Xiaoying Guo

Sorption Mechanisms of Phenanthrene, Lindane, and Atrazine with Various Humic Acid Fractions from a Single Soil Sample

The sorption behavior of organic compounds (phenanthrene, lindane, and atrazine) to sequentially extracted humic acids and humin from a peat soil was examined. The elemental composition, XPS and (13)C NMR data of sorbents combined with sorption isotherm data of the tested compounds show that nonspecific interactions govern sorption of phenanthrene and lindane by humic substances. Their sorption is dependent on surface and bulk alkyl carbon contents of the sorbents, rather than aromatic carbon. Sorption of atrazine by these sorbents, however, is regulated by polar interactions (e.g., hydrogen bonding). Carboxylic and phenolic moieties are key components for H-bonding formation. Thermal analysis reveals that sorption of apolar (i.e., phenanthrene and lindane) and polar (i.e., atrazine) compounds by humic substances exhibit dissimilar relationships with condensation and thermal stability of sorption domains, emphasizing the major influence of domain spatial arrangement on sorption of organic compounds with distinct polarity. Results of pH-dependent sorption indicate that reduction in sorption of atrazine by the tested sorbents is more evident than phenanthrene with increasing pH, supporting the dependence of organic compound sorption on its polarity and structure. This study highlights the different interaction mechanisms of apolar and polar organic compounds with humic substances.

Sorption of four hydrophobic organic compounds by three chemically distinct polymers: role of chemical and physical composition.

The sorption behavior of four hydrophobic organic contaminants (HOCs) (i.e., phenanthrene, naphthalene, lindane, and 1-naphthol) by three types of polymers namely polyethylene (PE), polystyrene (PS), and polyphenyleneoxide (PPO) was examined in this work. The organic carbon content-normalized sorption coefficients (K(oc)) of phenanthrene, lindane, and naphthalene by PEs of same composition but distinct physical makeup of domains increased with their crystallinity reduction (from 58.7 to 25.5%), suggesting that mobility and abundance of rubbery domains in polymers regulated HOC sorption. Cross-linking in styrene-divinylbenzene copolymer (PS2) created substantial surface area and porosity, thus, K(oc) values of phenanthrene, lindane, naphthalene, and 1-naphthol by PS2 were as high as 274.8, 212.3, 27.4, and 1.5 times of those by the linear polystyrene (PS1). The K(oc) values of lindane, naphthalene, and 1-naphthol by polar PPO were approximately 1-3 orders of magnitude higher than those by PS1, and PPO had comparable sorption for phenanthrene but higher sorption for naphthalene and 1-naphthol than PS2. This can be a result that a portion of O-containing moieties in PPO were masked in the interior part, while leaving the hydrophobic domains exposed outside, therefore demonstrating the great influence of the spatial arrangement of domains in polymers on HOC sorption.

Suspending multi-walled carbon nanotubes by humic acids from a peat soil.

Suspension of the pristine and COOH-substituted multi-walled carbon nanotubes (P- and C-MWCNTs) with different outer diameters (ODs) by humic acids (HAs) from a peat soil was examined. Under shaking condition, MWCNTs were not suspended within 5 d. Without HAs, C-MWCNTs were slightly suspended by sonication within 16 h, but no suspension was observed for the pristine ones (P-MWCNTs). HAs greatly enhanced suspension of both P- and C-MWCNTs. The suspension enhancement was attributed to HA sorption, which increased electrostatic repulsion and steric hindrance between individual MWCNTs. Introduction of O-containing hydrophilic moieties to MWCNTs via HA sorption enhanced the interactions of their surfaces with water through H-bonding. Suspending capability of various MWCNTs on suspended mass concentration basis by four HAs showed inconsistent orders with the increasing or decreasing trend of their ODs. However, the suspended surface area concentrations of both P- and C-MWCNTs by individual HAs consistently followed an order of P8 > P30 > P50, and C8 > C30 > C50 (P and C, respectively, refer to P- and C-MWCNTs, and the numbers represent their ODs). These data implied that MWCNTs with smaller OD could be more strongly suspended by a given HA relative to those with larger OD under sonication condition.

Sorption mechanisms of organic compounds by carbonaceous materials: site energy distribution consideration.

