Cation binding in a soil with low exchange capacity: Implication for the structural rigidity of soil organic matter

Two previous studies suggested that part of the cation sorption sites in soil organic matter with low exchange capacity have to be considered as “lonely”, i.e., too far from each other to allow direct cross‐linking by bivalent cations. The objective of this contribution was to understand the mechanisms controlling structural rigidity and physicochemical aging of the SOM (soil organic matter) and the role of water molecule bridges (WaMB) therein. For this, we evaluated the matrix rigidity of an organic surface layer of a Haplic Podzol on a quantitative basis, by assessing WaMB transition temperature (T*) directly after treatment with bivalent cations (Mg²⁺, Ca²⁺, or Ba²⁺) and after eight weeks of aging. Cation loading as well as cation type influenced matrix rigidity. Ba²⁺ induced the most rigid matrix and Mg²⁺ the weakest, which is in line with their binding strength in terms of Langmuir coefficient. The matrix rigidity increased with the cross‐linking activity, which is the product of loading and Langmuir constant of the respective cation. The aging process, however, was slowed down by the initial matrix rigidity, and the rigidity of the aged matrix decreased with increasing Langmuir constant. The degree of aging increased with increasing hydration enthalpy of the cation and decreased with increasing cation loading. Thus, directly after cation treatment, direct cross‐links by multivalent cations were most relevant, but WaMB increasingly gained influence on the matrix rigidity during aging. The untreated sample revealed a considerable number of WaMB, resulting in a fairly rigid and strongly cross‐linked matrix which, however, flexibly reacts on external influences like change in cation concentration or relative humidity. With these findings, the ideas on the relevance of indirect CaB‐WaMB associations between distant sorption sites for the rigidity and flexibility of the OM matrix as proposed in previous studies were confirmed on a mechanistic basis in this study.     

Short-term evolution of hydration effects on soil organic matter properties and resulting implications for sorption of naphthalene-2-ol

Purpose

Sorption of xenobiotics in soils and especially to soil organic matter (SOM) determines their mobility and bioavailability in ecosystems. However, SOM as the major sorbent may be altered in its physicochemical properties upon changes in boundary conditions such as hydration. Hence, the goal of this study was to determine the influence of soil hydration on physicochemical properties of SOM and the resulting effects on sorption of xenobiotics.

Materials and methods

Samples of a Histosol with 51?% SOM were adjusted to five water contents from 10 to 75?% (w/w based on dry soil mass) and aged for water contact times of 0?weeks to 3?years. The hydrated samples were characterized with respect to thermal properties of SOM and of the incorporated water via differential scanning calorimetry and with respect to hydration-induced swelling via ¹H-NMR relaxometry, and the sessile drop method was applied to determine their soil?Cwater contact angle. Sorption kinetics and isotherms of naphthalene-2-ol in the pre-treated peat samples were determined in batch experiments.

Results and discussion

SOM matrix rigidity varied with the water content and increased with water contact time. An initial minimum in SOM rigidity at ~30?% water content became maximum after ~20?weeks, also resulting in the strongest resistance towards water infiltration. We argue that the anomalies at 30?% water content are related to the critical water content for the formation of freezable water w _crit in the peat samples, which was 26.2?±?0.3?%. Conditions for water-assisted molecular bridging were assumably optimal at 30?% water content. Whereas parameters of naphthalene-2-ol sorption reflecting the sorbed amount were mainly altered by the wetting properties of SOM, sorption linearity and hysteresis were influenced by the anomalies in peat matrix properties at a water content around 30?%.

Conclusions

The study revealed that the interplay of SOM and water led to highly variable and complex changes in SOM physicochemical properties. These properties may serve as a predictor for sorption of xenobiotics in soil at varying hydration conditions enabling a more precise assessment of the environmental fate of xenobiotics.     

Inorganic and organic carbon dynamics in forested soils developed on contrasting geology in Slovenia—a stable isotope approach

Purpose

Soil carbon dynamics were studied at four different forest stands developed on bedrocks with contrasting geology in Slovenia: one plot on magmatic granodiorite bedrock (IG), two plots on carbonate bedrock in the karstic-dinaric area (CC and CD), and one situated on Pleistocene coalluvial terraces (FGS).

Materials and methods

Throughfall (TF) and soil water were collected monthly at each location from June to November during 2005–2007. In soil water, the following parameters were determined: T, pH, total alkalinity, concentrations of Ca²⁺ and Mg²⁺, dissolved organic carbon (DOC), and Cl^? as well as δ¹³C_DIC. On the other hand, in TF, only the Cl^? content was measured. Soil and plant samples were also collected at forest stands, and stable isotope measurements were performed in soil and plant organic carbon and total nitrogen and in carbonate rocks. The obtained data were used to calculate the dissolved inorganic carbon (DIC) and DOC fluxes. Statistic analyses were carried out to compare sites of different lithologies, at different spatial and temporal scales.

