Nitrogen and phosphorus mineralization in sediments of Taihu Lake after the removal of light fraction organic matter

Mineralization of organic matter (OM) in sediment is crucial for biogeochemical cycle of nitrogen (N) and phosphorus (P) in lake ecosystem. Light fraction OM (LFOM) is a reactive pool in sediment and is considered as labile fraction contributing to N and P cycling. In our study, the effect of LFOM on the process and characteristics of N and P mineralization in sediments of Taihu Lake were investigated with 77-day waterlogged incubation plus intermittent leaching at 27°C. Sediments from Yuantouzhu (Y) and Gonghu (G) were used, which were removed the LF. Results indicated that the organic nitrogen mineralized ranged from 14.3 to 19.5% of total nitrogen (193.49–378.93 mg kg⁻¹ sediment) and the organic phosphorus mineralized ranged from 5.7 to 7.9% of total phosphorus (19.86–60.65 mg kg⁻¹ sediment). The heavily polluted sediment had a higher mineralization rate and net mineral-N and mineral-P than slightly polluted sediment. LF stimulated the initial amounts of inorganic N and P and also can be the potential source for mineralization. After the LFOM removal, the net mineral-N of Y and G decreased 116.47 mg kg⁻¹ sediment and 48.03 mg kg⁻¹sediment, respectively, and the net mineral-P decreased 2.67 mg kg⁻¹sediment for Y and 4.82 mg kg⁻¹sediment for G. Two models were used to fit the observed mineral-N data vs. incubation days using a non-linear regression procedure: one is the effective cumulated temperature model, a thermodynamic model which assumes that N mineralization is affected by temperature; the other is the single first-order exponential model, which is a dynamic model. Based on root mean square error values for the two models, the effective cumulated temperature model made a better prediction of N mineralization than the other model for all the four treatments. The single first-order exponential model underestimated N mineralization during the first 14 days and the last 21 days, and overestimated it in the other days during the 77-day incubation. This indicated that temperature was the primary factor influencing N mineralization and the amount of mineral-N were correlated significantly with the effective cumulated temperature (T ≥ 15°C) and incubation time when waterlogged incubation plus intermittent leaching was used.     

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.     

In situ adsorption of mercury,methylmercury and other elements by iron oxyhydroxides and organic matter in lake sediments

Samples of authigenic material, sediment overlying water and oxic surface sediment (0–0.5-cm depth) from a perennially oxygenated lacustrine basin were analysed to investigate which solid phases are important for binding a suite of trace elements (Ag, As, Ca, Cd, Cu, Hg, In, methylmercury (MeHg), Mg, Mo, Pb, Sb and Zn). The authigenic material, which was collected with inert Teflon sheets deployed for several years across the sediment–water interface, contained mainly poorly crystallized Fe oxyhydroxides and natural organic matter, presumably humic substances derived from the watershed. Manganese oxyhydroxides were not present in the collected authigenic material due to the slightly acidic condition (pH = 5.6) of the lake that prevents the formation and recycling of these compounds. Conditional equilibrium constants for the adsorption of cationic (K_Fe–M) and anionic (K_Fe–A) trace elements onto the authigenic Fe oxyhydroxides were estimated from their concentrations in the authigenic material and in bottom water samples. These field-derived values of K_Fe–M and K_Fe–A were compared with those predicted by the surface complexation model, using laboratory-derived intrinsic adsorption constants and the water composition at the study site. Equilibrium constants (K_POM–M) were also calculated for the adsorption of the cationic trace elements onto the humic substances contained in the diagenetic material. The field-derived values of K_POM–M were compared to those predicted by the speciation code WHAM 6 for the complexation of the trace elements by dissolved humic substances in the lake. Combining the results of the present study with those on the distributions of trace elements in the porewater and solid-phase sediments reported in previous studies at the same site, it was determined whether the trace elements bind preferentially to Fe oxyhydroxides or natural organic matter in oxic sediments. The main inferences are that the anionic trace elements As, Mo and Sb, as well as the cationic metal Pb are preferentially bound to the authigenic Fe oxyhydroxides whereas the other trace elements, and especially Hg and MeHg, are preferentially bound to the humic substances.     

