Absorption of metals on sedimentary and peat humic acids

Humic acids isolated from marine sediments were found to be effective in absorption of various metal ions through chelation, cation exchange and surface adsorption. The quantities of metal ions complexed varied from 40 to 205 mg/g of organic matter. In the presence of equal concentrations of Co, Cu, Mn, Ni and Zn in the reaction media, humic acid and peatmoss, a rich source of humic compounds, showed preferential absorption for Cu. Copper constituted more than 50% of the metal ions complexed by organic matter. As compared with the other metal ions, its bonding strength was very firm because it could not be displaced by ferric ion or cation exchange reagents.Peatmoss, a rich source of humic acid, was found to absorb significant quantities of various metal ions. Under laboratory conditions each kg of peat absorbed about 1500 mg of various metal ions from solutions containing equal concentrations of Co, Cu, Mn, Ni and Zn. However, in the field trials with sea water, absorption of metals was limited to Zn (28.7 mg/kg), Cu (3.66 mg/kg) and Fe (2.0 mg/kg). Under-saturation of sea water for transition metals and super-saturation for alkali and alkaline earth metals appears to be a bottleneck in the effective utilization of peat as a means of recovery of metals from sea water.     

陆架边缘海环境下金属元素与有机质富集关系探讨

陆架边缘海是“河口—陆架”体系重要的碳汇,黏土矿物作为主要载体将有机质与金属元素吸附于表面或层间,通常表现为粒度、有机质和金属元素含量之间高度正相关。本文通过分析南黄海中部沉积物粒度、总有机碳、主微量元素,探讨三者之间分布特征和相互关系,进一步开展金属元素、有机质与黏土矿物吸附模拟实验,结果表明,酸性条件（pH=4）下适量的金属离子（Zn2+、Ni2+、Pb2+）明显促进伊利石对腐殖酸（有机质主要组成部分）吸附,腐殖酸吸附量达到20.06 mg/g,其中金属离子加入使腐殖酸吸附量提高6.25%;同时碱性条件（pH=8）下金属离子也能够促进伊利石对腐殖酸吸附,腐殖酸吸附量达到15.7 mg/g,金属离子加入使腐殖酸吸附量提高38.9%。金属离子的阳离子键桥作用促进伊利石吸附腐殖酸,且酸性环境下腐殖酸的吸附量高于碱性环境。证实了陆架边缘海背下金属元素的参与对黏土矿物吸附腐殖酸具有明显促进作用,有利于在全球碳循环过程形成边缘海“碳库”,同时海洋酸化可能造成海洋溶解有机质降低和重金属离子浓度升高,对陆架边缘海海洋生态系统平衡构成威胁。     

Distribution and formation conditions of noble metal mineralization in coal-bearing basins

Original data and a survey of the literature indicate that Au and Au-PGE mineralization are abundant in coal measures. Anomalous contents of noble metals have been established in basins with various types of basement, composed of granite, volcanic rocks, schist, and limestone. These basins are located in Au-and PGE-bearing ore districts, as well as at a considerable distance from known ore deposits and occurrences. Ore formation in coal-bearing basins may occur during sedimentation, peat accumulation, and diagenesis of organic matter or may be epigenetic. Noble metals are supplied to sedimentary basins as minerals that are transported by water and air and as ion species migrating along with surface and subsurface in-and exfiltration solutions of various chemical and genetic types. Ore mineralization concentrates in coal seams and host sedimentary beds of various grain size, including conglomerate, sand, and clay, as well as in zones of hydrothermal alteration superimposed on basement rocks and the sedimentary cover. The mode of occurrence of noble metals in coal basins is diverse as well (noble metal minerals, isomorphic admixtures in sulfides, and organic compounds). The data presented allow coal-bearing basins to be regarded as promising for economic noble metal mineralization fit for recovery as by-products in the course of coal mining.     

盆地流体中有机组分的成矿效应

盆地流体含有丰富的有机组分。有机质-金属耦合作用是盆地流体金属成矿机制的关键,具有极其重要的意义。有机质的成矿作用主要表现为：1)沉积有机质对盆地流体物理化学特征的制约;2)有机组分对金,属成矿元素在盆地流体中的迁移能力、迁移形式以及沉淀就位机制的制约;3)富有机质的地层作为地球化学还原障和H2S障对于流体中金属沉淀就位的制约;4)沉积有机质的演化对于盆地流体运移的制约(通过油气的阵发性析出和二次孔隙的产生)。     

The nature of metals—sediment—water interactions in freshwater bodies,with emphasis on the role of organic matter

