Effect of organic matter on DOM sorption on lake sediments

The effect of organic matter on the sorption of dissolved organic matter (DOM) on lake sediments is critical to understanding the fate and transport of contaminants at the sediment–water interface in lake ecosystems. Results indicate that DOM sorption on sediment is largely due to ligand exchange between the DOM and hydroxyl groups, and the amount of DOC sorbed is a linear function of added DOC. With increasing organic matter content the sediment has lower binding strength, higher releasing ability for DOM, and the higher amount of DOM sorbed by sediment naturally. There was no clear difference before and after the sediment was treated with H₂O₂, but the constant b implied that after the sediments were treated DOC release was promoted. Organic matter in the sediment tends to impede the sorption of DOC and results in a remarkable decrease in DOC sorption rates.     

Temporal variability in sources of dissolved organic carbon in the lower Mississippi river

Here we report on the temporal changes in the composition of dissolved organic carbon (DOC) collected in the tidal freshwater region of the lower Mississippi River. Lignin-phenols, bulk stable carbon isotopes, compound-specific isotope analyses (CSIA) and ¹³C nuclear magnetic resonance (NMR) spectrometry were used to examine the composition of high molecular weight dissolved organic matter (HMW DOM) at one station in the lower river over 6 different flow regimes in 1998 and 1999. It was estimated that the annual input of DOC delivered to the Gulf of Mexico from the Mississippi River was of 3.1 × 10⁻³ Pg, which represents 1.2% of the total global input of DOC from rivers to the ocean. Average DOC and HMW DOC were 489 ±163 and 115 ± 47 μM, respectively. ¹³C-NMR spectra revealed considerably more aliphatic structures than aromatic carbons in HMW DOC. Lignin phenols were significantly ¹³C-depleted with respect to bulk HMW DOM indicating that C₄ grass inputs to the HMW DOM were not significant. It is speculated that C₄ organic matter in the river is not being converted (via microbial decay) to HMW DOM as readily as C₃ organic matter is, because of the association of C₄ organic matter with finer sediments. The predominantly aliphatic ¹³C NMR signature of HMW DOM suggests that autochthonous production in the river may be more important as a source of DOC than previously thought. Increases in nutrient loading and decreases in the suspended load (because of dams) in the Mississippi River, as well as other large rivers around the world, has resulted in significant changes in the sources and overall cycling of riverine DOC.     

Organic matter compositions and DOM release from the sediments of the shallow lakes in the middle and lower reaches of Yangtze River region, China

The contents of different organic matter components and dissolved organic matter (DOM) release kinetics of the sediments from the middle and lower reaches of the Yangtze River region were investigated, and their relationships discussed. The results show that organic C (OC) ranged from 8.14 to 43.65 g kg⁻¹, dissolved organic C (DOC) from 0.38 to 1.38 g kg⁻¹, active organic C (AOC) from 1.12 to 4.45 g kg⁻¹, heavy fraction organic C (HFOC) from 6.86 to 39.08 g kg⁻¹, accounting for 2.42-9.34%, 8.66-29.72% and 84.29-93.18% of OC, respectively. With increasing of OC content the ratios of DOC to OC and AOC to OC decreased. The contents of AOC, DOC, light fraction organic C (LFOC) and their contribution ratios to OC in studied sediments were higher than those reported in soils. The DOM release process of the studied sediments includes rapid and slow stages, and the rapid release occurred within 30 min, mainly in 5 min. The DOM release kinetic data in this investigation can be best fitted by the Power Function model. The correlations between total N (TN), total P (TP), OC, DOC, AOC, LFOC, HFOC and the DOM release kinetic parameters (k, c, a, b, rate₃₀) of the sediments were significant. There were also significant correlations between TN, TP, OC, DOC, LFOC and HFOC in sediments. So the DOM release from sediment was not only related to the OC content, but also related to the organic matter composition characteristics, especially the contents of DOC, AOC and LFOC.     

