利用粘粒矿物修复重金属污染农业土壤研究进展

Heavy metal contamination of agricultural soils poses risks and hazards to humans.The remediation of heavy metal-polluted soils has become a hot topic in environmental science and engineering.In this review,the application of clay minerals for the remediation of heavy metal-polluted agricultural soils is summarized,in terms of their remediation effects and mechanisms,influencing factors,and future focus.Typical clay minerals,natural sepiolite,palygorskite,and bentonite,have been widely utilized for the in-situ immobilization of heavy metals in soils,especially Cd-polluted paddy soils and wastewater-irrigated farmland soils.Clay minerals are able to increase soil pH,decrease the chemical-extractable fractions and bioavailability of heavy metals in soils,and reduce the heavy metal contents in edible parts of plants.The immobilization effects have been confirmed in field-scale demonstrations and pot trials.Clay minerals can improve the environmental quality of soils and alleviate the hazards of heavy metals to plants.As main factors affecting the immobilization effects,the pH and water condition of soils have drawn academic attention.The remediation mechanisms mainly include liming,precipitation,and sorption effects.However,the molecular mechanisms of microscopic immobilization are unclear.Future studies should focus on the long-term stability and improvement of clay minerals in order to obtain a better remediation effect.     

中国福建省土壤的主要粘土矿物

The clay minerals of more than 200 soil samples collected from various sites of Fujian Province were studied by the X-ray diffraction method and transmission electron microscopy to study their distribution and evolution.Montmorillonite was found in coastal solonchak,paddy soils derived from marine deposit,lacustrine deposit and river deposit,and some lateritic red soil,red soil and yellow soil with a low weathering degree.Chlorite existed mainly in coastal solonchak and paddy soil developed from marine deposit.1.4nm intergradient mineral appeared frequently in yellow soil,red soil and lateritic red soil.The content of 1.4nm intergradient mineral increased with the decrease of weathering degree from lateritic red soil to red soil to yellow soil.Hydrous micas were more in coastal solonchak,paddy soils derived from marine deposit,lacustrine deposit and river deposit.and puple soil from purple shale than in other soils.Kaolinte was the most important clay mineral in the soils iun this province.The higher the soil weathering degree,the more the kaolinite existed.From yellow soil to red soil to lateritic red soil,kaolinite increased gradually,Kaolinite was the predominant clay mineral accompanied by few other minerals in typical lateritic red soil. Tubular halloysite was a widespread clay mineral in soils of Fujian Province with varying quantities.The soil derived from the paent rocks rich in feldspar contained more tubular halloysite.Spheroidal halloysite was found in a red soil and a paddy soil developed from olivine basalt gibbsite in the soils in this district was largely“primary gibbsite” which formed in the early weathering stage.Gibbsite decreased with the increase of weathering degree from yellow soil to red soil to lateritic red soil.Goethite also decreased in the same sequence while hematite increased.     

Incorporation of source contributions to improve the accuracy of soil heavy metal mapping using small sample sizes at a county scale

Estimating heavy metal(HM) distribution with high precision is the key to effectively preventing Chinese medicinal plants from being polluted by the native soil. A total of 44 surface soil samples were gathered to detect the concentrations of eight HMs(As, Hg, Cu, Cr, Ni, Zn, Pb, and Cd) in the herb growing area of Luanping County, northeastern Hebei Province, China. An absolute principal component score-multiple linear regression(APCS-MLR) model was used to quantify pollution source contributio...     

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.     

