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Speciation of aluminium in forest soil extracts by size exclusion chromatography with UV and ICP-AES detection and cation exchange fast protein liquid chromatography with ETAAS detection.

Aluminium speciation was studied in forest soil extracts by size exclusion chromatography (SE) with UV and inductively coupled plasma-atomic emission spectrometric (ICP-AES) detection and cation exchange fast protein liquid chromatography (FPLC) with ETAAS detection. Size exclusion chromatography was performed on a Superdex HR75 10/30 column. Isocratic clution with 0.15 mol dm(-3) NaCl in TRIS-HCl buffer (pH = 5.5) was applied over 100 min at a flow rate of 0.35 cm(3) min(-1). The chromatographic run was followed at 278 nm and separated Al species also determined 'off line' in 0.875 cm3 fractions by ICP-AES. The analytical procedure enabled speciation of high molecular weight Al complexes. Cation exchange FPLC was performed on a Mono S HR 5/5 column. Aqueous 8 mol dm(-3) NH4NO3 linear gradient elution was applied over 10 min at a flow rate of 1 cm3 min(-1). Separated Al species were collected in 0.5 cm3 fractions and Al determined 'off line' by ETAAS. The analytical procedure enabled speciation of some positively charged monomeric Al species. Negatively charged species were eluted with the solvent front. The combination of the two analytical techniques was successfully employed in speciation of Al in forest soil extracts. Water was used as an extracting solution. It was found experimentally that 80-95% of Al in aqueous extracts of forest soils exists in monomeric Al forms. Water soluble Al (30-40%) is bound to high molecular weight complexes with humic substances. The remaining monomeric Al in the low molecular weight fraction exists as AIF2+, Al-oxalate and Al-citrate species.

Aluminum↗

Aluminium speciation in forest soil solution--modelling the contribution of low molecular weight organic acids.

The concentrations of Al bound to identified low molecular weight organic acids (LMWOAs), phosphate and humic compounds in soil solutions (O1, O2, E, B1 and B2 horizons) from Fennoscandinavian coniferous forest soils were calculated. Two models were evaluated: WHAM (Winderemere Humic Aqueous Model) and a model treating the natural organic acids as monoprotic. The WHAM model was calibrated to find an average charge balance of unity, and then used for Al speciation. This was achieved considering approximately 80% of the natural fulvic acid to be 'active'. For the monoprotic model, constants obtained from previous fitting of soil solution data were used and the model was calibrated using acid/base titrations. The modelling confirms that the low molecular weight acids are important complex formers, binding on average 11-42% (O), 19-20% (E), and 0-30% (B) of the total Al in solution depending on the model used. The monoprotic model yielded higher concentrations than WHAM. Both models predicted that the major part of Al in solution was organically complexed to humic substances and LMWOAs, which was consistent with analytical values of 'quickly reacting' Al (monomenc inorganic forms; 12-14% of Al(tot) on average in the E and B1 solutions). Both models could predict the magnitude of the analytical values (RMSD = 4-5 microM). On average the WHAM model showed a better fit for the E horizon solutions and the monoprotic model for the upper B horizon. The pH dependence of the low molecular weight fraction of Al was modelled in the pH range 3-5.5 for a 'typical' O1 and E solution assuming no other changes in soil solution composition. The extrapolation showed that the models had a different pH dependence. The concentration of Al bound to LMWOAs in WHAM decreased with higher pH while the opposite was seen for the monoprotic model. Also the influence of the concentration of total Al in solution was modelled. The models showed similar trends but for the 'typical' O1 horizon sample the monoprotic model yielded higher concentrations of Al bound to LMWOAs than WHAM.

Aluminum↗

Effects of a fulvic acid on the adsorption of mercury and cadmium on goethite.