Diagenesis of vascular plant organic matter components during burial in lake sediments

Diagenetic changes are difficult to distinguish from variations in sources of organic matter to sediments. Organic geochemical comparisons of samples of wood, bark, and needles from a white spruce (Picea glauca) living today and one buried for 10,000 years in lake sediments have been used to identify the effects of diagenesis on vascular plant matter. Important biogeochemical changes are evident in the aged spruce components, even though the cellular structures of the samples are well preserved. Concentrations of total fatty acids dramatically diminish; unsaturated and shorter chainlength components are preferentially lost from the molecular distributions. Concentrations of total alcohols are similar in the modern and 10,000-year-old wood and bark but markedly lowered in the aged needles. Hydrocarbon concentrations and distributions show little diagenetic change in the 10,000-year-old plant materials. Cellulose components in the wood decrease relative to lignin components, although both types of materials remain in high concentration in comparison to other organic components. Aromatization of abietic acid proceeds more rapidly in buried spruce wood than in bark; retene is the dominant polyaromatic hydrocarbon in the aged wood. In contrast to the variety of changes evident in molecular compositions, neither ¹³C values nor C/N ratios differ significantly in the bulk organic matter of modern and aged spruce components.     

Effects of organic matter heterogeneity on sorption and desorption of organic contaminants by soils and sediments

This review highlights the major progress over the last decade on characterization of geochemically heterogeneous soil/sediment organic matter (SOM) and the impacts of SOM heterogeneity on sorption and desorption of hydrophobic organic contaminants (HOCs) under equilibrium and rate limiting conditions. Sorption and desorption by soils and sediments are fundamental processes controlling fate and transport of less polar and nonpolar organic pollutants in surface aquatic and groundwater systems. Recent studies have shown that soils and sediments exhibit an array of HOC sorption phenomena that are inconsistent with an early partition model based on an assumption of homogeneous gel-like SOM. Increasing data have revealed that isotherm nonlinearity, varied sorption capacity, sorption–desorption hysteresis, and slow rates of sorption and desorption are characteristics for HOC sorption by soils and sediments. These phenomena have been shown to result from different types of condensed SOM that exhibit capacity limiting sorption processes. Recent findings of glass transition phenomena and the nonlinear HOC sorption by humic acids provide a scientific foundation for drawing an analogy between humic acids and synthetic organic polymers that supports a dual mode model for sorption by soils and sediments. Humic acid is glassy or rigid at temperatures lower than its glass transition temperature and exhibits relatively nonlinear sorption isotherms for HOCs. Fractionation and quantification of SOM indicate that soils and sediments contain significant amounts of black carbon and kerogen of different origins. These particulate organic materials have rigid 3-dimensional structures and are often less polar compared to humic substances. Limited studies show that black carbon and kerogen exhibit nonlinear sorption for HOCs and may dominate the overall nonlinear sorption by soils and sediments.     

Effects of photoirradiation on the adsorption of dissolved organic matter to goethite

The effects of photoirradiation of dissolved organic matter (DOM) on its subsequent adsorption to the Fe(III)oxyhydroxide mineral goethite were investigated at 22°C in 0.10 mol L⁻¹ NaClO₄ solutions at pH 3.5 and 5.5, Photoirradiation of DOM decreased the abundance of high molecular-weight components and formed new lower molecular-weight components, including low molecular weight carboxylic acids (i.e., formic, malonic, and acetic acids). Adsorption of non-irradiated DOM decreased from pH 3.5 to 5.5 and was dominated by the intermediate molecular weight (1251-3750 Da) fraction, although the 451-1250 and 3751-11350 Da fractions also contributed to adsorption at pH 3.5. Irradiation resulted in a substantial decrease in DOM adsorption affinity at pH 3.5, primarily due to loss of components in the 1251-3750 and 3751-11350 Da fractions. Irradiation resulted in only a small decrease in DOM adsorption affinity at pH 5.5; the loss of components in the 3751-11350 Da fraction upon irradiation had little effect on adsorption because they played little or no role in the non-irradiated sample at this pH. Irradiation of DOM also affected its interactions with Fe in solution and the solution iron(II)/iron(III) speciation. The combined effects of irradiation followed by adsorption produced DOM that was lower in molecular weight and had a decreased UV-Vis absorptivity than either process, alone. Together, these two processes are likely to have important environmental consequences in terms of UV penetration of surface waters, contaminant mobility, and DOM bioavailability.     

