The lignin component of humic substances: Distribution among soil and sedimentary humic,fulvic, and base-insoluble fractions

Vanillyl, syringyl and cinnamyl phenols occur as CuO oxidation products of humic, fulvic and base-insoluble residual fractions from soils, peat and nearshore marine sediments. However, none of these lignin-derived phenols were released by CuO oxidation of deepsea sediment or its base-extractable organic fractions. Lignin analysis indicated that peat and coastal marine sediments contained significantly higher levels of recognizable vascular plant carbon (20–50%) than soils and offshore marine sediments (0–10%).Although accounting for less than 20% of the total sedimentary (bulk) lignin, lignin components of humic acid fractions compositionally and quantitatively resembled the corresponding bulk samples and baseinsoluble residues. Recognizable lignin, presumably present as intact phenylpropanoid units, accounted for up to 5% of the carbon in peat and coastal humic acids but less than 1% in soil humic acids. Fulvic acid fractions uniformly yielded less lignin-derived phenols in mixtures that were depleted in syringyl and cinnamyl phenols relative to the corresponding humic acid fractions.Within the vanillyl and syringyl families the relative distribution of acidic and aldehydic phenols is a sensitive measure of the degree of oxidative alteration of the lignin component The high acid/aldehyde ratios and the low phenol yields of soils and their humic fractions compared to peat and coastal sediments indicate extensive degradation of the lignin source material. Likewise, the progressively higher acid/aldehyde ratios and lower phenol yields along the sequence: plant tissues (plant debris)-humic acids-fulvic acids suggest that this pattern represents the diagenetic sequence for the aerobic degradation of lignin biopolymers.     

Metal distribution and nature of some Cu,Mn and V complexes in humic and fulvic acid fractions of soil organic matter

Organic matter from an arable soil derived from base rich parent material was extracted by alkali and fractionated on the basis of solubility in 0.1 N HCl, hot water and hot 6 N HCl and by selective adsorption on charcoal. The distribution of associated metals was determined and Cu had the largest proportion, 15%, associated with the organic matter. Moderate proportions of the total Al, Co, Ni, and V (3–8%) but only small amounts (?1%) of the Mn, Fe, Ti, Cr, Ba and Sr were extracted from the soil by alkali. The Fe and Ti were concentrated mainly in the humic fraction whereas Mn and V were both found largely in the fulvic acid.Electron paramagnetic resonance spectra of the various fractions were examined and attempts made to relate the spectra to the forms of some of the metals present. In the humic acid fraction Cu was present partly as a copper porphyrin-type complex but in the fulvic acid it was in some other complexed form. VO²⁺ occurred in complexed forms in the fulvic acid which were more covalent than VO²⁺ humic acid complexes, whereas the Mn²⁺ components of the humic and fulvic acids all had a high degree of ionicity.     

Influence of humic acid on bioavailability of heavy metals in sediments

The mimetic ocean environment and chemical method were used to research the bioavailability effect of humic acid on five heavy metals in sediment, including Cd, Cu, Zn, Pb and Ni. The sediment was separated into four containers with artificial seawater, and each of them had different concentrations of humic acid. The values of concentrations covered the whole range found in natural sediment （0.1%-10%）. According to the 48 hours LC50 of clam and distribution coefficient, metals were added in artificial seawater, and their speciation was determined at first and then after two days＇ incubation. It was found the bioavailability of heavy metals was reduced in the presence of humic acid. The obvious negative effect on Zn was observed, but the influence on Cd was not remarkable. In addition, the contents of Pb and Ni increased obviously in organic phase, and they are correlative with the concentrations of humic acid.     

