Geochemical evaluation of metals in groundwater at long‐term monitoring sites and active remediation sites

At many sites, long‐term monitoring (LTM) programs include metals as chemicals of concern, although they may not be site‐related contaminants and their detected concentrations may be natural. At other sites, active remediation of organic contaminants in groundwater results in changes to local geochemical conditions that affect metal concentrations. Metals should be carefully considered at both types of sites, even if they are not primary contaminants of concern. Geochemical evaluation can be performed at LTM sites to determine if the monitored metals reflect naturally high background and, hence, can be removed from the analytical program. Geochemical evaluation can also be performed pre‐ and post‐treatment at active remediation sites to document the effects of organics remediation on metals and identify the processes controlling metal concentrations. Examples from both types of sites are presented in this article. © 2008 Wiley Periodicals, Inc.     

Sequestration of metals in carbonated municipal solid waste incineration (MSWI) fly ash

Waste management is in need of a reliable and economical treatment method for metals in fly ashes from municipal solid waste incineration (MSWI). However, no state-of-the-art technique has gained wide acceptance yet. This paper is a synthesis of five elsewhere published investigations covering a project which aimed to assess the possibilities and limitations of adding carbon dioxide (CO2) to fly ash as a stabilization method. Carbonation factors that were studied are the partial pressure of carbon dioxide (CO2), the addition of water, the temperature, and the reaction time. Laboratory experiments were performed applying methods such as factorial experimental design, thermal analysis, scanning electron microscopy (SEM), X-ray diffraction (XRD), and leaching assays including pHstat titration and sequential extraction. Leaching data were verified and complemented using chemical equilibrium calculations. Data evaluation was performed by means of multivariate statistics such as multiple linear regression, principal component analysis (PCA), and partial least squares (PLS) modeling. It was found that carbonation is a good prospect for a stabilization technique especially with respect to the major pollutants lead (Pb) and zinc (Zn). Their mobility decreased with increasing factor levels. Dominating factors were the partial pressure of CO2 and the reaction time, while temperature and the addition of water were of minor influence. However, the treatment caused a mobilization of cadmium (Cd), requiring further research on possible countermeasures such as metal demobilization through enhanced silicate formation.     

Charge-based fractionation of oxyanion-forming metals and metalloids leached from recycled concrete aggregates of different degrees of carbonation: A comparison of laboratory and field leaching tests

The release and charge-based fractionation of As, Cr, Mo, Sb, Se and V were evaluated in leachates generated from recycled concrete aggregates (RCA) in a laboratory and at a field site. The leachates, covering the pH range 8.4-12.6, were generated from non-carbonated, and artificially and naturally carbonated crushed concrete samples. Comparison between the release of the elements from the non-carbonated and carbonated samples indicated higher solubility of the elements from the latter. The laboratory leaching tests also revealed that the solubility of the elements is low at the “natural pH” of the non-carbonated materials and show enhancement when the pH is decreased. The charge-based fractionation of the elements was determined by ion-exchange solid phase extraction (SPE); it was found that all the target elements predominantly existed as anions in both the laboratory and field leachates. The high fraction of the anionic species of the elements in the leachates from the carbonated RCA materials verified the enhanced solubility of the oxyanionic species of the elements as a result of carbonation. The concentrations of the elements in the leachates and SPE effluents were determined by inductively coupled plasma mass spectrometry (ICP-MS).     

Chemical stabilization of medical waste fly ash using chelating agent and phosphates: Heavy metals and ecotoxicity evaluation

Chemical stabilization of heavy metals in medical waste fly ash has been carried out using the following compounds: a chelating agent (Ashnite S803), a commercial acidic phosphoric acid solution (Ashnite R303) as well as basic one (Ashnite R201). In order to predict the leachability of heavy metals, Japanese Leaching Test (JLT-13) procedure was applied to the stabilized fly ash products. An ecotoxicity assessment of the stabilized fly ash products leachate and the unstabilized fly ash leachate was conducted using a battery of bioassays based on lettuce root elongation inhibition, Daphnia magna mortality and Vibrio fischeri photoinhibition. The results showed that the three stabilizing agents were able to significantly decrease (ANOVA, P < 0.05) the concentration of heavy metals in the leachates. Although the leachate from both stabilized and unstabilized fly ash were very toxic to lettuce and daphnids, the incorporation of these stabilizing agents diminished significantly (ANOVA, P < 0.05) the toxicity of the leachates towards the three tested organisms. Pearson correlation analysis was used to analyze the strength of the relationship between chemical elements concentration in the leachate and bioassays results. Most of the heavy metals in the leachate were significantly correlated (ANOVA, P < 0.05) with the toxicity values of the bioassays. However, the correlation was not found between the concentration of dissolved organic carbon (DOC) and the toxicity effect of the leachate to the tested organisms.     

