Ye Zhao

Sorption of simazine to corn straw biochars prepared at different pyrolytic temperatures.

Simazine sorption to corn straw biochars prepared at various temperatures (100-600 °C) was examined to understand its sorption behavior as influenced by characteristics of biochars. Biochars were characterized via elemental analysis, BET-N(2) surface area (SA), FTIR and (13)C NMR. Freundlich and dual-mode models described sorption isotherms well. Positive correlation between log K(oc) values and aromatic C contents and negative correlation between log K(oc) values and (O + N)/C ratios indicate aromatic-rich biochars have high binding affinity to simazine (charge transfer (π-π*) interactions) and hydrophobic binding may overwhelm H-bonding, respectively. Dual-mode model results suggest adsorption contribution to total sorption increases with carbonization degree. Positive correlation between amounts of adsorption (Q(ad)) and SA indicates pore-filling mechanism. Comparison between our results and those obtained with other sorbents indicates corn straw biochars produced at higher temperature can effectively retain simazine. These observations will be helpful for designing biochars as engineered sorbents to remove triazine herbicides.

Adsorption of tetracycline on soil and sediment: Effects of pH and the presence of Cu(II)

Tetracycline (TC) is frequently detected in the environment, however, knowledge on the environmental fate and transport of TC is still limited. Batch adsorption experiments of TC by soil and sediment samples were conducted. The distribution of charge and electrostatic potential of individual atoms of various TC species in the aqueous solution were determined using MOPAC version 0.034 W program in ChemBio3D Ultra software. Most of the adsorption isotherms on the soil, river and marine sediments were well fitted with the Freundlich and Polanyi-Manes (PMM) models. The single point organic carbon (OC)-normalized adsorption distribution coefficients (K(OC)) and PMM saturated adsorption capacity (Q(OC)(0)) values of TC were associated with the mesopore volume and clay content to a greater extent, indicating the mesopore volume of the soil and sediments and their clay content possibly influenced the fate and transport of TC in the natural environment. The adsorption of TC on soil and sediments strongly depended on the pH and presence of Cu(II). The presence of Cu(II) facilitated TC adsorption on soil and sediments at low pH (pH<5), possibly due to the metallic complexation and surface-bridging mechanism by Cu(II) adsorption on soil and sediments. The cation exchange interaction, metallic complexation and Coulombic interaction of mechanisms for adsorption of TC to soils and sediments were further supported by quantum chemical calculation of various TC species in different pH.

Sorption of endocrine disrupting chemicals by condensed organic matter in soils and sediments

Sorption of 17alpha-ethinyl estradiol (EE2) and bisphenol A (BPA) by nonhydrolyzable carbon (NHC), black carbon (BC), and bulk soils and sediments was examined. All sorption isotherms were nonlinear and fitted both Freundlich and Dubinin-Ashtakhov (DA) models. The single-point organic carbon (OC)-normalized distribution coefficient (K(OC)) of EE2 for the isolated NHC and BC was 2.7-4.8 times and 5.4-12.9 times greater, respectively, than that of the bulk samples. However, no clear trend in BPA K(OC) values was observed. Based on the contribution of soil/sediment organic matter (SOM) fractions to the overall sorption of BPA or EE2 by the bulk samples, condensed SOM (NHC and BC) generally played a dominant role to the overall sorption. The BPA adsorption capacity (Q(OC)(0)) from the DA model was higher than that of EE2 on NHC and there was obvious difference in isotherm nonlinearity (n) between EE2 and BPA. These results suggest that BPA may have more access to the pore sites of NHC samples than EE2. The pi-pi bonds formed between BPA and NHC or BC may be stronger than that between EE2 and NHC or BC. This would be attributed to the fact that BPA has two benzene rings, and can also be used to explain the difference in hexadecane-water partition coefficient (K(HW))-normalized K(OC) values (K(OC)/K(HW)) of BPA and EE2 after factoring out the hydrophobic effect. These findings could be useful for predicting fate and ecological risks of endocrine disrupting chemicals (EDCs) (e.g., EE2 and BPA) in natural environments especially when soils or sediments become receptors for EDCs.

