土壤胡敏素研究进展

土壤有机质是土壤的重要组成部分,在土壤肥力和生态环境等方面都具有重要作用.作为土壤有机质主体的腐殖物质的研究,一直受到各国学者的普遍重视.在土壤腐殖物质3组分中,以往的研究主要集中于可溶性的胡敏酸和富里酸,而对不溶性的胡敏素则较少涉及.从分离、结构和作用3个方面,综述了土壤胡敏素的研究现状和最新进展,并对今后的研究方向进行了展望,以促进胡敏素研究的继续深入开展.提出近期的研究重点主要包括:(1)比较不同分离方法获得的土壤胡敏素的差异,以达到方法上的可比性和统一性,同时提出更适宜的分离方法;(2)通过多种分析测试手段的相互补充验证,以获得对土壤胡敏素结构本质更加明确、清晰和深入的认识;(3)加强土壤胡敏素肥力和环境作用的研究,尤其应重视从分子水平上探明其构效关系,为生产实践和应用提供理论依据.     

Characterization of organic matter in a forest soil of coastal British Columbia by NMR and pyrolysis-field ionization mass spectrometry

Organic matter in the soil profile under a young Douglas-fir stand in coastal British Columbia was characterized by examining intact samples of fresh litterfall and organic horizons (LF, H), and fractions (floatables, humic acid [HA], fulvic acid [FA], humin [HU]) from the three mineral horizons (Ae, Bm, BC). Some 30–40% of the carbon in the mineral horizons was found in poorly-decomposed plant material floatable in water, a fraction whose characteristics changed little with depth, and which contained over 1% Fe. The proportion of soil C in HA plus FA was approximately 8%, but the ratio of C in FA/HA increased with depth. Solid-state ¹³C NMR spectra of litterfall, LH and H samples showed effects of decomposition, in particular a decrease in 0-alkyl C from litterfall to LH to H, and degradation of resolution from LF to H. For the mineral soil fractions, both floatables and de-ashed HU (HU_d prepared by HCl/HF treatment) indicated high levels of the original plant biopolymers, including a large alkyl component. Solution ¹³C spectra of the HAs from mineral horizons showed little difference with depth, except that peaks due to lignin were more pronounced for the Bm HA. The NMR spectra of FAs were high in 0-alkyl and carboxyl C. Pyrolysis-field ionization mass spectrometry confirmed and extended the results from NMR and chemical analyses, in particular demonstrating the accumulation of suberin in some fractions and the leaching and decomposition of lignin components with increasing depth in the mineral horizons. The general features of the HA, FA and HU_d from this forest soil, and the effects of decomposition and pedogenesis were similar to those widely found for agricultural and forest soils. However, the accumulation of suberin, and the leaching and decomposition of lignin are particularly associated with forest soils. The low proportion of soil C in HA and FA, and the high proportion in poorly decomposed, iron-rich plant fragments suggest that decomposition is somewhat limited at this site, which is classified as having low fertility. The high accumulations of alkyl C from suberin may also indicate, or contribute to inhibition of decomposition.     

Impact of Humin on Soil Adsorption and Remediation of Cd(II), Pb(II), and Cu(II)

In situ immobilization constitutes a promising technology for the mitigation of contaminants, through the reduction of metal bioavailability and mobility. This study investigated the adsorption isotherms and kinetic characteristics of humin extracted from peat soils. We also studied the influences of the pH, ionic strengths, and soluble organic matter concentrations of soil solutions on the adsorptive properties of humin, and compared its ability to detoxify potentially toxic metals in both actual and simulated soil solutions. The study results indicated that humin contains a massive population of oxygen-containing functional groups. Its adsorption capacity for Pb(II) was greater than that for Cu(II), which exceeded that for Cd(II). The adsorption of humin for Pb(II) conformed to the Freundlich model, while the adsorption of humin for Cd(II) and Cu(II) followed the Langmuir model. The adsorption kinetics of humin with respect to potentially toxic metals aligned well with second-order kinetics equations. As the pH was elevated, the potentially toxic metal adsorption by humin increased rapidly. Electrolyte ions and tartaric acids in solution both inhibited the adsorption of potentially toxic metals by humin, and its ability to inactivate potentially toxic metals. This was shown to be improved in actual field soil solutions in contrast to simulated soil solutions.     

