改进QuEChERS-气相色谱-质谱法快速分析测定农用土壤中多环芳烃

建立农用土壤中16种多环芳烃的改进QuEChERS快速提取净化方法及气相色谱-质谱检测方法,并通过对西安市周边农用土壤样品的分析,调查土壤中多环芳烃的污染情况.土壤样品用KOH饱和的甲醇碱化处理后,用丙酮-正已烷(1+1)为提取溶剂,涡旋混匀后超声提取,提取液按改进QuEChERS方法加入无水MgSO4、硅胶及正丙基乙二胺(PSA)进行净化,检测时选用DB -5 MS(30m×0.25 mm×0.25 μm)色谱柱分离,EI电离源及离子监测模式检测,16种多环芳烃的测定低限0.7～3.2μg/kg,加标回收率79.8％ ～ 109.6％,相对标准偏差均低于9.4％.检测的农用土壤样品中均检出有不同程度的多环芳烃残留,约16.7％的土壤样品为轻度污染.     

The importance of precision in sampling sludges, biowastes and treated soils in a regulatory framework

As part of the European Commission (EC)'s revision of the Sewage Sludge Directive and the development of a Biowaste Directive, there was recognition of the difficulty of comparing data from Member States (MSs) because of differences in sampling and analytical procedures. The ‘HORIZONTAL' initiative, funded by the EC and MSs, seeks to address these differences in approach and to produce standardised procedures in the form of CEN standards. This article is a preliminary investigation into aspects of the sampling of biosolids, composts and soils to which there is a history of biosolid application. The article provides information on the measurement uncertainty associated with sampling from heaps, large bags and pipes and soils in the landscape under a limited set of conditions, using sampling approaches in space and time and sample numbers based on procedures widely used in the relevant industries and when sampling similar materials.These preliminary results suggest that considerably more information is required before the appropriate sample design, optimum number of samples, number of samples comprising a composite, and temporal and spatial frequency of sampling might be recommended to achieve consistent results of a high level of precision and confidence.     

Raman spectroscopic study of the minerals diadochite and destinezite Fe3+2(PO4,SO4)2(OH)· 6H2O: implications for soil science

The two minerals diadochite and destinezite of formula Fe₂(PO₄,SO₄)₂(OH)· 6H₂O have been characterised by Raman spectroscopy and complemented with infrared spectroscopy. Both these minerals are found in soils and are identical except for their morphology. Diadochite is amorphous whereas destinezite is highly crystalline. The spectra of diadochite are broad and ill defined, whereas the spectra of destinezite are intense and well defined. Bands are assigned to phosphate and sulfate stretching and bending modes. Two symmetric stretching modes for both phosphate and sulfate support the concept of non‐equivalent phosphate and sulfate units in the mineral structure. Multiple water bending and stretching modes imply that non‐equivalent water molecules in the structure exist with different hydrogen‐bond strengths. Copyright © 2011 John Wiley & Sons, Ltd.     

Humic Acid Improves Zn Fertilization in Oxisols Successively Cultivated with Maize–Brachiaria

Zinc (Zn) is an essential micronutrient for plant growth, and Zn deficiency is a global issue, especially in tropical soils. This study aimed to investigate the effects of humic acid (HA) and the Zn addition (Zn sulfate + HA) on the growth of maize and brachiaria in two contrasting Oxisols. The potential complexation of Zn sulfate by HA was evaluated by Fourier-transform infrared (FTIR) spectroscopy analysis. Zinc content and its availability in solution and the shoot and root biomass of maize and brachiaria were determined. FTIR spectroscopy revealed the complexation of Zn sulfate by HA through its S and C functional groups. In both Oxisols, solution Zn increased due to the combined use of Zn and HA. In a soil type-dependent manner, maize biomass and Zn in its shoots were affected only by the exclusive use of Zn fertilization. In the Yellow Oxisol, brachiaria growth and Zn accumulated in its shoot were positively affected by the combined use of Zn fertilization with HA. In the Oxisol with lower organic matter content, HA can assure adequate supplying of residual Zn, while increasing growth of brachiaria cultivated in sequence to maize.     

A review of heavy metal contaminations in urban soils, urban road dusts and agricultural soils from China

This paper reviews quite a few heavy metal contamination related studies in several cities from China over the past 10 years. The concentrations, sources, contamination levels, sample collection and analytical tools of heavy metals in urban soils, urban road dusts and agricultural soils were widely compared and discussed in this study. The results indicate that nearly all the concentrations of Cr, Ni, Cu, Pb, Zn, As, Hg and Cd are higher than their background values of soil in China. Among the cities, the contamination levels of the heavy metals vary in a large range. The geoaccumulation index shows that the contamination of Cr, Ni, Cu, Pb, Zn and Cd is widespread in urban soils and urban road dusts of the cities. Generally, the contamination levels of Cu, Pb, Zn and Cd are higher than that of Ni and Cr. Agricultural soils are also significantly influenced by Cd, Hg and Pb derived from anthropogenic activities. The integrated pollution index (IPI) indicates that the urban soils and urban road dusts of the developed cities and the industrial cities have higher contamination levels of the heavy metals. The comparison of the IPIs of heavy metals in urban soils and urban road dusts of Shanghai, Hangzhou, Guangzhou and Hongkong reveals that the contamination levels of the metals in urban road dusts are higher than that in urban soils in the cities. Moreover, the main sources of the metals in urban soils, urban road dusts and agricultural soils are also different.     

