Effect of Stabilized nZVI Nanoparticles on the Reduction and Immobilization of Cr in Contaminated Soil: Column Experiment and Transport Modeling.

Batch and transport experiments were used to investigate the remediation of loamy sand soil contaminated with Cr(VI) using zero-valent iron nanoparticles (nZVI) stabilized by carboxymethylcellulose (CMC-nZVI). The effect of pH, ionic strength (IS), and flow rate on the removal efficiency of Cr(VI) were investigated under equilibrium (uniform transport) and non-equilibrium (two-site sorption) transport using the Hydrus-1D model. The overall removal efficiency ranged from 70 to over 90% based on the chemical characteristics of the CMC-nZVI suspension and the transport conditions. The concentration and pH of the CMC-nZVI suspension had the most significant effect on the removal efficiency and transport of Cr(VI) in the soil. The average removal efficiency of Cr(VI) was increased from 24.1 to 75.5% when the concentration of CMC-nZVI nanoparticles was increased from 10 to 250 mg L-1, mainly because of the increased total surface area at a larger particle concentration. Batch experiments showed that the removal efficiency of Cr(VI) was much larger under acidic conditions. The average removal efficiency of Cr(VI) reached 90.1 and 60.5% at pH 5 and 7, respectively. The two-site sorption model described (r2 = 0.96-0.98) the transport of Cr(VI) in soil quite well as compared to the uniform transport model (r2 = 0.81-0.98). The average retardation of Cr(VI) was 3.51 and 1.61 at pH 5 and 7, respectively, indicating earlier arrival for the breakthrough curves and a shorter time to reach maximum relative concentration at lower pH. The methodology presented in this study, combining column experiment and modeling transport using the Hydrus-1D model, successfully assessed the removal of Cr(VI) from polluted soils, offering innovative, cost-effective, and environmentally friendly remediation methodologies.

Heavy metal pollution and associated health risk assessment of urban dust in Riyadh, Saudi Arabia.

Depending on their particle size and concentration, heavy metals in urban dust pose a health hazard to humans. This study investigated the total concentration, health risk, integrated pollution load index (IPI), and enrichment factor (EF) of various heavy metals in urban dust at different locations in Riyadh City. Surface dust samples were collected from 50 different residential yards in the north, south, west, east, and central corners of the city and analyzed for cadmium (Cd), chromium (Cr), copper (Cu), manganese (Mn), nickel (Ni), lead (Pb), and zinc (Zn). With respect to concentrations heavy metals were in the following order Zn > Cu > Mn > Cr > Ni > Pb > Cd. The EF trends exposed repeated anthropogenic activities were responsible for Mn, Cr, and Ni, while Pb, Zn, and Cu appeared to come from Earth's crust. Since the heavy metal concentrations were lower than the threshold values, children and adults are exposed to lower health risk in investigated area. Also, there are no pollution of heavy metals in the dust with respect to IPI which is less than the critical limit (<1) with the exception of a sampling location in north side of the city with higher IPI showed unhealthy respiration conditions in particular areas. It was concluded that rapid industrialization and urbanization and their concentrations in dust may cause health problems in near future in north side as well as other sides of Riyadh City.

Potential short-term negative versus positive effects of olive mill-derived biochar on nutrient availability in a calcareous loamy sand soil.

