes can influence the characteristics of δ13C and δ18O,and their co-variance.Total organic matter content(TOC) in the sediments is higher with more terrestrial and submerged plants infilling.In northeastern and northwestern China,when organic matter in the lake sediments comes from endogenous floating organisms and algae,the δ13C value is high.δ13C is in the range of 4‰ to 0‰ when organic matter comes mainly from floating organisms(C/N<6);in the range of 4‰ to 8‰ when organic matter comes from diatoms(C/N=6 to 8);and 8‰ to 4‰ when organic matter comes from aquatic and terrestrial plants(C/N>8).     

Temporal and spatial differences in salinity and water chemistry in SW Florida estuaries: Effects of human-impacted watersheds

Three estuaries near Naples, Florida with variably modified watersheds have been investigated to understand the chemical consequences of altering drainage patterns. Blackwater River (near natural drainage, control site), Henderson Creek (moderately modified watershed), and Faka-Union Canal (severe channelization) were sampled for temperature, salinity, δ¹⁸O, δ¹³C of dissolved inorganic carbon (DIC), molality of CO₂ (ΣCO₂), and Mg:Ca and Sr:Ca ratios between freshwater and marine water end members over a 17-mo period. Carbon isotope composition followed similar seasonal patterns as salinity. Freshwater and seawater end members are more negative than the global average, likely reflecting equilibration with local carbon sources derived from mangrove leaf litter and groundwater. δ¹³C responds to differences in primary productivity between estuaries. Henderson Creek has higher primary productivity than Blackwater River (probable due to higher sewage input and agricultural runoff) and has more positive δ¹³C and lower ΣCO₂. δ¹⁸O is affected by seasonal input of freshwater from atmospheric precipitation, evaporation, and groundwater. Late summer and fall rains lower the δ¹⁸O of estuarine water, whereas evaporative conditions in the dry season elevate δ¹⁸O to values that can be more positive upstream than those from the Gulf of Mexico (estuarine inversion). Evaporation produces water in the Gulf of Mexico that is >1‰ more positive than the global sea surface average most of the year. The very negative δ¹⁸O values in Blackwater River and Henderson Creek likely reflect atmospheric and groundwater contribution. Mg:Ca and Sr:Ca ratios of Gulf water from all three estuaries are similar to global averages at low latitudes. Freshwater end members among estuaries are different in that Blackwater River has higher ratios, suggesting a groundwater contribution. Dolomitic rocks in the subsurface likely provide a source of Mg ions.     

Identification of important primary producers in a Chesapeake Bay tidal creek system using stable isotopes of carbon and sulfur

The use of multiple stable isotopes in the study of trophic relationships in temperate estuaries has usually been limited to euhaline systems, in which phytoplankton, benthic microalgae, andSpartina alterniflora are major sources of organic matter for consumers. Within large estuaries such as Chesapeake Bay, however, many species of consumers are found in the upper mesohaline to oligohaline portions. These lower salinity wetlands have a greater abundance of macrophytes that use C3 photosynthesis to fix carbon, in addition toS. alterniflora, which fixes carbon via the C4 photosynthetic pathway. In a broad survey of the biota and sediments of a brackish tidal creek tributary to Chesapeake Bay, combined δ¹³C and δ³⁴S measurements disclosed a balanced contribution to secondary production from phytoplankton, C3 macrophytes,Spartina sp., and benthic microalgae. Surface sediment δ¹³C suggested that the organic matter from C3 plants was derived both from allochthonous sources (terrestrial runoff) and from autochthonous production (marsh macrophytes). Unlike most estuarine systems studied to date, which are dominated by algae (phytoplankton and benthic microalgae) and C4 macrophytes, C3 plants are of greater importance in the diets of consumers in this low-salinity creek system.     