Results and discussion

Decomposition of soil organic matter (SOM) controlled by the climate can explain the ¹³C and ¹⁵?N enrichment in SOM at CC, CD, and FGS, while the soil microbial biomass makes an important contribution to the SOM at IG. The loss of DOC at a soil depth of 5 cm was estimated at 1 mol m^?2 year^?1 and shows no significant differences among the study sites. The DOC fluxes were mainly controlled by physical factors, most notably sorption dynamics, and microbial–DOC relationships. The pH and pCO₂ of the soil solution controlled the DIC fluxes according to carbonate equilibrium reactions. An increased exchange between DIC and atmospheric air was observed for samples from non-carbonate subsoils (IG and FGS). In addition, higher δ¹³C_DIC values up to ?19.4?‰ in the shallow soil water were recorded during the summer as a consequence of isotopic fractionation induced by molecular diffusion of soil CO₂. The δ¹³C_DIC values also suggest that half of the DIC derives from soil CO₂ indicating that 2 to 5 mol m^?2 year^?1 of carbon is lost in the form of dissolved inorganic carbon at CC and CD after carbonate dissolution.

Conclusions

Major difference in soil carbon dynamics between the four forest ecosystems is a result of the combined influence of bedrock geology, soil texture, and the sources of SOM. Water flux was a critical parameter in quantifying carbon depletion rates in dissolved organic and inorganic carbon forms.

     

Foliar Nitrogen Uptake from Wet Deposition and the Relation with Leaf Wettability and Water Storage Capacity

This study assessed the foliar uptake of ¹⁵N-labelled nitrogen (N) originating from wet deposition along with leaf surface conditions, measured by wettability and water storage capacity. Foliar ¹⁵N uptake was measured on saplings of silver birch, European beech, pedunculate oak and Scots pine and the effect of nitrogen form (NH ₄ ⁺ or NO ₃ ^? ), NH ₄ ⁺ to NO ₃ ^? ratio and leaf phenology on this N uptake was assessed. Next to this, leaf wettability and water storage capacity were determined for each tree species and phenological stage, and the relationship with ¹⁵NH ₄ ⁺ and ¹⁵NO ₃ ^? uptake was examined. Uptake rates were on average five times higher (p?<?0.05) for NH ₄ ⁺ than for NO ₃ ^? and four times higher for deciduous species than for Scots pine. Developing leaves showed lower uptake than fully developed and senescent leaves, but this effect was tree species dependent. The applied NH ₄ ⁺ to NO ₃ ^? ratio did only affect the amount of N uptake by senescent leaves. The negative correlation between measured leaf contact angles and foliar N uptake demonstrates that the observed effects of tree species and phenological stage are related to differences in leaf wettability and not to water storage capacity.     

Dynamics of soil extractable carbon and nitrogen under different cover crop residues

Purpose

Cover crop residue is generally applied to improve soil quality and crop productivity. Improved understanding of dynamics of soil extractable organic carbon (EOC) and nitrogen (EON) under cover crops is useful for developing effective agronomic management and nitrogen (N) fertilization strategies.

Materials and methods

Dynamics of soil extractable inorganic and organic carbon (C) and N pools were investigated under six cover crop treatments, which included two legume crops (capello woolly pod vetch and field pea), three non-legume crops (wheat, Saia oat and Indian mustard), and a nil-crop control (CK) in southeastern Australia. Cover crops at anthesis were crimp-rolled onto the soil surface in October 2009. Soil and crop residue samples were taken over the periods October?CDecember (2009) and March?CMay (2010), respectively, to examine remaining crop residue biomass, soil NH₄ ⁺?N and NO₃ ^??CN as well as EOC and EON concentrations using extraction methods of 2?M KCl and hot water. Additionally, soil net N mineralization rates were measured for soil samples collected in May 2010.

Results and discussion

The CK treatment had the highest soil inorganic N (NH₄ ⁺?N?+?NO₃ ^??CN) at the sampling time in December 2009 but decreased greatly with sampling time. The cover crop treatments had greater soil EOC and EON concentrations than the CK treatment. However, no significant differences in soil NH₄ ⁺?N, NO₃ ^??CN, EOC, EON, and ratios of EOC to EON were found between the legume and non-legume cover crop treatments across the sampling times, which were supported by the similar results of soil net N mineralization rates among the treatments. Stepwise multiple regression analyses indicated that soil EOC in the hot water extracts was mainly affected by soil total C (R ²?=?0.654, P?<?0.001), while the crop residue biomass determined soil EON in the hot water extracts (R ²?=?0.591, P?<?0.001).

Conclusions

The cover crop treatments had lower loss of soil inorganic N compared with the CK treatment across the sampling times. The legume and non-legume cover crop treatments did not significantly differ in soil EOC and EON pools across the sampling times. In addition, the decomposition of cover crop residues had more influence on soil EON than the decomposition of soil organic matter (SOM), which indicated less N fertilization under cover crop residues. On the other hand, the decomposition of SOM exerted more influence on soil EOC across the sampling times among the treatments, implying different C and N cycling under cover crops.     

