Ziying Wang

Impact of Deashing Treatment on Biochar Structural Properties and Potential Sorption Mechanisms of Phenanthrene

Knowledge of the mineral effects of biochars on their sorption of hydrophobic organic contaminants (HOCs) is limited. Sorption of phenanthrene (PHE) by plant-residue derived biochars (PLABs) and animal waste-derived biochars (ANIBs) obtained at two heating treatment temperatures (HTTs) (450 and 600 °C) and their corresponding deashed biochars was investigated. The decreased surface polarity and increased bulk polarity of biochars after deashing treatment indicated that abundant minerals of biochars benefit external exposure of polar groups associated organic matter (OM). Organic carbon (OC)-normalized distribution coefficients (K(oc)) of PHE by biochars generally increased after deashing, likely due to enhancement of favorable and hydrophobic sorption sites caused by mineral removal. Positive correlation between PHE log K(oc) by PLABs and bulk polarity combined with negative correlation between PHE log K(oc) values by ANIBs and surface polarity suggested PLABs and ANIBs have different sorption mechanisms, probably attributed to their large variation of ash content because minerals influenced OM spatial arrangement within biochars. Results of this work could help us better understand the impact of minerals, bulk/surface polarity, and sorption domain arrangement of biochars on their HOCs sorption and predict the fate of HOCs in soils after biochar application.

Assessment of herbicide sorption by biochars and organic matter associated with soil and sediment

Sorption of two herbicides, fluridone (FLUN) and norflurazon (NORO), by two types of biochars, whole sediment, and various soil/sediment organic matter (OM) fractions including nonhydrolyzable carbon (NHC), black carbon (BC) and humic acid (HA) was examined. The single-point organic carbon (OC)-normalized distribution coefficients (K(OC)) of FLUN and NORO at low solution concentration (C(e)=0.01S(W), solubility) for HA, NHC, and BC were about 3, 14, and 24 times and 3, 16, and 36 times larger than their bulk sediments, respectively, indicating the importance of different OM fractions in herbicide sorption. This study revealed that aliphatic moieties of the hydrothermal biochars and aromatic moieties of NHC samples, respectively, were possibly responsible for herbicide sorption. The hydrothermal biochar and condensed OM (i.e., NHC and BC) showed relatively high or similar herbicide sorption efficiency compared to the thermal biochar, suggesting that the hydrothermal biochar may serve as an amendment for minimizing off-site herbicide movement.

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.

Isolation and characterization of different organic matter fractions from a same soil source and their phenanthrene sorption.

Four humic acids (HAs) including de-ashed HAs (D-HAs), two humins (HMs), nonhydrolyzable carbons, and demineralized fraction (DM) were isolated separately from two soils and characterized detailedly; then their sorption of phenanthrene (Phen) was examined. The sequence of removal of HAs and minerals affected molecular composition of HMs. After de-ashing, thermal stability of HAs was improved; however, sorption (logKoc) also decreased due to removal of amorphous alkyl-C. Significant correlations between CO2 surface area of HAs with their sorption coefficients (n and Koc) suggested that pore filling could dominate Phen sorption. Alkyl-C could facilitate elevated thermal stability of OM and Phen sorption, supporting that thermal stability of OM was correlated with Phen sorption. The OM fraction composed of aromatic moieties (AMs) did not produce the highest logKoc, providing strong evidence to dispute the dominant role of AMs in Phen sorption. No correlations between the Koc values of Phen by all tested sorbents and their bulk or surface polarity were observed, suggesting that the role of bulk or surface polarity of OM fractions in regulating Phen sorption was dependent on soil sources. This work shows the major influence of bulk and surface composition of OM and amorphous alkyl-C isolated from a soil sample on hydrophobic organic compounds sorption.

Adsorption of diuron, fluridone and norflurazon on single-walled and multi-walled carbon nanotubes

The sorption behaviors of diuron (DIU), fluridone (FLU) and norflurazon (NOR) by a single-walled carbon nanotube (SWCNT) and three multi-walled carbon nanotubes (MWCNT) samples including MWCNT10 (<10nm, outer diameter), MWCNT20 (10-20 nm), and MWCNT40 (20-40 nm) were investigated. All adsorption isotherms were nonlinear and were well fitted with the Freundlich model and Dubinin Ashtakhov (DA) model. The linear relationships between the organic carbon (OC)-normalized saturated adsorption capacity (Q(0)(OC)) and surface area (SA) suggest that SA is presumably responsible for the adsorption of DIU and NOR on CNTs. While FLU, DIU, and NOR OC-normalized distribution coefficients (logK(OC)) of CNTs increased with increasing their hydrophobicity (logK(OW)) and the positive relationships between the logK(OW)-normalized logK(OC) (i.e., logK(OC)/logK(OW)) of FLU, DIU, and NOR and their hydrogen bonding ability indicate that the adsorption of FLU, DIU and NOR was mainly controlled by the hydrophobic interaction and hydrogen bonding. The higher logK(OC) or Q(0)(OC) values of MWCNT10 and SWCNT relative to other large MWCNTs and carbonaceous adsorbents suggest that MWCNT10 has the potential to serve as an adsorbent used to reduce the mobility of herbicides in agricultural and environmental applications.

