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The stabilizing effect of water molecule bridges on polar regions in humic substances (HSs) has been investigated by means of molecular dynamics (MD) simulations. The purpose of these investigations was to show the effect of water molecular bridges (WAMB) for cross-linking distant locations of hydrophilic groups. For this purpose, a tetramer of undecanoid fatty acids connected to a network of water molecules has been constructed, which serve as a model for spatially fixed aliphatic chains in HSs terminated by a polar (carboxyl) group. The effect of environmental polarity has been investigated by using solvents of low and medium polarity in force-field MD. A nonpolar environment simulated by n-hexane was chosen to mimic the stability of WAMB in a hydrophilic hotspot surrounded by a nonpolar environment, while the more polar acetonitrile environment was chosen to simulate a more even distribution of polarity around the carboxylic groups and the water molecules. The dynamics simulations show that the rigidity of the oligomer chains is significantly enhanced as soon as the water cluster is large enough to comprise all four carboxyl groups. Increasing the temperature leads to evaporization processes which destabilize the rigidity of the tetramer-water cluster. Embedding it into the nonpolar environment introduces a pronounced cage effect which significantly impedes removal of water molecules from the cluster region. On the other hand, a polar environment facilitates their diffusion from the polar region. One important consequence of these simulations is that although the local water network is the stabilizing factor for the organic matter matrix, the degree of stabilization is additionally affected by the presence of nonpolar surroundings.

Prediction of the sorption behavior of environmental pollutants is of utmost importance within the framework of risk assessments. In this work two approaches are presented with the aim to describe sorption of aromatic substances to geosorbents. First, analytical solutions of kinetic models were fitted to experimental data of batch sorption experiments with aniline and 1-naphthylamine onto animal manure-treated soil and the soil mineral montmorillonite. The models, accounting for equilibrium and nonequilibrium sorption coupled to transformation and/or irreversible sorption processes, could well reproduce the concentration course of the sorbates. Results suggest that the amounts transformed/degraded and irreversibly bound were higher for the soil than for the clay mineral. In the second part, quantum chemical calculations were performed on aniline and 1-naphthylamine interacting with acetic acid, acetamide, imidazole, and phenol as models of functional groups present in humic substances. Molecular modeling showed that formation of hydrogen bonds is the dominating binding mechanism in all modeled complexes, which are energetically very similar between aniline and 1-naphthylamine.

Summary The present study investigated the impact of long-term soil management on the metal retention capacity of soil. We examined the sorption behaviour of Cu, Cd and Zn in soils and in the various particle-size fractions of these soils, which had been amended with farmyard manure, mineral fertilizers or were fallow for 38 years in a long-term field experiment. The soils investigated contained different amounts and origins of organic matter and differed in soil pH, but the mineral phase showed less response to the different soil managements. Batch adsorption and desorption experiments as well as a sequential fractionation schema, which defines seven geochemical fractions, were used to investigate the retention properties of soil. Sequential extraction was conducted with original as well as with metal-spiked soils. Results showed that amounts of Cu, Cd and Zn retained differed by a factor of more than 3 among the treatments in the longterm field experiment, when a massive concentration of metal was added to soil. An increased sorption on

Summary The present work investigates the impact of site management on the retention of organic compounds in soil in a long-term field experiment and focuses on the role of particle size fractions. Specifically, we studied the influence of long-term farming practices on the soil’s ability to adsorb five hydrophobic organic compounds (HOCs), specifically naphthalene derivatives (naphthalene, 1-naphthol, 1-naphthylamine, 1-hydroxy-2-naphthoic acid, 1,4-naphthoquinone). We examined the sorption on soil and its particle-size fractions with varying amounts and origins of organic matter in soil amended with farmyard manure and mineral fertilizers over more than 40 years. The soil organic matter had no significant impact on the sorption behaviour of the HOCs. Adsorption on the clay and silt fraction provided a deeper insight into the mechanisms and indicates a strong affinity with adsorption sites of the mineral phase. Naphthalene derivatives with hydrogen atoms in their functional groups adsorbed more strongly than other compounds on to soils containing smaller amounts of organic carbon. Desorption experiments with five organic extractants showed partitioning models for HOCs between extractant and soil surface. Only in experiments with the most polar extractant, formamide, did we observe an influence of the compound’s functional groups on the desorption mechanisms. Column experiments with a HPLC-system and on-line UV-detection proved to be a satisfactory alternative to batch experiments. This approach should enable investigations of adsorption with larger numbers of compounds and soils at the same time.