Evolution and phosphorus fractionation in saline Spolic Technosols flooded with eutrophic water

Purpose

The aim of this study was to evaluate the behaviour of P in saline Spolic Technosols flooded with eutrophic water, with and without plant rhizosphere, in order to assess the role of these soils as sinks or sources of this nutrient.

Materials and methods

Samples were taken from basic (pH?~7.8), carbonated and acidic (pH?~6.2), de-carbonated soils of salt marshes polluted by mine wastes. Three treatments were assayed: pots with Sarcocornia fruticosa, pots with Phragmites australis and pots without plants (bare soil). The pots were flooded for 15?weeks with eutrophic water (PO ₄ ^3? ~6.92?mg?L^?1) and pH, Eh and water-soluble organic carbon and PO ₄ ^3? concentrations were monitored in the soil solution. A soil P fractionation was applied before and after the flooding period.

Results and discussion

The PO ₄ ^3? concentration in the soil solution decreased rapidly in both soils, with and without plant, being diminished by 80?C90?% after 3?h of flooding. The Fe/Mn/Al oxides and the Ca/Mg compounds played an important role in soil P retention. In pots with S. fruticosa, the reductive conditions due to flooding induced P release from metal oxides and P retention to Ca/Mg compounds. In turn, P. australis may have favoured the release of P from carbonates, which was transferred to Fe/Mn/Al compounds.

Conclusions

The retention of P by the soil was the main mechanism involved in the removal of PO ₄ ^3? from the eutrophic flooding water but to evaluate the capacity of these systems as long-term P sinks, the combined effect of metals, Ca/Mg compounds and specific plant species should be considered.     

An appreciation of the contribution of Frank Stevenson to the advancement of studies of soil organic matter and humic substances

Purpose

The aims of this paper are to outline the state of knowledge with regard to the chemistry of soil organic matter (SOM) prior to 1950; then, to review and evaluate the contributions made by Frank Stevenson during Stevenson’s research period (1950–1994); and subsequently to outline advances that are being made in the modern era.

Progress in the Stevenson period

Frank Stevenson’s research career began in the middle of the twentieth century when a number of techniques of colloid chemistry were available to him, but relatively few of the recently developed instrumental techniques and other procedures of analytical organic chemistry that have enabled significant advances to be made in the chemistry and properties of SOM components.The contributions that Frank Stevenson has made to the chemistry of SOM and of humic substances (HSs) are an integral part of his book (first and second editions) Humus Chemistry: Genesis, Composition, Reactions. The validity of the terms humus and HSs are being questioned as legitimate terms that describe definable components, and SOM is being viewed as a ‘continuum of progressively decomposing organic compounds’. The legitimacy of isolating the organic matter components from their native soil environment is questioned. Those who pose such questions would do well to consider how progress could have been made in the vital life sciences areas of, for example, proteomics and genomics, without the isolation of the relevant cellular components. We recognise the importance of clear and rigorous definitions of HS components and stress the need to isolate these components from the SOM matrix as a prerequisite to the study of the composition, structure and reactivity of these components. We disagree with proposals or suggestions that do not recognise HSs as a scientific entity, and we feel sure that Frank Stevenson would have supported this stance. Various studies of SOM and of HSs have taken place over the centuries, but progress was slow because the tools required to study such complex systems were not available. Frank Stevenson’s research involved many areas of humic chemistry, and his major advances were in aspects of functionality and in the interactions of humic functional groups with metals and to a lesser extent with anthropogenic organic chemicals. His studies of nitrogen and of ammonia in relation to organic matter also had a very great impact.

Progress in the modern era

Frank Stevenson can be said to have provided the stimulation that enabled beginners and established scientists to obtain a good grasp of the fundamentals of SOM and the humic sciences. His scientific contributions have catalysed many of the significant advances that have been made in the field since he retired. In the final section, some of the advances that have been made using modern analytical techniques are addressed and some of the controversial topics that have recently arisen are discussed.

     

Modalités de la contamination de deux chaînes trophiques dulçaquicoles par le cobalt 60

Introduction

A previous work (Amiard-Triquet and Foulquier, 1978) has covered the dynamics of water-borne contamination in organisms included into two freshwater food-chains: Here, we report the results obtained about the contamination of the same species bothvia water and food.

Experimental Procedures (Table I)

The specimens were continuously immersed in contaminated water and received radioactive food. The radioactivity level was the same for the water in which they were immersed and for the water used in the contamination of their prey. The level was adjusted at 4 μCi/l for the carp food-chain and 0.4 μCi/l for that of the crayfish. Daphnia were reared in a medium compo?ed of 2/5 of soil extract and 3/5 of river water (Table II). They were fed bacteria developed in this medium or uponChlorella cultivated apart and then introduced in the rearing tanks. The bulk of the medium varied between 5 and 30 l. The influence of the various components of the rearing medium on the physico-chemical form of⁶⁰Co was studied by chromatographic techniques using ion-exchange resins. Three groups of fiftyLymnaea were placed in three tanks containing 30 l of river water.Elodea which composed their food were immersed in the same tanks. Crayfishes and carps were reared in individual containers. Five times per week, they received, respectively, oneLymnaea or one hundredDaphnia. Water was changed and contaminated again each week.

