An improved method for determining the specific surface areas of topsoils with varied organic matter content, texture and clay mineral composition

Measuring the specific surface area (SSA) of soils that contain much organic matter (OM) is problematic. The adsorption of p-nitrophenol (pNP) from xylene at room temperature yielded realistic values for the SSA of a wide range of clays, oxides and subsoils. Here we have extended the same measurement to some topsoils with varied OM content, texture and clay mineral composition. Specifically, we have compared the surface areas measured by adsorption of N₂, and, applying the BET equation, with the values obtained by adsorption of pNP, before and after treatment of the samples with hydrogen peroxide. In all instances, the removal by H₂O₂ of organic matter – albeit in part only – led to a marked increase in the SSAs measured by nitrogen because of the exposure of micropores previously blocked or covered by OM. The surface areas measured by pNP were appreciably larger than those obtained by the standard BET equation, and showed little change after removal of organic matter. However, the surface area of two smectite-rich samples measured by pNP increased substantially after peroxidation, presumably because smectite crystals decomposed during treatment with H₂O₂. The results suggest that, under the experimental conditions used, pNP could diffuse without hindrance into and through organic matter, enabling it to adsorb on to micropore surfaces within clay aggregates (domains). In keeping with this suggestion, the relation between the surface areas measured by pNP and the corresponding values calculated from the clay and OM contents, and clay mineral composition, of the soils was close to 1:1. An even stronger relation was observed between the measured and calculated values for cation exchange capacity.     

Effects of mineral surface iron on the CPMAS 13C-NMR spectroscopic detection of organic matter from soil fractions in an agricultural topsoil with different amendments

The decrease of NMR visibility of the C signal in soil samples due to the association between organic carbon (OC) and the topsoil mineral surface was investigated. CPMAS ¹³C‐NMR spectra were obtained for soil particle‐size fractions (< 2 μm, 2–20 μm, > 20 μm) and bulk soils from an agricultural topsoil (Chernozem) that had received three different amendments (no fertilization, mineral fertilization (NPK), mineral (NPK) and organic (cattle manure) fertilizations) at Bad Lauchstädt, Germany. The soil organic carbon content of the three soils depended on the degree of soil fertilization. There was no constant relationship between the total NMR signal intensity and the total amount of organic carbon (TOC) for all size fractions. Indeed, a key role played in the C signal intensity by the paramagnetic ferric ion from the clay content in soil fractions and bulk soils was confirmed. Thus, we describe the variations of C signal intensity by taking into account the distribution of clay‐associated OC and non‐associated OC pools. Depending on the amendment, the C signal visibility was weakened by a factor of 2–4 for the clay‐associated OC. This estimation was rendered possible by combining mineral specific surface area (SSA) measurements with the N₂ gas adsorption method (BET method) and determination of TOC and iron concentrations. This approach contributes to the quantitative evaluation of the CPMAS ¹³C‐NMR detection.     

Predicting carbon content in illitic clay fractions from surface area, cation exchange capacity and dithionite-extractable iron

We used the specific surface area (SSA), the cation exchange capacity (CEC) and the content of dithionite‐extractable iron (Fe_d) to predict the content of organic carbon in illitic clay fractions of topsoils from loess. We determined SSA (BET‐N₂ method) and CEC of clay fractions after removing organic C or reducing oxides or both. The CEC and the SSA of the carbon‐ and oxide‐free clay fraction explained 56% and 54% of the variation in C content, respectively. The Fe_d content of the clay fractions was strongly and negatively related to the C content, and with the SSA of the carbon‐free clay fraction it predicted C content almost completely (R² = 0.96). The results indicate that the amount of cations adhering to the silicate clay minerals and the size of the silicate mineral surface area are important properties of the mineral phase for the storage potential of C. The reason for the negative relation between iron oxides and C content remains unclear.     

