Characterization of Heterogeneities and Domains in Aquatic and Sedimentary Organic Matter by 1 H Spin Diffusion: Potential for Elucidating the Formation Mechanisms

Although the information on domains and heterogeneities of natural organic matter (NOM) can provide insights into its formation mechanisms, the appropriate solid-state NMR technique for measuring them is still lacking. The traditional technique requires mobility differences in NOM whereas NOM components are primarily rigid. We introduced a new 1H spin diffusion technique, 1H-13C two-dimensional heteronuclear correlation (2D HETCOR) NMR with 1H spin diffusion, for characterization of domains and heterogeneities in aquatic and sedimentary organic matter. It was achieved by collecting a series of 2D HETCOR spectra with a variable mixing time, tm\u27, and monitoring the transfer of magnetization from one component to another. The rate of magnetization transfer provided the information on domains and heterogeneities because the magnetization of small domains or heterogeneities equilibrated faster than that of larger ones. Three samples, International Humic Substances Society (IHSS) Suwannee River NOM, IHSS Suwannee River humic acid (HA), and a sedimentary HA, were used. Two model polymers, a random copolymer poly(styrene-n-butyl methacrylate) with 0.6-nm heterogeneity and a block copolymer polystyrene-b-poly(methyl methacrylate) with a domain size of 5 nm, were included for calibration. Within tm \u3c 100 µs, half equilibration was reached for all three NOM samples and poly(styrene-n-butyl methacrylate), indicating that they were heterogeneous. In contrast, the spin diffusion of polystyrene-b-poly(methyl methacrylate) with 5-nm domain was much slower. Unlike the traditional spin diffusion technique, this technique did not require the differential mobility in NOM and was suitable for investigating the domains and heterogeneities of NOM, which are mostly rigid. © 2011, by the American Society of Limnology and Oceanography, Inc

Compositions and Constituents of Freshwater Dissolved Organic Matter Isolated by Reverse Osmosis

Dissolved organic matter (DOM) from riverine and lacustrine water was isolated using a reverse osmosis (RO) system. Solid-state 13C nuclear magnetic resonance (13C NMR) was used to quantitatively evaluate the compositions and constituents of DOM, which are compared with previous investigations on marine DOM. Results indicated that concentration factor (CF) was a key metric controlling yield and sorption of DOM on the RO system. The sorption was likely non-selective, based on the 13C NMR and δ13C analyses. Carbohydrates and lipids accounted for 25.0–41.5% and 30.2–46.3% of the identifiable DOM, followed by proteins (18.2–19.8%) and lignin (7.17–12.8%). The freshwater DOM contained much higher alkyl and aromatic C but lower alkoxyl and carboxyl C than marine DOM. The structural difference was not completely accounted for by using structure of high molecular weight (HMW) DOM, suggesting a size change involved in transformations of DOM during the transport from rivers to oceans

Role of Extractable and Residual Organic Matter Fractions on Sorption of Phenanthrene in Sediments

Two sediments were demineralized and sequentially fractionated into extracted fractions [free lipid (FL), bound lipid (BL) and lignin (LG)] and residual fractions [free lipid free (FLF), bound lipid free (BLF) and lignin free (LGF)]. The sorption isotherms of phenanthrene (Phen) were examined to evaluate the importance of various fractions on sorption. A lignin extraction procedure was for the first time applied to separate the lignin or degraded lignin fraction from sediment organic matter (SOM). The extracted LG was similar to model lignin in terms of elemental ratios and sorption behavior. FL and LG fractions were quite important, as their contents were much higher than reported values. Phen sorption for the extracted fractions was almost linear, whereas that for the residual fractions was nonlinear, especially for LGF with n 0.56-0.63. As the different organic fractions were removed sequentially, sorption energy distribution on the residual sediment organic matter (SOM) became more heterogeneous. In addition, increasing sorption capacity for the residual fractions, except for BLF with its high polarity, suggested that more sorption sites on the SOM matrix became accessible to Phen. The sorption capacity for LGF was comparable to that of condensed SOM. The residual fraction LGF generally controlled the overall sorption at low Phen concentration, but the extractable fraction FL surpassed the former fraction at high Phen concentration, demonstrating the importance of condensed SUM in the sorption of hydrophobic organic compounds (HOCs) in sediments. (c) 2012 Elsevier Ltd. All rights reserved

Interaction Mechanism of Benzene and Phenanthrene in Condensed Organic Matter: Importance of Adsorption (Nanopore-Filling)

Although microporosity and surface area of natural organic matter (NOM) are crucial to mechanistic evaluation of the sorption process for nonpolar organic contaminants (NOCs), they have wrongly been estimated by the N2 adsorption technique. Nuclear magnetic resonance spectroscopy (13C NMR), and benzene, carbon dioxide, and nitrogen adsorption techniques were used to characterize structural and surface properties for different condensed NOM samples, which were related to the sorption behavior of phenanthrene (Phen). It was found that the revised Freundlich model by taking the chemical activity into account can well describe the isotherms for benzene and Phen. The benzene and Phen adsorption volumes for the coal samples are similar to or lower than the CO2-nanopore volumes. Adsorption volumes of both benzene and Phen are significantly related to the aliphatic carbon structure, and their correlation lines are nearly overlapped, suggesting that the nanopore filling for Phen and benzene on the investigated samples is the dominating mechanism, and also is not affected by water molecules. The entrapment of benzene and/or the pore deformation in the NOM nanopore are likely responsible for the observed hysteresis of benzene. The above results demonstrate that Phen and benzene adsorption on the condensed NOM is closely associated with the aliphatic carbon structure of the investigated samples

Effects of Root-Zone Temperature and N, P, and K Supplies on Nutrient Uptake of Cucumber (Cucumis sativus L.) Seedlings in Hydroponics

