Study of the diffusion of trace elements and radionuclides in soils

Thin layer method of measuring diffusion processes was modified to shorten time and to increase efficiency of experiments. For this purpose small and fine glass capillaries of 20 mm length and inner diameter of several millimeters were used as diffusion cells. The diffusion of trace amounts of¹³⁷Cs, its dependence on soil moisture and interaction with the soil have been studied. Experimental technique. evaluation of records and the basic interpretation of the migration process are described.     

Adhesion of Pseudomonas putida NCIB 9816-4 to a naphthalene-contaminated soil

The effect of a soil contaminant on the initial adhesion to the soil of a contaminant-degrading soil microorganism in the exponential phase was investigated using naphthalene as the soil contaminant and Pseudomonas putida strain NCIB 9816-4 as the naphthalene-degrading bacteria. P. putida strain DK-1, which is not capable of degrading naphthalene, was used as a control. P. putida NCIB 9816-4 in the exponential phase showed the more adhesion to the soil than that in the stationary phase. In contrast, P. putida DK-1 showed the increased adhesion to the soil when it was in the stationary phase. P. putida NCIB 9816-4 in the exponential phase showed the preferred adhesion to the naphthalene-contaminated soil, whereas the adhesion of P. putida DK-1 was not affected by naphthalene. From the data of surface hydrophobicities of the cells and the soil, the microbial adhesion, especially the initial adhesion to the naphthalene-contaminated soil, takes place through the hydrophobic interaction. We suspect that the surface hydrophobicity of P. putida NCIB 9816-4 in the exponential phase might be increased during the uptake of naphthalene, which caused the preferred adhesion to the naphthalene-contaminated soil.     

Interaction of soil humic acids with herbicide paraquat analyzed by surface-enhanced Raman scattering and fluorescence spectroscopy on silver plasmonic nanoparticles

A study of the interaction between paraquat (methyl viologen) and humic acids, extracted from a soil amended over 30 years with crop residues, cow slurries and cattle manure, was carried out by two emission spectroscopies based on plasmonic effects: surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF). To carry out this study Ag nanoparticles were used. The complex formation was tested by analyzing the effect of the herbicide on humic acids, and by varying experimental parameters such as the pH and the laser excitation wavelength. The study of the vibrational bands led to infer information about the interaction mechanism of paraquat with humic acids and to find a correlation between this interaction and the humic acids structural modification induced by the different amendments added to soil.     

土壤/沉积物吸附有机污染物机理研究的进展

有机污染物与土壤、沉积和以及地表水中悬浮物（如腐殖质）之间的相互作用——吸咐与解吸是决定它们环境行为最重要的因素之一。自60年代末期以来,经各国科学院们的共同努力,该项工作取得了一些非常重要的研究成果,本文将对该领域的研究现状进行评述,并对其未来可能的发展方向提出自己的见解。     

Heterogeneous distribution of radiocesium in aerosols, soil and particulate matters emitted by the Fukushima Daiichi Nuclear Power Plant accident: retention of micro-scale heterogeneity during the migration of radiocesium from the air into ground and river systems

We analyzed ¹³⁷Cs in aerosols, rock, soil and river suspended sediment collected after the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident. Based on the results, we discuss the post-event behavior and transportation of radiocesium in the environment from the air into ground and river systems. First, radionuclides were emitted from the FDNPP as airborne ‘hot’ particles, which contained water-soluble fractions of radiocesium. Radiocesium was still present in a water-soluble fraction after deposition on the ground. Subsequent interaction of the ‘hot’ particles with water (e.g. rainfall) dissolved and strongly fixed the radiocesium on rock and soil particles, thus changing the radiocesium into insoluble forms. The distribution of ‘hot spots’ was possibly controlled by the initial position of deposition on the ground. Consequently, ‘hot spots’ were studded on the rock surface rather than being uniformly distributed. The distribution of radiocesium in river suspended particles was not homogeneous during water transportation, reflecting the heterogeneity of radiocesium in rock and soil. Leaching experiments demonstrated that radiocesium in rock, soil and river suspended sediment was fairly insoluble, showing that the adsorption reaction is irreversible. The micro-scale heterogeneous distribution of radiocesium in aerosols, soil and suspended particles was due to the presence of ‘hot’ particles in aerosols. Dissolution of radiocesium in the ‘hot’ particles in the aerosols and subsequent irreversible adsorption onto the soil particle complex are responsible for the preservation of the heterogeneity both in soil and in river suspended particles.     