Influence of the natural organic matter in the removal of caffeine from water by fixed-bed column adsorption

The removal of caffeine from tap water by F-400 granular activated carbon in fixed-bed adsorption experiments was carried out. Textural and chemical characterization of the adsorbent through N₂ adsorption–desorption isotherms, Fourier transform infrared spectrometry, isoelectric point determination and scanning electron microscopy studies was developed in studies previously reported. Caffeine breakthrough curves and total organic carbon profiles at different operation conditions (inlet concentration, volumetric flow rate and mass of adsorbent) were obtained. These experimental results showed a displacement of the natural organic matter from the active sites exerted by caffeine molecules due to their higher affinity to the surface carbon. This behavior led to an overshooting, a local outlet natural organic matter concentration higher than the feed quantity. A competitive effect seems to be observed in the removal of the target compound, decreasing the efficiency of the process. Axial dispersion coefficients and dimensionless numbers were estimated for the caffeine removal onto F-400 activated carbon. Therefore, the regeneration of the adsorbent by adsorption–desorption cycles was studied.     

Mineral phases formed in anoxic sediments by microbial decomposition of organic matter

Microbial decomposition of organic matter in recent sediments of the Landsort Deep—an anoxic basin of the central Baltic Sea—resulted in the formation of a characteristic assemblage of authigenic mineral precipitates of carbonates, sulfides. phosphates and amorphous silica, The dominant crystalline phases are a mixed Mn-carbonate [(Mn_0.85Ca_0.10Mg_0.05)CO₃]. Mn-sulfide [MnS] and Fecarbonate [FeCO₃]. Amorphous Fe-sulfide [FeS]. Mn-phosphate [Mn₃(PO₄)₂] and a mixed Fe-Ca-phosphate [(Fe_0.86Ca_0.14)₃(PO₄)₂] were identified by their chemical compositions only. The variability in composition of these solid phases and their mode of occurrence as a co-existing assemblage constrains the conditions and solution composition from which they precipitated. Estimates of activities for dissolved Fe. Mn. PO₄, CO₃ and S in equilibrium with such an assemblage are close to those found in recent anoxic interstitial water-sediment systems. It is important to have detailed knowledge of the composition and stability conditions of these solid precipitates in order to refine stoichiometric models of interstitial nutrient regeneration in anoxic sediments.     

Nanoparticles in natural systems II: The natural oxide fraction at interaction with natural organic matter and phosphate

Information on the particle size and reactive surface area of natural samples and its interaction with natural organic matter (NOM) is essential for the understanding bioavailability, toxicity, and transport of elements in the natural environment. In part I of this series (Hiemstra et al., 2010), a method is presented that allows the determination of the effective reactive surface area (A, m²/g soil) of the oxide particles of natural samples which uses a native probe ion (phosphate) and a model oxide (goethite) as proxy. In soils, the natural oxide particles are generally embedded in a matrix of natural organic matter (NOM) and this will affect the ion binding properties of the oxide fraction. A remarkably high variation in the natural phosphate loading of the oxide surfaces (Γ, μmol/m²) is observed in our soils and the present paper shows that it is due to surface complexation of NOM, acting as a competitor via site competition and electrostatic interaction. The competitive interaction of NOM can be described with the charge distribution (CD) model by defining a ≡NOM surface species. The interfacial charge distribution of this ≡NOM surface species can be rationalized based on calculations done with an evolved surface complexation model, known as the ligand and charge distribution (LCD) model. An adequate choice is the presence of a charge of −1 v.u. at the 1-plane and −0.5 v.u. at the 2-plane of the electrical double layer used (Extended Stern layer model).The effective interfacial NOM adsorption can be quantified by comparing the experimental phosphate concentration, measured under standardized field conditions (e.g. 0.01 M CaCl₂), with a prediction that uses the experimentally derived surface area (A) and the reversibly bound phosphate loading (Γ, μmol/m²) of the sample (part I) as input in the CD model. Ignoring the competitive action of adsorbed NOM leads to a severe under-prediction of the phosphate concentration by a factor ∼10 to 1000. The calculated effective loading of NOM is low at a high phosphate loading (Γ) and vice versa, showing the mutual competition of both constituents. Both constituents in combination usually dominate the surface loading of natural oxide fraction of samples and form the backbone in modeling the fate of other (minor) ions in the natural environment.Empirically, the effective NOM adsorption is found to correlate well to the organic carbon content (OC) of the samples. The effective NOM adsorption can also be linked to DOC. For this, a Non-Ideal Competitive adsorption (NICA) model is used. DOC is found to be a major explaining factor for the interfacial loading of NOM as well as phosphate. The empirical NOM-OC relation or the parameterized NICA model can be used as an alternative for estimating the effective NOM adsorption to be implemented in the CD model for calculation of the surface complexation of field samples. The biogeochemical impact of the NOM-PO₄ interaction is discussed.     