Chemical and biological extraction of metals present in E waste: A hybrid technology

Management of metal pollution associated with E-waste is widespread across the globe. Currently used techniques for the extraction of metals from E-waste by using either chemical or biological leaching have their own limitations. Chemical leaching is much rapid and efficient but has its own environmental consequences, even the future prospects of associated nanoremediation are also uncertain. Biological leaching on the other hand is comparatively a cost effective technique but at the same moment it is time consuming and the complete recovery of the metal, alone by biological leaching is not possible in most of the cases. The current review addresses the individual issues related to chemical and biological extraction techniques and proposes a hybrid-methodology which incorporates both, along with safer chemicals and compatible microbes for better and efficient extraction of metals from the E-waste.     

Impact of moisture on volatility of heavy metals in municipal solid waste incinerated in a laboratory scale simulated incinerator

In this work, the impact of moisture on the volatility of heavy metals present in municipal solid wastes (MSW) in a laboratory scale simulated incinerator was studied, using synthetic waste consisting of 5.4 g of wood powder, 2.6 g lava, 1.9 polythene, 0.19 g polyvinyl chloride, and a given quantity of water and heavy metals represented by lead, zinc and copper in forms of metallic, chlorides and oxides. It is found that the presence of high moisture in MSW will greatly reduce the volatilization of heavy metals in MSW in the incineration process. The volatilization behavior of chlorides, oxides and the metallic species with respect to the effect of moistures is quite different. For copper, the presence of moisture in MSW depresses the volatilization of oxides, and increases that of chloride and the metallic species, while in contrast, the volatilization of both lead and zinc is always depressed by the presence of moisture in MSW, regardless of the chemical forms used. The chemical mechanisms, which govern the volatilization behaviors of different chemical forms in the incineration process, are proposed. Hydrolysis, dewatering of hydrolyzed species, sublimation, chemical transformation of less volatiles to more volatiles or reverse, may participate in and affect the volatilization of heavy metals in MSW.     

A comparison of refuse attenuation in laboratory and field scale lysimeters

For this study, small and middle scale laboratory lysimeters, and a large scale field lysimeter in situ in Shanghai Refuse Landfill, with refuse weights of 187,600 and 10,800,000 kg, respectively, were created. These lysimeters are compared in terms of leachate quality (pH, concentrations of COD, BOD and NH3-N), refuse composition (biodegradable matter and volatile solid) and surface settlement for a monitoring period of 0-300 days. The objectives of this study were to explore both the similarities and disparities between laboratory and field scale lysimeters, and to compare degradation behaviors of refuse at the intensive reaction phase in the different scale lysimeters. Quantitative relationships of leachate quality and refuse composition with placement time show that degradation behaviors of refuse seem to depend heavily on the scales of the lysimeters and the parameters of concern, especially in the starting period of 0-6 months. However, some similarities exist between laboratory and field lysimeters after 4-6 months of placement because COD and BOD concentrations in leachate in the field lysimeter decrease regularly in a parallel pattern with those in the laboratory lysimeters. NH3-N, volatile solid (VS) and biodegradable matter (BDM) also gradually decrease in parallel in this intensive reaction phase for all scale lysimeters as refuse ages. Though the concrete data are different among the different scale lysimeters, it may be considered that laboratory lysimeters with sufficient scale are basically applicable for a rough simulation of a real landfill, especially for illustrating the degradation pattern and mechanism. Settlement of refuse surface is roughly proportional to the initial refuse height.     