Interaction between electrical double layers of soil colloids and Fe/Al oxides in suspensions

Phyllosilicates with net negative surface charge and Fe/Al oxides with net positive surface charge coexist in variable-charge soils, and the interaction between these oppositely charged particles affects the stability of mixed colloids, aggregation, and even the surface chemical properties of variable-charge soils. The interaction of the diffuse layers of electrical double layers between the negatively charged soil colloidal particles and the positively charged particles of goethite or gamma-Al(2)O(3) was investigated in this article through the comparison of zeta potentials between single-soil colloidal systems and binary systems containing soil colloids and Fe/Al oxides. The results showed that the presence of goethite and gamma-Al(2)O(3) increased the zeta potential of the binary system containing soil colloids and Fe/Al oxides, which clearly suggests the overlapping of the diffuse layers in soil colloids and Fe/Al oxides. The overlapping of the diffuse layers leads to a decrease in the effective negative charge density on soil colloid and thus causes a shift of pH-zeta potential curves toward the more positive-value side. The interaction of the electrical double layers is also related to the charge characteristics on the Fe/Al oxides: the higher the positive charge density on Fe/Al oxides, the stronger the interaction of the electrical double layers between the soil colloid particles and the Fe/Al oxides.     

Activities of Hydrolases and Oxidases as Influenced by the Application of Monocrotophos in Sandy Loam Soil of Rajasthan

Continuous and repeated use of pesticides affects soil microbial flora and fauna and hence indirectly affects the activity of diverse microbial enzymes present within it. The present study investigates the interaction effect of different concentrations of monocrotophos on diverse hydrolases and oxidases, viz., protease, alkaline phosphatase, acid phosphatase, cellulase, amylase, invertase, arginine deaminase, and dehydrogenase, present in sandy loam soil of Rajasthan under in vitro conditions for 30 days. Soil sample was inoculated with three different concentrations of monocrotophos, viz., 50, 100, and 150 μg kg^-1, and incubated in dark at room temperature. At regular interval of 5 days, sample was withdrawn and enzyme activity was calculated and compared with that of control. Application of various concentrations of monocrotophos enhanced the activity of diverse enzymes present in soil. Therefore, the study revealed synergistic or additive effect of monocrotophos on all the tested microbial enzyme entities. Increasing concentration of the pesticide, however, poses an antagonistic interaction on the increment of different enzymes activities. Therefore, it can be concluded from the study that monocrotophos impose a positive effect at low concentration of pesticide, whereas high concentration poses negative effect on the activity of different enzymes present in soil.     

Infrared and chemometrics study of the interaction between heavy metals and organic matter in soils

The study of the behavior of heavy metals in soils requires the knowledge of the complexation between soil constituents and metals and this information is not available from conventional analytical techniques such as atomic absorption. Since metals do not absorb mid infrared radiation, we wanted to characterize them using their interaction with the organic matter of soils. The use of chemometrics treatment of the spectroscopic data has demonstrated firstly that the interaction between soil constituents and metals takes place preferentially via organic matter, secondly the high difference between the complexation of lead and zinc into organic matter should be noted. The study of the infrared spectra shows that two bands at 1670-1690 and 1710 cm(-1) vary according to the concentration of lead, which seems to be preferentially complexed by the salicylate functionality.     