Spatial and Temporal Variability of Sediment Organic Matter Recycling in Two Temperate Eutrophicated Estuaries

This paper deals with the spatial and seasonal recycling of organic matter in sediments of two temperate small estuaries (Elorn and Aulne, France). The spatio-temporal distribution of oxygen, nutrient and metal concentrations as well as the organic carbon and nitrogen contents in surficial sediments were determined and diffusive oxygen fluxes were calculated. In order to assess the source of organic carbon (OC) in the two estuaries, the isotopic composition of carbon (δ ¹³C) was also measured. The temporal variation of organic matter recycling was studied during four seasons in order to understand the driving forces of sediment mineralization and storage in these temperate estuaries. Low spatial variability of vertical profiles of oxygen, nutrient, and metal concentrations and diffusive oxygen fluxes were monitored at the station scale (within meters of the exact location) and cross-section scale. We observed diffusive oxygen fluxes around 15 mmol m^?2 day^?1 in the Elorn estuary and 10 mmol m^?2 day^?1 in the Aulne estuary. The outer (marine) stations of the two estuaries displayed similar diffusive O₂ fluxes. Suboxic and anoxic mineralization was large in the sediments from the two estuaries as shown by the rapid removal of very high bottom water concentrations of NO _x ^? (>200 μM) and the large NH₄ ⁺ increase at depth at all stations. OC contents and C/N ratios were high in upstream sediments (11–15 % d.w. and 4–6, respectively) and decreased downstream to values around 2 % d.w. and C/N ≤ 10. δ ¹³C values show that the organic matter has different origins in the two watersheds as exemplified by lower δ ¹³C values in the Aulne watershed. A high increase of δ ¹³C and C/N values was visible in the two estuaries from upstream to downstream indicating a progressive mixing of terrestrial with marine organic matter. The Elorn estuary is influenced by human activities in its watershed (urban area, animal farming) which suggest the input of labile organic matter, whereas the Aulne estuary displays larger river primary production which can be either mineralized in the water column or transferred to the lower estuary, thus leaving a lower mineralization in Aulne than Elorn estuary. This study highlights that (1) meter scale heterogeneity of benthic biogeochemical properties can be low in small and linear macrotidal estuaries, (2) two estuaries that are geographically close can show different pattern of organic matter origin and recycling related to human activities on watersheds, (3) small estuaries can have an important role in recycling and retention of organic matter.     

Eutrophication and carbon sources in Chesapeake Bay over the last 2700 yr: human impacts in context

To compare natural variability and trends in a developed estuary with human-influenced patterns, stable isotope ratios (δ¹³C and δ¹⁵N) were measured in sediments from five piston cores collected in Chesapeake Bay. Mixing of terrestrial and algal carbon sources primarily controls patterns of δ¹³C_org profiles, so this proxy shows changes in estuary productivity and in delivery of terrestrial carbon to the bay. Analyses of δ¹⁵N show periods when oxygen depletion allowed intense denitrification and nutrient recycling to develop in the seasonally stratified water column, in addition to recycling taking place in surficial sediments. These conditions produced ¹⁵N-enriched (heavy) nitrogen in algal biomass, and ultimately in sediment. A pronounced increasing trend in δ¹⁵N of +4‰ started in about A.D. 1750 to 1800 at all core sites, indicating greater eutrophication in the bay and summer oxygen depletion since that time. The timing of the change correlates with the advent of widespread land clearing and tillage in the watershed, and associated increases in erosion and sedimentation. Isotope data show that the region has experienced up to 13 wet-dry cycles in the last 2700 yr. Relative sea-level rise and basin infilling have produced a net freshening trend overprinted with cyclic climatic variability. Isotope data also constrain the relative position of the spring productivity maximum in Chesapeake Bay and distinguish local anomalies from sustained changes impacting large regions of the bay. This approach to reconstructing environmental history should be generally applicable to studies of other estuaries and coastal embayments impacted by watershed development.     

The distribution and stable carbon isotopic composition of dissolved organic carbon in estuaries

The distributions of dissolved organic carbon (DOC) and the natural carbon isotope ratio of DOC (DO¹³C) in estuaries reflect the predominant sources and sinks of organic matter from both allochthonous and autochthonous origins. The traditional view is that DOC in land-margin ecosystems reflects mainly the mixing of land-derived and oceanic DOC. However, this view is not consistent with the bulk of our data from a survey of DOC and DO¹³C distributions in estuaries on the East and Gulf coasts of the USA. While it is accurate that the DOC in estuaries includes material derived from land and from the ocean, the distributions of DOC and DO¹³C in several estuaries reflect additional DOC inputs from estuarine phytoplankton and tidal marshes. Even when DOC concentrations were distributed conservatively, the isotopic composition of the DOC revealed the existence of a dynamic cycle of DOC input and removal in some systems.     

