A combination of ferric nitrate/EDDS-enhanced washing and sludge-derived biochar stabilization of metal-contaminated soils.

In this study, soil washing and stabilization as a two-step soil remediation strategy was performed to remediate Pb- and Cu-contaminated soils from shooting range and railway sites. Ferric nitrate (Fe(NO3)3) and [S,S]-ethylenediamine disuccinate (EDDS) were used as washing agents, whereas three types of sludge-derived biochars and phosphogypsum were employed as soil stabilizers. While Fe(NO3)3 extracted larger amounts of metals compared to EDDS (84% Pb and 64% Cu from shooting range soil; 30% Pb and 40% Cu from railway site soil), it caused severe soil acidification. Both Fe(NO3)3 and EDDS washing enhanced the mobility of residual metals in the two soils, which in most cases could be mitigated by subsequent 2-month stabilization by sludge-derived biochars or phosphogypsum. By contrast, the metal bioaccessibility could only be reduced by soil washing. Nutrient-rich sludge-derived biochar replenished available P and K in both soils, whereas Fe(NO3)3 washing provided available nitrogen (N). Soil amendment enhanced acid phosphatase activity but marginally improved soil dehydrogenase and urease activity in the treated soils, possibly due to the influence of residual metals. This study supported the integration of soil washing (by Fe(NO3)3 or EDDS) with soil stabilization (by sludge-derived biochars or phosphogypsum) for accomplishing the reduction of metal mobility and bioaccessibility, while restoring the environmental quality of the treated soils.

Effects of lead mineralogy on soil washing enhanced by ferric salts as extracting and oxidizing agents.

In this study, we evaluated the feasibility of using ferric salts including FeCl3 and Fe(NO3)3 as extracting and oxidizing agents for a soil washing process to remediate Pb-contaminated soils. We treated various Pb minerals including PbO, PbCO3, Pb3(CO3)2(OH)2, PbSO4, PbS, and Pb5(PO4)3(OH) using ferric salts, and compared our results with those obtained using common washing agents of HCl, HNO3, disodium-ethylenediaminetetra-acetic acid (Na2-EDTA), and citric acid. The use of 50 mM Fe(NO3)3 extracted significantly more Pb (above 96% extraction) from Pb minerals except PbSO4 (below 55% extraction) compared to the other washing agents. In contrast, washing processes using FeCl3 and HCl were not effective for extraction from Pb minerals because of PbCl2 precipitation. Yet, the newly formed PbCl2 could be dissolved by subsequent wash with distilled water under acidic conditions. When applying our washing method to remediate field-contaminated soil from a shooting range that had high concentrations of Pb3(CO3)2(OH)2 and PbCO3, we extracted more Pb (approximately 99% extraction) from the soil using 100 mM Fe(NO3)3 than other washing agents at the same process conditions. Our results show that ferric salts can be alternative washing agents for Pb-contaminated soils in view of their extracting and oxidizing abilities.

Simultaneous application of chemical oxidation and extraction processes is effective at remediating soil Co-contaminated with petroleum and heavy metals.

Chemical extraction and oxidation processes to clean up heavy metals and hydrocarbon from soil have a higher remediation efficiency and take less time than other remediation processes. In batch extraction/oxidation process, 3% hydrogen peroxide (H2O2) and 0.1 M ethylenediaminetetraacetic acid (EDTA) could remove approximately 70% of the petroleum and 60% of the Cu and Pb in the soil, respectively. In particular, petroleum was effectively oxidized by H2O2 without addition of any catalysts through dissolution of Fe oxides in natural soils. Furthermore, heavy metals bound to Fe-Mn oxyhydroxides could be extracted by metal-EDTA as well as Fe-EDTA complexation due to the high affinity of EDTA for metals. However, the strong binding of Fe-EDTA inhibited the oxidation of petroleum in the extraction-oxidation sequential process because Fe was removed during the extraction process with EDTA. The oxidation-extraction sequential process did not significantly enhance the extraction of heavy metals from soil, because a small portion of heavy metals remained bound to organic matter. Overall, simultaneous application of oxidation and extraction processes resulted in highly efficient removal of both contaminants; this approach can be used to remove co-contaminants from soil in a short amount of time at a reasonable cost.

A new approach for remediation of As-contaminated soil: ball mill-based technique.

In this study, a physical ball mill process instead of chemical extraction using toxic chemical agents was applied to remove arsenic (As) from contaminated soil. A statistical analysis was carried out to establish the optimal conditions for ball mill processing. As a result of the statistical analysis, approximately 70% of As was removed from the soil at the following conditions: 5 min, 1.0 cm, 10 rpm, and 5% of operating time, media size, rotational velocity, and soil loading conditions, respectively. A significant amount of As remained in the grinded fine soil after ball mill processing while more than 90% of soil has the original properties to be reused or recycled. As a result, the ball mill process could remove the metals bound strongly to the surface of soil by the surface grinding, which could be applied as a pretreatment before application of chemical extraction to reduce the load.

Enhanced-electrokinetic extraction of heavy metals from dredged harbor sediment.

In this study, the feasibility of an ex situ electrokinetic (EK) process combined with pre-oxidation using hydrogen peroxide (H2O2) and pre-washing using ethylenediaminetetraacetic acid (EDTA) was investigated in enhancing the extraction of Cu, Pb, and Zn from actual dredged harbor sediment. H2O2 pre-oxidation led to a change in the fractionation of Cu bound to organic matter and the sulfide fraction in the Fe-Mn oxides to the exchangeable fraction, but was not effective at removing metals. In contrast, EDTA pre-washing changed the Fe-Mn oxide-bound fractions of Cu and Pb into easily extractable fractions; 20.1, 27.5, and 32.8% of Cu, Pb, and Zn were removed, respectively. During EK treatment, metals were transported toward the anode by electromigration of negatively charged complexes such as metal-EDTA and metal-citrate. However, EK treatment did not significantly enhance the removal of metals because metals accumulated near the anodic region with an increase in the exchangeable fraction due to the short EK operating duration and low voltage gradient. Therefore, it is necessary to extend the EK operating duration and/or increase the voltage gradient for effective transportation and removal of metals from sediment.

