Stability and Mobility of Metal-Humic Complexes Isolated from Different Soils

The contamination of potable water aquifers by heavy metals is one of the most severe environmental threats. For the transport of heavy metals from various types of contaminated sites into the ground water and also into surface water aquifers, humic substances (HS) are recognized to be of main importance. Dissolved in natural waters humic substances are readily complexed with a variety of metal ions. Therefore, humic substances are of cardinal importance for the migration and, consequently, the pollution of ground waters with heavy metals. Our paper presents the results of a comprehensive comparison of several isolated humic acids of soils of different origin (different geochemical milieu) and their metal complexes. Two polluted sites in Germany, which differ in their geochemical milieu (pH-value) were selected. The aim of our experiments was to describe the properties of terrestrial humic substances depending on their origin and genesis as well as the effects of the transport of humic substance-bound metals into the water-unsaturated soil zone. After determination of heavy metals in the soils by photon activation analysis the activated soil was used as an inherent tracer in batch experiments with the isolated humic acid. After adsorption of the loaded humic acid on an XAD-8 resin column, the partition of metals mobilized by humic acids could be quantified. There are correlations of the formation of metal-humic complexes with the soil pedogenes, with the pH-value as well as with the humic acid concentration.     

The uniqueness of humic substances in each of soil,stream and marine environments

Definitive compositional differences are shown to exist for both fulvic acids and humic acids from soil, stream and marine environments by five different methods (¹H and ¹³C NMR spectroscopy, ¹⁴C age and δ¹³C isotopic analyses, amino acid analyses and pyrolysis-mass spectrometry). Definitive differences are also found between fulvic acids and humic acids within each environment. These differences among humic substances from various sources are more readily discerned because the method employed for the isolation of humic substances from all environments excludes most of the non-humic components and results in more purified humic isolates from water and soils. The major compositional aspects of fulvic acids and humic acids which determine the observed characteristic differences in each environment are the amounts and composition of saccharide, phenolic, methoxyl, aromatic, hydrocarbon, amino acids and nitrogen moieties.     

Silver binding by humic acid as determined by equilibrium ion-exchange and dialysis

One of the major challenges in environmental analytical chemistry is to develop methods for determining metal speciation in natural waters that contain low metal concentrations and dissolved organic matter (DOM). Because of its complex heterogeneous nature, metal binding to DOM cannot be predicted accurately using equilibrium models. Two independent speciation methods, the equilibrium ion-exchange technique (IET) and equilibrium dialysis (EqD), were used to determine silver binding by standard Suwannee River humic acid. Both approaches gave very similar results, although for a given silver loading, the concentration of free silver obtained by IET was somewhat higher than that determined by EqD. Our results suggest that any high-affinity binding sites present within the humic acid are likely saturated at [Ag(T)] > 10(-9) M. This comparison of free metal ion concentrations with two independent methods provides useful speciation information in the absence of reliable complexation constants for the reaction of silver with humic acid.     

Vertical Mobility of Soil Contaminants: Preliminary Results of a Survey on the Herbicide Atrazine

Abstract

Atrazine is considered a potential contaminant of water bodies, where it has been repeatedly detected. Its use in Italy is almost limited to the Northern part of the country where corn monocultures are common. Northern Italy is characterized by the presence of an area with soil quite permeable and where ground waters are often present at not very deep levels. In this area well waters, which represent the main source of drinking water, have been frequently found contaminated by atrazine. A program has been started aimed at studying the role of soil nature and local factors in the process of groundwater contamination. Two atrazine application rates were used at two sites with loamy and loamy-sandy soils. Results clearly show a different mobility of atrazine in the two soil types. Since the two sites have similar organic carbon levels, the major proportion of clay to sand and the lower pH of loamy soil may explain the lower vertical mobility of atrazine in this soil. Work is in progress to study atrazine behaviour to a soil depth of 30cm and the effect of repeated atrazine applications on ground water pollution.     