胡敏酸对铵钾在粘土矿物上交互作用的影响

Interaction of ammonium (NH+4) and potassium (K+) is typical in field soils. However, the effects of organic matter on interaction of NH+4 and K+have not been thoroughly investigated. In this study, we examined the changes in major physicochemical properties of three clay minerals (kaolinite, illite, and montmorillonite) after humic acid (HA) coating and evaluated the influences of these changes on the interaction of NH+4 and K+on clay minerals using batch experiments. After HA coating, the cation exchange capacity (CEC) and specific surface area (SSA) of montmorillonite decreased significantly, while little decrease in CEC and SSA occurred in illite and only a slight increase in CEC was found in kaolinite. Humic acid coating significantly increased cation adsorption and preference for NH+4, and this effect was more obvious on clay minerals with a lower CEC. Results of Fourier transform infrared spectrometry analysis showed that HA coating promoted the formation of H-bonds between the adsorbed NH+4 and the organo-mineral complexes. HA coating increased cation fixation capacity on montmorillonite and kaolinite, but the opposite occurred on illite. In addition, HA coating increased the competitiveness of NH+4 on fixation sites. These results showed that HA coating affected both the nature of clay mineral surfaces and the reactions of NH+4 and K+with clay minerals, which might influence the availability of nutrient cations to plants in field soils amended with organic matter.     

粘土矿物对土壤腐殖质化学性质的影响

Chemical characteristics of humic substances in soils with different mineralogical characteristics and under different utilization paterns in Zhangpu,Fujian Province,together with two pairs of cultivated soils in North China Plain were studied by chemical analysis,visible and IR spectroscopy and ^13C NMR spectrometry.For soils in Zhanpu the HA/FA ratio and both the aromaticity and the degree of humification of HA were higher in soils with montmorillonite as the predominant clay mineral than in those with kaolinite as the predominant clay mineral,provided these soils were under the same utilization pattern.While for each pair of soils with similar mineralogical characteristics the HA/FA ratio was higher and the C/H ratio and the contnet of carboxyl group of HA were lower in paddy soil than in upland soil.Among the upland soils(or paddy soils)studied the Ha/FA ratio of soil in Zhangpu with kaolinite as the predominant clay mineral was the lowest,and that of soil in Zhangpu with montmorillonite as the predominant clay mineral was the highest .the lowest.and that of soil in Zhangpu with montmorillonite as the predominant clay mineral was the highest It was concluded that the presence of montmorillonite favored the fromation and maturation of humic acid.     

三峡库区坡地表层风化特征研究

Extractability and mobility of Cu and Zn and their relationships with 1） accumulation of Cu and Zn and 2） soil pH were studied in three sandy soils （Wabasso, Ankona, and Winder） from commercial citrus groves in Florida, USA. The soils, with a broad range of Cu and Zn concentrations, were fractionated by a modified procedure of Amacher, while Cu and Zn mobility were evaluated using column leaching. The extractability of Cu and Zn increased with decreasing soil pH. Also with increasing total soil Cu and Zn for extractable Cu in the Wabasso sand a threshold level, where the metal extraction rate increased, was noted at 100 mg kg^-1, whereas for extractable Zn in the Wabasso sand the threshold level was found at 60 mg kg^-1 and in the Ankona sand at 120 mg kg^-1. These results suggested that the release potential of Cu and Zn was greater in the Wabasso sand than in the Ankona sand. The column leaching experiment showed that at total soil Cu or Zn concentrations 〈 100 mg kg^-1 all leachates had low Cu and Zn concentrations. However at total concentrations 〉 200 mg kg^-1 for Cu and 〉 150 mg kg^-1 for Zn with decreasing soil pH, the concentrations of both Cu and Zn in the leachates increased exponentially. Also in these sandy soils soluble Cu and Zn mainly originated from the exchangeable fractions, and pH was a key factor controlling Cu and Zn extractability and mobility.     

Heavy Metal Release from Some Industrial Wastes: Influence of Organic and Inorganic Acids, Clay Minerals, and Nanoparticles

Knowledge about heavy metal release from industrial solid wastes(ISWs) is crucial for better management of their environmental risks. This study was conducted to investigate the effect of organic and inorganic acids, clay minerals, and nanoparticles(NPs) on the release of heavy metals from sugar factory waste, ceramic factory waste, leather factory waste, and stone cutting waste. The influence of the extractants on heavy metal release from these ISWs was in the following descending order: citric acid oxalic acid nitric acid≥ sulfuric acid Ca Cl2. Addition of clay minerals and NPs as adsorbents decreased heavy metal release, which was significantly lower in NP-treated wastes than in the clay mineral-treated wastes. On the other hand, the presence of organic and inorganic acids increased heavy metal adsorption by NPs and clay minerals. These results suggest that NPs can be applied successfully in waste remediation,and organic and inorganic acids play an important role in the removal of heavy metals from the studied adsorbents.     