Sorption of heavy metals to organic matter and mineral soil constituents can hardly be separated experimentally. Here we studied the retention capacity of organic matter and minerals from soils in a long-term field experiment in which the organic carbon content had been altered, but the mineral phase had remained constant over time. The sorption of Cu, Cd and Zn showed a non-additive contribution of soil organic matter and minerals to the sorption capacity of soil. Sorption on organic matter exceeded mineral sorption from 6 to 13 times. This is the first time that sorption to soil organic matter is quantified in bulk soils.

This study investigated the effect of different farming practices over long time periods on the sorption-desorption behavior of Cu, Cd, and Zn in soils. Various amendments in a long-term field experiment over 44 y altered the chemical and physical properties of the soil. Adsorption isotherms obtained from batch sorption experiments with Cu, Cd, and Zn were well described by Freundlich equations for adsorption and desorption. The data showed that Cu was adsorbed in high amounts, followed by Zn and Cd. In most treatments, Cd ions were more weakly sorbed than Cu or Zn. Generally, adsorption coefficients K F increased among the investigated farming practices in the following order: sewage sludge ≤ fallow < inorganic fertilizer without N ≈ green manure < peat < Ca(NO 3 ) 2 < animal manure < grassland/extensive pasture. The impact of different soil management on the sorption properties of agricultural soils for trace metals was quantified. Results demonstrated that the soil pH was the main factor controlling the behavior of heavy metals in soil altered through management. Furthermore, the constants K F and n of isotherms obtained from the experiments significantly correlated with the amount of solid and water-soluble organic carbon (WSOC) in the soils. Higher soil pH and higher contents of soil organic carbon led to higher adsorption. Carboxyl and carbonyl groups as well as WSOC significantly influenced the sorption behavior of heavy metals in soils with similar mineral soil constituents.

Nitrogen dynamics in semi-natural environments is crucial for the development and ecological stability of these systems. The present paper shows the results of the reinvestigation of a 15N-tracer experiment, which was established in the Grossglockner massif in Austria at 2300 m a.s.l. in 1974/1975. We show that large quantities of nitrogen introduced by a single pulse labelling (amounting to approximately 1.7% of the nitrogen in the system) into an alpine grassland remain in the soil–plant system, with only 55% being lost during 27–28 years. In the first 10 cm of the four investigated soil profiles 40% of 15N was recovered, being mainly bound in organic forms. A simple site specific model was established on the basis of the results considering a biological, residual and labile N-pool, the latter being the source for N-losses. By the model a long mean residence time close to 100 years was derived for the remaining 15N.