Results

NH ₄ ⁺ ions produced in the rearing medium with organic metabolites extracted byDaphnia do not affect the physico-chemical form of⁶⁰Co. On the contrary, anionic complex forms appear under the influence of river water or soil extract components. The radioactivity ofDaphnia evolves during the contamination experiment as a function of the biological availability of the different physico-chemical states of cobalt. The maximum value of the overall contamination factor C^* is 70.3 after one week of experiment; the minimum value, 8.6 after ten months. The contamination dynamics for the other species are presented in Figures 3 and 4. The mean values at equilibrium for⁶⁰Co concentration in the organisms and for overall contamination factor C are assembled in Table III.

Discussion and Conclusions

Daphnia likely discriminate the different physico-chemical forms of⁶⁰Co, the availability of anionic complexes being low. The vector of contamination, water alone or both food and water, has not a striking influence upon the⁶⁰Co concentration in carp,Lymnaea and crayfish. The most highly developed species from the zoological point of view are the weakest in this concentration: Teleosts are not so contaminated as Crustaceans which are not so contaminated as Mollusks. On the other hand, the secondary consumers (carp, crayfish) are not so contaminated as the primary consumers (Lymnaea, Daphnia) which are not so contaminated as primary producers (Table III). Laboratory experiments andin situ measurements in seawater and freshwater environments reported in the literature confirm a general tendency to a decreasing of radiocobalt concentrations as a function of trophic level.     

Does the compositional change of soil organic matter in the rhizosphere and bulk soil of tea plants induced by tea polyphenols correlate with Pb bioavailability?

Purpose

Soil organic matter (SOM) plays a vital role in controlling metal bioavailability. However, the relationship between SOM and its fractions, including water-soluble substances (WSS), fulvic acid (FA), humic acid (HA), and soil microbial biomass (SMB), to metal bioavailability in plants has not been thoroughly investigated. This study examined the compositional change of SOM after tea polyphenols (TPs) were added to the soil and its correlation with Pb bioavailability.

Materials and methods

Ultisol samples were collected from Fuyang, spiked with two levels (0 and 300 mg kg^?1 DW) of Pb, and aged for 30 days. Four uniform seedlings were transplanted to each plastic pot, which were filled with 3 kg of air-dried soil. After successful transplantation, three levels (0, 300, and 600 mg kg^?1 DW) of TPs were amended as irrigation solution for the pots. The Pb concentrations in different tissues of the tea plants were determined after 6 months. SOM, WSS, FA, HA, and SMB were extracted and quantified using a Multi N/C Total Organic Carbon Analyser.

Results and discussion

Adding TPs to Pb-polluted soils alleviated Pb toxicity to microorganisms and increased SMB and the rhizosphere effect. The rhizosphere SOM was lower than bulk SOM in Pb-unspiked soils, while the opposite results were observed in Pb-spiked soils. A similar inconsistency for HA in the rhizosphere and bulk soil between Pb-unspiked and Pb-spiked soils might explain the difference in SOM. FA increased with the addition of TPs in both the rhizosphere and bulk soils, which might be the result of TP transformation. Positive correlations are present between the compositions of rhizosphere SOM and Pb in different tissues of the tea plant. SMB correlated negatively with Pb in young leaves and stems. Compared to rhizosphere soil, SOM components in bulk soil were less strongly correlated with Pb in tea plants.

Conclusions

Addition of TPs to soil changes the components of SOM and Pb bioavailability. SOM and its fractions, including WSS, FA, HA, and SMB, show a close relationship to Pb in different tissues of the tea plants.     

Stability of soil organic matter in two northeastern German fen soils: the influence of site and soil development

Purpose

Peatland soils play an important role in the global carbon (C) cycle due to their high organic carbon content. Lowering of the water table e.g. for agricultural use accelerates aerobic secondary peat decomposition and processes of earthification. Peatlands change from C sinks to C sources. We characterized soil organic matter (SOM) with special attention to human impact through drainage. Our aim was to gain knowledge of SOM quality and soil-forming processes in drained fen soils in northeastern Germany.

Materials and methods

Through techniques of representative landscape analysis, we identified two typical and representative sampling sites in different stages of land use, representing the most important hydrogenetic mire types in northeastern Germany. We adapted chemical fractionation procedures which include hot water extraction (C_hwe and N_hwe) for determination of the labile fraction. Furthermore, a stepwise acid hydrolysis procedure was performed to measure the chemical recalcitrant part of SOM as it is more resistant to biodegradability.

