Case study: Using soil washing/leaching for the removal of heavy metal at the twin cities army ammunition plant

COGNIS TERRAMET® soil leaching and Bescorp soil washing systems have been successfully combined to remediate an ammunition test burn area at the Twin Cities Army Ammunition Plant (TCAAP), New Brighton, Minnesota. This cleanup is the first in the country to successfully combine these two technologies, and it offers a permanent solution to heavy metal remediation. Over 20,000 tons of soil were treated in the project. The cleaned soil remained on-site, and the heavy metal contaminants were removed, recovered, and recycled. Eight heavy metals were removed from the contaminated soil achieving the very stringent cleanup criteria of <175 ppm for residual lead and achieving background concentrations for seven other project metals (antimony, cadmium, chromium, copper, mercury, nickel, and silver). Initial contaminant levels were measured as high as 86,000 ppm lead and 100,000 ppm copper, with average concentrations over 1,600 ppm each. In addition, both live and spent ordnance were removed in the soil treatment plant to meet the cleanup criteria. By combining soil washing and leaching, COGNIS and Bescorp were able to assemble a process which effectively treats all the soil fractions so that all soil material can be returned on-site, no wastewater is generated, and the heavy metals are recovered and recycled. No hazardous waste requiring landfill disposal was generated during the entire remedial operation.     

Effects of Decreased Atmospheric Heavy Metal Deposition in South Sweden on Terrestrial Birds and Small Mammals in Natural Populations

In southern Sweden, where exposure to long range distributedheavy metals is about the highest in Scandinavia, depositionsof cadmium (Cd) and lead (Pb) decreased about 20 and 70%,respectively, between mid-1980s and mid-1990s, as estimated bytheir concentrations in moss. Concentrations of Cd and Pb in tissues of the pied flycatcher (Ficedula hypoleuca) and bank vole (Clethrionomys glareolus) were also lower in 1996and 1997 compared to 1981 and 1982. It is concluded that the decreased deposition rate of these elements in southern Sweden had caused decreased exposure, and thus also to decreased potential risk of detrimental effects on insectivorous birds andherbivorous mammals. There was no indication that breeding results of pied flycatcher was influenced by the decreased deposition of toxic metals.     

Comparison of leaching characteristics of heavy metals from bottom and fly ashes in Korea and Japan

The objective of this research was to compare the leaching characteristics of heavy metals such as cadmium, chromium, copper, nickel, lead, etc., in Korean and Japanese municipal solid waste incineration (MSWI) ash. The rate of leaching of heavy metal was measured by KSLT and JTL-13, and the amount of heavy metals leached was compared with the metal content in each waste component. Finally, bio-availability testing was performed to assess the risks associated with heavy metals leached from bottom ash and fly ash. From the results, the value of neutralization ability in Japanese fly ash was four times higher than that in Korean fly ash. The reason was the difference in the content of Ca(OH)(2) in fly ash. The amount of lead leached exceeded the regulatory level in both Japanese and Korean fly ash. The rate of leaching was relatively low in ash with a pH in the range of 6-10. The bio-availability test in fly ash demonstrated that the amount of heavy metals leached was Pb>Cd>Cr, but the order was changed to Pb>Cr>Cd in the bottom ash. The leaching concentration of lead exceeded the Japanese risk level in all fly ashes from the two countries, but the leaching concentration of cadmium exceeded the regulatory level in Korean fly ash only.     

An analysis of the composition and metal contamination of plastics from waste electrical and electronic equipment (WEEE)

The compositions of three WEEE plastic batches of different origin were investigated using infrared spectroscopy, and the metal content was determined with inductively coupled plasma. The composition analysis of the plastics was based mainly on 14 samples collected from a real waste stream, and showed that the major constituents were high impact polystyrene (42 wt%), acrylonitrile–butadiene–styrene copolymer (38 wt%) and polypropylene (10 wt%). Their respective standard deviations were 21.4%, 16.5% and 60.7%, indicating a considerable variation even within a single batch. The level of metal particle contamination was found to be low in all samples, whereas wood contamination and rubber contamination were found to be about 1 wt% each in most samples. In the metal content analysis, iron was detected at levels up to 700 ppm in the recyclable waste plastics fraction, which is of concern due to its potential to catalyse redox reactions during melt processing and thus accelerate the degradation of plastics during recycling. Toxic metals were found only at very low concentrations, with the exception of lead and cadmium which could be detected at 200 ppm and 70 ppm levels, respectively, but these values are below the current threshold limits of 1000 ppm and 100 ppm set by the Restriction of Hazardous Substances directive.     