天然水体底质中腐植酸的光谱表征

分别用紫外-可见光谱、傅立叶变换红外光谱(FTIR)、三维荧光光谱和荧光等高线谱对提取的腐植酸和商品腐植酸进行了表征，并将分析结果与Aldrich和上海试剂二厂生产的腐植酸进行了比较。结果表明：3种底质腐植酸之间以及同商品腐植酸的紫外-可见光谱、傅立叶变换红外光谱(FTIR)相似，含有相同类型的官能团。对不同腐植酸的三维荧光光谱和荧光等高线谱的分析表明其在结构上存在一定的差异；腐植酸有较明显的荧光光谱特性，可以尝试使用三维荧光光谱技术来揭示其在结构上的差异。     

The Adsorption of Herbicides and Pesticides on Clay Minerals and Soils. Part 1. Isoproturon

The adsorption of isoproturon and two model compounds, N,N-dimethylurea and4-isopropylaniline, on clay minerals (bentonite,montmorillonite and kaolinite), organic matter (humic acid) and soil (with and without organic matter) has been studied using FT-infrared spectroscopy (IR), thermogravimetric analysis (TGA), high pressure liquid chromatography (HPLC) and X-ray diffraction (XRD).N,N-dimethylurea interacted with bentonite and montmorillonite by the coordination of the carbonyl group, directly or indirectly through water molecules, with exchangeable cations. Adsorption on humic acid was due to hydrogen bonding with the active sites of the adsorbent. The amino group ofN,N-dimethylurea appears tobe relatively inactive during adsorption. The mechanisms involved in the adsorption of 4-isopropylaniline were hydrogen bonding and protonation. No adsorption of 4-isopropylaniline was observed on kaolinite. The investigation of isoproturon suggested that both the carbonyl and amino groups of isoproturon were involved in interactions with the active sites of the adsorbents. Both the clay minerals and organic matter of soil contribute to the adsorption of organic compounds on soil but the clay minerals bentonite and montmorillonite play a major role in their adsorption on soil.     

The use of ultrafiltration for the separation and fractionation of organic ligands in fresh waters

The effects of various experimental conditions on the results obtained by using membrane filtration for the separation and fractionation of organic matter in fresh waters (mainly fulvic and humic substances) are described. The technique used (washing or concentration) and the initial concentration of the organic matter to be filtered are the most critical factors. The technique is used for the fractionation of eight water samples, one sample of peat interstitial water, five water extracts of soil and four water samples obtained by decomposition of leaves. The results are compared. A comparison is also made with results cited in the literature.     

Hyphenated techniques of thermal analysis for characterisation of soil humic substances

Our aim was to investigate the thermal behaviour of humic substances extracted from temperate and tropical soils by means of hyphenated techniques of thermal analysis (e. g. simultaneous thermal analysis DSC/TG coupled with mass spectrometry, MS, for the analysis of evolved gas, EGA) in order (i) to verify whether the chemical composition of isolated humic substances also reflected the differences in microbial parameters previously measured in related soil samples and (ii) to identify suitable indices of thermal stability. Our results show that the investigation of humic substances by thermal methods can provide information on soil organic matter dynamics. Differences in thermal behaviour between the two groups of soils were found. The indices of thermal stability here proposed, IR (index of thermal recalcitrance), and ID (index of thermal decomposability) clearly showed that in humic substances from tropical soils the thermally recalcitrant organic fraction dominated, whilst in temperate humic substances the opposite held. This agrees with previous results on the microbial dynamics and organic matter turnover of the respective soils and indicates that these indices of thermal stability could represent a useful tool in soil environmental quality investigations.     

Association of Am with humic substances isolated from river waters with different water quality

The association properties of Am with aquatic humic substances in a 0.01M NaClO₄ solution at pH 6-8 were studied on the basis of molecular size distribution. Ten humic substances isolated from river water with different water quality (pH 3.9-8.0 and dissolved organic carbon (DOC) concentration of 2-40 mg/l) were used for comparing their effects on the association of Am. The molecular size distribution of Am in the presence of humic substances from an uncolored river water (DOC 2 mg/l) was different from that at the experimental systems using humic substances from brownish and high DOC (14-40 mg/l) river waters.     

Polydisperse adsorbability composition of several natural and synthetic organic matrices

