Comparison of the structural,spectroscopic and phenanthrene binding characteristics of humic acids from soils and lake sediments

The structural, spectroscopic and phenanthrene binding characteristics were compared for humic acids (HA) extracted from two different sources: eight soils and six lake sediments. The elemental analysis revealed that HA from sediments had higher H/C, N/C, and (N + O)/C ratios compared to HA from soils, reflecting a lower degree of humification and more autochthonous organic input upon the formation of the HA for lake sediments versus soil environments. HA from soils exhibited a higher content of aromatic carbon structures than the sediment HA based on ¹³C NMR results. The source of HA was easily distinguished by comparing the synchronous fluorescence spectra of each HA group. The presence of a protein like fluorescence was prominent for the HA from sediment while it was minor for the HA from soil. Irrespective of the HA source, however, humification index (HIX) exhibited a common positive correlation with the aromatic content, and a negative correlation with O-alkyl carbon structures of the HA. The correlations were consistent with the general structural trends of humification processes, suggesting that HIX may serve as a source independent predictor to describe the structural information and humification degree of terrigenous HA. Aromatic carbon structures did contribute to enhancing the phenanthrene binding for both sources of HA. However, the primary structures associated with non-ideal phenanthrene binding (i.e., non-linear sorption isotherm) appear to differ by the HA source because the opposed correlations were obtained between aromaticity and the isotherm linearity for the two HA groups. Our results suggest that the HA structural function associated with specific non-linear sorption for hydrophobic organic contaminants (HOCs) may be more strongly governed by the HA source than by the apparent physico-chemical properties.     

Heavy metal and aluminium mobilization in soils from Galicia (NW spain) as a consequence of experimental acidification

In this paper the main results of an experimental acidification of 5 Galician soils are presented. The acid input caused decrease in pH and mobilization of Al and some heavy metals. Owing to the great differences in the soils studied, the type of metal released and its concentrations in solution varied greatly. pH and metal content of the soils were the factors most influencing metal mobilization. The acid input greatly enhanced the mobilization of Al in the most acidic soils, particularly those developed from mica schist or shale. Large increases in Mn were observed in the soils developed from serpentinite and mica schist. The greatest Zn increase took place in soils derived from granulite and shale. Nickel increased only in the soil developed on serpentinite. Mobilization of Cu and Pb did not occur in any soil.     

On the metal content and metal ion uptake of botanically specific peats and the derived humic acids

With respect to ten metals (Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga) which are continguous in the Periodic Table the natural metal content and the ability to take up metal ions has been determined for three peats of defined botanical origin, each peat being sampled at three different levels. A correlation is found between the natural metal content and botanical origin. Apart from aluminium, the concentration of individual metals increased in the series Sphagnum < fen sedge < reed, the increase being statistically significant (P = 0.001) for V, Mn, Co, Ni, and Ga and for the sum of the metal ions measured.No clear correlation emerged between botanical origin and metal uptake. The metal uptake by the humic acid derived from each peat sample was also determined, and correlated with the metal uptake of the source peat itself.In all the humic acid and peat metal-uptake experiments the selectivities were very similar. V, Cr, Cu, Ga were readily taken up while Mn, Co and Zn were consistently less preferred.     

Interaction of organic acids and pH on multi-heavy metal extraction from alkaline and acid mine soils

Vegetation at mining sites can produce increased heavy metal leaching by the organic acids and protons originating from root secretion and litter degradation. Batch experiments were conducted to investigate the effects of organic acids and pH on the extraction of Pb, Cd, Zn and Cu from an alkaline mine soil (sampled from a mining site of Chenzhou City, Hunan Province) and an acid mine soil (sampled from a mining site of Daxin county, Guangxi Province). The results showed that in the presence of organic acids (acetic, oxalic, malic, fumaric, tartaric and citric acids) at pH 7, the extraction of Pb, Cd, Zn and Cu from the acid mine soil was much higher than that from the alkaline mine soil, in which only citric acid with higher concentration was capable of extracting some heavy metals. Citric acid had the strongest ability in extracting heavy metals, followed by oxalic acid. Heavy metal extraction dramatically decreased with increasing pH. Moreover, at low pH, oxalic acid promoted the risk of Cu leaching; at high pH, the leaching of Pb, Zn, Cd and Cu was enhanced by both oxalic and citric acids. This indicated that those plants, which can produce substantial citric acid or oxalic acid by root secretion and litter degradation, should not be selected for the revegetation of mining sites.     

