Lanfang Han

Role of Structure and Microporosity in Phenanthrene Sorption by Natural and Engineered Organic Matter

Natural sorbents including one humic acid (HA), humins (HMs), nonhydrolyzable carbons (NHCs), and engineered sorbents (biochars) were subject to bleaching to selectively remove a fraction of aromatic C. The structural properties and sorption isotherm data of phenanthrene (Phen) by original and bleached sorbents were obtained. Significant correlations between Phen Koc values by all sorbents and their organic carbon (OC)-normalized CO2 cumulative surface area (CO2-SA/OC) suggested that nanopore-filling mechanism could dominate Phen sorption. After bleaching, natural sorbents still contained large amounts of aromatic C, which are resistant to bleaching, suggesting that they are derived from condensed or nonbiodegradable organic matter (OM). After eliminating the effect of aromatic C remaining in the bleached samples, a general trend of increasing CO2-SA/OC of natural sorbents with increasing aliphaticity was observed, suggesting that nanopores of natural sorbents are partially derived from their aliphatic moieties. Conversely, positive relationships between CO2-SA/OC or Phen logKoc of engineered sorbents and their aromaticity indicated the aromatic structures of engineered sorbents primarily contribute to their nanopores and dominate their sorption of HOCs. Therefore, this study clearly demonstrated that the role of structure and microporosity in Phen sorption is dependent on the sources of sorbents.

Properties of the plant- and manure-derived biochars and their sorption of dibutyl phthalate and phenanthrene

The properties of plant residue-derived biochars (PLABs) and animal waste-derived biochars (ANIBs) obtained at low and high heating treatment temperatures (300 and 450°C) as well as their sorption of dibutyl phthalate (DBP) and phenanthrene (PHE) were investigated in this study. The higher C content of PLABs could explain that CO2-surface area (CO2-SA) of PLABs was remarkably high relative to ANIBs. OC and aromatic C were two key factors influencing the CO2-SA of the biochars. Much higher surface C content of the ANIBs than bulk C likely explained that the ANIBs exhibited higher sorption of DBP and PHE compared to the PLABs. H-bonding should govern the adsorption of DBP by most of the tested biochars and π-π interaction play an important role in the adsorption of PHE by biochars. High CO2-SA (>200 m2 g−1) demonstrated that abundant nanopores of OC existed within the biochars obtained 450°C (HTBs), which likely result in high and nonlinear sorption of PHE by HTBs.

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.

The spatial distribution, accumulation and potential source of seldom monitored trace elements in sediments of Three Gorges Reservoir, China

The alteration of hydrologic condition of Three Gorges Reservoir (TGR) after impoundment has caused numerous environmental changes. This study investigated the distribution, accumulation and potential sources of the seldom monitored trace elements (SMTEs) in sediments from three tributaries (ZY, MX and CT) and one mainstream (CJ) in TGR during different seasons. The average contents of most SMTEs excluding Sb in the winter were similar to that in the summer. For Sb, its average concentrations in the summer and winter were roughly six and three times higher than its background value, respectively. Contamination factor (CF) and geoaccumulation index (Igeo) demonstrated that most of the sediments were obviously contaminated by Sb. The enrichment factors (EF) of Ga and Sb were higher than 2.0, revealing the possible anthropogenic inputs; However, the EFs of other SMTEs were lower than 1.5, indicating the natural inputs. Correlation and principal component analysis suggested the most SMTEs were positively correlated with major elements (Cr, Mn, Cu, Zn, As, Cd and Pb) and clay contents, which implies that SMTEs had the same sources with these major metals, and the fine particles might be a major carrier for transporting SMTEs from the rivers to the TGR.

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.

Pollution characteristics and source identification of trace metals in riparian soils of Miyun Reservoir, China

The South-to-North Water Diversion Project, one of Chinas largest water diversion projects, has aroused widespread concerns about its potential ecological impacts, especially the potential release of trace metals from shoreline soils into Miyun Reservoir (MYR). Here, riparian soil samples from three elevations and four types of land use were collected. Soil particle size distributions, contents and chemical fractionations of trace metals and lead (Pb) isotopic compositions were analyzed. Results showed that soil texture was basically similar in four types of land use, being mainly composed of sand, with minor portions of clay and silt, while recreational land contained more abundant chromium (Cr), copper (Cu), zinc (Zn) and cadmium (Cd), suggesting a possible anthropogenic source for this soil pollution. The potential ecological risk assessment revealed considerable contamination of recreational land, with Cd being the predominant contaminant. Chemical fractionations showed that Cu, arsenic (As), Pb and Cd had potential release risks. Additionally, the 206Pb/207Pb and 208Pb/207Pb values of soils were similar to those of coal combustion. By combining principal component analysis (PCA) with Pb isotopic results, coal combustion was identified as the major anthropogenic source of Zn, Cr, Cu, Cd and Pb. Moreover, isotope ratios of Pb fell in the scope of aerosols, indicating that atmospheric deposition may be the primary input pathway of anthropogenic Zn, Cr, Cu, Cd and Pb. Therefore, controlling coal combustion should be a priority to reduce effectively the introduction of additional Zn, Cu, Cd, and Pb to the area in the future.