The phenanthrene‐sorptive interface of an arable topsoil and its particle size fractions

Sorption of organic chemicals in soil is affected by the properties and availability of surfaces. These surfaces are composed of diverse mineral, organic and biological components, forming a soil's ‘biogeochemical interface’. Phenanthrene was used to probe the hydrophobic sorptive capacity of the interface of an arable soil. Batch sorption experiments were carried out with the bulk soil as well as the fine (0.2–6.3 µm) and coarse (6.3–63 µm) particle size fractions of two arable topsoil samples with different organic matter (OM) contents from a Eutric Cambisol. The specific surface area (SSA) of the bulk soil and particle size fractions was determined by BET‐N₂ and EGME sorption. OM composition was characterized by solid‐state ¹³C NMR spectroscopy. No clear relationship was found between phenanthrene sorption and SSA. We conclude that phenanthrene probes a specific fraction of the soil interface that is not well represented by the traditional methods of SSA detection such as BET‐N₂ and EGME sorption. The sorption behaviour of phenanthrene may therefore provide a useful additional tool to characterize the specific affinity of the soil biogeochemical interface for hydrophobic molecules. Sorption capacity for phenanthrene increased after particle‐size fractionation, indicating that the reduced availability of the interface caused by the aggregated structure is important for the sorptive capacity of a soil. This should be considered when projecting data obtained from extensively treated and fractionated samples to the actual interaction with biogeochemical interfaces as they are present in soil.     

Carbon storage in loess derived surface soils from Central Germany: Influence of mineral phase variables

The influence of the soil mineral phase on organic matter storage was studied in loess derived surface soils of Central Germany. The seven soils were developed to different genetic stages. The carbon content of the bulk soils ranged from 8.7 to 19.7 g kg^—1. Clay mineralogy was confirmed to be constant, with illite contents > 80 %. Both, specific surface area (SSA, BET‐N₂‐method) and cation exchange capacity (CEC) of bulk soils after carbon removal were better predictors of carbon content than clay content or dithionite‐extractable iron. SSA explained 55 % and CEC 54 % of the variation in carbon content. The carbon loadings of the soils were between 0.57 and 1.06 mg C m^—2, and therefore in the ”︁monolayer equivalent” (ME) level. The increase in SSA after carbon removal (ΔSSA) was significantly and positively related to carbon content (r² = 0.77). Together with CEC of carbon‐free samples, ΔSSA explained 90 % of the variation in carbon content. Clay (< 2 μm) and fine silt fractions (2—6.3 μm) contained 68—82 % of the bulk soil organic carbon. A significantly positive relationship between carbon content in the clay fraction and in the bulk soil was observed (r² = 0.95). The carbon pools of the clay and fine silt fractions were characterized by differences in C/N ratio, δ¹³C ratio, and enrichment factors for carbon and nitrogen. Organic matter in clay fractions seems to be more altered by microbes than organic matter in fine silt fractions. The results imply that organic matter accumulates in the fractions of smallest size and highest surface area, apparently intimately associated with the mineral phase. The amount of cations adhering to the mineral surface and the size of a certain and specific part of the surface area (ΔSSA) are the mineral phase properties which affect the content of the organic carbon in loess derived arable surface soils in Central Germany most. There is no monolayer of organic matter on the soil surfaces even if carbon loadings are in the ME level.     

Mineral surfaces and soil organic matter

The organic carbon content of soil is positively related to the specific surface area (SSA), but large amounts of organic matter in soil result in reduced SSA as determined by applying the Brunauer–Emmett–Teller (BET) equation to the adsorption of N₂. To elucidate some of the controlling mechanisms of this relation, we determined the SSA and the enthalpy of N₂ adsorption of separates with a density > 1.6 g cm^?3 from 196 mineral horizons of forest soils before and after removal of organic matter with NaOCl. Likewise, we investigated these characteristics before and after sorption of increasing amounts of organic matter to four mineral soil samples, oxides (amorphous Al(OH)₃, gibbsite, ferrihydrite, goethite, haematite), and phyllosilicates (kaolinite, illite). Sorption of organic matter reduced the SSA, depending on the amount sorbed and the type of mineral. The reduction in SSA decreased at larger organic matter loadings. The SSA of the mineral soils was positively related to the content of Fe oxyhydroxides and negatively related to the content of organic C. The strong reduction in SSA at small loadings was due primarily to the decrease in the micropores to which N₂ was accessible. This suggests preferential sorption of organic matter at reactive sites in or at the mouths of micropores during the initial sorption and attachment to less reactive sites at increasing loadings. The exponential decrease of the heat of gas adsorption with the surface loading points also to a filling or clogging of micropores at early stages of organic matter accumulation. Desorption induced a small recovery of the total SSA but not of the micropore surface area. Destruction of organic matter increased the SSA of all soil samples. The SSA of the uncovered mineral matrix related strongly to the amounts of Fe oxyhydroxides and the clay. Normalized to C removed, the increase in SSA was small in topsoils and illuvial horizons of Podzols rich in C and large for the subsoils containing little C. This suggests that micropores preferentially associate with organic matter, especially at small loadings. The coverage of the surface of the soil mineral matrix as calculated from the SSA before and after destruction of organic matter was correlated only with depth, and the relation appeared to be linear. We conclude that mineralogy is the primary control of the relation between surface area and sorption of organic matter within same soil compartments (i.e. horizons). But at the scale of complete profiles, the surface accumulation and stabilization of organic matter is additionally determined by its input.     