胡敏酸对高岭石吸附铜离子的强化作用

考察酸性条件特别是在近中性 pH范围内胡敏酸对高岭石吸附铜离子的强化作用。研究表明 ,胡敏酸的加入可以提高高岭石对铜离子的吸附率 ,甚至在pH 5～ 6附近高岭石对铜离子的吸附率也从约 5 0 %提高到约 6 5 %。当 pH <4时 ,由于高岭石表面铝的高溶出或胡敏酸阴离子基团离解程度降低等因素 ,使其表面对胡敏酸的吸附率有所降低 ,但与高岭石样品相比 ,胡敏酸高岭石复合体对铜离子的吸附仍然有明显的增加。胡敏酸对高岭石吸附铜离子的强化机制是 ,高岭石端面形成了Al—HA—Cu三元配合物 (B型 ) ,与传统的诸如pH、离子强度与离子初始浓度等介质条件影响不同。在 pH >7时高岭石端面及腐殖质基团去质子化增强 ,因而静电排斥降低了高岭石对胡敏酸的吸附 ,从而使得胡敏酸对铜离子在高岭石表面上的吸附作用有所减弱 ,此时可能出现胡敏酸铜及氢氧化铜的沉淀 ,铜离子的表观吸附率可能不会有明显变化     

Perchlorate mobilization of metals in serpentine soils

Natural processes and anthropogenic activities may result in the formation and/or introduction of perchlorate (ClO₄⁻) at elevated levels into the environment. Perchlorate in soil environments on Earth and potentially in Mars may modify the dynamics of metal release and their mobilization. Serpentine soils, known for their elevated metal concentrations, provide an opportunity to assess the extent that perchlorate may enhance metal release and availability in natural soil and regolith systems. Here, we assess the release rates and extractability of Ni, Mn, Co and Cr in processed Sri Lankan serpentine soils using a range of perchlorate concentrations (0.10–2.50 w/v ClO₄⁻) via kinetic and incubation experiments. Kinetic experiments revealed an increase of Ni, Mn, Co and Cr dissolution rates (1.33 × 10⁻¹¹, 2.74 × 10⁻¹¹, 3.05 × 10⁻¹² and 5.35 × 10⁻¹³ mol m⁻² s⁻¹, respectively) with increasing perchlorate concentrations. Similarly, sequential and single extractions demonstrated that Ni, Mn, Co and Cr increased with increasing perchlorate concentrations compared to the control soil (i.e., considering all extractions: 1.3–6.2 (Ni), 1.2–126 (Mn), 1.4–34.6 (Co) and 1.2–6.4 (Cr) times greater than the control in all soils). Despite the oxidizing capability of perchlorate and the accelerated release of Cr, the dominant oxidation state of Cr in solution was Cr(III), potentially due to low pH (<2) and Cr(VI) instability. This implies that environmental remediation of perchlorate enriched sites must not only treat the direct hazard of perchlorate, but also the potential indirect hazard of related metal contamination.     

Characterisation of brown coal humic acids and modified humic acids using pyrolysis gcms and other techniques

It has been proposed that Victorian brown coal can be considered as a two-component structure — a lignocellulosic “host”, containing various amounts of weakly bound or entrapped “guest” material together with very small amounts of inorganic and/or mineral matter. The latter predominantly consists of wax esters and/or terpenoid material. In this paper we describe attempts to gain structural information regarding the more complex, “host” component of the coal. Our initial model compound has been humic acid that can be readily obtained from the coal by alkaline extraction. It has been found that “pure” humic acid, free from material associated with the “guest” components of the coal, can be obtained by a highly selective, low-yielding alkaline extraction. This humic acid has been studied by nmr spectroscopy and pyrolysis gas chromatography-mass spectroscopy (py-gc/ms). The products arising from py-gc/ms have been compared with those obtained from similar pyrolysis of whole coals. Alkylation of humic acids using alkyl halides in the presence of base has been successfully carried out and reactivity of the resulting materials compared with those of the parent coal and humic acid.     