Sediment-water column exchange of persistent organic pollutants (PAH<Subscript>s</Subscript> and PCB<Subscript>s</Subscript>) and their transport vector in El Bey watershed,Tunisia

El Bey river, which drains 60% of the pollutant load of several urban cities in the northeast of Tunisia, provides a good example of the transfer of organic and metallic pollutants that result from industrial and urban activity, and can be used to show how these charges are transported and discharged into the Gulf of Tunis. Persistent organic pollutants (PAH and PCB) in dissolved, particulate matter, bed sediments, and three wastewater effluents in El Bey watershed were analyzed. PAH (∑14PAHs) concentration ranged from 0.248 to 9.955 mg L^?1 and from 0.836 to 28.539 mg L^?1 in dissolved and particulate fraction respectively. The particulate/dissolved partition coefficient value (Kd) was less than one which confirmed the affinity of PAH to be adsorbed. In sediment, the high-molecular weight PAHs were found principally with percentage between 50 and 100% witch present 239.99 to 5362.19 μg kg^?1, which is relatively higher in comparison with other estuaries river. Contrary to PAH patterns, PCB were bound to dissolve fraction. Kd _(PCB) value (Kd?>?1) reflected this affinity which is related to environment energy. The spatial distribution and profile of analyzed organic pollutants confirmed the direct impact of wastewater effluent on the organic pollution level in three compartment of El Bey watershed and his profiles suggested different transport patterns.     

Sources and bioavailability of polynuclear aromatic hydrocarbons in Galveston Bay, Texas

Oyster and sediment samples collected from six sites in Galveston Bay from 1986 to 1998 were analyzed for polynuclear aromatic hydrocarbons (PAHs). Total concentrations of parent PAHs in oysters ranged from 20 ng g⁻¹ at one site to 9,242 ng g⁻¹ at another and varied randomly with no clear trend over the 13 year period at any site. Concentrations of alkylated PAHs, which are indications of petroleum contamination, varied from 20 to 80,000 ng g⁻¹ in oysters and were in higher abundance than the parent PAHs, indicating that one source of the PAH contaminants in Galveston Bay was petroleum and petroleum products. Four to six ring parent PAHs, which are indicative of combustion source , were higher than those of 2–3 ring parent PAHs, suggesting incomplete combustion generated PAHs was another source of PAHs into Galveston Bay. Concentrations of parent PAHs in sediments ranged from 57 to 670 ng g⁻¹ and were much lower than those in oysters. Sediments from one site had a high PAH concentration of 5,800 ng g⁻¹. Comparison of the compositions and concentrations of PAHs between sediment and oysters suggests that oysters preferentially bioaccumulate four to six ring PAHs. PAH composition in sediments suggests that the sources of PAH pollution in Galveston Bay were predominantly pyrogenic, while petroleum related PAHs were secondary contributions into the Bay.     

Benthic fluxes and porewater concentration profiles of dissolved organic carbon in sediments from the North Carolina continental slope

Numerous studies of marine environments show that dissolved organic carbon (DOC) concentrations in sediments are typically tenfold higher than in the overlying water. Large concentration gradients near the sediment–water interface suggest that there may be a significant flux of organic carbon from sediments to the water column. Furthermore, accumulation of DOC in the porewater may influence the burial and preservation of organic matter by promoting geopolymerization and/or adsorption reactions. We measured DOC concentration profiles (for porewater collected by centrifugation and “sipping”) and benthic fluxes (with in situ and shipboard chambers) at two sites on the North Carolina continental slope to better understand the controls on porewater DOC concentrations and quantify sediment–water exchange rates. We also measured a suite of sediment properties (e.g., sediment accumulation and bioturbation rates, organic carbon content, and mineral surface area) that allow us to examine the relationship between porewater DOC concentrations and organic carbon preservation. Sediment depth-distributions of DOC from a downslope transect (300–1000 m water depth) follow a trend consistent with other porewater constituents (ΣCO₂ and SO₄²⁻) and a tracer of modern, fine-grained sediment (fallout Pu), suggesting that DOC levels are regulated by organic matter remineralization. However, remineralization rates appear to be relatively uniform across the sediment transect. A simple diagenetic model illustrates that variations in DOC profiles at this site may be due to differences in the depth of the active remineralization zone, which in turn is largely controlled by the intensity of bioturbation. Comparison of porewater DOC concentrations, organic carbon burial efficiency, and organic matter sorption suggest that DOC levels are not a major factor in promoting organic matter preservation or loading on grain surfaces. The DOC benthic fluxes are difficult to detect, but suggest that only 2% of the dissolved organic carbon escapes remineralization in the sediments by transport across the sediment-water interface.     

