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

The stability of TiO₂ nanoparticles in soil suspensions and their transport behavior through saturated homogeneous soil columns were studied. The results showed that TiO₂ could remain suspended in soil suspensions even after settling for 10 days. The suspended TiO₂ contents in soil suspensions after 24 h 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 TiO₂ (18.8-83.0%) readily passed through the soils columns, while TiO₂ was significantly retained by soils with higher clay contents and salinity. TiO₂ aggregate sizes in the column outflow significantly increased after passing through the soil columns. The estimated transport distances of TiO₂ in some soils ranged from 41.3 to 370 cm, indicating potential environmental risk of TiO₂ nanoparticles to deep soil layers.     

Impact of lime-stabilized biosolid application on Cu,Ni, Pb and Zn mobility in an acidic soil

A soil column leaching study was conducted on an acidic soil in order to assess the impact of lime-stabilized biosolid on the mobility of metallic pollutants (Cu, Ni, Pb and Zn). Column leaching experiments were conducted by injecting successively CaCl₂, oxalic acid and ethylenediaminetetraacetic acid (EDTA) solutions through soil and biosolid-amended soil columns. The comparison of leaching curves showed that the transport of metals is mainly related to the dissolved organic carbon, pH and the nature of extractants. Metal mobility in the soil and biosolid-amended soils is higher with EDTA than with CaCl₂ and oxalic acid extractions, indicating that metals are strongly bound to solid-phase components. The single application of lime-stabilized biosolid at a rate ranging from 15 to 30 t/ha tends to decrease the mobility of metals, while repeated applications (2?×?15 t/ha) increase metal leaching from soil. This result highlights the importance of monitoring the movement and concentrations of metals, especially in acid and sandy soils with shallow and smaller water bodies.     

Cu/La共掺杂TiO2光催化氧化水中的氨氮

采用水解-沉淀法制备了Cu/La共掺杂纳米TiO2催化剂,利用XRD、XPS和BET技术对其进行表征,并考察了在紫外灯下,共掺杂TiO2对氨氮的光催化氧化工艺条件。物相结构和比表面积测试结果表明,共掺杂催化剂具有较好的锐钛矿晶型,孔径分布为4～8 nm,Cu/La共掺杂TiO2La以La3+,Cu是以Cu2+、Cu+的形式掺杂进入TiO2的晶格。光催化实验表明:所得改性光催化剂对氨氮的去除及焦化废水的处理均具有较高的催化活性。     

Particulate copper in soils and surface runoff from contaminated sandy soils under citrus production

Soil contamination by copper (Cu) is a worldwide concern. Laboratory incubation and soil Cu characterization were conducted to examine the effects of external Cu loading and liming on Cu speciation in both bulk soil and particulates of an Alfisol and Spodosol under citrus production. Also, drainage water from the sites was evaluated for dissolved and particulate forms of Cu. Soil available Cu estimated by CaCl₂, NH₄OAc, or Mehlich-3 extraction significantly increased with external Cu loads and decreased with soil pH. Most increases in soil Cu occurred in the exchangeable and oxide-bound fractions. Organically bound Cu was the dominant fraction in both bulk soil and particulates, but more in particulates than bulk soil (P?≤?0.001). Organically bound Cu was highly correlated with total recoverable Cu (P?≤?0.01), increased significantly with external Cu loads (P?≤?0.001), and decreased with soil pH (P?≤?0.05). Lime addition converted part of Cu from available pools to more stable forms. Organically bound Cu complexes were found to dominate in soil solution or surface runoff. These results indicate that most Cu accumulated in the contaminated soils is highly mobile, and thus may impact citrus production and the environment.     

The growth and Cu and Zn uptake of pakchois (Brassica chinesis L.) in an acidic soil as affected by chicken or pig manure

In a pot experiment, pig manure (PM) and chicken manure (CM) were applied to an acidic soil at application rates of 2%, 4% and 8% (W/W) to evaluate their effects on the growth, Cu and Zn uptake and transfer of five cultivars of pakchoi (Brassica chinesis L.). The results showed that alkaline manures significantly increased the biomass of pakchois, and also pH and electrical conductivity of the soil. Both 0.01 M CaCl₂ and 1.0 M NH₄NO₃ salt solutions predict the Zn transfer from soil to pakchois well, but not for Cu. For the cultivar Siyueman, the transfer factors of Cu (or Zn) in the PM treatments were higher than that in the CM treatments. In our experiment the Cu and Zn concentrations in pakchois did not exceed the Chinese Food Hygiene Standard, but more attention should be paid to heavy metals risk on pakchois at lower soil pH and salt impairment by manures application.     