中国五个典型城市污水厂污泥中重金属的形态分布研究

Metal content and bioavailability are often the limiting factors for application of sewage sludge in agricultural fields. Sewage sludge samples were collected from five typical urban wastewater treatment plants in China to investigate their contents and distribution of various chemical fractions of Cu, Zn, Ni, Cr, Pb and Mo by using the BCR （Community Bureau of Reference） sequential extraction procedure. The sludges contained considerable amounts of organic matter （31.8%- 48.0%）, total N （16.3-26.4 g kg^-1） and total P （15.1-23.9 g kg^-1）, indicating high potential agricultural benefits of their practical applications. However, total Zn and Ni contents in the sludge exceeded the values permitted in China＇s control standards for pollutants in sludges from agricultural use （GB 4284-1984）. The residual fraction was the predominant fraction for Mo, Ni and Cr, the oxidizable fraction was the primary fraction for Cu and Pb, and the exchangeable and reducible fractions were principal for Zn. The distribution of different chemical fractions among the sludge samples refiected differences in their physicochemical properties, especially pH. The sludge pH was negatively correlated with the percentages of reducible fraction of Cu and exchangeable fraction of Zn. The sludges from these plants might not be suitable for agricultural applications due to their high contents of Zn, Ni and Cr, as well as high potential of mobility and bioavailability of Zn.     

Use of Biochar as an Amendment for Remediation of Heavy Metal-Contaminated Soils:Prospects and Challenges

Biochar (BC), known as the new black gold, is a stable, novel carbonaceous by-product that is synthesized through pyrolysis of biological materials in the absence of O₂. Recently, an emerging interest in the application of BC as a robust soil amendment has given rise to a broad research area in science and technology. It is considered a promising remediation option for heavy metal (HM)-contaminated soils to reduce HM bioavailability to plants. Remediation efficacy of BC depends on the porosity, composition, pyrolysis temperature, feedstock, and residence time of pyrolysis. This review article aimed to present an overview of BC use in the immobilization of HMs, i.e., Cd, As, Pb, Zn, Ni, Cu, Mn, Cr, and Sb, in contaminated soils. The remaining uncertain factors, including the specific soil HM immobilization mechanisms, long-term beneficial effects, and potential environmental risks associated with BC application are analyzed. Future research must be conducted to ensure that the management of environmental pollution is in accord with ecological sustainability and adaptation of the black gold biotechnology on a commercial basis for immobilization of HMs in contaminated soils.     

Total soil heavy‐metal concentrations and mobile fractions after 10 years of biowaste‐compost fertilization

The accumulation of heavy metals (HMs) in soils is the most often cited potential risk of compost application. As the ecological effects of metals are related to mobile fractions rather than to total concentrations in the soil, we measured the total (aqua regia–extractable) HM concentrations, the readily available water‐soluble and the potentially bioavailable LiCl‐extractable fraction of soil HMs in a field experiment after 10 y with total applications of 95, 175, and 255 t ha^–1 biowaste compost (fresh matter). Total soil concentrations of Cd, Cr, Cu, Ni, and Pb in the compost treatments were not significantly higher than in the unfertilized control. Total Zn concentrations increased in the treatment with the highest application rate, as expected from the calculation of the Zn load in the composts. In the mobile fractions, as measured in soil saturation extract and LiCl extract, Cd and Pb were not detectable. Concentrations of Cr, Ni, and Zn were in the range published for unpolluted soils in other studies and did not show any differences according to treatment. Easily exchangeable Cu (in LiCl extract) was increased with compost fertilization, most probably due to complexation with low‐molecular organic complexants. Except for Cd and Zn, the results of the mobile HM fractions in the soil were in good agreement with plant HM concentrations. In conclusion, fertilization with high‐quality biowaste compost at such rates and after 10 y of application gives no cause for concern with regard to both total HM concentrations and available HM fractions.     

