Some Aspects of the Mobility and Distribution of Toxic Heavy Metal Contaminants Insoil Profiles and River Sediments

Abstract

Investigations of the distribution and mobility of Pb, Ni, Cd and Hg have shown that Pb is strongly associated with humic substances in the top layer of soils and in river sediments, and that Pb shows the highest organophilicity. Ni is very organophilic, and Cd, somewhat less so. The hydrophilicity of Hg highly influences its movement in soil profiles and river sediments. The risk of contamination by these metals is characterized through the environment protection capacity (EPC_G) values which combine humus content and the quality and thickness of the humus layer in one parameter. The risk of contamination is highest at low EPC_G values. Increase of EPC_G decreases the risk of environmental contamination through binding of heavy metals to humic substances, decreasing their mobility.     

Antioxidant potential in the leaves of grape varieties (Vitis vinifera L.) grown in different soil compositions

Grape plant (Vitis vinifera L.) is a species of the family Vitaceae. It is an economically important fruit plant abundantly grown all over the world. Vitaceae comprised of 900 species distributed across tropical, sub-tropical and partially temperate sorts of climatic zones. In the current study we aimed to evaluate the antioxidant activities of grape leaves extract from different Pakistani varieties.We have analyzed the crude methanolic extract from the leaves of Pakistani grape varieties (i.e. NARC Black, Sundar Khani, Shogran-1, Shogran-2, Haita, Sheghali, Perlette, and Sultania-C) cultivated in various soil compositions. Total phenolic contents (TPC) of the extract were determind by using Folin-ciocalteu reagent method. Total flavonoid contents (TFC) were determind by the Aluminum Chloride Calorimetric method. Antioxidant activities of the extracts of different concentration were evaluated using Phosphomolybdenum method, Reducing power and DPPH (2, 2-disphenyl-1-picryl-hydrazyl) assays. Assays performed for grape varieties showed great antioxidant potential. All varieties significantly depicted with variation in polyphenolic contents and antioxidant potential with changes in the soil conditions. The highest TPC and TFC were quantified in Shogran-1 97.58 ± 0.09 (GAE, g⁻¹) and Sultania-C 97.47 ± 0.12 (µg QE/g DE) varieties respectively which were grown in (T6) and (T5), while lower were recorded in Sundar khani 5.16 ± 0.23 in (T6). Likewise, Shogran-1 128.26 ± 0.23 (µg AAE/g extract) variety grown in (T6) depicted highest total antioxidant capacity, NARC black 182.06 ± 0.24 (µg AAE/g extract) variety grown in (T6) resulted in maximum reducing power while DPPH free radical scavenging potential were determinded in Sultania-C 80.91 ± 0.10 (T4) equivalent µg/g. In the terms of bioassays, the promising results were showed by compost + sand + clay (T4), compost + clay + dung (T5) and sand + clay + dung (T6). Therefore, we conclude that variation in soil composition has a significant contribution in the quantity of phytochemicals and antioxidants expression. Our study further suggest that use of organic fertilizer (Compost) and loamy sort of soil enhance functioning of most of the varieties in terms of important phytochemicals.     

Synthesis of guar gum-based hydrogel for sugarcane field solid conditioning

The water crisis is increased everywhere in recent years, which has affected the water demand in different sectors like industries, agriculture, residential, etc. The present research aims to the development of superabsorbent polymer (SAP) using bio-material. The hydrogel is synthesized by grafting Guar gum (GG) with methyl methacrylate (MMA) and crosslinking with polyethylene glycol (PEG). The developed GG-based hydrogelwas characterized by various analytical instruments. The Scanning Electron Microscopy (SEM) demonstrated hydrogels havepores of size 50 ​μm–10 ​μm. The Transmission Electron Microscopy (TEM) analysis has shownthat thematerial consists of spherical shapesand particles of size 141.11nm–182.19 ​nm.The Fourier-Transform Infrared Spectroscopy (FTIR) and Thermogravimetric analysis (TGA) study have confirmedthepresence of functional groups of material, and thermal resistivity. The absorption capacity of developed hydrogelwas found to be 110 ​ml per gram (110% of its dry weight). The hydrogelwasapplied in the field of sugarcane crop and measured soil moisture content after 20 days of application. A better resultwas found of moisture content in the area of hydrogel application (28%) compared to the area without hydrogel application (10%). Moreover, the comparison of different hydrogels is also shown in a study, and the developed hydrogel proves good moisture retention capacity. This technology could be promising in terms of improving perennial crop productivity and combating moisture stress in agriculture. As a soil conditioning material for agricultural applications, the synthesized hydrogel showed tremendous potential.     

