Quantitative comparison of the nitrogen-containing pyrolysis products and amino acid composition of soil humic acids

Pyrrole and acetonitrile, major pyrolysis products of soil humic substances, vary characteristically in abundance with the degree of humification of the organic matter in the soil. Their origin, however, is uncertain because of the large amount of unidentifiable soil nitrogen. A quantitative relationship between amino acid composition and pyrrole and acetonitrile abundances has been established by Curie-point pyrolysis-gas chromatography of a group of test proteins, using polystyrene as an internal standard. The pyrolysis yields of these products from three humic acids extracted from the surface horizons of Scottish brown forest soils (Cambisols or Ochrepts) were entirely accounted for by the known hydrolysable amino acid content and composition, and the products were related to individual amino acids. The peptide amino acid was also found to be the overall source of the aromatic pyrolysis products toluene, phenol and p-cresol.     

Multielemental analysis of soil samples by fast-neutron activation

Neutron activation analysis (NAA) have been used for the determination of major, minor, and trace elements in 20 soil samples from 5 crop fields of the Crop Research Centre, Pantnagar, India. Fast neutron activation analysis (FNAA) and cyclic neutron activation analysis (CNAA) have been used to determine the concentrations of various elements. The results for minor and trace elements are compared with the level of abundances of world soils. The present study provides the basic data of elemental concentrations in soil samples of 5 major crop fields located in one of the leading agricultural universities of India for future measurements with the objectives of efficient use of fertilizers and pesticides in accordance with the high yield.     

Rapid molecular assessment of the bioturbation extent in sandy soil horizons under pine using ester-bound lipids by on-line thermally assisted hydrolysis and methylation-gas chromatography/mass spectrometry

Each plant species has a unique chemical composition, and also within a given plant the various tissues differ from one another in their chemistry. These different compositions can be traced back after decay of the plant parts when they are transformed into soil organic matter (SOM). As a result, the composition of SOM reflects not only the plant origin, but also the various tissues, and the composition consequently provides an estimate of the contribution of above-ground vs. below-ground litter. From the latter distribution the extent of bioturbation (mixing of above-ground litter with the mineral soil) can be assessed.Application of thermally assisted hydrolysis and methylation (THM) using tetramethylammonium hydroxide (TMAH) and subsequent analysis by gas chromatography/mass spectrometry (GC/MS) releases all typical cutin- and suberin-derived aliphatic monomers (mono-, di- and trihydroxyalkanoic acids, alpha,omega-alkanedioic acids) as their methyl esters and/or ethers in a rapid manner. Using the distribution of omega-hydroxyalkanoic acids that are present in pine needle cutin (C(12) and C(14)) and not in root suberin, and those that are present in roots but not in needles (C(20) and C(22)), the extent of bioturbation (mixing of above-ground plant litter with the mineral soil) can be assessed. Similarly, the (9,16-dihydroxyhexadecanoic acid+9,10,18-trihydroxyoctadecanoic acid)/(C(20) + C(22) alpha,omega-alkanedioic acids) ratio reflects the degree of bioturbation. Three mineral soil profiles under Corsican pine with an A horizon that exhibited extensive bioturbation phenomena, and underlying C horizons with hardly any or no bioturbation, were investigated in order to examine the applicability of such an approach. It appeared that the A horizons contained all four mentioned omega-hydroxyalkanoic acids, while the C horizons contained virtually only the C(20) and C(22) members. The results not only suggest that bioturbation occurs in the A horizons, but also that possible illuviation or other transport mechanisms of omega-hydroxyalkanoic acids seem hardly ever or never to occur, which is a prerequisite for applying this biomarker approach in assessing degrees of bioturbation.     

