利用可见光-近红外漫反射光谱技术预测铜冶炼厂周边区域土壤属性

Spatial and temporal monitoring of soil properties in smelting regions requires collection of a large number of sam-ples followed by laboratory cumbersome and time-consuming measurements.Visible and near-infrared diffuse reflectance spectroscopy (VNIR-DRS) provides a rapid and inexpensive tool to predict various soil properties simultaneously.This study evaluated the suitability of VNIR-DRS for predicting soil properties,including organic matter (OM),pH,and heavy metals (Cu,Pb,Zn,Cd,and Fe),using a total of 254 samples collected in soil profiles near a large copper smelter in China.Partial least square regression (PLSR) with cross-validation was used to relate soil property data to the reflectance spectral data by applying different preprocessing strategies.The performance of VNIR-DRS calibration models was evaluated using the coefficient of determination in cross-validation (R 2 cv) and the ratio of standard deviation to the root mean standard error of cross-validation (SD/RMSE cv).The models provided fairly accurate predictions for OM and Fe (R 2 cv > 0.80,SD/RMSE cv > 2.00),less accurate but acceptable for screening purposes for pH,Cu,Pb,and Cd (0.50 < R 2 cv < 0.80,1.40 < SD/RMSE cv < 2.00),and poor accuracy for Zn (R 2 cv < 0.50,SD/RMSE cv < 1.40).Because soil properties in conta-minated areas generally show large variation,a comparative large number of calibrating samples,which are variable enough and uniformly distributed,are necessary to create more accurate and robust VNIR-DRS calibration models.This study indicated that VNIR-DRS technique combined with continuously enriched soil spectral library could be a nondestructive alternative for soil environment monitoring.     

滩涂土壤有机质含量的反射光谱估算

Rapid determination of soil organic matter (SOM) using regression models based on soil reflectance spectral data serves an important function in precision agriculture. “deviation of arch”(DOA)-based regression and partial least squares regression (PLSR) are two popular modeling approaches to predict SOM. However, few studies have explored the accuracy of the DOA-based regression and PLSR models. Therefore, the DOA-based regression and PLSR were applied to the visible near-infrared (VNIR) spectra to estimate SOM content in the case of various dataset divisions. A two-fold cross-validation scheme was adopted and repeated 10 000 times for rigorous evaluation of the DOA-based models in comparison with the widely used PLSR model. Soil samples were collected for SOM analysis in the coastal area of northern Jiangsu Province, China. The results indicated that both modelling methods provided reasonable estimates of SOM, with PLSR outperforming DOA-based regression in general. However, the performance of PLSR for the validation dataset decreased more noticeably. Among the four DOA-based models, the linear model of the DOA provided the best estimation of SOM and a cutoff of SOM content (19.76 g kg^-1), and the performance for calibration and validation datasets was consistent. As the SOM content exceeded 19.76 g kg^-1, SOM became more effective in masking the spectral features of other soil properties to a certain extent. This work confirmed that reflectance spectroscopy combined with PLSR could serve as a non-destructive and cost-efficient way for rapid determination of SOM when hyperspectral data were available. The DOA-based model, which requires only 3 bands in the visible spectra, also provided SOM estimation with acceptable accuracy.     