Retention of dissolved organic matter by illitic soils and clay fractions: Influence of mineral phase properties

The dependency of the retention of dissolved organic carbon (DOC) on mineral phase properties in soils remains uncertain especially at neutral pH. To specifically elucidate the role of mineral surfaces and pedogenic oxides for DOC retention at pH 7, we sorbed DOC to bulk soil (illitic surface soils of a toposequence) and corresponding clay fraction (< 2 μm) samples after the removal of organic matter and after removal of organic matter and pedogenic oxides. The DOC retention was related to the content of dithionite‐extractable iron, specific surface area (SSA, BET‐N₂ method) and cation exchange capacity (pH 7). The reversibility of DOC sorption was determined by a desorption experiment. All samples sorbed 20–40 % of the DOC added. The DOC sorption of the clay fractions explained the total sorption of the bulk soils. None of the mineral phase properties investigated was able to solely explain the DOC retention. A sorption of 9 to 24 μg DOC m^–2 indicated that DOC interacted only with a fraction of the mineral surface, since loadings above 500 μg m^–2 would be expected for a carbon monolayer. Under the experimental conditions used, the surface of the silicate clay minerals seemed to be more important for the DOC sorption than the surface of the iron oxides. The desorption experiment removed 11 to 31 % of the DOC sorbed. Most of the DOC was strongly sorbed.     

Micropore characteristics of organic matter pools in cemented and non‐cemented podzolic horizons

In Podzols, organic matter (OM) is stabilized mainly by interaction with minerals, as a direct consequence of pedogenic processes. Metal–organic associations strongly affect OM surface features, particularly microporosity. Cemented ortstein horizons (CM) may form during podzolization, accompanied by a spatial arrangement of OM on mineral surfaces, which differs from that in non‐cemented horizons (N‐CM). To investigate the metal–organic associations and their changes during pedogenesis, we selected both N‐CM and CM podzolic horizons, isolated NaClO‐resistant OM and compared the specific surface area (SSA) before and after OM oxidation. The SSA was assessed by using N₂, to detect the pores in the range of micropores (< 2 nm) and mesopores (2–50 nm), and CO₂, to measure a smaller microporosity (< 0.5 nm), which is not accessible to N₂. Only the N‐CM samples showed the typical increase in N₂‐SSA after the removal of labile OM, while a decrease was found in all CM horizons. The CO₂‐SSA revealed a large number of small micropores characterizing OM, both before and after oxidation. The smallest micropore classes (< 0.5 nm) were, however, more abundant in NaClO‐resistant OM, which had therefore a larger number of N₂‐inaccessible surfaces than the labile pool. The N₂‐SSA data thus indicated a more homogeneous coverage of mineral surfaces by stabilized OM in CM samples. Because of the abundance of small micropores, OM in these podzolic B horizons had extremely large CO₂‐SSA values (about 800 m² g^?1), with sharp differences between the NaClO‐labile OM (290–380 m² g^?1) and the NaClO‐stabilized pool (1380–1860 m² g^?1), thus indicating very reactive illuvial organic materials.     