Sedimentary humic acid and fulvic acid as surface active substances

Surface tension of sedimentary fulvic acid (FA) and humic acid (HA) with molecular weight from < 10,000 to > 300,000 was measured at 5°C and 25°C, over a wide range of concentrations (0.114-107.4 g/l) at pH 8. HA was in the form of sodium humate. Surface tension decreases with an increase in HA and FA concentration and both HA and FA were found to be surface active materials with FA exhibiting the lowest surface tension (31 dynes/cm).Plots of surface tension vs. log concentration gave two straight lines with a break at a certain concentration similar to surfactants. From the concentration at the break point, aggregation concentration (AGC) was determined. For HA with molecular weight above 10,000, the AGC decreased with an increase in molecular weight. The more hydrophobic the HA, the greater was the tendency to form aggregates. Surface excess (surface concentration) was determined (2.3 × 10^?10?5.5 × 10^?10mol/cn²) from the slope of the plot of surface tension vs. log concentration for concentrations lower than the AGC. Adsorption of HA into the surface layer increased with increasing molecular weight of HA.     

Sedimentary humic acid and fulvic acid as fluorescent organic materials

Fluorescence and absorption spectra of sedimentary humic acid (HA) and fulvic acid (FA), with molecular weights ranging from < 10,000 to >300,000, were measured at 20°C and pH 8. The maximum excitation and emission wavelengths of HA were longer than those of FA, being independent of molecular weight. The excitation and emission maxima can be utilized to differentiate between sedimentary HA and FA. It is suggested that the fluorophors in HA are of a higher molecular weight aromatic groups than those in FA.Smaller molecules were found to have a greater fluorescence than larger ones for sedimentary humic substances and this phenomenon is similar to those obtained for humic substances of terrestrial origin. The absorption coefficient (1/g/cm) of HA decreased, while that of FA increased with the increase in molecular weight. It was shown that fluorescence intensity per weight concentration unit of HA increases and that of FA decreases with increasing absorption coefficient.     

Relationships between heavy metals and iron oxides,fulvic acids,particle size fractions in urban roadside soils

Urban roadside soils are the “recipients” of large amounts of heavy metals from a variety of sources including vehicle emissions, coal burning waste and other activities. The behavior of heavy metals in urban roadside soils depends on the occurrence as well as the total amount. Accordingly, knowledge of the interactions between heavy metals and other constituents in the soil is required to judge their environmental impact. In this study, correlations of heavy metal concentrations (Pb, Zn, Cu, Ag, Se, Ni, Cr and Ba) to iron extracted using dithionite–citrate–bicarbonate (DCB) buffer (Fe_DCB), fulvic acids and particle size fractions were examined from the Xuzhou urban roadside soils. Heavy metals except for Cr and fulvic acids had a positive significant correlation with Fe_DCB, indicating these metals and fulvic acids are principally associated with the surfaces of iron oxides of the soils. Significant positive correlations were also found between the contents of fulvic acids and heavy metals, showing these heavy metals (especially for Cu, Ni and Cr) form stable complexes with fulvic acids. Such finding is of importance with regard to the increased mobilization of heavy metals, e.g., into freshwater ecosystems. Ag, Se and Cr are independent of particle size fractions because of their low concentrations of Ag and Se in the studied soils. Pb, Zn, Cu, Ba and Ag are mainly enriched in the finer soil particles (especially <16 μm).     

Comparison of soil humic and fulvic acids of similar molecular weight

Soil fulvic acids were compared with humic acid of similar molecular weight. The elementary composition, total carbohydrate content and ¹³C-NMR spectral features differentiate these fractions and leads to consideration of fulvic acid as a separate chemical entity.     

Relationship of chemical fractions of heavy metals with microbial and enzyme activities in sludge and ash-amended acid lateritic soil from India