Chemical characterization of fractionated humic acids from lake and marine sediments

Humic acids from Recent lacustrine and marine sediments were divided into five components by extractions with organic solvents and characterized by elementary composition, ultraviolet, visible and infrared absorption spectra and n.m.r. spectra. The results suggest that sedimentary humic acids have a cyclic structure (40–50% of the total carbon), which is considered to be alicyclic rather than aromatic. No marked differences except for an absorption near 410 mμ were observed between humic acids from lake and marine sediments.     

The relationship between dissolved humic acids and soluble iron in estuaries

Dissolved humic acid and soluble iron appear to be chemically unassociated in estuaries despite their coincident removal. This conclusion is supported by differences in the aggregation kinetics of soluble iron and dissolved humic acid, the inability of extracted humic acid to stabilize laboratory preparations of ferric hydroxide, and decreasing ratios of humic acid carbon to soluble iron along the axes of some estuaries.     

The attenuation of chemical elements in acidic leachates from coal mineral wastes by soils

The chemical attenuation of acidity and selected elements (aluminum, arsenic, cadmium, cobalt, chromium, copper, fluorine, iron, manganese, nickel, and zinc) in acidic leachates from coal mineral wastes by four natural subsurface soils has been investigated using laboratory column methods Leachate solutions were allowed to percolate through the soils under simulated natural flow conditions, and the elemental concentrations in the influents and effluents were measured periodically Elemental retentions were substantial for all species except managanese, which was eluted in excess from all soils except the most calcareous Two processes appeared to operate in decreasing influent concentrations: (1) precipitation of solid phases caused by increased pH of the leachate as it percolated through the soil, and (2) adsorption of elements onto exchange and sorption sites naturally present in the soil and on iron and aluminum oxide precipitates formed in situ from leachate components because of the increased pH The soil property most important in retention was its alkalinity Thus, carbonaceous soils provide the best control material for acidic leachates from coal mineral wastes. Results show that natural soils can substantially reduce pollutant fluxes to the environment from acidic coal waste dumps and should be considered when selecting waste disposal sites Performed under the auspices of the U.S. Department of Energy     

Heavy metal distribution in karst soils from Croatia and Slovakia

With the use of the optimised three-step BCR sequential-extraction procedure it was possible to assess the mobility of selected elements in soil profiles from Croatian and Slovakian karst terrains. The soils in the Croatian karst were enriched in Cr, Ni, V, Mn, Cu, Cd and Mo, while soils from the Slovak Karst had high Pb and Zn concentrations. It was determined that the elements were most readily mobilised from the topsoil and the degree of mobility decreased with depth. Cr and Ni were mainly bound to the residual fraction, and Pb in the oxidisable fraction. Cu mobility was high in samples treated with agrochemicals throughout the soil profile.     

Fluorine mobilization from rocks under the action of organic acids

This paper presents the results of experimental study of fluorine leaching from rocks of various basicity by distilled water and multicomponent organic acid solution, in which the frequency distribution of dissociation constants of carboxyl groups correspond to that of natural soil solutions. It is shown that organic acids significantly enhance the intensity of fluorine leaching from rocks as compared to distilled water. A positive correlation was established between fluorine and magnesium extracted from different rocks by organic acids (r = 0.92). The correlation between fluorine and other main petrogenic elements is absent. Intensity of fluorine mobilization from rocks under the action of organic acids increases with the growth of basicity of the rocks with decreasing their chemical stability in the following sequence: meimechite > basaltic andesite > albitized rhyodacite > alkaline agpaitic granite.     

