Rural settlements in transition – agricultural and countryside crisis in the Central-Eastern Europe

The paper presents a synthesis of French and Bulgarian researches on the transition in villages in Central Eastern Europe. The main points focus on three questions, the rural unemployment and the crisis of small towns, the demographical deterioration, the new relations between villages and towns. A generalization of the rural central places' visual change and metaphors is proposed, completed by a typology of rural settlements. The question of the rural administrative divisions is discussed, with its implication for the future. As a whole the paper gives a contribution to the problematic of the likely development in the rural evolution pattern throughout Europe. This revised version was published online in July 2006 with corrections to the Cover Date.     

Strength characteristics and mechanisms of salt-rich soil–cement

Salt-rich soft soils have not only general characteristics of common soft soils, but also contain high contents of Mg²⁺, Cl^?, and SO₄^2?, which have negative effects on deep mixing method using cement to treat soft soils. Laboratory and field tests were conducted to investigate the effects of changing cement incorporating ratio, water content, cement mixing ratio, and contents of Mg²⁺, Cl^?, and SO₄^2? on the unconfined compressive strength of the salt-rich soil–cement. The microstructure of soil–cement and the mechanism for the strength change of salt-rich soil–cement were investigated using X-ray diffraction, scanning electronic microscopy (SEM), and backscattered diffraction technology. It was found that an increase of cement incorporating ratio enhanced the strength of soil–cement but reduced its strength when water is added. Different amounts of Mg²⁺, Cl^?, and SO₄^2? not only caused the difference in the microstructures of salt-rich soil–cement but also influenced the soil–cement strength.     

Study on model of correlation between chemical element contents in tree rings and tree roots in soil from the south of Beijing

Along with the rapid development of science and technology, natural matter and energy are further exploited and used. The pollution imposed on nature has also sharply increased. Only do we know the pollution history, can we make a correct appraisal of loc…     

Selection of better extractants to indicate Pb bioavailability in lead-contaminated agricultural soils of Zhejiang Province

The accumulation of Pb in the food chain is one of the great concerns as it can cause chronic health problems and the available Pb is easily absorbed by crops. To shed light on Pb bioavailability in lead-contaminated agricultural soils of Zhejiang Province, a series of plant growth experiments were performed in a greenhouse to select more suitable extractants from five commonly used extractants (0.1 M HCl, 1 M NH4OAc, 0.1 M CaCl2, DTPA-TEA and Mehlich 3). The results showed that 1 M NH4OAc can extract Pb best, indicating the Pb bioavailability, then, DTPA-TEA and 0.1 M HCl in the tested soils. In case 1 M NH4OAc was used as an extractant, the critical Pb concentrations in soils were 50.19 mg/kg, 21.16 mg/kg and 114.00 mg/kg (1 M NH4OAc extracted Pb) in silty loam, yellowish-red soil and purplish soil, respectively. When the values exceed the above ones, the contents of Pb in Chinese cabbage leaves will exceed the Chinese Tolerance Limit of Lead in Foods (GB14935-94), as a result, potential ecological risk and hazard to human health via the food chain will appear.     

Field-scale evaluation of the chemical–biological stabilization process for the remediation of hydrocarbon-contaminated soil

Developing countries face the challenge of growing their economy while reducing the negative environmental impacts of industry, thus requiring treatment technologies that are economical and effective. One recent technology developed in the tropical part of Mexico for the remediation of petroleum-contaminated soil was tested in this scale-up project at an industrial level, whereas previously it had only been tested at laboratory scale; 150 m³ of bentonitic mud, contaminated with weathered hydrocarbons (3.4°API) at ~50,000 ppm, was treated with 4 % Ca(OH)₂, 4 % organic amendment, and a fine-root tropical grass. Hydrocarbons in soil and in leachates, as well as pH, and acute toxicity (Microtox) were monitored for 28.8 months. At the end of the study, basal respiration, root density, and earthworm toxicity were also measured. The hydrocarbon concentration in soil was reduced to 45 %, and toxicity was eliminated. Hydrocarbons in leachates were reduced to ~1 mg/l, safe for human consumption. The pH adjustment depended on low soil moisture and was stabilized at 7.1. Intense revegetation resulted in good root density, within 90 % of nearby uncontaminated soil under pasture. Basal respiration was increased to levels comparable to uncontaminated tropical soils with agricultural use, pasture and gallery forest. At an industrial scale, strict moisture control was necessary for good pH stabilization. By controlling these conditions and applying this novel treatment process, it was possible to transform a heavily contaminated geological material into a non-toxic, fertile, soil-like substrate capable of maintaining a complete vegetative cover and microbial activity comparable to similar soils in a tropical environment.     