We studied the effect of humified organic matter (OM) on the mineralization of a representative labile organic compound in soil. In an incubation experiment, a 13 C-labeled 2-decanol was added to soil either alone (2-dec p ) or in mixture with two humic acids from compost (HAC p ) and lignite (HAL p ) which had different hydrophobic properties. Isotopic dilution (d 13 C) showed that after 3 months of incubation about 58, 40 and 28% of the added 13 C was retained in the whole soil treated with HAL p , HAC p and 2-dec p , respectively. The higher the hydrophobicity of the employed humic material, the larger was the sequestration of organic carbon in soil. Fractionation of incubated samples revealed that the labeled carbon progressively accumulated in the finest particle-size fractions. However, the high hydrophobicity of the lignite HA favored accumulation of 13 C also in the sand-sized fraction. The NMR spectra of humic extracts showed that the 13 C-methyl group in the original 2-decanol had been oxidized to a 13 C-carboxyl group during incubation for all treatments. This indicated that despite its hydrophilicity, the resulting carboxyl carbon was sequestered into the hydrophobic domains of the humic pool in soil. In fact, the residual 13 C was larger in humic than in fulvic extracts for the control sample (2-dec p ) and even more so in extracts from soil treated with both exogenous humic acids. Our results suggest that labile organic compounds may be effectively protected in soil by humified OM and their microbial mineralization substantially reduced. Innovative soil management practices employing hydrophobic humic substances may increase the biological stability of soil OM and thus contribute to significantly mitigate CO2 emissions from agricultural soils. q 2002 Elsevier Science Ltd. All rights reserved.

In a study on the behaviour of pesticides in a soil–plant–water system, the quick, easy, cheap, effective, rugged and safe (QuEChERS) method for analysing pesticide or metabolite residues in soil and maize (leaves, roots and kernels) was optimized and validated. The pesticides bentazone, chloridazon and terbuthylazine and their metabolites bentazone-methyl, chloridazon-desphenyl, chloridazon-methyl-desphenyl, terbuthylazine-desethyl and terbuthylazine-2-hydroxy were selected in this study. The QuEChERS extracts obtained from soil and maize matrices and the collected leachate were analysed by liquid chromatography–electrospray ionization–tandem mass spectrometry (LC–ESI–MS/MS) using a high-performance liquid chromatography and an ultra-high-performance liquid chromatography (UHPLC) analytical column. As expected, shorter run times and higher sensitivity were achieved with the UHPLC column. Validation studies focused on recovery, repeatability, matrix effects, limits of detection and quantification. Recoveries (and repeatability relative standard deviation (RSD)) of the spiked samples were in the range of 55 to 98 % (7.4–18) in soil, 23 to 101 % (1.7–20) in maize and 82 to 105 % (4.4–25) in leachate. Quantification limits were lower than 3.0 μg kg−1 in soil, 7.3 μg kg−1 in maize and 0.080 μg l−1 in leachate.

Summary Changes in farming practices over long times can affect the sorption behaviour of MCPA ((4-chloro-2-methylphenoxy)acetic acid). We studied the adsorption–desorption mechanisms of MCPA on soil with varied amounts and origins of soil organic matter obtained from a long-term field experiment with various organic amendments. The origin of the soil organic matter seems to be crucial for the sorption behaviour of MCPA. Samples of soil amended with sewage sludge sorbed MCPA more strongly than the soil under any other treatment. Peat-amended soil was second followed by soil receiving animal manure, green manure, mineral fertilizer without N and the fallowed soil. Both the carbon content and the origin of the organic matter are important for the sorption. A decrease of carbon content of a soil does not necessarily imply a reduction of sorption capacity for polar organic acids such as MCPA. Nevertheless, our adsorption–desorption experiments suggest that with decreasing carbon content the role of mineral sorption mechanisms could become more pronounced. Our results showed that interactions of soil organic matter and soil minerals distinctly influence adsorption properties for MCPA.