Effects of humic acid on heavy metal uptake by herbaceous plants in soils simultaneously contaminated by petroleum hydrocarbons

The effects of humic acid (HA) on heavy metal uptake by herbaceous plants in soil simultaneously contaminated with heavy metals and petroleum hydrocarbons were investigated. The results showed that HA reduced readily soluble and exchangeable forms of heavy metals in the contaminated soil but increased their plant-available forms. Potential bioavailability and leachability factors became larger than 1 after adding HA to the soil, except for those of Ni, suggesting that more heavy metals could be potentially phytoavailable for plant uptake. Furthermore, HA increased the accumulation of Pb, Cu, Cd, and Ni in the shoots and roots of selected plants. The greatest increase in the accumulation of heavy metals was 264.7 % in the shoot of Festuca arundinacea, with the bioconcentration factor (BCF) increasing from 0.30 to 1.10. Humic acid also increased the BCFs of the roots of Brassica campestris for Ni and Pb. These results suggest that HA amendment could enhance plant uptake of heavy metals, while concurrently reducing heavy metal leachability and preventing subsurface contamination, even in soils simultaneously contaminated with petroleum hydrocarbons.     

Dicarboxylic acids generated by thermal alteration of kerogen and humic acids

Significant amounts (up to 2% of organic geopolymers) of low molecular weight (LMW) dicarboxylic acids (C₂–C₁₀) have been detected during thermal alteration (270°C, 2 h) of kerogens and humic acids isolated from young or ancient lithified sediments. Their distribution is characterized by predominance of oxalic acid followed by succinic, fumaric and methylsuccinic acids. These acids are probably released by the breakdown of macromolecular structures, which have incorporated biogenic organic compounds, including diacids, during early diagenesis in sediments. Because of their reactivity, LMW diacids may play the following geochemically important roles under natural conditions: (1) the diacids dissolve carbonates and clay minerals to increase porosity and permeability, which enhances migration of oils and gas generated from catagenesis of kerogen dispersed in shale, and (2) the diacids may form organo-metal complexes, which are important for mobilization, transport and accumulation of trace metals in sedimentary basins.     

Electron paramagnetic resonance characteristics of the humic acids from a podzol

A study has been made of solid and solution electron paramagnetic resonance (EPR) spectra of humic acids from different horizons in a podzolic soil. Hyperfine splitting was observed in the solution spectra of humic acids from all horizons and depended on the strength of alkali and the period of dissolution. The upper organic horizons L, F and O₁ contained humic acids with some spectral characteristics in common with lignin. Humic acid from the lower horizons showed different spectra. At least 5 different radical signals were present.     

Extended saturated and monoaromatic tricyclic terpenoid carboxylic acids found in Tasmanian tasmanite

A series of tricyclic terpenoid carboxylic acids (C₂₀–C₄₀) was found in the acidic fraction of Tasmanian tasmanite bitumen, occurring as a mixture of stereoisomers with mainly the 13β(H), 14α(H)-and 13α(H),14α(H)-configurations. These dominant acidic tricyclic constituents have the same carbon skeleton as the ubiquitous tricyclic terpane biomarkers. A novel series of ring-C monoaromatic tricyclic terpenoid carboxylic acids was also characterized. The series ranges from C₁₉ to C₃₉ and is the acidic counterpart of the recently described series of monoaromatic tricyclic terpanes.     

The lognormal distribution of metal resources in mineral deposits

For national or global resource estimation of frequencies of metals a lognormal distribution has sometimes been assumed but never adequately tested. Tests of frequencies of Cu, Zn, Pb, Ag, Au, Mo, Re, Ni, Co, Nb₂O₃, REE₂O₃, Cr₂O₃, Pt, Pd, Ir, Rh, and Ru, contents in over 3000 well-explored mineral deposits display a poor fit to the lognormal distribution. Neither a lognormal distribution nor a power law is an adequate model of the metal contents across all deposits. When these metals are grouped into 28 geologically defined deposit types, only nine of the over 100 tests fail to be fit by the lognormal distribution, and most of those failures are in two deposit types suggesting problems with those types. Significant deviations from lognormal distributions of most metals when ignoring deposit types demonstrate that there is not a global lognormal or power law equation for these metals. Mean and standard deviation estimates of each metal within deposit types provide a basis for modeling undiscovered resources. When tracts of land permissive for specific deposit types are delineated, deposit density estimates and contained metal statistics can be used in Monte Carlo simulations to estimate total amounts of undiscovered metals with associated explicit uncertainties as demonstrated for undiscovered porphyry copper deposits in the Tibetan Plateau of China.