Ultrasound-assisted soil washing processes for the remediation of heavy metals contaminated soils: The mechanism of the ultrasonic desorption

Ultrasound-assisted soil washing processes were investigated for the removal of heavy metals (Cu, Pb, and Zn) in real contaminated soils using HCl and EDTA. The ultrasound-assisted soil washing (US/Mixing) process was compared with the conventional soil washing (Mixing) process based on the mechanical mixing. High removal efficiency (44.8% for HCl and 43.2% for EDTA) for the metals was obtained for the most extreme conditions (HCl 1.0 M or EDTA 0.1 M and L:S = 10:1) in the Mixing process. With the aide of ultrasound, higher removal efficiency (57.9% for HCl and 50.0% for EDTA) was obtained in the same extreme conditions and similar or higher removal efficiency (e.g., 54.7% for HCl 0.5 M and L:S = 10:1 and 50.5% for EDTA 0.05 M and L:S = 5:1) was achieved even in less extreme conditions (lower HCl or EDTA concentration and L:S ratio). Therefore, it was revealed that the US/Mixing was advantageous over the conventional Mixing processes in terms of metal removal efficiency, consumption of chemicals, amount of generated washing leachate, and volume/size of washing reactor. In addition, the heavy metals removal was enhanced for the smaller soil particles in the US/Mixing process. It was due to more violent movement of smaller particles in slurry phase and more violent sonophysical effects. In order to understand the mechanism of ultrasonic desorption, the desorption test was conducted using the paint-coated beads with three sizes (1, 2, and 4 mm) for the free and attached conditions. It was found that no significant desorption/removal of paint from the beads was observed without the movement of beads in the water including floatation, collision, and scrubbing. Thus, it was suggested that the simultaneous application of the ultrasound and mechanical mixing could enhance the physical movement of the particles significantly and the very high removal/desorption could be attained.     

Comparison of energy consumptions between ultrasonic, mechanical, and combined soil washing processes

Vigorous physical effects including micro-jet and micro-streaming can be induced in heterogeneous systems by acoustic cavitation. This can be useful for the removal of pollutants from contaminated soil particles. In this study, the diesel removal efficiencies in ultrasonic, mechanical, and combined soil washing processes have been compared considering the electrical energy consumptions for these processes. The combined process showed synergistic effects for both removal efficiency and effective volume also has the advantage of a short operation time compared to the sequential processes. Thus the ultrasonic soil washing process with mechanical mixing is considered a promising technology for industrial use.     

Ultrasound-assisted soil washing processes using organic solvents for the remediation of PCBs-contaminated soils

Ultrasonic soil washing processes using organic solvents were investigated for the development of novel remediation technologies for persistent organic pollutants (POPs)- contaminated soils. Aluminum foil erosion was first tested to understand sonophysical activity in water, methanol (polar) and n-hexane (nonpolar) in a 28 kHz double-bath-type sonoreactor. Significant sonophysical damage on the aluminum foil was observed at the antinodes for all solvents, and the order of degree of sonophysical damage was as follows: water > methanol > n-hexane. Subsequently, conventional (mechanical mixing only) and ultrasonic soil washing (mechanical mixing and ultrasound) techniques were compared for the removal of polychlorinated biphenyls (PCBs) from soil. Two types of contaminated soils, fresh (Soil A, C₀ = 2.5 mg/kg) and weathered (Soil B, C₀ = 0.5 mg/kg), were used and the applied soil-to-liquid (S:L) ratio was 1:5 and 1:10 for methanol and n-hexane, respectively. The polar solvent significantly increased washing efficiencies compared to the nonpolar solvent, despite the nonpolar nature of the PCBs. Washing efficiency was significantly enhanced in ultrasonic soil washing compared to conventional washing, owing to macro- and micro-scale sonophysical actions. The highest washing efficiencies of 90% for Soil A and 70% for Soil B were observed in the ultrasonic washing processes using methanol. Additionally, a single operation of the ultrasonic washing process was superior to two sequential processes with conventional mixing in terms of washing efficiency, consumption of washing agents, treatment of washing leachate, and operation time. Finally, the removal of PCBs in an organic solvent (methanol) was investigated in photolytic and sonolytic processes for the post-treatment of soil washing leachate. A photolysis efficiency of 80% was obtained within 60 min of UV exposure for intensities of 1.0, 2.0, and 4.0 W/cm². The primary mechanism of PCBs degradation is photolytic dechlorination. In contrast, no degradation was detected in the sonolytic process, as the excess organic solvent acted as a strong radical scavenger.     