A review with 227 references of the title subject is presented. It is divided into two main sections, viz., nature and properties of humic matter, and water—metal—sediment interactions.The first section deals with the essential properties of organic matter which occurs naturally in drainage sediments and waters. Discussion of the basic molecular structure of humic and fulvic acids is followed by some details of the chemical nature of functional groups within these structures which are important in metal-ion adsorption and complexing reactions which these materials can undergo. Information is also presented for colloidal and polyelectrolyte properties, complexation properties, and finally a summary discussion of metal-ion—humic-acid, metal-ion—fulvic-acid stability constants for both single ligand and mixed ligand systems completes the section.The second section comprises discussions of some specific aspects of interactions between metals, sediments and waters, including metal and organic speciation studies; sorption interactions between organic matter, clays and humic acids; chemical reaction between humic acids, heavy-metal minerals, clays and other silicate minerals; metal-ion adsorption—desorption studies, oxidation—reduction reactions between metal ions and humic acids; effects of sulphide ion on some of the above interactions and finally a summary of some relevant field geochemical dispersion studies.This second section describes both laboratory and field studies for each aspect.     

沿海表层沉积物中重金属的有效结合态

以浙江沿海表层沉积物为研究对象,系统地研究了重金属有效结合态与沉积环境、矿物组成和人为排放等环境因素之间的相互关系.结果表明:沿海表层沉积物中重金属的积累数量,呈现出潮汐河口沉积物>沿海沉积物>强潮汐河口沉积物的趋势,这反映了不同沉积类型对重金属富集作用的差异;重金属的有效结合态,总体上以铁锰氧化物结合态>碳酸盐结合态>硫化物及有机结合态>可交换态的顺序存在,但是不同的重金属或同种重金属在不同的采点,主要有效结合态的比例存在明显的差异,这不仅与重金属的地球化学性质、沉积环境和沉积物中的粘土矿物组成有关,更受到重金属污染物的人为排放量的影响.     

Organic geochemistry and pore water chemistry of sediments from Mangrove Lake,Bermuda

Mangrove Lake, Bermuda, is a small coastal, brackish-water lake that has accumulated 14 m of banded, gelatinous, sapropelic sediments in less than 10⁴ yr. Stratigraphic evidence indicates that Mangrove Lake's sedimentary environment has undergone three major depositional changes (peat, freshwater gel, brackish-water gel) as a result of sea level changes. The deposits were examined geochemically in an effort to delineate sedimentological and diagenetic changes. Gas and pore water studies include measurements of sulfides, ammonia, methane, nitrogen gas, calcium, magnesium, chloride, alkalinity, and pH. Results indicate that sulfate reduction is complete, and some evidence is presented for bacterial denitrification and metal sulfide precipitation. The organic-rich sapropel is predominantly algal in origin, composed mostly of carbohydrates and insoluble macromolecular organic matter called humin with minor amounts of proteins, lipids, and humic acids. Carbohydrates and proteins undergo hydrolysis with depth in the marine sapropel but tend to be preserved in the freshwater sapropel. The humin, which has a predominantly aliphatic structure, increases linearly with depth and composes the greatest fraction of the organic matter. Humic acids are minor components and are more like polysaccharides than typical marine humic acids. Fatty acid distributions reveal that the lipids are of an algal and/or terrestrial plant source. Normal alkanes with a total concentration of 75 ppm exhibit two distribution maxima. One is centered about n-C₂₂ with no odd/even predominance, suggestive of a degraded algal source. The other is centered at n-C₃₁ with a distinct odd/even predominance indicative of a vascular plant origin. Stratigraphic changes in the sediment correlate to observed changes in the gas and pore water chemistry and the organic geochemistry.     

The complexation of iron by marine humic acid

Cation exchange capacity measurements, performed before and after removal of humic acid from Narragansett Bay sediments, indicate that low concentrations of these organic substances strongly influence the ability of the sediment to react with metal ions. Atomic absorption and spectrophotometric methods allow quantitative determination of the extent of reaction between a naturally occurring humic acid and iron in artificial seawater. Humic acid-iron complexes are formed whose solubilities depend on the humic acid-iron ratio used in the experiment. This study suggests that humic acid is a transporting agent for trace metals in a marine environment.     