Fate of heavy metals and radioactive metals in gasification of sewage sludge

The fates of radioactive cadmium, strontium, cesium, cobalt, arsenic, mercury, zinc, and copper spiked into sewage sludge were determined when the sludge was gasified by a process that maximizes production of char from the sludge (ChemChar process). For the most part the metals were retained in the char product in the gasifier. Small, but measurable quantities of arsenic were mobilized by gasification and slightly more than 1% of the arsenic was detected in the effluent gas. Mercury was largely mobilized from the solids in the gasifier, but most of the mercury was retained in a filter composed of char prepared from the sludge. The small amounts of mercury leaving the gasification system were found to be associated with an aerosol product generated during gasification. The metals retained in the char product of gasification were only partially leachable with 50% concentrated nitric acid.     

Composting in small laboratory pilots: performance and reproducibility

Small-scale reactors (<10 l) have been employed in composting research, but few attempts have assessed the performance of composting considering the transformations of organic matter. Moreover, composting at small scales is often performed by imposing a fixed temperature, thus creating artificial conditions, and the reproducibility of composting has rarely been reported. The objectives of this study are to design an innovative small-scale composting device safeguarding self-heating to drive the composting process and to assess the performance and reproducibility of composting in small-scale pilots. The experimental setup included six 4-l reactors used for composting a mixture of sewage sludge and green wastes. The performance of the process was assessed by monitoring the temperature, O₂ consumption and CO₂ emissions, and characterising the biochemical evolution of organic matter. A good reproducibility was found for the six replicates with coefficients of variation for all parameters generally lower than 19%. An intense self-heating ensured the existence of a spontaneous thermophilic phase in all reactors. The average loss of total organic matter (TOM) was 46% of the initial content. Compared to the initial mixture, the hot water soluble fraction decreased by 62%, the hemicellulose-like fraction by 68%, the cellulose-like fraction by 50% and the lignin-like fractions by 12% in the final compost. The TOM losses, compost stabilisation and evolution of the biochemical fractions were similar to observed in large reactors or on-site experiments, excluding the lignin degradation, which was less important than in full-scale systems. The reproducibility of the process and the quality of the final compost make it possible to propose the use of this experimental device for research requiring a mass reduction of the initial composted waste mixtures.     

On-site analytical support: A cost-effective alternative to fixed laboratory services

Two recent projects involving soils remediation at Superfund sites in southern New Jersey and northeastern Pennsylvania exemplify the power of “real time” field analytical support in reducing time and expense during a project's remedial phase. The remediation efforts at both of these CERCLA sites were supported by ERM-FAST on-site analytical facilities which, in a “real-time” scenario, achieved all data quality objectives (DQOs), met all regulatory agency requirements, and satisfied the client's needs. Both of these sites offer illustrations of the effectiveness of field analysis for vastly differing site contaminants. The client benefited from substantial savings on analytical cost as well as the savings realized through efficient and effective process and schedule management.     

Characterizing soils contaminated with heavy metals: A uranium contamination case study

To stem rising remediation costs for soils contaminated with hazardous metals, increased emphasis is being placed on the development of in-situ and ex-situ treatment technologies. Often, a lack of basic information on the chemical and physical characteristics of the soil and contaminants hampers treatability studies used to design these technologies. This article proposes and demonstrates a characterization program to meet these information needs, employing standard analytical techniques coupled with advanced spectroscopy and microscopy techniques. To support treatments involving physical separation strategies, the program uses standard analytical techniques to characterize the soil and the association of contaminants with different soil fractions (e.g., size and density fractions). Where chemical treatments are required, spectroscopy and microscopy methods are employed to yield quantitative information on the oxidation state and speciation of the contaminant. Examples demonstrate the use of measured soil and contaminant characteristics in the screening of alternative treatment technologies and in the selection of soils for use in treatability studies. Also demonstrated is the use of these characterization tools in the design and optimization of treatment strategies and in support of risk assessment determinations.     