Fractionation of dissolved organic matter affected by polyvalent metal cations

The purpose of the study was to evaluate the influence of polyvalent cations known to form complexes with natural organic substances on the operational fractionation of dissolved organic matter (DOM) using XAD-8 adsorber resin. Dissolved organic matter solutions from a forest floor were treated with increasing concentrations of polyvalent metal cations (Ca²⁺, Al³⁺, Fe³⁺) at different pH levels. Then the concentrations of total dissolved organic carbon (DOC) and the distribution between hydrophilic and hydrophobic DOC were determined. The concentrations of total DOC decreased slightly when the C/metal ratio was less than 10, especially for Al and Fe. Hydrophilic DOC increased and hydrophobic DOC decreased with increasing concentrations of metal cations. Effects increased in the order Ca<Al<Fe and were more pronounced at low DOC concentrations and high pH values. The reason for the reduction of the DOC concentrations seemed to be the formation of insoluble metal–DOM complexes, while soluble metal–DOM complexes may induce an alteration of the distribution between hydrophilic and hydrophobic DOC. Thus, the polyvalent cations and their concentration need to be considered when DOM fraction distributions, determined with XAD-8 resin, of different waters are compared, especially at low DOC contents and high pH.     

Importance of CDOM Distribution and Photoreactivity in a Shallow Texas Estuary

This study examined freshwater discharge of dissolved organic matter (DOM) to the shallow Lavaca–Matagorda (LM) Bay estuarine system along the central Texas coast and investigated whether chromophoric DOM (CDOM) photochemical reactions have the potential to stimulate microbial activity within LM estuarine waters. Dissolved organic carbon (DOC) concentrations ranged from 3 to 10 mg C l⁻¹ and CDOM levels (reported as a ₃₀₅) ranged from 8 to 77 m⁻¹ during April and July, 2007, when the LM system was experiencing very high freshwater inputs. DOC and CDOM levels were well-correlated with salinities > 3, but exhibited considerable variability at salinities < 3. CDOM photobleaching rates (i.e., decrease in a ₃₀₅ resulting from exposure to solar radiation) for estuarine samples ranged from 0.014 to 0.021 h⁻¹, corresponding to photobleaching half-lives of 33–50 h. Our data indicate when Matagorda Bay waters photobleach; dissolved organic carbon utilization is enhanced perhaps due to enhanced microbial respiration of biologically labile photoproducts (BLPs). Net ecosystem metabolism calculations indicate that most of the LM system was net heterotrophic during our study. We estimate that BLP formation could support up to 20% of the daily microbial respiratory C demand in LM surface waters and combined with direct photochemical oxygen consumption could have an important influence on O₂ cycles in the LM system.     