Fluorine sorption by soils developed from various parent materials in Galicia (NW Spain)

Fluorine is a phytotoxic element that can reach the soil from various industrial activities. Fluorine sorption by soil is crucial to protect water and food chain from fluorine pollution. In Galicia (NW Spain), various activities emit fluorine into the atmosphere, mainly ceramic industries and an aluminium smelter. This study, aiming to investigate fluorine sorption by Galician soils, was conducted on natural soil horizons representative of the area. Most soils were acid and rich in organic matter and showed strong fluorine sorption. The lowest sorptions were exhibited by a near-neutral serpentinite-derived soil (1001 mg kg(-1)) and the B horizons of soils developed from quartz schist (989 mg kg(-1)), and the highest by the A horizons of amphibolite-derived soils (1783 mg kg(-1)). In soils developed from quartz schist, biotitic schist and amphibolite, A horizons sorbed more fluoride than the corresponding B horizons (average 1621 and 1324 mg kg(-1), respectively), while the opposite is true in granite-derived soils (average 1644 and 1324 mg kg(-1), respectively). In the A horizons, the F sorption significantly correlated to soil pH (r=-0.79), pH in NaF (r=0.83) and oxalate Al (r=0.81). In the B horizons, sorption correlated to soil pH (r=-0.78), oxalate Fe (r=0.71) and organic C (r=0.66). F sorption can be described by both the Langmuir and Freundlich equations. The concentration of free fluoride in the equilibrium solutions increased above pH 6.     

Instrumentelle Aktivierungsanalyse an Lunarem Material

Lunar soil samples of the Luna 16 Luna 20 missions were analysed by neutron activation in a neutron generator and a nuclear reactor, respectively, and following gammaspectrometry by NaI(T1) and Ge(Li) detectors. By 14 MeV neutron activation there were determined the abundances of 5 major elements (O, Mg, Al, Si, Fe) and by reactor activation the abundances of 18 major and trace elements (Na, K, Sc, Cr, Mn, Fe, Co, Mo, La, Ce, Sm, Eu, Tb, Yb, Lu, Hf, W, Th) and the detection limits of 4 additional elements (As, Rb, Sb, Cs). The standard rocks BM and GM of the ZGI were used as standards in the reactor activation analysis.     

Geochemistry of Holocene and late Pleistocene soils in the Rouge River and Scarborough Bluffs areas,South-Central Ontario,Canada

Concentrations of major, minor and trace elements were measured in four soil profiles from south-central Ontario. The mean concentration values reported are probably representative of elemental levels in soils formed from sediments reworked by lacustrine and fluvial processes and weathered over the last 12 000 years. The older soils in the sequence (R12, R15 and BRIM1) show declining Na, K, and Al, mainly from Ca dilution, especially in the lower horizons. Iron and Mg levels were not affected by the variations in the Ca concentrations. Arsenic, Br, and Sb concentrations did not increase appreciably in surface A horizons, indicating no measurable airfall influx of industrial pollutants. The relative increase in Mn/Al in the lower horizons of the older soils may be related to leaching by soil or ground water movement.     

Geochemistry of Spodosols formed in holocene till, Norra Storfjället Massif, northern Sweden

Silt and clay size fractions of soils, from a transect of six Spodosols formed in the Norra Storfjället Massif, were analyzed by neutron activation to determine the degree to which pedogenic processes have influenced the distribution of macro, micro and trace elements. The distributions of Mg, Ca and Fe, together with Co, Cr and other trace elements in the profiles, suggest the presence of different parent materials, with A and E horizons arising from an influx of aeolian sediment. Translocation processes, both physical and chemical, occurred in the soil concentrating Fe and Br in the spodic (Bs) horizons of the profiles. The rare earth elements (REEs) are predominantly associated with the heavy mineral fraction of the soil material. The distributions of chondrite normalized REEs patterns of the profiles indicate that light rare earth element (LREE) concentrations increase with horizon depth. The depletion of LREEs in the upper soil horizons confirms the presence of material that is chemically different from that in the lower horizons, thus indicating a distinct chemical difference from the local glacial deposits.     