Results and discussion

Total organic C decreased with increasing human impact and intensity of drainage. Conversely, C_hwe and N_hwe concentrations increased with increasing drainage and human impact. In contrast, the more recalcitrant fractions increased with soil depth.

Conclusions

Generally, there is a lack of existing data about SOM quality and the factors controlling its stability and decomposition in fen soils. For northeastern German fen soils, the data are even more inadequate. Influence of drainage seems to overlap natural influences of site on SOM quality. The used extraction scheme was suitable for the chemical fractionation of SOM into labile and more recalcitrant parts.     

Chemical and spectroscopic characteristics of humic acids in marshes from the Iberian Peninsula

Purpose

To characterise soil humic acids (HAs) extracted from Spanish marshes formed under different vegetation types (Spartina maritima (GSp), Juncus maritimus (GJc), Phragmites australis (GPh), and Scirpus maritimus (VSc)), soil depths (0–20, 20–40 and 40–60 cm), physiographic position (low and high marshes), wetland types (salt marshes and lagoons) and environmental conditions (Atlantic and Mediterranean coast).

Material and methods

Soil samples were collected in five Spanish marshes, three on the Galicia province and two on the Valencia province. Humic acids were extracted and their elemental composition, semiquinone-type free radical (SFR) content, FTIR and CPMAS ¹³C NMR spectra determined. Total carbon (TC), total nitrogen (TN), total sulphur (TS), CaCO₃ content, and field pH and Eh (mV) in the marsh soils sampled were also measured.

Results and discussion

The field pH and Eh values were typical of coastal areas submitted to periodic inundations and the highest TC, TN and TS contents were found in the soil of lagoon marshes as an effect of physiographic position and wetland type. The HAs, in general, were highly aliphatic and exhibited a low SFR content, which suggests a low humification degree of the SOM formed in the studied areas. This is a result of the anaerobic decomposition to which SOM is submitted and the high input of plant-derived organic matter (OM) by vegetation. However, among the studied sites low salt marsh and subsurface layer of the high salt marsh showed higher SFR content, simpler FTIR spectra, higher lignin degradation and lower O-alkyl C/alkyl C ratio than the lagoon marshes, thus suggesting the presence of a more humificated SOM in these sites.

Conclusions

From the different factors analysed, only physiographic position (low versus high salt marshes) and wetland type (marshes versus lagoons) caused variations in the HAs characteristics, because as the studied soils are under anaerobic conditions, they control the exportation of plant-derived OM and the allochthonous OM contribution in the studied areas.     

Defining soil geochemical baselines at small scales using geochemical common factors and soil organic matter as normalizers

Purpose

The establishment of geochemical baselines is essential for accurate evaluation of the present state of surface environments. In this study, normalization procedures (NP), which can improve the explanation of the natural variation of elements, were conducted using geochemical common factors (GCF) and soil organic matter (SOM) as normalizers to define the geochemical baselines of soil trace elements.

Materials and methods

Soil samples (n?=?345) were collected in Luhe County, Jiangsu, China, a county with a complex geologic setting and intensive anthropogenic influence. Conservative elements, Al, Ca, Fe, K, Mg, Mn, Na, P, and Ti; trace elements, As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn; and SOM were measured. Normalization procedures were conducted using multiple linear regressions between soil trace elements and SOM and GCFs, acquired from factor analysis of the soil major elements. Normalization procedures using univariate linear regressions between soil trace elements and conservative elements Al, Fe, and Ti were also conducted for comparison.

Results and discussion

Comparison of NPs using GCFs and SOM as normalizers with NPs, which use single conservative elements as normalizers, shows that the former is more accurate than the latter for As, Pb, and Zn and is as accurate for Cd, Cr, Cu, Hg, and Ni, when the most appropriate single conservative element is chosen. Small-scale geochemical baselines in the county are significantly different from regional-scale geochemical baselines for Jiangsu Province, China.

Conclusions

The application of regional-scale geochemical baselines at small scales may lead to estimation errors in determining anomalies and assessing environments. Baselines obtained from the NPs using GCFs and SOM as normalizers are more accurate.     

Molecular fingerprint of soil organic matter as an indicator of pedogenesis processes in Technosols

Purpose

Technosol management is one of the greatest challenges for the future, more specifically as regards supporting and/or restoring ecosystems. The understanding of natural soil organic matter (SOM) dynamic from Technosol may give important information about soil functioning and Technosol evolution.

Materials and methods

According to this, SOM from three French old mine Technosols, (an old tin mine, a lead and zinc, and a gold one which is arsenic-rich), were studied and characterized using thermochemolysis coupled with gas chromatography and mass spectrometry (GC-MS) with tetramethyl ammonium hydroxide (TMAH) as reagent and FTIR. The characterization and quantification of some specific biomacromolecules, used as biomarkers, indicate the specific level of incorporation relative to various subgroups. Global parameters of soils (pH, total organic matter, cation exchange capacity…) were also evaluated.