The removal kinetics of dissolved organic matter and the optical clarity of groundwater

Concentrations of dissolved organic matter (DOM) and ultraviolet/visible light absorbance decrease systematically as groundwater moves through the unsaturated zones overlying aquifers and along flowpaths within aquifers. These changes occur over distances of tens of meters (m) implying rapid removal kinetics of the chromophoric DOM that imparts color to groundwater. A one-compartment input-output model was used to derive a differential equation describing the removal of DOM from the dissolved phase due to the combined effects of biodegradation and sorption. The general solution to the equation was parameterized using a 2-year record of dissolved organic carbon (DOC) concentration changes in groundwater at a long-term observation well. Estimated rates of DOC loss were rapid and ranged from 0.093 to 0.21 micromoles per liter per day (μM d^?1), and rate constants for DOC removal ranged from 0.0021 to 0.011 per day (d^?1). Applying these removal rate constants to an advective-dispersion model illustrates substantial depletion of DOC over flow-path distances of 200 m or less and in timeframes of 2 years or less. These results explain the low to moderate DOC concentrations (20–75 μM; 0.26–1 mg L^?1) and ultraviolet absorption coefficient values (a ₂₅₄?<?5 m^?1) observed in groundwater produced from 59 wells tapping eight different aquifer systems of the United States. The nearly uniform optical clarity of groundwater, therefore, results from similarly rapid DOM-removal kinetics exhibited by geologically and hydrologically dissimilar aquifers.     

The behaviour of dissolved organic material,iron and manganese in estuarine mixing

Fractionation by ultra-filtration of the dissolved organic material (DOM) in the River Beaulieu, with typical concentrations of dissolved organic carbon (DOC) of 7–8 mg C/l, showed it to be mainly in the nominal molecular weight range of 10³–10⁵, with 16–23% of the total DOC in the fraction > 10⁵. The molecular weight distribution of DOM in the more alkaline River Test (average DOC, 2 mg C/l) was similar. In the River Beaulieu water, containing 136–314 βg Fe/l in ‘dissolved’ forms, 90% or more of this Fe was in the nominal molecular weight fraction > 10⁵. Experiments showed that DOM of nominal molecular weight <10⁵ could stabilize Fe(III) in ‘dissolved’ forms. The concentrations of ‘dissolved’ Fe in the river water probably reflect the presence of colloidal Fe stabilized by organic material and this process may influence the apparent molecular weight of the DOM. Dissolved. Mn (100–136 βg/l) in the River Beaulieu was mainly in true solution, probably as Mn(II), with some 30% in forms of molecular weight greater than ca 10⁴.During mi xing in the Beaulieu Estuary, DOC and dissolved Mn behave essentially conservatively. This contrasts with the removal of a large fraction of the dissolved Fe (Holliday and LISS, 1976, Est. Coastal Mar. Sci. 4, 349–353). Concentrations of lattice-held Fe and Mn in suspended particulate material were essentially uniform in the estuary, at 3.2 and 0.012%, respectively, whereas the non-lattice held fractions decreased markedly with increase in salinity. For Mn the decrease was linear and could be most simply accounted for by the physical mixing of riverborne and marine participates, although the possibility that some desorption occurs is not excluded. The non-linear decrease in the concentration of non-lattice held Fe in particulates reflected the more complex situation in which physical mixing is accompanied by removal of material from the ‘dissolved’ fraction.     

Increasing Iron Concentrations in UK Upland Waters

Iron distributions in rainfall, streams, soils and groundwaters are described for the Upper River Severn catchment of mid-Wales. Iron is mainly supplied from within-catchment sources with highest concentrations occurring under reducing conditions. Iron concentrations have doubled over the past 20 years (~5.0 μg yr⁻¹ for the forest and ~3.7 μg yr⁻¹ for the moorland). For the forested sites, the gradients are particularly high post-1993. UK rivers/lakes monitored by the UK Acid Waters Monitoring Network show similar increases. Generally, Fe correlates with dissolved organic carbon (DOC). The greatest rates of Fe increase coincide with those for DOC. Thermodynamic modelling using WHAM/Model VI indicates that Fe(III) is mainly in microparticulate form (probably oxyhydroxides) apart from under reducing conditions. It is proposed that Fe increases for surface waters are associated with increased microparticulate Fe(III) due to stabilisation against aggregation by binding of DOM to its surface. The results relate to acidification declines and deforestation leading to land disturbance and wetter conditions within the soil. There will be greater acidification reversal following tree harvesting due to lowering of atmospheric SO_x scavenging and this may have resulted in the greater increase in Fe in the later years of the study.     