Theoretical Study on the Effects of Spatial Structure of P Complexation Sites on the Soil Phosphorus Activation in Leonardite Humic Acid Complexes

Humic acid is an important active component in soil environment. The spatial structures of P complexation sites in humic acid complexes play an important role in soil phosphorus activation and fertilizer efficiency. To explore the effects of spatial structure, the three different coordination modes of iron-carboxyl in models were calculated by the ONIOM method available in the Gaussian09 package. The(U)B3LYP hybrid density functional was employed to optimize the configuration for the QM region, and the UFF force field was used to calculate for the MM region. The results show that the different spatial structures influence the soil phosphorus activation by affecting the electronic structure, Gibbs free energy and interaction energy of the models. And the effects are as follows: the unidentate structure model ~6P-Fe-MHA-UD, the bidentate chelating structure model ~6P-Fe-MHA-BD>the bidentate bridging structure model ~5P-Fe-MHA-BD-BG. It can be known that, the fertilizer efficiency can be improved through increasing the proportion of the unidentate structure and the bidentate chelating structure in production engineering. The research provides a theoretical basis for further optimization of the production of humic acid phosphate fertilizer.     

Evaluation of the surface affinity of water in three biochars using fast field cycling NMR relaxometry

Many soil functions depend on the interaction of water with soil. The affinity of water for soils can be altered by applying soil amendments like stone meal, manure, or biochar (a carbonaceous material obtained by pyrolysis of biomasses). In fact, the addition of hydrophobic biochar to soil may increase soil repellency, reduce water‐adsorbing capacity, inhibit microbial activity, alter soil filter, buffer, storage, and transformation functions. For this reason, it is of paramount importance to monitor water affinity for biochar surface (also referred to as ‘wettability’) in order to better address its applications in soil systems. In this study, we propose the use of fast field cycling NMR relaxometry technique with the application of a new mathematical model for data interpretation, as a valid alternative to the traditional contact angle (CA) measurements for biochar wettability evaluation. Either NMR or CA results revealed the same wettability trend for the biochars studied here. The advantage of NMR relaxometry over CA measurements lies in the possibility to obtain at the microscopic level a variety of different information in only one shot. In fact, while CA provides only wettability evaluation, NMR relaxometry also allows achievement of the mechanisms for water molecular dynamics on biochar surface, thereby leading to the possibility to understand better, in future research, the role of biochar in increasing soil quality and plant nutrition. Copyright © 2016 John Wiley & Sons, Ltd.     

Electrochemistry-mass spectrometry for mechanistic studies and simulation of oxidation processes in the environment

Electrochemistry (EC) coupled to mass spectrometry (MS) has already been successfully applied to metabolism research for pharmaceutical applications, especially for the oxidation behaviour of drug substances. Xenobiotics (chemicals in the environment) also undergo various conversions; some of which are oxidative reactions. Therefore, EC-MS might be a suitable tool for the investigation of oxidative behaviour of xenobiotics. A further evaluation of this approach to environmental research is presented in the present paper using sulfonamide antibiotics. The results with sulfadiazine showed that EC-MS is a powerful tool for the elucidation of the oxidative degradation mechanism within a short time period. In addition, it was demonstrated that EC-MS can be used as a fast and easy method to model the chemical binding of xenobiotics to soil. The reaction of sulfadiazine with catechol, as a model substance for organic matter in soil, led to the expected chemical structure. Finally, by using EC-MS a first indication was obtained of the persistence of a component under chemical oxidation conditions for the comparison of the oxidative stability of different classes of xenobiotics. Overall, using just a few examples, the study demonstrates that EC-MS can be applied as a versatile tool for mechanistic studies of oxidative degradation pathways of xenobiotics and their possible interaction with soil organic matter as well as their oxidative stability in the environment. Further studies are needed to evaluate the full range of possibilities of the application of EC-MS in environmental research.     

