Bei Wen

Stability of titania nanoparticles in soil suspensions and transport in saturated homogeneous soil columns.

The stability of TiO(2) nanoparticles in soil suspensions and their transport behavior through saturated homogeneous soil columns were studied. The results showed that TiO(2) could remain suspended in soil suspensions even after settling for 10 days. The suspended TiO(2) contents in soil suspensions after 24h were positively correlated with the dissolved organic carbon and clay content of the soils, but were negatively correlated with ionic strength, pH and zeta potential. In soils containing soil particles of relatively large diameters and lower solution ionic strengths, a significant portion of the TiO(2) (18.8-83.0%) readily passed through the soils columns, while TiO(2) was significantly retained by soils with higher clay contents and salinity. TiO(2) aggregate sizes in the column outflow significantly increased after passing through the soil columns. The estimated transport distances of TiO(2) in some soils ranged from 41.3 to 370 cm, indicating potential environmental risk of TiO(2) nanoparticles to deep soil layers.

The role of earthworms (Eisenia fetida) in influencing bioavailability of heavy metals in soils

The effects of earthworm (Eisenia fetida) activity on soil pH, dissolved organic carbon (DOC), microbial populations, fraction distribution and bioavailability of heavy metals (Zn, Cu, Cr, Cd, Co, Ni, and Pb) in five Chinese soils were investigated using pot experiments. A three-step extraction procedure recommended by the European Community Bureau of Reference (BCR; now Standards, Measurements and Testing Programme of the European Community) was used to fractionate the metals in soils into water soluble, exchangeable and carbonate bound (B1), Fe-oxides and Mn-oxides bound (B2) and organic matter and sulfide bound (B3). After the soils were treated with earthworms, the soil pH, water-soluble metal fraction and DOC increased. A significant correlation was obtained between the increased DOC and the increased metals in the water-soluble fraction. The heavy metals in fraction B1 increased after earthworm treatments, while those in fraction B3 decreased. No significant differences were observed for heavy metals in fraction B2. The microbial populations in soil were enumerated with the dilution plate method using several media in the presence of earthworms. The microbial populations increased due to earthworm activity. The biomass of wheat shoots and roots, and the heavy metal concentrations in wheat roots and shoots, were also increased due to the earthworm activity. The present results demonstrated that earthworm activity increases the mobility and bioavailability of heavy metals in soils.

Effect of organic acids on adsorption and desorption of rare earth elements

Effect of citric, malic, tartaric and acetic acids on adsorption of La, Ce, Pr and Nd by and desorption from four typical Chinese soils was studied. Generally, adsorption capacities of rare earth elements (REEs) were significantly correlated with the cation exchange capacity (CEC) of soils. In the presence of acetic acids adsorption of REEs was similar to that in the presence of Ca(NO3)2. However, in the presence of citric, malic and tartaric acids adsorption of REEs by Heilongjiang, Zhejiang and Guangdong soils decreased to varying extents if compared with that in the presence of nitrate and acetic acid. The significance of suppression followed the order of citric acid > malic acid > tartaric acid > acetic acid, which was consistent with the order of stability of complexes of REEs with these organic acids. However, the adsorption increased with increasing equilibrium solution pH. For Jiangxi soil with low soil pH, CEC and organic matter these organic acids exerted an even more serious suppression effect on the adsorption of REEs. Another feature of the relationship between the adsorption of REEs and equilibrium solution pH was that the adsorption of REEs decreased with increase of pH from 2 to 4.5 and then slightly increased with further increase of pH. Desorption of REEs varied with soils and with organic acids as well. REEs were released easily from Heilongjiang, Zhejiang and Guangdong soils in the presence of organic acid. Generally, desorption of REEs decreased with increasing equilibrium solution pH. Effect of organic acids on desorption of REEs from Jiangxi soil was more complicated. In the presence of citric and malic acids no decrement and/or slight increase in desorption of REEs were observed over the equilibrium solution pH from 3 to 6.5. The reasons for this were ascribed to the strong complexing capacity of citric and malic acids and low soil pH, CEC and organic matter of Jiangxi soil.

Coadsorption of ciprofloxacin and Cu(II) on montmorillonite and kaolinite as affected by solution pH.