Electron accepting capacity of dissolved organic matter as determined by reaction with metallic zinc

Information about the chemical electron accepting capacity (EAC) of dissolved organic matter (DOM) is scarce owing to a lack of applicable methods. We quantified the electron transfer from metallic Zn to natural DOM in batch experiments at DOC concentrations of 10–100 mg-C L^− 1 and related it to spectroscopic information obtained from UV-, synchronous fluorescence, and FTIR- spectroscopy. The electron donating capacity of DOM and pre-reduced DOM was investigated using Fe(CN)₆³⁻ as electron acceptor. Presence of DOM resulted in release of dissolved Zn, consumption of protons, and slower release of hydrogen compared to reaction of metallic Zn with water at pH 6.5. Comparison with reaction stoichiometry confirmed that DOM accepted electrons from metallic Zn. The release of dissolved Zn was dependent on pH, DOC concentration, ionic strength, and organic matter properties. The reaction appeared to be completed within about 24 h and was characterized by pseudo first order kinetics with rate constants of 0.5 to 0.8 h^− 1. EAC per mass unit of carbon ranged from 0.22 mmol g^− 1 C to 12.6 mmol g^− 1 C. Depending on the DOM, a calculated 28–127% of the electrons transferred from metallic Zn to DOM could be subsequently donated to Fe(CN)₆³⁻. EAC decreased with DOC concentration, and increased with aromaticity, carboxyl, and phenolic content of the DOM. The results indicate that an operationally defined EAC of natural DOM can be quantified by reaction with metallic Zn and that DOM properties control the electron transfer. Shortcomings of the method are the coagulation and precipitation of DOM during the experiment and the production of hydrogen and dissolved Zn by reaction of metallic Zn with water, which may influence the determined EAC.     

Estimating the potential for submergence for two wetlands in the Mississippi River Delta

We used a combined field and modeling approach to estimate the potential for submergence for one rapidly deteriorating (Bayou Chitigue Marsh) and one apparently stable (Old Oyster Bayou Marsh) saltmarsh wetland in coastal Louisiana, given two eustatic sea level rise scenarios: the current rate (0.15 cm year⁻¹); and the central value predicted by the Intergovernmental Panel on Climate Change (48 cm by the year 2100). We also used the model to determine what processes were most critical for maintaining and influencing salt marsh elevation including, mineral matter deposition, organic matter production, shallow subsidence (organic matter decomposition + primary sediment compaction), deep subsidence, and sediment pulsing events (e.g., hurricanes). Eight years of field measurements from feldspar marker horizons and surface elevation tables revealed that the rates of vertical accretion at the Bayou Chitigue Marsh were high (2.26 (0.09) cm yr⁻¹ (mean ± SE)) because the marsh exists at the lower end of the tidal range. The rate of shallow subsidence was also high (2.04 (0.1) cm yr⁻¹), resulting in little net elevation gain (0.22 (0.06) cm yr⁻¹). In contrast, vertical accretion at the Old Oyster Bayou Marsh, which is 10 cm higher in elevation, was 0.48 (0.09) cm yr⁻¹. However, there was a net elevation gain of 0.36 (0.08) cm yr⁻¹ because there was no significant shallow subsidence. When these rates of elevation gain were compared to rates of relative sea level rise (deep subsidence plus eustatic sea level rise), both sites showed a net elevation deficit although the Bayou Chitigue site was subsiding at approximately twice the rate of the Old Oyster Bayou site (1.1 cm yr⁻¹ versus 0.49 cm yr⁻¹ respectively). These field data were used to modify, initialize, and calibrate a previously published wetland soil development model that simulates primary production and mineral matter deposition as, feedback functions of elevation. Sensitivity analyses revealed that wetland elevation was most sensitive to changes in the rates of deep subsidence, a model forcing function that is difficult to measure in the field and for which estimates in the literature vary widely. The model also revealed that, given both the current rate of sea level rise and the central value estimate, surface elevation at both sites would fall below mean sea level over the next 100 years. Although these results were in agreement with the field study, they contradicted long term observations that the Old Oyster Bayou site has been in equilibrium with sea level for at least the past 50 years. Further simulations showed that the elevation at the Old Oyster Bayou site could keep pace with current rates of sea level rise if either a lower rate for deep subsidence was used as a forcing function, or if a periodic sediment pulsing function (e.g., from hurricanes) was programmed into the model.     