The polydisperse composition of nine dissolved organic materials (DOMs) from two river water sources, one ground water source, two biologically treated wastewater sources, and two commercial sources was analyzed based on their adsorbabilities by activated carbon. For each DOM, batch adsorption isotherms measured for both TOC and UV260 were analyzed using an overall isotherm model derived from the IAST-Freundlich expression. By accounting for the heterogeneity of each DOM with a log-normal distribution of the Freundlich parameter (K), its adsorption behavior was characterized with only four parameters (including three fitting ones). The average adsorptive strength (KM) and heterogeneity (sigma) determined for all DOMs, which were defined by the mean value and the standard deviation of the log-normal distribution of the Freundlich K, changed over the ranges 2.5-62.2 and 0.22-0.97 (mg/g)/(mg/l)(1/n), respectively, when the TOC index was used. Among all DOMs studied, a river water DOM at the upper stream was found least heterogeneous: the Freundlich K of its organic constituents varied in the range 10.8-190 (mg/g)/(mg/l)(1/n), as compared to a commercial humic acid that exhibited the broadest Freundlich K distribution of 0.01-1494.3 (mg/g)/(mg/l)(1/n). KM and sigma, along with other two parameters (the Freundlich exponent 1/n and the nonadsorbable organic fraction parameter Cnon/CT0), changed with both indices of TOC and UV260 in a regular manner, indicating that UV-absorbing organic molecules possessed adsorbabilities different from non-UV-absorbing ones. Also based on HPSEC chromatograms measured for solutions before adsorption, the molecular weight composition of all DOMs was also assessed and the molecular size impacts on adsorption characteristics of DOMs were briefly discussed.     

Characterization of heavy-metal-containing seepage water colloids by flow FFF, ultrafiltration, ELISA and AAS

Heavy-metal-containing humic colloids from seepage water samples of three different municipal waste disposal plants were characterized in terms of molecular weight, hydrodynamic radius and heavy metal content. The size distribution of the colloids was determined with ultrafiltration (UF) and flow field-flow fractionation (flow FFF). The humic colloids in the seepage water samples were characterized using an off-line coupling of flow FFF with an enzyme-linked immunosorbent assay (ELISA) for humic substances. The heavy metals in the different size fractions obtained by UF and flow FFF were determined using atomic absorption spectroscopy (AAS). The colloid size distributions obtained with UF showed a maximum of the distribution in the range 1–10 nm. Seepage water samples with high colloid concentrations had a second maximum in the range 0.1–1 m. The determination of colloid size with flow FFF gave different colloid size distributions for the three waste disposal seepage waters, whereas water from the oldest disposal plant showed the smallest colloid size with a maximum at 0.9 nm and water from the most recent plant showed the largest colloid size with a maximum at 1.3 nm. The determination of particle classes with regard to the chemical composition using a scanning electron microscope with energy dispersive X-ray fluorescence detector (SEM/EDX) showed that the particles can be divided into five classes: silicates, insoluble salts, iron(hydr)oxides, carbonates and organic colloids (humic colloids). Flow FFF/ELISA off-line coupling showed that the most frequently occurring colloids of the seepage waters were humic colloids and investigation of the UF-size-fractions with AAS showed that up to 77% of the total mass of a heavy metal element can be bound to particles, especially to humic colloids. Additionally, the distributions of the heavy metals Fe, Cu and Zn were investigated with flow FFF/AAS off-line coupling. These results also showed that a substantial amount of these heavy metals (up to 46%) was bound to humic colloids.     

Effect of surface-active compounds on voltammetric stripping analysis at the mercury film electrode

The effects of various organic compounds on the differential-pulse anodic-stripping voltammetric response at the in-situ plated mercury film electrode are explored. These effects vary from metal to metal and from one organic compound to another. The most pronounced effects are observed in measurements of copper. The main effect of the organic compound is to depress the peak current rather than change the peak shape or potential. The differences between the organic interferences observed at the mercury film electrode and those reported at the hanging mercury drop electrode are explained by the different morphology and geometry of the two electrodes. The implications of these interferences for the reliability and feasibility of stripping measurements in natural waters are discussed. Gelatin, camphor, humic acid, starch, agar, sodium dodecyl sulphate and albumin were used as representative organic compounds, and cadmium, lead, and copper as test metal ions.     

Identification of diffuse and point sources of dissolved organic carbon (DOC) in a small stream (Alb, Southwest Germany), using gel filtration chromatography with high-sensitivity DOC-detection

Using gel filtration chromatography and high-sensitivity UV and organic carbon (OC) detection, the quality and quantity of organic matter in a stream (the Alb, Southern Germany) has been studied in the winter season. In the catchment area and upstream of two sewage plant effluents the organic load has been low (below 1 mg/l TOC) and has been dominated by humic substances (more than 80%). Downstream of the sewage plants, TOC increased up to 5 mg/l while humic constituents decreased down to 30%. A detailed analysis showed that in the catchment area the humic fraction has been composed of fulvic acids with relatively high amounts of aliphatic structures. Downstream of the sewage plants, the humic fraction has been composed of fulvic acid precursors with associated non-humic matter. It is concluded that the quality and quantity of organic constituents in the stream has been dominated by the secondary effluents.Dedicated to Professor Dr. Dieter Klockow on the occasion of his 60th birthday     