The effects of an aquatic fulvic acid on the pH-dependent adsorption of Hg(II) and Cd(II) to particulate goethite (alpha-FeOOH) were studied in batch systems. The ionic medium consisted of 0.01 M HClO(4) and the total concentrations of mercury and cadmium were maintained at 10(-8) M with 203Hg and 109Cd as tracers. pH In the systems was varied in the range 3-10 by addition of HClO(4) and NaOH. All commercial chemicals were of analytical grade or better. An aquatic fulvic acid (20 ppm), previously isolated and characterised in detail, was used as a model for humic substances and its adsorption to goethite is included in this study. The adsorption of the fulvic acid (20 ppm) onto goethite decreased slowly from 90% at pH 3-7.5 to 10% at pH 10. In systems without fulvic acid the adsorption of mercury increased in a linear fashion from 10% at pH 3 to 70% at pH 10. In the presence of fulvic acid (20 ppm), the adsorption was almost quantitative in the intermediate pH range (pH 5-7), and exceeded 92% over the entire pH range. Thus, association between mercury and the fulvic acid enhanced adsorption in general although the largest impact was found at low pH. Adsorption of cadmium increased from nearly 0 to almost 100% at approximately pH 6. In the presence of fulvic acid, the adsorption increased below pH 7 and decreased above pH 7. The adsorption isotherm for mercury when the concentration was increased from 10(-8) to 1.8 x 10(-4) M showed a corresponding increase of K(d) (l/g) up to a total concentration at 10(-6) M. At higher mercury concentrations K(d) was lowered. In the presence of fulvic acid the corresponding relationship of K(d) was bi-modal, i.e. high values at low and intermediate concentrations of mercury. This behaviour suggests that in the absence of fulvic acid the adsorption follow the expected behaviour, i.e. adsorption sites with similar affinity for mercury. In the presence of fulvic acid, additional adsorption sites are available by the organic molecule (possibly sulfur groups) when it is associated to the goethite. The adsorption isotherm for cadmium indicates a lowering of K(d) at 10(-4) M. Cadmium had no competitive effect on mercury and vice versa. Zinc, however, affected the adsorption of cadmium but not the adsorption of mercury.

Adsorption↗

Removal of NOM in the different stages of the water treatment process.

Natural organic matter (NOM) is abundant in natural waters in Finland and in many ways affects the unit operations in water purification. In this study, the organic matter content in water in different stages of a full-scale treatment process over 1 year was measured. The full-scale treatment sequence, studied at the Rusko water treatment plant in Tampere, Finland, consisted of coagulation, flocculation, clarification by sedimentation or flotation, activated carbon (AC) filtration, and disinfection. High-performance size exclusion chromatography (HPSEC) was used for separation to determine changes in the humic substances content during the purification process. In addition, total organic carbon (TOC), KMnO4-number, and UV-absorbance at wavelength 254 nm (UV254) were measured. High molecular weight (HMW) matter was clearly easier to remove in coagulation and clarification than low molecular weight (LMW) matter. Furthermore, depending on the regeneration of the activated carbon filters, activated carbon filtration was effective to a degree but did not remove most of the lowest molecular weight compounds. Significant correlation was established among HPSEC, KMnO4, UV254 absorbance, and TOC. HPSEC proved to be a fast and relatively easy method to estimate NOM content in water and, in fact, gave more information than traditional methods on the type of NOM in a water sample. It also helped the process performance follow-up.

Absorption↗

Enumeration of 16S rDNA of Desulfotomaculum lineage 1 in rice field soil by real-time PCR with SybrGreen detection.

Real-time PCR is a new and highly sensitive method for the quantification of microbial organisms in environmental samples. This work was conducted to evaluate real-time PCR with SybrGreen (SG) detection as quantification method for Desulfotomaculum lineage 1 organisms in samples of rice field soil. The method was optimized in several parameters like SG concentration. These allowed quantitative PCR with different primer combinations yielding PCR products with lengths up to 1066 bp and with sensitivities of 10(2) targets for all assays. The detection limit in environmental DNA extracts (rice bulk soil and rice roots) was 10(6) targets per gram dry weight according to the dilution of the DNA extracts necessary to overcome PCR inhibition of humic substances. A verification, that the fluorescence increase was due to specific PCR products, was done by agarose gel electrophoresis since melting curve analysis of the PCR products did not show a distinct peak in the first derivative, when the environmental DNA extracts were used in PCR. Amplification with a primer combination specific for Desulfotomaculum lineage 1 organisms showed an abundance of this group of approximately 2% and 0.5% of the eubacterial 16S rDNA targets in rice bulk soil and rice root samples, respectively. Approximately half of this number was obtained in both habitats with a PCR assay specific for a Desulfotomaculum sequence cluster obtained previously from rice field soil.