Contamination and bioavailability of heavy metals in sediments from the Yangtze River Delta Region

The Yangtze River Delta Region is one of the most important economic development areas in China. In the process of its industrialization and urbanization, a great deal of wastewater is poured into rivers, lakes and coasts. Researches on contamination and bioavailability of heavy metals can help us to assess the ecological risks in the aquatic environment of the Yangtze River Delta. The samples were collected from three environmental compartments including the Yangtze River, Taihu Lake, and the south coast of Jiangsu. The concentrations of heavy metals were determined by ICP-MS. Metal speciation was determined by the sequential extraction procedure modified based on Tessier＇s scheme. Among the seven elements of Cu, Pb, Zn, Cr, Cd, Co, Ni detected, the contents of Cr, Zn did not vary significantly, while Cd and Pb varied significantly. Compared to the background values （loess in the basement）, all metals detected except Co, Cr exceeded the background level. Cd had the greatest exceeding values, reaching 2 to 7 times. Ni and Pb were followed. The contents of Zn were comparatively high in lake sediments, especially in the lake bays. Ni was enriched in fiver sediments and Cu was highest in sediments from the Yangtze River estuary. Cd and Pb were concentrated in the coastal sediments. Comparatively, in space, Cr was associated with the carbonate fractions in the bay of lake. Cu-bound Fe-Mn oxides and Ni in residual form were highest in the open lake. In the river environment, Fe/Mn oxide-bound Pb, exchangeable Cd were the highest fractions. In the estuary environment, Pb and Zn bound carbonates, Cd-bound Fe-Mn oxides are the largest fractions. Cd in the exchangeable fraction, Cu-bound Fe-Mn oxides had the larger proportions in the coast. In general, the bioavailability of Cu and Cd were high in lake environment, the available Pb, Cd were remarked in river environment, and Pb and Zn were easily assimilated by creatures in estuary.     

DDT residue in soil and water in and around the abounded area of DDT manufacturing factory

Due to the persistent nature of DDT, a persistent organic pollutant and its adverse environmental and health impacts, the present study was undertaken to examine the residual DDT in and around DDT manufacturing factory in Amman Gharh, Nowshera, NWFP. The factory was established in 1963 and remained in operation till 1994. Composite samples of soil, sediments and water were collected in and around the factory area, nearby DDT stores, main factory drain leading to river and nearby villages. Standard procedures were used for the collection, transportation and storage of samples for analysis. Physical parameters for the collected water samples measured were temperature, pH and conductance. Extraction of each sample for DDT analyses was carried out in triplicates using soxhlet extraction apparatus. The extract was transferred to well washed, clean; dry glass vial, sealed and put in the refrigerator. Gas Chromatograph with electron capture detector and capillary column was used for analysis. DDT in the samples was identified on the basis of their retention time and quantified on the basis of peak areas. It is evident from the analytical data obtained in the present study that both water and soil in and around the factory area are still contaminated with DDT, despite the closure of the factory since the past few years.     

Anomalous soil radon fluctuations – signal of earthquakes in Nepal and eastern India regions

The present paper deals with pre-seismic soil radon-222 recorded at two different locations 200 m apart, at Jadavpur University main campus, Kolkata, India. Solid state nuclear track detector method is used for detection of the radioactive radon gas. Two simultaneous 4-month long time series data have been analysed. Anomalous fluctuations in the radon datasets have been observed prior to recent earthquakes in Nepal and eastern India during the monitoring period, mainly, the massive 25th April 7.8 M Nepal earthquake. The simultaneous measurements assist in identifying seismogenic radon precursor efficiently.     