Molecular characterization of Cladium peat from the Florida Everglades: biomarker associations with humic fractions

The accumulation and preservation of peat soils in Everglades freshwater marshes and mangrove swamps is an essential process in the ecological functioning of these ecosystems. Human intervention and climate change have modified nutrient dynamics and hydroperiod in the Everglades and peat loss due to such anthropogenic activities is evident. However, not much is known on the molecular level regarding the biogeochemical characteristics, which allow peat to be preserved in the Everglades. Lipid biomarkers trapped within or bound to humic-type structures can provide important geochemical information regarding the origin and microbial transformation of OM in peat. Four lipid fractions obtained from a Cladium peat, namely the freely extractable fraction and those associated with humin, humic acid, and fulvic acid fractions, showed clear differences in their molecular distribution suggesting different OM sources and structural and diagenetic states of the source material. Both, higher plant derived and microbial lipids were found in association with these humic-type substances. Most biomarker distributions suggest an increment in the microbial/terrestrial lipid ratio from the free to humin to humic to fulvic fractions. Microbial reworking of lipids, and the incorporation of microbial biomarkers into the humic-type fractions was evident, as well as the preservation of diagenetic byproducts. The lipid distribution associated with the fulvic acids suggests a high degree of microbial reworking for this fraction. Evidence for this 3D structure was obtained through the presence of the relatively high abundance of α,ω-dicarboxylic acids and phenolic and benzenecarboxylic compounds. The increment in structural complexity of the phenolic and benzencarboxylic compounds in combination with the reduction in the carbon chain length of the dicarboxylic acids from the free to fulvic fraction suggests the latter to be structurally the most stable, compacted and diagenetically altered substrate. This analytical approach can now be applied to peat samples from other areas within the Everglades ecosystem, affected differently by human intervention with the aim to assess changes in organic matter preservation.     

Turnover of14C-labelled oat residues and small molecular organic compounds in two soils under different levels of mineral nutrition

Mineralization and redistribution of carbon from¹⁴C-labelled oat shoots and [¹⁴C(U)] labelled glucose, leucine, acetate and phenylacetate were studied in light loamy sand and medium clay loam under different levels of mineral nutrition. Losses of mineralized¹⁴C as CO₂ were greater in the sandy soil than in the clay soil. NPK and NPK+Ca fertilization increased the rates of decay of the introduced plant organic matter. Among the small molecular organic compounds glucose was degraded fastest and phenylacetate slowest. Incorporation of radioactive carbon into humus fractions varied and depended on the nature of the compound introduced and on the soil type. Carbon of glucose, phenylacetate and acetate was mainly incorporated into fulvic acids, whereas¹⁴C of leucine was almost evenly distributed between humic and fulvic acids and¹⁴C of oat residues in fulvic acids and humin fractions. There was significantly higher incorporation of¹⁴C into humic acids and lower incorporation into humins in the sandy soil compared to the clay soil. NPK+Ca decreased the conversion of¹⁴C from phenylacetate and acetate to bitumens and increased its content in humic acids, particularly in the clay soil. The incorporation of¹⁴C from phenylacetate to humins benefitted from mineral fertilization during the first 30 days of the experiment in both soils.     

DIFFERENCES IN PAH DESORPTION AND SEDIMENT ORGANIC MATTER COMPOSITION BETWEEN NON-VEGETATED AND RECENTLY VEGETATED FUEL-OILED SEDIMENTS

We assessed the desorption behavior of pyrene, chrysene, phenanthrene, and tri-alkylated (C₃) phenanthrene/anthracenes for non-vegetated and recently vegetated (< 2 yrs) fuel-oiled sediments collected from the Indiana Harbor Canal (IHC), Gary, IN. Bulk sediment and humin were analyzed for PAH concentrations, organic matter composition, and PAH desorption behavior. PAH desorption isotherms and kinetics were determined using batch aqueous extractions and a two compartment, first-order kinetic model. Vegetated sediments contained more plant carbon and were more nonpolar and less oxidized than non-vegetated sediments. Desorption kinetics indicated that PAH desorption was primarily controlled by a slow PAH-desorbing fraction (F₂) of IHC sediments. However, in vegetated sediments, particularly humin, PAH release from a faster PAH-desorbing fraction (F₁) increased as did the rates (k₂) of PAH desorption from the dominant slow PAH-desorbing fraction (F₂). We propose that vegetation provides aliphatic, nonpolar carbon to IHC sediments that facilitates more rapid PAH desorption from bulk sediment and humin.