Application of eggshell waste for the immobilization of cadmium and lead in a contaminated soil

Liming materials have been used to immobilize heavy metals in contaminated soils. However, no studies have evaluated the use of eggshell waste as a source of calcium carbonate (CaCO₃) to immobilize both cadmium (Cd) and lead (Pb) in soils. This study was conducted to evaluate the effectiveness of eggshell waste on the immobilization of Cd and Pb and to determine the metal availability following various single extraction techniques. Incubation experiments were conducted by mixing 0–5% powdered eggshell waste and curing the soil (1,246 mg Pb kg^?1 soil and 17 mg Cd kg^?1 soil) for 30 days. Five extractants, 0.01 M calcium chloride (CaCl₂), 1 M CaCl₂, 0.1 M hydrochloric acid (HCl), 0.43 M acetic acid (CH₃COOH), and 0.05 M ethylendiaminetetraacetic acid (EDTA), were used to determine the extractability of Cd and Pb following treatments with CaCO₃ and eggshell waste. Generally, the extractability of Cd and Pb in the soils decreased in response to treatments with CaCO₃ and eggshell waste, regardless of extractant. Using CaCl₂ extraction, the lowest Cd concentration was achieved upon both CaCO₃ and eggshell waste treatments, while the lowest Pb concentration was observed using HCl extraction. The highest amount of immobilized Cd and Pb was extracted by CH₃COOH or EDTA in soils treated with CaCO₃ and eggshell waste, indicating that remobilization of Cd and Pb may occur under acidic conditions. Based on the findings obtained, eggshell waste can be used as an alternative to CaCO₃ for the immobilization of heavy metals in soils.     

Longevity of organic layers of vertical flow ponds for sulfate reduction in treating mine drainages in South Korea

This study was carried out to evaluate longevity of available organic materials used for sulfate-reducing bacteria (SRB) activity in vertical flow ponds (VFPs) to treat mine drainage in South Korea. Spent mushroom compost samples (SMC) were tested as substrates in VFPs and analyzed for total organic carbon in VFPs, and were collected to analyze total organic carbon (TOC), T-N, T-P, K, metals and residual cellulose to check the longevity assessment. Chemical analysis revealed that the average contents of Fe, Al and Mn in SMC of VFPs were 19,907, 32,137 and 434 mg/kg, respectively. The contents of Fe and Al in SMC of VFPs were much higher than those of the unused SMC (control), but to the contrary, those of Mn showed a reversed tendency. Average TOC content of the controls was 64.19% but in one of the VFP substrates was as low as 15.92%. This might be resulted from SRB consumed the available organic carbon in SMC as VFPs system aged. Contents of T-N in VFPs tended to decrease as VFPs aged. The residual cellulose ranged from 3.88 to 6.72% (g/g). There existed a negative relationship between residual cellulose contents and ages of VFPs. Assuming that SMC in all VFPs had similar compositions when the VFPs were initially established, trend analysis predicted that the amount of carbon source for SRB might be available for 12–15 years further, depending on VFPs.

     

Chemically modified biochar produced from conocarpus waste increases NO<Subscript>3</Subscript> removal from aqueous solutions

Biochar has emerged as a universal sorbent for the removal of contaminants from water and soil. However, its efficiency is lower than that of commercially available sorbents. Engineering biochar by chemical modification may improve its sorption efficiency. In this study, conocarpus green waste was chemically modified with magnesium and iron oxides and then subjected to thermal pyrolysis to produce biochar. These chemically modified biochars were tested for NO₃ removal efficiency from aqueous solutions in batch sorption isothermal and kinetic experiments. The results revealed that MgO-biochar outperformed other biochars with a maximum NO₃ sorption capacity of 45.36 mmol kg^?1 predicted by the Langmuir sorption model. The kinetics data were well described by the Type 1 pseudo-second-order model, indicating chemisorption as the dominating mechanism of NO₃ sorption onto biochars. Greater efficiency of MgO-biochar was related to its high specific surface area (391.8 m² g^?1) and formation of strong ionic complexes with NO₃. At an initial pH of 2, more than 89 % NO₃ removal efficiency was observed for all of the biochars. We conclude that chemical modification can alter the surface chemistry of biochar, thereby leading to enhanced sorption capacity compared with simple biochar.     