Comparison of extractants and applicability of MALDI–TOF-MS in the analysis of soil proteinaceous material from different types of soil

In order to understand better the chemistry of soil proteinaceous material, there is a need for an effective extraction and purification method for different types of soil. The aim of this study was to test the effectiveness of different extractants and of phenol extraction for the extraction and purification of native soil proteinaceous material and the added protein (bovine serum albumin, BSA) from different types of soil, and to test the applicability of matrix-assisted laser desorption/ionization–time-of-flight-mass spectrometry (MALDI–TOF-MS) for the analysis of soil proteinaceous material. Extraction of three types of boreal soil was carried out with water or different buffers. Purification of the extracted proteinaceous material was carried out with phenol extraction, the concentration being measured using Bradford’s method, and the analysis performed with MALDI–TOF-MS. The concentration of extracted proteinaceous material was dependent on the soil and the extractant, and the amount of N in the extracted material was ca. 3–90% of soil total N, being highest for sandy soil and lowest for highly organic forest floor and fine-textured clay soil. Non-purified extracts contained high amounts of non-proteinaceous (e.g. humic) material, especially the highly organic soil; this material may cause artifacts with Bradford’s method. The recovery of BSA was dependent on soil and extractant, suggesting a different sorption mechanism for different types of soil. MALDI–TOF-MS spectra suggested that the molecular weight of the extracted compounds was mainly <10 kDa, but compounds in the range ca. 15–50 kDa were also detected. However, individual compounds could not be identified.     

Immobilization of Cu and As in two contaminated soils with zero-valent iron – Long-term performance and mechanisms

Immobilization of trace elements in contaminated soils by zero-valent iron (ZVI) is a promising remediation method, but questions about its long-term performance remain unanswered. To quantify immobilization and predict possible contaminant remobilization on long timescales detailed knowledge about immobilization mechanisms is needed. This study aimed at assessing the long-term effect of ZVI amendments on dissolved copper and arsenic in contaminated soils, at exploring the immobilization mechanism(s), and at setting up a geochemical model able to estimate dissolved copper and arsenic under different scenarios. Samples from untreated and ZVI-treated plots in two field experiments where ZVI had been added 6 and 15 years ago were investigated by a combination of batch experiments, geochemical modeling and extended X-ray absorption fine structure (EXAFS) spectroscopy. Dissolved copper and arsenic concentrations were described by a multisurface geochemical model with surface complexation reactions, verified by EXAFS. The ZVI remained “reactive” after 6–15 years, i.e. the dissolved concentrations of copper and arsenic were lower in the ZVI-treated than in the untreated soils. There was a shift in copper speciation from organic matter complexes in the untreated soil to surface complexes with iron (hydr)oxides in the ZVI-treated soil. The pH value was important for copper immobilization and ZVI did not have a stabilizing effect if pH was lower than about 6. Immobilization of arsenic was slightly pH-dependent and sensitive to the competition with phosphate. If phosphate was ignored in the modeling, the dissolution of arsenate was greatly underestimated.     

A new schedule for copper chemical speciation analysis in soil and water sediment

The speciation of heavy metals is very important to evaluate their environmental impact. This issue has become an interested topic many decades ago and many significative studies were carried out such as direct detecting, calculation with mathematical model represented in recent years as well as Tessier＇s work in 1979, BCR＇s work in 1993, etc. In all of them, the methods recommended by Tessier and BCR are most often used in practical study today. But it should be seen that experimental schedule and agents define these methods including BCR＇s method, which improved on Tessier＇s method, only. In many cases, there always are deviations between analytical results and real content of the speciation. Otherwise, steps of the extraction experiment are always strict and excessive in the experimental process. The method, which is fitting to extract the speciation of bioavailability and easy to assess the effect of metals in the environment, is very anticipant. In this paper, the sequential three steps schedule of speciation analysis of copper in soil and water sediment is discussed as an example based on the comparative results of experimental analysis with the schedules of BCR＇s （mended by Rauret et al. in 1999） and TDPA （diethylenetriamine pentacetic acid） extraction, respectively. The results from sequential three steps method and other methods recommended by prevenient work suggest that the analytical schedule of sequential three steps of separating speciation （the speciation of easy effect to life-form, the speciation available to life-form, and the speciation of no effect to life-form） is valuable for copper speciation analysis in soil and sediment. Because of easy process and saving time to evaluate its availability for life form,     

XANES analysis of the mechanisms of arsenic removal in biological iron and manganese treatment unit