基于冷原子吸收分光光度法的热解析-低温等离子体脱汞技术研究

研究含汞土壤的修复问题，采用热解析和低温等离子体综合技术探究新途径，调整温度、添加剂、时间等因素来判断脱汞效果并探究其不同形态，分析工艺过程废料的内部联系，并对废气处理进行分析实验。结论如下：(1)通过改良技术的BCR连续萃取法，得出研究区汞的形态主要为有机结合态(53%)。之后依次是氧化物结合态(33%)、酸可提取态(8%)、残渣态(6%)。(2)温度对热解析程度影响较大。在500℃以上的热解析条件下，土壤中的汞浓度不足1.5 mg·kg-1。(3)当选用400℃的解析温度时，40 min汞去除总体完成。在低于1 700 mg·kg-1的浓度下，汞去除率随着土壤中的含量的增大而减小。(4)氯化钙对于热解析的促进作用最强，柠檬酸、升华硫也有一定作用，硫化钠对于汞去除形成阻滞。(5)低温等离子体的最佳状态是电源设置电压为22 kV，频率为660 Hz。整个系统的汞去除程度可达近90%。     

Implementation of depth-dependent soil concentrations in multimedia mass balance models

In standard multimedia mass balance models, the soil compartment is modeled as a box with uniform concentrations, which often does not correspond with actual field situations. Therefore, the theoretically expected decrease of soil concentrations with depth was implemented in the multimedia model SimpleBox 3.0. The effects of this implementation on the model outcomes were explored for nine compounds in four environmental compartments. For compounds with a low penetration depth, the new model predicts substantially higher or lower concentrations in the vegetation compartment than the old model. For those compounds, predicted concentrations in surface water and air were higher in the new model, but the deviations from the old model were smaller than in the vegetation compartment. For compounds with a large penetration depth, the model adaptations show little effect. No field study was carried out to validate the results of the model calculations, but we did collect measured data on concentrations in vertical soil profiles from literature. According to those data, we concluded that the implementation of depth dependent soil concentrations might be a useful extension for steady state multimedia mass balance models. More field study has to be carried out to validate the model outcomes.     

Molecular evaluation of soil organic matter characteristics in three agricultural soils by improved off-line thermochemolysis: The effect of hydrofluoric acid demineralisation treatment

The molecular composition of soil organic matter (SOM) in three agricultural fields under different managements, was evaluated by off-line thermochemolysis followed by gas chromatography mass spectrometry analysis (THM-GC-MS). While this technique enabled the characterization of SOM components in coarse textured soil, its efficiency in heavy textured soils was seriously affected by the interference of clay minerals, which catalyzed the formation of secondary artifacts in pyrolysates. Soil demineralization with hydrofluoric acid (HF) solutions effectively improved the reliable characterization of organic compounds in clayey soils by thermochemolysis, while did not alter significantly the results of coarse textured soil. A wide range of lignin monomers and lipids molecules, of plant and microbial origin, were identified in the pyrograms of HF treated soils, thereby revealing interesting molecular differences between SOM management practices. Our results indicated that clay removal provided by HF pretreatment enhanced the capacity of thermochemolysis to be a valuable and accurate technique to study the SOM dynamics also in heavy-textured and OC-depleted cultivated soils.     