Natural and technogenic compounds of heavy metals in soils

The existing geological classification of heavy metals (HMs) is not suitable for their characterization in soils. The carriers of HMs in soils differ from those in the lithosphere. These are clay minerals; iron oxides, whose composition varies between the background and urban soils; various manganese oxides; and different groups of organic substances. The mineral composition of HM carriers can vary significantly. The main iron oxides are ferrihydrite, goethite, feroxyhyte, and lepidocrocite in the background soils and technogenic magnetite in the urban soils. The different structures of manganese oxides determine their affinity for specific HMs. Metallic iron and green rust are very efficient in artificial geochemical barriers, although they act as strong reducers there. HM compounds strongly vary in soils because of the unstable conditions.     

Predicting the Phytoextraction Duration to Remediate Heavy Metal Contaminated Soils

The applicability of phytoextraction to remediate soils contaminated with heavy metals (HMs) depends on, amongst others, the duration before remediation is completed. The impact of changes in the HM content in soil occurring during remediation on plant uptake has to be considered in order to obtain a reliable estimate of the phytoextraction duration. To simulate the decrease in the HM content in soil and to assess the resulting decrease in the uptake of HMs by plants, contaminated soil was mixed with uncontaminated, but otherwise similar soil. Uptake of Cd, Pb, and Zn by the indicator plant Lupinus hartwegii and the Zn hyperaccumulator Thlaspi caerulescens (La Calamine ecotype) was a log-linear function of the in-situ measured HM soil solution concentrations. Over a wide range in dissolved Cd and Zn concentrations, uptake of these HMs by T. caerulescens was (much) greater than by L. hartwegii. Experimentally derived regression models describing the relationships between soil, soil solution, and plant were implemented in a HM mass balance model used to obtain estimates of the phytoextraction duration. For our target soils, estimates of the Cd phytoextraction duration using L. hartwegii or T. caerulescens increased significantly by more than 100 or 50 years when experimental soil—soil solution—plant relationships were used instead of the assumption of constant plant uptake of Cd. The two approaches gave similar results for phytoextraction of Zn by T. caerulescens.     

Soil contamination in the impact zone of mining enterprises in the Bashkir Transural region

The results of long-term studies of the contents of bulk forms of metals (Cu, Zn, Fe, Ni, Pb, Mn, Co, and Cd) and their mobile compounds in soils of background and human-disturbed areas within the Krasnoural’sk–Sibai–Gai copper–zinc and Baimak–Buribai mixed copper mineralization zones in the Bashkir Transural region are discussed. It is shown that soils of the region are characterized by abnormally high natural total contents of heavy metals (HMs) typomorphic for ore mineralization: Cu, Zn, and Fe for the Sibai province and Cu, Zn, and Ni for the Baimak province. In the case of a shallow depth of the ores, the concentrations of HMs in the soils are close to or higher than the tentative permissible concentration values. The concentrations of mobile HM compounds in soils of background areas and their percentage in the total HM content strongly vary from year to year in dependence on weather conditions, position in the soil catenas, species composition of vegetation, and distance from the source of technogenic contamination. The high natural variability in the content of mobile HM compounds in soils complicates the reliable determination of the regional geochemical background and necessitates annual estimation of background parameters for the purposes of the ecological monitoring of soils. The bulk content of Cu and Zn content in soils near mining enterprises exceeds the regional geochemical background values by 2–12 times and the tentative permissible concentrations of these metals by 2–4 times. Anthropogenic contamination results in a sharp rise in the content of mobile HM compounds in soils. Their highest concentrations exceed the maximum permissible concentrations by 26 times for Cu, 18 times for Zn, and 2 times for Pb. Soil contamination in the impact zone of mining enterprises is extremely dangerous or dangerous. However, because of the high temporal variability in the migration and accumulation of HMs in the soils, the recent decline in the ore mining activities, and the construction of purification facilities, no definite temporal trends in the contents of HMs in the soils have been found in the studied region for the period from 1998 to 2015.     