Cadmium adsorption on plant- and manure-derived biochar and biochar-amended sandy soils: Impact of bulk and surface properties

To investigate the role of the bulk and surface composition of both biochar and biochar-amended soils in the adsorption of Cd(2+), as well as the influence of different biochars added to the soils on Cd(2+) adsorption, swine-manure-derived biochars (BSs) and wheat-straw-derived biochars (BWs) were produced at 300, 450, and 600°C. These biochars were added to a sandy soil to investigate the effect of biochars on the adsorption of Cd(2+) by soil. The significantly higher surface C content of the amended soils compared to their bulk C content suggests that the minerals of the biochar-amended soils are most likely covered primarily by biochars. The maximum adsorption capacity (Qmax,total) of the BSs was 10-15 times higher than that of the BWs due to the high polarity and ash content of the BSs. The polarity ((N+O)/C) of the low-temperature biochars greatly affected their Cd(2+) adsorption. The Qmax,total of the BS-amended soils increased with increasing dose, whereas the Qmax,total of the BW-amended soils showed the opposite behavior, which was attributed to the different surface composition characteristics of the two types of soil. The BSs were more effective in immobilizing Cd(2+) upon application to the soil relative to the BWs. This study elucidates the spatial distribution of biochars in biochar-amended soils and highlights the importance of the surface composition of the investigated samples in Cd(2+) adsorption.

Sorption of 17α-ethinyl estradiol, bisphenol A and phenanthrene to different size fractions of soil and sediment

The potential for negative effects caused by endocrine disrupting chemicals (EDCs) release into the environment is a prominent concern and numerous research projects have investigated possible environmental fate and toxicity. However, their sorption behavior by size fractions of soil and sediment has not been systematically represented. The sorption of bisphenol A (BPA), 17α-ethinyl estradiol (EE2) and phenanthrene (Phen) by different size fractions of soil and sediment were investigated. Sorption isotherms of EE2, BPA, and Phen by size fractions of soil (SL) and sediment (ST) were well fitted to the Freundlich model. The positive correlation between EE2, BPA and Phen sorption capacity (logK(d)) of size fractions and their organic carbon (OC) content suggests that OC of size fractions in SL and ST should regulate sorption, while the surface area (SA) of size fractions may not account for sorption of EE2, BPA and Phen. Each size fraction of ST had higher sorption capacity (K(d) or K(OC)) of EE2 and BPA than that of SL due to their difference in the polarity of organic matter (OM) between terrestrial and aquatic sources. Sorption capacity logK(d) for size fractions of SL and ST did not follow the order: clay>silt>sand due to the difference in OM abundance and composition between the size fractions. Large particle fractions of ST contributed about 80% to the overall sorption for any EE2, BPA, and Phen. This study was significant to evaluate size fractions of soil and sediment as well as their associated OM affecting EE2 and BPA sorption processes.

Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved.

The conventional hydrothermal reaction with iron powder, NaOH and H(2)O as reactants was reported to occur at temperature above 423K, and iron oxides (Fe(3)O(4) and NaFeO(2)) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H(2)O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe(3)O(4)/NaFeO(2) and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100mgL(-1) of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10mL simulative transformer oil, almost complete dechlorination was achieved by 750W microwave irradiation for 10min, with 0.3g iron powder, 0.3g NaOH and 0.6mL H(2)O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H(2)O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes.

Effect of cadmium on the physiological parameters and the subcellular cadmium localization in the potato (Solanum tuberosum L.)

The pollution of agricultural soils with cadmium (Cd) has become a serious problem worldwide. The potato (Solanum tuberosum L.) was used to investigate how different concentrations of Cd (1, 5, and 25mgkg(-1)) affected the physiological parameters and the subcellular distribution of Cd in the potato. The analyses were conducted using scanning electron microscopy coupled with energy dispersive X-ray (SEM-EDX). The results suggest that the leaf is the organ with the highest accumulation of Cd. The malondialdehyde (MDA) content increased and the chlorophyll content decreased in response to high level of Cd. The SEM-EDX microanalysis revealed that Cd was primarily deposited in the spongy and palisade tissues of the leaf. Furthermore, Cd was also detected in the cortex and the adjacent phloem and was observed inside the intercellular space, the interior surface of the plasma membrane, and on the surface of the elliptical starch granules in the tubers of the potato. Although low concentrations of Cd migrated from the root to the tuber, the accumulation of Cd in the tuber exceeded the standard for food security. Therefore, the planting of potato plants in farmland containing Cd should be seriously evaluated because Cd-containing potatoes might present high health risk to humans.