Benzothiazoles↗

Soil carbon content and character in an old-growth forest in northwestern Pennsylvania: a case study introducing pyrolysis molecular beam mass spectrometry (py-MBMS).

This study was conducted to: (1) test the utility of a new and rapid analytical method, pyrolysis molecular beam mass spectrometry (py-MBMS), for the measurement and characterization of carbon in forest soils, and (2) examine the effects of natural disturbance on soil carbon dynamics. An additional objective was to test the ability of py-MBMS to distinguish recent from more stable humic substances, and to relate this information to the ecology and history of the sites. To test the utility of the py-MBMS technique, we investigated soil carbon stocks in a chronosequence of stands arising from natural disturbance in the Tionesta Scenic and Research Natural Areas. Soil carbon increased with increasing time since disturbance; although the exact shape of the carbon accumulation curve is not known, it appears that the rate of carbon accretion is initially rapid and then levels off, with a possible maximum of 86 metric tons/ha to a depth of 30 cm. This study also demonstrates that py-MBMS is a valid method for characterizing soil carbon and can be used with little sample preparation. In addition, multivariate analysis of the mass spectra from Tionesta soils can distinguish both sites and depths on the basis of their pyrolysis products; both long-lived and short-lived carbon forms were identified.

Carbon↗

Predicting the release of metals from ombrotrophic peat due to drought-induced acidification.

Ombrotrophic peats in northern England and Scotland, close to industrial areas, have substantial contents of potentially toxic metals (Al, Ni, Cu, Zn, Cd and Pb) and of pollutant sulphur, all derived from atmospheric deposition. The peat sulphur, ordinarily in reduced form, may be converted to sulphuric acid under drought conditions, due to the entry of oxygen into the peats. The consequent lowering of soil solution pH is predicted to cause the release of metals held on ligand sites of the peat organic matter. The purpose of the present study was to explore, by simulation modelling, the extent of the metal response. Chemical variables (elemental composition, pH, metal contents) were measured for samples of ombrotrophic peats from three locations. Water extracts of the peats, and samples of local surface water, were also analysed, for pH, dissolved organic carbon (DOC) and metals. Metal release from peats due to acidification was demonstrated experimentally, and could be accounted for reasonably well using a speciation code (WHAM/Model VI). These data, together with information on metal and S deposition, and meteorology, were used to construct a simple description of peat hydrochemistry, based on WHAM/Model VI, that takes into account ion-binding by humic substances (assumed to be the "active" constituents of the peat with respect to ion-binding). The model was used to simulate steady state situations that approximated the observed soil pH, metal pools and dissolved metal concentrations. Then, drought conditions were imposed, to generate increased concentrations of H2SO4, in line with those observed during the drought of 1995. The model calculations suggest that the pH will decrease from the initial steady state value of 4.3 to 3.3-3.6 during rewetting periods following droughts, depending upon assumptions about the amount of potentially mobile soil S. The pH decreases will be accompanied by increases in concentrations of dissolved metals (Mg, Al, Ca, Ni, Cu, Zn, Cd, Pb) of an order of magnitude or more, depending upon assumptions about the replenishment of soil metal pools by deposition. In the most realistic scenario for present conditions, the severity of pH depressions will gradually decline due to the relatively slow depletion of the soil S pool by droughts. However, the magnitudes of heavy metal pulses will decline quite rapidly (over two or three droughts) because current and future metal deposition is unable to compensate for leaching losses from the soil pools.

Disasters↗

Preliminary study of prairies forested with Eucalyptus sp. at the northwestern Uruguayan soils.

The land cover change of Uruguayan Forestal Plan provoked biogeochemical changes on horizon Au(1) of Argiudols; in native prairies which were replaced by monoculture Eucalyptus sp. plantation with 20 year rotations as trees. Five fields forested and six natural prairies were compared. The results not only show a statistical significant soil acidification, diminution of soil organic carbon, increase of aliphaticity degree of humic substances, and increase of affinity and capacity of hydrolytic activity from soil microbial communities for forested sites with Eucalyptus sp. but also, a tendency of podzolization and/or mineralization by this kind of land cover changes, with a net soil organic lost of 16.6 tons ha(-1) in the horizon Au(1) of soil under Eucalyptus sp. plantation compared with prairie. Besides, these results point out the necessity of correction of the methodology used by assigned Uruguayan commission to assess the national net emission of greenhouse gases, since the mineralization and/or podzolization process detected in forested soil imply a overestimation of soil organic carbon. The biochemical parameters show a statistical significant correlation between the soil organic carbon status and these parameters which were presented as essential for the correct evaluation of Uruguayan soil carbon sink.

