CDOM and its contribution to the underwater light climate of a shallow, microtidal estuary in south-western Australia

Light attenuation (K_d) of photosynthetically active radiation (PAR) by chromophoric dissolved organic matter (CDOM), total suspended solids (TSS) and chlorophyll a (Chl a) were measured at nine stations along an estuarine gradient in the Swan River, Western Australia, over 15 months. There were strong spatial gradients associated with the marine-freshwater transition along the 32 km of estuary sampled, as well as seasonal gradients mainly associated with rainfall, 80% of which occurs between May and September. CDOM absorbances at 440 nm reached a maximum of 10.9 m⁻¹ with the freshwater inflow but concentrations of suspended matter remained low throughout the sampling period (1.0–21.0 mg l⁻¹) under the diurnal tides of the estuary. CDOM was the dominant constituent of K_d and a stepwise multiple regression showed that 66% (p < 0.0001) of the variation in K_d can be explained by CDOM and an additional 8% (p < 0.0001) by TSS. As a consequence of this result, analysis into the influence of river discharge rates on CDOM absorbance levels was examined for 2002 using data collected during this study, and for 2000 and 2001 using historical dissolved organic carbon (DOC) and river discharge data. The outcome of this analysis infers that greater river discharge rates result in increased CDOM absorbances in the Swan River estuary.     

Complexation of mercury by dissolved organic matter in surface waters of Galveston Bay, Texas

The chemical speciation of dissolved mercury in surface waters of Galveston Bay was determined using the concentrations of mercury-complexing ligands and conditional stability constants of mercury-ligand complexes. Two classes of natural ligands associated with dissolved organic matter were determined by a competitive ligand exchange-solvent solvent extraction (CLE-SSE) method: a strong class (L_s), ranging from 19 to 93 pM with an average conditional stability constant (K_HgLs) of 10²⁸, and a weak class (L_w) ranging from 1.4 to 9.8 nM with an average K_HgLs of 10²³. The range of conditional stability constants between mercury and natural ligands suggested that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. A positive correlation between the estuarine distribution of dissolved glutathione and that of mercury-complexing ligands supported this suggestion. Thermodynamic equilibrium modeling using stability constants for HgL, HgCl_x, Hg(OH)_x, and HgCl(OH) and concentrations of each ligand demonstrated that almost all of the dissolved mercury (> 99%) in Galveston Bay was complexed by natural ligands associated with dissolved organic matter. The importance of low concentrations of high-affinity ligands that may originate in the biological system (i.e., glutathione and phytochelatin) suggests that the greater portion of bulk dissolved organic matter may not be important for mercury complexation in estuarine surface waters.     

Geochemical cycling in the Hooghly estuary, India

U–Th decay series isotopes, δ¹⁸O and Si measurements in the river estuarine waters and sediments of the polluted Hooghly estuary as well as the surface waters of the Bay of Bengal, its high salinity end member, are reported. Dissolved Si indicates that there are probably two mixing regimes, dissolved U behaviour is nonconservative and δ¹⁸O behaves conservatively in the overall estuarine region. Isotopes of reactive elements, viz. ²³⁴Th and ²¹⁰Po, are removed from the estuarine waters in <2 days and <1 month, respectively, which is due to high suspended matter (30–301 mg l⁻¹). ²²⁸Ra and ²²⁶Ra are profusely released into the estuarine waters in the low to mid-salinity regions.As expected, the opposite trend is observed in the case of estuarine sediments and suspended matter. Reactive isotopes of Th, ²¹⁰Pb and ²¹⁰Po are enriched, whereas Ra isotopes are depleted with respect to their parent nuclides in the estuarine sediments and suspended matter. ²³²Th/Al ratio appears well suited to study the distribution and mixing of the bed load sediments of the Ganga–Brahmaputra (G–B) and the Hooghly rivers with those from other rivers on the Bay of Bengal floor.     