The coadsorption of ciprofloxacin (Cip) and Cu(II) on montmorillonite and kaolinite was studied between pH 4.0 and 9.5. At pH < 5.0, Cu(2+), Cip(+) and [Cu(II)(Cip(+/-))](2+) were the main species in solution. Between pH 5.0-7.0 [Cu(II)(Cip(+/-))](2+) was the dominant complex species. Above pH 8.0 [Cu(II)(Cip(-))(2)](0) precipitated. The presence of Cu(II) exerted no effect on the Cip sorption onto montmorillonite at low pH, whereas it increased Cip sorption on montmorillonite at pH > 6.0 due to the stronger affinity of Cip-Cu(II) complexes compared to sole Cip(-) or Cip(+/-), or Cip sorption via a Cu(II) bridge increased. In contrast, Cip increased Cu(II) adsorption on montmorillonite at pH < 7.0, whereas it decreased the adsorption of Cu(II) on kaolinite at pH 6.0-8.0. Cip was sorbed onto the kaolinite surface via interaction of carboxyl groups over the entire pH range. At pH 4.0-4.7, Cip(+) sorption onto kaolinites positively charged surface was more favorable than sorption of Cip-Cu(II) complexes. Batch experiments and FTIR analyses indicated that the coordination between Cip(+/-), Cip(-) and Cu(II) were most likely present on kaolinite surface at pH 7.0. At pH > 8.0, Cu(OH)(2) (s) and [Cu(II)(Cip(-))(2)](0) precipitated out of solution or on the montmorillonite or kaolinite surface, which was not considered evidence for either the sorption of Cip or the adsorption of Cu(II).

Survey of phthalate pollution in arable soils in China

The problem of pollution by phthalates is of global concern due to their widespread occurrence, toxicity and endocrine disruption properties. The contamination by phthalates such as dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP) in 23 arable soils throughout China was investigated to evaluate the present pollution situation. The survey results demonstrated that phthalates were ubiquitous pollutants in soils in China. The total concentrations of phthalates differed from one location to another, and ranged from 0.89 to 10.03 mg kg(-1) with a median concentration of 3.43 mg kg(-1). Among the phthalates, DEHP was dominant and detected in all 23 soils. DEP and DBP were also in abundance, and DMP was rarely detected. Similar contamination patterns were observed in all 23 soils. A distinct feature of phthalate pollution in China was that the average concentration in northern China was higher than that in southern China. In addition, a close relationship was observed between the concentration of phthalates in soils and the consumption of agricultural film. The correlation showed that the application of agriculture film might be a significant pollution source of phthalates in arable soils of China. The potential risk of phthalates in soils was assessed on the basis of current guide values and limits.

Enhanced cadmium accumulation in maize roots—the impact of organic acids

Low molecular weight organic acids are important components of root exudates and therefore, knowledge regarding the mechanisms of cadmium (Cd) uptake and distribution within plants under the influence of organic acids, is necessary for a better understanding of Cd behavior in the plant–soil system. In this study, acetic and malic acids increased the uptake of Cd by maize (Zea mays L. cv. TY2) roots and enhanced Cd accumulation in shoots under hydroponic conditions. Concentration-dependent net Cd influx in the presence and absence of organic acids could be resolved into linear and saturable components. The saturable component followed Michaelis–Menten kinetics, which indicated that Cd uptake across the plasma membrane was transporter-mediated. While the Km values were similar, the Vmax values in the presence of acetic and malic acids were respectively 6.0 and 3.0 times that of the control. Zinc transporters were the most probable pathways for Cd accumulation. It was hypothesized that Cd(II)–organic acid complexes associated with the root zone, could decompose and liberate Cd2+ for subsequent absorption by maize roots; and that in the layer of the roots or within the root free space, depletion of Cd2+ was buffered by the presence of Cd(II)–organic acid complexes. Plant response to elevated Cd levels involved overproduction of organic acids in maize roots as a resistance mechanism to alleviate Cd toxicity.