In the present work, the olive mill solid waste (OMSW)-derived biochar (BC) was produced at various pyrolytic temperatures (300-700°C) and characterized to investigate its potential negative versus positive application effects on pH, electrical conductivity (EC), and nutrients (P, K, Na, Ca, Mg, Fe, Mn, Zn, and Cu) availability in a calcareous loamy sand soil. Therefore, a greenhouse pot experiment with maize (Zea mays L.) was conducted using treatments consisting of a control (CK), inorganic fertilizer of NPK (INF), and 1% and 3% (w/w) of OMSW-derived BCs. The results showed that BC yield, volatile matter, functional groups, and zeta potential decreased with pyrolytic temperature, whereas BC pH, EC, and its contents of ash and fixed carbon increased with pyrolytic temperature. The changes in the BC properties with increasing pyrolytic temperatures reflected on soil pH, EC and the performance of soil nutrients availability. The BC application, especially with increasing pyrolytic temperature and/or application rate, significantly increased soil pH, EC, NH4OAc-extractable K, Na, Ca, and Mg, and ammonium bicarbonate-diethylenetriaminepentaacetic acid (AB-DTPA)-extractable Fe and Zn, while AB-DTPA-extractable Mn decreased. The application of 1% and 3% BC, respectively, increased the NH4OAc-extractable K by 2.5 and 5.2-fold for BC300, by 3.2 and 8.0-fold for BC500, and by 3.3 and 8.9-fold for BC700 compared with that of untreated soil. The results also showed significant increase in shoot content of K, Na, and Zn, while there was significant decrease in shoot content of P, Ca, Mg, and Mn. Furthermore, no significant effects were observed for maize growth as a result of BC addition. In conclusion, OMSW-derived BC can potentially have positive effects on the enhancement of soil K availability and its plant content but it reduced shoot nutrients, especially for P, Ca, Mg, and Mn; therefore, application of OMSW-derived BC to calcareous soil might be restricted.

Stability and Dynamic Aggregation of Bare and Stabilized Zero-Valent Iron Nanoparticles under Variable Solution Chemistry.

Surface modification of nanoscale zero-valent iron (nZVI) using polymer stabilizers (e.g., sodium carboxymethyl cellulose, CMC) is usually used to minimize aggregation, increase stability, and enhance transport of nZVI. We investigated the stability and dynamic aggregation of bare and CMC-nZVI as affected by variations in pH, ionic strength (IS), and nZVI particle concentration. CMC coating of nZVI resulted in smaller hydrodynamic size and larger zeta potential. The largest hydrodynamic size of nZVI was associated with bare nZVI at high IS (100 mM), pH close to the point of zero charge (PZC, 7.3-7.6), and larger particle concentration (1.0 g L-1). The increase in the zeta potential of CMC-nZVI reached one- to four-fold of that for bare nZVI, and was greater at pH values close to PZC, high IS, and larger particle concentration. The stability of CMC-nZVI was increased by 61.8, 93.1, and 57.5% as compared to that of bare nZVI at IS of 1, 50 and 100 mM, respectively. Calculations of Derjaguin, Landau, Verwey and Overbeek (DLVO) interaction energy were in agreement with stability results, and showed the formation of substantial energy barriers at low IS indicating greater nZVI stability. Our results suggest that at IS above 50 mM and nZVI particle concentration larger than 0.1 g L-1, the likelihood of nZVI aggregation is high. Nevertheless, CMC polymer stabilizer would enhance the stability and transport of nZVI even under these unfavorable solution chemistry conditions.

Conocarpus biochar as a soil amendment for reducing heavy metal availability and uptake by maize plants.

The objective of this study was to assess the use of Concarpus biochar as a soil amendment for reducing heavy metal accessibility and uptake by maize plants (Zea mays L.). The impacts of biochar rates (0.0, 1.0, 3.0, and 5.0% w/w) and two soil moisture levels (75% and 100% of field capacity, FC) on immobilization and availability of Fe, Mn, Zn, Cd, Cu and Pb to maize plants as well as its application effects on soil pH, EC, bulk density, and moisture content were evaluated using heavy metal-contaminated soil collected from mining area. The biochar addition significantly decreased the bulk density and increased moisture content of soil. Applying biochar significantly reduced NH4OAc- or AB-DTPA-extractable heavy metal concentrations of soils, indicating metal immobilization. Conocarpus biochar increased shoot dry biomass of maize plants by 54.5-102% at 75% FC and 133-266% at 100% FC. Moreover, applying biochar significantly reduced shoot heavy metal concentrations in maize plants (except for Fe at 75% FC) in response to increasing application rates, with a highest decrease of 51.3% and 60.5% for Mn, 28% and 21.2% for Zn, 60% and 29.5% for Cu, 53.2% and 47.2% for Cd at soil moisture levels of 75% FC and 100% FC, respectively. The results suggest that biochar may be effectively used as a soil amendment for heavy metal immobilization and in reducing its phytotoxicity.