Results and discussion

Results on bulk samples show that lipids are the most reactive group and therefore play the most important role in young soil pedogenesis. All of the results show that the behavior of SOM of the Technosol is similar to homolog non-anthropized soil and depends on vegetation type.

Conclusions

A slight inhibition of bacterial activity is observed which underlines a protective effect of Technosols on SOM degradation due to the low pH, the high clay content, and the presence of Al³⁺ and metal(loid)s. In fine, lipid fraction of SOM may act as a well-done fingerprint of pedogenesis processes in Technosols.

     

Laser-based spectroscopic methods to evaluate the humification degree of soil organic matter in whole soils: a review

Purpose

The objective of this review is to survey critically the results obtained by the application of laser-induced fluorescence spectroscopy (LIFS) and laser-induced breakdown spectroscopy (LIBS) to the evaluation of the humification degree (HD) of soil organic matter (SOM) directly in untreated, intact whole soils.

Materials and methods

A large number of soils of various origin and nature, either native or under various cultivations, land use, and management, at various depths, have been studied to evaluate the HD of their SOM directly in intact whole samples. The LIFS spectra were obtained by either a bench or a portable argon laser apparatus that emits UV-VIS light of high power, whereas the LIBS spectra were obtained using a Q-switched Nd:YAG laser at 1064 nm.

Results and discussion

The close correlations found by comparing H_LIF values of whole soil samples with values of earlier proposed humification indexes confirmed the applicability of LIFS to assess the HD of SOM in whole soils. The high correlation found between HD_LIBS values and H_LIF values showed the promising potential of LIBS for the evaluation HD of SOM.

Conclusions

The LIFS technique shows to be a valuable alternative to evaluate the HD of SOM by probing directly the whole solid soil sample, thus avoiding the use of any previous chemical and/or physical treatments or separation procedures of SOM from the mineral soil matrix. The emerging application of LIBS to evaluate the HD of SOM in whole soils appears promising and appealing due to its sensitivity, selectivity, accuracy, and precision.

     

The role of stromatolites in explaining patterns of carbon, nitrogen, phosphorus, and silicon in the Se?ovlje saltern evaporation ponds (northern Adriatic Sea)

Purpose

In summer 2007, biweekly benthic fluxes of the biogenic elements carbon (C), nitrogen (N), silicon (Si), and phosphorus (P) were studied in the Se?ovlje saltern (salt-making facility) in the northern Adriatic Sea, Slovenia in order to determine the impact of stromatolite (??petola??) on the geochemical properties of saltern sediments.

Materials and methods

The brine and pore waters were analyzed for salinity, NH ₄ ⁺ , NO ₃ ^? , PO ₄ ^3? , SiO ₄ ^4? , total dissolved nitrogen, total dissolved phosphorus, and fluorescent dissolved organic matter. The sediment was analyzed for organic carbon (OC), total nitrogen (TN), total and organic phosphorus (OP), and biogenic Si concentrations, as well as values of ?? ¹³C_OC and ?? ¹⁵N_TN.

Results and discussion

Nutrient concentrations in brine water increased along the salinity gradient due to different processes, such as the evaporative concentrations of seawater, bacterial activity, more pronounced transformation and degradation of organic matter, and regeneration of nutrients. The petola from the Se?ovlje saltern, which is predominately composed of cyanobacterial and diatom communities, develops during the early evaporation stage and survives during high salinity and halite crystallization. Nitrogen fixation and P removal were the principal biogeochemical processes controlling dissolved inorganic N and P concentrations. At higher salinities, N limitation was more important. Microbes decomposed at higher salinities, and the remineralized N and P nutrients were released from surface pore waters to the brine. OP remineralization was also an important process influencing the distribution of PO ₄ ^3? concentrations in pore waters deeper in the sediments. The increasing SiO ₄ ^4? concentrations with increasing salinity in the brine waters were due to dissolution of diatom frustules, while the decrease in pore water SiO ₄ ^4? was probably the consequence of microbial uptake.

Conclusions

This study provides a better understanding of nutrient cycling and the geochemical processes in the Se?ovlje saltern.     

A new model for cation exchange equilibrium considering the electrostatic field of charged particles

Purpose

The aim of this study was to establish a new equilibrium model for cation exchange that quantitatively describe the three important effects: (1) the effect of electrostatic field around soil particles on exchange adsorption; (2) the effect of ionic interaction energy on Boltzmann distribution of cations; and (3) the effect of hydration radius of cation species on cationic distribution between adsorption phase and solution phase.

Materials and methods

In this paper, the Li/Na, Li/K and K/Na exchange were studied theoretically and experimentally. Purified montmorillonite was used as the experimental material and it was H-saturated in advance. In experimental study, approximately 2.5?g of the H-saturated sample was weighed in each experiment, then LiOH/NaOH, LiOH/KOH or KOH/NaOH mixture solution was added. In each experiment, the suspension was allowed to equilibrate for 48?h with continuous shaking at 298?K in an incubator shaker, and then 1?mol/l HCl was used to adjust pH to pH?=?7 when equilibrium was reached. Finally, the suspension was centrifuged and the concentration and of Li⁺, Na⁺ or K⁺ in supernatant was determined.