An overview on the processes and technologies for recycling cathodic active materials from spent lithium-ion batteries

This paper aims to make an overview on the current status and new tendency for recycling cathodic active materials from spent lithium-ion batteries. Firstly, it introduces several kinds of pretreatment technologies, followed by the summary of all kinds of single recycling processes mainly focusing on organic acid leaching and synergistic extraction. Then, several examples of typical combined processes and industrial recycling processes are presented in detail. Meanwhile, the advantages, disadvantages and prospect of each single process, combined process, as well as industrial recycling processes, are discussed. Finally, based on a novel acidic organic solvent, the authors briefly introduce an environmental friendly process to directly recycle and resynthesize cathodic active material LiNi_1/3Co_1/3Mn_1/3O₂ from spent lithium-ion batteries. The preliminary experimental results demonstrated the advantages of low reaction temperature, high separation efficiency and organic solvent cycling and preventing secondary pollution to the environment. This process may be used for large-scale recycling of spent lithium-ion batteries after further study.     

A study of heavy metals and their fate in the composting of tannery sludge

Tannery waste is categorized as toxic and hazardous in Malaysia due to its high content of Cr (in excess of 500 mg/kg) and other heavy metals. Heavy metals, when in high enough concentrations, have the potential to be both phytotoxic and zootoxic. Heavy metals are found as contaminants in tannery sludge. This investigation aimed to identify the fate of chromium, cadmium, copper, lead, and zinc concentrations in tannery sludge throughout a 50-day composting cycle. The results of this study showed a general increase in the removal of Cr, Cd, Pb, and to a much smaller extent Zn and Cu, manifested by a decrease in their overall concentrations within the solid fraction of the final product (the decreases were likely the result of leaching). Furthermore, in using a sequential extraction method for sludge composting at different phases of treatment, a large proportion of the heavy metals were found to be associated to the residual fraction (70-80%) and fractions more resistant to extraction, X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of the metals were bound to bioavailable fractions X-(KNO3+H2O).     

Environmental effects of heavy metals derived from the e-waste recycling activities in China: A systematic review

As the world’s leading manufacturing country, China has become the largest dumping ground for e-waste, resulting in serious pollution of heavy metals in China. This study reviews recent studies on environmental effects of heavy metals from the e-waste recycling sites in China, especially Taizhou, Guiyu, and Longtang. The intensive uncontrolled processing of e-waste in China has resulted in the release of large amounts of heavy metals in the local environment, and caused high concentrations of metals to be present in the surrounding air, dust, soils, sediments and plants. Though the pollution of many heavy metals was investigated in the relevant researches, the four kinds of heavy metals (Cu, Pb, Cd and Cr) from e-waste recycling processes attracted more attention. The exceedance of various national and international standards imposed negative effects to the environment, which made the local residents face with the serious heavy metal exposure. In order to protect the environment and human health, there is an urgent need to control and monitor the informal e-waste recycling operations.     

Field and laboratory evaluation of the treatment of DNAPL source zones using emulsified zero‐valent iron

Emulsified zero‐valent iron (EZVI) is a surfactant‐stabilized, biodegradable emulsion that forms droplets consisting of a liquid‐oil membrane surrounding zero‐valent iron (ZVI) particles in water. This article summarizes the results obtained during the first field‐scale deployment of EZVI at NASA's Launch Complex 34 (LC34) located on Cape Canaveral Air Force Station, Florida, in August 2002 and presents the results of recent follow‐on laboratory tests evaluating the mechanisms, which contribute to the performance of the technology. The field‐scale demonstration evaluated the performance of EZVI containing nanoscale zero‐valent iron (NZVI) when applied to dense, nonaqueous phase liquid (DNAPL) trichloroethylene (TCE) in the saturated zone. Results of the field demonstration indicate substantial reductions in TCE soil concentrations (greater than 80 percent) at all but two soil boring locations and significant reductions in TCE groundwater concentrations (e.g., 60 percent to 100 percent) at all depths targeted with EZVI. Laboratory tests conducted in 2005 suggest that both NZVI particles and EZVI containing NZVI can provide significant reductions in TCE mass when used to treat TCE DNAPL in small test reactors. However, EZVI was able to reduce TCE concentrations to lower levels than were obtained with NZVI alone, likely as a result of the combined impact of sequestration of the TCE into the oil phase and degradation of the TCE with the NZVI. © 2006 Wiley Periodicals, Inc.     