Ultrasonic processes for the advanced remediation of contaminated sediments

Sediments play a fundamental role in the aquatic environment, so that the presence of contaminants poses severe concern for the possible negative effects on both environmental and human health. Sediment remediation is thus necessary to reduce pollutant concentrations and several techniques have been studied so far. A novel approach for sediment remediation is the use of Advanced Oxidation Processes, which include ultrasound (US). This paper focuses on the study of the ultrasonic effects for the simultaneous reduction of both organic and inorganic contaminants from sediments. To this end, the US technology was investigated as a stand-alone treatment as well as in combination with an electro-kinetic (EK) process, known to be effective in the removal of heavy metals from soil and sediments. The US remediation resulted in higher organic compound degradation, with an average 88% removal, but promising desorption yields (47–84%) were achieved for heavy metals as well. The combined EK/US process was found to be particularly effective for lead. Experimental outcomes highlighted the potential of the ultrasonic technology for the remediation of contaminated sediments and addressed some considerations for the possible scale-up.     

Effect of ultrasound on oil removal from soils

The soil-flushing method enhanced by ultrasonic waves is a new technique that potentially can become an effective method for in situ remediation of the ground contaminated by NAPL hydrocarbons. This study investigated the effectiveness of ultrasound enhancement in the soil-flushing method for a range of conditions involving soil type, soil density, flushing rate, and sonication power. The study was conducted in the laboratory using specially designed and fabricated equipment. The test results indicated that the rate of contaminant extraction increased considerably with increasing sonication power up to the level where cavitation occurred. The effectiveness of sonication-enhanced soil-flushing can be expressed as a function of (D(10))(2)*i, in which D(10) is the effective grain size, and i is the hydraulic gradient.     

激光诱导击穿光谱定量检测土壤微量重金属元素方法研究

在对激光诱导击穿光谱数据分析的基础上提出了一种可以用于元素定量分析的方法。该方法利用傅里叶分析的方法研究了光谱数据中的不同部分(白噪声、热辐射噪声和原子发射光谱),通过带通滤波实现发射光谱与大部分噪声的分离,得到仅含少量白噪声的发射光谱;通过计算待量化元素谱线与其对应单位强度特征谱线的相似度引入卷积强度来衡量待测谱线的强度。选取Cu 324.75nm作为分析线,Ti 337.28nm谱线作为参考线,采用上述方法对含微量Cu元素土壤样品进行了测量。实验结果显示:Cu元素含量和其卷积强度的线性系数达到0.997 9,计算得到土壤中Cu元素的检测限为44mg.kg-1,达到国家土壤环境质量标准规定的二级土壤中Cu含量要求,测量相对误差在10%以内,表明该方法能够满足土壤微量重金属检测简便、快速的要求。     

New concept to remove heavy metals from liquid waste based on electrochemical pH-switchable immobilized ligands