Tracing the flow of organic matter from primary producers to filter feeders in Ria Formosa lagoon, Southern Portugal

The flow of organic matter along the main navigation channel of Ria Formosa, Portugal, was assessed using determinations of suspended particulate matter (SPM), particulate organic matter (POM), and chlorophyll a (chla) concentrations in conjunction with stable isotope values of primary producers, particulate matter, and two filter feeders. SPM in the lagoon is dominated by inorganic particles comprising 80% of total weight with organic matter averaging about 20%. The algal component of the POM averaged about 5% with the remainder comprised of detritus. The δ¹³C values of primary producers ranged from ?9.1‰ in the intertidal seagrassZostera noltii to ?30.7‰ in the red seaweedBostrychia scorpioides revealing underlying differences in the mechanisms of carbon uptake. The δ¹³C value ofB. scorpioides, which develops entangled on the salt marsh speciesSpartina maritima, suggests that its main source of inorganic carbon is atmospheric CO₂. The δ¹³C values of the high marsh macrophyteSarcocornia perennis significantly increased with distance from the ocean while δ¹³C values ofZ. noltii decreased, probably because higher decomposition of organic matter at inner stations lowers the δ¹³CO₂ value in the water. The δ¹⁵N values of Ulvales, seagrasses, and marsh plants significantly increased from outer stations to inner stations. This increase may be due either to recycling of nitrogen (N) within the marsh (with loss of light N₂ or NH₄) or to inputs of isotopically heavy N from sewage. The δ¹⁵N values of particulate matter showed an opposite trend, which indicates higher microbial degradation of organic matter at the inner lagoon. The data demonstrate that the seston in the lagoon is a mixture of detritus from lagoon primary producers with a minor contribution of microalgae. The filter feeders are most likely assimilating a mixture of phytoplankton and microphytobenthos. Digestion of lagoon seston is selective. The δ¹⁵N values of both muscle and digestive gland of filter feeders showed the opposite gradient of particulate matter indicating that the depleted δ¹⁵N of SPM at inner stations was not assimilated or even ingested. Stable isotopes values did not differ between the filter-feeders—the musselMytilus galloprovincialis collected on buoys and the clamTapes decussatus collected in the sediment—suggesting a considerable mixture of benthic-pelagic organic matter throughout the water column. Assessment of the changes in isotopic decomposition of detritus as it decays is required to refine our understanding of organic matter transfers in detrital food webs.     

Macrophyte Abundance in Waquoit Bay: Effects of Land-Derived Nitrogen Loads on Seasonal and Multi-Year Biomass Patterns

Anthropogenic inputs of nutrients to coastal waters have rapidly restructured coastal ecosystems. To examine the response of macrophyte communities to land-derived nitrogen loading, we measured macrophyte biomass monthly for 6 years in three estuaries subject to different nitrogen loads owing to different land uses on the watersheds. The set of estuaries sampled had nitrogen loads over the broad range of 12 to 601 kg N ha⁻¹ year⁻¹. Macrophyte biomass increased as nitrogen loads increased, but the response of individual taxa varied. Specifically, biomass of Cladophora vagabunda and Gracilaria tikvahiae increased significantly as nitrogen loads increased. The biomass of other macroalgal taxa tended to decrease with increasing load, and the relative proportion of these taxa to total macrophyte biomass also decreased. The seagrass, Zostera marina, disappeared from the higher loaded estuaries but remained abundant in the estuary with the lowest load. Seasonal changes in macroalgal standing stock were also affected by nitrogen load, with larger fluctuations in biomass across the year and higher minimum biomass of macroalgae in the higher loaded estuaries. There were no significant changes in macrophyte biomass over the 6 years of this study, but there was a slight trend of increasing macroalgal biomass in the latter years. Macroalgal biomass was not related to irradiance or temperature, but Z. marina biomass was highest during the summer months when light and temperatures peak. Irradiance might, however, be a secondary limiting factor controlling macroalgal biomass in the higher loaded estuaries by restricting the depth of the macroalgal canopy. The relationship between the bloom-forming macroalgal species, C. vagabunda and G. tikvahiae, and nitrogen loads suggested a strong connection between development on watersheds and macroalgal blooms and loss of seagrasses. The influence of watershed land uses largely overwhelmed seasonal and inter-annual differences in standing stock of macrophytes in these temperate estuaries.     