Heavy metals in source-separated compost and digestates

The production of compost and digestate from source-separated organic residues is well established in Europe. However, these products may be a source of pollutants when applied to soils. In order to assess this issue, composts, solid and liquid digestates from Switzerland were analyzed for heavy metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) addressing factors which may influence the concentration levels: the treatment process, the composition, origin, particle size and impurity content of input materials, the season of input materials collection or the degree of organic matter degradation.Composts (n = 81) showed mean contents being at 60% or less of the legal threshold values. Solid digestates (n = 20) had 20–50% lower values for Cd, Co, Pb and Zn but similar values for Cr, Cu and Ni. Liquid digestates (n = 5) exhibited mean concentrations which were approximately twice the values measured in compost for most elements. Statistical analyses did not reveal clear relationships between influencing factors and heavy metal contents. This suggests that the contamination was rather driven by factors not addressed in the present study.According to mass balance calculations related to Switzerland, the annual loads to agricultural soils resulting from the application of compost and digestates ranged between 2% (Cd) and 22% (Pb) of total heavy metal loads. At regional scale, composts and digestates are therefore minor sources of pollution compared to manure (Co, Cu, Ni, Zn), mineral fertilizer (Cd, Cr) and aerial deposition (Pb). However, for individual fields, fertilization with compost or digestates results in higher heavy metal loads than application of equivalent nutrient inputs through manure or mineral fertilizer.     

A laboratory study on the MSW mechanical behavior in triaxial apparatus

Shear strength characterization of MSW materials is a mandatory task when performing analyses related to landfill design and landfill geometry improvements. Despite the considerable amount of research focusing on MSW mechanical behavior there remain certain aspects which are not completely understood and deserve attention in particular the case of the undrained behavior of MSW. This paper presents the results of a comprehensive laboratory testing program using a large-scale triaxial apparatus at the Federal University of Bahia, Salvador, Brazil. The effect of factors such as confining pressure, unit weight, fiber content, rate of loading and over-consolidation on the MSW mechanical response were investigated. Tested samples presented typical MSW shear/strain curves (concave upward) in all the tests, despite the pore water pressure reaching levels almost equal to the confining pressure. The obtained results show that increasing confining stress, unit weight, loading rate, fiber content and over-consolidation lead to an increase in the MSW shear strength. The importance of the fibrous components in the waste behavior is highlighted and graphs showing the variation of the MSW shear strength with fiber content in different drainage conditions are shown. The authors believe these results could be of interest to many companies, especially considering the new trend of plastic material recycling (prior landfilling) for energy recovery purposes.     

重金属在碱渣层中的分布及形态研究

采用自制动态吸附柱考察了碱渣层对重金属离子(Cu2+、Zn2+和Cd2+)的吸附截留能力.实验结果表明,在高浓度和高水力负荷条件下,碱渣对Cu2+、Zn2+和Cd2+的最大吸附量分别可达194.451,24.245,11.036 mg/g,穿透时间均达 60 h 以上,饱和吸附时间超过 80 h.通过 Testier ...     

Treatment of mercury‐contaminated soils with activated carbon: A laboratory,field, and modeling study

A series of laboratory batch leaching tests was conducted to evaluate the performance of different activated carbons in stabilizing mercury in soils. Based on the results of these experiments, an amendment application rate of 5 percent powdered activated carbon (PAC) was selected for in situ field application at a former industrial facility. A geochemical model was also developed to simulate the interactions between mercury and activated carbon in vadose‐zone soils. Modeling was used to (1) better understand possible mercury sequestration mechanisms and (2) predict the in situ performance of PAC. Model results indicate dissolved mercury concentrations observed in batch tests are consistent with equilibrium partitioning of mercury between dissolved organic matter, soil organic matter, and PAC. Activated carbon is predicted to reduce dissolved mercury concentrations via two mechanisms: (1) the formation of stable mercury complexes on PAC surfaces and (2) the direct adsorption of dissolved organic matter that would otherwise be available for mercury dissolution. Study results demonstrate PAC effectiveness for site soils with mercury concentrations below 200 mg/kg. © 2010 Wiley Periodicals, Inc.