Treatment of mixed contamination in water using cyclodextrin‐based materials

This study investigated the effectiveness of a cyclodextrin‐based solid material for the removal of mixed dissolved contaminants. The solid material was prepared by condensation of α‐cyclodextrin. The removal efficiency was found to be 70 percent for total heavy metals (cadmium, lead, chromium, iron, nickel, cobalt, and mercury) to 98 percent for polychlorinated biphenyls (PCBs). The optimum pH for heavy metal removal was approximately 5 and for PCBs it was in the range of 5–7. All of these heavy metals were successfully recovered from the spent cyclodextrin‐based material using nitric acid, allowing the material to be reused for further passes. The results also showed that the presence of alkaline and alkaline earth metals did not have a significant effect on the removal efficiency, indicating that the cyclodextrin‐based material could selectively remove the heavy metals of concern without being consumed by alkaline and alkaline‐earth metals. © 2006 Government of Canada.     

Reducing volatilization of heavy metals in phosphate-pretreated municipal solid waste incineration fly ash by forming pyromorphite-like minerals

This research investigated the feasibility of reducing volatilization of heavy metals (lead, zinc and cadmium) in municipal solid waste incineration (MSWI) fly ash by forming pyromorphite-like minerals via phosphate pre-treatment. To evaluate the evaporation characteristics of three heavy metals from phosphate-pretreated MSWI fly ash, volatilization tests have been performed by means of a dedicated apparatus in the 100-1000 °C range. The toxicity characteristic leaching procedure (TCLP) test and BCR sequential extraction procedure were applied to assess phosphate stabilization process. The results showed that the volatilization behavior in phosphate-pretreated MSWI fly ash could be reduced effectively. Pyromorphite-like minerals formed in phosphate-pretreated MSWI fly ash were mainly responsible for the volatilization reduction of heavy metals in MSWI fly ash at higher temperature, due to their chemical fixation and thermal stabilization for heavy metals. The stabilization effects were encouraging for the potential reuse of MSWI fly ash.     

Field trial experiment: Phytoremediation with Salix sp. on a dredged sediment disposal site in Flanders,Belgium

Remediation of heavy metal contamination in soil is a widespread environmental issue. Conventional remediation techniques are invasive and often too expensive, particularly if large areas of soil are contaminated. Phytoremediation is the use of plants to remediate soil and groundwater. Phytoremediation of inorganic comtaminants such as metals can be further catagorized into phytostabilization and phytoextraction. These techniques have gained an increasing amount of attention and research over the last ten years. Phytoextraction of heavy metals and periodical removal of harvestable plant parts results in a gradual decrease of pollutant levels in the top soil. Woody species such as Salix sp. (willow) do not represent the fastest phytoextraction procedure compared to uptake by herbaceous species; however, they offer the added advantage of possible reuse of the produced biomass (wood) for the production of renewable energy. Here we present the results of a field experiment conducted to evaluate the use of Salix to remediate soil contaminated with cadmium and zinc at a dredged sediment disposal site in Flanders, Belgium. © 2003 Wiley Periodicals, Inc.     

Recent applications of phytoremediation technologies

Although the application of microbe biotechnology has been successful with petroleum-based constituents, microbial digestion has met with limited success for widespread residual organic and metal pollutants located above the potentiometric surface. Vegetation-based remediation, on the other hand, shows potential for accumulating, immobilizing, and transforming low levels of persistent contamination from the subsurface. Agricultural bioremediation, called geobotany or phytoremediation, relies on the remediating abilities of contaminant-accumulating plants to remove contamination from soil or groundwater. In natural ecosystems, plants act to filter and metabolize substances generated by nature. Phytoremediation affirmatively applies this process to help clean up contamination created by artificial means. Plants have proven effective at remediating areas contaminated with organic chemical wastes such as petroleum products, solvents, wood preservatives, pesticides, and metals. Phytoremediation is not the best technology for every site but has shown success with lead, cadmium, zinc, and radionuclides. The phytoremediation process takes much longer than conventional methods to clean a site and is dependent upon the type and degree of contamination. Concentrations must be within a narrow range of tolerable levels and the presence of the contamination must be at the appropriate depth. Nevertheless, phytoremediation offers an effective alternative to conventional, engineered remedial plans that usually involve costly activities like excavation, treatment, and disposal of soil or pump-and-treat technologies for groundwater. Phytoremediation also seems to be a promising new technology for the treatment of stormwater, industrial wastewater, and sewage. The relative low costs of capital for start-up together with negligible operations and maintenance costs provide a strong incentive for further investigation and development of phytoremediation projects.     