A rapid estimation of organic carbon in silty lake sediments

A rapid and convenient method is described for the estimation of active organic carbon in silty lake sediments collected in regional geochemical surveys. The method utilizes measurement of optical density at 500 nm, of a 4 M nitric acid ? 0.1 M hydrochloric acid leach of a sediment sample and has a precision of ± 26% as determined from separate replicate analyses. An attractive feature of the method lies in its use of the same leach solution on which atomic absorption analyses of trace metals may be made.     

The distribution and source of organic matter in reservoir sediments

The bottom sediments of two reservoirs, one with significant river sediment input and one without, were analyzed for organic matter content. Lake Texoma sediments average 1.0% organic carbon, of which 0.26% organic carbon is deposited by the river sediments of the Red and Washita River deltas. In Fort Gibson reservoir, where there is minimal river sediment input, the organic carbon averages 1.2% and is deposited with a strong correlation to water depth (+0.9). There is a significant difference between the C/N ratio of Lake Texoma sediments (11.5) and Fort Gibson sediments (9.6). The higher C/N ratio is suggested to be a result of the larger input of terrestrial plant debris (with a high original C/N ratio) by the rivers draining into Lake Texoma and the relatively high resistance of the lignin material in the plant debris to decomposition in the reservoir sediments.     

Rapid sampling of organic matter in flooded soils and sediments

Estuaries and Coasts - A coring system using a compressed air supply and a sediment shaking procedure using a soil dispersant are described which greatly simplify and shorten the task of...     

Trace metals in oxic lake sediments: possible adsorption onto iron oxyhydroxides

Apparent overall equilibrium constants for the adsorption of Cd, Cu, Ni, Pb and Zn onto natural iron oxyhydroxides have been calculated from the partitioning of these trace metals in oxic lake sediments and the in situ measurement of trace metal concentrations in the associated pore waters. Such values obtained from lakes of various pH located on the Precambrian Shield, in the area of Sudbury, Ontario, are compared with equilibrium constants obtained for the adsorption of the trace metals onto iron oxyhydroxides in well-defined media.The field data are consistent with laboratory experiments reported in the literature and with theory. Both the influence of pH upon adsorption and the binding strength sequence observed for the field data agree with theory. At high sediment pH values, the partitioning of Cd, Ni and Zn between the pore waters and the natural iron oxyhydroxides is similar to those reported in the literature for the adsorption of these metals at low surface coverage onto amorphous iron oxyhydroxides in a NaNO₃ medium; deviation from this simple model is however observed for Cu and Pb, presumably due to the competitive action of dissolved ligands. At low sediment pH values, the adsorption is much higher than predicted by the simple model and can be explained by the formation of ternary complexes with the iron oxyhydroxide surface.     

Effects of weathering on organic matter in shales

The most drastic changes of the organic geochemical parameters examined (organic carbon, soluble organic matter content and composition, δC¹³ insoluble organic matter) occur over the near-surface 3 m intervals of two shallow core holes drilled into outcrops of the Upper Cretaceous Mancos Shale in Utah. This observation is believed to reflect the effects of weathering under the semi-arid climate of the study area. Therefore, organic geochemical data obtained from analysis of surface samples should be interpreted with caution.     