Agriculture↗

The environmental hazard caused by smelter slags from the Sta. Maria de la Paz mining district in Mexico.

The noxious potential of metallurgical tailings from the Ag/Pb/Zn/Cu mining district of Sta. María de la Paz (Mexico) is ascertained via the chemical characterization of slag material. Batch experiments using various extraction solutions (e.g. natural rainwater, water rich in humic substances, ammonium nitrate solution) revealed information on the dissolution behaviour of the elements Fe, Mn, Ni, Cu, Zn, As, Ba and Pb from slag with respect of grain size (slag material screened under 2 mm and analytically fine fraction) and elution time (2, 7.5, 24 and 240 h). An initial ecotoxicological assessment of the results is made and the environmental danger caused by large volumes of slag tailings is discussed.

Journal Article↗

Experimental approaches and analytical techniques for determining organic compound bound residues in soil and sediment.

Research has shown that many chemicals form persistent and permanently bound residues in soils and sediments that play an important role in soil and sediment detoxification processes, long-term compound partitioning behaviour and compound bioavailability and toxicity in soil and sediment. This article reviews the methodological approaches that have been applied to determine the nature of bound residues in soil and sediment, the application of specific analytical techniques, the type of information they generate, and their relative advantages and disadvantages. It begins by defining bound residues and discussing soil-compound interactions. The application of model compound studies for elucidating specific binding interactions is reviewed along with long-term laboratory and field soil incubation experiments. The use of radiolabelled compounds, isotopically labelled compounds and combinations of both in these experiments are outlined by examples from the literature, along with sequential extraction schemes for releasing bound residues from soil, sediment and humic materials. The importance of spectroscopic methods, and particularly nuclear magnetic resonance techniques for characterising the structure of bound residues in soil and sedimentary humic substances is discussed and illustrated by examples from the literature on the subject. The process of bound residue formation is highly complex and requires further research to establish the mechanisms of bound residue formation and their subsequent environmental and toxicological fate. Much of the uncertainty regarding the elucidation of bound residue formation arises from our poor understanding of the structure of soil and sedimentary organic matter. Significant advances in our understanding of the formation and fate of bound residues will be made when we develop a deeper insight into the complex and heterogeneous structure of soil and sedimentary organic matter.

Journal Article↗

Characterisation of soil-bound residue fractions of the fungicide dithianon by gel permeation chromatography and polyacrylamide gel electrophoresis.

The degradation of the (14)C-labelled fungicide dithianon in an orthic luvisol was investigated under standardized conditions in comparison to stimulated microbial activity by an amendment of maize straw. The compound is characterized by mineralization losses of approximately 33% and the formation of non-extractable bound residues of approximately 63% in 64 days. Despite the major role of microorganisms in mineralizing this compound, the formation of bound residues is not biotically induced. Gel permeation chromatography and polyacrylamide gel electrophoresis, as different size separation techniques of the humic acids fractions, showed differences in the distribution patterns of non-extractable residues depending on the addition of straw material. The results presented support the existence of humic substances in soil as a micellar system rather than as a biopolymer.

Journal Article↗

Organic matter components, aggregate stability and biological activity in a horticultural soil fertilized with different rates of two sewage sludges during ten years.

The effects of the application as fertilizer during ten years of two sewage sludges (aerobically and anaerobically digested, at rates of 400, 800, and 1200 kg of N/ha yr), on the aggregate stability and contents of related organic matter components, microbial biomass and levels of five enzymatic activities (alkaline phosphomonoesterase, phosphodiesterase, urease, arylsulphatase and dehydrogenase) were investigated. The application of both sludges at mid and high rates gave rise to significant increases of organic matter, humified substances and humic acids, but no effects on carbohydrates, microbial gums and aggregate stability were observed. As for biological activity in soils, the high variability of data led to a general absence of statistical significance despite the large differences between treatments observed. Significant increases of phosphodiesterase activity were nevertheless produced by the high rate of aerobic sludge and the mid and high rates of the anaerobic sludge.