Chemical characteristics and pollution sources of petroleum hydrocarbons and PAHs in sediments from the Beiluohe River,Northern China

To determine the degree of hydrocarbon contamination and the contribution of local petroleum industries to contaminant loadings in sediments from the Beiluohe River, China, 12 surface sediment samples were collected for geochemical analysis in 2005. Sediment samples were extracted by organic solvents, separated by silica gel column chromatography and the profiles of n-alkanes, biomarkers and polycyclic aromatic hydrocarbons (PAHs) in sediments were analyzed by gas chromatography with flame ionization detector and gas chromatography/mass spectroscopy. Concentrations of total hydrocarbons in the sediments varied from 12.1 to 3,761.5 μg g⁻¹ dry wt, indicating that most sediments in Beiluohe River was only slightly to moderately contaminated by hydrocarbons. Concentrations of PAHs for six samples (sum of 16 isomers) varied from 17.7 to 407.7 ng g⁻¹ dry wt and at present low levels of PAHs did not cause adverse biological effects in Beiluohe River sedimentary environment. PAH compositions, n-alkanes and biomarker profiles all suggested that there were different sources of contaminations in studied areas. n-Alkanes reflect two distinct sources: a fossil n-alkane series from crude oil at sites S40, S43, S87 and plantwax n-alkanes at sites S39 and S45. Judged by their PAH ratios, the sediments at site S15 were pyrolytic, sediments at S17 and S43 were petrogenic, and sediments at S39, S40 and S64 had a mixture source of pyrolytic and petrogenic.     

Terrigenous dissolved organic matter along an estuarine gradient and its flux to the coastal ocean

The contribution of terrigenous organic matter (TOM) to high molecular weight dissolved and particulate organic matter (POM) was examined along the salinity gradient of the Delaware Estuary. Dissolved organic matter (DOM) was fractionated by ultrafiltration into 1–30 kDa (HDOM) and 30 kDa–0.2 μm (VHDOM) nominal molecular weight fractions. Thermochemolysis with tetramethylammonium hydroxide (TMAH) was used to release and quantify lipids and lignin phenols. Stable carbon isotopes, fatty acids and lignin content indicated shifts in sources with terrigenous material in the river and turbid region and a predominantly algal/planktonic signal in the lower estuary and coastal ocean. Thermochemolysis with TMAH released significant amounts of short chain fatty acids (C₉–C₁₃), not seen by traditional alkaline hydrolysis, which appear to be associated with the macromolecular matrix. Lignin phenol distributions in HDOM, VHDOM and particles followed predicted sources with higher concentrations in the river and turbid region of the estuary and lower concentrations in the coastal ocean. TOM comprised 12% of HDOM within the coastal ocean and up to 73% of HDOM within the turbid region of the estuary. In the coastal ocean, TOM from high molecular weight DOM comprised 4% of total DOC. The annual flux of TOM from the Delaware Estuary to the coastal ocean was estimated at 2.0×10¹⁰ g OC year⁻¹ and suggests that temperate estuaries such as Delaware Bay can be significant sources of TOM on a regional scale.     

