Pyrolysis of exhausted biochar sorbent: Fates of cadmium and generation of products.

Biochar is a promising sorbent for Cd removal from water, while the disposal of the exhausted Cd-enriched biochar remains a challenge. In this study, pyrolysis was employed to treat the exhausted biochar under N2 and CO2 atmospheres at 600-900 °C, and the fate of Cd during pyrolysis and characteristics of high-valued products were determined. The results indicated that higher temperature and CO2 atmosphere favored the volatilization of Cd. Based on the toxicity characteristic leaching procedure (TCLP) results, the pyrolysis treatment under both atmospheres enhanced the stability of Cd, and the leached Cd concentration of regenerated biochar obtained at high temperatures (>800 °C) was lower than 1 mg/L. Compared with the pristine biochar, the regenerated biochar demonstrated higher carbon content and pH, whereas the contents of oxygen and hydrogen declined, and exhibited promising sorption properties (35.79 mg/g). The atmosphere played an important role in modifying biochar properties and syngas composition. The N2 atmosphere facilitated CH4 production, whereas the CO2 atmosphere increased the proportion of CO. These results implied that pyrolysis can be a valuable and environmental-friendly strategy for the treatment and reuse of exhausted biochar sorbent.

Comparison of cadmium adsorption by hydrochar and pyrochar derived from Napier grass.

Biochar (e.g. pyrochar and hydrochar) is considered a promising adsorbent for Cd removal from aqueous solution. Considering the vastly different physicochemical properties between pyrochar and hydrochar, the Cd2+ sorption capacity and mechanisms of pyrochars and hydrochars should be comparatively determined to guide the production and application of biochar. In this study, the hydrochars and pyrochars were prepared from Napier grass by hydrothermal carbonization (200 and 240 °C) and pyrolysis (300 and 500 °C), respectively, and the physicochemical properties and Cd2+ sorption performances of biochars were systematically determined. The pyrochars had higher pH and ash content as well as better stability, while the hydrochars showed more oxygen-containing functional groups (OFGs) and greater energy density. The pseudo second order kinetic model best fitted the Cd2+ sorption kinetics data of biochars, and the isotherm data of pyrochar and hydrochar were well described by Langmuir and Freundlich models, respectively. In comparison with hydrochar, the pyrochar exhibited better Cd2+ sorption capacity (up to 71.47 mg/g). With increasing production temperature, the Cd2+ sorption capacity of pyrochar elevated, while the reduction was found for hydrochar. The mineral interaction, complexation with surface OFGs, and coordination with π electron were considered the main mechanisms of Cd2+ removal by biochars. The minerals interaction and the complexation with OFGs was the dominant mechanism of Cd2+ removal by pyrochars and hydrochars, respectively. Therefore, the preparation technique and temperature have significant impacts on the sorption capacity and mechanisms of biochar, and pyrochar has better potential for Cd2+ removal than the congenetic hydrochar.

Pyrolysis of exhausted hydrochar sorbent for cadmium separation and biochar regeneration.

Sorption is considered a cost-effective technique for cadmium (Cd) removal from water, while the exhausted Cd-enriched sorbent should be properly disposed of. In this study, pyrolysis of exhausted hydrochar sorbent was conducted at 300-900 °C, and the behavior of Cd and the physicochemical properties and environmental applications of the regenerated biochar were investigated. The vaporization of adsorbed Cd in hydrochar was greatly enhanced by elevating pyrolysis temperature, and almost no Cd was observed in the regenerated biochars obtained at 700-900 °C. In comparison with the raw hydrochar, the regenerated biochars showed higher pH, ash content, and carbon content, while the contents of hydrogen and oxygen decreased. According to the toxicity characteristic leaching procedure result, the toxicity and mobility of Cd in hydrochar were greatly reduced after pyrolysis. Notably, the regenerated biochar showed much higher Cd sorption capacity (26.05-30.24 mg/g) than the raw hydrochar (6.70 mg/g). Surface complexation with oxygen-containing functional groups was the dominant Cd sorption mechanism for hydrochar, and precipitation between Cd2+ and carbonates dominated the Cd removal by the regenerated biochars. These results illuminated that pyrolysis can be an effective technique for the harmless disposal of exhausted hydrochar sorbent and the regeneration of valuable biochar.