Arylsulfatases↗

Mature green waste compost enhances growth and nitrogen uptake in wheat (Triticum aestivum L.) and oilseed rape (Brassica napus L.) through the action of water-extractable factors.

A series of field and pot trials were carried out to determine the effects of growing wheat and oilseed rape in soils supplemented with green waste composts and provided with additional fertilisers. It was shown consistently that the response of wheat and rape to compost and fertiliser applied together was greater than the responses to the individual additives, but only when very stable compost was used (>10 months processing). Experiments with 15N-labelled fertiliser showed that wheat was able to utilise the applied N more efficiently when cultivated in the stable compost. The enhanced growth was also demonstrated in hydroponic culture of oilseed rape with water extracts of green waste compost in the presence of compound fertiliser. However the effect was rapidly lost at higher dilutions of compost extract (>3). It was concluded that water-extractable growth promoters are present in stable green waste compost, but these only have measurable activity at high concentrations. The identity of the growth promoting factors remains to be found, but the literature suggests that water-extractable humic substances or cytokinins may be involved.

Brassica napus↗

Glyphosate immunosensor. Application for water and soil analysis.

A fully automated immunosensor for the herbicide glyphosate has been developed on the basis of the immunocomplex capture assay protocol. The sensor carries out on-line analyte derivatization prior to the assay and uses a selective anti-glyphosate serum, a glyphosate peroxidase enzyme tracer, and fluorescent detection. Under optimal conditions, the detection limit achieved is 0.021 microg/L with an analysis rate of 25 min per assay, autonomy of more than 48 h, and sensor reusability >500 analytical cycles. The immunosensor is able to discriminate structurally related molecules, such as aminomethylphosphonic acid, the main metabolite of glyphosate, and other related herbicides, such as glufosinate and glyphosine. Interferences from naturally occurring species (anions, cations, and humic substances) and their elimination were also studied. The immunosensor has been successfully applied to water and soil sample analysis, with good recoveries at levels lower than 1 microg/L. Results obtained with the immunosensor correlate well with data from a magnetic particle ELISA and LC/LC/MS chromatographic method.

Glycine↗

Modified pulsed-field gradient NMR experiments for improved selectivity in the measurement of diffusion coefficients in complex mixtures: application to the analysis of the Suwannee River fulvic acid.

To simplify the complex 1H NMR spectrum of a fulvic acid sample and gain structural and molecular size information, spectral editing techniques were used in conjunction with a general PFG NMR pulse sequence. These editing techniques exploit differences in T1 and T2 relaxation times as well as differences in coupling constants. The experiments were initially performed on a model mixture of glutamic acid and ethyl acetate in order to validate the method as a technique for measurement of diffusion coefficients. The editing experiments were then applied to the International Humic Substances Society Suwannee River fulvic acid standard. These editing techniques allowed more selective measurement of diffusion coefficients for broad classes of components within regions of the 1H NMR spectrum of the fulvic acid solution. The average radii of gyration calculated for the Suwannee River fulvic acid sample from the diffusion coefficients are in good agreement with literature values.

Acetates↗

Effect of experimental parameters on the ESI FT-ICR mass spectrum of fulvic acid.

Fulvic acid (FA) is a heterogeneous mixture of organic macromolecules found in the waters, soils, and sediments of the earth's surface. The ability of electrospray ionization (ESI) to effectively transfer large ions from the solution phase to the gas phase and the coupling of ESI to the high-mass-resolution capabilities of Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) provide a potential method for the mass spectrometric analysis of FA. Positive- and negative-ion ESI FT-ICR MS analyses of four reference International Humic Substances Society FAs were performed. The spray solution composition was found to have a dramatic effect on the ion distributions, with high-mass aggregates (m/z approximately 2000-4000) being formed in less polar spray solutions. Positive-ion spectra for each FA obtained under optimum conditions resulted in number-average molecular weights ranging from 1700 to 1900. The mass spectra were extremely complex, with ion distributions on the order of m/z approximately 500-3000. The presence of more than one ion at each nominal mass was routinely observed. Negative-ion ESI analysis of the FA samples resulted in the observation of multiply charged ions whose distributions could be affected by the acidification of the spray solution. Solution parameters which have been reported to affect molecular weight distributions of FA such as pH, ionic strength, and concentration of multivalent cations were found to have little or no effect on the observed m/z distributions.