华北矿区残留态铜、铅在土壤剖面中的分布与迁移

Residual heavy metals are commonly considered to be immobile in soils, leading to an underestimation of their environmental risk. This study investigated the distribution and transport of residual heavy metals along soil profiles, using the Xiaoqinling gold mining region in North China as a case study. Soil samples were collected at three depths from three locations near the tailing heap. The speciation of copper (Cu) and lead (Pb) (exchangeable, carbonate-bound, Fe-Mn oxide-bound, organic matter-bound, and residual fractions) was determined using a sequential extraction procedure. The residual fraction’s morphology was observed using scanning electron microscopy (SEM). Results showed that metal fraction distributions along the soil profiles were influenced by each fraction’s mobility. Residual fraction with high chemical stability cannot be transformed from or into other fractions. This led to the conclusion that the high concentration of residual metals in soils mainly resulted from residual fraction transport.The SEM analysis showed that fine particles (submicrons) were mainly attached to large particles and were likely released and transported by water flow. The more sorptive fractions (non-residual fractions) were mainly retained in the top soil, and the more mobile fractions (residual fraction) were mainly leached to the deep soil. Cu and Pb concentrations in the residual fraction decreased slightly and those in the non-residual fractions decreased significantly with soil depth. These suggest a relatively higher residual metal mobility along the soil pro?les. Therefore, residual metals can be transported in soils and their environmental risk can not be ignored in assessing soil contamination.     

4种湿地植物根系泌氧由根诱导的pH,Eh和Fe(II)变化和根际土壤中铅和锌的组分研究

A rhizobox experiment was conducted to compare iron (Fe) oxidation and changes of pH, redox potential (Eh) and fractions of zinc (Zn) and lead (Pb) in rhizosphere and non-rhizosphere soils of four emergent-rooted wetland plants (Echinodorus macrophyllus, Eleocharis geniculata, Hydrocotyle vulgaris and Veronica serpyllifolia) with different radial oxygen loss (ROL) from roots. The results indicated that all these wetland plants decreased pH and concentration of Fe(Ⅱ) but increased the Eh in the rhizosphere soils. Pb and Zn were transformed from unstable fractions to more stable fractions in the rhizosphere soils, so decreasing their potential metal mobility factors (MF). Among the four plants, E. macrophyllus, with the highest ROL and root biomass, possessed the greatest ability in formation of Fe plaque and in the reduction of heavy metal MFs in the rhizosphere soil. Wetland plants, with higher ROLs and root biomass, may thus be effective in decreasing potential long-term heavy metal bioavailabilities.     

在法国前铅和锌冶炼厂附近的城市土壤重金属的污染、分离和利用

smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry （FAAS or ETAAS）, depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical Soil contamination by metals from anthropogenic activities （e.g., mining and smelting） is a major concern for the environment and human health. Environmental availability of cadmium （Cd）, lead （Pb）, zinc （Zn）, copper （Cu）, and indium （In） in 27 urban soils located around two former Pb and Zn smelters in Northern France were studied by analysing the chemical forms of these metals and evaluating their phytoavailability. These metals were determined using flame or electrothermal absorption atomic spectrometry （FAAS or ETAAS）, depending on their concentration levels. After optimisation of the ETAAS method, characteristic mass of In in water and aqua regia were 9.9 and 18 pg, respectively, showing the high sensitivity of the analytical procedure. Metal partitioning was conducted using a four-step sequential extraction procedure. The results showed that Cd and Zn were mainly in the acid-extractable and reducible forms in the urban soils studied. In contrast, Pb and In were largely in the reducible fraction. However, in some samples, the amount of In extracted in the residual or exchangeable fraction was higher than that in the reducible fraction. Copper was mainly found in the reducible and residual fractions. A pot experiment was conducted in a glasshouse with seven soils （six contaminated and one uncontaminated） and two plant species, ryegrass and lettuce. The results showed transfer of metals from the contaminated soils to the shoots of ryegrass and the edible part of lettuce. The metal bioconcentration factor was in the order of Cd Cu > In > Zn Pb for lettuce leaves, whereas for ryegrass shoots, three orders were found, Cd > Zn > Cu In > Pb, Cd ≥ In > Zn > Cu Pb, and Zn > Cd > Cu > In > Pb, depending on the physico-chemical properties of the soils, such as pH, cation exchange capacity, carbonates, and organic matter. It was established that the metal toxicity was related to the contamination levels and the physico-chemical properties, including pH, organic matter, and in a lesser extent, Ca, Mg, and phosphorus contents, of the soils. However, it was shown that lettuce could grow on soils having high Cd and CaCO₃ contents. Cadmium was one of the most available metals while Pb was always the least available in the soils studied.     