Comparative study for differentiation of aquatic humic-type organic constituents by capillary zone electrophoresis using polyvinyl alcohol-coated capillary

Capillary zone electrophoresis (CZE) with UV detection (254 nm) was applied to characterize aquatic dissolved humic matter (DHM) from different environmental sources (lake, river and sea waters, in all 15 different samples). A series of separation examples of DHMs using a polyvinyl alcohol (PVA)-coated silica open tubular capillary were carried out in a phosphate buffer (40 mM) as a background electrolyte at neutral acidity (pH 6.8). The separative power of electropherograms was reasonable and the reproducibility was above the mark. Each electropherogram was characteristic of the corresponding humic sample. Special functional fulvic and humic acids or their overall mixtures separated with XAD, DAX and DEAE sorbing solids as well as the original dissolved organic matter (DOM) were nicely differentiated according to their environmental sources. The PVA coating of open tubular silica capillaries seems to be very potential in electrophoretic characterization and separation of different humic solutes at neutral acidities with low sample concentrations thus permitting a workable technique, in a growing series of CZE studies, for better compared results from different studies.     

Retention of Metamitron by Model and Natural Particulate Matter

Abstract

Adsorption isotherms of metamitron on model soil colloidal components: kaolinite, illite, montmorillonite, iron oxide and humic acid, and their binary associations were obtained using a batch equilibration procedure. Sorption parameters, K_f and n_f, were calculated by fitting the sorption data to the Freundlich equation and results obtained for binary associations were compared with those obtained for the individual model components. The sorption efficiency of the humic acids and their binary associations was measured as Koc. The adsorption behaviour of the < 2 μm fraction of two soils from Southern Spain was also studied as natural particulate matter. Montmorillonite and humic acids were found to be the most important components responsible for metamitron retention by the model adsorbents studied. On the contrary, metamitron showed little interaction with kaolinite, illite or iron oxide. These individual adsorption behaviours were reproduced in the montmorillonite-iron oxide-humic acid binary systems, but with differences suggesting changes on the surface properties upon association. Differences in Koc values of isolated humic acids and their associations indicate that the interaction transforms the humic acid surfaces and suggest different types of bonding between colloids and metamitron. The results obtained with model adsorbents and their associations were in agreement with the highest adsorption of metamitron found for the natural clay fraction of two soils which displayed the largest adsorption in that with the highest content in montmorillonite and organic carbon. The importance of organic matter and montmorillonite in metamitron adsorption by colloidal components was also shown by the decrease in K_f and the increase in Koc observed after removal of organic matter from the soil clay fraction with the highest organic carbon content.     

Characterization of the health of southern Appalachian red spruce (Piceae rubens) through determination of calcium, magnesium, and aluminum concentrations in foliage and soil

The red spruce (Picea rubens) is a conifer whose southern native range is limited to high elevation sites in the Appalachian Mountains. Red spruce decline has been reported to involve atmospheric deposition of acidic anions, which may affect cation mobility in soil, primarily calcium, magnesium, and aluminum. In this work, the concentrations of these elements were determined in red spruce foliage and surrounding soil at high elevation locations in the Great Smoky Mountains and on the Blue Ridge Parkway by inductively coupled plasma optical emission spectrometry (ICP-OES). Few differences in foliar or soil concentrations were observed at the sites, indicating that elevation and geography do not affect these values. A comparison of foliar concentrations in seedlings, saplings, and mature trees demonstrated few differences, suggesting that life stage does not affect these elemental concentrations. A previously-developed model to estimate forest health using soil calcium/aluminum ratios suggested that all sites had a significant risk of adverse health effects. However, comparisons of foliar calcium/aluminum ratios and calcium and magnesium concentrations to values obtained in the mid-1990s showed an improvement in these parameters, presumably due to decreased acidic deposition.     