The dynamics of incorporation of fresh organic residues into the various fractions of soil organic matter have yet to be clarified in terms of chemical structures and mechanisms involved. We studied by 13 C-dilution analysis and CPMAS- 13 C-NMR spectroscopy the distribution of organic carbon from mixed or mulched maize residues into specific defined fractions such as carbohydrates and humic fractions isolated by selective extractants in a year-long incubation of three European soils. The contents of carbohydrates in soil particle size fractions and relative δ 13 C values showed no retention of carbohydrates from maize but rather decomposition of those from native organic matter in the soil. By contrast, CPMAS- 13 C-NMR spectra of humic (HA) and fulvic acids (FA) extracted by alkaline solution generally indicated the transfer of maize C (mostly carbohydrates and peptides) into humic materials, whereas spectra of organic matter extracted with an acetone solution (HE) indicated solubilization of an aliphatic-rich, hydrophobic fraction that seemed not to contain any C from maize. The abundance of 13 C showed that all humic fractions behaved as a sink for C from maize residues but the FA fraction was related to the turnover of fresh organic matter more than the HA. Removal of hydrophobic components from incubated soils by acetone solution allowed a subsequent extraction of HA and, especially, FA still containing much C from maize. The combination of isotopic measurements and NMR spectra indicated that while hydrophilic compounds from maize were retained in HA and FA, hydrophobic components in the HE fraction had chemical features similar to those of humin. Our results show that the organic compounds released in soils by mineralization of fresh plant residues are stored mainly in the hydrophilic fraction of humic substances which are, in turn, stabilized against microbial degradation by the most hydrophobic humic matter. Our findings suggest that native soil humic substances contribute to the accumulation of new organic matter in soils.

The sorption and desorption behaviors of four phenoxyalkanoic acid herbicides and their metabolites on four agricultural soils and soil particle size fractions were examined. Generally, there was a trend of increasing adsorption and decreasing desorption in the order mecoprop < MCPA < dichlorprop < 2,4-D. The significant increase in adsorption of the phenolic metabolites can be explained by their lower polarity and enhanced partition in the organic soil matrix. Estimation of sorption distribution coefficients from particle size fraction adsorption data was possible for a sandy soil and a silty Cambisol soil only. It is suggested that increasing steric demand, for example, molecular volume, and slight changes in the polarity of the compounds affect their adsorption properties. Comparison of adsorption and desorption data of structurally similar compounds obtained from a variety of soils allows investigation of structure-induced differences in sorption strength.

Regional origin assignment of highly valuable milk products such as butter, is of considerable importance for legal, fiscal and trade controls within the European Union (EU). It is also of value for ensuring fair competition and as a means of protecting consumers against fraud due to mislabelling. Conventional chemical methods of analysis are not able to determine the regional provenance of butter unambiguously. Therefore, stable isotope ratio determinations of the light elements (C,N,O,S; bioelements) and the heavy element, Sr (a trace element), have been used for this purpose. Stable isotope ratios of these elements in natural cycles, their variations due to climate and geology, the abiotic and biological fractionation of isotopes and, finally, the reasons for regional differences in multielement stable isotope ratios of butter are discussed. Results are given for butter from several European countries and from outside the EU. The results indicate that stable isotope ratios and subsequent discriminant analysis based on data for samples of certified origin can enable the reliable detection of the regional provenance of butter.

The analysis of O-isotopic composition of nitrate has many potential applications in studies of environmental processes. O-isotope nitrate analysis requires samples free of other oxygen-containing compounds. More than 100% of non-NO3- oxygen relative to NO3- oxygen can still be found in forest soil water samples after cleanup if improper cleanup strategies, e.g., adsorption onto activated carbon, are used. Such non-NO3- oxygen compounds will bias O-isotopic data. Therefore, an efficient cleanup method was developed to isolate nitrate from natural water samples. In a multistep cleanup procedure using adsorption onto water-insoluble poly(vinylpyrrolidone), removal of almost all other oxygen-containing compounds, such as fulvic acids, and isolation of nitrate was achieved. The method supplied samples free of non-NO3- oxygen which can be directly combusted to CO2 for subsequent O-isotope analysis.

