Adel R.A. Usman

Pyrolysis temperature induced changes in characteristics and chemical composition of biochar produced from conocarpus wastes

Conocarpus wastes were pyrolyzed at different temperatures (200–800 °C) to investigate their impact on characteristics and chemical composition of biochars. As pyrolysis temperature increased, ash content, pH, electrical conductivity, basic functional groups, carbon stability, and total content of C, N, P, K, Ca, and Mg increased while biochar yield, total content of O, H and S, unstable form of organic C and acidic functional groups decreased. The ratios of O/C, H/C, (O + N)/C, and (O + N + S)/C tended to decrease with temperature. The data of Fourier transformation infrared indicate an increase in aromaticity and a decrease in polarity of biochar produced at a high temperature. With pyrolysis temperature, cellulose loss and crystalline mineral components increased, as indicated by X-ray diffraction analysis and scanning electron microscope images. Results suggest that biochar pyrolized at high temperature may possess a higher carbon sequestration potential when applied to the soil compared to that obtained at low temperature.

Effects of rapeseed residue on lead and cadmium availability and uptake by rice plants in heavy metal contaminated paddy soil.

Rapeseed (Brassica napus L.) has been cultivated for biodiesel production worldwide. Winter rapeseed is commonly grown in the southern part of Korea under a rice-rapeseed double cropping system. In this study, a greenhouse pot experiment was conducted to assess the effects of rapeseed residue applied as a green manure alone or in combinations with mineral N fertilizer on Cd and Pb speciation in the contaminated paddy soil and their availability to rice plant (Oryza sativa L.). The changes in soil chemical and biological properties in response to the addition of rapeseed residue were also evaluated. Specifically, the following four treatments were evaluated: 100% mineral N fertilizer (N100) as a control, 70% mineral N fertilizer+rapeseed residue (N70+R), 30% mineral N fertilizer+rapeseed residue (N30+R) and rapeseed residue alone (R). The electrical conductivity and exchangeable cations of the rice paddy soil subjected to the R treatment or in combinations with mineral N fertilizer treatment, N70+R and N30+R, were higher than those in soils subjected to the N100 treatment. However, the soil pH value with the R treatment (pH 6.3) was lower than that with N100 treatment (pH 6.9). Use of rapeseed residue as a green manure led to an increase in soil organic matter (SOM) and enhanced the microbial populations in the soil. Sequential extraction also revealed that the addition of rapeseed residue decreased the easily accessible fraction of Cd by 5-14% and Pb by 30-39% through the transformation into less accessible fractions, thereby reducing metal availability to the rice plant. Overall, the incorporation of rapeseed residue into the metal contaminated rice paddy soils may sustain SOM, improve the soil chemical and biological properties, and decrease the heavy metal phytoavailability.

Heavy metal contamination in sediments and mangroves from the coast of Red Sea: Avicennia marina as potential metal bioaccumulator.

The aim of this study was to investigate the concentrations and pollution status of heavy metals (Cu, Cd, Ni, Pb, Zn and Cr) in the mangrove surface sediments from the Farasan Island, Coast of Red Sea, Saudi Arabia. The ability of mangroves (Avicennia marina) to accumulate and translocate heavy metal within their different compartments was also investigated. Five sampling sites were chosen for collection of sediments and different compartments (leaf, branch and root) of A. marina. The results showed that the maximum and average concentrations of Cd, Cu and Pb in the studied area exceeded their world average concentration of shale. Additionally, only the maximum concentration of Zn exceeded its world average shale concentration. Based on the quality guidelines of sediment (SQGs), the collected sediment samples were in moderate to heavy rate for Cu, non-polluted to heavy rate for Pb and Zn, and non-polluted to moderate rate for Cr and Ni. The average metal concentrations of A. marina in the studied area were observed in the order Cu (256.0-356.6mgkg(-1))>Zn (29.5-36.8mgkg(-1))>Cr (8.15-14.9mgkg(-1))>Ni (1.37-4.02mgkg(-1))>Cd (not detectable-1.04mgkg(-1))>Pb (not detectable). Based on bio-concentration factors (BCF), their most obtained values were considered too high (>1), suggesting that A. marina can be considered as a high-efficient plant for bioaccumulation of heavy metals. Among all metals, Cu and Cr were highly bio-accumulated in different parts of A. marina. In terms of heavy metal contamination control via phyto-extraction, our findings suggest also that A. marina may be classified as potential accumulator for Cu in aboveground parts, as indicated by higher metal accumulation in the leaves combined with bio-concentration factor (BCF) and translocation factor (TF) values >1.