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.

Sorption of four hydrophobic organic contaminants by biochars derived from maize straw, wood dust and swine manure at different pyrolytic temperatures.

Sorption behavior of acetochlor (ACE), dibutyl phthalate (DBP), 17α-Ethynyl estradiol (EE2) and phenanthrene (PHE) with biochars produced from three feedstocks (maize straw (MABs), pine wood dust (WDBs) and swine manure (SWBs)) at seven heat treatment temperatures (HTTs) was evaluated. The bulk polarity of these biochars declined with increasing HTT while the aromaticity and CO2-surface area (CO2-SA) rose. The surface OC contents of biochars were generally higher than bulk OC contents. The organic carbon (OC)-normalized CO2-SA (CO2-SA/OC) of biochars significantly correlated with the sorption coefficients (n and logK(oc)), suggesting that pore filling could dominate the sorption of tested sorbates. SWBs had higher logK(oc) values compared to MABs and WDBs, due to their higher ash contents. Additionally, the logK(oc) values for MABs was relatively greater than that for WDBs at low HTTs (≤400 °C), probably resulting from the higher CO2-SA/OC, ash contents and aromaticity of MABs. Surface polarity and the aliphatic C may dominate the sorption of WDBs obtained at relatively low HTTs (≤400 °C), while aromatic C affects the sorption of biochars at high HTTs. Results of this work aid to deepen our understanding of the sorption mechanisms, which is pivotal to wise utilization of biochars as sorbents for hazardous organic compounds.

Characterization and Phenanthrene Sorption of Natural and Pyrogenic Organic Matter Fractions

Pyrogenic humic acid (HA) is released into the environment during the large-scale application of biochar. However, the biogeochemistry of pyrogenic organic matter (PyOM) fractions and their sorption of hydrophobic organic compounds (HOCs) are poorly understood in comparison with natural organic matter (NOM) fractions. HA and humin (HM) fractions isolated from soils and the oxidized biochars were characterized. Sorption of phenanthrene (PHE) by these fractions was also examined. The characterization results demonstrate that pyrogenic HAs are different from natural HAs, with the former having lower atomic H/C ratios, more abundant aromatic C, and higher concentrations of surface carboxylic groups. Compared with the fresh biochars, the Koc of PHE on their oxidized biochars, pyrogenic HA, and HM fractions were undiminished, which is encouraging for the use of biochar in soil remediation. The PyOM fractions exhibited stronger nonlinear sorption than the NOM fractions. In addition, the PyOM fractions had higher sorption capacity than the NOM fractions due to their low polar C content and high aryl C content. The results obtained from this work will shed new light on the impact of the addition of biochar on the biogeochemistry of soil organic matter and on the fate of HOCs in biochar-amended soil.

Effects of chemical oxidation on phenanthrene sorption by grass- and manure-derived biochars

The oxidation of biochar in the natural environment has been widely observed. However, its influence on the sorption of hydrophobic organic compounds (HOCs) by biochars, especially biochars with high contents of minerals, remains poorly understood. In this study, sorption of phenanthrene (PHE) by grass straw-based biochars (GRABs) and animal waste-based biochars (ANIBs) produced at 450°C before and after oxidation with HNO3 was investigated. The biochar samples were characterized using elemental analysis, X-ray photoelectron spectroscopy, 13C nuclear magnetic resonance, and CO2 adsorption. Characterization results demonstrate that HNO3 treatment of biochars caused O enrichment, loss of alkyl C, and rise of aromaticity. The organic C-normalized surface area (CO2-SA/OC) of both GRABs and ANIBs generally increased after oxidation. The sorption nonlinearity of PHE by the biochars was weakened after HNO3 treatment. The sorption capacity of PHE by oxidized GRABs was consistently elevated compared with the untreated samples, indicating that the high sorption capacity of PHE by GRABs may be maintained for a long time after being added into soils. By contrast, PHE sorption by ANIBs was unchanged or attenuated after oxidation. Polar groups facilitated the sorption of PHE by GRABs, while inhibited that by ANIBs. Pore-filling and π-π electron donor-acceptor interactions regulated PHE sorption by GRABs. Our results imply that GRABs are promising sorbents for environmental applications in view of their long-lasting sorption capacity.