Absorption on resins is often used as secondary step in the treatment of water-based effluents, in order to reach very low concentrations. The separation of the trapped effluents from the resins and the regeneration of the resins for further use create wide volumes of secondary effluents coming from the washings of the resins with chemical reagents. We propose an alternative solution based on a “surface strategy” through adsorption phenomena and electrical control of the expulsion stage. The final goal is to limit or ideally to avoid the use of chemical reagents at the expulsion (or regeneration) stage of the depolluting process. Heavy metal ions were captured on active filters composed by a conducting surface covered by poly-4-vinylpyridine (P₄VP). Due to pyridine groups those polymer films have chelating properties for copper ions. Our strategy for electrical triggering of the copper expulsion in aqueous medium is based on pH sensitive chelating groups. Applying moderate electro-oxidizing conditions generates acidic conditions in the vicinity of the electrode, i.e. “inside” the polymer film. This allows a “switch-off” of the complexing properties of the film from the basic form of pyridine to pyridinium. Interestingly, no buffer washing is necessary to restore (or “switch-on”) the complexing properties of the polymer film because the pH of the external medium is left unchanged by the electrochemical effect that affects only the vicinity of the electrode. Switch-on/switch-off cycles are followed and attested by IR spectroscopy and EQCM method.     

土壤中酚的超声波提取

以合成土样为对象,研究了超声波辅助提取苯酚的条件及其提取效率。用中档超声波场辐射试样2×30s,30ml丙酮-正己烷(体积比1:1)分两次萃取10.0g合成土样中的苯酚,这时所获收率最高。在选定条件下用于实际土样分析,以索氏萃取4h的结果为对照基准,本方法的平均回收率为97.8％,RSD为1.5％。     

二元液态金属Cu-Ni和Ag-Cu凝固过程的分子动力学模拟研究

用Quantum Sutton-Chen多体势对Ag6Cu4和CuNi液态金属凝固过程进行了分子动力学模拟研究.在冷却速率2×1012到2×1014K/s范围内,CuNi总是形成fcc晶体结构,而Ag6Cu4总是形成非晶态结构.考虑到CuNi及AgCu中原子半径之比分别为1.025和1.13,那么模拟结果证实了原子的尺寸差别是非晶态合金形成的一个主要影响因素.此外采用键对及原子多面体类型指数法对凝固过程中微观结构组态变化的分析,不但能说明二十面体结构在非晶态合金形成和稳定性中所起的关键作用,又有助于对液态金属的凝固过程、非晶态结构特征的深入理解.     

土壤重金属沿山地森林海拔梯度的分布特征

采用电感耦合等离子体发射光谱法与石墨炉原子吸收光谱法,研究了14种重金属(Fe,Al,Ti,Cu,Cr,Mn,V,Zn,Ni,Co,Pb,Se,Cd,As)沿山地森林海拔梯度的分布特征.结果表明海拔梯度对14种重金属中的6种重金属浓度(Fe,A1,Ti,V,Pb与As)有显著的影响,对其他八种重金属浓度(Cu,Cr,M...     

含矿物中成药及其胃肠消化液中五种重金属元素的测定研究

传统含雄黄中成药中可能含有多种微量元素及高含量的砷等有毒元素.对含雄黄的三种中成药分别采用微波消解与电热板消解进行处理,用电感耦合等离子体质谱(ICP-MS)及电感耦合发射光谱(ICP-AES)法检测其中的As,Hg,Cu,Cd,Pb.此外,还研究了含雄黄中成药经模拟人工胃肠消化后消化液中有毒有害金属含量.结果显示,三...     

Ultrasonic enhancement of the supercritical extraction from ginger

This work examines the concurrent use of power ultrasound during the extraction of pungent compounds from a typical herb (ginger) with supercritical CO₂. A power ultrasonic transducer with an operating frequency of 20 kHz is connected to an extraction vessel and the extraction of gingerols from freeze-dried ginger particles (4–8 mm) is monitored. In the presence of ultrasound, we find that both the extraction rate and the yield increase. The higher extraction rate is attributed to disruption of the cell structures and an increase in the accessibility of the solvent to the internal particle structure, which enhances the intra-particle diffusivity. While cavitation would readily account for such enhancement in ambient processes, the absence of phase boundaries should exclude such phenomena above the critical point. Possible alternate mechanisms for the cell structure damage are discussed.     