In situ Remediation of Metals Comes of Age

Since the early 1970s, technologies for remediating organic contamination in soils and groundwater have evolved through three stages with primary emphasis on (1) gross removal processes, (2) active in situ treatment, and (3) risk-based closure and natural attentuation. Technologies for treating metals contamination are evolving through similar stages. In the late 1990s, metals remediation has arrived at the second stage in which a wide range of in situ technologies are available either to extract metals directly from the subsurface or to render them immobile and harmless. In situ geochemical fixation is an example of a commercial technology capable of addressing a wide range of metals contamination sites. Four case histories demonstrate the versatility of this approach. Other promising technologies for treating metals contamination are also emerging. These include geokinetics, biocatalytic precipitation processes, phytoremediation, and artificial wetlands. As our knowledge continues to grow, the most elegant solutions to metals contamination will rely more and more heavily on the soil's natural capacity to stabilize and immobilize metals over time.     

Survey of mercury,cadmium and lead content of household batteries

The objective of this work was to provide updated information on the development of the potential impact of heavy metal containing batteries on municipal waste and battery recycling processes following transposition of the new EU Batteries Directive 2006/66/EC. A representative sample of 146 different types of commercially available dry and button cells as well as lithium-ion accumulators for mobile phones were analysed for their mercury (Hg)-, cadmium (Cd)- and lead (Pb)-contents. The methods used for preparing the cells and analysing the heavy metals Hg, Cd, and Pb were either developed during a former study or newly developed. Several batteries contained higher mass fractions of mercury or cadmium than the EU limits. Only half of the batteries with mercury and/or lead fractions above the marking thresholds were labelled. Alkaline–manganese mono-cells and Li-ion accumulators, on average, contained the lowest heavy metal concentrations, while zinc–carbon batteries, on average, contained the highest levels.     

Effect of chelating agents in phytoremediation of heavy metals

Chelate‐assisted metal uptake by plants has only recently been discovered in the remediation industry. The simultaneous accumulation of lead, arsenic, copper, and cadmium in plants after application of chelating agents to soil is a promising technology enhancement for phytoremediation. One of the most powerful and commonly used chelating agents is ethylene diamine tetra acetic acid (EDTA), which forms complexes with many of the metal contaminants within the natural environment. This study was conducted to determine the efficiency of an emergent wetland plant species Typha sp. and floating wetland macrophytes such as Pistia sp., Azolla sp., Lemna sp., Salvinia sp., and Eichhornia sp. in phytoremediation of various heavy metals with addition of a chelating agent such as EDTA. EDTA addition to the treatment systems increased the uptake of heavy metals by plants, which was much pronounced with lead and copper. However, the pattern of uptake by plants was similar as that of heavy metals without EDTA amendments. © 2012 Wiley Periodicals, Inc.     

Arbuscular mycorrhizal fungi involvement in zinc and cadmium speciation change and phytoaccumulation

Over the past few years, there has been a greater study and understanding of the application of phytoremediation to remediate contaminated soil. The enhancement of phytoaccumulation of heavy metals—zinc (Zn), cadmium (Cd), arsenic (As), and selenium (Se)—in plants has been shown by inoculation of roots using arbuscular mycorrhizal fungi (AMF). This article presents the results of in vitro lab experiments conducted to verify the effects of AMF ( Glomus intraradices) hyphae on speciation of essential Zn and nonessential Cd heavy metals in order to change these metals from a water‐ insoluble carbonate to a soluble and phytoavailable form. Results show that in the presence of heavy metals in a nonavailable form to plants, endomycorrhizal hyphae can change the metal from carbonate to a water‐ soluble species. This phenomenon is more apparent with a nonessential (Cd) than with an essential metal (Zn). Zn saturation is reached in the G. intraradices colonized roots at around 400 ppm, independently of initial ZnCO₃ concentrations. Cd saturation is not reached; in the lower Cd treatment, the plant/media metal ratio is 3:1, and in the higher treatment, the ratio is 1:1. © 2005 Wiley Periodicals, Inc.     