Metal Extractability in Binary and Multi-metals Spiked Calcareous Soils

In the present study, a laboratory experiment was designed to compare the 0.01 M calcium chloride (CaCl₂) and diethylenetriaminepentaacetic acid (DTPA) extraction methods for their ability to predict cadmium (Cd), copper (Cu), iron (Fe), Manganese (Mn), nickel (Ni), and zinc (Zn) availability and mobility in five calcareous soils. The soils were spiked with different amounts of metals (0, 50, 100, 200, and 400 mg kg^?1) both in binary (Cu and Zn; Ni and Cd; Fe and Mn) and in multi-systems (Cd, Cu, Fe, Mn, Ni, and Zn) and incubated for 1 months at field capacity. In metal-spiked soils, both extraction methods showed a linear relationship of extractable to total metals for all soils. The fraction of total metals extracted by DTPA was much higher than the fraction extracted by CaCl₂, which was attributed to the formation of soluble metal-complexes in the complexing extracts calculated by the Visual Minteq program. DTPA extraction method showed higher selectivity for Cu over other metals both in binary and in multi-systems. Different order of metals extractability was found in binary and multi-systems for both extraction methods. Solid/solution distribution coefficient (K_d) was calculated by the ratio of the solid phase to soil solution concentration of metals extracted by CaCl₂ or DTPA extraction methods. Both in binary and in multi-systems, the average K_d (l kg^?1) of metals by soils were in the order of Mn (5398) > Fe (4413) > Zn (3376) > Cu (2520) > Ni (969) > Cd (350) in the CaCl₂-extractable metals and Fe (35) ≥ Ni (34) > Zn (18) > Mn (11.2) > Cu (6.3) > Cd (4) in the DTPA-extractable metals. Results showed that among the six studied metals, Cd had the lowest K_d, implying a relative higher mobility in these calcareous soils. The Visual Minteq indicated that in the CaCl₂-extraction method and in both binary and multi-systems the dominant species for Cu, Mn, Ni, and Zn were Cu²⁺, Mn²⁺, Ni²⁺ and Zn²⁺, respectively, while for Cd and Fe, the dominant species were CdCl⁺ and Fe(OH)²⁺, respectively.     

Evaluation of fly ash,apatite and rice straw derived-biochar in varying combinations for in situ remediation of soils contaminated with multiple heavy metals

ABSTRACT

In

-situ sorbent amendment is a relatively low-cost, low-impact approach for remediation of soil contaminated with heavy metals (HMs), and thus is considered a way to be favored in developing countries. In this study, materials of non-hazardous, alkaline agronomic and industrial by-products were used as sorbents to explore their capacity of in situ immobilization of multiple HMs in mining-impacted arable soil. These sorbents included fly ash (FA), biochar (BC) and apatite (AP) and they were implemented with varying ratios of combinations. Results of soil microcosm tests showed that after incubation for 90 days, concentrations of Pb, Zn, and Cd in their exchangeable forms determined by a sequential extraction method significantly decreased in amended soils, as opposed to the unamended control. Of the five sets of amendments, the composite of FA, BC, and AP resulted in the maximum reduction (up to 80%) in the mobility of Pb, Zn, and Cd in soils. The mechanisms underlying the immobilization of HMs in amended soils might involve processes of surface precipitation, ion exchange and complexation, in which the physicochemical properties of sorbent materials played an important role. The immobilization efficacy of sorbent amendments on HMs in soil was further supported by pot experiments in which significant inhibition of HM accumulation in the belowground and aboveground tissues of maize was observed after 50-day cultivation in amended soils as compared with control soil. Together, these results suggest that the application of cost-saving and environmentally friendly materials derived from wastes as sorbents to remediate soils contaminated with multiple HMs is promising for developing countries like Vietnam.     

VARIATION AND INTERRELATIONS AMONG NUTRIENT ELEMENTS IN WHEAT LEAVES USED FOR FORAGE

Dual purpose wheat provides valuable forage resources for cattle in the southern Great Plains during winter. In this study, 96 recombinant inbred lines (RILs) were analyzed for variation in concentrations of 11 mineral elements in leaves. The mean concentration was 133.4 mg kg^?1 for manganese (Mn) and 293 mg kg^?1 for iron (Fe), being much higher than the 30 mg kg ^?1 recommended for each of these two minor mineral elements. Mean concentrations of zinc (Zn) (24.1 mg kg^?1) and copper (Cu) (4.4 mg kg^?1) were much lower than recommended concentrations. A highly significant correlation was detected between major minerals, magnesium (Mg) and calcium (Ca) (r = 0.9272**) and between minor minerals, Fe and nickel (Ni) (r = 0.8905**). Copper had no significant correlation with any minerals except Zn (r = 0.2529*), whereas Zn had significant correlations with all of the tested minerals except Cu, Mn, and Ni. The interrelations between different minerals provided information for effective selection strategy for ideal mineral concentrations in breeding of dual purpose wheat.     