The nutrient uptake and allocation of cucumber (Cucumis sativus L.) seedlings at different root-zone temperatures (RZT) and different concentrations of nitrogen (N), phosphorus (P), and potassium (K) nutrients were examined. Plants were grown in a nutrient solution for 30 d at two root-zone temperatures (a diurnally fluctuating ambient 10°C-RZT and a constant 20° C-RZT) with the aerial parts of the plants maintained at ambient temperature (10°C -30°C). Based on a Hoagland nutrient solution, seven N, P, and K nutrient concentrations were supplied to the plants at each RZT. Results showed that total plant and shoot dry weights under each nutrient treatment were significantly lower at low root-zone temperature (10°C-RZT) than at elevated root-zone temperature (20°C-RZT). But higher root dry weights were obtained at 10°C-RZT than those at 20°C-RZT. Total plant dry weights at both 10°C-RZT and 20°C-RZT were increased with increased solution N concentration, but showed different responses under P and K treatments. All estimated nutrient concentrations (N, P, and K) and uptake by the plant were obviously influenced by RZT. Low root temperature (10°C-RZT) caused a remarkable reduction in total N, P, and K uptake of shoots in all nutrient treatments, and more nutrients were accumulated in roots at 10 degrees C-RZT than those at 20°C-RZT. N, P, and K uptakes and distribution ratios in shoots were both improved at elevated root-zone temperature (20° C-RZT). N supplies were favorable to P and K uptake at both 10°C-RZT and 20°C-RZT, with no significantly positive correlation between N and P, or N and K uptake. In conclusion, higher RZT was more beneficial to increase of plant biomass and mineral nutrient absorption than was increase of nutrient concentration. Among the three element nutrients, increasing N nutrient concentration in solution promoted better tolerance to low RZT in cucumber seedlings than increasing P and K. In addition, appropriately decreased P concentration favors plant growth

Interaction Mechanism of Benzene and Phenanthrene in Condensed Organic Matter: Importance of Adsorption (Nanopore-Filling)

Although microporosity and surface area of natural organic matter (NOM) are crucial to mechanistic evaluation of the sorption process for nonpolar organic contaminants (NOCs), they have wrongly been estimated by the N2 adsorption technique. Nuclear magnetic resonance spectroscopy (13C NMR), and benzene, carbon dioxide, and nitrogen adsorption techniques were used to characterize structural and surface properties for different condensed NOM samples, which were related to the sorption behavior of phenanthrene (Phen). It was found that the revised Freundlich model by taking the chemical activity into account can well describe the isotherms for benzene and Phen. The benzene and Phen adsorption volumes for the coal samples are similar to or lower than the CO2-nanopore volumes. Adsorption volumes of both benzene and Phen are significantly related to the aliphatic carbon structure, and their correlation lines are nearly overlapped, suggesting that the nanopore filling for Phen and benzene on the investigated samples is the dominating mechanism, and also is not affected by water molecules. The entrapment of benzene and/or the pore deformation in the NOM nanopore are likely responsible for the observed hysteresis of benzene. The above results demonstrate that Phen and benzene adsorption on the condensed NOM is closely associated with the aliphatic carbon structure of the investigated samples

Long-Term Litter Decomposition Controlled by Manganese Redox Cycling

Litter decomposition is a keystone ecosystem process impacting nutrient cycling and productivity, soil properties, and the terrestrial carbon (C) balance, but the factors regulating decomposition rate are still poorly understood. Traditional models assume that the rate is controlled by litter quality, relying on parameters such as lignin content as predictors. However, a strong correlation has been observed between the manganese (Mn) content of litter and decomposition rates across a variety of forest ecosystems. Here, we show that long-term litter decomposition in forest ecosystems is tightly coupled to Mn redox cycling. Over 7 years of litter decomposition, microbial transformation of litter was paralleled by variations in Mn oxidation state and concentration. A detailed chemical imaging analysis of the litter revealed that fungi recruit and redistribute unreactive Mn2+ provided by fresh plant litter to produce oxidative Mn3+ species at sites of active decay, with Mn eventually accumulating as insoluble Mn3+/4+ oxides. Formation of reactive Mn3+ species coincided with the generation of aromatic oxidation products, providing direct proof of the previously posited role of Mn3+-based oxidizers in the breakdown of litter. Our results suggest that the litter-decomposing machinery at our coniferous forest site depends on the ability of plants and microbes to supply, accumulate, and regenerate short-lived Mn3+ species in the litter layer. This observation indicates that biogeochemical constraints on bioavailability, mobility, and reactivity of Mn in the plant–soil system may have a profound impact on litter decomposition rates

Mass Loss and Chemical Structures of Wheat and Maize Straws in Response to Ultravoilet-B Radiation and Soil Contact

The role of photodegradation, an abiotic process, has been largely overlooked during straw decomposition in mesic ecosystems. We investigated the mass loss and chemical structures of straw decomposition in response to elevated UV-B radiation with or without soil contact over a 12-month litterbag experiment. Wheat and maize straw samples with and without soil contact were exposed to three radiation levels: a no-sunlight control, ambient solar UV-B, and artificially elevated UV-B radiation. A block control with soil contact was not included. Compared with the no-sunlight control, UV-B radiation increased the mass loss by 14-19% and the ambient radiation by 9-16% for wheat and maize straws without soil contact after 12 months. Elevated UV-B exposure decreased the decomposition rates of both wheat and maize straws when in contact with soil. Light exposure resulted in decreased O-alkyl carbons and increased alkyl carbons for both the wheat and maize straws compared with no-sunlight control. The difference in soil contact may influence the contribution of photodegradation to the overall straw decomposition process. These results indicate that we must take into account the effects of photodegradation when explaining the mechanisms of straw decomposition in mesic ecosystems