Stabilization of lead and copper contaminated firing range soil using calcined oyster shells and fly ash

A stabilization/solidification treatment scheme was devised to stabilize Pb and Cu contaminated soil from a firing range using renewable waste resources as additives, namely waste oyster shells (WOS) and fly ash (FA). The WOS, serving as the primary stabilizing agent, was pre-treated at a high temperature to activate quicklime from calcite. Class C FA was used as a secondary additive along with the calcined oyster shells (COS). The effectiveness of the treatment was evaluated by means of the toxicity characteristic leaching procedure (TCLP) and the 0.1 M HCl extraction tests following a curing period of 28 days. The combined treatment with 10 wt% COS and 5 wt% FA cause a significant reduction in Pb (>98 %) and Cu (>96 %) leachability which was indicated by the results from both extraction tests (TCLP and 0.1 M HCl). Scanning electron microscopy–energy dispersive X-ray spectroscopy (SEM–EDX) analyses are used to investigate the mechanism responsible for Pb and Cu stabilization. SEM–EDX results indicate that effective Pb and Cu immobilization using the combined COS–FA treatment is most probably associated with ettringite and pozzolanic reaction products. The treatment results suggest that the combined COS–FA treatment is a cost effective method for the stabilization of firing range soil.     

Effects of carbon nanotube and biochar on bioavailability of Pb,Cu and Sb in multi-metal contaminated soil

This study examined the effects of carbon nanotube and biochar on the bioavailability of Pb, Cu and Sb in the shooting range soils for developing low-cost remediation technology. Commercially available multi-walled carbon nanotube (MWCNT) and biochar pyrolyzed from soybean stover at 300 °C (BC) at 0.5, 1 and 2.5% (w w^?1) were used to remediate the contaminated soil in an incubation experiment. Both DTPA (bioavailable) and TCLP (leaching) extraction procedures were used to compare the metal/loid availability and leaching by the amendments in soil. The addition of BC was more effective in immobilizing mobile Pb and Cu in the soil than that in MWCNT. The BC reduced the concentrations of Pb and Cu in the soil by 17.6 and 16.2%, respectively. However, both MWCNTs and BC increased Sb bioavailability by 1.4-fold and 1.6-fold, respectively, in DTPA extraction, compared to the control. The toxicity characteristic leaching procedure (TCLP) test showed that the leachability of Pb in the soil amended with 2.5% MWCNT was 1.3-fold higher than that the unamended soil, whereas the BC at 2.5% decreased the TCLP-extractable Pb by 19.2%. Precipitation and adsorption via electrostatic and π–π electron donor–acceptor interactions were postulated to be involved in the interactions of Pb and Cu with surfaces of the BC in the amended soils, whereas ion exchange mechanisms might be involved in the immobilization of Cu in the MWCNT-amended soils. The application of BC derived from soybean stover can be a low-cost technology for simultaneously immobilizing bioavailable Pb and Cu in the shooting range soils; however, neither of amendments was effective in Sb immobilization.     

Impact of natural and calcined starfish (<Emphasis Type="Italic">Asterina pectinifera</Emphasis>) on the stabilization of Pb,Zn and As in contaminated agricultural soil

Metal stabilization using soil amendments is an extensively applied, economically viable and environmentally friendly remediation technique. The stabilization of Pb, Zn and As in contaminated soils was evaluated using natural starfish (NSF) and calcined starfish (CSF) wastes at different application rates (0, 2.5, 5.0 and 10.0 wt%). An incubation study was conducted over 14 months, and the efficiency of stabilization for Pb, Zn and As in soil was evaluated by the toxicity characteristic leaching procedure (TCLP) test. The TCLP-extractable Pb was reduced by 76.3–100 and 91.2–100 % in soil treated with NSF and CSF, respectively. The TCLP-extractable Zn was also reduced by 89.8–100 and 93.2–100 % in soil treated with NSF and CSF, respectively. These reductions could be associated with the increased metal adsorption and the formation of insoluble metal precipitates due to increased soil pH following application of the amendments. However, the TCLP-extractable As was increased in the soil treated with NSF, possibly due to the competitive adsorption of phosphorous. In contrast, the TCLP-extractable As in the 10 % CSF treatment was not detectable because insoluble Ca–As compounds might be formed at high pH values. Thermodynamic modeling by visual MINTEQ predicted the formation of ettringite (Ca₆Al₂(SO₄)₃(OH)₁₂·26H₂O) and portlandite (Ca(OH)₂) in the 10 % CSF-treated soil, while SEM–EDS analysis confirmed the needle-like structure of ettringite in which Pb was incorporated and stabilized in the 10 % CSF treatment.     