Characteristic of heavy metals in biochar derived from sewage sludge

This study investigates the characteristic of heavy metals (Pb, Zn, Cu, Cd, Cr, Ni and As) in biochar derived from sewage sludge at different pyrolysis temperatures (300, 400, 500, 600 and 700 °C). The heavy metal concentrations, chemical speciation distribution, leaching toxicity, and bio-available contents were investigated using ICP-OES after microwave digestion, a sequential extraction procedure recommended by the Community Bureau of Reference (BCR), an improved nitric acid–sulphuric acid method, and diethylenetriamine pentaacetic acid (DTPA) extraction method, respectively. The results showed that a great percentage of the heavy metals remained in biochar, the concentrations of heavy metals in biochar (except Cd in B7) were higher than that in sludge, and the enrichment of the heavy metals in biochar enhanced with the pyrolysis temperature. Although the effect of pyrolysis temperature on the chemical speciation distribution, the leaching toxicity and the bio-available contents of heavy metals in biochar was inconsistent, the potential risk of biochar on soil and groundwater contamination was lower than sewage sludge.     

Effect of an uncontrolled fire and the subsequent fire fight on the chemical composition of landfill leachate

Landfill leachates sampled during and after an accidental landfill fire were analysed and the levels of selected metals and chemical compounds compared to those occurring in the leachate under normal conditions. The fire at the landfill site was put out by excavation and cooling by use of water. The investigation during the fire and fire fight revealed a moderate increase in the level of nitrogen and also in pH and conductivity. Heavy metals and COD in the leachate showed considerably increased levels. In general, the determined variables appeared to normalise within one week after the fire was extinguished. It can be concluded that landfill fires extinguished by excavation may lead to elevated leachate levels of especially COD and heavy metals, but that this is only a short-term effect.     

Sources of heavy metal contamination in Swedish wood waste used for combustion

In this paper, wood waste (RWW) recovered for heat production in Sweden was studied. Previous research has concluded that RWW contains elevated amounts of heavy metals, causing environmental problems during waste management. This study extends previous work on RWW by analysing which pollution sources cause this contamination. Using existing data on the metal contents in various materials, and the amounts of these materials in RWW, the share of the elevated amounts of metals in RWW that these materials explain was quantified. Six different materials occurring in RWW were studied and the results show that they explain from 70% to 100% of the amounts of arsenic, chromium, lead, copper and zinc in RWW. The most important materials contributing to contamination of RWW are surface-treated wood, industrial preservative-treated wood, plastic and galvanised fastening systems. These findings enable the development and evaluation of strategies aiming to decrease pollution and resource loss from handling RWW. It is argued that source separation and measures taken further downstream from the generation site, such as treatment, need to be combined to substantially decrease the amount of heavy metals in RWW.     

Microbial Activity in Relation to Small Scale Patterns of Heavy Metals and Substrate Quality in Spruce Mor Layers (Of) in Southern Sweden