Fe_3O_4@SiO_2/TiO_2核壳结构纳米颗粒降解TNT溶液

针对TNT炸药废水具有成分复杂、排放量大、有毒等特点,立足于炸药废水在排放前的降解处理,研究开发一种基于核壳结构Fe3O4@SiO2/TiO2纳米颗粒的高效、可控回收、无二次污染且成本低的光催化降解方法。利用高温碳还原法和溶胶凝胶法制备了具有核壳结构的Fe3O4@SiO2/TiO2纳米颗粒。XRD分析表明,内核Fe3O4呈现磁铁矿特征,表面覆盖的纳米TiO2为锐钛矿型。磁滞回线测试结果显示,复合颗粒的饱和磁化强度为46.5 emu/g,N2吸附-解吸分析结果表明,该颗粒具有典型的介孔结构。使用Fe3O4@SiO2/TiO2纳米颗粒在紫外光下对含TNT废水进行降解,降解率达到81.9%,且颗粒的回收率达到88.4%,为实现高效、可控回收、无二次污染光催化-吸附降解TNT奠定了基础。     

Copper availability and bioavailability are controlled by rhizosphere pH in rape grown in an acidic Cu-contaminated soil

We evaluated how root-induced changes in rhizosphere pH varied and interacted with Cu availability and bioavailability in an acidic soil. Rape was grown on a Cu-contaminated acidic soil, which had been limed at 10 rates. Soil Cu bioavailability was not influenced by liming. However, liming significantly decreased CaCl₂-extracted Cu for pH between 3.7 and 5.1. Little effect was found for pH above 5.1. For soil pH < 4.4, CaCl₂-Cu contents were smaller in rhizosphere than uncropped soil. Rhizosphere alkalisation occurred at pH < 4.8, while acidification occurred at greater pH. This explained the changes of CaCl₂-Cu in the rhizosphere at low pH and the absence of pH dependency of Cu bioavailability to rape. In addition, apoplastic Cu in roots increased with increasing soil pH, most probably as a result of increased dissociation and affinity of cell wall compounds for Cu.     

Enhanced Photocatalysis of Pentachlorophenol by Metal-Modified Titanium (IV) Oxide

The effects of four metals (Ag, Au, Pt, and Cu) doped on TiO₂ on the photocatalysis of pentachlorophenol (PCP) were investigated. The results of this study indicated that all four metals-doped TiO₂ catalysts were able to enhance the efficiency of PCP photocatalysis with an optimum metallic content of 0.1 wt%. For the metal-doped TiO₂ samples (Au, Pt, and Cu), the patterns of light absorption were significantly extended toward visible light spectra in the wavelengths between 400 and 800 nm. The photocatalysis of PCP was pH dependent with the maximum degradation rate achieved in the solution at pH 3. The formation of chloride ion corresponded with the concentration of PCP degraded which confirmed that dechlorination was the major pathway of PCP photocatalysis. The overall toxicities of PCP samples were reduced with the extension of light exposure using the microtox test. The results of PCP photocatalysis are also discussed based on the characteristics of metal/TiO₂ including X-ray differential (XRD) patterns, Brunquer Emmett Teller (BET) specific area analysis, and Ultra Violet (UV)-Vis absorption spectra.     

Enhanced-electrokinetic remediation of copper–pyrene co-contaminated soil with different oxidants and pH control