Heavy metal phyto-accretion, biochemical responses and non-carcinogenic human health risks of genetically diverse wheat genotypes cultivated with sewage of municipal origin.

Current study explored the effects of municipal sewage (MS) irrigation on heavy metal phyto-accretion, biochemical responses and human health risks of diverse wheat genotypes along with recycled municipal sewage (RMS). Mean concentrations of PO43-, NO3--N, chemical oxygen demand, biological oxygen demand, K, Co, Cu, Cd, Cr and Ni were found higher in MS than irrigation criteria. This led to significant increase in heavy metal contents in roots, stem and grains of MS irrigated wheat genotypes compared to RMS and control treatments. No adverse health risk effects for individual or multiple metals were recorded in RMS irrigated wheat genotypes on grounds of lowest heavy metal accumulation. Multivariate techniques i.e. principal component analyses (PCA) and hierarchical agglomerative cluster analyses (HACA) identified tolerant (inefficient metal accumulators) and sensitive (efficient metal accumulators) wheat genotypes in MS and RMS. Tolerant wheat genotypes showed lowest accumulation of heavy metals, efficient biochemical mechanisms to combat oxidative stress and lower health risks to adults/children. Cultivation of identified tolerant wheat genotypes is recommended in areas receiving municipal wastes to reduce human and environmental health risks. Moreover, genetic potential of identified tolerant wheat genotypes from MS and RMS can be utilized in breeding heavy metal tolerant wheat germplasm worldwide.

Study amino acid contents, plant growth variables and cell ultrastructural changes induced by cadmium stress between two contrasting cadmium accumulating cultivars of Brassica rapa ssp. chinensis L. (pak choi).

Cadmium (Cd) is an inauspicious abiotic traction that not only influences crop productivity and its growth parameters, but also has adverse effects on human health if these crops are consumed. Among crops, leafy vegetables which are the good source of mineral and vitamins accumulate more Cd than other vegetables. It is thus important to study photosynthetic variables, amino acid composition, and ultrastructural localization of Cd differences in response to Cd accumulation between two low and high Cd accumulating Brassica rapa ssp. chinensis L. (pak choi) cultivars, differing in Cd accumulation ability. Elevated Cd concentrations significantly lowered plant growth rate, biomass, leaf gas exchange and concentrations of amino acids collated to respective controls of both cultivars. Electron microscopy indicated that the impact of high Cd level on ultrastructure of leaf cells was associated to affecting cell functionalities, i.e. irregular cell wall, withdrawal of cell membrane, and chloroplast structure which has negative impact on photosynthetic activities, thus causing considerable plant growth suppression. Damage in root cells were observed in the form of enlargement of vacuole. The energy dispersive micro X-ray spectroscopy of both cultivars leaves indicated that cellular structure exhibited exudates of Cd-dense material. Ultrastructural damages and phytotoxicity were more pronounced in high accumulator cultivar as compared to the low accumulator cultivar. These findings are useful in determining the mechanisms of differential Cd-tolerance among cultivars with different Cd tolerance abilities at cellular level.

Variations in cadmium and nitrate co-accumulation among water spinach genotypes and implications for screening safe genotypes for human consumption.

Vegetables are important constituents of the human diet. Heavy metals and nitrate are among the major contaminants of vegetables. Consumption of vegetables and fruits with accumulated heavy metals and nitrate has the potential to damage different body organs leading to unwanted effects. Breeding vegetables with low heavy metal and nitrate contaminants is a cost-effective approach. We investigated 38 water spinach genotypes for low Cd and nitrate co-accumulation. Four genotypes, i.e. JXDY, GZQL, XGDB, and B888, were found to have low co-accumulation of Cd (<0.71 mg/kg dry weight) and nitrate (<3100 mg/kg fresh weight) in the edible parts when grown in soils with moderate contamination of both Cd (1.10 mg/kg) and nitrate (235.2 mg/kg). These genotypes should be appropriate with minimized risk to humans who consume them. The Cd levels in the edible parts of water spinach were positively correlated with the concentration of Pb or Zn, but Cd, Pb, or Zn was negatively correlated with P concentration. These results indicate that these three heavy metals may be absorbed into the plant in similar proportions or in combination, minimizing the influx to aerial parts. Increasing P fertilizer application rates appears to prevent heavy metal and nitrate translocation to shoot tissues and the edible parts of water spinach on co-contaminated soils.