便携式X射线荧光光谱分析仪测定土壤中重金属

应用NITON XL3t600型便携式X射线荧光谱分析仪对土壤中主要重金属污染物Cu,Zn,Pb,Cr和As进行了测试。结果表明,Cu,Zn,Pb,Cr和As元素的最低检出限分别为:23.96,11.69,8.58,19.23,6.24mg.kg-1;对土壤成分分析标准物质GSS-5进行5次重复测定,准确度在96%～102%之间,RSD在1.0%～7.6%范围内,表明仪器对于土壤中较高浓度重金属检测准确度和精密度良好;田间进行原位检测,相对标准偏差均小于20%,与国标方法检测结果相比,准确度在55%～119%之间。通过实验室测试和田间原位检测,验证了便携式X射线荧光谱分析仪检测土壤中重金属元素有较好的准确度和精密度,适用于土壤中重金属的快速检测。     

Evaluation of the potential of ultrasound technology combined with mild temperatures to reduce cadmium content of edible crab (Cancer pagurus)

The consumption of crustaceans is correlated with certain health risks, particularly due to several highly toxic elements they contain, including cadmium (Cd). Although Cd content in one sole crab generally exceeds the total weekly recommended intake of cadmium as established by EFSA (especially in brown meat), efficient modern strategies to reduce Cd content in crabs still have not yet been developed. The objective of this research was therefore to evaluate the potential use of ultrasound technology in combination with temperature (50°–80 °C) with the purpose of releasing Cd from brown crab (Cancer pagurus), thereby reducing the Cd content in its meat. Female crabs were immersed in a water bath at 50, 65, and 80 °C in presence or absence of ultrasound; Cd concentration in the water was monitored along time. At the end of the process, Cd content in brown and white crab meat was likewise quantified. Treatment temperature did not bear an influence on the release of Cd in absence of ultrasound, but proved to be an important variable when ultrasound assisted the process. Ultrasound increased Cd release rates 8.7-, 2.1- and 2.7-fold in conjunction with the treatments at 50, 65 and 80 °C, respectively. The maximum percentage of Cd extracted (22.8%) was observed at 50 °C for an ultrasound input power of 200 W. These results have demonstrated for the first time that the application of ultrasound during the crab–cooking process could serve as an effective physical procedure for reducing the Cd content of crabs, thereby improving the product’s safety for consumers.     

微波消解-ICP-AES法测定钒钛矿区优势植物中重金属含量

采用微波消解——电感耦合等离子发射光谱法(ICP-AES)对攀枝花某钒钛矿区十种优势植物地上部分和地下部分中Pb,Zn,Cu,Cr,Cd,Ti等无机元素含量进行了测定。结果表明,该方法相对标准偏差均在5.0%以下,通过加标回收实验,回收率在92.90%-103.85%之间,与传统的方法相比,本法具有较好的准确度和精密度,且灵敏度较高,能同时测量多种元素等优点。     

Electrochemical sensors of heavy metals using novel polymer-modified glassy carbon electrodes

Electroanalytical determination of heavy metals using stripping voltammetry is commonly employed and has many advantages over other methods. The sensitivity of the technique is greatly improved by employing different modified electrodes. Seven novel polymer-modified glassy carbon electrodes have been developed in this investigation for the trace analysis of heavy metals such as zinc, cadmium, lead, arsenic, and copper in formulated samples of waters by square wave stripping voltammetry. Very good responses have been observed for all the metals, while all the modified electrodes employed. The poly(3,4-ethylenedioxythiophene)-modified electrode has resulted in very low limit of detection (LOD) value. Comparison is made between literature results of LOD and the results obtained in this study. An independent atomic absorption spectroscopic analysis of the industrial wastewater sample was carried out and the results compared. The suitability of the method for practical application was ascertained by applying the procedure for the wastewater from a plating industry.     