Electrokinetic (EK) remediation has potential to simultaneously remove heavy metals and organic compounds from soil, but the removal percent of these pollutants is very low in general if no enhancing treatment is applied. This study developed a new enhanced-EK remediation technology to decontaminate a heavy metal–organic compound co-contaminated soil by applying different oxidants and pH control. A red soil was used as a model clayed soil, and was spiked with pyrene and Cu at about 500 mg kg^?1 for both to simulate real situation. Bench-scale EK experiments were performed using four oxidants (H₂O₂, NaClO, KMnO₄, and Na₂S₂O₈) and controlling electrolyte pH at 3.5 or 10. After the treatments with 1.0 V cm^?1 of voltage gradient for 335 h, soil pH, electrical conductivity, and the concentrations and chemical fractionations of soil pyrene and Cu were analyzed. The results showed that there was significant migration of pyrene and Cu from the soil, and the removal percent of soil pyrene and Cu varied in the range of 30–52% and 8–94%, respectively. Low pH favoured the migration of soil Cu, while KMnO₄ was the best one for the degradation of pyrene among the tested oxidants, although it unfortunately prevented the migration of soil Cu by forming Cu oxide. Application of Na₂S₂O₈ and to control the catholyte pH at 3.5 were found to be the best operation conditions for decontaminating the Cu-pyrene co-contaminated soil.     

Adsorption and breakdown of penicillin antibiotic in the presence of titanium oxide nanoparticles in water

The fate and transport of antibiotics in natural water systems is controlled in part by interactions with nanometer (10⁻⁹ m) metal oxide particles. Experiments were performed by mixing solutions of ampicillin (AMP), a common, penicillin-class human and veterinary antibiotic, with 25 nm-TiO₂ (anatase) nanoparticles at different pH conditions. Both sorption and degradation of AMP were observed in the AMP-nanoparticle solutions. For AMP concentrations from ∼3 μM to 2.9 mM the overall AMP removal from solution can be described by linear isotherms with removal coefficients (K_r) of 3028 (±267) L kg⁻¹ at pH 2, 11,533 (±823) L kg⁻¹ at pH 4, 12,712 (±672) L kg⁻¹ at pH 6, and 1941 (±342) L kg⁻¹ at pH 8. Mass spectral analysis of AMP solutions after removal of the solid nanoparticles yielded ions that indicate the presence of peniclloic acid, penilloic acid and related de-ammoniated by-products as possible compounds resulting from the degradation of AMP at the TiO₂ surface.     

Soil pH and Anion Abundance Affects on Copper Adsorption

Abstract

Copper (Cu) input to agricultural soils results from Cu containing pesticides and/or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2–9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0–100 mg L^?1 in the equilibration solution, 95–99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl₂ or Ca(NO₃)₂ as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500–2000 mg L^?1, the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2–7.9. In a high pH soil (pH = 9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

Photocatalytic reduction of carbon dioxide over Cu/TiO<Subscript>2</Subscript> photocatalysts

The photocatalytic reduction of CO₂ with H₂O was investigated using Cu/TiO₂ photocatalysts in aqueous solution. For this purpose, Cu/TiO₂ photocatalysts (with 0.2, 0.9, 2, 4, and 6 wt.% of Cu) have been synthesized via sol-gel method. The photocatalysts were extensively characterized by means of inductively coupled plasma optical emission spectrometry (ICP-OES), N₂ physisorption (BET), XRD, UV-vis DRS, FT-IR, Raman spectroscopy, TEM-EDX, and photoelectrochemical measurements. The as-prepared photocatalysts contain anatase as a major crystalline phase with a crystallite size around 13 nm. By increasing the amount of Cu, specific surface area and band gap energy decreased in addition to the formation of large agglomeration of CuO. Results revealed that the photocatalytic reduction of CO₂ decreased in the presence of Cu/TiO₂ in comparison to pure TiO₂, which might be associated to the formation of CuO phase acting as a recombination center of generated electron-hole pair. Decreasing of photoactivity can also be connected with a very low position of conduction band of photocatalysts with high Cu content, which makes H₂ production necessary for CO₂ reduction more difficult.     

Influence of titanium dioxide nanoparticles on speciation and bioavailability of arsenite

In this study, the influence of the co-existence of TiO₂ nanoparticles on the speciation of arsenite [As(III)] was studied by observing its adsorption and valence changing. Moreover, the influence of TiO₂ nanoparticles on the bioavailability of As(III) was examined by bioaccumulation test using carp (Cyprinus carpio). The results showed that TiO₂ nanoparticles have a significant adsorption capacity for As (III). Equilibrium was established within 30 min, with about 30% of the initial As (III) being adsorbed onto TiO₂ nanoparticles. Most of aqueous As (III) was oxidized to As(V) in the presence of TiO₂ nanoparticles under sunlight. The carp accumulated considerably more As in the presence of TiO₂ nanoparticles than in the absence of TiO₂ nanoparticles, and after 25-day exposure, As concentration in carp increased by 44%. Accumulation of As in viscera, gills and muscle of the carp was significantly enhanced by the presence of TiO₂ nanoparticles.     