便携式X射线荧光光谱法(PXRF)在矿区农田土壤 重金属快速检测中的应用研究

针对我国普遍存在的土壤重金属污染问题,迫切需要开展土壤重金属的快速检测与评价方法研究。本文采用便携式X射线荧光光谱法(PXRF)和传统实验室方法对云南会泽铅锌矿区农田土壤As、Pb、Cu和Zn进行测定,分析了PXRF法的应用效果。结果表明:1PXRF法测定的精密度与准确度满足我国农田土壤环境质量检测技术规范中规定的仪器检测要求;2土壤As、Pb、Cu和Zn的PXRF法测定值与传统实验室测定值具有良好的一致性,Pb、Cu和Zn的决定性系数均大于0.70;3基于PXRF法原位测定、PXRF法异位测定和传统实验室测定结果的研究区土壤As、Pb、Cu和Zn具有相似的空间分布规律。可见,PXRF法可用于矿区周边农田土壤As、Pb、Cu和Zn的快速检测、污染筛查与评价。     

Heavy metal contamination of agricultural soils around a chromite mine in Vietnam

Abstract

In Vietnam, the Co Dinh mine is the largest chromite mine in the country. Mining, ore dressing and disposal of the tailings provide obvious sources of heavy metal contamination in the mine area. The present study examined the influence of chromite mining activities on the adjacent lowland paddy field by investigating heavy metal and As levels in the mine tailings, sediments, paddy soils and water. At paddy fields located near the mine tailings, the total contents of Cr, Co and Ni were 5,750, 375 and 5,590?mg?kg^?1, and the contents of their water-extractable form were 12.7, 1.16 and 32.3?mg?kg^?1, respectively. These results revealed severe contamination of lowland paddy soils with Cr, Co and Ni as a result of mining activity, suggesting serious health hazards through agricultural products, including livestock in this area. The principal source of the pollution was sediment inflow owing to the collapse of the dike, which was poorly constructed by heaping up soil. Moreover, water flowing out from the mining area was also polluted with Cr and Ni (15.0–41.0 and 20.0–135?μg?L^?1, respectively). This might raise another problem of heavy metal pollution of watercourses in the area, indicating the need for further investigation and monitoring of fluctuations of water quality with seasonal changes.     

基于可见光-近红外漫反射光谱的红壤有机质预测及其最优波段选择

有机质是土壤肥力、土壤质量的重要指标,同时也是土壤碳库的重要组成部分。传统的土壤有机质测试方法费时、繁琐,难以满足快速监测土壤有机质含量的需求。近年来,具有无损、快速、简便等优点的可见-近红外光谱技术的应用为土壤有机质的快速监测提供了有效途径。     

Heavy metal contamination of soils in a mining area in South Africa and its impact on some biotic systems

In soils, animals and plants from selected sites in the Rustenburg mining area, a part of the South African ore belt, the heavy metal burden was examined. These sites belong to different soil types and are characterized by different land-use (agriculture, grassland). The heavy metal contamination of the soil samples is relatively high and is dominated by chromium and nickel, metals, which are extracted in the mine near the sampling sites. These high heavy metal concentrations had no clear inhibitory influence on micro-organisms or the enzyme activity of soils. It appears that the high clay content of the soils may counteract the influence of heavy metals. On the other hand, tolerant microbial populations may have been established. In addition, the investigated culture plants there was no correlation between the heavy metal content of the soils and the concentrations in roots and shoots. The dangerous, potential contamination of organs in humans seems to be modest, with the exception of tobacco leaves. The heavy metal content of tissues in the examined animals reflect the environmental habitat in situ with no obvious influence on the health of the animals.     

应用反射光谱法对土壤粘土矿物的鉴定的初步研究

The characteristics of the reflectance spectra of clay minerals and their influences on the reflectance spectra of soils are dealt with in the paper.The results showed that dominant clay minerals in soils could be distinguished in light of the spectral -form parameters of the reflectance spectra of soils,thus making it possible to develop a quick method to determine clay minerals by means of reflectance spectra of soils in the lab.and providing a theoretic basis for remote sensing of clay minerals in soils with a high resolution imaging spectrometer.     