Effect of microbial inoculation and EDTA on the uptake and translocation of heavy metal by corn and sunflower

A greenhouse experiment was carried out to study the effect of microbial inoculation and EDTA as synthetic chelator on heavy metals (Zn, Cu, Pb and Cd) uptake into and translocation within corn (Zea mays) and sunflower (Helianthus annuus) grown on contaminated soil. Four treatments were included: the control, EDTA as synthetic chelator, inoculation with arbuscular mycorrhizal fungi (AMF), and the inoculation with yeast. Microbial inoculation increased biomass of both species of agricultural crop plants, but EDTA addition decreased only biomass of sunflower. The results also showed that EDTA was more effective than microbial inoculation at increasing the concentrations of all metals in plants. Generally, there were significant differences among the treatments in the most metals taken up, especially by corn plants, with an order: AM fungi>yeast>EDTA>control except for Pb. It was found that the efficiency of EDTA in increasing Pb uptake was significantly higher than that of microbial inoculation treatments. The most effective treatments to stimulate the translocation of the studied metals from roots to shoots were EDTA and/or AM fungi. Overall, the maximum metal uptake and phytoextraction efficiencies were pronounced for corn either with AM fungi treatment for Zn, Cu and Cd or after EDTA addition for Pb. However, heavy metals uptake was not high enough to achieve extraction rates which would be necessary for practical use.

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.

Soil pollution assessment and identification of hyperaccumulating plants in chromated copper arsenate (CCA) contaminated sites, Korea.

In recent decades, heavy metal contamination in soil adjacent to chromated copper arsenate (CCA) treated wood has received increasing attention. This study was conducted to determine the pollution level (PL) based on the concentrations of Cr, Cu and As in soils and to evaluate the remediative capacity of native plant species grown in the CCA contaminated site, Gangwon Province, Korea. The pollution index (PI), integrated pollution index (IPI), bioaccumulation factors (BAF(shoots) and BAF(roots)) and translocation factor (TF) were determined to ensure soil contamination and phytoremediation availability. The 19 soil samples from 10 locations possibly contaminated with Cr, Cu and As were collected. The concentrations of Cr, Cu and As in the soil samples ranged from 50.56-94.13 mg kg(-1), 27.78-120.83 mg kg(-1), and 0.13-9.43 mg kg(-1), respectively. Generally, the metal concentrations decreased as the distance between the CCA-treated wood structure and sampling point increased. For investigating phytoremediative capacity, the 19 native plant species were also collected in the same area with soil samples. Our results showed that only one plant species of Iris ensata, which presented the highest accumulations of Cr (1120 mg kg(-1)) in its shoot, was identified as a hyperaccumulator. Moreover, the relatively higher values of BAF(shoot) (3.23-22.10) were observed for Typha orientalis, Iris ensata and Scirpus radicans Schk, suggesting that these plant species might be applicable for selective metal extraction from the soils. For phytostabilization, the 15 plant species with BAF(root) values>1 and TF values<1 were suitable; however, Typha orientalis was the best for Cr.

An assessment of the utilization of waste resources for the immobilization of Pb and Cu in the soil from a Korean military shooting range

Military shooting range soils contaminated by heavy metals have been subjected to remediation efforts to alleviate the detrimental effects of exposure on humans and the surrounding environment. Waste materials can be used as cost-effective soil amendments to immobilize heavy metals in contaminated soils. In this study, naturally occurring lime-based waste materials including egg shells, oyster shells, and mussel shells were assessed for their effectiveness toward heavy metal immobilization in military shooting range soil in Korea. Soil was treated in batch leaching experiments with 0, 2.5, 5, 10, and 15% of each lime-based waste material. The results showed that the lime-based waste materials effectively reduced water-soluble Pb at an application rate of 2.5% by weight of the soil. Increase in soil pH from 6.6 to 8.0 was considered to be the main chemistry of Pb immobilization, which was supported by the formation of insoluble Pb species at high pH values as confirmed by the visual MINTEQ thermodynamic model. In contrary, water-soluble Cu was increased in the lime-based waste material-treated soils when compared to the untreated soil. This was likely attributed to the formation of soluble Cu–DOC (dissolved organic carbon) complexes as all lime-based waste materials applied increased DOC contents in the soil. Therefore, care must be taken in selecting the appropriate amendment for immobilizing metals in shooting range soils.