Colloid‐facilitated transport of metolachlor through intact soil columns

Abstract

This study evaluated the role of water dispersible colloids with diverse physicochemical and mineralogical characteristics in facilitating the transport of metolachlor through macropores of intact soil columns. The soil columns represented upper solum horizons of an Alfisol in the Bluegrass region of Kentucky. Three different colloid suspensions tagged with metolachlor [2‐chloro‐N‐(2‐ethyl‐6‐methylphenyl)‐N‐(2‐methoxy‐l‐methylethyl)acetamide] were introduced at a constant flux into undisturbed soil columns. The eluents were collected and analyzed periodically for colloid and metolachlor concentrations. Colloid recovery in the eluents ranged from 54 to 90 %. The presence of colloids enhanced the transport of metolachlor by 22 to 70 % depending on the colloid type and mobility. Colloids with higher pH, organic carbon, cation exchange capacity (CEC), total exchangeable bases (TEB), surface area (SA), and electrophoretic mobility (EM), showed better mobility, greater affinity for interaction with the herbicide and, thus, greater potential to co‐transport metolachlor. In contrast, increased level of kaolinite, Fe, and Al inhibited metolachlor adsorption and transport. In spite of the increased transportability of metolachlor by the presence of soil colloids, the colloid bound herbicide portion accounted for a very small part of the observed increase. This suggests that surface site exclusion mechanisms and preferential sorption induced by the presence of colloids are more important than ion exchange phenomena in promoting herbicide mobility in subsurface environments.     

Effect of particle size of titanium dioxide nanoparticle aggregates on the degradation of one azo dye

Introduction

Titanium dioxide (TiO₂) nanoparticle powders have been extensively studied to quickly photodegrade some organic pollutants; however, the effect of the particle size of TiO₂ nanoparticle aggregates on degradation remains unclear because microscale aggregates form once the nanoparticle powders enter into water.

Methods

The degradation of azo dye by different particle sizes of TiO₂ nanoparticle aggregates controlled by NaCl concentrations was investigated to evaluate the particle size effect. Removal reactions of reactive black 5 (RB5) with TiO₂ nanoparticles followed pseudo-first-order kinetics.

Results

The increase of TiO₂ dosage from 40 to 70?mg/L enhanced the degradation. At doses around 100?mg/L TiO₂, degradation rates decreased which could be the result of poor UV light transmittance at high-particle concentrations. At average particle sizes of TiO₂ nanopowders less than around 500?nm, the degradation rates increased with decreasing particle size. As the average particle size exceeded 500?nm, the degradation rates were not significantly changed.

Conclusions

For the complete degradation experiments, the mineralization rates of total organic carbon disappearance are generally following the RB5 decolorization kinetic trend. These findings can facilitate the application of TiO₂ nanoparticles to the design of photodegradation treatments for wastewater.     

Electrosorption and photocatalytic one-stage combined process using a new type of nanosized TiO2/activated charcoal plate electrode

In the present study, an activated charcoal (AC) plate was prepared by physical activation method. Its surface was coated with TiO₂ nanoparticles by electrophoretic deposition (EPD) method. The average crystallite size of TiO₂ nanoparticles was determined approximately 28 nm. The nature of prepared electrode was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer–Emmett–Teller (BET) surface area measurement before and after immobilization. The electrosorption and photocatalytic one-stage combined process was investigated in degradation of Lanasol Red 5B (LR5B), and the effect of dye concentration, electrolyte concentration, pH, voltage, and contact time was optimized and modeled using response surface methodology (RSM) approach. The dye concentration of 30 mg L^?1, Na₂SO₄ concentration of 4.38 g L^?1, pH of 4, voltage of 250 mV, and contact time of 120 min were determined as optimum conditions. Decolorization efficiency increased in combined process to 85.65 % at optimum conditions compared to 66.03 % in TiO₂/AC photocatalytic, 20.09 % in TiO₂/AC electrosorption, and 1.91 % in AC photocatalytic processes.     