Biological iron and manganese removal utilizing indigenous iron and manganese oxidizing bacteria （IRB hereafter） in groundwater can also be applied to arsenic removal according to our pilot-scale test. The arsenic removal probably occurred through sorption and complexation of arsenic to iron and manganese oxides formed by enzymic action of IRB. We investigated the chemical properties of iron and manganese oxides in IRB floc and the valence state of arsenic sorbed to the floc to clarify the mechanisms of the arsenic [especially As （Ⅲ）] removal. The floc samples were collected from two drinking water plants using IRB （Jyoyo and Yamatokoriyama, Japan）, and our pilot - scale test site where arsenic and iron removal using IRB is under way （Mukoh, Japan）. The Jyoyo and Yamatokoriyama IRB floc samples were subjected to As （Ⅲ） and As（Ⅴ） sorption experiments. The elemental composition of the floc samples was measured. XANES spectra were collected on As, Fe and Mn K-edges at synchrotron radiation facility Spring 8 （Hyogo, Japan）. FT-IR and the X-ray diffraction spectra of the samples were also obtained. The IRB floc contained ca. 35 % Fe, 0.3%-3.5% Mn and 2%-6% P. The samples were highly amorphous and contained ferrihidrites and hydrated iron phosphate. According to XANES analyses of IRB, As associated with IRB was in ＋5 valence state when As （Ⅲ） （or As （Ⅴ）） was added in laboratory sorption test, Fe in ＋3 valence state, and Mn a mixture of＋3 and ＋4 valence states. Small shift was observed in the XANES spectra of IRB on As K-edge as the equilibration time of the sorption experiment was increased. Gradual oxidation of a small amount of As （Ⅲ） associated with IRB or change in arsenic binding with sorption site were the probable mechanism.     

Influence of plant on the extractability of estrogen in the rhizospheric soil

Livestock wastes applied to agricultural land are potential sources of steroidal hormones （estradiol （E2）, estrone （E1）, and estriol （E3）） that can adversely affect the aquatic ecosystem as endocrine disruptors. But the effects of plants on the fate of estrogen in the environment are not clearly known. In the present report, the behavior of E1, E2 and E3 added to the rhizospheric soil in various concentrations and its effect on plant growth were examined by estrogen batch sorption test, plant pot test and estrogen extraction test. Trifolium repens was grown on the soil spiked with E2 or a mixture of E1, E2 and E3. Pots without plant were prepared as controls. All pots were watered in 50 ml dose almost every day, and the rhizosheric soil and plant body were collected 7, 19, 26, 33 days after planting. The soil was sequentially extracted with Milli-Q water, and methanol / 1M acetic acid solvent followed by methanol wash at the solid to liquid ratio of 1 ： 4 （g/mL）. Extracts were analyzed for El, E2 and E3 using a Shimadzu GCMS-QP5050. Plant dry weight （4 hours, 105 ℃） was measured as an indicator of plant growth. In batch sorption tests, E1 and E2 concentrations in the liquid phase significantly decreased within 24 hours after the addition of estrogen. The sum of methanol / 1M acetic acid extractable E 1 and E2 in the soil decreased to half of the initial added amount within 7 days. Reduction in total estrogenic activity of the soil extracts （estimated as 0.01CE1＋CE2＋0.1CE3 where CE1, CE2 and CE3 are respective El, E2 and E3 concentrations per unit soil weight） continued for 1 month due to slow oxidation of E2 to E1. Desorption of E2 from soil during the pot experiment was higher than expected from the sorption experiment.     

Problems of soil and groundwater pollution in the disposal of “marble” slurries in NW Sicily

This work deals with disposal of slurries generated during the cutting and polishing processes of slabs of decorative sedimentary carbonate rocks in the north western Sicily. At present, they are used as fillers of dismantled quarries near the sawmills and, as a final step of reclamation, are covered with earth layers. In spite of such inexpensive solution, there is lack of knowledge about the composition of the waste. In order to assess if there is any threat for the environment and to suggest indications for alternative solutions, such as recycling or inactivation processes, the slurries were analysed by XR diffraction, simultaneous thermal analysis, ICP/MS, ionic chromatography, FTIR, UV-Vis, COD and TOC measurements, grain size analysis. Results indicate that the slurries can threaten the groundwater, because of the high chemical oxygen demand; furthermore they can modify the mechanism of groundwater recharge, because of their grain size distribution. Some laboratory tests show that, even in very aggressive conditions, the solid pollutants persist in the waste and slowly release into water the products of their degradation. The slurry therefore should be subjected to inactivation treatment before disposal or, alternatively, recycled as secondary raw material for a suitable process.     