Heavy metal pollution of agricultural soils and sediments in Liaoning Province,China

Heavy metal pollution of soils and sediments in Liaoning Province, Northeast China, was investigated. Fifty seven samples of agricultural soils and 8 samples of sediments were collected in 1996 from paddy or upland fields and irrigation channels, respectively, in Shenyang, Fushun, Liaoyang, Anshan, and Tieling regions, and concentrations of total and 0.1 mol L^-1 HCI-extractable Cd, Cu, Pb, and Zn were analyzed using ICP spectrometry. Seventeen samples of unpolished rice were also collected from selected paddy fields and total concentrations of the four elements were determined.–

Both paddy and upland soils were polluted with Cd: average total concentration was 0.70, 0.57, and 0.53 mg kg^-1 in the western and southern parts of Shenyang, and Anshan, respectively, and significantly higher than the background level of 0.32 mg kg^-1. Cd concentrations of four samples exceeded even 1 mg kg^-1, which corresponds to the critical level of Cd contamination in China. About 65% of the total Cd was extracted with 0.1 mol L^-1 HCI, suggesting that Cd was relatively mobile compared with other metals. The level of Cd pollution was, however, lower than that previously reported and serious polIution was not observed for Cu, Pb, and Zn. Accordingly, Cd concentration in upland rice was within the range of the unpolluted level in this study. Nevertheless, Cd concentration in a sediment of irrigation channels in the western part of Shenyang exceeded 16 mg kg^-1, indicating the possibility of further contamination of agricultural soils. In conclusion, soils and sediments were still polluted with Cd in the southern part of Shenyang, Anshan, and especially in the western part of Shenyang, and further countermeasures are urgently required to ensure safe food production in these regions.     

南宁河洲生态农业规划区土壤重金属污染评价

对南宁河洲生态农业规划区土壤中Cd、As、Pb、Hg、Cu、Zn等重金属含量进行了调查和分析测定．应用模糊评判法进行评价。结果表明．其土壤主要受Cd和As的污染；12个试点中4个点为尚清洁，8个点为轻污染。     

Assessment of soil contamination by potentially toxic elements in the aljustrel mining area in order to implement soil reclamation strategies

Land pollution due to past mining activities is a major environmental issue in many European countries. The Aljustrel mine (SW Portugal), located in the western sector of the Iberian Pyrite Belt (IBP) presents a negative visual and environmental impact as a consequence of the mining activity that has developed since the Roman era. Its impacts are also a restraint on the life quality of the population. The exposure of pyrite and other sulphides to air are responsible for the pollution observed in soils, surface water and stream sediments. This paper investigates the pollution load of potential toxic elements in soil samples collected around the Aljustrel mining area. The aim is to assess the levels of soil contamination with respect to average concentrations of toxic elements in the region and to understand the partitioning and availability of pollutants in the area. The results showed severe soil contamination (mainly As, Cd, Cu, Pb and Zn). The concentrations of As (up to 3936 mg kg⁻¹) and certain heavy metals (up to 5414 mg kg⁻¹ Cu, 61·6 mg kg⁻¹ Cd, 20 000 mg kg⁻¹ Pb and 20 000 mg kg⁻¹ Zn) are two orders of magnitude above the regional South Portuguese Zone (SPZ) background values. The median concentrations of As, Cd, Cu, Pb and Zn exceed the values established for world soils, the European Union, Portugal and Andalusia. The results suggest that the distribution patterns of Co, Cr and Ni element concentrations in the Aljustrel area are primarily influenced by the lithology and geochemistry nature of bedrock. The soil background of this geological domain is characterized by relatively high heavy metal contents, essentially derived from the parent rocks. Copyright © 2010 John Wiley & Sons, Ltd.