Sorptive stabilization of organic matter by microporous goethite: sorption into small pores vs. surface complexation

Stabilization of organic matter (OM) by sorption to minerals is thought to be due to (i) sorption into small pores (Ø < 50 nm) that prevents hydrolytic enzymes approaching and decomposing the organic substrate or (ii) reduced availability of organic molecules after formation of strong multiple bonds by complexation of organic ligands at mineral surfaces. We tested these two potential mechanisms by studying the binding of dissolved OM to microporous goethite (α‐FeOOH). The size of organic molecules dissolved prior to and after equilibration with goethite was determined using atomic force microscopy (AFM). The goethite–OM complexes were analysed for bulk and surface elemental composition (by X‐ray photoelectron spectroscopy, XPS), specific surface area (SSA) and mesopore and micropore volumes (by N₂ adsorption/desorption), by scanning electron microscopy (SEM), and by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The absolute density of goethite–OM complexes was determined by gas pycnometry and the sorbed OM’s apparent density was calculated by assuming no major changes in the volumes of the goethite upon sorption of OM. The stability of the OM–mineral interactions was tested in desorption experiments and by treatment with NaOCl. Surface accumulation of OM by sorption decreased the N₂‐accessible SSA of the goethite, mostly because micropores (Ø < 2 nm) were rendered inaccessible to N₂. The decrease in accessibility of micropores was most pronounced at small surface OM concentrations. The majority of dissolved organic molecules detected with AFM prior to interaction with goethite were globular with a diameter of 4–10 nm, the rest were mainly linear, 20–100 nm long and 4–8 nm thick. After contact with goethite, the latter type of molecules dominated, which suggests preferential sorption of globular molecules. Their size exceeded or equalled the size of micropores and small mesopores (Ø < 10 nm) and so sorption therein is unlikely. Also, the changes in volumes of pores with a size of 2–50 nm were smaller than the estimated volume of the OM sorbed. The apparent density of sorbed OM always exceeded that of the freeze‐dried OM and was largest at small surface concentrations. DRIFT spectroscopy showed that most carboxyl groups at the goethite surface were in their complexed form. The proportion of complexed carboxyl groups dropped at larger surface concentrations, parallel to the decrease in micropore volume. Thus, micropores seem to favour the formation of multiple complex bonds per molecule. Scanning electron microscopy showed that at small surface concentrations, OM coated the goethite crystals and crystallites tightly, while at larger surface concentrations bulky accumulations of OM were more abundant. Even strongly desorbing reagents such as NaOH and Na pyrophosphate released only part of the sorbed OM. Treatment with NaOCl removed mainly bulky accumulations of OM; the OM tightly bound to goethite crystals was hardly affected by NaOCl. We conclude that molecules tightly bound via multiple complex bonds, probably at the mouths of small pores, are barely desorbable and resist the attack of chemical reagents and probably also of enzymes.     

Adsorption of Copper,Zinc, and Cadmium on Goethite,Aluminum‐Substituted Goethite,and a System of Kaolinite–Goethite: Surface Complexation Modeling

Abstract

Goethite, aluminum‐(Al)‐substituted goethite (GA2), and a system of kaolinite–goethite were examined for their ability to adsorb copper (Cu), zinc (Zn), and cadmium (Cd) as a function of pH, in two ionic strengths and two different metal concentrations. Specific surface area was determined by BET‐N₂, whereas the charge development on the solid surface was studied in the pH range ～3.5 to ～10.0 by potentiometric titration under continuous flow of argon.

Constant capacitance (CCM) and the double‐layer model (DLM) were used to fit the titration and adsorption data with the help of the least‐square optimization program FITEQL32. In both models, surface site density was fixed at Ns=2.31 sites nm^?2, whereas for CCM capacitance density was set at C=1.06. Alternatively, bibliographic suggestions for these two parameters were examined.

Aluminum‐substituted goethite exhibited higher specific surface area and adsorbed all three metals in lower pH values than the other solids. Moreover, GA2 exhibited point of zero salt effect (PZSE) higher than goethite, approaching that corresponding to Al₂O₃, possibly due to Al‐substitution, and the system exhibited PZSE values much higher than kaolinite, approaching that corresponding to goethite. The adsorption order for all three solids was Cu>Zn>Cd in any case, thus more Cu is adsorbed at a certain pH than Zn and even more than Cd, whereas the increase of metal concentration shifts the adsorption curve toward higher pH values.

Constant capacitance described the titration data satisfactorily, but by altering the Ns and C values, the fit became worse. Adsorption data are described by CCM, by emphasizing the formation of monodentate surface complex. Bidentate complex, in most of the cases, was of no importance in describing the data despite the evidence of its presence in recent spectroscopic studies for Cu and Cd on goethite. Alteration of Ns and C values worsened the fit in any case, and bidentate complex vanished. The DLM exhibited the worse fit in any case.     