Character of transitions causing the physicochemical aging of a sapric histosol

Physicochemical aging of soil organic matter is assured by the dynamic character of weak interactions stabilizing its supramolecular structure. However, aging is difficult to monitor, due to low organic matter content in most soils and relatively large time constants. In order to overcome those problems, a model soil, sapric histosol, was exposed to the accelerated aging after a short heating event to 110 °C, and its thermal characteristics were monitored over several months. Classical and temperature modulated differential scanning calorimetry, microcalorimetry and solid-state NMR were used to elucidate the character of involved transitions. The heating event caused separation of an initially broad transition into two processes; a melting, which showed almost no response on the previous heating and a step transition, which is associated with the disruption of water molecule bridges (WaMB) between molecular segments of organic matter. Both processes are preceded by a preparatory phase, starting at subambient temperatures, in which aliphatic domains probably recrystallize and water molecules condensate forming WaMB stabilizing the physical structure of sapric histosol. The aliphatic moieties showed a particular behavior reflected in higher imperfection in crystallite structure upon slow cooling, which was attributed to their interaction with surrounding porous and heterogeneous structures. The results show that soil organic matter aging, considered as a natural process driven by thermodynamic principles, is caused by successive development of WaMB. This is potentially accompanied by recrystallization of aliphatic structures and both processes lead to higher physicochemical stability of soil organic matter.     

Polyvinylpyrrolidone Adsorption on Na-Montmorillonite. Effect of the Polymer Interfacial Conformation on the Colloidal Behavior and Binding of Chemicals

Adsorption behavior of polyvinylpyrrolidone (PVP) on sodium montmorillonite, a swelling clay mineral, was investigated in diluted solutions at an ionic strength of 0.01 M, representative of environmental soil solution conditions. Physicochemical methods such as microcalorimetry, light scattering absorbance, photon correlation spectroscopy, microelectrophoresis, X-ray diffraction, and sedimentation volume measurements were used to characterize the colloidal behavior of montmorillonite particles with various PVP loadings. The extent and properties of the adsorbed PVP train, loop, and end fractions in the particle-stabilizing process have been specified. The interaction study of chemicals such as anionic surfactant sodium dodecyl sulfate and nonionized 4-monochlorophenol as well as their mixture also underlines the importance of the PVP interfacial conformations for the adsorbent capacity of this organoclay. Copyright 2000 Academic Press.     

Sorption–Spectrophotometric and Test Determination of Zinc(II) as the Mixed-Ligand Complex of 1,10-Phenanthroline and Bromophenol Blue

The interaction of Zn(II), Cd(II), and Pb(II) with 1,10-phenanthroline noncovalently immobilized on silica in the presence of Bromophenol Blue was studied. The optimum conditions of the reaction and the composition of mixed-ligand complexes that are formed at the surface were found, and a scheme was proposed for the interaction at the interface. A sorption–spectrophotometric procedure and a test scale were developed for the determination of zinc with detection limits of 0.011 and 0.018 mg/L, respectively. The procedure was used for the determination of labile zinc species in soil.     

Investigation of MMT adsorption on soils by Diffuse Reflectance Infrared Spectroscopy (DRIFTS) and Headspace Analysis Gas-phase Infrared Spectroscopy (HAGIS)

Diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) and headspace analysis gas-phase infrared spectroscopy (HAGIS) were used to investigate interactions between soils and the gasoline additive methylcyclopentadienylmanganese tricarbonyl (MMT). Various soil samples, as well as alumina and silica substrates, were studied. Each substrate exhibited a splitting or broadening of the degenerate e ν(CO) band of MMT, suggesting an interaction involving one or two of the CO ligands. The adsorption was shown to be reversible under relatively mild conditions using HAGIS. The proposed interaction is of the Brønsted type, involving the carbonyl oxygen and a surface-bound water or hydroxyl group. This type of interaction could stabilize MMT by inhibiting photo-ejection of CO ligands, a common first step in the decomposition of organometallic carbonyl compounds such as MMT. © 1998 John Wiley & Sons, Ltd.     

Synthesis and application of molecularly imprinted polymer on selective solid-phase extraction for the determination of monosulfuron residue in soil

A novel sample clean-up procedure using molecularly imprinted polymer as the solid-phase extraction material for the determination of monosulfuron residue in soil samples has been developed. The molecularly imprinted polymer (MIP) was synthesized by non-covalent method with monosulfuron as the template. The selectivity and affinity of the MIP was evaluated by equilibrium adsorption and HPLC experiments, which demonstrated that the MIP has specific affinity for the template. The template-MIP interaction was studied by investigating the influence of different mobile phases on the retention of the template, which provided basic knowledge for the selection of the washing and elution solutions in the molecularly imprinted solid-phase extraction (MISPE) process. The study indicated that polar organic solvents with hydrogen bonding abilities have stronger eluting strength for the monosulfuron. After the MISPE procedure, a clean baseline was obtained in the HPLC quantification analysis. The recoveries of the method using the combination of MISPE and HPLC were above 93% and the R.S.D. was less than 3.2% in the soil sample determinations. Low detection limit (0.08 microg g(-1), when defined as 3 times of the noise) was also obtained in the method evaluation study.     