Expert system for nuclide identification and interpretation of gamma-spectrum analysis

Trace element data (Sc, Cr, Co, Hf, Ta and Th) are reported for a weathering profile of gabbroic rocks located near Serpa, Portugal. The results obtained for the whole rock samples showed that: (i) Co and Sc contents decrease upwards the profile. Co appears to be mobilized in the soil probably as soluble cation; (ii) Cr tends to remain in the profile; and (iii) Hf and Th concentrate in the upper horizons. Trace element distribution in different size fractions of the upper horizons revealed: (i) Sc, Cr and Co have a more uniform distribution than Hf, Ta and Th; (ii) Hf and Ta are concentrated in the intermediate fractions; and (iii) Th is concentrated in the finer fractions, probably due to incorporation in weathering resistant minerals, specially in the initial stages of weathering.     

Use of the diffusive gradients in thin films technique (DGT) with various diffusive gels for characterization of sewage sludge-contaminated soils

The diffusive gradients in thin film technique (DGT) was used for characterization of South Moravian arable soils (sampling sites Zlín, Tuřany, and Chrlice) amended by sewage sludge in the 1980s. Two types of polyacrylamide diffusive gel with different pore size (APA gels—cross-linked with agarose and RG gels—cross-linked with bis-acrylamide) were employed. The (bio)available parts of Cd, Cu, and Ni and the proportions of inorganically and organically complexed species of these metals were assessed. The degree of metal resupply from the soil solid phase to the soil solution was also determined. Metal concentrations obtained by the DGT technique were lower by almost 4 to 5 orders of magnitude in comparison with those obtained by extraction with aqua regia. DGT concentrations of metals were also lower by approximately 1 to 2 orders of magnitude in comparison with those obtained by extraction with sodium nitrate (commonly used for assessment of the (bio)available part of metals). Results obtained by DGT measurement were expected to be closer to the actual content of available metal species than results obtained by extraction with sodium nitrate. Using RG gels together with APA gels provided resolution of inorganically and organically complexed metal species and their proportional representation. Inorganic metal species (particles smaller than 1 nm) formed a predominant part of assessed metal content in all studied soil samples and horizons. However, there was the exception of the cadmium content in the middle profile of Chrlice sandy soil sample. Ratio R values indicated that resupply of Cd, Cu, and Ni from the solid phase to the soil solution varied for individual soil samples and individual depth profiles. Mobile and labile species of Cd, Cu, and Ni were much more closely related to upper rather than deeper horizons. This observation correlates very well with the mechanical treatment and amendment of the studied soils.     

Native surface structure of natural soil particles determined by combining atomic force microscopy and X-ray photoelectron spectroscopy

A procedure was developed for handling natural soil particles and probing their native surface structure by atomic force microscopy (AFM) under water. This procedure was used to investigate the nanometer scale organisation of organic matter at the surface of sand particles taken from three soil horizons. The latter were selected for the contrasted properties of their organic matter, namely Podzol E and Bh horizons and a Cambisol A–B horizon. The presence of an adsorbed layer was visualised at the surface of Podzol Bh and Cambisol particles in the form of aggregated structures that interacted with the AFM probe. Surface analysis by X-ray photoelectron spectrometry (XPS) confirmed the carbonaceous nature of this adsorbed layer. Displacement of organic matter by the scanning probe was directly evidenced for Podzol Bh sand particles. Such displacement was not observed for Cambisol particles. A dramatic effect of drying on the concentration, nanometer scale distribution and properties of the adsorbed organic matter was clearly demonstrated by combining AFM imaging and XPS analysis. The procedure developed here gives access to direct, nanoscale information of the surface structure of sand particles and offers promising prospects for the characterisation of other environmentally-relevant particles in native conditions.     