Summary In a long-term field experiment started in 1956 on a clay loam soil at Uppsala, Sweden, changes of organic carbon in the topsoils receiving various organic amendments at the rate of 200 kg C ha'1 year'1 were studied to determine soil organic matter characteristics, variations of δ13C in the soil and to estimate a carbon balance. Fallow and mineral fertilizer without N led to a significant decrease of soil organic matter (SOM) in the soil, green manure maintained the SOM content, and animal manure and peat increased the SOM content significantly. The stable portion of the added organic materials after 37 years of continuous input was 12·8, 27·3, and 56·7%, for green manure, animal manure and peat, respectively. This was reflected by half-lives of organic carbon originating from the amendments between 3·0 (green manure) and 14·6 years (peat). The isotopic composition of SOM changed both due to mineralization (continuous fallow) and the addition of amendments is topically different from soil humus (green manure, animal manure). The isotopic effect was used to calculate the percentage of carbon derived from animal manure present for the year 1993. This value (55·4%) was larger than that derived from the carbon balance, which indicated a priming effect of the animal manure on the initial soil humus. Mineralization of microbially available organic substances led to an increase in the degree of humification on plots not receiving organic amendments. Adding peat and animal manure resulted in a decrease of the humification index due to the continuous input of poorly humified material. The extinction ratio (E4/E6) and ratio of fulvic acid to humic acid changed considerably in the peat treated plots. Fourier transform infrared (FTIR)-measurements of the extracts showed that peat characteristics can be detected in peat treated soils. The other amendments did not alter the characteristics of the extractable humic substances.

The present paper describes changes in soil organic carbon (SOC) and extractable humic acids (HAs) in a long-term field experiment with different tillage treatments (minimum tillage (MT), reduced tillage (RT) and conventional tillage (CT)). This field experiment is located in the east of Vienna in a Pannonian climate and it was started in 1988. The methodological approach included elemental analyses, FT-IR, 13C NMR and fluorimetric measurements. Both MT and RT revealed significant depth gradients of yields of extractable HAs. In CT no depth gradient was observable, neither for HA yields nor for observed molecular characteristics. This indicated a destruction of the gradient by mixing of the soil in CT. Especially MT showed an increase of aromatic moieties with depth, suggesting an increased humification of HAs in the lower soil layers. Gradients with similar trends were indicated for the carbonylic, the amidic and probably the hydroxylic groups in HAs extracted from MT and RT samples. The data revealed with FT-IR and solid-state 13C NMR spectroscopy were convincing, plausible and meaningful, the highly sensitive fluorescence spectroscopy was limited because of strong quenching by inner filter effects, compromising data reliability. However, the fluorescence results based on a defined HAs concentration (and comparing soils from the same site) were in line with results from the other methods (13C NMR and FT-IR). As a consequence, the influence of tillage treatments can be followed by absence or presence of depth gradients of the according molecular characteristics in extracted HAs.

[1] The aim of this paper was to synthesize a series of investigations from a long-term field experiment addressing the turnover of organic matter in soil. This paper is based on four organic matter inputs (soil treatments): none (fallow), small amounts of roots+stubble cropped without N fertilizer (no-N), moderate additions of animal manure, and moderate additions of peat. After 42 years, soil carbon stocks declined in the fallow and no-N treated soil but increased in the animal manure and peat-amended soil. Gentle fractionation of soil particles and aggregates revealed that the silt-sized fraction contained most of the soil C and was most responsive to changes in input of organic matter. The clay-sized fraction ( clay > fine sand > coarse sand. The highest natural abundance of 13C and 15N was found in the clay-sized fraction, the fallow being most enriched in 13C and the animal manure-treated soil in 15N, indicating that the organic matter of the clay-sized fraction had been turned over most intensively. The 13C inventory showed that the transfer from silt- to clay-sized carbon was most intensive in the soil treated with animal manure and least intensive in the peat-treated soil. Bacterial diversity increased from sand- to clay-sized fractions revealed by 16S rRNA genes. Fungal activity was highest in coarse-sized fractions as indicated by enzyme measurements. The quality and amount of organic matter input had no significant effect on the community structure of soil bacteria.