Influence of the agricultural exploitation processes on the productivity capacity control of soils

Summary Soil productivity and health were analyzed using an experimental procedure designed for this kind of studies. The continuous loss of fertile soil obliged the Food and Agriculture Organization (FAO) to declare soil as an item to be protected as a support of the world society welfare. The procedure here described is in accordance with the premises necessary for a rational and sustainable development of soil and the resources it contains and can be used to study any soil all over the world. The study was carried out using soil microbial population as a bioindicator of soil health. Microbial activity was followed using the microcalorimetric technique. The microcalorimetric study can be complemented through a deep analysis of soil physical, chemical and biological properties together with a study of the environmental properties that have a strong influence on the afore mentioned properties and, thus on the microbial activity in soil. The different properties follow different ASTM, ISS/FAO, USDA, etc. well defined standards. The experimental procedure reported in this work could be very helpful to create a data basis that could be useful to quantify and control soil potentiality or design soil decontamination and recovery systems.     

Ab Initio Molecular Dynamics Simulations of the Interaction between Organic Phosphates and Goethite

Today’s fertilizers rely heavily on mining phosphorus (P) rocks. These rocks are known to become exhausted in near future, and therefore effective P use is crucial to avoid food shortage. A substantial amount of P from fertilizers gets adsorbed onto soil minerals to become unavailable to plants. Understanding P interaction with these minerals would help efforts that improve P efficiency. To this end, we performed a molecular level analysis of the interaction of common organic P compounds (glycerolphosphate (GP) and inositol hexaphosphate (IHP)) with the abundant soil mineral (goethite) in presence of water. Molecular dynamics simulations are performed for goethite–IHP/GP–water complexes using the multiscale quantum mechanics/molecular mechanics method. Results show that GP forms monodentate (M) and bidentate mononuclear (B) motifs with B being more stable than M. IHP interacts through multiple phosphate groups with the 3M motif being most stable. The order of goethite–IHP/GP interaction energies is GP M < GP B < IHP M < IHP 3M. Water is important in these interactions as multiple proton transfers occur and hydrogen bonds are formed between goethite–IHP/GP complexes and water. We also present theoretically calculated infrared spectra which match reasonably well with frequencies reported in literature.     

Adsorption of tetracycline onto goethite in the presence of metal cations and humic substances

Adsorption of tetracycline, one of the most widely used antibiotics, onto goethite was studied as a function of pH, metal cations, and humic acid (HA) over a pH range 3-10. Five background electrolyte cations (Li(+), Na(+), K(+), Ca(2+), and Mg(2+)) with a concentration of 0.01 M showed little effect on the tetracycline adsorption at the studied pH range. While the divalent heavy metal cation, Cu(2+), could significantly enhance the adsorption and higher concentration of Cu(2+), stronger adsorption was found. The results indicated that different adsorption mechanisms might be involved for the two types of cations. Background electrolyte cations hardly interfere with the interaction between tetracycline and goethite surfaces because they only form weak outer-sphere surface complexes. On the contrary, Cu(2+) could enhance the adsorption via acting as a bridge ion to form goethite-Cu(2+)-tetracycline surface complex because Cu(2+) could form strong and specific inner-sphere surface complexes. HA showed different effect on the tetracycline sorption under different pH condition. The presence of HA increased tetracycline sorption dramatically under acidic condition. Results indicated that heavy metal cations and soil organic matters have great effects on the tetracycline mobility in the soil environment and eventually affect its exposure concentration and toxicity to organisms.