The influence of metals, Cd, Cr, Cu, Ni, Pb and Zn, on the microbial biomass and enzyme activities of an amended acid lateritic soil were investigated under field conditions receiving a one-time application of 52 t ha^–1 of sludge, coal ash and their mixtures at 1:3, 1:1 and 3:1 proportions, and including control and chemical fertilizer treatment at crop-specific recommended doses. Paddies and peanuts were grown in the experimental plots and soil was sampled twice after 6 months and 1 year after amendment application. The heavy metals in the soil were fractionated using sequential extraction and the increments in their concentrations in amended soil with respect to the control were determined. Concentrations of Cd, Ni and Zn were determined to have increased in their mobile fractions and were more pronounced in soil collected during the second sampling, which was associated with a decrease in soil organic carbon. The size of the microbial biomass carbon and the soil enzyme activities increased with the addition of an amendment and was highest at equal proportions of coal ash and sludge. Further increase in the proportion of sludge resulted in a significant decrease in biomass carbon. Simple correlation revealed significant and strong negative relations of mobile fractions of Cd and Ni with the ratio between microbial biomass C and organic carbon in soil, while the organic carbon content and the pH were positively correlated. The microbial activities were determined to be sensitive to the concentrations of some heavy metals in mobile fractions and therefore indicated possibilities of being useful as indicators for evaluation of toxic effects of sludge-borne metals on soil organisms.     

Sorption of metals on humic acid

The sorption on humic acid (HA) of metals from an aqueous solution containing Hg(II). Fe(III), Pb, Cu, Al, Ni, Cr(III), Cd, Zn, Co and Mn, was investigated with special emphasis on effects of pH, metal concentration and HA concentration. The sorption efficiency tended to increase with rise in pH, decrease in metal concentration and increase in HA concentration of the equilibrating solution. At pH 2.4. the order of sorption was: Hg? Fe? Pb? CuAl ? Ni ? CrZnCdCoMn. At pH 3.7. the order was: Hg and Fe were always most readily removed, while Co and Mn were sorbed least readily. There were indications of competition for active sites (CO₂H and phenolic OH groups) on the HA between the different metals. We were unable to find correlations between the affinities of the eleven metals to sorb on HA and their atomic weights, atomic numbers, valencies, and crystal and hydrated ionic radii. The sorption of the eleven metals on the HA could be described by the equation $\text{Y =}\text{100}\text{[1 + exp ? (A + BX)]}$, where Y = % metal removed by HA; X = mgHA; and A and B are empirical constants.     

Molecular weight distribution,analytical and spectroscopic characterization of humic fractions sequentially isolated by organic solvents from a brown coal humic acid

A sequential fractionation procedure employing a series of selected mild organic solvents of different polarity has been applied for the isolation of chemically different organic fractions from a brown coal humic acid. Elemental composition, molecular weight distribution, i.r. and electron spin resonance analysis were carried out on the isolated humic fractions. They were characterized by: (a) a low polydispersity, (b) a decreasing aliphatic and increasing aromatic character along the series, (c) very different molecular weight which significantly correlated with E₄/E₆ ratios (particle aggregation and molecular association) and free radical concentrations (chemical and biochemical activity). Significant correlations were found between physico-chemical parameters of the isolated humic fractions, i.e. M_n, M_w, E₄/E₆ ratios, spins/g contents and the dielectric constants of the solvents used. This suggested the efficiency of the applied procedure in isolating chemically different organic fractions from the bulk, original humic acid.     

Mobility and bioavailability of selected heavy metals in coal ash- and sewage sludge-amended acid soil

A sequential extraction procedure has been used to study the changes in the distribution and mobility of Cd, Cr, Cu, Ni, Pb and Zn in an acid lateritic soil amended with alkaline coal ash and neutral sludge individually and with their mixture of equal proportions at 25, 50 and 75 Mg/ha application rates and grown in a crop with peanuts. A separate set of experiments consisting of the same treatments was repeated with the addition of lime at 2 Mg/ha. Increases in total heavy-metal levels with application of various amendments were mainly associated with increases in the insoluble and less mobile forms of metals except for Cd, which showed an increase in its exchangeable form. An increase in pH of the amended soil restricted the metal mobility in their labile forms and was more pronounced after liming the treatments. Positive yield responses were observed in the amended soil, the magnitude being higher in only sludge-applied treatments. The vegetative plant parts showed maximum accumulation of metals indicating a physiological barrier in the transfer of metals from the root to the kernel. Linear relationships of total concentrations of heavy metals in soil with that in the crop were observed. Lime addition to the treatments further reduced the transfer and accumulation of metals from the soil to the plant, even though the relationship remained linear.     