Simultaneous sorption and catalytic oxidation of trivalent antimony by Canna indica derived biochars.

The simultaneous sorption and oxidation of Sb(III) on biochars were investigated using batch experiments. The biochars were derived from Canna indica at different pyrolysis temperatures (300-600 °C, referred as CIB300-CIB600), and characterized by FTIR, BET, XRD, SEM-EDS, EPR and Boehm titration. The Sb(III) sorption data could be well fitted by both the Langmuir and Freundlich models, and the pseudo-second order model is best for describing the kinetic data. The maximum Sb(III) sorption capacity of CIB300 was 16.1 mg g-1, which was greater than that of other biochars. Inner-sphere complexation with oxygen-containing functional groups and coordination with π electrons are the possible sorption mechanisms. It is worthwhile to note that 4.7-32.3% of Sb(III) was oxidized to Sb(V) after sorption equilibration, demonstrating the occurrence of Sb(III) oxidation during the sorption process. Further study of oxidation under anoxic condition confirmed the catalytic role of biochar for Sb(III) oxidation, and free radicals in biochars were crucial for electron transfer. CIB400 exhibited the highest catalytic oxidative ability for Sb(III), which could be ascribe to its reserve of more electroactive polyphenolic macromolecule and less electroinactive cellulose. These results imply that biochars have good potential as a green effective sorbent for remediation of Sb(III) contaminated water, and simultaneously reduce the toxicity of Sb(III) by catalytic oxidation.

Endophytic bacterium Sphingomonas SaMR12 promotes cadmium accumulation by increasing glutathione biosynthesis in Sedum alfredii Hance.

A hydroponic experiment was conducted to verify the effects of inoculation with endophytic bacteria Sphingomonas SaMR12 on root growth, cadmium (Cd) uptake, reactive oxygen species (ROS), antioxidases, glutathione (GSH) and the related gene expression of Sedum alfredii Hance under different levels of Cd such as 0, 10, 25, 100 and 400 µM. The results showed that inoculation of SaMR12 improved Cd accumulation and upregulated glutathione synthase (GS) expression, but slightly reduced malondialdehyde (MDA) concentration and alleviated Cd-induced damage in roots. However it didn't alter the activities of antioxidant enzymes. When Cd concentration exceeded 25 µM, SaMR12 increased the concentration of GSH and the expression level of GSH1. At high Cd treatment levels (100 and 400 µM), SaMR12 significantly reduced H2O2 concentration and enhanced expression level of 1-Cys peroxiredoxin PER1 and ATPS genes. These results indicate that although SaMR12 has no significant effects on antioxidases activities, it reduces H2O2 concentration by enhancing GSH concentration and relevant genes expression, and subsequently improves Cd tolerance and accumulation.

Improvement of cadmium uptake and accumulation in Sedum alfredii by endophytic bacteria Sphingomonas SaMR12: effects on plant growth and root exudates.

Inoculating endophytic bacteria was proven as a promising way to enhance phytoremediation. By a hydroponic experiment, the role of this study was to clarify the effects of inoculating endophytic bacterium Sphingomonas SaMR12 on phytoremediation, with special emphasis on changes of cadmium uptake, plant growth, root morphology, and organic acids secretion at different cadmium treated levels (0, 5, 50, and 100 µM). The results showed that SaMR12 inoculation improved the accumulation of cadmium as well as plant biomass, length of roots, number of root tips, and root surface area. Root secretion of oxalic, citric, and succinic acids was also increased after inoculated, which may alleviate the cadmium toxicity to plant or inhibit the rising trend of oxidative stress of plant. The major finding of this work suggested that in the root, SaMR12 improves cadmium bioavailability and absorption facility by increasing root-soil contact area and root organic acid secretion; and in the shoot, SaMR12 increases cadmium tolerance by alleviating oxidative stress of plant, so as to enhance the capability of cadmium extraction by plant.