Sorption of naphthalene, lindane, and atrazine on 10 kinds of carbonaceous materials which included four kinds of graphene, three kinds of graphite, two kinds of carbon nanotubes and one kind of mesoporous carbon was investigated. The approximate sorption site energy distributions were calculated based on Dubinin-Ashtakhov (DA) model. The average sorption site energy and standard deviation of the site energy distribution were deduced and applied to analyze the interaction between sorbents and sorbates, and the sorption site heterogeneity. The introduction of oxygen-containing functional groups to the sorbents caused a decrease in their average sorption energy for the studied compounds. However, relative to the decrease in average site energy, the reduction in number of sorption sites as indicated by surface area more strongly reduced their sorption capacity to the tested carbonaceous materials based on the result of the linear regression analysis. Sorption site heterogeneity of the sorbents decreased as their oxygen contents increased, which is attributed to the better dispersion of the oxygen-containing materials as indicated by their TEM images. The method proposed in this study to quantify the average sorption site energy and heterogeneity is helpful for a better understanding of the sorption mechanisms of organic pollutants to carbonaceous materials.

Impact of the Simulated Diagenesis on Sorption of Naphthalene and 1-Naphthol by Soil Organic Matter and its Precursors

Soil organic matter (SOM) in a peat soil, humic acid, and humin and their precursors (i.e., cellulose and lignin) were treated at high temperature (250 and 400 °C) with high pressure in a sealed platinum reaction kittle to simulate the influence of diagenesis on their composition and structure, and impact of the simulated diagenesis on sorption behaviors of hydrophobic organic compounds (HOCs) (i.e., naphthalene and 1-naphthol) by these samples was investigated. High temperature and pressure treatment greatly influenced chemical composition and physical properties of the original samples and their sorption for both naphthalene and 1-naphthol. Sorption of naphthalene by all samples was jointly regulated by hydrophobic and π-π interactions with their alkyl and aromatic carbon moieties, which was derived from the positive correlation between total hydrophobic carbon content of all sorbents and their organic carbon content-normalized sorption coefficients (Koc) for this compound (p = 0.075). However, sorption of 1-naphthol by the tested sorbents was governed by hydrogen bonding with their O-containing polar functionalities, as derived from the positive correlation between Koc values of 1-Naph and their polarity index ((O+N)/C). Difference in sorption mechanisms of naphthalene and 1-naphthol by the original and treated samples noted the great influence of chemical composition of sorbates on their interaction and essential roles of specific interactions (e.g., hydrogen bonding) in sorption of polar compound (i.e., 1-naphthol) to these sorbents. Surface area (SA) and porosity data of sorbents obtained from N2 sorption-desorption isotherms at 77 K showed that new SA and pores were created during the diagenetic process of all original samples, which provided substantial sorption sites and thus enhanced sorption of naphthalene and 1-naphthol. Among all tested samples, physicochemical properties of cellulose were most strongly affected by the simulated diagenetic process, and impact of such a process on its sorption intensity for the tested compounds was the most significant. The characterization data of the treated sorbents showed that the high temperature and pressure treatment similarly simulated the naturally occurring diagenesis of SOMs and their precursors, which is a first attempt. These findings are valuable for better understanding of the sorption behaviors of HOCs to SOM and its precursors as affected by diagenesis, which in turn is critical for elucidating the transport and fate of HOCs in the environment.

Sorption mechanisms of sulfamethazine to soil humin and its subfractions after sequential treatments

Sorption mechanisms of an antibiotic sulfamethazine (SMT) to humin (HM) isolated from a peat soil and its subfractions after sequential treatments were examined. The treatments of HM included removal of ash, O-alkyl carbon, lipid, and lignin components. The HF/HCl de-ashing treatment removed a large amount of minerals (mainly silicates), releasing a fraction of hydrophobic carbon sorption domains that previously were blocked, increasing the sorption of SMT by 33.3%. The de-O-alkyl carbon treatment through acid hydrolysis greatly reduced polarity of HM samples, thus weakening the interaction between sorbents with water at the interfaces via H-bonding, leaving more effective sorption sites. Sorption of SMT via mechanisms such as van der Waals forces and π-π interactions was enhanced by factors of 2.04-2.50. After removing the lipid/lignin component with the improved Soxhlet extraction/acid hydrolysis, the organic carbon content-normalized sorption enhancement index Eoc was calculated. The results demonstrated that the Eoc-lipid for SMT (16.9%) was higher than Eoc-lignin (10.1%), implying that removal of unit organic carbon mass of lipid led to a higher increase in sorption strength than that of lignin. As each component was progressively removed from HM, the sorption strength and isotherm nonlinearity of the residual HM samples for SMT were gradually enhanced. The Koc values of SMT by HM samples were positively correlated with their aromatic carbon contents, implying that π-π electron donor-acceptor interactions between the benzene ring of sorbate and the aromatic domains in HM played a significant role in their interactions.