Effects of sugar cane monocultures on origin and characteristics of dissolved organic matter in the Manguaba lagoon in northeast Brazil

Brazil has extensive sugar cane monocultures, which significantly alter hydrogeochemical material fluxes. We studied dissolved organic matter (OM) fluxes in the Manguaba lagoon-estuary system, which drains a sugar cane monoculture-dominated hinterland and discharges into the Atlantic coastal ocean. The OM fluxes into the lagoon originate from baseflow, field runoff and sugar cane factory effluents. In the study, dissolved organic carbon (DOC) concentration, δ¹³C DOC and UV absorbance were analysed along a freshwater-seawater salinity gradient that encompasses river (DOC 9-11 mg l⁻¹, δ¹³C −22.2‰ to −25.5‰); lagoon (4-11 mg l⁻¹, −20.5‰ to −24.8‰); estuary (3-9 mg l⁻¹, −22.6‰ to −25.3‰) and coastal waters (1.64 mg l⁻¹, −21‰) with different intra-seasonal runoff conditions. We used the carbon isotope data to quantify the sugar cane derived DOC. Where river water meets brackish lagoon water, substantial loss of DOC occurs during rainy conditions, when suspended sediment from eroded fields in the river is very high. During dry weather, at much lower suspension levels, DOC increases, however, presumably from addition of photolysed resuspended sedimentary OM. In the estuary, mixing of DOC is strictly conservative. Ca. 1/3 of riverine DOM discharged into the lagoon has a sugar cane source. Within the lagoon on avg. 20% of the bulk DOM is comprised of sugar cane DOM, whereas during heavy rainfall the amount increases to 31%, due to intensified drainage flow and soil erosion. In the estuary, 14-26% is of sugar cane origin. The sugar cane-derived component follows the mixing patterns of bulk DOM.     

Insights into estuarine benthic dissolved organic carbon (DOC) dynamics using δC-DOC values, phospholipid fatty acids and dissolved organic nutrient fluxes

Benthic dissolved organic carbon (DOC) flux rates and changes in DOC isotope ratios, along with nutrient fluxes, phospholipid fatty acids concentration and carbon isotope ratios were measured in productive estuarine sediments over a diel cycle to determine the mechanisms driving benthic-pelagic coupling of DOC. There was uptake of DOC during the dark and efflux during the light at all sites. DOC uptake rates were related to benthic respiration (dark O₂ uptake) and effluxes were coupled to the trophic status (ratio of production to respiration) of the sediments. Highest uptake and efflux rates were observed at two high nutrient concentration sites. The DOC:DON ratio of water column dissolved organic matter (DOM) decreased during the dark and increased during the light indicating preferential uptake and release of carbon rich dissolved organic matter. The calculated carbon isotope ratio of the DOC taken up by the benthos was significantly more depleted than the bulk water column DOC pool, suggesting preferential uptake of selected components of the water column DOC pool. Generally the isotope ratio of the DOC released during the light was more enriched than that taken up during the dark, which suggests that the benthos has the potential to significantly alter the estuarine DOC pool. Uptake and efflux were coupled to respiration and algal grazing/mineralization, therefore increased nutrient loading may shift the composition of the estuarine DOC pool through changes in the magnitude of benthic DOC fluxes. A combination of biological (diel shifts in DOC production and consumption) and abiotic processes (flocculation) appear to be driving the observed benthic DOC dynamics at the study sites. This study was the first to measure carbon isotopic changes in the water column DOC pool due to benthic processes, and shows that the benthos can alter the estuarine DOC pool through diel differences in DOC uptake and efflux.     