Selective recovery of dissolved Fe, Al, Cu, and Zn in acid mine drainage based on modeling to predict precipitation pH.

Mining activities have caused serious environmental problems including acid mine drainage (AMD), the dispersion of mine tailings and dust, and extensive mine waste. In particular, AMD contaminates soil and water downstream of mines and generally contains mainly valuable metals such as Cu, Zn, and Ni as well as Fe and Al. In this study, we investigated the selective recovery of Fe, Al, Cu, Zn, and Ni from AMD. First, the speciation of Fe, Al, Cu, Zn, and Ni as a function of the equilibrium solution pH was simulated by Visual MINTEQ. Based on the simulation results, the predicted pHs for the selective precipitation of Fe, Al, Cu, and Zn/Ni were determined. And recovery yield of metals using simulation is over 99 %. Experiments using artificial AMD based on the simulation results confirmed the selective recovery of Fe, Al, Cu, and Zn/Ni, and the recovery yields of Fe/Al/Cu/Zn and Fe/Al/Cu/Ni mixtures using Na2CO3 were 99.6/86.8/71.9/77.0 % and 99.2/85.7/73.3/86.1 %, respectively. After then, the simulation results were applied to an actual AMD for the selective recovery of metals, and the recovery yields of Fe, Al, Cu, and Zn using NaOH were 97.2, 74.9, 66.9, and 89.7 %, respectively. Based on the results, it was concluded that selective recovery of dissolved metals from AMD is possible by adjusting the solution pH using NaOH or Na2CO3 as neutralizing agents.

Environmental assessment on electrokinetic remediation of multimetal-contaminated site: a case study.

In this study, an environmental assessment on an electrokinetic (EK) system for the remediation of a multimetal-contaminated real site was conducted using a green and sustainable remediation (GSR) tool. The entire EK process was classified into major four phases consisting of remedial investigations (RIs), remedial action construction (RAC), remedial action operation (RAO), and long-term monitoring (LTM) for environmental assessment. The environmental footprints, including greenhouse gas (GHG) emissions, total energy used, air emissions of criteria pollutants, such as NOx, SOx, and PM10, and water consumption, were calculated, and the relative contribution in each phase was analyzed in the environmental assessment. In the RAC phase, the relative contribution of the GHG emissions, total energy used, and PM10 emissions were 77.3, 67.6, and 70.4%, respectively, which were higher than those of the other phases because the material consumption and equipment used for system construction were high. In the RAO phase, the relative contributions of water consumption and NOx and SOx emissions were 94.7, 85.2, and 91.0%, respectively, which were higher than those of the other phases, because the water and electricity consumption required for system operation was high. In the RIs and LTM phases, the environmental footprints were negligible because the material and energy consumption was less. In conclusion, the consumable materials and electrical energy consumption might be very important for GSR in the EK remediation process, because the production of consumable materials and electrical energy consumption highly affects the GHG emissions, total energy used, and air emissions such as NOx and SOx.

Arsenic speciation and bioaccessibility in arsenic-contaminated soils: sequential extraction and mineralogical investigation.

In this study, a combination of sequential extraction and mineralogical investigation by X-ray diffraction and X-ray photoelectron spectroscopy was employed in order to evaluate arsenic solid-state speciation and bioaccessibility in soils highly contaminated with arsenic from mining and smelting. Combination of these techniques indicated that iron oxides and the weathering products of sulfide minerals played an important role in regulating the arsenic retention in the soils. Higher bioaccessibility of arsenic was observed in the following order; i) arsenic bound to amorphous iron oxides (smelter-2), ii) arsenic associated with crystalline iron oxides and arsenic sulfide phase (smelter-1), and iii) arsenic associated with the weathering products of arsenic sulfide minerals, such as scorodite, orpiment, jarosite, and pyrite (mine). Even though the bioaccessibility of arsenic was very low in the mine soil, its environmental impact could be significant due to its high arsenic concentration and mobility.

Selective recovery of Cu, Zn, and Ni from acid mine drainage.

In Korea, the heavy metal pollution from about 1,000 abandoned mines has been a serious environmental issue. Especially, the surface waters, groundwaters, and soils around mines have been contaminated by heavy metals originating from acid mine drainage (AMD) and mine tailings. So far, AMD was considered as a waste stream to be treated to prevent environmental pollutions; however, the stream contains mainly Fe and Al and valuable metals such as Ni, Zn, and Cu. In this study, Visual MINTEQ simulation was carried out to investigate the speciation of heavy metals as functions of pH and neutralizing agents. Based on the simulation, selective pH values were determined to form hydroxide or carbonate precipitates of Cu, Zn, and Ni. Experiments based on the simulation results show that the recovery yield of Zn and Cu were 91 and 94 %, respectively, in a binary mixture of Cu and Zn, while 95 % of Cu and 94 % of Ni were recovered in a binary mixture of Cu and Ni. However, the recovery yield and purity of Zn and Ni were very low because of similar characteristics of Zn and Ni. Therefore, the mixture of Cu and Zn or Cu and Ni could be recovered by selective precipitation via pH adjustment; however, it is impossible to recover selectively Zn and Ni in the mixture of them.