Importance of heavy metal-organic matter interactions in natural waters

The role of organic ligands in metal complexing in natural waters has received little attention because of uncertainties regarding both the abundance and nature of dissolved organic carbon compounds. Recent data show that the bulk of dissolved organic matter in natural waters consists of highly oxidized and chemically and biologically stable polymeric compounds closely resembling soil humic substances. Average molar concentrations of these aquatic humics in major U.S. rivers range from 5 × 10^?6to 3 × 10^?5 moles 1^?1. Fractional elution of soil organic matter by meteoric waters may be considered to be the main process contributing to the presence of humic matter in rivers. The aquatic humic polymers participate in complex formation through ionizable functional groups with a range of differential acidities. The stabilities of metal-humic complexes in natural waters are higher than those of the corresponding inorganic metal complexes. Quantitative evaluation of the metal-organic interactions can be approached by applying variable equilibrium functions which take into account the differential physico-chemical characteristics of the active complexing sites on the polymer molecule. Assuming an average humic concentration of 10 mg 1^?1, complexation of trace metals can be significant even in the presence of excess concentrations of major cations.     

Effect of organic matter and selected heavy metals on sorption of acenaphthene,fluorene and fluoranthene onto various clays and clay minerals

The effects of organic matter (80% humic and 15% fulvic acid) and coexistence of heavy metals (Ni, Pb and Zn) on sorption of three polycyclic aromatic hydrocarbons (PAHs)—acenaphthene, fluorene and fluoranthene—were examined for kaolinite, 60% kaolinite?+?40% sand, and 43% kaolinite?+?42% sand?+?15% bentonite. In total 108 batch sorption tests of PAHs were conducted for three types of clay mineral mixtures in six possible combinations of soil organic matter and heavy metal contents from no heavy metals and organic matter added to maximum organic matter added with spiked heavy metals. Results showed that the existence of metals increased the sorption of PAHs onto kaolinite from 4.7% for acenaphthene to 17.9% for fluoranthene. Organic matter in a kaolinite-sand-bentonite matrix could increase PAH sorption by up to 140% for fluoranthene. In all cases, increases were greater for fluoranthene, a larger PAH molecule. Heavy metals coexisting with organic matter led to enhanced sorption of PAHs compared to clay minerals without organic matter. Synergistic effects of organic matter and heavy metals on PAH sorption increments in the mixtures studied were such that the overall sorption could be 10–41% higher than that based on summation of the separate effects of metals and organics.     

Preparation and characterization of humic acid cross-linked with organic bridging groups

Cross-linking of humic substances with organic bridging groups is thought to contribute to the humification of soil organic matter. Model cross-linked humic substances were prepared by cross-linking Amherst soil humic acid by a diepoxide and a polycarboxylic acid, applying procedures established for cross-linking of polymers and textile fabrics. Products of the cross-linking reactions were analyzed by FTIR and ¹³C CPMAS NMR. Physicochemical properties of the products were determined by solubility experiments and thermal analysis. The incorporation of the cross-linker into the matrix of the humic acid by covalent linkages was confirmed by both the disappearance of bands of the reactive functional groups of the cross-linker in the FTIR spectrum and the increase of signals related to the incorporation of the cross-linker into the matrix of the humic acid in the FTIR and ¹³C CPMAS NMR spectra. The formation of covalent ester and ether linkages by the cross-linking reaction was indicated. Water solubilities at pH 6.2 of the cross-linked samples as determined by UV/Vis spectrometry were reduced compared to controls. Fewer water molecule bridges were formed in the cross-linked samples, which was attributed to a lower number of available functional groups and increased distances between humic acid strands caused by the cross-linking molecules. Reduced reactivities of humic acid strands in the cross-linked samples further indicated successful cross-linking. The reactions investigated in this study can be regarded as models for reactions occurring in natural soils to test the significance of cross-linking reactions in the humification process of soil organic matter and the physico-chemical properties and ecological function of organic matter in geosolids.     

An experimental study of heavy metal attenuation and mobility in sandy loam soils

Column flow-through experiments reacting wastewater solutions with sandy loam soil samples were performed to study heavy metal attenuation by two soils with different physical and chemical properties. Reacted soil columns were leached with synthetic acid rain to study the mobility of attenuated heavy metals under leaching conditions. This study demonstrates that cation exchange, surface adsorption, chelation with solid organic material, and precipitation were the important attenuation mechanisms for the heavy metals (Cd, Cr, Cu, Mo, Ph, and Zn). Adsorption on soil hydrous oxide surfaces was the primary attenuation mechanism for Cd and Zn in both soils, and for Cu in a soil with low organic matter content. Wastewater solution pH is also an important factor that influences the retention of heavy metals. Cadmium, Cu, Cr, and Zn became mobile after prolonged application of spiked wastewater solution, either through saturation of soil adsorption sites or due to decreasing pH. Only Cr, Pb, and Mo, which are attenuated primarily through precipitation, show significant net retention by soil. Acid rain water removed heavy metals left in the column residual pore solution and weakly sorbed heavy metals in the soils, and has the ability to mobilize some strongly attenuated heavy metals, especially when the soil organic matter content is high. The results have important applications in predicting heavy metal mobility in contaminated soil, the disposal of acid mine drainage, and assessing the risks of landfall leachate leakage.     