Influence of allophane and organic matter contents on surface properties of Andosols

The aim of this study was to use nitrogen gas adsorption to study the complex surface properties of a wide range of Andosol Ah and Bw horizons; N₂ gas adsorption not only provides specific surface area, SSA, but it also yields complementary information about micropore volume and hydrophilic and/or hydrophobic surface properties. Total SSAs were positively related to micropore SSA which was, in its turn, positively interrelated to the dimensionless parameter C of the Brunauer‐Emmett‐Teller (BET) equation (micropore N₂ filling) and microporous allophane content. The more allophanic the Andosol horizon sample, the larger were its total, micropore and mesopore SSAs. On the other hand, strong negative exponential relationships were obtained between either total or micropore or mesopore SSA and soil organic carbon content, with a SSA threshold at an organic carbon content of c. 8–10%, the SSAs being extremely small at larger organic carbon content values. Both SSA_BET and C_BET decreased non‐linearly as a function of the organic C/allophane ratio, with either a SSA_BET or a C_BET threshold at an organic C/allophane ratio value of 3–5, above which both SSA_BET and C_BET were very small (mostly the aluandic Andosol Ah horizons). The more the soil allophanes are assumed to be coated, the more hydrophobic the soil surfaces become and the smaller both SSA_BET and C_BET become; nitrogen gas has a permanent quadrupole moment and therefore acts as a polar probe when surfaces are sufficiently hydrophobic. The antagonistic roles played by allophanes and organic matter in both the SSAs and the values of the dimensionless parameter C in the BET equation were also highlighted by (i) multiple linear regressions between the SSAs and both allophane and organic carbon contents and (ii) principal‐component analysis of SSA_BET, C_BET and soil constituent (allophane, ferrihydrite and organic C) contents.     

Effects of N placement,carbon distribution and temperature on N2O emissions in clay loam and loamy sand soils

Changes in the profile distribution of soil C stocks for conventional versus no‐tillage can affect N₂O losses. Uncertainty remains whether deep N placement into a wetter layer in humid areas would affect N₂O losses. This study evaluated the effects of soil carbon profile distribution (inverted, normal), depth of nitrogen placement (5 cm, 15 cm), temperature (10, 20 and 30 °C) and soil texture (clay loam, loamy sand) on N₂O emissions from soil cores in a 216‐h incubation after simulated rainfall. N₂O losses were larger from the clay loam than from the loamy sand, and cumulative N₂O emissions from the inverted profile, with greater C levels at depth, were more than those from the profile with more C near the upper surface. Cumulative N₂O losses from the inverted clay loam profile with deep N placement (1.16 mg N per kg dry soil; 0.71% of applied N) on average were almost double those in the loamy sand (0.62 mg N per kg dry soil; 0.42%). The smallest N₂O losses were measured from the profiles with more C close to the upper surface with a shallow placement of N for the clay loam (0.19 mg N per kg dry soil; 0.12%) and loamy sand (0.33 mg N per kg dry soil; 0.23%). An exponential relationship between N₂O fluxes and temperature was measured. We conclude that large N₂O losses may occur under the combination of greater soil C content at deeper layers (ploughed soils) and moist profiles after N application (humid regions). Deep N placement appears to aggravate rather than ameliorate these concerns.     

Identifying potential management zones in a layered soil using several sources of ancillary information

Variation in soil texture has a profound effect on soil management, especially in texturally complex soils such as the polder soils of Belgium. The conventional point sampling approach requires high sampling intensity to take into account such spatial variation. In this study we investigated the use of two ancillary variables for the detailed mapping of soil texture and subsequent delineation of potential management zones for site‐specific management. In an 11.5 ha arable field in the polder area, the apparent electrical conductivity (EC_a) was measured with an EM38DD electromagnetic induction instrument. The geometric mean values of the EC_a measured in both vertical and horizontal orientations strongly correlated with the more heterogeneous subsoil clay content (r = 0.83), but the correlation was weaker with the homogenous topsoil clay content (r = 0.40). The gravimetric water content at wilting point (θg_{(?1.5 MPa)}) correlated very well (r = 0.96) with the topsoil clay content. Thus maps of topsoil and subsoil clay contents were obtained from 63 clay analyses supplemented with 117θg_{(?1.5 MPa)} and 4048EC_a measurements, respectively, using standardized ordinary cokriging. Three potential management zones were identified based on the spatial variation of both top and subsoil clay contents. The influence of subsoil textural variation on crop behaviour was illustrated by an aerial image, confirming the reliability of the results from the small number of primary samples.     