Adsorption of heavy metals in glacial till soil

The charged sites on soil particles are important for the retention/adsorption of metals. Metallic counterions can neutralize the intrinsic charges on the surfaces of soil particles by forming complexes. In this study, efforts have been made to determine the effect of surface potential, pH, and ionic strength on the adsorption of four metal ions, hexavalent chromium Cr(VI), trivalent chromium Cr(III), nickel Ni(II) and cadmium Cd(II), in glacial till soil. Batch tests were performed to determine the effect of pH (2–12) and ionic strength (0.001–0.1 M KCl) on zeta potential of the glacial till soil. The point of zero charge (pH _PZC ) of glacial till was found to be 7.0±2.5. Surface charge experiments revealed the high buffering capacity of the glacial till. Batch adsorption experiments were conducted at natural pH (8.2) using various concentrations of selected metals. The adsorption data was described by the Freundlich adsorption model. Overall glacial till shows lower adsorption affinity to Cr(VI) as compared to cationic metals, Cr(III), Ni(II) and Cd(II).     

Aggregation of humic acid in solution: Contributions of different fractions

The role of lipid components in the aggregation of several humic acids isolated from different sources was investigated using surface tensiometry. A combination of aqueous alkaline and organic solvent extractions was used to isolate two humic-like fractions (HA₁ and HA₂) and one lipid-like fraction from each humic acid. Fraction HA₁ represents approximately two-thirds of the total organic carbon of the original humic acid and under alkaline conditions is a weak surfactant that lowers the surface tension of water by only a small amount. The HA₂ fraction represents up to one-third of the humic acid and significantly lowers the surface tension of water. It is also intimately associated with the lipid fraction. Unlike the original humic acid samples, HA₂ does not show micelle-like aggregation over the concentration range studied. Aggregate formation is discussed as an emergent characteristic that results from the interaction of the humic acid’s components with the lipid components serving a facilitative role.     

An evaluation of Rock-Eval pyrolysis for the study of Australian coals including their kerogen and humic acid fractions

Rock-Eval pyrolysis was performed on lithotype and depth profiles of Tertiary brown coals and a coalification profile of Permian bituminous coals. The humic acid and kerogen fractions from the coals are also investigated by this technique along with the effect of base extraction on the kerogen fraction. Structural variations between brown coal lithotypes are primarily reflected by changes in Oxygen Index Value. This result was supported by the results from the depth profile (same lithotype). A wide range of Hydrogen Indices (independent of depth) but similar Oxygen Indices were observed. The results from the Qualification profile show that the Oxygen Indices varied with rank, whereas Hydrogen Indices show a greater dependence on coal type. A plot of $\text{H}\text{C}$versus Hydrogen Index produced good correlations with the brown (0.77) and bituminous (0.90) samples lying on two separate lines intersecting at high H/C. This result (and higher correlation for bituminous samples) reflects the expected dependence of hydrogen index on oxygen content (present primarily as hydroxyl groups). A high correlation (0.95) between quantitative IR data (K 2920 cm mg^?1) and Hydrogen Indices supports previous conclusions regarding the dependence of Hydrogen Indices on the aliphatic structure of the samples.     

Structural relationships between a brown coal and its kerogen and humic acid fractions

A South Australian Tertiary brown coal is fractionated into humic acid and kerogen fractions. These related samples are then subjected to a number of different analytical techniques including infrared and¹³C-Nuclear Magnetic Resonance spectroscopies and pertrifluoroacetic acid oxidation. Structural conclusions are drawn from an integrated consideration of the data. Brown coal aliphatic structure is concentrated in the kerogen and the solvent soluble polar acid fractions. The humic acids are the most aromatic and contain a high degree of hydrogen bonding. Only very minor amounts of long polymethylene chain structures are observed in the humic acids, in complete contrast to the kerogen fraction. Different organic detrital origins are proposed for the coal fractions.     