Characterization of the health of southern Appalachian red spruce (Piceae rubens) through determination of calcium,magnesium, and aluminum concentrations in foliage and soil

The red spruce (Picea rubens) is a conifer whose southern native range is limited to high elevation sites in the Appalachian Mountains. Red spruce decline has been reported to involve atmospheric deposition of acidic anions, which may affect cation mobility in soil, primarily calcium, magnesium, and aluminum. In this work, the concentrations of these elements were determined in red spruce foliage and surrounding soil at high elevation locations in the Great Smoky Mountains and on the Blue Ridge Parkway by inductively coupled plasma optical emission spectrometry (ICP-OES). Few differences in foliar or soil concentrations were observed at the sites, indicating that elevation and geography do not affect these values. A comparison of foliar concentrations in seedlings, saplings, and mature trees demonstrated few differences, suggesting that life stage does not affect these elemental concentrations. A previously-developed model to estimate forest health using soil calcium/aluminum ratios suggested that all sites had a significant risk of adverse health effects. However, comparisons of foliar calcium/aluminum ratios and calcium and magnesium concentrations to values obtained in the mid-1990s showed an improvement in these parameters, presumably due to decreased acidic deposition.     

Determination of thorium and light rare-earth elements in soil water and its high molecular mass organic fractions by inductively coupled plasma mass spectrometry and on-line-coupled size-exclusion chromatography

Inductively coupled plasma mass spectrometry (ICP–MS) has been used for the determination of thorium and light rare-earth elements (LREEs) in soil and soil water samples from a mineral deposit (Morro do Ferro, Minas Gerais, Brazil). Size-exclusion chromatography (SEC) on-line coupled to ICP–MS and UV-detection was applied to verify possible association/complexation of these elements with organic matter in soil water separated by a centrifugation technique. Concentrations of DOC in soil waters are in the range of 10 to 500 mg L^–1 and correlate with the organic carbon content of the soil (r=0.950; p<0.001). Concentrations of 30 to 40 g L^–1 for the LREEs (La, Ce, Nd) and up to 14 g L^–1 for Th were measured in soil waters of highest DOC content. SEC chromatograms of these waters showed the association of elements with different nominal high-molecular-mass ranges, characteristic of soil humic and fulvic acids: >10,000 Da, with a retention time of about 10 min; 7000 to 8000 Da with retention times of 13 to 15 min; and 2000 to 4000 Da with retention times around 23 min. Elemental peaks associated with dissolved organic matter below 1000 Da were not observed, suggesting that complexation with simple plant organic acids or inorganic ligands is of minor importance in the environment studied in this work.     

Comparative characteristic studies on soil and commercial humic acids

Summary Two commercial and eight soil humic acids were characterized to evaluate the use of commercial humic materials in soil and environmental studies. Significant differences between commercial and soil humic acids were observed in ash content, major and micro-element constituents, E₄/E₆ ratio, total acidity and ¹³C-NMR spectroscopy; but data from stability constant and IR-spectroscopy were almost identical. The commercial materials appeared to be significantly less aromatic and more aliphatic in nature as compared with representative soil humic acids. The above discrepancies were interpreted as indicating an origin of the respective commercial product other than soil. The two commercial humic acids investigated may not originate from the same source material as evidenced by clear-cut differences in the intensity of the ¹³C-NMR spectra in almost all chemical shift regions. Due to the observed structural, compositional and characteristic dissimilarities, both between soil and commercial humic acids and between different commercial ones, the commercial humic products are not recommended to be used as analogues of real soil humic acids in soil and environmental studies.     

Liquid chromatography/mass spectrometry stable isotope analysis of dissolved organic carbon in stream and soil waters

A commercial interface coupling liquid chromatography (LC) to a continuous‐flow isotope ratio mass spectrometry (CF‐IRMS) instrument was used to determine the δ¹³C of dissolved organic carbon (DOC) in natural waters. Stream and soil waters from a farmland plot in a hedgerow landscape were studied. Based on wet chemical oxidation of dissolved organics the LC/IRMS interface allows the on‐line injection of small volumes of water samples, an oxidation reaction to produce CO₂ and gas transfer to the isotope ratio mass spectrometer. In flow injection analysis (FIA) mode, bulk DOC δ¹³C analysis was performed on aqueous samples of up to 100 μL in volume in the range of DOC concentration in fresh waters (1–10 mg C.L^–1). Mapping the DOC δ¹³C spatial distribution at the plot scale was made possible by this fairly quick method (10 min for triplicate analyses) with little sample manipulation. The relative contributions of different plot sectors to the DOC pool in the stream draining the plot were tentatively inferred on the basis of δ¹³C differences between the hydrophilic and hydrophobic components. Copyright © 2011 John Wiley & Sons, Ltd.