Mercury and trace element fractionation in Almaden soils by application of different sequential extraction procedures

A comparative evaluation of the mercury distribution in a soil sample from Almaden (Spain) has been performed by applying three different sequential extraction procedures, namely, modified BCR (three steps in sequence), Di Giulio–Ryan (four steps in sequence), and a specific SEP developed at CIEMAT (six steps in sequence). There were important differences in the mercury extraction results obtained by the three procedures according to the reagents applied and the sequence of their application. These findings highlight the difficulty of setting a universal SEP to obtain information on metal fractions of different mobility for any soil sample, as well as the requirement for knowledge about the mineralogical and chemical characteristics of the samples. The specific six-step CIEMAT sequential extraction procedure was applied to a soil profile (Ap, Ah, Bt1, and Bt2 horizons). The distribution of mercury and major, minor, and trace elements in the different fractions were determined. The results indicate that mercury is mainly released with 6 M HCl. The strong association of mercury with crystalline iron oxyhydroxides, present in all the horizons of the profile, and/or the solubility of some mercury compounds in such acid can explain this fact. Minor mercury is found in the fraction assigned to oxidizable matter and in the final insoluble residue (cinnabar).     

Chemometric analysis of soil pollution data using the Tucker N-way method

N-way methods, particularly the Tucker method, are often the methods of choice when analyzing data sets arranged in three- (or higher) way arrays, which is the case for most environmental data sets. In the future, applying N-way methods will become an increasingly popular way to uncover hidden information in complex data sets. The reason for this is that classical two-way approaches such as principal component analysis are not as good at revealing the complex relationships present in data sets. This study describes in detail the application of a chemometric N-way approach, namely the Tucker method, in order to evaluate the level of pollution in soil from a contaminated site. The analyzed soil data set was five-way in nature. The samples were collected at different depths (way 1) from two locations (way 2) and the levels of thirteen metals (way 3) were analyzed using a four-step-sequential extraction procedure (way 4), allowing detailed information to be obtained about the bioavailability and activity of the different binding forms of the metals. Furthermore, the measurements were performed under two conditions (way 5), inert and non-inert. The preferred Tucker model of definite complexity showed that there was no significant difference in measurements analyzed under inert or non-inert conditions. It also allowed two depth horizons, characterized by different accumulation pathways, to be distinguished, and it allowed the relationships between chemical elements and their biological activities and mobilities in the soil to be described in detail.     

Sorption, desorption and extraction of cadmium from some arable and forest soils

Summary The behavior of cadmium labeled with ¹⁰⁹Cd in different depth horizons of arable and forest soils were studied under static (batch) conditions in three interconnected processes, which consist of sorption, desorption and extraction. In the sorption, Cd²⁺ was applied in the aqueous calcium nitrate solution. Both untreated soils and peroxide treated soils were used in order to remove organic matter from some of the soil samples used in parallel. The influence of the V/m ratio on the sorption coefficients was investigated in preliminary experiments with untreated soils. Contrary to the usually short-term sorption, a long-term sorption of cadmium was investigated in untreated and treated soil horizons, which lasted more than fortnight. Kinetic studies of sorption were carried out and cadmium concentration dependence in aqueous phase of the second order kinetic constants was observed. For evaluation of sorption and desorption processes Freundlich isotherms were used. It was found that the Freundlich adsorption intensity coefficient is more time dependent than the absorption capacity coefficient, and the sorption itself consists of rapid and slow processes according to the soil constituents. Desorption and extraction processes revealed the possibility of cadmium recovery from various soil horizons. Based on the obtained results two- or three-stage theory of cadmium retention in soils was proposed. Some new insight into the role of organic matter in the sorption/desorption process of cadmium is also presented.     

Cluster analysis of the elemental composition of five austrian peats

The elemental composition of peat depends on the plant residues from which the peat was formed. The concentrations of 45 elements were determined for five peat samples by plasma emission spectrometry. Literature data on the composition of three bogs was added. The elemental abundances of six rock or soil categories, the elemental compositions of several peat-forming plants, and the results of the elemental analyses of bog samples, were examined by the SIMCA method. A clear difference was found between fens and raised bogs. Factor analysis of the elemental compositions shows that the concentrations of most of the elements reflect their natural abundance in the surrounding region. Some concentrations are influenced by anthropogenic pollution, e.g. lead, and by plant metabolism. The cluster analysis together with the training sets shows the degree of the deposition of mineral material from adjacent rivers and the type of plant growth which formed the peat.     