Effects of heavy metals on some soil biological parameters

The soils most polluted by heavy metals are probably alluvial soils. One of them is the alluvium of the Litavka River. The heavy metal content was much higher in some cases than the threshold values, allowed by the Czech standards. The effect of soil contamination on enzyme activity is presented. Generally, the values of enzymatic activities were highest in the soil above the source of contamination and they decrease as they approach the source of contamination. All measured parameters were affected by heavy metal concentrations. Our results demonstrate that several parameters of microbial activity could be used as good indicators of increasing concentrations of Cd, Pb and Zn in soil.     

Rapid quantification of humic and fulvic acids by HPLC in natural waters

A simple method based on high-performance size-exclusion chromatography (HPSEC) has been developed for rapid quantification of humic and fulvic acids (HA and FA) in stream waters. A Tsk-gel column was used to separate natural dissolved organic matter (DOM) into two components: peak A and B. In terms of HPSEC chromatograms and fluorescence patterns, peak A and B were similar to the corresponding XAD-extracted HA and FA, respectively. It is suggested that peak A fraction mainly consisted of HA, and peak B fraction FA. The similar separation of HA and FA using HPSEC and a conventional XAD method suggests the consistency of molecular size distribution and physical–chemical properties of DOM. HPSEC offers a simple and rapid method for the quantification of HA and FA instead of tedious extractions of humic substances. Analyses of natural water samples show that the calculation of HA/FA based on UV absorbance was under- or over-estimated, the calibration using the extracted HS allows a more accurate quantification. The fast screening of HA and FA provides useful quantitative and qualitative information that can be used in environmental or monitoring studies.     

江都市土壤重金属分布特征及污染评价

江都市土壤重金属含量分布及污染现状评价结果显示,江都市土壤环境质量总体良好,但局部地区土壤污染严重,其中通扬运河以北地区土壤环境质量优于通扬运河以南地区。土壤中镉、汞、锌含量空间分布不均匀,局部土壤含量超过国家土壤二级标准,由点源污染所致,其中镉、汞为江都市土壤主要致污染因子,导致局部土壤严重污染。建议对不同污染程度土壤土地采取不同利用方式,需进行合理调整规划。     

Some inter-relationships of kerogen and humic acid fractions in the Victorian brown coal pale lithotype

The structural relationship between the kerogen, humic acid and solvent extractable acid fractions in a Victorian brown coal pale lithotype have been examined by IR, solid state ¹³C-NMR, elemental analysis and pyrolysis-gas chromatography. The solvent extractable acids and the kerogen fractions are highly aliphatic which is somewhat unusual, whereas the humic acids are composed substantially of phenolic constituents of probable lignin origin. This coal lithotype is an unusual low rank coal because of its high humic acid content. Its repeated occurrence over the limited depth profile examined here precludes a variation in coalification effects. The data suggest independent biological origins for the humic acid and kerogen fractions, and at the current level of maturation, the humic acid to kerogen transformation is little advanced in the pale lithotype. The kerogen is surprisingly aliphatic which suggests a more open marine (or lacustrine) environment than previously supposed.     

青海东部地区土壤重金属污染评价

在青海东部地区表层、深层土壤重金属调查基础上,根据国家《土壤重金属污染评价标准》(GB15618-1995),对土壤中重金属污染状况进行评价;重点选择甘河滩地区,对区内单点样、植物样、水样、地球化学剖面结果进行探讨;比较了Cd、Hg在不同时期污染形势的变化。综合分析认为,青海省东部地区重金属污染总体上并不严重,但在甘河滩一带Zn、Cd、Pb在不同介质中形成较为明显的循环污染,污染程度已达深层,不适宜农业发展;时间尺度上,Cd污染有加剧趋势,Hg污染状况有所改善。