Stable isotope analysis of 15N/14N and 18O/16O-nitrate was used to investigate the nitrate dynamics and potential groundwater pollution in an Alpine forest stand in Tyrol/Austria. The dynamics of delta15-N(nitrate) values were followed in a forest ecosystem. The stable isotopic values of the throughfall are comparable with other studies. The completely decoupled dynamics of the delta15-N(nitrate) of the precipitation and the surface water was observed. High variations in delta15N-nitrate values in rainfall indicate that nitrate of different sources is deposited at that site. A significant correlation between the delta15N(nitrate) values of the surface water and soil water was obtained, while no significant correlation between the delta15N(nitrate) values of any precipitation sample with the surface water could be found. This suggests that the main source of nitrate in soil water originates from microbiological activity such as nitrification reactions and less from nitrate input by deposition. The results of delta18O(nitrate) measurements strongly supported the microbiological origin of nitrate in the surface and soil water In an additional lysimeter experiment, 15N-labelled nitrate was applied to study nitrate transport in soil. After 130 days and the collection of 300 L leachate, a total of 52% of the applied nitrate was detected in seepage water.

The influence of dissolved humic substances on the transport of (4-chloro-2-methylphenoxy) acetic acid (MCPA) in a sandy soil with a low organic carbon content was studied in a column experiment. Soil columns were eluted with aqueous solutions containing different fractions of humic substances. More than 70% of the applied compound was found in the leachate in all sandy soil experiments, but distinct differences were obtained depending on the composition of the eluent. The addition of both humic and fulvic acids to the eluent affected the leaching behaviour of MCPA. While the presence of humic acids increased and accelerated the movement of MCPA in the investigated sandy soil, fulvic acids caused the opposite effect: increased retention was observed relative to the control. We concluded that a possible carrier transport or retention strongly depends on the composition of the dissolved organic matter. Thus, changes in the composition of dissolved organic matter may affect MCPA movement into deeper soil layers.

Publisher Summary This chapter combines a physical fractionation procedure following low energy sonication, the determination of natural abundances of 13 C/ 12 C, enzyme activities, and assessment of bacterial diversities by using 16S rDNA-based methods to evaluate the effect of different amendments on soil organic matter in the Ultuna long-term field experiment located in central Sweden, on a Eutric Cambisol. The purpose of the study was to evaluate the contribution of different particle size fractions to the medium-term storage of organic carbon (OC) and to investigate the response of microbial processes to a range of long-term OC-inputs. The response of xylanase and invertase to different organic amendments can be easily detected in the sand fraction. 168 rRNA-based analyses showed increasing microbial diversity and abundance with decreasing particle size. Analysis of bacterial diversity and enzyme measurements suggested different metabolic activities in different particle size fractions.

In the North Tyrolean Limestone Alps a site was investigated over a four-year period (1998-2001) in order to assess the nitrogen saturation status, the nitrogen budget (quantification of the net uptake of nitrogen by the canopy and of the nitrogen mineralization, nitrogen uptake from roots and N2O emission rates, proof of the origin of nitrate in the soil water with stable isotope analyses), and the effects of the actual nitrogen input on ground water quality. The main goals were to quantify the nitrogen input rate, the nitrogen pools in above-ground and below-ground compartments, nitrogen turnover processes in the soil as well as the output into the groundwater and into the atmosphere. The findings are based on continuous and discontinuous field measurements as well as on model results. While nitrogen input exceeded the Critical Loads of the WHO (1995), nitrogen deficiency and nutrient imbalances were verified by needle analyses. The atmospheric input of inorganic nitrogen was higher than the nitrogen output in 50 cm soil depth. A tracer experiment with 15N helped to prove that not more than half of the applied nitrate could be discharged. This allows the conclusion that nitrogen is stored in the system and that the site cannot yet be said to be saturated with nitrogen. The same result was also obtained by modelling. In addition, it was proved that the nitrogen discharge did not stem from deposition but from processes within the system.