Analysis of estuarine colour components during non-monsoon period through Ocean Colour Monitor

Simultaneous acquisition of water samples, radiance and irradiance measurements were carried out from 40 stations in the Mandovi–Zuari estuaries during February to May 2002. From the samples collected, inherent and apparent optical properties (IOP and AOP) such as absorption coefficient (a), upwelling diffuse attenuation coefficient (k_u) and subsurface reflectance (R) were derived. Using these optical properties, radiative transfer at each water column is examined. On the basis of the radiative transfer outcome, band-ratio algorithms are derived for three optically active substances (OAS), viz, chlorophyll-a, suspended sediment and coloured dissolved organic matter (CDOM). The respective algorithms are 670/555, 490/670 and 412/670 nm for chlorophyll-a, suspended sediment and CDOM. These algorithms are applied to Ocean Colour Monitor (OCM), onboard Indian Remote Sensing Satellite (IRS)-Polar Satellite Launch Vehicle (P4), scenes (digital data), to synoptically analyze these OAS. The synoptic analysis of OAS revealed different hydrodynamic characteristics of the estuaries during non-monsoon seasons.     

Contrasting behaviour of trace metals in the Scheldt estuary in 1978 compared to recent years

Dissolved and particulate trace metals (Cu, Cd, Pb, Zn, Ni, Fe and Mn) measured at six stations along the Scheldt estuary in October/November 1978 are compared with more recent data. Based on Ca content in the suspended matter, three distinct geochemical regions could be distinguished: the upper estuary (salinity 1–7) dominated by fluvial mud, mid-estuary (salinity 7–17) where the composition of the suspended matter remained relatively constant, and the lower estuary where marine mud prevailed. Re-suspension of sediments is the major factor controlling the composition of the particles in the upstream region. Anoxic conditions prevailed in the upper part of the estuary extending to a salinity of 15 in 1978, while at present the seaward boundary of the anoxic water body is located at less saline waters. Furthermore, the present-day metal load is much lower than in 1978. As a consequence of the changed situation, maxima in dissolved concentrations of redox-sensitive metals in the mid/lower estuary have moved as well, which affects the trace metal re-distribution pattern. In the anoxic zone, exchange processes between dissolved and particulate metal fractions were strongly redox regulated, with Fe and Mn as excellent examples. Iron was removed from the dissolved phase in the early stages of mixing resulting in an increase in the suspended particulate matter of the leachable ‘non-residual' Fe fraction from 2 to 3.5%. Due to its slower kinetics, removal of Mn from solution occurred in mid-estuary where oxygen concentrations increased. Cu, Cd and Zn on the contrary were mobilised from the suspended particles during estuarine mixing. External inputs of Pb, and to a lesser extent of Cu, in the lower estuary resulted in the increase of their particulate and the dissolved concentrations. Calculated K_d (distribution coefficient) values were used to assess the redistribution between the dissolved and particulate phase of the investigated metals. Due to the existence of the anoxic water body in the upper estuary, the importance of redox processes in determining the K_d values could be demonstrated. The sequence of K_d values in the upper estuary (Fe, Cd, Zn, Pb > Cu > Ni, Mn) is significantly different from that in the lower estuary (Fe > Mn > Pb, Ni, Zn, Cu, Cd). Thus, in such a dynamic estuary single metal-specific K_d values cannot be used to describe redistribution processes.     

Relationships between suspended particulate material, light attenuation and Secchi depth in UK marine waters

Measurements of sub-surface light attenuation (K_d), Secchi depth and suspended particulate material (SPM) were made at 382 locations in transitional, coastal and offshore waters around the United Kingdom (hereafter UK) between August 2004 and December 2005. Data were analysed statistically in relation to a marine water typology characterised by differences in tidal range, mixing and salinity. There was a strong statistically significant linear relationship between SPM and K_d for the full data set. We show that slightly better results are obtained by fitting separate models to data from transitional waters and coastal and offshore waters combined. These linear models were used to predict K_d from SPM. Using a statistic (D) to quantify the error of prediction of K_d from SPM, we found an overall prediction error rate of 23.1%. Statistically significant linear relationships were also evident between the log of Secchi depth and the log of K_d in waters around the UK. Again, statistically significant improvements were obtained by fitting separate models to estuarine and combined coastal/offshore data – however, the prediction error was improved only marginally, from 31.6% to 29.7%. Prediction was poor in transitional waters (D = 39.5%) but relatively good in coastal/offshore waters (D = 26.9%).SPM data were extracted from long term monitoring data sites held by the UK Environment Agency. The appropriate linear models (estuarine or combined coastal/offshore) were applied to the SPM data to obtain representative K_d values from estuarine, coastal and offshore sites. Estuarine waters typically had higher concentrations of SPM (8.2–73.8 mg l⁻¹) compared to coastal waters (3.0–24.1 mg l⁻¹) and offshore waters (9.3 mg l⁻¹). The higher SPM values in estuarine waters corresponded to higher values of K_d (0.8–5.6 m⁻¹). Water types that were identified by large tidal ranges and exposure typically had the highest K_d ranges in both estuarine and coastal waters. In terms of susceptibility to eutrophication, large macrotidal, well mixed estuarine waters, such as the Thames embayment and the Humber estuary were identified at least risk from eutrophic conditions due to light-limiting conditions of the water type.     