Microelectrode Study of Oxygen Uptake and Organic Matter Decomposition in The Sediments of Xiamen Western Bay

Sediment cores were sampled from Xiamen Western Bay at five sites during the summer and winter of 2006 and Hg–Au microelectrodes were used to make on board measurements of the concentration gradients of dissolved oxygen, Mn²⁺, and Fe²⁺ within the sediments. The O₂ concentrations decreased sharply from about 200 μmol L⁻¹ in the bottom seawater to zero within a depth of a few millimeters into the sediment. Dissolved Mn²⁺ was detected below the oxic zones with peak concentrations up to 600 μmol L⁻¹, whereas dissolved Fe²⁺ had peak concentrations up to 1,000 μmol L⁻¹ in deeper layers. The elemental contents of organic carbon and nitrogen within the sediments were analyzed and their C/N ratios were in the range of 9.0 to 10.1, indicative of heavy terrestrial origin. Sediments from two sites near municipal wastewater discharge outlets had higher organic contents than those from the other sites. These high organic contents corresponded to shallow O₂ penetration depths, high dissolved Mn²⁺ and Fe²⁺ concentrations, and negative redox potentials within the sediments. This indicated that the high organic matter content had promoted microbial respiration within the sediments. Overall, the organic content did not show any appreciable decrease with increasing sediment depths, so a quadratic polynomial function was used to fit the curve of O₂ profiles within the sediments. Based on the O₂ profiles, O₂ fluxes across the seawater and sediment interface were estimated to be in the range 6.07 to 14.9 mmol m⁻² day⁻¹, and organic carbon consumption rates within the surface sediments were estimated to be in the range 3.3 to 20.8 mgC cm⁻³ a⁻¹. The case demonstrated that biogeochemistry within the sediments of the bay was very sensitive to human activities such as sewage discharge.     

Watershed Export Events and Ecosystem Responses in the Mission–Aransas National Estuarine Research Reserve, South Texas

While inputs from land are recognized as important resources supporting production in estuaries, the role that storm events play in resource delivery and the response of estuarine systems to pulsed inputs are less well appreciated. Temporal variations in (1) watershed export via the Mission and Aransas rivers and (2) nutrient and organic matter dynamics in Copano Bay were examined in the Mission?CAransas National Estuarine Research Reserve, south Texas. Inorganic nutrient, dissolved organic matter (DOM), and particulate organic matter (POM) concentrations in the rivers varied substantially with discharge, as did carbon and nitrogen stable isotope ratios of POM. Accounting for these variations was critical for calculating robust watershed export estimates. In Copano Bay, soluble reactive phosphorus, POM, and DOM remained elevated for several months following major runoff events, whereas inorganic nitrogen was rapidly depleted. Chlorophyll-a concentrations and POC-??¹³C in Copano Bay showed that increased POM concentrations were linked to enhanced in situ production.     

Understanding the enhanced aqueous solubility of styrene by terrestrial dissolved organic matter using stable isotope mass balance and FTIR

We present a new stable isotope mass balance method for measuring the enhanced aqueous solubility of specific organic compounds in the presence of natural dissolved organic matter (DOM). It involves interfacing a standard dissolved organic carbon (DOC) analyzer with a stable isotope ratio monitoring system, is applicable to a wide range of model organic compounds and can be tuned to provide maximum precision for a given range of compound solubility and initial natural DOC concentration. Using ¹³C-labeled styrene as a model compound, we applied the method to investigate the reactivity of Dismal Swamp DOM as a function of season, nominal molecular size and chemical composition as determined using Fourier Transform Infrared Spectroscopy (FTIR). The solubility enhancement of styrene ranged from 23% to 118% relative to deionized water, while DOC-normalized enhancements varied from about 0.04 to 0.35 μM styrene/μM DOC as a function of season and nominal molecular weight. Statistical analysis of FTIR spectra reveals a strong positive correlation between the styrene concentration and the carboxyl content of the natural DOM. Reactivity differences between high molecular weight (HMW), low molecular weight (LMW) and total DOM samples are consistent with potential variations in their higher order structures.