Benzopyrans↗

Anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA).

The potential for anaerobic degradation of methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) was investigated in laboratory incubations of sediments from a petroleum-contaminated aquifer and in aquatic sediments. The addition of humic substances (HS) stimulated the anaerobic degradation of MTBE in aquifer sediments in which Fe(III) was available as an electron acceptor. This is attributed to the fact that HS and other extracellular quinones can stimulate the activity of Fe(III)-reducing microorganisms by acting as an electron shuttle between Fe(III)-reducing microorganisms and insoluble Fe(III) oxides. MTBE was not degraded in aquifer sediments without Fe(III) and HS. [14C]-MTBE added to aquatic sediments adapted for anaerobic MTBE degradation was converted to 14CO2 in the presence or absence of HS or the HS analog, anthraquione-2,6-disulfonate. Unamended aquatic sediments produced 14CH4 as well as 14CO2 from [14C]-MTBE. The aquatic sediments also rapidly consumed TBA under anaerobic conditions and converted [14C]-TBA to 14CH4 and 14CO2. An adaptation period of ca. 250-300 days was required prior to the most rapid anaerobic MTBE degradation in both sediment types, whereas TBA was metabolized in the aquatic sediments without a lag. These results demonstrate that, under the appropriate conditions, MTBE and TBA can be degraded in the absence of oxygen. This suggests that it may be possible to design strategies for the anaerobic remediation of MTBE in petroleum-contaminated subsurface environments.

Anaerobiosis↗

Formate ion decomposition in water under UV irradiation at 253.7 nm.

Formate ion (HCO2-) occurs in natural waters as a result of photooxidation of humic substances. Under UV irradiation, as applied in water purification (253.7 nm), formate ion decomposed following split-rate pseudo-zero-order kinetics (k1 and k2 are initial and final rate constants, respectively). In the presence of dissolved oxygen (DO), it was found that (a) k1 < k2, (b) k1 and k2 increased with initial formate ion concentration ([HCO2-]0 = (1.73-38.3) x 10(-5) mol L(-1)) and absorbed UV intensity (Ia = (1.38-3.99) x 10(-6) mol quanta L(-1) s(-1)), and (c) k1 and k2 were relatively insensitive to initial pH (pHo = 5.41-8.97) in buffer-free solutions. Both rate constants decreased with increasing carbonate alkalinity ((0-1.0) x 10(-3) mol L(-1)) and k1 was virtually unchanged in phosphate buffer at pH0 between 5.25 and 9.92. Carbonate buffer lowered the rate of formate ion decay, possibly due to scavenging of OH* radicals. Initial rate constant k1 slightly increased with temperature (15-35 degrees C), while k2 remained unchanged. The reaction pH increased rapidly during irradiation of buffer-free NaHCO2 solution to approach an equilibrium level as [HCO2-] reached the method detection level (MDL). The pH profile of buffer-free formate ion decay was estimated using closed-system equilibrium analysis. DO utilization during UV irradiation was 0.5 mol of O2/mol of HCO2-, while nonpurgeable organic carbon (NPOC) measurements on kinetic samples closely followed the HCO2- profile, thus strongly suggesting the transformation of HCO2- -C to CO2 in the presence of DO. In DO-free water, k1 > k2 was observed. Furthermore, k(1,DO FREE) > k(1,DO) (k(1,DO) = k1) and k(2,DO FREE) < k(2,DO) (k(2,DO) = k2). The effect of dual acid solutions on HCO2- decay was examined in a mixture of NaHCO2 and sodium oxalate (Na2C2O4). HCO2- decomposed readily until [HCO2-] approximately equal to MDL but at a lower rate than in buffer-free HCO2- solutions, while C2O4(2-) remained virtually unchanged. C2O4(2-) decay commenced following near complete conversion of HCO2-.

Formates↗