Single-solute and bi-solute sorption of phenanthrene and dibutyl phthalate by plant- and manure-derived biochars

The spatial arrangement of biochar and the exact underlying interaction mechanisms of biochar and hydrophobic organic compounds both remain largely unknown. The sorption of dibutyl phthalate (DBP) and phenanthrene (PHE) to plant- and manure-derived biochars in both single- and bi-solute systems was investigated. The significant positive relation between surface polarity and ash content suggests that minerals benefit the external distribution of polar groups on particle surfaces. PHE and DBP sorption by the biochars was regulated by their surface polarity. The PHE generally displayed a pronounced enhancement of DBP sorption, likely resulting from the formation of biochar-PHE-DBP complexes, suggesting that DBP and PHE had different sorption sites on the biochars. The enhancement of Cd(2+) (a soft Lewis acid) on DBP sorption implied that π-π interactions should not dominate DBP sorption by biochars. The influence of Cd(2+) on PHE sorption by biochars would depend on the balance between suppressive sorption by Cd(2+)PHE bonding and enhanced sorption by Cd(2+)-complexed functionalities, and the amounts of Cd(2+) adsorbed by biochars determined the relative role of increased sorption by Cd(2+) in the overall PHE sorption.

Variation in sorption of propiconazole with biochars: The effect of temperature, mineral, molecular structure, and nano-porosity.

Sorption behavior of propiconazole (PROPI) by plant-residue derived biochars (PLABs) and animal waste-derived biochars (ANIBs) obtained at three heating treatment temperatures (HTTs) (300, 450 and 600 °C) (e.g., BCs300, BCs450, and BCs600) and their corresponding de-ashed BCs450 was investigated. PLABs belonged to high- or medium-C biochars and ANIBs were low-C biochars. Surface C concentrations of the tested biochars were generally higher than their corresponding bulk C. Surface polar groups were mainly composed of O-containing groups of minerals within biochars. The nonlinearity coefficients (n) of propiconazole (PROPI) sorption isotherms ranged from 0.23 to 0.64, which was significantly and negatively related to organic carbon (OC)-normalized CO2-surface area (CO2-SA/OC) of biochars. This correlation along with the positive relationship between CO2-SA/OC and aromaticity indicates that pore-filling in nanopores within aromatic C dominate nonlinear PROPI sorption. HTTs or C contents do not necessarily regulate PROPI sorption. Removal of minerals from BCs450 elevated PROPI sorption because minerals may exert certain influence on sorption via impacting spatial arrangement of polar groups and/or organic matter (OM)-mineral interactions. This study helps to better understand sorption behavior of PROPI to biochars and evaluate the potential role of biochar in water treatment systems.

Lead in the soil-mulberry (Morus alba L.)-silkworm (Bombyx mori) food chain: translocation and detoxification.

The translocation of lead (Pb) in the soil-mulberry-silkworm food chain and the process of Pb detoxification in the mulberry-silkworm chain were investigated. The amount of Pb in mulberry, silkworm, feces and silk increased in a dose-responsive manner to the Pb contents in the soils. Mulberry roots sequestered most of the Pb, ranging from 230.78 to 1209.25 mg kg(-1). Over 92% of the Pb in the mulberry leaves was deposited in the cell wall, and 95.29-95.57% of the Pb in the mulberry leaves was integrated with oxalic acid, pectates and protein, and it had low bioavailability. The Pb concentrations in the silkworm feces were 4.50-4.64 times higher than those in the leaves. The synthesis of metallothioneins in three tissues of the silkworms was induced to achieve Pb homeostasis under Pb stress. These results indicated the mechanism involved in Pb transfer along the food chain was controlled by the detoxification of Pb in different trophic levels. Planting mulberry and rearing silkworm could be a promising approach for the remediation of Pb-polluted soils due to the Pb tolerance of mulberry and silkworm.