应用ICP-MS检测不同种植制度土壤中重金属含量

随着社会的发展,人们越来越关心人类活动对环境和食品污染造成的影响。以北京市大兴区不同种植制度的土壤作为实验材料,借助于ICP-MS对土壤中重金属进行了测定,以确定人类活动对土壤生态环境的影响。结果显示,长期种植水果的土壤中和长期小麦玉米轮作的土壤中重金属含量显著高于种植蔬菜的土壤：Cr,Mn,Ni,Cu,Zn,As和Cd以长期种植水果的土壤中含量最高;Ti和Pb以长期小麦玉米轮作的土壤中含量最高,它们甚至高出其他土壤几倍。分析原因除了与人们施用的化肥、灌溉用水有关以外,还与种植果树等作物收获部分较少有关,而种植蔬菜大部分器官都收获,带走了许多重金属。     

Simultaneous adsorption of dyes and heavy metals from multicomponent solutions using fly ash

In wastewaters originating from dye industry there are amounts of dyes (very common methyl orange, methylene blue—MB) and heavy metals (cadmium, copper, nickel mainly from the organo-metallic dyes). They tend to adsorb in a competitive process and modify the substrate. Advanced removal is usually proposed via adsorption and the use of modified fly ash as a substrate is sustainable solution. The main constituents of fly ash (silica, alumina, iron oxide and un-burned carbon), are the priority compounds which favour the heavy metal adsorption and are active sites in dyes’ adsorption processes. The paper studies the effect of MB adsorbed on the fly ash surface on the removal efficiency of cadmium, copper and nickel ionic species from complex, multi-cationic dye solutions. The adsorption efficiency and kinetics are evaluated from the complex, multicomponent systems and possible influences are discussed. High efficiencies are obtained at low heavy metal concentrations (as it is the real case for the dyes industry) whereas at medium values, competitive processes lower the individual efficiencies of copper, nickel or cadmium from mixtures.     

Impact of different ultrasound-assisted processes for preparation of collagen hydrolysates from Asian bullfrog skin on characteristics and antioxidative properties

This study focused on impact of ultrasound-assisted process (UAP) at pre-treatment (UP) and simultaneous treatment (US) during papain hydrolysis for preparing collagen hydrolysate (CH) from Asian bullfrog skin. Ultrasonication times were varied (10, 20, 30 min), and CH prepared using papain hydrolysis without UAP was used as control. Different UAPs provided CH with various hydroxyproline contents, α-amino group contents, surface hydrophobicities, and antioxidative activities. UP at 20 min (UP-20) and US at 30 min (US-30) provided highly antioxidative CHs, which were selected for further studies on their Oxygen reactive absorbance capacity (ORAC) and molecular characteristics. CHs from UP-20 and US-30 had higher ORAC than that of control group (p ≤ 0.05). Slight difference in amino acid composition was detected between samples. Based on these results, molecular characteristic styles, molecular weight profile, antioxidative peptide content, and secondary structure of each sample were obtained. These results indicate that UP and US used varied enzymatic hydrolysis patterns and modified molecular conformation of CH, resulting in enhanced antioxidative activity. Therefore, different UAPs as UP and US could be effectively used in preparation of CH using papain hydrolysis from Asian bullfrog skin, which could improve production process efficiency by enhancing their bioactivity, particularly antioxidative activity.     

Proximal and remote sensing techniques for mapping of soil contamination with heavy metals

Heavy metal soil contamination is a severe environmental problem globally, and its mapping is vital for environmental managers and policymakers to determine its distributions and hotspots. This paper reviewed multiple proximal and remote sensing spectroscopy for convenient and inexpensive method of obtaining soil reflectance spectroscopy or environmental covariates, which can be used for mapping heavy metal soil contamination. Furthermore, spatial prediction using proximal remote-sensed data and environmental covariates was discussed. We suggested that mapping of the spatial distributions of metal species may be important due to the different bioavailabilities and toxicities of various species. The assimilation of multiple proximal/remote-sensed sensors may promote the horizontal and vertical mapping of soil heavy metals. Moreover, combining the advantages of satellite and unmanned aerial vehicle-based hyperspectral imaging systems will facilitate the development of a space–aeronautic incorporation hyperspectral observation technology that can monitor soil environment rapidly and accurately at a large scale.