Release of dissolved organic matter during oxic and anoxic decomposition of salt marsh cordgrass

Chromophoric dissolved organic matter (CDOM), as the light absorbing fraction of bulk dissolved organic matter (DOM), plays a number of important roles in the global and local biogeochemical cycling of dissolved organic carbon (DOC) and in controlling the optical properties of estuarine and coastal waters. Intertidal areas such as salt marshes can contribute significant amounts of the CDOM that is exported to the ocean, but the processes controlling this CDOM source are not well understood. In this study, we investigate the production of DOM and CDOM from the decomposition of two salt marsh cordgrasses, Spartina patens, a C₄ grass, and Typha latifolia, a C₃ grass, in well-controlled laboratory experiments. During the seven-week incubation period of the salt marsh grasses in oxic and anoxic seawater, changes in dissolved organic carbon (DOC) concentrations, dissolved nitrogen (DN) concentrations, stable carbon isotopic composition of DOC (DOC-δ¹³C), and CDOM fluorescence demonstrate a significant contribution of DOC and CDOM to estuarine waters from salt marsh plants, such as Spartina and Typha species. In the natural environment, however, the release processes of CDOM from different cordgrass species could be controlled largely by the in situ oxic and anoxic conditions present during degradation which affects both the production and decomposition of DOC and CDOM, as well as the optical properties of CDOM in estuarine and coastal waters.     

Distribution, partitioning and fluxes of dissolved and particulate organic C, N and P in the eastern North Pacific and Southern Oceans

Concurrent distributions of dissolved and suspended particulate organic carbon (DOC and POC_susp), nitrogen (DON and PON_susp) and phosphorus (DOP and POP_susp), and of suspended particulate inorganic phosphorus (PIP_susp), are presented for the open ocean water column. Samples were collected along a three-station transect from the upper continental slope to the abyssal plain in the eastern North Pacific and from a single station in the Southern Ocean. The elemental composition of surface sedimentary organic matter (SOM) was also measured at each location, and sinking particulate organic matter (POM_sink) was measured with moored sediment traps over a 110-d period at the abyssal site in the eastern North Pacific only. In addition to elemental compositions, C : N, C : P and N : P ratios were also calculated. Surface and deep ocean concentrations of dissolved organic matter (DOM) and inorganic nutrients between the two sites displayed distinct differences, although suspended POM (POM_susp) concentrations were similar. Concentrations of DOM and POM_susp displayed unique C, N and P distributions, with POM_susp concentrations generally about 1–2 orders of magnitude less than the corresponding DOM concentrations. These differences were likely influenced by different biogeochemical factors: whereas the dissolved constituents may have been influenced more by the physical regime of the study site, suspended particulate matter may have been controlled to a greater extent by biological and chemical alteration. Up to 80% of total particulate P in POM_susp, POM_sink and SOM consisted of PIP. For all organic matter pools measured, elemental ratios reveal that organic P is preferentially remineralized over organic C and organic N at both sites. Increases in C : P and N : P ratios with depth were also observed for DOM at both sites, suggesting that DOP is also preferentially degraded over C and N as a function of depth. A simple one-dimensional vertical eddy diffusion model was applied to estimate the contributions of dissolved and suspended particulate organic C, N and P fluxes from the upper mixed layer into the permanent thermocline. Estimated vertical DOM fluxes were 28–63% of the total organic matter fluxes; POM_susp and POM_sink fluxes were 8–20 and 28–52% of the total.     