Effect of biosolid hydrochar on toxicity to earthworms and brine shrimp

The hydrothermal carbonization of sewage sludge has been studied as an alternative technique for the conversion of sewage sludge into value-added products, such as soil amendments. We tested the toxicity of biosolid hydrochar (Sewchar) to earthworms. Additionally, the toxicity of Sewchar process water filtrate with and without pH adjustment was assessed, using brine shrimps as a model organism. For a Sewchar application of 40 Mg ha^?1, the earthworms significantly preferred the side of the vessel with the reference soil (control) over side of the vessel with the Sewchar treatments. There was no acute toxicity of Sewchar to earthworms within the studied concentration range (up to 80 Mg ha^?1). Regarding the Sewchar process water filtrate, the median lethal concentration (LC50) to the shrimps was 8.1% for the treatments in which the pH was not adjusted and 54.8% for the treatments in which the pH was adjusted to 8.5. The lethality to the shrimps significantly increased as the amount of Sewchar process water filtrate increased. In the future, specific toxic substances in Sewchar and its process water filtrate, as well as their interactions with soil properties and their impacts on organisms, should be elucidated. Additionally, it should be identified whether the amount of the toxic compounds satisfies the corresponding legal requirements for the safe application of Sewchar and its process water filtrate.     

Satellite observations of Mexico City pollution outflow from the Tropospheric Emissions Spectrometer (TES)

Concurrent tropospheric O₃ and CO vertical profiles from the Tropospheric Emission Spectrometer (TES) during the MILAGRO/INTEX-B aircraft campaigns over the Mexico City Metropolitan Area (MCMA) and its surrounding regions were used to examine Mexico City pollution outflow on a regional scale. The pollution outflow from the MCMA occurred predominantly at 600–800 hPa as evident in O₃, CO, and NO_x enhancements in the in situ aircraft observations. TES O₃ and CO are sensitive to the MCMA pollution outflow due to their relatively high sensitivities at 600–800 hPa. We examined O₃, CO, and their correlation at 600–800 hPa from TES retrievals, aircraft measurements, and GEOS-Chem model results. TES captures much of the spatial and day-to-day variability of O₃ seen in the in situ data. TES CO, however, shows much less spatial and day-to-day variability compared with the in situ observations. The ΔO₃/ΔCO slope is significantly higher in the TES data (0.43) than the in situ data (0.28) due partly to the lack of variability in TES CO. Extraordinarily high ΔO₃/ΔCO slope (0.81) from TES observations at 618 hPa over the Eastern U.S. was previously reported by Zhang et al. [Zhang, L., Jacob, D.J., Bowman, K.W., et al., 2006. Ozone–CO correlations determined by the TES satellite instrument in continental outflow regions. Geophys. Res. Lett. 33, L18804. 10.1029/2006GL026399.]. Thus the application of TES CO–O₃ correlation to map continental pollution outflow needs further examination.     

Overview of surface ozone variability in East Asia-North Pacific region during IGAC/APARE(1994—1996)

IntroductionDuringthelastdecade ,theEastAsiancontinentalrimregionhasbeencharacterizedbyhighanthropogenicemissionsduetotherapidindustrialization .Airpollutioninthisregionhascreatedmuchattentiontothescientistsovertheworld(Kato,1992 ;Akimoto ,1994a ;Aardenne…     

Formation of disinfection by-products in chlorinated swimming pool water.

The formation of five volatile disinfection by-products (DBPs: chloroform, bromodichloromethane, chloral hydrate, dichloroacetonitrile, and 1,1,1-trichloropropanone) by the chlorination of the materials of human origin (MHOs: hair, lotion, saliva, skin, and urine) in a swimming pool model system was examined. Chlorination reactions took place with a sufficient supply of chlorine residuals (0.84 mg Cl2/l < total chlorine < 6.0 mg Cl2/l) in 300 ml glass bottles containing either ground water or surface water as a reaction medium at 30 degrees C and pH 7.0, for either 24 or 72 h. A longer reaction period of 72 h or a higher content of organic materials led to the increased formation of DBPs. Of the DBPs formed by the reaction, chloroform was a major compound found in both ground and surface waters. The formation of chloroform and bromodichloromethane per unit total organic carbon (TOC) concentration was suppressed when all types of MHOs were added to the surface water that already contained DBP precursors such as humic substances. However, the formation of dichloroacetonitrile was promoted, probably due to the increased degradation reactions of nitrogen-containing compounds such as urea and proteins of human origin. In conclusion, the materials of swimmers' origin including hair, lotion, saliva, skin, and urine add to the levels of DBPs in swimming pool water, and any mitigation measures such as periodic change of water are needed to protect swimmers from elevated exposures to these compounds.