苏州城市河道底泥对磷酸盐的吸附与释放特征

为了探讨苏州古城区河道底泥对磷酸盐的吸附-释放特征,文中分别从改变上覆水的pH值、底泥吸附-释放动力学和等温吸附实验三个方面进行了研究。结果表明:(1)随着上覆水pH值的增大,苏州河道底泥对磷的吸附量逐渐减小;(2)底泥对磷的吸附过程是一个复合动力学过程,通常包括快吸附和慢吸附两个过程。底泥对磷的快速吸附在2h内快速进行,之后为慢吸附过程,到6h左右,基本达到一种动态吸附平衡;底泥对磷释放的动力学过程也包括快释放和慢释放过程。底泥释放磷在1·5h内快速进行,之后进入慢释放过程,磷酸盐含量基本稳定,达到释放平衡;(3)底泥具有较大的吸附磷的能力。随着上覆水的磷酸盐浓度增高,底泥吸附磷酸盐的量也增加。上覆水与底泥的比值越大,底泥对磷的吸附率越小。     

The formation and detection of metal dispersion halos in organic lake sediments

The application of organic-rich lake sediment (gyttja) to exploration geochemistry is discussed. Gyttja was collected from some 42 lake sites in the Red Lake-Uchi Lake volcanic-sedimentary sequences.The existance of free sulphide ion in most gyttja is confirmed and theoretical calculations are used to define the approximate concentrations of sulphide ion which determine whether the accumulation of Cu⁺, Cu²⁺, Zn²⁺ and Fe²⁺ is by metal sulphide precipitation, organic complexing or both. These calculations show that in the sediments collected in this study, the accumulation of copper will probably be by metal sulphide formation, whereas for zinc, organic complexing and possibly sulphide precipitation are likely mechanisms.It is shown that the background concentrations of copper and zinc on a dry matter basis increase with the content of organic matter in the sediment and it is further shown that the quantity of interstitial water in the sediment increases linearly with the organic content. Also it is demonstrated that the organic matter in the sediment is dispersed in the interstitial water in approximately the same concentration irrespective of the sediment composition.On the assumption that copper sulphide colloids are dispersed in the interstitial water of the sediment, it is suggested that the copper content of gyttja should be expressed as μg/g interstitial water for meaningful interpretation. Similarly, the zinc content should be expressed relative to the organic matter content.The ability of reagents to selectively extract only chemically dispersed metals and not silicate lattice metals from gyttja is discussed.Both the analytical procedures and the interpretations are applied to the samples collected.     

Land-derived organic matter in surface sediments from the Gulf of Mexico

Lignin oxidation products and ¹³C/¹²C ratios were compared as indicators of land-derived organic matter in surface sediments from the western Gulf of Mexico. Whole sediments were reacted with cupric oxide to yield phenolic oxidation products that indicated the types and relative amounts of the lignins that were present.Measurements of lignin concentration and carbon isotope abundances both indicated a sharp offshore decrease of land-derived organic matter in most areas of the western Gulf. This decrease results primarily from mixing of terrestrial and marine organic matter. The terrestrially derived material in these sediments has a lignin content similar to that of grasses and tree leaves. Flowering plants contribute most of the sedimented lignin compounds. These lignins apparently occur in the form of well-mixed plant fragments that are transported to sea by rivers and deposited primarily on the inner continental shelf.     

Dissolved organic matter in pore water of carbonate sediments from Bermuda

Pore water samples from seven nearshore areas in Bermuda were obtained under in situ conditions and analyzed for dissolved organic carbon, dissolved carbohydrates, dissolved free amino acids and dissolved humic substances. The concentration of dissolved organic carbon is higher than in the overlying nearshore waters indicating significant diagenetic remobilization of carbon in these recently deposited carbonate sediments. Dissolved carbohydrates decrease with depth due to microbial utilization.     

Sulfate reduction and the nature of organic matter in estuarine sediments

The reduction of sulfate by sulfate reducing bacteria in the anoxic zone is an extremely important process during early diagenesis of marine sediments. Our data from Great Bay, NH reinforce the proposal that the rate of sulfate reduction is directly proportional to the reactivity of the organic matter or the amount of readily metabolizable organic matter present in the sediment and, hence, the source of the organic material in the anoxic zone. It appears that organic matter rich in marine organic remains is more easily degraded in the anoxic zone and that sulfate reduction rates can vary considerably in an estuarine system where many types of organic material may be deposited.