河口硅酸盐物理化学过程研究——Ⅲ、河口活性硅转移机理的现场验证初步研究—悬浮物中硅、铁和铝的含量分布

在本研究第二篇中,我们通过实验室模拟研究,发现海水中Fe+++或Al+++离子在适当pH条件下生成Fe(OH)₃或Al(OH)₃胶体沉淀后,对活性硅有相当大的吸附能力;同时还通过吸附热计算、淋洗脱附实验和重溶解实验,判断上述吸附并不是一般可逆的离子交换吸附,而比较可能是化学吸附,吸附后基本上不转化为高聚硅酸结构,而比较可能进行结构重排转入内部结构中去.根据这些结果,我们提出一个关于河口活性硅地球化学转移的理论图象:即活性硅主要通过由于pH和盐度提高而生成的铁、铝等元素氢氧化物胶体沉淀的吸附而转移,再进一步转化为比较稳定的铁、铝的硅酸盐化合物形式,沉积到海底.为了进一步验证这个理论图象的现实性,我们再度在九龙江口进行了一些现场取样分析研究,试图通过河口各处海水悬浮物中各化合形式硅、铁、铝的分布变化资料,加以初步归纳总结,并和理论图象相对照.     

The relative importance of chlorophyll,dissolved and particulate material,and seawater to the vertical extinction of light

The attenuation of light by chlorophyll, particulate and dissolved material, and seawater off the coast of north-west Africa showed distinct cross-shelf variations. Attenuation was most rapid nearshore because of absorption by non-biological particles. This particulate matter was probably aeolian material from the nearby Sahara Desert of resuspended sand from the sediment. Regardless of the source, the marked light extinction resulted in decreased phytoplankton growth nearshore. Light attenuation characteristics of the region were anomalous when compared to those of other ocenic regimes.     

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

Mobilization of metals from riverine suspended matter in seawater

Suspended matter from rivers in the Russian Far East was leached by seawater to assess the extent of Zn, Cd, Pb, and Cu release from the land-derived solids to estuarine and coastal waters. The concentration of solids in the leaching experiments was 0.25 g/l. The suspended matter used varied in metal content from background levels to heavily contaminated.The concentration of Zn, Cd, Pb, and Cu in the leaching solution after 1, 4, 24, 48, and 96 h was determined by anodic stripping voltammetry. Measurable Cd was transferred from river suspended matter to seawater with both background and elevated Cd concentrations, though the amount of Cd released was different. The increase in Zn and Pb in solution was observed only at the enriched concentration of metals in the suspended solids. The Cu transfer into solution was more pronounced from material with elevated Cu concentration, but the amount of degradable organic matter in the solid phase was more important.The losses of metals from the riverine solids varied from 60% to 80% of total concentration for Cd to negligible for Pb, independent of contamination. The Zn loss depended on the initial concentration in the solids and decreased from 11–16% for the heavily contaminated suspended matter to 3–8% for the moderately enriched ones and to negligible for the pristine solids. Cu loss varied from 1% to 30% of total content, with no clear dependence on concentration in the suspended matter.The significance of additional input of dissolved metals to estuarine and coastal waters from remobilization was assessed by comparison with the initial concentration of dissolved metals in river water. Such experiments could be used to assess the water quality impact of atmospheric fallout of contaminated solids and storm drainage from the urbanized areas, in addition to river suspended matter studies.     

The role of suspended matter in the biogeochemical cycles in the Adige River estuary (Northern Adriatic Sea)

Suspended matter and sediments from the Adige River mouth were analysed in an attempt to elucidate the transfer of heavy metals from the river to the sea. The vertical profile of grain-size spectra of suspended matter in front of the river mouth has shown that the riverine particles are limited to the upper brackish layer.Particulate matter was found to have a large specific surface area, up to 20 m² g⁻¹ in the estuarine sample. High quantities of quartz and phyllosilicates (micas and clay minerals) were found in the riverine suspended matter. The quartz content of the suspended matter from the brackish layer was found to be diminishing and with the organic matter becoming the essential component (22%). Higher levels of trace metals were usually detected in suspended matter samples (40 ppm Ni, 200 ppm Cr, 60 ppm Pb, 100 ppm Cu, 320 ppm Zn, and 0·9 ppm Cd) than in sediments.The observed similarity of physico-chemical, mineralogical and geochemical characteristics of riverine suspended matter and recent marine sediments, indicates that most of the riverborne particulate matter is deposited in the proximity of the Adige River mouth.The peculiar characteristics of the chromium level (high bulk concentration and its abundance in the organic fraction of the particular matter) when compared to the other trace metals, indicates the anthropogenic influence on its biogeocycle.     