Environmental behaviors of mercury and lead in the soil of polymetallic deposit areas in western Hunan Province

Western Hunan Province is one of the most typical assembling areas of cryogenic metallic deposit in China, as well as a main ore-forming zone for some heavy metals. In the region, Hg and Pb pollution was caused by abnormally high concentrations of Hg, Pb in the natural environment and Hg, Pb exploiting/smelting and other human activities, which make the damage to human health more complicated. Generally, heavy metal pollutants in soil are often long-lasting and consequent, with their emission and/or transport into the environment, resulting in growing hazards to human health posed by elevated heavy metal concentrations in air, water, and food. Therefore, monitoring and understanding their behaviors in soil environment is the most important and urgent task. In this paper, the environmental behaviors and pollution characteristics of soil polluted by Hg and Pb in typical Hg and Pb mining areas in western Hunan were studied. Main results are presented as follows： （1） Western Hunan Province is a high regional geochemical abnormal region on Hg and Pb. The concentrations of Hg and Pb in soils in mercury mining areas were 1 315 and 3. l times higher than the average background of soils in China, respectively. While those in soils in lead mining areas are 14.1 and 6.1 times higher. By using the index of geoaccumulation （Igeo）, it was found that either mercury mining area or lead mining area in western Hunan Province has been polluted by the two elements, the majority of soils in mercury mining areas are seriously polluted by Hg, moderately or light polluted by Pb, while the majority of soils in lead mining areas are moderately or moderately-highly polluted by Pb and moderately-highly polluted by Hg. （2） By the BCR extraction procedures, both Hg and Pb in soils are dominated by residual form, followed by organic-sulfide form. Fe-Mn oxides and acid-exchangeable form are rather low. The total concentrations and each species of Hg and Pb in soils show positive correlations with the concentrations of sands, and negative ones with the concentrations of clays in soils.     

REE concentrations in agricultural soil in Sweden and Italy: Comparison of weak MMI® extraction with near total extraction data

Rare Earth Element (REE) concentrations in agricultural soil obtained from the Mobile Metal Ion (MMI^®) weak extraction technique are compared with soil total concentrations (sodium peroxide fusion followed by acid dissolution) for 118 and 174 agricultural soil samples from Italy and Sweden, respectively. Spatial distribution maps and statistics for both analytical techniques are compared between the two national datasets. In spite of similarity of REE concentration in two countries, the median values of REE is higher than Italy but extreme concentration of REE in Italy is due to young volcanic activities. Extractability of REEs is significantly higher in Swedish soils than in Italian soils. Heavy Rare Earth Element (HREE) in Sweden show higher concentrations compared to Italy in MMI^® extraction data where correlate with REE mineralisation. Principal Component Analysis (PCA) is used to elucidate correlations and anomalies in the REE distribution. Results show that there is a clear correlation between REE anomalies and natural factors such as lithology of the underlying bedrock, the presence of mineralisations, pH of soils, climate and precipitation. According to the PCA results, anomalous behaviour of Eu, Ce, Tb and Gd can be explained by the dominant mineralogy of the parent material and the variable affinity of REEs to bind to clay minerals and clay-size particles.     

Interpretation of unsaturated soil behaviour in the stress – Saturation space,I: Volume change and water retention behaviour

Unsaturated soil behaviour, such as volume change, shear strength and yield stress, is usually interpreted and modelled in terms of stress and suction. This approach is consistent with laboratory tests where suction is a controllable variable. However, it also suffers some limitations. This paper (Parts I and II) presents an alternative approach for interpreting unsaturated soil behaviour, which is built in the space of stress versus degree of saturation. In Part I, a new volume change equation is proposed in terms of stress and degree of saturation, to give a better explanation to the non-linear change of soil compressibility under constant suctions. The soil compression index is assumed to be a function of the effective degree of saturation and is interpolated from the known compressibility at the fully saturated state and that at a dry state. An alternative approach to simulate hydraulic hysteresis and hydro-mechanical interaction is then introduced, which enables the calculation of the effective degree of saturation under complex stress and suction paths. The proposed volume change equation and the approach to describe saturation variation, which are two fundamental aspects to establish constitutive laws for unsaturated soils, are validated against a variety of experimental data in literature.