The optimization of microwave digestion procedures and application to an evaluation of potentially toxic element contamination on a former industrial site

The optimization of a microwave dissolution procedure for potentially toxic elements in a contaminated soil sample has been evaluated using a central composite design approach. By considering the operating parameters of temperature, digestion time, microwave power and acid volume it was possible to identify the following optimum conditions: temperature, 160 °C; power, 750 W; digestion time, 25 min; and, an aqua regia volume of 13 mL. These microwave digestion conditions were then applied to 19 samples obtained from a former industrial site in Newcastle upon Tyne. Of the range of potentially toxic elements present at the site as a consequence of former industrial activity (As, Cd, Cr, Cu, Mo, Ni, Pb and Zn), the majority of topsoil samples indicated elevated concentrations of one or more of these elements. In particular, data obtained using either inductively coupled plasma mass spectrometry or flame atomic absorption spectroscopy indicates the high and wide concentration of Pb on the site (188-60300 mg/kg). Comparing the resulting potentially toxic elements data with UK soil guidelines values (SGVs) suggests at least parts of the site represent areas of potential human health risk. It was found that lead soil values exceeded the SGV on 17 out of the 19 sampling sites; similarly for As 6 out of 19 sampling sites exceeded the SGV. While for Cd, Cr and Ni the soil levels were below the stated SGVs.     

Analysis of cypermethrin residues and its main degradation products in soil and formulation samples by gas chromatography-electron impact-mass spectrometry in the selective ion monitoring mode

A fast, simple and inexpensive sample preparation method based on the matrix solid-phase extraction (SPE) technique is proposed for the isolation of cypermethrin and its metabolite residues from soils. Both the extraction and clean-up procedures were carried out in two steps and target compounds were determined by gas chromatography coupled with electron-impact mass spectrometry (GC-EI/MS). The characteristic ions and fragmentation mechanism of cypermethrin were evaluated by electron impact ionization mass spectrometry (EI/MS). After the optimization of different parameters, such as the extraction solvent, the pesticide was extracted from the matrix with methanol/acetone in a Soxhlet extractor, cleaned up on a Florisil column by elution with a mixture of 30% ethyl acetate in n-hexane and analyzed by gas chromatography-electron impact ionization mass spectrometry (GC-EI/MS) in the selected ion-monitoring mode (SIM) with permethrin as internal standard. Recovery was in the range 77–118% with relative standard deviations (RSD) between 2.5% and 10.2%. The limit of detection (LOD) was 6.5?µg/kg for cypermethrin. The developed method was linear in the injection range 6–30?ng, with correlation coefficients greater than 0.9957.     

New Sediment and Soil CRMs for Extractable Trace Metal Content

Abstract

The lack of uniformity in leaching procedures used to measure broadly defined forms of heavy metals does not allow the results to be compared world-wide nor the methods to be validated since the results obtained are “operationally defined”. An attempt was made to certify several mineral soils CRMs for single extraction by using acetic acid, EDTA and DTPA for Cd, Cr, Cu, Ni, Pb and Zn. Recently, to complete the series of soil CRMs, an organically enriched soil was prepared SO25. For sediments a CRM 601 was produced and certified for metals extractable by using the BCR three step sequential extraction. Not all the trace elements were certified and only indicative values were given for some of them due to poor reproducibility. We performed a systematic study of the effect of the variables identified as potential sources of uncertainty in the use of this scheme. With this study the sources of uncertainty were revealed and an optimised version of the protocol was proposed. With this new version it was possible to certify all the trace elements studied. New sediment material S33 is now proposed for certification and additional data are given for the sediment CRM 601. This modified procedure was also applied to a soil CRM 483 and good results were obtained. This procedure may thus be applied to polluted soils.     

Mineralogy, size, morphology and porosity of aggregates and their relationship with soil susceptibility to water erosion

Soil erosion has been considered as the main process related to losses of soil mass and decrease of productivity in cultivated lands as well as on e of the most important processes in landscape evolution. Attention has been paid to many pedological variables affecting intensity of erosion, but little to the influence of iron compounds on the type, size, shape and porosity of soil aggregates. In the present study, three lithopedodomains which were assumed to be closely related to the dominant lithology of the soil parent material, varying in the degree of water erosion intensity, were selected for further analysis which focused mainly on the influence of iron oxide mineralogy on the soil aggregation. Powder X-ray diffractometry, 80 K Mössbauer data and SEM images are used to correlate all these variables with observed erosion activity in the field. The present data indicate that the more the soil is rich in iron (hematite and/or goethite) or aluminium (gibbsite) (hydr)oxide, the smaller are its aggregates and is porous. Soils derived from metabasic rocks are much more susceptible to collapse under wetting than those from other lithologies. They have the highest iron and clay content. Schist-derived soil is richer in muscovite, has bigger aggregates and porous and are less prone to collapse, while the granite-derived soil presents relatively intermediate resistance, when humid.     

Investigation of vertical migration of alpha-emitting nuclides in soils for southern regions of the republic of Belarus

An investigation of vertical distribution of alpha-emitting nuclides for various types of soils using solid state nuclear track detectors (SSNTD) has been carried out. As SSNTD the DNC-film was used. Experimental system for measurement of total alpha activity in the samples of soils, including devices and equipment for selection of probes, exposition, chemical etching of detectors, automated accounting of tracks has been developed. The method of determination of specific activity of alpha emitting nuclides has been created. A comparison results of measurements with the method pointed out and radiochemical method as well as x-y-spectrometry method has been carried out.