Effect of Immobilizing Substances and Salinity on Heavy Metals Availability to Wheat Grown on Sewage Sludge-Contaminated Soil

The objective of the investigation was to evaluate the effect of immobilizing substances and NaCl salinity on the availability of heavy metals: Zn, Cd, Cu, Ni, and Pb to wheat (Triticum aestivum L.). In greenhouse pot experiment, a sewage sludge amended soil was treated with the following immobilizing substances: three clay minerals (Na-bentonite, Ca-bentonite and zeolite), iron oxides (goethite and hematite), and phosphate fertilizers (superphosphate and Novaphos). The pots were planted with wheat and were irrigated either with deionized or saline water containing 1600 mg L−1 NaCl. Wheat was harvested two times for shoot metal concentrations and biomass measurements. Metal species in soil solution were estimated using the software MINEQL+. The addition of metal immobilizing substances to the soil significantly decreased metal availability to wheat. The largest reduction in metal bioavailability was found for bentonites. The irrigation with saline water (1600 mg L−1 NaCl) resulted in a significant increase in metal chloride species (MCl+ and MCl2 0). The highest metal complexation with Cl occurred for Cd, which was about 53% of its total soil solution concentration. The total concentration of Cd (CdT) in soil solution increased by 1.6–2.8-fold due to saline water. The NaCl salinity caused a significant increase in uptake and shoot concentration of Cd for two harvests and small but significant increase in shoot Pb concentration for the second harvest. It was concluded that the use of bentonites is the most promising for the reduction of heavy metal availability to plants. Saline water containing 1600 mg L− 1 NaCl increased the availability of Cd and Pb to wheat and decreased the efficiency of bentonites to immobilize soluble Cd.

Toxicity of synthetic chelators and metal availability in poultry manure amended Cd, Pb and As contaminated agricultural soil.

Chelating agents added to contaminated soils may increase solubility and phytoextraction efficiency of soil metals. However, they can create negative effects on soil biological quality. A 90-day incubation experiment was conducted to evaluate mixed effects of chelating agents and poultry manure on changes in available Cd, Pb and As, CO2-C efflux, microbial biomass C, dissolved organic C (DOC), and N mineralization in metal-polluted agricultural soil. Application of poultry manure resulted in a considerable increase in soil pH, DOC, CO2-C efflux, net N mineralization, net N nitrification, and microbial biomass C compared to those in unmanured soil. Availability of arsenic increased twice in manure amended soil due to changes in pH and DOC. However, adding poultry manure did not affect the concentrations of available Pb and Cd compared to those in control soil. Chelating agents increased CO2-C efflux, DOC, and metal availability but decreased microbial biomass C and net N mineralization. Maximum decrease in microbial biomass C, net N mineralization, and net N nitrification, was observed in EDTA applied soil possibly due to high metal availability to soil microorganisms. Overall results revealed that the application of synthetic chelators in combination with poultry manure enhances available As and demonstrates better environment for soil biota.

Equilibrium and kinetic mechanisms of woody biochar on aqueous glyphosate removal.

We investigated the removal of aqueous glyphosate using woody (dendro) biochar obtained as a waste by product from bioenergy industry. Equilibrium isotherms and kinetics data were obtained by adsorption experiments. Glyphosate adsorption was strongly pH dependent occurring maximum in the pH range of 5-6. The protonated amino moiety of the glyphosate molecule at this pH may interact with π electron rich biochar surface via π-π electron donor-acceptor interactions. Isotherm data were best fitted to the Freundlich and Temkin models indicating multilayer sorption of glyphosate. The maximum adsorption capacity of dendro biochar for glyphosate was determined by the isotherm modeling to be as 44 mg/g. Adsorption seemed to be quite fast, reaching the equilibrium <1 h. Pseudo-second order model was found to be the most effective in describing kinetics whereas the rate limiting step possibly be chemical adsorption involving valence forces through sharing or exchanging electrons between the adsorbent and sorbate. The FTIR spectral analysis indicated the involvement of functional groups such as phenolic, amine, carboxylic and phosphate in adsorption. Hence, a heterogeneous chemisorption process between adsorbate molecules and functional groups on biochar surface can be suggested as the mechanisms involved in glyphosate removal.