Spatial distribution, health risk assessment, and isotopic composition of lead contamination of street dusts in different functional areas of Beijing, China.

Street dusts from heavy density traffic area (HDTA), tourism area (TA), residential area (RA), and educational area (EA) in Beijing were collected to explore the distribution, health risk assessment, and source of lead (Pb). The average concentration of Pb in TA was the highest among the four areas. Compared with other cities, Pb concentrations in Beijing were generally at moderate or low levels. The average value (14.05) of ecological risk index (RI) indicated that Pb was at “low pollution risk” status. According to the calculation on hazard index (HI), the ingestion of dust particles of children and adults was the major route of exposure to street dusts in four studied areas, followed by dermal contact. The lower values of HI than 1 further suggested that non-carcinogenic risks of Pb in the street dusts were in the low range. Comparing 206Pb/207Pb and 208Pb/207Pb ratios of street dusts with other environmental samples, it was found that atmospheric deposition of coal combustion dust might be the main pathway for anthropogenic Pb input to the street dusts in four functional areas.

HNO 3 modified biochars for uranium (VI) removal from aqueous solution

The HNO3 treatment was used to chemically modify the biochars produced from wheat straw (WH) and cow manure for U(VI) removal from aqueous solution. Macroscopic experiments proved that the enrichment of U(VI) on the biochars was regulated by surface complexation and electrostatic interactions. FTIR and XPS analyses confirmed that the highly efficient adsorption of U(VI) was due to the carboxyl groups on the biochar surfaces. The reducing agents of the R-CH2OH groups facilitated U(VI) adsorption on the untreated biochars. Owing to the higher contents of surface COO groups and more negative surface charge, the modified biochars showed enhanced U(VI) adsorption ability than the untreated ones. The maximum adsorption capacity of U(VI) by the oxidized WH was calculated to be 355.6 mg/g at pH 4.5 and 298 K, which was an improvement of 40 times relative to the untreated WH and was higher than that of most carbon-based adsorbents.

Oxidation resistance of biochars as a function of feedstock and pyrolysis condition

Assessing biochars ability to resist oxidation is fundamental to understanding its potential to sequester carbon. Chemical oxidation exhibits good performance in estimating the oxidation resistance of biochar. Herein, oxidation resistance of 14 types of biochars produced from four feedstocks at different pyrolysis conditions (hydrothermal versus thermal carbonization) was investigated via hydrogen peroxide oxidation with varying concentrations. The oxidation resistance of organic carbon (C) of hydrochars was relatively higher than that of 250°C pyrochars (P250) but was comparable to that of 450°C pyrochars (P450). Both hydrochars and P450 from ash-rich feedstocks contained at least three different C pools (5.9-18.3% labile, 43.2-56.5% semi-labile and 26.9-45.9% stable C). Part (<33%) of aromatic C within 600°C pyrochars (P600) was easily oxidizable, which consisted of amorphous C. The influence of pyrolysis temperature upon oxidation resistance of biochars depended on the feedstock. For ash-rich feedstock (rice straw, swine manure and poultry litter), the oxidation resistance of biochars was determined by both aromaticity and mineral components, and mineral protection was regulated by pyrolysis conditions. The amorphous silicon within hydrochars and P450 could interact with C, preventing C from being oxidized, to some extent. Nevertheless, this type of protection did not occur for P250 and P600.

Effect of minerals on the stability of biochar

The stability of biochar is a major determinant of its potential for carbon sequestration. In previous studies, the biochar stability was evaluated by analyzing the oxidation resistance property of biochar, for which, K2Cr2O7/H2O2 oxidation and thermogravimetric analysis (TGA) were widely used to measure the high oxidation resistance of biochars. In this study, rice straw (RI)- and swine manure (SW)-derived biochars produced at different heating treatment temperatures (HTTs) and their corresponding de-ashed biochars and iron-biochars were selected to investigate the effect of minerals on these biochars stability. There was a significantly positive correlation between carbon remaining values (CRVs) obtained after K2Cr2O7/H2O2 oxidation and ash (mineral) contents of biochars (p < 0.05). Moreover, the decreasing CRVs of most biochars were observed after de-ashing treatment. These K2Cr2O7/H2O2 oxidation results indicated that endogenous minerals in biochars can protect biochars from chemical oxidation. On the other hand, the R50 (C recalcitrance index) values of iron-biochars (33.3-57.4%) were lower than those of corresponding biochars (38.6-60.8%), indicating that Fe-bearing mineral formed in biochars can promote the thermal decomposition of biochars. In H2O2 oxidation, the different change trend of CRVs between biochars produced at 450 °C and biochars produced at 600 °C after iron mineral treatment showed that the effect of exogenous Fe-bearing mineral on biochar stability was related to biochar category regulated by HTTs. This study indicated that endogenous minerals could increase biochar stability, and exogenous Fe-bearing minerals had dissimilar effects on different kinds of biochars, which critically regulates the potential of biochar for long-term carbon sequestration.