Adsorption isotherms of copper and zinc in clay minerals of calcareous soils and their effects on X-ray diffraction

Reactions of elements with the water mineral interface are important and affect their bioavailability and transportation within soil. Effects of metal sorption on X-ray-diffraction (XRD-photographs) of clay minerals have been not studied. Therefore, sorption experiments were done on clay fractions of two calcareous soils using 12 concentrations of 0–2000 mg L^?1 Zn(NO₃)₂ and Cu(NO₃)₂. Langmuir and Freundlich isotherms’ coefficients were determined. After sorption, XRD-diffraction were prepared and compared with those of initial samples. Langmuir (R² = 0.996–0.999 and SE = 0.001–0.002) and Freundlich equation were the best-model for Zn and Cu-sorption, respectively. Sorption energy was higher for Zn than Cu, whereas the maximum concentration of sorbed-Cu was higher than that of Zn. Distribution coefficient (K_d) of Cu were more (threefold) than that of Zn. The K_d values representing the slope of Freundlich isotherms decreased according to linear regression equations (R² = 0.72–0.91) as the equilibrium concentrations of metals increased. No significant differences were observed among XRD-photographs of applied concentrations (some negligible differences were found in position/sharpness of peaks). Dry-XRD-method resulted in omission of intensity peaks at 2θ which may interfere in recognition of clays that show a maximum intensity >1.4 nm in the mentioned 2θ. Zinc can become more leachable especially in Shekarbani-soil-series, whereas, Cu highly adsorb on clay minerals and can show less tendency to transportation.     

Remediation of a soil contaminated with heavy metals by immobilizing compounds

The labile fraction of heavy metals (HM) in soils is the most important for toxicity for plants and microorganisms. Thus, it is crucial to reduce this fraction in contaminated soils to decrease the negative effect of HM. In a greenhouse experiment, the effects of several additives on the labile fractions of Zn, Cd, Cu, Ni, and Pb were investigated in a soil contaminated during long‐term sewage‐sludge application. The accumulation of HM was studied in the aboveground biomass of wheat (Triticum aestivum L.). The additives used were the clay minerals Na‐bentonite, Ca‐bentonite, and zeolite; the Fe oxides hematite and goethite; the phosphate fertilizers superphosphate and Novaphos. Wheat was planted three times during 5 months, allowed to grow for 7 w, and harvested. Dry matter and HM content of shoots were determined after each harvest. Soil samples were taken after the first and third harvest, and the NH₄NO₃‐extractable HM contents were determined. After the addition of 2% Na‐bentonite as well as 2% Ca‐bentonite, a strong reduction of the labile HM soil fraction and shoot HM concentration was observed. At the end of the experiment, the labile fraction was reduced due to the addition of Na‐bentonite and Ca‐bentonite by 24% and 31% for Zn, by 37% and 36% for Cd, by 41% and 43% for Cu, by 54% and 61% for Ni, and by 48% and 41% for Pb, respectively. Furthermore, the shoot HM concentrations with the exception of Zn were reduced below the phytotoxicity range. Accordingly, the shoot dry‐matter production was significantly increased. The addition of phosphate fertilizers (notably Novaphos) strongly reduced the bioavailability of Pb for wheat plants. By addition of 0.05% Novaphos, the labile fraction and the shoot concentration of Pb were lowered by 39% and 64%, respectively. However, the addition of Fe oxides and zeolite resulted only in a small reduction in HM bioavailability to wheat plants. Among the studied additives, Na‐bentonite and Ca‐bentonite have the most promising potential to reduce the bioavailability for the studied HM.