Results and discussion

In theoretical study, firstly, considering the ionic interaction energy in bulk solution, a modified Poisson?CBoltzmann equation was obtained; secondly, considering the electrostatic field around soil particles, the relationship between the selectivity coefficient and surface potential of particles was established; and thirdly, the modification factors were introduced to modify the effective charge of two cation species that involved in exchange because of the difference in hydration radius. Finally, the new models for describing cation exchange equilibrium were developed. Both theoretical and experimental results showed that the electrostatic field, the ionic interaction energy and the difference in hydration radius of two cation species strongly influenced cation distribution or cation exchange equilibrium. The results indicated that the effective charge could be obtained through either experimental determination or theoretical calculation, and the theoretically predicted values met the experimental results well. Therefore, the ion exchange selectivity series of different cation species with the same valence could be evaluated quantitatively.

Conclusions

New equilibrium models for describing cation exchange were established, for which the three important effects was quantitatively taken into account: the electrostatic field on exchange adsorption, the ionic interaction energy on Boltzmann distribution and the hydration radius of cation species. Both theoretical analyses and experimental results demonstrated that the cation hydration radius and the ionic interaction energy strongly influenced the exchange equilibrium considering the electrostatic field of charged particles.     

An initial study on soil wettability effects during entrapped LNAPL removal by surfactant flooding in coarse-grained sand media

Purpose

Non-ideal or fractional wettability conditions may exist at field sites. It was hypothesized that fractional wettability could cause larger entrapped LNAPL saturations and unexpected soil interactions during surfactant remediation. Soil wettability effects during entrapped LNAPL recovery by surfactant flooding in coarse-grained sand were investigated through a comparative study. The main objective was to identify the impacts of soil wettability on LNAPL removal via submicellar concentration surfactant flooding to remobilize entrapped LNAPL.

Materials and methods

A baseline for comparison was established by testing an ideal water-wet soil (silica sand) along with a fractionally wet soil. Two LNAPLs were tested: LNAPL from a contaminated field site and heptane, which represented an ideal lab-grade fluid. Contact angle, interfacial tension, capillary pressure–saturation, and column tests were performed to characterize wettability and identify the effects of soil wettability during entrapped LNAPL recovery. Two anionic surfactants were used for the column experiments: sodium dodecyl-benzene-sulfonate and a field site anionic surfactant. To further investigate the effects of LNAPL contact time within the soil, columns tests were performed at two different LNAPL contact times.

Results and discussion

Contact angle measurements and column tests conducted with the field LNAPL revealed its potential to establish non water-wet wettability conditions. Column test results indicated that fluid entrapment was independent of fluid type, and the wettability and contact time conditions studied. Entrapped LNAPL saturations after water flooding were approximately 19 %. Entrapped LNAPL removal by mobilization occurred at the predetermined submicellar surfactant concentration (0.5 g/L) with a maximum removal of 43 %. Entrapped LNAPL removal from fractionally wet columns was higher in comparison to water-wet columns and was found to increase with contact time.

Conclusions

Entrapped LNAPL saturations after water imbibition were not impacted by the wettability conditions studied. The fractionally wet soil behaved differently during the surfactant-flood; higher LNAPL removal was achieved suggesting that non-ideal wettability had a positive impact. The presence of NAPL-wet mineral grains might have favored pore scale interactions causing NAPL redistribution and increasing NAPL-surfactant solution interfacial areas contributing to LNAPL removal. Pore scale studies and subsequent testing is recommended to further this study’s findings.     

Effects of fertilization practices on aluminum fractions and species in a wheat soil

Purpose

To better understand the effect of fertilizer practices on soil acidification and soil organic matter (SOM) stocks in a rice-wheat system, a field experiment was conducted to (i) investigate the influence of fertilizer practices on the Al forms in solid phases and the distribution of Al species in water extracts and (ii) explore the relationship between the Al forms, the quantity and composition of SOM, and soil acidity.

Materials and methods

Seven fertilizer treatments including CL (no fertilizer), NK, PK, NPK, N₂PK (PK and 125 % of N), NP₂K (NK and 125 % of P), and organic fertilizer (OF) were applied to induce various changes in pH and SOM composition (i.e., total C and N contents, C/N ratio, and SOM recalcitrant indices) in a rice-wheat system. After 6-year cultivation, different pools of Al forms (i.e., amorphous Al; organically bound Al of varying stability; exchangeable Al; water-soluble inorganic Al³⁺, Al-OH, Al-F, Al-SiO₃, and Al-SO₄; and organic Al monomers) were quantified and related with SOM composition and soil pH during the wheat phase.