Controls on the stable carbon isotopic composition of biogenic methane produced in a tidal freshwater estaurine sediment

The δ¹³C value of methane in sediments from a tidal freshwater site in the White Oak River Estuary, North Carolina, exhibited a relatively small, but consistent, seasonal variation (∼3‰) with isotopically heavier values occurring during the warmer months (−66.1‰ summer, −69.2‰ winter). These isotopic shifts could have resulted from changes in: (1) isotopic compositions of precursor molecules; (2) kinetic isotope effects associated with methane production; or (3) pathways of methane production. Methane production rate and isotopic data from sediment incubation experiments and field measurements were used to determine the relative contributions of these factors to the observed seasonal variations. Although changes in δ¹³C values of biogenic methane are typically thought to result from changes in pathways of methane production, this study showed that a significant amount (36 ± 22%) of the seasonal variations between the δ¹³C value of methane produced in sediment incubation experiments could be attributed to changes in the δ¹³C value of the ΣCO₂ pool. This was due to increased methane production rates and removal of ¹²CO₂ with increasing temperature, a prevalent feature of methanogenic systems that may account for some of the frequently observed ¹³C enrichment in methane during warmer months. Combining the change in the δ¹³C value of the ΣCO₂ pool with temperature-controlled changes in fractionation (α) resulting from kinetic isotope effects accounted for (53 ± 22%) of the ¹³C enrichment observed during summer sediment incubation experiments. Although large pathway changes were not observed in sediment incubation experiments, the remaining differences in δ¹³C values could have resulted from smaller, undetectable changes in the percentage of methane production from acetate (∼14%) and/or a shift in the δ¹³C values of methane produced from acetate (∼4‰).     

The nature of O18/O16 and C13/C12 secular trends in sedimentary carbonate rocks

Measurements on 170 carbonate rocks show decreasing δO¹⁸ of similar magnitude for both limestones and dolomites over a time span of ~ 2800 m.y. The Proterozoic dolomites are on average heavier by ~5%. in δO¹⁸ than their coeval limestones. The data may indicate displacement in δC¹³ of about 3%. at approximately 570 m.y. ago, with Precambrian carbonates being heavier in δC¹³ at a given δO¹⁸ level than their Phanerozoic counterparts. The compilation of the previously published data is consistent with the above described features.     

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.     

Spatial and seasonal variability in elemental content, δ13C, and δ15N ofThalassia testudinum from South Florida and its implications for ecosystem studies

Elemental and isotopic composition of leaves of the seagrassThalassia testudinum was highly variable across the 10,000 km² and 8 years of this study. The data reported herein expand the reported range in carbon:nitrogen (C:N) and carbon:phosphorus (C:P) ratios and δ¹³C and δ¹⁵N values reported for this species worldwide; 13.2–38.6 for C:N and 411–2,041 for C:P. The 981 determinations in this study generated a range of ?13.5‰ to ?5.2‰ for δ¹³C and ?4.3‰ to 9.4‰ for δ¹⁵N. The elemental and isotope ratios displayed marked seasonality, and the seasonal patterns could be described with a simple sine wave model. C:N, C:P, δ¹³C, and δ¹⁵N values all had maxima in the summer and minima in the winter. Spatial patterns in the summer maxima of these quantities suggest there are large differences in the relative availability of N and P across the study area and that there are differences in the processing and the isotopic composition of C and N. This work calls into question the interpretation of studies about nutrient cycling and food webs in estuaries based on few samples collected at one time, since we document natural variability greater than the signal often used to imply changes in the structure or function of ecosystems. The data and patterns presented in this paper make it clear that there is no threshold δ¹⁵N value for marine plants that can be used as an unambiguous indicator of human sewage pollution without a thorough understanding of local temporal and spatial variability.