The implications of sample preparation on the particle size distribution of soil

Particle size distribution (PSD) is among basic parameters in soil and sediment characterization and provides essential information in sedimentological and environmental studies. The problem with the PSD determination is that for any given sample the result depends not only on the method used but also on the sample pre‐treatment, making them seldom comparable. In this study, the PSD of seven non‐treated and pre‐treated soil samples were determined by four granulometric methods (pipette, sedigraph, particle counter and laser diffraction analysis). Samples were subjected to pre‐treatments commonly used in sample preparation for the PSD determination, i.e., addition of dispersant (sodium metaphosphate) and removal of the organic matter (with hydrogen peroxide). The total organic carbon (TOC) analysis was used to estimate the content of organic matter before and after its removal. The effect of different pre‐treatments was evaluated based on the PSD variations and the changes in the specific surface area (SSA) of the samples. The results highlighted differences in the PSD curves of samples depending on the granulometric method and pre‐treatment applied. The most pronounced difference was the higher amount of clay fraction determined by settling techniques. The role of hydrogen peroxide in disruption of aggregates was evident in the increase in the SSA as well as the share of fine fraction determined by all four techniques, while sodium metaphosphate made no modifications of the SSA but acted in favour of prolonging settling of clay particles and increasing its content obtained by settling techniques.     

Removal of Cu2+ and Cd2+ from Aqueous Solution by Bentonite Clay Modified with Binary Mixture of Goethite and Humic Acid

Pre-modification of bentonite clay with goethite, humic acid, and a binary mixture of goethite and humic acid reagents increased its cation exchange capacity from 95 to 105.32, 120.4, and 125.8 meq/100 g of bentonite clay, respectively. The effective pre-modification of bentonite clay with goethite, humic acid, and goethite–humic acid reagents was confirmed from their Fourier transform infrared spectra which suggested that modification was effective on the AlAlOH and Si–O sites for goethite and humic acid modification and AlAlOH for goethite–humic acid modification. The presence of 0.001 M NaNO₃ electrolyte increased the adsorption capacity of bentonite clay. Temperature was observed to favor the adsorption of Cu²⁺ and Cd²⁺ onto both the raw and modified bentonite clay samples. The goethite–humic acid-modified bentonite gave the best adsorption capacity of ≈10 and 16 mg/g at 30 and 50°C, respectively, for both metal ions. The inner sphere complexation mechanism was suggested for the adsorption of both metal ions onto the modified adsorbents. Modifying bentonite clay with a binary mixture of goethite and humic acid reduced the selectivity of bentonite clay for either Cu²⁺ or Cd²⁺. Preadsorbed goethite and humic acid on bentonite clay will further reduce the mobility of heavy metal ions in soils and in aquatic environments.     

Microbiological characterization and nitrate reduction in subsurface soils

Summary Two borings (20 m depth) were performed in a sandy-clayey soil over a limestone bed and in a sandy soil with lumps of clay in some depths. Bacteria were found in the deeper soil layers of both profiles. The methods used to detect bacteria were those normally used for topsoil layers, plate counts of bacteria, ATP content, and direct microscopy. Measurements of CO₂ evolution showed that the potential for bacterial activity was present in all depths of the two profiles. However, the activity was strongly dependent on the presence of easily available organic C. An indication of the denitrification potential was obtained by measuring the N₂O evolution. Under aerobic incubation without the addition of glucose, N₂O was detected only in the topsoil. When glucose was added to the soil samples, N₂O was found at a low level in the deeper soil layers. Under anaerobic incubation, N₂O was detected in all deeper layers, and increased markedly when glucose was added to the soil samples.     