Tidal exchange between a freshwater tidal marsh and an impacted estuary: the Scheldt estuary, Belgium

Tidal marsh exchange studies are relatively simple tools to investigate the interaction between tidal marshes and estuaries. They have mostly been confined to only a few elements and to saltwater or brackish systems. This study presents mass-balance results of an integrated one year campaign in a freshwater tidal marsh along the Scheldt estuary (Belgium), covering oxygen, nutrients (N, P and Si), carbon, chlorophyll, suspended matter, chloride and sulfate. The role of seepage from the marsh was also investigated. A ranking between the parameters revealed that oxygenation was the strongest effect of the marsh on the estuarine water. Particulate parameters showed overall import. Export of dissolved silica (DSi) was more important than exchange of any other nutrient form. Export of DSi and import of total dissolved nitrogen (DIN) nevertheless contributed about equally to the increase of the Si:N ratio in the seepage water. The marsh had a counteracting effect on the long term trend of nutrient ratios in the estuary.     

Isotopic and Elemental Variations of Carbon and Nitrogen in a Mangrove Estuary

Variations in elemental and isotopic ratios of suspended particulate matter (SPM) were investigated in the Guayas River Estuary Ecosystem (GREE) that empties into the Gulf of Guayaquil, Ecuador. Detritus in the system was identified on the basis of extremely high carbon:chlorophyll aratios (>1000). This material had mean δ¹³C of −26·4±0·3, δ¹⁵N of +4·8±0·2, and (C:N)_atomicof 14·1±0·9. The isotopic data were comparable to measurements reported for fresh and degrading mangrove leaves, whereas the elemental ratio was comparatively enriched in nitrogen. Isotope measurements of SPM throughout the GREE were more similar to values for riverine material and detritus compared with that for the coastal end-member. Values indicative ofin situproduced algae, sewage and shrimp pond effluent were only found at selected sites. Bacterial bioassays, which were used to document potential sources of dissolved organic matter in the GREE, were isotopically similar to SPM. This correspondence coupled with the relatively low (C:N)_aof SPM could be explained by bacterial immobolization of nitrogen onto detritus. Finally, tidal variations of (C:N)_aand δ¹³C at a brackish mangrove site were similar in magnitude to spatial variations encountered throughout the GREE. Based on these results, the authors caution that care must be taken when samples are taken for food-web studies in these systems.     

Patterns in tropical seagrass photosynthesis in relation to light, depth and habitat

Seagrass meadows across north-eastern Australia, survive a range of environmental conditions in coastal bays, reefs, estuarine and deepwater habitats through adaptation of a range of structural, morphological and physiological features. The aim of this study was to investigate the influence of spatial features (habitat type, site and depth) and photon flux on the photosynthetic performance of 11 tropical seagrass species. Pulse amplitude modulated (PAM) fluorometry was used to generate rapid light curves from which measures of maximal electron transport rate (ETR_max), photosynthetic efficiency (α), saturating irradiance (E_k) and effective quantum yield (ΔF/F_m′) were derived. The amount of light absorbed by leaves (absorption factor) was also determined for each population. In intertidal habitats many seagrass species exhibited typical sun-type responses with a close coupling of both ETR_max and E_k with photon flux. Photosynthetic performance ranged from minima in Thalassodendron ciliatum to maxima in Syringodium isoetifolium. The absence of a coupling between photosynthetic performance and photon flux in subtidal populations was most likely due to highly variable light climates and possible light attenuation, and hence the photo-biology of estuarine and deepwater seagrasses exhibited photosynthetic responses indicative of light limitation. In contrast seagrass species from shallow reef and coastal habitats for the most part exhibited light saturation characteristics. Of all the variables examined ETR_max, E_k and ΔF/F_m′ were most responsive to changing light climates and provide reliable physiological indicators of real-time photosynthetic performance of tropical seagrasses under different light conditions.     