Accurate measurement of uranium isotope ratios in soil samples using thermal ionization mass spectrometry equipped with a warp energy filter

A chemical and mass-spectrometric procedure for uranium isotopic analysis using a thermal ionisation mass spectrometer equipped with a Wide Aperture Retardation Potential energy filter has been developed and applied to uranium isotopic measurements for various soil samples. Soil samples were digested using a microwave digestor. Uranium was isolated from soil samples by the chemical separation procedure based on the use of anion-exchange resin and UTEVA extraction chromatography column. The isotope ratios were measured for two certified reference materials by using a VG Sector 54-30 thermal ionisation mass spectrometer in dynamic mode with Faraday cup and Daly ion counting system. Replicates of standard reference materials showed excellent analytical agreement with established values supporting the reliability and accuracy of the method. Precision of the ²³⁵U/²³⁸U ratio was achieved by a correction factor of 0.22% amu as a function of ion-beam intensity with sample loads of around 250?ng of U. The resulting reproducibility for standards and soil samples was better than 0.2% at two standard deviations (SD). Uranium isotopic compositions have been determined in several reference soil samples such as Buffalo river sediment, NIST 2704, river sediment SRM 4350b and ocean sediment NIST-4357 and a Chernobyl soil sample. There was a significant deviation from the natural uranium in comparison with Chernobyl soil samples.     

Reflection–absorption infrared sensing device for detection of semivolatile aromatic compounds in soils

In this article, a new IR-sensing device is described for the examination of chlorinated aromatic compounds in soils. To prepare this sensing device, a 20-mL glass vial was modified for use in the analysis of soil samples by conventional Fourier-transform infrared (FT-IR) spectroscopy. In this sampling device, an aluminium plate coated with a hydrophobic film was placed on top of the cap of the sample vial to absorb the analytes that evaporated from the soil matrix. After this absorption process was complete, the cap was placed in an FT-IR spectrometer, and the absorbed analytes were detected in the reflection–absorption (RA) mode. To accelerate the rate of evaporation of the analytes, the soil samples were heated to various temperatures. Meanwhile, other factors, such as the moisture content, sampling time, thickness of the hydrophobic film, and the volatilities and concentrations of the analytes, were also examined to optimize the analytical conditions. The results indicated that the time required to reach equilibrium conditions was short, and evaporation/absorption could be achieved within 10?min. With a water content of 10% (v/w) or less, the intensities of the analytical signals were increased greatly when compared with those of dry samples; when the water content was above 10% (v/w), these intensities decreased, partially as a result of the heating efficiency. After examining the compounds that had different vapour pressures, the analytical results indicated that this method was applicable to the examination of compounds that had vapour pressures below 1.0?Torr. Using the optimal conditions determined in this study, the detection limits for semivolatile aromatic compounds were lower than 100?ng/g, and the regression coefficients of the standard curves for compounds that had a vapour pressure lower than 1.0?Torr were larger than 0.99 in the concentration range of 1–100?µg/g.     

Analysis of PCBs in soils and sediments by microwave-assisted extraction,headspace-SPME and high resolution gas chromatography with ion-trap tandem mass spectrometry

A procedure for the determination of seven indicator PCBs in soils and sediments using microwave-assisted extraction (MAE) and headspace solid-phase microextraction (HS-SPME) prior to GC-MS/MS is described. Optimization of the HS-SPME was carried out for the most important parameters such as extraction time, sample volume and temperature. The adopted methodology has reduced consumption of organic solvents and analysis runtime. Under the optimized conditions, the method detection limit ranged from 0.6 to 1?ng/g when 5?g of sample was extracted, the precision on real samples ranged from 4 to 21% and the recovery from 69 to 104%. The proposed method, which included the analysis of a certified reference material in its validation procedure, can be extended to several other PCBs and used in the monitoring of soil or sediments for the presence of PCBs.     

Preconcentration of cobalt using Amberlyst 36 as a solid-phase extractor and its determination in various environmental samples by flame atomic absorption spectrometry

A new and simple column-solid-phase extraction method has been developed to separate and preconcentrate trace cobalt in water and soil prior to its determination by flame atomic absorption spectrometry (FAAS). Different factors such as pH of sample solution, sample volume, amount of resin, flow rate of aqueous solution, volume and concentration of eluent, and matrix effects for preconcentration were optimized. Under optimized experimentally established conditions, an analytical detection limit of 0.44?µg?L^?1, precision (RSD) of 1.9%, enrichment factor of 200, and capacity of resin of 82?mg?g^?1 were obtained. The method was applied for cobalt determination by FAAS in tap water, natural drinking water, soil, and roadside dust samples. The accuracy of the method is confirmed by analysing standard reference material (Montana Soil, SRM 2711).