Characterization of sedimentary humic matter by alkaline hydrolysis

Humic matter fractions from modern sediments of Lake Huron and Lake Michigan have been compared. Large yields of saccharinic acids from alkaline hydrolysis suggest that these fractions contain large portions of carbohydrate materials. Evidence for contributions of aquatic lipid (C-16 fatty acids) and of liginin (phenolic acids) to these sediments is also present in the hydrolysis products. Qualitative differences among fulvic acid, humic acid and humin from the same lake are minor, suggesting common (or similar) organic sources for these fractions. The lability of sedimentary humic matter to alkaline hydrolysis is inversely related to its degree of exposure to oxidative weathering. Lability may also be related to diagenetic state as fulvic acids generally yield greater quantities of hydrolysis components than humic acids which in turn yield more than humin.     

Organic carbon and cation associations in humic material from pond water and sediment

Organic matter was isolated from the water columns and sediments of two pond systems in the south-eastern United States. Water column material was ultrafiltered to provide three fractions, i.e. <0.45 μm, but > 50,000 daltons; <50,000 daltons, but > 5000 daltons; and <5000 daltons. Sedimentary organic matter was separated into humic acid and fulvic acid fractions based on solubility criteria and the humic acid fraction was ultrafiltered to provide the same fractions as the water column isolates. All fractions were analysed for organic carbon, Al, Ca, Cu, Fe, Mg and Mn. Infra-red spectra were also measured for the sedimentary organic fractions. Organic matter isolated from the water column of the two ponds had similar organic carbon and elemental distributions, as did the organic matter isolated from the two sediments. However, significant differences in the organic carbon and elemental distributions were observed for water column and sedimentary organic matter isolated from the same pond. These studies have relevance to diagenetic alterations of organic matter and geochemical cycles of elements within lakes.     

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.     

Metal Speciation in Water of the Flooded Mine “Arsenic” (Karelia,Russia): Equilibrium-Kinetic Modeling with a Focus on the Influence of Humic Substances

Equilibrium-kinetic modeling allows investigating metal behavior in the water–rock-organic matter system with time to evaluate anthropogenic effects on the environment. In the article, the interactions of stagnant mine drainage water of the flooded mine “Arsenic” with ore and gangue minerals were simulated using different organic matter incorporation approaches. If the model is closed to humic substances (no additional organic matter input), most fulvic acids are bound in the Fe fulvate complex. While under the removal of Fe fulvate from the model, the Cu fulvate becomes prevalent, the contribution of the fulvate complexes with Zn, Mg, and Ca also increases. This scenario simulates the organo-mineral complexes behavior well and allows identifying the sequence of metal binding to organic ligands as follows Fe?>?Cu?>?Zn?>?Mg?>?Ca. The second scenario imitates the constant input of organic matter to the model (open system regarding humic substances). The dissolved metal concentrations in the model solution are extremely high in comparison to the mine drainage water. This scenario demonstrates that excessive input of organic matter leads to the accumulation of the metals in a dissolved form and blocks the secondary mineral formation despite the faster dissolution of the primary minerals under a more acidic pH than in the first scenario. However, despite the differences between the model solution and the mine drainage water, this scenario is useful to address specific issues associated with changes in natural and anthropogenic conditions. Both scenarios show the importance of organic matter incorporation to the equilibrium-kinetic models.

     

Investigation of vertical distribution and morphology of indigenous organic matter at Sleeping Bear site,Michigan

This study evaluates the nature and origin of particulate organic carbon and organic coatings on aquifer sands upgradient from a fuel spill site near the Sleeping Bear Dunes National Lakeshore in Michigan. The distribution of carbon was found to be highly complex due to the occurrence of high organic carbon horizons, bounded above and below by high carbonate sediments. The organic coatings on the sands were examined using white light and fluorescence microscopy and by scanning electron microscopy. Core samples were analyzed for organic and inorganic carbon, solution pH, humic/fulvic acid ratios, and insoluble organic matter content (that is, humin) as a function of depth from the ground surface. The organic geochemistry of the soil profile at this site was found to be significantly influenced by the carbonates producing a sharp boundary of precipitated organic matter. This boundary was followed by coatings of predominantly fulvic acid salts on mineral grains deeper in the soil column. The coatings extended into the aquifer. The existence of native organic films on sand grains is well documented in the soils literature. The study reported here was greatly aided by this information and provides the framework for future studies concerning the influence of carbon distribution, chemical identity, and morphology on contaminant fate and transport processes.     