Relationship between the extractable metals from soils and metals taken up by maize roots and shoots

Two extraction procedures, i.e. a single extraction procedure using low-molecular-weight-organic-acids (LMWOAs) as extractant and a sequential extraction procedure recommended by the European Community Bureau of Reference (BCR), were performed to extract metal fractions from wet rhizosphere soil. And the extracted soil solutions were further fractionated as colloidal and truly dissolved fractions. Heavy metals in maize roots were experimentally defined as metals adsorbed on cell wall and metals taken up by cross-membrane by washing with CaCl(2). The correlation coefficients between extractable metals from soil and taken up by maize roots and shoots were compared between two extraction methods, and a good correlation was obtained if LMWOAs were used. In contrast, the correlation coefficients were poor when the BCR method was used.

Accumulation and uptake of light rare earth elements in a hyperaccumulator Dicropteris dichotoma

Dicropteris dichotoma, a natural perennial fern, grows in acidic soil in southern China. It hyperaccumulates several light rare earth elements La, Ce, Pr and Nd (LREEs) up to about 0.7% of its dry leaf biomass. Through electron microscopic and X-ray microanalyses, LREEs deposits were observed in the cell wall, intercellular space, plasmalemma, vesicles and vacuoles of the root endodermis and stele cells but not in the Casparian band of the fern adventitious root. In addition, LREE deposits were observed in the phloem and xylem of the fern rhizome. These results indicate that at least a portion of the LREEs can be transported symplastically. Histidine and organic acids appear to play a role in stimulating the accumulation of LREEs. This was evident in ferns cultivated in soil amended by histidine, malic and citric acids over a 60-day period. Concentrations of LREEs in D. dichotoma leaves increased by 21-78% as opposed to control, which only increased by 6-10%. While this suggests that histidine and organic acids promote the uptake and sequestration of LREEs in D. dichotoma, the enhancement mechanism of each acid appears to differ. Histidine promoted sequestration of LREEs by forming complexes with LREEs in cells. Organic acids, however, increased the release of LREE from soil, and the uptake of LREEs by fern roots. Most of the LREEs (81-89%) in the cell wall are the result of one of these mechanisms involved in LREE hyperaccumulation. Mass analysis indicated that the molecular weight of LREE-binding peptides was approximately 2000

Modeling the transport of TiO2 nanoparticle aggregates in saturated and unsaturated granular media: Effects of ionic strength and pH

This study aims to explore the mechanisms governing the transport and retention kinetics of TiO(2) nanoparticle aggregates (NPAs) in flow-through columns of packed sand, particularly under unsaturated conditions. The study was carried out at different pHs (2.6, 7.1, and 9.6) and ionic strengths (ISs) (1.0, 10, and 50 mM). A two-site kinetic attachment model was used to describe transport behaviors of TiO(2) NPAs. At low ISs (i.e., 1.0 and 10 mM) and in neutral/alkaline conditions, high mobility of TiO(2) NPAs was observed in both saturated and unsaturated conditions. However, the retention of TiO(2) NPAs was substantially enhanced at the high IS (50 mM) and in extremely acidity condition (pH = 2.6), because of increased aggregation and straining of TiO(2) NPAs during their transport course. The breakthrough curves (BTCs) of TiO(2) NPAs under unsaturated and saturated conditions almost overlapped, suggesting that decreasing the water saturation did not enhance the retention of TiO(2) NPAs in sand columns. This was probably due to the repulsive interactions existed between negatively charged air-water and TiO(2) NPAs systems that resulted in unfavorable attachment conditions. The two-site kinetic attachment model provided a good description for the BTCs of TiO(2) NPAs both in saturated and unsaturated conditions. The fitted parameters could successfully explain the transport behaviors of TiO(2) NPAs under various solution chemistries.

Immobilization of pentachlorophenol in soil using carbonaceous material amendments.

In this study, three pentachlorophenol (PCP) laboratory-spiked and one field-contaminated soil were amended with 2.0% char, humic acid (HA) and peat, respectively. The amended soils were aged for either 7 or 250 days. After amendment, CaCl(2) extractability of PCP was significantly decreased. Desorption kinetics indicated that the proposed amendment could lead to a strong binding and slow desorption of PCP in soils. Amendment with char reduced the bioaccumulation factor (BAF) of PCP most significantly for earthworms (Eisenia fetida) in all soils studied. The results of both physicochemical and biological tests suggested that amendment reduced PCP bioavailability quickly and enduringly, implying that carbonaceous material amendment, especially char amendment, was a potentially attractive in situ remediation method for sequestration of PCP in contaminated soil.