Measurement of radiocesium in Irish peatland soils

Results are presented for soils taken from twelve peatland sites in Ireland. Two depth horizons, 0–5 and 5–15 cm, were sampled on each site and sampling was carried out in summer and autumn. Deposition of Chernobyl¹³⁷Cs varied between 0.4 and 4.6 kBq m^–2, which is at the lower end of values reported by other authors for Irish agricultural soils. The data showed that the relative percentages of activity and deposition remained internally consistent in each soil horizon for Chernobyl and weapons fallout sources on both sampling occasions: this provided evidence that sampling and analytical procedures were consistent. An apparent reversal in the relative importance of weapons fallout in soils was found when deposition data were compared to the same data presented in activity format, and this same reversal was found for both soil horizons. Different conclusions may erroneously be drawn from data depending on the parameter by which we make measurements. Presentation of results should be carefully considered and depends on the purpose for which a study is intended. A statistically significant change in bulk density of the deeper soil horizon was found between summer and autumn. Changes in bulk density important to bear in mind that in addition to analytical errors, sampling methods can only provide estimations which themselves have inherent sources of error.     

Functional Gene Abundances (nahAc, alkB, xylE) in the Assessment of the Efficacy of Bioremediation

In this study, we compared the mineralization rates of three selected (14)C-labeled hydrocarbon compounds, octacosane, toluene, and naphthalene, with the presence of the corresponding functional genes (alkB, xylE, nahAc) in a large number of soil samples representing different types of soil and petroleum hydrocarbon contamination. Functional genes were enumerated by the replicate limited dilution (RLD) polymerase chain reaction (PCR) technique. RLD-PCR was further compared to real-time PCR measurements for nahAc and xylE for some samples. At a heating oil-contaminated site, octacosane mineralization rates were higher (on average 0.0015 day(-1)) when compared to aerobic naphthalene and toluene mineralization (on average 0.00003 and 0.0007 day(-1)). The corresponding gene abundances measured by RLD-PCR were on average 0.95, 0.3, and 0.13 x 10(3) gene copies g(-1) soil for alkB, nahAc, and xylE, respectively. At a site contaminated with gasoline, the situation was the opposite: Toluene mineralization was the highest (on average 0.0031 day(-1)), and only xylE genes could be detected (on average 0.13 x 10(3) gene copies g(-1) soil by RLD-PCR). XylE and nahAc gene abundances were correlated with the (14)C-toluene and naphthalene mineralization activities, respectively, in samples from aerobic layers. AlkB gene abundances were not correlated with the octacosane mineralization. Real-time PCR was a more sensitive method than RLD-PCR by a factor of 1,200 for nahAc and 300 for xylE. In conclusion, functional gene abundances seemed to reflect the type of the contamination. With optimized assays, the gene abundances can be used to assess bioremediation efficacy.     

Molecular features of organic matter in diagnostic horizons from andosols as seen by analytical pyrolysis

Andosols are usually formed from volcanic substrates, with thick A horizons high in organic carbon mainly in the form of stabilized humic fractions. The peculiar properties of these soils are, to large extent, affected by poorly crystalline materials like allophanes, imogolite and other Fe and Al oxyhydroxides that induce intense organo-mineral interactions which are considered to play a relevant role in OM protection against biodegradation as regards other soils developed under similar climatic conditions. Little is known about the molecular composition of this stabilized OM in a soil scenario often considered as an efficient C-sink in terms of C sequestration processes.

Whole soil samples in addition to isolated humic and fulvic acids from organic A horizons of three soils with andic properties and one non-andic soil (Sodic Cambisol) from the island of Tenerife (Canary Islands, Spain) were analysed by double shot pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS) in order to get some insight on the molecular composition of different structural domains of progressive structural stability.