The within-site correlations between soil respiration rates,lead (Pb), mercury (Hg) and cadmium (Cd) concentrations andorganic matter quality variables were investigated at four sites in southern Sweden. The aim was to study whether the within-site variation in heavy metal concentrations could beused to monitor biological effects of regional deposition of heavy metals. Two sites in the south-west, one in the mid-southof the country, and one in south-east were investigated. At the south-eastern, least contaminated, site there were no correlations between soil respiration rate, and either organicmatter quality variables or heavy metal concentrations. At the remaining sites, negative correlations were found between Pb andsoil respiration rate. However, at two of these three sites there was a covariation with cellulose that could account for these correlations. The within-site variation of pH and total nitrogen (N) was low, and did not show any correlative general trends with either respiration rate or heavy metals. Meta analysis showed that negative correlations between Pb or Hg, on the one hand, and cellulose or hemicellulose on the other weregenerally found in within-site investigations. However, this does not necessarily explain the correlation between Pb and soil respiration, as was shown for the southernmost site. A PLS model of soil respiration rates at this site, using allmeasured variables, including heavy metals, explained more variation than a model developed using only mor layer thickness,pH, carbohydrate, ash and nitrogen concentrations, as independent variables. Thus there is a risk of toxic effects from Pb even at the levels found in south-western Sweden today(>120 g Pb * g dw^-1). However, since the correlationsbetween heavy metals and cellulose were not significantly different at the different sites, random sampling variation could not be ruled out as an explanation of the different results for the different sites. The causes of the correlationbetween organic matter quality and heavy metals have not yet been clarified. Analysis of mor samples incubated in thelaboratory for 2 yr with 1200 g Pb * g dw^-1 or 5 gHg * g dw^-1 did not show any differences in carbohydrate composition, compared to control samples. This shows that within-site studies of correlations between respiration rate and heavy metals have to be combined with studies of metal additions to soils and analysis of organic matter quality beforeany valid conclusions can be made.     

Sorbents for the removal of airborne heavy metals from incinerator effluent

The effectiveness of inorganic alumino-silicate sorbents (alumina and kaolinite) to adsorb airborne lead and cadmium from the effluent stream of a simulated waste incinerator was studied. A 20 kW (68,000 BTU/h) flow reactor was used to achieve the temperature and residence times typical of a waste incinerator. Solutions containing lead or cadmium were introduced yielding airborne metals concentrations between 15 and 150 ppm. Gas samples were drawn into a particle impactor that collected the airborne particles and condensed phase metal aerosols, separating them into ten size ranges from 0.2 μm to greater than 10 μm. Metals to sorbent mass ratios between 0.03 and 1.56 were investigated. Scavenging efficiency increased as the ratio of sorbent to injected metal mass was increased. The scavenging efficiencies were as high as 76% for lead scavenged by kaolinite to as low as 14% for cadmium scavenged by alumina.     

Phytoremediation of zinc and cadmium: A study of arbuscular mycorrhizal hyphae

Arbuscular mycorrhizal fungi (AMF) are microscopic fungi naturally occurring in soil that form a symbiosis with plant roots, producing a highly elaborated hyphal mycelium network in soil.In vitro lab experiments were conducted to determine whether extraradical mycorrhizal hyphae are directly involved in sequestration and uptake of essential zinc and nonessential cadmium by plant roots under toxic concentrations. The research is a continuation of an initial study presented in the Spring 2005 issue of Remediation that focused on the specific role of AMF in the speciation of heavy metals. Thus, this article presents a more expanded view. Results show that zinc and cadmium heavy metals are sequestered and translocated to plant roots via extraradical AMF hyphae. Root/growth media accumulation factors reached 5:1 and 18:1 for zinc and cadmium, respectively. Phytoremediation of heavy metal–contaminated soils can be enhanced by mycorrhizal inoculation. © 2005 Wiley Periodicals, Inc.     

Metal speciation in landfill leachates with a focus on the influence of organic matter

This study characterises the heavy-metal content in leachates collected from eight landfills in France. In order to identify heavy metal occurrence in the different size fractions of leachates, a cascade filtration protocol was applied directly in the field, under a nitrogen gas atmosphere to avoid metal oxidation. The results of analyses performed on the leachates suggest that most of the metals are concentrated in the <30 kDa fraction, while lead, copper and cadmium show an association with larger particles. Initial speciation calculations, without considering metal association with organic matter, suggest that leachate concentrations in lead, copper, nickel and zinc are super-saturated with respect to sulphur phases. Speciation calculations that account for metal complexation with organic matter, considered as fulvic acids based on C1(s) NEXAFS spectroscopy, show that this mechanism is not sufficient to explain such deviation from equilibrium conditions. It is therefore hypothesized that the deviation results also from the influence of biological activity on the kinetics of mineral phase precipitation and dissolution, thus providing a dynamic system. The results of chemical analyses of sampled fluids are compared with speciation calculations and some implications for the assessment of metal mobility and natural attenuation in a context of landfill risk assessment are discussed.