Sorption model for dissolved and particulate aluminium in the Conway estuary, UK

Dissolved Al carried in river water apparently undergoes a fractional removal at the early stages of mixing in the Conway estuary. On the other hand, dissolved Al behaves almost conservatively in high salinity (>13) estuarine waters. In order to understand the geochemistry of Al in these estuarine waters, simple empirical sorption models have been used. Partitioning of Al occurs between solid and solution phases with a distribution coefficient, K_d, which varies from 0.67 × 10⁵ to 3.38 × 10⁶ ml g⁻¹ for suspended particle concentrations of 2–64 mg l⁻¹. The K_d values in general decrease with increasing suspended particulate matter and this tendency termed the “particle concentration effect” is quite pronounced in these waters. The sorption model derived by previous workers for predicting concentrations of dissolved Al with changing suspended sediment loads has been applied to these data. Reasonable fits are obtained for K_d values of 10⁵, 10⁶ and 10⁷ ml g⁻¹ with various values of α. Further, a sorption model is proposed for particulate Al concentrations in these waters that fits the data extremely well defined by a zone with K_d value 10⁷ ml g⁻¹ and C₀ values 16 × 10⁻⁶ mg ml⁻¹ and 92 × 10⁻⁶ mg ml⁻¹. These observations provide strong evidence of sorption processes as key mechanisms influencing the distribution of dissolved and particulate Al in the Conway estuary and present new insight into Al geochemistry in estuaries.     

Variations in the natural abundance of 15N in estuarine suspended particulate matter: A specific indicator of biological processing

In this study, the ¹⁴N:¹⁵N ratio of suspended particulate material collected from the Tamar river estuary, south-west England, is described. Three populations of particles, distinguishable by their ¹⁵N content, were observed. This investigation has shown that populations of estuarine particles are generated by biological transformations in situ and that the ¹⁵N content of estuarine particles does not merely reflect hydrodynamic mixing of the freshwater and seawater source particulate material.     

Abundance, size distribution, and stable carbon and nitrogen isotopic compositions of marine organic matter isolated by tangential-flow ultrafiltration

Tangential-flow ultrafiltration was used to isolate particulate and high-molecular-weight dissolved material from seawater collected at various depths and geographic regions of the Pacific and Atlantic Oceans. Ultrafiltration proved to be a relatively fast and efficient method for the isolation of hundreds of milligrams of material. Optical and electron microscopy of the isolated materials revealed that relatively fragile materials were recovered intact. Depth-weighted results of the size distribution of organic matter in seawater indicated that ˜ 75% of marine organic carbon was low-molecular-weight (LMW) dissolved organic carbon (< 1 nm), ˜ 24% was high-molecular-weight (HMW) dissolved organic carbon (1–100 nm), and ˜ 1% was particulate organic carbon (> 100 nm). The distribution of carbon in surface water was shifted to greater relative abundances of larger size fractions, suggesting a diagenetic sequence from macromolecular material to small refractory molecules. The average C:N ratios of particulate organic matter (POM) and HMW dissolved organic matter (DOM) were 7.7 and 16.7, respectively. Differences in C:N ratios between POM and HMW DOM were large and invariant with depth and geographic region, indicating that the aggregation of HMW DOM to form POM must be of minor significance to overall carbon dynamics. The stable carbon isotope composition (δ¹³C) of POM averaged −22.7%. in surface water and −25.2%. in subsurface water. Several possible explanations for the observed isotopic shift with depth were explored, but we were unable to discern the cause. The δ¹³C of HMW DOM samples was relatively constant and averaged −21.7%., indicating a predominantly marine origin for this material. The δ¹⁵N values of POM were highly variable (5.8–15.4%.), and the availability of nitrate in surface waters appeared to be the major factor influencing δ¹⁵N values in the equatorial Pacific. In the upwelling region nitrate concentrations were relatively high and δ¹⁵N values of POM were low, whereas to the north and south of the upwelling nitrate concentrations were low and δ¹⁵N values were high. The δ¹⁵N values of HMW DOM reflected the same trends observed in the POM fraction and provided the first such evidence for biological cycling of dissolved organic nitrogen (DON). Using the observed δ¹⁵N values and an estimate of meridional advection velocity, we estimated a turnover time of 0.3 to 0.5% day⁻¹ for HMW DON. These results suggest a major role for DON in the upper ocean nitrogen cycle.     

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze River) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0–2 cm) were 5–10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C₂₆-C₃₃ long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC₁₅ to nC₂₂ compounds. Long-chain (>C₂₀) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (<C₂₀) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk δ ¹³C_TOCTOC. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.