Results and discussion

Fertilizer types significantly changed soil pH and SOM composition and which explained 84 % of the variance of Al forms using redundancy analysis. An interaction between soil pH and SOM quality on Al forms also existed but only accounted for a very small (6 %) portion of the variation. Compared to CL and chemical fertilizer, OF practice with relative low SOM stabilization is likely to favor the formation of amorphous Al in order to bind more SOM. The decrease in exchangeable acidity and water-extractable Al via hydroxyl-Al precipitation but not in the form of organo-aluminum complexes evidenced this phenomenon. In contrast, chemical fertilizer input increased exchangeable Al and water extract Al (especially Al³⁺), partly at the expense of organically bound Al. The destabilization of organic-aluminum complexes was a mechanism of pH buffering evidenced by the increased soluble Al-dissolved organic matter (DOM) as soil pH decreases. Further, the magnitude of this trend was much greater for elevated N input compared with P input.

Conclusions

Chemical fertilizer with relative high SOM stabilization favored the formation of exchangeable Al and soluble Al resulting in soil acidification, whereas OF with relative low SOM stabilization tended to transform exchangeable Al and soluble Al to amorphous Al, thereby alleviating soil acidification and enhancing C stocks in a rice-wheat system.

     

Short-Term Physiological Responses of Mosses to Atmospheric Ammonium and Nitrate

Many bryophytes rely to a large extent on atmospheric deposition for their nutrient uptake.However, increasing levels of atmospheric ammonium NH ₄ ⁺ and nitrate NO ₃ ^- attract concern as to the possible harmful effects onbryophytes from these two nutrient sources. Changes in nitrate reductase (NR) activities, cation(Ca, K and Mg), total nitrogen (N) and organic acid concentrations were investigated for themosses, Racomitrium lanuginosum, Rytidiadelphus loreus and Philonotis fontana, in response to asingle field misting with 3 mol m^-3 NH ₄ ⁺ and NO ₃ ^- . Increases of 20% were recordedfor tissue N content, 48 hr after misting with N containing solutions. When labelled NH ₄ ⁺ or NO ₃ ^- were applied to R. Lanuginosum at 1, 3 and 6mol m^-3 concentrations, partitioning ofincorporated ¹⁵N between different tissueregions occured, with the highest N uptake in the upper stem and leaves. High concentrations ofapplied N resulted in reduced efficiency of N uptake. NH ₄ ⁺ applications caused declines in NR activities, organic acidsand cations, whereas, NO ₃ ^- treatments causedthe reverse response. Changes in cation contents, organic acids and NR activity reflect short-termregulation of N metabolism in the presence of defined N sources, as well as potential mechanismsof regulating cell pH homoeostasis. The consistency of physiological responses, especially NRactivities, over short-term pollution episodes, provides evidence for their use as indicators of both NH ₄ ⁺ and NO ₃ ^- pollution.     

The impact of restoration processes on the selected soil properties and organic matter transformation of mountain fens under <Emphasis Type="Italic">Caltho-Alnetum</Emphasis> community in the Babiogórski National Park in Outer Flysch Carpathians,Poland

Purpose

The objective of this study was to determine the impact of restoration processes on the selected soil properties and organic matter transformation of mountain fens under the Caltho-Alnetum community in the Babiogórski National Park in Outer Flysch Carpathians.

Materials and methods

Restoration processes were conducted on three degraded mountain fens in the Babiogórski National Park in Outer Flysch Carpathians, Poland. The degradation degree of soils was the criterion for the selection of habitats for further studies. To determine the influence of restoration processes on mountain fen soil properties and organic matter transformation, samples were collected in 2011 and 2013. The soil samples were assayed for pH, base cation concentration, hydrolytic acidity, organic carbon and total nitrogen content, total exchangeable base cation concentration, cation exchange capacity, and base saturation. Organic matter fractions were extracted by IHSS method. Quantitative and qualitative study of organic matter was based on fraction composition analysis and the ratio of humic acid carbon to fulvic acid carbon. The research results were statistically verified.

Results and discussion

Based on morphological and chemical properties, the studied mountain fen soils can be classified as Sapric Dranic Eutric Histosols and Sapric Dranic Dystric Histosols according to WRB guidelines (2015). Before restoration processes, the mountain fen soils subjected to a different water regime showed various contents of total nitrogen and organic carbon. The decreasing of the groundwater level was reflected in pH, calcium ion content, exchangeable base cation concentration, and base saturation. The increase of the groundwater level had influence on chemical properties of mountain fen soils such as pH, total exchangeable base cation concentration, hydrolytic acidity, cation exchange capacity, and base saturation. Three-year restoration processes did not cause significant changes in the composition of humic substance fractions.

Conclusions

Mountain fens under Caltho-Alnetum community are priority habitats in Babiogórski National Park in Outer Flysch Carpathians, Poland. These habitats responded to restoration processes in varying degrees depending on the extent of their degradation. The least degraded mountain fen was characterized by a short response time on the restoration processes. The reaction of higher degraded habitats was weaker.