RHIZOtest: A plant-based biotest to account for rhizosphere processes when assessing copper bioavailability

The ability of the free ion activity model (FIAM), the terrestrial biotic ligand model (TBLM), the diffusive gradients in thin films (DGT) technique and a plant-based biotest, the RHIZOtest, to predict root copper (Cu) concentration in field-grown durum wheat (Triticum turgidum durum L.) was assessed on 44 soils varying in pH (3.9-7.8) and total Cu (32-184 mg kg⁻¹). None of the methods adequately predicted root Cu concentration, which was mainly correlated with total soil Cu. Results from DGT measurements and even more so FIAM prediction were negatively correlated with soil pH and over-estimated root Cu concentration in acidic soils. TBLM implementation improved numerically FIAM prediction but still failed to predict adequately root Cu concentration as the TBLM formalism did not considered the rhizosphere alkalisation as observed in situ. In contrast, RHIZOtest measurements accounted for rhizosphere alkalisation and were mainly correlated with total soil Cu.     

Adsorption of Pb,Cd, Cu,Zn, and Ni to titanium dioxide nanoparticles: effect of particle size,solid concentration,and exhaustion

Purpose  

Adsorption of metals (Pb, Cd, Cu, Ni, Zn) to TiO₂ nanoparticles and bulk particles was examined for use as a contaminant removal substrate as a function of particle size, sorbent concentration, and exhaustion.     

Sorption–desorption and transport of trimethoprim and sulfonamide antibiotics in agricultural soil: effect of soil type,dissolved organic matter,and pH

Use of animal manure is a main source of veterinary pharmaceuticals (VPs) in soil and groundwater through a series of migration processes. The sorption–desorption and transport of four commonly used VPs including trimethoprim (TMP), sulfapyridine, sulfameter, and sulfadimethoxine were investigated in three soil layers taken from an agricultural field in Chongming Island China and two types of aqueous solution (0.01 M CaCl₂ solution and wastewater treatment plant effluent). Results from sorption–desorption experiments showed that the sorption behavior of selected VPs conformed to the Freundlich isotherm equation. TMP exhibited higher distribution coefficients (K _d?=?6.73–9.21) than other sulfonamides (K _d?=?0.03–0.47), indicating a much stronger adsorption capacity of TMP. The percentage of desorption for TMP in a range of 8–12 % is not so high to be considered significant. Low pH (<pK _a of tested VPs) and rich soil organic matter (e.g., 0–20 cm soil sample) had a positive impact on sorption of VPs. Slightly lower distribution coefficients were obtained for VPs in wastewater treatment plant (WWTP) effluent, which suggested that dissolved organic matter might affect their sorption behavior. Column studies indicated that the transport of VPs in the soil column was mainly influenced by sorption capacity. The weakly adsorbed sulfonamides had a high recovery rate (63.6–98.0 %) in the leachate, while the recovery rate of TMP was only 4.2–10.4 %. The sulfonamides and TMP exhibited stronger retaining capacity in 20–80 cm and 0–20 cm soil samples, respectively. The transport of VPs was slightly higher in the columns leached by WWTP effluent than by CaCl₂ solution (0.01 M) due to their sorption interactions.     

Cellular uptake and mutagenic potential of metal oxide nanoparticles in bacterial cells

Extensive production and consumption of nanomaterials such as ZnO and TiO₂ has increased their release and disposal into the environment. The accumulation of nanoparticles (NPs) in ecosystem is likely to pose threat to non-specific targets such as bacteria. The present study explored the effect of ZnO and TiO₂ NPs in a model bacterium, Salmonella typhimurium. The uptake of ZnO and TiO₂ bare NPs in nano range without agglomeration was observed in S. typhimurium. TEM analysis demonstrated the internalization and uniform distribution of NPs inside the cells. Flow cytometry data also demonstrates that both ZnO and TiO₂ NPs were significantly internalized in the S. typhimurium cells in a concentration dependent manner. A significant increase in uptake was observed in the S. typhimurium treated even with 8 and 80 ng mL⁻¹ of ZnO and TiO₂ NPs with S9 after 60 min, possibly the formation of micelles or protein coat facilitated entry of NPs. These NPs exhibited weak mutagenic potential in S. typhimurium strains TA98, TA1537 and Escherichia coli (WP2uvrA) of Ames test underscoring the possible carcinogenic potential similar to certain mutagenic chemicals. Our study reiterates the need for re-evaluating environmental toxicity of ZnO and TiO₂ NPs presumably considered safe in environment.