The effect of water table depth on emissions of N2O from a grassland soil

Nitrous oxide (N₂O) emissions were measured by the closed chamber technique from five plots along a transect in a nitrogen‐fertilised grassland, together with soil water content, soil temperature and water table depth, to investigate the effect of water table depth on N₂O emissions. N₂O fluxes varied from <1 g N₂O‐N ha^?1 day^?1 to peaks of around 500–1200 g N₂O‐N ha^?1 day^?1 after N fertiliser applications. There was no significant difference in overall average water table depth between four of the five plots, but significant short‐term temporal variations in water table depth did occur. Rises in the water table were accompanied by exponential increases in N₂O emissions, through the associated increases in the water‐filled pore space of the topsoil. Modelling predicted that if the water table could be managed such that it was kept to no less than 35 cm below the ground surface, fluxes during the growing season would be reduced by 50%, while lowering to 45 cm would reduce them by over 80%. The strong implication of these results is that draining grasslands, so that the water tables are only rarely nearer to the surface than 35 cm when N is available for denitrification, would substantially reduce N₂O emissions.     

Adsorption of the insecticidal protein of Bacillus thuringiensis subsp. kurstaki by minerals: effects of inorganic salts

The persistence of the insecticidal protein of Bacillus thuringiensis (Bt) is enhanced by the reactivity with soil particles and may constitute a hazard to the soil ecosystem; however, studies on the fate of the Bt toxin in soil, especially in the presence of inorganic salts, are limited. The effects of different concentrations of KNO₃, KH₂PO₄ and NH₄H₂PO₄ on the adsorption of Bacillus thuringiensis toxin by kaolinite, montmorillonite, goethite and silicon dioxide were investigated. Results showed that small salt concentrations tended to enhance toxin adsorption, whereas large concentrations (> 10 mmol litre^?1) inhibited sorption. Similar results were observed regardless of the order in which toxin and inorganic salt were added. The degree to which individual salts affected adsorption decreased in the sequence for minerals, goethite > kaolinite ≥ montmorillonite > silicon dioxide, and for ions, H₂PO₄^? > NO₃^?, NH₄⁺ > K⁺. Our results indicate that inorganic salts can markedly influence the adsorption of Bt toxin by soil minerals. This investigation will help in evaluating the behaviour and fate of Bt toxins in the soil environment.     

Iron oxide mineralogy of some soils of two river terrace sequences in Spain

The iron oxides of soils of two river terrace sequences in Spain which show an increasing degree of redness with age were studied. Clay fractions contained only small amounts of oxalate-extractable Fe. Goethite and hematite, the only crystalline Fe-oxides identified, were determined quantitatively by X-ray diffraction (XRD) after concentrating the Fe-oxides by boiling in $\text{5N}$ NaOH and subtracting the step-counted diffractogram of the deferrated clay from that of the non-deferrated clay, obtaining thus a “pure” Fe-oxide diffractogram. EDTA extracted hematite preferentially to goethite as is seen by loss of red colour and by XRD. A good correlation was found between the content of hematite in the fine earth and a redness rating based on Munsell notations.In the Guadalquivir River sequence, Fe_d and Fe_d/Fe_t increased with age. The amount of both goethite and hematite formed from silicate-Fe increased with soil age but hematite increased more than goethite, possibly due to the xeric soil environment. Also, goethite increased in crystallinity as indicated by a decrease in XRD line broadening and Fe_o/Fe_d ratios. No such trends were found in the Esla River sequence, possibly because the initial alluvium was already highly weathered as shown by high Fe_d/Fe_t values (0.8) irrespective of terrace level.Al substitution in goethite calculated from XRD increased with soil age, reflecting the increasing acidity of the soils. Al substitution in hematite was markedly lower.     

Removal of Phosphate from Waste Waters by Adsorption

In this study, the adsorption of phosphate on gas concrete from aqueous solutions has been studied as functions of temperature, mixing rates and suspension pH. Over 99% of phosphate removal was found. The chemical composition of the gas concrete has been defined by X-ray analysis. Experimental data was fitted to the Langmuir equation in order to Langmuir coefficients. After calculating Langmuir coefficients, adsorption free energy (Δ G ⁰ _ads.) has been determined. In order to gather information about adsorption mechanism, electrophoretic mobilites of particles were measured at various pHs by using Zeta meter 3.0+. It has been found that the adsorption is driven by the interactions between the ionizations of CaO and Al₂O₃ and the formation of AlPO₄. According to the BET (N₂) measurements, the specific surface area of gas concrete was found as 22 m²g^-1. The surface area after adsorption has been found as 17 m²g^-1. The surface area covered by adsorbate has been found as 5.23 m²g^-1 by usinga_s = n^s _m. a_m. N_A. These two areas determined by BET and Langmuir model were close to each other (BET: 22 m²g^-1–17 m²g^-1).