Clear differences were found between soils, both in thermal desorption and pyrolysis behaviour of humic substances. In general the results suggest large yields of aliphatic (both alkyl and carbohydrate-derived pyrolysis compounds) pointing to high-performance processes of incorporation of aliphatic humic constituents in andosols probably favoured by interactions with amorphous minerals, whereas in non-andic soils the latter are comparatively less stabilized and are removed in early pyrolysis stages as if they occurred as loosely joined, thermoevaporation-released products.

In fact, compared to Cambisol, humic and fulvic acids from andic soils led to comparatively richer pyrograms and compound assemblages. The lack of similar amounts of these loosely joined, mainly aliphatic structures after thermal desorption of the whole andic soils indicate an origin for humic substances based on rapid sequestration of C-forms of recent (litter or microbial) origin.     

Molecular features of organic matter in diagnostic horizons from andosols as seen by analytical pyrolysis

Andosols are usually formed from volcanic substrates, with thick A horizons high in organic carbon mainly in the form of stabilized humic fractions. The peculiar properties of these soils are, to large extent, affected by poorly crystalline materials like allophanes, imogolite and other Fe and Al oxyhydroxides that induce intense organo-mineral interactions which are considered to play a relevant role in OM protection against biodegradation as regards other soils developed under similar climatic conditions. Little is known about the molecular composition of this stabilized OM in a soil scenario often considered as an efficient C-sink in terms of C sequestration processes.Whole soil samples in addition to isolated humic and fulvic acids from organic A horizons of three soils with andic properties and one non-andic soil (Sodic Cambisol) from the island of Tenerife (Canary Islands, Spain) were analysed by double shot pyrolysis-gas chromatography–mass spectrometry (Py-GC/MS) in order to get some insight on the molecular composition of different structural domains of progressive structural stability.Clear differences were found between soils, both in thermal desorption and pyrolysis behaviour of humic substances. In general the results suggest large yields of aliphatic (both alkyl and carbohydrate-derived pyrolysis compounds) pointing to high-performance processes of incorporation of aliphatic humic constituents in andosols probably favoured by interactions with amorphous minerals, whereas in non-andic soils the latter are comparatively less stabilized and are removed in early pyrolysis stages as if they occurred as loosely joined, thermoevaporation-released products.In fact, compared to Cambisol, humic and fulvic acids from andic soils led to comparatively richer pyrograms and compound assemblages. The lack of similar amounts of these loosely joined, mainly aliphatic structures after thermal desorption of the whole andic soils indicate an origin for humic substances based on rapid sequestration of C-forms of recent (litter or microbial) origin.     

Determination of low molecular weight organic acids in soil solution by HPLC

An HPLC method employing an ion exclusion column was developed for the determination of low molecular weight organic acids in soil solution. The method includes extensive sample pretreatment using ultrafiltration and cation exchange. The method showed linear calibration graphs (r>0.99) and the limits of detection in the range 0.1-26 muM. The recovery of eleven added acids ranged from 89 to 102%. Soil solutions of five horizons of a podzolised soil were analysed. The results showed that these compounds made up 1-3% of the dissolved organic carbon and 0-14% of the acidity. Identification of the major acids was also carried out by capillary zone electrophoresis.     

Isotope beating effects in the analysis of polymer distributions by Fourier transform mass spectrometry

For Fourier transform mass spectrometry analysis of high mass ions, the signals from closely spaced isotope peaks undergo periodic destructive interference, producing a beat pattern in the time-domain signal. The mass spectra that are obtained by sampling transient signals for less than two beat periods exhibit an error in the relative abundances that are measured. This effect is shown to cause significant errors in the measurement of the relative abundances of the components of polymer distributions, leading to errors in the derived average molecular weights for such samples. Computer simulations show that isotope beating causes this error to increase as the duration of an acquired transient becomes short compared to the beating period. This error becomes insignificant when the transient is acquired for longer than twice the beat period. Experimental data are presented for polymers in which an oligomeric distribution of monoisotopic peaks is produced by stored waveform inverse Fourier transform ejection of all ¹³C-containing isotope peaks. The data show that the isotope beating-induced abundance errors are eliminated when there are no isotope peaks present.