Accumulation of copper in the Permian Kupferschiefer: A result of post-depositional redox reactions

Within the Central European Zechstein Basin the Permian Kupferschiefer has been deposited under anoxic conditions. In most parts of the basin, the metal content does not exceed values commonly observed in black shales. However, in areas near to the Zechstein sea-shore which are simultaneously related to rift zones a significant base metal enrichment is observed. Organic geochemical analyses of the copper-mineralized sections in the Kupferschiefer from Southwest Poland show that significant changes in the composition of organic matter are associated with the metal enrichment processes. Porphyrins, commonly abundant constituents of the shale, have been decomposed by oxidizing fluids. Additionally, aliphatic hydrocarbons have been largely removed from the bitumen and alkylated aromatic systems were affected by side-chain degradation. This particular type of alteration is explained by ascending oxidizing solutions which transported high amounts of base metals from Lower Permian red beds into the Kupferschiefer horizon acting as a geochemical trap. The metal precipitation is suggested to be a result of thermochemical sulphide production with organic matter acting as hydrogen source. In areas such as the Lower Rhine Basin in the bottom section of the Kupferschiefer the base metals lead and zinc as well as barium have been accumulated from basinal Carboniferous formation waters. Copper enrichment is not observed because potential source rocks are missing in this area. However, the observed compositional changes of the organic matter do not point towards thermochemical redox processes.     

Comparison of organic geochemistry and metal enrichment in two black shales: Cambrian Alum Shale of Sweden and Devonian Chattanooga Shale of United States

In most black shales, such as the Chattanooga Shale and related shales of the eastern interior United States, increased metal and metalloid contents are generally related to increased organic carbon content, decreased sedimentation rate, organic matter type, or position in the basin. In areas where the stratigraphic equivalents of the Chattanooga Shale are deeply buried and and the organic material is thermally mature, metal contents are essentially the same as in unheated areas and correlate with organic C or S contents. This paradigm does not hold for the Cambrian Alum Shale Formation of Sweden where increased metal content does not necessarily correlate with organic matter content nor is metal enrichment necessarily related to land derived humic material because this organic matter is all of marine source. In southcentral Sweden the elements U, Mo, V, Ni, Zn, Cd and Pb are all enriched relative to average black shales but only U and Mo correlate to organic matter content. Tectonically disturbed and metamorphosed allochthonous samples of Alum Shale on the Caledonian front in western Sweden have even higher amounts for some metals (V, Ni, Zn and Ba) relative to the autochthonous shales in this area and those in southern Sweden.     

Depositional environments of the Senonian chert, phosphorite and oil shale sequence in Israel as deduced from their organic matter composition

In the Upper Cretaceous sequence of the Negev (southern Israel) the organic matter in phosphorites and cherts differs from that associated with oil shales in its higher content of humic substances and lower kerogen content, and in its more intensive microbial alteration. The n-alkane distribution pattern of the oil shales, phosphorites and cherts indicates that marine biota, probably algae, are the main organic precursors of their organic matter. In some of the oil shales, however, some contribution of terrestrial organic matter is also evident. Similar high phytane/pristane ratios indicate that the organic matter in the oil shales as well as in the phosphorites and cherts accumulated under reducing conditions. The main differences in the organic matter composition are attributed to early diagenetic processes rather than to different biotic precursors or to late modifications due to temperature-induced maturation. The depositional model suggested for the sequence involves upwelling conditions at the boundary between the deep Tethys and the shallow shelf, which induced high organic productivity deep into the inner shelf. Bottom water circulation enabled intensive microbial alteration of the organic matter, followed by a winnowing process leading to phosphorite formation. Since humification is considered an oxygen-consuming reaction, these processes favoured the formation of oxygen-enriched humic substances and the oxidation of humic substances already present. These humic substances are relatively resistant to further alteration and their conversion into kerogen is thus retarded. Subsequently, syndepositional tectonic activity resulted in the introduction of less saline water, restriction of bottom-water circulation and the establishment of a density stratification in the water body. Consequently, aeration of the bottom layer and the sediments was inhibited, microbial alteration was reduced and later winnowing processes were prevented. Such conditions favoured the formation of kerogen directly, rather than through humic substances, and also favoured the preservation of most of the organic matter in the form of oil shale deposits instead of phosphorites.